EP1761610A2

EP1761610A2 - Pigment mixture

Info

Publication number: EP1761610A2
Application number: EP05757232A
Authority: EP
Inventors: Dieter Heinz; Ralf Anselmann; Klaus Boehm; Sabine Schoen
Original assignee: Merck Patent GmbH
Current assignee: Merck Patent GmbH
Priority date: 2004-07-01
Filing date: 2005-06-30
Publication date: 2007-03-14
Also published as: DE102004032121A1; US20080305184A1; WO2006002911A3; US7887849B2; WO2006002911A2

Abstract

The invention relates to a pigment mixture consisting of at least two constituents, constituent A being uncoated, monocoated or multicoated glass lamellae, and constituent B being nacreous pigments based on phyllosilicates, SiO2 lamellae, Fe2O3 lamellae or A12O3 lamellae. The invention also relates to the use of said pigment mixture, inter alia, in paints, dyes, especially printing inks, plastics, powder paints, pastes and cosmetic formulations.

Description

pigment mixture

The present invention relates to a pigment mixture consisting of at least two components, where component A comprises coated un or singly or multiply coated glass flakes and component B comprises coated or uncoated BiOCl pigments or pearlescent pigments based on phyllosilicates, SiO ₂ - or Fβ ₂ θ ₃ - or A ^ Os platelets, as well as their use, inter alia, in paints, inks, printing inks, plastics, powder coatings, ceramic glazes, plastic films and cosmetic formulations.

Pearlescent pigments are thin platelets of a colorless or colored transparent or semi-transparent material. Pearlescent pigments based on mica platelets have been known for more than 30 years.

Pearlescent pigments based on glass platelets have a much higher gloss and a significantly higher brilliance than pearlescent pigments based on mica. The reason for this is that the glass plates have a better plane-parallel surface required for the reflection.

This advantage of the much higher gloss and glitter effect is often offset by disadvantages in terms of processability. For example, glass slides are not as easy to print as mica-based pearlescent pigments. The use of mica-based effect pigments in printing is described, for example, in "Effect pigments for the printing industry - from design to printing" by Merck KGaA, published 09/2003. In automotive paints containing glass slides, the performance properties are degraded, e.g. DOI (= Depth of Image) or Stippentest. When incorporating glass platelets into plastics, the abrasive properties are evident in addition to the flow lines.

The object of the present invention is to increase the processability of glass platelets, in particular in technical applications. Surprisingly, it has now been found that it is possible to combine the advantageous performance properties of commercial pearlescent pigments based on mica, SiO ₂ or Al ₂ O ₃ with the good luster and glitter properties of pearlescent pigments based on glass flakes, if coated or uncoated

Glass slides mixed with the conventional pearlescent pigments.

By mixing pearlescent pigments based on different base substrates, an unexpected synergy effect is created, which gives the application systems high gloss and at the same time the

Processability of glass slides significantly increased. The pigment mixture of the invention is characterized by a very strong glitter and a strong brilliance, can be very well incorporated into the various application media and achieved excellent hiding power.

The mixing ratio of component A and component B is preferably from 10:90 to 50:50. Preferred mixtures contain components A and B in the ratios 10:90, 20:80, 25:75, 30:70, 40:60 and 50:50 Component A is contained in the pigment mixture of the invention to a maximum of 50% by weight.

The present invention thus relates to a pigment mixture comprising at least two components, component A comprising uncoated or mono- or multi-coated glass flakes and component B coated or uncoated BiOCl pigments and / or pearlescent pigments based on phyllosilicates, SiO ₂ -, Fe ₂ O. ₃ - or AI ₂ O ₃ platelets are.

The invention also relates to the formulations containing the pigment mixture according to the invention.

As an essential constituent, the pigment mixture according to the invention contains glass platelets. Preferably, the glass flakes are provided with one or more layers of metal oxides, metal sulfides, metal oxynitrides, Metal suboxides, metals and their mixtures completely or partially coated.

Suitable pearlescent pigments based on coated glass flakes are known, for example, from WO 97/46624, WO 02/090448 A2 and

WO 03/006558 A2.

The thickness of the glass platelets is preferably <1 μm, in particular <0.9 μm, and very particularly preferably <0.8 μm. The glass slides may be covered with one or more layers. The glass platelets are preferably coated with colored or colorless metal oxides, metal hydroxides, metal suboxides or oxynitrides. Suitable metal oxides are in particular TiO ₂ , Fe ₂ O ₃ , Fe ₃ O ₄ , FeO (OH), SnO ₂ , Cr ₂ O ₃ , ZrO ₂ , ZnO, CuO, NiO, vanadium and manganese oxides and other metal oxides alone or in a mixture in a single layer or in successive layers. Also suitable for occupying titanium suboxides and titanium nitrides.

