EP2435517A1 - Particule revêtue contenant en tant que couche extérieure une matrice renfermant des nanoparticules intégrées - Google Patents

Particule revêtue contenant en tant que couche extérieure une matrice renfermant des nanoparticules intégrées

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Publication number
EP2435517A1
EP2435517A1 EP10724269A EP10724269A EP2435517A1 EP 2435517 A1 EP2435517 A1 EP 2435517A1 EP 10724269 A EP10724269 A EP 10724269A EP 10724269 A EP10724269 A EP 10724269A EP 2435517 A1 EP2435517 A1 EP 2435517A1
Authority
EP
European Patent Office
Prior art keywords
matrix
particles according
metal
particles
outer 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Withdrawn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
EP10724269A
Other languages
German (de)
English (en)
Inventor
Matthias Quenzer
Alfred HENNEMANN
Marc Entenmann
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 EP2435517A1 publication Critical patent/EP2435517A1/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Withdrawn legal-status Critical Current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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/66—Additives characterised by particle size
    • C09D7/67—Particle size smaller than 100 nm
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/66—Additives characterised by particle size
    • C09D7/68—Particle size between 100-1000 nm
    • 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
    • C01P2006/40—Electric properties
    • 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
    • C08K9/04—Ingredients treated with organic substances
    • C08K9/06—Ingredients treated with organic substances with silicon-containing 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
    • 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
    • C09C2200/40—Interference pigments comprising an outermost surface 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
    • C09C2200/40—Interference pigments comprising an outermost surface coating
    • C09C2200/402—Organic protective coating
    • C09C2200/405—High molecular weight materials, e.g. polymers
    • 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
    • C09C2200/00—Compositional and structural details of pigments exhibiting interference colours
    • C09C2200/40—Interference pigments comprising an outermost surface coating
    • C09C2200/409—Mixed inorganic-organic 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

