US20020160194A1 - Multi-layered magnetic pigments and foils - Google Patents

Multi-layered magnetic pigments and foils Download PDF

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Publication number
US20020160194A1
US20020160194A1 US09/844,261 US84426101A US2002160194A1 US 20020160194 A1 US20020160194 A1 US 20020160194A1 US 84426101 A US84426101 A US 84426101A US 2002160194 A1 US2002160194 A1 US 2002160194A1
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US
United States
Prior art keywords
magnetic
pigment
layer
flake
pigment flake
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Abandoned
Application number
US09/844,261
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English (en)
Inventor
Roger Phillips
Charlotte LeGallee
Charles Markantes
Paul Coombs
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Flex Products Inc
Original Assignee
Flex Products Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Flex Products Inc filed Critical Flex Products Inc
Priority to US09/844,261 priority Critical patent/US20020160194A1/en
Assigned to FLEX PRODUCTS, INC. reassignment FLEX PRODUCTS, INC. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: LEGALLEE, CHARLOTTE R., COOMBS, PAUL G., MARKANTES, CHARLES T., PHILLIPS, ROGER W.
Priority to JP2003507196A priority patent/JP4353792B2/ja
Priority to CNB028088328A priority patent/CN1288674C/zh
Priority to EP07021051.3A priority patent/EP1918332B1/de
Priority to ES02765768T priority patent/ES2386137T3/es
Priority to AT07021052T priority patent/ATE535578T1/de
Priority to EP07021053.9A priority patent/EP1918333B1/de
Priority to KR1020077024998A priority patent/KR100856105B1/ko
Priority to AU2002329168A priority patent/AU2002329168A1/en
Priority to PT07021052T priority patent/PT1921117E/pt
Priority to ES07021052T priority patent/ES2377534T3/es
Priority to DK07021052.1T priority patent/DK1921117T3/da
Priority to KR1020077024999A priority patent/KR100856430B1/ko
Priority to EP07021050.5A priority patent/EP1918331B1/de
Priority to CN2006100770079A priority patent/CN1854204B/zh
Priority to KR1020087018022A priority patent/KR100931623B1/ko
Priority to EP07021052A priority patent/EP1921117B1/de
Priority to AT02765768T priority patent/ATE557068T1/de
Priority to EP02765768A priority patent/EP1412432B1/de
Priority to KR1020077024997A priority patent/KR100856533B1/ko
Priority to EP07021054.7A priority patent/EP1918334B1/de
Priority to KR1020037014038A priority patent/KR100915147B1/ko
Priority to KR1020077025000A priority patent/KR100856429B1/ko
Priority to PCT/US2002/001059 priority patent/WO2003000801A2/en
Publication of US20020160194A1 publication Critical patent/US20020160194A1/en
Priority to US10/360,964 priority patent/US6818299B2/en
Priority to US10/637,605 priority patent/US6838166B2/en
Priority to JP2007274512A priority patent/JP4937879B2/ja
Priority to JP2007293763A priority patent/JP4863512B2/ja
Priority to JP2008331550A priority patent/JP5132540B2/ja
Priority to CY20121100043T priority patent/CY1112965T1/el
Abandoned legal-status Critical Current

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    • 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
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/16—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by features of a layer formed of particles, e.g. chips, powder or granules
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B42—BOOKBINDING; ALBUMS; FILES; SPECIAL PRINTED MATTER
    • B42D—BOOKS; BOOK COVERS; LOOSE LEAVES; PRINTED MATTER CHARACTERISED BY IDENTIFICATION OR SECURITY FEATURES; PRINTED MATTER OF SPECIAL FORMAT OR STYLE NOT OTHERWISE PROVIDED FOR; DEVICES FOR USE THEREWITH AND NOT OTHERWISE PROVIDED FOR; MOVABLE-STRIP WRITING OR READING APPARATUS
    • B42D25/00—Information-bearing cards or sheet-like structures characterised by identification or security features; Manufacture thereof
    • B42D25/30—Identification or security features, e.g. for preventing forgery
    • B42D25/36—Identification or security features, e.g. for preventing forgery comprising special materials
    • B42D25/369—Magnetised or magnetisable materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M3/00—Printing processes to produce particular kinds of printed work, e.g. patterns
    • B41M3/14—Security printing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B42—BOOKBINDING; ALBUMS; FILES; SPECIAL PRINTED MATTER
    • B42D—BOOKS; BOOK COVERS; LOOSE LEAVES; PRINTED MATTER CHARACTERISED BY IDENTIFICATION OR SECURITY FEATURES; PRINTED MATTER OF SPECIAL FORMAT OR STYLE NOT OTHERWISE PROVIDED FOR; DEVICES FOR USE THEREWITH AND NOT OTHERWISE PROVIDED FOR; MOVABLE-STRIP WRITING OR READING APPARATUS
    • B42D25/00—Information-bearing cards or sheet-like structures characterised by identification or security features; Manufacture thereof
    • B42D25/20—Information-bearing cards or sheet-like structures characterised by identification or security features; Manufacture thereof characterised by a particular use or purpose
    • B42D25/29—Securities; Bank notes
    • 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
    • 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
    • C09C1/0078—Pigments consisting of flaky, non-metallic substrates, characterised by a surface-region containing free 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
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/62—Metallic pigments or fillers
    • B42D2033/16—
    • B42D2035/24—
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/51—Particles with a specific particle size distribution
    • C01P2004/52—Particles with a specific particle size distribution highly monodisperse size distribution
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/54—Particles characterised by their aspect ratio, i.e. the ratio of sizes in the longest to the shortest dimension
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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    • 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
    • C01P2004/00—Particle morphology
    • C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
    • C01P2004/82—Particles consisting of a mixture of two or more inorganic phases two phases having the same anion, e.g. both oxidic phases
    • C01P2004/84—Particles consisting of a mixture of two or more inorganic phases two phases having the same anion, e.g. both oxidic phases one phase coated with the other
    • C01P2004/86—Thin layer coatings, i.e. the coating thickness being less than 0.1 time the particle radius
    • 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
    • C01P2006/42—Magnetic properties
    • 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
    • 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
    • C01P2006/65—Chroma (C*)
    • 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
    • C01P2006/66—Hue (H*)
    • 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
    • C01P2006/90—Other properties not specified above
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C2200/00—Compositional and structural details of pigments exhibiting interference colours
    • C09C2200/10—Interference pigments characterized by the core material
    • C09C2200/1004—Interference pigments characterized by the core material the core comprising at least one inorganic oxide, e.g. Al2O3, TiO2 or SiO2
    • C09C2200/1008—Interference pigments characterized by the core material the core comprising at least one inorganic oxide, e.g. Al2O3, TiO2 or SiO2 comprising at least one metal layer adjacent to the core material, e.g. core-M or M-core-M
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C2200/00—Compositional and structural details of pigments exhibiting interference colours
    • C09C2200/10—Interference pigments characterized by the core material
    • C09C2200/102—Interference pigments characterized by the core material the core consisting of glass or silicate material like mica or clays, e.g. kaolin
    • C09C2200/1025—Interference pigments characterized by the core material the core consisting of glass or silicate material like mica or clays, e.g. kaolin comprising at least one metal layer adjacent to core material, e.g. core-M or M-core-M
    • 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
    • C09C2200/10—Interference pigments characterized by the core material
    • C09C2200/1087—Interference pigments characterized by the core material the core consisting of bismuth oxychloride, magnesium fluoride, nitrides, carbides, borides, lead carbonate, barium or calcium sulfate, zinc sulphide, molybdenum disulphide or graphite
    • C09C2200/1091—Interference pigments characterized by the core material the core consisting of bismuth oxychloride, magnesium fluoride, nitrides, carbides, borides, lead carbonate, barium or calcium sulfate, zinc sulphide, molybdenum disulphide or graphite comprising at least one metal layer adjacent to the core material, e.g. core-M or M-core-M
    • 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
    • C09C2200/24—Interference pigments comprising a metallic reflector or absorber layer, which is not adjacent to the core
    • 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
    • C09C2200/30—Interference pigments characterised by the thickness of the core or layers thereon or by the total thickness of the final pigment particle
    • C09C2200/301—Thickness of the core
    • 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
    • C09C2220/20—PVD, CVD methods or coating in a gas-phase using a fluidized bed
    • 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
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    • 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
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    • 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
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    • Y10T428/2991—Coated
    • Y10T428/2993—Silicic or refractory material containing [e.g., tungsten oxide, glass, cement, etc.]

Definitions

  • the present invention relates generally to pigments and foils.
  • the present invention relates to multilayered pigment flakes and foils which have magnetic layers, and pigment compositions that incorporate multilayer pigment flakes having magnetic layers.
  • pigments, colorants, and foils have been developed for a wide variety of applications.
  • magnetic pigments have been developed for use in applications such as decorative cookware, creating patterned surfaces, and security devices.
  • color shifting pigments have been developed for such uses as cosmetics, inks, coating materials, ornaments, ceramics, automobile paints, anti-counterfeiting hot stamps, and anti-counterfeiting inks for security documents and currency.
  • Color shifting pigments, colorants, and foils exhibit the property of changing color upon variation of the angle of incident light, or as the viewing angle of the observer is shifted.
  • the color-shifting properties of pigments and foils can be controlled through proper design of the optical thin films or orientation of the molecular species used to form the flake or foil coating structure. Desired effects can be achieved through the variation of parameters such as thickness of the layers forming the flakes and foils and the index of refraction of each layer.
  • the changes in perceived color which occur for different viewing angles or angles of incident light are a result of a combination of selective absorption of the materials comprising the layers and wavelength dependent interference effects.
  • the interference effects which arise from the superposition of light waves that have undergone multiple reflections, are responsible for the shifts in color perceived with different angles.
  • the reflection maxima changes in position and intensity, as the viewing angle changes, due to changing interference effects arising from light path length differences in the various layers of a material which are selectively enhanced at particular wavelengths.
  • One manner of producing a multilayer thin film structure is by forming it on a flexible web material with a release layer thereon.
