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WO2025219190A1 - Préparation de pigments à effet pour revêtement en poudre - Google Patents

Préparation de pigments à effet pour revêtement en poudre

Info

Publication number
WO2025219190A1
WO2025219190A1 PCT/EP2025/059770 EP2025059770W WO2025219190A1 WO 2025219190 A1 WO2025219190 A1 WO 2025219190A1 EP 2025059770 W EP2025059770 W EP 2025059770W WO 2025219190 A1 WO2025219190 A1 WO 2025219190A1
Authority
WO
WIPO (PCT)
Prior art keywords
effect pigment
pearlescent
pigments
pigment preparation
silvery
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
PCT/EP2025/059770
Other languages
English (en)
Inventor
Michael GRÜNER
Günter KAUPP
Christian Rummer
Alexander WENZLIK
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Eckart GmbH
Original Assignee
Eckart 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
Application filed by Eckart GmbH filed Critical Eckart GmbH
Publication of WO2025219190A1 publication Critical patent/WO2025219190A1/fr
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

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Classifications

    • 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
    • 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
    • A61K8/25—Silicon; Compounds thereof
    • 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
    • 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
    • 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
    • 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
    • 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
    • C09C1/0045—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 a carbonaceous material, e.g. carbon black, graphite, SWNT, MWNT incorporated within an inorganic material
    • 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
    • C09D17/00—Pigment pastes, e.g. for mixing in paints
    • C09D17/004—Pigment pastes, e.g. for mixing in paints containing an inorganic pigment
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/03—Powdery paints
    • C09D5/032—Powdery paints characterised by a special effect of the produced film, e.g. wrinkle, pearlescence, matt finish
    • 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
    • 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/66—Additives characterised by particle size
    • C09D7/67—Particle size smaller than 100 nm
    • 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/70—Additives characterised by shape, e.g. fibres, flakes or microspheres
    • 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
    • A61K2800/41—Particular ingredients further characterized by their size
    • A61K2800/412—Microsized, i.e. having sizes between 0.1 and 100 microns
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/42—Colour properties
    • A61K2800/43—Pigments; Dyes
    • A61K2800/436—Interference pigments, e.g. Iridescent, Pearlescent
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/51—Particles with a specific particle size distribution
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/60—Optical properties, e.g. expressed in CIELAB-values
    • C01P2006/65—Chroma (C*)

Definitions

  • the present invention relates to effect pigment preparations of metal pigments and special pearlescent pigments of silvery color and absorbing properties.
  • the invention also relates to the use of this effect pigment preparation in powder coatings and powder coatings containing this effect pigment preparation.
  • Metal effect pigments, and particularly aluminum effect pigments involve a high degree of explosion risks during handling, storage, transportation and processing. Mainly for these reasons aluminum effect pigments for liquid coating applications are delivered in form of pastes. In powder coatings the pigments, however, need to have a powdered form as the removal of solvent before processing into the powder coating would be too expensive and too risky with respect to safety demands.
  • WO 2011/095447 A2 discloses mixtures of perlite with other effect pigments to enhance sparkle effects in applications such as coatings, plastics, printing inks or cosmetics.
  • the amount of perlite is preferably lower than the amount of the effect pigment.
  • WO 2013/175339 A1 discloses a mixture of metallic effect pigments and pearlescent pigments, wherein the amount of metallic pigment dominates. This mixture is safer with respect to aluminothermic reactions of the aluminum effect pigments. The amount of metallic effect pigments here is clearly higher than the amount of the pearlescent pigments.
  • US 5,277,711 A discloses mixtures of iron oxide coated aluminum pigments with iron oxide coated mica pigments in a powdery state.
  • WO 2020/208134 A1 discloses mixtures of metal effect pigments with silvery pearlescent pigments which are intended to be used in automotive coatings. Metal pigments offered for such coatings are always delivered in form of pastes. It is an object of this invention to provide a metallic effect pigment, particularly an aluminum effect pigment which can be transported, handled, stored and processed in a form without the risk of a powder explosion or metallic flammability. In the application the optical effect should still provide a metallic impression with good hiding power and a silvery appearance.
  • an effect pigment preparation comprising or consisting of a mixture of a first component which is a flaky metal effect pigment based on aluminum or aluminum alloys having a median particle size d50,M and as a second component a pearlescent pigment of a filler having a median particle size d50,P any of: i) a silvery, absorbing pearlescent pigment comprising a transparent substrate with a refractive index of lower than 1.6 and an absorbing coating with a refractive index of > 2.0 or ii) a silvery transparent pearlescent pigment, which comprises a transparent substrate with a refractive index of lower than 1.6 and a coating with at least one transparent metal oxide with a refractive index of > 2.0 or iii) an uncoated transparent platelet with a refractive index of lower than 1.6, and mixtures of any of the second components i), ii) and iii), wherein the ratio by weight of the second component to the first component is in a range of 2.5 to 8.0,
  • flaky metal effect pigment is an aluminum or aluminum alloy-based effect pigment. Such metal pigments are most commonly used in powder coatings and stand for a silvery, metallic appearance. Most preferably the flaky metal effect pigment is suitable to be used in a powder coating. Such metal pigments, particularly aluminum effect pigments have special demands regarding their electrostatic chargeability. For example, aluminum pigments obtained by dry- or wet-milling which are covered with saturated fatty acids like most generally stearic acid which leads to leafing-pigments. Examples thereof are Standart® PC 200, Standart® PC 100 (both from Eckart GmbH) or Blitz 2091 (Benda-Lutz).
