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US20120010300A1 - Effect pigments based on coated glass flakes - Google Patents

Effect pigments based on coated glass flakes Download PDF

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Publication number
US20120010300A1
US20120010300A1 US13/242,530 US201113242530A US2012010300A1 US 20120010300 A1 US20120010300 A1 US 20120010300A1 US 201113242530 A US201113242530 A US 201113242530A US 2012010300 A1 US2012010300 A1 US 2012010300A1
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Prior art keywords
glass flake
glass
effect pigments
flake
pigments according
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US13/242,530
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Ralf Anselmann
Klaus Ambrosius
Marcus Mathias
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Individual
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/0015—Pigments exhibiting interference colours, e.g. transparent platelets of appropriate thinness or flaky substrates, e.g. mica, bearing appropriate thin transparent coatings
    • C09C1/0021—Pigments exhibiting interference colours, e.g. transparent platelets of appropriate thinness or flaky substrates, e.g. mica, bearing appropriate thin transparent coatings comprising a core coated with only one layer having a high or low refractive index
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • 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
    • C09C1/0015—Pigments exhibiting interference colours, e.g. transparent platelets of appropriate thinness or flaky substrates, e.g. mica, bearing appropriate thin transparent coatings
    • C09C1/0024—Pigments exhibiting interference colours, e.g. transparent platelets of appropriate thinness or flaky substrates, e.g. mica, bearing appropriate thin transparent coatings comprising a stack of coating layers with alternating high and low refractive indices, wherein the first coating layer on the core surface has the high refractive index
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/36—Pearl essence, e.g. coatings containing platelet-like pigments for pearl lustre
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/02—Amorphous compounds
    • 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
    • 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
    • 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
    • C09C2220/10—Wet methods, e.g. co-precipitation
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
    • Y10T428/2991—Coated
    • Y10T428/2993—Silicic or refractory material containing [e.g., tungsten oxide, glass, cement, etc.]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
    • Y10T428/2991—Coated
    • Y10T428/2993—Silicic or refractory material containing [e.g., tungsten oxide, glass, cement, etc.]
    • Y10T428/2996—Glass particles or spheres

Definitions

  • the present invention relates to effect pigments based on thin glass flakes, to a method for the production of such pigments and their use in plastics, paints, coatings, powder coatings, inks, printing inks, glasses, ceramic products, agriculture foils, and in cosmetic formulations.
  • iridescent luster effects can be achieved using so called nacreous or pearlescent pigments.
  • Various alternative techniques have been developed to create colour/lustre effects.
  • the most important, economic and common way to make these pigments is to coat a platelet shaped carrier with high refractive substances like TiO 2 , Fe 2 O 3 , SnO 2 , ZrO 2 , Cr 2 O 3 or combinations of these or with alternating layers of high and/or low refractivity. So far the nearly exclusively used carrier is wet ground muscovite mica. It is cheap, readily available and easy to cleave into smooth and very thin platelets. These can be classified into any desired particle size distribution. Additionally, pigments based on mica are very stable towards chemical, mechanical or thermal treatment.
  • Natural mica contains impurities like quartz which makes the processing more complicated (abrasion of grinding tools, waste) or like Fe, Mn, Cu which makes the masstone yellowish grey rather than white. When ground it yields platelets showing a broad distribution of thicknesses and diameters. This can be reduced by proper classification but will never lead to uniform shape.
  • U.S. Pat. No. 3,331,699 discloses that glass flakes may be coated with a translucent layer of particles of a metal oxide having a high index of refraction, such as titanium dioxide, provided there is first deposited on the glass flakes a nucleating substance which is insoluble in the acidic solution from which the translucent layer of metal oxide is deposited.
  • a metal oxide having a high index of refraction such as titanium dioxide
  • the patent does not mention the necessity of a smooth transparent film, not particles, being necessary for quality interference pigments to be developed.
  • the patent teaches that the nature of the glass is not critical, but that the presence of the nucleated surface is critical.
  • U.S. Pat. No. 5,436,077 teaches a glass flake substrate which has a metal covering layer on which is formed a dense protective covering layer of a metal oxide such as titanium dioxide.
  • a metal oxide such as titanium dioxide.
