IR-absorbing Intaglio ink

• US 8,080,307 B2
• Filed: 11/16/2006
• Issued: 12/20/2011
• Est. Priority Date: 11/25/2005
• Status: Active Grant

• Current Assignee: Sicpa Holding SA
• Original Assignee: Sicpa Holding SA
• Inventors: Demartin Maeder, Marlyse, Despland, Claude-Alain, Mueller, Edgar, Degott, Pierre
• Primary Examiner(s): Wu, David W
• Assistant Examiner(s): Nguyen, Vu A
• Application Number:
  US12/093,982
• Publication Number:
  US 20080241492A1
• Time in Patent Office: 1,860 Days
• Field of Search: 428/29, 428/195.1, 428/199, 428/211.1, 283/57, 283/58, 283/71, 283/72, 283/88, 283/904
• US Class Current: 428/211.1
• CPC Class Codes: B41M 3/14 Security printing securities B42D25/29
• CPC Class Codes: C09D 11/03 characterised by features other than the chemical nature of the binder
• CPC Class Codes: C09D 11/50 Sympathetic, colour changing or similar inks
• CPC Class Codes: Y10S 283/904 Credit card
• CPC Class Codes: Y10T 428/24802 Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.]
• CPC Class Codes: Y10T 428/24835 including developable image or soluble portion in coating or impregnation [e.g., safety paper, etc.]
• CPC Class Codes: Y10T 428/24934 including paper layer

Abstract

Pasty ink for the engraved steel die printing process, having a viscosity value above 3 Pa·s, preferably above 5 Pa·s at 40° C., and comprising an infrared absorbing material, wherein said infrared absorbing material is a transition element compound whose IR-absorption is a consequence of electronic transitions within the d-shell of transition element atoms or ions.

Claims

1. Security document, wherein said security document is printed with an IR-absorbing ink, said IR-absorbing ink that is printed on the security document being an ink for an engraved steel die printing process, comprising:

a polymeric organic binder and an IR-absorbing material,

said ink having a pasty consistency with a viscosity value at 40°

C. of at least 3 Pa·

s, wherein said infrared absorbing material comprises a transition element compound, and wherein infrared absorption of the infrared absorbing material is a consequence of electronic transitions within the d-shell of transition element atoms or ions,

said IR-absorbing material is present in a concentration from 10% to 50% by weight of the ink, and contains IR-absorbing transition element atoms or ions at a concentration of at least 10% by weight, and absorbs in the near infrared range (700 to 1100 nm), and has a CIE (1976) diffuse reflectance lightness (L*) value greater than 70 as measured on the neat powder, and is transparent in some range between 1100 and 2500 nm.

2. Security document according to claim 1, wherein said ink has a pasty consistency with a viscosity value at 40°

C. of at least 5 Pa·

s.

3. Security document according to claim 1, wherein said transition element atoms or ions comprise at least one atom selected from the group consisting of Ti, V, Cr, Mn, Fe, Co, Ni, and Cu.

4. Security document according to claim 1, wherein said transition element atoms or ions comprise at least one ion selected from the group of ions consisting of Ti³⁺, VO²⁺, Cr⁵⁺, Fe²⁺, Ni²⁺, Co²⁺, and Cu²⁺.

5. Security document according to claim 1, wherein said IR-absorbing material comprising said IR-absorbing transition element atoms or ions is a glass, in which there is a coordination of the transition element atoms or ions to phosphate and/or fluoride anions present in the glass.

6. Security document according to claim 1, wherein said IR-absorbing material comprising IR-absorbing transition element atoms or ions comprises a glass, and said glass is a phosphate- and/or fluoride-comprising glass.

7. Security document according to claim 1, wherein said infrared absorbing material comprising said IR-absorbing transition element atoms or ions is a crystalline compound, being composed of one or more cations and one or more anions.

8. Security document according to claim 7, wherein said anion is selected from the group consisting of phosphate (PO₄³⁻

), hydrogenophosphate (HPO₄²⁻

), pyrophosphate (P₂O₇⁴⁻

), metaphosphate (P₃O₉³⁻

), polyphosphate, silicate (SiO₄⁴⁻

), the condensed polysilicates;

titanate (TiO₃²⁻

), the condensed polytitanates, vanadate (VO₄³⁻

), the condensed polyvanadates, molybdate (MoO₄²⁻

), tungstate (WO₄²⁻

), the condensed polytungstates, fluoride (F⁻

), oxide (O²⁻

), and hydroxide (OH⁻

).

