EFFECT PIGMENTS

Abstract

Temperature-stable effect pigments based on multicoated flake-form substrates, and the use thereof in paints, coatings, printing inks, plastics and in particular in glazes, enamels, ceramic or glass-like materials.

Claims

1. An effect pigment based on a multicoated flake-form substrates, wherein a surface of the substrate has at least one layer sequence comprising: (A) a base layer comprising a high-refractive-index coating having a refractive index of n≥1.8; (B) a pseudobrookite layer, which may optionally be doped with one or more oxides in amounts of ≤10% by weight, based on the weight of layer (B); (C) a low-refractive-index layer having a refractive index of n<1.8; (D) a layer comprising a high-refractive-index coating comprising at least 2 colorless metal-oxide layers; (E) a pseudobrookite layer, which may optionally be doped with one or more oxides in amounts of ≤10% by weight, based on the weight of layer (E); and optionally (F) an outer protective layer.

2. The effect pigment of claim 1, wherein the flake-form substrates is selected from the group consisting of phyllosilicates, BiOCl, SiC, TiC, WC, B.sub.4C, BN, graphite, TiO.sub.2, Fe.sub.2O.sub.3 flakes, doped or undoped Al.sub.2O.sub.3 flakes, doped or undoped glass flakes, doped or undoped SiO.sub.2 flakes, and mixtures thereof.

3. The effect pigment of claim 1, wherein the phyllosilicate comprises natural mica, synthetic mica, kaolin or talc.

4. The effect pigment of claim 1, wherein layer (A) comprises one or more metal oxides.

5. The effect pigment of claim 1, wherein the metal oxide of layer (A) is selected from the group consisting of TiO.sub.2, Fe.sub.2O.sub.3, Fe.sub.3O.sub.4, Fe(O)OH, BiOCl, Cr.sub.2O.sub.3, ZnO, Ce.sub.2O.sub.3, ZrO.sub.2, SnO.sub.2, Co.sub.2O.sub.3, Ti suboxides titanium oxynitrides, titanium nitride, CoO, Co.sub.2O.sub.3, Co.sub.3O.sub.4, VO.sub.2, V.sub.2O.sub.3, NiO, WO.sub.3, MnO, Mn.sub.2O.sub.3, and mixtures of the said oxides.

6. The effect pigment of claim 1, wherein layer (B) and/or layer (E) is doped with one or more oxides or oxide mixtures selected from the group consisting of Al.sub.2O.sub.3, Ce.sub.2O.sub.3, B.sub.2O.sub.3, ZrO.sub.2, SnO.sub.2, Cr.sub.2O.sub.3, CoO, Co.sub.2O.sub.3, Co.sub.3O.sub.4, and Mn.sub.2O.sub.3.

7. The effect pigment of claim 1, wherein layer (C) comprises SiO.sub.2, MgO*SiO.sub.2, CaO*SiO.sub.2, Al.sub.2O.sub.3*SiO.sub.2, B.sub.2O.sub.3*SiO.sub.2, or of a mixture of the said compounds.

8. The effect pigment of claim 1, wherein layer (D) comprises at least two metal-oxide layers, where the metal oxides are selected from the group consisting of SnO.sub.2, TiO.sub.2, Al.sub.2O.sub.3, Cr.sub.2O.sub.3, Fe.sub.2O.sub.3, and mixtures thereof.

9. The effect pigment of claim 1, wherein layer (D) comprises metal-oxide layers (D1) and (D2): (D1) SnO.sub.2 layer; (D2) TiO.sub.2 layer.

10. The effect pigment of claim 1, wherein layer (D) comprises metal-oxide layers (D1), (D2) and (D3): (D1) Al.sub.2O.sub.3 layer; (D2) TiO.sub.2 layer; and (D3) Al.sub.2O.sub.3 layer.

11. The effect pigment of claim 1, wherein layer (D) comprises metal-oxide layers (D1), (D2) and (D3): (D1) SnO.sub.2 layer (D2) TiO.sub.2 layer; and (D3) SnO.sub.2 layer.