  • Aluminum pigments obtained by wet-milling with lubricants comprising unsaturated fatty acids, like oleic acid are not suitable per se in powder coatings. These aluminum pigments are too explosive during the application in powder coatings.
  • Aluminum pigments obtained by dry milling with either saturated fatty acids (leafing) or unsaturated fatty acids (non-leafing) under controlled oxygen conditions are applicable in powder coatings.
  • Commercially available examples are PC 20 (leafing,) or PCN 8810 (non-leafing), both from Eckart GmbH.
  • the metallic pigments are leafing pigments wherein an aluminum effect pigment is coated with a fluoroalkyl silane as disclosed in WO 2009/077191 A1.
  • the metallic pigments are coated with a polysiloxane and most preferably with a polysiloxane as disclosed in EP 2318463 B1 and as described below in formula (IV) within this invention.
  • the flaky metal effect pigments are coated with an enveloping passivation layer which also ensures electrostatic chargeability.
  • the passivation layers are SiO2, polymer and mixtures or combinations thereof.
  • the flaky metal effect pigments may comprise or consist of examples of commercially available aluminum effect pigments with silica coating for powder coating are PCR (Eckart GmbH) or Powdal XT (Schlenk Metallic Pigments GmbH).
  • the polymer is preferably a (meth)acrylate-based polymer and most preferably this polymer comprises or even consists of a polymerized three- functional methacrylate monomer.
  • a 3-dimensional polymer film is formed by polymerizing adequate monomers in a dispersion of flaky aluminium pigments in a solvent. The polymerization can be affected by initiators or by heat treatment.
  • Suitable acrylate or methacrylate based monomers are methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, 2-ethylhexyl acrylate, isodecyl acrylate, lauryl, stearyl acrylate, butoxylated acrylate, dimethylaminoethyl acrylate (DAMEA,) diethylaminoethyl acrylate, 2-hydroxybutyl acrylate, hydroxyethyl acrylate, 2-hydroxypropyl acrylate, methoxyethyl acrylate, butoxyethyl acrylate, glycidyl acrylate, cyclohexyl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, 2- ethylhexyl methacrylate, isodecyl me
  • Most preferred (meth)acrylate monomers are trimethylolpropane triacrylate, trimethylolpropane trimethacrylate and mixtures thereof.
  • examples of commercially available products are PCA or HCP (Eckart GmbH) or PCF (Toyo Aluminium).
  • the aluminum flakes may be coated with a binder material suitable for powder coating which can be, for example, coated onto the aluminum flakes via a spray drying process as disclosed in WO 2005/063897 A2.
  • powder coating resins which are preferably polyester based systems can be coated onto aluminum flakes via a so-called spontaneous precipitation which is disclosed in WO 2017/167450 A1.
  • Suitable products may be also aluminum flakes coated with a combination of a silica layer and a polymer layer.
  • the flaky metal effect pigments based on aluminum or aluminum alloys preferably have a median particle size d50,M in a range of 4.0 to 50 ⁇ m. More preferably the flaky metal effect pigments have a d50,M in a range of 5.0 to 44.0 ⁇ m, even more preferably in a range of 6.0 to 40.0 ⁇ m and most preferably in a range of 6.0 to 35.0 ⁇ m.
  • the particles size distribution is preferably determined by laser granulometry using the Fraunhofer approximation. It is determined as volume weighted distribution of equivalent spheres.
  • the flaky metal effect pigments of the first component have an average particle thickness hM in a range of more than 50 to 1.500 nm and more preferably in a range of 150 nm to 800 nm. Below of 50 nm average thickness the metal pigments are not mechanically stable enough to be mixed with the second component without becoming damaged. Furthermore, such pigments are usually very expensive as they are produced either by physical vapor deposition (PVD) or by more cumbersome wet-milling technologies (EP 1621586 B1, EP 2102294 B1) compared to the standard procedures.
  • PVD physical vapor deposition
  • EP 1621586 B1, EP 2102294 B1 more cumbersome wet-milling technologies
  • the flaky metal effect pigments based on aluminum preferably have no coating which would impart a color impression.
  • the flaky metal effect pigments are not coated with metal oxides of high (>1.8) refractive index or absorbing properties in the visible wavelength region. Therefore, in very preferred embodiments the flaky metal effect pigments are not coated with metal oxides such as iron oxides and more specifically not coated with any of Fe2O3, Fe3O4, Fe(OH)3, TiO2, ZrO2 or ZnO or combinations or mixtures thereof.
  • the second component is a silvery pearlescent pigment of a filler having a median particle size d50,P.
  • the median size is preferably in a range of 6.0 to 40 ⁇ m and more preferably in a range of 7.0 to 30 ⁇ m. They may be determined in the same way as for the first component.
  • Silvery absorbing pearlescent pigments of type i) The pearlescent pigments of type i) used in the effect pigment preparation are silvery, absorbing pearlescent pigments with optical properties reflecting a metallic look. These pearlescent pigments usually have optical properties such that the resulting color in reflection is essentially a neutral silver tone or a slightly colored tone and cover a color region from absorbing grey to anthracite shades. With respect to pearlescent pigments generally the color tone “anthracite” is also often referred to as “black”.
  • the term “silvery, absorbing pearlescent pigments” is used for pearlescent pigments which have a combination of neutral silver or slightly colored reflection color and grey to anthracite absorption color tones providing a metallic-like characteristic.