  • the nature of the glass is unimportant, the metallic coating provides the desired appearance and the overcoating of the metal oxide is present to protect the metallic layer from corrosive environments.
  • EP 0 912 640 B1 teaches the coating of thick flakes of C glass having a first coating comprising iron oxide or rutile titanium dioxide thereon.
  • the disadvantage of C glass is the limited thermal stability.
  • the rutile pigments prepared according to the corresponding examples were calcined at temperatures not higher than 600° C. It is well known that the calcining temperature is of essential importance for the stability of rutile pigments, especially for outdoor applications. To yield sufficiently stabilized rutile TiO 2 layers on a substrate calcining temperatures of at least 800° C. are requested.
  • EP 0 289 240 B1 discloses the manufacturing of extremely thin glass flakes at reasonable costs. According to the claimed process the glass flakes cannot be only made in any desired composition, e. g., from pure SiO 2 , but also in any thickness tailored for the application wanted down to below 0.8 ⁇ m.
  • the present invention relates to effect pigments based on glass flakes with a thickness of ⁇ 1.0 ⁇ m coated with one or more layers with a high and/or a low reflective index.
  • the thickness of the glass flakes is preferably ⁇ 0.8 ⁇ m and especially ⁇ 0.5 ⁇ m.
  • Especially preferred are thin glass flakes with a softening point ⁇ 800° C.
  • Glass can be classified for example as A glass, C glass, E glass, ECR glass.
  • quartz glass is preferred but the production of this glass is very expensive.
  • Glass types which fulfill the feature of the requested softening point are quartz glass, and any other glass composition having a softening point of ⁇ 800° C.
  • Glass flakes which fulfill the requirements are special glasses like e. g. Schott Duran or Supremax types
  • the softening point in the present invention is defined, according to ASTM C 338 as the temperature at which a uniform fiber of glass with a diameter of 0.55-0.75 mm and a length of 23.5 cm increases its length by 1 mm/min when the upper 10 cm is heated at a rate of 5° C./min.
  • Suitable glass flakes preferably prepared according to EP 0 289 240 B1 are characterized in that they contain an average particle size in the range of 5-1000 ⁇ m, preferably in the range of 5-150 ⁇ m.
  • Preferred glass flakes have an average particle size in the range of 5-150 ⁇ m and a thickness of 0.1-0.5 ⁇ m, preferably of 0.1-0.3 ⁇ m.
  • the aspect ratio of glass flakes is in the range of 10-300, preferably in the range of 50-200.
  • the glass particles can be coated with one or more layers selected from the group consisting of metal oxides, metal suboxides, metal fluorides, metal oxyhalides, metals chalcogenides, metal nitrides, metal sulfides, metal carbides, or mixtures thereof.
  • suitable metal oxides are TiO 2 , Fe 2 O 3 , TiFe 2 O 5 , Ti suboxides, Fe 3 O 4 , Cr 2 O 3 , Al 2 O 3 , SiO 2 , ZrO 2 , ZnO, SnO 2 , CoO, Co 3 O 4 , VO 2 , V 2 O 3 , Sn(Sb)O 2 or mixtures thereof.
  • the TiO 2 layer can be in the rutile or anatase modification, preferably the TiO 2 layer is rutile.
  • glass flakes coated with TiO 2 and/or Fe 2 O 3 are particularly preferred.
  • Metal sulfide coatings on glass flakes are preferably selected from sulfides of tin, silver, lanthanum, rare earth metals, preferably cerium, chromium, molybdenum, tungsten, iron, cobalt and/or nickel.
  • the glass flakes can be coated in the same way as e. g. mica based pearl lustre pigments.
  • Coatings with a metal oxide may be accomplished by any known methods, such as hydrolysis of a metal salt by heating or alkali, which deposits hydrated metal oxide, optionally followed by calcination.
  • the procedure involves the dispersing of the thin glass flake particles and combining that dispersion with a precursor which forms a hydrous metal oxide film coating on the flakes.
  • the appropriate metal salts are added.
  • the pH of the resulting dispersion is maintained at an appropriate level during the addition of the metal salts by simultaneous feeding a suitable base, for example sodium hydroxide, to cause precipitation of the hydrous metal dioxide on the glass flakes.
