EP2900763A1 - Pigments métalliques ferromagnétiques revêtus, procédé pour les fabriquer et leur utilisation - Google Patents

Pigments métalliques ferromagnétiques revêtus, procédé pour les fabriquer et leur utilisation

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Publication number
EP2900763A1
EP2900763A1 EP13766955.2A EP13766955A EP2900763A1 EP 2900763 A1 EP2900763 A1 EP 2900763A1 EP 13766955 A EP13766955 A EP 13766955A EP 2900763 A1 EP2900763 A1 EP 2900763A1
Authority
EP
European Patent Office
Prior art keywords
metal
pigments
coating
coated
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Withdrawn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
EP13766955.2A
Other languages
German (de)
English (en)
Inventor
Sebastian HÖFENER
Oliver Struck
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Eckart GmbH
Original Assignee
Eckart GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Eckart GmbH filed Critical Eckart GmbH
Publication of EP2900763A1 publication Critical patent/EP2900763A1/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Withdrawn legal-status Critical Current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
    • C09C1/62—Metallic pigments or fillers
    • 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
    • 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
    • C09C3/10—Treatment with macromolecular organic 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
    • 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
    • C09D5/38—Paints containing free metal not provided for above in groups C09D5/00 - C09D5/36
    • 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
    • C01P2004/20—Particle morphology extending in two dimensions, e.g. plate-like
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/20—Particle morphology extending in two dimensions, e.g. plate-like
    • C01P2004/24—Nanoplates, i.e. plate-like particles with a thickness from 1-100 nanometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/54—Particles characterised by their aspect ratio, i.e. the ratio of sizes in the longest to the shortest dimension
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
    • 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
    • C01P2006/42—Magnetic properties
    • 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
    • C09C2200/401—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
    • C09C2200/40—Interference pigments comprising an outermost surface coating
    • C09C2200/402—Organic 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
    • C09C2200/40—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
    • C09C2210/00—Special effects or uses of interference pigments
    • C09C2210/60—Interference with laser-light, laser markable pigments

Definitions

  • Coated ferromagnetic metal pigments process for their preparation and their use
  • the invention relates to coated magnetic metal pigments and to processes for their preparation.
  • the invention further relates to coating compositions comprising coated magnetic metal pigments and coated articles.
  • DE 101 14446 A1 describes platelet-shaped iron pigments, which are characterized in that they are prepared from reducing-treated carbonyl iron powder.
  • the disclosed iron pigments are ferromagnetic, but uncoated and, for example, susceptible to corrosion. When drying a metal paste containing these iron pigments, there is a great risk that the dry iron pigments lead to spontaneous combustion.
  • Soft iron pigments which have a certain, for some applications, but insufficient corrosion protection. In addition, these pigments showed a very poor application behavior in the powder coating.
  • metallic effect pigments are treated with a coating.
  • the coating is characterized in that it has a
  • the mixed layer contains an inorganic network and at least one organic component, wherein the organic component is an organic oligomer and / or polymer which is at least partially in contact with the inorganic network via one or more organic network former is covalently linked.
  • metallic effect pigments with coating are also generally known. These metallic effect pigments are chemically crosslinkable and / or under the action of heat, IR radiation, UV radiation and / or
  • Electron-beam crosslinkable oligomeric and / or polymeric binder coated This chemically reactive binder coating allows for implementation of the metal pigment with the binder of a paint or a printing ink. Under the binder coating, a
  • Pre-coating with S1O2 be arranged.
  • EP 1 541 642 A1 discloses magnetic pigments which are incorporated without coating into a lacquer. This is followed by curing at 82 ° C. Due to the lack of a protective layer, these pigments are oxidation labile and discolor at higher curing temperatures, e.g. in the powder coating (200 ° C) and coil coating paint (280 ° C) are common. This discoloration results in non-reproducible hues. Furthermore, it was found that such unprotected pigments are not adequately protected from acid and base attacks despite the surrounding paint.
  • Polymer can be coated. On this coating are then
  • Orientation aids arranged, which allow a covalent attachment to the binder of a paint or a paint.
  • DE 40 30 727 A1 discloses synthetic resin-coated metallic effect pigments, in particular aluminum effect pigments.
  • Aluminum effect pigments and aluminum alloy effect pigments are Aluminum effect pigments and aluminum alloy effect pigments.
  • Metal effect pigments with improved chemical resistance are likewise described in WO 2008/095697 A1. According to the teaching of WO 2008/095697 A1, the metallic effect pigments are provided with a homogeneous synthetic resin coating.
  • the object of the present invention is to provide pigments which can be applied in particular in a powder coating and are suitable for providing a particular optical effect as a result of their orientability.
  • such pigments are characterized by good coverage in a powder coating.
  • the pigments should be too bright and color-stable and have a clear optical effect, for example in the form of a clearly recognizable image after a magnetic alignment.
  • coated metal pigments according to claim 1 or aspect 1 wherein the metal pigments comprise a metal core and a coating enveloping the metal core,
  • metal core to at least 60 wt .-% of at least one
  • the coating enveloping the metal core comprises at least one enveloping metal oxide layer and at least one enveloping chemically nonreactive one
  • the content of the at least one metal oxide layer is at least 9 wt .-% and the content of the at least one plastic layer is at least 0.4 wt .-%, each based on the weight of the uncoated metal pigment, and wherein the at least one metal oxide layer enveloping the metal core is not an oxidation product of the metal core.
  • the object underlying the invention is achieved by providing a coating agent or cosmetic, which is the inventive
  • Metal pigments preferably metallic effect pigments.
  • the object underlying the invention is achieved by a coated article which contains or has the metal pigments according to the invention, preferably metallic effect pigments, or which contains the inventive composition
  • the object on which the invention is based is also achieved by the use of the metal pigments according to the invention, preferably metallic effect pigments, in a coating agent or cosmetic.
  • Preferred developments of the uses according to the invention are given in the claim 14 or the aspects 24 to 25.
  • the object on which the invention is based is furthermore achieved by providing a process for producing one of the metal pigments according to the invention, which comprises the following steps:
  • step (2b) curing or polymerizing the ferromagnetic layer coated in step (2a) with the educt (s) of a chemically non-reactive plastic layer
  • Plastic layer coated metal pigments with at least one enveloping metal oxide layer are plastic layer coated metal pigments with at least one enveloping metal oxide layer.
  • the aforementioned metal pigments are metallic effect pigments, i. platelet-shaped metal pigments, acts. Further preferred developments of the uses according to the invention are given in the aspects 27 to 29.
  • Ferromagnetic metal pigments are occasionally used in coating compositions, such as printing inks, to cause metal ic effects, wherein the orientation of the ferromagnetic metal pigments in an application medium, for example a printing ink, can be selectively influenced by applying a magnetic field.
  • an application medium for example a printing ink
  • the Ferricon pigments of Eckart GmbH are offered for flexographic, gravure and screen printing. Problem is however
  • iron pigments For example, at high temperatures, such as occur in coating processes such as powder coating or coil coating coating, oxidation of the iron pigments may occur, which may result, inter alia, in color changes of the pigments. Further, for example, iron pigments
  • the power available to orient the pigments is substantially determined by the amount of magnetic material in the individual pigment and by the strength of the magnetic field. An increase in the strength of the magnetic field is not possible for technical or economic reasons in the rule.
  • metal pigments with an inventive at least two-layer coating structure having at least one enveloping metal oxide layer and at least one enveloping chemically non-reactive plastic layer are distinguished by a particular stability even against mechanical influences, for example abrasive influences.
  • Metal pigments act, are cushioned by the outer enveloping chemically non-reactive plastic layer.
  • the term "metal pigment” for the purposes of the present invention includes spherical and platelet-shaped metal particles, unless otherwise specified.
  • the term "metallic effect pigment” in the sense of the present invention denotes platelet-shaped metal particles.
  • the platelet-shaped metal pigments of the invention which are also referred to as metallic effect pigments, have proved to be particularly advantageous.
  • their platelet shape allows a directed reflection of
  • Metallic effect pigments in particular iron effect pigments, an aspect ratio in a range from 2000: 1 to 5: 1, more preferably from 1 150: 1 to 15: 1, even more preferably up to 850: 1 to 20: 1.
  • Embodiments prefer that the aspect ratio of the metallic effect pigments according to the invention in a range of 700: 1 to 90: 1, preferably in a range of 670: 1 to 120: 1, and more preferably in a range of 650: 1 to 150: 1.
  • the metal pigments according to the invention comprise a metal core and a coating enveloping the metal core.
  • the metal core here consists of at least 60 wt .-% of at least one at room temperature (25 ° C) ferromagnetic metal, based on the weight of the uncoated metal pigment.
  • ferromagnetic metals which already exhibit ferromagnetic properties in their pure form, such as iron, cobalt and nickel
  • alloys such as AINiCo, SmCo, Nd2Fei 4 B, Ni 8 oFe2o and NiFeCo alloys can be used.
  • iron, cobalt and nickel in particular iron.
  • metal core is at least 50 wt%, more preferably at least 60 wt%, of iron, based on the weight of the metal core.
  • the iron can be present in elemental form or else, for example, as an oxide in the form of a superficial oxide layer.
  • alloying constituent in the sense of the present invention means the uncoated metal pigment.