  • the silvery, absorbing pearlescent pigments are selected from the following types: a) pearlescent pigments comprising a transparent substrate which is coated with a high- refractive index layer with n > 1.8, which comprises or consists of an iron-oxide with Fe(ll)- ions, b) pearlescent pigments comprising a transparent substrate which is coated with a high- refractive index layer with n > 1.8, which comprises or consists of titanium suboxide or a pearlescent pigment comprising a substrate with a high-refractive index with n > 1.8 layer, which comprises or consists of a titanium suboxide that is optionally coated with a high- refractive index layer with n > 1.8, c) pearlescent pigments comprising a transparent substrate which is coated with a high- ref
  • the optical properties of the silvery, absorbing pearlescent pigments useable for the effect pigment preparation can be evaluated by making a drawdown of a colorless lacquer (preferably BASF farblos ZM 26- 3025) with a pigmentation height of 10 wt.% of the pearlescent pigment using a 100 ⁇ m doctor 25 blade on a black/white cartoon paper.
  • the total content of non-volatile components in the lacquer should be 30 wt.%.
  • the optical properties of the dried drawdowns are measured with a BYK-Mac instrument.
  • the chroma C*15° of such a drawdown of the silvery pearlescent pigments measured on black background is ⁇ 15, more preferably ⁇ 14 and most preferably ⁇ 10.
  • the hiding power of the silvery pearlescent pigment in such drawdowns can be defined as the ratio of the L*75°,black/L*75°,white-values measured on the black to white background, respectively. This ratio is preferably higher than 70%. This high hiding power is mainly achieved by the absorbing layer of the pearlescent pigments.
  • the lightness is represented by the L*15° value which is close to the angle of reflection and preferably this value measured on the drawdowns on black background is above 90 and more preferably above 100 for the pearlescent pigments of the effect pigment preparation in this particular application.
  • the silvery pearlescent pigments used in the effect pigment preparation are pearlescent pigments comprising a transparent substrate which is coated with a high-refractive index layer with n > 1.8, which comprises or consists of an iron-oxide with Fe(II)- ions.
  • the silvery pearlescent pigment a) has a coating comprising a metal oxide layer comprising Ti and Fe, wherein the iron is mainly Fe(II) ions, which is preferably an ilmenite (FeTiO3) layer or a magnetite (Fe3O4) layer or mixtures thereof.
  • the pearlescent pigment has a coating comprising a first layer of TiO2 followed by a metal oxide layer containing Fe(II)-ions, preferably consisting of ilmenite.
  • Pearlescent pigments with a coating comprising a homogeneously distributed ilmenite (FeTiO3) have been described in EP 1620511 A2.
  • Pearlescent pigments with a coating comprising first a TiO2 layer followed by an inhomogeneously distributed ilmenite layer have been described in WO 2012/130776 A1.
  • Further examples of such pearlescent pigments are disclosed in EP 246523 A2, EP 3119840 A1 (with an Al2O3 substrate) or EP 681009 A2 (with a further high-refractive index coating).
  • the silvery pearlescent pigment comprises the following structure: (a1) a transparent platelet-shaped synthetic substrate, (a2) a titanium oxide layer, followed by (a3) a metal oxide layer comprising Ti- and Fe-ions, wherein the Fe-ions are mainly Fe(II)-ions.
  • the silvery pearlescent pigment has a layer of ilmenite (FeTiO3).
  • the pearlescent pigment has an iron(III) oxide content of less than 0.5% by weight, based on the total weight of the pigment. All other amounts of Fe-ions in iron oxides are in the reduced Fe(II) oxidation state. A higher amount of remaining Fe(III)-ions would lead to an undesired brownish absorption color.
  • the amounts of Fe(II) or Fe(III) can be determined with M Kunststoffbauer spectroscopy or with XPS analysis, possibly combined with sputter profiles.
  • the total amount of iron compounds, calculated as elemental iron, in the silvery, absorbing pearlescent pigment according to the invention is less than 5.0% by weight, preferably in a range from 1% by weight to 4.3% by weight, particularly preferably in a range from 1.4% by weight to 2.9% by weight and very particularly preferably in a range from 1.5% by weight to 2.3% by weight, based in each case on the total weight of the pearlescent pigment.
  • the total amount of iron compounds, calculated as elemental iron, in the silvery, absorbing pearlescent pigment according to the invention is less than 5.0% by weight, preferably in a range from 1% by weight to 4.3% by weight, particularly preferably in a range from 1.4% by weight to 2.9% by weight and very particularly preferably in a range from 1.5% by weight to 2.3% by weight, based in each case on the total weight of the pearlescent pigment.
  • the pearlescent pigment of type a) has an iron/titanium weight ratio as a function of the coating, in accordance with formula (I): F raction o (I) f the coating (wt. %) is in a range from 1.0 to 25.0.
  • iron content stands for the amount of iron compounds, calculated as elemental iron
  • titanium content stands for the amount of titanium compounds, calculated as elemental titanium, in each case in the pearlescent pigment and based on the total weight of the pearlescent pigment
  • the “fraction of the coating (% by weight)” stands for the weight fraction, based on the total weight of the pearlescent pigment, of the overall coating applied to the substrate.
  • this parameter is in a range from 1.2 to 8.0, preferably in a range from 2.0 to 7.5, particularly preferably in a range from 2.5 to 7.0, and very particularly preferably in a range from 3.0 to 6.0.