Preferred coated glass flake pigments have the following structure:

Glass slide + Fe ₂ O ₃ layer

Glass slide + SiO ₂ layer + TiO ₂ layer

Glass flake + TiO ₂ layer Glass flake + TiO ₂ layer + SiO ₂ layer + TiO ₂ / Fe ₂ O ₃ layer

Glass flake + TiO ₂ / Fe ₂ O ₃ layer + SiO ₂ layer + TiO ₂ / Fe ₂ O ₃ layer

Glass flake + TiO ₂ layer + SiO ₂ layer + Cr ₂ O ₃ layer

Glass slide + SiO ₂ layer + Fe ₂ O ₃ layer

Glass slide + Cr ₂ O ₃ layer Glass slide + Ag

Glass slide + Au

Glass flake + Fe ₂ O ₃ layer + SiO ₂ layer + TiO ₂ / Fe ₂ O ₃ layer

Glass flake + SiO ₂ layer + TiO ₂ layer + SiO ₂ layer + TiO ₂ layer

Glass flake + SiO ₂ layer + TiO ₂ / Fe ₂ O ₃ layer + SiO ₂ layer + TiO ₂ / Fe ₂ O ₃ layer Glass flake + SiO ₂ layer + Fe ₂ O ₃ layer + SiO ₂ layer + TiO ₂ / Fe ₂ O ₃ layer

Instead of the outer metal oxide layer, a semitransparent layer of a metal may also be used. Suitable metals for this purpose are, for example, Cr, Ti, Mo, W, Al, Cu, Ag, Au or Ni.

To achieve special color effects, it is additionally possible to introduce finely divided particles in the nanometer size range in layers. For example, finely divided TiO ₂ or ZnO or finely divided carbon (carbon black) with particle sizes in the range from 10 to 250 nm have proved to be suitable. The light-scattering properties of such particles also make it possible to influence the gloss and hiding power in a more targeted manner.

Particularly preferred glass flakes are platelets or glass flakes coated with TiO ₂ and / or Fe ₂ O ₃ , which initially have an SiO ₂ layer and are subsequently coated with TiO ₂ and / or Fe ₂ O ₃ . Suitable glass flakes can be produced as described for example in patent literature EP 0 289 240 B1, WO 97/46624, WO 02/090448 A2, WO 03/006558 A2 and WO 2004/055119 A1.

The coated or uncoated glass flakes are admixed to component B preferably in amounts of 1-50% by weight, in particular 3-25% by weight and very particularly preferably 5-15% by weight. However, the particular composition of the pigment mixture according to the invention is dependent on the application medium to be pigmented and the desired effect.

Component B is pearlescent pigments based on platelet-shaped, transparent or semitransparent substrates of sheet silicates, such as natural and synthetic mica, talc, sericite, kaolin, or other siliceous materials, and on the basis of SiO ₂ -, Fe ₂ O ₃ and Al ₂ O ₃ platelets coated with colored or colorless metal oxides, nitrides or suboxides, such as TiO ₂ , titanium suboxides, titanium oxynitrides, Fe ₂ O ₃ , Fe ₃ O ₄ , FeO (OH), SnO ₂ , Cr ₂ O ₃ , ZnO, ZrO ₂ , CuO, Pseudobrookit, NiO, manganese and tungsten oxides and other metal oxides are coated alone or in admixture in a uniform layer or in successive layers. Such pearlescent pigments are known, for example, from German patents and patent applications 14 67 468, 19 59 998, 20 09 566, 22 14 454, 22 15

191, 22 44 298, 23 13 331, 25 22 572, 31 37 808, 31 37 809, 31 51 343, 31 51 354, 31 51 355, 32 11 602, 32 35 017, and P 38 42 330 known and im commercially available, eg under the trademark Iriodin ^® from Merck KGaA, Darmstadt, Germany. Particularly preferred pigment preparations contain, as component B, TiO ₂ / mica, Fe ₂ O ₃ / mica and / or TiO ₂ / Fe ₂ O ₃ mica pigments.

