EP3207096A1 - Poudre de pigment métallique à effet enrobé par dépôt physique en phase vapeur - Google Patents

Poudre de pigment métallique à effet enrobé par dépôt physique en phase vapeur

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Publication number
EP3207096A1
EP3207096A1 EP15778688.0A EP15778688A EP3207096A1 EP 3207096 A1 EP3207096 A1 EP 3207096A1 EP 15778688 A EP15778688 A EP 15778688A EP 3207096 A1 EP3207096 A1 EP 3207096A1
Authority
EP
European Patent Office
Prior art keywords
metallic effect
effect pigment
coated
pvd
powder
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
EP15778688.0A
Other languages
German (de)
English (en)
Inventor
Christian Lang
Nina LANG
Fabian Piech
Frank J. MAILE
Thomas Müller
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.)
Schlenk Metallic Pigments GmbH
Original Assignee
Schlenk Metallic Pigments 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 Schlenk Metallic Pigments GmbH filed Critical Schlenk Metallic Pigments GmbH
Publication of EP3207096A1 publication Critical patent/EP3207096A1/fr
Pending legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/0015—Pigments exhibiting interference colours, e.g. transparent platelets of appropriate thinness or flaky substrates, e.g. mica, bearing appropriate thin transparent coatings
    • C09C1/0021—Pigments exhibiting interference colours, e.g. transparent platelets of appropriate thinness or flaky substrates, e.g. mica, bearing appropriate thin transparent coatings comprising a core coated with only one layer having a high or low refractive index
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
    • C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/62—Metallic pigments or fillers
    • C09C1/64—Aluminium
    • C09C1/642—Aluminium treated with inorganic compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/006—Combinations of treatments provided for in groups C09C3/04 - C09C3/12
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/06—Treatment with inorganic compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/06—Treatment with inorganic compounds
    • C09C3/063—Coating
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/12—Treatment with organosilicon 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
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • C09D11/101—Inks specially adapted for printing processes involving curing by wave energy or particle radiation, e.g. with UV-curing following the printing
    • 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
    • C09D5/031—Powdery paints characterised by particle size or shape
    • 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
    • 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
    • C09D5/033—Powdery paints characterised by the additives
    • C09D5/035—Coloring agents, e.g. pigments
    • 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
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
    • C01P2004/82—Particles consisting of a mixture of two or more inorganic phases two phases having the same anion, e.g. both oxidic phases
    • C01P2004/84—Particles consisting of a mixture of two or more inorganic phases two phases having the same anion, e.g. both oxidic phases one phase coated with the other
    • C01P2004/86—Thin layer coatings, i.e. the coating thickness being less than 0.1 time the particle radius
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/12—Surface area
    • 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
    • C09C2200/00—Compositional and structural details of pigments exhibiting interference colours
    • C09C2200/10—Interference pigments characterized by the core material
    • C09C2200/1054—Interference pigments characterized by the core material the core consisting of a metal
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C2200/00—Compositional and structural details of pigments exhibiting interference colours
    • C09C2200/10—Interference pigments characterized by the core material
    • C09C2200/1054—Interference pigments characterized by the core material the core consisting of a metal
    • C09C2200/1058—Interference pigments characterized by the core material the core consisting of a metal comprising a protective coating on the metallic layer
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C2200/00—Compositional and structural details of pigments exhibiting interference colours
    • C09C2200/40—Interference pigments comprising an outermost surface coating
    • C09C2200/402—Organic protective coating
    • C09C2200/407—Organosilicon materials, e.g. silanes, silicones
    • 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
    • C09C2210/00—Special effects or uses of interference pigments
    • C09C2210/60—Interference with laser-light, laser markable pigments

Definitions

  • the invention relates to powders of coated PVD metallic effect pigment, highly concentrated slurries of coated PVD metallic effect pigment and their use in powder coatings and masterbatches. Furthermore, the invention relates to their use for the laser marking of plastics.
  • Metal effect pigments are frequently used in paints, inks, printing inks, powder coatings, cosmetics or plastics for coloring and in particular for producing a metallic effect.
