EP0368973B1 - Air-gap interference pigments, manufacture and use thereof - Google Patents

Air-gap interference pigments, manufacture and use thereof

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Publication number
EP0368973B1
EP0368973B1 EP89906006A EP89906006A EP0368973B1 EP 0368973 B1 EP0368973 B1 EP 0368973B1 EP 89906006 A EP89906006 A EP 89906006A EP 89906006 A EP89906006 A EP 89906006A EP 0368973 B1 EP0368973 B1 EP 0368973B1
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EP
European Patent Office
Prior art keywords
pigments
treatment
air gap
air
platelet
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.)
Expired
Application number
EP89906006A
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German (de)
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EP0368973A1 (en
Inventor
Hans Kolb
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Naintsch Mineralwerke GmbH
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Naintsch Mineralwerke GmbH
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Publication of EP0368973A1 publication Critical patent/EP0368973A1/en
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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
    • C09C1/40—Compounds of aluminium
    • C09C1/42—Clays
    • 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
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/20—Two-dimensional structures
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/20—Two-dimensional structures
    • C01P2002/22—Two-dimensional structures layered hydroxide-type, e.g. of the hydrotalcite-type
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/20—Particle morphology extending in two dimensions, e.g. plate-like
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/54—Particles characterised by their aspect ratio, i.e. the ratio of sizes in the longest to the shortest dimension
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C2200/00—Compositional and structural details of pigments exhibiting interference colours
    • C09C2200/10—Interference pigments characterized by the core material
    • C09C2200/102—Interference pigments characterized by the core material the core consisting of glass or silicate material like mica or clays, e.g. kaolin

Definitions

  • Air gap interference pigments their production and use
  • the invention relates to platelet-shaped pigments which differ from previously known pigments by a new, characteristic structure.
  • colorants are divided into inorganic and organic colorants.
  • the inorganic colorants include the inorganic pigments, which are further converted into inorganic white pigments (e.g. barium sulfate, titanium dioxide, zinc oxide), inorganic colored pigments (e.g. chrome yellow, iron oxide red, cobalt blue), inorganic black pigments (e.g. iron oxide black, pigment black), inorganic luminous pigments (e.g. phosphorescent pigments fluorescent pigments) and inorganic gloss pigments.
  • inorganic white pigments e.g. barium sulfate, titanium dioxide, zinc oxide
  • inorganic colored pigments e.g. chrome yellow, iron oxide red, cobalt blue
  • inorganic black pigments e.g. iron oxide black, pigment black
  • inorganic luminous pigments e.g. phosphorescent pigments fluorescent pigments
  • inorganic gloss pigments e.g. phosphorescent pigments fluorescent pigments
  • These pigments are essentially based on purely metallic reflection. Without going into the theory of metallic reflection in detail, it can also be understood as a refraction, but due to the very high refractive index of the metal, the light only enters the surface for a very short distance, on the order of magnitude less angstroms, and is then reflected. Examples of such metallic effect pigments are aluminum and copper-zinc alloys.
  • Pearlescent pigments have a platelet-shaped substrate which has a diameter / thickness ratio of at least 1:50, but usually 1: 100 and above and which is covered with a thin layer of a highly light-refractive oxide.
  • a high refractive index difference must exist between the platelet-shaped substrate and the applied oxide layer, for example as with mica 1.5 and rutile 2.6 to 2.9 or other metal oxides to 3.
  • the oxide layer applied to the platelet-shaped substrate must be tight and without an air layer issue.
  • the thickness of the oxide layer must be such that light rays reflected on the surface as a result of the high refractive index differences come to interference.
  • Examples of such pearlescent pigments are titanium dioxide on mica, see here for example
  • the pearlescent pigments thus represent interference pigments in which the above-mentioned features are realized.
  • the effect of the pearlescent pigments is largely dependent on the grain size or the platelet diameter. With a diameter of less than 15 ⁇ m, the pearlescent pigments only have a matt, diffuse, not very strong pearlescent effect and good hiding power, with grain sizes between 5 and 25 ⁇ m they have a silk gloss and moderate hiding power, with a grain size between 10 and 40 ⁇ m they have a pronounced pearlescent and medium hiding power, with a grain size between 3 and 10 ⁇ m they have a shimmering pearlescent with a low hiding power and with a grain size between 20 and 200 ⁇ m they have a tinsel luster with poor hiding power.
  • Hiding power is understood here to mean the covering power on a normative base when the respective pigment is stirred into a transparent or film-forming organic binder, it being noted that such pigments can only be used in organic binders, but not in inorganic binders.
  • the colored interference pigments can be divided into two groups:
  • Fire-colored metal bronzes which are obtained by coating metals by oxidative treatment of the surface with a thin metal oxide layer, which is translucent due to the small thickness.
  • the metal-reflecting substrate reflects the light passing through the oxide layer almost completely and interference occurs in the penetrating and reflected beam, which leads to color effects in connection with the oxide color.
  • interference colors of a clear type appear, which give rise to a gold tone, a silver tone, a red tone, a green tone, etc., whereas the previously mentioned pearlescent pigments show a colored pearlescent luster.
  • Colored pearlescent pigments multi-layer interference absorption pigments: The same requirements apply as for pearlescent pigments, but in addition to the titanium dioxide layer there is another layer of a translucent but light-absorbing oxide, such as iron oxide or chromium oxide. Examples of such pigments are iron oxide over titanium oxide on mica. Depending on the thickness of the oxide layers, interference pigments with a pronounced metal character, such as silver, gold, bronze, or also extremely colored pigments are formed.
  • Air gap interference pigments :
  • the new air gap interference pigments differ from the pearlescent pigments and the colored interference pigments in that the colors are caused by air gaps between them, which are very small, for example in the range of 1/10 ⁇ m and even significantly less.
  • the material layer lying above and below the air gaps can consist of the same material and thus also have the same refractive index.
