Document authentification

• US 20050019603A1
• Filed: 10/21/2002
• Published: 01/27/2005
• Est. Priority Date: 10/31/2001
• Status: Active Grant

• Current Assignee: Merck Patent GmbH (Merck & Co., Inc.)
• Original Assignee: Merck Patent GmbH (Merck & Co., Inc.)
• Inventors: Kathirgamanathan, Poopathy
• Granted Patent: US 7,767,315 B2
• Time in Patent Office: Days
• US Class Current: 428/690
• CPC Class Codes: B41M 3/144 using fluorescent, luminescent or iridescent effects
• CPC Class Codes: B42D 25/29 Securities; Bank notes
• CPC Class Codes: C09K 11/06 containing organic luminescent materials
• CPC Class Codes: C09K 2211/10 Non-macromolecular compounds
• CPC Class Codes: C09K 2211/1003 Carbocyclic compounds
• CPC Class Codes: C09K 2211/1018 Heterocyclic compounds
• CPC Class Codes: C09K 2211/18 Metal complexes
• CPC Class Codes: D21H 21/48 Elements suited for physical verification, e.g. by irradiation
• CPC Class Codes: Y10T 428/24802 Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.]
• CPC Class Codes: Y10T 428/31993 Of paper

Abstract

A method producing authenticatable documents by incorporating a fluorescent organometallic complex in the toner or in the paper in which the fluorescent organometallic complex gives off light with a characteristic spectrum when exposed to UV light.

Claims

1. A method of forming an authenticatable or identifiable article which comprises marking the article or incorporating in or on the article a fluorescent metal organic complex.

2. A method as claimed in any claim 1 in which the fluorescent material is of general formula

(Lα

)_n>

M←

Lp

where Lα and

Lp are organic ligands M is a rare earth, transition metal, lanthanide or an actinide as specified herein and n is the valence state of the metal M, the ligands Lα

can be the same or different and there can be a plurality of ligands Lp which can be the same or different.

3. A method as claimed in claim 1 or 2 in which the fluorescent material of general formula (Lα

)_nM₁M₂ where M₁ is the same as M above, M₂ is a non rare earth metal, Lα

is as specified herein and n is the combined valence state of M₁ and M₂.

4. A method as claimed in any one of claims 1 to 3 in which the complex also comprises one or more neutral ligands Lp and the complex has the general formula (Lα

)_nM₁M₂ (Lp).

5. A method as claimed in any one of claims 1 to 3 in which Lα

and Lp are selected from compounds of formula (I) to (XXVI) herein.

6. A method as claimed in claim 1 in which the complex is selected from binuclear, trinclear and polynuclear organometallic complexes of formula

(Lm)_xM₁←

M₂(Ln)_y or

where L is a bridging ligand and where M₁ is a rare earth metal and M₂ is M₁ or a non rare earth metal, Lm and Ln are the same or different organic ligands Lα

as defined above, x is the valence state of M₁ and y is the valence state of M₂ or

7. A method as claimed in any one of claims 3 to 6 in which the metal M₂ is any metal which is not a rare earth, transition metal, lanthanide or an actinide.

8. A method as claimed in any one of claims 3 to 7 in which the metal M₂ is selected from lithium, sodium, potassium, rubidium, caesium, beryllium, magnesium, calcium, strontium, barium, copper (I), copper (II), silver, gold, zinc, cadmium, boron, aluminium, gallium, indium, germanium, tin (II), tin (IV), antimony (II), antimony (IV), lead (II), lead (IV) and metals of the first, second and third groups of transition metals in different valence states e.g. manganese, iron, ruthenium, osmium, cobalt, nickel, palladium(II), palladium(IV), platinum(II), platinum(IV), cadmium, chromium. titanium, vanadium, zirconium, tantulum, molybdenum, rhodium, iridium, titanium, niobium, scandium and yttrium.

9. An authenticatable or identifiable article, item or document in which the article, item or document or a marking on the article, item or document incorporates a fluorescent metal organic complex.

10. An article, item or document as claimed in claim 9 in which the fluorescent material is of general formula

(Lα

)_n>

M←

Lp

where Lα and

Lp are organic ligands, M is a rare earth, transition metal, lanthanide or an actinide as specified herein and n is the valence state of the metal M, the ligands Lα

can be the same or different and there can be a plurality of ligands Lp which can be the same or different.