  • the metal core to at least 90 wt .-%, preferably at least 97 wt .-%, more preferably at least 99 wt% and even more preferably at least 99.9 wt .-% of ferromagnetic Metal, in particular iron, consists, in each case based on the weight of
  • the iron can be present in elemental form or else, for example, as an oxide in the form of a superficial oxide layer. Due to the high proportion of ferromagnetic metal, it is possible to achieve significant effects even with very weak magnets or extremely high-contrast effects with strong magnets. In particular, it is preferred that the metal core consists entirely of iron, with only trace amounts of other constituents.
  • trace amount in the sense of the present invention denotes amounts of a total of at most 0.01% by weight.
  • Alloys in particular steel alloys to use, whereby specific properties are achieved by the selective alloying of components.
  • the corrosion resistance of iron-containing pigments can be increased. This allows, for example, the Reduction or even prevention of oxidation of the pigment before
  • the contrast strength decreases with applied magnetic field with identical magnetic field strength, so that such pigments are particularly suitable, for example, for less contrasting motifs where greater importance is placed on, for example, a particularly strong gloss of the individual pigments.
  • Particularly preferred examples of corresponding alloying pigments are steel pigments.
  • ferrous metal cores are used.
  • Ferrous pigments in the sense of
  • the present invention refers to pigments which comprise at least 60% by weight of iron, based on the weight of the metal core without oxygen. It is particularly preferred to use either iron pigments or ferromagnetic steel pigments.
  • iron pigment in the sense of the present invention means that the metal core consists of at least 90% by weight of iron.
  • the iron pigments consist of at least 97% by weight, more preferably at least 99% by weight, even more preferably at least 99.5% by weight of iron.
  • the term "steel pigment" in the sense of the present invention means that the metal core consists of at least 70 wt .-% of iron, at least 80 wt .-% of iron, cobalt and nickel and at least 2, preferably at least 3 metals as alloying constituents in addition to iron in a proportion of more than 1 wt .-% comprises.
  • Each percent by weight refers to the weight of the metal core without oxygen, which may be present, for example, in the form of a superficial oxidation layer.
  • metals that can be used as alloying constituents are tungsten, molybdenum, vanadium, cobalt, nickel, niobium, chromium, silicon and manganese.
  • ferromagnetic in the sense of the present invention corresponds to the term familiar to the person skilled in the art.
  • ferromagnetic metals are iron, cobalt and nickel. In such metals form Weissche districts, which exert influence on the magnetic properties of the corresponding substances. They are further characterized by the Curie temperature, which is the temperature describes over which the ferromagnetic properties are lost.
  • the ferromagnetic metals according to the invention have a Curie temperature of at least 100 ° C., preferably of
  • At least 150 ° C even more preferably at least 250 ° C, and most preferably at least 400 ° C.
  • the upper limit of the relative permeability of the metal in question ⁇ ⁇ is preferably> 75, more preferably> 150, even more preferably> 250, and even more preferably> 350, in each case measured at 20 ° C.
  • the measurement of the permeability can take place, for example, by means of the Gouy balance or by means of SQUIDs.
  • the metal cores used according to the invention are not nanoparticles.
  • nanoparticles means particles in the nanometer range
  • the platelet-shaped metal cores have an aspect ratio in the range of 2000: 1 to 5: 1, more preferably from 1: 150: 1 to 15: 1, even more preferably from 850: 1 to 20: 1.
  • the aspect ratio of the platelet-shaped metal cores be in a range of 700: 1 to 90: 1, preferably in a range of 670: 1 to 120: 1, and more preferably in a range of 650: 1 to 150 : 1 is.
  • the metal cores according to the invention are for the most part in elemental metal form. In further embodiments, it is therefore preferred that the
  • Oxygen content of the metal core is at most 15 wt .-%, preferably at most 12 wt .-%, more preferably at most 8 wt .-%, even more preferably at most 5 wt .-% and most preferably at most 3 wt .-% is, in each case on the weight of the metal core.
  • a coloring oxide layer can be produced on the surface of the metal cores.
  • the iron pigments of the invention are characterized by a very high proportion of iron.
  • very pure iron which is prepared by the decomposition of vaporous iron pentacarbonyl Fe (CO) s in cavity decomposers. This has an iron content of about 97 wt .-% and still contains about 1, 5 wt .-% carbon and about 1 wt .-%
  • the impurities can be further removed, so that an iron content of at least 99.5 wt .-% is achieved.
  • the use of such pigments is particularly preferred since this high-purity iron has a high ductility and can therefore be milled or shaped particularly easily to form particularly high-quality iron effect pigments.
  • the steel pigments according to the invention typically exhibit inferior magnetization than the iron pigments according to the invention
  • the addition of further alloying constituents makes it possible to tailor desired material properties in order to meet desired requirements.
  • the steel pigments of the invention comprise at least 7 wt .-%, preferably at least 10 wt .-%, more preferably at least 12 wt .-% chromium, each based on the weight of the metal core without oxygen.
  • the metal cores used according to the invention can be present in various forms. For example, spherical or approximately spherical
  • Pigments are used, in particular if haptic effects are to be achieved and optical effect negligible or even unwanted.
  • platelet-shaped metal cores are preferred, which offer particularly interesting optical properties due to a directed reflection of the light.
  • the reflection of incident light can be clearly changed by aligning the coated metallic effect pigments of the invention in a magnetic field.
  • the shape of the coated metal pigments according to the invention typically resembles strongly the shape of the metal cores used. Thus, for example, a platelet shape is retained even after application of the coating according to the invention.
  • the metal pigments according to the invention are characterized by at least one metal oxide layer and at least one chemically non-reactive plastic layer, which surround the metal core.
  • both the metal oxide layer as also the chemically non-reactive plastic layer distinct layers, and therefore no mixed layers.
  • the coating can be made thinner overall, while at the same time a high stability of the corresponding pigments,
  • Powder coating agent is given.
  • Plastic layer arranged.
  • Such a layer structure has proved to be particularly effective, for example, with increased resistance to chemicals.
  • a layer structure with an enveloping metal oxide layer, wherein this metal oxide layer is not an oxidation product of the metal core, and a subsequently arranged chemically non-reactive plastic layer prevents the escape of metal ions, for example iron ions from a ferrous metal core, into the surrounding medium, for example a powder coating.
  • At least one chemically non-reactive plastic layer to be applied according to the invention is provided between the metal core and at least one enveloping element to be applied according to the invention
  • Metal oxide layer arranged.
  • Metal pigments with such a layer structure are characterized, for example, by a particular hardness.
  • Pigments with an external hard metal oxide layer may be advantageous if the metal pigments are applied after application, for example in the form of a
  • Powder coating, on the surface of a coating, for example a paint, are arranged and against mechanical, for example, abrasive,
  • the pigments of the invention show less, preferably no, abrasion and are therefore resistant to wear.
  • color pigments may also be present in a coating composition according to the invention in addition to the metal pigments according to the invention.
  • the color pigments serve for a desired coloring of the coating composition according to the invention.
  • the coated metal pigments can also be dyed directly in order to achieve desired color effects, for example when used in a coating composition according to the invention.
  • Plastic layer therefore does not react significantly with the binder of a
  • Coating agent such as a paint, for example one
  • Powder paint or a color.
  • no reaction takes place between the cured plastic layer and the binder of a coating agent.
  • the "chemically non-reactive plastic layer” is by no means a coating of as yet unhardened binder, as disclosed in WO 2005/063897 A2
  • a binder is characterized in that it is used later, for example as a resin Hardening system or by free-radical polymerization, but in this case, the metal pigments are irreversibly incorporated into the cured powder coating.
  • the proportion by weight of the plastic layers, based on the weight of the uncoated metal pigment, depends essentially on the specific surface of the uncoated metal pigment.
  • the weight fraction of the at least one plastic layer is at least 0.9 wt .-%, preferably at least 1, 2 wt .-%, more preferably at least 1, 5 wt .-% and even more preferably at least 1, 7 wt .-%, each based on the weight of the metal core.
  • the at least one chemically non-reactive plastic layer consists essentially of a plastic which consists of the group consisting of polyacrylate, polymethacrylate, polyacrylamide, Polyacrylonitrile, polyvinyl chloride, polyvinyl acetate, polyamide, polyalkene, polydiene, polyalkyne, polyalkylene glycol, epoxy, polyester, polyether, polyol, polyurethane, polycarbonate, polyethylene terephthalate, and mixtures thereof.
  • Plastic layer substantially of a plastic selected from the group consisting of polyacrylate, polymethacrylate, polyurethane, polyester and mixtures thereof.
  • Plastic layer are characterized for example by an increased UV resistance. Increased UV stability is desirable when the metal pigments of the present invention are used in outdoor applications, such as automotive finishes, architectural finishes, etc.