12. The effect pigment of claim 1, wherein layers (B) and (E) have an equal layer thicknesses.

13. The effect pigment of claim 1, wherein the outer protective layer (F) comprises SnO.sub.2.

14. The effect pigment of claim 1, wherein layers (C) and (D) have a total combined layer thickness of 50-115 nm.

15. The effect pigment of claim 1, having at least one of the following structures: substrate+TiO.sub.2+pseudobrookite+SiO.sub.2+SnO.sub.2+TiO.sub.2+SnO.sub.2+pseudobrookite; substrate+Fe.sub.2O.sub.3+pseudobrookite+SiO.sub.2+SnO.sub.2+TiO.sub.2+SnO.sub.2+pseudobrookite; substrate+Cr.sub.2O.sub.3+pseudobrookite+SiO.sub.2+SnO.sub.2+TiO.sub.2+SnO.sub.2+pseudobrookite; substrate+TiO.sub.2+pseudobrookite+MgO*SiO.sub.2+SnO.sub.2+TiO.sub.2+SnO.sub.2+pseudobrookite; substrate+Fe.sub.2O.sub.3+pseudobrookite+MgO*SiO.sub.2+SnO.sub.2+TiO.sub.2+SnO.sub.2+pseudobrookite; substrate+Cr.sub.2O.sub.3+pseudobrookite+MgO*SiO.sub.2+SnO.sub.2+TiO.sub.2+SnO.sub.2+pseudobrookite; substrate+TiO.sub.2+pseudobrookite+CaO*SiO.sub.2+SnO.sub.2+TiO.sub.2+SnO.sub.2+pseudobrookite; substrate+Fe.sub.2O.sub.3+pseudobrookite+CaO*SiO.sub.2+SnO.sub.2+TiO.sub.2+SnO.sub.2+pseudobrookite; substrate+Cr.sub.2O.sub.3+pseudobrookite+CaO*SiO.sub.2+SnO.sub.2+TiO.sub.2+SnO.sub.2+pseudobrookite; substrate+TiO.sub.2+pseudobrookite+Al.sub.2O.sub.3*SiO.sub.2+SnO.sub.2+TiO.sub.2+SnO.sub.2+pseudobrookite; substrate+Fe.sub.2O.sub.3+pseudobrookite+Al.sub.2O.sub.3*SiO.sub.2+SnO.sub.2+TiO.sub.2+SnO.sub.2+pseudobrookite; substrate+Cr.sub.2O.sub.3+pseudobrookite+Al.sub.2O.sub.3*SiO.sub.2+SnO.sub.2+TiO.sub.2+SnO.sub.2+pseudobrookite; substrate+TiO.sub.2+pseudobrookite+SiO.sub.2+TiO.sub.2+SnO.sub.2+pseudobrookite; substrate+TiO.sub.2+pseudobrookite+SiO.sub.2+SnO.sub.2+TiO.sub.2+pseudobrookite; substrate+TiO.sub.2+pseudobrookite+SiO.sub.2+TiO.sub.2+SnO.sub.2+pseudobrookite+SnO.sub.2; substrate+TiO.sub.2+pseudobrookite+SiO.sub.2+SnO.sub.2+TiO.sub.2+pseudobrookite+SnO.sub.2; substrate+TiO.sub.2+pseudobrookite+SiO.sub.2+SnO.sub.2+Fe.sub.2O.sub.3+SnO.sub.2+pseudobrookite; substrate+TiO.sub.2+pseudobrookite+SiO.sub.2+SnO.sub.2+Cr.sub.2O.sub.3+SnO.sub.2+pseudobrookite; or substrate+TiO.sub.2+pseudobrookite+SiO.sub.2+Al.sub.2O.sub.3+TiO.sub.2+Al.sub.2O.sub.3+pseudobrookite.

16. A paint, coating, printing ink, security printing ink, plastic, ceramic material, ceramic colour, glaze, engobe, enamel, glass, absorber for laser marking of plastics and papers, cosmetic formulation, pigment preparations, or dry preparation comprising the effect pigment of claim 1.

17. A formulation comprising the effect pigment of claim 1.

18. The formulation of claim 17, comprising the effect pigment and at least one constituent selected from the group consisting of absorbents, astringents, antimicrobial substances, antioxidants, antiperspirants, antifoaming agents, antidandruff active compounds, antistatics, binders, biological additives, bleaches, chelating agents, deodorisers, emollients, emulsifiers, emulsion stabilisers, dyes, humectants, film formers, fillers, fragrances, flavours, insect repellents, preservatives, corrosion-protection agents, cosmetic oils, solvents, oxidants, plant constituents, buffer substances, reducing agents, surfactants, propellant gases, opacifiers, UV filters, UV absorbers, denaturing agents, aloe vera, avocado oil, coenzyme Q10, green tea extract, viscosity regulators, perfume, inorganic pigments, metal pigments, ceramic pigments, functional pigments, ceramic colour bodies, functional pigments, and vitamins.

Description

EXAMPLES

Example 1

[0192] 100 g of natural mica having a particle size of 10-60 μm are heated to 80° C. in 2 l of demineralised water with stirring. When this temperature has been reached, 44 g of TiCl.sub.4 solution (400 g/l of TiCl.sub.4) is metered in at pH 1.8, during which the pH is kept constant using 32% sodium hydroxide solution. The pH is subsequently adjusted to pH 2.8 by means of sodium hydroxide solution, and 600 ml of an aqueous FeCl.sub.3 solution (w(Fe)=7%) and 462 ml of an aqueous TiCl.sub.4 solution (200 g of TiCl.sub.4/l) are added simultaneously at this pH and 75° C. Throughout the addition time, the pH is kept constant by simultaneous dropwise addition of a 32% sodium hydroxide solution. After stirring for a further 0.5 h, the pH is raised to 7.5, and 650 ml of sodium water-glass solution (13% by weight of SiO.sub.2) are slowly metered in at this pH, during which the pH is kept constant using 10% hydrochloric acid. After stirring for a further 0.5 h, the pH is lowered to pH 1.8 using 10% hydrochloric acid, and a solution of 5 g of SnCl.sub.4×5 H.sub.2O and 41 ml of hydrochloric acid (20%) is metered in. 105 ml of TiCl.sub.4 solution (400 g/l of TiCl.sub.4) are then slowly metered in at the same pH. This is then followed by a further addition of a solution consisting of 5 g of SnCl.sub.4×5 H.sub.2O and 41 ml of hydrochloric acid (20%). The pH is in each case kept constant at 1.8 using 32% sodium hydroxide solution. The pH is subsequently adjusted to pH 2.8 again by means of sodium hydroxide solution. Finally, the outermost layer is applied by parallel addition of 650 ml of an aqueous FeCl.sub.3 solution (w(Fe)=7%) and 499 ml of an aqueous TiCl.sub.4 solution (200 g of TiCl.sub.4/l) and simultaneous titration with sodium hydroxide solution (w=10%). After stirring for a further 0.5 h at pH 3.0, the coated mica substrate is filtered off, washed and dried at 110° C. for 16 h. Finally, the effect pigment obtained is calcined at 850° C. for 0.5 h and sieved.

