EP3999018A1 - Colouring effect pigments and production thereof - Google Patents

Colouring effect pigments and production thereof

Info

Publication number
EP3999018A1
EP3999018A1 EP20739308.3A EP20739308A EP3999018A1 EP 3999018 A1 EP3999018 A1 EP 3999018A1 EP 20739308 A EP20739308 A EP 20739308A EP 3999018 A1 EP3999018 A1 EP 3999018A1
Authority
EP
European Patent Office
Prior art keywords
oxide
layer
pigments
metal
metal oxide
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP20739308.3A
Other languages
German (de)
French (fr)
Inventor
Torsten LECHNER
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.)
Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
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 Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Publication of EP3999018A1 publication Critical patent/EP3999018A1/en
Pending legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/0015—Pigments exhibiting interference colours, e.g. transparent platelets of appropriate thinness or flaky substrates, e.g. mica, bearing appropriate thin transparent coatings
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
    • A61K8/0241—Containing particulates characterized by their shape and/or structure
    • A61K8/0254—Platelets; Flakes
    • A61K8/0258—Layered structure
    • A61K8/0266—Characterized by the sequence of layers
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
    • A61K8/0241—Containing particulates characterized by their shape and/or structure
    • A61K8/0254—Platelets; Flakes
    • A61K8/0258—Layered structure
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
    • A61K8/25—Silicon; Compounds thereof
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
    • A61K8/26—Aluminium; Compounds thereof
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00—Preparations for care of the hair
    • A61Q5/06—Preparations for styling the hair, e.g. by temporary shaping or colouring
    • A61Q5/065—Preparations for temporary colouring the hair, e.g. direct dyes
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00—Preparations for care of the hair
    • A61Q5/10—Preparations for permanently dyeing the hair
    • 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
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/0015—Pigments exhibiting interference colours, e.g. transparent platelets of appropriate thinness or flaky substrates, e.g. mica, bearing appropriate thin transparent coatings
    • C09C1/0051—Pigments exhibiting interference colours, e.g. transparent platelets of appropriate thinness or flaky substrates, e.g. mica, bearing appropriate thin transparent coatings comprising a stack of coating layers with alternating low and high refractive indices, wherein the first coating layer on the core surface has the low refractive index
    • C09C1/0075—Pigments exhibiting interference colours, e.g. transparent platelets of appropriate thinness or flaky substrates, e.g. mica, bearing appropriate thin transparent coatings comprising a stack of coating layers with alternating low and high refractive indices, wherein the first coating layer on the core surface has the low refractive index comprising at least one optically active layer with at least one organic material layer, e.g. liquid crystal 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
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/62—Metallic pigments or fillers
    • C09C1/64—Aluminium
    • C09C1/648—Aluminium treated with inorganic and organic, e.g. polymeric, compounds
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/10—General cosmetic use
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/42—Colour properties
    • A61K2800/43—Pigments; Dyes
    • A61K2800/436—Interference pigments, e.g. Iridescent, Pearlescent
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/60—Particulates further characterized by their structure or composition
    • A61K2800/61—Surface treated
    • A61K2800/62—Coated
    • A61K2800/621—Coated by inorganic compounds
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/60—Particulates further characterized by their structure or composition
    • A61K2800/65—Characterized by the composition of the particulate/core
    • A61K2800/651—The particulate/core comprising inorganic material
    • 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
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C2200/00—Compositional and structural details of pigments exhibiting interference colours
    • C09C2200/10—Interference pigments characterized by the core material
    • C09C2200/1054—Interference pigments characterized by the core material the core consisting of a metal
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C2220/00—Methods of preparing the interference pigments
    • C09C2220/10—Wet methods, e.g. co-precipitation
    • C09C2220/106—Wet methods, e.g. co-precipitation comprising only a drying or calcination step of the finally coated pigment

Definitions

  • the present application relates to effect pigments which comprise a substrate platelet and a coating, the coating having at least one layer which comprises a metal oxide and / or metal oxide hydrate.
  • the application also describes a process for producing the effect pigments.
  • Developer components and coupler components which, under the influence of oxidizing agents such as hydrogen peroxide, form the actual dyes with one another.
  • Oxidation dyes are characterized by very long-lasting coloring results.
  • color pigments are generally understood to mean insoluble, coloring substances. These are present undissolved in the form of small particles in the coloring formulation and are only deposited on the outside of the hair fibers and / or the skin surface. Therefore, they can usually be removed without residue by a few washes with detergents containing surfactants. Various products of this type are available on the market under the name of hair mascara.
  • EP 2168633 B1 deals with the problem of producing long-lasting hair colorations using pigments.
  • the document teaches that when using the combination of a pigment, an organic silicon compound, a film-forming polymer and a solvent Produce colorations on hair that are particularly resistant to shampooing.
  • Metallic luster pigments or metallic effect pigments are widely used in many areas of technology. They are used, for example, for coloring paints, printing inks, inks, plastics, glasses, ceramic products and preparations for decorative cosmetics such as nail polish. They are characterized above all by their attractive angle-dependent color impression (goniochromy) and their metallic-like sheen.
  • effect pigments in particular for hair colorations, which, on the one hand, have a high wash and rub fastness and, on the other hand, do not adversely affect hair properties such as handling and haptics.
  • the effect pigments used had a high covering power and could be applied to the hair in thin layers.
  • a material to be colored, in particular hair can be colored with a broad spectrum of metallic colors.
  • the effect pigments should in particular be suitable for coloring systems that do not require the use of oxidizing agents and / or oxidation dye precursors.
  • an effect pigment comprising a) a substrate platelet and b) a coating, the coating having at least one layer which
  • the effect pigment has a substrate platelet.
  • the substrate platelet preferably has an average thickness of at most 50 nm, preferably less than 30 nm, particularly preferably at most 25 nm, for example at most 20 nm.
  • the average thickness of the substrate platelets is at least 1 nm, preferably at least 2.5 nm, particularly preferably at least 5 nm, for example at least 10 nm.
  • Preferred ranges for the thickness of the substrate plate are 2.5 to 50 nm, 5 to 50 nm, 10 to 50 nm; 2.5 to 30 nm, 5 to 30 nm, 10 to 30 nm; 2.5 to 25 nm, 5 to 25 nm, 10 to 25 nm, 2.5 to 20 nm, 5 to 20 nm and 10 to 20 nm.
  • Each substrate platelet preferably has a thickness that is as uniform as possible.
  • the substrate plate is preferably constructed monolithically. Monolithic means in this one
  • the substrate platelet is preferably constructed homogeneously, i.e. there is no concentration gradient within the platelet.
  • the substrate platelet is not constructed in layers and has no particles or particles distributed therein.
  • the size of the substrate platelet can be matched to the particular application, for example the desired effect on a keratinic material.
  • the substrate platelets have a mean largest diameter of about 2 to 200 ⁇ m, in particular about 5 to 100 ⁇ m.
  • the aspect ratio expressed by the ratio of the mean size to the mean thickness, is at least 80, preferably at least 200, more preferably at least 500, particularly preferably more than 750.
  • the mean size of the uncoated substrate platelets is here understood the d50 value of the uncoated substrate platelets. Unless otherwise stated, the d50 value was determined using a Sympatec Helos device with Quixel wet dispersion. For sample preparation, the sample to be examined was predispersed in isopropanol for a period of 3 minutes.
  • the substrate platelet can be constructed from any material which can be brought into a platelet shape.
  • substrate platelets can be of natural origin, but also synthetically produced.
  • Materials from which the substrate platelets can be constructed are, for example, metals and metal alloys, metal oxides, preferably aluminum oxide, inorganic compounds and minerals such as mica and
  • the substrate platelets are preferably constructed from a metal or an alloy.
  • metals suitable for effect pigments can be considered as the metal.
  • metals include iron and steel, and all air and water-resistant (semi) metals such as platinum, tin, zinc, chromium, molybdenum and silicon, and their alloys such as aluminum bronze and brass.
  • Preferred metals are aluminum, copper, silver and gold.
  • Preferred substrate platelets are
  • Substrate platelets made of aluminum can be produced, among other things, by punching out of aluminum foil or using common grinding and atomizing techniques. So are for example
  • the substrate platelets can have various shapes. For example, lamellar or lenticular metal flakes or so-called vacuum metallized pigments (VMP) can be used as substrate flakes.
  • Lamellar substrate platelets are characterized by an irregularly structured edge and are also referred to as "cornflakes” due to their appearance.
  • Lenticular substrate platelets have an essentially regular round edge and are also referred to as "silver dollars" because of their appearance.
  • the substrate platelets made of metal or metal alloy can be passivated, for example by anodizing (oxide layer) or chromating.
  • the surface properties and / or optical properties of the effect pigment can be changed and the mechanical and chemical resistance of the effect pigments can be increased.
  • only the upper and / or lower side of the substrate platelet can be coated, with the side surfaces being cut out.
  • the entire surface of the optionally passivated substrate platelets, including the side surfaces, is preferably covered by the layer.
  • the substrate platelets are preferably completely encased by the coating.
  • the coating can consist of one or more layers. In a preferred embodiment
  • the coating has only one layer A.
  • the coating has a total of at least two, preferably two or three, layers. It may be preferred for the coating to have two layers A and B, layer B being different from layer A. Layer A is preferably located between layer B and the surface of the substrate wafer. In yet another preferred embodiment, the coating has three layers A, B and C. In this embodiment, layer A is located between layer B and the surface of the substrate platelet, and layer C is located on layer B, which layer is different from layer B below.
  • Suitable materials for the layers A and optionally B and C are all substances that can be permanently applied to the substrate platelets.
  • the materials should preferably be able to be applied in film form.
  • the entire surface is the optionally passivated Substrate platelets, including the side surfaces, are encased by layer A or by layers A and B or by layers A, B and C.
  • the metal oxide and / or metal oxide hydrate (i) is selected from the group consisting of silicon (di) oxide, silicon oxide hydrate, aluminum oxide, aluminum oxide hydrate, boron oxide, germanium oxide, manganese oxide, magnesium oxide, iron oxide, cobalt oxide, chromium oxide, titanium dioxide,
  • Vanadium oxide, zirconium oxide, tin oxide, zinc oxide and mixtures thereof Vanadium oxide, zirconium oxide, tin oxide, zinc oxide and mixtures thereof.
  • the layer A preferably has at least one low refractive index metal oxide and / or metal oxide hydrate.
  • Layer A preferably comprises at least 95% by weight of low-refractive-index metal oxide (hydrate).
  • Low refractive index materials have a refractive index of at most 1.8, preferably at most 1.6.
  • the low refractive index metal oxides which are suitable for layer A include, for example, silicon (di) oxide, silicon oxide hydrate, aluminum oxide, aluminum oxide hydrate, boron oxide, germanium oxide, manganese oxide, magnesium oxide and mixtures thereof, silicon dioxide being preferred.
  • the layer A preferably has a thickness of 1 to 100 nm, particularly preferably 5 to 50 nm, particularly preferably 5 to 20 nm.
  • Layer B is different from layer A and can include at least one
  • High refractive index materials have a refractive index of at least 1.9, preferably at least 2.0 and particularly preferably at least 2.4.
  • Layer B preferably comprises at least 95% by weight, particularly preferably at least 99% by weight, of high-index metal oxide (s).
  • the layer B contains a (highly refractive) metal oxide, it preferably has a thickness of at least 50 nm.
  • the thickness of layer B is preferably not more than 400 nm, particularly preferably at most 300 nm.
  • High refractive index metal oxides suitable for layer B are, for example, selectively light-absorbing (ie colored) metal oxides such as iron (III) oxide (a- and y-Fe 2 O 3, red), cobalt (II) oxide (blue), chromium (III) oxide (green) ), Titanium (III) oxide (blue, is usually mixed with titanium oxynitrides and
  • Colorless, high-index oxides such as titanium dioxide and / or zirconium oxide are also suitable.
  • layer B can contain a selectively absorbing dye, preferably 0.001 to 5% by weight, particularly preferably 0.01 to 1% by weight, based in each case on the total amount of layer B.
  • a selectively absorbing dye preferably 0.001 to 5% by weight, particularly preferably 0.01 to 1% by weight, based in each case on the total amount of layer B.
  • Organic and inorganic dyes are suitable , which can be stably built into a metal oxide coating.
  • dyes have a solubility in water (760 mmHg) at 25 ° C. of more than 0.5 g / L and are therefore not to be regarded as pigments.
  • layer B can comprise a metal particle carrier layer with metal particles applied to the surface of the metal particle carrier layer.
  • the metal particles directly cover part of the metal particle carrier layer.
  • the effect pigment has areas in which there are no metal particles, i.e. areas which are not covered with the metal particles.
  • the metal particle carrier layer comprises a metal layer and / or a metal oxide layer.
  • the metal particle carrier layer comprises a metal layer and a metal oxide layer, the arrangement of these layers is not limited.
  • the metal particle carrier layer comprises at least one metal layer. It is further preferred that the metal layer has an element selected from tin (Sn), palladium (Pd), platinum (Pt) and gold (Au).
  • the metal layer can be formed, for example, by adding alkali to a metal salt solution containing the metal.
  • the metal particle carrier layer contains a metal oxide layer, this preferably does not include any
  • the metal oxide layer preferably contains an oxide of at least one element selected from the group consisting of Mg (magnesium), Sn (tin), Zn (zinc), Co (cobalt), Ni (nickel), Fe (iron), Zr ( Zirconium), Ti (titanium) and Ce (cerium). Particularly preferably contains
  • Metal particle carrier layer iii) in the form of a metal oxide layer, a metal oxide of Sn, Zn, Ti and Ce.
  • the production of the metal particle carrier layer in the form of a metal oxide layer can take place, for example, by hydrolysis of an alkoxide of a metal, which forms the metal of the metal oxide, in a sol-gel process.
  • the thickness of the metal particle carrier layer is preferably not more than 30 nm.
  • the metal particles can include at least one element selected from the group consisting of aluminum (Al), titanium (Ti), chromium (Cr), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu) , Zinc (Zn), ruthenium (Ru), rhodium (Rh), palladium (Pd), silver (Ag), tin (Sn), platinum (Pt), gold (Au) and their alloys. It is particularly preferred that the metal particles have at least one element selected from copper (Cu), nickel (Ni) and silver (Ag).
  • the average particle diameter of the metal particles is preferably not more than 50 nm, more preferably not more than 30 nm.
  • the distance between the metal particles is preferably not more than 10 nm.
  • Suitable methods for forming the metal particles are vacuum evaporation, sputtering, chemical vapor deposition (CVD), electroless plating, or the like. Of these methods, electroless plating is particularly preferred.
  • the effect pigments have a further layer C, comprising a metal oxide (hydrate), which is different from the layer B below.
  • Suitable metal oxides are, for example, silicon (di) oxide, silicon oxide hydrate, aluminum oxide,
  • the layer C preferably has a thickness of 10 to 500 nm, particularly preferably 50 to 300 nm.
  • the coating of the effect pigment has at least one layer which, in addition to the metal oxide and / or the metal oxide hydrate, also comprises a coloring compound from the group of pigments.
  • the at least one layer which comprises (i) a metal oxide and / or metal oxide hydrate and (ii) a coloring compound from the group of pigments, can be layer A, B and / or C. In the event that the coating has only one layer A, the layer A also contains the coloring compound from the group of pigments.
  • metal oxide comprises, both layers A and B or only one of the two layers can comprise the coloring compound from the group of pigments.
  • Layer A preferably contains the coloring compound from the group of pigments.
  • each of layers A, B and C can contain a coloring compound from the group of pigments.
  • two of the three layers can be the coloring
  • the coloring compound from the group of pigments can be in layers A and B, in layers A and C or in layers B and C. As well only one of the three layers can comprise a coloring compound from the group of pigments.
  • the coloring compound from the group of pigments in layer A, B or C can be.
  • an effect pigment comprising a
  • Coating with layers A, B and C is the coloring compound from the group of pigments in layer A and / or C.
  • the coating has layers A, B and C, layers A and C are included
  • each of the layers A and C can contain a coloring compound from the group of pigments.
  • only one of the layers A and C can contain the coloring compound from the group of pigments.
  • the coloring compound from the group of pigments is in layer A and / or C.