  • the various layers are deposited on the web by methods well known in the art of forming thin coating structures, such as PVD, sputtering, or the like.
  • the multilayer thin film structure is then removed from the web material as thin film color shifting flakes, which can be added to a polymeric medium such as various pigment vehicles for use as an ink or paint.
  • additives can be added to the inks or paints to obtain desired color shifting results.
  • Color shifting pigments or foils are formed from a multilayer thin film structure that includes the same basic layers. These include an absorber layer(s), a dielectric layer(s), and optionally a reflector layer, in varying layer orders.
  • the coatings can be formed to have a symmetrical multilayer thin film structure, such as:
  • absorber/dielectric/reflector/dielectric/absorber [0009] absorber/dielectric/reflector/dielectric/absorber; or
  • Coatings can also be formed to have an asymmetrical multilayer thin film structure, such as:
  • U.S. Pat. No. 5,135,812 to Phillips et al. which is incorporated by reference herein, discloses color-shifting thin film flakes having several different configurations of layers such as transparent dielectric and semi-transparent metallic layered stacks.
  • a symmetric three layer optical interference coating is disclosed which comprises first and second partially transmitting absorber layers which have essentially the same material and thickness, and a dielectric spacer layer located between the first and second absorber layers.
  • Color shifting platelets for use in paints are disclosed in U.S. Pat. No. 5,571,624 to Phillips et al., which is incorporated by reference herein. These platelets are formed from a symmetrical multilayer thin film structure in which a first semi-opaque layer such as chromium is formed on a substrate, with a first dielectric layer formed on the first semi-opaque layer. An opaque reflecting metal layer such as aluminum is formed on the first dielectric layer, followed by a second dielectric layer of the same material and thickness as the first dielectric layer. A second semi-opaque layer of the same material and thickness as the first semi-opaque layer is formed on the second dielectric layer.
  • a first semi-opaque layer such as chromium
  • An opaque reflecting metal layer such as aluminum is formed on the first dielectric layer, followed by a second dielectric layer of the same material and thickness as the first dielectric layer.
  • U.S. Pat. No. 4,838,648 to Phillips et al. discloses a thin film magnetic color shifting structure wherein the magnetic material can be used as the reflector or absorber layer.
  • One disclosed magnetic material is a cobalt nickel alloy.
  • Phillips '648 discloses flakes and foils with the following structures:
  • Patterned surfaces have been provided by exposing magnetic flakes to a magnetic force to effect a physical alteration in the structure of the pigment.
  • U.S. Pat. No. 6,103,361 to Batzar et al. uses pigments made of magnetizable materials to decorate cookware.
  • Batzar is directed toward controlling the orientation of stainless steel flakes in a fluoropolymer release coating to make patterns where at least some of the flakes are longer than the coating thickness.
  • the patterned substrate is formed by applying magnetic force through the edges of a magnetizable die positioned under a coated base to alter the orientation of the flakes within the coating, thereby inducing an imaging effect or pattern.
  • Batzar does not discuss the use of optical thin film stacks or platelets employing a magnetic layer.
  • the stainless steel flakes used in Batzar are suitable for decorating cookware, they are poorly reflecting.
  • U.S. Pat. No. 2,570,856 to Pratt et al (hereinafter “Pratt”) is directed to metallic flake pigments which are based on ferromagnetic metal platelets. Like Batzar, however, Pratt uses poorly reflecting metals and does not teach the use of thin film optical stacks.
  • U.S. Pat. Nos. 5,364,689 and 5,630,877 to Kashiwagi et al. disclose methods and apparatus for creating magnetically formed painted patterns.
  • the Kashiwagi patents teach use of a magnetic paint layer, which includes nonspherical magnetic particles in a paint medium. A magnetic field with magnetic field lines in the shape of the desired pattern is applied to the paint layer. The final pattern is created by the different magnetic particle orientations in the hardened paint.
  • Schmid uses aluminum platelets and then coats these platelets with magnetic materials.
  • the overlying magnetic material downgrades the reflective properties of the pigment because aluminum is the second brightest metal (after silver), meaning any magnetic material is less reflective.
  • Schmid starts with aluminum platelets generated from ballmilling, a method which is limited in terms of the layer smoothness that can be achieved.
  • Patent Publication EP 710508A1 to Richter et al. discloses methods for providing three dimensional effects by drawing with magnetic tips.
  • Richter describes three dimensional effects achieved by aligning magnetically active pigments in a spatially-varying magnetic field.
  • Richter uses standard pigments (barium ferrite, strontium ferrite, samarium/cobalt, Al/Co/Ni alloys, and metal oxides made by sintering and quick quenching, none of which are composed of optical thin film stacks. Rather, the particles are of the hard magnetic type.
  • Richter uses electromagnetic pole pieces either on top of the coating or on both sides of the coating. However, Richter uses a moving system and requires “drawing” of the image. This “drawing” takes time and is not conducive to production type processes.
  • Stepgroever U.S. Pat. No. 3,791,864 to Steingroever (hereinafter “Steingroever”) describes a method for patterning magnetic particles by orienting them with a magnetic pattern generated in an underlying prime coating that has previously been patterned by a magnetic field.
  • the prime coat contains magnetic particles of the type MO ⁇ 6Fe 2 O 3 where M can be one or more of the elements Ba, Sr, Co, or Pb.
  • M can be one or more of the elements Ba, Sr, Co, or Pb.
  • a pigment vehicle with magnetic particles suspended therein is then applied.
  • the magnetic particles suspended therein are finally oriented by the magnetic force from the magnetic pattern in the primer, creating the final pattern.
  • Steingroever suffers from a diffuse magnetic image in the prime coat, which in turn passes a diffuse image to the topcoat.
  • This reduction in resolution is because high magnetic fields are limited in the resolution they can create.
  • This limitation is due to high magnetic field lines surrounding the intended magnetic image, thereby affecting untargeted magnetic particles in the prime coat and blurring the image.
  • pigment flakes and foils which have magnetic properties.
  • the pigment flakes can have a symmetrical stacked coating structure on opposing sides of a magnetic core layer, can have an asymmetrical coating structure with all of the layers on one side of the magnetic layer, or can be formed with one or more encapsulating coatings around a magnetic core.
  • the coating structure of the flakes and foils includes at least one magnetic layer and optionally one or more of a reflector layer, dielectric layer, and absorber layer. In color shifting embodiments of the invention, the coating structure includes the dielectric layer overlying the magnetic and reflector layers, and the absorber layer overlying the dielectric layer.
  • Non color shifting embodiments of the invention include a magnetic layer between two reflector layers or encapsulated by a reflector layer, a magnetic layer between two dielectric layers or encapsulated by a dielectric layer, a dielectric layer between two magnetic layers or encapsulated by a magnetic layer, and a magnetic layer encapsulated by a colorant layer.
  • the color shifting embodiments exhibit a discrete color shift so as to have a first color at a first angle of incident light or viewing and a second color different from the first color at a second angle of incident light or viewing.
  • the pigment flakes can be interspersed into liquid media such as paints or inks to produce colorant compositions for subsequent application to objects or papers.
  • the foils can be laminated to various objects or can be formed on a carrier substrate.
  • FIG. 1 is a schematic representation of the coating structure of a magnetic flake according to one embodiment of the invention.
  • FIG. 2 is a schematic representation of the coating structure of a magnetic flake according to another embodiment of the invention.
  • FIG. 3 is a schematic representation of the coating structure of a magnetic flake according to an alternative embodiment of the invention.
  • FIG. 4 is a schematic representation of the coating structure of a magnetic flake according to another embodiment of the invention.
  • FIG. 5 is a schematic representation of the coating structure of a magnetic flake according to a further embodiment of the invention.
  • FIG. 6 is a schematic representation of the coating structure of a magnetic flake according to a further embodiment of the invention.
  • FIG. 7 is a schematic representation of the coating structure of a magnetic flake according to an alternative embodiment of the invention.
  • FIG. 8 is a schematic representation of the coating structure of a magnetic flake according to a further embodiment of the invention.
  • FIG. 9 is a schematic representation of the coating structure of a magnetic flake according to yet a further embodiment of the invention.
  • FIG. 10 is a schematic representation of the coating structure of a magnetic flake according to another alternative embodiment of the invention.
  • FIG. 11 is a schematic representation of the coating structure of a magnetic flake according to another embodiment of the invention.
  • FIG. 12 is a schematic representation of the coating structure of a magnetic flake according to a further embodiment of the invention.
  • FIG. 13 is a schematic representation of the coating structure of a magnetic foil according to one embodiment of the invention.
  • FIG. 14 is a schematic representation of the coating structure of a magnetic foil according to another embodiment of the invention.
  • FIG. 15 is a schematic representation of the coating structure of a magnetic foil according to a further embodiment of the invention.
  • FIG. 16 is a schematic representation of the coating structure of an optical article according to an additional embodiment of the invention.
  • FIG. 17 is a schematic representation of the coating structure of an optical article according to a further embodiment of the invention.
  • the present invention relates to multilayer pigment flakes and foils which have magnetic layers, and pigment compositions which incorporate the magnetic flakes.
  • the flakes and foils can be used both to create security features which are not visually perceptible, and to create three dimensional-like images for security devices or to add decorative features to a product.
  • the nonvisual security features are provided by burying the magnetic layer between other layers within a flake or foil so that only the overlying layers are exposed.
  • the three dimensional-like effects can be provided by exposing the flake or foil to an external magnetic force, thereby orienting the plane of some of the pigments normal to the surface of the coating.
  • the un-oriented pigments lie with their planar surface parallel to the surface of the coating.
  • the three dimensional-like effect is due to the alignment of the particles such that the aspect ratio is oriented with the magnetic field, i.e. the longest part of the pigment aligns itself along the magnetic field lines. In such case, the face of the pigment is turned away from the observer to various extents depending on the magnitude of the magnetic force. In the limit or maximum orientation, the coating appears black in color.
