EP2435519A1 - Particules revêtues et leur utilisation - Google Patents

Particules revêtues et leur utilisation

Info

Publication number
EP2435519A1
EP2435519A1 EP10724268A EP10724268A EP2435519A1 EP 2435519 A1 EP2435519 A1 EP 2435519A1 EP 10724268 A EP10724268 A EP 10724268A EP 10724268 A EP10724268 A EP 10724268A EP 2435519 A1 EP2435519 A1 EP 2435519A1
Authority
EP
European Patent Office
Prior art keywords
sio
particles
flakes
metal
layer
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.)
Withdrawn
Application number
EP10724268A
Other languages
German (de)
English (en)
Inventor
Matthias Quenzer
Marc Entenmann
Matthias Kuntz
Renate Bonn-Walter
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.)
Merck Patent GmbH
Original Assignee
Merck Patent GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Merck Patent GmbH filed Critical Merck Patent GmbH
Publication of EP2435519A1 publication Critical patent/EP2435519A1/fr
Withdrawn legal-status Critical Current

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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
    • C09C1/0051—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 low and high refractive indices, wherein the first coating layer on the core surface has the low refractive index
    • C09C1/0057—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 low and high refractive indices, wherein the first coating layer on the core surface has the low 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
    • 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
    • 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
    • C09C1/0051—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 low and high refractive indices, wherein the first coating layer on the core surface has the low refractive index
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • 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
    • 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
    • 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
    • C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/02—Processes for applying liquids or other fluent materials performed by spraying
    • B05D1/04—Processes for applying liquids or other fluent materials performed by spraying involving the use of an electrostatic field
    • B05D1/06—Applying particulate materials
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/50—Solid solutions
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • 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
    • C09C2200/1004—Interference pigments characterized by the core material the core comprising at least one inorganic oxide, e.g. Al2O3, TiO2 or SiO2
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C2200/00—Compositional and structural details of pigments exhibiting interference colours
    • C09C2200/10—Interference pigments characterized by the core material
    • C09C2200/102—Interference pigments characterized by the core material the core consisting of glass or silicate material like mica or clays, e.g. kaolin
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C2200/00—Compositional and structural details of pigments exhibiting interference colours
    • C09C2200/10—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
    • C09C2200/30—Interference pigments characterised by the thickness of the core or layers thereon or by the total thickness of the final pigment particle
    • C09C2200/301—Thickness of the core
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C2200/00—Compositional and structural details of pigments exhibiting interference colours
    • C09C2200/30—Interference pigments characterised by the thickness of the core or layers thereon or by the total thickness of the final pigment particle
    • C09C2200/302—Thickness of a layer with high refractive material
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C2200/00—Compositional and structural details of pigments exhibiting interference colours
    • C09C2200/30—Interference pigments characterised by the thickness of the core or layers thereon or by the total thickness of the final pigment particle
    • C09C2200/303—Thickness of a layer with low refractive material
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C2200/00—Compositional and structural details of pigments exhibiting interference colours
    • C09C2200/40—Interference pigments comprising an outermost surface coating
    • C09C2200/401—Inorganic protective 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
    • C09C2200/00—Compositional and structural details of pigments exhibiting interference colours
    • C09C2200/50—Interference pigments comprising a layer or a core consisting of or comprising discrete particles, e.g. nanometric or submicrometer-sized particles
    • C09C2200/505—Inorganic particles, e.g. oxides, nitrides or carbides
    • 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
    • C09C2200/50—Interference pigments comprising a layer or a core consisting of or comprising discrete particles, e.g. nanometric or submicrometer-sized particles
    • C09C2200/507—Organic particles, e.g. polymers or dyes