  • the at least one plastic layer essentially consists of
  • Examples of monomers for the preparation of polyacrylates and polymethacrylates are isoamyl acrylate, lauryl acrylate, stearyl acrylate, butoxyethyl acrylate, ethoxy-diethylene glycol acrylate, methoxytriethylene glycol acrylate, methoxy polyethylene glycol acrylate, methoxy dipropylene glycol acrylate, phenoxyethyl acrylate, phenoxy polyethylene glycol acrylate, tetrahydrofurfuryl acrylate, isobornyl acrylates, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate , 2-hydroxy-3-phenoxypropyl acrylate, 2- Acryloyloxyethylsuccinklare, 2-acryloyloxyethylphthalic acid, 2-acryloyloxyethyl-2-hydroxyethylphthalic acid, triethylene glycol diacrylate, neopentyl glycol diacrylate, 1, 6-
  • Ditrimethylolpropane tetraacrylate methyl methacrylate, ethyl methacrylate, n- Butyl methacrylate, isobutyl methacrylate, 2-ethylhexyl methacrylate, isodecyl methacrylate, n-lauryl methacrylate, tridecyl methacrylate, n-stearyl methacrylate,
  • Methoxydiethylene glycol methacrylate methoxypolyethylene glycol methacrylate
  • Phenoxyethyl methacrylate isobornyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2-hydroxybutyl methacrylate, 2-
  • Methacryloyloxyethylsuccinic acid 2-methacroyloxyethylhexahydrophthalic acid, 2-methacryloyloxyethyl 2-hydroxypropylphthalate, ethylene glycol dimethacrylate,
  • Neopentyl glycol dimethacrylate or mixtures thereof are Neopentyl glycol dimethacrylate or mixtures thereof.
  • At least one monomer having at least two, more preferably three, reactive double bonds (crosslinkers) is used.
  • the monomer preferably contains or consists of 1,6-hexanediol diacrylate, 1,9-nonanediol diacrylate, dimethylol tricyclodecanediacrylate
  • Trimethylolpropane trimethacrylate or mixtures thereof Trimethylolpropane trimethacrylate or mixtures thereof.
  • Acrylic acid and / or methacrylic acid and other free-radically polymerizable unsaturated compounds are examples of acrylic acid and / or methacrylic acid and other free-radically polymerizable unsaturated compounds.
  • the plastic layer is selected from the group consisting of polyamide, polycarbonate, polyvinyl chloride,
  • the plastic is up to a temperature of at least 180 ° C, more preferably of at least 260 ° C, even more preferably up to a temperature of at least 350 ° C,
  • Plastic coating of the platelet-shaped metal pigments does not melt and / or decompose at the aforementioned temperature. The test for a possible
  • the metal oxide layers according to the invention are selected from the group consisting of silicon oxide, aluminum oxide, boron oxide, zirconium oxide, cerium oxide, iron oxide, titanium oxide, chromium oxide, tin oxide, molybdenum oxide, their hydrated oxides, their hydroxides and mixtures thereof.
  • the at least one metal oxide layer is characterized in that the at least one
  • Metal oxide layer consists essentially of silicon oxide.
  • the term “consisting essentially of silicon oxide” means that the layer predominantly consists of silicon oxide, preferably of SiO 2 , but also up to 20% by weight of water, based on the
  • Silicon oxide layer may contain. Further, in a sol-gel synthesis from tetraalkoxysilanes, the silica may contain up to 5% by weight of alkoxy groups which have not been hydrolyzed and condensed.
  • At least one, preferably all, of the at least one enveloping metal oxide layer consists of a silicon oxide layer or
  • Silicon oxide layers preferably a Si0 2 layer or Si0 2 layers, and / or aluminum oxide layer or aluminum oxide layers, preferably an Al 2 0 3 layer or Al 2 0 3 layers.
  • at least one, preferably all, of the at least one enveloping one is present Metal oxide layer of a silicon oxide layer (s), preferably a SiCV layer.
  • at least one, preferably all, of the at least one enveloping metal oxide layer consists of an aluminum oxide layer or aluminum oxide layers, preferably an Al 2 O 3 layer or Al 2 O 3 layers.
  • the at least one enveloping metal oxide layer is a (number: 1) silicon oxide layer, preferably a (number: 1) SiCV layer.
  • Weight fraction of the metal oxide layer at least 10.2 wt .-%, more preferably at least 10.7 wt .-% and particularly preferably at least 1 1, 3 wt .-%, each based on the weight of the metal core.
  • Weight fraction of the metal oxide layer in a range of 9 to 45 wt .-%, more preferably in a range of 10.2 to 38 wt .-% and particularly preferably in a range of 10.7 to 33 wt .-% and most preferably in a range of 1 1, 3 to 27 wt .-%, each based on the weight of
  • metal pigments according to the invention preferably metallic effect pigments
  • metal ions such as iron ions
  • a paint, a paint, a cosmetic, etc. To protect environmental influences and on the other to prevent metal ions, such as iron ions, in the environment, such as a paint, a paint, a cosmetic, etc. are delivered.
  • Coating according to the invention based on an effective shielding of the metal core from the surrounding medium. It is assumed that corrosive substances, such as H + or OH - ions, by combining the protective effects of at least one metal oxide layer and at least one chemically non-reactive plastic layer are particularly effectively stopped. In particular, it is assumed that in this case a strong shielding of large amounts of corrosive substances is achieved by the metal oxide layer (s) to be used according to the invention. On the other hand, the chemically non-reactive plastic layers seem to allow a particularly efficient inclusion of small amounts of corrosive substances or metal ions. At further, corrosive substances, such as H + or OH - ions, by combining the protective effects of at least one metal oxide layer and at least one chemically non-reactive plastic layer are particularly effectively stopped. In particular, it is assumed that in this case a strong shielding of large amounts of corrosive substances is achieved by the metal oxide layer (s) to be used according to the invention. On the other hand, the chemically non
  • Embodiments therefore prefer that at least one chemically unreactive plastic layer be present under a metal oxide layer to effectively trap small amounts of corrosive substances passing through the metal oxide layer.
  • metal oxide layer which is not an oxidation product of the metal core, under the chemically non-reactive plastic layer. This seems to be particularly advantageous when, for example, conditions are used in which in particular the escape of metal ions should be prevented.
  • metal ions released correspondingly from the metal core appear to be captured particularly effectively by the combination of a metal oxide layer as first barrier layer and a chemically non-reactive plastic layer as second barrier layer.
  • the weight ratio of the at least one metal oxide layer according to the invention to at least one chemically non-reactive plastic layer is preferably at least 1 to 1, more preferably at least 7 to 6, even more preferably at least 6 to 5 and most preferably at least 5 to 4.
  • Weight ratio of the at least one metal oxide layer to the at least one chemically non-reactive plastic layer in a range from 1: 1 to 36: 1, preferably in a range from 7: 6 to 30: 1, more preferably in a range from 6: 5 to 27: 1, even more preferably in a range of 5: 4 to 24: 1.
  • the metal pigments of the invention are characterized by a
  • the sum of the contents of the polymer layer and the metal oxide layer in a range of 9.4 to 68 wt .-%, preferably in a range of 1 1 to 54 wt .-%, more preferably in a Range of 1 1, 7 to 49 wt .-%, even more preferably in a range of 12.3 to 43 wt .-%, each based on the weight of
  • ranges are preferred which by a plastic amount of 0.4 wt .-% to 23 wt .-% and a metal oxide of 9 wt .-% to 45 wt .-%, preferably a plastic amount of 0, 9 wt .-% to 21 wt .-% and a metal oxide 10.2 wt .-% to 38 wt .-%, more preferably a plastic amount of 1, 2 wt .-% to 18 wt .-% and a metal oxide amount of 10.7 wt.% To 33 wt.%, Even more preferably one Plastic amount 1, 7 wt .-% to 15 wt .-% and a metal oxide amount of 1 1, 3 wt .-% to 27 wt .-%, are labeled, in each case based on the weight of the metal core.
  • the at least one chemically non-reactive plastic layer consists essentially of polyacrylate and / or polymethacrylate and the at least one metal oxide layer consists essentially of silicon oxide, preferably S1O2, wherein the weight ratio of the at least one metal oxide layer to the at least one chemically non-reactive plastic layer is within a range of 1 : 1 to 36: 1 and the sum of the content of the at least one chemically non-reactive plastic layer and the at least one
  • Metal oxide layer in a range of 1 1 to 54 wt .-%, based on the weight of the metal core, is located.
  • the at least one chemically non-reactive plastic layer consists essentially of polyacrylate and / or polymethacrylate and the at least one metal oxide layer in the
  • the weight ratio of the at least one metal oxide layer to the at least one plastic layer is in the range of 5: 4 to 24: 1.
  • one or more organofunctional silanes can be applied between the SiO 2 layer and the plastic layer, which contain at least one free-radically polymerizable double bond, preferably at least one acrylate and / or methacrylate group.
  • the metal pigments according to the invention Due to the relatively small thicknesses of the metal oxide layer and the relatively large plastic layer thickness, the metal pigments according to the invention have two significant advantages. On the one hand, the covering power, ie the area covered per unit weight of pigment according to the invention, is still very good, compared with the coverage of an uncoated metal pigment. The thicker the covering power, ie the area covered per unit weight of pigment according to the invention, is still very good, compared with the coverage of an uncoated metal pigment. The thicker the covering power, ie the area covered per unit weight of pigment according to the invention, is still very good, compared with the coverage of an uncoated metal pigment. The thicker the covering power, ie the area covered per unit weight of pigment according to the invention, is still very good, compared with the coverage of an uncoated metal pigment. The thicker the covering power, ie the area covered per unit weight of pigment according to the invention, is still very good, compared with the coverage of an uncoated metal pigment. The thicker the covering
  • Has layer thickness since then less fines content is incorporated into the coating of larger pigments and this can thus contribute to the coverage by a statistical distribution in the paint as before.
  • a combination of a thin metal oxide layer with a chemically non-reactive plastic layer surprisingly allows the ferromagnetic
  • Metal pigments can be applied well by methods such as powder coating and specific patterns can be achieved using magnets.