  • the presently disclosed flakes are not composed only of magnetizable materials, but include both magnetizable and nonmagnetizable materials.
  • the invention encompasses pigment flakes wherein a magnetic layer is buried within one or more reflector layers.
  • the pigment flakes comprise a magnetic core surrounded by dielectric layers.
  • the pigment flakes include a dielectric core surrounded by magnetic layers.
  • the present invention presents a significant improvement over the prior art by substantially achieving higher chroma and brightness.
  • the present invention accomplishes two objectives: 1) the reflectivity of the reflector layer is maintained; and 2) color shifting pigments without the inner core of magnetic material cannot be distinguished by an observer from such pigment with the core of magnetic material.
  • two coated objects viewed side by side, one with and one without the magnetic material in the coating would look the same to the observer.
  • the magnetic color shifting pigment provides a covert security feature in addition to the color shifting effect.
  • a magnetic covert signature in the pigment could be read by a Faraday rotator detector, for example.
  • the pigment flakes and foils have substantial shifts in chroma and hue with changes in angle of incident light or viewing angle of an observer.
  • Such an optical effect known as goniochromaticity or “color shift,” allows a perceived color to vary with the angle of illumination or observation.
  • Such pigment flakes and foils exhibit a first color at a first angle of incident light or viewing and a second color different from the first color at a second angle of incident light or viewing.
  • the pigment flakes can be interspersed into liquid media such as paints or inks to produce various color shifting colorant compositions for subsequent application to objects or papers.
  • the foils can be laminated to various objects or can be formed on a carrier substrate.
  • the color shifting pigment flakes can have a symmetrical stacked coating structure on opposing sides of a magnetic core layer, can have an asymmetrical coating structure with a majority of the layers on one side of the magnetic layer, or can be formed with one or more encapsulating coatings which surround a magnetic core.
  • the coating structure of the flakes and foils generally includes a magnetic core, which includes a magnetic layer and other optional layers, a dielectric layer overlying the magnetic core, and an absorber layer overlying the dielectric layer.
  • the color shifting flakes and foils of the invention can be formed using conventional thin film deposition techniques, which are well known in the art of forming thin coating structures.
  • thin film deposition techniques include physical vapor deposition (PVD), chemical vapor deposition (CVD), plasma enhanced (PE) variations thereof such as PECVD or downstream PECVD, sputtering, electrolysis deposition, and other like deposition methods that lead to the formation of discrete and uniform thin film layers.
  • the color shifting pigment flakes of the invention can be formed by various fabrication methods.
  • the pigment flakes can be formed by a web coating process in which various layers are sequentially deposited on a web material by conventional deposition techniques to form a thin film structure, which is subsequently fractured and removed from the web, such as by use of a solvent, to form a plurality of thin film flakes.
  • one or more thin film layers including at least the magnetic layer is deposited on a web to form a film, which is subsequently fractured and removed from the web to form a plurality of pigment preflakes.
  • the preflakes can be fragmented further by grinding if desired.
  • the preflakes are then coated with the remaining layer or layers in a sequential encapsulation process to form a plurality of pigment flakes.
  • magnetic particles can be coated in a sequential encapsulation process to form a plurality of pigment flakes.
  • each respective encapsulating layer is a continuous layer composed of one material and having substantially the same thickness around the flake structure.
  • the encapsulating layer can be a colored dielectric material or an organic layer with added colorant.
  • FIG. 1 depicts a reflective magnetic flake (“RMF”) 20 according to one embodiment of the invention.
  • the RMF 20 is a three layer design having a generally symmetrical thin film structure with a central magnetic layer 22 and at least one reflector layer on either or both of the opposing major surfaces of the central magnetic layer.
  • RMF 20 comprises a magnetic layer interdisposed between a reflector layer 24 and an opposing reflector layer 26 .
  • the RMF 20 can be used as a pigment flake or can be used as a core section with additional layers applied thereover such as in a color shifting pigment. In the case of color shifting pigments, maintaining the high reflective layer is extremely important to preserve high brightness and chroma. Each of these layers in the coating structure of RMF 20 is discussed below in greater detail.
  • the magnetic layer 22 can be formed of any magnetic material such as nickel, cobalt, iron, gadolinium, terbium, dysprosium, erbium, and their alloys or oxides.
  • a cobalt nickel alloy can be employed, with the cobalt and nickel having a ratio by weight of about 80% and about 20%, respectively. This ratio for each of these metals in the cobalt nickel alloy can be varied by plus or minus about 10% and still achieve the desired results.
  • cobalt can be present in the alloy in an amount from about 70% to about 90% by weight
  • nickel can be present in the alloy in an amount from about 10% to about 30% by weight.
  • alloys include Fe/Si, Fe/Ni, FeCo, Fe/Ni/Mo, and combinations thereof.
  • Hard magnetics of the type SmCo 5 , NdCo 5 , Sm 2 Co 17 , Nd 2 Fe 14 B, Sr 6 Fe 2 O 3 , TbFe 2 , Al—Ni—Co, and combinations thereof, can also be used as well as spinel ferrites of the type Fe 3 O 4 , NiFe 2 O 4 , MnFe 2 O 4 , CoFe 2 O 4 , or garnets of the type YIG or GdIG, and combinations thereof.
  • the magnetic material may be selected for its reflecting or absorbing properties as well as its magnetic properties.
  • the magnetic material When utilized to function as a reflector, the magnetic material is deposited to a thickness so that it is substantially opaque. When utilized as an absorber, the magnetic material is deposited to a thickness so that it is not substantially opaque. A typical thickness for the magnetic material when utilized as an absorber is from about 2 nm to about 20 nm.
  • the “soft” magnets are preferred in some embodiments of the invention.
  • hard magnets also called permanent magnets
  • a ferromagnetic material is any material that has a permeability substantially greater than 1 and that exhibits magnetic hysteresis properties.
  • the magnetic materials used to form magnetic layers in the flakes and foils of the invention have a coercivity of less than about 2000 Oe, more preferably less than about 300 Oe.
  • Coercivity refers to the ability of a material to be demagnetized by an external magnetic field. The higher the value of coercivity, the higher the magnetic field required to de-magnetize the material after the field is removed.
  • the magnetic layers used are preferably “soft” magnetic materials (easily demagnetized), as opposed to “hard” magnetic materials (difficult to demagnetize) which have higher coercivities.
  • the coercivities of the foils, pigments or colorants of the magnetic color shifting designs according to the invention are preferably in a range of about 50 Oe to about 300 Oe. These coercivities are lower than in standard recording materials.
  • preferred embodiments of the invention which use soft magnets in magnetic color shifting pigments and magnetic non color shifting pigments are an improvement over conventional technologies.
  • the use of soft magnetic materials in pigment flakes allows for easier dispersion of the flakes without clumping.
  • the magnetic layer 22 can be formed to have a suitable physical thickness of from about 200 angstroms ( ⁇ ) to about 10,000 ⁇ , and preferably from about 500 ⁇ to about 1,500 ⁇ .
  • ⁇ angstroms
  • the optimal magnetic thickness will vary depending on the particular magnetic material used and the purpose for its use. For example, a magnetic absorber layer will be thinner than a magnetic reflector layer based on the optical requirements for such layers, while a covert magnetic layer will have a thickness based solely on its magnetic properties.
  • the reflector layers 24 and 26 can be composed of various reflective materials. Presently preferred materials are one or more metals, one or more metal alloys, or combinations thereof, because of their high reflectivity and ease of use, although non-metallic reflective materials could also be used.
  • suitable metallic materials for the reflector layers include aluminum, silver, copper, gold, platinum, tin, titanium, palladium, nickel, cobalt, rhodium, niobium, chromium, and combinations or alloys thereof. These can be selected based on the f desired.
  • the reflector layers 24 , 26 can be formed to have a suitable physical thickness of from about 400 ⁇ to about 2,000 ⁇ , and preferably from about 500 ⁇ to about 1,000 ⁇ .
  • opposing dielectric layers may optionally be added to overlie reflector layers 24 and 26 . These opposing dielectric layers add durability, rigidity, and corrosion resistance to RMF 20 .
  • an encapsulating dielectric layer may be formed to substantially surround reflector layers 24 , 26 and magnetic layer 22 .
  • the dielectric layer(s) may be optionally clear, or may be selectively absorbing so as to contribute to the color effect of the pigment flake. Examples of suitable dielectric materials for the dielectric layers are described hereafter.
  • FIG. 2 depicts a magnetic color shifting pigment flake 40 based upon a RMF according to one embodiment of the invention.
  • the flake 40 is a generally symmetrical multilayer thin film structure having layers on opposing sides of a RMF 42 .
  • first and second dielectric layers 44 and 46 are disposed respectively on opposing sides of RMF 42
  • first and second absorber layers 48 and 50 are disposed respectively on each of dielectric layers 44 and 46 .
  • the RMF is as discussed hereinabove for FIG. 1 while the dielectric and absorber layers are discussed below in greater detail.
  • the dielectric layers 44 and 46 act as spacers in the thin film stack structure of flake 40 . These layers are formed to have an effective optical thickness for imparting interference color and desired color shifting properties.
  • the dielectric layers may be optionally clear, or may be selectively absorbing so as to contribute to the color effect of a pigment.
  • the optical thickness is a well known optical parameter defined as the product ⁇ d, where ⁇ is the refractive index of the layer and d is the physical thickness of the layer.
  • the optical thickness of a layer is expressed in terms of a quarter wave optical thickness (QWOT) that is equal to 4 ⁇ d/ ⁇ , where ⁇ is the wavelength at which a QWOT condition occurs.
  • QWOT quarter wave optical thickness
  • the optical thickness of dielectric layers can range from about 2 QWOT at a design wavelength of about 400 nm to about 9 QWOT at a design wavelength of about 700 nm, and preferably 2-6 QWOT at 400-700 nm, depending upon the color shift desired.
  • the dielectric layers typically have a physical thickness of about 100 nm to about 800 nm, depending on the color characteristics desired.