Also preferred are TiO ₂ and / or Fe ₂ O ₃ -coated SiO ₂ - Al ₂ or θ ₃ flakes. The coating of the SiO ₂ platelets with one or more metal oxides can be carried out, for example, as in WO 93/08237

(wet-chemical coating) or DE-OS 196 14 637 (CVD method). Preferred SiO ₂ flakes are colorless, ie they contain no colorants.

Component B may also contain multi-layer pigments as pearlescent pigment. Such multilayered pigments, in particular based on mica and TiO _2, are known, for example, from German Laid-Open Applications DE 196 18 563, DE 196 18 566, DE 196 18 569, DE 197 07 805, DE 197 07 806, DE 197 46 067, and WO 00/12096 usually alternately high and low refractive layers, preferably of metal oxides, on. Preferred multilayered pigments contain up to 7 layers, preferably 3, 5 or 7 layers.

Component B may also consist of a mixture of different pearlescent pigments. It is possible to mix both multilayered pigments with singly coated pearlescent pigments and pearlescent pigments based on different substrates. However, component B preferably consists only of a pearlescent pigment, in particular of a single-coated mica flake. The pearlescent pigments of component B are preferably based on mica, Al ₂ O ₃ -, Fβ ₂ θ ₃ - and SiO ₂ flakes which microns thickness between 0.3 and 5 generally, and in particular between 0.4 and 2, 0 μm, own. The expansion in the other two dimensions is usually between 1 and 250 μm, preferably between 2 and 100 μm, and in particular between 5 and 60 μm.

Component B may also be coated or uncoated BiOCl pigments. Such pigments which are suitable in particular for offset printing, are commercially available, for example from the company. Engelhard under the name ^® Mearlite Ultra Fine OFS and the Fa. Merck KGaA under the name Biflair ^®. The commercially available BiOCl pigments have particle sizes of 1-50 microns. For the pigment mixture according to the invention, in particular BiOCl pigments with particle sizes of 5-20 μm, preferably of <15 μm, are suitable.

Preferably, component A and component B each have particle sizes in the range of 5-200 microns.

To increase the light, water and weather stability, it is often advisable, depending on the field of application, to subject the pigments of component A and / or B to a subsequent coating or after-treatment. As post-coatings or post-treatments are, for example, in DE-PS 22 15 191, DE-OS 31 51 354, DE-OS 32 35 017 or DE-OS 33 34 598 described methods in question. As a result of this subsequent coating, the chemical stability is further increased or the handling of the pigment, in particular the incorporation into different media, is facilitated. To improve the wettability, dispersibility and / or compatibility with the application media, functional coatings of Al ₂ O ₃ or ZrO ₂ or their mixtures or mixed phases can be applied to the pigment surface. Furthermore, organic or organic / inorganic combined Nach¬ coatings are possible, for example with silanes, such as described in EP 0090259, EP 0 634 459, WO 99/57204, WO 96/32446, WO 99/57204, US 5,759,255, US 5,571,851, WO 01/92425 or in JJ. Ponjee, Philips Technical Review, Vol. 3, 81 ff. And PH Harding JC Berg, J. Adhesion Sei. Technol. Vol. 11 no. 4, p. 471-493.

The additionally applied substances account for only about 0.1 to 5 wt.%, Preferably 0.5 to 3.0 wt.%, Of the pigments of component A and / or B.

The pigment mixture of the invention is relatively simple and easy to handle. The desired amount of coated or uncoated glass slides is added to component B. The mixing is done by conventional mixing equipment, such as e.g. Rhönradmischer, paddle mixer, Taumelmischer, Lädigemischer. The finished pigment mixture can then be incorporated by simple stirring in the application system. A complex grinding and dispersing of the pigments is not required.

The pigment mixture according to the invention can be used, for example, for the pigmentation of paints, powder coatings, industrial coatings, automotive coatings, paints, printing inks, plastics, plastic films, agricultural films, seed coating, button pastes, for the refinement of foods, drug coatings, dragees and tablets. The concentration of the pigment mixture in the application system to be pigmented is generally between 0.1 and 70% by weight, preferably between 0.1 and 50% by weight and in particular between 1, 0 and 10% by weight, based on the total solids content of the system , It is usually dependent on the specific application.

Preferably, the pigment mixture according to the invention is suitable for printing inks because of its hiding power and the very strong glittering effect, in particular for screen printing, intaglio printing, flexographic printing, offset printing,

Overprint varnishing, pad printing, screen printing, paper coating, doctoring and air knife.