  • a suitable base for example sodium hydroxide
  • An aqueous acid for example hydrochloric acid, can be used for adjusting the pH.
  • the coated platelets can, if desired, be washed and dried before being calcined to the final pigment. The procedure is described in detail in U.S. Pat. No.
  • the effect pigments of the present invention are preferably prepared by wet-chemically coating of the glass flakes or by gas phase decomposition of volatile metal compounds (CVD, PVD) or electroless plating.
  • the effect pigments obtained in this way are characterized in that one or more homogeneous layers enrobing the uniform thin glass flakes.
  • the layer thickness ranges from 0.1 to 1000 nm, preferably from 0.2 to 300 nm.
  • the optical layer thickness will in general be adapted to the particular application.
  • Preferred pigments are coated with one or two layers.
  • a surface treatment includes for example the processes described in DE-C 22 15 191, DE-A 31 51 354, DE-A 32 35 017 or DE-A 33 34 598, DE 40 30 727 A1, EP 0 649 886 A2, WO 97/29059, WO 99/57204, U.S. Pat. No. 5,759,255.
  • This surface treatment further enhances the chemical stability of the pigments and/or facilitates the handling of the pigment, especially its incorporation into various application media.
  • the effect pigments of the present invention are advantageous useful for many purposes, such as the coloring of plastics, glasses, ceramic products, agriculture foils, decorative cosmetic formulations and in particular coatings, especially automotive coatings, and inks, including printing inks. All customary printing processes can be employed, for example offset printing, intaglio printing, bronze printing, flexographic printing. Furthermore they can be used as functional pigments like conductive pigments, as magnetic pigments or to make media, for example plastics, board products and papers, laser-markable.
  • the effect pigments of the present invention are also advantageously useful for these applications in admixture with filler pigments or transparent and hiding white, colored and black organic and inorganic pigments and also with conventional transparent, colored and black luster pigments based on metal oxide coated mica, TiO 2 flakes, SiO 2 flakes or Al 2 O 3 flakes and coated or uncoated metal pigments, BiOCI pigments, platelet shaped iron oxides, or graphite flakes.
  • inventive pigment mixtures can contain organic or inorganic colourants, thixotropy agents, wetting agents, dispersing agents, water, organic solvent or solvent mixtures, etc.
  • the pigment mixtures of the invention are simple and easy to handle.
  • the pigment mixtures can be incorporated into the system in which it is used by simple mixing. Laborious milling and dispersing procedures for the pigments are not necessary.
  • the coated glass flakes of the invention can be used for pigmenting and/or coating materials, printing inks, plastics, agricultural films, button pastes, for the coating of seed, for the colouring of food, coatings of foods, medicaments or cosmetic formulations.
  • concentration of the pigments in the system in which it is to be used for pigmenting is generally between 0.01 and 50% by weight, preferably between 0.1 and 5% by weight, based on the overall solids content of the system. This concentration is generally dependent on the specific application.
  • Plastics comprising the pigment mixture of the invention in amounts of 0.1 to 50% by weight, in particular from 0.5 to 7% by weight, are frequently notable for a particular brilliance.
  • the glass flakes are employed in amounts of 0.5 to 10% by weight.
  • the pigment is incorporated into the printing ink in amounts of 2-50% by weight, preferably 5-30% by weight and in particular 8-15% by weight.
  • the invention likewise provides pigment preparations comprising coated glass flakes, optionally effect pigments, binders and, if desired, additives, the said preparations being in the form of substantially solvent-free, free-flowing granules.
  • Such granules contain up to 95% by weight of the inventive pigments.
  • the present invention therefore also provides formulations containing the pigments of the invention.
  • the coating is continued by adjusting the pH to 1.8 with dilute HCl and then titrating 63.5 ml of TiCl 4 -solution (400 g TiCl 4 /l DI water) against 10% NaOH over a period of about 3 h. Having reached the desired layer thickness the coating is stopped, stirred for another 15 min, filtered, washed with DI water and dried. After calcination at 800° C. for 30 min a silverwhite rutile pigment is yielded.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Pigments, Carbon Blacks, Or Wood Stains (AREA)
  • Paints Or Removers (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)
  • Cosmetics (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The present invention relates to effect pigments based on thin glass flakes and to a method for the production of such pigments. The resulting pigment can be used in any application for which pearlescent pigments have been heretofore used such as, for example, in plastics, paints, inks, cosmetic formulations, coatings including solvent or waterborne automotive paint systems, powder coatings, inks and agriculture foils.