Definitions

  • the present invention relates to the use of particles comprising a substrate and a surface or surface near SiO 2 layer or a surface or near-surface layer containing SiO 2 particles embedded in a matrix in electrostatic coating processes, the surface or near-surface layer being at least 2.5 Wt .-% of SiO 2 based on the total weight of the total weight, a powder coating containing such particles, electrostatic coating methods and such particles per se.
  • An essential coating method is the electrostatic powder coating, in electrostatic powder spraying (EPS) from a grounded container with fluidized powder coating by means of an injector, the powder particles are electrostatically charged with a corona gun and the powder coating through a DC high voltage field from the corona gun to grounded workpiece is moved. Since electrostatically applicable powder coatings essentially consist only of plastic powders and pigments and contain no solvents, no solvent emissions or coating sludge are formed in the electrostatic powder coating and this coating process is therefore particularly environmentally friendly.
  • EPS electrostatic powder spraying
  • the present invention thus relates to the use of particles comprising a substrate and a surface or near-surface SiO 2 layer or a surface or near-surface layer containing SiO 2 particles embedded in a matrix in electrostatic coating processes, wherein the surface or near-surface layer has at least 2.5 wt. % SiO 2 based on total weight of the particles.
  • the particles according to the invention preferably pigments, in particular effect pigments such as pearlescent pigments, can be easily fluidized triboelectrically and then applied electrostatically to organic powders or powder mixtures.
  • Pigments which contain a near-surface SiO 2 content of at least 2.5% by weight of SiO 2, based on the total weight of the particles can be applied as a superficial layer to a non-baked powder coating layer, where they are used directly as sole or in admixture with powder coatings in almost any of them Ratio of low to high concentration, but preferably in greatly increased concentrations of 6 to 100 wt .-%, preferably 10 to 80 wt .-%, are applied as harnesspigmenttechnische.
  • the particles according to the invention comprise a substrate and a surface or near-surface SiO 2 layer or a surface or near-surface layer containing SiO 2 particles embedded in a matrix, wherein the surface or near-surface layer comprises at least 2.5% by weight of SiO 2, based on the total weight of the particles ,
  • the surface or near-surface layer preferably contains 2.5 to 5% by weight, in particular 3 to 5% by weight, of S1O 2, based on the total weight of the particles.
  • the SiO 2 layer according to the invention may contain in addition to SiO 2 and hydroxides and / or oxide hydrates of silicon. Particles containing the surface or near-surface SiO 2 layer or the surface or near-surface layer containing the SiO 2 particles embedded in a matrix as the outer layer are particularly suitable for use in electrostatic coating processes.
  • particles containing an outer SiO 2 layer may preferably be used in electrostatic coating processes.
  • the surface or near-surface layer essential to the invention comprises SiO 2 particles embedded in a matrix.
  • the SiO 2 particles are enveloped by the matrix and / or immobilized in the matrix. It is preferably an organic-inorganic hybrid layer which consists of an organic matrix and SiO 2 particles.
  • the matrix may consist of one or more polymeric substances. Preferred examples of these are polyorganosiloxanes or polymers, preferably thermoplastic polymers.
  • the matrix preferably contains amino groups. Particular preference is given to amino-containing polyorganosiloxanes and / or amino-containing polymers.
  • the immobilization of the SiO 2 particles is preferably carried out in polyorganosiloxanes by using reactive silanes.
  • suitable silanes are alkylsilanes, monoamino and diaminosilanes, methacrylsilanes, epoxysilanes, and mixtures of two or more silanes. Due to the better charge behavior, the use of amino-functional silanes is preferred. Particular preference is given to monofunctional silanes having terminal amino groups. However, it is also an encapsulation using hard, largely insoluble, but thermoplastic polymeric materials (such as polyamides, polyepoxides, polyolefins, polyglycols, polymeric surfactants) possible. As pure substances in particular polyester and polyacrylates are preferred.
  • thermoplastic polymers in particular of amino-containing thermoplastic polymers.
  • a variant in which an aminosilane is used as crosslinking agent for the thermoplastic polymer sheath eg polyepoxide is particularly preferred.
  • thermoplastic polymers used for coating are preferably selected so that they are solid on the particle at room temperature. As a result, they differ substantially from the viscous, adhesive coatings specified in WO 98/46682. It has been found that the coatings according to the prior art preferentially detach during the firing of the powder coating layer and then influence the mechanical properties of the paint surface, in particular the abrasion stability of the paint layers being adversely affected. If, however, the occupation according to the invention is selected with amino-containing polyorganosiloxanes and / or with hard thermoplastic polymers, the detachment is prevented or largely avoided.
  • the SiO 2 particles immobilized in the matrix are preferably nanoparticles.
  • nanoparticles are to be understood as meaning particles which preferably have an average primary particle size, determined by means of a Malvern ZETASIZER (dynamic light scattering) or transmission electron microscope, of 3 to 500 nm, in particular of 5 to 200 nm and very particularly preferably of 10 to 120 nm.
  • the distribution of the Particle sizes narrow, ie the fluctuation range is less than 100% of the average, more preferably at most 50% of the average value (after particle distribution function, determined by dynamic light scattering).