  • the coatings according to the invention also appear to permit subsequent orientation during the curing process, which produces particularly pronounced effects. By choosing the strength of the magnet this special effect, such as a particularly strong
  • the coatings according to the invention provide excellent protection against corrosive environmental influences and prevent the escape of metal ions, in particular heavy metal ions, which otherwise can, for example, lead to disruptions of the coating system during curing.
  • the transparent Coating with a small layer thickness have the inventive
  • one or more further layers may be arranged between the at least one enveloping metal oxide layer and the at least one enveloping chemically non-reactive plastic layer.
  • This one or more additional layers may, for example, likewise be additional metal oxide layers.
  • Plastic layer in the sense of the present invention represent.
  • the aforementioned further layers comprise, as adhesion promoters and / or further layer components, organofunctional silanes, titanates, aluminates, phosphonic acids (for example VPS: vinylphosphonic acid), phosphoric acid esters and / or zirconates, with organofunctional silanes being particularly preferred. Because of their known hydrolysis and condensation reactions, for example, these compounds can bind particularly well to the metal surface or metal oxide surface.
  • the compounds should have at least one chemically polymerizable group, which preferably the
  • plastic layer for example, polyacrylates and / or
  • the organofunctional silane preferably has at least one functional group which can be chemically reacted with an acrylate group and / or methacrylate group of the polyacrylate and / or polymethacrylate.
  • Free-radically polymerizable organic functional groups have proven to be very suitable.
  • the at least one functional group is selected from the group consisting of acrylic, methacrylic, vinyl, allyl, ethynyl and other organic groups having unsaturated functions.
  • the organofunctional silane has at least one acrylate and / or methacrylate group, since these with those for the production of the polyacrylate and / or Polymethacrylates used acrylate or methacrylate compounds can be implemented without any problems to form a homogeneous plastic layer.
  • (methacryloxymethyl) methyldimethoxysilane may, methacryloxymethyltrimethoxysilane, (methacryloxymethyl) methyldiethoxysilane, methacryloxymethyltriethoxysilane, 2-Acryloxyethylmethyldimethoxysilan, 2-methacryloxyethyltrimethoxysilane, 3-acryloxypropylmethyldimethoxysilane, 2-acryloxyethyltrimethoxysilane, 2-methacryloxyethyltriethoxysilane, 3-acryloxypropyltrimethoxysilane , 3-acryloxypropyltrimethoxysilane , 3-acryloxypropyltripropoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriacetoxysilane, 3-methacryloxypropymethyl
  • silanes can act as adhesion promoters between metal oxide layer and
  • Plastic layer or between metal oxide layer, preferably silicon oxide layer and plastic layer act.
  • silanes can be at least partially polymerized into the plastic layer, as described in WO 2008/095697 A1, which is hereby incorporated by reference.
  • Plastic layer which "consists essentially of polyacrylate and / or polymethacrylate" understood that such a layer by acrylate and / or
  • methacrylate-containing silanes can be modified.
  • a plastic layer consisting essentially of "polyacrylate and / or methacrylate” is understood to mean that the plastic layer consists essentially of acrylate, methacrylate or mixtures of acrylate and methacrylate, the proportion of the acrylates and / or methacrylate-containing silanes used being at most equal to that
  • the molar ratio of acrylate and / or methacrylate-containing is preferably Silanes to acrylate and / or methacrylate monomers at 1: 2 to 1:40, preferably from 1: 3 to 1: 30.
  • this invention does not cover layers in which the acrylate- and / or methacrylate-containing silanes are incorporated into the at least one metal oxide layer, in particular silicon oxide layer, during a sol-gel process.
  • Such layers are described in EP 1812519 B1. It has been found that the technology described there, the layers can not be produced reliably reproducible to give the metal pigments the required stabilities.
  • One or more further layers can likewise be arranged between the metal cores and the at least one enveloping metal oxide layer and the at least one chemically non-reactive plastic layer.
  • a layer of iron oxide can be arranged between the enveloping metal oxide layer and the metal pigments. This iron oxide layer can be formed, for example, by a superficial oxidation of the pigment in contact with air
  • the at least one metal oxide layer which synergistically interacts with the at least one chemically non-reactive plastic layer is not the oxidation product of the uncoated metal pigment.
  • the metal oxide layer, which synergistically cooperates with the at least one chemically non-reactive plastic layer is applied in a separate step.
  • the separate step can be, for example, a wet-chemical coating or a gas-phase coating, for example by means of PVD or CVD.
  • the enveloping metal oxide layer (s) and the enveloping chemically non-reactive plastic layer (s) directly follow each other.
  • the enveloping metal oxide layer or the enveloping chemically non-reactive plastic layer directly on the metal pigment surface or directly on the metal oxide layer as
  • the iron oxide layer are applied.
  • the metal pigments in addition to an optional metal oxide layer, in particular iron oxide layer, have only one (number: 1) enveloping metal oxide layer and only one (number: 1) enveloping chemically non-reactive plastic layer.
  • the layer thicknesses of the metal oxide layers and the plastic layers on the metal pigments are determined, for example, by means of SEM images on suitable transverse sections.
  • the pigments are applied in a varnish and this cured. It is important to ensure the best possible orientation of the platelets in the application medium.
  • the metallic effect pigments can be previously pretreated by means of suitable additives. Then the hardened lacquer is sanded and, after usual sample preparation, the cross section in the SEM is considered. For counting, only particles are selected which are good
  • Coatings have a very good contrast to the metal core. If it is not possible to distinguish between the layer thicknesses of the metal oxide layer and the plastic layer, locally resolved EDX analyzes can be used before the layer thicknesses are measured.
  • the term "average layer thickness" in the sense of the invention denotes the arithmetic mean of the layer thicknesses of the layers of at least 20 metal pigments. If the coating is uneven, then the arithmetic mean of the thinnest and the thickest part of the coating of the respective particle is formed. Individual serious deviations, which are based for example on the inclusion of already coated fine pigment in the coating, are not taken into account in the calculation of the mean layer thickness.
  • the content of metal oxide can be carried out via an elemental analysis.
  • the Si content may be determined in relation to the content of the metal used as the substrate, and based on this, the amount of S1O 2 can be calculated.
  • the metallic effect pigments according to the invention preferably have a mean pigment diameter (D 5 o) from a range of 1 ⁇ m to 200 ⁇ m, preferably from 3 ⁇ to 120 ⁇ , even more preferably from 5 ⁇ to 80 ⁇ , on. Also very suitable pigment diameters from a range of 10 ⁇ to 50 ⁇ , preferably from 15 ⁇ to 40 ⁇ , have proven.
  • the d 5 o values of the length distribution of the pigments are preferably in a range from 5 ⁇ m to 40 ⁇ m, preferably from 6 ⁇ m to 30 ⁇ m, more preferably from 7 ⁇ m to 25 ⁇ m, and particularly preferably from 7. 5 ⁇ to 20 ⁇ .
  • Such pigments preferably have non-leafing properties, i. the iron effect pigments are predominantly not oriented at or in the vicinity of the surface of an application medium, for example a color or lacquer film. It does not therefore come to a "floating" of the iron effect pigments, for example, they are ground with oleic acid as a lubricant and therefore coated with this substance.
  • the average pigment diameter (D 50 ) is in a range of 0.7 to 60 ⁇ m, preferably in a range of 0.8 to 40 ⁇ m, and more preferably in a range of 1 to 33 ⁇ lies,
  • D 50 in the sense of the present invention denotes the particle size at which 50% of the aforementioned volume-average particle size distribution determined by means of laser granulometry is below the stated value.
  • the measurements can be carried out, for example, using the particle size analyzer HELOS from Sympatec GmbH, Clausthal-Zellerfeld, Germany.
  • the dispersion of a dry powder can take place here with a dispersion unit of the Rodos T4.1 type at a primary pressure of, for example, 4 bar.
  • size distribution curve of the particles for example, with a device of the Fa.
  • Quantachrome (device: Cilas 1064) according to the manufacturer's instructions. For this purpose, 1, 5 g of the pulverulent coating material in about 100 ml of ethanol dispersed, 300 seconds in an ultrasonic bath (device: Sonorex IK 52, Fa. Bandelin) treated and then by means of a Pasteur pipette in the
  • the average thickness (h 5 o) of the metallic effect pigments according to the invention is in a range of 24 nm to 500 nm, preferably in a range of 27 nm to 430 nm, more preferably in a range of 31 nm to 380 nm, more preferably in a range of 33 nm to 340 nm.
  • the metallic effect pigments according to the invention in particular iron effect pigments, preferably have a thickness distribution determined by means of thickness counting using scanning electron microscopy (SEM), which in the illustration as
  • Total cycle distribution has a h 5 o value in a range of 24 nm to 1 10 nm, preferably in a range of 27 nm to 90 nm, more preferably in a range of 31 nm to 85 nm, and still more preferably in a range of 33 to 77 nm, lies.
  • the pigments according to the invention preferably have an h 90 value in a range from 25 nm to 130 nm, more preferably in a range from 30 nm to 110 nm and even more preferably in a range from 33 nm to 87 nm.
  • Iron effect pigments have a hio value of the thickness distribution in a range from 1 1 nm to 45 nm, more preferably in a range from 13 nm to 38 nm and particularly preferably in a range from 17 nm to 34 nm.
