阅读说明：本技术 效果颜料 (Effect pigments ) 是由 L·哈姆 C·格里斯曼 N·内里斯谢尔 M·耶克尔 于 2020-04-28 设计创作，主要内容包括：本发明涉及基于多层涂覆的薄片状基材的温度稳定效果颜料,及其在油漆、涂料、印刷墨、塑料中的用途,特别是在釉料、搪瓷、陶瓷或玻璃类材料中的用途。(The invention relates to temperature-stable effect pigments based on multilayer-coated platelet-shaped substrates, and to the use thereof in paints, coatings, printing inks, plastics, in particular in glazes, enamels, ceramics or glass-like materials.)

1. Effect pigment based on a multilayer-coated platelet-shaped substrate, characterized in that the effect pigment has at least one layer sequence on the substrate surface,

(A) the high-refractive-index coating has a refractive index n of not less than 1.8,

(B) pseudobrookite layer, which may optionally be doped with one or more oxides in an amount of < 10% by weight, based on layer (B),

(C) a low refractive index layer having a refractive index n <1.8,

(D) a high refractive index coating consisting of at least two colourless metal oxide layers,

(E) pseudobrookite layer, which may optionally be doped with one or more oxides in an amount of ≦ 10 wt.%, based on layer (E), and optionally,

(F) an outer protective layer.

2. The effect pigment of claim 1, wherein the platelet-shaped substrate is selected from the group consisting of phyllosilicate platelets, BiOCl platelets, SiC platelets, TiC platelets, WC platelets, B₄C flake, BN flake, graphite flake, TiO flake₂Flake, Fe₂O₃Flake, doped or undoped Al₂O₃Flakes, doped or undoped glass flakes, doped or undoped SiO₂Flakes or mixtures thereof.

3. The effect pigment according to claim 1 or 2, characterized in that the phyllosilicate platelets are natural mica, synthetic mica, kaolin or talc.

4. The effect pigment according to one or more of claims 1 to 3, characterized in that the layer (A) consists of one or more metal oxides.

5. The effect pigment according to one or more of claims 1 to 4, characterized in that the metal oxide of the layer (A) is selected from TiO₂、Fe₂O₃、Fe₃O₄、Fe(O)OH、BiOCl、Cr₂O₃、ZnO、Ce₂O₃、ZrO₂、SnO₂、Co₂O₃Titanium suboxide (partially reduced TiO)₂Which has a structure selected from<4 to 2 oxidation state, and lower oxides or mixtures thereof), titanium oxynitride, titanium nitride, CoO, Co₂O₃、Co₃O₄、VO₂、V₂O₃、NiO、WO₃、MnO、Mn₂O₃Or mixtures of the above oxides.

6. The effect pigment according to one or more of claims 1 to 5, characterized in that layer (B) and/or (E) is doped with one or more oxides or mixtures of oxides selected from the following: al (Al)₂O₃、Ce₂O₃、B₂O₃、ZrO₂、SnO₂、Cr₂O₃、CoO、Co₂O₃、Co₃O₄、Mn₂O₃。

7. The effect pigment according to one or more of claims 1 to 6, characterized in that layer (C) consists of SiO₂,MgO*SiO₂,CaO*SiO₂,Al₂O₃*SiO₂,B₂O₃*SiO₂Or a mixture of said compounds.

8. The effect pigment according to one or more of claims 1 to 7, characterized in that layer (D) consists of at least two metal oxide layers, wherein the metal oxides are selected from SnO₂,TiO₂,Al₂O₃,Cr₂O₃,Fe₂O₃Or mixtures thereof.

9. The effect pigment according to one or more of claims 1 to 8, characterized in that layer (D) consists of metal oxide layers (D1) and (D2)

(D1)SnO₂Layer(s)

(D2)TiO₂And (3) a layer.

10. The effect pigment according to one or more of claims 1 to 8, characterized in that layer (D) consists of metal oxide layers (D1), (D2) and (D3)

(D1)Al₂O₃Layer(s)

(D2)TiO₂Layer(s)

(D3)Al₂O₃And (3) a layer.

11. The effect pigment according to one or more of claims 1 to 8, characterized in that the layer (D) consists of metal oxide layers (D1), (D2) and (D3)

(D1)SnO₂Layer(s)

(D2)TiO₂Layer(s)

(D3)SnO₂And (3) a layer.

12. The effect pigment according to one or more of claims 1 to 11, characterised in that layers (B) and (E) have the same layer thickness.

13. The effect pigment according to one or more of claims 1 to 12, characterized in that the outer protective layer (F) consists of SnO₂And (4) forming.

14. The effect pigment according to one or more of claims 1 to 13, characterized in that the total layer thickness of layers (C) and (D) is in the range from 50 to 115 nm.

15. The effect pigment according to one or more of claims 1 to 14, characterized by having the following structure:

substrate + TiO₂+ pseudobrookite + SiO₂+SnO₂+TiO₂+SnO₂+ pseudobrookite

Base material + Fe₂O₃+ pseudobrookite + SiO₂+SnO₂+TiO₂+SnO₂+ pseudobrookite

-substrate + Cr₂O₃+ pseudobrookite + SiO₂+SnO₂+TiO₂+SnO₂+ pseudobrookite

Substrate + TiO₂+ pseudobrookite + MgO SiO₂+SnO₂+TiO₂+SnO₂+ pseudobrookite

Base material + Fe₂O₃+ pseudobrookite + MgO SiO₂+SnO₂+TiO₂+SnO₂+ pseudobrookite

-substrate + Cr₂O₃+ pseudobrookite + MgO SiO₂+SnO₂+TiO₂+SnO₂+ pseudobrookite

Substrate + TiO₂+ pseudobrookite + CaO × SiO₂+SnO₂+TiO₂+SnO₂+ pseudobrookite

Base material + Fe₂O₃+ pseudobrookite + CaO × SiO₂+SnO₂+TiO₂+SnO₂+ pseudobrookite

-substrate + Cr₂O₃+ pseudobrookite + CaO × SiO₂+SnO₂+TiO₂+SnO₂+ pseudobrookite

Substrate + TiO₂+ pseudobrookite + Al₂O₃*SiO₂+SnO₂+TiO₂+SnO₂+ pseudobrookite

Base material + Fe₂O₃+ pseudobrookite + Al₂O₃*SiO₂+SnO₂+TiO₂+SnO₂+ pseudobrookite

-substrate + Cr₂O₃+ pseudobrookite + Al₂O₃*SiO₂+SnO₂+TiO₂+SnO₂+ pseudobrookite

Substrate + TiO₂+ pseudobrookite + SiO₂+TiO₂+SnO₂+ pseudobrookite

Substrate + TiO₂+ pseudobrookite + SiO₂+SnO₂+TiO₂+ pseudobrookite

Substrate + TiO₂+ pseudobrookite + SiO₂+TiO₂+SnO₂+ pseudobrookite + SnO₂

Substrate + TiO₂+ pseudobrookite + SiO₂+SnO₂+TiO₂+ pseudobrookite + SnO₂

Substrate + TiO₂+ pseudobrookite + SiO₂+SnO₂+Fe₂O₃+SnO₂+ pseudobrookite

Substrate + TiO₂+ pseudobrookite + SiO₂+SnO₂+Cr₂O₃+SnO₂+ pseudobrookite

Substrate + TiO₂+ pseudobrookite + SiO₂+Al₂O₃+TiO₂+Al₂O₃+ pseudobrookite.

16. Use of the effect pigments according to one or more of claims 1 to 15 in paints, coatings, printing inks, security printing inks, plastics, ceramic materials, ceramic colours, glazes, engobes, enamels and glasses, as absorbers for laser marking of plastics and papers, in cosmetic preparations, for the preparation of pigment preparations and dry preparations.

17. A formulation comprising the effect pigment according to one or more of claims 1 to 15.

18. A formulation according to claim 17, characterized in that, in addition to the effect pigments according to the invention, they comprise at least one component selected from the group consisting of: absorbents, astringents, antimicrobial substances, antioxidants, antiperspirants, antifoaming agents, anti-dandruff active compounds, antistatic agents, binders, biological additives, bleaching agents, chelating agents, deodorants, emollients, emulsifiers, emulsion stabilizers, dyes, humectants, film formers, fillers, fragrances, flavors, insect repellents, preservatives, anti-corrosion agents, cosmetic oils, solvents, oxidants, botanical ingredients, buffer substances, reducing agents, surfactants, gas propellants, sunscreens, UV filters, UV absorbers, denaturants, aloe vera, avocado oil, coenzyme Q10, green tea extract, viscosity modifiers, fragrances, inorganic pigments, metallic pigments, ceramic pigments, functional pigments, ceramic colorants, functional pigments, and vitamins.

The disadvantage of the gold-colored multilayer pigments known from the prior art, for example from EP 0839167B 1, US 6,692,561B 1, US 6,599355B 1, US 6,579,355B, US 2015/0259538 a1, US 5,958,125 a1, WO98/53011, WO 99/20695, is that they are temperature-unstable at temperatures >900 ℃. CN 101289580A discloses a gold-effect pigment based on mica flakes, but it has the disadvantage that it has a relatively low chroma C for multilayer pigments.

The object of the present invention was to find temperature-stable and intensely colored multilayer pigments, in particular intensely colored gold-effect pigments, based on platelet-shaped substrates having a layer sequence, which are characterized in that no phase reactions occur between the individual layers of the multilayer pigment at temperatures >800 ℃, preferably >900 ℃, in particular >1000 ℃. Furthermore, at the same time no migration of the layer to the surrounding frit occurs. Thus, the stack remains substantially unchanged during the firing operation. It is only this way that it is ensured that the desired effects of the multilayer pigments, such as pearlescent effects, gloss and intense colour, are always present regardless of the application, for example in the case of ceramic applications (cast ceramics, porcelain, sanitary ceramics or tiles and other glazes in which temperatures >800 ℃ act on the effect pigments during the firing operation).

