DE4104310A1 - Flaky pigment having metal substrate with iron oxide coating - prodn. by pptn. from aq. soln., used in paint, plastics, cosmetics or magneto=optical medium - Google Patents

Flaky pigment having metal substrate with iron oxide coating - prodn. by pptn. from aq. soln., used in paint, plastics, cosmetics or magneto=optical medium

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Publication number
DE4104310A1
DE4104310A1 DE19914104310 DE4104310A DE4104310A1 DE 4104310 A1 DE4104310 A1 DE 4104310A1 DE 19914104310 DE19914104310 DE 19914104310 DE 4104310 A DE4104310 A DE 4104310A DE 4104310 A1 DE4104310 A1 DE 4104310A1
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Germany
Prior art keywords
oxide layer
iron
iron oxide
iii
platelet
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DE19914104310
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German (de)
Inventor
Constanze Dr Prengel
Gerhard Dr Herget
Marita Jekel
Angelika Decker
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Merck Patent GmbH
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Merck Patent GmbH
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Publication date
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Priority to DE19914104310 priority Critical patent/DE4104310A1/en
Publication of DE4104310A1 publication Critical patent/DE4104310A1/en
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/0015—Pigments exhibiting interference colours, e.g. transparent platelets of appropriate thinness or flaky substrates, e.g. mica, bearing appropriate thin transparent coatings
    • C09C1/0021—Pigments exhibiting interference colours, e.g. transparent platelets of appropriate thinness or flaky substrates, e.g. mica, bearing appropriate thin transparent coatings comprising a core coated with only one layer having a high or low refractive index
    • 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
    • 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
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q1/00—Make-up preparations; Body powders; Preparations for removing make-up
    • A61Q1/02—Preparations containing skin colorants, e.g. pigments
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/0015—Pigments exhibiting interference colours, e.g. transparent platelets of appropriate thinness or flaky substrates, e.g. mica, bearing appropriate thin transparent coatings
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/62—Metallic pigments or fillers
    • 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
    • A61K2800/41—Particular ingredients further characterized by their size
    • A61K2800/412—Microsized, i.e. having sizes between 0.1 and 100 microns
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C2200/00—Compositional and structural details of pigments exhibiting interference colours
    • C09C2200/10—Interference pigments characterized by the core material
    • C09C2200/1054—Interference pigments characterized by the core material the core consisting of a metal
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C2200/00—Compositional and structural details of pigments exhibiting interference colours
    • C09C2200/30—Interference pigments characterised by the thickness of the core or layers thereon or by the total thickness of the final pigment particle
    • C09C2200/301—Thickness of the core
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C2220/00—Methods of preparing the interference pigments
    • C09C2220/10—Wet methods, e.g. co-precipitation
    • 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
    • C09C2220/103—Wet methods, e.g. co-precipitation comprising a drying or calcination step after applying each layer
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • 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

Abstract

Flaky pigment (I) has a flaky metal substrate (II) and metal oxide coating(s) (III). The novelty is that the metal oxide coating (IIIA) applied to the (II) surface is an Fe oxide. (IIIA) pref. consists of or contains Fe2O3. The thickness of (III) is varied to produce different interference colours. (IIIA) pref. is covered with other (III), consisting of TiO2, ZrO2, SnO2, Cr2O3, BiOCl, FeO, Fe2O3, Al2O3, SiO2 and/or ZnO. (II) consists of steel flakes. It is produced as follows: an aq. (II) suspension is treated with a Fe salt soln. at constant temp. and constant pH, pref. 4-10, then sepd. and opt. washed, dried and/or calcined. Other (III) may be pptd. on (IIIA) before sepn. or after washing, drying and/or calcination. USE/ADVANTAGE - (I) is claimed for pigmenting lacquers, paints, plastics or cosmetics. It is also useful e.g. in magneto-optical recording. (I) is pearlescent and has high covering power, high weathering resistance, body colour, high lustre and a brilliant colour sparkle. It is produced without using organic, i.e. flammable, solve

Description

Die Anmeldung betrifft ein plättchenförmiges Pigment, welches ein plättchenförmiges metallisches Substrat enthält, das mit einer oder mehreren Metalloxidschichten bedeckt ist.The application relates to a platelet-shaped pigment, which contains a platelet-shaped metallic substrate with one or more metal oxide layers is covered.