The matching of the properties of the printing material, printing ink and the pigment mixture according to the invention are dependent on the particular printing process. The pigment mixture is usually incorporated into the printing ink in amounts of 2-35% by weight, preferably 5-25% by weight, and especially 8-20% by weight. Offset inks may contain the pigment mixture up to 40% by weight and more.

The printing inks containing the pigment mixture of the invention show purer hues, a more intense gloss and are better printable due to the good viscosity.

In offset printing inks, very finely divided pigments are preferably used, in particular pigments having particle sizes of <15 μm. Particular preference is given to offset printing inks comprising 1-30% by weight of component B and 1-15% by weight of component A. The mixing ratio of component A and B is in the range from 10:90 to 50:50 The pigment mixture according to the invention is preferably contained in the offset printing ink to a maximum of 30% by weight. Suitable binders are e.g. Gloss overprint varnish or bronze varnish uncolored, e.g. from the company Geb. Schmidt, K + E or Jänecke and Schneemann.

Screen printing inks preferably contain 1-15% by weight of component B, preferably pearlescent pigments, and 1-7.5% of component A. The mixing ratio of component A and B is in the range of 10:90 and 50:50. The mixture from component A and B is preferably contained in the screen printing ink to a maximum of 15 wt.%. Suitable binders are e.g. Helizarin MT from BASF AG.

Rotary screen printing inks preferably contain 1-13% by weight of component B, preferably pearlescent pigments, and 1-6.5% of component A. The mixing ratio of component A and B is in the range of 10:90 and 50:50. The mixture from component A and B is preferably up to 15 wt.% Contain ent in the rotary ink. Suitable binders are e.g. Tubiscreen MET-H from the company CHT.

The pigment mixture according to the invention is likewise very well suited for paper coating. The coating preferably contains 1-7% by weight of component B, preferably pearlescent pigments, and 1-3.5%. to component A. The mixing ratio of component A and B is in the range of 10:90 and 50:50. The mixture of component A and B is preferably contained in the coating at a maximum of 7% by weight. Suitable binders are, for example Pröll Aqua Jet Fa. Pröll.

In the production of a gravure printing ink, between 1-30% by weight of component B, preferably pearlescent pigments, and between 1-15% by weight of component A are stirred into the finished printing ink. The mixing ratio of component A and B is in the range of 10:90 and 50:50. The mixture of components A and B is preferably contained in the gravure ink to a maximum of 30%.

Printing inks for flexographic printing preferably contain 1-30% by weight of component B, in particular pearlescent pigments, and 1-15% by weight of component A. The mixing ratio of component A and B is in the range from 10:90 to 50:50. The mixture from component A and B is preferably at most 30 wt.% Contained in the flexographic ink. Suitable binders are e.g. Flexographic binder Weilburger Senolith carrier paint from the company Weilburger Graphics GmbH.

With the pigment mixture according to the invention, all printing materials known to those skilled in the art, in particular textiles, paper and films, can be printed very well.

Plastics containing the pigment mixture of the invention in amounts of 0.01 to 50 wt.%, In particular 0.1 to 7.0 wt.%, Often characterized by a special color effect, but also by a sparkle effect.

In the paint sector, in particular in automotive finishes, the pigment mixture is also used for 3-layer structures in amounts of 0.1-10% by weight, preferably 1 to 3% by weight. In varnish, the pigment mixture according to the invention has the advantage that the desired effect is achieved by a single-coat coating (single-layer system or base coat in the 2-layer structure). In comparison with paint finishes, only

Component B contains, instead of the pigment mixture according to the invention, show coatings with the pigment mixture according to the invention a clearer depth effect and a glittering effect.

In the pigmentation of binder systems e.g. for inks and inks for gravure, offset or screen printing,

Rotary screen printing or as a precursor for printing inks, for example in the form of highly pigmented pastes, granules, pellets, etc., have in particular pigment mixtures with spherical particles, eg full glass or hollow spheres, polymer spheres, SiO ₂ spheres, and / or with spherical colorants, such as TiO ₂ , carbon black, chromium oxide, iron oxide and organic color pigments have proven to be particularly suitable.

Precursors for printing inks, e.g. in granular form, as pellets, briquettes, etc., in addition to the binder and additives up to 98 wt.% Of the pigment mixture according to the invention.

Also suitable is the pigment mixture according to the invention for pigment preparations and for the production of pastes and dry preparations, such as e.g. Granules, pellets, briquettes, sausages, balls, etc.

The invention thus also relates to formulations containing the pigment mixture according to the invention.

