Organic solvent based ink for invisible marking/identification

• US 5,990,197 A
• Filed: 01/05/1998
• Issued: 11/23/1999
• Est. Priority Date: 10/28/1996
• Status: Expired due to Fees

• Current Assignee: Authentix, Inc.
• Original Assignee: Eastman Chemical Company
• Inventors: Weaver, Max Allen, Krutak, James John Sr., Escano, Nelson Zamora
• Primary Examiner(s): Jagannathan, Vasu
• Assistant Examiner(s): Shosho, Callie E.
• Application Number:
  US08/981,805
• Time in Patent Office: 687 Days
• Field of Search: 523/160, 523/161, 106/31.13, 106/31.14, 106/31.15, 106/31.32, 106/31.64, 524/539, 524/540, 528/289, 528/298, 528/282, 528/283
• US Class Current: 523/160
• CPC Class Codes: B41M 3/144 using fluorescent, luminescent or iridescent effects
• CPC Class Codes: C08G 63/68 Polyesters containing atoms other than carbon, hydrogen and oxygen C08G63/64 takes precedence
• CPC Class Codes: C08G 63/6856 Dicarboxylic acids and dihydroxy compounds
• CPC Class Codes: C08L 2666/02 Organic macromolecular compounds, natural resins, waxes or and bituminous materials
• CPC Class Codes: C08L 67/025 containing polyether sequences
• CPC Class Codes: C09B 69/105 containing a methine or polymethine dye
• CPC Class Codes: C09B 69/108 containing a phthalocyanine dye
• CPC Class Codes: C09D 11/36 based on non-aqueous solvents
• CPC Class Codes: C09D 11/50 Sympathetic, colour changing or similar inks
• CPC Class Codes: G01N 21/91 using penetration of dyes, e.g. fluorescent ink

Abstract

An organic solvent based polyester ink formulation having a fluorescing compound therein is suitable for ink jet printing applications. The ink is useful for producing invisible printing/markings on the surface of a variety of materials for identification, authentication, sorting, etc. Suitable printing substrates include porous and non-porous materials such as plastic, film, sheeting, fabric, paper, high gloss paper; metal, foils, plates; rubber; glass; cellophane; wood; and the like. The ink formulation contains at least one organic soluble polyester, having at least one near infrared fluorophore copolymerized therein, dissolved in an organic solvent. Suitable organic solvents include a C₃ -C₆ carbon ketone, a C₃ -C₆ carbon organic ester, a C₁ -C₃ carbon alcohol, or a combination thereof. In a preferred embodiment, the polyester containing the copolymerized near infrared fluorophore is dissolved in a solvent comprising a C₃ -C₆ carbon ketone and a C₁ -C₃ carbon alcohol.

Claims

1. A composition of matter comprising:

a) from about 1 and about 10 weight percent of a non-sulfo containing, organic solvent soluble polyester having from about 0.1 ppm by weight to about 10% by weight of a thermally stable near infrared fluorophore copolymerized therein;

b) between about 1 and about 5 weight percent of a binder selected from a cellulose ester or a condensed phenolic resin;

c) between about 0.01 and about 0.5 weight percent of a corrosion inhibitor;

d) between about 0.50 and about 1.0 weight percent of an organic solvent soluble electrolyte; and

e) the remainder of said composition having at least one C₃ -C₆ aliphatic ketone, at least one C₃ -C₆ aliphatic ester, or a combination thereof, wherein all weight percentages are based on the total weights of the constituents a-e.

2. The composition of claim 1 wherein said organic solvent soluble polyester comprises:

a) monomer residues of at least one dicarboxylic acid selected from the group consisting of C₆ -C₁₂ aliphatic dicarboxylic acids, 1,4-cyclohexane-dicarboxylic acid, C₃ -C₁₂ oxa-aliphatic dicarboxylic acids which contain one or more oxygen atoms in the aliphatic chain and mixtures thereof; and

b) monomer residues of at least one diol selected from the group consisting of diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol, polyethylene glycols having number average molecular weights from about 100 to about 10,000 and polypropylene glycols having number average molecular weights of from about 200 to about 6,000.

3. The composition of claim 1 wherein said thermally stable near infrared fluorophore includes a monomer residue at least one functional group which is reactive under polyester forming conditions wherein said amount of said near infrared fluorophore copolymerized with said at least one organic solvent soluble polyester is based on the total weights of the organic solvent soluble polyester and near infrared fluorophore.