In EP 03 28 906 ist ein plättchenförmiges Pigment angegeben, bei dem ein plättchenförmiges metallisches Substrat mit einer Titanoxidschicht und gegebenenfalls weiteren darüberliegenden Metalloxidschichten bedeckt ist. Dabei wird die Titanoxid­ schicht durch Hydrolyse einer organischen Titanat-Esterver­ bindung bei einem pH zwischen 4 und 8 aus einem organischen Medium auf das Substrat aufgebracht.EP 03 28 906 specifies a platelet-shaped pigment in which a platelet-shaped metallic substrate with a Titanium oxide layer and, if necessary, further layers above it Metal oxide layers is covered. The titanium oxide layer by hydrolysis of an organic titanate esterver binding at a pH between 4 and 8 from an organic Medium applied to the substrate.

Nachteilig bei diesem Verfahren ist, daß wegen der Verwendung organischer, i.a. brennbarer Lösungsmittel besondere Sicher­ heitsvorkehrungen getroffen werden müssen. Daneben ist das Verfahren auf die Abscheidung mit Hilfe von Titanat-Esterver­ bindungen beschränkt.A disadvantage of this method is that because of the use more organic, generally flammable solvents particularly safe precautions must be taken. It’s next to it Deposition process using titanate esterver ties limited.

Die Aufgabe der vorliegenden Erfindung bestand darin, neue Perlglanzpigmente auf der Basis plättchenförmiger Metall- Substrate anzugeben, bei deren Herstellung die Nachteile, welche bei dem in EP 03 28 906 angegebenen Verfahren auf­ treten, nicht oder nur in geringerem Maße beobachtet werden. The object of the present invention was to create new ones Pearlescent pigments based on platelet-shaped metal Specify substrates, the disadvantages of which are produced, which in the process specified in EP 03 28 906 occur, not observed or only to a lesser extent.  

Darüberhinaus sollen diese neuen Perlglanzpigmente ein hohes Deckvermögen, eine hohe Wetterbeständigkeit und neben der Körperfarbe auch einen hohen Glanz und ein brillantes Farbspiel aufweisen. Weiterhin soll durch die Bereitstellung der neuen Perlglanzpigmente die Palette verfügbarer Perl­ glanzpigmente für verschiedenartigste Anwendungen und ins­ besondere für die Pigmentierung von Lacken, Farben, Kunst­ stoffen oder Kosmetika vergrößert werden.In addition, these new pearlescent pigments are said to be high Opacity, high weather resistance and in addition to the Body color also has a high gloss and brilliant Show play of colors. Furthermore, by providing the range of available pearls of the new pearl luster pigments luster pigments for various applications and ins especially for the pigmentation of paints, paints, art fabrics or cosmetics are enlarged.

Es wurde gefunden, daß diese Aufgaben durch die Bereitstel­ lung eines plättchenförmigen Pigments gelöst werden können, welches ein plättchenförmiges metallisches Substrat enthält, das mit einer oder mehreren Metalloxidschichten bedeckt ist, wobei die auf die Substratoberfläche aufgebrachte Metalloxid­ schicht eine Eisenoxidschicht ist.It has been found that these tasks are provided by the platelet-shaped pigment can be solved, which contains a platelet-shaped metallic substrate, which is covered with one or more metal oxide layers, wherein the metal oxide deposited on the substrate surface layer is an iron oxide layer.

Die plättchenförmigen Metallsubstrate können z. B. aus Aluminium, Titan, Bronze, Zinn, Eisen oder auch weiteren Metallen oder geeigneten Legierungen wie z. B. Stählen oder Edelstählen bestehen, wobei die hier vorgenommene Aufzählung von Materialien die Erfindung nicht begrenzen, sondern nur beispielhaft erläutern soll. Bei Verwendung von Stahl- oder Edelstahlplättchen als Substrate werden allerdings häufig Perlglanzpigmente mit besonders günstigen Eigenschaften erhalten, so daß derartige Substratmaterialien vielfach bevorzugt sind.The platelet-shaped metal substrates can e.g. B. from Aluminum, titanium, bronze, tin, iron or others Metals or suitable alloys such as B. steels or Stainless steels exist, the list made here of materials do not limit the invention, but only should explain by way of example. When using steel or Stainless steel plates as substrates are common Pearlescent pigments with particularly favorable properties obtained, so that such substrate materials many times are preferred.

Die Größe der plättchenförmigen Metallsubstrate ist an sich nicht kritisch und es können daher Partikel in der für die beabsichtigte Anwendung geeigneten Größe verwendet werden. The size of the platelet-shaped metal substrates is in itself not critical and therefore particles in the for the intended application suitable size can be used.  

In der Regel liegt die Partikelgröße etwa zwischen 1 µm und 200 µm und insbesondere zwischen 5 µm-100 µm, während die Dicke zwischen 0,01 µm-20 µm und insbesondere 0,1 µm-5 µm beträgt.As a rule, the particle size is between 1 µm and 200 microns and especially between 5 microns-100 microns, while the Thickness between 0.01 µm-20 µm and in particular 0.1 µm-5 µm is.

