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WO1998053010A1 - Paillettes de dioxyde de titane revetues d'oxyde metallique - Google Patents

Paillettes de dioxyde de titane revetues d'oxyde metallique Download PDF

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Publication number
WO1998053010A1
WO1998053010A1 PCT/EP1997/002650 EP9702650W WO9853010A1 WO 1998053010 A1 WO1998053010 A1 WO 1998053010A1 EP 9702650 W EP9702650 W EP 9702650W WO 9853010 A1 WO9853010 A1 WO 9853010A1
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WO
WIPO (PCT)
Prior art keywords
titanium dioxide
metal oxide
pigment
pigments
drying
Prior art date
Application number
PCT/EP1997/002650
Other languages
German (de)
English (en)
Inventor
Stephanie Andes
Gerd Bauer
Günter BRENNER
Dieter BRÜCKNER
Michael Schmelz
Andrea Heyland
Matthias Kuntz
Karl Osterried
Gerhard Pfaff
Original Assignee
Merck Patent Gmbh
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
Priority to DE19618568A priority Critical patent/DE19618568A1/de
Application filed by Merck Patent Gmbh filed Critical Merck Patent Gmbh
Priority to DE59709110T priority patent/DE59709110D1/de
Priority to JP10549831A priority patent/JP2000515927A/ja
Priority to BR9710754-9A priority patent/BR9710754A/pt
Priority to EP97923992A priority patent/EP0931112B1/fr
Priority to PCT/EP1997/002650 priority patent/WO1998053010A1/fr
Priority to US09/230,261 priority patent/US6238472B1/en
Publication of WO1998053010A1 publication Critical patent/WO1998053010A1/fr

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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
    • C09C1/0018—Pigments exhibiting interference colours, e.g. transparent platelets of appropriate thinness or flaky substrates, e.g. mica, bearing appropriate thin transparent coatings uncoated and unlayered plate-like particles
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
    • A61K8/29—Titanium; Compounds thereof
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q17/00—Barrier preparations; Preparations brought into direct contact with the skin for affording protection against external influences, e.g. sunlight, X-rays or other harmful rays, corrosive materials, bacteria or insect stings
    • A61Q17/04—Topical preparations for affording protection against sunlight or other radiation; Topical sun tanning preparations
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/02—Ingredients treated with inorganic substances
    • 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
    • C09C1/0021—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
    • 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
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/42—Colour properties
    • A61K2800/43—Pigments; Dyes
    • 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
    • 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
    • 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
    • C09C2200/306—Thickness of an absorbing 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
    • C09C2200/30—Interference pigments characterised by the thickness of the core or layers thereon or by the total thickness of the final pigment particle
    • C09C2200/308—Total thickness of the pigment particle
    • 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
    • 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

