Washable color changing compositions

• US 5,486,228 A
• Filed: 07/05/1994
• Issued: 01/23/1996
• 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., Krieger, Cheryl D..
• Primary Examiner(s): KLEMANSKI, HELENE G
• Application Number:
  US08/270,485
• Time in Patent Office: 567 Days
• Field of Search: 106/21 R, 106/21 A, 106/23 B, 106/22 B
• US Class Current: 106/31.32
• 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 5/061 Special surface effect
• 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 washable multiple coloring composition system is disclosed whose coloring effect is changed upon treatment with a second coloring composition, once the second coloring composition has been deposited over the undercolor coloring composition. The washable multiple ink system comprises:

(a) an undercolor aqueous coloring composition comprising a compatable surfactant in an amount sufficient to provide washability and an undercolor dye whose coloring ability is destroyed in the presence of a pH of about 10 or greater and/or by a reducing agent; and

(b) an overcolor aqueous coloring composition comprising a compatable surfactant in an amount sufficient to provide washability, a colorant capable of maintaining its characteristic color in the presence of a pH of about 10 or greater and/or a reducing agent, a base in an amount sufficient to yield a pH of the overcolor composition of about 10 or greater, and/or a reducing agent.

Claims

1. A washable multiple coloring composition system comprising:

(a) an undercolor aqueous coloring composition comprising a compatible surfactant in an amount sufficient to provide washability to said undercolor aqueous coloring composition and an undercolor dye whose coloring ability is destroyed in the presence of a pH of about 10 or greater; and

(b) an overcolor aqueous coloring composition comprising a compatible surfactant in an amount sufficient to provide washability to said overcolor aqueous coloring composition, a colorant capable of maintaining its characteristic color in the presence of a pH of about 10 or greater and an effective amount of a base sufficient to yield a pH of said overcolor aqueous coloring composition of about 10 or greater.

2. The multiple coloring composition system of claim 1, said base being present in an amount sufficient to yield a pH of said overcolor aqueous coloring composition of from about 10 to about 12.

3. The multiple coloring composition system of claim 1, said surfactant in said overcolor aqueous coloring composition being present in an amount from about 20% to about 55% by weight.

4. The multiple coloring composition system of claim 2, said base added in an amount of from about 0.1% to about 20% 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 polymethine dyes, triphenylmethane dyes, cyanine dyes, methine dyes, and azo dyes which are unstable in the presence of a pH of about 10 or greater.

6. The multiple coloring composition of claim 5, wherein said undercolor dye of said undercolor coloring composition is selected from the group consisting of Basic Blue 69, Basic Red 14, Basic Red 49, Acid Green 3, Acid Violet 19 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, xanthene dyes, pthalocyanine dyes, and azo dyes which are stable in the presence of a pH of about 10 or greater.

8. The multiple coloring composition system of claim 1, wherein said colorant of said overcolor coloring composition is selected from the group consisting of Acid Red 52, Acid Red 87, Acid Red 92, Acid Red 388, Food Red 14, Acid Green 26, Solvent Green 7, Direct Blue 199, and mixtures thereof.

9. The multiple coloring composition system of claim 1, wherein said overcolor aqueous coloring composition further comprises a reducing agent.

10. The multiple coloring composition system of claim 9, wherein said reducing agent is selected from the group consisting of hydrogen sulfide, sodium sulfite, sodium hypochlorite and hydrogen peroxide.

11. The multiple coloring composition system of claim 1, wherein said base is selected from the group consisting of ammonium hydroxide, sodium hydroxide and sodium carbonate.

12. The multiple coloring composition system of claim 1, wherein said undercolor and said overcolor coloring compositions further comprise a humectant in an amount of from about 0% to about 30% by weight.

13. The multiple coloring composition system of claim 1, wherein said undercolor and said overcolor coloring compositions further comprise a drying agent in an amount of from about 5% to about 30% by weight.

14. The multiple coloring composition system of claim 1, wherein said colorant of said overcolor aqueous coloring composition is present in an amount of from about 0.1% to about 15% by weight.

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

16. The multiple coloring composition system of claim 15, wherein said preservative is present in said undercolor and said overcolor coloring compositions in an amount of from about 0.1% to about 5% by weight.

32. The multiple coloring composition system of claim 1, said surfactant of said undercolor aqueous coloring composition being present in an amount of from about 20% to about 55% by weight.

33. The multiple coloring composition of claim 1, wherein said surfactant is an anionic surfactant selected from the group consisting of diphenyl oxide disulfonate and sodium naphthalene sulfonate.

17. A washable ink composition system comprising:

(a) an undercolor aqueous ink comprising a compatible surfactant in an amount sufficient to provide washability and an undercolor dye whose coloring ability is destroyed in the presence of a pH of about 10 or greater in an amount of from about 0.1% to about 15% by weight of the undercolor ink; and

(b) an overcolor aqueous ink comprising from about 20% to about 55% by weight of a compatible surfactant;

from about 1% to about 20% by weight of said overcolor ink of a reducing agent;

from about 0.1% to about 10% by weight of said overcolor ink of a base; and

from about 0.1% to about 15% by weight of said overcolor ink of an overcolor colorant which maintains its characteristic color in the presence of a reducing agent and a pH of about 10 or greater.

