Colorless fast-drying ink compositions for printing concealed images detectable by fluorescence

• US 5,286,286 A
• Filed: 07/31/1992
• Issued: 02/15/1994
• Est. Priority Date: 05/16/1991
• Status: Expired due to Term

• Current Assignee: Xerox Corporation (Xerox Holdings Corp.)
• Original Assignee: Xerox Corporation (Xerox Holdings Corp.)
• Inventors: Davidson, Anthony R., Breton, Marcel P., Winnik, Francoise M.
• Primary Examiner(s): Bell, Mark L.
• Assistant Examiner(s): EINSMANN, MARGARET V
• Application Number:
  US07/922,882
• Time in Patent Office: 564 Days
• Field of Search: 106/21 R, 106/21 A, 106/22 B, 106/21, 106/22
• US Class Current: 106/31.15
• CPC Class Codes: B41M 3/144 using fluorescent, luminescent or iridescent effects
• CPC Class Codes: C09D 11/30 Inkjet printing inks
• CPC Class Codes: C09D 11/328 characterised by dyes

Abstract

Disclosed is an ink composition consisting essentially of water, diethylene glycol-monobutyl ether, glycerol, an optional cyclohexyl pyrrolidinone component, a dye selected from the group consisting of dyes containing dansyl chromophores and dyes containing porphyrin chromophores, an optional biocide, and an optional polyalkylene oxide/bisphenol-A additive.

Claims

1. An ink composition consisting essentially of water, diethylene glycol-monobutyl ether, glycerol, an optional cyclohexyl pyrrolidinone component, a dye selected from the group consisting of dyes containing dansyl chromophores and dyes containing porphyrin chromophores, an optional biocide, and an optional polyalkylene oxide additive.

2. An ink composition according to claim 1 wherein diethylene glycol-monobutyl ether is present in an amount of from about 4 to about 15 percent by weight, glycerol is present in an amount of from about 2 to about 12 percent by weight, cyclohexyl pyrrolidinone is present in an amount of from 0 to about 10 percent by weight, and the dye is present in an amount of from about 0.01 to about 4 percent by weight.

3. An ink composition according to claim 1 wherein water is present in an amount of from about 65 to about 90 percent by weight, diethylene glycol-monobutyl ether is present in an amount of from about 6 to about 12 percent by weight, glycerol is present in an amount of from about 2 to about 8 percent by weight, cyclohexyl pyrrolidinone is present in an amount of from about 1 to about 5 percent by weight, and the dye is present in an amount of from about 0.01 to about 2 percent by weight.

4. An ink composition according to claim 1 wherein the polyalkylene oxide additive is of the formula ##STR3## wherein R¹ and R² are independently selected from the group consisting of hydrogen, alkyl groups with from 1 to about 8 carbon atoms, and alkoxy groups with from 1 to about 8 carbon atoms, R³ and R⁴ are independently selected from the group consisting of alkyl groups with from 1 to about 4 carbon atoms, and x and y are each independently a number of from about 100 to about 400.

5. An ink composition according to claim 1 wherein the ink has a viscosity of from about 1.05 to about 10 centipoise at 25°

C.

6. An ink composition according to claim 1 wherein the ink has a surface tension of from about 28 to about 35 dynes per centimeter.

7. An ink composition according to claim 1 wherein the ink exhibits a drying time of less than about 1 second on plain paper.

8. An ink composition according to claim 1 wherein the dye is selected from the group consisting of 5,10,15,20-tetrakis-(1-methyl-4-pyridyl)-21H,23H-porphine tetra-p-tosylate salt;

5,10,15,20-tetrakis-(1-methyl-4-pyridyl)-21H,23H-porphine tetrachloride salt;

5,10,15,20-tetrakis-(1-methyl-4-pyridyl)-21H,23H-porphine tetrabromide salt;

5,10,15,20-tetrakis-(1-methyl-4-pyridyl)-21H,23H-porphine tetra-acetate salt;

5,10,15,20-tetrakis-(1-methyl-4-pyridyl)-21H,23H-porphine tetra-perchlorate salt;

5,10,15,20-tetrakis-(1-methyl-4-pyridyl)-21H,23H-porphine tetrafluoroborate salt;

5,10,15,20-tetrakis-(1-methyl-4-pyridyl)-21H,23H-porphine tetra-perchlorate salt;

5,10,15,20-tetrakis-(1-methyl-4-pyridyl)-21H,23H-porphine tetra-triflate salt;

5,10,15,20-tetrakis-(1-hydroxymethyl-4-pyridyl)-21H,23H-porphine tetra-p-tosylate salt;