Surprisingly, it has been found that effect pigments based on platelet-shaped substrates comprising two pseudobrookite layers separated from each other by a sufficiently thick spacer layer are stable at temperatures >800 ℃ because no or substantially no phase reactions occur between the individual layers of the multilayer system.

The present invention accordingly relates to effect pigments based on platelet-shaped substrates which have at least one layer sequence on their surface,

(A) the high-refractive-index coating has a refractive index n of not less than 1.8,

(B) pseudobrookite layer, which may optionally be doped with one or more oxides in an amount of < 10% by weight, based on layer (B),

(C) a low refractive index layer having a refractive index n <1.8,

(D) a high refractive index layer with a refractive index n of more than or equal to 1.8 and composed of at least two colorless metal oxide layers,

(E) pseudobrookite layer, which may optionally be doped with one or more oxides in an amount of ≦ 10 wt.%, based on layer (E), and optionally,

(F) an outer protective layer.

The effect pigments according to the invention are distinguished by very high temperature stability, high tinctorial strength, high hiding power and high gloss and are therefore particularly suitable for high-temperature applications, for example in glazes and ceramic frits.

The invention also relates to the use of the pigments according to the invention as absorbers for laser marking and laser welding in paints, coatings, printing inks, security printing inks, plastics, in cosmetic preparations, in particular for high-temperature applications, for example for the coloration of glazes and ceramic frits. The pigments according to the invention are also suitable for the preparation of pigment preparations and for the preparation of dry preparations, such as ceramic pigments, granules, chips, pellets, agglomerates and the like. The dry formulations are suitable, in particular, for printing inks and paints.

Suitable base substrates for the effect pigments according to the invention are translucent and transparent platelet-shaped substrates. Preferred substrates are phyllosilicate platelets, SiC, TiC, WC, B₄C. BN, graphite, TiO₂And Fe₂O₃Flakes of, doped or undoped Al₂O₃Flakes, doped or undoped glass flakes, doped or undoped SiO₂Flakes of TiO₂Flakes, BiOCl flakes and mixtures thereof. Among the phyllosilicates, particular preference is given to natural and synthetic mica flakes, muscovite, talc and kaolin. The synthetic mica used as the substrate is preferably fluorophlogopite or zinc phlogopite.

The glass flakes may consist of all types of glass known to the person skilled in the art, as long as they are temperature-stable within the firing range used. Suitable glasses are, for example, quartz, A glass, E glass, C glass, ECR glass, recycled glass, alkali borate glass, alkali silicate glass, borosilicate glass, quartz glass, glass ceramics, glass materials, and glass materials, and glass materials,Glass, laboratory instrument glass or optical glass.

The refractive index of the glass flakes is preferably from 1.45 to 1.80, in particular from 1.50 to 1.70. The glass substrate is particularly preferably composed of C glass, ECR glass or borosilicate glass.

Synthetic substrate flakes, e.g. glass flakes, SiO₂Flakes of Al₂O₃The flakes, may be doped or undoped. If they are dopedThe dopant is then preferably Al, N, B, Ti, Zr, Si, In, Sn or Zn or mixtures thereof. Furthermore, other ions from the transition metal (V, Cr, Mn, Fe, Co, Ni, Cu, Y, Nb, Mo, Hf, Sb, Ta, W) group and ions from the lanthanide group may be used as dopants.

In Al₂O₃In the case of (2), the substrate is preferably undoped or doped with TiO₂、ZrO₂Or ZnO. Al (Al)₂O₃The sheet is preferably corundum. Suitable Al₂O₃The flakes are preferably doped or undoped alpha-Al₂O₃Flakes, in particular doped with TiO₂Or ZrO₂alpha-Al of (2)₂O₃A sheet.

If the substrate is doped, the doping proportion is preferably from 0.01 to 5% by weight, in particular from 0.10 to 3% by weight, based on the substrate.

The size of the base substrate is not critical per se and may be matched to a particular application. In general, the thickness of the platelet-shaped substrate is between 0.05 and 5 μm, in particular between 0.1 and 4.5. mu.m.

Substrates having different particle sizes may also be employed. Especially preferred are mixtures of mica fractions (fractions) of mica N (10-60 microns), mica F (5-20 microns) and/or mica M (<15 microns). Furthermore, preference is given to the N and S fraction (10-130 μm) and the F and S fraction (5-130. mu.m).

A typical example of a particle size distribution (measured using a malvern Mastersizer 2000) is:

D₁₀:1 to 50 μm, in particular 2 to 45 μm, very particularly preferably 5 to 40 μm,

D₅₀7-275 μm, in particular 10-200 μm, very particularly preferably 15-150 μm,

D₉₀15 to 500. mu.m, in particular 25 to 400 μm, very particularly preferably 50 to 200. mu.m.

In this patent application, "high refractive index" means a refractive index ≧ 1.8, and "low refractive index" means a refractive index < 1.8.

According to the invention, the sequence of layers (A) to (E) or (A) to (F) of the effect pigments is of crucial importance for the stability and the optical properties of the pigments.

Layer (A) is a high refractive index layer having a refractive index n.gtoreq.1.8, preferably n.gtoreq.2.0. Layer (a) may be colorless or may be absorbing in the visible wavelengths. The layer (a) preferably consists of a metal oxide or a mixture of metal oxides. The metal oxide is preferably selected from TiO₂、ZrO₂、ZnO、SnO₂、Cr₂O₃、Ce₂O₃、BiOCl、Fe₂O₃、Fe₃O₄FeO (OH), Ti suboxide (partially reduced TiO)₂Having a slave<4 to 2 oxidation state and lower oxides such as Ti₃O₅、Ti₂O₃Up to TiO), titanium oxynitride and titanium nitride, CoO, Co₂O₃、Co₃O₄、VO₂、V₂O₃、NiO、WO₃、MnO、Mn₂O₃Or mixtures of said oxides. The layer (A) is preferably made of TiO₂、Fe₂O₃、Cr₂O₃Or SnO₂And (4) forming.

The layer (A) preferably has a layer thickness of from 1 to 15nm, in particular from 1 to 10 nm, very particularly from 1 to 5 nm.

The pseudobrookite layers (B) and (E) may be the same or different. The layers are preferably identical in composition. The pseudobrookite layer is preferably made entirely of Fe₂TiO₅And (4) forming. However, Fe is due to slight variations in the iron/titanium ratio and the resulting crystal lattice vacancies₂TiO₅May be slightly over-stoichiometric or under-stoichiometric.

The layer may be prepared by simultaneous addition and precipitation of an iron-containing salt solution and a titanium-containing salt solution or by co-precipitation from a single solution containing iron and titanium salts.

The pseudobrookite layer is preferably composed of 100% crystalline pseudobrookite.

Layers (B) and (E) may optionally additionally incorporate one or more oxides or oxide mixtures, preferably metal oxides, to increase stability and/or dye strength. The oxide is preferably selected from Al₂O₃、Ce₂O₃、B₂O₃、ZrO₂、SnO₂、Cr₂O₃、CoO、Co₂O₃、Co₃O₄、Mn₂O₃. The proportion by weight of the oxide or oxide mixture in the pseudobrookite layer is preferably not more than 5% by weight, in particular in the range from 1 to 5% by weight, very particularly preferably from 1 to 3% by weight, based on layer (B) or layer (E).

The layers (B) and (E) preferably each, independently of one another, have a layer thickness of from 60 to 120 nm, in particular from 70 to 110 nm, in particular from 80 to 100 nm.

Of particular importance for the stability of the effect pigments according to the invention is that the layers (B) and (E) are separated from one another by a separating layer (C) and a separating layer (D). The distance between layers (B) and (E) should preferably be from 40 to 100 nm, in particular from 45 to 90 nm, especially from 50 to 80 nm.

The refractive index of the low refractive index layer (C) is n<1.8, preferably n<1.7, preferably made of SiO₂、MgO*SiO₂、CaO*SiO₂、Al₂O₃*SiO₂、B₂O₃*SiO₂Or mixtures of the above compounds. In addition, the silicate layer may further incorporate an alkaline earth metal ion or an alkali metal ion. Layer (C) is preferably a "silicate" layer. Layer (C) very particularly preferably consists of doped or undoped silicon dioxide.

The layer (C) preferably has a layer thickness of 40 to 90 nm, in particular 40 to 70 nm, in particular 50 to 60 nm.

The high-refractive-index coating (D) has a refractive index n.gtoreq.1.8, preferably n.gtoreq.2.0, and is composed of at least two colorless metal oxide layers. Layer (D) preferably consists of 2 or 3 colourless metal oxide layers. These metal oxides are preferably selected from SnO₂、TiO₂、Al₂O₃、Fe₂O₃、Cr₂O₃Or mixtures thereof.

The coating of layer (D) preferably consists of metal oxide layers (D1) and (D2)

(D1)SnO₂Layer(s)

(D2)TiO₂Layer(s)

Or

Is composed of metal oxide layers (D1), (D2) and (D3)

(D1)Al₂O₃Layer(s)

(D2)TiO₂Layer(s)

(D3)Al₂O₃Layer(s)

Or

(D1)SnO₂Layer(s)

(D2)TiO₂Layer(s)

(D3)SnO₂And (3) a layer.