[0193] A temperature-stable golden multilayered pigment having high brightness is obtained.

Example 2

[0194] 100 g of natural mica having a particle size of 10-25 μm are heated to 80° C. in 2 l of demineralised water with stirring. When this temperature has been reached, 44 g of TiCl.sub.4 solution (400 g/l of TiCl.sub.4) is metered in at pH 1.8, during which the pH is kept constant using 32% sodium hydroxide solution. The pH is subsequently adjusted to pH 2.8 by means of sodium hydroxide solution, and 600 ml of an aqueous FeCl.sub.3 solution (w(Fe)=7%) and 462 ml of an aqueous TiCl.sub.4 solution (200 g of TiCl.sub.4/l) are added simultaneously at this pH and 75° C. Throughout the addition time, the pH is kept constant by simultaneous dropwise addition of a 32% sodium hydroxide solution. After stirring for a further 0.5 h, the pH is raised to 7.5, and 650 ml of sodium water-glass solution (13% by weight of SiO.sub.2) are slowly metered in at this pH, during which the pH is kept constant using 10% hydrochloric acid. After stirring for a further 0.5 h, the pH is lowered to pH 1.8 using 10% hydrochloric acid, and a solution of 5 g of SnCl.sub.4×5 H.sub.2O and 41 ml of hydrochloric acid (20%) is metered in. 105 ml of TiCl.sub.4 solution (400 g/l of TiCl.sub.4) are then slowly metered in at the same pH. This is then followed by a further addition of a solution consisting of 5 g of SnCl.sub.4×5 H.sub.2O and 41 ml of hydrochloric acid (20%). The pH is in each case kept constant at 1.8 using 32% sodium hydroxide solution. The pH is subsequently adjusted to pH 2.8 again by means of sodium hydroxide solution. Finally, the outermost layer is applied by parallel addition of 650 ml of an aqueous FeCl.sub.3 solution (w(Fe)=7%) and 499 ml of an aqueous TiCl.sub.4 solution (200 g of TiCl.sub.4/l) and simultaneous titration with sodium hydroxide solution (w=10%). After stirring for a further 0.5 h at pH 3.0, the coated mica substrate is filtered off, washed and dried at 110° C. for 16 h. Finally, the effect pigment obtained in this way is calcined at 850° C. for 0.5 h and sieved.

[0195] A temperature-stable golden multilayered pigment having high brightness and good hiding power is obtained.

Example 3

[0196] 100 g of natural mica having a particle size of 20-180 μm are heated to 80° C. in 2 l of demineralised water with stirring. When this temperature has been reached, 38 g of TiCl.sub.4 solution (400 g/l of TiCl.sub.4) is metered in at pH 1.8, during which the pH is kept constant using 32% sodium hydroxide solution. The pH is subsequently adjusted to pH 2.8 by means of sodium hydroxide solution, and 508 ml of an aqueous FeCl.sub.3 solution (w(Fe)=7%) and 431 ml of an aqueous TiCl.sub.4 solution (200 g of TiCl.sub.4/l) are added simultaneously at this pH and 75° C. Throughout the addition time, the pH is kept constant by simultaneous dropwise addition of a 32% sodium hydroxide solution. After stirring for a further 0.5 h, the pH is raised to 7.5, and 650 ml of sodium water-glass solution (13% by weight of SiO.sub.2) are slowly metered in at this pH, during which the pH is kept constant using 10% hydrochloric acid. After stirring for a further 0.5 h, the pH is lowered to pH 1.8 using 10% hydrochloric acid, and a solution of 5 g of SnCl.sub.4×5 H.sub.2O and 41 ml of hydrochloric acid (20%) is metered in. 105 ml of TiCl.sub.4 solution (400 g/l of TiCl.sub.4) are then slowly metered in at the same pH. A further addition of a solution consisting of 5 g of SnCl.sub.4×5 H.sub.2O and 41 ml of hydrochloric acid (20%) is subsequently carried out. The pH is in each case kept constant at 1.8 using 32% sodium hydroxide solution. The pH is subsequently adjusted to pH 2.8 again by means of sodium hydroxide solution. Finally, the outermost layer is applied by parallel addition of 650 ml of an aqueous FeCl.sub.3 solution (w(Fe)=7%) and 499 ml of an aqueous TiCl.sub.4 solution (200 g of TiCl.sub.4/l) and simultaneous titration with sodium hydroxide solution (w=10%). After stirring for a further 0.5 h at pH 3.0, the coated mica substrate is filtered off, washed and dried at 110° C. for 16 h. Finally, the effect pigment is calcined at 850° C. for 0.5 h and sieved.

[0197] A temperature-stable golden multilayered pigment having a strong glitter effect is obtained.