5,10,15,20-tetrakis-[1-(2-hydroxyethyl)-4-pyridyl]-21H,23H-porphine tetrachloride salt;

5,10,15,20-tetrakis-[1-(3-hydroxypropyl)-4-pyridyl]-21H,23H-porphine tetra-p-tosylate salt;

5,10,15,20-tetrakis-[1-(2-hydroxypropyl)-4-pyridyl]-21H,23H-porphine tetra-p-tosylate salt;

5,10,15,20-tetrakis-[1-(2-hydroxyethoxyethyl)-4-pyridyl]-21H,23H-porphine tetra-p-tosylate salt;

5,10,15,20-tetrakis-[1-(2-hydroxyethoxypropyl)-4-pyridyl]-21H,23H-porphine tetra-p-tosylate salt;

5,10,15,20-tetrakis-[4-(trimethylammonio)phenyl]-21H,23H-porphine tetra-p-tosylate salt;

5,10,15,20-tetrakis-[4-(trimethylammonio)phenyl]-21H,23H-porphine tetrachloride salt;

5,10,15,20-tetrakis-[4-(trimethylammonio)phenyl]-21H,23H-porphine tetrabromide salt;

5,10,15,20-tetrakis-[4-(trimethylammonio)phenyl]-21H,23H-porphine tetra-acetate salt;

5,10,15,20-tetrakis-[4-(trimethylammonio)phenyl]-21H,23H-porphine tetra-perchlorate salt;

5,10,15,20-tetrakis-[4-(trimethylammonio)phenyl]-21H,23H-porphine tetrafluoroborate salt;

5,10,15,20-tetrakis-[4-(trimethylammonio)phenyl]-21H,23H-porphine tetra-triflate salt;

meso-(N-methyl-X-pyridinium)_n -(phenyl)4-n-21H,23H-porphine tetra-p-tosylate salt, where n is an integer of value 0, 1, 2, or 3, and where X=4-(para), 3-(meta), or 2-(ortho) and refers to the position of the nitrogen in the pyridinium substituent;

meso-tetrakis-[o-(N-methylnicotinamido)phenyl]-21H,23H-porphine tetra-methyl sulfonate salt;

5,10,15,20-tetrakis-(2-sulfonatoethyl-4-pyridyl)-21H,23H-porphine chloride salt;

5,10,15,20-tetrakis-(carboxymethyl-4-pyridyl)-21H,23H-porphine chloride salt;

5,10,15,20-tetrakis-(carboxyethyl-4-pyridyl)-21H,23H-porphine chloride salt;

5,10,15,20-tetrakis-(carboxyethyl-4-pyridyl)-21H,23H-porphine bromide salt;

5,10,15,20-tetrakis-(carboxylate-4-pyridyl)-21H,23H-porphine bromide salt;

2,3,7,8,12,13,17,18-octa-(2-hydroxyethyl)-21H-23H-porphine;

2,3,7,8,12,13,17,18-octa-(2-hydroxyethoxyethyl)-21H-23H-porphine;

2,3,7,8,12,13,17,18-octa-(2-aminoethyl)-21H-23H-porphine;

2,3,7,8,12,13,17,18-octa-(2-hydroxyethoxypropyl)-21H-23H-porphine; and

mixtures thereof.

9. An ink composition according to claim 1 wherein the dye is selected from the group consisting of dansyl-L-alanine;

Dansyl-L-α

-amino-n-butyric acid;

α

-dansyl-L-arginine;

dansyl-L-asparagine;

dansyl-L-aspartic acid;

dansyl-L-cysteic acid;

N,N'"'"'-didansyl-L-cystine;

dansyl-L-glutamic acid;

dansyl-L-glutamine;

N-dansyl-trans-4-hydroxy-L-proline;

dansyl-L-isoleucine;

dansyl-L-leucine;

di-dansyl-L-lysine;

N-ε

-dansyl-L-lysine;

dansyl-L-methionine;

dansyl-L-norvaline;

dansyl-L-phenylalanine;

dansyl-L-proline;

N-dansyl-L-serine;

N-dansyl-L-threonine;

Nα

-dansyl-L-tryptophan;

N,O-di-dansyl-L-tyrosine monocyclohexylammonium salt;

dansyl-L-valine;

dansyl-γ

-amino-n-butyric acid;

dansyl-DL-α

-amino-n-butyric acid;

dansyl-DL-aspartic acid;

dansyl-DL-glutamic acid;

dansylglycine;

dansyl-DL-leucine;

dansyl-DL-methionine;

dansyl-DL-norleucine;

dansyl-DL-norvaline;

dansyl-DL-phenylalanine;

dansylsarcosine;

N-dansyl-DL-serine;

N-dansyl-DL-threonine;

Nα

-dansyl-DL-tryptophan;

dansyl-DL-valine;

dansyl-DL-α

-aminocaprylic acid cyclohexylamine salt;

(dansylaminoethyl)-trimethylammonium perchlorate;

didansylcadaverine;

monodansylcadaverine;

dansylputrescine;

dansylspermidine;

didansyl-1,4-diamino-butane;

didansyl-1,3-diamino-propane;

didansylhistamine; and

mixtures thereof.

