Marking system

• US 6,124,377 A
• Filed: 07/01/1998
• Issued: 09/26/2000
• Est. Priority Date: 07/01/1998
• Status: Expired due to Term

• Current Assignee: Crayola LLC (Hallmark Cards Incorporated)
• Original Assignee: Binney & Smith Inc.
• Inventors: Urbanski, Arthur N., Kaiser, Richard J.
• Primary Examiner(s): Jagannathan, Vasu
• Assistant Examiner(s): Shosho, Callie E.
• Application Number:
  US09/108,526
• Time in Patent Office: 818 Days
• Field of Search: 523/161, 106/31.07, 106/31.09, 106/31.13, 106/31.16, 106/31.17, 106/31.18, 106/31.19, 106/31.2, 106/3.21, 106/31.22, 503/201, 503/213, 503/214, 503/217, 503/219, 503/221, 427/151, 428/913, 428/914
• US Class Current: 523/161
• CPC Class Codes: B41M 3/001 using chemical colour-formers or chemical reactions, e.g. leuco dyes or acids
• CPC Class Codes: C08K 5/17 Amines; Quaternary ammonium compounds
• CPC Class Codes: C09D 11/50 Sympathetic, colour changing or similar inks
• CPC Class Codes: C09D 5/00 Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced electrically insulating plastics, resins or waxes H01B3/30; Filling pastes
• CPC Class Codes: C09D 7/41 Organic pigments; Organic dyes

Abstract

A marking system that advantageously minimizes messiness during use is disclosed. The marking system comprises a marking composition comprising at least one color precursor in the form of a leuco dye. A marking instrument can be utilized to store the marking composition and/or apply the marking composition to a desired substrate. The substrate is provided with a coating comprising at least one color-triggering developer. Upon application of the leuco dye to the substrate, a chromophore, and hence, color, is formed. If, however, color is inadvertently triggered on an unintended surface, thereby resulting in an unwanted stain, the stain can be readily removed.

Claims

1. A marking system comprising:

a composition comprising at least one color precursor and at least one additive selected from the group consisiting of surfactants, antioxidants, buffers, and any combination thereof;

a substrate provided with a coating that comprises a color-triggering developer; and

a marking instrument for applying said composition to said substrate to form at least one color mark exhibiting a fabric fugitivity defined in terms of Δ

E, wherein the Δ

E is about 5 or less.

2. The marking system of claim 1, wherein said composition further comprises at least one flame retardant.

3. The marking system of claim 2, wherein the at least one flame retardant is selected from the group consisting of trisnonylphonyl phosphite, brominated chlorinated olefins, and combinations thereof.

4. The marking system of claim 1, wherein said composition comprises at least one antioxidant selected from the group consisting of 3,5-bis (1,1-dimethylethyl)-4-hydroxy benzenepropanoic acid,2,2-bis[[3-[3.5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]-1-oxopropoxy]methyl]1,3-propanediyl ester;

Vitamin E;

Tinuvins;

butylated hydroxytoluene;

butylated hydroxyanisole; and

any combination thereof.

5. The marking system of claim 1, wherein said composition comprises at least one antioxidant, which is present in a concentration of from about 1% to about 30% by weight of said composition.

6. The marking system of claim 1, wherein the buffer is selected from the group consisting of non-water-soluble tertiary amines, and combinations thereof.

7. The marking system of claim 6, wherein the non-water-soluble tertiary amine is selected from the group consisting of tributyl amine, trihexyl amine, tridodecyl amine, tridecyl amine, trioctyl amine, and combinations thereof.

8. The marking system of claim 7, wherein the at least one non-water-soluble tertiary amine is present in a concentration of from about 0.0002% to about 1.5% by weight of said composition.

9. The marking system of claim 8, wherein the at least one non-water-soluble tertiary amine is present in a concentration of from about 0.05% to about 1.5% by weight of said composition.

10. The marking system of claim 1, wherein the color precursor is present in a concentration of from about 0.1% to about 10% by weight of said composition.

11. The marking system of claim 10, wherein the color precursor is present in a concentration of about 0.5% to about 2% by weight of said composition.

