Method for making article with and detecting water based inks containing near infrared fluorophores

• US 5,665,151 A
• Filed: 11/18/1996
• Issued: 09/09/1997
• Est. Priority Date: 10/23/1995
• Status: Expired due to Term

• Current Assignee: Authentix, Inc.
• Original Assignee: Eastman Chemical Company
• Inventors: Krutak, James John Sr., Escano, Nelson Zamora
• Primary Examiner(s): Acquah, Samuel A.
• Application Number:
  US08/751,629
• Time in Patent Office: 295 Days
• Field of Search: 528/275, 528/281, 528/282, 528/283, 528/288, 528/289, 528/290, 528/291, 528/292, 528/295, 528/298, 528/302, 528/303, 528/308, 524/602, 524/603, 524/604, 524/606, 524/608, 106/21 R, 106/21 A, 106/21 D, 106/22 R, 106/23 D, 428/395, 252/301.16
• US Class Current: 106/31.15
• CPC Class Codes: C08G 63/6856 Dicarboxylic acids and dihydroxy compounds
• CPC Class Codes: C08G 63/6886 Dicarboxylic acids and dihydroxy compounds
• CPC Class Codes: C09D 11/104 Polyesters
• CPC Class Codes: C09D 11/30 Inkjet printing inks
• CPC Class Codes: C09D 11/50 Sympathetic, colour changing or similar inks
• CPC Class Codes: Y10T 428/2969 Polyamide, polyimide or polyester

Abstract

The present invention provides inks which contain a near infrared fluorophoric compound incorporated into a water-dissipatible polyester backbone. The inks of the present invention are preferably colorless or "invisible" but could be made slightly colored if desirable. Specifically, the inks of the present invention comprise:

A. between about 1 and 10 weight percent of at least one water-dissipatable polyester having from about 0.1 ppm by weight to about 10% by weight of a thermally stable near infrared fluorophoric compound copolymerized therein;

B. between about 5 and 75 weight percent of at least aliphatic humectant;

C. between about 0 and 15 weight percent of at least one lower aliphatic alcohol of no more than 3 carbon atoms;

D. water and optionally up to about 2 weight percent of one or more additives;

wherein the weight percentages of components A-D equal 100%.

Claims

1. A method for invisibly marking, for identification purposes, an article with a water-dispersible polymer, wherein said polymer has from about 0.1 to about 10.0 ppm of a residue of a near infrared flourescing compound copolymerized therein, which comprises applying to said article a composition comprising

A. between about 1 and 10 weight percent of at least one water-dissipatable polyester comprising:

(i) monomer residues of at least one dicarboxylic acid;

(ii) about 4 to 25 mole percent, based on the total of all acid, hydroxy and amino equivalents, of monomer residues of at least one difunctional sulfomonomer containing at least one sulfonate group bonded to an aromatic ring where the functional groups are selected from the group consisting of hydroxy, carboxyl, carboxylate ester and amino;

(iii) monomer residues of at least one diol or a mixture of diol and a diamine; and

optionally,

(iv) monomer residues of at least one difunctional monomer reactant selected from the group consisting of hydroxycarboxylic acids, amino carboxylic acids and aminoalkanols;

provided that at least 20 percent of the groups linking the monomeric units are ester linkages;

said water-dissipatable polyester having from about 0.1 ppm by weight to about 10% by weight of a thermally stable near infrared fluorophoric compound copolymerized therein;

B. between about 5 and 75 weight percent of at least one humectant;

C. between about 0 and 15 weight percent of at least one lower aliphatic alcohol of no more than 3 carbon atoms;

D. water and optionally up to about 2 weight percent of one or more additives;

wherein the weight percentages of components A-D equal 100%.

2. The method of claim 1 wherein said water-dissipatable polyester is a sulfopolyester and wherein the diol of component (iii), based upon 100 mole % diol comprises

(a) at least 15 mole percent of a diol having the formula H(OCH₂ CH₂)_n OH, where n is 2 to about 20, or

(b) about 0.1 to less than about 15 mole percent of a poly(ethylene glycol) having the formula H(OCH₂ CH₂)_n OH, where n is 2 to about 500, provided that the mole percent of said poly(ethylene glycol) is inversely proportional to the value of n.

3. The method of claim 1 comprising:

A. said water dissipatible polyester;

B. between about 45 and 75 weight percent of said humectant;

C. between about 2 and about 15 weight percent of said lower aliphatic alcohol;

D. water;

between about 0.01 and about 0.50 weight percent of at least one corrosion inhibitor; and

between about 0.01 and about 0.30 weight percent of at least one biocide.