  • the effect pigment prefferably has a substrate platelet made of aluminum and a layer A comprising silicon dioxide.
  • the substrate platelet has a layer A and a layer C
  • the effect pigment has a substrate platelet made of aluminum and layers A and C comprising silicon dioxide.
  • Pigments in the context of the present invention are understood to mean coloring compounds which at 25 ° C. in water have a solubility of less than 0.5 g / L, preferably less than 0.1 g / L, even more preferably less than 0, 05 g / L.
  • the water solubility can for example take place by means of the method described below: 0.5 g of the pigment are in one
  • Suitable color pigments can be of inorganic and / or organic origin.
  • the effect pigment has at least one coloring compound from the group of inorganic and / or organic pigments.
  • Preferred color pigments are selected from synthetic or natural inorganic pigments.
  • Inorganic color pigments of natural origin can be made from chalk, ocher, umber, green earth, burnt Terra di Siena or graphite, for example.
  • inorganic color pigments black pigments such as B. iron oxide black, colored pigments such. B.
  • Ultramarine or iron oxide red and fluorescent or phosphorescent pigments can be used.
  • Colored metal oxides, hydroxides and oxide hydrates, mixed-phase pigments, sulfur-containing silicates, silicates, metal sulfides, complex metal cyanides, metal sulfates, metal chromates and / or molybdates are particularly suitable.
  • Particularly preferred color pigments are black iron oxide (CI 77499), yellow iron oxide (CI 77492), red and brown iron oxide (CI 77491), manganese violet (CI 77742), ultramarines (sodium aluminum sulfosilicates, CI 77007, Pigment Blue 29), chromium oxide hydrate (CI77289 ), Iron blue (Ferric Ferrocyanide, CI77510) and / or carmine (Cochineal).
  • Colored pigments which are also particularly preferred are colored pearlescent pigments. These are usually based on mica and / or mica and can be coated with one or more metal oxides. Mica is one of the layered silicates. The most important representatives of these silicates are muscovite, phlogopite, paragonite, biotite, lepidolite and margarite. To produce the pearlescent pigments in connection with metal oxides, the mica, predominantly muscovite or phlogopite, is mixed with a
  • synthetic mica coated with one or more metal oxide (s) can also be used as a pearlescent pigment.
  • Particularly preferred pearlescent pigments are based on natural or synthetic mica (mica) and are coated with one or more of the aforementioned metal oxides. The color of the respective pigments can be changed by varying the
  • Layer thickness of the metal oxide (s) can be varied.
  • pigments based on mica are synthetically produced mica flakes coated with metal oxide, in particular based on synthetic fluorophlogopite (INCI: Synthetic
  • the synthetic fluorophlogopite platelets are, for example, with tin oxide,
  • the metal oxide layers can also have pigments such as iron (III) hexacyanidoferrate (II / III) or carmine red.
  • Such mica pigments are available, for example, under the name SYNCRYSTAL from Eckart.
  • a preferred effect pigment is characterized in that it contains at least one coloring compound from the group of pigments, which is selected from the group of colored metal oxides, metal hydroxides, metal oxide hydrates, silicates, metal sulfides, complex metal cyanides, metal sulfates, bronze pigments and / or colored Pigments based on mica or mica coated with at least one metal oxide and / or a metal oxychloride.
  • the effect pigment is characterized in that it contains at least one coloring compound from the group of pigments, which is selected from pigments based on mica or mica, which are mixed with one or more metal oxides from the group of titanium dioxide (CI 77891) , black iron oxide (CI 77499), yellow iron oxide (CI 77492), red and / or brown iron oxide (CI 77491, CI 77499), manganese violet (CI 77742), ultramarines (sodium aluminum sulfosilicates, CI 77007, pigment blue 29), chromium oxide hydrate (CI 77289), chromium oxide (CI 77288) and / or iron blue (Ferric Ferrocyanide, CI 77510) are coated.
  • the group of pigments which is selected from pigments based on mica or mica, which are mixed with one or more metal oxides from the group of titanium dioxide (CI 77891) , black iron oxide (CI 77499), yellow iron oxide (CI 77492), red and / or brown iron
  • borosilicates are based on metal oxide-coated platelet-shaped borosilicates. These are coated, for example, with tin oxide, iron oxide (s), silicon dioxide and / or titanium dioxide. Such borosilicate-based pigments are available, for example, under the name MIRAGE from Eckart or Reflecks from BASF SE.
  • Colorona® Very particularly preferred pigments with the trade name Colorona® are, for example: Colorona Copper, Merck, MICA, CI 77491 (IRON OXIDES)
  • particularly preferred pigments with the trade name Unipure® are, for example: Unipure Red LC 381 EM, Sensient CI 77491 (Iran Oxides), Silica
  • particularly preferred pigments with the trade name Unipure® are, for example: Unipure Red LC 381 EM, Sensient CI 77491 (Iran Oxides), Silica
  • the effect pigment can also contain one or more coloring compounds from the group of organic pigments.
  • the organic pigments are correspondingly insoluble, organic dyes or color lakes, for example from the group of nitroso, nitro, azo, xanthene, anthraquinone, isoindolinone, isoindoline, quinacridone, perinone, perylene , Diketopyrrolopyorrol-, indigo, thioindido, dioxazine, and / or triarylmethane compounds can be selected.
  • organic pigments are, for example, carmine, quinacridone,
  • Phthalocyanine, Sorgho blue pigments with the color index numbers CI 42090, CI 69800, CI 69825, CI 73000, CI 74100, CI 74160, yellow pigments with the color index numbers CI 11680, CI 1 1710, CI 15985, CI 19140, CI 20040, CI 21 100, CI 21108, CI 47000, CI 47005, green pigments with the color index numbers CI 61565, CI 61570, CI 74260, orange pigments with the color index numbers CI 11725, CI 15510, CI 45370, CI 71105, red pigments with the color index numbers CI 12085, CI 12120, CI 12370, CI 12420, CI 12490, CI 14700, CI 15525, CI 15580, CI 15620, CI 15630, CI 15800, CI 15850, CI 15865,
  • the effect pigment is characterized in that it contains a coloring compound from the group of organic pigments which is selected from the group consisting of carmine, quinacridone, phthalocyanine, sorghum, blue pigments with the color index numbers CI 42090 , CI 69800, CI 69825, CI 73000, CI 74100, CI 74160, yellow pigments with the color index numbers CI 11680, CI 11710, CI 15985, CI 19140, CI 20040, CI 21100, CI 21108, CI 47000, CI 47005, green pigments with the color index numbers CI 61565, CI 61570, CI 74260, orange pigments with the color index numbers CI 11725, CI 15510, CI 45370, CI 71105, red pigments with the color index numbers CI 12085, CI 12120, CI 12370 , CI 12420, CI 12490, CI 14700,
  • the organic pigment can also be a colored lacquer.
  • the term “colored varnish” is understood to mean particles which comprise a layer of absorbed dyes, the unit of particles and dyestuff being included in the above.
  • the particles can be, for example, inorganic substrates, which can be aluminum, silica, calcium borosilicate, calcium aluminum borosilicate or also aluminum.
  • the alizarin color varnish for example, can be used as the color varnish.
  • suitable coloring compounds from the group of pigments are inorganic and / or organic pigments which have been modified with a polymer.
  • the polymer modification can, for example, increase the affinity of the pigments for the respective material of the at least one layer.
  • the particle size of the coloring compound used depends in particular on the layer in which the coloring layer is present.
  • the coloring compound preferably has a particle size Dgo which is smaller than the layer thickness of the at least one layer.
  • the particle size D95 of the coloring compound is more preferably smaller than the layer thickness of the at least one layer.
  • the particle size D99 of the coloring compound is even more preferably smaller than the layer thickness of the at least one layer. That is very particularly preferred
  • Particle size D100 of the coloring compound smaller than the layer thickness of the at least one layer can be determined, for example, using dynamic light scattering (DLS) or static light scattering (SLS).
  • D90 means that 90% of the particles of the coloring compound are smaller than the layer thickness of the at least one layer.
  • D95 means that 95% of the particles of the coloring compound are smaller than the layer thickness of the at least one layer, etc.
  • the amount of coloring compound from the group of pigments in the layer, comprising
  • Layers A and C serve in particular as protection against corrosion and also for chemical and physical stabilization.
  • Layers A and C particularly preferably contain silicon dioxide or aluminum oxide, which are applied by the sol-gel process.
  • a further subject of the application is a method for producing a
  • Effect pigments comprising a) a substrate platelet and b) a coating, the coating having at least one layer which
  • step (ß) Coating the substrate platelet suspended in step (a) with a layer which comprises (i) a metal oxide and / or metal oxide hydrate and (ii) a coloring compound from the group of pigments, using a sol-gel process. It is preferred that a metal alkoxide and a coloring compound from the group of pigments are used in the sol-gel process.
  • the metal alkoxide used in the sol-gel process is selected from the group consisting of tetramethyl orthosilicate, tetraethyl orthosilicate, tetraisopropyl orthosilicate and mixtures thereof, tetraethyl orthosilicate being preferred.
  • the substrate platelet used in step (a) has already been coated with at least one layer of a metal oxide and / or metal oxide hydrate.
  • An exemplary manufacturing process comprises dispersing the uncoated substrate flakes or the substrate flakes already coated with layer A or with layers A and B and the coloring compound from the group of pigments in a solution of a metal alkoxide such as tetraethyl orthosilicate or aluminum triisopropoxide (usually in a solution of organic solvent or a mixture of organic solvent and water with at least 50% by weight organic solvent such as a C1 to C4 alcohol), and adding a weak base or acid to hydrolyze the metal alkoxide, thereby forming a film comprising the metal oxide and the coloring compound the group of pigments on the surface of the (coated) substrate platelets.
  • a metal alkoxide such as tetraethyl orthosilicate or aluminum triisopropoxide
  • Layer B can be produced, for example, by hydrolytic decomposition of one or more organic metal compounds and / or by precipitation of one or more dissolved metal salts and, if necessary, subsequent aftertreatment (for example, transferring a hydroxide-containing layer formed into the oxide layers by annealing).
  • each of the layers A, B and / or C can contain a mixture of two or more metal oxides (hydrate) s, each of the layers preferably comprises only one metal oxide (hydrate).
  • the effect pigments based on coated substrate platelets preferably have a thickness of 70 to 500 nm, particularly preferably 100 to 400 nm, particularly preferably 150 to 320 nm, for example 180 to 290 nm.
  • the small thickness of the coated substrate platelets is achieved in particular in that the thickness of the uncoated substrate platelets is small, but also in that the thicknesses of the coatings A and, if present, C are set to the smallest possible value.
  • layer A, B or C is additionally modified by organic compounds such as silanes, phosphoric acid esters, titanates, borates or carboxylic acids.
  • the organic compounds are bound to the surface of the outermost layer A, B or C, preferably containing metal oxide.
  • the outermost layer denotes the layer that is spatially furthest from that
  • the organic compounds are preferably functional silane compounds which can bind to the layer A, B or C containing metal oxide. These can be either mono- or bifunctional compounds. Examples of bifunctional organic compounds are methacryloxypropenyltrimethoxysilane, 3- methacryloxypropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, 2-acryloxyethyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 2-methacryloxyethyltriethoxysilane, 2-acryloxyethyltriethoxysilane, 3-methacryloxypropyl tris (methoxyethoxy) silane, 3- methacryloxypropyltris (butoxyethoxy) silane, 3-methacryloxypropyltris (propoxy) silane, 3- methacryloxypropyltris (butoxy) silane, 3-acryloxypropyltris (propoxy
  • Vinyltriethoxysilane vinylethyldichlorosilane, vinylmethyldiacetoxysilane, vinylmethyldichlorosilane,
  • Vinylmethyldiethoxysilane vinyltriacetoxysilane, vinyltrichlorosilane, phenylvinyldiethoxysilane, or
  • Phenylallyldichlorosilane Furthermore, a modification with a monofunctional silane, in particular an alkylsilane or arylsilane, can take place. This has only one functional group which can covalently bond to the surface of the effect pigment (i.e. to the outermost metal oxide-containing layer) or, if it is not completely covered, to the metal surface.
  • hydrocarbon residue of the silane points away from the effect pigment.
  • a different degree of hydrophobization of the silane is possible.
  • Examples of such silanes are hexadecyltrimethoxysilane, propyltrimethoxysilane, etc.
  • Effect pigments based on silicon dioxide-coated are particularly preferred.
  • Aluminum substrate platelets modified with a monofunctional silane surface. Octyltrimethoxysilane, octyltriethoxysilane, and hecadecyltrimethoxysilane are particularly preferred
  • Hecadecyltriethoxysilane The changed surface properties / hydrophobicity can improve adhesion, abrasion resistance and alignment in the application.
  • a silane with at least one basic group is also used in the sol-gel process.
  • the sol-gel process for producing layers A or C comprises dispersing the uncoated substrate flakes or substrate flakes already coated with layers A and B, the coloring compound from the group of pigments and a silane with at least one basic group in a solution of a metal alkoxide.
  • the silanes are preferably silanes with one, two or three silicon atoms, with one or more hydroxyl groups or hydrolyzable groups per molecule and with at least one basic group.
  • the basic group can be, for example, an amino group, an alkylamino group or a dialkylamino group, which is preferably connected to a silicon atom via a linker.
  • the silane with at least one basic group is preferably selected from the group consisting of
  • (3-aminopropyl) triethoxysilane and / or (3-aminopropyl) trimethoxysilane are preferably used.
  • the metal alkoxide used in the sol-gel process is preferably selected from the group consisting of tetramethyl orthosilicate, tetraethyl orthosilicate, tetraisopropyl orthosilicate and mixtures thereof. Tetraethyl orthosilicate is preferably used. Alternatively or in addition to the
  • alkyltrialkoxysilanes can be used in the sol-gel process to produce layers A and / or C. Particularly preferably, alkyltrialkoxysilanes can be used in addition or as an alternative to a tetraalkoxysilane in the sol-gel process for producing a layer which comprises (i) silicon dioxide as metal oxide and / or metal oxide hydrate and (ii) a coloring compound from the group of pigments.
  • Suitable alkyltrialkoxysilanes include, for example, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, octyltrimethoxysilane, octyltriethoxysilane, dodecyltrimethoxysilane, or octyldoxecyl silane, or octyldoxecyltrimethoxysilane, or octyldoxecyl silane, or octyldoxecyl silane, or octyldoxecyl silane, or octyltriethoxecyl silane
  • the colored silicon dioxide layer makes up around 40% by weight, based on the total weight of the effect pigment.

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Abstract

The invention relates to effect pigments which comprise a) a substrate platelet and b) a covering. The covering comprises at least one layer which comprises (i) a metal oxide and/or metal oxide hydrate and (ii) a dyeing compound from the group of pigments. The invention also relates to a method for dyeing effect pigments.

Description

Farbige Effektpigmente und deren Herstellung Colored effect pigments and their production
Gegenstand der vorliegenden Anmeldung sind Effektpigmente, die ein Substratplättchen und eine Beschichtung umfassen, wobei die Beschichtung mindestens eine Schicht aufweist, die ein Metalloxid und/oder Metalloxidhydrat umfasst. Die Anmeldung beschreibt ferner ein Verfahren zur Herstellung der Effektpigmente. The present application relates to effect pigments which comprise a substrate platelet and a coating, the coating having at least one layer which comprises a metal oxide and / or metal oxide hydrate. The application also describes a process for producing the effect pigments.
Die Veränderung von Form und Farbe von keratinischen Fasern, insbesondere von Haaren, stellt einen wichtigen Bereich der modernen Kosmetik dar. Zur Veränderung der Haarfarbe kennt der Fachmann je nach Anforderung an die Färbung diverse Färbesysteme. Für permanente, intensive Färbungen mit guten Echtheitseigenschaften und guter Grauabdeckung werden üblicherweise Oxidationsfärbemittel verwendet. Solche Färbemittel enthalten üblicherweise Oxidationsfarbstoffvorprodukte, sogenannte The change in the shape and color of keratinic fibers, in particular of hair, represents an important area of modern cosmetics. The person skilled in the art knows various coloring systems for changing the hair color, depending on the coloring requirements. Oxidation dyes are usually used for permanent, intense dyeings with good fastness properties and good gray coverage. Such colorants usually contain oxidation dye precursors, so-called
Entwicklerkomponenten und Kupplerkomponenten, die unter dem Einfluss von Oxidationsmitteln wie beispielsweise Wasserstoffperoxid untereinander die eigentlichen Farbstoffe ausbilden. Developer components and coupler components which, under the influence of oxidizing agents such as hydrogen peroxide, form the actual dyes with one another.