18. The ink composition system according to claim 17, wherein said base is present in an amount of from about 0.1% to about 20% by weight.

19. The ink composition system according to claim 17, wherein said undercolor dye and said overcolor colorant are each present in an amount of from about 1% to about 6% by weight.

34. The multiple coloring composition of claim 17, wherein said surfactant is an anionic surfactant selected from the group consisting of diphenyl oxide disulfonate and sodium naphthalene sulfonate.

20. A washable color changing marking system comprising at least an undercolor marking instrument and an overcolor marking instrument, said undercolor marking instrument containing from about 20% to about 55% of a compatable surfactant and an undercolor ink composition comprising a dye whose coloring ability is destroyed in the presence of a pH of about 10 or greater, and said overcolor marking instrument containing an overcolor ink, said ink comprising

(1) from about 20% to about 55% of a compatible surfactant;

(2) from about 0.1% to about 10% by weight of a base; and

(3) from about 0.1% to about 15% by weight of a colorant which maintains its characteristic color in the presence of a pH of about 10 or greater.

21. The marking system of claim 20, wherein said overcolor ink further comprises a reducing agent.

22. The marking system of claim 21 wherein said reducing agent is sodium sulphite.

23. The marking system of claim 20, wherein said base is sodium hydroxide.

24. The marking system of claim 21, wherein said system further comprises at least a third marking instrument, said third marking instrument containing an undercolor ink composition comprising a dye whose coloring ability is destroyed in the presence of a reducing agent.

25. The marking system of claim 20, wherein said marker comprises and ink reservoir coupled to a nib.

35. The multiple coloring composition of claim 20, wherein said surfactant is an anionic surfactant selected from the group consisting of diphenyl oxide disulfonate and sodium naphthalene sulfonate.

26. A washable paint composition system comprising:

(a) an undercolor aqueous paint comprising from about 20% to about 55% of a compatible surfactant and an undercolor dye whose coloring ability is destroyed in the presence of a pH of about 10 or greater; and

(b) an overcolor aqueous paint comprising from about 20% to about 55% of a compatible surfactant;

from about 0.1% to about 20% by weight of a base;

from about 0.1% to about 15% by weight of an overcolor dye that maintains its characteristic color in the presence of a pH of about 10 or greater; and

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

27. A washable coloring composition comprising

(a) from about 20% to about 55% of a compatible surfactant;

(b) from about 0.1% to about 10% by weight of a base;

(c) from about 1% to about 20% by weight of a reducing agent; and

(d) from about 0.1% to about 15% by weight of a colorant which maintains its characteristic color in the presence of both a pH of about 10 or greater and a reducing agent.

28. A washable multiple coloring composition system comprising:

(a) a first undercolor aqueous coloring composition comprising from about 20% to about 55% by weight of a compatible surfactant and an undercolor dye whose coloring ability is destroyed in the presence of a pH of about 10 or greater;

(b) a second undercolor aqueous coloring composition comprising from about 20% to about 55% by weight of a compatible surfactant and an undercolor dye whose coloring ability is destroyed in the presence of a reducing agent; and

(c) an overcolor aqueous coloring composition comprising from about 20% to about 55% by weight of a compatible surfactant, from about 0.1% to about 15% by weight of a colorant capable of maintaining its characteristic color in the presence of a pH of about 10 or greater, an effective amount of a base sufficient to yield a pH of said overcolor aqueous coloring composition of about 10 or greater, and from about 1% to about 20% by weight of a reducing agent.

29. The multiple coloring composition system of claim 28, said base being present in an amount sufficient to yield a pH of said overcolor aqueous coloring composition of from about 10 to about 12.

36. The multiple coloring composition of claim 28, wherein said surfactant is an anionic surfactant selected from the group consisting of diphenyl oxide disulfonate and sodium naphthalene sulfonate.

30. A washable ink composition system comprising:

(a) a first undercolor aqueous ink comprising from about 20% to about 55% by weight of a compatible surfactant and an undercolor dye whose coloring ability is destroyed in the presence of a pH of about 10 or greater in an amount of from about 0.1% to about 15% by weight of the undercolor ink;

(b) a second undercolor aqueous ink comprising from about 20% to about 55% by weight of a compatible surfactant and an undercolor dye whose coloring ability is destroyed in the presence of a reducing agent; and

(c) an overcolor aqueous ink comprising from about 20% to about 55% by weight of a compatible surfactant, from about 1% to about 20% by weight of said overcolor ink of a reducing agent;

from about 0.1% to about 10% by weight of said overcolor ink of a base; and

from about 0.1% to about 15% by weight of said overcolor ink of an overcolor colorant which maintains its characteristic color in the presence of a reducing agent and a pH of about 10 or greater.