4. The method of claim 1 further comprising

A. said water-dissipatable polyester;

B. between about 20 and about 60 weight percent of said humectant;

C. between about 0.50 and about 1.5 weight percent of at least one surface active agent;

D. water;

between about 0.01 and about 0.5 weight percent of at least one corrosion inhibitor;

between about 0.01 and about 0.3 weight percent of at least one biocide.

5. The method composition of claim 1 comprising

A. said water-dissipatable polyester;

B. between about 4 and about 8 weight percent of said humectant;

C. between about 0.35 and about 0.65 weight percent of at least one surface active agents;

D. water;

between about 0.75 and about 1.25 weight percent of at least one defoaming agent;

between about 0.01 and about 0.50 weight percent of at least one corrosion inhibitor;

between about 0.01 and about 0.3 weight percent of at least one biocide.

6. The method of claim 1 comprising

A. said water-dissipatable polyester;

B. between about 30 and about 50 weight percent of said at least one humectant;

C. between about 5 and about 15 weight percent of said at least one alcohol;

D. water;

between about 0.01 and about 0.50 weight percent of at least one corrosion inhibitor;

between about 0.01 and about 0.30 weight percent of at least one biocide.

7. The method of claim 1, wherein the near infrared flourescing compound is selected from the group consisting of phthalocyanines, 2,3-naphthalocyanines and squaraines and correspond to Formulae II, III and IV:

##STR24## wherein Pc and Nc represent the phthalocyanine and 2,3-naphthalocyanine moieties of Formulae IIa and IIIa, ##STR25## respectively, covalently bonded to a moiety selected from the group consisting of hydrogen, and metals, halometals, organometallic groups, and oxymetals selected from a group consisting of AlCl, AlBr, AlF, AlOH, AlOR₅, AlSR₅, Ca, CrF, Fe, Ge, GaCl, GaBr, GaF, GaOR₅, GaSr₅, InCl, Mg, Mn, SiCl₂, SiF₂, SnCl₂, Sn(OR₆)₂, Si(OR₆)₂, Sn(SR₆)₂, Si(SR₆)₂, Sn and Zn,

wherein R₅ and R₆ are selected from the group consisting of hydrogen, alkyl, aryl, aroyl, heteroaryl, lower alkanoyl, trifluoroacetyl and groups of the formulae ##STR26## R₇, R₈ and R₉ are independently selected from the group consisting of alkyl, phenyl or phenyl substituted with lower alkyl, lower alkoxy or halogen;

X is selected from the group consisting of oxygen, sulfur, selenium, tellurium and a group of the formula --N--R₁₀, wherein R₁₀ is hydrogen, cycloalkyl, alkyl, acyl alkyl-sulfonyl, or aryl or R₁₀ and R taken together form an aliphatic or aromatic ring with the nitrogen atom to which they are attached;

Y is selected from the group consisting of alkyl, aryl, halogen or hydrogen;

R is selected from the group consisting of unsubstituted or substituted alkyl, alkenyl, alkynyl, C₃ -C₈ cycloalkyl, aryl, heteroaryl, ##STR27## or --(X--R)_m is selected from the group consisting of alkylsulfonylamino, arylsulfonylamino, or a group selected from the formulae --X(C₂ H₄ O)_z R¹, ##STR28## wherein R¹ is hydrogen or R as defined above;

Z is an integer of from 1-4;

or two --(X--R)_m groups can be taken together to form divalent substituents of the formula ##STR29## wherein each X¹ is independently selected from the group consisting of --O--, --S--, or --N--R₁₀ and A is selected from the group consisting of ethylene;

propylene;

trimethylene; and

said groups constituted with C₁ -C₄ alkyl, C₁ -C₄ alkoxy, aryl and cycloalkyl;

1,2-phenylene and 1,2-phenylene containing 1-3 substituents selected from the group consisting of C₁ -C₄ alkyl, C₁ -C₄ alkoxy and halogen;

R₁ and R₂ are independently selected from the group consisting of hydrogen, lower alkyl, lower alkoxy, halogen, aryloxy, lower alkylthio, arylthio, lower alkylsulfonyl;

arylsulfonyl;

lower alkylsulfonylamino, arylsulfonylamino, cycloalkylsulfonylamino, carboxy, unsubstituted and substituted carbamoyl and sulfamoyl, lower alkoxycarbonyl, hydroxy, lower alkanoyloxy, ##STR30## R₃ and R₄ are independently selected from the group consisting of hydrogen, lower alkyl, alkenyl or aryl;

n is an integer from 0-12;

n₁ is an integer from 0-24, m is an integer from 4-16;

m₁ is an integer from 0-16;

provided that the sums of n+m and n₁ +m₁ are 16 and 24, respectively, provided that at least one polyester reactive group is present.

