Intensely coloured and/or optically variable pigments having an electrically conductive core

• US 8,940,189 B2
• Filed: 12/11/2008
• Issued: 01/27/2015
• Est. Priority Date: 12/19/2007
• Status: Expired due to Fees

• Current Assignee: Merck Patent GmbH (Merck & Co., Inc.)
• Original Assignee: Merck Patent GmbH (Merck & Co., Inc.)
• Inventors: Krietsch, Burkhard, Kuntz, Matthias, Rueger, Reinhold
• Primary Examiner(s): Nguyen, Khanh Tuan
• Application Number:
  US12/809,290
• Publication Number:
  US 20100270510A1
• Time in Patent Office: 2,238 Days
• Field of Search: 252/500, 106/430, 106/436, 106/418, 106/417, 428/403, 427/58, 427/126.3
• US Class Current: 252/500
• CPC Class Codes: C01P 2006/40 Electric properties
• CPC Class Codes: C08K 3/22 of metals
• CPC Class Codes: C08K 9/02 Ingredients treated with inorganic substances
• CPC Class Codes: C09C 1/0021 comprising a core coated with only one layer having a high or low refractive index
• CPC Class Codes: C09C 1/0024 comprising a stack of coating layers with alternating high and low refractive indices, wherein the first coating layer on the core surface has the high refractive index
• CPC Class Codes: C09C 2200/1004 the core comprising at least one inorganic oxide, e.g. Al2O3, TiO2 or SiO2
• CPC Class Codes: C09D 11/037 characterised by the pigment
• CPC Class Codes: C09D 5/24 Electrically-conducting paints conductive materials H01B1/00
• CPC Class Codes: C09D 5/36 Pearl essence, e.g. coatings containing platelet-like pigments for pearl lustre
• CPC Class Codes: C09D 7/62 modified by treatment with other compounds
• CPC Class Codes: C09D 7/69 Particle size larger than 1000 nm
• CPC Class Codes: Y10T 428/2991 Coated

Abstract

The present invention relates to intensely colored and/or optically variable pigments which have a flake-form transparent or semitransparent electrically conductive core and at least one coloring dielectric layer surrounding the core, to a process for the preparation of such pigments, and to the use thereof.

Claims

1. A pigment powder comprising a pigment comprising a flake-form transparent or semitransparent electrically conductive core and at least one coloring dielectric layer surrounding the electrically conductive core, wherein the electrically conductive core has a transparent or semitransparent flake-form substrate and a coating located on all or both sides of the substrate, where the coating has a single- or multilayered structure and at least the outer layer of the coating represents an electrically conductive layer comprising metal oxides doped with gallium, aluminium, indium, thallium, germanium, tin, phosphorus, arsenic, antimony, selenium, tellurium, molybdenum, tungsten and/or fluorine, said electrically conductive layer having a layer thickness of at least 15 nm, and wherein the transparent or semitransparent substrate is synthetic or natural mica, talc, kaolin, glass flakes, flake-form SiO₂ or flake-form Al₂O₃, and wherein said pigment powder is not electrically conductive.

2. The pigment Pigments according to claim 1, wherein the coloring dielectric layer surrounding the core is a layer comprising a material having a refractive index n≧

1.8.

3. The pigment according to claim 2, further comprising additional coloring layers which surround the coloring dielectric layer and are alternately a material having a refractive index n<

1.8 and a material having a refractive index n≧

1.8; and

are located on the layer comprising a material having a refractive index n≧

1.8.

4. The pigment according to claim 2, wherein the layer comprising a material having a refractive index n≧

1.8 is TiO₂, titanium oxide hydrate, titanium suboxides, Fe₂O₃, FeOOH, SnO₂, ZnO, ZrO₂, Ce₂O₃, CoO, Co₃O₄, V₂O₅, Cr₂O₃ and/or mixed phases thereof.

5. The pigment according to claim 1, wherein the coloring dielectric layer surrounding the core is a layer comprising a material having a refractive index n<

1.8.

6. The pigment according to claim 5, further comprising additional coloring layers which surround the coloring dielectric layer and are alternately a material having a refractive index n≧

1.8 and a material having a refractive index n<

1.8; and

are located on the layer comprising a material having a refractive index n<

1.8.

7. The pigment according to claim 6, wherein a layer comprising a material having a refractive index n≧

1.8 in each case forms the outermost layer of the pigment.

8. The pigment according to claim 5, wherein the layer comprising a material having a refractive index n<

1.8 is SiO₂, silicon oxide hydrate, Al₂O₃, aluminium oxide hydrate, mixed phases thereof or MgF₂.

9. The pigment according to claim 1, wherein the metal oxide of the conductive layer is tin oxide, zinc oxide, indium oxide and/or titanium oxide.

10. The pigment according to claim 1, having intrinsic electrical conductivity.

11. A process for the preparation of intensely colored and/or optically variable pigments according to claim 1, comprising:

a) optionally coating of a flake-form transparent or semitransparent substrate with one or more dielectric layers,

b) coating of the substrate on both or all sides with an electrically conductive layer, giving an electrically conductive core,

c) coating of the electrically conductive core on all sides with at least one coloring dielectric layer.

12. The process according to claim 11, wherein the coating of the flake-form substrate in a), b), and/or c) is carried out by a sol-gel process or by wet-chemical methods from inorganic starting materials.

13. The process according to claim 11, wherein the electrically conductive layer is produced by wet-chemical methods from inorganic starting materials by deposition of a precipitate on the substrate, preventing the formation of a co-precipitate.

14. The process according to claim 11, wherein in c), a layer system comprising a plurality of coloring dielectric layers lying one above the other, each of which surrounds the underlying layer and which alternately is a material having a refractive index n≧

1.8 and a material having a refractive index n<

1.8, is applied, where the first layer surrounding the conductive core may either be a material having a refractive index n≧

1.8 or a material having a refractive index n<

1.8, and the outermost layer of the pigment is a material having a refractive index n≧

1.8.

15. The process according to claim 11, wherein the layer surrounding the electrically conductive core is TiO₂ and/or titanium oxide hydrate.

16. The process according to claim 11, wherein the layer surrounding the electrically conductive core is SiO₂ and/or silicon oxide hydrate.

17. The process according to claim 11, wherein the electrically conductive layer is an antimony-doped tin oxide.

18. In a material selected from paint, coating, printing ink, plastic, security product, film, formulation, ceramic material, glass, paper dry preparations, or pigment preparation, wherein in each case said material contains a pigment, the improvement wherein said pigment is according to claim 1.

19. A material according to claim 18, wherein the pigment is employed as a mixture with organic and/or inorganic colorants and/or electrically conductive materials.

20. A material according to claim 18, wherein the pigment is employed in security products which are subjected to the influence of an electromagnetic field.

21. A pigment powder consisting of a pigment consisting of a flake-form transparent or semitransparent electrically conductive core and at least one coloring dielectric layer surrounding the electrically conductive core, wherein the electrically conductive core has a transparent or semitransparent flake-form substrate and a coating located on all or both sides of the substrate, where the coating has a single- or multilayered structure and at least the outer layer of the coating represents an electrically conductive layer consisting of metal oxides doped with gallium, aluminium, indium, thallium, germanium, tin, phosphorus, arsenic, antimony, selenium, tellurium, molybdenum, tungsten and/or fluorine, said electrically conductive layer having a layer thickness of at least 15 nm, and wherein the transparent or semitransparent substrate is synthetic or natural mica, talc, kaolin, glass flakes, flake-form SiO₂ or flake-form Al₂O₃, wherein the pigment powder is not electrically conductive.