  • average thickness or "h 5 o" in the context of the invention refers to the arithmetic mean of the thicknesses of at least 100 metallic effect pigments, preferably 100 metallic effect pigments, by means of scanning electron microscopy (SEM). Here is on the best possible orientation of the platelets in
  • the metallic effect pigments can be previously pretreated by means of suitable additives. Subsequently, the cured paint sanded and considered after conventional sample preparation of the cross section in the SEM. For counting, only particles are selected which are good
  • the metallic effect pigments are obtained by grinding
  • semolina obtained, for example, iron semolina.
  • iron semolina for example, high-purity iron obtained from carbonyl iron powder is used. If necessary, the semolina is classified to obtain a desired size distribution.
  • the process for the preparation of thin, platelet-shaped iron pigments preferably comprises the grinding of an iron semolina having an average particle size DGrello, 50 in the range of 0.7 ⁇ to 50 ⁇ , preferably in the range of 0.9 ⁇ to 32 ⁇ , more preferably in the range of 1, 1 ⁇ to 21 ⁇ and even more preferably in the range of 1, 2 ⁇ to 9 ⁇ , and most preferably in the range of 1, 3 to 7.
  • the milled iron grit a particle size distribution with a dGneß.io ⁇ 4,0 ⁇ , a dGr confuse.so ⁇ 7,0 ⁇ and a dGr garbage, 9o ⁇ 1 1, 0 ⁇ .
  • the milled iron semolina has a particle size distribution with a d Gr explorer, io ⁇ 2.7 ⁇ , a d G rie, 5o ⁇ 5.3 ⁇ and a d G neß, 9o ⁇ 7,2 ⁇ .
  • iron semolina be one according to the following formula
  • AdGrie (dGr garbage, 90 - dGr understand, 10) / dGr understand, 50
  • calculated size distribution which is in the range of 0.7 to 0.6, more preferably 0.8 to 1, 5 and particularly preferably in the range of 0.9 to 1.4.
  • Such a semolina is preferably used in dry grinding.
  • the semolina can also be converted into platelet-shaped pigments by wet grinding. After milling, a classification may be required to obtain the desired uncoated flaky metal pigment fraction.
  • the metal semolina may also contain other metals such as zinc and / or aluminum. For example, up to 10% by weight, preferably up to 5% by weight, more preferably up to 3% by weight, of further metals which are not ferromagnetic at room temperature, based on the weight of the uncoated metal pigment, may be present.
  • the metal grit used for grinding can be produced, for example, by means of atomization.
  • iron semolina for example, high-purity iron or a steel alloy, preferably high-purity iron, is used.
  • iron and optionally alloying constituents are fused together and sprayed or atomized the molten metal produced to a ferrous semolina.
  • the iron-containing semolina thus obtained may then be classified, for example using a cyclone, to obtain a starting semolina having a desired size distribution.
  • the metal semolina preferably iron grits or steel grits, having the desired size distribution subsequently becomes uncoated platelet-shaped
  • the grinding of the metal semolina takes place predominantly according to the Hametagsche dry grinding process.
  • Grinding conditions such as mill size, diameter, - rotational speed, ball size, grinding time with the addition of lubricant, such as stearic or oleic acid, to prevent cold welding of metal particles and with grinding media, such.
  • lubricant such as stearic or oleic acid
  • Metal cores according to a thickness count with scanning electron microscopy (SEM) a h 5 o value in a range of 15 to 100 nm, preferably from 20 to 80 nm, more preferably from 23 to 75 nm and most preferably from 26 to 67 nm ,
  • a via thickness counting by scanning electron microscopy (SEM) determined thickness distribution with a h 90 value 23-150 nm, preferably 28-130 nm, more preferably 26-100 nm and more preferably from 29 to 83 nm, up.
  • the platelet-shaped metal cores have a hi 0 value of the thickness distribution in the range from 12 to 70 nm and particularly preferably from 15 to 65 nm.
  • the plate-shaped metal cores have a thickness distribution with scanning electron microscopy (SEM) determined relative width of the thickness distribution Ah, which by means of the corresponding total cycle curve of the relative frequency according to the formula
  • the uncoated metal cores are preferably characterized by an aspect ratio of from 1: 150: 1 to 15: 1, more preferably from 850: 1 to 20: 1 and particularly preferably from 700: 1 to 90: 1.
  • the semolina particles for example iron particles or steel particles, are ground in two stages. In the first stage, the semolina particles are pre-formed and ground in the second stage until the completely flat-shaped metallic effect pigments are obtained.
  • metallic effect pigments obtained by physical vapor deposition such as iron pigments or steel pigments, preferably iron pigments, which are also referred to below as PVD iron effect pigments or PVD steel effect pigments.
  • PVD metallic effect pigments have an absolutely flat surface. In this case, by coating with metal oxide and a chemically non-reactive
  • platelet-shaped metal pigments after being clad with the two-layered coating according to the present invention, nevertheless have excellent resistance to environmental corrosive influences and prevent metal ions, especially heavy metal ions, from being released into the environment.
  • PVD metal pigments in particular PVD iron pigments and PVD steel pigments, are suitable in particular with regard to the smooth surface for use in paints, printing inks, paints and cosmetics.
  • Metal pigments in particular metallic effect pigments, in a coating composition.
  • Metallic pigments can be used, water-based paints, powder coatings,
  • Nail varnishes, polymers and coil coating formulations Nail varnishes, polymers and coil coating formulations.
  • the metal pigments according to the invention have proven to be particularly advantageous when used in
  • Coating agents such as powder coatings, cosmetic formulations such Nail varnishes and coil-coating varnishes proved. Particularly advantageous is the use in powder coatings considered.
  • the invention further relates to a coating agent, the inventive
  • Metal pigments preferably iron pigments and steel pigments, in particular iron pigments.
  • Coating agent a paint, such. a coil coating varnish, a varnish concentrate, a printing ink, an ink concentrate, a paint, a color concentrate, a
  • Powder coating or a powder coating concentrate is provided.
  • the metal pigments according to the invention have a good application behavior in processes such as powder coating. Furthermore, for example, no appreciable amounts of metal ions, in particular heavy metal ions, preferably iron ions, will be released to the coating agent. In addition to an undesirable intrinsic coloration, which may arise as a result, naturally also interaction with constituents of the coating agent is a major problem.
  • Coating agents can be used to coat a wide variety of objects. Examples are car bodies, facade elements, printed matter, such as printed films, paper, cardboard,
  • a particularly preferred application of the pigments of the invention is in the field of powder coating.
  • Powder coatings are used, for example, in industrial series production for coating electrically conductive and temperature-resistant materials.
  • the powder coating to be applied is present as a solid and solvent-free powder.
  • the powder coatings used as a primer or single-coat topcoat are almost completely recyclable.
  • the environmentally friendly and versatile powder coatings contain binders, pigments, fillers and crosslinkers as well as optional additives. Under a binder According to the invention, the definition given in DIN 55 945 is understood. That is, the binder includes both the film former and nonvolatile auxiliaries such as plasticizers and driers.
  • a application of the finely powdered powder coatings is usually electrostatic before burning or by
  • Coil coating is also known as a very environmentally friendly coating process. Coating and drying take place continuously in a closed system, whereby the rinsing of chemical residues is also eliminated in the no-rinse process. Furthermore, by an optimized process management, a contract efficiency of almost 100% can be achieved, while otherwise in most painting, for example, greater losses due to over spraying are available. However, since the paint is baked in the coil coating at temperatures of 240 to 280 ° C, oxidation phenomena in conventional metal pigments are analogous to
  • Powder coating observed. The problems and observations discussed above with regard to the powder coating therefore also apply to coil coating.
  • the metal pigments according to the invention such as iron pigments and steel pigments, in particular metallic effect pigments, can be combined with raw materials, auxiliaries and active ingredients suitable for the respective application.
  • Metallic pigments in the formulation may be between 0.001% by weight for rinse-off products and 40.0% by weight for leave-on products.
  • the metal pigments according to the invention are particularly suitable for use in cosmetics, e.g. Body powder,
  • Hair styling compositions such as hair spray, hair mousse, hair gel, hair wax, hair mascara, permanent or semi-permanent hair colors, temporary
  • Hair colors, skin care compositions such as lotions, gels, emulsions as well
  • Metal oxides coated natural mica such as the product group Prestige Fa. Eckart
  • BiOCI platelets such as the product group Prestige Fa. Eckart
  • TiG platelets such as the product group MIRAGE Fa Eckart
  • pearlescent pigments based on high refractive index coated metal oxide synthetic mica or based on highly refractive with metal oxides coated glass flakes such as the product group MIRAGE Fa Eckart
  • Al 2 0 3 Si0 2 or Ti0 2 - platelets
  • metallic effect pigments such as, for example, the product group Visionaire from Eckart
  • the colorants may be selected from inorganic or organic pigments.
  • the pigments of the invention are particularly suitable for use in
  • thermoplastic, thermoset or elastomeric polymers are particularly preferred. Particularly preferred are thermoplastic polymers.
  • thermoplastics examples include: polyoxyalkylenes, polycarbonates (PC), polyesters such as polybutylene terephthalate (PBT) or polyethylene terephthalate (PET), polyolefins such as polyethylene or polypropylene (PP), poly (meth) acrylates, polyamides, vinylaromatic (co) polymers such as polystyrene, impact-modified Polystyrene such as HI-PS, or ASA, ABS or AES polymers, polyarylene ethers such as
  • Polyphenylene ethers PPE
  • polysulfones polyurethanes
  • polylactides polylactides
  • halogen-containing polymers imid phenomenon wise polymers
  • imid phenomenon wise polymers cellulose esters
  • silicone polymers thermoplastic elastomers
  • mixtures of different thermoplastics may be single- or multi-phase polymer blends.