Example 4

[0198] 100 g of natural mica having a particle size <15 μm are heated to 80° C. in 2 l of demineralised water with stirring. When this temperature has been reached, 53 g of TiCl.sub.4 solution (400 g/l of TiCl.sub.4) is metered in at pH 1.8, during which the pH is kept constant using 32% sodium hydroxide solution. The pH is subsequently adjusted to pH 2.8 by means of sodium hydroxide solution, and 640 ml of an aqueous FeCl.sub.3 solution (w(Fe)=7%) and 501 ml of an aqueous TiCl.sub.4 solution (200 g of TiCl.sub.4/l) are added simultaneously at this pH and 75° C. Throughout the addition time, the pH is kept constant by simultaneous dropwise addition of a 32% sodium hydroxide solution. After stirring for a further 0.5 h, the pH is raised to 7.5, and 650 ml of sodium water-glass solution (13% by weight of SiO.sub.2) are slowly metered in at this pH, during which the pH is kept constant using 10% hydrochloric acid. After stirring for a further 0.5 h, the pH is lowered to pH 1.8 using 10% hydrochloric acid, and a solution of 5 g of SnCl.sub.4×5 H.sub.2O and 41 ml of hydrochloric acid (20%) is metered in. 105 ml of TiCl.sub.4 solution (400 g/l of TiCl.sub.4) are then slowly metered in at the same pH. This is then followed by a further addition of a solution consisting of 5 g of SnCl.sub.4×5 H.sub.2O and 41 ml of hydrochloric acid (20%). The pH is in each case kept constant at 1.8 using 32% sodium hydroxide solution. The pH is subsequently adjusted to pH 2.8 again by means of sodium hydroxide solution. Finally, the outermost layer is applied by parallel addition of 650 ml of an aqueous FeCl.sub.3 solution (w(Fe)=7%) and 499 ml of an aqueous TiCl.sub.4 solution (200 g of TiCl.sub.4/l) and simultaneous titration with sodium hydroxide solution (w=10%). After stirring for a further 0.5 h at pH 3.0, the coated mica substrate is filtered off, washed and dried at 110° C. for 16 h. Finally, the effect pigment obtained in this way is calcined at 850° C. for 0.5 h and then sieved.

[0199] A temperature-stable golden multilayered pigment having high hiding power is obtained.

Example 5

[0200] 100 g of Al.sub.2O.sub.3 flakes having a particle size of 5-30 μm are heated to 80° C. in 2 l of demineralised water with stirring. When this temperature has been reached, 44 g of TiCl.sub.4 solution (400 g/l of TiCl.sub.4) is metered in at pH 1.8, during which the pH is kept constant using 32% sodium hydroxide solution. The pH is subsequently adjusted to pH 2.8 by means of sodium hydroxide solution, and 600 ml of an aqueous FeCl.sub.3 solution (w(Fe)=7%) and 462 ml of an aqueous TiCl.sub.4 solution (200 g of TiCl.sub.4/l) are added simultaneously at this pH and 75° C. Throughout the addition time, the pH is kept constant by simultaneous dropwise addition of a 32% sodium hydroxide solution. After stirring for a further 0.5 h, the pH is raised to 7.5, and 650 ml of sodium water-glass solution (13% by weight of SiO.sub.2) are slowly metered in at this pH, during which the pH is kept constant using 10% hydrochloric acid. After stirring for a further 0.5 h, the pH is lowered to pH 1.8 using 10% hydrochloric acid, and a solution of 5 g of SnCl.sub.4×5 H.sub.2O and 41 ml of hydrochloric acid (20%) is metered in. 105 ml of TiCl.sub.4 solution (400 g/l of TiCl.sub.4) are then slowly metered in at the same pH. A further addition of a solution consisting of 5 g of SnCl.sub.4×5 H.sub.2O and 41 ml of hydrochloric acid (20%) is subsequently carried out. The pH is in each case kept constant at 1.8 using 32% sodium hydroxide solution. The pH is subsequently adjusted to pH 2.8 again by means of sodium hydroxide solution. Finally, the outermost layer is applied by parallel addition of 650 ml of an aqueous FeCl.sub.3 solution (w(Fe)=7%) and 499 ml of an aqueous TiCl.sub.4 solution (200 g of TiCl.sub.4/l) and simultaneous titration with sodium hydroxide solution (w=10%). After stirring for a further 0.5 h at pH 3.0, the Al.sub.2O.sub.3 flakes coated in this way are filtered off, washed and dried at 110° C. for 16 h. Finally, the effect pigment obtained is calcined at 850° C. for 0.5 h and sieved.

[0201] A temperature-stable golden multilayered pigment having a strong glitter effect is obtained.

Example 6

[0202] 100 g of borosilcate glass flakes having a particle size of 20-200 μm are heated to 80° C. in 2 l of demineralised water with stirring. When this temperature has been reached, 38 g of TiCl.sub.4 solution (400 g/l of TiCl.sub.4) is metered in at pH 1.8, during which the pH is kept constant using 32% sodium hydroxide solution. The pH is subsequently adjusted to pH 2.8 by means of sodium hydroxide solution, and 508 ml of an aqueous FeCl.sub.3 solution (w(Fe)=7%) and 431 ml of an aqueous TiCl.sub.4 solution (200 g of TiCl.sub.4/l) are added simultaneously at this pH and 75° C. Throughout the addition time, the pH is kept constant by simultaneous dropwise addition of a 32% sodium hydroxide solution. After stirring for a further 0.5 h, the pH is raised to 7.5, and 650 ml of sodium water-glass solution (13% by weight of SiO.sub.2) are slowly metered in at this pH, during which the pH is kept constant using 10% hydrochloric acid. After stirring for a further 0.5 h, the pH is lowered to pH 1.8 using 10% hydrochloric acid, and a solution of 5 g of SnCl.sub.4×5 H.sub.2O and 41 ml of hydrochloric acid (20%) is metered in. 105 ml of TiCl.sub.4 solution (400 g/l of TiCl.sub.4) are then slowly metered in at the same pH. This is then followed by a further addition of a solution consisting of 5 g of SnCl.sub.4×5 H.sub.2O and 41 ml of hydrochloric acid (20%). The pH is in each case kept constant at 1.8 using 32% sodium hydroxide solution. The pH is subsequently adjusted to pH 2.8 again by means of sodium hydroxide solution. Finally, the outermost layer is applied by parallel addition of 650 ml of an aqueous FeCl.sub.3 solution (w(Fe)=7%) and 499 ml of an aqueous TiCl.sub.4 solution (200 g of TiCl.sub.4/l) and simultaneous titration with sodium hydroxide solution (w=10%). After stirring for a further 0.5 h at pH 3.0, the glass flakes coated in this way are filtered off, washed and dried at 110° C. for 16 h. Finally, the effect pigment is calcined at 850° C. for 0.5 h and sieved.