Description

  • This application is a divisional of U.S. application Ser. No. 10/473,710 filed on Nov. 10, 2003, which is incorporated entirely by reference herein.
  • The present invention relates to effect pigments based on thin glass flakes, to a method for the production of such pigments and their use in plastics, paints, coatings, powder coatings, inks, printing inks, glasses, ceramic products, agriculture foils, and in cosmetic formulations.
  • Since more than 40 years iridescent luster effects can be achieved using so called nacreous or pearlescent pigments. Various alternative techniques have been developed to create colour/lustre effects. The most important, economic and common way to make these pigments is to coat a platelet shaped carrier with high refractive substances like TiO2, Fe2O3, SnO2, ZrO2, Cr2O3 or combinations of these or with alternating layers of high and/or low refractivity. So far the nearly exclusively used carrier is wet ground muscovite mica. It is cheap, readily available and easy to cleave into smooth and very thin platelets. These can be classified into any desired particle size distribution. Additionally, pigments based on mica are very stable towards chemical, mechanical or thermal treatment. But there are some disadvantages of mica, since it is a natural product and shows inconsistencies from source to source and even from batch to batch. This has to be overcome by adjusting the processing parameters. Natural mica contains impurities like quartz which makes the processing more complicated (abrasion of grinding tools, waste) or like Fe, Mn, Cu which makes the masstone yellowish grey rather than white. When ground it yields platelets showing a broad distribution of thicknesses and diameters. This can be reduced by proper classification but will never lead to uniform shape.
  • In the past researchers tried to find corresponding alternatives to mica which keep the advantages of it but did not contain the above mentioned disadvantages.
  • A wide variety of other platy materials have been proposed as substitute for mica in the patent literature. These include non-soluble inorganic materials such as glass, enamel, china clay, porcelain, natural stones or other silicaceous substances, metal objects and surfaces of organic polymer materials such as polycarbonate as disclosed for example in U.S. Pat. Nos. 3,123,485, 3,219,734, 3,616,100, 3,444,987, 4,552,593 and 4,735,869. While glass has been mentioned as a possibility on many occasions, for instance in U.S. Pat. No. 3,331,699, commercial pearlescent products are not made using glass and experience has shown that products made using glass as the platelet substrate have rather poor quality.
  • U.S. Pat. No. 3,331,699 discloses that glass flakes may be coated with a translucent layer of particles of a metal oxide having a high index of refraction, such as titanium dioxide, provided there is first deposited on the glass flakes a nucleating substance which is insoluble in the acidic solution from which the translucent layer of metal oxide is deposited. The patent does not mention the necessity of a smooth transparent film, not particles, being necessary for quality interference pigments to be developed. The patent teaches that the nature of the glass is not critical, but that the presence of the nucleated surface is critical. It is further stated that there are only a small number of metal oxide compounds which are insoluble in the acidic solution and capable of forming a nucleated surface on the glass flakes; tin oxide and a fibrous boehmite form of alumina monohydrate are the only two such materials disclosed. As demonstrated in the examples below, products prepared according to the teachings of this patent are poor in quality.
  • U.S. Pat. No. 5,436,077 teaches a glass flake substrate which has a metal covering layer on which is formed a dense protective covering layer of a metal oxide such as titanium dioxide. In this patent, the nature of the glass is unimportant, the metallic coating provides the desired appearance and the overcoating of the metal oxide is present to protect the metallic layer from corrosive environments.
  • EP 0 912 640 B1 teaches the coating of thick flakes of C glass having a first coating comprising iron oxide or rutile titanium dioxide thereon. The disadvantage of C glass is the limited thermal stability. As disclosed in the EP 0 912 640 B1 the rutile pigments prepared according to the corresponding examples were calcined at temperatures not higher than 600° C. It is well known that the calcining temperature is of essential importance for the stability of rutile pigments, especially for outdoor applications. To yield sufficiently stabilized rutile TiO2 layers on a substrate calcining temperatures of at least 800° C. are requested.