  • Classic metallic effect pigments are platelet-shaped metal pigments, the metallic effect being based on the directed reflection of incident light on the areally formed metal pigments, which are aligned in parallel in the coating.
  • metallic effect pigments have been known for some time and are produced by PVD (Physical Vapor Deposition) processes.
  • PVD Physical Vapor Deposition
  • the preparation of metallic pigments by a PVD vapor deposition process is described, for example, in US 2,839,378.
  • PVD pigments have a relatively homogeneous, low thickness (in the range of 5 nm to 70 nm) and a very smooth surface with very few surface defects and provide a high degree of light reflection, in particular on a smooth surface on which they can align very evenly, the application leads of PVD pigments to a mirror-like appearance. Furthermore, PVD pigments are characterized by a high hiding power.
  • PVD aluminum effect pigments are commercially available. These are usually offered as dispersions having a solids content of aluminum pigment of 10 to 20 wt .-%. Commercial examples of such aluminum pigments produced by PVD processes are particularly Decomet ® (Fa. Schlenk), as well Metasheen ® or Metalure ®.
  • PVD aluminum effect pigments are commonly present as low concentration slurries with aluminum pigment solids contents in the range of 10 to 20 weight percent. Due to their exceptional fineness, the associated high surface area and the agglomeration properties, PVD pigment powders and highly concentrated PVD pigment slurries having concentrations of 70% by weight or more have heretofore been unknown. Especially against the background of ecological concerns and legislative requirements, it is of great interest to provide a low-solvent PVD pigment dispersion in highly concentrated form or a solvent-free embodiment in the form of PVD pigment powder. The provision of such PVD pigment powders opens up new applications such as use in powder coatings or in a plastic masterbatch.
  • the object of the present invention is to provide PVD metallic effect pigments which are present in powder form or in highly concentrated form.
  • the PVD pigment powders should be able to be obtained substantially free of agglomerates and have a good redispersibility.
  • the object of the invention is also to provide a process for producing such PVD metallic effect pigment powders and highly concentrated slurries.
  • the object is achieved by a powder of coated PVD metallic effect pigment, wherein the coated PVD metallic effect pigment is a PVD metallic effect pigment and a metal oxide layer, wherein the metal oxide layer is 5 to 45 wt .-%, based on the total weight of the coated PVD metallic effect pigment.
  • Powder can be obtained which has a very narrow particle size distribution, which is substantially agglomerate-free and very free-flowing.
  • the metal oxide-coated (preferably Si0 2 -coated) PVD metallic effect pigments despite their high surface area and their
  • the powder of coated PVD metallic effect pigments according to the invention is distinguished by a very good redispersibility and is outstandingly suitable in particular for producing highly concentrated slurries. It is also very free-flowing, essentially free of agglomerates and leads to coatings with excellent metallic gloss.
  • the metallic effect pigment in the powder or slurry of the invention is a physical vapor deposition (PVD) process
  • Metal effect pigment which in the context of the present invention is also referred to as PVD metallic effect pigment.
  • the metal is preferably selected from the group consisting of aluminum, magnesium, chromium, silver, copper, zinc, tin, manganese, Iron, cobalt, zirconium, gold, titanium, iron, platinum, palladium, nickel, tantalum, molybdenum, steel, and mixtures and alloys thereof, in particular of aluminum, titanium, chromium, zirconium, copper, zinc, gold, silver, tin , Steel, iron and alloys thereof and / or mixtures thereof, more preferably aluminum, titanium, chromium, zirconium, copper, zinc, gold, silver, tin, and alloys and / or mixtures thereof.
  • the metal of the metallic effect pigment is particularly preferably aluminum and its alloys, as well as chromium, most preferably aluminum.
  • the preparation of the PVD metallic effect pigments is carried out according to conventional techniques, see, for example, US Pat. No. 2,941,894 and US Pat. No. 4,321,087 or else the conventional PVD processes as described in "Vacuum Coating, Volume 1-5 '(VDI -Verlag, ed. Kienel), in particular processes with or without reactive gas, resistance or radiation-heated processes, electron beam technology, etc.