  • the particles essential to the invention may be fillers and / or pigments, preferably pigments, in particular effect pigments.
  • the advantage of separation avoidance with further advantages, such as e.g. Combine color or shine.
  • Suitable substrates for the particles according to the invention are all types of materials.
  • the shape of the substrates is not critical and can be expertly adapted to the particular circumstances.
  • substrates are preferably platelet-shaped
  • Substrates for example, platelet-shaped TiO 2 , synthetic or natural mica, glass flakes, aluminum oxide flakes, metal flakes, platelet-shaped SiO 2 or platelet-shaped iron oxide or flaky graphite.
  • the metal platelets may consist inter alia of the elemental metals, such as aluminum, silver or titanium, but also of mixtures or alloys, such as bronze or steel, preferably they are made of aluminum and / or titanium.
  • the metal platelets can be passivated by appropriate treatment.
  • synthetic or natural mica, platelet-shaped SiO 2 , aluminum oxide platelets or glass platelets are used as finely divided substrates.
  • the thickness of the substrates is usually between 0.005 and 5 microns, in particular between 0.1 and 4.5 microns.
  • the expansion in the length or width of the substrates according to the invention is usually between 1 and 250 ⁇ m, preferably between 2 and 200 ⁇ m and in particular between 2 and 100 ⁇ m.
  • Platelet-shaped substrates according to this invention in particular when the particles according to the invention are pigments, have the advantage that special effects can be achieved with these materials.
  • interference systems can be formed on the platelet-shaped layer
  • Substrates may be applied, which show a special gloss, great color strength or angle-dependent colors. This is of particular interest in the use of paints, especially car paints. Platelet-shaped pigments are accordingly particularly preferred as particles according to the invention.
  • pigments based on glass flakes or aluminum oxide platelets are preferably metallic substrates such. As aluminum used.
  • a preferred embodiment of the present invention provides for the use of pure flak materials such as mica, Al 2 O 3 flakes, graphite flakes, glass flakes or SiO 2 flakes, or any inorganic flake particles, in particular Al 2 O 3 flakes, glass flakes or SiO 2 .
  • the substrates according to the invention can be coated with one or more transparent, semitransparent and / or opaque layers comprising metal oxides, metal oxide hydrates, metal suboxides, metals, metal fluorides, metal nitrides, metal oxynitrides or mixtures of these materials.
  • Metal nitride, metal oxynitride layers or mixtures thereof may be low (refractive index ⁇ 1.8) or high refractive index (refractive index> 1.8). These layers preferably function as a coloring system, whereby the color impression can be caused by both absorption and interference.
  • Suitable metal oxides and metal oxide hydrates are all metal oxides or metal oxide hydrates known to the person skilled in the art, such as, for example, Silica, hydrated silica, iron oxide, tin oxide, cerium oxide, zinc oxide, chromium oxide, titanium oxide, especially titanium dioxide, titanium oxide hydrate and mixtures thereof, e.g. Ilmenite or pseudobrookite.
  • the titanium suboxides can be used as metal suboxides.
  • Suitable metals are e.g. Chromium, aluminum, nickel, silver, gold, titanium, copper or alloys, for example, magnesium fluoride is suitable as the metal fluoride.
  • metal nitrides or metal oxynitrides for example, the nitrides or oxynitrides of the metals titanium, zirconium and / or tantalum can be used. To be favoured
  • Metal oxide, metal, metal fluoride and / or Metallloxidhydrat Anlagenen and most preferably applied metal oxide and / or metal oxide hydrate layers on the substrates.
  • multi-layer constructions of high-refractive and low-refractive index metal oxide, metal oxide hydrate, metal or metal fluoride layers can also be present, alternating preferably high and low refractive index layers.
  • layer packages of a high and a low-refractive layer wherein one or more of these layer packages can be applied to the substrates.
  • the order of the high- and low-index layers can be adapted to the substrates in order to include the substrates in the multi-layer structure.
  • the metal oxide, metal oxide hydrate, metal suboxide, metal, metal fluoride, metal nitride, metal oxynitride layers may be spiked or doped with colorants or other elements.
  • Suitable colorants or other elements are, for example, organic or inorganic color pigments such as colored metal oxides, eg magnetite, chromium oxide or color pigments such as Berlin Blue, ultramarine, bismuth vanadate, thenard blue, or organic color pigments such as indigo, azo pigments, phthalocyanines or carmine red or elements such as yttrium or antimony.
  • the application of one or more transparent, semi-transparent and / or opaque layers of the above-mentioned materials to the substrates is preferred in the present invention.
  • Pigments, in particular platelet-shaped, containing these layers show a high color diversity with respect to their body color and in many cases can show an angle-dependent change of color (color flop) due to interference.
  • the combination of these color properties with the outer nanoparticle-containing layer according to the invention gives rise to particular advantages in the applications, in particular during incorporation into powder coatings.
  • a large freedom in the color design of the powder coatings is created, which is not possible with paints and pigments from the prior art alone.
  • the user can choose a desired color effect and is not dependent on the addition of further, improving the processability of powder coatings materials.