  • This parameter especially ensures that the pearlescent pigment has a silvery color as demanded in the effect pigment preparation.
  • the silvery, absorbing pearlescent pigments comprise a transparent substrate which is coated with a high-refractive index layer with n > 1.8 which comprises or consists of a titanium suboxide or a substrate with a high-refractive index n > 1.8 layer comprising or consisting of a titanium suboxide that is optionally coated with a high-refractive index layer with n > 1.8.
  • the high-refractive coating layer with n > 1.8 of the second kind of pigment is made from a different material than the substrate ⁇ s titanium suboxide and is preferably TiO2.
  • the titanium suboxide content can be less than 5% based on the total pigment and the main component of said titanium suboxide is Ti2O3.
  • the silvery pearlescent pigments comprise a transparent substrate which is coated with a high-refractive index layer with n > 1.8, which comprises or consists of titanium oxynitride.
  • the titanium oxynitrides can be expressed by the general formula: TixNyOz (III) wherein x is 0.2 to 0.6, y is 0.05 to 0.6 and z is 0.1 to 0.9, which comprises a solid solution of 25 nitrogen in titanium monoxide.
  • Such pearlescent pigments have been described in US 4,623,396 A.
  • Pearlescent pigments with intense blue color or a bluish fade have been described in EP 332071 A1 or in EP 735115 A1.
  • a first TiO2 layer is reduced with ammonia at temperatures in the range of 750 °C to 850 °C. If the optical thickness of the TiO2 layer deposited in a first step is in the range of 50 to 100 nm silvery effect pigments are obtained.
  • pearlescent pigments are described were a flakyTiO2 substrate is first formed by solidification of a hydrolysable aqueous solution of a titanium compound on an endless band. These substrates can be coated with further TiO2 or other metal oxides and calcined under reducing conditions.
  • the pearlescent pigment of the effect pigment preparation comprises a transparent substrate which is coated with a layer comprising carbon, wherein the carbon is enclosed in a particulate form in another metal oxide layer or is formed as a separate, individual layer on at least one high-refractive index layer.
  • DE 4227082 A1 pearlescent pigments were disclosed, wherein pearlescent substrates or TiO2 coated pearlescent pigments were coated with organofunctional silanes and calcined or pyrolyzed under inert gas atmosphere yielding a pearlescent pigment containing carbon in silica matrix and having a darker color.
  • the transparent metal oxide with high refractive index is preferably TiO2, ZrO2, ZnO, SnO2 and more preferably TiO2 or SnO2.
  • a commercially available product is Ronaflux Specular Silver (Merck KGaA).
  • Most preferred embodiments of variant d) have the following structures: - transparent substrate+ a-C/nc-graphite layer + TiO2 - transparent substrate+ TiO2 + a-C/nc-graphite layer.
  • the pearlescent pigment of the effect pigment preparation comprises a transparent substrate platelet coated with a first layer comprising or consisting of a mixture of the oxides of titanium, iron and at least one of cobalt and chromium and a second layer on the first layer, wherein the second layer comprises an oxide of titanium.
  • Such pearlescent pigments have a black absorption color and are described in US 6,361,593 B2 and US 6,290,766 B1. Commercially available Products are Vegetable Black Olive (Sun Colors and Effects).
  • mixtures or combinations of the pearlescent pigments a) to e) itself or pearlescent pigments with mixtures or combinations of the various coating layers mentioned in the pearlescent pigments a) to e) can be used.
  • pearlescent pigments comprising a coating of mixtures or combinations of titanium suboxide and titanium oxynitride may be used.
  • the silvery, absorbing pearlescent pigments are taken from the following group: a) pearlescent pigments of type a), wherein the pearlescent pigment has a coating comprising a metal oxide layer comprising Ti- and Fe-ions, wherein the Fe-ions are mainly Fe(II) ions, which is preferably an ilmenite (FeTiO3) layer, magnetite (Fe3O4) or mixtures thereof or b) pearlescent pigments of type b), wherein the titanium suboxide can be represented by the formula TinO2n-1 (II) wherein n is an integer of 1 to 10, or c) pearlescent pigments of type c), wherein the titanium oxynitride can be represented by the formula TixNyOz (III) wherein x is 0.2 to 0.6, y is 0.05 to 0.6 and z is 0.1 to 0.9, which
  • the high-refractive index layers of the silvery pearlescent pigments of type a), b) or c) preferably have an index of refraction n of > 2.0 and more preferably n > 2.3.
  • the silvery, absorbing pearlescent pigments of type i) or of silvery, transparent pearlescent pigments of type ii) have a transparent substrate like natural mica, synthetic mica, glass, perlite, SiO2, Al2O3 and mixtures thereof. More preferably the transparent substrates are chosen from natural mica, synthetic mica, glass, and mixtures thereof and most preferably is synthetic mica. Pearlescent pigments based on substrates like SiO2 or Al2O3 are rare in powder coating industry as they are the costliest ones.
  • the silvery, absorbing pearlescent pigments have the highest opacity of all pigments or fillers of the second component due to their absorbing properties in the visible wavelength region. They also have a more metallic look compared to the pearlescent pigments of type ii). Consequently also the pigment preparation as a whole has the highest opacity and best metallic look.
  • the silvery transparent pearlescent pigments of type ii) are conventional silvery pearlescent pigments which comprise a transparent substrate and at least one coating of a transparent metal oxide with a refractive index of ⁇ 2.0.
  • the transparent coating is any of TiO2, ZrO2 SnO2, and ZnO and combinations thereof.