  • the refractive index itself can be small and be of the order of 1.5 to 1.6 (biotite 1.6 to 1.66, muscovite 1.55 to 1.64, vermiculite 1.58, pyrophyllite 1.55 to 1 , 6, talc 1.58 to 1.54).
  • the diameter / thickness ratio of the platelet-shaped substrate can be in the range from 1: 5 to a maximum of 1:50.
  • the substrate must be platelet-shaped; the diameter / thickness ratio of the plate can be well below 50; in the platelet itself there must be fine air gaps with a thickness of significantly less than 1 ⁇ m, so that the platelet is made up of platelet-shaped solid substance-air gap-platelet-shaped solid substance; the refractive index of the platelet-shaped substrate can be low, around 1.5 or below; in contrast to the pearlescent pigments and the colored interference pigments, after the production of the air gap interference pigments, these can be subjected to a post-grinding, whereby the grain sizes can be approached down to the smallest unit, in which at least one layer package of solid substance-air gap solid substance is also contained . Furthermore, there must not be as much plane parallelism between the top and bottom of the plate as with pearlescent pigments or colored pearlescent pigments.
  • the present invention thus relates to platelet-shaped air gap interference pigments which are distinguished by closely adjacent layers of medium to low refractive index minerals with interposed air gaps of less than 1 ⁇ m in thickness.
  • the platelets have a diameter / thickness ratio in the range from 1: 5 to 1:50.
  • the mineral layers can be monomineral or heteromineral. A high plane parallelism is not necessary.
  • each substrate is colored, add a certain additive color to the interferences solid-air gap-solid or solid-gas-solid. If, for example, the substrate with a low refractive index has a somewhat gray to bluish tint, a silver effect is produced; if the substrate has a brownish tint, then there is a gold effect; if the substrate has a greenish tint, a silver-bronze effect is produced.
  • the air gap must not exceed 1 ⁇ m. If it were too large, when the pigment is embedded in a binder, it enters the air gap. However, if the organic binding agent entered the air gap, this would be eliminated and the desired gloss effect would inevitably disappear.
  • phyllosilicates (leaf silicates) are of particular interest, in which the essential component of the silicates, the SiO 4 tetrahedra, is two-dimensionally networked in rings.
  • Phyllosilicates are characterized by a platelet shape and excellent splittability perpendicular to the platelet axis.
  • two structural elements can be distinguished in phyllosilicates, namely a tetrahedral layer (Si, Al, Fe 3 ) and an octahedral layer with octahedral medium-sized cations.
  • the phyllosilicates can be systematically built up through a variable combination of the octahedron and tetrahedron layers, which are divided into two-layer, three-layer and four-layer minerals.
  • Specific examples of phyllosilicates which can be used according to the invention are mica, hydro-mica, illite, muscovite, biotite, phlogopite, pyrophtyllite, chlorite and talc.
  • the formation of layers of medium-low to low-index minerals with intermediate, at most 1 ⁇ m thick thin air gaps, essential to the invention can be brought about by the fact that three- and four-layer phyllosilicates undergo a temperature treatment above the H 2 O-, OH- or fluorine - be subjected to the escape temperature.
  • a temperature treatment only water up to a temperature of about 250 ° C. is expelled first, from a temperature in the larger range of 400 to 600 ° C. then also OH and F. Later, new phases are formed, with the OH ions escaping between there are several 100 ° temperature differences between the grid and the emergence of the new phases can.
  • manipulation of the color can be brought about by leaching the phyllosilicates with chemicals.
  • the leaching can take place before and / or after the temperature treatment and can be carried out with acids, preferably hydrochloric acid, or by adding foreign ions, expediently as leaching in corresponding salt solutions, as hydrothermal treatment or as pressure treatment or vacuum treatment in such salt solutions.
  • the temperature treatment according to the invention can be carried out both in normal air, in inert gases, in a reducing atmosphere or in a pure oxygen atmosphere.
  • the use of different atmospheres in temperature treatment creates special effects by forcing ion types with several valences into certain valences.
  • chlorite which takes on a gold effect (trivalent iron) during a temperature treatment in an oxidizing atmosphere (air)
  • a silver effect can be achieved by temperature treatment in an inert atmosphere.
  • platelet-shaped air gap interference pigments according to the invention no change in grinding. They are weather-resistant and chemically inert and are therefore suitable for use in a wide variety of areas, in particular for pigmentation, effecting, coloring and utilizing the platelet structure in pigment pastes, paints and varnishes based on organic and inorganic binders, paper and cardboard, building materials, plastics, alloys and melts, ceramics and glasses, roof coatings and cosnetics (personal care products).
  • binder decomposition does not occur, as is the case with titanium dioxide modifications.
  • the procedure for producing the platelet-shaped air gap interference pigments according to the invention is as follows:
  • the 0.125 to 0.5 mm fraction is sieved out of the mined raw material and subjected to gravity sorting.
  • the fraction with predominantly platelet-shaped material is submitted to a strong field magnetic separation and the magnetic fraction is separated off.
  • This concentrate is calcined at 500 to 1,100 ° C; the burning time depends on the grain distribution and composition.
  • the calcined product is ground and sieved into the desired grain fractions.
  • Plastics and casting resins can be formulated, for example, from 70% by weight polyester resin and 30% by weight air gap interference pigment.
  • a decorative resin, for example for surfboards, can be built up from 98% by weight of casting resin and 2% by weight of air gap interference pigment.
  • the new air gap interference pigments can be used, for example, as a scattering agent for wallpapers; in the ceramic field, the new pigments can be embedded in the glaze or directly in the fragments.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Pigments, Carbon Blacks, Or Wood Stains (AREA)
  • Paints Or Removers (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)
  • Coloring (AREA)
  • Steroid Compounds (AREA)
  • Road Signs Or Road Markings (AREA)

Abstract

Laminated air-gap interference pigments are characterized by contiguous layers of medium- to low-refraction minerals with thin intercalated air-gaps less than 1 mu m thick, and by a diameter-to-thickness ratio of the laminae between 1:5 and 1:50. The pigments are obtained by subjecting three- and four-layer phyllosilicates to a heat treatment at a temperature greater than that at which H20, OH or F are released.