9. Security document according to claim 7, wherein said infrared absorbing material is selected from the group of compounds consisting of copper (II) fluoride (CuF₂), copper hydroxyfluoride (CuFOH), copper hydroxide (Cu(OH)₂), copper phosphate (Cu₃(PO₄)₂*2H₂O), anhydrous copper phosphate (Cu₃(PO₄)₂, basic copper(II) phosphates, copper(II) pyrophosphate (Cu₂(P₂O₇)*3H₂O), anhydrous copper(II) pyrophosphate (Cu₂(P₂O₇)), copper(II) metaphosphate (Cu₃(P₃O₉)₂), iron(II) fluoride (FeF₂*4H₂O), anhydrous iron(II) fluoride (FeF₂), iron(II) phosphate (Fe₃(PO₄)₂*8H₂O, Vivianite), lithium iron(II) phosphate (LiFePO₄, Triphylite), sodium iron(II) phosphate (NaFePO₄, Maricite), iron(II) silicates, iron(II) carbonate (FeCO₃, Ankerite, Siderite);

nickel(II) phosphate (Ni₃(PO₄)₂*8H₂O), titanium(III) metaphosphate (Ti(P₃O₉)), Ca₂Fe(PO₄)₂*4H₂O, (Anapaite), and MgFe(PO₄)F, (Wagnerite).

10. Security document according to claim 1, wherein said IR-absorbing material includes IR-absorbing transition element atoms or ions bound to a component of said polymeric organic binder of said ink.

11. Security document according to claim 10, wherein said polymeric organic binder of said ink contains specific binding sites for transition element ions.

12. Security document according to claim 11, wherein said transition element ions are Cu²⁺ and/or Fe²⁺.

13. Security document according to claim 11, wherein said binding sites are phosphate groups which are cross-linked into, or grafted onto a polymer backbone.

14. Security document according to claim 1, wherein said IR-absorbing material is an IR-absorbing complex of a transition element atom or ion and a binding site contained in the polymer.

15. Security document according to claim 14, wherein said IR-absorbing complex of a transition element atom or ion and a binding site contained in the polymer is an organic thioruea-copper(II) complex dissolved in said binder.

16. Security document according to claim 1, wherein said IR-absorbing material has a CIE (1976) diffuse reflectance lightness (L*) value higher than 80, as measured on the neat powder.

17. Security document according to claim 1, wherein said IR-absorbing material contains IR-absorbing transition element atoms or ions at a concentration of 20% or more by weight.

18. Security document according to claim 1, wherein said IR-absorbing material contains IR-absorbing transition element atoms or ions at a concentration of 40% or more by weight.

19. Security document according to claim 1, comprising said IR-absorbing material in a concentration in the range from 20% to 50% by weight of the ink.

20. Security document according to claim 1, said ink comprising an organic compound as an additional IR-absorber.

21. Security document according to claim 20, wherein said additional IR-absorber displays a narrower IR-absorption peak than the transition metal based IR-absorbing material.

22. Security document according to claim 1, wherein said security document is printed with at least two said IR-absorbing inks, wherein said IR-absorbing inks differ in their levels of IR-absorption.

23. Security document according to claim 1, carrying said IR-absorbing ink printed with an Intaglio plate having zones of different engraving depth, such as to result in printed zones of different levels of IR-absorption.

24. Security document according to claim 1, carrying at least one further IR-absorbing ink containing an organic IR-absorber.

25. Security document according to claim 1, wherein the security document is selected from the group consisting of a banknote, a passport, a check, a voucher, an ID- or transaction card, a stamp and a tax label.

26. Security document according to claim 9, wherein said infrared absorbing material comprises the basic copper(II) phosphates, and the basic copper(II) phosphates comprise Cu₂(PO₄)₂(OH) (Libethenite), Cu₃(PO₄)₂(OH)₃ (Cornetite), Cu₅(PO₄)₃(OH)₄ (Pseudomalachite), or CuAl₆(PO₄)₄(OH)₈.5H₂O (Turquoise).

27. Security document according to claim 9, wherein said infrared absorbing material comprises the iron(II) silicates, and the iron(II) silicates comprise Fe₂SiO₄, Fayalite;

or Fe_xMg_2-xSiO₄, Olivine.

28. Process of manufacturing a security document according to claim 1 comprising applying said IR-absorbing ink onto said security document by an engraved steel die printing process.

29. Process according to claim 28, wherein further materials are incorporated into said polymeric organic binder.