[0203] A temperature-stable golden multilayered pigment having a very strong glitter effect is obtained.

Example 7

[0204] 100 g of SiO.sub.2 flakes having a particle size of 10-40 μm are heated to 80° C. in 2 l of demineralised water with stirring. When this temperature has been reached, 44 g of TiCl.sub.4 solution (400 g/l of TiCl.sub.4) is metered in at pH 1.8, during which the pH is kept constant using 32% sodium hydroxide solution. The pH is subsequently adjusted to pH 2.8 by means of sodium hydroxide solution, and 600 ml of an aqueous FeCl.sub.3 solution (w(Fe)=7%) and 462 ml of an aqueous TiCl.sub.4 solution (200 g of TiCl.sub.4/l) are added simultaneously at this pH and 75° C. Throughout the addition time, the pH is kept constant by simultaneous dropwise addition of a 32% sodium hydroxide solution. After stirring for a further 0.5 h, the pH is raised to 7.5, and 650 ml of sodium water-glass solution (13% by weight of SiO.sub.2) are slowly metered in at this pH, during which the pH is kept constant using 10% hydrochloric acid. After stirring for a further 0.5 h, the pH is lowered to pH 1.8 using 10% hydrochloric acid, and a solution of 5 g of SnCl.sub.4×5 H.sub.2O and 41 ml of hydrochloric acid (20%) is metered in. 105 ml of TiCl.sub.4 solution (400 g/l of TiCl.sub.4) are then slowly metered in at the same pH. A further addition of a solution consisting of 5 g of SnCl.sub.4×5 H.sub.2O and 41 ml of hydrochloric acid (20%) is subsequently carried out. The pH is in each case kept constant at 1.8 using 32% sodium hydroxide solution. The pH is subsequently adjusted to pH 2.8 again by means of sodium hydroxide solution. Finally, the outermost layer is applied by parallel addition of 650 ml of an aqueous FeCl.sub.3 solution (w(Fe)=7%) and 499 ml of an aqueous TiCl.sub.4 solution (200 g of TiCl.sub.4/l) and simultaneous titration with sodium hydroxide solution (w=10%). After stirring for a further 0.5 h at pH 3.0, the SiO.sub.2 flakes coated in this way are filtered off, washed and dried at 110° C. for 16 h. Finally, the effect pigment is calcined at 850° C. for 0.5 h and sieved.

[0205] A temperature-stable golden multilayered pigment having high brightness and good hiding power is obtained.

Example 8

[0206] 100 g of synthetic mica having a particle size of 10-40 μm are heated to 80° C. in 2 l of demineralised water with stirring. When this temperature has been reached, 44 g of TiCl.sub.4 solution (400 g/l of TiCl.sub.4) is metered in at pH 1.8, during which the pH is kept constant using 32% sodium hydroxide solution. The pH is subsequently adjusted to pH 2.8 by means of sodium hydroxide solution, and 600 ml of an aqueous FeCl.sub.3 solution (w(Fe)=7%) and 462 ml of an aqueous TiCl.sub.4 solution (200 g of TiCl.sub.4/l) are added simultaneously at this pH and 75° C. Throughout the addition time, the pH is kept constant by simultaneous dropwise addition of a 32% sodium hydroxide solution. After stirring for a further 0.5 h, the pH is raised to 7.5, and 650 ml of sodium water-glass solution (13% by weight of SiO.sub.2) are slowly metered in at this pH, during which the pH is kept constant using 10% hydrochloric acid. After stirring for a further 0.5 h, the pH is lowered to pH 1.8 using 10% hydrochloric acid, and a solution of 5 g of SnCl.sub.4×5 H.sub.2O and 41 ml of hydrochloric acid (20%) is metered in. 105 ml of TiCl.sub.4 solution (400 g/l of TiCl.sub.4) are then slowly metered in at the same pH. This is then followed by a further addition of a solution consisting of 5 g of SnCl.sub.4×5 H.sub.2O and 41 ml of hydrochloric acid (20%). The pH is in each case kept constant at 1.8 using 32% sodium hydroxide solution. The pH is subsequently adjusted to pH 2.8 again by means of sodium hydroxide solution. Finally, the outermost layer is applied by parallel addition of 650 ml of an aqueous FeCl.sub.3 solution (w(Fe)=7%) and 499 ml of an aqueous TiCl.sub.4 solution (200 g of TiCl.sub.4/l) and simultaneous titration with sodium hydroxide solution (w=10%). After stirring for a further 0.5 h at pH 3.0, the coated mica substrate is filtered off, washed and dried at 110° C. for 16 h. Finally, the effect pigment obtained in this way is calcined at 850° C. for 0.5 h and sieved.

