Washable ink compositions

• US 5,043,013 A
• Filed: 08/15/1989
• Issued: 08/27/1991
• Est. Priority Date: 12/30/1987
• Status: Expired due to Term

• Current Assignee: Milliken Research Corporation
• Original Assignee: Milliken Research Corporation
• Inventors: Moore, Patrick D., Wagner, Judy A., Kluger, Edward W.
• Primary Examiner(s): Dixon, Jr., William R.
• Assistant Examiner(s): Kelmanski, Helene
• Application Number:
  US07/394,346
• Time in Patent Office: 742 Days
• Field of Search: 106/20, 106/22
• US Class Current: 106/31.32
• CPC Class Codes: C09B 69/00 Dyes not provided for by a single group of this subclass
• CPC Class Codes: C09D 11/17 characterised by colouring agents

Abstract

A washable aqueous ink composition having a viscosity of from about 1.0 to about 6.0 centipoises and containing from about 10 to about 50% by weight of one or more polymeric colorants of the formula: ##STR1## wherein: X is a polar group such as sulfonic acids, sulfonic acid salts, sulfonamides, sulfonates or the like;

R is alkylene; Y is H, alkanoyl, carbamoyl, or the like;

R₁ is nitrogen, oxygen, sulfur, or a sulfur-containing divalent linking group;

a is an integer of from six to about forty;

b and c are each independently selected from one or two;

d is an integer of from one to four; the product of (a) (b) (c) is an integer of from 6 to about 40;

and CHROM is a chromophore such as nitro, nitroso, monoaxo, disazo and trisazo, diarylmethane, triarylmethane, xanthane, acridine, methine, thiazole, indamine, azine, oxazine, or anthraquinone, wherein the (RO)_a moiety is bonded to a carbocyclic aromatic ring of the (CHROM) through R₁.

Claims

1. A washable, aqueous ink composition for a color marking pen which comprises an ink composition having a viscosity of from about 1.0 to about 6.0 centipoises and from about 10% to about 50% by weight of one or more polymeric colorants of the formula:

space="preserve" listing-type="equation">[(X).sub.d --(CHROM)--{[R.sub.1 (RO).sub.a Y].sub.b }.sub.c ]X.sub.d --(CHROM)--{R.sub.1 [(RO).sub.a --Y].sub.b }.sub.c

wherein;

X is a polar group selected from sulfonic acids, sulfonic acid salts, sulfonamides, sulfonates, carboxylic acids, carboxylic acid salts, carboxylic acid amides, carboxylic aldehydes, ureas, thioureas, nitro groups, hydroxy groups, polyethers, and hydroxyalkylethers;

R is unsubstituted or substituted straight or branched alkylene of 2-4 carbons, or mixtures thereof;

Y is selected from H, alkanoyl, aroyl, alkoxycarbonyl, unsubstituted or substituted carbamoyl, diacetate, methyl or --CH₂ CH(R₂)--X;

R₁ is selected from nitrogen, oxygen, sulfur, or a sulfurcontaining divalent linking group;

R₂ is hydrogen or a lower alkyl group containing one to about five carbon atoms;

a is an integer of from 6 to about 40;

b and c are each independently selected from one or two;

d is an integer of from one to four;

the product of (a) (b) (c) is an integer of from 6 to about 40;

and CHROM is a chromophore selected from nitro, nitroso, monoazo, disazo and trisazo, diarylmethane, triarylmethane, xanthane, acridine, methine, thiazole, indamine, azine, oxazine, or anthraquinone, wherein the (RO)_a moiety is bonded to a carbocyclic aromatic ring of the (CHROM) through R₁.

2. The composition as defined in claim 1 of the formula:

##STR18## wherein R₃, R₄ or R₅ are selected from hydrogen, lower alkyl, lower alkoxy, halogen, trifluoroalkyl, SO₃ Z, SO₂ N(R₆)R₇, and CON(R₆)R₇ ;

R₆ and R₇ are hydrogen, or alkyl;

Z is hydrogen or a cation selected from sodium, potassium, or ammonium, and (a) is an integer of from about 5 to about 15.

3. The composition as defined in claim 1 of the formula:

##STR19## wherein R₈ is selected from H, lower alkyl, lower alkoxy, halogen, or trifluoroalkyl;

R₉ is selected from alkyl, alkoxy, or halogen, and f is zero or one;

Z is H or a cation selected from Na, K, or ammonium; and

(a) is an integer of from about 3 to about 10.