The coating of layer (D) preferably has a layer thickness of 10 to 25 nm, in particular 11 to 21 nm, particularly preferably 12 to 17 nm. The sum of all layer thicknesses of the individual metal oxide layers (D1), (D2), (D3) and any other layer of the coating of layer (D) should not exceed 25 nm.

In order to enable the layers (C) and (D) to act as separate layers and thereby facilitate the reduced phase reaction between the respective pseudobrookite layers (B) and (E), the total thickness of the layers (C) and (D) should not exceed a thickness range of 120 nm, should preferably be between 50 and 115nm, in particular 51 and 91 nm, and very particularly preferably 62 and 77 nm.

If the layer (A) or (D) consists of TiO₂Composition of, TiO₂May be in the rutile or anatase form.

Particularly preferred effect pigments have the following structure:

substrate + TiO₂+ pseudobrookite + SiO₂+SnO₂+TiO₂+SnO₂+ pseudobrookite

Base material + Fe₂O₃+ pseudobrookite + SiO₂+SnO₂+TiO₂+SnO₂+ pseudobrookite

-substrate + Cr₂O₃+ pseudobrookite + SiO₂+SnO₂+TiO₂+SnO₂+ pseudobrookite

Substrate + TiO₂+ pseudobrookite + MgO SiO₂+SnO₂+TiO₂+SnO₂+ pseudobrookite

Base material + Fe₂O₃+ pseudobrookite + MgO SiO₂+SnO₂+TiO₂+SnO₂+ pseudobrookite

-substrate + Cr₂O₃+ pseudobrookite + MgO SiO₂+SnO₂+TiO₂+SnO₂+ pseudobrookite

Substrate + TiO₂+ pseudobrookite + CaO × SiO₂+SnO₂+TiO₂+SnO₂+ pseudobrookite

Base material + Fe₂O₃+ pseudobrookite + CaO × SiO₂+SnO₂+TiO₂+SnO₂+ pseudobrookite

-substrate + Cr₂O₃+ pseudobrookite + CaO × SiO₂+SnO₂+TiO₂+SnO₂+ pseudobrookite

Substrate + TiO₂+ pseudobrookite + Al₂O₃*SiO₂+SnO₂+TiO₂+SnO₂+ pseudobrookite

Base material + Fe₂O₃+ pseudobrookite + Al₂O₃*SiO₂+SnO₂+TiO₂+SnO₂+ pseudobrookite

-substrate + Cr₂O₃+ pseudobrookite + Al₂O₃*SiO₂+SnO₂+TiO₂+SnO₂+ pseudobrookite

Substrate + TiO₂+ pseudobrookite + SiO₂+TiO₂+SnO₂+ pseudobrookite

Substrate + TiO₂+ pseudobrookite + SiO₂+SnO₂+TiO₂+ pseudobrookite

Substrate + TiO₂+ pseudobrookite + SiO₂+TiO₂+SnO₂+ pseudobrookite + SnO₂

Substrate + TiO₂+ pseudobrookite + SiO₂+SnO₂+TiO₂+ pseudobrookite + SnO₂

Substrate + TiO₂+ pseudobrookite + SiO₂+SnO₂+Fe₂O₃+SnO₂+ pseudobrookite

Substrate + TiO₂+ pseudobrookite + SiO₂+SnO₂+Cr₂O₃+SnO₂+ pseudobrookite

Substrate + TiO₂+ pseudobrookite + SiO₂+Al₂O₃+TiO₂+Al₂O₃+ pseudobrookite.

Particularly preferred effect pigments have the following structure:

natural mica flakes + TiO₂+ pseudobrookite + SiO₂+SnO₂+TiO₂+SnO₂+ pseudobrookite

-natural mica flakes + Fe₂O₃+ pseudobrookite + SiO₂+SnO₂+TiO₂+SnO₂+ pseudobrookite

-natural mica flakes + Cr₂O₃+ pseudobrookite + SiO₂+SnO₂+TiO₂+SnO₂+ pseudobrookite

Natural mica flakes + TiO₂+ pseudobrookite + MgO SiO₂+SnO₂+TiO₂+SnO₂+ pseudobrookite

-natural mica flakes + Fe₂O₃+ pseudobrookite + MgO SiO₂+SnO₂+TiO₂+SnO₂+ pseudobrookite

-natural mica flakes + Cr₂O₃+ pseudobrookite + MgO SiO₂+SnO₂+TiO₂+SnO₂+ pseudobrookite

Natural mica flakes + TiO₂+ pseudobrookite + CaO × SiO₂+SnO₂+TiO₂+SnO₂+ pseudobrookite

-natural mica flakes + Fe₂O₃+ pseudobrookite + CaO × SiO₂+SnO₂+TiO₂+SnO₂+ pseudobrookite

-natural mica flakes + Cr₂O₃+ pseudobrookite + CaO × SiO₂+SnO₂+TiO₂+SnO₂+ pseudobrookite

Natural mica flakes + TiO₂+ pseudobrookite + Al₂O₃*SiO₂+SnO₂+TiO₂+SnO₂+ pseudobrookite

-natural mica flakes + Fe₂O₃+ pseudobrookite + Al₂O₃*SiO₂+SnO₂+TiO₂+SnO₂+ pseudobrookite

-natural mica flakes + Cr₂O₃+ pseudobrookite + Al₂O₃*SiO₂+SnO₂+TiO₂+SnO₂+ pseudobrookite

Natural mica flakes + TiO₂+ pseudobrookite + SiO₂+TiO₂+SnO₂+ pseudobrookite

Natural mica flakes + TiO₂+ pseudobrookite + SiO₂+SnO₂+TiO₂+ pseudobrookite

Natural mica flakes + TiO₂+ pseudobrookite + SiO₂+TiO₂+SnO₂+ pseudobrookite + SnO₂

Natural mica flakes + TiO₂+ pseudobrookite + SiO₂+SnO₂+TiO₂+ pseudobrookite + SnO₂

Natural mica flakes + TiO₂+ pseudobrookite + SiO₂+SnO₂+Fe₂O₃+SnO₂+ pseudobrookite

Natural mica flakes + TiO₂+ pseudobrookite + SiO₂+SnO₂+Cr₂O₃+SnO₂+ pseudobrookite

Natural mica flakes + TiO₂+ pseudobrookite + SiO₂+Al₂O₃+TiO₂+Al₂O₃+ pseudobrookite

-synthetic mica flakes + TiO₂+ pseudobrookite + SiO₂+SnO₂+TiO₂+SnO₂+ pseudobrookite

-synthetic mica flakes + Fe₂O₃+ pseudobrookite + SiO₂+SnO₂+TiO₂+SnO₂+ pseudobrookite

-synthetic mica flakes + Cr₂O₃+ pseudobrookite + SiO₂+SnO₂+TiO₂+SnO₂+ pseudobrookite

-synthetic mica flakes + TiO₂+ pseudobrookite + MgO SiO₂+SnO₂+TiO₂+SnO₂+ pseudobrookite

-synthetic mica flakes + Fe₂O₃+ pseudobrookite + MgO SiO₂+SnO₂+TiO₂+SnO₂+ pseudobrookite

-synthetic mica flakes + Cr₂O₃+ pseudobrookite + MgO SiO₂+SnO₂+TiO₂+SnO₂+ pseudobrookite

-synthetic mica flakes + TiO₂+ pseudobrookite + CaO × SiO₂+SnO₂+TiO₂+SnO₂+ pseudobrookite

-synthetic mica flakes + Fe₂O₃+ pseudobrookite + CaO × SiO₂+SnO₂+TiO₂+SnO₂+ pseudobrookite

-synthetic mica flakes + Cr₂O₃+ pseudobrookite + CaO × SiO₂+SnO₂+TiO₂+SnO₂+ pseudobrookite

-synthetic mica flakes + TiO₂+ pseudobrookite + Al₂O₃*SiO₂+SnO₂+TiO₂+SnO₂+ pseudobrookite

-synthetic mica flakes + Fe₂O₃+ pseudobrookite + Al₂O₃*SiO₂+SnO₂+TiO₂+SnO₂+ pseudobrookite

-synthetic mica flakes + Cr₂O₃+ pseudobrookite + Al₂O₃*SiO₂+SnO₂+TiO₂+SnO₂+ pseudobrookite

-synthetic mica flakes + TiO₂+ pseudobrookite + SiO₂+TiO₂+SnO₂+ pseudobrookite

-synthetic mica flakes + TiO₂+ pseudobrookite + SiO₂+SnO₂+TiO₂+ pseudobrookite

-synthetic mica flakes + TiO₂+ pseudobrookite + SiO₂+TiO₂+SnO₂+ pseudobrookite + SnO₂

-synthetic mica flakes + TiO₂+ pseudobrookite + SiO₂+SnO₂+TiO₂+ pseudobrookite + SnO₂

-synthetic mica flakes + TiO₂+ pseudobrookite + SiO₂+SnO₂+Fe₂O₃+SnO₂+ pseudobrookite

-synthetic mica flakes + TiO₂+ pseudobrookite + SiO₂+SnO₂+Cr₂O₃+SnO₂+ pseudobrookite

-synthetic mica flakes + TiO₂+ pseudobrookite + SiO₂+Al₂O₃+TiO₂+Al₂O₃+ pseudobrookite

