WO2003006558A2 - Multilayer pigments based on glass flakes - Google Patents
Multilayer pigments based on glass flakes Download PDFInfo
- Publication number
- WO2003006558A2 WO2003006558A2 PCT/EP2002/007219 EP0207219W WO03006558A2 WO 2003006558 A2 WO2003006558 A2 WO 2003006558A2 EP 0207219 W EP0207219 W EP 0207219W WO 03006558 A2 WO03006558 A2 WO 03006558A2
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- WIPO (PCT)
- Prior art keywords
- tio
- glass flakes
- metal
- layer
- refractive index
- Prior art date
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Classifications
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/06—Glass compositions containing silica with more than 90% silica by weight, e.g. quartz
-
- 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
- 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
- C09C1/003—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 comprising at least one light-absorbing layer
- C09C1/0039—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 comprising at least one light-absorbing layer consisting of at least one coloured inorganic material
-
- 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
- C09C1/003—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 comprising at least one light-absorbing layer
- C09C1/0039—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 comprising at least one light-absorbing layer consisting of at least one coloured inorganic material
- C09C1/0042—Sub-stoichiometric inorganic materials
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
-
- C—CHEMISTRY; METALLURGY
- 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
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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
- 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
- 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
- C09C2200/302—Thickness of a layer with high refractive material
-
- 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
- C09C2200/303—Thickness of a layer with low refractive material
-
- 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
- C09C2220/106—Wet methods, e.g. co-precipitation comprising only a drying or calcination step of the finally coated pigment
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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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/25—Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
- Y10T428/252—Glass or ceramic [i.e., fired or glazed clay, cement, etc.] [porcelain, quartz, 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
- Y10T428/25—Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
- Y10T428/256—Heavy metal or aluminum or compound thereof
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/25—Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
- Y10T428/256—Heavy metal or aluminum or compound thereof
- Y10T428/257—Iron oxide or aluminum oxide
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
- Y10T428/2991—Coated
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
- Y10T428/2991—Coated
- Y10T428/2993—Silicic or refractory material containing [e.g., tungsten oxide, glass, cement, etc.]
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
- Y10T428/2991—Coated
- Y10T428/2993—Silicic or refractory material containing [e.g., tungsten oxide, glass, cement, etc.]
- Y10T428/2996—Glass particles or spheres
Definitions
- the present invention relates to multilayer pigments based on 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, for laser-marking of papers and plastics and in cosmetic formulations.
- Multilayer interference pigments with alternating layers of high and low refractive index are known. They differ in respect of the carrier material and of the material of the individual layers, and in the preparation process.
- the layers are prepared either by precipitation in a wet process or by vapor deposition or sputtering under vacuum.
- the layers applied to the carrier or to a release layer are all optically active and contribute to the development of the interference colors.
- U.S. P. 4,434,010 discloses a multilayer interference pigment consisting of a central layer of a reflective metal, such as aluminum, and alternating layers of two transparent dielectric materials of high and low refractive index respectively, such as titanium dioxide and silicon dioxide, for example.
- This multilayer pigment is used preferably for counterfeit- protected products like securities or banknotes.
- JP H7-759 discloses a multilayer interference pigment with metallic lustre, for which a substrate is coated with alternate layers of titanium dioxide and silicon dioxide.
- the substrate comprises flakes of aluminum, gold or silver, or of mica or glass, with a coating of metals.
- the depth effect which is characteristic of and desired for interference pigments, however, cannot be generated. This is because of the total reflection of the light at the metal layer which forms the core. Consequently, the interference effect remains limited to the layers which are located on top of the metal layer.
- U.S. P. 3,438,796 and U.S. P. 5,135,812 describe, for example, metal lustre pigments having a central essentially non-transparent aluminum film coated on both sides in alternation with dielectric films of low refractive index, such as silicon dioxide or magnesium fluoride, and with partially transparent metal films, such as films of chromium or aluminum, for example. Owing to the preparation process, the central metal film of these pigments is coated only on the top and bottom sides of the platelets, while the side areas constitute broken edges and lie open towards the medium.
- dielectric films of low refractive index such as silicon dioxide or magnesium fluoride
- partially transparent metal films such as films of chromium or aluminum
- JP 1992/93206 claims lustre pigments on the basis of glass flakes or mica particles which are covered with a reflecting metal layer and with alternating layers of SiO 2 and TiO 2 .
- Disadvantages of this invention are the technically very complex and costly preparation process and the frequent difficulty in reproducing the pigments in the desired product quality.
- U.S. P. 3,331 ,699 discloses that glass flakes may be coated with a translucent layer of particles of 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 that smooth transparent films, not particles, are 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. Patent 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 0 289 240 B1 discloses the manufacturing of extremely thin glass flakes at reasonable costs. According to the claimed process the glass flakes can be made in any desired composition, e. g., from pure Si0 2 and also in any thickness tailored for the intended application down to below
- an interference pigment which is based on multiply coated glass flakes and comprises a particular arrangement of 30 optically functional layers by means of which particular optical effects are achieved.