Description

Luftspaltlnterferenzpigmente, ihre Herstellung und Verwendung Air gap interference pigments, their production and use
Die Erfindung bezieht sich auf plättchenförmige Pigmente, die sich durch einen neuen, charakteristischen Aufbau von bisher bekannten Pigmenten unterscheiden.The invention relates to platelet-shaped pigments which differ from previously known pigments by a new, characteristic structure.
Gemäß DIN 55944 werden Farbmittel in anorganische und organische Farbmittel eingeteilt. Zu den anorganischen Farbmitteln zählen die anorganischen Pigmente, die weiter in anorganische Weißpigmente (z.B. Bariumsulfat, Titandioxid, Zinkoxid), anorganische Buntpigmente (z.B. Chromgelb, Eisenoxidrot, Cobaltblau), anorganische Schwarzpigmente (z.B.Eisenoxidschwarz, Pigmentruß), anorganische Leuchtpigmente (z.B.phosphoreszierende Pigmente, fluoreszierende Pigmente) und anorganische Glanzpigmente unterteilt werden. Zu der letztgenannten Gruppe gehören die folgenden Untergruppen:According to DIN 55944, colorants are divided into inorganic and organic colorants. The inorganic colorants include the inorganic pigments, which are further converted into inorganic white pigments (e.g. barium sulfate, titanium dioxide, zinc oxide), inorganic colored pigments (e.g. chrome yellow, iron oxide red, cobalt blue), inorganic black pigments (e.g. iron oxide black, pigment black), inorganic luminous pigments (e.g. phosphorescent pigments fluorescent pigments) and inorganic gloss pigments. The latter group includes the following sub-groups:
Metalleffektpigmente:Metallic effect pigments:
Diese Pigmente basieren im wesentlichen auf rein metallischer Reflexion. Ohne im einzelnen auf die Theorie der metallischen Reflexion einzugehen, ist diese auch als Brechung aufzufassen, doch tritt infolge des sehr hohen Brechungsquotienten des Metalles das Licht nur einen sehr kurzen Weg, in der Größenordnung weniger Angström, in die Oberfläche ein und wird dann zurückgeworfen. Beispiele für derartige Metalleffektpigmente sind Aluminium sowie Kupfer—Zink-Legierungen.These pigments are essentially based on purely metallic reflection. Without going into the theory of metallic reflection in detail, it can also be understood as a refraction, but due to the very high refractive index of the metal, the light only enters the surface for a very short distance, on the order of magnitude less angstroms, and is then reflected. Examples of such metallic effect pigments are aluminum and copper-zinc alloys.
Perlglanzpigmente:Pearlescent Pigments:
Perlglanzpigmente weisen ein plättchenförmiges Substrat auf, das ein Durchmesser/Dicken-Verhältnis von mindestens 1:50, meistens jedoch 1:100 und darüber aufweist und das mit einer dünnen Schicht eines hoch-lichtbrechenden Oxids bedeckt ist. Zwischen dem plättchenförmigen Substrat und der aufgebrachten Oxidschicht muß ein hoher Brechungsquotientenunterechied gegeben sein, etwa wie bei Glimmer 1,5 und Rutil 2,6 bis 2,9 oder anderen Metalloxiden bis 3. Weiterhin muß die auf das pblättchenförmige Substrat aufgebrachte Oxidschicht dicht und ohne Luftschicht anliegen. Die Dicke der Oxidschicht muß so beschaffen sein, daß oberflächig infolge der hohen Brechungsquotientenunterschiede reflektierte Lichtstrahlen zur Interferenz gelangen. Beispiele für derartige Perlglanzpigmente sind Titandioxid auf Glimmer, siehe hiezu beispielsweisePearlescent pigments have a platelet-shaped substrate which has a diameter / thickness ratio of at least 1:50, but usually 1: 100 and above and which is covered with a thin layer of a highly light-refractive oxide. A high refractive index difference must exist between the platelet-shaped substrate and the applied oxide layer, for example as with mica 1.5 and rutile 2.6 to 2.9 or other metal oxides to 3. Furthermore, the oxide layer applied to the platelet-shaped substrate must be tight and without an air layer issue. The thickness of the oxide layer must be such that light rays reflected on the surface as a result of the high refractive index differences come to interference. Examples of such pearlescent pigments are titanium dioxide on mica, see here for example
- DE 31 51 354 A1,- DE 31 51 354 A1,
- DE 31 51 355 A1,- DE 31 51 355 A1,
- DE 32 35 017 A1, - EP 01 142 695 A1 und- DE 32 35 017 A1, - EP 01 142 695 A1 and
- DE 35 17 430 A1.- DE 35 17 430 A1.
Die Perlglanzpigmente stellen somit Ihterferenzpigmente dar, in welchen die vorstehend angeführten Merkmale verwirklicht sind. Der Effekt der Perlglanzpigmente ist wesentlich von der Korngröße bzw. vom Plättchendurchmesser abhängig. Bei einem Durchmesser unter 15 μm weisen die Perlglanzpigmente nur einen matten, diffusen, nicht sehr starken Perleffekt und ein gutes Deckvermögen auf, bei Korngrößen zwischen 5 und 25 μm haben sie einen Seidenglanz und ein mäßiges Deckvermögen, bei einer Korngröße zwischen 10 und 40 μm haben sie einen ausgeprägten Perlglanz und ein mittleres Deckvermögen, bei einer Korngröße zwischen 3 und 10 μm haben sie einen schimmernden Perlglanz mit einem geringen Deckvermögen und bei einer Korngröße zwischen 20 und 200 μm haben sie einen Flitterglanz mit einem schlechten Deckvermögen. Unter Deckvermögen wird hiebei die Deckkraft auf einer normativen Unterlage bei Einrühren des jeweiligen Pigmentes in ein durchsichtiges oder filmbildendes organisches Bindemittel verstanden, wobei festzuhalten ist, daß derartige Pigmente nur in organischen Bindemitteln Anwendung finden können, nicht aber in anorganischen Bindemitteln.The pearlescent pigments thus represent interference pigments in which the above-mentioned features are realized. The effect of the pearlescent pigments is largely dependent on the grain size or the platelet diameter. With a diameter of less than 15 μm, the pearlescent pigments only have a matt, diffuse, not very strong pearlescent effect and good hiding power, with grain sizes between 5 and 25 μm they have a silk gloss and moderate hiding power, with a grain size between 10 and 40 μm they have a pronounced pearlescent and medium hiding power, with a grain size between 3 and 10 μm they have a shimmering pearlescent with a low hiding power and with a grain size between 20 and 200 μm they have a tinsel luster with poor hiding power. Hiding power is understood here to mean the covering power on a normative base when the respective pigment is stirred into a transparent or film-forming organic binder, it being noted that such pigments can only be used in organic binders, but not in inorganic binders.