  • the coated PVD metallic effect pigment comprises a metal oxide layer, i. the PVD metallic effect pigment is coated with a metal oxide layer.
  • a metal oxide layer This is in particular a layer of silicon dioxide, aluminum oxide, titanium dioxide, iron oxide, tin oxide, zinc oxide or mixtures thereof.
  • the metal oxide is silicon dioxide, which is subsumed in the context of the present invention under metal oxide, since metal oxide in the context of the present invention in the broadest sense also includes semi-metal oxides. It is also possible to apply two or more layers of different oxides.
  • the metal oxide layer is colorless.
  • the metal oxide layer is preferably applied wet-chemically, in particular by a sol-gel process.
  • the metal oxide layer is applied after the preparation of the PVD metallic effect pigments, ie the PVD metallic effect pigments according to the invention are so-called post-coated PVD metallic effect pigments.
  • the metal oxide layer is preferably applied wet-chemically.
  • the PVD metallic effect pigments according to the invention are not just a multilayer PVD effect pigment in which both the metal layer and a dielectric layer (eg a metal oxide layer) are applied by means of PVD processes, as described, for example, in WO2006 / 069663.
  • PVD metallic effect pigments according to the invention preferably do not have the following layer structure: an aluminum oxide or aluminum oxide / hydroxide-containing layer produced by wet-chemical oxidation, a high refractive index metal chalcogenide layer having a refractive index greater than 1.95 and optionally an oxide layer made from a material having one Refractive index smaller than 1, 8, wherein the alumina or alumina / hydroxide-containing layer and the high refractive index metal chalcogenide layer or the alumina or alumina / hydroxide containing layer and the oxide layer of a material having a refractive index less than 1, 8 or all three Layers together form a mixed layer
  • silicon dioxide layers which are applied by the sol-gel process, and in particular completely envelop the metallic edges.
  • This method comprises dispersing the metal pigments in a solution of a metal alkoxide such as tetraethyl orthosilicate (usually in a solution of organic solvent or a mixture of organic solvent and water with at least 50% by weight of organic solvent such as a short chain alcohol) and adding a weak base or acid to hydrolyze the metal alkoxide to form a film of the metal oxide on the surface of the pigments.
  • a metal alkoxide such as tetraethyl orthosilicate
  • sol-gel processes are well known, see, eg, The Chemistry of Silica, Ralph Her, Wiley and Sons, 1979, Gerhard Jonschker, practice of sol-gel technology, Vincnetz Verlag, 2012. Particularly preferred are Decomet ® - pigments Series 1000 used. These are aluminum PVD pigments.
  • the metal oxide layer which on the one hand contributes to passivation of the highly reactive PVD metallic effect pigments and on the other hand enables good drying to give the pigment powder, makes up 5 to 45% by weight, preferably 30 to 44% by weight, in particular 35 to 43% by weight. particularly preferably from 37 to 42, and very particularly preferably from 39 to 40,% by weight, based on the total weight of the coated metallic effect pigment.
  • the thickness of this metal oxide layer is usually between 2 and 100 nm.
  • organic compounds such as silanes, phosphoric acid esters, titanates, borates or carboxylic acids can be made, these organic compounds are bonded to the metal oxide.
  • the organic compounds are preferably functional silane compounds which can bind to the metal oxide layer. These may be either mono- or difunctional compounds. Examples of bifunctional organic compounds are methacryloxypropenyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3- acryloxypropyltrimethoxysilane, 2-acryloxyethyltrimethoxysilane, 3-methacryloxy propyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 2-Methacryloxyethyl- triethoxysilane, 2-acryloxyethyltriethoxysilane, 3-methacryloxypropyl silane (methox- yethoxy) 3-Methacryloxypropyltris (butoxyethoxy) silane, 3-methacryloxypropyltris (propoxy) silane, 3-methacryloxypropyltris (butoxy) silane, 3-acryloxypropyltris (methoxyethoxy) si
  • a modification with a monofunctional silane in particular an alkylsilane or arylsilane, take place.