-Al₂O₃Flake + TiO₂+ pseudobrookite + SiO₂+SnO₂+TiO₂+SnO₂+ pseudobrookite

-Al₂O₃Flake + Fe₂O₃+ pseudobrookite + SiO₂+SnO₂+TiO₂+SnO₂+ pseudobrookite

-Al₂O₃Flake + Cr₂O₃+ pseudobrookite + SiO₂+SnO₂+TiO₂+SnO₂+ pseudobrookite

-Al₂O₃Flake + TiO₂+ pseudobrookite + MgO SiO₂+SnO₂+TiO₂+SnO₂+ pseudobrookite

-Al₂O₃Flake + Fe₂O₃+ pseudobrookite + MgO SiO₂+SnO₂+TiO₂+SnO₂+ pseudobrookite

-Al₂O₃Flake + Cr₂O₃+ pseudobrookite + MgO SiO₂+SnO₂+TiO₂+SnO₂+ pseudobrookite

-Al₂O₃Flake + TiO₂+ pseudobrookite + CaO × SiO₂+SnO₂+TiO₂+SnO₂+ pseudobrookite

-Al₂O₃Flake + Fe₂O₃+ pseudobrookite + CaO × SiO₂+SnO₂+TiO₂+SnO₂+ pseudobrookite

-Al₂O₃Flake + Cr₂O₃+ pseudobrookite + CaO × SiO₂+SnO₂+TiO₂+SnO₂+ pseudobrookite

-Al₂O₃Flake + TiO₂+ pseudobrookite + Al₂O₃*SiO₂+SnO₂+TiO₂+SnO₂+ pseudobrookite

-Al₂O₃Flake + Fe₂O₃+ pseudobrookite + Al₂O₃*SiO₂+SnO₂+TiO₂+SnO₂+ pseudobrookite

-Al₂O₃Flake + Cr₂O₃+ pseudobrookite + Al₂O₃*SiO₂+SnO₂+TiO₂+SnO₂+ pseudobrookite

-Al₂O₃Flake + TiO₂+ pseudobrookite + SiO₂+TiO₂+SnO₂+ pseudobrookite

-Al₂O₃Flake + TiO₂+ pseudobrookite + SiO₂+SnO₂+TiO₂+ pseudobrookite

-Al₂O₃Flake + TiO₂+ pseudobrookite + SiO₂+TiO₂+SnO₂+ pseudobrookite + SnO₂

-Al₂O₃Flake + TiO₂+ pseudobrookite + SiO₂+SnO₂+TiO₂+ pseudobrookite + SnO₂

-Al₂O₃Flake + TiO₂+ pseudobrookite + SiO₂+SnO₂+Fe₂O₃+SnO₂+ pseudobrookite

-Al₂O₃Flake + TiO₂+ pseudobrookite + SiO₂+SnO₂+Cr₂O₃+SnO₂+ pseudobrookite

-Al₂O₃Flake + TiO₂+ pseudobrookite + SiO₂+Al₂O₃+TiO₂+Al₂O₃+ pseudobrookite

-SiO₂Flake + TiO₂+ pseudobrookite + SiO₂+SnO₂+TiO₂+SnO₂+ pseudobrookite

-SiO₂Flake + Fe₂O₃+ pseudobrookite + SiO₂+SnO₂+TiO₂+SnO₂+ pseudobrookite

-SiO₂Flake + Cr₂O₃+ pseudobrookite + SiO₂+SnO₂+TiO₂+SnO₂+ pseudobrookite

-SiO₂Flake + TiO₂+ pseudobrookite + MgO SiO₂+SnO₂+TiO₂+SnO₂+ pseudobrookite

-SiO₂Flake + Fe₂O₃+ pseudobrookite + MgO SiO₂+SnO₂+TiO₂+SnO₂+ pseudobrookite

-SiO₂Flake + Cr₂O₃+ pseudobrookite + MgO SiO₂+SnO₂+TiO₂+SnO₂+ pseudobrookite

-SiO₂Flake + TiO₂+ pseudobrookite + CaO × SiO₂+SnO₂+TiO₂+SnO₂+ pseudobrookite

-SiO₂Flake + Fe₂O₃+ pseudobrookite + CaO × SiO₂+SnO₂+TiO₂+SnO₂+ pseudobrookite

-SiO₂Flake + Cr₂O₃+ pseudobrookite + CaO × SiO₂+SnO₂+TiO₂+SnO₂+ pseudobrookite

-SiO₂Flake + TiO₂+ pseudobrookite + Al₂O₃*SiO₂+SnO₂+TiO₂+SnO₂+ pseudobrookite

-SiO₂Flake + Fe₂O₃+ pseudobrookite + Al₂O₃*SiO₂+SnO₂+TiO₂+SnO₂+ pseudobrookite

-SiO₂Flake + Cr₂O₃+ pseudobrookite + Al₂O₃*SiO₂+SnO₂+TiO₂+SnO₂+ pseudobrookite

-SiO₂Flake + TiO₂+ pseudobrookite + SiO₂+TiO₂+SnO₂+ pseudobrookite

-SiO₂Flake + TiO₂+ pseudobrookite + SiO₂+SnO₂+TiO₂+ pseudobrookite

-SiO₂Flake + TiO₂+ pseudobrookite + SiO₂+TiO₂+SnO₂+ pseudobrookite + SnO₂

-SiO₂Flake + TiO₂+ pseudobrookite + SiO₂+SnO₂+TiO₂+ pseudobrookite + SnO₂

-SiO₂Flake + TiO₂+ pseudobrookite + SiO₂+SnO₂+Fe₂O₃+SnO₂+ pseudobrookite

-SiO₂Flake + TiO₂+ pseudobrookite + SiO₂+SnO₂+Cr₂O₃+SnO₂+ pseudobrookite

-SiO₂Flake + TiO₂+ pseudobrookite + SiO₂+Al₂O₃+TiO₂+Al₂O₃+ pseudobrookite.

Wherein SiO is₂And Al₂O₃The flakes may be doped or undoped. Al (Al)₂O₃The lamellae are preferably doped. SiO 2₂The flakes are preferably undoped.

The metal oxide layer(s) are preferably applied by wet-chemical methods, it being possible to use wet-chemical coating methods developed for the preparation of pearlescent pigments; processes of this type are described, for example, in u.s.3087828, u.s.3087829, u.s.3553001, DE 1467468, DE 1959988, DE 2009566, DE 2214545, DE 2215191, DE 2244298, DE 2313331, DE 2522572, DE 3137808, DE 3137809, DE 3151343, DE 3151354, DE 3151355, DE 3211602, DE 3235017, DE 19618568, EP 0659843, or in further patent documents and other publications known to the person skilled in the art.

In the case of wet coating, the substrate flakes are suspended in water and one or more hydrolysable metal salts are added at a pH suitable for hydrolysis, the pH being selected so that the metal oxide or metal oxide hydrate precipitates directly on the flakes without secondary precipitation. The pH is generally kept constant by simultaneous metered addition of bases and/or acids. The effect pigments are subsequently separated off, washed and dried and optionally calcined, the calcination temperature being able to be optimized in accordance with the coating present in each case. Generally, the calcination temperature is between 250-1000 deg.C, preferably between 350-900 deg.C. If desired, the pigments can be isolated, dried and optionally calcined after application of the individual coatings and then resuspended to precipitate additional coatings.

For SiO₂The application of the layer preferably uses the process described in DE 19618569. For SiO₂For the preparation of the layers, preference is given to using sodium or potassium waterglass solutions.

Furthermore, the coating can also be carried out by gas-phase coating in a fluidized-bed reactor, for example, the processes proposed in EP 0045851 and EP 0106235 for the preparation of pearlescent pigments can be used accordingly.

The shade of the pigment can be varied within a wide range by selecting different coating weights or the thickness of the resulting layer. Fine tuning of a certain hue can be controlled by visual or measurement techniques to approach the desired color, thereby overriding the mere choice of amounts.

In order to increase the stability to light, water and weather, the effect pigments according to the invention, depending on the area of application, often propose inorganic or organic post-coatings or post-treatments (layer (F)). Suitable after-coatings or after-treatments are, for example, the processes described in German patents 2215191, DE A3151354, DE A3235017 or DE A3334598The method is carried out. This post-coating further increases the chemical and photochemical stability or simplifies the processing of the effect pigments, in particular in various media. To improve wettability, dispersibility and/or compatibility with the user medium, the pigment surface may be coated with SnO₂、Al₂O₃、ZrO₂Or a mixture thereof. Furthermore, organic aftercoatings can also be used, for example silanes, such as EP0090259, EP 0634459, WO99/57204, WO96/32446, WO99/57204, U.S.5,759,255, U.S.5,571,851, WO01/92425 or J.J.Ponjie, Philips Technical Review, Vol.44, No.3,81ff. and P.H.Harding J.C.berg, J.Adhesion Sci.Technol, Vol.11, No. 4, p.471 493. Layer (F) is preferably SnO₂Of (2) a layer of (a).

Coating in this patent application refers to complete coverage/coating of the platelet-like substrate.

The effect pigments according to the invention have an increased temperature and thermal stability compared with unstabilized effect pigments. The stabilized effect pigments can be added without problems to the engobe and glaze. The glaze may be matte to glossy, or transparent to opaque, depending on the desired effect.

The effect pigments according to the invention are also suitable for the production of flowable pigment preparations and dry preparations, in particular for printing inks and paints, preferably automotive paints, consisting of the pigment according to the invention, a binder and optionally one or more additives.

The effect pigments according to the invention are compatible with a wide variety of color systems, preferably from the fields of paints, coatings and printing inks. For the preparation of printing inks for use, for example, in gravure, flexographic, offset and offset overprint varnishes, a variety of binders, in particular of the water-soluble type, are suitable, for example those of the type described by BASF, Marabu,Sericol, Hartmann, Gebr.Schmidt, Sicpa, Aarberg, Siegwerk, GSB-Wahl, Follmann, Ruco or Coates Screen INKS GmbH. The printing ink may be built on a water or solvent base.