Definitions

  • the invention relates to very thin pearlescent pigments based on platelet-shaped titanium dioxide coated with metal oxide or coated with metal oxide hydrate.
  • Pearlescent pigments based on Giimmer which have further metal oxide layers on a titanium dioxide layer
  • Aluminum oxide, zirconium oxide, zinc oxide and tin oxide are mentioned as colorless oxides for a second metal oxide layer
  • iron oxide, nickel oxide, cobalt oxide, copper oxide and chromium oxide are mentioned as oxides which have their own color.
  • the deposition of a second metal oxide on the titanium dioxide hydrate layer leads to a clear stabilization with regard to the light sensitivity of this layer.
  • Titanium dioxide pigments containing iron oxide in particular have been used successfully for many years.
  • US Pat. No. 3,874,890 describes a process for the production of gold-colored pearlescent pigments, in which a mica pigment coated with Ti0 2 and / or Zr0 2 is first coated with iron (II) hydroxide, which is then oxidized to Fe 2 0 3 .
  • US 4744832 describes a pearlescent pigment based on platelet-shaped substrates coated with metal oxides, in particular mica, the metal oxide layer containing both titanium and iron and the pigment having a multilayer structure, with a first
  • Layer of Ti0 2 in the rutile form is followed by a layer of pseudobrookite and an iron oxide layer.
  • Mica pigments are widely used in the printing and coatings industry, in cosmetics and in plastics processing. They are characterized by interference colors and a high gloss.
  • mica pigments are not suitable for the formation of extremely thin layers because mica as a substrate for the metal oxide layers of the pigment already has a thickness of 200 to 1200 nm.
  • a further disadvantage is that the thickness of the mica platelets fluctuates significantly around an average value within a certain fraction, which is determined by the platelet size.
  • mica is a naturally occurring mineral that is contaminated by foreign ions. Furthermore, technically very complex and time-consuming preparation steps are necessary. Above all, this includes grinding and classifying.
  • Pearlescent pigments based on thick mica platelets and coated with metal oxides have a clear scattering component due to the thickness of the edge, especially with finer grain size distributions below 20 ⁇ m.
  • Thin glass plates which are obtained by rolling a glass melt with subsequent grinding, have been proposed as a replacement for mica.
  • Interference pigments based on such materials have color effects which are superior to those of conventional mica-based pigments.
  • the glass flakes have a very large average thickness of approximately 10-15 ⁇ m and a very wide distribution of thicknesses (typically between 4 and 20 ⁇ m), while the thickness of interference pigments is typically not greater than 3 ⁇ m.
  • EP 0,384,596 describes a process in which hydrated alkali silicate is subjected to an air jet at temperatures of 480-500 ° C., whereby bubbles with thin walls form; the bubbles are then crushed and you get platelet-shaped
  • DE 11 36 042 describes a continuous belt process for the production of platelet-like or flake-like oxides or oxide hydrates of metals of the IV and V groups and of the iron group of the periodic table. In this case, if necessary, a separating layer of, for example, silicone varnish is first applied to a continuous belt in order to later detach the
  • EP 0.240.952 and EP 0.236.952 have proposed a continuous belt process for the production of various platelet-shaped materials, including silicon dioxide, aluminum oxide and titanium dioxide.
  • a thin liquid film of a defined thickness of a precursor of the platelet-shaped material is applied to a smooth belt using a roller system; the film is dried and peeled off the tape, forming platelet-shaped particles. The particles are then optionally annealed, ground and classified.
  • the thickness of the platelets obtained by the process described in EP 0 240 952 is relatively well defined, since the film is applied very uniformly, for example, to the continuous belt using a roller system.
  • the layer thickness of the platelets is given in the examples as 0.3 to 3.0 ⁇ m.
  • a first roll is wetted with the precursor used by partially immersing this roll in a storage container filled with the precursor.
  • the film is transferred from this reel to a second reel rotating in the same direction, which is in very close contact with the first.
  • the film is unwound from the second roll onto the continuous belt.
  • the use of very expensive precursor materials and, in particular, the increased demands on job security that have to be made when using organometallic compounds are disadvantageous.
  • the complete chemical conversion of the precursor into the desired layer material generally requires a strong heating of the film and the strip material. In addition to the considerable thermal load on the strip material, the high energy consumption and the limitation of the process speed have a very disadvantageous effect on the economy of the process.
  • WO 93/08 237 describes platelet-shaped pigments, consisting of a platelet-shaped matrix of silicon dioxide, which can contain soluble or insoluble colorants and which is coated with one or more reflective layers of metal oxides or metals.
  • the platelet-shaped matrix is produced by solidifying water glass on an endless belt.
  • DE 1 273 098 describes the production of a mother-of-pearl pigment by vapor deposition of ZnS, MgF2, ZnO, CaF2 and TiO2 films on an endless belt.