  • This has only one functional group which can covalently bond to the surface of the post-coated metal pigment (ie to the metal oxide layer) or, if not completely covered, to the metal surface.
  • the hydrocarbon radical of the silane points away from the pigment.
  • a different degree of hydrophobization of the pigment is achieved. Examples of such silanes are hexadecyltrimethoxysilane, propyltrimethoxysilane, etc.
  • silica-coated aluminum effect pigments in the powder according to the invention or the slurry according to the invention which are surface-modified with a monofunctional silane are particularly preferred.
  • Octyltrimethoxysilane, octyltriethoxysilane, hecadecyltrimethoxysilane and hexadecyltriethoxysilane are particularly preferred. Due to the changed surface properties / Hydrophobing can be achieved an improvement of the agglomerate-free drying, as well as a better alignment in the application.
  • the coated PVD metallic effect pigments can also be coated with a further layer, preferably a polymer layer, in particular of (meth) acrylic resins.
  • a polymer layer which is preferably poorly soluble in water and solvents, can further improve the chemical stability of the pigments as well as the incorporation into paints as needed.
  • the average particle size (D50 value) of the coated metallic effect pigments according to the invention is usually in the range from 1 to 250 micrometers, preferably from 2 to 150 micrometers and in particular from 5 to 50 micrometers.
  • the BET surface area of the coated PVD metallic effect pigments of the invention is very high, compared to conventional silver dollar pigments or cornfiake pigments, and is preferably in the range of 15 and 90 m 2 / g, in particular 18 to 40 m 2 / g, more preferably 22 and 35 m 2 / g.
  • the BET surface area is the specific surface area, measured by the BET method (DIN 66132). Due to the very high surface area of a PVD metallic effect pigment (also referred to as VMPs) compared to a conventional pigment, the production of a VMP powder or a VMP paste is a great challenge. In the present invention, however, it has been possible to produce a PVD powder or a PVD paste having excellent properties.
  • the powder of coated PVD metallic effect pigment according to the invention is distinguished by excellent redispersibility (assessed visually by homogeneous pasting, or grindometer) and flowability (derivable from bulk density DIN 53466, filling density according to DIN EN ISO 3923-1, flow time in accordance with DIN EN ISO 4490).
  • the redispersibility is evaluated as follows.
  • the redispersion of the dried powder in the binder (eg medium A) takes place in the speed mixer (DAC 250 SP apparatus) at defined rotational speeds over a period of 80 s (1000 rpm for 10 s, 2000 rpm for 15 s, 30 s) : 2500 rpm; for 10 s: 2000 rpm; for 5s: 1000 rpm).
  • the batch is knife-coated with a 24 or 38 ⁇ m doctor blade and visually assessed for agglomerates. The less agglomerates form, the better the redispersibility.
  • an increase in the gloss can be observed with the increase in redispersibility.
  • the gloss of the coatings obtained is determined either by measurement (Tri-Gloss from Byk-Garner) or by visual comparison with the slurry obtained directly after coating without drying and the dried material.
  • the roughening has proved to be suitable, the methodology of which is described in more detail in the experimental area.
  • the dispersibility of the powder the quality of the resulting powder of coated PVD metallic effect pigment is recognizable.
  • the present powder according to the invention is a uniform fine-grained powder. Coatings using the coated PVD metallic effect pigment powder of the present invention in the form of the powder or in the form of a slurry exhibit very good metallic gloss.
  • the present invention thus makes it possible to provide a new, ecologically and production-technically very advantageous low-solvent or solvent-free embodiment of the PVD metallic effect pigments, wherein a similar metallic luster as of PVD metallic effect pigments can be achieved from low-concentration slurries.
  • the PVD metallic effect pigment powder according to the invention is preferably used in a powder coating.
  • Powder coatings are organic, usually thermosetting coating powders with a solids content of 100%.
  • reactive binder polymers are used which can crosslink with one another or via a crosslinker to give branched macromolecules.