  • This final layer may be in addition to the layer packets above or part of a layer package, and for example of TiO 2, titanium suboxides, Fe 2 ⁇ 3, SnO 2, ZnO, Ce 2 ⁇ 3, CoO, CO 3 O 4, V 2 O 5, Cr 2 ⁇ 3 and / or mixtures thereof, such as ilmenite or pseudobrookite exist. TiO 2 is particularly preferred.
  • the thickness of the metal oxide, metal oxide hydrate, metal suboxide, metal, metal fluoride, metal nitride, metal oxynitride layers or a mixture thereof is usually 3 to 300 nm and in the case of metal oxide, metal oxide hydrate, metal suboxide, metal fluoride, metal nitride , Metalloxy- nitride layers or a mixture thereof preferably 20 to 200 nm.
  • the thickness of the metal layers is preferably 4 to 50 nm.
  • the coating of the substrates with one or more transparent, semitransparent and / or opaque layers containing metal oxides, metal oxide hydrates, metal suboxides, metals, metal fluorides, metal nitrides, metal oxynitrides or mixtures of these materials can be carried out in any manner known to those skilled in the art, for example wet-chemically, by means of sol-gel , CVD and / or PVD methods.
  • a coating with these materials is wet-chemically, in the case of metals also preferably by CVD method. At the wet-chemical
  • the substrates are suspended in water and admixed with one or more hydrolyzable metal salts at a pH which is suitable for the hydrolysis and which is chosen so that the metal oxides or metal oxide hydrates are precipitated directly on the platelets, without it Precipitation comes.
  • the pH is usually kept constant by simultaneous addition of a base or acid. If desired, the substrates may after
  • all of the desired transparent, semi-transparent and / or opaque layers may be precipitated and then calcined in total at first, usually at temperatures from 600 to 1500 0 C, preferably at temperatures of 800-1150 0 C.
  • the substrate particles can be coated in aqueous dispersion at pH 6.5 with an SiO 2 precursor compound, which forms an SiO 2 layer upon hydrolyzing.
  • an SiO 2 precursor compound As a SiO 2 precursor compound
  • all types of tetraalkoxysilanes, especially tetraethoxy and tetrabutoxysilane, as well as K or Na water glasses are used.
  • the addition can usually within 60 to 90 minutes at preferably 75 0 C. After the preparation and drying at usually 130 to constant weight, several SiO 2 precursor compound, which forms an SiO 2 layer upon hydrolyzing.
  • SiO 2 precursor compound In particular, all types of tetraalkoxysilanes, especially tetraethoxy and tetrabutoxysilane, as well as K or Na water glasses are used.
  • the addition can usually within 60 to 90 minutes at preferably 75 0 C. After the preparation and drying at usually 130 to constant weight, several
  • Calcined hours at preferably 600 - 700 0 C calcined.
  • the calcination temperature and duration must be adapted to the respective substrate.
  • the layer according to the invention is a surface or near-surface layer containing SiO 2 particles embedded in a matrix
  • this can be applied in a variety of ways to the substrates. This can be done for example by a nasstechnische precipitation (eg by salting out) or steaming. However, these processes are very energy consuming (eg drying). Therefore, another object of the present invention is a method for producing the particles according to the invention, wherein a substrate, nanoparticles and a matrix-forming material or a precursor of the matrix-forming material preferably at 20 0 C to 200 0 C, in particular at 50 ° C. to 150 ° C, using dynamic mixing processes reacted together and then processed by methods familiar to those skilled in the art.
  • the method according to the invention can be carried out in a simple manner and allows great variability with respect to the precursors and conditions that can be used. It is the person skilled in the art to adapt the optimum configuration of the method according to the invention to the necessary conditions.
  • Another object of the present invention is a powder coating containing the inventive.
  • the particles can in this case in a concentration range of 0.5 to 100 wt .-%, in particular from 6 to 100 wt .-%, particularly preferably 20 to 40 wt .-%, based on the
  • the powder coatings For example, they may be radiation-curing, physically drying or chemically curing.
  • binders for example based on acrylates, methacrylates, polyesters, polyurethanes, nitrocellulose, ethylcellulose, polyamide, polyvinyl butyrate, phenolic resins, maleic resins, starch or polyvinyl alcohol, amine resins, alkyd resins, epoxy resins, polytetrafluoroethylene, Polyvinylidenfluoriden, polyvinyl chloride or mixtures thereof suitable.
  • Preferred polymeric binders for powder coatings are, for example, polyesters, epoxies, polyurethanes, acrylates or mixtures thereof. The selection of further powder coating constituents is familiar to the person skilled in the art.
  • the particles according to the invention can also be used advantageously in admixture with organic dyes and / or pigments, such as transparent and opaque white, colored and black pigments, as well as platelet-shaped iron oxides, organic pigments, holographic pigments, LCPs (liquid crystal polymers) and conventional transparent , colored and black luster pigments on the basis of metal oxide-coated platelets based on mica, glass, Fe 2 ⁇ 3 , SiO 2 , etc., can be used.
  • organic dyes and / or pigments such as transparent and opaque white, colored and black pigments, as well as platelet-shaped iron oxides, organic pigments, holographic pigments, LCPs (liquid crystal polymers) and conventional transparent , colored and black luster pigments on the basis of metal oxide-coated platelets based on mica, glass, Fe 2 ⁇ 3 , SiO 2 , etc.
  • the particles according to the invention can be mixed in any ratio with commercially available pigments and fillers.
  • fillers are e.g. natural and synthetic mica, nylon
  • the preparation of the powder coatings according to the invention is simple and easy to handle.
  • the particles according to the invention are mixed with the powder coating, for example with a paddle or tumble mixer.