[0207] A temperature-stable golden multilayered pigment having high brightness and moderate hiding power is obtained.

Example 9

[0208] 100 g of mica having a particle size of 10-60 μm are heated to 80° C. in 2 l of demineralised water with stirring. When this temperature has been reached, 44 g of TiCl.sub.4 solution (400 g/l of TiCl.sub.4) is metered in at pH 1.8, during which the pH is kept constant using 32% sodium hydroxide solution. The pH is subsequently adjusted to pH 2.8 by means of sodium hydroxide solution, and 1040 ml of an aqueous solution containing FeCl.sub.3 (w(Fe)=4%) and TiCl.sub.4 (95 g of TiCl.sub.4/l) is added at this pH and 75° C. Throughout the addition time, the pH is kept constant by simultaneous dropwise addition of a 32% sodium hydroxide solution. After stirring for a further 0.5 h, the pH is raised to 7.5, and 650 ml of sodium water-glass solution (13% by weight of SiO.sub.2) are slowly metered in at this pH, during which the pH is kept constant using 10% hydrochloric acid. After stirring for a further 0.5 h, the pH is lowered to pH 1.8 using 10% hydrochloric acid, and a solution of 5 g of SnCl.sub.4×5 H.sub.2O and 41 ml of hydrochloric acid (20%) is metered in. 105 ml of TiCl.sub.4 solution (400 g/l of TiCl.sub.4) are then slowly metered in at the same pH. This is then followed by a further addition of a solution consisting of 5 g of SnCl.sub.4×5 H.sub.2O and 41 ml of hydrochloric acid (20%). The pH is in each case kept constant at 1.8 using 32% sodium hydroxide solution. The pH is subsequently adjusted to pH 2.8 again by means of sodium hydroxide solution. Finally, the outermost layer is applied by parallel addition of 1150 ml of a solution containing FeCl.sub.3 (w(Fe)=4%) and TiCl.sub.4 (95 g of TiCl.sub.4/l) and simultaneous titration with sodium hydroxide solution (w=10%). After stirring for a further 0.5 h at pH 3.0, the mica substrate coated in this way is filtered off, washed and dried at 110° C. for 16 h. Finally, the effect pigment obtained in this way is calcined at 850° C. for 0.5 h and sieved.

[0209] A temperature-stable golden multilayered pigment having high brightness is obtained.

Example 10

[0210] 100 g of natural mica having a particle size of 5-40 μm are heated to 80° C. in 2 l of demineralised water with stirring. When this temperature has been reached, 44 g of TiCl.sub.4 solution (400 g/l of TiCl.sub.4) is metered in at pH 1.8, during which the pH is kept constant using 32% sodium hydroxide solution. The pH is subsequently adjusted to pH 2.8 by means of sodium hydroxide solution, and 600 ml of an aqueous FeCl.sub.3 solution (w(Fe)=7%) and 462 ml of an aqueous TiCl.sub.4 solution (200 g of TiCl.sub.4/l) are added simultaneously at this pH and 75° C. Throughout the addition time, the pH is kept constant by simultaneous dropwise addition of a 32% sodium hydroxide solution. After stirring for a further 0.5 h, the pH is raised to 7.5, and 650 ml of sodium water-glass solution (13% by weight of SiO.sub.2) are slowly metered in at this pH, during which the pH is kept constant using 10% hydrochloric acid. After stirring for a further 0.5 h, the pH is lowered to pH 1.8 using 10% hydrochloric acid, and a solution of 5 g of SnCl.sub.4×5 H.sub.2O and 41 ml of hydrochloric acid (20%) is metered in. 105 ml of TiCl.sub.4 solution (400 g/l of TiCl.sub.4) are then slowly metered in at the same pH. This is then followed by a further addition of a solution consisting of 5 g of SnCl.sub.4×5 H.sub.2O and 41 ml of hydrochloric acid (20%). The pH is in each case kept constant at 1.8 using 32% sodium hydroxide solution. The pH is subsequently adjusted to pH 2.8 again by means of sodium hydroxide solution. Finally, the outermost layer is applied by parallel addition of 650 ml of an aqueous FeCl.sub.3 solution (w(Fe)=7%) and 499 ml of an aqueous TiCl.sub.4 solution (200 g of TiCl.sub.4/l) and simultaneous titration with sodium hydroxide solution (w=10%). After stirring for a further 0.5 h at pH 3.0, the coated mica substrate is filtered off, washed and dried at 110° C. for 16 h. Finally, the effect pigment obtained in this way is calcined at 850° C. for 0.5 h and sieved.

[0211] A temperature-stable golden multilayered pigment having high brightness and a fine texture is obtained.