12. The marking system of claim 1, wherein the color precursor comprises at least one leuco dye intermediate.

13. The marking system of claim 12, wherein the leuco dye intermediate is not water soluble.

14. The marking system of claim 12, wherein the leuco dye intermediate is selected from the group consisting of diarylphthalide dyes, fluoran dyes, indolyphthalide dyes, acylluecoazine dyes, leucoauramine dyes, spiropyrane dyes, rhodaminelactam dyes, triarylmethane dyes, and chromene dyes, and combinations thereof.

15. The marking system of claim 12, wherein the leuco dye intermediate is selected from the group consisting of Spiro(12H-benzo(a)xanthene-12,1'"'"'(3'"'"'H)isobenzofuran-3'"'"'-one,9-(diethylamino),3-[Butyl-2-methylindol-3-yl]-3-(1-octyl-2-methylindol-3-yl)-1(3H)isobenzofuranone, 2-'"'"'phenylamino-3'"'"'-methyl-6'"'"'-(dibutylamino)spiro[isobenzofuran-1(3H),9'"'"'-(9H)-xanthen]-3-one, substituted Phthalide, COPIKEM®

7Grape, 2'"'"'-Di(phenylmethyl)amino-6'"'"'-(diethylamino)spiro(isobenzofuran-1(3H),9'"'"'(9H)xanthen)-3-one.

16. The marking system of claim 1, wherein the marking composition comprises at least one surfactant having an hydrophilic-lipophilic balance of about 6 or less.

17. The marking composition of claim 1, wherein the marking composition comprises at least one surfactant forming a surfactant blend, wherein the surfactant blend has a hydrophilic-lipophilic balance of from about 3 to about 6.

18. The marking composition of claim 1, wherein the marking composition comprises at least one surfactant selected from the group consisting of acetylinic diol based surfactants, ethoxylated acetylinic diols, dibasic ester microemulsion concentrates including water, and combinations thereof.

19. The marking system of claim 1, wherein the coating further comprises a binder.

20. The marking system of claim 19 wherein the binder is a starch-modified latex.

21. The marking system of claim 19, wherein the coating further comprises a cross-linker for cross-linking the binder.

22. The marking system of claim 21, wherein the cross-linker is selected from the group consisting of zirconium salts, zinc salts, and combinations thereof.

23. The marking system of claim 1, wherein said substrate is formed from a material selected from the group consisting of paper and plastic.

24. The marking system of claim 1, wherein the developer is selected from the group consisting of Lewis acids and combinations thereof.

25. The marking system of claim 24, wherein the Lewis acid is selected from the group consisting of activated clays, phenolic resins, zinc containing resins, and combinations thereof.

26. The marking system of claim 25, wherein the Lewis acid is selected from zinc containing resins and combinations thereof.

27. The marking system of claim 24, wherein the developer comprises a zincated carboxylic resin.

28. The marking system of claim 1, wherein the developer is present in a concentration of at least 12% by weight of the coating.

29. The marking system of claim 1, wherein the developer is dispersed in water.

30. The marking system of claim 1, wherein the coating further comprises a void cell former.

31. The marking system of claim 30, wherein the void cell former comprises calcium carbonate.

32. The marking system of claim 1, wherein the coating is provided in a concentration of at least about 10 grams of dry coating per square meter of substrate surface.

33. The marking system of claim 1, wherein said marking instrument is selected from the group consisting of markers, paintbrushes, pencils, pens, stamps, stamp pads, and crayons.

34. The marking system of claim 1, wherein the substrate further comprises an encapsulated solvent that is capable of being ruptured when said marking instrument applies said composition to said substrate.

35. The marking system of claim 1, wherein the color mark exhibits a fabric fugitivity defined in terms of Δ

E, wherein the Δ

E is about 3 or less.

36. The marking system of claim 1, wherein the marking composition further comprises at least one dye blocker.

37. The marking system of claim 36, wherein the at least one dye blocker is selected from the group consisting of novolac epoxies and tannic acid.

38. The marking composition of claim 36, wherein the at least one dye blocker is present in a concentration of about 0.5% to about 15% by weight of the marking composition.