  • this process like the process described in US Pat. No. 4,879,140, in which platelet-shaped pigments with Si and SiO 2 layers are obtained by plasma deposition from SiH4 and SiCl4, is associated with a very high outlay on equipment.
  • the object of the invention is to provide high-gloss titanium dioxide-containing pearlescent pigments with a layer thickness of less than 500 nm and a layer thickness tolerance of less than 10%.
  • This object is achieved according to the invention by a pearlescent pigment with a multilayer structure, a layer of another metal oxide or metal oxide hydrate being followed by a core of platelet-shaped titanium dioxide, obtainable by solidifying an aqueous solution of a thermally hydrolyzable titanium compound on an endless belt, detaching the resulting layer, coating of the titanium dioxide platelets obtained without intermediate drying in the wet process with another metal oxide, separation, drying and optionally calcining the material obtained.
  • the other metal oxide or metal oxide hydrate that is applied to the titanium dioxide is Fe 2 0 3 , Fe 3 0 4 , FeOOH, Cr 2 0 3 , CuO, Ce 2 0 3) Al 2 0 3 , Si0 2 , B.VO 4 , NiTi0 3 , CoTi0 3 and antimony-doped, fluorine-doped or indium-doped tin oxide.
  • a third layer of a further metal oxide or metal oxide hydrate is present on the second layer made of another metal oxide or metal oxide hydrate.
  • This further metal oxide or metal oxide hydrate is aluminum oxide or aluminum oxide hydrate, silicon dioxide or silicon dioxide hydrate, Fe 2 0 3 , Fe 3 ⁇ 4 , FeOOH, Zr0 2l Cr 2 0 3 and antimony-doped, fluorine-doped or indium-doped tin oxide.
  • the aqueous solution of a thermally hydrolyzable titanium compound for the production of the titanium dioxide flakes on the endless belt is preferably an aqueous titanium tetrachloride solution.
  • the concentration of the titanium salt in these solutions is 7 to 30% by weight, preferably 8 to 15% by weight.
  • this object is achieved according to the invention by a method for producing the pigments according to the invention by an aqueous solution of a thermally hydrolyzable titanium compound is applied as a thin film to an endless belt,
  • the liquid film is solidified by drying and the titanium dioxide is developed from the precursor by a chemical reaction
  • the resulting layer is then removed from the belt and washed
  • the titanium dioxide platelets obtained are suspended in water after or without intermediate drying and are coated with another metal oxide and optionally with further metal oxides,
  • coated titanium dioxide platelets are separated from the aqueous suspension, dried and optionally calcined.
  • the coating of the titanium dioxide platelets with metal oxides or metal oxide hydrates can also be e.g. in a fluidized bed reactor by gas phase coating, e.g. the methods proposed in EP 0.045.851 and EP 0.106.235 for the production of pearlescent pigments can be used accordingly.
  • the invention also relates to the use of the pigments according to the invention for pigmenting lacquers, printing inks, plastics, cosmetics and glazes for ceramics and glasses.
  • the pigments according to the invention are based on platelet-shaped titanium dioxide. These platelets have a thickness between 10 nm and 500 nm, preferably between 40 and 150 nm. The extent in the other two dimensions is between 2 and 200 ⁇ m and in particular between 5 and 50 ⁇ m.
  • the layer of another metal oxide which is applied to the titanium dioxide platelets has a thickness of 5 to 300 nm, preferably between 5 and 150 nm.
  • the pigments according to the invention are produced in a three-stage process.
  • platelet-shaped titanium dioxide particles are produced using an endless belt.
  • Roller applicators and flowers can be used as suitable applicators.
  • the belt speed is between 2 and 400 m / min, preferably 5-200 m / min.
  • the coated strip then runs through a drying section 4 in which the layer is dried at temperatures between 30 and 200 ° C.
  • a drying section 4 in which the layer is dried at temperatures between 30 and 200 ° C.
  • commercially available infrared, circulating air and UV dryers can be used as dryers.
  • the tape is passed through the release baths 5 with a suitable release medium, for example deionized water, where the dried layer is removed from the tape.
  • a suitable release medium for example deionized water
  • the tape is dried in a post-dryer 6 before it is re-coated.
  • the endless belt should be made of a chemically and thermally resistant plastic to ensure a sufficient service life and high drying temperatures.
  • Materials such as polyethylene terephthalate (PET) or other polyesters and polyacrylates are suitable for this.
  • the film width is typically between a few centimeters up to several meters.
  • the thickness is between 10 ⁇ m and a few mm, whereby these two parameters are optimized with regard to the respective requirements.
  • the titanium dioxide flakes detached from the tape are coated in a second process step without prior drying with another metal oxide by a known method.
  • iron (III) salts can be used as described, for example, in US Pat. No. 3,987,828 and US Pat. No. 3,087,829, and iron (II) - salt, as described in US Pat. No. 3,874,890, the initially formed coating of iron (II) hydroxide being oxidized to the iron (III) oxide hydrate.
  • the preferred starting point is iron (III) salts.