Definitions

  • the present invention relates to particles comprising a coated substrate and, as outer layer, to a layer comprising a matrix and nanoparticles, to a process for producing particles thus coated and to their use, in particular in powder coatings.
  • An essential coating method is the electrostatic powder coating, wherein in electrostatic powder spraying (EPS) from a grounded container with fluidized powder coating by means of injector, the powder particles are electrostatically charged with a corona gun and the powder coating by a DC high voltage field of the EPS
  • Corona gun is moved to the grounded workpiece. Since electrostatically applicable powder coatings essentially consist only of plastic powders and pigments and contain no solvents, no solvent emissions or paint sludges are formed in the electrostatic powder coating and this coating process is therefore particularly environmentally friendly.
  • the present invention thus relates to particles comprising a coated substrate and as outer layer a layer comprising a matrix and nanoparticles.
  • particles preferably pigments, in particular effect pigments, such as, for example, Pearlescent pigments which have an outer layer comprising a matrix and nanoparticles, in particular silicon dioxide particles, can easily be fluidized triboelectrically and then be electrostatically applied analogously to organic powders or powder mixtures.
  • effect pigments such as, for example, Pearlescent pigments which have an outer layer comprising a matrix and nanoparticles, in particular silicon dioxide particles
  • the particles according to the invention may be fillers and / or
  • Pigments act, preferably are pigments, in particular effect pigments. In this way, the advantage of separation avoidance with further advantages, such as e.g. Combine color or shine.
  • the coating according to the invention of the particles has made it possible to produce triboelectrically easily chargeable particles, in particular pigment particles, which are easily fluidizable with organic powders.
  • the particles according to the invention preferably have a specific powder resistance in the measuring cell according to Kleber (W. Kleber et al.,
  • the particles according to the invention are therefore suitable for use in electrostatic powder applications, owing to their easy fluidizability and complete distribution as primary particles, in particular for use in powder coatings.
  • the applied powder coating layers have a much more homogeneous appearance and often a higher gloss due to the better fluidization compared to conventional effect pigments and the prior art.
  • the weathering stability of the powder coating layers produced with the particles according to the invention is also significantly increased.
  • An essential feature of the particles according to the invention is the outer layer, which comprises a matrix and nanoparticles.
  • the nanoparticles 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 inorganic nanoparticles.
  • 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 nanoparticles preferably takes place in polyorganosiloxanes by using reactive silanes.
  • suitable silanes are alkylsilanes, monoamino and diaminosilanes, methacrylsilanes,
  • Epoxysilanes as well as 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. Preference is also given to using combinations of one or more polyorganosiloxanes, in particular of polyorganosiloxanes containing amino groups, and thermoplastic polymers, in particular of amino-containing thermoplastic polymers.
  • thermoplastic polymeric materials such as polyamides, polyepoxides, polyolefins, polyglycols, polymeric surfactants
  • thermoplastic polymers in combinations of polyorganosiloxanes with thermoplastic polymers, a variant in which an aminosilane is used as the crosslinking polymer heat-shrinking (e.g., polyepoxide) is particularly preferred.
  • the thermoplastic polymers used 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, detachment is prevented or largely avoided.
  • An essential component of the particles according to the invention are the nanoparticles contained in the outer layer. Under nanoparticles in the
  • particles are to be understood 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 is narrow, ie the fluctuation range is less than 100% of the mean value, particularly preferably at most 50% of the mean value (according to particle distribution function, determined by dynamic light scattering).
  • nanoparticles examples include fumed silica, micronized color pigments, carbon black, organic polymers, micronized waxes, hollow microspheres, nanoscale metals and mixtures of different nanoparticles.
  • the nanoparticles can also be surface-treated as described in WO 2008/071286.
  • Particularly preferred nanoparticles-on-the-base-of-silica are used.
  • the proportion of nanoparticles according to the invention is preferably at least 2.5% by weight, based on the total weight of the pigment. Particularly preferred is a proportion of 2.5 to 5 wt .-%, in particular from 3 to 5 wt .-%.
  • a particularly preferred embodiment of the present invention relates to particles, in particular effect pigments, comprising a coated substrate and as outer layer a layer comprising a matrix of amino-containing polyorganosiloxanes, in particular in
  • thermoplastic polymers and SiO 2 nanoparticles, in particular with a particle size of 10 to 120 nm.
  • 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.
  • Suitable substrates are preferably platelet-shaped substrates, for example platelet-shaped TiO 2 , synthetic or natural mica, glass platelets, aluminum oxide platelets, metal platelets, platelet-shaped SiO 2 or platelet-shaped iron oxide.
  • Metal flakes 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 preferably used as finely divided substrates.
  • the thickness of the substrates is usually between 0.05 and 5 .mu.m, in particular between 0.1 and 4.5 microns.
  • the extent in the longitudinal or the 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 applied to the platelet-shaped substrates, which show a particular gloss, high 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.
  • the substrates according to the invention may 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.
  • the metal oxide, metal oxide hydrat, metal suboxide, metal, metal fluoride, metal nitride, metal oxynitride 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, For example, silica, Siliziumoxidhydrat, iron oxide, tin oxide, cerium oxide, zinc oxide, chromium oxide, titanium oxide, in particular titanium dioxide, titanium oxide and mixtures thereof, such as ilmenite or pseudobrookite.
  • the titanium suboxides can be used as metal suboxides.
  • Suitable metals are, for example, chromium, aluminum, nickel, silver, GoId, titanium, copper or alloys, as metal fluoride, for example, magnesium fluoride is suitable.
  • metal nitrides or metal oxynitrides for example, the nitrides or oxynitrides of the metals titanium, zirconium and / or tantalum can be used. Preference is given to applying metal oxide, metal, metal fluoride and / or metal oxide hydrate layers and very particularly preferably metal oxide and / or metal oxide hydrate layers to the substrates. Furthermore, 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 index layer it being possible for one or more of these layer packages to 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.
  • 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
  • organic color pigments such as indigo, azo pigments, phthalocyanines or carmine red or elements such as yttrium or antimony.
  • Pigments, especially platelet-shaped, comprising these layers exhibit a wide variety of colors with respect to their body color, and can be an angle-dependent change in the color (F ⁇ rMlopJ_ Struktur_lnien c in many cases erenz_ Attachen.-through-the-combination of these color characteristics, the inventive outer Nanoparticle-containing layer have particular advantages in the applications, especially when incorporated 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.