  • TiO2 is used which can be in rutile or anatase modification. In more preferred embodiments TiO2 is used in the rutile modification.
  • transparent coating it is meant that the metal oxide has essentially no absorption in the visible wavelength region (400 to 780 nm). With “essentially no absorption” it is meant that the absorption coefficient of the metal oxide k is below of 0.01 is this wavelength region (referring to literature values).
  • transparent high refractive index metal oxide it is well known in the art that the silvery color will develop at optical thicknesses in a range of about 80 to 160 nm and more preferably in a range of 90 to 140 nm.
  • the geometrical thicknesses are in a range of 30 to 60 nm, more preferred in a range of 35 to 45 nm.
  • a further metal oxide layer is located onto the transparent substrate and the transparent high refractive metal oxide layer as described in US 2008/168924 A1.
  • so-called multilayer pearlescent pigments may be employed which contain an alternating layer sequence of transparent high / low / high refractive index layers.
  • the low refractive index layers have a refractive index of ⁇ 1.6 in the visible wavelength region and may be preferably SiO2, Al2O3 or MgF2.
  • the transparent pearlescent pigments of type ii) are pearlescent pigments with the following structures: natural mica / TiO2 natural mica / TiO2 / SiO2 / TiO2 synthetic mica / TiO2 synthetic mica / TiO2 / TiO2 glass flake / TiO2 glass flake / TiO2 glass flake / TiO2 / SiO2 / TiO2 SiO2 / TiO2 / TiO2 / TiO2 / TiO2 / TiO2 / TiO2 / TiO2 / TiO2 / TiO2 / TiO2.
  • Most preferred embodiments have the following structures: natural mica / TiO2 natural mica / TiO2 / SiO2 / TiO2 synthetic mica / TiO 2 synthetic mica / TiO2 / SiO2 / TiO2 glass flake / TiO2 glass flake / TiO2 / SiO2 / TiO2.
  • the thicknesses of the TiO 2 and possibly also the SiO 2 -layers layers are adjusted such to provide a silvery interference color.
  • Suitable silvery multilayer pearlescent pigments of type ii) were described in EP 2346950 B1 or EP 1213330 B1.
  • the plane parallel orientation of the effect pigments is usually less developed and here various colors produced by non-alignment may also add to yield an overall silvery effect.
  • the silvery pearlescent pigments of type i) or ii) according to the invention may be provided with an outer top-coating which comprises a metal oxide.
  • This protective layer further enhances the light stability, weather stability and/or chemical stability of the pearlescent pigment. Especially the photoactivity of any TiO2 layers and the concomitant destroying of organic resins in coatings may be effectively reduced by these protective layers.
  • Such pearlescent pigments may be used in architectural powder coatings.
  • the external protective layer of the silver-colored pigments according to the invention can comprise, or preferably consist of, one, two or three metal oxide layers and/or metal hydroxide layers and/or metal oxide hydrate layers of the elements Si, Al, Zr, Sn, Zn or Ce.
  • Such weather stable external protective layers are described in EP 0888 410 B1, EP 063210910 A1, EP 1727864 B1, EP 1682622 B1, EP 2691478 B1 or EP 2904052 B1, for example.
  • organofunctional agents preferably by organofunctional silanes.
  • organofunctional coatings may be applied, but in preferred embodiments they are not applied.
  • the amount of the metal oxides in the top-coating is generally low as this top coating is aimed to alter optical properties of the pearlescent pigments as low as possible.
  • the amount may be in a range of 0.1 to 4.0 wt.%, more preferably in a range of 0.2 to 3.0 wt.% and most preferably in a range of 0.3 to 2.0 wt.%, each referred to the total amount of pearlescent pigment of type i) or ii).
  • the pearlescent pigments of type i) or ii) may be coated on their surface with a leafing-agent.
  • a leafing-agent will affect an enhanced concentration of the coated pigments near to the top of the final application coating, e.g. a powder coating. In such coatings the brilliance will be enhanced and more sparkling and better opacity may be observed.
  • the leafing-agent will be any of a phosphate-based additive, a phosphonate-based additive, a phosphite based additive, an alkyl silane or a polysiloxane or mixtures thereof.
  • the polysiloxane of the organofunctional surface modification has a polysiloxane according to formula (IV):
  • R 1 is a saturated or unsaturated, straight-chain or branched alkyl radical having 1 to 30 carbon atoms and/or an aryl, alkylaryl or arylalkyl radical having 6 to 30 carbon atoms.
  • R 2 , R 3 , R 4 and R 5 independently represent saturated or unsaturated, straight-chain or branched alkylidene radicals having 1 to 6 carbon atoms and/or aryl radicals, alkylaryl radicals and/or arylalkyl radicals having 6 to 12 carbon atoms.
  • R7and R8 independently each represent O, OH or a saturated or unsaturated, straight-chain or branched alkyl radical having 1 to 6 carbon atoms and/or an aryl, alkylaryl or arylalkyl radical having 6 to 9 carbon atoms and wherein X represents O or OH.
  • At least one of R7, R8 or X are bonded to the surface of the pearlescent pigments of type i) or ii) or to the surface of filler of type iii).
  • Such modified pearlescent pigments are further described in detail in EP 2698403 B1.
  • the organic surface modification may be chosen from organic phosphorus-containing additives as disclosed in EP 1812518 B1.