  • an aqueous suspension of the titanium dioxide platelets at a temperature of 60 to 90 ° C and an iron (III) chloride solution is metered in at a pH of 2.5 to 4.5. The pH value is kept constant by simultaneous dosing of 32% sodium hydroxide solution. After working up and drying at 110 ° C., a red pigment is obtained.
  • the coating with magnetite (Fe 3 ⁇ 4 ) is carried out by hydrolysis of an iron (II) salt solution, for example iron (II) sulfate, at a pH of 8.0 in the presence of potassium nitrate.
  • an iron (II) salt solution for example iron (II) sulfate
  • the exact precipitation examples are described in EP 0 659 843.
  • a black pigment is obtained after working up and drying at 100 ° C.
  • a coating of the titanium dioxide platelets with yellow FeO (OH) in the goethite modification is also preferred.
  • An aqueous FeS0 4 solution is metered into a suspension of the titanium dioxide platelets in a nitrogen atmosphere at 70 ° C. Then the pH is adjusted to 4 with a 10% Na 2 CO 3 solution and oxygen is introduced into the suspension. After working up and drying at 110 ° C., a yellow pigment is obtained. With regard to the exact precipitation conditions, reference is made to EP 0 659 843.
  • chromium oxide Another metal oxide that is preferentially struck on the titanium dioxide platelets is chromium oxide.
  • the deposition can easily be effected by the thermal hydrolysis which occurs when ammonia evaporates from an aqueous solution of a hexamine-chromium (III) derivative, or by thermal hydrolysis of a chromium salt solution which is buffered with borax.
  • the coating with chromium oxide is described in US 3087828 and 3,087,829.
  • the pigments according to the invention do not have to be calcined in every case. Drying at temperatures of 110 ° C is sufficient for certain applications. If the pigment is calcined, temperatures between 400 ° C and 1000 ° C are set, the preferred range being between 400 ° C and 700 ° C.
  • the pigment of the invention can additionally be coated with sparingly soluble, firmly adhering inorganic or organic colorants.
  • Colored lacquers and in particular aluminum colored lacquers are preferably used.
  • an aluminum hydroxide layer is struck, which is then varnished with a colored varnish. The process is described in more detail in DE 24 29 762 and DE 29 28 287.
  • An additional coating with complex salt pigments in particular cyanoferrate complexes, such as for example Powell Blau and Turnbulls Blau, as described in EP 0 141 173 and DE 23 13 332, is also preferred.
  • the pigment according to the invention can also be coated with organic dyes and in particular with phthalocyanine or metal phthalocyanine and / or indanthrene dyes according to DE 40 09 567.
  • organic dyes and in particular with phthalocyanine or metal phthalocyanine and / or indanthrene dyes according to DE 40 09 567.
  • a suspension of the pigment is prepared in a solution of the dye and this is then brought together with a solvent in which the dye is sparingly soluble or insoluble.
  • Metal chalcogenides or metal chalcogenide hydrates and carbon black can also be used for an additional coating. It is also possible to subject the pigments to a post-coating or post-treatment which further increases the light, weather and chemical stability, or to facilitate the handling of the pigment, in particular the incorporation into different media.
  • the following layers are, for example, those described in DE-PS 22 15 191, DE-
  • the pigments according to the invention represent the ideal state which can be attained as far as possible with pearlescent pigments, since they consist only of optically functional layers and an otherwise customary carrier material, such as mica or glass plates, which does not contribute to the optical effect, is missing. Due to the thickness of the mica, mica pigments are up to 25 times thicker with the same thickness of the functional layers. With regard to technical applications, this results in intrinsic advantages that no other conventional pearlescent pigment can achieve. For example, lacquer layers can be made thinner and the necessary amount of pigment can be reduced because the pigments are more optically active due to the lack of the “filler” carrier material.
  • a circumferential belt made of polyethylene terephthalate (width: 0.3 m, speed: 20 m / min) is coated with a 20% titanium tetrachloride solution in counter-rotation on an application roller.
  • the coating solution contains 0.3% by weight of surfactant (DISPERSE-AYD W-28, manufacturer: DANIEL PRODUCTS COMPANY).
  • the aqueous film on the belt is dried in a drying section by exposure to hot air at 70 ° C. and the layer formed is detached from the belt in a detachment basin filled with deionized water.
  • the platelet-shaped titanium dioxide particles are filtered and washed with deionized water.
  • the silvery, shiny platelets have a layer thickness of 100 ⁇ 10 nm. To coat them with another metal oxide, they are redispersed in deionized water.
  • the Snd4 solution is added to the TiO 2 suspension at 3 ml / min and the pH 1.8 is kept constant with 32% NaOH solution. After the SnO 2 coating, the suspension is stirred for 15 minutes at constant temperature and pH.
  • the pH is then adjusted to 3.0 with 32% NaOH solution and an aqueous 8% iron (III) chloride solution is metered in at a rate of 3 ml / min, the pH being increased by simultaneous addition of the NaOH Solution is kept constant.
  • the FeCI 3 addition is continued until the desired interference color is reached.
  • the pigment obtained is filtered off, washed with deionized water and dried at 110 ° C. for 12 hours.
  • the pigment has the desired interference color and a red body color.