  • the last layer of a coating described above on the substrate, to which the outer nanoparticle-containing layer according to the invention is then applied is a high-index metal oxide.
  • This last layer may additionally be on the above-mentioned layer packages or part of a layer package and eg of TiO 2 , titanium suboxides, Fe 2 O 3 , SnO 2 , ZnO, Ce 2 O 3 , CoO, Co 3 O 4 , V 2 O 5 , Cr 2 O 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- nitridsehiehten-or-a-Misehung-preferably-2ö-to-200 nn ⁇
  • the thickness of the metal layers is preferably 4 to 50 nm.
  • the coating of the substrates with one or more transparent, semi-transparent and / or opaque layers comprising metal oxides, metal oxide hydrates, metal suboxides, metals, metal fluorides, metal nitrides,
  • wet-chemical by means of SoI-GeI, CVD and / or PVD method.
  • a coating with these materials is wet-chemically, in the case of metals also preferably by CVD method.
  • all organic or inorganic compounds of the corresponding metals are suitable, in particular the halides, nitrates, sulfates, carbonates, phosphates or oxalates, preferably the corresponding halides are used.
  • Such methods are e.g. described in DE 14 67 468, DE 19 59 988, DE 20 09 566, DE 22 14 545,
  • one or more hydrolyzable metal salts at a suitable pH for the hydrolysis, which is chosen so that the metal oxides or metal oxide are precipitated directly on the platelets, without causing precipitation.
  • the pH is usually by simultaneous addition of a base or acid
  • the substrates may after
  • -3Q and / or opaque layers are precipitated-and-subsequently-total calcined, usually at temperatures of 600 to 1500 0 C, preferably at temperatures of 800 to 1150 0 C.
  • a particularly preferred embodiment of the present invention are effect pigments, in particular pearlescent pigments, comprising a coated, platelet-shaped substrate, in particular mica, glass or SiO 2 platelets, and as outer layer a layer comprising a matrix of amino-containing polyorganosiloxanes, in particular in combination with thermoplastic polymers, and SiO 2 nanoparticles, in particular with a particle size of 10 to 120 nm. More preferably, the platelet-shaped substrate is coated alternately with high and low refractive index layers as described above.
  • the outer layer essential to the invention comprising a matrix and nanoparticles 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 ° C to 200 ° C, in particular at 50 0 C. to 150 0 C, reacted using dynamic mixing processes with each other 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 embodiment of the method according to the invention to the necessary specifications.
  • the use of the particles of the invention in plastics, paints, coatings or paints is also an object of the present invention.
  • the particles according to the invention for electrostatic or tribostatic coating can be used advantageously.
  • the particles can be used here in a concentration range of 0.5 to 100 wt .-%, in particular from 0.5 to 20 wt .-%, based on the total content of all coating components.
  • Powder coatings, liquid coatings, printing inks for gravure, offset, screen or flexo printing, toner for copiers and laser printers can be, for example, radiation-curing, physically drying or chemically curing.
  • a plurality of binders e.g.
  • paints may be powder paints or water- or solvent-based paints, the selection of the paint components is subject to the general knowledge of the skilled person.
  • Common polymeric binders for powder coatings are, for example, polyesters, epoxies, polyurethanes, acrylates or mixtures thereof.
  • plastics all common plastics are suitable for the incorporation of the shaped articles according to the invention, e.g. Duromeric or thermoplastic plastics.
  • Duromeric or thermoplastic plastics e.g. Tetrachloroethylene
  • Additives can be found, for example, in RD 472005 or in R. Glausch, M. Kieser, R. Maisch, G. Pfaff, J. Weitzel, pearlescent pigments, Curt R. Vincentz Verlag, 1996, 83 et seq., The disclosure content of which is included here.
  • the particles according to the invention are particularly preferably used in powder coatings. Particularly preferred are polyester powder coatings,
  • Epoxy powder coatings polyester-epoxy powder coatings, acrylate powder coatings and mixtures of these powder coatings.
  • Powder coatings, automotive coatings and coatings for outdoor applications are particularly preferred, since in these applications an increase in the weathering stability is particularly advantageous.
  • 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 O 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 O 3 , SiO 2 , etc.
  • the particles according to the invention can be mixed in any ratio with commercially available pigments and fillers.
  • suitable fillers are natural and synthetic mica, nylon powder, pure or filled melanin resins, talc, glasses, kaolin, oxides or hydroxides of magnesium, calcium, zinc, BiOCl 1 barium sulfate,
  • 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.
  • the resulting powder coating is stable on storage, ie there is no segregation. If the powder coating according to the invention is applied to the material to be coated, this is done in such a way that the material surface is completely covered with a homogeneous powder coating layer.
  • 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.
  • 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.
  • the pigment powder is pressure-less in the measuring cell according to Kleber (W. Kleber et al., Electrostatic and Electrophoretic Coating, Reports of the 5th Lecture, Information and Workshop, October 10-14, 1972,
  • the volume resistance is determined by means of a commercially available ohm meter (tera-ohm meter from Fischer).
  • Example 1 Preparation of a silver effect pigment according to the invention by coating a commercial pigment using SiO 2 particles and reactive aminosilanes
  • Iriodin® 9111 rutile fine satin WR (Merck, Darmstadt, Germany) are initially charged and heated to 80 ° C. with stirring in a plowshare mixer. Thereafter, with stirring, 30 g of Dynasylan® AMMO (3-aminopropyltrimethoxysilane, Evonik, Frankfurt, Germany) after a further 15 minutes 30 g of Aerosil® R972 (hydrophobized with dimethyldichlorosilane fumed silica, based on hydrophilic pyrogenic Kieselklar_e._der_Ea ⁇ -Evonik.-FrankfurVDeutschland ) are added uniformly within about 3 minutes.
  • Dynasylan® AMMO 3-aminopropyltrimethoxysilane, Evonik, Frankfurt, Germany
  • Aerosil® R972 hydrophobized with dimethyldichlorosilane fumed silica, based on hydrophilic pyrogenic Kieselklar_e._der_
  • the mixture is then on 110 0 C heated and stirred for a further 30 minutes.
  • the product is screened at 63 ⁇ m mesh size.
  • the pigment thus obtained has a specific powder resistance of 10 GOhm in the measuring cell according to adhesive (starting pigment 10 MOhm).
  • the flowability of this pigment is significantly improved.
  • the mixture with powder coating needs a lower one
  • Example 2 Preparation of a silver effect pigment according to the invention by coating a commercial pigment using SiO 2 particles and a thermoplastic polyacrylate
  • Example 3 Comparison of the performance of the inventive particles of Examples 1 and 2 with particles of the prior art in powder coatings
  • the powder coatings are each by DryBIending of 95 wt .-% of a commercially available powder coating_mit_5J3ew. ⁇ % of an devispiqmentes prepared and by means of electrostatic coating on a support applied (spray gun Optiselect from ITW Gema with slotted nozzle or with impact, process conditions: conveying air 2.7 bar, dosing air 50%, voltage 100 kV, current 100 ⁇ A).
  • the effect pigments are Iriodin® 9111 rutile fine satin WR and the products prepared therefrom