  • Suitable materials for dielectric layers 44 and 46 include those having a “high”index of refraction, defined herein as greater than about 1.65, as well as those have a “low” index of refraction, which is defined herein as about 1.65 or less.
  • Each of the dielectric layers can be formed of a single material or with a variety of material combinations and configurations.
  • the dielectric layers can be formed of only a low index material or only a high index material, a mixture or multiple sublayers of two or more low index materials, a mixture or multiple sublayers of two or more high index materials, or a mixture or multiple sublayers of low index and high index materials.
  • the dielectric layers can be formed partially or entirely of high/low dielectric optical stacks, which are discussed in further detail below.
  • the remaining portion of the dielectric layer can be formed with a single material or various material combinations and configurations as described above.
  • suitable high refractive index materials for the dielectric layer include zinc sulfide (ZnS), zinc oxide (ZnO), zirconium oxide (ZrO 2 ), titanium dioxide (TiO 2 ), diamond-like carbon, indium oxide (In 2 O 3 ), indium-tin-oxide (ITO), tantalum pentoxide (Ta2O5), ceric oxide (CeO 2 ), yttrium oxide (Y 2 O 3 ), europium oxide (Eu 2 O 3 ), iron oxides such as (II)diiron(III) oxide (Fe 3 O 4 ) and ferric oxide (Fe 2 O 3 ), hafnium nitride (HfN), hafnium carbide (HfC), hafnium oxide (HfO 2 ), lanthanum oxide (La 2 O 3 ), magnesium oxide (MgO), neodymium oxide (Nd 2 O 3 ), praseodymium oxide (Pr 6 O 11
  • Suitable low refractive index materials for the dielectric layer include silicon dioxide (SiO 2 ), aluminum oxide (Al 2 O 3 ), metal fluorides such as magnesium fluoride (MgF 2 ), aluminum fluoride (AlF 3 ), cerium fluoride (CeF 3 ), lanthanum fluoride (LaF 3 ), sodium aluminum fluorides (e.g., Na 3 AlF 6 or Na 5 Al 3 Fl 4 ), neodymium fluoride (NdF 3 ), samarium fluoride (SmF 3 ), barium fluoride (BaF 2 ), calcium fluoride (CaF 2 ), lithium fluoride (LiF), combinations thereof, or any other low index material having an index of refraction of about 1.65 or less.
  • metal fluorides such as magnesium fluoride (MgF 2 ), aluminum fluoride (AlF 3 ), cerium fluoride (CeF 3 ), lanthanum fluoride (LaF 3 ), sodium aluminum
  • organic monomers and polymers can be utilized as low index materials, including dienes or alkenes such as acrylates (e.g., methacrylate), perfluoroalkenes, polytetrafluoroethylene (Teflon), fluorinated ethylene propylene (FEP), combinations thereof, and the like.
  • dienes or alkenes such as acrylates (e.g., methacrylate), perfluoroalkenes, polytetrafluoroethylene (Teflon), fluorinated ethylene propylene (FEP), combinations thereof, and the like.
  • dielectric materials are typically present in non-stoichiometric forms, often depending upon the specific method used to deposit the dielectric material as a coating layer, and that the above-listed compound names indicate the approximate stoichiometry.
  • silicon monoxide and silicon dioxide have nominal 1:1 and 1:2 silicon:oxygen ratios, respectively, but the actual silicon:oxygen ratio of a particular dielectric coating layer varies somewhat from these nominal values.
  • Such non-stoichiometric dielectric materials are also within the scope of the present invention.
  • the dielectric layers can be formed of high/low dielectric optical stacks, which have alternating layers of low index (L) and high index (H) materials.
  • L low index
  • H high index
  • the color shift at angle will depend on the combined refractive index of the layers in the stack.
  • LH indicates discrete layers of a low index material and a high index material.
  • the high/low dielectric stacks are formed with a gradient index of refraction.
  • the graded index is produced by a gradual variance in the refractive index, such as low-to-high index or high-to-low index, of adjacent layers.
  • the graded index of the layers can be produced by changing gases during deposition or co-depositing two materials (e.g., L and H) in differing proportions.
  • Various high/low optical stacks can be used to enhance color shifting performance, provide antireflective properties to the dielectric layer, and change the possible color space of the pigments of the invention.
  • the dielectric layers can each be composed of the same material or a different material, and can have the same or different optical or physical thickness for each layer. It will be appreciated that when the dielectric layers are composed of different materials or have different thicknesses, the flakes exhibit different colors on each side thereof and the resulting mix of flakes in a pigment or paint mixture would show a new color which is the combination of the two colors. The resulting color would be based on additive color theory of the two colors coming from the two sides of the flakes. In a multiplicity of flakes, the resulting color would be the additive sum of the two colors resulting from the random distribution of flakes having different sides oriented toward the observer.
  • the absorber layers 48 , 50 of flake 40 can be composed of any absorber material having the desired absorption properties, including materials that are uniformly absorbing or non-uniformly absorbing in the visible part of the electromagnetic spectrum. Thus, selective absorbing materials or nonselective absorbing materials can be used, depending on the color characteristics desired.
  • the absorber layers can be formed of nonselective absorbing metallic materials deposited to a thickness at which the absorber layer is at least partially absorbing, or semi-opaque.
  • Nonlimiting examples of suitable absorber materials include metallic absorbers such as chromium, aluminum, nickel, silver, copper, palladium, platinum, titanium, vanadium, cobalt, iron, tin, tungsten, molybdenum, rhodium, and niobium, as well as their corresponding oxides, sulfides, and carbides.
  • Other suitable absorber materials include carbon, graphite, silicon, germanium, cermet, ferric oxide or other metal oxides, metals mixed in a dielectric matrix, and other substances that are capable of acting as a uniform or selective absorber in the visible spectrum.
  • Various combinations, mixtures, compounds, or alloys of the above absorber materials may be used to form the absorber layers of flake 40 .
  • suitable alloys of the above absorber materials include Inconel (Ni—Cr—Fe), stainless steels, Hastalloys (e.g., Ni—Mo—Fe; Ni—Mo—Fe—Cr; Ni—Si—Cu) and titanium-based alloys, such as titanium mixed with carbon (Ti/C), titanium mixed with tungsten (Ti/W), titanium mixed with niobium (Ti/Nb), and titanium mixed with silicon (Ti/Si), and combinations thereof.
  • the absorber layers can also be composed of an absorbing metal oxide, metal sulfide, metal carbide, or combinations thereof.
  • one preferred absorbing sulfide material is silver sulfide.
  • suitable compounds for the absorber layers include titanium-based compounds such as titanium nitride (TiN), titanium oxynitride (TiN x O y ), titanium carbide (TiC), titanium nitride carbide (TiN x C z ), titanium oxynitride carbide (TiN x O y C z ), titanium silicide (TiSi 2 ), titanium boride (TiB 2 ), and combinations thereof.
  • titanium-based compounds such as titanium nitride (TiN), titanium oxynitride (TiN x O y ), titanium carbide (TiC), titanium nitride carbide (TiN x C z ), titanium oxynitride carbide (TiN x O y C z ), titanium silicide (TiSi 2 ), titanium boride (TiB 2 ), and combinations thereof.
  • the absorber layers can be composed of a titanium-based alloy disposed in a matrix of Ti, or can be composed of Ti disposed in a matrix of a titanium-based alloy.
  • the absorber layer also could be formed of a magnetic material, such as a cobalt nickel alloy. This simplifies the manufacture of the magnetic color shifting device or structure by reducing the number of materials required.
  • the absorber layers are formed to have a physical thickness in the range from about 30 ⁇ to about 500 ⁇ , and preferably about 50 ⁇ to about 150 ⁇ , depending upon the optical constants of the absorber layer material and the desired peak shift.
  • the absorber layers can each be composed of the same material or a different material, and can have the same or different physical thickness for each layer.
  • an asymmetrical color shifting flake can be provided which includes a thin film stack structure with the same layers as on one side of RMF 42 as shown in FIG. 2. Accordingly, the asymmetrical color shifting flake includes RMF 42 , dielectric layer 44 overlying RMF 42 , and absorber layer 48 overlying dielectric layer 44 . Each of these layers can be composed of the same materials and have the same thicknesses as described above for the corresponding layers of flake 40 .
  • asymmetrical color shifting flakes can be formed by a web coating process such as described above in which the various layers are sequentially deposited on a web material to form a thin film structure, which is subsequently fractured and removed from the web to form a plurality of flakes.
  • flake 40 can be formed without the absorber layers.
  • opposing dielectric layers 44 and 46 are formed of high/low (H/L) dielectric optical stacks such as described previously.
  • QW quarterwave
  • FIG. 3 depicts a reflective magnetic flake or particle (“RMP”) 60 according to another embodiment of the invention.
  • the RMP 60 is a two layer design with a reflector layer 62 substantially surrounding and encapsulating a core magnetic layer 64 . By inserting the magnetic layer within the reflector layer, the optical properties of the reflector layer are not downgraded and the reflector layer remains highly reflective.
  • the RMP 60 can be used as a pigment particle or can be used as a core section with additional layers applied thereover.
  • the magnetic layer and reflector layer can be composed of the same materials discussed with respect to RMF 20 .
  • a dielectric layer may optionally be added to overlie reflector layer 62 , to add durability, rigidity, and corrosion resistance to RMP 60 .
  • the dielectric layer may be optionally clear, or may be selectively absorbing so as to contribute to the color effect of the pigment flake.
  • FIG. 4 depicts alternative coating structures (with phantom lines) for a magnetic color shifting pigment flake 80 in the form of an encapsulate based upon either the RMF or the RMP according to other embodiments of the invention.
  • the flake 80 has a magnetic core section 82 , which is either a RMF or a RMP, which can be overcoated by an encapsulating dielectric layer 84 substantially surrounding magnetic core section 82 .
  • An absorber layer 86 which overcoats dielectric layer 84 , provides an outer encapsulation of flake 80 .
  • the hemispherical dashed lines on one side of flake 80 in FIG. 4 indicate that dielectric layer 84 and absorber layer 86 can be formed as contiguous layers around magnetic core section 82 .