31. A washable color changing marking system comprising at least a first undercolor marking instrument and a second undercolor marking instrument and at least one overcolor marking instrument, said first undercolor marking instrument containing a first undercolor ink composition comprising from about 20% to about 55% by weight of a compatible surfactant and a dye whose coloring ability is destroyed in the presence of a pH of about 10 or greater, said second undercolor marking instrument containing a second undercolor ink composition comprising from about 20% to about 55% by weight of a compatible surfactant and comprising an undercolor dye whose coloring ability is destroyed in the presence of a reducing agent, and said overcolor marking instrument containing an overcolor ink, said overcolor ink comprising

(1) from about 20% to about 55% by weight of a compatible surfactant;

(2) from about 0.1% to about 10% by weight of a base; and

(3) from about 0.1% to about 15% by weight of a colorant which maintains its characteristic color in the presence of a pH of about 10 or greater, and from about 1% to about 20% by weight of a reducing agent and wherein said pH of said overcolor ink is about 10 or greater.

37. A washable multiple coloring composition system comprising:

(a) an undercolor aqueous coloring composition comprising a compatible surfactant in an amount sufficient to provide washability to said undercolor aqueous coloring composition and an undercolor dye whose coloring ability is destroyed in the presence of a reducing agent; and

(b) an overcolor aqueous coloring composition comprising a compatible surfactant in an amount sufficient to provide washability to said overcolor aqueous coloring composition, a colorant capable of maintaining its characteristic color in the presence of a reducing agent, and a reducing agent.

38. The multiple coloring composition system of claim 37, wherein said surfactant in said overcolor aqueous coloring composition is present in an amount from about 20% to about 55% by weight.

39. The multiple coloring composition system of claim 37, wherein said surfactant in said undercolor aqueous coloring composition is present in an amount of from about 20% to about 55% by weight.

40. The multiple coloring composition system of claim 37, wherein said surfactant is an anionic surfactant.

41. The multiple coloring composition system of claim 40, wherein said anionic surfactant is selected from the group consisting of diphenyl oxide disulfonate and sodium naphthalene sulfonate.

42. The multiple coloring composition system of claim 37, wherein said overcolor aqueous coloring composition further comprises a base in an amount sufficient to elevate the pH of said overcolor aqueous coloring composition to about 10 or greater.

43. The multiple coloring composition system of claim 42, wherein said base is present in an amount of from about 0.1% to about 20% by weight of said overcolor aqueous coloring composition.

44. The multiple coloring composition system of claim 37, wherein said reducing agent is selected from the group consisting of hydrogen sulfide, sodium sulfite, sodium hypochlorite and hydrogen peroxide.

45. The multiple coloring composition system of claim 37, wherein said reducing agent is present in an amount of from about 1% to about 20%.

46. The multiple coloring composition system of claim 37, wherein said undercolor dye of said undercolor coloring composition is selected from the group consisting of polymethine dyes, triphenylmethane dyes, cyanine dyes, methine dyes, and azo dyes which are unstable in the presence of a of about 10 or greater.

47. The multiple coloring composition system of claim 46, wherein said undercolor dye of said undercolor coloring composition is selected from the group consisting of Basic Blue 69, Basic Red 14, Basic Red 49, Acid Green 3, Acid Violet 19 and mixtures thereof.

48. The multiple coloring composition system of claim 37, wherein said colorant of said overcolor coloring composition is selected from the group consisting of xanthene dyes, phthalocyanine dyes, and azo dyes.

49. The multiple coloring composition system of claim 48, wherein said colorant of said overcolor coloring composition is selected from the group consisting of Acid Red 52, Acid Red 87, Acid Red 92, Acid Red 388, Food Red 14, Acid Green 26, Solvent Green 7, Direct Blue 199, and mixtures thereof.

50. A washable ink composition system comprising:

(a) an undercolor aqueous ink comprising a compatible surfactant in an amount sufficient to provide washability and an undercolor dye whose coloring ability is destroyed in the presence of a reducing agent in an amount of from about 0.1% to about 15% by weight of the undercolor ink; and

(b) an overcolor aqueous ink comprising from about 20% to about 55% by weight of a compatible surfactant; and

from about 0.1% to about 15% by weight of said overcolor ink of an overcolor colorant which maintains its characteristic color in the presence of a reducing agent.

51. A washable color changing marking system comprising at least an undercolor marking instrument and an overcolor marking instrument, said undercolor marking instrument containing from about 20% to about 55% of a compatible surfactant and an undercolor ink composition comprising from about 20% to about 55% of a compatible surfactant and from about 0.1% to about 15% by weight of a colorant which maintains its characteristic color in the presence of a reducing agent.

52. A washable paint composition system comprising:

(a) an undercolor aqueous paint comprising from about 20% to about 55% of a compatible surfactant and an undercolor dye whose coloring ability is destroyed in the presence of a reducing agent; and

(b) an overcolor aqueous paint comprising from about 20% to about 55% of a compatible surfactant;

from about 0.1% to about 15% by weight of an overcolor dye that maintains its characteristic color in the presence of a reducing agent; and

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