Bunte Interferenzpigmente:Colorful interference pigments:
Die bunten Interferenzpigmente können in zwei Gruppen unterteilt werden:The colored interference pigments can be divided into two groups:
Feuergefärbte Metallbronzen, die dadurch erhalten werden, daß Metalle durch oxidative Behandlung der Oberfläche mit einer dünnen metalloxidischen Schicht überzogen werden, welche wegen der geringen Dicke lichtdurchlässig ist. Der metallreflektierende Untergrund reflektiert das durch die Oxidschicht durchtretende Licht nahezu vollständig und es tritt im eindringenden und reflektierten Strahl eine Interferenz ein, die im Zusammenhang mit der Oxidfarbe zu Farbeffekten führt. Bei den feuergefärbten Metallbronzen treten Interferenzfarben klarer Art auf, die etwa einen Goldton, einen Silberton, einen Rotton, einen Grünton usw. hervorrufen, wogegen die zuvor erwähnten Perlglanzpigmente einen Buntperlglanz zeigen.Fire-colored metal bronzes, which are obtained by coating metals by oxidative treatment of the surface with a thin metal oxide layer, which is translucent due to the small thickness. The metal-reflecting substrate reflects the light passing through the oxide layer almost completely and interference occurs in the penetrating and reflected beam, which leads to color effects in connection with the oxide color. In the case of the fire-colored metal bronzes, interference colors of a clear type appear, which give rise to a gold tone, a silver tone, a red tone, a green tone, etc., whereas the previously mentioned pearlescent pigments show a colored pearlescent luster.
Bunt-Perlglanzpigmente (Mehrschichtinterferenz-Absorptions-Pigmente): Hier treffen die gleichen Voraussetzungen zu wie bei den Perlglanzpigmenten, zusätzlich zur Titandioxidschicht kommt jedoch noch eine weitere Schicht eines lichtdurchlässigen, aber lichtabsorbierenden Oxids, wie Eisenoxid oder Chromoxid, hinzu. Beispiele für derartige Pigmente sind Eisenoxid über Titanoxid auf Glimmer. Je nach der Dicke der Oxidschichten entstehen Interferenzpigmente mit einem ausgesprochenen Metallcharakter, wie Silber, Gold, Bronze, oder auch ausgesprochen farbige Pigmente.Colored pearlescent pigments (multi-layer interference absorption pigments): The same requirements apply as for pearlescent pigments, but in addition to the titanium dioxide layer there is another layer of a translucent but light-absorbing oxide, such as iron oxide or chromium oxide. Examples of such pigments are iron oxide over titanium oxide on mica. Depending on the thickness of the oxide layers, interference pigments with a pronounced metal character, such as silver, gold, bronze, or also extremely colored pigments are formed.
Luftspalt-Interferenzpigmente:Air gap interference pigments:
Die neuen Luftspalt-Interferenzpigmente unterscheiden sich von den Perlglanzpignenten und den bunten Interferenzpigmenten dadurch, daß die Farben durch zwischenliegende Luftspalten, die sehr klein sind, etwa im Bereich von 1/10 μm und noch wesentlich darunter, hervorgerufen werden. Die über und unter den Luftspalten liegende Materialschicht kann durchaus aus dem gleichen Material bestehen und damit auch den gleichen Brechungsquotienten aufweisen. Der Brechungsquotient selbst kann klein sein und etwa in der Größenordnung von 1,5 bis 1,6 liegen (Biotit 1,6 bis 1,66, Muskovit 1,55 bis 1,64, Vermikulit 1,58, Pyrophyllit 1,55 bis 1,6, Talk 1,58 bis 1,54). Das Durchmesser/- Dicken-Verhältnis des plättchenförmigen Substrats kann im Bereich von 1:5 bis maximal 1:50 liegen. Charakteristisch für die neuen Luftspaltinterferenzpigmente sind die folgenden Parameter: Das Substrat muß plättchenförmig sein; das Durchmesser/Dicken-Verhältnis des Plättchens kann deutlich unter 50 liegen; im Plättchen selbst müssen feine Luftspalten mit deutlich unter 1 μm Stärke vorhanden sein, sodaß das Plättchen aufgebaut ist aus plättchenförmiger Festeubstanz-Luftspalt-plättchenförmiger Festsubstanz; der Brechungsquotient des plättchenförmigen Substrats kann niedrig sein, etwa um 1,5 oder darunter liegen; im Gegensatz zu den Perlglanzpigmenten und den bunten Interferenzpigmenten können nach der Herstellung der Luftspaltinterferenzpigmente diese einer Nachmahlung unterzogen werden, wobei mit den Korngrößen bis an die kleinste Einheit herangegangen werden kann, in welcher noch mindestens ein Schichtpaket aus Festsubs-tenz-Luftspalt-Festsubstanz enthalten ist. Ferner muß keine so hohe Planparallelität zwischen Ober- und Unterseite des Plättchens vorhanden sein wie bei Perlglanzpigmenten oder Bunt-Perlglanzpigmenten.The new air gap interference pigments differ from the pearlescent pigments and the colored interference pigments in that the colors are caused by air gaps between them, which are very small, for example in the range of 1/10 μm and even significantly less. The material layer lying above and below the air gaps can consist of the same material and thus also have the same refractive index. The refractive index itself can be small and be of the order of 1.5 to 1.6 (biotite 1.6 to 1.66, muscovite 1.55 to 1.64, vermiculite 1.58, pyrophyllite 1.55 to 1 , 6, talc 1.58 to 1.54). The diameter / thickness ratio of the platelet-shaped substrate can be in the range from 1: 5 to a maximum of 1:50. The following parameters are characteristic of the new air gap interference pigments: the substrate must be platelet-shaped; the diameter / thickness ratio of the plate can be well below 50; in the platelet itself there must be fine air gaps with a thickness of significantly less than 1 μm, so that the platelet is made up of platelet-shaped solid substance-air gap-platelet-shaped solid substance; the refractive index of the platelet-shaped substrate can be low, around 1.5 or below; in contrast to the pearlescent pigments and the colored interference pigments, after the production of the air gap interference pigments, these can be subjected to a post-grinding, whereby the grain sizes can be approached down to the smallest unit, in which at least one layer package of solid substance-air gap solid substance is also contained . Furthermore, there must not be as much plane parallelism between the top and bottom of the plate as with pearlescent pigments or colored pearlescent pigments.