Oxidationsfärbemittel zeichnen sich durch sehr langanhaltende Färbeergebnisse aus. Oxidation dyes are characterized by very long-lasting coloring results.
Bei dem Einsatz von direktziehenden Farbstoffen diffundieren bereits fertig ausgebildete Farbstoffe aus dem Färbemittel in die Haarfaser hinein. Im Vergleich zur oxidativen Haarfärbung weisen die mit direktziehenden Farbstoffen erhaltenen Färbungen eine geringere Haltbarkeit und schnellere If substantive dyes are used, dyes that have already been developed diffuse from the dye into the hair fiber. Compared to oxidative hair coloring, the coloring obtained with substantive coloring agents is shorter and faster
Auswaschbarkeit auf. Färbungen mit direktziehenden Farbstoffen verbleiben üblicherweise für einen Zeitraum zwischen 5 und 20 Haarwäschen auf dem Haar. Washability on. Colorations with substantive dyes usually remain on the hair for a period of between 5 and 20 washes.
Für kurzzeitige Farbveränderungen auf dem Haar und/oder der Haut ist der Einsatz von Farbpigmenten bekannt. Unter Farbpigmenten werden im Allgemeinen unlösliche, farbgebende Substanzen verstanden. Diese liegen ungelöst in Form kleiner Partikel in der Färbeformulierung vor und lagern sich lediglich von außen auf den Haarfasern und/oder der Hautoberfläche ab. Daher lassen sie sich in der Regel durch einige Wäschen mit Tensid-haltigen Reinigungsmitteln wieder rückstandslos entfernen. Unter dem Namen Haar-Mascara sind verschiedene Produkte dieses Typs auf dem Markt erhältlich. The use of color pigments is known for brief color changes on the hair and / or the skin. Color pigments are generally understood to mean insoluble, coloring substances. These are present undissolved in the form of small particles in the coloring formulation and are only deposited on the outside of the hair fibers and / or the skin surface. Therefore, they can usually be removed without residue by a few washes with detergents containing surfactants. Various products of this type are available on the market under the name of hair mascara.
Wünscht sich der Anwender besonders langanhaltende Färbungen, so ist die Verwendung von oxidativen Färbemitteln bislang seine einzige Option. Doch trotz vielfacher Optimierungsversuche lässt sich bei der oxidativen Haarfärbung ein unangenehmer Ammoniakgeruch bzw. Amingeruch nicht vollständig vermeiden. Auch die mit dem Einsatz der oxidativen Färbemittel nach wie vor verbundene If the user wants particularly long-lasting coloring, the use of oxidative coloring agents has so far been his only option. However, despite multiple attempts at optimization, an unpleasant smell of ammonia or amine cannot be completely avoided with oxidative hair coloring. Also those associated with the use of oxidative dyes as before
Haarschädigung wirkt sich auf das Haar des Anwenders nachteilig aus. Hair damage adversely affects the user's hair.
EP 2168633 B1 beschäftigt sich mit der Aufgabenstellung, langanhaltende Haarfärbungen unter Einsatz von Pigmenten zu erzeugen. Die Schrift lehrt, dass sich bei Verwendung der Kombination aus einem Pigment, einer organischer Silicium-Verbindung, einem filmbildenden Polymer und einem Lösungsmittel auf Haaren Färbungen erzeugen lassen, die gegenüber Shampoonierungen besonders widerstandsfähig sind. EP 2168633 B1 deals with the problem of producing long-lasting hair colorations using pigments. The document teaches that when using the combination of a pigment, an organic silicon compound, a film-forming polymer and a solvent Produce colorations on hair that are particularly resistant to shampooing.
Metallische Glanzpigmente oder Metalleffektpigmente finden breite Anwendung in vielen Bereichen der Technik. Sie werden beispielsweise zur Einfärbung von Lacken, Druckfarben, Tinten, Kunststoffen, Gläsern keramischen Produkten und Zubereitungen der dekorativen Kosmetik wie Nagellack eingesetzt. Sie zeichnen sich vor allem durch ihren reizvollen winkelabhängigen Farbeindruck (Goniochromie) und ihren metallartig wirkenden Glanz aus. Metallic luster pigments or metallic effect pigments are widely used in many areas of technology. They are used, for example, for coloring paints, printing inks, inks, plastics, glasses, ceramic products and preparations for decorative cosmetics such as nail polish. They are characterized above all by their attractive angle-dependent color impression (goniochromy) and their metallic-like sheen.
Haare mit einem Metallic Finish oder metallischen Reflexen sind im Trend. Durch den Metallic-Ton wirkt das Haar dicker und glänzender. Hair with a metallic finish or metallic reflections are trendy. The metallic shade makes the hair appear thicker and shinier.
Es besteht Bedarf, Effektpigmente, insbesondere für Haarfärbungen, bereitzustellen, die einerseits eine hohe Wasch- und Reibechtheit und andererseits die Haareigenschaften wie Handhabbarkeit und Haptik nicht negativ beeinträchtigen. Dazu wäre es wünschenswert, wenn die eingesetzten Effektpigmente eine hohe Deckkraft aufwiesen und in dünnen Schichten auf dem Haar aufgebracht werden könnten. Ebenfalls wäre es wünschenswert, wenn mit Hilfe der Effektpigmente ein zu färbendes Material, insbesondere Haare, mit einem breiten Spektrum an metallischen Farben gefärbt werden kann. There is a need to provide effect pigments, in particular for hair colorations, which, on the one hand, have a high wash and rub fastness and, on the other hand, do not adversely affect hair properties such as handling and haptics. For this purpose it would be desirable if the effect pigments used had a high covering power and could be applied to the hair in thin layers. It would also be desirable if, with the aid of the effect pigments, a material to be colored, in particular hair, can be colored with a broad spectrum of metallic colors.
Die Effektpigmente sollten insbesondere für Färbesysteme geeignet sein, die ohne den Einsatz von Oxidationsmitteln und/oder Oxidationsfarbstoffvorprodukte auskommen. The effect pigments should in particular be suitable for coloring systems that do not require the use of oxidizing agents and / or oxidation dye precursors.
Überraschenderweise hat sich nun herausgestellt, dass die vorgenannten Aufgaben hervorragend gelöst werden können durch ein Effektpigment, umfassend a) ein Substratplättchen und b) eine Beschichtung, wobei die Beschichtung mindestens eine Schicht aufweist, die Surprisingly, it has now been found that the aforementioned objects can be achieved outstandingly by an effect pigment comprising a) a substrate platelet and b) a coating, the coating having at least one layer which
(i) ein Metalloxid und/oder Metalloxidhydrat und (i) a metal oxide and / or metal oxide hydrate and
(ii) eine farbgebende Verbindung aus der Gruppe der Pigmente (ii) a coloring compound from the group of pigments
umfasst. includes.
Das Effektpigment weist ein Substratplättchen auf. The effect pigment has a substrate platelet.
Das Substratplättchen weist vorzugsweise eine durchschnittliche Dicke von höchstens 50 nm, vorzugsweise weniger als 30 nm, besonders bevorzugt höchstens 25 nm, beispielsweise höchstens 20 nm auf. Die durchschnittliche Dicke der Substratplättchen beträgt mindestens 1 nm, vorzugsweise mindestens 2,5 nm, besonders bevorzugt mindestens 5 nm, beispielsweise mindestens 10 nm. The substrate platelet preferably has an average thickness of at most 50 nm, preferably less than 30 nm, particularly preferably at most 25 nm, for example at most 20 nm. The average thickness of the substrate platelets is at least 1 nm, preferably at least 2.5 nm, particularly preferably at least 5 nm, for example at least 10 nm.
Bevorzugte Bereiche für die Dicke des Substratplättchens sind 2,5 bis 50 nm, 5 bis 50 nm, 10 bis 50 nm; 2,5 bis 30 nm, 5 bis 30 nm, 10 bis 30 nm; 2,5 bis 25 nm, 5 bis 25 nm, 10 bis 25 nm, 2,5 bis 20 nm, 5 bis 20 nm und 10 bis 20 nm. Vorzugsweise weist jedes Substratplättchen eine möglichst einheitliche Dicke auf. Preferred ranges for the thickness of the substrate plate are 2.5 to 50 nm, 5 to 50 nm, 10 to 50 nm; 2.5 to 30 nm, 5 to 30 nm, 10 to 30 nm; 2.5 to 25 nm, 5 to 25 nm, 10 to 25 nm, 2.5 to 20 nm, 5 to 20 nm and 10 to 20 nm. Each substrate platelet preferably has a thickness that is as uniform as possible.
Das Substratplättchen ist vorzugsweise monolithisch aufgebaut. Monolithisch bedeutet in diesem The substrate plate is preferably constructed monolithically. Monolithic means in this one
Zusammenhang aus einer einzigen abgeschlossenen Einheit ohne Brüche, Schichtungen oder Context from a single closed unit without breaks, stratifications or
Einschlüsse bestehend, wobei jedoch innerhalb des Substratplättchens Gefügewechsel auftreten können. Das Substratplättchen ist vorzugsweise homogen aufgebaut, d.h. dass innerhalb des Plättchens kein Konzentrationsgradient auftritt. Insbesondere ist das Substratplättchen nicht schichtartig aufgebaut und weist keine darin verteilten Teilchen oder Partikel auf. Existing inclusions, but microstructure changes can occur within the substrate platelet. The substrate platelet is preferably constructed homogeneously, i.e. there is no concentration gradient within the platelet. In particular, the substrate platelet is not constructed in layers and has no particles or particles distributed therein.
Die Größe des Substratplättchens kann auf den jeweiligen Anwendungszweck, beispielsweise dem gewünschten Effekt auf einem keratinischen Material, abgestimmt werden. In der Regel haben die Substratplättchen einen mittleren größten Durchmesser von etwa 2 bis 200 pm, insbesondere etwa 5 bis 100 pm. The size of the substrate platelet can be matched to the particular application, for example the desired effect on a keratinic material. As a rule, the substrate platelets have a mean largest diameter of about 2 to 200 μm, in particular about 5 to 100 μm.
In einer bevorzugten Ausführungsform beträgt der Formfaktor (Aspect Ratio), ausgedrückt durch das Verhältnis der mittleren Größe zur durchschnittlichen Dicke, mindestens 80, vorzugsweise mindestens 200, mehr bevorzugt mindestens 500, besonders bevorzugt mehr als 750. Dabei wird als mittlere Größe der un beschichteten Substratplättchen der d50-Wert der unbeschichteten Substratplättchen verstanden. Der d50-Wert wurde, soweit nicht anders angegeben, mit einem Gerät des Typs Sympatec Helos mit Quixel-Nassdispergierung bestimmt. Dabei wurde zur Probenvorbereitung die zu untersuchende Probe für eine Dauer von 3 Minuten in Isopropanol vordispergiert. In a preferred embodiment, the aspect ratio, expressed by the ratio of the mean size to the mean thickness, is at least 80, preferably at least 200, more preferably at least 500, particularly preferably more than 750. The mean size of the uncoated substrate platelets is here understood the d50 value of the uncoated substrate platelets. Unless otherwise stated, the d50 value was determined using a Sympatec Helos device with Quixel wet dispersion. For sample preparation, the sample to be examined was predispersed in isopropanol for a period of 3 minutes.
Das Substratplättchen kann aus jedem Material, das in Plättchenform gebracht werden kann, aufgebaut sein. The substrate platelet can be constructed from any material which can be brought into a platelet shape.
Sie können natürlichen Ursprungs, aber auch synthetisch hergestellt sein. Materialien, aus denen die Substratplättchen aufgebaut sein können, sind beispielsweise Metalle und Metalllegierungen, Metalloxide, vorzugsweise Aluminiumoxid, anorganische Verbindungen und Mineralien wie Glimmer und They can be of natural origin, but also synthetically produced. Materials from which the substrate platelets can be constructed are, for example, metals and metal alloys, metal oxides, preferably aluminum oxide, inorganic compounds and minerals such as mica and
(Halb)Edelsteine, sowie Kunststoffe. Vorzugsweise sind die Substratplättchen aus einem Metall oder einer Legierung aufgebaut. (Semi) precious stones and plastics. The substrate platelets are preferably constructed from a metal or an alloy.
Als Metall kommt jedes, für Effektpigmente geeignete Metall in Betracht. Derartige Metalle sind unter anderem Eisen und Stahl, sowie alle luft- und wasserbeständigen (Halb)metalle wie beispielsweise Platin, Zinn, Zink, Chrom, Molybdän und Silicium, sowie deren Legierungen wie Aluminiumbronzen und Messing. Bevorzugte Metalle sind Aluminium, Kupfer, Silber und Gold. Bevorzugte Substratplättchen sind Any metal suitable for effect pigments can be considered as the metal. Such metals include iron and steel, and all air and water-resistant (semi) metals such as platinum, tin, zinc, chromium, molybdenum and silicon, and their alloys such as aluminum bronze and brass. Preferred metals are aluminum, copper, silver and gold. Preferred substrate platelets are
Aluminiumplättchen und Messingplättchen, wobei Substratplättchen aus Aluminium besonders bevorzugt sind. Substratplättchen aus Aluminium können unter anderem durch Herausstanzen aus Aluminiumfolie oder nach gängigen Mahl- und Verdüsungstechniken hergestellt werden. So sind beispielsweise Aluminum platelets and brass platelets, with aluminum substrate platelets being particularly preferred. Substrate platelets made of aluminum can be produced, among other things, by punching out of aluminum foil or using common grinding and atomizing techniques. So are for example
Aluminiumplättchen aus dem Hallverfahren, einem Nassmahlverfahren, erhältlich. Aluminum plates from the Hall process, a wet grinding process, available.
Andere Metallplättchen, beispielsweise aus Bronze, können in einem Trockenmahlverfahren wie dem Hametagverfahren erhalten werden. Other metal flakes, such as bronze, can be obtained in a dry milling process such as the Hametag process.
Die Substratplättchen können verschiedene Formen aufweisen. Als Substratplättchen können beispielsweise lamellare oder lentikuläre Metallplättchen oder auch sogenannte vacuum metallized Pigments (VMP) verwendet werden. Lamellare Substratplättchen zeichnen sich durch einen unregelmäßig strukturierten Rand aus und werden aufgrund ihres Erscheinungsbildes auch als "cornflakes" bezeichnet. Lentikuläre Sustratplättchen weisen einen im Wesentlichen regelmäßigen runden Rand auf und werden aufgrund ihres Erscheinungsbildes auch als "silverdollars" bezeichnet. The substrate platelets can have various shapes. For example, lamellar or lenticular metal flakes or so-called vacuum metallized pigments (VMP) can be used as substrate flakes. Lamellar substrate platelets are characterized by an irregularly structured edge and are also referred to as "cornflakes" due to their appearance. Lenticular substrate platelets have an essentially regular round edge and are also referred to as "silver dollars" because of their appearance.
Die Substratplättchen aus Metall oder Metalllegierung können passiviert sein, beispielsweise durch Eloxieren (Oxidschicht) oder Chromatieren. The substrate platelets made of metal or metal alloy can be passivated, for example by anodizing (oxide layer) or chromating.
Durch eine Beschichtung können die Oberflächeneigenschaften und/oder optischen Eigenschaften des Effektpigments verändert sowie die mechanische und chemische Belastbarkeit der Effektpigmente erhöht werden. Es können beispielsweise lediglich die obere und/oder untere Seite des Substratplättchens beschichtet sein, wobei die Seitenflächen ausgespart sind. Vorzugsweise ist die gesamte Oberfläche der gegebenenfalls passivierten Substratplättchen, einschließlich der Seitenflächen, von der Schicht bedeckt. Die Substratplättchen sind vorzugsweise vollständig von der Beschichtung umhüllt. By means of a coating, the surface properties and / or optical properties of the effect pigment can be changed and the mechanical and chemical resistance of the effect pigments can be increased. For example, only the upper and / or lower side of the substrate platelet can be coated, with the side surfaces being cut out. The entire surface of the optionally passivated substrate platelets, including the side surfaces, is preferably covered by the layer. The substrate platelets are preferably completely encased by the coating.