The following examples are intended to illustrate the invention without, however, limiting it.

Examples

I. Preparation of the Pigment Mixtunq

The desired amount of Ronastar ^® Noble Sparks (pearlescent pigment based on glass flake particle size of 20-200 microns coated with SiO ₂ and TiO _2, Fa. Merck KGaA) is added to Iriodin ^® 103 (pearlescent pigment based on mica having a particle size of 10 -60 μm coated with TiO ₂ from Merck KGaA) and mixed with a Röhnrad mixer.

example 1

The following pigment mixtures are prepared:

Example 1a: Ronastar ^® Noble Sparks / Iriodin 103 ^® in a ratio of 50: 50th

Example 1 b:

Ronastar ^® Noble Sparks / Iriodin ^® 103 in the ratio 25: 75 miles.

Example 1c:

Ronastar ^® Noble Sparks / Iriodin ^® 103 at 10: 90th

Example 1d:

Glass slides coated with Fe ₂ O ₃ + Iriodin ^® 103 in the ratio 50: 50.

Example 1e:

With TiO ₂ / SiO ₂ / TiO ₂ coated glass plates + Iriodin ^® 103 in the ratio

25:75.

Example 1f:

MJT TiO ₂ coated glass flake + Iriodin 103 ^® in a ratio of 10: 90th

Example 1q:

With Fe ₂ O ₃ and SiO ₂ coated glass flake + Iriodin 103 ^® in a ratio of 50: 50th

Example 1 h:

SiO ₂ / TiO ₂ / SiO ₂ / TiO ₂ coated multilayer pigments based on glass platelets + Iriodin ^® 103 in a ratio of 10:90. II. Glaπzmessungen

A pigment mixture consisting of pearlescent pigments based on mica flakes and coated glass flakes shows significantly higher gloss values (measured according to Gardner, DIN 67530, ISO 2813, ASTM D 523) than the coated glass flake alone:

The addition of Ronastar ^® Noble Sparks enhances the gloss effect of Iriodin ^® 103 far beyond the expected effect (gloss booster effect ").

I. Application Examples

Example A1: - Screen printing

To produce 1 kg of printing ink 850 g binders are (Helizarin MT Fa. BASF AG) and 150 g pigment mixture consisting of 120 g of Iriodin ^® 123 (TiO ₂ / mica pigment of particle size 5-20 microns Fa. Merck KGaA) and 30 g Ronastar ^® Noble Sparks stirred with a propeller mixer at approx. 800-1200 rpm and then printed.

On paper and textiles, the printed product shows a very pronounced glittering effect and the addition of Ronastar ^® Noble Sparks increases the brilliance and gloss in comparison to pure Iriodin ^® 123 twice. Example A2: - Rotatioπssiebdruck

For the preparation of 1 kg of printing ink are 880 g binder (Tubiscreen MET-H Fa. CHT) and 120 g of pigment mixture consisting of 100 g of Iriodin ^® 225 (TiO ₂ / mica pigment of particle size 10-60 microns of Fa.

Merck KGaA) and g Ronastar ^® Noble Sparks min stirred 20 with a propeller stirrer at about 800-1200 U /, and then printed.

On textiles, the print shows a very strong shine with a very pronounced glittering effect.

Example A3: - paper coating

To produce 1 kg of printing ink 920 g Proell Aqua Jet be the Fa. Proll and 80 g of pigment mixture consisting of 70 g of Iriodin ^® 100 _(TiO2 / mica pigment of particle size of 10-60 .mu.m of Fa. Merck KGaA) and 10 g Ronastar ^® Noble Sparks stirred with a propeller mixer at about 800-1200 rpm and then printed.

The coated paper shows a very brilliant and pronounced glittering effect.

Example A4: - gravure printing

To produce 1 kg of printing ink 750 g Rotations¬ gravure binder Sicpa be 50.36 Fa. Sicpa and 250 g pigment mixture consisting of 200 g of Iriodin ^® 305 Solar Gold (multilayer pigment based on mica coated with Pseudobrookit particle size of 10-60 microns of Fa. Merck KGaA) and 50 g of Noble Ronastar ^® Sparks with a propeller at about 800-1200 U / min with stirring and then printed.

On paper and textiles, the printed product shows a very pronounced glittering effect and the addition of Ronastar ^® Noble Sparks doubles the brilliance and gloss compared to pure Iriodin ^® 305.