Gegenstand der vorliegenden Erfindung sind somit plättchenförmige Luftspalt-Interferenzpigmente, die sich durch eng aneinanderliegende Schichten mittel- bis niedrigbrechender Minerale mit zwischengelagerten Luftspalten von unter 1 μm Stärke auszeichnen. Die Plättchen weisen ein Durchmesser/- Dicken-Verhältnis im Bereich 1:5 bis 1:50 auf. Die Minerallagen können monomineralisch oder heteromineralisch ausgebildet sein. Eine hohe Planparallelität ist nicht erforderlich.The present invention thus relates to platelet-shaped air gap interference pigments which are distinguished by closely adjacent layers of medium to low refractive index minerals with interposed air gaps of less than 1 μm in thickness. The platelets have a diameter / thickness ratio in the range from 1: 5 to 1:50. The mineral layers can be monomineral or heteromineral. A high plane parallelism is not necessary.
Im erfindungsgemäßen Luftspalt-Interferenzpigment tritt dann, wenn das jeweilige Substrat gefärbt ist, bei den Interferenzen Festsubstanz-Luftspalt—Festsubstanz oder Festkörper-Gas-Festkörper eine bestimmte additive Farbe hinzu. Wenn etwa das Substrat mit niedrigem Brechungsquotienten eine etwas graue bis bläuliche Tönung hat, so entsteht ein Silbereffekt, weist das Substrat eine bräunliche Tönung auf, so entsteht ein Goldeffekt, hat das Substrat eine grünliche Tönung, so entsteht ein Silber-Bronze-Effekt.In the air gap interference pigment according to the invention occurs when that each substrate is colored, add a certain additive color to the interferences solid-air gap-solid or solid-gas-solid. If, for example, the substrate with a low refractive index has a somewhat gray to bluish tint, a silver effect is produced; if the substrate has a brownish tint, then there is a gold effect; if the substrate has a greenish tint, a silver-bronze effect is produced.
Wie bereits erwähnt, darf der Luftspalt 1 μm nicht überschreiten. Würde er zu groß, so tritt bei der Einbettung des Pigmentes in ein Bindemittel dieses in den Luftspalt ein. Mit dem Eintreten des organischen Bindemittels in den Luftspalt würde dieser jedoch eliminiert und dadurch der angestrebte Glanzeffekt zwangsläufig verschwinden.As already mentioned, the air gap must not exceed 1 μm. If it were too large, when the pigment is embedded in a binder, it enters the air gap. However, if the organic binding agent entered the air gap, this would be eliminated and the desired gloss effect would inevitably disappear.
Obgleich es Minerale mit betont plättchenförmiger Ausbildung in den verschiedensten Mineralgruppen gibt, ist diejenige der Silikate von besonderer Bedeutung. Innerhalb der Gruppe der Silikate kommt wiederum im vorliegenden Zusammenhang den Phyllosilikaten (Blattsilikaten) spezielles Interesse zu, bei denen der wesentliche Baustein der Silikate, der SiO4-Tetraeder, in Ringen zweidimensional vernetzt ist. Phyllosilikate zeichnen sich durch eine plättchenförmige Ausbildung und eine vorzügliche Spaltbarkeit senkrecht zur Plättchenachse aus. Grundsätzlich lassen sich bei den Phyllosilikaten zwei Strukturelemente unterscheiden, nämlich eine Tetraederschicht (Si, Al, Fe3) und eine Oktaederschicht mit oktaedrischen mittelgroßen Kationen. Durch variable Kombination der Oktaeder- und der Tetraederschichten kennen die Phyllosilikate systematisch aufgebaut werden, wobei es zur Einteilung in Zweischicht-, Dreischicht- und Vierschichtminerale kommt. Spezifische Beispiele für erfindungsgemäß einsetzbare Phyllosilikate sind Glimmer, Hydroglimmer, Illite,Muskovit, Biotit, Phlogopit, Pyrophtyllit, Chlorite und Talk.Although there are minerals with a pronounced platelet-like formation in the most diverse mineral groups, that of the silicates is of particular importance. Within the group of silicates, phyllosilicates (leaf silicates) are of particular interest, in which the essential component of the silicates, the SiO 4 tetrahedra, is two-dimensionally networked in rings. Phyllosilicates are characterized by a platelet shape and excellent splittability perpendicular to the platelet axis. Basically, two structural elements can be distinguished in phyllosilicates, namely a tetrahedral layer (Si, Al, Fe 3 ) and an octahedral layer with octahedral medium-sized cations. The phyllosilicates can be systematically built up through a variable combination of the octahedron and tetrahedron layers, which are divided into two-layer, three-layer and four-layer minerals. Specific examples of phyllosilicates which can be used according to the invention are mica, hydro-mica, illite, muscovite, biotite, phlogopite, pyrophtyllite, chlorite and talc.