Example 11

[0212] 100 g of talc having a particle size <10 μm are heated to 80° C. in 2 l of demineralised water with stirring. When this temperature has been reached, 44 g of TiCl.sub.4 solution (400 g/l of TiCl.sub.4) is metered in at pH 1.8, during which the pH is kept constant using 32% sodium hydroxide solution. The pH is subsequently adjusted to pH 2.8 by means of sodium hydroxide solution, and 600 ml of an aqueous FeCl.sub.3 solution (w(Fe)=7%) and 462 ml of an aqueous TiCl.sub.4 solution (200 g of TiCl.sub.4/l) are added simultaneously at this pH and 75° C. Throughout the addition time, the pH is kept constant by simultaneous dropwise addition of a 32% sodium hydroxide solution. After stirring for a further 0.5 h, the pH is raised to 7.5, and 650 ml of sodium water-glass solution (13% by weight of SiO.sub.2) are slowly metered in at this pH, during which the pH is kept constant using 10% hydrochloric acid. After stirring for a further 0.5 h, the pH is lowered to pH 1.8 using 10% hydrochloric acid, and a solution of 5 g of SnCl.sub.4×5 H.sub.2O and 41 ml of hydrochloric acid (20%) is metered in. 105 ml of TiCl.sub.4 solution (400 g/l of TiCl.sub.4) are then slowly metered in at the same pH. This is then followed by a further addition of a solution consisting of 5 g of SnCl.sub.4×5 H.sub.2O and 41 ml of hydrochloric acid (20%). The pH is in each case kept constant at 1.8 using 32% sodium hydroxide solution. The pH is subsequently adjusted to pH 2.8 again by means of sodium hydroxide solution. Finally, the outermost layer is applied by parallel addition of 650 ml of an aqueous FeCl.sub.3 solution (w(Fe)=7%) and 499 ml of an aqueous TiCl.sub.4 solution (200 g of TiCl.sub.4/l) and simultaneous titration with sodium hydroxide solution (w=10%). After stirring for a further 0.5 h at pH 3.0, the talc flakes coated in this way are filtered off, washed and dried at 110° C. for 16 h. Finally, the effect pigment obtained in this way is calcined at 850° C. for 0.5 h and sieved.

[0213] A temperature-stable golden multilayered pigment having high hiding power is obtained.

Example 12

[0214] 100 g of natural mica having a particle size of 10-60 μm are heated to 85° C. in 2 l of demineralised water with stirring. When this temperature has been reached, 30 g of FeCl.sub.3 solution (w(Fe)=14%) is metered in at pH 3.1, during which the pH is kept constant using 32% sodium hydroxide solution. The pH is subsequently adjusted to pH 2.8 by means of sodium hydroxide solution, and 600 ml of an aqueous FeCl.sub.3 solution (w(Fe)=7%) and 462 ml of an aqueous TiCl.sub.4 solution (200 g of TiCl.sub.4/l) are added simultaneously at this pH and 75° C. Throughout the addition time, the pH is kept constant by simultaneous dropwise addition of a 32% sodium hydroxide solution. After stirring for a further 0.5 h, the pH is raised to 7.5, and 650 ml of sodium water-glass solution (13% by weight of SiO.sub.2) are slowly metered in at this pH, during which the pH is kept constant using 10% hydrochloric acid. After stirring for a further 0.5 h, the pH is lowered to pH 1.8 using 10% hydrochloric acid, and a solution of 5 g of SnCl.sub.4×5 H.sub.2O and 41 ml of hydrochloric acid (20%) is metered in. 105 ml of TiCl.sub.4 solution (400 g/l of TiCl.sub.4) are then slowly metered in at the same pH. This is then followed by a further addition of a solution consisting of 5 g of SnCl.sub.4×5 H.sub.2O and 41 ml of hydrochloric acid (20%). The pH is in each case kept constant at 1.8 using 32% sodium hydroxide solution. The pH is subsequently adjusted to pH 2.8 again by means of sodium hydroxide solution. Finally, the outermost layer is applied by parallel addition of 650 ml of an aqueous FeCl.sub.3 solution (w(Fe)=7%) and 499 ml of an aqueous TiCl.sub.4 solution (200 g of TiCl.sub.4/l) and simultaneous titration with sodium hydroxide solution (w=10%). After stirring for a further 0.5 h at pH 3.0, the coated mica substrate is filtered off, washed and dried at 110° C. for 16 h. Finally, the effect pigment obtained in this way is calcined at 850° C. for 0.5 h and sieved.

[0215] A temperature-stable reddish, golden multilayered pigment having high brightness is obtained.

Example 13

[0216] 100 g of natural mica flakes having a particle size of 10-60 μm are heated to 75° C. in 2 l of demineralised water with stirring. When this temperature has been reached, 50 g of CrCl.sub.3 solution (w(CrCl.sub.3)=19% is metered in at pH 5.9, during which the pH is kept constant using 32% sodium hydroxide solution. The pH is subsequently adjusted to pH 2.8 by means of sodium hydroxide solution, and 600 ml of an aqueous FeCl.sub.3 solution (w(Fe)=7%) and 462 ml of an aqueous TiCl.sub.4 solution (200 g of TiCl.sub.4/l) are added simultaneously at this pH and 75° C. Throughout the addition time, the pH is kept constant by simultaneous dropwise addition of a 32% sodium hydroxide solution. After stirring for a further 0.5 h, the pH is raised to 7.5, and 650 ml of sodium water-glass solution (13% by weight of SiO.sub.2) are slowly metered in at this pH, during which the pH is kept constant using 10% hydrochloric acid. After stirring for a further 0.5 h, the pH is lowered to pH 1.8 using 10% hydrochloric acid, and a solution of 5 g of SnCl.sub.4×5 H.sub.2O and 41 ml of hydrochloric acid (20%) is metered in. 105 ml of TiCl.sub.4 solution (400 g/l of TiCl.sub.4) are then slowly metered in at the same pH. This is then followed by a further addition of a solution consisting of 5 g of SnCl.sub.4×5 H.sub.2O and 41 ml of hydrochloric acid (20%). The pH is in each case kept constant at 1.8 using 32% sodium hydroxide solution. The pH is subsequently adjusted to pH 2.8 again by means of sodium hydroxide solution. Finally, the outermost layer is applied by parallel addition of 650 ml of an aqueous FeCl.sub.3 solution (w(Fe)=7%) and 499 ml of an aqueous TiCl.sub.4 solution (200 g of TiCl.sub.4/l) and simultaneous titration with sodium hydroxide solution (w=10%). After stirring for a further 0.5 h at pH 3.0, the coated mica substrate is filtered off, washed and dried at 110° C. for 16 h. Finally, the effect pigment obtained in this way is calcined at 850° C. for 0.5 h and sieved.