8. The method of claim 7, wherein the near infrared fluorescing compound is a squaraine compound of Formula IV, wherein R₁ and R₂ are independently carboxy or lower alkoxycarbonyl.

9. The method of claim 7, wherein the near infrared fluorescing compound is a 2,3-naphthalocyanine compound of Formula III, wherein Y is hydrogen, n₁ is 24, and m₁ is 0.

10. The method of claim 7, wherein the near infrared fluorescing compound is a 2,3-naphthalocyanine compound of Formula III, wherein the naphthalocyanine moiety is bonded to SiCl₂, Si(OH)₂, or Si(OR₆)₂.

11. The method of claim 7, wherein the near infrared fluorescing compound is a phthalocyanine compound of Formula II, wherein X is oxygen, R is aryl, Y is hydrogen, m is 4, and n is 12;

and wherein the phthalocyanine moiety is bonded to a moeity selected from the group consisting of AlCl, AlOH, AlOCOCF₃, AlOR₅, SiCl₂, Si(OH)₂, and Si(OR₆)₂.

12. The method of claim 7 wherein said near infrared fluorescing compound is covalently bonded to a moeity selected from the group consisting of hydrogen, and metals, halometals, organometallic groups, and oxymetals selected from a group consisting of AlCl, AlBr, AlF, AlOH, AlOR₅, AlSR₅, GaCl, GaBr, GaF, GaOR₅, GaSr₅, Mg, SiCl₂, SiF₂, SnCl₂, Sn(OR₆)₂, Si(OR₆)₂, Sn(SR₆)₂, Si(SR₆)₂, Sn and Zn.

13. A method for detecting an invisible mark on an article comprising the steps of exposing said marked article to infrared radiation sufficient to cause said mark to fluoresce and detecting said fluorescence, wherein said mark is formed from an ink comprising

A. between about 1 and 10 weight percent of at least one water-dissipatable polyester comprising:

(i) monomer residues of at least one dicarboxylic acid;

(ii) about 4 to 25 mole percent, based on the total of all acid, hydroxy and amino equivalents, of monomer residues of at least one difunctional sulfomonomer containing at least one sulfonate group bonded to an aromatic ring where the functional groups are selected from the group consisting of hydroxy, carboxyl, carboxylate ester and amino;

(iii) monomer residues of at least one diol or a mixture of diol and a diamine; and

optionally,

(iv) monomer residues of at least one difunctional monomer reactant selected from the group consisting of hydroxycarboxylic acids, amino carboxylic acids and aminoalkanols;

provided that at least 20 percent of the groups linking the monomeric units are ester linkages;

said water-dissipatable polyester having from about 0.1 ppm by weight to about 10% by weight of a thermally stable near infrared fluorophoric compound copolymerized therein;

B. between about 5 and 75 weight percent of at least one humectant;

C. between about 0 and 15 weight percent of at least one lower aliphatic alcohol of no more than 3 carbon atoms;

D. water and optionally up to about 2 weight percent of one or more additives;

wherein the weight percentages of components A-D equal 100%.

14. The method of claim 13 wherein said water-dissipatable polyester is a sulfopolyester and wherein the diol of component (iii), based upon 100 mole % diol comprises

(a) at least 15 mole percent of a diol having the formula H(OCH₂ CH₂)_n OH, where n is 2 to about 20, or

(b) about 0.1 to less than about 15 mole percent of a poly(ethylene glycol) having the formula H(OCH₂ CH₂)_n OH, where n is 2 to about 500, provided that the mole percent of said poly(ethylene glycol) is inversely proportional to the value of n.

15. The method of claim 13 wherein said water-dissipatable polyester is a sulfopolyester and wherein the diol of component (iii), based upon 100 mole % diol comprises

(a) at least 15 mole percent of a diol having the formula H(OCH₂ CH₂)_n OH, where n is 2 to about 20, or

(b) about 0.1 to less than about 15 mole percent of a poly(ethylene glycol) having the formula H(OCH₂ CH₂)_n OH, where n is 2 to about 500, provided that the mole percent of said poly(ethylene glycol) is inversely proportional to the value of n.