  • conventional powder coating binders can be used, in particular epoxy resins, carboxyl- and hydroxyl-containing polyesters, OH and GMA acrylate resins, as well as modified resins for special fields of application. It is also possible to use customary additives such as leveling agents, structuring agents, waxes, fillers.
  • the amount of coated PVD metallic effect pigment powder according to the invention is in the range from 0.01 to 2% by weight, preferably 0.2 to 0.8%.
  • the curing of the powder coatings on the substrate can be carried out by baking or by radiation energy.
  • powder coatings can be used in particular in the metal coating, household appliances, facade coatings, furniture coating and automotive painting.
  • the invention also includes a slurry of coated PVD metallic effect pigment in a solvent (preferably a medicinal white oil), wherein the coated PVD metallic effect pigment comprises a PVD metallic effect pigment and a metal oxide layer, wherein the metal oxide layer is 5 and 45 wt%, based on the Total weight of the coated metallic effect pigment, characterized in that the slurry contains 70% by weight or more coated PVD metallic effect pigment.
  • the content of coated PVD metallic effect pigment is 75 wt% or more, more preferably 80 wt% to 99 wt%, or preferably 85 wt% to 97 wt%, preferably 90 wt% % to 95% by weight.
  • solvents for the slurry common solvents such as medicinal white oils, eg Shell Ondina Oil 941, may be used.
  • highly concentrated slurries can be readily prepared from the powder of the present invention, and they are characterized by good dispersion and stability properties, and lead to coatings with very good metallic gloss.
  • Such highly concentrated slurries may also be referred to as pastes.
  • Part of the invention is therefore also a paste of coated PVD metallic effect pigment in a solvent (preferably a medicinal white oil), wherein the coated PVD Metallic effect pigment comprises a PVD metallic effect pigment and a metal oxide layer, wherein the metal oxide layer constitutes 5 and 45 wt .-%, based on the total weight of the coated metallic effect pigment, characterized in that the paste contains 70 wt .-% or more coated PVD metallic effect pigment.
  • a solvent preferably a medicinal white oil
  • PVD metallic effect pigment slurry or a PVD metallic effect pigment powder are in paints, lacquers, masterbatches, printing inks, plastics, cosmetic preparations, security printing or security printing. Due to their decorative metallic luster (chrome-like luster), they are predestined especially for the printing industry, the decorative paint sector, cosmetics and the security sector.
  • Part of the invention are further powder paints containing a PVD metallic effect pigment powder according to one of the preceding claims.
  • a masterbatch comprising a PVD metallic effect pigment powder according to one of the preceding claims and a plastic.
  • the term masterbatch is generally understood to mean plastic additives in the form of granules with levels of colorants that are higher than in the end use. Masterbatches increase process reliability compared to pastes, powders or liquid additives and are very easy to process. They are added to the plastic (crude polymer) for dyeing.
  • Suitable plastics in the context of the present invention are all natural or synthetic polymers which can be mixed with a metallic effect pigment. Prominent examples are, for example, polyolefins, in particular PE, PP, polyamides, polyesters, polyacrylates, polycarbonates, etc. Polypropylene (PP) is particularly suitable.
  • Such masterbatches can also be used in particular for packaging materials, such as, for example, cosmetic packaging, in which the resulting chromium-like effects are particularly desirable.
  • the amount of coated PVD metallic effect pigment (in the form of the powder or as a highly concentrated slurry in oil) in the masterbatch according to the invention is from 5 to 5% by weight, preferably 2.5 to 3%, based on the solids.
  • the coated PVD metallic effect pigments have an unexpectedly good orientation in the plastic.
  • no curling / waves of the coated PVD metallic effect pigments in the plastic was detected (TEM measurement).
  • Part of the invention is thus also a plastic material in which a powder according to the invention or a slurry according to the invention (or paste according to the invention) in a plastic (raw polymer) are included.
  • a powder according to the invention or a slurry according to the invention or paste according to the invention in a plastic (raw polymer) are included.