- the invention therefore provides interference pigments on the basis of multiply coated glass flakes which contain at least three alternating layers 5 with a high and a low refractive index.
- the layer structure is as of follows:
- the invention also provides the pigments of the invention for the use in paints, lacquers, printing inks, plastics, agricultural foils, ceramic materials, glasses and cosmetic formulations and for the use in laser-marking of papers and plastics.
- 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 - 0.8 ⁇ m, preferably of 0.2 - 0.5 ⁇ m.
- the aspect ratio of glass flakes is in the range of 10 - 300, preferably in the range of 50 - 200.
- the glass flakes can be coated in the same way as conventional 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 under alkaline conditions, which deposits hydrated metal oxide, 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.
- Materials particularly suitable for the coating (C) of high refractive index are colorless or colored metal oxides such as TiO 2 , Fe 2 0 3 , TiFe 2 O5, Fe 3 O 4 ,
- the TiO 2 layers additionally can contain absorbing material, e.g. carbon, or coated therewith. Also of particular interest are multiply coated glass flakes whose Ti0 2 coating (C) is partially reduced and which as well as unchanged TiO 2 contains reduced titanium species having oxidation states from ⁇ 4 to 2 (lower oxides as
- Ti 3 O 5 Ti 2 0 3 through TiO, titanium oxynitrides and also titanium nitride). It is also possible to use colorless high refractive materials, for example metal oxides such as zirconium dioxide, in particular titanium dioxide, which have been colored with selectively absorbing colorants, by incorporation of colorants in the metal oxide layer, by doping thereof with selectively absorbing metal cations or by coating the metal oxide layer with a colorant like for example prussian blue or carmine.
- the thickness of the layer (C) is 10 - 550 nm, preferably 15 - 400 nm and, in particular, 20 - 350 nm.
- the layer packet of (A) + (B) may be present up to four times in the pigment of the invention, there are other preferred embodiments.
- the pigment of the invention may have a further absorbing or nonabsorbing layer [(S1 ), (A1), (B1), (C1 )].
- the thickness of the interlayers is 1 - 50 nm, preferably 1 - 40 nm and, in particular, 1- 30 nm.
- the inventive pigments may contain a plurality of identical or different combinations (layer packets) of (A) + (B).
- the multilayer coated glass flakes obtained in this way are characterised in that at least three homogeneous layers are surrounding the uniform thin glass flakes.
- the pigments of the invention are easy to produce by virtue of the generation of three or more interference layers of high and low refractive index, precisely defined thickness and smooth surface on the thin glass flakes.
- the sequences of high refractive index layers in the multilayer stack can be arranged arbitrary as long as a low refractive index layer is present in between.
- the metal oxide layers are preferably applied by wet-chemical means, it being possible to use the wet-chemical coating techniques developed for the production of pearl lustre pigments; techniques of this kind are described, for example, in DE 14 67 468, DE 19 59 988, DE 20 09 566, DE 22 14 545, DE 22 15 191 , DE 22 44 298, DE 23 13 331 , DE 25 22 572, DE 31 37 808, DE 31 37 809, DE 31 51 343, DE 31 51 354, DE 31 51 355, DE 32 11 602, DE 32 35 017, DE 38 42 330 or else in further patent documents and other publications.
- aqueous titanium salt solution is added slowly to a suspension of the substrate to be coated, heated to about 50 - 100 °C, and a substantially constant pH of about 0.5 - 5 is maintained by simultaneous metered addition of a base, for example aqueous ammonia solution or aqueous alkali metal hydroxide solution. As soon as the desired layer thickness of the TiO 2 precipitate has been reached, the addition of both titanium salt solution and base is terminated.
- a base for example aqueous ammonia solution or aqueous alkali metal hydroxide solution.
- the preferred designs for the inventive multilayer pigments are:
- the effect pigments of the present invention are advantageously useful for many purposes, such as the coloring of plastics, glasses, ceramic products, agricultural 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, bronzing, flexographic printing.
- the pigment mixture of the invention is simple and easy to handle.
- the pigment mixture can be incorporated into the system in which it is used by simple stirring. Laborious milling and dispersing of the pigments is 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 coloring of food, coatings of medicaments or cosmetic formulations.
- concentration of the pigments in the system in which it is to be used 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 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 multilayer coated glass flakes, optionally effect pigments, binders and, if desired, additives, said preparations being in the form of substantially solvent-free, free-flowing powders or 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.
- Coating with SiO 2 is then carried out by adding 3 ml/min of dilute sodium silicate solution (from 7.3 g of sodium silicate solution with 8 % Na and
- the pigment obtained has an intense green interference color.
- the division of the TiO 2 layers is as follows: 1 st layer: about 170 nm
- Total layer about 260 nm.
- the thickness of the SiO 2 interlayer is about 5 nm.