16. The method of claim 13, wherein the near infrared flourescing compound is selected from the group consisting of phthalocyanines, 2,3-naphthalocyanines and squaraines and correspond to Formulae II, III and IV:

##STR31## wherein Pc and Nc represent the phthalocyanine and 2,3-naphthalocyanine moieties of Formulae IIa and IIIa, ##STR32## respectively, covalently bonded to a moeity selected from the group consisting of hydrogen, and metals, halometals, organometallic groups, and oxymetals selected from a group consisting of AlCl, AlBr, AlF, AlOH, AlOR₅, AlSR₅, Ca, CrF, Fe, Ge, GaCl, GaBr, GaF, GaOR₅, GaSr₅, InCl, Mg, Mn, SiCl₂, SiF₂, SnCl₂, Sn(OR₆)₂, Si(OR₆)₂, Sn(SR₆)₂, Si(SR₆)₂, Sn and Zn,

wherein R₅ and R₆ are selected from the group consisting of hydrogen, alkyl, aryl, aroyl, heteroaryl, lower alkanoyl, trifluoroacetyl and groups of the formulae ##STR33## R₇, R₈ and R₉ are independently selected from the group consisting of alkyl, phenyl or phenyl substituted with lower alkyl, lower alkoxy or halogen;

X is selected from the group consisting of oxygen, sulfur, selenium, tellurium and a group of the formula --N--R₁₀, wherein R₁₀ is hydrogen, cycloalkyl alkyl acyl, alkylsulfonyl, or aryl or R₁₀ and R taken together form an aliphatic or aromatic ring with the nitrogen atom to which they are attached;

Y is selected from the group consisting of alkyl, aryl, halogen or hydrogen;

R is selected from the group consisting of unsubstituted or substituted alkyl, alkenyl, alkynyl, C₃ -C₈ cycloalkyl, aryl, heteroaryl, ##STR34## or --(X--R)_m is selected from the group consisting of alkylsulfonylamino, arylsulfonylamino, or a group selected from the formulae --X(C₂ H₄ O)_z R¹, ##STR35## wherein R¹ is hydrogen or R as defined above;

Z is an integer of from 1-4;

or two --(X--R)_m groups can be taken together to form divalent substituents of the formula ##STR36## wherein each X¹ is independently selected from the group consisting of --O--, --S--, or --N--R₁₀ and A is selected from the group consisting of ethylene;

propylene;

trimethylene; and

said groups substituted with C₁ -C₄ alkyl, C₁ -C₄ alkoxy, aryl and cycloalkyl;

1,2-phenylene and 1,2-phenylene containing 1-3 substituents selected from the group consisting of C₁ -C₄ alkyl, C₁ -C₄ alkoxy and halogen;

R₁ and R₂ are independently selected from the group consisting of hydrogen, lower alkyl, lower alkoxy, halogen, aryloxy, lower alkylthio, arylthio, lower alkylsulfonyl;

arylsulfonyl;

lower alkylsulfonylamino, arylsulfonylamino, cycloalkylsulfonylamino, carboxy, unsubstituted and substituted carbamoyl and sulfamoyl, lower alkoxycarbonyl, hydroxy, lower alkanoyloxy, ##STR37## R₃ and R₄ are independently selected from the group consisting of hydrogen, lower alkyl, alkenyl or aryl;

n is an integer from 0-12;

n₁ is an integer from 0-24, m is an integer from 4-16;

m₁ is an integer from 0-16;

provided that the sums of n+m and n₁ +m₁ are 16 and 24, respectively, provided that at least one polyester reactive group is present.

17. The method of claim 13, wherein the near infrared fluorescing compound is a squaraine compound of Formula IV, wherein R₁ and R₂ are independently carboxy or lower alkoxycarbonyl.

18. The method of claim 13, wherein the near infrared fluorescing compound is a 2,3-naphthalocyanine compound of Formula III, wherein Y is hydrogen, n₁ is 24, and m₁ is 0.

19. The method of claim 13, wherein the near infrared fluorescing compound is a 2,3-naphthalocyanine compound of Formula III, wherein the naphthalocyanine moiety is bonded to SiCl₂, Si(OH)₂, or Si(OR₆)₂.

20. The method of claim 13, wherein the near infrared fluorescing compound is a phthalocyanine compound of Formula II, wherein X is oxygen, R is aryl, Y is hydrogen, m is 4, and n is 12;

and wherein the phthalocyanine moiety is bonded to AlCl, AlOH, AlOCOCF₃, AlOR₅, SiCl₂, Si(OH)₂, or Si(OR₆)₂.

21. The method of claim 13 wherein said near infrared fluorescing compound is covalently bonded to hydrogen or to various metals, halometals, organometallic groups, and oxymetals selected from a group consisting of AlCl, AlBr, AlF, AlOH, AlOR₅, AlSR₅, GaCl, GaBr, GaF, GaOR₅, GaSr₅, Mg, SiCl₂, SiF₂, SnCl₂, Sn(OR₆)₂, Si(OR₆)₂, Sn(SR₆)₂, Si(SR₆)₂, Sn and Zn.