Color changing compositions using acids

• US 5,489,331 A
• Filed: 07/05/1994
• Issued: 02/06/1996
• Est. Priority Date: 07/31/1992
• Status: Expired due to Term

• Current Assignee: Crayola LLC (Hallmark Cards Incorporated)
• Original Assignee: Binney & Smith Inc.
• Inventors: Miller, Richard E., Couch, Charlene R.
• Primary Examiner(s): KLEMANSKI, HELENE G
• Application Number:
  US08/270,454
• Time in Patent Office: 581 Days
• Field of Search: 106/21 R, 106/21 A, 106/23 B, 106/22 B
• US Class Current: 106/31.43
• CPC Class Codes: B05D 1/36 Successively applying liquids or other fluent materials, e.g. without intermediate treatment
• CPC Class Codes: B05D 2401/20 Aqueous dispersion or solution
• CPC Class Codes: B05D 2451/00 Type of carrier, type of coating (Multilayers)
• CPC Class Codes: B05D 7/54 No clear coat specified
• CPC Class Codes: B44D 2/00 Special techniques in artistic painting or drawing, e.g. oil painting, water painting, pastel painting, relief painting
• CPC Class Codes: B44F 1/10 Changing, amusing, or secret pictures
• CPC Class Codes: C09D 11/50 Sympathetic, colour changing or similar inks
• CPC Class Codes: C09D 7/00 Features of coating compositions, not provided for in group C09D5/00 driers C09F9/00; Processes for incorporating ingredients in coating compositions

Abstract

A multiple coloring composition system is disclosed whose coloring effect is changed upon treatment with an overcolor, once the overcolor coloring composition has been deposited over the undercolor coloring composition. The multiple ink system comprises:

(a) an undercolor aqueous coloring composition comprising an undercolor dye whose coloring ability is destroyed in the presence of an acid; and

(b) an overcolor aqueous coloring composition comprising a colorant capable of maintaining its characteristic color in the presence of a pH of about 4 or less; and an acid sufficient to bring the pH of the overcolor composition to about 4 or less.

Claims

1. A multiple coloring composition system comprising:

(a) an undercolor aqueous coloring composition comprising an undercolor dye whose coloring ability is destroyed in the presence of a pH of about 4 or less; and

(b) an overcolor aqueous coloring composition comprising a colorant capable of maintaining its characteristic color in the presence of a pH of about 4 or less and an effective amount of an acid sufficient to yield a pH of said overcolor coloring composition of about 4 or less.

2. The multiple coloring composition system of claim 1, said acid being present in an amount sufficient to yield a pH of said overcolor aqueous coloring composition of from about 2 to about 4.

3. The multiple coloring composition system of claim 2, wherein said acid is selected from the group consisting of phosphoric acid, sulfuric acid, citric acid, and mixtures thereof.

4. The multiple coloring composition system of claim 3, said acid added in an amount of from about 5% to about 30% by weight of said overcolor aqueous coloring composition.

5. The multiple coloring composition system of claim 1, wherein said undercolor dye of said undercolor coloring composition is selected from the group consisting of xanthene dyes, pthalocyanine dyes, and azo dyes which are unstable in the presence of a pH of about 4 or less.

6. The multiple coloring composition system of claim 5, wherein said undercolor dye of said undercolor coloring composition is selected from the group consisting of Acid Red 92, Acid Yellow 1, Solvent Red 48, Solvent Green 7, and mixtures thereof.

7. The multiple coloring composition system of claim 1, wherein said colorant of said overcolor coloring composition is selected from the group consisting of pigments, polymethine dyes, triphenylmethane dyes, and azo dyes which are stable in the presence of a pH of about 4 or less.

8. The multiple coloring composition system of claim 7, wherein said colorant of said overcolor coloring composition is selected from the group consisting of Acid Blue 93, Acid Yellow 23, Acid Green 3, Acid Violet 19, pigments, and mixtures thereof.

9. The multiple coloring composition system of claim 1, wherein said overcolor aqueous coloring composition further comprises an anti-oxidant.