  • the magnetic core section 82 and dielectric layer can be in the form of a thin film core flake stack, in which opposing dielectric layers 84 a and 84 b are preformed on the top and bottom surfaces but not on at least one side surface of magnetic core section 82 (RMF), with absorber layer 86 encapsulating the thin film stack.
  • An encapsulation process can also be used to form additional layers on flake 80 such as a capping layer (not shown).
  • the pigment flake 80 exhibits a discrete color shift such that the pigment flake has a first color at a first angle of incident light or viewing and a second color different from the first color at a second angle of incident light or viewing.
  • flake 80 can be formed without the absorber layer.
  • dielectric layer 84 is formed of contiguous high/low (H/L) dielectric optical coatings similar to the dielectric optical stacks described previously.
  • FIG. 5 depicts another alternative coating structure for a color shifting pigment flake 100 according to the present invention.
  • the flake 100 includes a magnetic core section 82 and a single dielectric layer 84 , which extends over top and bottom surfaces of magnetic core section 82 to form a dielectric-coated preflake 86 .
  • the core section 82 can be an RMF, RMP, or a magnetic layer.
  • the dielectric-coated preflake 86 has two side surfaces 88 and 90 . Although side surface 90 is homogeneous and formed only of the dielectric material of dielectric layer 84 , side surface 88 has distinct surface regions 88 a , 88 b , 88 c of dielectric, magnetic core section, and dielectric, respectively.
  • the dielectric-coated preflake 86 is further coated on all sides with an absorber layer 92 .
  • the absorber layer 92 is in contact with dielectric layer 84 and magnetic core section 82 at side surface 88 .
  • the structure of pigment flake 100 typically occurs because of a preflake coating process similar to the one disclosed in U.S. application Ser. No. 09/512,116 described previously.
  • the preflakes can be a dielectric-coated flake, in which a dielectric coating completely encapsulates an RMF or RMP (see FIG. 4), or a magnetic layer (see FIG. 10).
  • the preflakes are broken into sized preflakes using any conventional fragmentation process, such as by grinding.
  • the sized preflakes will include some sized preflakes having top and bottom dielectric layers with no dielectric coating on the side surfaces of the preflake, such as shown for the embodiment of flake 40 in FIG. 2 in which RMF 42 is coated with top and bottom dielectric layers 44 and 46 .
  • sized preflakes will have a single dielectric layer extending over both top and bottom surfaces of the magnetic core flake section, leaving one side surface of the magnetic core flake section exposed, such as shown for dielectric-coated preflake 86 in FIG. 5. Because of the fragmentation process, substantially all of the sized preflakes have at least a portion of a side surface exposed. The sized preflakes are then coated on all sides with an absorber layer, such as shown in the flakes of FIGS. 4 and 5.
  • FIG. 6 depicts a composite magnetic flake (“CMF”) 120 which comprises a central dielectric support layer 122 with first and second magnetic layers 124 , 126 on opposing major surfaces thereof.
  • CMF composite magnetic flake
  • the CMF 120 can be used as a pigment flake by itself or can be used as a magnetic core section with additional layers applied thereover.
  • the magnetic layers 124 , 126 can be formed of any of the magnetic materials described previously.
  • the dielectric material used for support layer 122 is preferably inorganic, since inorganic dielectric materials have been found to have good characteristics of brittleness and rigidity.
  • Various dielectric materials that can be utilized include metal fluorides, metal oxides, metal sulfides, metal nitrides, metal carbides, combinations thereof, and the like.
  • the dielectric materials may be in either a crystalline, amorphous, or semicrystalline state. These materials are readily available and easily applied by physical or chemical vapor deposition processes.
  • suitable dielectric materials include magnesium fluoride, silicon monoxide, silicon dioxide, aluminum oxide, titanium dioxide, tungsten oxide, aluminum nitride, boron nitride, boron carbide, tungsten carbide, titanium carbide, titanium nitride, silicon nitride, zinc sulfide, glass flakes, diamond-like carbon, combinations thereof, and the like.
  • support layer 122 may be composed of a preformed dielectric or ceramic preflake material having a high aspect ratio such as a natural platelet mineral (e.g., mica peroskovite or talc), or synthetic platelets formed from glass, alumina, silicon dioxide, carbon, micaeous iron oxide, coated mica, boron nitride, boron carbide, graphite, bismuth oxychloride, various combinations thereof, and the like.
  • a natural platelet mineral e.g., mica peroskovite or talc
  • synthetic platelets formed from glass, alumina, silicon dioxide, carbon, micaeous iron oxide, coated mica, boron nitride, boron carbide, graphite, bismuth oxychloride, various combinations thereof, and the like.
  • various semiconductive and conductive materials having a sufficient ratio of tensile to compressive strength can function as a support layer.
  • examples of such materials include silicon, metal siicides, semiconductive compounds formed from any of the group III, IV, or V elements, metals having a body centered cubic crystal structure, cermet compositions or compounds, semiconductive glasses, various combinations thereof, and the like. It will be appreciated from the teachings herein, however, that any support material providing the functionality described herein and capable of acting as a rigid layer with glass-like qualities would be an acceptable substitute for one of these materials.
  • the thickness of support layer 122 can be in a range from about 10 nm to about 1,000 nm, preferably from about 50 nm to about 200 nm, although these ranges should not be taken as restrictive.
  • FIG. 7 depicts a composite magnetic particle (“CMP”) 140 according to another embodiment of the invention.
  • the CMP 140 is a two layer design with a magnetic layer 142 substantially surrounding and encapsulating a central support layer 144 such as a dielectric layer. By inserting the support layer within the magnetic layer, CMP 140 is significantly stabilized and rigid. The support layer adds rigidity and durability to the pigment flake.
  • the magnetic layer 142 can be formed of any of the magnetic materials described previously.
  • the support layer 144 can be formed of the same materials described hereinabove for support layer 122 of CMF 120 .
  • the CMP 140 can be used as a pigment particle by itself or can be used as a magnetic core section with additional layers applied thereover. For example, an outer dielectric layer may be added to overlie and encapsulate magnetic layer 142 . This outer dielectric layer adds durability, rigidity, and corrosion resistance to CMP 140 .
  • FIG. 8 depicts a coating structure for a color shifting pigment flake 160 in the form of an encapsulate.
  • the flake 160 has a thin core layer 162 , which can be formed of a dielectric or other material as taught hereinabove for support layer 122 .
  • the core layer 162 is overcoated on all sides with a magnetic layer 164 , which can be composed of the same materials as described above for magnetic layer 22 of RMF 20 .
  • a reflector layer 168 can be applied over magnetic layer 164 .
  • Suitable materials for reflector layer 168 include those materials described for reflector layer 24 of RMF 20 .
  • the reflector layer effectively provides the reflective function of flake 160 , shielding magnetic layer 164 from being optically present.
  • the core layer 162 and magnetic layer 164 can be provided as a CMP 166 which is overcoated with the other layers.
  • CMP 166 can be replaced with a CMF such as shown in FIG. 6.
  • An encapsulating dielectric layer 170 substantially surrounds reflector layer 168 and magnetic layer 164 .
  • An absorber layer 172 which overlays dielectric layer 170 , provides an outer encapsulation of flake 160 .
  • Suitable preferred methods for forming the dielectric layer include vacuum vapor deposition, sol-gel hydrolysis, CVD in a fluidized bed, downstream plasma onto vibrating trays filled with particles, and electrochemical deposition.
  • a suitable SiO 2 sol-gel process is described in U.S. Pat. No. 5,858,078 to Andes et al., the disclosure of which is incorporated by reference herein.
  • Other examples of suitable sol-gel coating techniques useful in the present invention are disclosed in U.S. Pat. No.
  • Suitable preferred methods for forming the absorber layers include vacuum vapor deposition, and sputtering onto a mechanically vibrating bed of particles, as disclosed in commonly assigned copending patent application Ser. No. 09/389,962, filed Sep. 3, 1999, entitled “Methods and Apparatus for Producing Enhanced Interference Pigments,” which is incorporated by reference herein in its entirety.
  • the absorber coating may be deposited by decomposition through pyrolysis of metal-organo compounds or related CVD processes which may be carried out in a fluidized bed as described in U.S. Pat. Nos. 5,364,467 and 5,763,086 to Schmid et al., the disclosures of which are incorporated by reference herein. If no further grinding is carried out, these methods result in an encapsulated core flake section with dielectric and absorber materials therearound.
  • Various combinations of the above coating processes may be utilized during manufacture of pigment flakes with multiple encapsulating coatings.
  • the absorber coating powdered flakes or other coated preflakes are placed on a square-shaped vibrating conveyor coater in a vacuum coating chamber as disclosed in U.S. application Ser. No. 09/389,962, discussed above.
  • the vibrating conveyor coater includes conveyor trays which are configured in an overlapping inclined arrangement so that the powdered flakes travel along a circulating path within the vacuum chamber. While the flakes circulate along this path they are effectively mixed by constant agitation so that exposure to the vaporized absorber coating material is uniform. Efficient mixing also occurs at the end of each conveyor tray as the flakes drop in a waterfall off of one tray and onto the next tray.
  • the absorber can be sequentially coated on the flakes as they repeatably move under a coating material source.
  • FIG. 9 depicts a dielectric coated magnetic flake (“DMF”) 180 according to a further embodiment of the invention.
  • the DMF 180 is a three layer design having a generally symmetrical thin film structure with a central magnetic layer and at least one dielectric layer on either or both of the opposing major surfaces of the central magnetic layer.
  • DMF 180 includes a magnetic layer 182 sandwiched in between a dielectric layer 184 and an opposing dielectric layer 186 . By inserting the magnetic layer between the dielectric layers, the DMF has increased rigidity and durability.
  • FIG. 10 depicts a dielectric coated magnetic particle (“DMP”) 200 according to another embodiment of the invention.
  • the DMP 200 is a two layer design with a dielectric layer 202 substantially surrounding and encapsulating a central magnetic layer 204 .