4. The composition of claim 3 wherein the amount of said near infrared fluorophore copolymerized with said polyester is from about 1,000 ppm by weight to about 5% by weight.

5. The composition of claim 3 wherein said near infrared fluorophores are selected from the group consisting of phthalocyanines, naphthalocyanines and squaraines corresponding to Formulae I, II and III:

##STR9## wherein Pc and Nc represent the phthalocyanine and naphthalocyanine moieties of Formulae Ia and IIa, ##STR10## respectively, covalently bonded to hydrogen or metals selected from the group consisting of AlCl, AlBr, AlF, AlOH, AlOR₅, AlSR₅, Ca, Co, CrF, Cu, Fe, Ge, Ge(OR₆), Ga, InCl, Mg, Mn, Ni, Pb, Pt, Pd, SiCl₂, SiF₂, SnCl₂, Sn(OR₆)₂, Si(OR₆)₂, Sn(SR₆)₂, Si(SR₆)₂, Sn, TiO, VO and Zn,

wherein R₅ and R₆ are selected from the group consisting of hydrogen, alkyl, aryl, heteroaryl, lower alkanoyl, trifluoroacetyl, and groups of the formulae;

##STR11## R₇, R₈ and R₉ are independently selected from alkyl, phenyl, phenyl substituted with lower alkyl, phenyl substituted with lower alkoxy or halogen;

X is selected from oxygen, sulfur, selenium, tellurium or a group of the formula --N(R₁₀)--, wherein R₁₀ is selected from hydrogen, cycloalkyl, alkyl, acyl, lower 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 alkyl, aryl, halogen or hydrogen;

R is selected from alkyl, alkenyl, alkynyl, cycloalkyl, aryl, heteroaryl, ##STR12## (X--R) is selected from alkylsulfonylamino, arylsulfonylamino, or a group selected from the formulae --X(C₂ H₄ O)_z R'"'"', ##STR13## wherein R'"'"' is selected from hydrogen or R as defined above;

z is an integer of from 1-4;

or two (X--R) groups can be taken together to form divalent substituents of the formula ##STR14## wherein each X¹ is independently selected from --O--, --S--, or --N(R₁₀)-- and A is selected from the group consisting of ethylene;

propylene;

trimethylene; and

such 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 C₁ -C₄ alkyl, C₁ -C₄ alkoxy or 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, lower alkanoylamino, arylsulfonylamino, cycloalkylsulfonylamino, carboxy, unsubstituted and substituted carbamoyl and sulfamoyl, lower alkoxycarbonyl, hydroxy, lower alkanoyloxy, ##STR15## R₃ and R₄ are independently selected from hydrogen, lower alkyl, alkenyl or aryl;

n is an integer from 0-16;

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

m₁ is an integer from 0-24;

provided that the sums of n+m and n₁ +m₁ are 16 and 24, respectively.

6. The composition of claim 5 wherein said near infrared fluorophore compound is a squaraine compound of Formula III, wherein R₁ and R₂ are independently carboxy, or lower alkoxycarbonyl.

7. The composition of claim 5 wherein said near infrared fluorophore compound is a 2,3-naphthalocyanine compound of Formula II, wherein Y is hydrogen, n₁ is 24 and m₁ is 0.

8. The composition of claim 5 wherein said near infrared fluorophore compound is a 2,3-naphthalocyanine compound of Formula II, wherein the naphthalocyanine moiety is bonded to SiCl₂, (Si(OH)₂, or Si(OR₆)₂.

9. The composition of claim 5 wherein said near infrared fluorophore compound is a phthalocyanine compound of Formula II, wherein X is oxygen or sulfur, 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.

10. The composition of claim 1 wherein said near infrared fluorophore monomer includes two functional groups which are reactive under polyester forming conditions which allow copolymerization of said near infrared fluorophore into said at least one organic solvent soluble polyester.

11. The composition of claim 1 wherein said corrosion inhibitor is 1H-benzotriazole.

12. The composition of claim 1 wherein said electrolytes are selected from alkali metal salts of thiocyanic or ammonium salts of sulfuric acid.

13. The composition of claim 12 wherein said electrolytes are selected from sodium thiocyanate, potassium thiocyanate, tetrabutylammonium hydrogen sulfate or tetrabutylammonium sulfate.