  • For the preparation of pearlescent pigments the transparency and the thickness of the platy substrate are very important. For the first time
  • EP 0 289 240 B1 discloses the manufacturing of extremely thin glass flakes at reasonable costs. According to the claimed process the glass flakes cannot be only made in any desired composition, e. g., from pure SiO2, but also in any thickness tailored for the application wanted down to below 0.8 μm.
  • It is an object of the present invention to overcome the problems of the prior art and to provide novel effect pigments which have advantageous application properties. This object is achieved by the inventive effect pigments based on very thin glass flakes having the following characteristics:
  • (1) thickness of the glass flakes ≦1.0 μm
  • (2) high temperature and mechanical stability
  • (3) smooth surfaces
  • The present invention relates to effect pigments based on glass flakes with a thickness of ≦1.0 μm coated with one or more layers with a high and/or a low reflective index. The thickness of the glass flakes is preferably ≦0.8 μm and especially ≦0.5 μm. Especially preferred are thin glass flakes with a softening point ≧800° C.
  • Glass can be classified for example as A glass, C glass, E glass, ECR glass. For the present invention quartz glass is preferred but the production of this glass is very expensive. Glass types which fulfill the feature of the requested softening point are quartz glass, and any other glass composition having a softening point of ≧800° C. Glass flakes which fulfill the requirements are special glasses like e. g. Schott Duran or Supremax types The softening point in the present invention is defined, according to ASTM C 338 as the temperature at which a uniform fiber of glass with a diameter of 0.55-0.75 mm and a length of 23.5 cm increases its length by 1 mm/min when the upper 10 cm is heated at a rate of 5° C./min.
  • Suitable glass flakes preferably prepared according to EP 0 289 240 B1 are characterized in that they contain an average particle size in the range of 5-1000 μm, preferably in the range of 5-150 μm. Preferred glass flakes have an average particle size in the range of 5-150 μm and a thickness of 0.1-0.5 μm, preferably of 0.1-0.3 μm. The aspect ratio of glass flakes is in the range of 10-300, preferably in the range of 50-200.
  • The glass particles can be coated with one or more layers selected from the group consisting of metal oxides, metal suboxides, metal fluorides, metal oxyhalides, metals chalcogenides, metal nitrides, metal sulfides, metal carbides, or mixtures thereof.
  • Examples of suitable metal oxides are TiO2, Fe2O3, TiFe2O5, Ti suboxides, Fe3O4, Cr2O3, Al2O3, SiO2, ZrO2, ZnO, SnO2, CoO, Co3O4, VO2, V2O3, Sn(Sb)O2 or mixtures thereof. The TiO2 layer can be in the rutile or anatase modification, preferably the TiO2 layer is rutile. Especially preferred are glass flakes coated with TiO2 and/or Fe2O3.
  • Metal sulfide coatings on glass flakes are preferably selected from sulfides of tin, silver, lanthanum, rare earth metals, preferably cerium, chromium, molybdenum, tungsten, iron, cobalt and/or nickel.
  • The glass flakes can be coated in the same way as e. g. mica based pearl lustre pigments. Coatings with a metal oxide may be accomplished by any known methods, such as hydrolysis of a metal salt by heating or alkali, which deposits hydrated metal oxide, optionally followed by calcination.
  • In general, the procedure involves the dispersing of the thin glass flake particles and combining that dispersion with a precursor which forms a hydrous metal oxide film coating on the flakes.
  • After the glass is dispersed in water and placed in an appropriate vessel, the appropriate metal salts are added. The pH of the resulting dispersion is maintained at an appropriate level during the addition of the metal salts by simultaneous feeding a suitable base, for example sodium hydroxide, to cause precipitation of the hydrous metal dioxide on the glass flakes. An aqueous acid, for example hydrochloric acid, can be used for adjusting the pH. The coated platelets can, if desired, be washed and dried before being calcined to the final pigment. The procedure is described in detail in U.S. Pat. No. 5,433,779 and in the German Patents 14 67 468, 19 59 998, 20 09 566, 22 14 545, 22 15 191, 22 44 298, 23 13 331, 25 22 572, 31 37 808, 31 37 809, 31 51 343, 31 51 354, 31 51 355, 32 11 602 and 32 53 017.