  • This can be prepared either by mixing a masterbatch as described above with a plastic or by mixing a plastic with a powder according to the invention or a slurry according to the invention.
  • the coated PVD metallic effect pigments in plastic are outstandingly suitable for laser marking, in particular a type of cold marking.
  • a transparent polymer as a plastic and the coated PVD metallic effect pigments (introduced as a masterbatch) as a laser-sensitive component
  • the laser irradiation in the polymer matrix induces carbonization, which causes a kind of foaming, causing gas bubbles to float. This causes a marking that is not noticeable on the surface (a kind of cold marking).
  • Suitable examples are PP as polymers.
  • Suitable lasers are well known to those skilled in the art and include, for example, YAG lasers (1064 nm).
  • Part of the invention thus also the use of a masterbatch according to claim 13 or 14 or a plastic material according to claim 15 for the laser marking of a plastic.
  • the invention also includes a method of laser marking a plastic, comprising providing a masterbatch according to claim 13 or 14 or a plastic material according to claim 15, and irradiating laser light from a selected area of the plastic such that the laser-sensitive coated PVD metallic effect pigments (preferred Si0 2 - coated aluminum PVD pigments) are at least partially converted in this area.
  • the preferred embodiments described above for the powder according to the invention, the slurry according to the invention, the masterbatch according to the invention and the PVD metallic effect pigments used according to the invention also apply, in each case individually and in combination, to the use for laser marking and the process for the laser marking of plastics .
  • the laser-sensitive coated PVD metallic effect pigment which is a PVD metallic effect pigment and a Metal oxide layer, wherein the metal oxide layer from 5 to 45 wt .-%, preferably 30 - 44 wt .-%, based on the total weight of the coated PVD metallic effect pigment makes.
  • an aluminum PVD effect pigment having a silicon dioxide layer as the metal ox layer which constitutes 5 to 45% by weight, preferably 30 to 44% by weight, based on the total weight of the coated PVD aluminum effect pigment.
  • the PVD metallic effect pigments coated according to the invention which are preferably SiO 2 -coated aluminum PVD pigments
  • SiO 2 -coated aluminum PVD pigments in a polypropylene matrix become so-called "melting pearls" with a size range of approximately 5 to 150 nm, which scatter only slightly in the visible spectral range.
  • the marked area for example in the form of a label, is largely transparent.
  • uncoated Al flakes lead to 'fused beads' with a size range of about 5 to 600 nm, which scatter more in the visible spectral range.
  • the laser-marked areas have a translucent effect in this case.
  • EDX analyzes of the 'melt beads' of Si0 2 -coated aluminum PVD pigments seem to suggest that there is a largely homogeneous distribution of Al, Si, Ca and O in the 'melt beads' as an indication of a ternary or quaternary phase could speak of A-Si-O- (Ca).
  • the melt pearls are also predominantly spherical structures, which are partially shell-like.
  • the ternary or quaternary phase A-Si-O- (Ca) could account for the lower bead size by reducing the coarsening due to higher energy dissipation.
  • EXD analyzes show a largely homogeneous distribution of Al and O, and only small traces of Si and Ca.
  • Aluminum pigments coated in accordance with the invention appear to undergo a surprising new mechanism in laser marking in plastics.
  • the advantage of this is that the laser-processed areas are largely transparent, and have a smooth surface, ie have no other haptic than the surrounding non-laser-marked areas.
  • Suitable plastics are polyolefins, especially PE and PP, polyamides, polyesters, polyacrylates, polycarbonates etc, as well as high temperature resistant polymers such as polyethersulfones, polyamide-imides and Polyetheretherketone. Particularly suitable are polypropylenes (PP).
  • the plastics may contain conventional additives such as stabilizers, plasticizers, fillers, reinforcing agents and other dyes or color pigments.
  • markings in the form of labels, graphic or symbolic markings are suitable for very different fields of application. They are particularly suitable for packaging of any kind, in particular for packaging for cosmetic articles and for food.