4. The composition as defined in claim 1 of the formula:

##STR20## wherein R₃, R₄ and R₅ are selected from H. lower alkyl, lower alkoxy, halogen, trifluoroalkyl, SO₃ Z, SO₂ N(R₆)R₇, CON(R₆ )R₇ wherein R₆ and R₇ are H or alkyl, and Z is H or a cation selected from Na, K, or ammonium;

R₁₀ and R₁₁ are selected from hydroxyalkoxy, hydroxypolyalkyleneoxy, alkoxyalkylene, alkoxypolyalkyleneoxy or alkyl; and

(a) in an integer of from about 10 to about 20.

5. The composition as defined in claim 1 of the formula:

##STR21## wherein R₃, R₄ and R₅ are selected from H, lower alkyl, lower alkoxy, halogen, trifluoroalkyl, SO₃ Z, SO₂ N(R₆)R₇, CON(R₆)R₇ wherein R₆ and R₇ are H or alkyl, and Z is H or a cation selected from Na, K or ammonium;

g is an integer equal to one or two, and (a) is an integer of from about 5 to about 10.

6. The composition as defined in claim 1 of the formula:

##STR22## wherein R₃, R₄ and R₅ are selected from H, lower alkyl, lower alkoxy, halogen, trifluoroalkyl, SO₃ Z, SO₂ N(R₆)R₇, CON(R₆)R₇ wherein R₆ and R₇ are H or alkyl, and Z is H or a cation selected from Na, K, or ammonium;

R₁₂ is an alkylene group containing from one to about five carbons, and (a) is an integer of from about 5 to about 10.

7. The composition as defined in claim 1 of the formula:

##STR23## wherein R₃ is selected from H, lower alkyl, lower alkoxy, halogen, trifluoroalkyl, SO₃ Z, SO₂ N(R₆)R₇, CON(R₆)R₇ wherein R₆ and R₇ are H or alkyl, and Z is H or a cation selected from Na, K, or ammonium; and

R₁₃ is cyano, R₁₄ NHCO, or COOZ, and R₁₄ is selected from hydrogen, lower alkyl containing one to five carbons, hydroxyalkylene, hydroxyl-polyalkyleneoxy, alkoxyalkylene, or alkoxypolyalkyleneoxy.

8. The composition as defined in claim 1 wherein CHROM is:

##STR24## wherein R₁₅ is COOZ;

R₃ and R₄ are selected from H, lower alkyl, lower alkoxy, halogen, trifluoroalkyl, SO₃ Z, SO₂ N(R₆)R₇, CON(R₆)R₇ wherein R₆ and R₇ are H or alkyl, and Z is H or a cation selected from Na, K, or ammonium; and

(a) is an integer of from about 5 to about 10.

9. The composition as defined in claim 1 of the formula:

##STR25## wherein Z is H or a cation selected from Na, K, or ammonium;

(a) is an integer of from about 5 to about 10. and R₁₆ is H or OH.

10. The washable ink composition of claim 1 wherein the polymeric colorant containing a polar chromophore has incorporated therein from about 40 percent to about 85 percent by weight of poly(alkylene oxide).

11. The washable ink composition of claim 1 wherein the polymeric colorant in the ink composition has incorporated therein from about 5 percent by weight to about 40 percent by weight of poly(alkylene oxide) units.

12. The washable ink composition of claim 1 wherein the poly(alkylene oxide) is derived from ethylene oxide.

13. The washable, aqueous ink composition for a color pen of claim 1 which comprises nib, felt, wick, and recording type markers.

14. The washable ink composition of claim 1 containing from about 5 percent to about 20 percent by weight of humectant.

15. The washable ink composition of claim 1 containing from about 0.02 percent to about 0.5 percent by weight of biocide.

16. The washable ink composition of claim 1 containing from about 0.1 percent to about 0.5 percent by weight of chelating agent.

17. The washable ink composition of claim 1 wherein the pH is maintained from 6.0 to about 7.5.

18. The washable ink composition of claim 1 wherein the residual colorant fabric staining is rated at a numerical value of zero to ten delta E*ab units.

19. The washable ink composition of claim 1 wherein the residual colorant skin staining is rated at zero to about 1.5 units.

20. The washable ink composition of claim 1 wherein Y is selected from H, diacetate and methyl.