11. An article, item or document as claimed in claim 10 in which the fluorescent material of general formula (Lα

)_nM₁M₂ where M₁ is the same as M above, M₂ is a non rare earth metal, Lα

is as specified herein and n is the combined valence state of M₁ and M₂.

12. An article, item or document as claimed in claim 10 or 11 in which the complex also comprises one or more neutral ligands Lp and the complex has the general formula (Lα

)_nM₁M₂ (Lp).

13. An article, item or document claimed in any one of claims 11 or 12 in which the metal M₂ is any metal which is not a rare earth, transition metal, lanthanide or an actinide.

14. An article, item or document claimed in claim 10 in which Lα

and Lp are selected from compounds of formula (I) to (XXVI) herein.

15. An article, item or document claimed in claim 10 in which the complex is selected from binuclear, trinclear and polynuclear organometallic complexes of formula

16. An article, item or document as claimed in claim 13 or 15 in which the metal M₂ is selected from lithium, sodium, potassium, rubidium, caesium, beryllium, magnesium, calcium, strontium, barium, copper (I), copper (II), silver, gold, zinc, cadmium, boron, aluminium, gallium, indium, germanium, tin (II), tin (IV), antimony (II), antimony (IV), lead (II), lead (IV) and metals of the first, second and third groups of transition metals in different valence states e.g. manganese, iron, ruthenium, osmium, cobalt, nickel, palladium(II), palladium(IV), platinum(II), platinum(IV), cadmium, chromium. titanium, vanadium, zirconium, tantulum, molybdenum, rhodium, iridium, titanium, niobium, scandium and yttrium.

17. An article as claimed in any one of claims 9 to 16 which comprises a paper document and in which the paper incorporates the fluorescent metal organic complex.

18. An article as claimed in claim 17 in which the fluorescent metal organic complex is incorporated in the paper in the form of material strips containing the fluorescent metal organic complex.

19. An article as claimed in claim 18 in which visible markings on the document comprise a medium which incorporates the fluorescent metal organic complex.

20. An article as claimed in claim 19 in which the medium is ink, paint or toner.

21. An article, item or document as claimed in any one of claims 9 to 20 which is made from cloth, a plastics material, wood, ceramic material or a metal.

22. A method of forming an authenticatable or identifiable article which comprises the step of marking the article with, or incorporating in or on the article, a fluorescent organic complex having the general chemical formula:

(Lα

)_n>

M←

Lp

where Lα and

Lp are organic ligands, M is an element selected from the group consisting of rare earth elements, transition elements, lanthanide series elements and actinide series elements, n is the valence state of the element M, Lα

is an organic complex which consists of a single ligand or multiple ligands which may be the same or different, and Lp is an organic complex which consists of a single ligand or multiple ligands which may be the same or different.

25. A method according to claim 22 wherein Lα

and Lp are selected from the group of compounds consisting of compounds having the formula (I) to (XXVI).

26. A method according to claim 22 wherein the fluorescent organic complex is selected from the group consisting of binuclear, trinuclear and polynuclear organometallic complexes of the general chemical formula

23. A method of forming an authenticatable or identifiable article which comprises the step of marking the article with, or incorporating in or on the article, a fluorescent organic complex having the general chemical formula (Lα

)_nM₁M₂, where M₁ is an element selected from the group consisting of rare earth elements, transition elements, lanthanide series elements and actinide series elements, M₂ is a non-rare earth metal, Lα

is an organic complex which consists of a single ligand or multiple ligands which may be the same or different, and n is the combined valence state of M₁ and M₂.

24. A method according to claim 23 wherein the fluorescent organic complex has the general chemical formula (Lα

)_nM₁M₂(Lp), where Lp is an organic complex which consists of a single ligand or multiple ligands which may be the same or different.

27. A method according to claim 23 wherein the element M₂ is any metal which is not a rare earth element, transition element, lanthanid series element or actinide series element.