10. A process which comprises incorporating into an ink jet printer an ink composition consisting essentially of water, diethylene glycol-monobutyl ether, glycerol, an optional cyclohexyl pyrrolidinone component, a dye selected from the group consisting of dyes containing dansyl chromophores and dyes containing porphyrin chromophores, an optional biocide, and an optional polyalkylene oxide additive, and causing droplets of the ink composition to be ejected in an imagewise pattern onto a substrate.

11. A process according to claim 10 wherein diethylene glycol-monobutyl ether is present in an amount of from about 4 to about 15 percent by weight, glycerol is present in an amount of from about 2 to about 12 percent by weight, cyclohexyl pyrrolidinone is present in an amount of from 0 to about 10 percent by weight, and the dye is present in an amount of from about 0.01 to about 4 percent by weight.

12. A process according to claim 10 wherein water is present in an amount of from about 65 to about 90 percent by weight, diethylene glycol-monobutyl ether is present in an amount of from about 6 to about 12 percent by weight, glycerol is present in an amount of from about 2 to about 8 percent by weight, cyclohexyl pyrrolidinone is present in an amount of from about 1 to about 5 percent by weight, and the dye is present in an amount of from about 0.01 to about 2 percent by weight.

13. A process according to claim 10 wherein the polyalkylene oxide additive is of the formula ##STR4## wherein R¹ and R² are independently selected from the group consisting of hydrogen, alkyl groups with from 1 to about 8 carbon atoms, and alkoxy groups with from 1 to about 8 carbon atoms, R³ and R⁴ are independently selected from the group consisting of alkyl groups with from 1 to about 4 carbon atoms, and x and y are each independently a number of from about 100 to about 400.

14. A process according to claim 10 wherein the ink has a viscosity of from about 1.05 to about 10 centipoise at 25°

C.

15. A process according to claim 10 wherein the ink has a surface tension of from about 28 to about 35 dynes per centimeter.

16. A process according to claim 10 wherein the ink exhibits a drying time of less than about 1 second on plain paper.

17. A process according to claim 10 wherein the dye is selected from the group consisting of 5,10,15,20-tetrakis-(1-methyl-4-pyridyl)-21H,23H-porphine tetra-p-tosylate salt;

5,10,15,20-tetrakis-(1-methyl-4-pyridyl)-21H,23H-porphine tetrachloride salt;

5,10,15,20-tetrakis-(1-methyl-4-pyridyl)-21H,23H-porphine tetrabromide salt;

5,10,15,20-tetrakis-(1-methyl-4-pyridyl)-21H,23H-porphine tetra-acetate salt;

5,10,15,20-tetrakis-(1-methyl-4-pyridyl)-21H,23H-porphine tetra-perchlorate salt;

5,10,15,20-tetrakis-(1-methyl-4-pyridyl)-21H,23H-porphine tetrafluoroborate salt;

5,10,15,20-tetrakis-(1-methyl-4-pyridyl)-21H,23H-porphine tetra-perchlorate salt;

5,10,15,20-tetrakis-(1-methyl-4-pyridyl)-21H,23H-porphine tetra-triflate salt;

5,10,15,20-tetrakis-(1-hydroxymethyl-4-pyridyl)-21H,23H-porphine tetra-p-tosylate salt;

5,10,15,20-tetrakis-[1-(2-hydroxyethyl)-4-pyridyl]-21H,23H-porphine tetrachloride salt;

5,10,15,20-tetrakis-[1-(3-hydroxypropyl)-4-pyridyl]-21H,23H-porphine tetra-p-tosylate salt;

5,10,15,20-tetrakis-[1-(2-hydroxypropyl)-4-pyridyl]-21H,23H-porphine tetra-p-tosylate salt;

5,10,15,20-tetrakis-[1-(2-hydroxyethoxyethyl)-4-pyridyl]-21H,23H-porphine tetra-p-tosylate salt;