Die erfindungswesentliche Ausbildung eng aneinander liegender Schichten mittel- bis niedrigbrechender Minerale mit zwischengelagerten, höchstens 1 μm starken dünnen Luftspalten kann nach einem weiteren Aspekt der Erfindung dadurch herbeigeführt werden, daß Drei- und Vierschichtphyllosilikate einer Temperaturbehandlung oberhalb der H2O-, OH- oder Fluor-Entweichungstemperatur unterzogen werden. Bei einer Temperaturbehandlung wird zuerst lediglich Wasser bis zu einer Temperatur von etwa 250°C ausgetrieben, ab einer Temperatur im größeren Bereich von 400 bis 600°C dann auch OH und F. Später entstehen neue Phasen, wobei zwischen dem Austritt der OH-Ionen aus dem Gitter und dem Entstehen der neuen Phasen auch mehrere 100° Temperaturdifferenz bestehen können. Wesentlich ist es, daß weder durch den Austritt des Wassers noch durch den Austritt von OH und F ein radikaler Gitterzusammenbruch und eine Neuorientierung eintreten muß. Gleichzeitig mit dem Austritt des H2O,OH und F gehen farbliche Veränderungen vor sich (Goldeffekte, Silbereffekte, Perlmuttereffekte). Untersuchungen im Rasterelektomenmikroskop haben gezeigt, daß beispielsweise eine Temperaturbehandlung von Chloriten bei 900 bis 1.000°C zu Phasenneubildungen führt, wobei die Chlorite in dünne laminare Blätterbüschel aufgebrochen sind, d.h., die einzelnen Plättchen weisen sehr dünne, kleine Luftspaltschichten auf. Es kommt oft zur Ausbildung orientierter Enstatitschichten mit kleinen Glimmer- und/oder Quarzzwischenlagen, welche paketweise durch dünne Luftschichten getrennt sind. Eine Goldfärbung tritt dadurch ein, daß an den einzelnen Luftschichten Reflexionen auftreten, welche zu Phasendifferenzen führen, die Phasendifferenzfarbe durch die Absorption des bräunlichen Enstatits beeinflußt wird, sodaß letztendlich ein Goldschimmer entsteht.According to a further aspect of the invention, the formation of layers of medium-low to low-index minerals with intermediate, at most 1 μm thick thin air gaps, essential to the invention, can be brought about by the fact that three- and four-layer phyllosilicates undergo a temperature treatment above the H 2 O-, OH- or fluorine - be subjected to the escape temperature. In the case of a temperature treatment, only water up to a temperature of about 250 ° C. is expelled first, from a temperature in the larger range of 400 to 600 ° C. then also OH and F. Later, new phases are formed, with the OH ions escaping between there are several 100 ° temperature differences between the grid and the emergence of the new phases can. It is essential that there is no need for a radical lattice breakdown and reorientation due to the water or OH and F leaks. At the same time as the H 2 O, OH and F emerge, color changes occur (gold effects, silver effects, mother-of-pearl effects). Investigations in the scanning electron microscope have shown that, for example, a temperature treatment of chlorites at 900 to 1,000 ° C leads to new phases, the chlorites being broken up into thin laminar tufts of leaves, ie the individual platelets have very thin, small air gap layers. Oriented entstatite layers with small layers of mica and / or quartz are often formed, which are separated in packages by thin layers of air. A gold coloring occurs because reflections occur at the individual air layers, which lead to phase differences, the phase difference color is influenced by the absorption of the brownish entstatite, so that ultimately a gold shimmer is created.
Durch Variation des Brechungsquotienten, Variation der einzelnen Schichtpaketdicken zwischen dem Luftspalt und Variation der Absoiptionsverhältnisse (Durchlichtfarben) lassen sich Farbeffekte in breitem Spielraum erzeugen.By varying the refraction quotient, varying the individual layer packet thicknesses between the air gap and varying the absorption conditions (transmitted light colors), color effects can be generated in a wide range.
In weiterer Ausgestaltung des erfindungsgemäßen Herstellungsverfahrens hat sich gezeigt, daß eine Manipulation der Farbe durch Laugung der Phyllosilikate mit Chemikalien bewirkt werden kann. Die Laugung kann vor und/oder nach der Temperaturbehandlung erfolgen und kann mit Säuren, bevorzugt Salzsäure, oder durch Zuführung von Fremdionen vorgenonmen werden, zweckmäßig als Laugung in entsprechenden Salzlösungen, als hydrothermale Behandlung oder als Druckbehandlung oder Vakuumbehandlung in derartigen Salzlösungen.In a further embodiment of the manufacturing process according to the invention, it has been shown that manipulation of the color can be brought about by leaching the phyllosilicates with chemicals. The leaching can take place before and / or after the temperature treatment and can be carried out with acids, preferably hydrochloric acid, or by adding foreign ions, expediently as leaching in corresponding salt solutions, as hydrothermal treatment or as pressure treatment or vacuum treatment in such salt solutions.
Die erfindungsgemäße Temperaturbehandlung kann sowohl in normaler Luft, in inerten Gasen, in reduzierender Atmosphäre oder in reiner Sauerstoffatmosphäre durchgeführt werden. Durch Anwendung verschiedener Atmosphären bei der Temperaturbehandlung entstehen besondere Effekte dadurch, daß Ionensorten mit mehreren Wertigkeiten in bestimmte Wertigkeiten gezwungen werden. Beispielsweise kann bei einem Chlorit, der bei einer Temperaturbehandlung in oxidierender Atmosphäre (Luft) einen Goldeffekt annimmt (dreiwertiges Eisen), durch Temperaturbehandlung in inerter Atmosphäre ein Silbereffekt (zweiwertiges Eisen) erreicht werden.The temperature treatment according to the invention can be carried out both in normal air, in inert gases, in a reducing atmosphere or in a pure oxygen atmosphere. The use of different atmospheres in temperature treatment creates special effects by forcing ion types with several valences into certain valences. For example, in the case of chlorite, which takes on a gold effect (trivalent iron) during a temperature treatment in an oxidizing atmosphere (air), a silver effect (divalent iron) can be achieved by temperature treatment in an inert atmosphere.