  • the pearlescent pigments or fillers of types i) to iii) are coated on the surface with at least one organic phosphorus-containing additive having the general formula (V) R 9 R 10 P(O)(OR 11 ) (V) and/or of the general formula (VI) R 9 P(O)(OR 11 )(OR 12 ) (VI)
  • R 9 and R 10 independently of one another are hydrogen or a linear or branched alkyl radical having 6 to 30 carbon atoms, with the proviso that R 9 and R 10 are not simultaneously hydrogen, and R 11 and R 12 independently of one another are H or alkyl having 1 to 10 carbon atoms.
  • R9 and R10 independently of one another are a linear or branched alkyl radical having 8 to 20 carbon atoms and most preferably 8 to 18 C-atoms.
  • R 11 and R 12 independently of one another are H.
  • These additive are organofunctional phosphinic or phosphonic acids.
  • the pearlescent pigments of type i) or ii) or the filler of type iii) may be coated on their surface with an organofunctional phosphorus-containing additive represented by formula (IIV): (R 9 -O)n-P(O)(OR 11 )3-n (VII)
  • R 9 and R 11 have the meaning as described above and n is 1 or 2.
  • the organofunctional phosphoric esters described in this formula can be a mixture of mono or bifunctional species.
  • R 11 is H and preferably R 9 is an alkyl radical having 6 to 18 C-atoms and more preferably 8 to 16 C-atoms.
  • the pearlescent pigments of type i) or ii) or the filler of type iii) may be coated on their surface with an alkyl silane of formula (VIII): R 9 Si(OR 13 )3 (VIII)
  • R 13 is H or an alkyl radical having 1 to 4, preferably 1 or 2 C-atoms.
  • the effect pigment preparation comprises or consists of a mixture of a first component and a second component which were described in detail before. In preferred embodiments the effect pigment preparation consists of these two components of the mixture. In this case the effect pigment preparation has a maximum of compatibility to all desired applications, preferably to powder coatings. Generally the mixture is contained in the effect pigment preparation in an amount of 70 to 100 wt.%, referred to the total amount of the effect pigment preparation.
  • the amount of the mixture is in a range of 80 to 100 wt.%, furthermore preferably the amount of the mixture is in a range of 90 to 100 wt.%, even more preferably the amount of the mixture is in a range of 95 to 100 wt.% and most preferably the amount of the mixture is in a range of 98 to 100 wt.%, each based on the amount of the total pigment preparation.
  • the pigment preparation is available in powder form which means that no solvents or only a minimum amount of solvent is contained therein.
  • the maximum amount of solvent contained in the effect pigment preparation is 2.0 wt.%, preferably 1.0 wt.% and more preferably 0.5 wt.%, and most preferably 0.3 wt.%, each based on the amount of the total pigment preparation.
  • the solvent content may be indirectly determined by determining the non-volatile content of the pigment preparation, preferably using a moisture analyzer like Ultra-X 3031D at a maximum temperature of 160 °C.
  • Other components which might be present in the effect pigment preparation are e.g. binder and preferably binder suitable for powder coating, additives, waxes or other fillers.
  • the effect pigment preparation is preferably excluded in plastic parts which contain a plastic material which is selected from the group consisting of polypropylene (PP high density polyethylene (HDPE), low density polyethylene (LDPE), linear low-density polyethylene (LLDPE), polyethylene terephthalate (PET), polystyrene (PS), polyurethane (PUR), polyacrylate, polyamide (PA) or nylons, polyvinylchloride (PVC), polycarbonate (PC) and ABS / MABS.
  • the two components have a ratio by weight of the second component to the first component in a range of 2.5 to 8.0, preferably in a range of 3.0 to 6.0 and most preferably in a range of 3.5 to 5.0.
  • ratios of 2.5 Below of a ratio of 2.5 the desired security with respect to dust explosion risks or inflammability may not be secured.
  • the hiding power of the effect pigment preparation in the final application becomes too low. It might be compensated by using a higher total amount of the effect pigment preparation in the final application formulation, but such increase might be limited by other factors. In powder coatings, for example, it is hardly possible to increase the total amount of the effect pigment preparation to an amount of about 8 wt.% of the total formulation.
  • the range of the ratios of the two components of the mixture of the effect pigment preparation may depend in detail on the fineness and of the thickness of the metal effect pigment (first component). Finer and thinner flaky metal pigments will tend to be more sensitive to dust explosion risks, because of their higher specific surface.
  • the two components of the effect pigment preparation have a similar particle size distribution. This may be expressed in first instance by a comparison of the median values d50,M of the flaky metal effect pigments and d50,P of the second component.
  • the d50,M of the flaky metal effect pigments (first component) and the d50,P of the second component do not differ more than ⁇ 10.0 ⁇ m, more preferably do not differ more than ⁇ 7.5 ⁇ m and most preferably do not differ more than ⁇ 5.0 ⁇ m. If the particle sizes differ too strong a separation of the two components during the final application process may occur.
  • a further embodiment of the present invention is the use of the effect pigment preparation in applications which demand a VOC free or VOC low formulations such as powder coating or cosmetics, preferably powder cosmetics.
  • powder cosmetic applications are pressed eye shadow, eye shadow pencil, loose eye shadow, eye shadow powder, mascara, and brow pencil. Most preferred applications are powder coatings.
  • the effect pigment preparation may be used in amounts of, for example, a range of 0.5 to 8.0 wt.%, more preferably in an amount in a range of 1.0 to 6.0 wt.% and most preferably in an amount in a range of 2.0 to 5.0 wt.%, each referred to the total amount of the powder coating formulation.