The effect pigments according to the invention are suitable for use in decorative cosmetics and personal care applications, such as nail varnishes, lipsticks, compact powders, gels, lotions, soaps, toothpastes, skin lotions, emulsions, soaps, shampoos, BB creams, CC creams, color cosmetics, foundations, mascaras, hair, eyelashes and eyebrow products, etc., as well as in paints, industrial coatings and powder coatings, plastics and ceramics.

In decorative cosmetics, the effect pigments according to the invention are preferably used in a concentration of from 0.5 to 25% by weight, in particular from 1 to 20% by weight, very particularly preferably from 1 to 10% by weight, based on the formulation. In the case of cosmetic preparations for personal care applications, the effect pigments according to the invention are preferably used in a concentration of from 0.1 to 5% by weight, and very particularly preferably from 0.5 to 4% by weight, based on the preparation.

It goes without saying that the effect pigments according to the invention can also be used advantageously in mixtures with, for example,

metallic effect pigments, for example based on iron or aluminium flakes;

synthetic mica flakes, natural mica flakes, glass flakes, Al based on metal oxide coating₂O₃Flake, Fe₂O₃Flakes or SiO₂Flake pearlescent pigments;

-an absorption pigment;

-effect pigments;

synthetic mica flakes, natural mica flakes, glass flakes, Al based on metal oxide coating₂O₃Flake, Fe₂O₃Flakes or SiO₂A flake multilayer pigment (preferably comprising 2, 3, 4, 5 or 7 layers);

-an organic dye;

-an organic pigment;

inorganic pigments, such as transparent and opaque white, colored and black pigments; in particular temperature-stable ceramic pigments;

-flake-like iron oxides;

-carbon black;

-a ceramic colour body;

functional pigments, such as infrared-reflective or conductive pigments.

The effect pigments according to the invention can be mixed with commercially available pigments and/or other commercially available fillers in any proportion.

Commercially available fillers which may be mentioned are, for example, natural and synthetic mica, nylon powder, pure or filled melamine resins, talc, glass, kaolin, oxides or hydroxides of aluminum, magnesium, calcium, zinc, BiOCl, barium sulfate, calcium carbonate, magnesium carbonate, carbon, boron nitride and physical or chemical combinations of these substances. There is no limitation on the particle shape of the filler. It may be, for example, in the form of a flake, a sphere or a needle, as required.

The effect pigments according to the invention can of course also be combined with cosmetic raw materials and any type of auxiliaries in the formulations. These include, inter alia, oils, fats, waxes, film formers, preservatives and auxiliaries which generally determine the application properties, such as thickeners and rheological additives, for example bentonite, hectorite, silicon dioxide, Ca silicates, gelatin, high molecular weight carbohydrates and/or surface-active auxiliaries, etc.

The preparations comprising the effect pigments according to the invention may be of the lipophilic, hydrophilic or hydrophobic type. In the case of multiphase formulations having a discrete aqueous phase and a non-aqueous phase, the effect pigments according to the invention can in each case be present in only one of the two phases or can also be distributed over both phases.

The pH of the formulation may be from 1 to 14, preferably from 2 to 11, particularly preferably from 4 to 10.

No limitation is set on the concentration of the effect pigments according to the invention in the formulation. Depending on the application, they may be from 0.001 (rinse-off products, e.g. shower gels) to 60%. Furthermore, the effect pigments according to the invention can also be combined with cosmetically active compounds. Suitable active compounds are, for example, insect repellents, inorganic UV filters, e.g. TiO₂UV A/BC protective filters (e.g. OMC, B3, MBC), also in capsule form, anti-ageing active compounds, vitamins and their derivatives (e.g. vitamin A, C, E, etc.), self-tanning agents (e.g. vitamin E A, C, E, etc.)Such as, inter alia, DHA, erythrose, etc.) and other cosmetically active compounds, such as bisabolol, LPO, ectoin, emblic leafflower fruit, allantoin, bioflavonoids and derivatives thereof.

The organic UV filters are generally used in amounts of from 0.5 to 10% by weight, preferably from 1 to 8% by weight, and the inorganic UV filters in amounts of from 0.1 to 30% by weight, based on the formulation.

In addition, the formulations may further comprise conventional skin-protecting or skin-caring active compounds, such as aloe vera, avocado oil, coenzyme Q10, green tea extract, and active compound complexes.

The present invention likewise relates to formulations which, in particular, in addition to the effect pigments according to the invention, comprise at least one component selected from the group consisting of: absorbents, astringents, antimicrobial substances, antioxidants, antiperspirants, antifoams, antidandruff active compounds, antistatic agents, binders, biological additives, bleaches, chelating agents, deodorants, emollients, emulsifiers, emulsion stabilizers, dyes, humectants, film formers, fillers, fragrances, flavors, insect repellents, preservatives, anticorrosion agents, cosmetic oils, solvents, oxidants, botanical ingredients, buffer substances, reducing agents, surfactants, gas propellants, sunscreens, UV filters and UV absorbers, denaturants, aloe vera, avocado oil, coenzyme Q10, green tea extract, viscosity modifiers, fragrances, inorganic pigments, such as transparent or opaque white, colored and black pigments, metallic pigments, temperature stable ceramic pigments, ceramic color bodies, functional pigments, such as infrared-reflective pigments or conductive pigments, and vitamins.

Furthermore, the invention relates to the use of the effect pigments according to the invention in paints, coatings, printing inks, security printing inks, plastics, ceramic materials, glass, glazes, as tracers, as absorbers for laser marking of plastics and paper, and in cosmetic preparations. The pigments according to the invention are also suitable for the preparation of pigment preparations and for the preparation of dry preparations, such as granules, chips, pellets, agglomerates and the like. The dry formulations are particularly suitable for paints and printing inks.

The invention furthermore relates to preparations, such as ceramic pigments, paints, tiles, cast ceramics, sanitary ceramics, enamels, glazes, clays, glass and ceramic products, comprising the effect pigments according to the invention.

The following examples are intended to illustrate the invention, but not to limit it. Unless otherwise indicated, the percentage figures relate to weight percentages.

Detailed Description

Examples

Example 1

100 grams of natural mica with a particle size of 10-60 microns was heated to 80 ℃ in 2 liters of deionized water and stirred. When this temperature had been reached, 44 g of TiCl were metered in at a pH of 1.8₄Solution (400 g/l TiCl₄) During this time, the pH was kept constant with 32% sodium hydroxide solution. The pH is subsequently adjusted to 2.8 with the aid of sodium hydroxide solution, and 600 ml of FeCl are added at the same time at this pH and 75 ℃₃Aqueous solution (w (fe) ═ 7%) and 462 ml of TiCl₄Aqueous solution (200 g TiCl)₄L). The pH was maintained throughout the addition by the simultaneous dropwise addition of 32% sodium hydroxide solution. After stirring for a further 0.5 h, the pH was raised to 7.5 and 650 ml of an aqueous sodium silicate solution (13% by weight SiO) were slowly metered in at this pH₂) During this time, the pH was kept constant with 10% hydrochloric acid. After stirring for a further 0.5 h, the pH is lowered to 1.8 with 10% hydrochloric acid and 5 g of SnCl are metered in₄ x 5H₂O and 41 ml of hydrochloric acid (20%). 105 ml of TiCl are then slowly metered in at the same pH₄Solution (400 g/l TiCl₄). Then 5 g of SnCl is added₄x5H₂O and 41 ml hydrochloric acid (20%). In each case, the pH was maintained at 1.8 using 32% sodium hydroxide solution. The pH is subsequently adjusted to 2.8 again with the aid of sodium hydroxide solution. Finally, 650 ml of FeCl were added in parallel₃Aqueous solution (w (fe) ═ 7%) and 499 ml of TiCl₄Aqueous solution (200 g TiCl)₄/l) and titrated simultaneously with sodium hydroxide solution (w ═ 10%) to apply the outermost layer. After stirring for a further 0.5 h at a pH of 3.0, filtration is carried outThe coated mica substrate was washed and dried at 110 ℃ for 16 hours. Finally, the effect pigment obtained is calcined at 850 ℃ for 0.5 hour and sieved.

A temperature-stable, golden multilayer pigment with high brightness is obtained.

Example 2

100 grams of natural mica with a particle size of 10-25 microns was heated to 80 ℃ in 2 liters of deionized water and stirred. When this temperature had been reached, 44 g of TiCl were metered in at a pH of 1.8₄Solution (400 g/l TiCl₄) The pH was kept constant during this process with 32% sodium hydroxide solution. The pH is subsequently adjusted to 2.8 with the aid of sodium hydroxide solution, and 600 ml of FeCl are added at the same time at this pH and 75 ℃₃Aqueous solution (w (fe) ═ 7%) and 462 ml of TiCl₄Aqueous solution (200 g TiCl)₄L). The pH was maintained throughout the addition by the simultaneous dropwise addition of 32% sodium hydroxide solution. After stirring for a further 0.5 h, the pH was raised to 7.5 and 650 ml of an aqueous sodium silicate solution (13% by weight SiO) were slowly metered in at this pH₂) During this time, the pH was kept constant with 10% hydrochloric acid. After stirring for a further 0.5 h, the pH is lowered to 1.8 with 10% hydrochloric acid and 5 g of SnCl are metered in₄x5H₂O and 41 ml of hydrochloric acid (20%). 105 ml of TiCl are then slowly metered in at the same pH₄Solution (400 g/l TiCl₄). Then 5 g of SnCl is added₄x5H₂O and 41 ml hydrochloric acid (20%). In each case, the pH was maintained at 1.8 using 32% sodium hydroxide solution. The pH is subsequently adjusted to 2.8 again with the aid of sodium hydroxide solution. Finally, 650 ml of FeCl were added in parallel₃Aqueous solution (w (fe) ═ 7%) and 499 ml of TiCl₄Aqueous solution (200 g TiCl)₄/l) and titrated simultaneously with sodium hydroxide solution (w ═ 10%) to apply the outermost layer. After stirring at a pH of 3.0 for a further 0.5 h, the coated mica substrate was filtered off, washed and dried at 110 ℃ for 16 h. Finally, the effect pigments obtained in this way were calcined at 850 ℃ for 0.5 h and sieved.