  • Particularly suitable is the so-called bonding method in which the powder coating base under nitrogen as inert gas on a
  • the powder coating of the invention can on any materials, such as iron, steel, aluminum, copper, bronze, brass and metal foils but also conductive modified surfaces of glass, ceramic and concrete u. ⁇ ., As well as on non-conductive surfaces such as wood, glass, ceramics, plastics, inorganic building materials or other materials for decorative and / or protective purposes are applied.
  • Another object of the present invention is therefore a process for coating materials comprising the electrostatic application of particles comprising a substrate and a surface or near-surface SiO 2 layer in electrostatic coating process, wherein the surface or near-surface SiO 2 layer at least 2.5 wt % SiO 2 based on total weight of the particles.
  • the particles according to the invention can be applied as a component of a powder coating described above.
  • the particles according to the invention can be applied electrostatically directly as a powder.
  • Electro- or tribostatic coating processes are familiar to the person skilled in the art and are described, for example, in US Pat. in Römpp Lexikon, paints and printing inks, Georg Thieme Verlag, 10th edition 1997, page 185 et seq and page 575ff described.
  • Another preferred subject matter of the invention is thus a process in which a powder coating is applied electrostatically before application of the particles according to the invention and then a baking step takes place.
  • the particle powder is preferably charged by shaking triboelectrically and filled in the application unit. If a commercially available powder coating gun is used, the powder output is preferably set as low as possible, but the current flow is preferably adjusted to a higher value which is directly matched to the type of powder. is presented. Current strengths of 30-50 ⁇ A have proven to be advantageous here.
  • Powder coating layer which may contain pigments, usually 0 - 6 wt .-%, applied, it is preferably also kept in the application of this first layer, the current flow low, in particular 5 to 20 uA are advantageous here.
  • the method is relatively insensitive to the set voltage.
  • the second layer can also be applied as a highly concentrated layer, whereby the particle content can be increased from the usual DryBIend concentrations from 5% to 6-100%. Preferably, 20-40% are used here. Powder coatings prepared by the above-described bonding method can also be used. However, it is always possible to use further lacquer layers, e.g. Apply clear coat, if desired.
  • a reverse layer sequence is also possible by first electrostatically applying the particles directly onto the conductive substrate to be coated and then applying a clear or semitransparent powder coating layer. All layers are then finally thermally baked together at higher temperatures.
  • high-gloss powder coatings sparkling and / or living depth effects and scratch-resistant, UV-stable and / or weather-stable layers can be obtained with the present invention.
  • pigments based on SiO 2 flakes a perfect color pit is obtained.
  • pigments based on glass flakes particularly good pearlescent effects are obtained, in particular on a white basecoat.
  • better effects can be achieved with the particles and processes of the invention than with powder coatings or powder coating processes according to the prior art.
  • the particles are on the surface and protect the organic binder.
  • Example 1 Production of SiO 2 coated particles
  • a 10% strength by weight dispersion of the particles to be coated in water is adjusted to pH 6.5 and mixed with stirring with 5% by weight of a SiO 2 precursor compound, which forms an SiO 2 layer upon hydrolysis while stirring.
  • a SiO 2 precursor compound which forms an SiO 2 layer upon hydrolysis while stirring.
  • all types of tetraalkoxysilanes, in particular tetraethoxy and tetrabutoxysilane, and K or Na water glasses are used as SiO 2 precursor compounds.
  • the Addition is carried out within 60 to 90 minutes at 75 0 C after the addition is stirred for 60 minutes, filtered, washed with demineralized water and calcined after drying at 130 0 C to constant weight for several hours at 600 - 700 0 C finally.
  • the calcination temperature and duration must be adapted to the respective particle material.
  • a standard powder coating (Tiger Black Series 59 PN 82170 from Tiger Coatings, Austria) by means of a
  • Spray gun (Optiselect the company ITW Gema with slot or with
  • a pigment prepared according to Example 1 is directly by means of a spray gun (Optiselect the company ITW Gema with
  • Iriodin ® 111 Iriodin ® 6103 Icy White and Color Stream ® Artic Fire be coated.
  • Sodium silicate glass is used as the SiO 2 precursor compound.
  • Each 200g of pigment are suspended in 1, 91 VE water and heated to 75 ° C, then 21, 81 g of sodium silicate (dissolved in 220ml DI water) are added. The addition takes place within 180 minutes at 75 ° C.
  • the pH is kept constant by adding HCL (20%).
  • the mixture is then stirred for 15 min. With HCL (20%) is in 40 min. lowered to pH 2 for complete precipitation of the SiO 2 .
  • the suspension is then washed, filtered, dried at 120 ° C for 16 h in a drying oven and then calcined in a muffle furnace at 850 0 C for 25 min.
  • the pigments obtained in this way can be fluidized very well and can be applied in high concentrations (> 10% by weight) or neat.
  • the pigment distribution on the sheet thus obtained is very good and it sets a strong pearlescent effect.
  • Colorstream ® Artic Fire shows a strong color-travel. If, however, the above-mentioned pigments are applied in a high concentration or pure without the SiO 2 secondary coating, so-called pigment spicers result during application.
  • the pigments are then strongly agglomerated on the surface and after firing are these are not completely embedded in the binder and can still be wiped by hand from the surface.