Die Beschichtung kann aus einer oder aus mehreren Schichten bestehen. In einer bevorzugten The coating can consist of one or more layers. In a preferred
Ausführungsform weist die Beschichtung lediglich eine Schicht A auf. In einer ebenfalls bevorzugten Ausführungsform weist die Beschichtung insgesamt mindestens zwei, vorzugsweise zwei oder drei, Schichten auf. Es kann bevorzugt sein, die Beschichtung zwei Schichten A und B aufweist, wobei die Schicht B von der Schicht A verschieden ist. Vorzugsweise befindet sich Schicht A zwischen der Schicht B und der Oberfläche des Substratplättchens. In noch einer bevorzugten Ausführungsform weist die Beschichtung drei Schichten A, B und C auf. In dieser Ausführungsform befindet sich zwischen der Schicht B und der Oberfläche des Substratplättchens die Schicht A und auf der Schicht B befindet sich eine Schicht C, die von der darunterliegenden Schicht B verschieden ist. In the embodiment, the coating has only one layer A. In a likewise preferred embodiment, the coating has a total of at least two, preferably two or three, layers. It may be preferred for the coating to have two layers A and B, layer B being different from layer A. Layer A is preferably located between layer B and the surface of the substrate wafer. In yet another preferred embodiment, the coating has three layers A, B and C. In this embodiment, layer A is located between layer B and the surface of the substrate platelet, and layer C is located on layer B, which layer is different from layer B below.
Als Materialien für die Schichten A und gegebenenfalls B und C eignen sich alle Substanzen, die dauerhaft auf die Substratplättchen aufgebracht werden können. Die Materialien sollten mit Vorzug filmartig aufbringbar sein. Vorzugsweise ist die gesamte Oberfläche der gegebenenfalls passivierten Substratplättchen, einschließlich der Seitenflächen, von der Schicht A oder von den Schichten A und B oder von den Schichten A, B und C umhüllt. Suitable materials for the layers A and optionally B and C are all substances that can be permanently applied to the substrate platelets. The materials should preferably be able to be applied in film form. Preferably, the entire surface is the optionally passivated Substrate platelets, including the side surfaces, are encased by layer A or by layers A and B or by layers A, B and C.
Es ist bevorzugt, dass das Metalloxid und/oder Metalloxidhydrat (i) ausgewählt ist aus der Gruppe bestehend aus Silicium(di)oxid, Siliciumoxidhydrat, Aluminiumoxid, Aluminiumoxidhydrat, Boroxid, Germaniumoxid, Manganoxid, Magnesiumoxid, Eisenoxid, Cobaltoxid, Chromoxid, Titandioxid, It is preferred that the metal oxide and / or metal oxide hydrate (i) is selected from the group consisting of silicon (di) oxide, silicon oxide hydrate, aluminum oxide, aluminum oxide hydrate, boron oxide, germanium oxide, manganese oxide, magnesium oxide, iron oxide, cobalt oxide, chromium oxide, titanium dioxide,
Vanadiumoxid, Zirkonoxid, Zinnoxid, Zinkoxid und deren Gemischen. Vanadium oxide, zirconium oxide, tin oxide, zinc oxide and mixtures thereof.
Die Schicht A weist vorzugsweise mindestens ein niedrigbrechendes Metalloxid und/oder Metalloxidhydrat auf. Vorzugsweise umfasst Schicht A mindestens 95 Gew.-% niedrigbrechendes Metalloxid(hydrat). Niedrigbrechende Materialien weisen einen Brechungsindex von höchstens 1 ,8, bevorzugt höchstens 1 ,6 auf. The layer A preferably has at least one low refractive index metal oxide and / or metal oxide hydrate. Layer A preferably comprises at least 95% by weight of low-refractive-index metal oxide (hydrate). Low refractive index materials have a refractive index of at most 1.8, preferably at most 1.6.
Zu den niedrigbrechenden Metalloxiden, die für die Schicht A geeignet sind, zählen beispielsweise Silicium(di)oxid, Siliciumoxidhydrat, Aluminiumoxid, Aluminiumoxidhydrat, Boroxid, Germaniumoxid, Manganoxid, Magnesiumoxid und deren Gemische, wobei Siliciumdioxid bevorzugt ist. Die Schicht A weist bevorzugt eine Dicke von 1 bis 100 nm, besonders bevorzugt 5 bis 50 nm, insbesondere bevorzugt 5 bis 20 nm, auf. The low refractive index metal oxides which are suitable for layer A include, for example, silicon (di) oxide, silicon oxide hydrate, aluminum oxide, aluminum oxide hydrate, boron oxide, germanium oxide, manganese oxide, magnesium oxide and mixtures thereof, silicon dioxide being preferred. The layer A preferably has a thickness of 1 to 100 nm, particularly preferably 5 to 50 nm, particularly preferably 5 to 20 nm.
Die Schicht B, falls vorhanden, ist von der Schicht A verschieden und kann mindestens ein Layer B, if present, is different from layer A and can include at least one
hochbrechendes Metalloxid enthalten. Hochbrechende Materialien weisen einen Brechungsindex von mindestens 1 ,9, bevorzugt mindestens 2,0 und besonders bevorzugt mindestens 2,4 auf. Vorzugsweise umfasst die Schicht B mindestens 95 Gew.-%, besonders bevorzugt mindestens 99 Gew.-% an hochbrechenden Metalloxid(en). contain highly refractive metal oxide. High refractive index materials have a refractive index of at least 1.9, preferably at least 2.0 and particularly preferably at least 2.4. Layer B preferably comprises at least 95% by weight, particularly preferably at least 99% by weight, of high-index metal oxide (s).
Enthält die Schicht B ein (hochbrechendes) Metalloxid, weist sie vorzugsweise eine Dicke von mindestens 50 nm auf. Vorzugsweise beträgt die Dicke von Schicht B nicht mehr als 400 nm, besonders bevorzugt höchstens 300 nm. If the layer B contains a (highly refractive) metal oxide, it preferably has a thickness of at least 50 nm. The thickness of layer B is preferably not more than 400 nm, particularly preferably at most 300 nm.
Für Schicht B geeignete hochbrechende Metalloxide sind beispielsweise selektiv lichtabsorbierende (d.h. farbige) Metalloxide, wie beispielsweise Eisen(lll)oxid (a- und y-Fe203, rot), Cobalt(ll)oxid (blau), Chrom(lll)oxid (grün),Titan(lll)oxid (blau, liegt üblicherweise im Gemisch mit Titanoxynitriden und High refractive index metal oxides suitable for layer B are, for example, selectively light-absorbing (ie colored) metal oxides such as iron (III) oxide (a- and y-Fe 2 O 3, red), cobalt (II) oxide (blue), chromium (III) oxide (green) ), Titanium (III) oxide (blue, is usually mixed with titanium oxynitrides and
Titannitriden vor) und Vanadium(V)oxid (orange) sowie deren Gemische. Es eignen sich auch farblose hochbrechende Oxide wie Titandioxid und/oder Zirkonoxid. Titanium nitrides before) and vanadium (V) oxide (orange) and their mixtures. Colorless, high-index oxides such as titanium dioxide and / or zirconium oxide are also suitable.
Schicht B kann zusätzlich zu einem hochbrechenden Metalloxid einen selektiv absorbierenden Farbstoff enthalten, vorzugsweise 0,001 bis 5 Gew.-%, besonders bevorzugt 0,01 bis 1 Gew.-%, jeweils bezogen auf die Gesamtmenge der Schicht B. Geeignet sind organische und anorganische Farbstoffe, die sich stabil in eine Metalloxidbeschichtung einbauen lassen. Farbstoffe im Sinne der vorliegenden Erfindung besitzen eine Löslichkeit in Wasser (760 mmHg) bei 25 °C von mehr als 0,5 g/L und sind daher nicht als Pigmente anzusehen. In addition to a high-index metal oxide, layer B can contain a selectively absorbing dye, preferably 0.001 to 5% by weight, particularly preferably 0.01 to 1% by weight, based in each case on the total amount of layer B. Organic and inorganic dyes are suitable , which can be stably built into a metal oxide coating. For the purposes of the present invention, dyes have a solubility in water (760 mmHg) at 25 ° C. of more than 0.5 g / L and are therefore not to be regarded as pigments.
Alternativ zu einem Metalloxid kann Schicht B eine Metallpartikelträgerschicht mit auf der Oberfläche der Metallpartikelträgerschicht aufgebrachten Metallpartikeln umfassen. In einer bevorzugten As an alternative to a metal oxide, layer B can comprise a metal particle carrier layer with metal particles applied to the surface of the metal particle carrier layer. In a preferred
Ausführungsform bedecken die Metallpartikel direkt einen Teil der Metallpartikelträgerschicht. In dieser Ausführungsform weist das Effektpigment Bereiche auf, in denen sich keine Metallpartikel befinden, d.h. Bereiche, die nicht mit den Metallpartikeln bedeckt sind. Embodiment, the metal particles directly cover part of the metal particle carrier layer. In this embodiment, the effect pigment has areas in which there are no metal particles, i.e. areas which are not covered with the metal particles.
Die Metallpartikelträgerschicht eine Metallschicht und/oder eine Metalloxidschicht umfassen. The metal particle carrier layer comprises a metal layer and / or a metal oxide layer.
Wenn die Metallpartikelträgerschicht eine Metallschicht und eine Metalloxidschicht umfasst, ist die Anordnung dieser Schichten nicht limitiert. If the metal particle carrier layer comprises a metal layer and a metal oxide layer, the arrangement of these layers is not limited.
Es ist bevorzugt, dass die Metallpartikelträgerschicht wenigstens eine Metallschicht umfasst. Es ferner bevorzugt, dass die Metallschicht ein Element ausgewählt aus Zinn (Sn), Palladium (Pd), Platin (Pt) und Gold (Au) aufweist. It is preferred that the metal particle carrier layer comprises at least one metal layer. It is further preferred that the metal layer has an element selected from tin (Sn), palladium (Pd), platinum (Pt) and gold (Au).
Die Metallschicht kann beispielsweise durch Zugabe von Alkali zu einer das Metall enthaltenden Metallsalzlösung gebildet werden. The metal layer can be formed, for example, by adding alkali to a metal salt solution containing the metal.
Enthält die Metallpartikelträgerschicht eine Metalloxidschicht, umfasst diese vorzugsweise kein If the metal particle carrier layer contains a metal oxide layer, this preferably does not include any
Siliciumdioxid. Die Metalloxidschicht enthält vorzugsweise ein Oxid von mindestens einem Element, ausgewählt aus der Gruppe bestehend aus von Mg (Magnesium), Sn (Zinn), Zn (Zink), Co (Kobalt), Ni (Nickel), Fe (Eisen), Zr (Zirkonium), Ti (Titan) und Ce (Cer). Besonders bevorzugt enthält die Silicon dioxide. The metal oxide layer preferably contains an oxide of at least one element selected from the group consisting of Mg (magnesium), Sn (tin), Zn (zinc), Co (cobalt), Ni (nickel), Fe (iron), Zr ( Zirconium), Ti (titanium) and Ce (cerium). Particularly preferably contains
Metallpartikelträgerschicht iii) in Form einer Metalloxidschicht ein Metalloxid von Sn, Zn, Ti und Ce. Metal particle carrier layer iii) in the form of a metal oxide layer, a metal oxide of Sn, Zn, Ti and Ce.
Die Herstellung der Metallpartikelträgerschicht in Form einer Metalloxidschicht kann beispielsweise durch Hydrolyse eines Alkoxids eines Metalls, das das Metall des Metalloxids bildet, in einem Sol-Gel Verfahren erfolgen. The production of the metal particle carrier layer in the form of a metal oxide layer can take place, for example, by hydrolysis of an alkoxide of a metal, which forms the metal of the metal oxide, in a sol-gel process.
Die Dicke der Metallpartikelträgerschicht beträgt vorzugsweise nicht mehr als 30 nm. The thickness of the metal particle carrier layer is preferably not more than 30 nm.
Die Metallpartikel kann wenigstens ein Element umfassen, welches ausgewählt ist aus der Gruppe bestehend aus Aluminium (AI), Titan (Ti), Chrom (Cr), Eisen (Fe), Kobalt (Co), Nickel (Ni), Kupfer (Cu), Zink (Zn), Ruthenium (Ru), Rhodium (Rh), Palladium (Pd), Silber (Ag), Zinn (Sn), Platin (Pt), Gold (Au) und deren Legierungen. Es ist insbesondere bevorzugt, dass die Metallpartikel wenigstens ein Element ausgewählt aus Kupfer (Cu), Nickel (Ni) und Silber (Ag) aufweisen. The metal particles can include at least one element selected from the group consisting of aluminum (Al), titanium (Ti), chromium (Cr), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu) , Zinc (Zn), ruthenium (Ru), rhodium (Rh), palladium (Pd), silver (Ag), tin (Sn), platinum (Pt), gold (Au) and their alloys. It is particularly preferred that the metal particles have at least one element selected from copper (Cu), nickel (Ni) and silver (Ag).
Der durchschnittliche Partikeldurchmesser der Metallpartikel beträgt vorzugsweise nicht mehr als 50 nm, mehr bevorzugt nicht mehr als 30 nm. Der Abstand zwischen den Metallpartikeln beträgt vorzugsweise nicht mehr als 10 nm. The average particle diameter of the metal particles is preferably not more than 50 nm, more preferably not more than 30 nm. The distance between the metal particles is preferably not more than 10 nm.
Als Verfahren zur Bildung der Metallpartikel eignen sich Vakuumverdampfung, Sputtern, Chemical Vapor Deposition (CVD), stromloses Plattieren oder dergleichen. Von diesen Verfahren ist das stromlose Plattieren besonders bevorzugt. Suitable methods for forming the metal particles are vacuum evaporation, sputtering, chemical vapor deposition (CVD), electroless plating, or the like. Of these methods, electroless plating is particularly preferred.
Gemäß einer bevorzugten Ausführungsform weisen die Effektpigmente eine weitere Schicht C, umfassend ein Metalloxid(hydrat), die von der darunterliegenden Schicht B verschieden ist, auf. According to a preferred embodiment, the effect pigments have a further layer C, comprising a metal oxide (hydrate), which is different from the layer B below.
Geeignete Metalloxide sind beispielsweise Silicium(di)oxid, Siliciumoxidhydrat, Aluminiumoxid, Suitable metal oxides are, for example, silicon (di) oxide, silicon oxide hydrate, aluminum oxide,
Aluminiumoxidhydrat, Zinkoxid, Zinnoxid, Titandioxid, Zirkonoxid, Eisen(lll)oxid und Chrom(lll)oxid. Aluminum oxide hydrate, zinc oxide, tin oxide, titanium dioxide, zirconium oxide, iron (III) oxide and chromium (III) oxide.
Bevorzugt ist Siliciumdioxid. Silica is preferred.
Die Schicht C weist vorzugsweise eine Dicke von 10 bis 500 nm, besonders bevorzugt 50 bis 300 nm auf. The layer C preferably has a thickness of 10 to 500 nm, particularly preferably 50 to 300 nm.
Die Beschichtung des Effektpigments weist mindestens eine Schicht auf, die neben dem Metalloxid und/oder dem Metalloxidhydrat ferner eine farbgebende Verbindung aus der Gruppe der Pigmente umfasst. The coating of the effect pigment has at least one layer which, in addition to the metal oxide and / or the metal oxide hydrate, also comprises a coloring compound from the group of pigments.
Die mindestens eine Schicht, die (i) ein Metalloxid und/oder Metalloxidhydrat und (ii) eine farbgebende Verbindung aus der Gruppe der Pigmente umfasst, kann Schicht A, B und/oder C sein. Im Fall, dass die Beschichtung lediglich eine Schicht A aufweist, enthält die Schicht A auch die farbgebende Verbindung aus der Gruppe der Pigmente. The at least one layer, which comprises (i) a metal oxide and / or metal oxide hydrate and (ii) a coloring compound from the group of pigments, can be layer A, B and / or C. In the event that the coating has only one layer A, the layer A also contains the coloring compound from the group of pigments.