  • each of the layers in the coating structures of DMF 180 and DMP 200 can be formed of the same materials and thickness as corresponding layers described in previous embodiments.
  • the dielectric layer in DMF 180 and DMP 200 can be formed of the same materials and in the same thickness ranges as taught hereinabove for dielectric layer 44 of flake 40
  • the magnetic layers in DMF 180 and DMP 200 can be formed of the same materials and in the same thickness ranges as taught hereinabove for magnetic layer 22 of flake 20 .
  • the DMF 180 and DMP 200 can each be used as a pigment flake or particle, or can be used as a magnetic core section with additional layers applied thereover. FIG.
  • the flake 220 is a three-layer design having a generally symmetrical multilayer thin film structure on opposing sides of a magnetic core section 222 , which can be a DMF or a DMP.
  • first and second absorber layers 224 a and 224 b are formed on opposing major surfaces of magnetic core section 222 .
  • These layers of flake 220 can be formed by a web coating and flake removal process as described previously.
  • FIG. 11 further depicts an alternative coating structure (with phantom lines) for color shifting flake 220 , in which the absorber layer is coated around magnetic core section 222 in an encapsulation process. Accordingly, absorber layers 224 a and 224 b are formed as part of a continuous coating layer 224 substantially surrounding the flake structure thereunder.
  • pigment flake 220 may be embodied either as a multilayer thin film stack flake or a multilayer thin film encapsulated particle. Suitable materials and thicknesses for the absorber, dielectric, and magnetic layers of flake 220 are the same as taught hereinabove.
  • Some flakes of the invention can be characterized as multilayer thin film interference structures in which layers lie in parallel planes such that the flakes have first and second parallel planar outer surfaces and an edge thickness perpendicular to the first and second parallel planar outer surfaces.
  • Such flakes are produced to have an aspect ratio of at least about 2:1, and preferably about 5-15:1 with a narrow particle size distribution.
  • the aspect ratio of the flakes is ascertained by taking the ratio of the longest planar dimension of the first and second outer surfaces to the edge thickness dimension of the flakes.
  • One presently preferred method of fabricating a plurality of pigment flakes, each of which having the multilayer thin film coating structure of flake 40 shown in FIG. 2, is based on conventional web coating techniques used to make optical thin films.
  • flake 40 is described hereinbelow, the other flake structures taught herein can also be fabricated with a procedure similar to the one described hereinbelow.
  • a first absorber layer is deposited on a web of flexible material such as polyethylene terephthalate (PET) which has an optional release layer thereon.
  • PET polyethylene terephthalate
  • the absorber layer can be formed by a conventional deposition process such as PVD, CVD, PECVD, sputtering, or the like.
  • the above mentioned deposition methods enable the formation of a discrete and uniform absorber layer of a desired thickness.
  • a first dielectric layer is deposited on the absorber layer to a desired optical thickness by a conventional deposition process.
  • the deposition of the dielectric layer can be accomplished by a vapor deposition process (e.g., PVD, CVD, PECVD), which results in the dielectric layer cracking under the stresses imposed as the dielectric transitions from the vapor into the solid phase.
  • the magnetic core is then deposited.
  • a first 1 reflector layer is then deposited by PVD, CVD, or PECVD on the first dielectric layer, taking on the characteristics of the underlying cracked dielectric layer.
  • Magnetic layers are then applied by e-beam evaporation, sputtering, electrodeposition, or CVD, followed by a second reflector layer being deposited.
  • a second dielectric layer being deposited on the second reflector layer and preferably having the same optical thickness as the first dielectric layer.
  • a second absorber layer is deposited on the second dielectric layer and preferably has the same physical thickness as the first absorber layer.
  • the flexible web is removed, either by dissolution in a preselected liquid or by way of a release layer, both of which are well known to those skilled in the art.
  • a plurality of flakes are fractured out along the cracks of the layers during removal of the web from the multilayer thin film.
  • This method of manufacturing pigment flakes is similar to that more fully described in U.S. Pat. No. 5,135,812 to Phillips et al., the disclosure of which is incorporated by reference herein.
  • the pigment flakes can be further fragmented if desired by, for example, grinding the flakes to a desired size using an air grind, such that each of the pigment flakes has a dimension on any surface thereof ranging from about 2 microns to about 200 microns.
  • an annealing process can be employed to heat treat the flakes at a temperature ranging from about 200-300° C., and preferably from about 250-275° C., for a time period ranging from about 10 minutes to about 24 hours, and preferably a time period of about 15-60 minutes.
  • flake 240 is deposited according to another embodiment of the invention.
  • flake 240 is a multilayer design having a generally symmetrical thin film structure on opposing sides of a magnetic layer such as a reflective magnetic core 242 , which can be any non-color shifting magnetic pigment flake or particle having reflective properties described herein or known in the art.
  • reflective magnetic core 242 can be a single reflective magnetic layer such as a monolithic layer of Ni or other magnetic reflective metal, or can be a multilayer magnetic structure such as Al/Fe/Al.
  • a first colored layer such as selective absorber layer 244 a and a second colored layer such as selective absorber layer 244 b are formed on opposing major surfaces of reflective magnetic core 242 .
  • These colored layers of flake 240 can be formed by a web coating and flake removal process as described previously.
  • FIG. 12 further depicts an alternative coating structure (with phantom lines) for flake 240 , in which a colored layer such as selective absorber layer 244 is coated around reflective magnetic core 242 in an encapsulation process. Accordingly, selective absorber layers 244 a and 244 b are formed as part of a contiguous coating layer 244 substantially surrounding the flake structure thereunder.
  • Suitable encapsulation methods for forming flake 240 are as described in a copending U.S. Application Serial No. 09/626,041, filed Jul. 27, 2000, the disclosure of which is incorporated by reference herein.
  • pigment flake 240 may be embodied either as a multilayer thin film stack flake or a multilayer thin film encapsulated particle. Suitable materials and thicknesses for use in the reflective magnetic core of flake 240 are the same as taught hereinabove, so long as both reflective and magnetic properties are maintained.
  • the colored layers of flake 240 can be formed of a variety of different absorbing and/or reflecting materials in one or more layers.
  • the colored layers such as selective absorber layers are formed to have a thickness of from about 0.05 ⁇ m to about 5 110 ⁇ m, and more preferably from about 1 ⁇ m to about 2 ⁇ m, by conventional coating processes for dye stuffs, when an organic dye material is utilized to form the selective absorber layers.
  • the colored layers are formed to have a thickness of from about 0.05 ⁇ m to about 0.10 ⁇ m when colored metallics or other inorganic colorant materials are utilized.
  • suitable organic dyes that can be used to form the selective absorber layers of flake 240 include copper phthalocyanine, perylene-based dyes, anthraquinone 17 based dyes, and the like; azo dyes and azo metal dyes such as aluminum red (RLW), aluminum copper, aluminum bordeaux (RL), aluminum fire-red (ML), aluminum red (GLW), aluminum violet (CLW), and the like; as well as combinations or mixtures thereof.
  • Such dyes can be applied by conventional coating techniques and even by evaporation.
  • the colored layers of flake 240 can also be formed of a variety of conventional organic or inorganic pigments applied singly or dispersed in a pigment vehicle. Such pigments are described in the NPIRI Raw Materials Data Handbook, Vol. 4, Pigments (1983), the disclosure of which is incorporated by reference herein.
  • the selective absorber layers of flake 240 comprise a solgel matrix holding a colored pigment or dye.
  • the selective absorber layer can be formed of aluminum oxide or silicon dioxide applied by a sol-gel process, with organic dyes absorbed into pores of the sol-gel coating or bound to the surface of the coating.
  • Suitable organic dyes used in the sol-gel coating process include those available under the trade designations Aluminiumrot GLW (aluminum red GLW) and Aluminiumviolett CLW (aluminum violet CLW) from the Sandoz Company.
  • Aluminum red GLW is an azo metal complex containing copper
  • aluminum violet CLW is a purely organic azo dye.
  • sol-gel coating techniques useful in the present invention are disclosed in the following: U.S. Pat. No. 4,756,771 to Brodalla (1988); Zink et al., Optical Probes and Properties of Aluminosilicate Glasses Prepared by the SolGel Method, Polym. Mater. Sci. Eng., 61, pp. 204-208 (1989); and McKieman et al., Luminescence and Laser Action of Coumarin Dyes Doped in Silicate and Aluminosilicate Glasses Prepared by the Sol-Gel Technique, J. Inorg. Organomet. Polym., 1(1), pp. 87-103 (1991); the disclosures of all of these are incorporated herein by reference.
  • the colored layers of flake 240 can be formed of an inorganic colorant material.
  • suitable inorganic colorants include selective absorbers such as titanium nitride, chromium nitride, chromium oxide, iron oxide, cobalt-doped alumina, and the like, as well as colored metallics such as copper, brass, titanium, and the like.
  • additional dielectric, absorber, and/or other optical coatings can be formed around each of the above flake or particle embodiments, or on a composite reflective film prior to flake formation, to yield further desired optical characteristics.
  • additional coatings can provide additional color effects to the pigments.
  • a colored dielectric coating added to a color shifting flake would act as a color filter on the flake, providing a subtractive color effect which changes the color produced by the flake.
  • the pigment flakes of the present invention can be interspersed within a pigment medium to produce a colorant composition which can be applied to a wide variety of objects or papers.
  • the pigment flakes added to a medium produces a predetermined optical response through radiation incident on a surface of the solidified medium.
  • the pigment medium contains a resin or mixture of resins which can be dried or hardened by thermal processes such as thermal cross-linking, thermal setting, or thermal solvent evaporation or by photochemical cross-linking.
  • Useful pigment media include various polymeric compositions or organic binders such as alkyd resins, polyester resins, acrylic resins, polyurethane resins, vinyl resins, epoxies, styrenes, and the like.
  • Suitable examples of these resins include melamine, acrylates such as methyl methacrylate, ABS resins, ink and paint formulations based on alkyd resins, and various mixtures thereof.