A temperature-stable, golden multilayer pigment having high brightness and good hiding power is obtained.

Example 3

100 grams of natural mica with a particle size of 20-180 microns was heated to 80 ℃ in 2 liters of deionized water and stirred. When this temperature had been reached, 38 g of TiCl were added at a pH of 1.8₄Solution (400 g/l TiCl₄) Metered in, during which the pH is kept constant using 32% sodium hydroxide solution. The pH is subsequently adjusted to 2.8 with the aid of sodium hydroxide solution, at which pH and 75 ℃ 508 ml of FeCl are simultaneously added₃Aqueous solution (w (fe) ═ 7%) and 431 ml of TiCl₄Aqueous solution (200 g/l TiCl)₄). The pH was maintained throughout the addition by the simultaneous dropwise addition of 32% sodium hydroxide solution. After stirring for 0.5 h, the pH was raised to 7.5 and 650 ml of an aqueous sodium silicate solution (13% by weight SiO) were slowly metered in at this pH₂) During this time, the pH was kept constant with 10% hydrochloric acid. After stirring for a further 0.5 h, the pH is lowered to 1.8 with 10% hydrochloric acid and 5 g of SnCl are metered in₄ x 5H₂O and 41 ml of hydrochloric acid (20%). 105 ml of TiCl are then slowly metered in at the same pH₄Solution (400 g/l TiCl₄). Then further adding 5 g SnCl₄ x 5H₂O and 41 ml hydrochloric acid (20%). In each case, the pH was maintained at 1.8 using 32% sodium hydroxide solution. The pH is subsequently adjusted to 2.8 again by means of sodium hydroxide solution. Finally, 650 ml of FeCl were added in parallel₃Aqueous solution (w (fe) ═ 7%) and 499 ml of TiCl₄Aqueous solution (200 g TiCl)₄/l) and simultaneously titrated with sodium hydroxide solution (w ═ 10%) to apply the outermost layer. After stirring at a pH of 3.0 for a further 0.5 h, the coated mica substrate was filtered off, washed and dried at 110 ℃ for 16 h. Finally, the effect pigments are calcined at 850 ℃ for 0.5 hour and sieved.

A temperature-stable, golden multilayer pigment with a strong glittering effect is obtained.

Example 4

100 grams of natural mica having a particle size of less than 15 microns was heated to 80 ℃ in 2 liters of deionized water and stirred. When this temperature had been reached, 53 g of TiCl were added at a pH of 1.8₄Solution (400 g/l TiCl₄) Metered in, during which the pH is kept constant with 32% sodium hydroxide solution. The pH is subsequently adjusted to 2.8 with the aid of sodium hydroxide solution, and 640 ml of FeCl are added at the same time at this pH and 75 ℃₃Aqueous solution (w (fe) ═ 7%) and 501 ml of TiCl₄Aqueous solution (200 g TiCl)₄L). The pH was maintained throughout the addition by the simultaneous dropwise addition of 32% sodium hydroxide solution. After stirring for a further 0.5 h, the pH was raised to 7.5 and 650 ml of an aqueous sodium silicate solution (13% by weight SiO) were slowly metered in at this pH₂) During this time, the pH was kept constant with 10% hydrochloric acid. After stirring for a further 0.5 h, the pH is lowered to 1.8 with 10% hydrochloric acid and 5 g of SnCl are metered in₄ x 5H₂O and 41 ml of hydrochloric acid (20%). 105 ml of TiCl are then slowly metered in at the same pH₄Solution (400 g/l TiCl₄). Then 5 g of SnCl is added₄ x 5H₂O and 41 ml hydrochloric acid (20%). In each case, the pH was maintained at 1.8 using 32% sodium hydroxide solution. The pH is subsequently adjusted to 2.8 again with the aid of sodium hydroxide solution. Finally, 650 ml of FeCl were added in parallel₃Aqueous solution (w (fe) ═ 7%) and 499 ml of TiCl₄Aqueous solution (200 g TiCl)₄/l) and simultaneously titrated with sodium hydroxide solution (w ═ 10%) to apply the outermost layer. After stirring at a pH of 3.0 for a further 0.5 h, the coated mica substrate was filtered off, washed and dried at 110 ℃ for 16 h. Finally, the effect pigments obtained in this way were calcined at 850 ℃ for 0.5 h and sieved.

A temperature-stable, golden multilayer pigment having high hiding power is obtained.

Example 5

100 g of Al with the grain diameter of 5-30 microns₂O₃The flakes were heated to 80 ℃ in 2 liters of deionized water and stirred. When it has reachedAt this temperature, 44 g of TiCl were added at a pH of 1.8₄Solution (400 g/l TiCl₄) Metered in, during which the pH is kept constant with 32% sodium hydroxide solution. The pH is subsequently adjusted to 2.8 with the aid of sodium hydroxide solution, and 600 ml of FeCl are added at the same time at this pH and 75 ℃₃Aqueous solution (w (fe) ═ 7%) and 462 ml of TiCl₄Aqueous solution (200 g TiCl)₄L). The pH was maintained throughout the addition by the simultaneous dropwise addition of 32% sodium hydroxide solution. After stirring for a further 0.5 h, the pH was raised to 7.5 and 650 ml of an aqueous sodium silicate solution (13% by weight SiO) were slowly metered in at this pH₂) During this time, the pH was kept constant with 10% hydrochloric acid. After stirring for a further 0.5 h, the pH is lowered to 1.8 with 10% hydrochloric acid and 5 g of SnCl are metered in₄ x 5H₂O and 41 ml of hydrochloric acid (20%). 105 ml of TiCl are then slowly metered in at the same pH₄Solution (400 g/l TiCl₄). Then further adding 5 g SnCl₄ x 5H₂O and 41 ml hydrochloric acid (20%). In each case, the pH was maintained at 1.8 using 32% sodium hydroxide solution. The pH is subsequently adjusted to 2.8 again with the aid of sodium hydroxide solution. Finally, 650 ml of FeCl were added in parallel₃Aqueous solution (w (fe) ═ 7%) and 499 ml of TiCl₄Aqueous solution (200 g TiCl)₄/l) and simultaneously titrated with sodium hydroxide solution (w ═ 10%) to apply the outermost layer. After stirring for a further 0.5 h at a pH of 3.0, the Al applied in this way is filtered off₂O₃The flakes were washed and dried at 110 ℃ for 16 hours. Finally, the effect pigments obtained were calcined at 850 ℃ for 0.5 hour and sieved.

A temperature-stable, golden multilayer pigment with a strong glittering effect is obtained.

Example 6

100 grams of borosilicate glass flakes having a particle size of 20-200 microns were heated to 80 ℃ in 2 liters of deionized water and stirred. When this temperature had been reached, 38 g of TiCl were added at a pH of 1.8₄Solution (400 g/l TiCl₄) MeterThe amount was added during which the pH was kept constant using 32% sodium hydroxide solution. The pH is subsequently adjusted to 2.8 with the aid of sodium hydroxide solution, at which pH and 75 ℃ 508 ml of FeCl are simultaneously added₃Aqueous solution (w (fe) ═ 7%) and 431 ml of TiCl₄Aqueous solution (200 g TiCl)₄L). The pH was maintained throughout the addition by the simultaneous dropwise addition of 32% sodium hydroxide solution. After stirring for 0.5 h, the pH was raised to 7.5 and 650 ml of an aqueous sodium silicate solution (13% by weight SiO) were slowly metered in at this pH₂) During this time, the pH was kept constant with 10% hydrochloric acid. After stirring for a further 0.5 h, the pH is lowered to 1.8 with 10% hydrochloric acid and 5 g of SnCl are metered in₄ x 5H₂O and 41 ml of hydrochloric acid (20%). 105 ml of TiCl are then slowly metered in at the same pH₄Solution (400 g/l TiCl₄). Then adding 5 g SnCl₄ x5H₂O and 41 ml hydrochloric acid (20%). In each case, the pH was maintained at 1.8 using 32% sodium hydroxide solution. The pH is subsequently adjusted to 2.8 again with the aid of sodium hydroxide solution. Finally, 650 ml of FeCl were added in parallel₃Aqueous solution (w (fe) ═ 7%) and 499 ml of TiCl₄Aqueous solution (200 g TiCl)₄/l) and simultaneously titrated with sodium hydroxide solution (w ═ 10%) to apply the outermost layer. After stirring at a pH of 3.0 for a further 0.5 h, the glass flakes coated in this way were filtered off, washed and dried at 110 ℃ for 16 h. Finally, the effect pigments were calcined at 850 ℃ for 0.5 hour and sieved.

A temperature-stable, gold-coloured multilayer pigment is obtained with a very strong glittering effect.