Im Fall, dass die Beschichtung des Effektpigments zwei Schichten A und B aufweist und jede ein In the event that the coating of the effect pigment has two layers A and B and each one
Metalloxid umfasst, können beide Schichten A und B oder nur eine der beiden Schichten die farbgebende Verbindung aus der Gruppe der Pigmente umfassen. Vorzugsweise enthält Schicht A die farbgebende Verbindung aus der Gruppe der Pigmente. If metal oxide comprises, both layers A and B or only one of the two layers can comprise the coloring compound from the group of pigments. Layer A preferably contains the coloring compound from the group of pigments.
Im Fall, dass die Beschichtung die Schichten A, B und C aufweist und jede ein Metalloxid(hydrat) umfasst, kann jede der Schichten A, B und C eine farbgebende Verbindung aus der Gruppe der Pigmente enthalten. Alternativ können in dieser Ausführungsform zwei der drei Schichten die farbgebende In the event that the coating has layers A, B and C and each comprises a metal oxide (hydrate), each of layers A, B and C can contain a coloring compound from the group of pigments. Alternatively, in this embodiment, two of the three layers can be the coloring
Verbindung aus der Gruppe der Pigmente enthalten. Entsprechend kann die farbgebende Verbindung aus der Gruppe der Pigmente in Schicht A und B, in Schicht A und C oder in Schicht B und C sein. Ebenso kann nur eine der drei Schichten eine farbgebende Verbindung aus der Gruppe der Pigmente umfassen. Entsprechend kann die farbgebende Verbindung aus der Gruppe der Pigmente in Schicht A, B oder C sein. In einer besonders bevorzugten Ausführungsform eines Effektpigments, umfassend eine Compound from the group of pigments. Correspondingly, the coloring compound from the group of pigments can be in layers A and B, in layers A and C or in layers B and C. As well only one of the three layers can comprise a coloring compound from the group of pigments. Correspondingly, the coloring compound from the group of pigments in layer A, B or C can be. In a particularly preferred embodiment of an effect pigment, comprising a
Beschichtung mit den Schichten A, B und C, ist die farbgebende Verbindung aus der Gruppe der Pigmente in Schicht A und/oder C. Coating with layers A, B and C is the coloring compound from the group of pigments in layer A and / or C.
Im Fall, dass die Beschichtung die Schichten A, B und C aufweist, die Schichten A und C ein In the case that the coating has layers A, B and C, layers A and C are included
Metalloxid(hydrat) umfassen und die Schicht B eine Metallschicht mit darauf aufgebrachten Metallpartikeln umfasst, kann jede der Schichten A und C eine farbgebende Verbindung aus der Gruppe der Pigmente enthalten. Alternativ kann in dieser Ausführungsform nur eine der Schichten A und C die farbgebende Verbindung aus der Gruppe der Pigmente enthalten. Comprise metal oxide (hydrate) and the layer B comprises a metal layer with metal particles applied thereon, each of the layers A and C can contain a coloring compound from the group of pigments. Alternatively, in this embodiment only one of the layers A and C can contain the coloring compound from the group of pigments.
In einer besonders bevorzugten Ausführungsform eines Effektpigments, umfassend eine Beschichtung mit den Schichten A, B und C, ist die farbgebende Verbindung aus der Gruppe der Pigmente in Schicht A und/oder C. In a particularly preferred embodiment of an effect pigment comprising a coating with layers A, B and C, the coloring compound from the group of pigments is in layer A and / or C.
Es ist insbesondere bevorzugt, dass das Effektpigment ein Substratplättchen aus Aluminium und eine Schicht A, umfassend Siliciumdioxid, aufweist. Weist das Effektpigment auf Basis eines It is particularly preferred for the effect pigment to have a substrate platelet made of aluminum and a layer A comprising silicon dioxide. Has the effect pigment based on a
Substratplättchens eine Schicht A und eine Schicht C auf, ist es bevorzugt, dass das Effektpigment ein Substratplättchen aus Aluminium und Schichten A und C, umfassend Siliciumdioxid, aufweist. If the substrate platelet has a layer A and a layer C, it is preferred that the effect pigment has a substrate platelet made of aluminum and layers A and C comprising silicon dioxide.
Unter Pigmenten im Sinne der vorliegenden Erfindung werden farbgebende Verbindungen verstanden, welche bei 25 °C in Wasser eine Löslichkeit von weniger als 0,5 g/L, bevorzugt von weniger als 0,1 g/L, noch weiter bevorzugt von weniger als 0,05 g/L besitzen. Die Wasserlöslichkeit kann beispielsweise mittels der nachfolgend beschriebenen Methode erfolgen: 0,5 g des Pigments werden in einem Pigments in the context of the present invention are understood to mean coloring compounds which at 25 ° C. in water have a solubility of less than 0.5 g / L, preferably less than 0.1 g / L, even more preferably less than 0, 05 g / L. The water solubility can for example take place by means of the method described below: 0.5 g of the pigment are in one
Becherglas abgewogen. Ein Rührfisch wird hinzugefügt. Dann wird ein Liter destilliertes Wasser hinzugegeben. Dieses Gemisch wird unter Rühren auf einem Magnetrührer für eine Stunde auf 25 °C erhitzt. Sind in der Mischung nach diesem Zeitraum noch ungelöste Bestandteile des Pigments sichtbar, so liegt die Löslichkeit des Pigments unterhalb von 0,5 g/L. Sofern sich die Pigment-Wasser-Mischung aufgrund der hohen Intensität des gegebenenfalls feindispergiert vorliegenden Pigments nicht visuell beurteilten lässt, wird die Mischung filtriert. Bleibt auf dem Filterpapier ein Anteil an ungelösten Pigmenten zurück, so liegt die Löslichkeit des Pigments unterhalb von 0,5 g/L. Weighed beaker. A stir fry is added. Then one liter of distilled water is added. This mixture is heated to 25 ° C. for one hour while stirring on a magnetic stirrer. If undissolved constituents of the pigment are still visible in the mixture after this period, the solubility of the pigment is below 0.5 g / L. If the pigment-water mixture cannot be assessed visually due to the high intensity of the pigment which may be present in finely dispersed form, the mixture is filtered. If a proportion of undissolved pigments remains on the filter paper, the solubility of the pigment is below 0.5 g / L.
Geeignete Farbpigmente können anorganischen und/oder organischen Ursprungs sein. Suitable color pigments can be of inorganic and / or organic origin.
In einer bevorzugten Ausführungsform weist das Effektpigment mindestens eine farbgebende Verbindung aus der Gruppe der anorganischen und/oder organischen Pigmente auf. Bevorzugte Farbpigmente sind ausgewählt aus synthetischen oder natürlichen anorganischen Pigmenten. Anorganische Farbpigmente natürlichen Ursprungs können beispielsweise aus Kreide, Ocker, Umbra, Grünerde, gebranntem Terra di Siena oder Graphit hergestellt werden. Weiterhin können als In a preferred embodiment, the effect pigment has at least one coloring compound from the group of inorganic and / or organic pigments. Preferred color pigments are selected from synthetic or natural inorganic pigments. Inorganic color pigments of natural origin can be made from chalk, ocher, umber, green earth, burnt Terra di Siena or graphite, for example. Furthermore, as
anorganische Farbpigmente Schwarzpigmente wie z. B. Eisenoxidschwarz, Buntpigmente wie z. B. inorganic color pigments black pigments such as B. iron oxide black, colored pigments such. B.
Ultramarin oder Eisenoxidrot sowie Fluoreszenz- oder Phosphoreszenzpigmente eingesetzt werden. Ultramarine or iron oxide red and fluorescent or phosphorescent pigments can be used.
Besonders geeignet sind farbige Metalloxide, -hydroxide und -oxidhydrate, Mischphasenpigmente, schwefelhaltige Silicate, Silicate, Metallsulfide, komplexe Metallcyanide, Metallsulfate, -Chromate und/oder -molybdate. Insbesondere bevorzugte Farbpigmente sind schwarzes Eisenoxid (CI 77499), gelbes Eisenoxid (CI 77492), rotes und braunes Eisenoxid (CI 77491), Manganviolett (CI 77742), Ultramarine (Natrium-Aluminiumsulfosilikate, CI 77007, Pigment Blue 29), Chromoxidhydrat (CI77289), Eisenblau (Ferric Ferrocyanide, CI77510) und/oder Carmine (Cochineal). Colored metal oxides, hydroxides and oxide hydrates, mixed-phase pigments, sulfur-containing silicates, silicates, metal sulfides, complex metal cyanides, metal sulfates, metal chromates and / or molybdates are particularly suitable. Particularly preferred color pigments are black iron oxide (CI 77499), yellow iron oxide (CI 77492), red and brown iron oxide (CI 77491), manganese violet (CI 77742), ultramarines (sodium aluminum sulfosilicates, CI 77007, Pigment Blue 29), chromium oxide hydrate (CI77289 ), Iron blue (Ferric Ferrocyanide, CI77510) and / or carmine (Cochineal).
Ebenfalls besonders bevorzugte Farbpigmente sind farbige Perlglanzpigmente. Diese basieren üblicherweise auf Mica- und/oder Glimmerbasis und können mit einem oder mehreren Metalloxiden beschichtet sein. Glimmer gehört zu den Schicht-Silicaten. Die wichtigsten Vertreter dieser Silicate sind Muscovit, Phlogopit, Paragonit, Biotit, Lepidolith und Margarit. Zur Herstellung der Perlglanzpigmente in Verbindung mit Metalloxiden wird der Glimmer, überwiegend Muscovit oder Phlogopit, mit einem Colored pigments which are also particularly preferred are colored pearlescent pigments. These are usually based on mica and / or mica and can be coated with one or more metal oxides. Mica is one of the layered silicates. The most important representatives of these silicates are muscovite, phlogopite, paragonite, biotite, lepidolite and margarite. To produce the pearlescent pigments in connection with metal oxides, the mica, predominantly muscovite or phlogopite, is mixed with a
Metalloxid beschichtet. Metal oxide coated.
Alternativ zu natürlichem Glimmer kann auch ggfs mit einem oder mehrere Metalloxide(en) beschichtetes, synthetisches Mica als Perlglanzpigment verwendet werden. Besonders bevorzugte Perlglanzpigmente basieren auf natürlichem oder synthetischem Mica (Glimmer) und sind mit einem oder mehreren der zuvor genannten Metalloxide beschichtet. Die Farbe der jeweiligen Pigmente kann durch Variation der As an alternative to natural mica, synthetic mica coated with one or more metal oxide (s) can also be used as a pearlescent pigment. Particularly preferred pearlescent pigments are based on natural or synthetic mica (mica) and are coated with one or more of the aforementioned metal oxides. The color of the respective pigments can be changed by varying the
Schichtdicke des oder der Metalloxids(e) variiert werden. Layer thickness of the metal oxide (s) can be varied.
Ebenfalls bevorzugte Pigmente auf Glimmerbasis sind mit Metalloxid beschichtete synthetisch hergestellte Glimmerplättchen, insbesondere basierend auf synthetischem Fluorphlogopit (INCI: Synthetic Likewise preferred pigments based on mica are synthetically produced mica flakes coated with metal oxide, in particular based on synthetic fluorophlogopite (INCI: Synthetic
Fluorphlogopite). Die synthetischen Fluorphlogopitplättchen sind beispielsweise mit Zinnoxid, Fluorophlogopite). The synthetic fluorophlogopite platelets are, for example, with tin oxide,
Eisenoxid(en) und/oder Titandioxid beschichtet. Die Metalloxidschichten können ferner Pigmente wie Eisen(lll)-hexacyanidoferrat(ll/lll) oder Karminrot aufweisen. Solche Glimmerpigmente sind beispielsweise unter der Bezeichnung SYNCRYSTAL von Eckart erhältlich. Iron oxide (s) and / or titanium dioxide coated. The metal oxide layers can also have pigments such as iron (III) hexacyanidoferrate (II / III) or carmine red. Such mica pigments are available, for example, under the name SYNCRYSTAL from Eckart.
Entsprechend ist ein bevorzugtes Effektpigment dadurch gekennzeichnet, dass es mindestens eine farbgebende Verbindung aus der Gruppe der Pigmente enthält, die ausgewählt ist aus der Gruppe der farbigen Metalloxide, Metallhydroxide, Metalloxidhydrate, Silicate, Metallsulfide, komplexen Metallcyanide, Metallsulfate, Bronzepigmente und/oder aus farbigen Pigmenten auf Mica- oder Glimmerbasis, die mit mindestens einem Metalloxid und/oder einem Metalloxychlorid beschichtet sind. In einer weiteren bevorzugten Ausführungsform ist das Effektpigment dadurch gekennzeichnet, dass es mindestens eine farbgebende Verbindung aus der Gruppe der Pigmente enthält, die ausgewählt ist aus Pigmenten auf Mica- oder Glimmerbasis, die mit einem oder mehreren Metalloxiden aus der Gruppe aus Titandioxid (CI 77891), schwarzem Eisenoxid (CI 77499), gelbem Eisenoxid (CI 77492), rotem und/oder braunem Eisenoxid (CI 77491 , CI 77499), Manganviolett (CI 77742), Ultramarine (Natrium- Aluminiumsulfosilikate, CI 77007, Pigment Blue 29), Chromoxidhydrat (CI 77289), Chromoxid (CI 77288) und/oder Eisenblau (Ferric Ferrocyanide, CI 77510) beschichtet sind. Correspondingly, a preferred effect pigment is characterized in that it contains at least one coloring compound from the group of pigments, which is selected from the group of colored metal oxides, metal hydroxides, metal oxide hydrates, silicates, metal sulfides, complex metal cyanides, metal sulfates, bronze pigments and / or colored Pigments based on mica or mica coated with at least one metal oxide and / or a metal oxychloride. In a further preferred embodiment, the effect pigment is characterized in that it contains at least one coloring compound from the group of pigments, which is selected from pigments based on mica or mica, which are mixed with one or more metal oxides from the group of titanium dioxide (CI 77891) , black iron oxide (CI 77499), yellow iron oxide (CI 77492), red and / or brown iron oxide (CI 77491, CI 77499), manganese violet (CI 77742), ultramarines (sodium aluminum sulfosilicates, CI 77007, pigment blue 29), chromium oxide hydrate (CI 77289), chromium oxide (CI 77288) and / or iron blue (Ferric Ferrocyanide, CI 77510) are coated.
Weitere geeignete Pigmente basieren auf Metalloxid-beschichteten plättchenförmigen Borosilikaten. Diese sind beispielsweise mit Zinnoxid, Eisenoxid(en), Siliciumdioxid und/oder Titandioxid beschichtet. Solche Borosilikat-basierten Pigmente sind beispielsweise unter der Bezeichnung MIRAGE von Eckart oder Reflecks von BASF SE erhältlich. Further suitable pigments are based on metal oxide-coated platelet-shaped borosilicates. These are coated, for example, with tin oxide, iron oxide (s), silicon dioxide and / or titanium dioxide. Such borosilicate-based pigments are available, for example, under the name MIRAGE from Eckart or Reflecks from BASF SE.
Beispiele für besonders geeignete Pigmente sind im Handel beispielsweise unter den Examples of particularly suitable pigments are commercially available, for example under
Handelsbezeichnungen Rona®, Colorona®, Xirona®, Dichrona® und Timiron® von der Firma Merck, Ariabel® und Unipure® von der Firma Sensient, Prestige® von der Firma Eckart Cosmetic Colors, Flamenco®, Cellini®, Cloisonne®, Duocrome®, Gemtone®, Timica®, MultiReflections, Chione von der Firma BASF SE und Sunshine® von der Firma Sunstar erhältlich. Trade names Rona®, Colorona®, Xirona®, Dichrona® and Timiron® from Merck, Ariabel® and Unipure® from Sensient, Prestige® from Eckart Cosmetic Colors, Flamenco®, Cellini®, Cloisonne®, Duocrome® , Gemtone®, Timica®, MultiReflections, Chione from BASF SE and Sunshine® from Sunstar.