  • the effect pigment preparation may be added to the powder coating preparation by the well-known dry blend or bonding method.
  • a further embodiment of the present invention is a formulation such as a powder coating formulation, a cosmetic formulation or a VOC free coating application which contains the effect pigment preparation. All preferred embodiments regarding the effect pigment preparation and all preferred embodiments regarding the first and the second components of the mixture do equally apply to such formulations.
  • a powder coating formulation which contains a suitable binder and the effect pigment preparation.
  • binders typically polymers based on polyacrylates, polyesters, polyurethanes, polyepoxides and are used.
  • the powder coating formulation may contain additives, additional fillers, degassing agents, film-forming agents, flame-retardant agents, adhesion promoters, corrosion inhibitors, light-stabilizing agents, flatting agents, photo initiators, polymerization inhibitors, polymerization initiators, radical interceptors, anticaking agents, slip agents, radiation curing reactive thinners, thermally cross-linkable reactive thinners, UV absorbers, leveling agents, cross linking catalysts, waxes, and mixtures thereof.
  • Example series 1 A polysiloxane additive was manufactured according to paragraphs [0133] to [0134] of EP 2698403 B1.
  • the pearlescent pigment was dried under vacuum at 100 °C for 1 hour.
  • the cup cover was closed and it was placed into a SpeedMixer® and mixed for 30 sec. at 1300 rpm. Afterwards, the cover was opened, and the pigment cake was removed from cladding by using a spatula. This mixing procedure was repeated for three more times.
  • Example 3 Effect pigment preparation prepared as in Example 1, but Symic C604 was first further pre-coated with a weather stabilizing metal oxide and then the polysiloxane modification according to Example 2 (paragraph [0139]) of EP 2698403 B1.
  • Example 4 Effect pigment preparation prepared as in Example 1, but as component two a silvery transparent pearlescent pigment based on a synthetic mica substrate and a TiO2 coating (Symic C001, Eckart GmbH) was used without precoating of the polysiloxane additive from Example 1.
  • Example 5 Effect pigment preparation prepared as in Example 1, but as component two a filler based on a synthetic mica substrate (Synafil 1050, Eckart GmbH) was used without precoating of the polysiloxane additive from Example 1.
  • Comparative Examples 1a to 1c Mixtures of Symic C604 with PCU 2000 (ca 20 ⁇ m) were prepared according to example 1 but with various ratios according to table 1.
  • Comparative Example 2 PCU 2000 (polymer coated aluminium flakes from Eckart GmbH for powder coating with d50,M of about 25.8 ⁇ m) without mixture with pearlescent pigment.
  • Comparative Example 3 Symic C604 (Eckart GmbH)
  • Comparative Example 4 PCU 1000 (polymer coated aluminium flakes from Eckart GmbH for powder coating with d50,M of 14.0 ⁇ m).
  • Table 1 Ratio of samples of Effect pigment preparations S ample Content Content Ratio second first pearlescent component component to metal [%] (flaky metal pigment pigment) [%] E xample 1 80 20 4.0 Example 2 80 20 4.0 Example 3 80 20 4.0 Example 4 80 20 4.0 Example 5 80 20 4.0 Comp.
  • the explosion sphere was – taking into account the current air pressure - evacuated before the start of the test to such an extent that after the dust/air mixture had been blown in normal pressure (1013 mbar) prevailed in the sphere.
  • Standardized pyrotechnic igniters manufactured: Sobbe GmbH, Fabrik Elektrischer Zünder
  • 2 detonators with a total energy of 2 kJ determination of the dust explosion capability and the LEL
  • the dust concentration was varied stepwise over a wide concentration range. An overpressure of ⁇ 0.3 bar above the pressure generated by the ignition initial was assessed as an explosion and the tested sample was therefore classified as explosive.
  • the sample was inflamed on one side using a Bunsen burner wherein the duration time was 5 min at maximum. It was assessed whether: the sample was inflammable at all or whether the sample expired after the burner was removed or the burning time for a distance of 200 mm. If the burning time was equal or less than 20 minutes the experiment was repeated twice and an average value was determined from these three trials.
  • B5 Optical evaluation, Powder Coating applications and optical testing The samples of all Examples and Comparative Examples were mixed with a commercially available powder coating binder (068 /80020 from Tiger Coatings GmbH ) in a dry blend. In most cases the concentration of the effect pigment preparation was 2.0 wt.%, referred to the total powder coating formulation.
  • Example 5b Only in Example 5b the concentration of the effect pigment preparation was doubled (4.0 wt.%).
  • the powder coating formulations were applied onto steel panels using a Corona manual gun (PEM-X1 from Wagner GmbH) at a voltage of 70 kV. The panels were each cured at a temperature of 200 °C for 15 min. The panels were measured regarding their optical properties using a BYK Mac colorimeter. Results are summarized in Table 3. L*15° is a measure of the brilliance, C*15° is a measure of the chroma.
  • Example 1a 2 min 14s explosive 86.1 19.5 0.6 good extinct Comparative after Example 1b explosive 83.8 19.8 1.5 good ignition Comparative Example 1c / explosive 80 20.8 2.5 good Comparative Example 2 3min 45s explosive 70.5 18.9 0.3 very good Comparative Non- not Example 3 flammable explosive 53.7 26.9 6.2 medium Comparative Example 4 / explosive 74.2 15.6 0.3 very good
  • Table 2 showed that all inventive Examples 1 to 4 were non- flammable and not explosive. Furthermore, brightness (L*15°) and the Flop-index improved compared to the applications with the pure metal effect pigments (Comparative Example 2 and 4). The hiding power was of course decreased compared to the pure metal effect pigment samples but was still good.