  • the flakes combined with the pigment media produce a colorant composition that can be used directly as a paint, ink, or moldable plastic material.
  • the colorant composition can also be utilized as an additive to conventional paint, ink, or plastic materials.
  • the pigment medium also preferably contains a solvent for the resin.
  • a solvent for the resin generally, either an organic solvent or water can be used.
  • a volatile solvent can also be used in the medium.
  • the volatile solvent it is preferable to use a solvent which is both volatile as well as dilutable, such as a thinner.
  • faster drying of the pigment medium can be achieved by increasing the amount of the solvent with a low boiling point composition such as methyl ethyl ketone (MEK).
  • MEK methyl ethyl ketone
  • the flakes can be optionally blended with various additive materials such as conventional pigment flakes, particles, or dyes of different hues, chroma and brightness to achieve the color characteristics desired.
  • the flakes can be mixed with other conventional pigments, either of the interference type or noninterference type, to produce a range of other colors.
  • This preblended composition can then be dispersed into a polymeric medium such as a paint, ink, plastic or other polymeric pigment vehicle for use in a conventional manner.
  • suitable additive materials that can be combined with the flakes of the invention include non-color shifting high chroma or high reflective platelets which produce unique color effects, such as MgF 2 /Al/MgF 2 platelets, or SiO 2 /Al/SiO 2 platelets.
  • lamellar pigments such as multi-layer color shifting flakes, aluminum flakes, graphite flakes, glass flakes, iron oxide, boron nitride, mica flakes, interference based TiO 2 coated mica flakes, interference pigments based on multiple coated plate-like silicatic substrates, metal-dielectric or all-dielectric interference pigments, and the like; and non-lamellar pigments such as aluminum powder, carbon black, ultramarine blue, cobalt based pigments, organic pigments or dyes, rutile or spinel based inorganic pigments, naturally occurring pigments, inorganic pigments such as titanium dioxide, talc, china clay, and the like; as well as various mixtures thereof.
  • pigments such as aluminum powder or carbon black can be added to control lightness and other color properties.
  • the magnetic color shifting flakes of the present invention are particularly suited for use in applications where colorants of high chroma and durability are desired.
  • high chroma durable paint or ink can be produced in which variable color effects are noticeable to the human eye.
  • the color shifting flakes of the invention have a wide range of color shifting properties, including large shifts in chroma (degree of color purity) and also large shifts in hue (relative color) with a varying angle of view.
  • an object colored with a paint containing the color shifting flakes of the invention will change color depending upon variations in the viewing angle or the angle of the object relative to the viewing eye.
  • the pigment flakes of the invention can be easily and economically utilized in paints and inks which can be applied to various objects or papers, such as motorized vehicles, currency and security documents, household appliances, architectural structures, flooring, fabrics, sporting goods, electronic packaging/housing, product packaging, etc.
  • the color shifting flakes can also be utilized in forming colored plastic materials, coating compositions, extrusions, electrostatic coatings, glass, and ceramic materials.
  • the foils of the invention have a nonsymmetrical thin film coating structure, which can correspond to the layer structures on one side of an RMF in any of the above described embodiments related to thin film stack flakes.
  • the foils can be laminated to various objects or can be formed on a carrier substrate.
  • the foils of the invention can also be used in a hot stamping configuration where the thin film stack of the foil is removed from a release layer of a substrate by use of a heat activated adhesive and applied to a countersurface.
  • the adhesive can be either coated on a surface of the foil opposite from the substrate, or can be applied in the form of a UV activated adhesive to the surface on which the foil will be affixed.
  • FIG. 13 depicts a coating structure of a color shifting foil 300 formed on a substrate 302 , which can be any suitable material such as a flexible PET web, carrier substrate, or other plastic material.
  • a suitable thickness for substrate 302 is, for example, about 2 to 7 mils.
  • the foil 300 includes a magnetic layer 304 on substrate 302 , a reflector layer 306 on magnetic layer 304 , a dielectric layer 308 on reflector layer 306 , and an absorber layer 310 on dielectric layer 308 .
  • the magnetic, reflector, dielectric and absorber layers can be composed of the same materials and can have the same thicknesses as described above for the corresponding layers in flakes 20 and 40 .
  • the foil 300 can be formed by a web coating process, with the various layers as described above sequentially deposited on a web by conventional deposition techniques to form a thin film foil structure.
  • the foil 300 can be formed on a release layer of a web so that the foil can be subsequently removed and attached to a surface of an object.
  • the foil 300 can also be formed on a carrier substrate, which can be a web without a release layer.
  • FIG. 14 illustrates one embodiment of a foil 320 disposed on a web 322 having an optional release layer 324 on which is deposited a magnetic layer 326 , a reflector layer 328 , a dielectric layer 330 , and an absorber layer 332 .
  • the foil 320 may be utilized attached to web 322 as a carrier when a release layer is not employed.
  • foil 320 may be laminated to a transparent substrate (not shown) via an optional adhesive layer 334 , such as a transparent adhesive or ultraviolet (UV) curable adhesive, when the release layer is used.
  • the adhesive layer 334 is applied to absorber layer 332 .
  • FIG. 15 depicts an alternative embodiment in which a foil 340 having the same thin film layers as foil 320 is disposed on a web 322 having an optional release layer 324 .
  • the foil 340 is formed such that absorber layer 332 is deposited on web 322 .
  • the foil 340 may be utilized attached to web 322 as a carrier, which is preferably transparent, when a release layer is not employed.
  • the foil 340 may also be attached to a substrate such as a countersurface 342 when the release layer is used, via an adhesive layer 334 such as a hot stampable adhesive, a pressure sensitive adhesive, a permanent adhesive, and the like.
  • the adhesive layer 334 can be applied to magnetic layer 326 and/or to countersurface 342 .
  • the optical stack of the foil is arranged so that the optically exterior surface is adjacent the release layer.
  • absorber layer 332 is optically present on the exterior.
  • release layer 324 is a transparent hardcoat that stays on absorber layer 332 to protect the underlying layers after transfer from web 322 .
  • the optical article 400 includes a substrate 402 having an upper surface 404 and a lower surface 406 .
  • the substrate 402 can be flexible or rigid and can be formed of any suitable material such as paper, plastic, cardboard, metal, or the like, and can be opaque or transparent.
  • Non-overlapping paired first and second coating structures 408 , 410 are disposed on upper surface 404 so as to overlie non-overlapping first and second regions on surface 404 .
  • first and second coating structures 408 , 410 are not superimposed but are physically separated from each other on surface 404 , although in an abutting relationship.
  • first coating structure 408 can be in the form of a rectangle or square and is disposed within a recess 412 formed by second coating structure 410 , also being in the form of a rectangle or square that forms a border or frame that surrounds first coating structure 408 .
  • first coating structure 408 , 410 can be viewed simultaneously.
  • the first coating structure 408 has a first pigment 414 formed of magnetic pigment flakes or particles, such as color shifting magnetic flakes, constructed in the manner hereinbefore described to provide a magnetic signature.
  • the magnetic properties of pigment 414 are provided by a non-optically observable magnetic-layer within one or more of the magnetic flakes or particles.
  • the second coating structure 410 has a second pigment 416 formed of non-magnetic pigment flakes or particles, such as color shifting non-magnetic flakes.
  • the second coating structure 410 could be formed to contain the magnetic pigments and the first coating structure 408 could be formed to contain the non-magnetic pigments.
  • the pigments 414 , 416 are dispersed in a solidified liquid pigment vehicle 418 , 420 of a conventional type so that the pigments 414 , 416 produce the desired optical characteristics.
  • the liquid vehicle can be a conventional ink vehicle or a conventional paint vehicle of a suitable type.
  • optical article 400 can be formed by using a suitable magnetic foil structure, such as the color shifting magnetic foils disclosed hereinabove, in place of coating structure 408 , and by using a non-magnetic foil structure such as a conventional color shifting foil in place of coating structure 410 .
  • the magnetic properties of the magnetic foil structure are thus provided by a magnetic layer which is not optically observable.
  • Non-overlapping paired first and second foil structures, one magnetic and one non-magnetic, would be disposed on upper surface 404 of substrate 402 so as to overlie non-overlapping first and second regions on surface 404 .
  • FIG. 17 another embodiment of the invention is depicted in the form of an optical article 450 having overlapping paired optical structures.
  • the optical article 450 includes a substrate 452 having an upper surface region 454 .
  • the substrate 452 can be formed of the same materials as described for substrate 402 shown in FIG. 16.
  • a magnetic pigment coating structure 456 overlies upper surface region 454 of substrate 452 .
  • the magnetic pigment coating structure 456 includes a plurality of multilayer magnetic pigments 458 , such as those described previously, which are dispersed in a solidified pigment vehicle.
  • the magnetic properties of the pigment coating structure 456 are provided by a non-optically observable magnetic layer within each of the multilayer magnetic pigments 458 .
  • a non-magnetic pigment coating structure 460 overlies at least a portion of magnetic pigment coating structure 456 .
  • the non-magnetic pigment coating structure 460 includes a plurality of non-magnetic pigments 462 dispersed in a solidified pigment vehicle.
  • a non-magnetic pigment coating structure can be used in place of magnetic pigment coating structure 456 overlying upper surface region 454 of substrate 452 .
  • a magnetic pigment coating structure is then used in place of non-magnetic pigment coating structure 460 .
  • optical article 450 can be formed by using a suitable magnetic foil structure, such as the color shifting magnetic foils disclosed hereinabove, in place of coating structure 456 .
  • a non-magnetic foil structure such as a conventional color shifting foil is then used in place of coating structure 460 .
  • a non-magnetic foil structure can be used in place of coating structure 456 , and a magnetic foil structure is then used in place of coating structure 460 .
  • the respective pigment coating or foil structures in optical articles 400 or 450 can be selected to provide identical coloring or identical color shifting effects to articles 400 and 450 , or can be selected to provide different colors or different color shifting effects.