  • the concentration of the pigments of the invention is at least 0.2% by weight, based on the total weight of the metal pigment-containing polymer.
  • the concentration of the pigments according to the invention is at most 13% by weight, based on the total weight of the metal pigment-containing polymer. Higher.
  • the proportion of the pigments according to the invention in the polymer 0.2 to 13 wt .-%, preferably 0.5 to 1 1 wt .-%, still more preferably 0.8 to 8 wt .-%, in each case based on the total weight of the metal pigment-containing polymer.
  • the plastics containing the pigment according to the invention can also be used in laser marking. Upon irradiation, the laser beam heats the struck pigments according to the invention, which then become visible
  • Embodiments preferred that at least 0.001 wt .-% according to the invention Pigment are contained in the polymer, based on the total weight of the pigment-containing polymer. On the other hand, in further embodiments it is preferred that at most 0.7% by weight of pigment is included, based on the total weight of the polymer containing the pigment. According to further preferred embodiments, the proportion of the invention
  • Pigments in the polymer of 0.001 to 0.7 wt .-%, preferably 0.005 to 0.5 wt .-% and still more preferably 0.01 to 0.1 wt .-%, each based on the
  • the object of the invention is achieved by providing a process for producing a pigment according to the invention, the process comprising the following steps:
  • step (2b) curing or polymerizing the ferromagnetic layer coated in step (2a) with the educt (s) of the chemically non-reactive plastic layer
  • Plastic layer coated metal pigments with metal oxide are particularly preferable that the above-mentioned metal pigments are
  • Metallic pigments in particular metallic effect pigments, are iron-containing pigments with at least 60% by weight of iron, based on the weight of the metal core without oxygen, such as iron pigments and steel pigments, in particular iron pigments.
  • a chemically non-reactive plastic layer is applied last as the outermost layer, as described for example in steps (1 b) and (1 c). This seems especially for
  • Plastic layer repeated or performed with other metal oxides or reactants of a chemically non-reactive plastic layer to provide a coating with multiple metal oxide layers and / or chemically non-reactive plastic layers.
  • the coating of metal pigments with metal oxide can be carried out in a conventional manner.
  • the metal oxides can under
  • metal salts such as metal halides, in particular the metal chlorides are applied.
  • the metal oxide layer (s) are preferably uncalcined metal oxide layers.
  • the metal oxide layers are applied by means of sol-gel method.
  • the corresponding metal alkoxides are hydrolyzed with the addition of water, and preferably acids or bases as catalysts, wherein the corresponding metal oxides and / or metal oxide on the metal pigments and coat them.
  • the alkoxy groups are preferably methoxy, ethoxy,
  • the alkoxy groups are methoxy and / or ethoxy groups.
  • the coating with metal oxide by means of sol-gel process is usually carried out in organic solvent in the presence of small amounts of water, such as for example 1 to 10% by volume, preferably 2 to 5% by volume, of water, based on the total volume of the hydrous organic solvent.
  • the organic solvents used are preferably alcohols, glycols, esters, ketones and mixtures of these solvents. Particularly suitable is the use of alcohols, glycols or mixtures thereof. Alcohols are particularly preferably used.
  • the alcohol is preferably selected from the group consisting of methanol, ethanol,
  • Isopropanol, n-propanol, t-butanol, n-butanol, isobutyl alcohol, pentanol, hexanol and mixtures thereof is selected.
  • Ethanol and / or isopropanol have proven to be very suitable.
  • glycol butyl glycol, propyl glycol, ethylene glycol or mixtures thereof are preferably used.
  • the metal pigments preferably metallic effect pigments, are dispersed in the organic solvent with the optional addition of water. To this suspension either acid or base is added as catalyst.
  • the dispersion is heated.
  • the water required for the hydrolysis may already be contained in the organic solvent or added at a later time.
  • the acid may be organic and / or inorganic acid.
  • the organic acid is preferably selected from the group consisting of formic acid, acetic acid, propionic acid, oxalic acid, malonic acid, maleic acid, succinic acid, anhydrides of said acids and mixtures thereof.
  • the inorganic acid can be selected from the group consisting of
  • Nitric acid, sulfuric acid, phosphoric acid, hydrochloric acid, boric acid, hydrofluoric acid and their mixtures are selected.
  • sulfuric acid, phosphoric acid, hydrochloric acid, boric acid, hydrofluoric acid and their mixtures are selected.
  • Nitric acid and / or hydrofluoric acid used are Nitric acid and / or hydrofluoric acid used.
  • the basic catalyst is an amine. These may be primary, secondary or tertiary amines.
  • the amine is selected from the group consisting of dimethylethanolamine (DMEA), monoethanolamine (MEA), diethanolamine (DEA), triethanolamine (TEA), ethylenediamine (EDA), t-butylamine, monomethylamine, dimethylamine, trimethylamine, monoethylamine, Diethylamine, T ethylamine,
  • DMEA dimethylethanolamine
  • MEA monoethanolamine
  • DEA diethanolamine
  • TEA triethanolamine
  • EDA ethylenediamine
  • t-butylamine monomethylamine, dimethylamine, trimethylamine, monoethylamine, Diethylamine, T ethylamine
  • Ethylenediamine, monoethylamine, diethylamine, monomethylamine, dimethylamine, thethylamine or mixtures thereof have proven to be very suitable as basic amine catalyst.
  • inorganic bases such as ammonia, hydrazine, sodium hydroxide, potassium hydroxide, ammonium hydroxide, ammonium carbonate, ammonium hydrogencarbonate, sodium carbonate, sodium hydrogencarbonate, potassium carbonate, sodium hydrogencarbonate or mixtures thereof may also be used.
  • Ammonia and / or hydrazine have proven to be very suitable.
  • the metal alkoxide is a metal alkoxide
  • Tetraalkoxysilane used. As tetraalkoxysilane are preferably
  • Tetraethoxysilane and / or oligomers of tetraethoxysilane proved.
  • the metal oxide-coated metal pigments are separated and the chemically non-reactive
  • the chemically non-reactive plastic layer can be built up by polymerization of suitable monomers.
  • the monomers may have functionalities selected from the group consisting of amino, hydroxy, thiol, epoxy, acrylate, methacrylate, vinyl, allyl, alkenyl, alkynyl, carboxy, carboxylic anhydride, Isocyanate, cyanate, ureido, carbamate, ester groups and mixtures thereof are selected.
  • crosslinking monomers or reactive oligomers or polymers, i. polyfunctional (meth) acrylates suitable.
  • reactive oligomers or polymers i. polyfunctional (meth) acrylates suitable.
  • Pentaerythritol tetraacrylate dipentaerythritol pentaacrylate or mixtures thereof.
  • tri- and higher functional (meth) acrylates in particular trifunctional (meth) acrylates, are preferred.
  • (meth) acrylate in the sense of the present invention includes methacrylates and acrylates.
  • Plastic layer can be done thermally in preferred embodiments.
  • Polymerization initiators preferably of radical initiators. It is about commercially available, usually organic or inorganic peroxides or diazonium compounds. Examples of such compounds are:
  • Peroxydicarbonates eg diisopropyl peroxydicarbonate, di-n-butyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, dicyclohexyl peroxydicarbonate), alkyl peresters (eg cumylperneodecanoate, t-butyl perneodecanoate, t-amyl perpivalate, t-butyl per 2-ethylhexanoate, t-butyl perisobutyrate, t-butyl perbenzoate), dialkyl peroxides (eg dicumyl peroxide, t-
  • the educts of the plastic layer may also be reactive polymers selected from the group consisting of polyacrylates, poly (meth) acrylates, polyethers, polyesters, polyamines, polyamides, polyols, polyurethanes, polyolefins and mixtures thereof are selected.
  • the metal oxide-coated metal pigments are dispersed in a, preferably organic, solvent and the suspension is brought to the reaction temperature. Then the educts of the
  • Plastic layer for example in the form of organic monomers and / or reactive oligo- / polymers, and optionally added polymerization initiators, for example by dropwise addition, whereby the chemically non-reactive plastic layer (organic polymer layer) on the metalloxidbe Anlageneten Metal pigments is formed.
  • the dispersion is stirred or agitated during the application of the plastic layer.
  • the chemically non-reactive plastic layer can also by spraying the reactants of the plastic layer, for example, the organic monomers and / or reactive organic oligomers and / or reactive
  • organic polymers and optionally of polymerization initiators in a fluidized bed in which the metal oxide coated metal pigments are fluidized applied.
  • the coating takes place in a liquid phase.
  • these are preferably filtered off from the suspension.
  • the application of at least one chemically non-reactive plastic layer takes place in the form of a thermal
  • first at least one chemically non-reactive plastic layer is applied, subsequently at least one metal oxide layer and further below at least one further chemically non-reactive plastic layer.
  • the latter plastic layer is the outermost layer of the coating according to the invention.
  • the metal pigments according to the invention are preferably pelletized, granulated, strand-granulated, extruded, briquetted, tableted and thus lie in an im essentially dust-free, preferably dust-free, compacted form.
  • the metal pigments of the invention can be handled easily and in coating compositions, such as paints, paints,
  • Printing inks, powder coatings, plastics, cosmetics, etc. are easily incorporated.
  • the metal pigments according to the invention are incorporated in powder coating.