  • Example 5a was also excellent with respect to flammability and explosion potential, but the brightness was rather low.
  • the hiding power was low here because of the very low content of aluminum pigment.
  • the filler material naturally does not contribute to hiding power.
  • Example 5b the hiding power and the brightness already improved.
  • Mixtures of flaky aluminum pigments with fillers are thus recommended for applications where the metallic optical properties are not desired on a high level. They are a cost-effective alternative to pure metal pigments or the even more costlier absorbing pearlescent pigments.
  • Comparative Examples 1a to c show that the flammability and the dust explosion potential are still high if the ratio of pearlescent pigment to flaky metal pigment is too low.

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Abstract

La présente invention concerne une préparation de pigments à effet, comprenant ou consistant en un mélange d'un premier composant qui est un pigment à effet métallique pailleté à base d'aluminium ou d'alliages d'aluminium ayant une taille de particule médiane d50,M et, en tant que second composant, d'un pigment nacré d'une charge ayant une taille de particule médiane d50,P qui est l'un quelconque parmi : i) un pigment nacré absorbant, argenté, comprenant un substrat transparent ayant un indice de réfraction inférieur à 1,6 et un revêtement absorbant ayant un indice de réfraction > 2,0 ou ii) un pigment nacré transparent argenté, qui comprend un substrat transparent ayant un indice de réfraction inférieur à 1,6 et un revêtement par au moins un oxyde métallique transparent ayant un indice de réfraction > 2,0 ou iii) des paillettes transparentes non revêtues ayant un indice de réfraction inférieur à 1,6, et des mélanges de l'un quelconque des seconds composants i), ii) et iii), le rapport en poids du second composant au premier composant étant dans une plage de 2,5 à 8,0, la préparation de pigment à effet étant sous une forme pulvérulente et ces deux composants du mélange étant contenus dans la préparation de pigments à effet dans une quantité de 70 à 100% en poids, rapportée à la quantité totale de la préparation de pigments à effet.
PCT/EP2025/059770 2024-04-17 2025-04-09 Préparation de pigments à effet pour revêtement en poudre Pending WO2025219190A1 (fr)

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EP2102294B1 (fr) 2006-12-22 2012-06-20 Eckart GmbH Pigments d'aluminium fins ayant une plage de répartition d'épaisseur étroite, leur procédé de réalisation et leur utilisation
WO2009077191A1 (fr) 2007-12-19 2009-06-25 Eckart Gmbh Pigments à effet métallique, procédé de fabrication et utilisation de ceux-ci et vernis pulvérulent
EP2318463B1 (fr) 2008-07-08 2014-10-01 Eckart GmbH Pigments métalliques, procédé de fabrication ainsi qu'utilisation de ces pigments et peinture en poudre
EP2346950B1 (fr) 2009-08-19 2013-07-31 Eckart GmbH Pigments nacrés multicouche très brillants dotés d'une teinte de polarisation argentée et d'une étroite distribution granulométrique et leur procédé de production
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EP2691478B1 (fr) 2011-03-28 2016-07-20 Eckart GmbH Pigments nacrés stables aux intempéries, procédé de fabrication correspondant et utilisation
CN103183972A (zh) * 2011-12-21 2013-07-03 默克专利股份有限公司 效果颜料
WO2013175339A1 (fr) 2012-05-22 2013-11-28 Basf Se Procédé de préparation de pigments à effet d'aluminium enduits d'oxyde de métal
EP2698403B1 (fr) 2012-08-17 2018-01-03 Eckart GmbH Pigments nacrés modifiés en surface et leur utilisation dans les laques en poudre
EP2904052B1 (fr) 2012-10-02 2017-07-05 Eckart GmbH Pigments perlescents résistants aux intempéries, leur procédé de fabrication et d'utilisation
EP3119840A1 (fr) 2014-03-20 2017-01-25 Merck Patent GmbH Pigments à effet
EP3230384A1 (fr) 2014-12-12 2017-10-18 Merck Patent GmbH Pigments non métalliques à propriétés métalliques
WO2017167450A1 (fr) 2016-03-30 2017-10-05 Eckart Gmbh Pigment à effets recouverts de liants organiques pour peintures en poudre, procédé de fabrication et utilisation de ces pigment à effets
WO2020208134A1 (fr) 2019-04-12 2020-10-15 Eckart Gmbh Mélange de pigments à effet transparent aux fréquences radar, formulations et revêtements associés
US20220145082A1 (en) * 2019-04-12 2022-05-12 Eckart Gmbh Radar frequency transparent effect pigment mixture, formulations and coatings thereof
EP3795645A1 (fr) 2019-09-20 2021-03-24 Merck Patent GmbH Pigments
WO2024079087A1 (fr) * 2022-10-14 2024-04-18 Eckart Gmbh Pièces en plastique recyclables ayant un aspect métallique et pouvant être reconnues automatiquement par spectroscopie nir et pouvant être triées
WO2024132896A1 (fr) * 2022-12-21 2024-06-27 Eckart Gmbh Mélanges transparents aux ondes radar de pigments à effet métallique avec des pigments à effet semi-conducteur ou avec des pigments nacrés absorbants argentés et formulations de revêtement de ceux-ci

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