  • the plastic material to be marked may, for example, be a shaped body (deep-drawn, blow-molded or also stripped) as well as a film or a lacquer. If the plastic contains, in addition to the coated metallic effect pigments according to the invention, further color pigments or dyes, it is possible, for example, to obtain very high-quality, colored and shiny metallic marked objects.
  • Part of the invention are therefore also laser-marked plastics, which were prepared by the process according to the invention, and which may be present in the form of moldings, films, paints or coatings.
  • Part of the invention is also a method for producing a PVD
  • the PVD metallic effect pigments prepared by processes known in the prior art are coated by a sol-gel process, preferably with a SiO 2 layer.
  • This method comprises dispersing the metal pigments in a solution of a metal alkoxide such as tetraethyl orthosilicate (usually in a solution of organic solvent or a mixture of organic solvent and water with at least 50% by weight of organic solvent such as a short chain alcohol) and adding a weak base for the hydrolysis of Metallalkoxids, whereby a film of the metal oxide is formed on the surface of the pigments.
  • Sol-gel processes are known to the person skilled in the art, as already stated above. Particular preference is given to using Decomet® pigments of the 1000 series.
  • the preferred embodiments mentioned above in connection with the product claims with regard to preferred components, modification methods and weights also apply to the present method.
  • the coated pigment particles are separated by means of a solid-liquid separation. This can be done by various techniques, in particular by centrifuging, decanting and filtering. Preferably, the pigment particles are filtered off. The filtration preferably takes place by means of a suction filter (in particular glass frits) at room temperature. By applying a vacuum, a solids content of 5-35% (solids content based on the composition of the slurry) is obtained over a period of 1 minute to 60 minutes.
  • the resulting particles may be further washed with ethanol or other solvents, or subjected directly to drying step c).
  • the drying takes place at a temperature of 100 ° C to 140 ° C, preferably at 1 10 ° C to 130 ° C, more preferably 1 15 ° C to 125 ° C, most preferably at 120 ° C.
  • a furnace is taken, in particular a rotary kiln, etc., but it can also be used other drying ovens or laboratory ovens such as the laboratory oven company Memmert oven UF1 10 Plus or Ultramat Sartorius M35.
  • the drying step is preferably carried out in 6 hours to 18 hours, in particular 10 to 14 hours.
  • the powder of coated PVD metallic effect pigment according to the invention is distinguished by excellent redispersibility and flowability.
  • 0.2 g of the dried powder are mixed in a 25 ml plastic cup with 1.8 g of isopropanol.
  • This dispersion is mixed with 3 g of the binder medium A (a nitricellulose-based paint).
  • Mixing takes place in a speed mixer (device: DAC 250 SP) with one revolution (10 s 1000 rpm, for 15 s: 2000 rpm, for 30 s: 2500 rpm, for 10 s: 2000 rpm; 5s: 1000 rpm), mixed again briefly with a spatula and then knife-coated onto a coated paper with a 24 m spiral doctor blade onto the substrate.
  • the doctor blade dries after five minutes at room temperature and can then be measured with a gloss meter (Tri-Gloss from Byk-Gardner). The agglomeration is determined visually.
  • the bulk density or the bulk density of an aluminum powder in the unit g / ml or g / cm3 is determined
  • a measuring cylinder made of brass (capacity 50 ml) is placed on the balance and weighed to 0.
  • a sufficient quantity of the aluminum powder is placed on a piece of ounce paper (Pergamyn Echo, 35 g / m 2 , unbleached, satined) and carefully loosened with the spatula in the cloister (3x). Now the powder is slowly filled in the metal cylinder, which stands on a paper, scraped off with a sheet and weighed.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Pigments, Carbon Blacks, Or Wood Stains (AREA)
  • Paints Or Removers (AREA)
  • Cosmetics (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

La présente invention concerne une poudre constituée d'un pigment métallique à effet à enrobage déposé par dépôt physique en phase vapeur (PVD), des suspensions à concentrations élevées en pigment métallique à effet à enrobage déposé par PVD, et l'utilisation de ces suspensions dans des peintures en poudre et des mélanges maîtres. La poudre constituée d'un pigment métallique à effet à enrobage déposé par PVD selon l'invention est caractérisée en ce qu'elle présente un facteur de redispersion élevé et en ce qu'elle est particulièrement appropriée pour la fabrication de suspensions à concentration élevée. La poudre a en outre une très bonne aptitude à l'écoulement, elle est sensiblement exempte d'agglomérats et permet d'obtenir des revêtements présentant un bel effet métallisé.
