Security document with reversibly photochromic printing inks

• US 5,807,625 A
• Filed: 06/17/1996
• Issued: 09/15/1998
• Est. Priority Date: 01/12/1988
• Status: Expired due to Fees

• Current Assignee: Sicpa Holding SA
• Original Assignee: Sicpa Holding SA
• Inventors: Bretler, Haim, Amon, Albert, Bleikolm, Anton
• Primary Examiner(s): YAMNITZKY, MARIE ROSE
• Application Number:
  US08/664,713
• Time in Patent Office: 820 Days
• Field of Search: 428/195, 428/199, 428/201, 428/206, 428/207, 428/211, 428/321.5, 428/323, 428/327, 428/402, 428/402.21, 428/913, 428/916, 428/197, 283/72, 283/85, 283/901, 283/902, 427/197, 427/256, 427/258, 427/288
• US Class Current: 428/195.1
• CPC Class Codes: B41M 3/142 using chemical colour-formers or chemical reactions, e.g. leuco-dye/acid, photochromes
• CPC Class Codes: B42D 25/29 Securities; Bank notes
• CPC Class Codes: B42D 25/378 Special inks
• CPC Class Codes: C09D 11/50 Sympathetic, colour changing or similar inks
• CPC Class Codes: Y10S 283/901 Concealed data
• CPC Class Codes: Y10S 283/902 Anti-photocopy
• CPC Class Codes: Y10S 428/913 Material designed to be responsive to temperature, light, moisture
• CPC Class Codes: Y10S 428/916 Fraud or tamper detecting
• 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 428/24851 Intermediate layer is discontinuous or differential
• CPC Class Codes: Y10T 428/24893 including particulate material
• CPC Class Codes: Y10T 428/24901 including coloring matter
• CPC Class Codes: Y10T 428/24934 including paper layer
• CPC Class Codes: Y10T 428/249997 Encapsulated liquid
• CPC Class Codes: Y10T 428/25 Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
• CPC Class Codes: Y10T 428/254 Polymeric or resinous material

Abstract

Photochromic printing inks are disclosed which are in particular used for the printing of security documents. Prints are normally nearly colorless and become colored when energy irradiated, such as by ultraviolet light. This photocoloration is reversible. The printing inks contain photochromic compounds which are protected against other ink components. Methods are described to prepare the inks, to print security documents, and to detect counterfeiting.

Claims

1. A security document comprising a substrate having an ink pattern on a surface thereof, said ink comprising binder and particles of at least one photodyestuff consisting of a solid solution or dispersion of photochromic compound and polymeric protecting composition, wherein said polymeric protecting composition is a light-transparent thermoplastic having a melting point between 50°

and 150°

C., a barrier for any ink component which is capable of irreversibly interfering with the photochromic reaction sites on said photochromic compound, inert to the photochromic compound, and which is further a barrier for oxygen.

2. The security document of claim 1 wherein said photochromic compound is a spiro-indolino-naphthoxazine or spirobenzopyrane.

3. The security document of claim 1 wherein said photochromic compound is a fulgide or fulgimide.

4. The security document of claim 1 wherein said photochromic compound is a spiro(1,8a)-dihydroindolizine.

5. The security document of claim 1 wherein said photodyestuff is a solid solution and said particles have a particle size of from 1 to 20 micrometers.

6. The security document of claim 1 wherein said photodyestuff is a dispersion.

7. The security document of claim 1 having a non-photochromic ink pattern thereon.

8. A security document comprising a substrate having an ink pattern on a surface thereof, said ink comprising a solid solution or dispersion of photochromic compound and a binder, wherein said binder has an acid number below 10 and is free from carboxyl groups and their salts and from other functional groups which are capable of interfering irreversibly with the photochromic compound, said binder being further capable of forming a light transparent thermoplastic film after chemical hardening which contains said photochromic compound as solid solution or dispersion and further acts as barrier for oxygen and for ink components which are capable of interfering with the photochromic reaction sites of said photochromic compound.

9. The security document of claim 8 wherein said photochromic compound is a spiro-indolino-naphthoxazine or spirobenzopyrane.

10. The security document of claim 8 wherein said photochromic compound is a fulgide or fulgimide.

11. The security document of claim 8 wherein said photochromic compound is a spiro(1,8a)-dihydroindolizine.

12. The security document of claim 8 wherein said ink is a solid solution.

13. The security document of claim 8 wherein said ink is a dispersion.

14. The security document of claim 8 having a non-photochromic ink pattern thereon.

15. A method for the printing of security documents, comprising the following steps:

A) selecting a photochromic composition comprising

(1) a thermoplastic binder,

(2) a liquid phase,

(3) and at least one photochromic compound, said binder being free from carboxyl groups and their salts and from other functional groups which are capable of interfering irreversibly with the photochromic compound, said binder being further capable of forming a light transparent film after chemical hardening which contains said photochromic compound as solid solution or dispersion and further acts as barrier for oxygen and for ink components which are capable of interfering with the photochromic reaction sites of said photochromic compound,

(B) selecting a non-photochromic printing ink,

(C) printing with these inks simultaneously or in the course of the same printing procedure a flat substrate accepting the inks of steps (A) and (B) according to the predetermined patterns,

(D) drying the print obtained in step (C),

(E) collecting a printing security document showing photochromic lines or patterns and non-photochromic lines and patterns.

16. The method of claim 15 wherein said binder has an acid number below 10.

17. The method of claim 15 wherein said binder is a polymer or a prepolymer curable to said polymer binder by other than ionic reaction mechanisms.

18. The method of claim 15 wherein said photochromic compound is a spiro-indolino-naphthoxazine or spirobenzopyrane.

19. The method of claim 15 wherein said photochromic compound is a fulgide or fulgimide.

20. The method of claim 15 wherein said photochromic compound is a Spiro (1,8a) -dihydroindolizine.

21. The method of claim 15 wherein said binder is a thermoplast having a melting point between 50°

and 150°

C.

23. The method according to claim 15, wherein after step (A) and prior to step (B) said photochromic solid solution or dispersion is dried and micronized thereby forming photodyestuff particles which subsequently are mixed with an additional binder.

24. The method of claim 23 wherein said photodyestuff is added in an amount of 0.5 to 50% by weight of the total composition.

25. The method of claim 24 wherein said micronized particles have a particle size between 1 to 20 micrometers.

26. The method of claim 25 comprising mixing the printing inks of step (A) and (B) and collecting in step (E) a printed security document showing photochromic lines or patterns where the printed color reversibly changes by photochromism to another color.

22. The method of claim 41 comprising mixing the printing inks of step (A) and (B) and collecting in step (E) a printed security document showing photochromic lines or patterns where the printed color reversibly changes by photochromism to another color.