Die erfindungsgemäßen plättchenförmigen Luftspaltinterferenzpigmente geben beim Mahlen keine Veränderung. Sie sind verwitterungsbeständig und chemisch inert und eignen sich daher zur Anwendung auf den verschiedensten Gebieten, insbesondere zur Pigmentierung, Effektgebung, Farbgebung und Ausnutzung der Plättchenstruktur bei Pigmentpasten, Farben und Lacken auf Basis organischer und anorganischer Bindemittel, Papier und Pappe, Baustoffen, Kunststoffen, Legierungen und Schmelzungen, Keramiken und Gläsern, Dachbeschichtungen und Kosnetika (Köerperpflegemittel). Infolge des niedrigen Brechungsquotienten und der geringen Lichtdispersion treten Bindemittelzersetzungen wie bei Titandioxidmodifikationen nicht auf.Give the platelet-shaped air gap interference pigments according to the invention no change in grinding. They are weather-resistant and chemically inert and are therefore suitable for use in a wide variety of areas, in particular for pigmentation, effecting, coloring and utilizing the platelet structure in pigment pastes, paints and varnishes based on organic and inorganic binders, paper and cardboard, building materials, plastics, alloys and melts, ceramics and glasses, roof coatings and cosnetics (personal care products). As a result of the low refractive index and the low light dispersion, binder decomposition does not occur, as is the case with titanium dioxide modifications.
Zur Herstellung der erfindungsgemäßen plättchenförmigen Luftspaltinterferenzpigmente kann wie folgt vorgegangen werden:The procedure for producing the platelet-shaped air gap interference pigments according to the invention is as follows:
Aus dem bergmännisch gewonnenen Rohgut wird die Komfraktion 0,125 bis 0,5 mm ausgesiebt und einer Schwerkraftsortierung unterworfen. Die Fraktion mit vorwiegend plättchenförmigem Material wird einer Starkfeld-Magnetscheidung aufgegeben und die magnetische Fraktion wird abgetrennt. Dieses Konzentrat wird bei 500 bis 1.100°C kalziniert; die Brenndauer richtet sich nach Kornverteilung und Zusammensetzung. Das kalzinierte Produkt wird gemahlen und in die gewünschten Kornfraktionen gesiebt.The 0.125 to 0.5 mm fraction is sieved out of the mined raw material and subjected to gravity sorting. The fraction with predominantly platelet-shaped material is submitted to a strong field magnetic separation and the magnetic fraction is separated off. This concentrate is calcined at 500 to 1,100 ° C; the burning time depends on the grain distribution and composition. The calcined product is ground and sieved into the desired grain fractions.
Die Anwendung der neuen Luftspaltinterferenzpigmente wird in den nachfolgenden Beispielen veranschaulicht:The application of the new air gap interference pigments is illustrated in the following examples:
BEISPIEL 1 -Lack für FußboderibeschichtungenEXAMPLE 1 Lacquer for floor coatings
20 Gew.-% Luftspaltinterferenzpigment verschiedener Feinheit, je nach Effekt20% by weight air gap interference pigment of different fineness, depending on the effect
50 " Säurehärtendes Bindemittel , z.B. Viamin HP 36450 "acid-curing binder, e.g. Viamin HP 364
20 " Lösungsmittel20 "solvent
10 " Paratoluolsulfonsäure (Härter)10 "paratoluenesulfonic acid (hardener)
BEISPIEL 2 -Effektlack für WandbeschichtungenEXAMPLE 2 -Effect paint for wall coatings
20 Gew.-% Luftspaltinterferenzpigment verschiedener Feinheit, je nach Effekt 15 "20 wt .-% air gap interference pigment of different fineness, depending on the effect 15 "
0,2 " Pignentverteiler A (Netzmittel)0.2 "Pignent distributor A (wetting agent)
0,2 " NH3 0.2 "NH 3
0,1 " Preventol (Fungizid)0.1 "Preventol (fungicide)
0,4 " Tylose MH 2000 XP (Verdicker)0.4 "Tylose MH 2000 XP (thickener)
0,3 " Nopco 8034 E (Entschäumer)0.3 "Nopco 8034 E (defoamer)
1 " Texanol (Filmbildehilfsmittel)1 "Texanol (film forming aid)
62,8 " Acronal 290 D (Bindemittel) BEISPIEL 3 - Effektbeschichtung für Dekorplatten auf anorganischer Bindemittelbasis:62.8 "Acronal 290 D (binder) EXAMPLE 3 - Effect coating for decorative panels based on inorganic binders:
15,6 Gew.-% Wasser15.6% by weight water
18,6 " Natrosol 250 H 4 BR 2 % LSG 0,5 " VP Hydropalat 3043 (Netzmittel) 0,2 " Nopco 8034 E (Entschäumer) 1,0 " Texanol (Koalescent) 0,6 " Betolin Quart 10 (Stabilisator) 8,5 " Acronal 290 D (Disp. BM)18.6 "Natrosol 250 H 4 BR 2% LSG 0.5" VP Hydropalat 3043 (wetting agent) 0.2 "Nopco 8034 E (defoamer) 1.0" Texanol (coalescent) 0.6 "Betolin Quart 10 (stabilizer) 8.5 "Acronal 290 D (Disp. BM)
30 " Betolin EP 219 (Wasserglas BM)30 "Betolin EP 219 (water glass BM)
25 " Luftspaltinterferenzpigment (gold, Silber)25 "air gap interference pigment (gold, silver)
Kunststoffe und Gießharze lassen sich beispielsweise aus 70 Gew.-% Polyesterharz und 30 Gew.-% Luftspaltinterferenzpigment formulieren. Ein Dekorharz, beispielsweise für Surfbretter, kann aus 98 Gew.-% Gießharz und 2 Gew.-% Luftspaltinterferenzpigment aufgebaut werden.Plastics and casting resins can be formulated, for example, from 70% by weight polyester resin and 30% by weight air gap interference pigment. A decorative resin, for example for surfboards, can be built up from 98% by weight of casting resin and 2% by weight of air gap interference pigment.