  • Binder system of the powder coating is
  • the present invention relates to a further embodiment.
  • coated metal pigments preferably coated metallic effect pigments, which have been prepared according to the aforementioned process or one of its variants.
  • the alignment of the metal pigments according to the invention is carried out using a magnetic field which can be applied, for example, during the coating process. Additionally or alternatively, however, the magnetic field can also be used for alignment after the coating process, for example during the curing process, such as can be found in the powder coating.
  • a source for the magnetic field for example, electromagnets or permanent magnets can be used.
  • temperature-stable magnets for coating processes in which the orientation preferably takes place at least in one process step in which, for example, high temperatures act on the substrate, it has proven advantageous to use temperature-stable magnets. For example, polymer-coated magnets have proven to be very advantageous for effecting reproducible alignment of the pigments under many possible conditions.
  • the magnets can be attached directly to the back of the coated substrate in order to achieve the strongest possible effect.
  • a form can be attached between magnet and substrate which partially shields the magnetic field.
  • a stamped iron sheet can be used.
  • an orientation of the pigments is limited to the recessed segments of the relevant shape, so that a
  • a mold is inserted between the magnet and the substrate, this mold having an irregular permeability to the magnetic field.
  • this form has recesses.
  • materials are used for the mold, which greatly attenuate the magnetic field.
  • the magnet can be arranged on the rear side and / or front side of the coated substrate.
  • the front and back overlay patterns can be achieved, however, when mounting on the front must be maintained a certain distance from the applied coating agent.
  • the magnetization of the magnets may already be sufficient to allow a fixation.
  • a variety of mounting options are available to the person skilled in the art, such as staples, adhesive, adhesive tape, holders, etc.
  • staples such as staples, adhesive, adhesive tape, holders, etc.
  • continuous process control is possible in which, for example, a magnet on a belt of a material to be coated during the
  • Coating process is performed to effect the alignment of the metal pigments.
  • magnets may for example be mounted on conveyor belts which are passed by the material to be coated or the coated material.
  • magnets may be connected to, for example, a continuously guided
  • the magnet is preferably in an endless loop, for example
  • the magnet For the preparation of mass-produced articles, it may be preferable to remove the magnet directly after alignment of the metal pigments according to the invention in order to be able to use it for aligning the next pigments. Care must be taken here that the pattern produced is not adversely affected by, for example, a non-uniform removal of the magnet.
  • the magnet may be preferable to keep the magnet fixed to the coated material until the curing of the coating agent in order to achieve the best possible alignment and thus the best possible alignment.
  • particularly good contrasts can be achieved even with relatively weak magnets in the Puvlerlackbe Anlagenung when the magnets are fixed during the curing process on the coated material.
  • multiple magnets may be used one upon another or at different times, such as during coating, after coating, and during an optional existing curing process, to produce specific patterns with, for example, different contrast, etc. Examples of further preferred embodiments are given in the following aspects.
  • the present invention relates to coated
  • Metal pigments comprising a metal core and a coating enveloping the metal core, the metal core consisting of at least 60% by weight of at least one ferromagnetic metal, the coating enveloping the metal core having at least one enveloping metal oxide layer and at least one enveloping chemically non-reactive plastic layer, wherein the content of the at least one enveloping metal oxide layer at least 9 wt .-% and the content of the at least one enveloping plastic layer at least 0.4 wt .-%, each based on the weight of the uncoated metal pigment, wherein the at least one of the metal core enveloping
  • Metal oxide layer is not an oxidation product of the metal core.
  • the present invention relates to coated
  • Metal pigments according to aspect 1, wherein the weight ratio of the at least one enveloping metal oxide layer to the at least one enveloping chemically non-reactive plastic layer is greater than 1: 1.
  • the present invention relates to coated
  • Metal pigments according to one of the preceding aspects wherein the content of the at least one enveloping metal oxide layer is at most 45% by weight and / or the content of the at least one enveloping plastic layer is at most 23% by weight, in each case based on the weight of the uncoated metal pigment.
  • the present invention relates to coated
  • Weight ratio of the at least one enveloping metal oxide layer to the at least one enveloping chemically non-reactive plastic layer in a range from 1: 1 to 36: 1, preferably in a range from 7: 6 to 30: 1, more preferably in a range from 6: 5 to 27: 1, more preferably in the range of 5: 4 to 24: 1.
  • the present invention relates to coated metal pigments according to any one of the preceding aspects, wherein the sum of the contents of the at least one enveloping chemically non-reactive
  • Plastic layer and the at least one enveloping metal oxide layer in a range from 9.4 to 68 wt .-%, preferably in a range of 1 1 to 54% by weight, more preferably in a range of 1 1, 7 to 49 wt. %, even more preferably in a range from 12.3 to 43 wt .-%, in each case based on the weight of the uncoated metal pigment.
  • the present invention relates to coated
  • Metal pigment is platelet-shaped.
  • the present invention relates to coated
  • Metal pigments according to any preceding aspect wherein the metal core is at least 60% by weight of at least one ferromagnetic metal selected from the group consisting of iron, cobalt and nickel.
  • the present invention relates to coated
  • Metal pigments according to any one of the preceding aspects wherein the metal core consists of at least 60% by weight of iron.
  • the present invention relates to coated
  • the present invention relates to coated
  • At least one enveloping metal oxide layer is arranged between the metal core and the at least one encapsulating plastic layer, wherein the at least one
  • enveloping metal oxide layer is not an oxidized layer of the metal core.
  • the present invention relates to coated
  • Metal pigments according to one of the preceding aspects wherein at least one chemically non-reactive plastic layer between the metal core and the at least one enveloping metal oxide layer is arranged.
  • the present invention relates to coated
  • Metal pigments according to one of the preceding aspects wherein at least at least one, preferably all, of the coating metal oxide layers of the coating, which are not oxidation products of the metal core, are selected from the group consisting of silicon oxide, aluminum oxide, boron oxide,
  • the present invention relates to coated
  • Metal pigments according to one of the preceding aspects wherein at least at least one, preferably all, of the enveloping metal oxide layers of the coating is selected from the group consisting of silicon oxide, its oxide hydrates, its hydroxides and mixtures thereof.
  • the present invention relates to coated
  • Polyacrylonitrile Polyvinyl chloride, polyvinyl acetate, polyamide, polyalkene, polydiene, polyalkyne, polyalkylene glycol, epoxy resin, polyester, polyether, polyol, polyurethane, polycarbonate, polyethylene terephthalate, and mixtures thereof.
  • the present invention relates to coated
  • Metallic pigments according to one of the preceding aspects, wherein at least one, preferably all, enveloping chemically non-reactive plastic layers of the coating consist essentially of polyacrylate, polymethacrylate or
  • the present invention relates to coated
  • the in the Plastic coating layers contained essentially of polyacrylate, polymethacrylate or mixtures thereof
  • the coating metal oxide contained in the coating consists essentially of silicon oxide, its oxide hydrates, its hydroxides and mixtures thereof, and the weight ratio of the at least one enveloping metal oxide layer to the at least one enveloping chemically non-reactive plastic layer in a range of 6: 5: 1 to 27: 1
  • the present invention relates to coated
  • the present invention relates to coated
  • Metal pigments according to one of the preceding aspects wherein the at least one enveloping chemically non-reactive plastic layer is obtained by initiator-induced radical polymerization.
  • the present invention relates to a coating agent containing coated metallic pigments according to any one of the preceding aspects.
  • the present invention relates to a coating agent, wherein the coating agent is selected from the group consisting of powder coatings and coil coating coating compositions.
  • the present invention relates to a coated article comprising metal pigments according to any one of aspects 1 to 18 or a coating agent according to any of aspects 19 to 20.
  • the present invention relates to a cosmetic, such as a nail varnish, which contains coated metal pigments according to any one of aspects 1 to 18.
  • the present invention relates to a use of coated metal pigments according to any one of aspects 1 to 18 in one
  • Coating agent or cosmetic Coating agent or cosmetic.
  • the present invention relates to the use according to aspect 23, wherein the coating agent is a powder coating and coil coating
  • the present invention relates to the use according to any one of aspects 23 to 24, wherein the cosmetic is selected from the group consisting of body powder, face powder, pressed and loose powder, face makeup, powder cream, cream makeup, emulsion makeup, wax makeup, foundation, mousse makeup , Cheek rouge, eye make-up like eye shadow,
  • the cosmetic is particularly preferably a nail polish.
  • the present invention relates to a method for
  • step (1 c) curing or polymerizing the ferromagnetic metal pigments coated in step (1 b) with the educt (s) of an enveloping chemically non-reactive plastic layer,
  • step (2c) coating the enveloping chemical obtained in step (2b) chemically
  • non-reactive plastic layer coated metal pigments having at least one enveloping metal oxide layer.
  • the aforementioned metal pigments are metallic effect pigments, i. platelet-shaped metal pigments, acts. Furthermore, the aforementioned metal pigments are preferably
  • iron-containing metal pigments more preferably iron pigments or
  • Steel pigments in particular iron pigments.
  • the present invention relates to a method according to aspect 26, wherein educt (s) of the enveloping chemically non-reactive
  • Plastic layer vinyl and / or (meth) acrylate-functional monomers may be used.
  • the present invention relates to a method according to one of the aspects 26 to 27, wherein the at least one enveloping chemically non-reactive plastic layer, preferably all enveloping chemically non-reactive plastic layers, is thermally cured.