28. A method according to claim 27 wherein the element M₂ is selected from the group consisting of lithium, sodium, potassium, rubidium, caesium, beryllium, magnesium, calcium, strontium, barium, copper (I), copper (II), silver, gold, zinc, cadmium, boron, aluminium, gallium, indium, germanium, tin (II), tin (IV), antimony (II), antimony (IV), lead (II), lead (IV) and metals of the first, second and third groups of transition metals in different valence states including manganese, iron, ruthenium, osmium, cobalt, nickel, palladium(II), palladium(IV), platinum(II), platinum(IV), cadmium, chromium. titanium, vanadium, zirconium, tantulum, molybdenum, rhodium, iridium, titanium, niobium, scandium and yttrium.

29. An authenticatable or identifiable article, item or document wherein the article, item or document, or at least a marking on such article, item or document, incorporates a fluorescent organic complex having the general chemical formula

(Lα

)_n>

M←

Lp

where Lα and

L_p are organic ligands, M is an element selected from the group consisting of rare earth elements, transition elements, lanthanide series elements and actinide series elements, n is the valence state of the element M, Lα

is an organic complex which consists of a single ligand or multiple ligands which may be the same or different, and Lp is an organic complex which consists of a single ligand or multiple ligands which may be the same or different.

30. An article, item, document or marking according to claim 29 wherein the fluorescent organic complex is of the general formula (Lα

)_nM₁M₂ where M₁ is the same as M above, M₂ is a non-rare earth metal, Lα

is an organic complex which consists of a single ligand or multiple ligands which may be the same or different, and n is the combined valence state of M₁ and M₂.

31. An article, item, document or marking according to claim 29 wherein the complex has the general formula (Lα

)_nM₁M₂ (Lp).

32. An article, item, document or marking according to claim 31 wherein M₂ is any metal which is not a rare earth element, transition element, lanthanide series element or actinide series element.

33. An article, item, document or marking according to claim 29 wherein Lα

and Lp are selected from the group of compounds consisting of compounds having the formula (I) to (XXVI).

34. An article, item, document or marking according to claim 29 wherein the fluorescent organic complex is selected from the group consisting of binuclear, trinuclear and polynuclear organometallic complexes of the general chemical formula

35. An article, item, document or marking according to claim 31 wherein M₂ is selected from the group consisting of lithium, sodium, potassium, rubidium, caesium, beryllium, magnesium, calcium, strontium, barium, copper (I), copper (II), silver, gold, zinc, cadmium, boron, aluminium, gallium, indium, germanium, tin (II), tin (IV), antimony (II), antimony (IV), lead (H), lead (IV), and metals of the first, second and third groups of transition metals in different valence states including manganese, iron, ruthenium, osmium, cobalt, nickel, palladium(II), palladium(IV), platinum(II), platinum(IV), cadmium, chromium. titanium, vanadium, zirconium, tantulum, molybdenum, rhodium, iridium, titanium, niobium, scandium and yttrium.

36. An article, item, document or marking according to claim 34 wherein M₂ is selected from the group consisting of lithium, sodium, potassium, rubidium, caesium, beryllium, magnesium, calcium, strontium, barium, copper (I), copper (II), silver, gold, zinc, cadmium, boron, aluminium, gallium, indium, germanium, tin (II), tin (IV), antimony (II), antimony (IV), lead (II), lead (IV), and metals of the first, second and third groups of transition metals in different valence states including manganese, iron, ruthenium, osmium, cobalt, nickel, palladium(II), palladium(IV), platinum(II), platinum(IV), cadmium, chromium. titanium, vanadium, zirconium, tantulum, molybdenum, rhodium, iridium, titanium, niobium, scandium and yttrium.

37. A paper document wherein the paper incorporates a fluorescent organic complex having general chemical formula

(Lα

)_nM←

Lp

where Lα and

Lp are organic ligands, M is an element selected from the group consisting of rare earth elements, transition elements, lanthanide series elements and actinide series elements, n is the valence state of the element M, Lα

is an organic complex which consists of a single ligand or multiple ligands which may be the same or different, and Lp is an organic complex which consists of a single ligand or multiple ligands which may be the same or different.

38. A paper document according to claim 37 wherein the fluorescent organic complex is incorporated into the paper in the form of material strips containing the fluorescent organic complex.

39. A paper document according to claim 38 wherein visible markings on the document comprise a medium which incorporates the fluorescent organic complex.