10. The multiple coloring composition system of claim 9, wherein said anti-oxidant is present in an amount of from about 0.1% to about 3% by weight.

11. The multiple coloring composition system of claim 10, wherein said anti-oxidant is selected from the group consisting of citric acid, ascorbic acid, sodium hypophosphite, and mixtures thereof.

12. The multiple coloring composition system of claim 1, wherein said undercolor aqueous coloring composition further comprises a stabilizing base.

13. The multiple coloring composition system of claim 12, wherein said stabilizing base is present in an amount of from about 0.2% to about 2%.

14. The multiple coloring composition system of claim 13, wherein said stabilizing base is selected from the group consisting of sodium hydroxide, sodium carbonate, monosodium EDTA, and mixtures thereof.

15. The multiple coloring composition system of claim 1, wherein said undercolor and said overcolor aqueous coloring compositions further comprise a humectant.

16. The multiple coloring composition system of claim 15, wherein said humectant is present in an amount of from about 0% to about 30% by weight.

17. The multiple coloring composition system of claim 16, wherein said humectant is selected from the group consisting of glycerin, propylene glycol, diethylene glycol, and mixtures thereof.

18. The multiple coloring composition system of claim 1, wherein said undercolor and said overcolor aqueous coloring compositions further comprise a preservative.

19. The multiple coloring composition system of claim 18, wherein said preservative is present in said undercolor coloring composition in an amount of from about 0.2% to about 5% by weight.

20. The multiple coloring composition of claim 19, wherein said preservative is selected from the group consisting of an aqueous bicyclic oxazolidines solution, a 3-iodo-2-propynyl butyl carbamate, and mixtures thereof.

21. The multiple coloring composition of claim 19, wherein a base is present in the said undercolor coloring composition in an effective amount to yield a pH of said undercolor of from about 7.0 to about 9.0.

22. The multiple coloring composition system of claim 21, wherein said base is present in an amount of from about 0.2% to about 2% by weight.

23. The multiple coloring composition system of claim 22, wherein said base is selected from the group consisting of sodium hydroxide, sodium carbonate, monosodium EDTA, and mixtures thereof.

24. An ink composition comprising:

(a) an undercolor aqueous ink comprising an undercolor dye whose coloring ability is destroyed in the presence of a pH of about 4 or less in an amount of from about 0.5% to about 6% by weight of the undercolor ink; and

(b) an overcolor aqueous ink comprising from about 0.5% to about 40% by weight of said overcolor ink of an acid; and

from about 0.5% to about 6% by weight of said overcolor ink of a colorant which maintains characteristic color in the presence of a pH of about 4 or less.

25. A coloring changing marking system comprising at least one undercolor marking instrument and an overcolor marking instrument, said undercolor marking instrument containing an undercolor ink composition comprising a dye whose coloring ability is destroyed in the presence of a pH of about 4 or less, and said overcolor writing instrument containing an overcolor aqueous ink composition comprising (1) from about 0.5% to about 40% by weight of an acid;

and (2) from about 0.5% to about 6% by weight of a colorant which maintains its characteristic color in the presence of a pH of about 4 or less.

26. The color changing marking system of claim 25, wherein said marking instrument comprises a fluid reservoir and a nib in fluid connection with said fluid reservoir.

27. A paint composition comprising:

(a) an undercolor aqueous paint comprising an undercolor dye whose coloring ability is destroyed in the presence of a pH of about 4 or less; and

(b) an overcolor aqueous paint comprising from about 0.5% to about 40% by weight of an acid;

from about 0.5% to about 6% by weight of an overcolor dye that maintains its characteristic color in the presence of a pH of about 4 or less; and

a thickener in an amount of from about 1% to about 5% by weight.

28. A coloring composition comprising

(a) from about 0.5% to about 30% by weight of an acid;

and (c) from about 0.5% to about 6% by weight of a colorant which maintains its characteristic color in the presence of a pH of about 4 or less.