Ganz besonders bevorzugte Pigmente mit der Handelsbezeichnung Colorona® sind beispielsweise: Colorona Copper, Merck, MICA, CI 77491 (IRON OXIDES) Very particularly preferred pigments with the trade name Colorona® are, for example: Colorona Copper, Merck, MICA, CI 77491 (IRON OXIDES)
Colorona Passion Orange, Merck, Mica, CI 77491 (Iran Oxides), Alumina Colorona Passion Orange, Merck, Mica, CI 77491 (Iran Oxides), Alumina
Colorona Patina Silver, Merck, MICA, CI 77499 (IRON OXIDES), CI 77891 (TITANIUM DIOXIDE) Colorona Patina Silver, Merck, MICA, CI 77499 (IRON OXIDES), CI 77891 (TITANIUM DIOXIDE)
Colorona RY, Merck, CI 77891 (TITANIUM DIOXIDE), MICA, CI 75470 (CARMINE) Colorona RY, Merck, CI 77891 (TITANIUM DIOXIDE), MICA, CI 75470 (CARMINE)
Colorona Oriental Beige, Merck, MICA, CI 77891 (TITANIUM DIOXIDE), CI 77491 (IRON OXIDES) Colorona Dark Blue, Merck, MICA, TITANIUM DIOXIDE, FERRIC FERROCYANIDE Colorona Oriental Beige, Merck, MICA, CI 77891 (TITANIUM DIOXIDE), CI 77491 (IRON OXIDES) Colorona Dark Blue, Merck, MICA, TITANIUM DIOXIDE, FERRIC FERROCYANIDE
Colorona Chameleon, Merck, CI 77491 (IRON OXIDES), MICA Colorona Chameleon, Merck, CI 77491 (IRON OXIDES), MICA
Colorona Aborigine Amber, Merck, MICA, CI 77499 (IRON OXIDES), CI 77891 (TITANIUM DIOXIDE) Colorona Blackstar Blue, Merck, CI 77499 (IRON OXIDES), MICA Colorona Aborigine Amber, Merck, MICA, CI 77499 (IRON OXIDES), CI 77891 (TITANIUM DIOXIDES) Colorona Blackstar Blue, Merck, CI 77499 (IRON OXIDES), MICA
Colorona Patagonian Purple, Merck, MICA, CI 77491 (IRON OXIDES), CI 77891 (TITANIUM DIOXIDE), Colorona Patagonian Purple, Merck, MICA, CI 77491 (IRON OXIDES), CI 77891 (TITANIUM DIOXIDE),
CI 77510 (FERRIC FERROCYANIDE) CI 77510 (FERRIC FERROCYANIDE)
Colorona Red Brown, Merck, MICA, CI 77491 (IRON OXIDES), CI 77891 (TITANIUM DIOXIDE) Colorona Red Brown, Merck, MICA, CI 77491 (IRON OXIDES), CI 77891 (TITANIUM DIOXIDE)
Colorona Russet, Merck, CI 77491 (TITANIUM DIOXIDE), MICA, CI 77891 (IRON OXIDES) Colorona Russet, Merck, CI 77491 (TITANIUM DIOXIDES), MICA, CI 77891 (IRON OXIDES)
Colorona Imperial Red, Merck, MICA, TITANIUM DIOXIDE (CI 77891), D&C RED NO. 30 (CI 73360) Colorona Majestic Green, Merck, CI 77891 (TITANIUM DIOXIDE), MICA, CI 77288 Colorona Imperial Red, Merck, MICA, TITANIUM DIOXIDE (CI 77891), D&C RED NO. 30 (CI 73360) Colorona Majestic Green, Merck, CI 77891 (TITANIUM DIOXIDE), MICA, CI 77288
(CHROMIUM OXIDE GREENS) Colorona Light Blue, Merck, MICA, TITANIUM DIOXIDE (CI 77891), FERRIC FERROCYANIDE (CI 77510) (CHROMIUM OXIDE GREENS) Colorona Light Blue, Merck, MICA, TITANIUM DIOXIDE (CI 77891), FERRIC FERROCYANIDE (CI 77510)
Colorona Red Gold, Merck, MICA, CI 77891 (TITANIUM DIOXIDE), CI 77491 (IRON OXIDES) Colorona Red Gold, Merck, MICA, CI 77891 (TITANIUM DIOXIDE), CI 77491 (IRON OXIDES)
Colorona Gold Plus MP 25, Merck, MICA, TITANIUM DIOXIDE (CI 77891), IRON OXIDES (CI 77491) Colorona Carmine Red, Merck, MICA, TITANIUM DIOXIDE, CARMINE Colorona Gold Plus MP 25, Merck, MICA, TITANIUM DIOXIDE (CI 77891), IRON OXIDES (CI 77491) Colorona Carmine Red, Merck, MICA, TITANIUM DIOXIDE, CARMINE
Colorona Blackstar Green, Merck, MICA, CI 77499 (IRON OXIDES) Colorona Blackstar Green, Merck, MICA, CI 77499 (IRON OXIDES)
Colorona Bordeaux, Merck, MICA, CI 77491 (IRON OXIDES) Colorona Bordeaux, Merck, MICA, CI 77491 (IRON OXIDES)
Colorona Bronze, Merck, MICA, CI 77491 (IRON OXIDES) Colorona Bronze, Merck, MICA, CI 77491 (IRON OXIDES)
Colorona Bronze Fine, Merck, MICA, CI 77491 (IRON OXIDES) Colorona Bronze Fine, Merck, MICA, CI 77491 (IRON OXIDES)
Colorona Fine Gold MP 20, Merck, MICA, CI 77891 (TITANIUM DIOXIDE), CI 77491 (IRON OXIDES) Colorona Sienna Fine, Merck, CI 77491 (IRON OXIDES), MICA Colorona Fine Gold MP 20, Merck, MICA, CI 77891 (TITANIUM DIOXIDES), CI 77491 (IRON OXIDES) Colorona Sienna Fine, Merck, CI 77491 (IRON OXIDES), MICA
Colorona Sienna, Merck, MICA, CI 77491 (IRON OXIDES) Colorona Sienna, Merck, MICA, CI 77491 (IRON OXIDES)
Colorona Precious Gold, Merck, Mica, CI 77891 (Titanium dioxide), Silica, CI 77491 (Iran oxides), Tin oxide Colorona Precious Gold, Merck, Mica, CI 77891 (Titanium dioxide), Silica, CI 77491 (Iran oxides), Tin oxide
Colorona Sun Gold Sparkle MP 29, Merck, MICA, TITANIUM DIOXIDE, IRON OXIDES, MICA, CI 77891 , CI 77491 (EU) Colorona Sun Gold Sparkle MP 29, Merck, MICA, TITANIUM DIOXIDE, IRON OXIDES, MICA, CI 77891, CI 77491 (EU)
Colorona Mica Black, Merck, CI 77499 (Iran oxides), Mica, CI 77891 (Titanium dioxide) Colorona Mica Black, Merck, CI 77499 (Iran oxides), Mica, CI 77891 (Titanium dioxide)
Colorona Bright Gold, Merck, Mica, CI 77891 (Titanium dioxide), CI 77491 (Iran oxides) Colorona Bright Gold, Merck, Mica, CI 77891 (Titanium dioxide), CI 77491 (Iran oxides)
Colorona Blackstar Gold, Merck, MICA, CI 77499 (IRON OXIDES) Colorona Blackstar Gold, Merck, MICA, CI 77499 (IRON OXIDES)
Colorona SynCopper, Merck, Synthetic Fluorphlogopite (and) Iran Oxides Colorona SynCopper, Merck, Synthetic Fluorphlogopite (and) Iran Oxides
Colorona SynBronze, Merck, Synthetic Fluorphlogopite (and) Iran Oxides Colorona SynBronze, Merck, Synthetic Fluorphlogopite (and) Iran Oxides
Weiterhin besonders bevorzugte Pigmente mit der Handelsbezeichnung Xirona® sind beispielsweise:Other particularly preferred pigments with the trade name Xirona® are, for example:
Xirona Golden Sky, Merck, Silica, CI 77891 (Titanium Dioxide), Tin Oxide Xirona Golden Sky, Merck, Silica, CI 77891 (Titanium Dioxide), Tin Oxide
Xirona Caribbean Blue, Merck, Mica, CI 77891 (Titanium Dioxide), Silica, Tin Oxide Xirona Caribbean Blue, Merck, Mica, CI 77891 (Titanium Dioxide), Silica, Tin Oxide
Xirona Kiwi Rose, Merck, Silica, CI 77891 (Titanium Dioxide), Tin Oxide Xirona Kiwi Rose, Merck, Silica, CI 77891 (Titanium Dioxide), Tin Oxide
Xirona Magic Mauve, Merck, Silica, CI 77891 (Titanium Dioxide), Tin Oxide Xirona Magic Mauve, Merck, Silica, CI 77891 (Titanium Dioxide), Tin Oxide
Xirona Le Rouge, Merck, Iran Oxides (and) Silica Xirona Le Rouge, Merck, Iran Oxides (and) Silica
Zudem sind besonders bevorzugte Pigmente mit der Handelsbezeichnung Unipure® beispielsweise: Unipure Red LC 381 EM, Sensient CI 77491 (Iran Oxides), Silica In addition, particularly preferred pigments with the trade name Unipure® are, for example: Unipure Red LC 381 EM, Sensient CI 77491 (Iran Oxides), Silica
Unipure Black LC 989 EM, Sensient, CI 77499 (Iran Oxides), Silica Unipure Black LC 989 EM, Sensient, CI 77499 (Iran Oxides), Silica
Unipure Yellow LC 182 EM, Sensient, CI 77492 (Iran Oxides), Silica Unipure Yellow LC 182 EM, Sensient, CI 77492 (Iran Oxides), Silica
Zudem sind besonders bevorzugte Pigmente mit der Handelsbezeichnung Unipure® beispielsweise: Unipure Red LC 381 EM, Sensient CI 77491 (Iran Oxides), Silica In addition, particularly preferred pigments with the trade name Unipure® are, for example: Unipure Red LC 381 EM, Sensient CI 77491 (Iran Oxides), Silica
Unipure Black LC 989 EM, Sensient, CI 77499 (Iran Oxides), Silica Unipure Black LC 989 EM, Sensient, CI 77499 (Iran Oxides), Silica
Unipure Yellow LC 182 EM, Sensient, CI 77492 (Iran Oxides), Silica Im Rahmen einer weiteren Ausführungsform kann das Effektpigment auch ein oder mehrere farbgebende Verbindungen aus der Gruppe der organischen Pigmente enthalten. Unipure Yellow LC 182 EM, Sensient, CI 77492 (Iran Oxides), Silica In the context of a further embodiment, the effect pigment can also contain one or more coloring compounds from the group of organic pigments.
Bei den organischen Pigmenten handelt es sich um entsprechend unlösliche, organische Farbstoffe oder Farblacke, die beispielsweise aus der Gruppe der Nitroso-, Nitro- Azo-, Xanthen-, Anthrachinon-, Isoindolinon-, Isoindolin-, Chinacridon-, Perinon-, Perylen- , Diketopyrrolopyorrol-, Indigo-, Thioindido-, Dioxazin-, und/oder Triarylmethan-Verbindungen ausgewählt sein können. The organic pigments are correspondingly insoluble, organic dyes or color lakes, for example from the group of nitroso, nitro, azo, xanthene, anthraquinone, isoindolinone, isoindoline, quinacridone, perinone, perylene , Diketopyrrolopyorrol-, indigo, thioindido, dioxazine, and / or triarylmethane compounds can be selected.
Als besonders gut geeignete organische Pigmente können beispielsweise Carmin, Chinacridon, Particularly suitable organic pigments are, for example, carmine, quinacridone,
Phthalocyanin, Sorgho, blaue Pigmente mit den Color Index Nummern CI 42090, CI 69800, CI 69825, CI 73000, CI 74100, CI 74160, gelbe Pigmente mit den Color Index Nummern CI 11680, CI 1 1710, CI 15985, CI 19140, CI 20040, CI 21 100, CI 21108, CI 47000, CI 47005, grüne Pigmente mit den Color Index Nummern CI 61565, CI 61570, CI 74260, orange Pigmente mit den Color Index Nummern CI 11725, CI 15510, CI 45370, CI 71105, rote Pigmente mit den Color Index Nummern CI 12085, CI 12120, CI 12370, CI 12420, CI 12490, CI 14700, CI 15525, CI 15580, CI 15620, CI 15630, CI 15800, CI 15850, CI 15865,Phthalocyanine, Sorgho, blue pigments with the color index numbers CI 42090, CI 69800, CI 69825, CI 73000, CI 74100, CI 74160, yellow pigments with the color index numbers CI 11680, CI 1 1710, CI 15985, CI 19140, CI 20040, CI 21 100, CI 21108, CI 47000, CI 47005, green pigments with the color index numbers CI 61565, CI 61570, CI 74260, orange pigments with the color index numbers CI 11725, CI 15510, CI 45370, CI 71105, red pigments with the color index numbers CI 12085, CI 12120, CI 12370, CI 12420, CI 12490, CI 14700, CI 15525, CI 15580, CI 15620, CI 15630, CI 15800, CI 15850, CI 15865,
CI 15880, CI 17200, CI 26100, CI 45380, CI 45410, CI 58000, CI 73360, CI 73915 und/oder CI 75470 genannt werden. CI 15880, CI 17200, CI 26100, CI 45380, CI 45410, CI 58000, CI 73360, CI 73915 and / or CI 75470.
In einer weiteren besonders bevorzugten Ausführungsform ist das Effektpigment dadurch gekennzeichnet, dass es eine farbgebende Verbindungen aus der Gruppe der organischen Pigmente enthält, die ausgewählt ist aus der Gruppe bestehend aus Carmin, Chinacridon, Phthalocyanin, Sorgho, blaue Pigmente mit den Color Index Nummern CI 42090, CI 69800, CI 69825, CI 73000, CI 74100, CI 74160, gelbe Pigmente mit den Color Index Nummern CI 11680, CI 11710, CI 15985, CI 19140, CI 20040, CI 21100, CI 21108, CI 47000, CI 47005, grüne Pigmente mit den Color Index Nummern CI 61565, CI 61570, CI 74260, orange Pigmente mit den Color Index Nummern CI 11725, CI 15510, CI 45370, CI 71105, rote Pigmente mit den Color Index Nummern CI 12085, CI 12120, CI 12370, CI 12420, CI 12490, CI 14700, CI 15525, CI 15580, CI 15620, CI 15630, CI 15800, CI 15850, CI 15865, CI 15880, CI 17200,In a further particularly preferred embodiment, the effect pigment is characterized in that it contains a coloring compound from the group of organic pigments which is selected from the group consisting of carmine, quinacridone, phthalocyanine, sorghum, blue pigments with the color index numbers CI 42090 , CI 69800, CI 69825, CI 73000, CI 74100, CI 74160, yellow pigments with the color index numbers CI 11680, CI 11710, CI 15985, CI 19140, CI 20040, CI 21100, CI 21108, CI 47000, CI 47005, green pigments with the color index numbers CI 61565, CI 61570, CI 74260, orange pigments with the color index numbers CI 11725, CI 15510, CI 45370, CI 71105, red pigments with the color index numbers CI 12085, CI 12120, CI 12370 , CI 12420, CI 12490, CI 14700, CI 15525, CI 15580, CI 15620, CI 15630, CI 15800, CI 15850, CI 15865, CI 15880, CI 17200,
CI 26100, CI 45380, CI 45410, CI 58000, CI 73360, CI 73915, CI 75470 und Mischungen daraus. CI 26100, CI 45380, CI 45410, CI 58000, CI 73360, CI 73915, CI 75470 and mixtures thereof.
Bei dem organischen Pigment kann es sich weiterhin auch um einen Farblack handeln. Unter der Bezeichnung Farblack wird im Sinn der Erfindung Partikel verstanden, welche eine Schicht aus absorbierten Farbstoffen umfassen, wobei die Einheit aus Partikel und Farbstoff unter den o.g. The organic pigment can also be a colored lacquer. In the context of the invention, the term “colored varnish” is understood to mean particles which comprise a layer of absorbed dyes, the unit of particles and dyestuff being included in the above.
Bedingungen unlöslich ist. Bei den Partikeln kann es sich beispielsweise um anorganische Substrate handeln, die Aluminium, Silica, Calciumborosilkat, Calciumaluminiumborosilikat oder auch Aluminium sein können. Conditions is insoluble. The particles can be, for example, inorganic substrates, which can be aluminum, silica, calcium borosilicate, calcium aluminum borosilicate or also aluminum.