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Inorganic Chemistry (AREA)
  • Nanotechnology (AREA)
  • Paints Or Removers (AREA)
  • Pigments, Carbon Blacks, Or Wood Stains (AREA)

Abstract

L'invention concerne des particules contenant un substrat revêtu, et en tant que couche extérieure une couche renfermant une matrice et des nanoparticules, un procédé de préparation de telles particules revêtues et leur utilisation, notamment dans des vernis pulvérulents.
EP10724269A 2009-05-29 2010-05-12 Particule revêtue contenant en tant que couche extérieure une matrice renfermant des nanoparticules intégrées Withdrawn EP2435517A1 (fr)

Applications Claiming Priority (2)

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DE102009023157A DE102009023157A1 (de) 2009-05-29 2009-05-29 Beschichtete Partikel
PCT/EP2010/002950 WO2010136124A1 (fr) 2009-05-29 2010-05-12 Particule revêtue contenant en tant que couche extérieure une matrice renfermant des nanoparticules intégrées

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EP2435517A1 true EP2435517A1 (fr) 2012-04-04

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WO (1) WO2010136124A1 (fr)

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EP2501646A4 (fr) * 2009-11-20 2015-07-29 3M Innovative Properties Co Compositions pigmentaires inorganiques comprenant des nanoparticules modifiées en surface et leurs procédés de fabrication
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
DE102013113885A1 (de) * 2013-12-11 2015-06-11 Eckart Gmbh Beschichtete Metallpigmente, Verfahren zu deren Herstellung und deren Verwendung, Beschichtungsmittel und Gegenstand
US11118061B2 (en) * 2018-12-17 2021-09-14 Viavi Solutions Inc. Article including at least one metal portion
US11740532B2 (en) 2018-12-17 2023-08-29 Viavi Solutions Inc. Article including light valves

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WO2010136124A1 (fr) 2010-12-02

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