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  • Chemical & Material Sciences (AREA)
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  • Life Sciences & Earth Sciences (AREA)
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  • Veterinary Medicine (AREA)
  • Public Health (AREA)
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  • Pigments, Carbon Blacks, Or Wood Stains (AREA)
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Abstract

L'invention concerne un pigment nacré coloré, constitué d'un noyau en dioxyde de titane lamellaire et d'une ou plusieurs couches d'autres oxydes métalliques ou hydrates d'oxydes métalliques, s'obtenant par durcissement d'une solution aqueuse d'un composé de titane thermo-hydrolysable sur une bande sans fin, séparation de la bande résultante, enduction des paillettes de dioxyde de titane obtenues, après ou sans séchage intermédiaire, par procédé par voie humide, avec un ou plusieurs autres oxydes métalliques ou hydrates d'oxydes métalliques, par exemple Fe2O3, Fe3O4, FeOOH ou bien Cr2O3, séparation, séchage et éventuellement calcination du matériau obtenu.
PCT/EP1997/002650 1996-05-09 1997-05-23 Paillettes de dioxyde de titane revetues d'oxyde metallique WO1998053010A1 (fr)

Priority Applications (7)

Application Number Priority Date Filing Date Title
DE19618568A DE19618568A1 (de) 1996-05-09 1996-05-09 Metalloxidbeschichtete Titandioxidplättchen
DE59709110T DE59709110D1 (de) 1997-05-23 1997-05-23 Metalloxidbeschichtete titandioxidplättchen
JP10549831A JP2000515927A (ja) 1997-05-23 1997-05-23 金属酸化物を塗布した二酸化チタン薄片
BR9710754-9A BR9710754A (pt) 1997-05-23 1997-05-23 Plaquetas de dióxido de titânio revestida com óxido metálico.
EP97923992A EP0931112B1 (fr) 1997-05-23 1997-05-23 Paillettes de dioxyde de titane revetues d'oxyde metallique
PCT/EP1997/002650 WO1998053010A1 (fr) 1996-05-09 1997-05-23 Paillettes de dioxyde de titane revetues d'oxyde metallique
US09/230,261 US6238472B1 (en) 1997-05-23 1997-05-23 Metal oxide coated titanium dioxide lamellas

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19618568A DE19618568A1 (de) 1996-05-09 1996-05-09 Metalloxidbeschichtete Titandioxidplättchen
PCT/EP1997/002650 WO1998053010A1 (fr) 1996-05-09 1997-05-23 Paillettes de dioxyde de titane revetues d'oxyde metallique

Publications (1)

Publication Number Publication Date
WO1998053010A1 true WO1998053010A1 (fr) 1998-11-26

Family

ID=26025541

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP1997/002650 WO1998053010A1 (fr) 1996-05-09 1997-05-23 Paillettes de dioxyde de titane revetues d'oxyde metallique

Country Status (2)

Country Link
DE (1) DE19618568A1 (fr)
WO (1) WO1998053010A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6602340B1 (en) * 1997-12-17 2003-08-05 Merck Patent Gmbh Transparent medium with angular-selective transmitting or reflecting properties
CN104069847A (zh) * 2014-04-10 2014-10-01 西安工程大学 稀土铕掺杂纳米TiO2空心玻璃微珠的制备方法

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DE10041979A1 (de) * 2000-08-26 2002-03-14 Basf Coatings Ag Beschichtungsstoffe und ihre Verwendung zur Herstellung deckender farbgebender Beschichtungen
US6485556B1 (en) * 2001-10-10 2002-11-26 Engelhard Corporation Interference pigments
DE102009051171A1 (de) 2009-10-29 2011-05-05 Merck Patent Gmbh Pigmente
EP2559739B1 (fr) * 2011-08-16 2014-04-16 JDS Uniphase Corporation Fabrication de pigments diffractifs par dépôt de vapeur chimique à lit fluidisé
DE102013012023A1 (de) 2013-07-19 2015-01-22 Merck Patent Gmbh Pigmentgemisch
DE102016004164A1 (de) 2016-04-11 2017-10-12 Merck Patent Gmbh Pigmentgemisch
EP3517579B1 (fr) 2018-01-23 2022-10-26 Merck Patent GmbH Mélange de pigments interférentiels rouge, bleu et vert
DE102019003072A1 (de) 2019-04-30 2020-11-05 Merck Patent Gmbh Effektpigmente
DE102019003073A1 (de) 2019-04-30 2020-11-05 Merck Patent Gmbh Pigment/Fritten-Gemisch
US20210087403A1 (en) 2019-09-20 2021-03-25 Merck Patent Gmbh Pigments
EP3974395A1 (fr) 2020-09-25 2022-03-30 Merck Patent GmbH Mélange de pigment et de frittes
EP4389828A1 (fr) 2022-12-19 2024-06-26 Merck Patent GmbH Pigments à effet avec au moins une couche de tio2, dans laquelle le tio2 est dopé avec du ti(3+) et du fluorure