Im Papier- und Pappesektor lassen sich die neuen Luftspaltinterferenzpigmente beispielsweise als Abstreumittel von Tapeten anwenden, auf dem Keramikgebiet können die neuen Pigmente in die Glasur oder direkt in den Scherben eingelagert werden. In the paper and cardboard sector, the new air gap interference pigments can be used, for example, as a scattering agent for wallpapers; in the ceramic field, the new pigments can be embedded in the glaze or directly in the fragments.

Claims

PATENTANSPRÜCHE: PATENT CLAIMS:
1. Plättchenförmige Luftspaltinterferenzpigmente, gekennzeichnet durch eng aneinanderliegende Schichten mittel- bis niedrigbrechender Minerale mit zwischengelagerten Luftspalten von unter 1 μm Stärke, wobei die Plättchen ein Durchmesser/Dicken-Verhältnis von 1:5 bis 1:50 aufweisen.1. Platelet-shaped air gap interference pigments, characterized by closely adjacent layers of medium to low refractive index minerals with interposed air gaps of less than 1 μm in thickness, the platelets having a diameter / thickness ratio of 1: 5 to 1:50.
2. Pigmente nach Anspruch 1, dadurch gekennzeichnet, daß die Minerallagen monomineralisch oder heteromineralisch sind.2. Pigments according to claim 1, characterized in that the mineral layers are monomineral or heteromineral.
3. Verfahren zur Herstellung der Luftspaltinterferenzpigmente nach einem der Ansprüche 1 oder 2, dadurch gekennzeichnet, daß Drei- und Vierschichtphyllosilikate einer Temperaturbehandlung oberhalb der H2O-, OH- oder F-Entweichungstemperatur unterzogen werden.3. A process for the preparation of the air gap interference pigments according to one of claims 1 or 2, characterized in that three- and four-layer phyllosilicates are subjected to a temperature treatment above the H 2 O, OH or F escape temperature.
4. Verfahren nach Anspruch 3, dadurch gekennzeichnet, daß die Temperaturbehandlung in einem Bereich von 250 bis 1.100°C erfolgt.4. The method according to claim 3, characterized in that the temperature treatment is carried out in a range from 250 to 1100 ° C.
5. Verfahren nach Anspruch 3 oder 4, dadurch gekennzeichnet, daß vor und/oder nach der Termperaturbehandlung die Phyllosilikate einer Laugung mit Chemikalien unterworfen werden.5. The method according to claim 3 or 4, characterized in that the phyllosilicates are subjected to a leaching with chemicals before and / or after the thermal treatment.
6. Verfahren nach einem der Ansprüche 3 bis 5, dadurch gekennzeichnet, daß die Temperaturbehandlung an Luft, in inerten Gasen, in reduzierenden Gasen oder in oxidierenden Gasen vorgenommen wird.6. The method according to any one of claims 3 to 5, characterized in that the temperature treatment in air, in inert gases, in reducing gases or in oxidizing gases is carried out.
7. Verfahren nach Anspruch 5, dadurch gekennzeichnet, daß die chemische Behandlung als normale Laugung, Temperaturlaugung, hydrothermale Behandlung, Druckbebandlung oder Vakuumbehandlung ausgeführt wird.7. The method according to claim 5, characterized in that the chemical treatment is carried out as normal leaching, temperature leaching, hydrothermal treatment, pressure treatment or vacuum treatment.
8. Verfahren nach einem der Ansprüche 3 bis 7, dadurch gekennzeichnet, daß in die Phyllosilikate organische Komplexe oder färbende Fremdionen eingebaut werden.8. The method according to any one of claims 3 to 7, characterized in that organic complexes or coloring foreign ions are incorporated into the phyllosilicates.
9. Verwendung der Pigmente nach den Ansprüchen 1 oder 2 zur Pigmentierung, Effektgebung, Farbgebung und Ausnutzung der Plättchenstruktur bei Pigmentpasten, Farben und Lacken auf Basis organischer und anorganischer Bindemittel, Papier und Pappe, Baustoffen, Kunststoffen, Legierungen und Schmelzungen, Keramiken und Gläsern, Dachbeschichtungen und Körperpflegemitteln. 9. Use of the pigments according to claims 1 or 2 for pigmenting, effecting, coloring and utilizing the platelet structure in pigment pastes, paints and varnishes based on organic and inorganic binders, paper and cardboard, building materials, plastics, alloys and melts, ceramics and glasses, Roof coatings and personal care products.
EP89906006A 1988-05-26 1989-05-26 Air-gap interference pigments, manufacture and use thereof Expired EP0368973B1 (en)

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AT0138588A AT405838B (en) 1988-05-26 1988-05-26 USE OF PLATE-SHAPED AIR GAP INTERFERENCE PIGMENTS
AT1385/88 1988-05-26

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US3311485A (en) * 1963-10-28 1967-03-28 Minnesota Mining & Mfg Mica pigments
EP0050936A1 (en) * 1980-10-23 1982-05-05 ENGLISH CLAYS LOVERING POCHIN & COMPANY LIMITED Improvements in or relating to the preparation of aqueous suspensions of talc
DE3507595A1 (en) * 1985-03-04 1986-09-04 R. Wendel KG, 6340 Dillenburg Metal-effect enamel coatings
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WO1989011508A1 (en) 1989-11-30

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