Derartige Metallpartikel sind i.a. kommerziell verfügbar; allerdings ist es häufig erforderlich, die Metallpartikel vor einer Anwendung des erfindungsgemäßen Beschichtungsverfahrens zu reinigen und von zur Modifizierung der Oberfläche aufge­ brachten Verbindungen, Fettspuren oder anderen Verunreini­ gungen u.ä. zu reinigen.Such metal particles are generally commercially available; however, it is often necessary to pre-coat the metal particles an application of the coating method according to the invention to clean and up to modify the surface brought connections, grease traces or other contaminants gungen and the like to clean.

Die plättchenförmigen Metallsubstrate werden dann in Wasser suspendiert und es wird zunächst ein solcher pH eingestellt,The platelet-shaped metal substrates are then in water suspended and such a pH is first set,

  • - daß keine Metallauflösung stattfindet und- that no metal dissolution takes place and
  • - daß die in Wasser gelösten Eisenverbindungen, welche zudosiert werden, als Hydroxid ausgefällt werden.- That the iron compounds dissolved in water, which be metered in as hydroxide are precipitated.

Es hat sich gezeigt, daß der pH der wäßrigen Suspension vorteilhaft etwa zwischen 3,5 und 11 eingestellt wird. Im stark sauren Milieu wird für die meisten Metalle eine zu starke Metallauflösung beobachtet; dagegen sind viele Metalle - mit Ausnahme amphoterer Metalle wie z. B. Al - im stark Alkalischen zwar stabil, jedoch ist hier zur Vermeidung von Nebenfällungen eine sehr sorgfältige Zudosierung der gelösten Eisenverbindung erforderlich. Bevorzugt sind pH-Werte zwischen 4 und 10. It has been shown that the pH of the aqueous suspension is advantageously set between about 3.5 and 11. in the strongly acidic milieu becomes a too for most metals strong metal dissolution observed; against it are many metals - With the exception of amphoteric metals such as B. Al - im strong Alkaline is stable, but is here to avoid Incidental precipitation a very careful metering of the dissolved Iron connection required. PH values are preferred between 4 and 10.  

Die Zugabe der in Wasser gelösten Eisen(II)- oder Eisen(III)verbindung erfolgt so, daß das ausgefällte Eisen­ oxidhydrat unmittelbar auf dem Eisen niedergeschlagen wird und es zu keinen Nebenfällungen in der Suspension kommt. Als Eisen(III)-Verbindungen werden vorzugsweise Eisen(III)­ halogenide verwendet, während Ammoniumeisen(II)sulfat, Eisen(II)halogenide und insbesondere Eisen(II)sulfat geeig­ nete Eisen(II)-Verbindungen sind. Werden bei der Zugabe von Eisen(II)-Verbindungen gleichzeitig Oxidationsmittel, vor­ zugsweise Nitrat oder Chlorat, in stöchiometrischer Menge zudosiert, erhält man homogene und sehr glatte Mischoxid­ schichten, wie dies in DE 36 17 430 beschrieben ist. Misch­ oxidschichten können auch durch eine partielle Reduktion von Eisen(III)oxidschichten erhalten werden. In der Regel ist die Verwendung von Eisen(III)oxidschichten bevorzugt, es können aber auch zur Erzeugung spezieller Farbeffekte Mischoxid­ schichten gebildet werden.The addition of the iron (II) - or dissolved in water Iron (III) connection takes place so that the precipitated iron oxide hydrate is deposited directly on the iron and there are no secondary precipitation in the suspension. As Iron (III) compounds are preferably iron (III) halides used while ammonium iron (II) sulfate, Iron (II) halides and especially iron (II) sulfate are suitable nete iron (II) compounds. When adding Iron (II) compounds at the same time oxidizing agent preferably nitrate or chlorate, in a stoichiometric amount metered in, you get homogeneous and very smooth mixed oxide layers, as described in DE 36 17 430. Mixed oxide layers can also be reduced by a partial reduction of Iron (III) oxide layers can be obtained. As a rule, that is Use of iron (III) oxide layers preferred, it can but also to create special color effects mixed oxide layers are formed.

Während der Fällung der in Wasser gelösten Eisenverbindung wird der pH-Wert möglichst weitgehend konstant gehalten. Am zweckmäßigsten geschieht dies durch gleichzeitige Zugabe einer Base, wie z. B. KOH, NaOH oder Ammoniak; es ist jedoch auch möglich, ein geeignetes Puffersystem zu verwenden.During the precipitation of the iron compound dissolved in water the pH is kept as constant as possible. At the This is most conveniently done by simultaneous addition a base such as B. KOH, NaOH or ammonia; However, it is it is also possible to use a suitable buffer system.