Example 7

100 grams of silica flakes having a particle size of 10-40 microns were heated to 80 ℃ in 2 liters of deionized water and stirred. When this temperature had been reached, 44 g of TiCl were metered in at a pH of 1.8₄Solution (400 g/l TiCl₄) During this time, the pH was kept constant with 32% sodium hydroxide solution. The pH is subsequently adjusted to 2.8 by means of sodium hydroxide solution, and p is added theretoH value and 75 ℃ while adding 600 ml of FeCl₃Aqueous solution (w (fe) ═ 7%) and 462 ml of TiCl₄Aqueous solution (200 g TiCl)₄L). The pH was maintained throughout the addition by the simultaneous dropwise addition of 32% sodium hydroxide solution. After stirring for a further 0.5 h, the pH was raised to 7.5 and 650 ml of an aqueous sodium silicate solution (13% by weight SiO) were slowly metered in at this pH₂) During this time, the pH was kept constant with 10% hydrochloric acid. After stirring for a further 0.5 h, the pH is lowered to 1.8 with 10% hydrochloric acid and 5 g of SnCl are metered in₄ x 5H₂O and 41 ml of hydrochloric acid (20%). 105 ml of TiCl are then slowly metered in at the same pH₄Solution (400 g/l TiCl₄). Then further adding 5 g SnCl₄ x 5H₂O and 41 ml hydrochloric acid (20%). In each case, the pH was maintained at 1.8 using 32% sodium hydroxide solution. The pH is subsequently adjusted to 2.8 again with the aid of sodium hydroxide solution. Finally, 650 ml of FeCl were added in parallel₃Aqueous solution (w (fe) ═ 7%) and 499 ml of TiCl₄Aqueous solution (200 g TiCl)₄/l) and titrated simultaneously with sodium hydroxide solution (w ═ 10%) to apply the outermost layer. After stirring for a further 0.5 h at a pH of 3.0, the SiO coated in this way is applied₂The flakes were filtered off, washed and dried at 110 ℃ for 16 hours. Finally, the effect pigments were calcined at 850 ℃ for 0.5 hour and sieved.

A temperature-stable, golden multilayer pigment having high brightness and good hiding power is obtained.

Example 8

100 grams of synthetic mica having a particle size of 10-40 microns was heated to 80 ℃ in 2 liters of deionized water and stirred. When this temperature had been reached, 44 g of TiCl were added at a pH of 1.8₄Solution (400 g/l TiCl)₄) Metered in, during which the pH is kept constant with 32% sodium hydroxide solution. The pH is subsequently adjusted to 2.8 with the aid of sodium hydroxide solution, and 600 ml of FeCl are added at the same time at this pH and 75 ℃₃Aqueous solution (w (fe) ═ 7%) and 462 ml of TiCl₄Aqueous solution (200 g T)iCl₄Per liter). The pH was maintained throughout the addition by the simultaneous dropwise addition of 32% sodium hydroxide solution. After stirring for 0.5 h, the pH was raised to 7.5 and 650 ml of an aqueous sodium silicate solution (13% by weight SiO) were slowly metered in at this pH₂) During this time, the pH was kept constant with 10% hydrochloric acid. After stirring for a further 0.5 h, the pH is lowered to 1.8 with 10% hydrochloric acid and 5 g of SnCl are metered in₄ x 5H₂O and 41 ml of hydrochloric acid (20%). 105 ml of TiCl are then slowly metered in at the same pH₄Solution (400 g/l TiCl₄). Then adding 5 g SnCl₄ x 5H₂O and 41 ml hydrochloric acid (20%). In each case, the pH was maintained at 1.8 using 32% sodium hydroxide solution. The pH is subsequently adjusted to 2.8 again with the aid of sodium hydroxide solution. Finally, 650 ml of FeCl were added in parallel₃Aqueous solution (w (fe) ═ 7%) and 499 ml of TiCl₄Aqueous solution (200 g TiCl)₄/l) and simultaneous titration with sodium hydroxide solution (w ═ 10%) were carried out to coat the outermost layer. After stirring at a pH of 3.0 for a further 0.5 h, the coated mica substrate was filtered off, washed and dried at 110 ℃ for 16 h. Finally, the effect pigments obtained in this way were calcined at 850 ℃ for 0.5 h and sieved.

A temperature-stable, golden multilayer pigment having high brightness and moderate hiding power is obtained.

Example 9

100 grams of mica with a particle size of 10-60 microns was heated to 80 ℃ in 2 liters of deionized water and stirred. When this temperature had been reached, 44 g of TiCl were added at a pH of 1.8₄Solution (400 g/l TiCl)₄) Metered in, during which the pH is kept constant with 32% sodium hydroxide solution. The pH is subsequently adjusted to 2.8 with the aid of sodium hydroxide solution, and 1040 ml of FeCl are added at this pH and 75 ℃₃(w (Fe) ═ 4%) and TiCl₄(95 g TiCl)₄Per liter) of water. The pH was maintained throughout the addition by the simultaneous dropwise addition of 32% sodium hydroxide solution. After stirring for 0.5 h, the pH was raised to 7.5 and 650 ml of an aqueous sodium silicate solution (13% by weight of SiO) are slowly metered in at this pH value₂) During this time, the pH was kept constant with 10% hydrochloric acid. After stirring for a further 0.5 h, the pH is lowered to 1.8 with 10% hydrochloric acid and 5 g of SnCl are metered in₄ x 5H₂O and 41 ml of hydrochloric acid (20%). 105 ml of TiCl are then slowly metered in at the same pH₄Solution (400 g/l TiCl₄). Then adding 5 g SnCl₄ x 5H₂O and 41 ml hydrochloric acid (20%). In each case, the pH was maintained at 1.8 using 32% sodium hydroxide solution. The pH is subsequently adjusted to 2.8 again with the aid of sodium hydroxide solution. Finally, 1150 ml FeCl-containing solution was added in parallel₃(w (Fe) ═ 4%) and TiCl₄(95 g TiCl)₄/l) and titrated simultaneously with sodium hydroxide solution (w ═ 10%) to coat the outermost layer. After stirring for a further 0.5 h at a pH of 3.0, the mica substrate coated in this way is filtered off, washed and dried at 110 ℃ for 16 h. Finally, the effect pigments obtained in this way were calcined at 850 ℃ for 0.5 h and sieved.

A temperature-stable, golden multilayer pigment having high brightness is obtained.

Example 10

100 grams of natural mica with a particle size of 5-40 microns was heated to 80 ℃ in 2 liters of deionized water and stirred. When this temperature had been reached, 44 g of TiCl were added at a pH of 1.8₄Solution (400 g/l TiCl)₄) Metered in, during which the pH is kept constant with 32% sodium hydroxide solution. The pH is subsequently adjusted to 2.8 with the aid of sodium hydroxide solution, and 600 ml of FeCl are added at the same time at this pH and 75 ℃₃Aqueous solution (w (fe) ═ 7%) and 462 ml of TiCl₄Aqueous solution (200 g TiCl)₄Per liter). The pH was maintained throughout the addition by the simultaneous dropwise addition of 32% sodium hydroxide solution. After stirring for 0.5 h, the pH was raised to 7.5 and 650 ml of an aqueous sodium silicate solution (13% by weight SiO) were slowly metered in at this pH₂) During this time, the pH was kept constant with 10% hydrochloric acid. Then, the product is processedAfter stirring for 0.5 h, the pH is lowered to 1.8 with 10% hydrochloric acid, and 5 g of SnCl are then metered in₄ x 5H₂O and 41 ml of hydrochloric acid (20%). 105 ml of TiCl are then slowly metered in at the same pH₄Solution (400 g/l TiCl₄). Then adding 5 g SnCl₄ x 5H₂O and 41 ml hydrochloric acid (20%). In each case, the pH was maintained at 1.8 using 32% sodium hydroxide solution. The pH is subsequently adjusted to 2.8 again with the aid of sodium hydroxide solution. Finally, 650 ml of FeCl were added in parallel₃Aqueous solution (w (fe) ═ 7%) and 499 ml of TiCl₄Aqueous solution (200 g TiCl)₄/l) and simultaneous titration with sodium hydroxide solution (w ═ 10%) were carried out to coat the outermost layer. After stirring at a pH of 3.0 for a further 0.5 h, the coated mica substrate was filtered off, washed and dried at 110 ℃ for 16 h. Finally, the effect pigments obtained in this way were calcined at 850 ℃ for 0.5 h and sieved.

A temperature-stable, gold-colored multilayer pigment having high brightness and fine texture is obtained.

Example 11

100 g of talc having a particle size of less than 10 μm are heated to 80 ℃ in 2 l of deionized water and stirred. When this temperature had been reached, 44 g of TiCl were metered in at a pH of 1.8₄Solution (400 g/l TiCl₄) During this time, the pH was kept constant with 32% sodium hydroxide solution. The pH is subsequently adjusted to 2.8 with the aid of sodium hydroxide solution, and 600 ml of FeCl are added at the same time at this pH and 75 ℃₃Aqueous solution (w (fe) ═ 7%) and 462 ml of TiCl₄Aqueous solution (200 g TiCl)₄L). The pH was maintained throughout the addition by the simultaneous dropwise addition of 32% sodium hydroxide solution. After stirring for 0.5 h, the pH was raised to 7.5 and 650 ml of an aqueous sodium silicate solution (13% by weight SiO) were slowly metered in at this pH₂) The pH was kept constant during this process with 10% hydrochloric acid. After stirring for a further 0.5 h, the pH is lowered to 1.8 with 10% hydrochloric acid and 5 g of SnCl are metered in₄ x 5H₂O and 41 ml hydrochloric acid (20)%) was added. 105 ml of TiCl are then slowly metered in at the same pH₄Solution (400 g/l TiCl₄). Then adding 5 g SnCl₄ x 5H₂O and 41 ml hydrochloric acid (20%). In each case, the pH was maintained at 1.8 using 32% sodium hydroxide solution. The pH is subsequently adjusted to 2.8 again with the aid of sodium hydroxide solution. Finally, 650 ml of FeCl were added in parallel₃Aqueous solution (w (fe) ═ 7%) and 499 ml of TiCl₄Aqueous solution (200 g TiCl)₄/l) and simultaneously titrated with sodium hydroxide solution (w ═ 10%) to apply the outermost layer. After stirring for a further 0.5 h at a pH of 3.0, the talc flakes coated in this way were filtered off, washed and dried at 110 ℃ for 16 h. Finally, the effect pigments obtained in this way were calcined at 850 ℃ for 0.5 h and sieved.