  • The effect pigments of the present invention are preferably prepared by wet-chemically coating of the glass flakes or by gas phase decomposition of volatile metal compounds (CVD, PVD) or electroless plating.
  • The effect pigments obtained in this way are characterized in that one or more homogeneous layers enrobing the uniform thin glass flakes.
  • Preferred effect pigments of the present invention are given in the following:
    • glass flake+TiO2 (rutile)
    • glass flake+Fe2O3
    • glass flake+Fe3O4
    • glass flake+TiFe2O5
    • glass flake+Cr2O3
    • glass flake+ZrO2
    • glass flake+Sn(Sb)O2
    • glass flake+BiOCI
    • glass flake+Al2O3
    • glass flake+Ce2S3
    • glass flake+MoS2
  • In general, the layer thickness ranges from 0.1 to 1000 nm, preferably from 0.2 to 300 nm. The optical layer thickness will in general be adapted to the particular application. Preferred pigments are coated with one or two layers.
  • To enhance the light and weather stability it is frequently advisable, depending on the field of application, to subject the coated glass flakes to a surface treatment. Useful surface treatments include for example the processes described in DE-C 22 15 191, DE-A 31 51 354, DE-A 32 35 017 or DE-A 33 34 598, DE 40 30 727 A1, EP 0 649 886 A2, WO 97/29059, WO 99/57204, U.S. Pat. No. 5,759,255. This surface treatment further enhances the chemical stability of the pigments and/or facilitates the handling of the pigment, especially its incorporation into various application media.
  • The effect pigments of the present invention are advantageous useful for many purposes, such as the coloring of plastics, glasses, ceramic products, agriculture foils, decorative cosmetic formulations and in particular coatings, especially automotive coatings, and inks, including printing inks. All customary printing processes can be employed, for example offset printing, intaglio printing, bronze printing, flexographic printing. Furthermore they can be used as functional pigments like conductive pigments, as magnetic pigments or to make media, for example plastics, board products and papers, laser-markable.
  • The effect pigments of the present invention are also advantageously useful for these applications in admixture with filler pigments or transparent and hiding white, colored and black organic and inorganic pigments and also with conventional transparent, colored and black luster pigments based on metal oxide coated mica, TiO2 flakes, SiO2 flakes or Al2O3 flakes and coated or uncoated metal pigments, BiOCI pigments, platelet shaped iron oxides, or graphite flakes.
  • Additionally, the inventive pigment mixtures can contain organic or inorganic colourants, thixotropy agents, wetting agents, dispersing agents, water, organic solvent or solvent mixtures, etc.
  • The pigment mixtures of the invention are simple and easy to handle. The pigment mixtures can be incorporated into the system in which it is used by simple mixing. Laborious milling and dispersing procedures for the pigments are not necessary.
  • The coated glass flakes of the invention can be used for pigmenting and/or coating materials, printing inks, plastics, agricultural films, button pastes, for the coating of seed, for the colouring of food, coatings of foods, medicaments or cosmetic formulations. The concentration of the pigments in the system in which it is to be used for pigmenting is generally between 0.01 and 50% by weight, preferably between 0.1 and 5% by weight, based on the overall solids content of the system. This concentration is generally dependent on the specific application.
  • Plastics comprising the pigment mixture of the invention in amounts of 0.1 to 50% by weight, in particular from 0.5 to 7% by weight, are frequently notable for a particular brilliance.
  • In the coating sector, especially in automotive finishing, the glass flakes are employed in amounts of 0.5 to 10% by weight.
  • In the pigmentation of binder systems, for example for paints and printing inks for intaglio, offset or screen printing, the pigment is incorporated into the printing ink in amounts of 2-50% by weight, preferably 5-30% by weight and in particular 8-15% by weight.