Mit zunehmender Dicke der abgeschiedenen Eisenoxidhydrat­ schichten werden Interferenzfarben erzielt, die von silber über gold, rot und violett bis hin zu blau und schließlich zu Interferenzfarben höherer Ordnung gehen. Wird nur eine Eisenoxidschicht abgeschieden, wird die Beschichtung bei der gewünschten Interferenzfarbe abgebrochen. Das beschichtete Substrat wird in der Regel aus dem Reaktionsgemisch abge­ trennt, mit Wasser gewaschen und getrocknet. Dabei wird insbesondere bei höheren Trocknungstemperaturen häufig eine relativ starke Sinterung der Eisenoxidschicht beobachtet, so daß sich die Interferenzfarbe in Abhängigkeit von der Trock­ nungstemperatur und -dauer ändert. In der Regel wird bei Temperaturen zwischen 100°C und 900°C getrocknet; die Trocknungsdauer kann einige Minuten bis mehrere Stunden betragen und liegt üblicherweise zwischen 15 Minuten und etwa 3 Stunden.With increasing thickness of the deposited iron oxide hydrate layers of interference colors are achieved, that of silver over gold, red and purple to blue and finally to Interference colors of higher order go. Will only be one Deposited iron oxide layer, the coating is in the desired interference color canceled. That coated  Substrate is usually removed from the reaction mixture separates, washed with water and dried. Doing so especially at higher drying temperatures relatively strong sintering of the iron oxide layer was observed, see that the interference color depending on the dry temperature and duration changes. As a rule, at Temperatures between 100 ° C and 900 ° C dried; the Drying time can range from a few minutes to several hours amount and is usually between 15 minutes and about 3 hours.

Es ist häufig erwünscht, zusätzlich eine oder mehrere weitere Metalloxidschichten auf der Eisenoxidschicht abzuscheiden. Die Ausfällung weiterer Schichten kann unmittelbar im Anschluß an die Eisenoxidhydratabscheidung erfolgen, d. h. vor Trocknung der Eisenoxidhydratschicht. Es ist aber auch möglich, daß die Eisenoxidschicht zunächst getrocknet wird und erst dann weitere Metalloxide aufgebracht werden.It is often desirable to add one or more more Deposit metal oxide layers on the iron oxide layer. The precipitation of further layers can take place immediately in the Follow up on the iron oxide hydrate separation, d. H. in front Drying the iron oxide hydrate layer. It is also possible that the iron oxide layer is first dried and only then are further metal oxides applied.

Üblicherweise werden für die zusätzlichen Schichten farblose Oxide gewählt, wie z. B. Titandioxid, Zirkondioxid, Aluminiumoxid, Antimonoxid, Zinkoxid, Siliziumdioxid, Magnesiumoxid oder Zinndioxid, die jeweils allein oder auch im Gemisch aufgebracht werden können. Die zusätzlichen Schichten dienen häufig zur Erhöhung der mechanischen Stabi­ lität und/oder zur Verstärkung und/oder Modifizierung des Farbeffekts; sie sind dann i.a. dünner als die zuerst auf­ gebrachte Eisenoxidschicht. So ist z. B. aus DE 14 67 468 bekannt, daß eine verhältnismäßig dünne Aluminiumoxidschicht eine Stabilisierung der Eisenoxidschicht bewirkt, während die Farbe der Schichten wegen des niedrigen Brechungsindex von Aluminiumoxid nur verhältnismäßig wenig beeinflußt wird. Usually, the additional layers become colorless Oxides chosen such. B. titanium dioxide, zirconium dioxide, Aluminum oxide, antimony oxide, zinc oxide, silicon dioxide, Magnesium oxide or tin dioxide, either alone or also can be applied in a mixture. The additional Layers are often used to increase the mechanical stability lity and / or to reinforce and / or modify the Color effect; then they are generally thinner than that first on brought iron oxide layer. So z. B. from DE 14 67 468 known to have a relatively thin aluminum oxide layer stabilizes the iron oxide layer, while the Color of the layers due to the low refractive index of Alumina is affected relatively little.  