5,10,15,20-tetrakis-[1-(2-hydroxyethoxypropyl)-4-pyridyl]-21H,23H-porphine tetra-p-tosylate salt;

5,10,15,20-tetrakis-[4-(trimethylammonio)phenyl]-21H,23H-porphine tetra-p-tosylate salt;

5,10,15,20-tetrakis-[4-(trimethylammonio)phenyl]-21H,23H-porphine tetrachloride salt;

5,10,15,20-tetrakis-[4-(trimethylammonio)phenyl]-21H,23H-porphine tetrabromide salt;

5,10,15,20-tetrakis-[4-(trimethylammonio)phenyl]-21H,23H-porphine tetra-acetate salt;

5,10,15,20-tetrakis-[4-(trimethylammonio)phenyl]-21H,23H-porphine tetra-perchlorate salt;

5,10,15,20-tetrakis-[4-(trimethylammonio)phenyl]-21H,23H-porphine tetrafluoroborate salt;

5,10,15,20-tetrakis-[4-(trimethylammonio)phenyl]-21H,23H-porphine tetra-triflate salt;

meso-(N-methyl-X-pyridinium)_n -(phenyl)4-n-21H,23H-porphine tetra-p-tosylate salt, where n is an integer of value 0, 1, 2, or 3, and where X=4-(para), 3-(meta), or 2-(ortho) and refers to the position of the nitrogen in the pyridinium substituent;

meso-tetrakis-[o-(N-methylnicotinamido)phenyl]-21H,23H-porphine tetra-methyl sulfonate salt;

5,10,15,20-tetrakis-(2-sulfonatoethyl-4-pyridyl)-21H,23H-porphine chloride salt;

5,10,15,20-tetrakis-(carboxymethyl-4-pyridyl)-21H,23H-porphine chloride salt;

5,10,15,20-tetrakis-(carboxyethyl-4-pyridyl)-21H,23H-porphine chloride salt;

5,10,15,20-tetrakis-(carboxyethyl-4-pyridyl)-21H,23H-porphine bromide salt;

5,10,15,20-tetrakis-(carboxylate-4-pyridyl)-21H,23H-porphine bromide salt;

2,3,7,8,12,13,17,18-octa-(2-hydroxyethyl)-21H-23H-porphine;

2,3,7,8,12,13,17,18-octa-(2-hydroxyethoxyethyl)-21H-23H-porphine;

2,3,7,8,12,13,17,18-octa-(2-aminoethyl)-21H-23H-porphine;

2,3,7,8,12,13,17,18-octa-(2-hydroxyethoxypropyl)-21H-23H-porphine; and

mixtures thereof.

18. A process according to claim 10 wherein the dye is selected from the group consisting of dansyl-L-alanine;

Dansyl-L-α

-amino-n-butyric acid;

α

-dansyl-L-arginine;

dansyl-L-asparagine;

dansyl-L-aspartic acid;

dansyl-L-cysteic acid;

N,N'"'"'-di-dansyl-L-cystine;

dansyl-L-glutamic acid;

dansyl-L-glutamine;

N-dansyl-trans-4-hydroxy-L-proline;

dansyl-L-isoleucine;

dansyl-L-leucine;

di-dansyl-L-lysine;

N-ε

-dansyl-L-lysine;

dansyl-L-methionine;

dansyl-L-norvaline;

dansyl-L-phenylalanine;

dansyl-L-proline;

N-dansyl-L-serine;

N-dansyl-L-threonine;

Nα

-dansyl-L-tryptophan;

N,O-di-dansyl-L-tyrosine monocyclohexylammonium salt;

dansyl-L-valine;

dansyl-γ

-amino-n-butyric acid;

dansyl-DL-α

-amino-n-butyric acid;

dansyl-DL-aspartic acid;

dansyl-DL-glutamic acid;

dansylglycine;

dansyl-DL-leucine;

dansyl-DL-methionine;

dansyl-DL-norleucine;

dansyl-DL-norvaline;

dansyl-DL-phenylalanine;

dansylsarcosine;

N-dansyl-DL-serine;

N-dansyl-DL-threonine;

Nα

-dansyl-DL-tryptophan;

dansyl-DL-valine;

dansyl-DL-α

-aminocaprylic acid cyclohexylamine salt;

(dansylaminoethyl)-trimethylammonium perchlorate;

didansylcadaverine;

monodansylcadaverine;

dansyl-putrescine;

dansylspermidine;

didansyl-1,4-diamino-butane;

didansyl-1,3-diamino-propane;

didansylhistamine; and

mixtures thereof.