PIGMENTS HAVING A VIEWING ANGLE DEPENDENT SHIFT OF COLOR, METHOD FOR PRODUCING SAID PIGMENTS, USE OF SAID PIGMENTS IN SECURITY APPLICATIONS, COATING COMPOSITION COMPRISING SAID PIGMENTS AND A DETECTING DEVICE

• US 6,695,905 B2
• Filed: 08/14/2002
• Issued: 02/24/2004
• Est. Priority Date: 02/16/2000
• Status: Expired due to Term

• Current Assignee: Sicpa Holding SA
• Original Assignee: Sicpa Holding SA
• Inventors: Müller, Edgar, Rozumek, Olivier
• Primary Examiner(s): KOSLOW, CAROL M
• Application Number:
  US10/182,734
• Publication Number:
  US 20030015123A1
• Time in Patent Office: 559 Days
• Field of Search: 106/415, 428/690, 252/301.36, 252/301.35, 252/301.16, 252/301.4 R, 252/301.4 H
• US Class Current: 106/415
• CPC Class Codes: B42D 25/378 Special inks
• CPC Class Codes: B42D 25/382 absorbing or reflecting infrared light
• CPC Class Codes: B42D 25/387 absorbing or reflecting ultraviolet light
• CPC Class Codes: C01P 2004/84 one phase coated with the other
• CPC Class Codes: C09B 67/0098 Organic pigments exhibiting interference colours, e.g. nacrous pigments
• CPC Class Codes: C09C 1/0015 Pigments exhibiting interference colours, e.g. transparent platelets of appropriate thinness or flaky substrates, e.g. mica, bearing appropriate thin transparent coatings
• CPC Class Codes: C09C 2200/1054 the core consisting of a metal
• CPC Class Codes: C09C 2200/301 Thickness of the core
• CPC Class Codes: C09C 2200/304 Thickness of intermediate layers adjacent to the core, e.g. metallic layers, protective layers, rutilisation enhancing layers or reflective layers
• CPC Class Codes: C09C 2200/305 Thickness of intermediate layers within the stack
• CPC Class Codes: C09C 2210/50 Fluorescent, luminescent or photoluminescent properties
• CPC Class Codes: C09C 2220/20 PVD, CVD methods or coating in a gas-phase using a fluidized bed
• CPC Class Codes: C09D 5/36 Pearl essence, e.g. coatings containing platelet-like pigments for pearl lustre

Abstract

The invention describes luminescent optically variable pigments (OVP), methods for obtaining such pigments, as well as the use of such pigments as security elements in inks, coatings and articles. The luminescence centers are preferably incorporated into the dielectric material of the OVP'"'"'s optical<i>Fabry-Perot</i> resonance cavity, allowing for the machine-discrimination of luminescent OVP from simple mixtures of luminescents and non-luminescent OVP.

Claims

1. A pigment comprising an interference structure having at least two thin film layers of different materials, said pigment having a viewing angle dependent shift of color, wherein the interference structure has a light-transmitting dielectric layer which comprises at least one luminescent material.

2. A pigment according to claim 1, wherein the interference structure comprises at least one light-transmitting dielectric layer having first and second surfaces essentially parallel to each other and at least one semi-transparent, partially reflecting layer arranged on each of said first and second surfaces of the dielectric layer with the luminescent material being present in at least one of the dielectric layers.

3. A pigment according to claim 1, wherein the interference structure comprises an opaque totally reflecting layer having first and second surfaces essentially parallel to each other and at least one sequence arranged on at least one of said first and second surfaces of the opaque totally reflecting layer, said sequence comprising at least one dielectric layer and at least one semitransparent partially reflecting layer with the dielectric layer of said sequence being adjacent to the totally reflecting layer and the luminescent material being present in at least one of the dielectric layers.

4. A pigment according to claim 3, wherein at least one of the dielectric layers comprises at least a first and a second sub-layer, these being dielectric layers themselves, wherein the luminescent material is present in at least one of the sub-layers.

5. A pigment according to claim 4, wherein the first sub-layer is adjacent to at least one of the first or second surfaces of the opaque totally reflecting layer and contains the luminescent material, and the second sub-layer is of a material having a refractive index equal or less than 1.50.