Es ist aber auch möglich, daß auf eine relativ dünne Eisen­ oxidschicht eine oder mehrere dickere zusätzliche Schichten weiterer Metalloxide aufgebracht werden, wobei diese dann die beobachteten Farbeffekte auch dann dominieren, wenn die zusätzlichen Schichten nur einen relativ niedrigen Brechungs­ index aufweisen. Erfindungsgemäße Pigmente, welche nur eine Eisenoxidschicht oder zusätzlich eine weitere Metalloxid­ schicht aufweisen, sind i.a. bevorzugt, und in Zweischicht­ systemen ist die zusätzlich aufgebrachte Metalloxidschicht vorzugsweise dünner als die Eisenoxidschicht. Der Massen­ anteil der aufgebrachten Metalloxide an dem Pigment beträgt etwa 1-70% und vorzugsweise 2-50%; in Zweischichtsystemen liegt das Verhältnis aus dem Massenanteil der Eisenoxid­ schicht zum Massenanteil der weiteren Metalloxidschicht vorzugsweise zwischen 1 und 20.But it is also possible that on a relatively thin iron oxide layer one or more thicker additional layers further metal oxides are applied, these then the observed color effects dominate even if the additional layers only have a relatively low refractive index have index. Pigments according to the invention, which are only one Iron oxide layer or an additional metal oxide layer, are generally preferred, and in two layers systems is the additionally applied metal oxide layer preferably thinner than the iron oxide layer. The masses proportion of the applied metal oxides in the pigment about 1-70% and preferably 2-50%; in two-layer systems is the ratio of the mass fraction of iron oxide layer to the mass fraction of the further metal oxide layer preferably between 1 and 20.

Die neuen Pigmente stellen eine wesentliche Bereicherung der Technik dar. Sie sind durch ein ausgezeichnetes Deckvermögen gekennzeichnet und zeigen gleichzeitig eine vom Beobachtungs­ winkel abhängige Interferenzfarbe, die durch die Dicke der Metalloxidschichten nahezu variiert und gezielt eingestellt werden kann. Darüberhinaus zeigen die Pigmente wegen der i.a. sehr gleichmäßigen Oberfläche der Metallplättchen einen hohen Glanz. Anwendungsgebiete ergeben sich sowohl in der Kosmetik, wo die erfindungsgemäßen Pigmente z. B. in Pudern, Salben, Emulsionen, Fettstiften etc. eingesetzt werden, als auch in der Technik, z. B. zur Pigmentierung von Farben, Lacken oder Kunststoffen. Die erfindungsgemäßen Pigmente eignen sich ganz besonders als Druckfarben für verschiedenste Druckverfahren, wie z. B. für den Siebdruck. Weiterhin können die erfindungs­ gemäßen Pigmente, insbesondere z. B. Stahlplättchen mit einer Eisenoxidschicht, magnetisiert werden. Die magnetische Wech­ selwirkung führt zu einer hohen Ordnung der Pigmentteilchen in Beschichtungen und damit zu sehr viel höheren Packungs­ dichten, was sich z. B. in einer erhöhten korrosionsschützen­ den Wirkung oder in einer sehr hohen Leitfähigkeit nieder­ schlägt. Weiter können die erfindungsgemäßen Pigmente z. B. in magneto-optischen Anzeigen eingesetzt werden.The new pigments represent a significant addition to the Technology. They are characterized by excellent opacity marked and at the same time show one from the observation Angle dependent interference color, which is determined by the thickness of the Metal oxide layers varied almost and set specifically can be. In addition, because of the i.a. very even surface of the metal platelets a high Shine. Areas of application arise both in cosmetics, where the pigments of the invention z. B. in powders, ointments, Emulsions, fat sticks etc. are used, as well as in the technology, e.g. B. for pigmenting paints, varnishes or Plastics. The pigments according to the invention are very suitable especially as printing inks for various printing processes, such as B. for screen printing. Furthermore, the fiction appropriate pigments, especially e.g. B. steel plate with a  Iron oxide layer to be magnetized. The magnetic change interaction leads to a high order of the pigment particles in coatings and therefore in much higher packs write what z. B. in an increased corrosion protection the effect or in a very high conductivity beats. Furthermore, the pigments according to the invention can, for. B. in magneto-optical displays are used.

Die folgenden Beispiele sollen die Erfindung erläutern, ohne sie zu begrenzen.The following examples are intended to illustrate the invention without limit them.