  • The invention likewise provides pigment preparations comprising coated glass flakes, optionally effect pigments, binders and, if desired, additives, the said preparations being in the form of substantially solvent-free, free-flowing granules. Such granules contain up to 95% by weight of the inventive pigments. A pigment preparation in which the glass flakes of the invention are pasted up with a binder and with water and/or an organic solvent, with or without additives, and the paste is subsequently dried and brought into a compact particulate form, e. g. granules, pellets, briquettes, a masterbatch or tablets, is particularly suitable as a precursor for printing inks.
  • The present invention therefore also provides formulations containing the pigments of the invention.
  • In order to further illustrate the invention, various non-limiting examples are set forth below. In these, as well as throughout the balance of this specification and claims, all parts and percentages are by weight and all temperatures are in degrees centigrade unless otherwise indicated.
    • EXAMPLES Example 1 (Rutile Silver Pigment) Prior Art
  • 200 g flakes of E-glass (thickness: 5 μm; diameter: 10-40 μm; specific surface area: approximately 0.2 m2/g) are suspended in 2 l of deionized water. With vigorous stirring the suspension is heated to 80° C. After having adjusted the pH to 2.0 with dilute HCl a first layer of SnO2 is precipitated onto the glass flakes by feeding a solution of 3 g SnCl4×5 H2O (in 10 ml conc. HCl plus 50 ml of DI water) into the suspension under simultaneous neutralization with 10% NaOH over a period of about 1 h. To complete the reaction the suspension is kept stirring for another 15 min. The coating is continued by adjusting the pH to 1.8 with dilute HCl and then titrating 63.5 ml of TiCl4-solution (400 g TiCl4/l DI water) against 10% NaOH over a period of about 3 h. Having reached the desired layer thickness the coating is stopped, stirred for another 15 min, filtered, washed with DI water and dried. After calcination at 800° C. for 30 min a silverwhite rutile pigment is yielded.
    • Example 2 Rutile Silver Pigment
  • 200 g flakes of E-glass (thickness: 0.5 μm; diameter: 10-40 μm; specific surface area: approximately 1.7 m2/g) are suspended in 2 l of DI water. The coating is carried out the same way as in example 1. Titration periods keep the same, only the amounts of solutions are adjusted to the different base material:
    • 5 g SnCl4×5 H2O (in 15 ml conc. HCl plus 75 ml DI water)
    • 196.3 ml of TiCl4 solution (400 g TiCl4/l DI water)
  • After calcination at 800° C. for 30 min a brilliant silverwhite rutile pigment is yielded.
    • Examples 3 and 4 Rutile Interference Green Pigment
  • The coatings are started in the same ways as for examples 1 and 2, only the amount of TiO2 (400 g TiCl4/l DI water) coated was increased to yield green interference type pigments. The further steps are again carried out as described in examples 1 and 2.
  • To evaluate their properties draw down cards are made from all of these pigments. Additionally sprayed panels were prepared. The pigments based on glass flakes with a thickness of 5.0 μm and 0.5 μm are checked for their coloristics and their visual performance.
  • Results: draw downcards and panels pigments with a thickness of 5.0 μm showed very weak performance making a “dilute” impression. For the silver little brilliance and little hiding effect was observed while for the green a dull colour and little brilliance are found;
      • a little better is the effect in the sunlight as some larger flakes show a kind of sparkle;
      • completely different is the situation with a thickness of 0.5 μm pigments: They exceeded comparable mica pigments regarding brilliance, luster and (for the green) chroma;
      • particularly impressing is the high transparency combined with clear color;
      • looking with the microscope shows that the surfaces of all pigments are well and uniformly coated and that the differences result mostly from the imperfect orientation of the 5 μm particles;

Claims (19)

1-12. (canceled)
13. Effect pigments comprising glass flakes with a thickness of ≦1.0 μm, which glass flakes are coated with one or two layers of TiO2 in the rutile modification, Fe2O3, TiFe2O5, Ti suboxides, Fe3O4, Cr2O3, Al2O3, SiO2, ZrO2, ZnO, SnO2, CoO, Co3O4, VO2, V2O3, Sn(Sb)O2 or mixtures thereof to form said effect pigments.
14. Effect pigments according to claim 13, wherein the softening point of the glass flakes is ≧800° C.
15. Effect pigments according to claim 13, wherein the metal oxide is TiO2 in the rutile modification.
16. Effect pigments according to claim 15, characterized in that the glass flakes are coated with TiO2 in the rutile modification, Fe2O3 or a mixture of TiO2 in the rutile modification and Fe2O3.