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FR1273230A (fr) * 1959-11-14 1961-10-06 Jenaer Glaswerk Schott & Gen Matière de charge et matériau présentant un éclat nacré artificiel et procédé our les obtenir
DE1136042B (de) * 1959-11-14 1962-09-06 Jenaer Glaswerk Schott & Gen Fuellstoffe und Werkstoffe mit kuenstlichem Perlmuttglanz und Verfahren zum Herstellen der Fuellstoffe
DE1467468A1 (de) * 1961-06-28 1968-12-12 Du Pont Glimmerschuppenpigment
FR2198984A1 (fr) * 1972-09-09 1974-04-05 Merck Patent Gmbh
US3874984A (en) * 1971-07-29 1975-04-01 Columbia Ribbon Carbon Mfg Pressure-sensitive transfer elements
EP0045851A1 (fr) * 1980-08-08 1982-02-17 BASF Aktiengesellschaft Procédé pour la fabrication de pigments micacés en forme d'écailles recouvertes d'oxydes métalliques et leur utilisation
JPS61295234A (ja) * 1985-06-11 1986-12-26 Sumitomo Chem Co Ltd 金属酸化物被覆薄片状酸化チタン
US4744832A (en) * 1985-08-07 1988-05-17 Merck Patent Gesellschaft Mit Beschrankter Haftung Iron oxide coated perlescent pigments
EP0307747A1 (fr) * 1987-09-11 1989-03-22 MERCK PATENT GmbH Pigments à lustre doré

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1273230A (fr) * 1959-11-14 1961-10-06 Jenaer Glaswerk Schott & Gen Matière de charge et matériau présentant un éclat nacré artificiel et procédé our les obtenir
DE1136042B (de) * 1959-11-14 1962-09-06 Jenaer Glaswerk Schott & Gen Fuellstoffe und Werkstoffe mit kuenstlichem Perlmuttglanz und Verfahren zum Herstellen der Fuellstoffe
DE1467468A1 (de) * 1961-06-28 1968-12-12 Du Pont Glimmerschuppenpigment
US3874984A (en) * 1971-07-29 1975-04-01 Columbia Ribbon Carbon Mfg Pressure-sensitive transfer elements
FR2198984A1 (fr) * 1972-09-09 1974-04-05 Merck Patent Gmbh
EP0045851A1 (fr) * 1980-08-08 1982-02-17 BASF Aktiengesellschaft Procédé pour la fabrication de pigments micacés en forme d'écailles recouvertes d'oxydes métalliques et leur utilisation
JPS61295234A (ja) * 1985-06-11 1986-12-26 Sumitomo Chem Co Ltd 金属酸化物被覆薄片状酸化チタン
US4744832A (en) * 1985-08-07 1988-05-17 Merck Patent Gesellschaft Mit Beschrankter Haftung Iron oxide coated perlescent pigments
EP0307747A1 (fr) * 1987-09-11 1989-03-22 MERCK PATENT GmbH Pigments à lustre doré

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
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DATABASE WPI Week 8706, Derwent World Patents Index; AN 87-039671, XP002037924 *
DE 1 136 042 A in der Anmeldung erwähnt *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6602340B1 (en) * 1997-12-17 2003-08-05 Merck Patent Gmbh Transparent medium with angular-selective transmitting or reflecting properties
CN104069847A (zh) * 2014-04-10 2014-10-01 西安工程大学 稀土铕掺杂纳米TiO2空心玻璃微珠的制备方法
CN104069847B (zh) * 2014-04-10 2016-05-25 西安工程大学 稀土铕掺杂纳米TiO2空心玻璃微珠的制备方法

Also Published As

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