Beispiel 1example 1

200 g Stahlplättchen (Stainless Steel 316 L, Fo-1117-89, Fa. United States Bronze Powders Incorporated, Flemington, NJ) werden unter Rühren (900 rpm) bei 80°C in 1,2 l voll­ entsalztem Wasser suspendiert und mit 200 ml 15%iger NaOH- Lösung versetzt. Es wird bei 80°C 30 Minuten gerührt und anschließend werden die Stahlplättchen abfiltriert und mit 8 l vollentsalztem Wasser gewaschen. Die gereinigten Stahl­ plättchen werden dann mehrere Stunden bei 120°C getrocknet.200 g steel plate (Stainless Steel 316 L, Fo-1117-89, United States Bronze Powders Incorporated, Flemington, NJ) are full with stirring (900 rpm) at 80 ° C in 1.2 l deionized water and suspended with 200 ml of 15% NaOH Solution added. It is stirred at 80 ° C for 30 minutes and then the steel plates are filtered off and with Washed 8 liters of deionized water. The cleaned steel platelets are then dried at 120 ° C. for several hours.

25 g der gereinigten Stahlplättchen werden in 500 ml vollent­ salztem Wasser suspendiert und auf 75°C erhitzt. Mit 5%iger HCl wird ein pH von 4 eingestellt und anschließend werden innerhalb von 160 Minuten bei 200 ml wäßrige FeCl3-Lösung (Fe-Gehalt 2,1 Massenprozent) hinzudosiert. Während des Zudosierens der FeCl3-Lösung wird der pH der Suspension durch Zugabe von 15%iger wäßriger NaOH-Lösung bei 4 gehalten. 25 g of the cleaned steel plates are suspended in 500 ml of fully deionized water and heated to 75 ° C. A pH of 4 is set with 5% HCl and then metered in over a period of 160 minutes with 200 ml of aqueous FeCl 3 solution (Fe content 2.1% by mass). While the FeCl 3 solution is being metered in, the pH of the suspension is kept at 4 by adding 15% strength aqueous NaOH solution.

Anschließend wird bei 75°C 30 Minuten lang nachgerührt. Das erhaltene Pigment wird abfiltriert, mit vollentsalztem Wasser neutral gewaschen und mehrere Stunden bei 120°C getrocknet.The mixture is then stirred at 75 ° C for 30 minutes. The The pigment obtained is filtered off with deionized water washed neutral and dried at 120 ° C for several hours.

Das getrocknete Pigment weist eine stahlgraue Körperfarbe und eine grün-blaue Interferenzfarbe auf und ist durch ein hohes Deckvermögen gekennzeichnet. Wird das Pigment 30 Minuten bei 800°C geglüht, erhält man ein rauhes, schwarzes Pigment.The dried pigment has a steel gray body color and a green-blue interference color and is characterized by a high Marked opacity. The pigment is at 30 minutes Annealed at 800 ° C, you get a rough, black pigment.

Beispiel 2Example 2

50 g der vorgereinigten Stahlplättchen aus Beispiel 1 werden in 1 l vollentsalztem Wasser suspendiert und auf 75°C erhitzt. Anschließend wird mit 5%iger wäßriger HCl ein pH von 4 eingestellt und es werden innerhalb von 75 Minuten 81 ml einer wäßrigen FeCl3-Lösung (Fe-Gehalt 2,1 Massenprozent) zudosiert.50 g of the pre-cleaned steel flakes from Example 1 are suspended in 1 l of completely deionized water and heated to 75.degree. A pH of 4 is then set with 5% aqueous HCl and 81 ml of an aqueous FeCl 3 solution (Fe content 2.1% by mass) are metered in over the course of 75 minutes.

Danach wird mit 5%iger wäßriger HCl ein pH von 2,2 einge­ stellt und innerhalb 30 Minuten werden 27 ml einer wäßrigen TiCl4-Lösung (350 g/l TiCl4) zugegeben. Es wird 30 Minuten nachgerührt und das erhaltene Pigment wird dann abfiltriert, neutral gewaschen und mehrere Stunden getrocknet.Then a pH of 2.2 is set with 5% aqueous HCl and 27 ml of an aqueous TiCl 4 solution (350 g / l TiCl 4 ) are added within 30 minutes. The mixture is stirred for 30 minutes and the pigment obtained is then filtered off, washed neutral and dried for several hours.

Das erhaltene Pigment hat eine schwarz-graue Körperfarbe und eine grün-silberne Interferenzfarbe und ein hohes Deck­ vermögen. Wird das Pigment 30 Minuten bei 500°C getrocknet, weist es eine blau-violette Interferenzfarbe auf, während bei einer Glühtemperatur von 300°C eine kupfer-rote Interferenz­ farbe resultiert; in beiden Fällen ändert sich die Körper­ farbe nicht.The pigment obtained has a black-gray body color and a green-silver interference color and a high deck capital. If the pigment is dried at 500 ° C for 30 minutes, it shows a blue-violet interference color, while at a copper-red interference at an annealing temperature of 300 ° C color results; in both cases the body changes color not.