39. The marking system of claim 1, wherein the coating further comprises at least one plasticizer.

40. The marking system of claim 39, wherein the plasticizer is selected form the group consisting of citrate esters, dibutyl phthalate, and combinations thereof.

41. The marking system of claim 39, wherein the substrate further comprises a microcapsule wherein the at least one plasticizer is incorporated into the microcapsule.

42. The marking system of claim 1, wherein said composition is dissolved in at least one solvent.

43. The marking system of claim 42, wherein the at least one solvent is present in a concentration of from about 30% to about 90% by weight of said composition.

44. The marking system of claim 42, wherein the at least one solvent is selected from the group consisting of dimethyl adipate, diethyl succinate, dibutyl phthalate, chlorinated fluorinated toluenes, and combinations thereof.

45. The marking system of claim 42, wherein said at least one solvent is nonaqueous.

46. The marking system of claim 1, wherein said composition includes at least one antioxidant, wherein said at least one antioxidant comprises 3,5-bis (1,1-dimethylethyl)-4-hydroxy benzenepropanoic acid,2,2-bis[[3-[3.5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]-1-oxopropoxy]methyl]1,3-propanediyl ester.

47. The marking system of claim 1, wherein the composition includes at least one buffer, wherein said at least one buffer comprises trihexyl amine, tridecyl amine, or a combination thereof.

48. The marking system of claim 1, wherein the composition includes at least one surfactant, wherein the at least one surfactant comprises acetylinic diol based surfactants, ethoxylated acetylinic diol based surfactants, or combinations thereof.

49. The marking system of claim 1, wherein the composition comprises at least one surfactant, at least one antioxidant, and at least one buffer.

50. The marking system of claims 49, further comprising a flame retardant.

51. The marking system of claim 49, wherein the at least one antioxidant comprises 3,5-bis (1,1-dimethylethyl)-4-hydroxy benzenepropanoic acid,2,2-bis[[3-[3.5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]-1-oxopropoxy]methyl]1,3-propanediyl ester;

the at least one buffer comprises trihexyl amine, tridecyl amine, or a combination thereof; and

the at least one surfactant comprises acetylinic diol based surfactants, ethoxylated acetylinic diol based surfactants, or combinations thereof.

52. The marking system of claim 1, wherein the at least one antioxidant comprises 3,5-bis (1,1-dimethylethyl)-4-hydroxy benzenepropanoic acid,2,2-bis[[3-[3.5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]-1-oxopropoxy]methyl]1,3-propanediyl ester;

wherein the at least one buffer comprises trihexyl amine, tridecyl amine, or a combination thereof; and

wherein the at least one surfactant comprises acetylinic diol based surfactants, ethoxylated acetylinic diol based surfactants, or combinations thereof.

53. A marking system comprising:

a composition comprising at least one color precursor and at least one additive selected from the group consisting of surfactants, antioxidants, buffers, flame retardants, dye blockers, and combinations thereof;

a substrate provided with a coating that comprises a color-triggering developer; and

a marking instrument for applying said composition to said substrate to form at least one color mark.

54. The marking system of claim 53, wherein the composition includes at least one surfactant, at least one antioxidant, and at least one buffer.

55. The marking system of claims 54, wherein the at least one antioxidant comprises 3,5-bis (1,1-dimethylethyl)-4-hydroxy benzenepropanoic acid,2,2-bis[[3-[3.5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]-1-oxopropoxy]methyl]1,3-propanediyl ester.

56. The marking system of claim 54, wherein the at least one buffer comprises trihexyl amine, tridecyl amine, or a combination thereof.

57. The marking system of claim 54, wherein the at least one surfactant comprises acetylinic diol based surfactants, ethoxylated acetylinic diol based surfactants, or combinations thereof.

58. The marking system of claim 53, wherein the at least one antioxidant comprises 3,5-bis (1,1-dimethylethyl)-4-hydroxy benzenepropanoic acid,2,2-bis[[3-[3.5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]-1-oxopropoxy]methyl]1,3-propanediyl ester;

wherein the at least one buffer comprises trihexyl amine, tridecyl amine, or a combination thereof; and

wherein the at least one surfactant comprises acetylinic diol based surfactants, ethoxylated acetylinic diol based surfactants, or combinations thereof.