Example A5: - Flexographic printing

To produce 1 kg of printing ink 700 g Flexodruckbinder Weilburger Senolith be ^® carrier coating from. Weilburger Graphics GmbH and 300 g pigment mixture consisting of 200 g of Iriodin ^® 225 and 100 g Ronastar ^® Noble Sparks with a propeller at about 800-1200 U / min stirred in and then printed.

On paper and textiles, the printed product shows a very pronounced glittering effect and the addition of Ronastar ^® Noble Sparks increases the brilliance and gloss by double compared to pure Iriodin ^® 225.

Example A6: - offset printing

To produce 1 kg of printing ink (700 g Binder gloss overprint varnish of Fa. Gebr. Schmidt), 150 g of pigment mixture consisting of 150 g of Iriodin ^® 100 _(TiO2 / mica pigment of particle size of 10-60 .mu.m of Fa. Merck KGaA) and 150 g Ronastar ^® Noble Sparks stirred with a propeller stirrer at approx. 800-1200 rpm and then printed.

The printed paper shows a high gloss and a very fine and intense sparkle effect.

Example A7: - offset printing

For the preparation of 1 kg of printing ink (700 g binder gloss overprint varnish from Gebr. Schmidt) 150 g of pigment mixture consisting of 150 g Biflair ^® (BiOCl pigment with a particle size of 7-15 microns from. Merck KGaA) and g Ronastar ^® Noble Sparks min stirred 150 with a propeller at about 800-1200 U /, and then printed.

The printed paper shows an extremely high silky shine and a very fine and intense sparkle effect.

Example 3: - Plastic

To plastic granules of polypropylene PP Stamylan PPH 10 (DSM) or polystyrene 143 E (BASF) is a 1: 1 mixture of each

a) 1% SiO ₂ platelets of particle size 5-40 μm, coated with TiO ₂ ,

b) 1% Iriodin 103 ^®

c) 1: 1 mixture of Ronastar ^® Noble Sparks / Iriodin 103 ^®

stirred in. The pigmented granules are then processed on a spraying machine to platelets (size 9 X 6 cm).

When using the pigments under a) and b) are obtained plastic platelets with high gloss. The plastic flakes from Example c) show a higher gloss and in addition a very high glittering effect.

Claims

claims

1. pigment mixture containing at least two components, wherein component A uncoated or mono- or multi-coated glass flakes and component B coated or uncoated

BiOCl pigments or pearlescent pigments based on layer silicates, SiO ₂ , Fe ₂ O ₃ or Al ₂ O ₃ platelets.

2. Pigment mixture according to claim 1, characterized in that component A and component B each have particle sizes of 5-200 microns.

3. Pigment mixture according to claim 1 or 2, characterized in that component A and component B in the ratio 10: 90 to 50: 50 are mixed.

4. Pigment mixture according to one of claims 1 to 3, characterized in that the glass platelets with TiO ₂ and / or Fe ₂ O _{3 are} completely or partially coated.

5. Pigment mixture according to one of claims 1 to 4, characterized in that the glass platelets on the surface initially have a SiO ₂ coating and are then coated with one or more metal oxides.

6. Pigment mixture according to one of claims 1 to 5, characterized in that the pearlescent pigment based on phyllosilicates, SiO ₂ -, Fe ₂ O ₃ - or Al ₂ O ₃ platelets with one or more metal oxides, metal hydroxides, metal suboxides and / or Metal oxynitrides is coated.

7. Pigment mixture according to one of claims 1 to 6, characterized in that component B is a pearlescent pigment based on phyllosilicates, which is coated with TiO ₂ and / or Fe ₂ O ₃ .

8. Pigment mixture according to one of claims 1 to 7, characterized in that it is the layered silicate to natural or synthetic mica.

9. Pigment mixture according to one of claims 1 to 8, characterized in that the mixture contains up to 50 wt.% Of component A, based on the components A and B in the mixture.

10. Use of the pigment mixture according to one of claims 1 to 9 in paints, varnishes, powder coatings, industrial coatings, automotive coatings,

Printing inks, plastics, plastic films, agricultural films, for button pastes, for seed coloring, in cosmetic formulations and for the refining of foodstuffs and for the production of pastes, dry preparations and pigments.

11. Use of the pigment mixture according to one of claims 1 to 9 in screen printing, rotary screen printing, gravure printing, flexographic printing, offset printing, overprint varnishing, pad printing, screen printing, for doctoring and air knife and paper coating.

12. Formulations containing a pigment mixture according to one of claims 1 to 9.