Claims (9)

1. Plättchenförmiges Pigment, welches ein plättchenförmiges metallisches Substrat enthält, das mit einer oder meh­ reren Metalloxidschichten bedeckt ist, dadurch gekenn­ zeichnet, daß die auf die Substratoberfläche aufge­ brachte Metalloxidschicht eine Eisenoxidschicht ist.1. Platelet-shaped pigment which contains a platelet-shaped metallic substrate which is covered with one or more metal oxide layers, characterized in that the metal oxide layer applied to the substrate surface is an iron oxide layer. 2. Pigment nach Anspruch 1, dadurch gekennzeichnet, daß die Eisenoxidschicht im wesentlichen aus Eisen(III)oxid besteht.2. Pigment according to claim 1, characterized in that the Iron oxide layer consisting essentially of iron (III) oxide consists. 3. Pigment nach Anspruch 1, dadurch gekennzeichnet, daß die Eisenoxidschicht Eisen(III)oxid enthält.3. Pigment according to claim 1, characterized in that the Iron oxide layer contains iron (III) oxide. 4. Pigment nach einem der Ansprüche 1-3, dadurch gekenn­ zeichnet, daß die Schichtdicke der Metalloxidschicht oder -schichten zur Erzeugung verschiedener Interferenz­ farben variiert ist.4. Pigment according to any one of claims 1-3, characterized records that the layer thickness of the metal oxide layer or layers to create various interference colors is varied. 5. Pigment nach einem der Ansprüche 1-4, dadurch gekenn­ zeichnet, daß sich über der auf das Substrat aufgebrach­ ten Eisenoxidschicht mindestens eine weitere Oxidschicht befindet, welche aus TiO2, ZrO2, SnO2, Cr2O3, BiOCl, FeO, Fe2O3, A12O3, SiO2, ZnO oder Gemischen dieser Metalloxide besteht. 5. Pigment according to any one of claims 1-4, characterized in that there is at least one further oxide layer above the iron oxide layer applied to the substrate, which consists of TiO 2 , ZrO 2 , SnO 2 , Cr 2 O 3 , BiOCl, FeO , Fe 2 O 3 , A1 2 O 3 , SiO 2 , ZnO or mixtures of these metal oxides. 6. Verfahren zur Herstellung von Pigmenten nach einem der Ansprüche 1-5, dadurch gekennzeichnet, daß eine wäßrige Suspension der plättchenförmigen metallischen Substrate bei weitgehend konstanter Temperatur und weitgehend konstantem pH mit einer Eisensalzlösung versetzt wird und die auf diese Weise beschichteten metallischen Substrate anschließend abgetrennt und gegebenenfalls gewaschen, getrocknet und/oder geglüht werden.6. Process for the production of pigments according to one of the Claims 1-5, characterized in that an aqueous Suspension of the platelet-shaped metallic substrates at largely constant temperature and largely constant pH is mixed with an iron salt solution and the metallic coated in this way Subsequently substrates separated and, if necessary washed, dried and / or annealed. 7. Verfahren nach Anspruch 6, dadurch gekennzeichnet, daß auf die Eisenoxidschicht eine oder mehrere weitere Metalloxidschichten aufgefällt werden, wobei die Fällung vor der Abtrennung der Stahlplättchen aus der Suspension oder auch auf das gewaschene, getrocknete und/oder geglühte, mit Eisenoxid beschichtete Stahlplättchen, erfolgen kann.7. The method according to claim 6, characterized in that one or more others on the iron oxide layer Metal oxide layers are noticed, the precipitation before the steel plates are separated from the suspension or also on the washed, dried and / or annealed steel plates coated with iron oxide, can be done. 8. Verfahren nach einem der Ansprüche 6 oder 7, dadurch gekennzeichnet, daß die Abscheidung des Eisenoxids bei einem pH zwischen 4 und 10 erfolgt.8. The method according to any one of claims 6 or 7, characterized characterized in that the deposition of the iron oxide at a pH between 4 and 10 takes place. 9. Verwendung der plättchenförmigen Pigmente nach einem der Ansprüche 1-8 zur Pigmentierung von Lacken, Farben, Kunststoffen oder Kosmetika.9. Use of the platelet-shaped pigments according to one of the Claims 1-8 for pigmenting lacquers, paints, Plastics or cosmetics.
DE19914104310 1991-02-13 1991-02-13 Flaky pigment having metal substrate with iron oxide coating - prodn. by pptn. from aq. soln., used in paint, plastics, cosmetics or magneto=optical medium Withdrawn DE4104310A1 (en)