  • the present invention relates to a method according to one of the aspects 26 to 28, wherein at least one enveloping chemically non-reactive plastic layer, preferably all enveloping chemically non-reactive plastic layers, radically using a
  • Curing starter is (are) cured.
  • Figure 1 shows two powder coated metal sheets.
  • the left was coated with a metal pigment of the invention according to Comparative Example 1 -1.
  • the right sheet was coated with a metal pigment of the invention according to Example 1 -1. It can be seen that the pigments according to the invention show a clear have better coverage, which is why the bright base sheet leads to a lighter coating on the left sheet metal.
  • TMPTMA trimethylolpropane trimethacrylate
  • AIBN azo-bis (isobutyronitrile)
  • Example 1-2 1a, 1b 1 4.5 1 148.3
  • Example 1-3 1a, 1b 1 14 1 148.3
  • Example 1-5 1a, 1b 1 4.5 1 167
  • Example 1-6 1a, 1b 1 16.9 1 167
  • Example 1-7 1a, 1b 1 2,8 1 167
  • Example 1-8 1a, 1b 1 1.2 1 167
  • Example 1-13 1a, 1b 1 2.9 1 117
  • Example 1-23 1a, 1b 1 2.9 1 117
  • the resulting pastes were dried under vacuum with a slight stream of inert gas at 100 ° C and then sieved with 71 ⁇ mesh size.
  • the respective metallic effect pigment was used together with the powder coating Tiger, Tiger Coatings GmbH & Co. KG, and with 0.2% Aeroxide Alu C (Evonik) by means of ThermoMix incorporated for 4 minutes at level 4.
  • the pigmentation level was 5.0% by weight, since with higher pigmentation a verifiable application behavior can be achieved.
  • the powder paint was weighed out to 95.0% by weight.
  • the total amount of powder paint in the mixer was 300 g plus 0.6 g of Aeroxide Alu C.
  • ThermoMix is a commercial kitchen mixer (Vorwerk).
  • the addition Aeroxide Alu C is A ⁇ Os particles, which takes over the function of a Rieselstoffs in this application.
  • the powder coatings were used with the
  • OptiSelect applied in a commercially available powder booth.
  • the spray booth was sprayed for 20 seconds according to the parameters given in Table 1, then the coating of the substrate was carried out and then the adhesions to the
  • the spray pattern was evaluated on the basis of the baked powder coating.
  • the focus was mainly on the cover.
  • sheets with very poor coverage here the background can still be recognized
  • very good coverage background no longer visible
  • black spots were thrown. As black spots be areas on the
  • Powder coating surface referred to by an inhomogeneous distribution of
  • Variant 1 Temperature-sensitive magnetic mat (removal before curing)
  • the magnetic mat is attached to the aluminum sheet before the powder coating application. This is followed by the powder coating application known to the person skilled in the art. Subsequently, the magnet is removed before the aluminum sheet is transferred to the curing in the oven (oven temperature 200 ° C 12 min).
  • a single-pole multi-pole magnetic mat strip structure, Permaflex 928 PE / PVDF single-sided multipolar, Rhine magnet
  • an axially magnetized mat areal structure, Permaflex 928 PE / PVDF axially magnetized, Rhine magnet
  • the axially magnetized mat produced a homogeneous square from which in the middle the L-value was measured according to CIE-LAB. Subsequently, the L values of the non-magnetized region were recorded and the difference was determined in accordance with magnetized - not magnetized (in the table Diff Contrast magn / not magn).
  • Variant 2 Temperature-stable magnetic mat (when hardened, the magnetic mat remains fixed to the substrate)
  • the temperature-stable magnetic mat (MAGNETOplast magnetic film 1, 0 mm, Haas & Co Magnettechnik GmbH, one-sided multipole, and ZG-dimagn 1, 0 from OK-Steinl, one-sided multipole) is before the powder coating application with the help of a
  • Line width of the strip was too low.
  • Example 1-1 12 1 4.2 ++ 2.73 spicy ++ +++++ medium
  • Example 1-2 14.8 4.4 ++ 2.87 sharp ++ ++++ out of focus / medi
  • Example 1-3 14.5 16.4 ++ 1, 40 um 0 +++++
  • Example 1-4 14.5 19.7 + 1, 47 out of focus 0 nb
  • Example 1-6 16, 1 20,6 + 1, 46 out of focus 0 +++++
  • Example 1-8 15.8 0.9 ++ 2.04 spicy +++ nb
  • Ferricon 200 with only one silicon oxide layer is not as a powder coating
  • the pigment changes its color during curing due to oxidation processes, which show in a yellowing. If both layers are combined, the corresponding products are powder-coatable and resistant to oxidation.
  • the coated test panel was placed in a horizontal position. It was applied 1 drop of 10% HCl with the exposure times 180 min. Furthermore, 1 drop of 1 M NaOH was applied with the reaction times 180 min.
  • Example 1 shows no attack after 180 minutes.
  • the metallic effect pigments according to one of Examples 1 -7, 1 -9 and 1 -15 were stirred with a pigmentation of 4 wt .-% in the base 359 (by International Lacquers) with a brush and then transferred to commercially available nail polish bottles. Hereafter, the nail polish was stored at RT for a period of 4 weeks. This showed no gelation of the nail polish.

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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)
  • Paints Or Removers (AREA)
  • Pigments, Carbon Blacks, Or Wood Stains (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne des pigments métalliques revêtus qui comprennent un noyau de métal et un revêtement entourant le noyau de métal. Le noyau de métal se compose à au moins 60 % en poids d'au moins un métal ferromagnétique. Le revêtement entourant le noyau de métal comprend au moins une couche d'oxyde métallique enveloppante et au moins une couche de matière plastique enveloppante chimiquement non réactive. La teneur de la ou des couches d'oxyde métallique est d'au moins 9 % en poids et la teneur de la ou des couches de matière plastique est d'au moins 0,4 % en poids, ramenée à chaque fois au poids du pigment métallique non revêtu. La ou les couches d'oxyde métallique entourant le noyau de métal ne sont pas un produit d'oxydation du noyau de métal. L'invention concerne en outre un procédé de fabrication des pigments métalliques, ainsi que leur utilisation.
EP13766955.2A 2012-09-25 2013-09-24 Pigments métalliques ferromagnétiques revêtus, procédé pour les fabriquer et leur utilisation Withdrawn EP2900763A1 (fr)

Applications Claiming Priority (2)

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DE102012109055.6A DE102012109055A1 (de) 2012-09-25 2012-09-25 Beschichtete ferromagnetische Metallpigmente, Verfahren zu deren Herstellung und deren Verwendung
PCT/EP2013/069762 WO2014048887A1 (fr) 2012-09-25 2013-09-24 Pigments métalliques ferromagnétiques revêtus, procédé pour les fabriquer et leur utilisation

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DE102014015151A1 (de) * 2014-10-13 2016-04-14 Schlenk Metallic Pigments Gmbh PVD-Metalleffektpigmentpulver
EP3050929A1 (fr) 2015-01-28 2016-08-03 Eckart GmbH Pigments revêtus, son procédé de fabrication et d'utilisation, agent de revêtement et objet

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DE4030727A1 (de) 1990-09-28 1992-04-02 Eckart Standard Bronzepulver Kunstharzbeschichtete metallpigmente, verfahren zu ihrer herstellung und ihre verwendung
DE19820112A1 (de) 1998-05-06 1999-11-11 Eckart Standard Bronzepulver Mit reaktiven Orientierungshilfsmitteln beschichtete Effektpigmente
DE10114445A1 (de) 2001-03-23 2002-09-26 Eckart Standard Bronzepulver Weicheisenpigmente
DE10114446A1 (de) 2001-03-23 2002-09-26 Eckart Standard Bronzepulver Eiseneffektpigmente
US20050123764A1 (en) 2003-12-05 2005-06-09 Hoffmann Rene C. Markable powder and interference pigment containing coatings
DE10361437A1 (de) 2003-12-23 2005-07-28 Eckart Gmbh & Co. Kg Metallpigmente mit vernetzbarer Bindemittelbeschichtung, Beschichtungszusammensetzung, Verfahren zur Herstellung der beschichteten Metallpigmente und deren Verwendung
DE102005037611A1 (de) 2005-08-05 2007-02-15 Eckart Gmbh & Co. Kg Metalleffektpigmente mit anorganisch/organischer Mischschicht, Verfahren zur Herstellung solcher Metalleffektpigmente und deren Verwendung
KR101285519B1 (ko) 2005-10-13 2013-07-17 도요 알루미늄 가부시키가이샤 피복 금속 안료 및 그 제조 방법, 그리고 그것을 함유하는도료 조성물
DE102007006820A1 (de) 2007-02-07 2008-08-14 Eckart Gmbh & Co.Kg Chemikalienbeständige Metalleffektpigmente, Verfahren zu deren Herstellung und Verwendung derselben
US20100193726A1 (en) * 2007-08-30 2010-08-05 Sumitomo Electric Industries, Ltd. Soft magnetic material, dust core, method for producing soft magnetic material, and method for producing dust core
EP2128203A1 (fr) 2008-05-28 2009-12-02 Eckart GmbH Pigments à effet métallique contenant du cuivre, en forme de petites lames, leur procédé de fabrication et leur utilisation
DE102009028667A1 (de) * 2009-08-19 2011-03-03 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Korrosionsschutzpigment mit Kern-Hülle-Struktur

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