Als Farblack kann beispielsweise der Alizarin-Farblack eingesetzt werden. Ebenfalls geeignete farbgebende Verbindungen aus der Gruppe der Pigmente sind anorganische und/oder organische Pigmente, die mit einem Polymer modifiziert wurden. Durch die Polymermodifikation kann beispielsweise die Affinität der Pigmente zu dem jeweiligen Material der mindestens einen Schicht erhöht werden. The alizarin color varnish, for example, can be used as the color varnish. Likewise suitable coloring compounds from the group of pigments are inorganic and / or organic pigments which have been modified with a polymer. The polymer modification can, for example, increase the affinity of the pigments for the respective material of the at least one layer.
Die Teilchengröße der eingesetzten farbgebende Verbindung richtet sich insbesondere danach, in welcher Schicht die farbgebende Schicht vorhanden ist. Die farbgebende Verbindung weist vorzugsweise eine Teilchengröße Dgo auf, welche kleiner als die Schichtdicke der mindestens einen Schicht ist. Mehr bevorzugt ist die Teilchengröße D95 der farbgebenden Verbindung kleiner als die Schichtdicke der mindestens einen Schicht. Noch mehr bevorzugt ist die Teilchengröße D99 der farbgebenden Verbindung kleiner als die Schichtdicke der mindestens einen Schicht. Ganz besonders bevorzugt ist die The particle size of the coloring compound used depends in particular on the layer in which the coloring layer is present. The coloring compound preferably has a particle size Dgo which is smaller than the layer thickness of the at least one layer. The particle size D95 of the coloring compound is more preferably smaller than the layer thickness of the at least one layer. The particle size D99 of the coloring compound is even more preferably smaller than the layer thickness of the at least one layer. That is very particularly preferred
Teilchengröße D100 der farbgebenden Verbindung kleiner als die Schichtdicke der mindestens einen Schicht. Die Teilchengröße der farbgebenden Verbindung kann beispielsweise unter Verwendung von dynamischer Lichtstreuung (DLS) oder statischer Lichtstreuung (SLS) bestimmt werden. D90 bedeutet, dass 90% der Teilchen der farbgebenden Verbindung kleiner sind als die Schichtdicke der mindestens einen Schicht. Entsprechend bedeutet D95, dass 95% der Teilchen der farbgebenden Verbindung kleiner sind als die Schichtdicke der mindestens einen Schicht, usw. Particle size D100 of the coloring compound smaller than the layer thickness of the at least one layer. The particle size of the coloring compound can be determined, for example, using dynamic light scattering (DLS) or static light scattering (SLS). D90 means that 90% of the particles of the coloring compound are smaller than the layer thickness of the at least one layer. Accordingly, D95 means that 95% of the particles of the coloring compound are smaller than the layer thickness of the at least one layer, etc.
Die Menge an farbgebender Verbindung aus der Gruppe der Pigmente in der Schicht, umfassendThe amount of coloring compound from the group of pigments in the layer, comprising
(b1) ein Metalloxid und/oder Metalloxidhydrat und (b1) a metal oxide and / or metal oxide hydrate and
(b2) eine farbgebende Verbindung aus der Gruppe der Pigmente, (b2) a coloring compound from the group of pigments,
beträgt vorzugsweise bis zu 5 Gew.-%, bezogen auf das Gesamtgewicht der Schicht. is preferably up to 5% by weight, based on the total weight of the layer.
Die Schichten A und C dienen insbesondere auch als Korrosionsschutz als auch der chemischen und physikalischen Stabilisierung. Besonders bevorzugt enthalten die Schichten A und C Siliciumdioxid oder Aluminiumoxid, die nach dem Sol-Gel-Verfahren aufgebracht werden. Layers A and C serve in particular as protection against corrosion and also for chemical and physical stabilization. Layers A and C particularly preferably contain silicon dioxide or aluminum oxide, which are applied by the sol-gel process.
Entsprechend ist ein weiterer Gegenstand der Anmeldung ein Verfahren zur Herstellung eines Accordingly, a further subject of the application is a method for producing a
Effektpigments, umfassend a) ein Substratplättchen und b) eine Beschichtung, wobei die Beschichtung mindestens eine Schicht aufweist, die Effect pigments comprising a) a substrate platelet and b) a coating, the coating having at least one layer which
(i) ein Metalloxid und/oder Metalloxidhydrat und (i) a metal oxide and / or metal oxide hydrate and
(ii) eine farbgebende Verbindung aus der Gruppe der Pigmente umfasst, umfassend die Schritte: (ii) comprises a coloring compound from the group of the pigments, comprising the steps:
(a) Suspendieren des Substratplättchens in einem organischen oder wässrigen Lösungsmittel und (a) suspending the substrate wafer in an organic or aqueous solvent and
(ß) Beschichten des in Schritt (a) suspendierten Substratplättchens mit einer Schicht, die (i) ein Metalloxid und/oder Metalloxidhydrat und (ii) eine farbgebende Verbindung aus der Gruppe der Pigmente umfasst, unter Verwendung eines Sol-Gel-Verfahrens. Es ist bevorzugt, dass in dem Sol-Gel-Verfahren ein Metallalkoxid und eine farbgebende Verbindung aus der Gruppe der Pigmente eingesetzt werden. (ß) Coating the substrate platelet suspended in step (a) with a layer which comprises (i) a metal oxide and / or metal oxide hydrate and (ii) a coloring compound from the group of pigments, using a sol-gel process. It is preferred that a metal alkoxide and a coloring compound from the group of pigments are used in the sol-gel process.
Es ist ferner bevorzugt, dass das in dem Sol-Gel-Verfahren eingesetzte Metallalkoxid ausgewählt ist aus der Gruppe bestehend aus Tetramethylorthosilikat, Tetraethylorthosilikat, Tetraisopropylorthosilikat und Mischungen daraus, wobei Tetraethylorthosilikat bevorzugt ist. It is further preferred that the metal alkoxide used in the sol-gel process is selected from the group consisting of tetramethyl orthosilicate, tetraethyl orthosilicate, tetraisopropyl orthosilicate and mixtures thereof, tetraethyl orthosilicate being preferred.
In einer bevorzugten Ausführungsform des Herstellungsverfahrens wurde das in Schritt (a) eingesetzte Substratplättchen bereits mit mindestens einer Schicht aus einem Metalloxid und/oder Metalloxidhydrat beschichtet. In a preferred embodiment of the production process, the substrate platelet used in step (a) has already been coated with at least one layer of a metal oxide and / or metal oxide hydrate.
Ein beispielhaftes Herstellverfahren umfasst das Dispergieren der unbeschichteten Substratplättchen oder der bereits mit Schicht A oder mit den Schichten A und B beschichteten Substratplättchen und der farbgebenden Verbindung aus der Gruppe der Pigmente in einer Lösung eines Metallalkoxids wie Tetraethylorthosilikat oder Aluminiumtriisopropanolat (üblicherweise in einer Lösung von organischem Lösungsmittel oder einer Mischung von organischem Lösungsmittel und Wasser mit mindestens 50 Gew.- % organisches Lösungsmittel wie ein C1 bis C4-Alkohol), und Zugabe einer schwachen Base oder Säure zur Hydrolysierung des Metallalkoxids, wodurch ein Film, umfassend das Metalloxid und die farbgebende Verbindung aus der Gruppe der Pigmente, auf der Oberfläche der (beschichteten) Substratplättchen entsteht. An exemplary manufacturing process comprises dispersing the uncoated substrate flakes or the substrate flakes already coated with layer A or with layers A and B and the coloring compound from the group of pigments in a solution of a metal alkoxide such as tetraethyl orthosilicate or aluminum triisopropoxide (usually in a solution of organic solvent or a mixture of organic solvent and water with at least 50% by weight organic solvent such as a C1 to C4 alcohol), and adding a weak base or acid to hydrolyze the metal alkoxide, thereby forming a film comprising the metal oxide and the coloring compound the group of pigments on the surface of the (coated) substrate platelets.
Die Schicht B kann beispielsweise durch hydrolytische Zersetzung einer oder mehrerer organischer Metallverbindungen und/oder durch Fällung eines oder mehrerer gelöster Metallsalze sowie eine ggf. anschließende Nachbehandlung (zum Beispiel Überführen einer gebildeten hydroxidhaltigen Schichten in die Oxidschichten durch Tempern) hergestellt werden. Layer B can be produced, for example, by hydrolytic decomposition of one or more organic metal compounds and / or by precipitation of one or more dissolved metal salts and, if necessary, subsequent aftertreatment (for example, transferring a hydroxide-containing layer formed into the oxide layers by annealing).
Obwohl jede der Schichten A, B und/oder C ein Gemisch von zwei oder mehreren Metalloxid(hydrat)en enthalten kann, umfasst jede der Schichten vorzugsweise jeweils nur ein Metalloxid(hydrat). Although each of the layers A, B and / or C can contain a mixture of two or more metal oxides (hydrate) s, each of the layers preferably comprises only one metal oxide (hydrate).
Die Effektpigmente auf Basis von beschichteten Substratplättchen weisen vorzugsweise eine Dicke von 70 bis 500 nm, besonders bevorzugt 100 bis 400 nm, insbesondere bevorzugt 150 bis 320 nm, beispielsweise 180 bis 290 nm, auf. Die geringe Dicke der beschichteten Substratplättchen wird insbesondere dadurch erzielt, dass die Dicke der unbeschichteten Substratplättchen gering ist, aber auch dadurch, dass die Dicken der Beschichtungen A und, falls vorhanden, C auf einen möglichst kleinen Wert eingestellt werden. The effect pigments based on coated substrate platelets preferably have a thickness of 70 to 500 nm, particularly preferably 100 to 400 nm, particularly preferably 150 to 320 nm, for example 180 to 290 nm. The small thickness of the coated substrate platelets is achieved in particular in that the thickness of the uncoated substrate platelets is small, but also in that the thicknesses of the coatings A and, if present, C are set to the smallest possible value.
Die Haftung und Abriebbeständigkeit von Effektpigmenten auf Basis von Substratplättchen an/in einem Material, vorzugsweise keratinischen Material, kann deutlich erhöht werden, in dem die äußerste Schicht, je nach Aufbau Schicht A, B oder C, zusätzlich durch organische Verbindung wie Silane, Phosphorsäureester, Titanate, Borate oder Carbonsäuren modifiziert wird. Dabei sind die organischen Verbindungen an die Oberfläche der äußersten, vorzugsweise Metalloxid-haltigen, Schicht A, B oder C gebunden. Die äußerste Schicht bezeichnet die Schicht, die räumlich am weitesten von dem The adhesion and abrasion resistance of effect pigments based on substrate platelets on / in a material, preferably keratinous material, can be significantly increased by adding the outermost layer, Depending on the structure, layer A, B or C is additionally modified by organic compounds such as silanes, phosphoric acid esters, titanates, borates or carboxylic acids. The organic compounds are bound to the surface of the outermost layer A, B or C, preferably containing metal oxide. The outermost layer denotes the layer that is spatially furthest from that
Substratplättchen entfernt ist. Bei den organischen Verbindungen handelt es sich vorzugsweise um funktionelle Silanverbindungen, die an die Metalloxid-haltige Schicht A, B oder C binden können. Hierbei kann es sich entweder um mono- als auch um bifunktionelle Verbindungen handeln. Beispiele für bifunktionelle organische Verbindungen sind Methacryloxypropenyltrimethoxysilan, 3- Methacryloxypropyltrimethoxysilan, 3-Acryloxypropyltrimethoxysilan, 2-Acryloxyethyltrimethoxysilan, 3- Methacryloxypropyltriethoxysilan, 3-Acryloxypropyltrimethoxysilan, 2-Methacryloxyethyltriethoxysilan, 2- Acryloxyethyltriethoxysilan, 3-Methacryloxypropyltris(methoxyethoxy)silan, 3- Methacryloxypropyltris(butoxyethoxy)silan, 3-Methacryloxypropyltris(propoxy)silan, 3- Methacryloxypropyltris(butoxy)silan, 3-Acryloxypropyltris(methoxyethoxy)silan, 3- Acryloxypropyltris(butoxyethoxy)silan, 3-Acryloxypropyltris(butoxy)silan, Vinyltrimethoxysilan, Substrate plate is removed. The organic compounds are preferably functional silane compounds which can bind to the layer A, B or C containing metal oxide. These can be either mono- or bifunctional compounds. Examples of bifunctional organic compounds are methacryloxypropenyltrimethoxysilane, 3- methacryloxypropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, 2-acryloxyethyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 2-methacryloxyethyltriethoxysilane, 2-acryloxyethyltriethoxysilane, 3-methacryloxypropyl tris (methoxyethoxy) silane, 3- methacryloxypropyltris (butoxyethoxy) silane, 3-methacryloxypropyltris (propoxy) silane, 3- methacryloxypropyltris (butoxy) silane, 3-acryloxypropyltris (methoxyethoxy) silane, 3- acryloxypropyltris (butoxyethoxy) silane, 3-acryloxypropyltris (butoxy) silane, vinyl trimethoxysilane
Vinyltriethoxysilan, Vinylethyldichlorsilan, Vinylmethyldiacetoxysilan, Vinylmethyldichlorsilan, Vinyltriethoxysilane, vinylethyldichlorosilane, vinylmethyldiacetoxysilane, vinylmethyldichlorosilane,
Vinylmethyldiethoxysilan, Vinyltriacetoxysilan, Vinyltrichlorsilan, Phenylvinyldiethoxysilan, oder Vinylmethyldiethoxysilane, vinyltriacetoxysilane, vinyltrichlorosilane, phenylvinyldiethoxysilane, or
Phenylallyldichlorsilan. Des Weiteren kann eine Modifizierung mit einem monofunktionellen Silan, insbesondere eines Alkylsilans oder Arylsilans, erfolgen. Dieses weist nur eine funktionelle Gruppe auf, welche kovalent an die Oberfläche des Effektpigments (d.h. an die äußerste Metalloxid-haltige Schicht) oder, bei nicht ganz vollständiger Bedeckung, an die Metalloberfläche anbinden kann. Der Phenylallyldichlorosilane. Furthermore, a modification with a monofunctional silane, in particular an alkylsilane or arylsilane, can take place. This has only one functional group which can covalently bond to the surface of the effect pigment (i.e. to the outermost metal oxide-containing layer) or, if it is not completely covered, to the metal surface. The
Kohlenwasserstoffrest des Silans weist vom Effektpigment weg. Je nach der Art und Beschaffenheit des Kohlenwasserstoffrests des Silans wird ein unterschiedlicher Grad der Hydrophobierung des The hydrocarbon residue of the silane points away from the effect pigment. Depending on the type and nature of the hydrocarbon radical of the silane, a different degree of hydrophobization of the
Effektpigments erreicht. Beispiele für solche Silane sind Hexadecyltrimethoxysilan , Propyltrimethoxysilan, etc. Besonders bevorzugt sind Effektpigmente auf Basis von Siliciumdioxid-beschichteten Effect pigments achieved. Examples of such silanes are hexadecyltrimethoxysilane, propyltrimethoxysilane, etc. Effect pigments based on silicon dioxide-coated are particularly preferred
Aluminiumsubstratplättchen mit einem monofunktionellen Silan Oberflächen modifiziert. Besonders bevorzugt sind Octyltrimethoxysilan, Octyltriethoxysilan, Hecadecyltrimethoxysilan sowie Aluminum substrate platelets modified with a monofunctional silane surface. Octyltrimethoxysilane, octyltriethoxysilane, and hecadecyltrimethoxysilane are particularly preferred
Hecadecyltriethoxysilan. Durch die veränderten Oberflächeneigenschaften / Hydrophobierung kann eine Verbesserung bezüglich Haftung, Abriebfestigkeit und Ausrichtung in der Anwendung erzielt werden. Hecadecyltriethoxysilane. The changed surface properties / hydrophobicity can improve adhesion, abrasion resistance and alignment in the application.
Es kann bevorzugt sein, dass in dem Sol-Gel-Verfahren ferner ein Silan mit mindestens einer basischen Gruppe eingesetzt wird. It can be preferred that a silane with at least one basic group is also used in the sol-gel process.