A temperature-stable, golden multilayer pigment having high hiding power is obtained.

Example 12

100 grams of natural mica with a particle size of 10-60 microns was heated to 85 ℃ in 2 liters of deionized water and stirred. When this temperature has been reached, 30 g of FeCl are added at a pH of 3.1₃The solution (w (fe) ═ 14%) is metered in, during which the pH is kept constant with 32% sodium hydroxide solution. The pH is subsequently adjusted to 2.8 with the aid of sodium hydroxide solution, and 600 ml of FeCl are added at the same time at this pH and 75 ℃₃Aqueous solution (w (fe) ═ 7%) and 462 ml of TiCl₄Aqueous solution (200 g TiCl)₄Per liter). The pH was maintained throughout the addition by the simultaneous dropwise addition of 32% sodium hydroxide solution. After stirring for 0.5 h, the pH was raised to 7.5 and 650 ml of an aqueous sodium silicate solution (13% by weight SiO) were slowly metered in at this pH₂) During this time, the pH was kept constant with 10% hydrochloric acid. After stirring for a further 0.5 h, the pH is lowered to 1.8 with 10% hydrochloric acid and 5 g of SnCl are metered in₄ x 5H₂O and 41 ml of hydrochloric acid (20%). 105 ml of TiCl are then slowly metered in at the same pH₄Solution (400 g/l TiCl₄). Then go furtherOne-step addition of 5 g SnCl₄ x 5H₂O and 41 ml hydrochloric acid (20%). In each case, the pH was maintained at 1.8 using 32% sodium hydroxide solution. The pH is subsequently adjusted to 2.8 again with the aid of sodium hydroxide solution. Finally, 650 ml of FeCl were added in parallel₃Aqueous solution (w (fe) ═ 7%) and 499 ml of TiCl₄Aqueous solution (200 g TiCl)₄/l) and simultaneous titration with sodium hydroxide solution (w ═ 10%) were carried out to coat the outermost layer. After stirring at a pH of 3.0 for a further 0.5 h, the coated mica substrate was filtered off, washed and dried at 110 ℃ for 16 h. Finally, the effect pigments obtained in this way were calcined at 850 ℃ for 0.5 h and sieved.

A temperature-stable reddish, gold-colored multilayer pigment having high brightness is obtained.

Example 13

100 grams of natural mica flakes having a particle size of 10-60 microns were heated to 75 ℃ in 2 liters of deionized water and stirred. When this temperature had been reached, 50 g of CrCl were added at pH 5.9₃Solution (w (CrCl)₃) 19%) were metered in, during which the pH was kept constant with 32% sodium hydroxide solution. The pH is subsequently adjusted to 2.8 with the aid of sodium hydroxide solution, and 600 ml of FeCl are added at the same time at this pH and 75 ℃₃Aqueous solution (w (fe) ═ 7%) and 462 ml of TiCl₄Aqueous solution (200 g TiCl)₄Per liter). The pH was maintained throughout the addition by the simultaneous dropwise addition of 32% sodium hydroxide solution. After stirring for 0.5 h, the pH was raised to 7.5 and 650 ml of an aqueous sodium silicate solution (13% by weight SiO) were slowly metered in at this pH₂) During this time, the pH was kept constant with 10% hydrochloric acid. After stirring for a further 0.5 h, the pH is lowered to 1.8 with 10% hydrochloric acid and 5 g of SnCl are metered in₄ x 5H₂O and 41 ml of hydrochloric acid (20%). 105 ml of TiCl are then slowly metered in at the same pH₄Solution (400 g/l TiCl₄). Then adding 5 g SnCl₄ x 5H₂O and 41 ml hydrochloric acid (20%). In each case, 32% of the total amount was usedThe sodium hydroxide solution maintained the pH at 1.8. The pH is subsequently adjusted to 2.8 again with the aid of sodium hydroxide solution. Finally, 650 ml of FeCl were added in parallel₃Aqueous solution (w (fe) ═ 7%) and 499 ml of TiCl₄Aqueous solution (200 g TiCl)₄/l) and simultaneous titration with sodium hydroxide solution (w ═ 10%) were carried out to coat the outermost layer. After stirring at a pH of 3.0 for a further 0.5 h, the coated mica substrate was filtered off, washed and dried at 110 ℃ for 16 h. Finally, the effect pigments obtained in this way were calcined at 850 ℃ for 0.5 h and sieved.

A temperature-stable, greenish-golden multilayer pigment with high brightness is obtained.

Example 14

100 g of Al with the grain diameter of 5-30 microns₂O₃Flakes (doped with TiO)₂) Heated to 80 ℃ in 2 l of deionized water and stirred. When this temperature had been reached, 44 g of TiCl were added at a pH of 1.8₄Solution (400 g/l TiCl)₄) Metered in, during which the pH is kept constant with 32% sodium hydroxide solution. The pH is subsequently adjusted to 2.8 with the aid of sodium hydroxide solution, and 600 ml of FeCl are added at the same time at this pH and 75 ℃₃Aqueous solution (w (fe) ═ 7%) and 462 ml of TiCl₄Aqueous solution (200 g TiCl)₄Per liter). The pH was maintained throughout the addition by the simultaneous dropwise addition of 32% sodium hydroxide solution. After stirring for 0.5 h, the pH was raised to 7.5 and 650 ml of an aqueous sodium silicate solution (13% by weight SiO) were slowly metered in at this pH₂) During this time, the pH was kept constant with 10% hydrochloric acid. After stirring for a further 0.5 h, the pH is lowered to 1.8 with 10% hydrochloric acid and 5 g of SnCl are metered in₄ x 5H₂O and 41 ml of hydrochloric acid (20%). 105 ml of TiCl are then slowly metered in at the same pH₄Solution (400 g/l TiCl₄). Then adding 5 g SnCl₄ x 5H₂O and 41 ml hydrochloric acid (20%). In each case, the pH was maintained at 1.8 using 32% sodium hydroxide solution. The pH is subsequently adjusted again by means of sodium hydroxide solutionTo 2.8. Finally, 650 ml of FeCl were added in parallel₃Aqueous solution (w (fe) ═ 7%) and 499 ml of TiCl₄Aqueous solution (200 g TiCl)₄/l) and simultaneous titration with sodium hydroxide solution (w ═ 10%) were carried out to coat the outermost layer. After stirring for a further 0.5 h at a pH of 3.0, the Al applied in this way is filtered off₂O₃The flakes were washed and dried at 110 ℃ for 16 hours. Finally, the effect pigments obtained were calcined at 850 ℃ for 0.5 hour and sieved.

A temperature-stable, golden multilayer pigment with a strong glittering effect is obtained.

Example 15

100 g of Al with the grain diameter of 5-30 microns₂O₃Flakes (doped with ZrO)₂) Heated to 80 ℃ in 2 l of deionized water and stirred. When this temperature had been reached, 44 g of TiCl were added at a pH of 1.8₄Solution (400 g/l TiCl)₄) Metered in, during which the pH is kept constant with 32% sodium hydroxide solution. The pH is subsequently adjusted to 2.8 with the aid of sodium hydroxide solution, and 600 ml of FeCl are added at the same time at this pH and 75 ℃₃Aqueous solution (w (fe) ═ 7%) and 462 ml of TiCl₄Aqueous solution (200 g TiCl)₄Per liter). The pH was maintained throughout the addition by the simultaneous dropwise addition of 32% sodium hydroxide solution. After stirring for 0.5 h, the pH was raised to 7.5 and 650 ml of an aqueous sodium silicate solution (13% by weight SiO) were slowly metered in at this pH₂) During this time, the pH was kept constant with 10% hydrochloric acid. After stirring for a further 0.5 h, the pH is lowered to 1.8 with 10% hydrochloric acid and 5 g of SnCl are metered in₄ x 5H₂O and 41 ml of hydrochloric acid (20%). 105 ml of TiCl are then slowly metered in at the same pH₄Solution (400 g/l TiCl₄). Then adding 5 g SnCl₄ x 5H₂O and 41 ml hydrochloric acid (20%). In each case, the pH was maintained at 1.8 using 32% sodium hydroxide solution. The pH is subsequently adjusted to 2.8 again with the aid of sodium hydroxide solution. Finally, 650 ml of FeCl were added in parallel₃Aqueous solution(w (Fe) ═ 7%) and 499 ml of TiCl₄Aqueous solution (200 g TiCl)₄/l) and simultaneous titration with sodium hydroxide solution (w ═ 10%) were carried out to coat the outermost layer. After stirring for a further 0.5 h at a pH of 3.0, the Al applied in this way is filtered off₂O₃The flakes were washed and dried at 110 ℃ for 16 hours. Finally, the effect pigments obtained were calcined at 850 ℃ for 0.5 hour and sieved.

A temperature-stable, golden multilayer pigment with a strong glittering effect is obtained.

The gold-colored multilayer pigments of examples 1 to 15 are stable at temperatures of 1000 ℃ and above and show no impairment of the optical properties at these temperatures.