  • optical features can be used by selecting appropriate coatings or foils with the desired optical characteristics to add various security features to optical articles 400 and 450 .
  • the pigment coating or foil structures used in articles 400 and 450 may have substantially the same color or color effects, e.g., the same color shifting effects, only one of the pigment coating or foil structures in the articles carries a covert magnetic signature. Therefore, although a human eye cannot detect the magnetic features of the pigment coating or foil structure, a magnetic detection system such as a Faraday rotator detector can be used to detect the magnetic covert signature in the pigment or foil and any information magnetically encoded therein.
  • a magnetic detection system such as a Faraday rotator detector can be used to detect the magnetic covert signature in the pigment or foil and any information magnetically encoded therein.
  • a structure or device formed with the pigments of the invention can be placed in a bar code pattern which would produce a color shifting bar code device that can appear on a label or on an article itself.
  • a bar code would function as a color shifting bar code that could be read by both optical and magnetic readers.
  • Such a bar code color shifting device would provide three security features, the bar code itself, the color shifting characteristic, and the magnetic characteristic.
  • information can be encoded in the magnetic layers of the pigments of the invention.
  • the magnetic layers could record typical information which is carried by a credit card in a magnetic stripe.
  • pigments of the invention could be utilized for putting the numbers on the bottoms of checks so that the information carried by the check could be read magnetically as with present day checks while also providing an optical variable feature.
  • a three layer magnetic coating sample was prepared with 1000 ⁇ Aluminum, 1000 ⁇ Iron, and 1000 ⁇ Aluminum (Al/Fe/Al).
  • the coating sample was prepared in a roll coater, using a 2 mil polyester web coated with an organic release layer (soluble in acetone).
  • the particles were filtered and sized by exposing the particles in isopropyl alcohol to ultrasonic agitation for 5 minutes using a Branson sonic welder.
  • Particle size was determined using a Horiba LA-300 particle sizing instrument (laser scattering based system). The mean particle size was determined to be 44 ⁇ m (22 ⁇ m standard deviation) in the planar dimension, with a gaussian distribution.
  • the pigment particles were filtered and dried.
  • a dry weight of magnetic pigment to binder (Du Pont auto refinish paint vehicle) in the ratio of 1:4 was drawn down onto a thin cardboard sheet (Leneta card).
  • a “drawdown” is a paint or ink sample spread on paper to evaluate the color.
  • a drawdown is formed with the edge of a putty knife or spatula by “drawing down” a small glob of paint or ink to get a thin film of the paint or ink.
  • the draw-down is made using a Mayer rod pulled across a Leneta card and through a small glob of paint.
  • a conventional sheet magnet was placed underneath the card while the drawing down was occurring and left in place until the paint vehicle dried.
  • the result of the magnetic fields on this pigment sample was to create parallel bright and dark areas in the pigment.
  • the bright aluminum areas of the pigment sample had a reflective luminance, Y, of 53% whereas the dark areas had a reflective luminance of 43%.
  • a magnetic ink sample was prepared by mixing a 0.5 g sample of the magnetic pigment of Example 1 (Al/Fe/Al) with 3.575 g of standard Intaglio ink vehicle (high viscosity ink vehicle) and 0.175 g of an ink dryer. The ink sample was drawn down onto paper using a flat putty knife. A magnetic strip with the word “FLEX” cut out from it was placed beneath the paper during the drawing down step. The pattern of the magnetic lines in the dried magnetic ink was readily visible as black and white (silver color) strips with the word “FLEX” readily apparent. The optical image of the word “FLEX” in the ink sample was visible at normal incidence and at approximately a 45 degree angle of viewing.
  • a magnetic ink sample was prepared as in Example 2 using an Intaglio ink vehicle and coated over paper having a sheet magnet placed behind it.
  • the magnet had a cut out of a stylized letter “F.”
  • the cut out “F” was embossed upward away from the paper and was bright silver in appearance.
  • the “F” stood out over the surrounding area by about 6 microns. This was caused by the paper pushed slightly into the “F” recess of the magnet by the force of the putty knife drawing down the highly viscous Intaglio ink.
  • the “F” area remained bright with the Al/Fe/Al flakes oriented parallel to the surface of the paper but in a stepped-up height above the surrounding coating.
  • a stylized letter “F” was cut out of a flexible sheet magnet using an exacto knife.
  • a draw-down card was placed on top of and in contact with the sheet magnet.
  • a magnetic color shifting pigment according to the invention was mixed with an acrylic resin based vehicle and applied to the card with a #22 wire metering rod.
  • the resultant draw-down had striped superimposed black lines that replicated the field pattern outside of the stylized “F” in the sheet magnet below the card.
  • the entire surface of the drawn-down card exhibited color shifting effects. Where the pattern of the stylized “F” was observed, the stylized “F” only had color shifting effects, while the background had both color shifting effects and the superimposed black lines.
US09/844,261 2001-04-27 2001-04-27 Multi-layered magnetic pigments and foils Abandoned US20020160194A1 (en)

Priority Applications (30)

Application Number Priority Date Filing Date Title
US09/844,261 US20020160194A1 (en) 2001-04-27 2001-04-27 Multi-layered magnetic pigments and foils
KR1020077024999A KR100856430B1 (ko) 2001-04-27 2002-01-16 다층 자성 안료 및 박
CN2006100770079A CN1854204B (zh) 2001-04-27 2002-01-16 多层磁性颜料片和箔
AT02765768T ATE557068T1 (de) 2001-04-27 2002-01-16 Mehrschichtige magnetische pigmente und folien
KR1020087018022A KR100931623B1 (ko) 2001-04-27 2002-01-16 다층 자성 안료 및 박
ES02765768T ES2386137T3 (es) 2001-04-27 2002-01-16 Pigmentos y láminas magnéticos multicapa
AT07021052T ATE535578T1 (de) 2001-04-27 2002-01-16 Mehrschichtige magnetische pigmente und folien
EP07021053.9A EP1918333B1 (de) 2001-04-27 2002-01-16 Mehrschichtige magnetische Pigmente
KR1020077024998A KR100856105B1 (ko) 2001-04-27 2002-01-16 다층 자성 안료 및 박
AU2002329168A AU2002329168A1 (en) 2001-04-27 2002-01-16 Multi-layered magnetic pigments and foils
PT07021052T PT1921117E (pt) 2001-04-27 2002-01-16 Pigmentos e películas metalizadas magnéticos multicamada
ES07021052T ES2377534T3 (es) 2001-04-27 2002-01-16 Pigmentos magnéticos de multi-capas y papeles metalizados
DK07021052.1T DK1921117T3 (da) 2001-04-27 2002-01-16 Flerlagede magnetiske pigmenter og folier
CNB028088328A CN1288674C (zh) 2001-04-27 2002-01-16 多层磁性颜料片和箔
EP07021050.5A EP1918331B1 (de) 2001-04-27 2002-01-16 Mehrschichtige magnetische Pigmente
JP2003507196A JP4353792B2 (ja) 2001-04-27 2002-01-16 多層磁性ピグメントおよび箔
EP07021051.3A EP1918332B1 (de) 2001-04-27 2002-01-16 Mehrschichtige magnetische Pigmente
EP07021052A EP1921117B1 (de) 2001-04-27 2002-01-16 Mehrschichtige magnetische Pigmente und Folien
PCT/US2002/001059 WO2003000801A2 (en) 2001-04-27 2002-01-16 Multi-layered magnetic pigments and foils
EP02765768A EP1412432B1 (de) 2001-04-27 2002-01-16 Mehrschichtige magnetische pigmente und folien
KR1020077024997A KR100856533B1 (ko) 2001-04-27 2002-01-16 다층 자성 안료 및 박
EP07021054.7A EP1918334B1 (de) 2001-04-27 2002-01-16 Mehrschichtige magnetische Pigmente
KR1020037014038A KR100915147B1 (ko) 2001-04-27 2002-01-16 다층 자성 안료 및 박
KR1020077025000A KR100856429B1 (ko) 2001-04-27 2002-01-16 다층 자성 안료 및 박
US10/360,964 US6818299B2 (en) 2001-04-27 2003-02-07 Multi-layered magnetic pigments and foils
US10/637,605 US6838166B2 (en) 2001-04-27 2003-08-08 Multi-layered magnetic pigments and foils
JP2007274512A JP4937879B2 (ja) 2001-04-27 2007-10-22 多層磁性ピグメントおよび箔
JP2007293763A JP4863512B2 (ja) 2001-04-27 2007-11-12 多層磁性ピグメントおよび箔
JP2008331550A JP5132540B2 (ja) 2001-04-27 2008-12-25 多層磁性ピグメントおよび箔
CY20121100043T CY1112965T1 (el) 2001-04-27 2012-01-16 Μαγνητικα πιγμεντα απο περισσοτερες στρωσεις και φυλλα

Applications Claiming Priority (1)

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US09/844,261 US20020160194A1 (en) 2001-04-27 2001-04-27 Multi-layered magnetic pigments and foils

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US10/637,605 Continuation US6838166B2 (en) 2001-04-27 2003-08-08 Multi-layered magnetic pigments and foils

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US10/360,964 Expired - Lifetime US6818299B2 (en) 2001-04-27 2003-02-07 Multi-layered magnetic pigments and foils
US10/637,605 Expired - Lifetime US6838166B2 (en) 2001-04-27 2003-08-08 Multi-layered magnetic pigments and foils

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US10/637,605 Expired - Lifetime US6838166B2 (en) 2001-04-27 2003-08-08 Multi-layered magnetic pigments and foils

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US (3) US20020160194A1 (de)
EP (6) EP1921117B1 (de)
JP (4) JP4353792B2 (de)
KR (6) KR100856533B1 (de)
CN (2) CN1854204B (de)
AT (2) ATE557068T1 (de)
AU (1) AU2002329168A1 (de)
CY (1) CY1112965T1 (de)
DK (1) DK1921117T3 (de)
ES (2) ES2377534T3 (de)
PT (1) PT1921117E (de)
WO (1) WO2003000801A2 (de)

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