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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)
  • Pigments, Carbon Blacks, Or Wood Stains (AREA)
  • Paints Or Removers (AREA)

Abstract

L'invention concerne l'utilisation de particules comportant un substrat et une couche de SiO2 de surface ou proche de la surface, ou une couche de surface ou proche de la surface, contenant des particules de SiO2, intégrée à une matrice, dans des procédés de revêtement électrostatiques. La couche de surface ou proche de la surface, contient au moins 2,5 % en poids de SiO2 par rapport au poids total des particules. L'invention concerne également un vernis pulvérulent contenant de telles particules, des procédés de revêtement électrostatiques et lesdites particules.
EP10724268A 2009-05-29 2010-05-12 Particules revêtues et leur utilisation Withdrawn EP2435519A1 (fr)

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DE102009023158A DE102009023158A1 (de) 2009-05-29 2009-05-29 Beschichtete Partikel und deren Verwendung
PCT/EP2010/002947 WO2010136122A1 (fr) 2009-05-29 2010-05-12 Particules revêtues et leur utilisation

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DE102009058297A1 (de) 2009-12-01 2011-06-09 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. N-Allylcarbamat-Verbindungen und deren Verwendung, insbesondere in strahlungshärtenden Beschichtungen
WO2022129201A1 (fr) 2020-12-18 2022-06-23 Eckart Gmbh Agent de matité lamellaire pour peinture en poudre et peintures en poudre

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