[0217] A temperature-stable greenish, golden multilayered pigment having high brightness is obtained.

Example 14

[0218] 100 g of Al.sub.2O.sub.3 flakes (doped with TiO.sub.2) having a particle size of 5-30 μm are heated to 80° C. in 2 l of demineralised water with stirring. When this temperature has been reached, 44 g of TiCl.sub.4 solution (400 g/l of TiCl.sub.4) is metered in at pH 1.8, during which the pH is kept constant using 32% sodium hydroxide solution. The pH is subsequently adjusted to pH 2.8 by means of sodium hydroxide solution, and 600 ml of an aqueous FeCl.sub.3 solution (w(Fe)=7%) and 462 ml of an aqueous TiCl.sub.4 solution (200 g of TiCl.sub.4/l) are added simultaneously at this pH and 75° C. Throughout the addition time, the pH is kept constant by simultaneous dropwise addition of a 32% sodium hydroxide solution. After stirring for a further 0.5 h, the pH is raised to 7.5, and 650 ml of sodium water-glass solution (13% by weight of SiO.sub.2) are slowly metered in at this pH, during which the pH is kept constant using 10% hydrochloric acid. After stirring for a further 0.5 h, the pH is lowered to pH 1.8 using 10% hydrochloric acid, and a solution of 5 g of SnCl.sub.4×5 H.sub.2O and 41 ml of hydrochloric acid (20%) is metered in. 105 ml of TiCl.sub.4 solution (400 g/l of TiCl.sub.4) are then slowly metered in at the same pH. A further addition of a solution consisting of 5 g of SnCl.sub.4×5 H.sub.2O and 41 ml of hydrochloric acid (20%) is subsequently carried out. The pH is in each case kept constant at 1.8 using 32% sodium hydroxide solution. The pH is subsequently adjusted to pH 2.8 again by means of sodium hydroxide solution. Finally, the outermost layer is applied by parallel addition of 650 ml of an aqueous FeCl.sub.3 solution (w(Fe)=7%) and 499 ml of an aqueous TiCl.sub.4 solution (200 g of TiCl.sub.4/l) and simultaneous titration with sodium hydroxide solution (w=10%). After stirring for a further 0.5 h at pH 3.0, the Al.sub.2O.sub.3 flakes coated in this way are filtered off, washed and dried at 110° C. for 16 h. Finally, the effect pigment obtained is calcined at 850° C. for 0.5 h and sieved.

[0219] A temperature-stable golden multilayered pigment having a strong glitter effect is obtained.

Example 15

[0220] 100 g of Al.sub.2O.sub.3 flakes (doped with ZrO.sub.2) having a particle size of 5-30 μm are heated to 80° C. in 2 l of demineralised water with stirring. When this temperature has been reached, 44 g of TiCl.sub.4 solution (400 g/l of TiCl.sub.4) is metered in at pH 1.8, during which the pH is kept constant using 32% sodium hydroxide solution. The pH is subsequently adjusted to pH 2.8 by means of sodium hydroxide solution, and 600 ml of an aqueous FeCl.sub.3 solution (w(Fe)=7%) and 462 ml of an aqueous TiCl.sub.4 solution (200 g of TiCl.sub.4/l) are added simultaneously at this pH and 75° C. Throughout the addition time, the pH is kept constant by simultaneous dropwise addition of a 32% sodium hydroxide solution. After stirring for a further 0.5 h, the pH is raised to 7.5, and 650 ml of sodium water-glass solution (13% by weight of SiO.sub.2) are slowly metered in at this pH, during which the pH is kept constant using 10% hydrochloric acid. After stirring for a further 0.5 h, the pH is lowered to pH 1.8 using 10% hydrochloric acid, and a solution of 5 g of SnCl.sub.4×5 H.sub.2O and 41 ml of hydrochloric acid (20%) is metered in. 105 ml of TiCl.sub.4 solution (400 g/l of TiCl.sub.4) are then slowly metered in at the same pH. A further addition of a solution consisting of 5 g of SnCl.sub.4×5 H.sub.2O and 41 ml of hydrochloric acid (20%) is subsequently carried out. The pH is in each case kept constant at 1.8 using 32% sodium hydroxide solution. The pH is subsequently adjusted to pH 2.8 again by means of sodium hydroxide solution. Finally, the outermost layer is applied by parallel addition of 650 ml of an aqueous FeCl.sub.3 solution (w(Fe)=7%) and 499 ml of an aqueous TiCl.sub.4 solution (200 g of TiCl.sub.4/l) and simultaneous titration with sodium hydroxide solution (w=10%). After stirring for a further 0.5 h at pH 3.0, the Al.sub.2O.sub.3 flakes coated in this way are filtered off, washed and dried at 110° C. for 16 h. Finally, the effect pigment obtained is calcined at 850° C. for 0.5 h and sieved.

[0221] A temperature-stable golden multilayered pigment having a strong glitter effect is obtained.

[0222] The golden multilayered pigments of Examples 1 to 15 are all stable at temperatures of ≥1000° C. and exhibit no impairment with respect to the optical properties at these temperatures.