EP15778688.0A 2014-10-13 2015-10-13 Poudre de pigment métallique à effet enrobé par dépôt physique en phase vapeur Pending EP3207096A1 (fr)

Applications Claiming Priority (2)

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DE102014015151.4A DE102014015151A1 (de) 2014-10-13 2014-10-13 PVD-Metalleffektpigmentpulver
PCT/EP2015/073642 WO2016059033A1 (fr) 2014-10-13 2015-10-13 Poudre de pigment métallique à effet enrobé par dépôt physique en phase vapeur

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JP (1) JP6800148B2 (fr)
KR (1) KR102448349B1 (fr)
CN (1) CN106795379A (fr)
BR (1) BR112017006824B1 (fr)
CA (1) CA2962010C (fr)
DE (1) DE102014015151A1 (fr)
MX (1) MX2017004734A (fr)
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SI3315563T1 (sl) * 2016-10-28 2020-08-31 Ewald Doerken Ag Protikorozijski zaščitni pigment in njegova uporaba
CA3086897A1 (fr) * 2017-07-24 2019-01-31 Sumitomo Metal Mining Co., Ltd. Produit broye de melange-maitre comprenant des microparticules absorbantes dans l'infrarouge ainsi que procede de fabrication de celui-ci, dispersion liquide qui comprend ce produit broye de melange-maitre comprenant des microparticules absorbantes dans l'infrarouge, encre comprenant un materiau absorbant dans l'infrarouge, encre prevenant la ...
KR102541874B1 (ko) 2017-12-06 2023-06-13 엑카르트 게엠베하 보호 캡슐화를 가진 판상 pvd 알루미늄 안료 및 보호 캡슐화를 가진 판상 pvd 알루미늄 안료를 제조하는 방법
US11920244B2 (en) 2018-07-24 2024-03-05 Hewlett-Packard Development Company, L.P. Device housing with metallic luster
JP2022521470A (ja) * 2019-02-05 2022-04-08 シルバーライン リミテッド 新規製品
RU2730990C1 (ru) * 2020-01-29 2020-08-26 Александр Валентинович Чуфинев Способ стабилизации пигментов в цветных фотосшиваемых гель-лаках
EP3896130A1 (fr) 2020-04-17 2021-10-20 Ferroglobe Innovation, S.L. Procédé d'obtention de poudre colorée contenant du métal, poudre ainsi obtenue et son utilisation en tant que pigment métallique
CN115885018A (zh) * 2020-06-22 2023-03-31 埃卡特美国公司 具有反射芯的效应颜料
CN113061356B (zh) * 2021-03-26 2022-01-04 安徽诚易金属新材料有限公司 一种高光泽多用途磁性铝颜料及其制备方法
JP2022163850A (ja) 2021-04-15 2022-10-27 旭化成株式会社 複合金属顔料組成物及びその製造方法
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JP2017533982A (ja) 2017-11-16
US20170306159A1 (en) 2017-10-26
KR20170070045A (ko) 2017-06-21
MX2017004734A (es) 2017-11-30
WO2016059033A1 (fr) 2016-04-21
BR112017006824A2 (pt) 2017-12-12
JP6800148B2 (ja) 2020-12-16
DE102014015151A1 (de) 2016-04-14
CA2962010A1 (fr) 2016-04-21
BR112017006824B1 (pt) 2022-08-09
CA2962010C (fr) 2023-03-21
KR102448349B1 (ko) 2022-09-27
RU2017111326A3 (fr) 2018-11-15
CN106795379A (zh) 2017-05-31
RU2678656C2 (ru) 2019-01-30

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