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EP0571836A1 (en) * 1992-05-27 1993-12-01 BASF Aktiengesellschaft Brilliant pigments consisting of flaky metallic substrates with multiple coatings
EP0580022A2 (en) * 1992-07-16 1994-01-26 BASF Aktiengesellschaft Brilliant pigments based on aluminium platelets coated with metal oxide and with total carbon content lower than one tenth per cent weight
EP0593991A2 (en) * 1992-10-19 1994-04-27 The Mearl Corporation Intensely colored nacreous pigments
EP0632110A1 (en) * 1993-07-02 1995-01-04 BASF Aktiengesellschaft Brilliant pigments containing bismuth vanadate
EP0673980A2 (en) * 1994-03-24 1995-09-27 Silberline Limited Coloured flaky iron or iron alloy pigments
EP0655486A3 (en) * 1993-11-25 1995-11-29 Basf Ag Magnetisable brilliant pigments.
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EP0747453A2 (en) * 1995-06-05 1996-12-11 Toyo Aluminium Kabushiki Kaisha Colored titanium flakes, process for their preparation and resin composition containing colored titanium flakes
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US6369147B1 (en) 1999-01-25 2002-04-09 Ciba Specialty Chemicals Corporation Color effect pigments and method of forming the same
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WO2003000801A3 (en) * 2001-04-27 2003-02-27 Flex Products Inc Multi-layered magnetic pigments and foils
EP1549279A2 (en) * 2002-10-11 2005-07-06 Nicholas V. Dr. Perricone Topical use of microfine calcined alumina
WO2006018213A2 (en) * 2004-08-19 2006-02-23 Eckart Gmbh & Co. Kg Electrically conductive pigments having a ferromagnetic core, the production thereof and their use
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EP0571836A1 (en) * 1992-05-27 1993-12-01 BASF Aktiengesellschaft Brilliant pigments consisting of flaky metallic substrates with multiple coatings
EP0580022A2 (en) * 1992-07-16 1994-01-26 BASF Aktiengesellschaft Brilliant pigments based on aluminium platelets coated with metal oxide and with total carbon content lower than one tenth per cent weight
EP0580022A3 (en) * 1992-07-16 1994-09-14 Basf Ag Brilliant pigments based on aluminium platelets coated with metal oxide and with total carbon content lower than one tenth per cent weight
EP0593991A2 (en) * 1992-10-19 1994-04-27 The Mearl Corporation Intensely colored nacreous pigments
EP0593991A3 (en) * 1992-10-19 1994-09-14 Mearl Corp Intensely colored nacreous pigments
US5411586A (en) * 1993-07-02 1995-05-02 Basf Aktiengesellschaft Luster pigments containing bismuth vanadate
EP0632110A1 (en) * 1993-07-02 1995-01-04 BASF Aktiengesellschaft Brilliant pigments containing bismuth vanadate
EP0655486A3 (en) * 1993-11-25 1995-11-29 Basf Ag Magnetisable brilliant pigments.
EP0673980A2 (en) * 1994-03-24 1995-09-27 Silberline Limited Coloured flaky iron or iron alloy pigments
EP0673980A3 (en) * 1994-03-24 1996-02-07 Silberline Ltd Coloured flaky iron or iron alloy pigments.
EP0717088A3 (en) * 1994-12-14 1999-01-07 Basf Corporation Opacification of optically variable pigments for use in waterborne coating compositions
EP0852977A1 (en) * 1995-03-14 1998-07-15 Nittetsu Mining Co., Ltd. Powder having multilayer film on its surface and process for preparing the same
EP0852977B1 (en) * 1995-03-14 2003-06-04 Nittetsu Mining Co., Ltd. Powder having multilayer film on its surface and process for preparing the same
EP0742271A2 (en) * 1995-05-12 1996-11-13 MERCK PATENT GmbH Coloured pigments
EP0742271A3 (en) * 1995-05-12 1998-05-27 MERCK PATENT GmbH Coloured pigments
US5766334A (en) * 1995-06-05 1998-06-16 Toyo Aluminium K. K. Colored titanium flakes, process for their preparation and resin composition containing colored titanium flakes
EP0747453A3 (en) * 1995-06-05 1997-04-16 Toyo Aluminium Kk Colored titanium flakes, process for their preparation and resin composition containing colored titanium flakes
EP0747453A2 (en) * 1995-06-05 1996-12-11 Toyo Aluminium Kabushiki Kaisha Colored titanium flakes, process for their preparation and resin composition containing colored titanium flakes
EP0803549A2 (en) * 1996-04-25 1997-10-29 Ciba SC Holding AG Brilliant coloured pigments
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