6. A pigment according to claim 5, wherein the second sub-layer is of MgF₂ or AlF₃.

7. A pigment according to claim 1, wherein the interference structure comprises an opaque totally reflecting layer having first and second surfaces essentially parallel to each other and at least one sequence arranged on at least one of said first and second surfaces of the opaque totally reflecting layer, said sequence comprising at least one electrically conducting layer of a high work-function, at least one dielectric layer and at least one semitransparent partially reflecting layer with the electrically conducting layer being adjacent to the totally reflecting layer and an electroluminescent material being present in at least one of the dielectric layers.

8. A pigment according to claim 1, wherein the interference structure comprises at least one light-transmitting dielectric layer with a first and a second surface and at least one semi-transparent partially reflecting layer of a high refractive index material, having and index of refraction of at least 2.00, arranged on at least one of the first and second surface of the dielectric material, wherein the luminescent material is present in the high refractive index material.

9. A pigment according to claim 1, wherein the interference structure comprises at least one opaque, totally reflecting layer having a first and a second surface and at least one semi-transparent partially reflecting layer of a high refractive index material, having and index of refraction of at least 2.00, arranged on one of the first and second surfaces of the dielectric material, wherein the luminescent material is present in the high refractive index material.

10. A pigment according to claim 1, wherein at least one of the dielectric layers is of a dielectric material selected from the group of materials consisting of the tri-fluorides of the rare-earth elements, of bismuth, and of mixtures thereof, as well as the complex fluorides containing trivalent ions of the rare-earth elements, of bismuth, or of mixtures thereof, and monovalent or divalent ions of the alkali, alkaline-earth, or transition-metal elements including zinc, or of mixtures thereof, and contains a luminescent material selected from the group of luminescent ions.

11. A pigment according to claim 10, wherein the rare-earth elements are selected from the group consisting of yttrium and the elements of the lanthanide series.

12. A pigment according to claim 1, wherein at least one of the dielectric layers is of a dielectric material selected from the group of materials consisting of the tri-fluorides of elements of the third main group of the periodic table or bismuth, the trivalent transition elements, the mixtures thereof, as well as the complex fluorides containing elements of the third main group of the periodic table or bismuth, and monovalent or divalent alkali or alkaline earth or zinc ions, or mixtures thereof.

13. A pigment according to claim 1, wherein at least one of the dielectric layers containing said luminescent material is selected from the group consisting of the difluorides of the second main group of the periodic table, zinc, cadmium, and mixtures thereof.

14. A pigment according to claim 1, wherein the dielectric layer containing said luminescent material is selected from the group of organic or metal-organic compounds.

15. A pigment according to claim 1, wherein said luminescent material is a transition element ion.

16. A pigment according to claim 1, wherein said luminescent material is a rare-earth element ion.

17. A pigment according to claim 1, wherein said luminescent material is an organic or a metal-organic compound.

18. A pigment according to claim 1, wherein the dielectric layer is of an organic or a metal-organic polymer.

19. A pigment according to claim 18, wherein the said luminescent material is selected from the group consisting of organic compounds, and metal-organic compounds.

20. A method for producing a pigment according to claim 7, comprising the step of depositing at least one of the dielectric layers containing the luminescent material by a physical vapor deposition method.

21. A method according to claim 20, wherein the physical vapor deposition method is selected from the group consisting of sputtering, magnetron sputtering, thermal evaporation, and electron-beam assisted evaporation.

22. A method for producing a pigment according to claim 7, comprising the step of depositing at least one of the dielectric layers containing the luminescent material by a chemical vapor deposition method.

23. A method according to claim 22, wherein the chemical vapor deposition method is selected from the group consisting of thermal reaction deposition, reactive sputtering, and fluidized bed coating.

24. A method for producing a pigment according to claim 7, comprising the step of depositing at least one of the dielectric layers containing the luminescent material by a wet chemical method.

25. A method according to claim 24, wherein the wet chemical method is selected from the group consisting of controlled hydrolyses of precursor materials in solution.

26. A method for producing a pigment according to claim 7, comprising the step of producing at least one of the dielectric layers containing said luminescent material by extrusion or co-extrusion.

27. A printing ink comprising a pigment according to claim 7.

28. A security document comprising a layer of printing ink according to claim 27.