- 100 g glass flakes with a maximum diameter of 40 ⁇ m (average 22 ⁇ m) and an average thickness of 0.5 ⁇ m (refractive index 1.5) are suspended in 2 I of deionized water.
- the suspension is heated to 75 °C, adjusted to a pH of 1.8 with dilute hydrochloric acid, first of all coated with Sn0 2 by adding 3.3 ml/min of SnCI 4 solution (from 2.2 g of SnCI 4 and 7.5 ml of cone. hydrochloric acid in 100 ml of deionized water).
- the pH is held constant using 32 % sodium hydroxide solution.
- Triethanolamine Triethanolamine 0,50 % (1)
- Isopropyl myristate Isopropyl Myristate 8,00 % (4)
- phase C Heat all ingredients of phase C to 75 °C while stirring until everything is melted. Add Blanose and Veegum separately to cold water of phase B under high agitation (Turrax). Heat to 75 °C and add the remaining ingredients of phase B and mix until the mixture is smooth and uniform. Add ingredients of phase A. At 75 °C incorporate phase C into phase A/B and homogenize for 2 min. Add phase D at 40 °C. Cool down to room temperature while stirring and adjust pH to 6,0 - 6,5 einstellen (e.g. citric acid solution).
- pH e.g. citric acid solution
- PE-HD polyethylene
- adhesion agent 1 kg
- 10 kg of polyethylene (PE-HD) granules are uniformly wetted in a tumble mixer with 2 g of adhesion agent.
- 10 g coated glass flakes according to Example 4 and 2 g of Iriodin LS 825 conductive pigment from Merck KGaA, Darmstadt, Germany with a particle size ⁇ 15 ⁇ m are added and the components are mixed for 2 minutes.
Abstract
Description
Claims
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AU2002328827A AU2002328827A1 (en) | 2001-07-12 | 2002-07-01 | Multilayer pigments based on glass flakes |
MXPA04000119A MXPA04000119A (en) | 2001-07-12 | 2002-07-01 | Multilayer pigments based on glass flakes. |
JP2003512318A JP2005502738A (en) | 2001-07-12 | 2002-07-01 | Multilayer pigments based on glass flakes |
EP02764606.6A EP1474486B1 (en) | 2001-07-12 | 2002-07-01 | Multilayer pigments based on glass flakes |
US10/483,182 US7604862B2 (en) | 2001-07-12 | 2002-07-01 | Multilayer pigments based on glass flakes |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP01117004 | 2001-07-12 | ||
EP01117004.0 | 2001-07-12 |
Publications (2)
Publication Number | Publication Date |
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WO2003006558A2 true WO2003006558A2 (en) | 2003-01-23 |
WO2003006558A3 WO2003006558A3 (en) | 2004-09-10 |
Family
ID=8178030
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP2002/007219 WO2003006558A2 (en) | 2001-07-12 | 2002-07-01 | Multilayer pigments based on glass flakes |
Country Status (9)
Country | Link |
---|---|
US (1) | US7604862B2 (en) |
EP (1) | EP1474486B1 (en) |
JP (4) | JP2005502738A (en) |
CN (2) | CN101104748B (en) |
AU (1) | AU2002328827A1 (en) |
IN (1) | IN2004KO00171A (en) |
MX (1) | MXPA04000119A (en) |
RU (1) | RU2323238C2 (en) |
WO (1) | WO2003006558A2 (en) |
Cited By (46)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2004055119A1 (en) * | 2002-12-17 | 2004-07-01 | Merck Patent Gmbh | Silvery white interference pigments having a high luster and based on transparent substrate laminae |
WO2004061012A2 (en) | 2002-12-31 | 2004-07-22 | Engelhard Corporation | Improved effect pigment comprising a mixture of at least 2 substrate materials |
EP1469042A2 (en) | 2003-03-27 | 2004-10-20 | MERCK PATENT GmbH | Pigment composition and use in cosmetic, food and pharmaceutical preparations |
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CN101104748B (en) | 2012-08-22 |
RU2323238C2 (en) | 2008-04-27 |
JP6166594B2 (en) | 2017-07-19 |
JP2010174255A (en) | 2010-08-12 |
RU2004102396A (en) | 2005-05-10 |
US7604862B2 (en) | 2009-10-20 |
AU2002328827A1 (en) | 2003-01-29 |
CN1622981A (en) | 2005-06-01 |
AU2002328827A8 (en) | 2005-11-03 |
JP2017128743A (en) | 2017-07-27 |
US20040170838A1 (en) | 2004-09-02 |
WO2003006558A3 (en) | 2004-09-10 |
CN101104748A (en) | 2008-01-16 |
EP1474486B1 (en) | 2019-04-03 |
JP2013177639A (en) | 2013-09-09 |
MXPA04000119A (en) | 2004-05-21 |
IN2004KO00171A (en) | 2006-02-17 |
JP2005502738A (en) | 2005-01-27 |
EP1474486A2 (en) | 2004-11-10 |
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