17. Effect pigments according to claim 13, wherein the glass flakes are coated with one layer.
18. A method of preparing effect pigments according to claim 13, comprising coating the glass flakes by wet chemical coating, by chemical or physical vapor deposition or electroless plating and optionally calcining the coated glass flakes.
19. A product selected from the group consisting of plastics, coatings, powder coatings, paints, inks, printing inks, glasses, ceramic products, agriculture foils and cosmetic formulations, comprising effect pigments according to claim 13 and a carrier.
20. A product selected from the group consisting of conductive pigments, magnetic pigments and dopants for the laser-marking of papers and plastics, comprising effect pigments according to claim 13.
21. A pigment formulation containing the effect pigments according to claim 13 and a carrier.
22. Effect pigments according to claim 13, which are as follows:
glass flake+TiO2 (rutile)
glass flake+Fe2O3
glass flake+Fe3O4
glass flake+TiFe2O5
glass flake+Cr2O3
glass flake+ZrO2
glass flake+Sn(Sb)O2
glass flake+BiOCI
glass flake+Al2O3
glass flake+Ce2S3 or
glass flake+MoS2.
23. Effect pigments according to claim 13, which are as follows:
glass flake+Fe2O3
glass flake+Fe3O4
glass flake+TiFe2O5
glass flake+Cr2O3
glass flake+ZrO2
glass flake+Sn(Sb)O2
glass flake+BiOCI
glass flake+Al2O3
glass flake+Ce2S3 or
glass flake+MoS2.
24. Effect pigments according to claim 13, which are as follows:
glass flake+TiO2 (rutile).
25. Effect pigments according to claim 13, wherein the glass have a thickness of ≦0.8 μm.
26. Effect pigments according to claim 25, which are as follows:
glass flake+TiO2 (rutile)
glass flake+Fe2O3
glass flake+Fe3O4
glass flake+TiFe2O5
glass flake+Cr2O3
glass flake+ZrO2
glass flake+Sn(Sb)O2
glass flake+BiOCI
glass flake+Al2O3
glass flake+Ce2S3 or
glass flake+MoS2.
27. Effect pigments according to claim 13, wherein the glass have a thickness of ≦0.5 μm.
28. Effect pigments according to claim 27, which are as follows:
glass flake+TiO2 (rutile)
glass flake+Fe2O3
glass flake+Fe3O4
glass flake+TiFe2O5
glass flake+Cr2O3
glass flake+ZrO2
glass flake+Sn(Sb)O2
glass flake+BiOCI
glass flake+Al2O3
glass flake+Ce2S3 or
glass flake+MoS2.
29. Effect pigments according to claim 13, wherein the glass flakes are quartz glass.
30. Effect pigments according to claim 13, wherein the glass flakes are amorphous glass.
US13/242,530 2001-05-09 2011-09-23 Effect pigments based on coated glass flakes Abandoned US20120010300A1 (en)

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US10/473,710 US7226503B2 (en) 2001-05-09 2002-04-11 Effect pigments based on coated glass flakes
US11/712,393 US20070212487A1 (en) 2001-05-09 2007-03-01 Effect pigments based on coated glass flakes
US12/816,637 US20100255047A1 (en) 2001-05-09 2010-06-16 Effect pigments based on coated glass flakes
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US12/816,637 Abandoned US20100255047A1 (en) 2001-05-09 2010-06-16 Effect pigments based on coated glass flakes
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EP1463777A2 (en) 2004-10-06
US20070212487A1 (en) 2007-09-13
CN101054479A (en) 2007-10-17
AU2002302524A1 (en) 2002-11-18
US20040134385A1 (en) 2004-07-15
CN1592769A (en) 2005-03-09
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US20100255047A1 (en) 2010-10-07
KR100903223B1 (en) 2009-06-17
JP2010024460A (en) 2010-02-04
US7226503B2 (en) 2007-06-05
JP2004533510A (en) 2004-11-04
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WO2002090448A2 (en) 2002-11-14
TWI292773B (en) 2008-01-21

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