Zusätzlich oder alternativ zu der nachträglichen Modifikation können Haftung und/oder In addition or as an alternative to the subsequent modification, liability and / or
Abriebbeständigkeit von Effektpigmenten auf Basis von Substratplättchen an/in einem Material, vorzugsweise keratinischem Material, deutlich erhöht werden, in dem bei der Herstellung der äußersten Schicht, je nach Aufbau Schicht A, B oder C, zusätzlich Silane mit mindestens einer basischen Gruppe eingesetzt werden. Dies ist insbesondere vorteilhaft, wenn die Schicht A oder die Schicht C die äußerste Schicht sind und als Metalloxid(hydrat) Siliciumdioxid umfassen. In dieser Ausführungsform der Erfindung umfasst das Sol-Gel-Verfahren zur Herstellung der Schichten A oder C das Dispergieren der unbeschichteten Substratplättchen oder bereits mit Schichten A und B beschichteter Substratplättchen, der farbgebenden Verbindung aus der Gruppe der Pigmente und eines Silans mit mindestens einer basischen Gruppe in einer Lösung eines Metallalkoxids. Die Silane sind bevorzugt Silane mit einem, zwei oder drei Siliciumatomen, mit einer oder mehreren Hydroxylgruppen oder hydrolysierbare Gruppen pro Molekül und mit mindestens einer basischen Gruppe. Abrasion resistance of effect pigments based on substrate platelets on / in a material, preferably keratinic material, can be significantly increased by using additional silanes with at least one basic group in the production of the outermost layer, depending on the structure of layer A, B or C. This is particularly advantageous if the layer A or the layer C are the outermost layer and comprise silicon dioxide as the metal oxide (hydrate). In this embodiment of the invention, the sol-gel process for producing layers A or C comprises dispersing the uncoated substrate flakes or substrate flakes already coated with layers A and B, the coloring compound from the group of pigments and a silane with at least one basic group in a solution of a metal alkoxide. The silanes are preferably silanes with one, two or three silicon atoms, with one or more hydroxyl groups or hydrolyzable groups per molecule and with at least one basic group.
Bei der basischen Gruppe kann es sich beispielsweise um eine Aminogruppe, eine Alkylaminogruppe oder um eine Dialkylaminogruppe handeln, die bevorzugt über einen Linker mit einem Siliciumatom verbunden ist. The basic group can be, for example, an amino group, an alkylamino group or a dialkylamino group, which is preferably connected to a silicon atom via a linker.
Das Silan mit mindestens einer basischen Gruppe ist vorzugsweise ausgewählt aus der Gruppe bestehend aus The silane with at least one basic group is preferably selected from the group consisting of
- (3-Aminopropyl)triethoxysilan - (3-aminopropyl) triethoxysilane
- (3-Aminopropyl)trimethoxysilan - (3-aminopropyl) trimethoxysilane
-1 -(3-Aminopropyl)silantriol -1 - (3-aminopropyl) silanetriol
- (2-Aminoethyl)triethoxysilan - (2-aminoethyl) triethoxysilane
- (2-Aminoethyl)trimethoxysilan - (2-aminoethyl) trimethoxysilane
-1 -(2-Aminoethyl)silantriol -1 - (2-aminoethyl) silanetriol
- (3-Dimethylaminopropyl)triethoxysilan - (3-Dimethylaminopropyl) triethoxysilane
- (3-Dimethylaminopropyl)trimethoxysilan - (3-Dimethylaminopropyl) trimethoxysilane
-1-(3-Dimethylaminopropyl)silantriol -1- (3-dimethylaminopropyl) silanetriol
- (2-Dimethylaminoethyl)triethoxysilan. - (2-Dimethylaminoethyl) triethoxysilane.
- (2-Dimethylaminoethyl)trimethoxysilan - (2-dimethylaminoethyl) trimethoxysilane
- 1 -(2-Dimethylaminoethyl)silantriol - 1 - (2-dimethylaminoethyl) silanetriol
und Mischungen daraus. and mixtures thereof.
Bevorzugt werden (3-Aminopropyl)triethoxysilan und/oder (3-Aminopropyl)trimethoxysilan eingesetzt. (3-aminopropyl) triethoxysilane and / or (3-aminopropyl) trimethoxysilane are preferably used.
Das in dem Sol-Gel-Verfahren eingesetzte Metallalkoxid ist vorzugsweise ausgewählt aus der Gruppe bestehend aus Tetramethylorthosilikat, Tetraethylorthosilikat, Tetraisopropylorthosilikat und Mischungen daraus. Vorzugsweise wird Tetraethylorthosilikat eingesetzt. Alternativ oder zusätzlich zu dem The metal alkoxide used in the sol-gel process is preferably selected from the group consisting of tetramethyl orthosilicate, tetraethyl orthosilicate, tetraisopropyl orthosilicate and mixtures thereof. Tetraethyl orthosilicate is preferably used. Alternatively or in addition to the
Tetraalkoxysilan können Alkyltrialkoxysilane in dem Sol-Gel-Verfahren zur Herstellung der Schichten A und/oder C eingesetzt werden. Insbesondere bevorzugt können Alkyltrialkoxysilane zusätzlich oder alternativ zu einem Tetraalkoxysilan in dem Sol-Gel-Verfahren zur Herstellung einer Schicht, die (i) Siliciumdioxid als Metalloxid und/oder Metalloxidhydrat und (ii) eine farbgebende Verbindung aus der Gruppe der Pigmente umfasst, eingesetzt werden. Geeignete Alkyltrialkoxysilane umfassen beispielsweise Methyltrimethoxysilan, Methyltriethoxysilan , Ethyltrimethoxysilan, Ethyltriethoxysilan.Hexyltrimethoxysilan, Hexyltriethoxysilan, Octyltrimethoxysilan, Octyltriethoxysilan, Dodecyltrimethoxysilan, Dodecyltriethoxysilan, Octyldecyltrimethoxysilan und/oder Octyldecyltriethoxysilan. Tetraalkoxysilane, alkyltrialkoxysilanes can be used in the sol-gel process to produce layers A and / or C. Particularly preferably, alkyltrialkoxysilanes can be used in addition or as an alternative to a tetraalkoxysilane in the sol-gel process for producing a layer which comprises (i) silicon dioxide as metal oxide and / or metal oxide hydrate and (ii) a coloring compound from the group of pigments. Suitable alkyltrialkoxysilanes include, for example, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, octyltrimethoxysilane, octyltriethoxysilane, dodecyltrimethoxysilane, or octyldoxecyl silane, or octyldoxecyltrimethoxysilane, or octyldoxecyl silane, or octyldoxecyl silane, or octyltriethoxecyl silane
Beispiel example
Zunächst wurden 200 g Al-Plättchen in Form von VMPs (Dicke zwischen 20 nm und 30 nm, dso = 12 pm) in Isopropanol suspendiert. Zu dieser Mischung wurden 46 g Tetraethoxysilan und 1 g Pigment Blue 15 (C.l. 74160, D99 = 20 nm) gegeben und die erhaltene Mischung wurde auf 60 °C erwärmt. Anschließend wurden 100 g Wasser und im Anschluss 6 g Ammoniak zugegeben und die erhaltene Mischung wurde für weitere 4 h gerührt. Danach wird die Mischung über eine Glasfritte abfiltriert und der erhaltene First, 200 g of Al platelets in the form of VMPs (thickness between 20 nm and 30 nm, dso = 12 μm) were suspended in isopropanol. 46 g of tetraethoxysilane and 1 g of Pigment Blue 15 (C.I. 74160, D99 = 20 nm) were added to this mixture and the mixture obtained was heated to 60 ° C. 100 g of water were then added, followed by 6 g of ammonia, and the mixture obtained was stirred for a further 4 hours. Thereafter, the mixture is filtered off through a glass frit and the obtained
Filterkuchen bei 120 °C für 12 h getrocknet. Die gefärbte Siliciumdioxidschicht macht rund 40 Gew.-%, bezogen auf das Gesamtgewicht des Effektpigments, aus. Filter cake dried at 120 ° C. for 12 h. The colored silicon dioxide layer makes up around 40% by weight, based on the total weight of the effect pigment.

Claims

Patentansprüche Claims
1. Effektpigment, umfassend a) ein Substratplättchen und b) eine Beschichtung, 1. Effect pigment, comprising a) a substrate platelet and b) a coating,
wobei die Beschichtung mindestens eine Schicht aufweist, die wherein the coating has at least one layer which
(i) ein Metalloxid und/oder Metalloxidhydrat und (i) a metal oxide and / or metal oxide hydrate and
(ii) eine farbgebende Verbindung aus der Gruppe der Pigmente (ii) a coloring compound from the group of pigments
umfasst. includes.
2. Effektpigment gemäß Anspruch 1 , dadurch gekennzeichnet, dass die Beschichtung das 2. Effect pigment according to claim 1, characterized in that the coating is the
Substratplättchen vollständig umhüllt. Substrate plate completely encased.
3. Effektpigment gemäß Anspruch 1 oder Anspruch 2, dadurch gekennzeichnet, dass die Beschichtung eine Schicht aufweist. 3. Effect pigment according to claim 1 or claim 2, characterized in that the coating has a layer.
4. Effektpigment gemäß Anspruch 1 oder Anspruch 2, dadurch gekennzeichnet, dass die Beschichtung insgesamt mindestens zwei, vorzugsweise zwei oder drei, Schichten aufweist. 4. Effect pigment according to claim 1 or claim 2, characterized in that the coating has a total of at least two, preferably two or three, layers.
5. Effektpigment gemäß einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, dass das Metalloxid und/oder Metalloxidhydrat (i) ausgewählt ist aus der Gruppe bestehend aus Silicium(di)oxid, 5. Effect pigment according to one of claims 1 to 4, characterized in that the metal oxide and / or metal oxide hydrate (i) is selected from the group consisting of silicon (di) oxide,
Siliciumoxidhydrat, Aluminiumoxid, Aluminiumoxidhydrat, Boroxid, Germaniumoxid, Manganoxid, Magnesiumoxid, Eisenoxid, Cobaltoxid, Chromoxid, Titandioxid, Vanadiumoxid, Zirkonoxid, Zinnoxid, Zinkoxid und deren Gemischen. Silicon oxide hydrate, aluminum oxide, aluminum oxide hydrate, boron oxide, germanium oxide, manganese oxide, magnesium oxide, iron oxide, cobalt oxide, chromium oxide, titanium dioxide, vanadium oxide, zirconium oxide, tin oxide, zinc oxide and mixtures thereof.
6. Effektpigment gemäß einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, dass das Metalloxid und/oder Metalloxidhydrat (i) Siliciumdioxid ist. 6. Effect pigment according to one of claims 1 to 5, characterized in that the metal oxide and / or metal oxide hydrate (i) is silicon dioxide.
7. Effektpigment gemäß einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, dass das 7. Effect pigment according to one of claims 1 to 6, characterized in that the
Substratplättchen aus einem Metall, vorzugsweise Aluminium, oder aus einer Legierung ist. Substrate plate made of a metal, preferably aluminum, or of an alloy.
8. Effektpigment gemäß einem der Ansprüche 1 bis 7, dadurch gekennzeichnet, dass die mindestens eine Schicht nass-chemisch, vorzugsweise unter Verwendung eines Sol-Gel-Verfahrens, aufgebracht wurde. 8. Effect pigment according to one of claims 1 to 7, characterized in that the at least one layer was applied wet-chemically, preferably using a sol-gel process.
9. Effektpigment gemäß einem der Ansprüche 1 bis 8, dadurch gekennzeichnet, dass an der 9. Effect pigment according to one of claims 1 to 8, characterized in that on the
Beschichtung eine monofunktionelle oder bifunktionelle organische Verbindung, vorzugsweise ein Silan, gebunden ist. Coating a monofunctional or bifunctional organic compound, preferably a silane, is bonded.
10. Effektpigment gemäß einem der Ansprüche 1 bis 9, dadurch gekennzeichnet, dass die Teilchengröße Dgo, vorzugsweise die Teilchengröße D95, mehr bevorzugt die Teilchengröße D99 und ganz besonders bevorzugt die Teilchengröße D100, der farbgebenden Verbindung kleiner als die Schichtdicke der mindestens einen Schicht ist. 10. Effect pigment according to one of claims 1 to 9, characterized in that the particle size Dgo, preferably the particle size D95, more preferably the particle size D99 and very particularly preferably the particle size D100, the coloring compound is smaller than the layer thickness of the at least one layer.
11. Verfahren zur Herstellung eines Effektpigments, umfassend a) ein Substratplättchen und b) eine Beschichtung, wobei die Beschichtung mindestens eine Schicht aufweist, die 11. A method for producing an effect pigment, comprising a) a substrate platelet and b) a coating, wherein the coating has at least one layer which
(i) ein Metalloxid und/oder Metalloxidhydrat und (i) a metal oxide and / or metal oxide hydrate and
(ii) eine farbgebende Verbindung aus der Gruppe der Pigmente umfasst, umfassend die Schritte: (ii) comprises a coloring compound from the group of the pigments, comprising the steps:
(a) Suspendieren des Substratplättchens in einem organischen oder wässrigen Lösungsmittel,(a) suspending the substrate wafer in an organic or aqueous solvent,
(ß) Beschichten des in Schritt (a) suspendierten Substratplättchens mit einer Schicht, die (ß) Coating of the substrate platelet suspended in step (a) with a layer which
(i) ein Metalloxid und/oder Metalloxidhydrat und (i) a metal oxide and / or metal oxide hydrate and
(ii) eine farbgebende Verbindung aus der Gruppe der Pigmente umfasst, unter (ii) comprises a coloring compound from the group of pigments, among
Verwendung eines Sol-Gel-Verfahrens. Using a sol-gel process.
12. Verfahren gemäß Anspruch 11 , dadurch gekennzeichnet, dass in dem Sol-Gel-Verfahren 12. The method according to claim 11, characterized in that in the sol-gel process
Metallalkoxid und eine farbgebende Verbindung aus der Gruppe der Pigmente eingesetzt werden. Metal alkoxide and a coloring compound from the group of pigments are used.
13. Verfahren einem der Ansprüche 11 oder 12, dadurch gekennzeichnet, dass das in dem Sol-Gel- Verfahren eingesetzte Metallalkoxid ausgewählt ist aus der Gruppe bestehend aus 13. The method according to any one of claims 11 or 12, characterized in that the metal alkoxide used in the sol-gel process is selected from the group consisting of
Tetramethylorthosilikat, Tetraethylorthosilikat, Tetraisopropylorthosilikat und Mischungen daraus, wobei Tetraethylorthosilikat bevorzugt ist. Tetramethyl orthosilicate, tetraethyl orthosilicate, tetraisopropyl orthosilicate and mixtures thereof, with tetraethyl orthosilicate being preferred.
14. Verfahren gemäß einem der Ansprüche 11 bis 13, dadurch gekennzeichnet, dass in dem Sol-Gel- Verfahren ferner ein Silan mit mindestens einer basischen Gruppe eingesetzt wird. 14. The method according to any one of claims 11 to 13, characterized in that a silane with at least one basic group is also used in the sol-gel process.
15. Verfahren gemäß einem der Ansprüche 11 bis 14, dadurch gekennzeichnet, dass das in Schritt (a) eingesetzte Substratplättchen bereits mit mindestens einer Schicht aus einem Metalloxid und/oder Metalloxidhydrat beschichtet wurde. 15. The method according to any one of claims 11 to 14, characterized in that the substrate platelet used in step (a) has already been coated with at least one layer of a metal oxide and / or metal oxide hydrate.
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DE102019210686A1 (en) * 2019-07-19 2021-01-21 Henkel Ag & Co. Kgaa Process for coloring keratinic material, comprising the use of an organosilicon compound, a colored effect pigment and a film-forming polymer I.
DE102019210692A1 (en) * 2019-07-19 2021-01-21 Henkel Ag & Co. Kgaa Process for coloring keratinic material, comprising the use of an organosilicon compound, a colored effect pigment and a film-forming polymer III
DE102019210689A1 (en) * 2019-07-19 2021-01-21 Henkel Ag & Co. Kgaa Process for coloring keratinic material, comprising the use of an organosilicon compound, a coated effect pigment and a film-forming polymer II

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WO2021013513A1 (en) 2021-01-28

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