14. An ink composition for use in an ink jet printer, said ink comprising

a) from about 1 and about 10 weight percent of at least one organic solvent soluble polyester comprising:

i) 100 mole percent of monomer residues of at least one dicarboxylic acid selected from C₆ -C₁₂ aliphatic dicarboxylic acids, 1,4-cyclohexane-dicarboxylic acid and C₃ -C₁₂ oxa-aliphatic dicarboxylic acids which contain one or more oxygen atoms in the aliphatic chain and mixtures thereof; and

ii) 100 mole percent monomer residues of at least one diol selected from diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol, polyethylene glycols having number average molecular weights from about 100 to about 10,000 and polypropylene glycols having number average molecular weights of from about 200 to about 6,000, wherein said polyester has from about 0.1 ppm by weight to about 10% by weight of at least one thermally stable near infrared fluorophore copolymerized therein and the diacid residues and diol residues total 200 mole percent;

b) between about 1 and about 5 weight percent of a binder selected from a cellulose ester or a condensed phenolic resin;

c) between about 0.01 and about 0.5 weight percent of a corrosion inhibitor;

d) between about 0.50 and about 1.0 weight percent of an organic solvent soluble electrolyte; and

e) the remainder of said composition consisting of at least one C₄ -C₆ aliphatic ketone, at least one C₄ -C₆ aliphatic ester, or a combination thereof, wherein all weight percentages are based on the total weights of the constituents a-e.

15. A method for detecting an article having a fluorescing ink printed thereon, said ink having detectable fluorescence when exposed to near infrared radiation, said method comprising the steps of:

a) applying to a surface of said article a fluorescing ink comprising;

i) from about 1 and about 10 weight percent of at least one non-sulfo containing, organic solvent soluble polyester having from about 0.1 ppm by weight to about 10% by weight of at least one thermally stable near infrared fluorophore copolymerized therein;

ii) between about 1 and about 5 weight percent of a binder selected from a cellulose ester or a condensed phenolic resin;

iii) between about 0.01 and about 0.5 weight percent of a corrosion inhibitor;

iv) between about 0.50 and about 1.0 weight percent of an organic solvent soluble electrolyte; and

v) the remainder of said composition consisting of at least one C₃ -C₆ aliphatic ketone, at least one C₃ -C₆ aliphatic ester, or a combination thereof, wherein all weight percentages are based on the total weights of the constituents (i)-(v);

b) using an excitation means to subject said fluoresceing ink to an excitation radiation whereby said fluoresceing ink produces a detectable fluorescence; and

c) using a detection means to detect said detectable fluorescence.

16. The method of claim 15 wherein said article has porous surface characteristics.

17. The method of claim 15 wherein said article has non-porous surface characteristics.

18. A composition of matter comprising:

a. between about 1 and about 10 weight percent of at least one non-sulfo containing, organic soluble polyester having from about 0.1 ppm by weight to about 10% by weight of at least one thermally stable near infrared fluorophore copolymerized therein;

b. between about 1 and about 5 weight percent of an organic solvent polymeric binder resin selected from the group consisting of condensed phenolic, polyketones, polyamides and polyurethanes;

c. between about 0.01 and about 0.5 weight percent of a corrosion inhibitor;

d. between about 0.50 and about 1.0 weight percent of an organic soluble electrolyte; and

e. the remainder of said ink consisting of an organic solvent comprising at least 40 weight percent of at least one lower aliphatic alcohol and up to 60 weight percent of at least one compound selected from the group consisting of a C₃ -C₆ aliphatic ketone, a C₃ -C₆ aliphatic ester and mixtures thereof, with all of the weight percentages in a-d being based on the total weights of components a-e.

19. The composition of claim 18 wherein said organic solvent soluble polyester comprises:

a) 100 mole percent of monomer residues of at least one dicarboxylic acid selected from the group consisting of C₆ -C₁₂ aliphatic dicarboxylic acids, 1,4-cyclohexane-dicarboxylic acid, C₃ -C₁₂ oxa-aliphatic dicarboxylic acids which contain one or more oxygen atoms in the aliphatic chain and mixtures thereof; and

b) 100 mole percent monomer residues of at least one diol selected from the group consisting of diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol, polyethylene glycols having number average molecular weights from about 100 to about 10,000 and polypropylene glycols having number average molecular weights of from about 200 to about 6,000, wherein said polyester has from about 0.1 ppm by weight to about 10% by weight of at least one thermally stable near infrared fluorophore copolymerized therein and the diacid residues and diol residues total 200 mole percent.

20. The composition of claim 19 wherein said thermally stable near infrared fluorophore includes a monomer residue at least one functional group which is reactive under polyester forming conditions wherein said amount of said near infrared fluorophore copolymerized with said at least one organic solvent soluble polyester is based on the total weights of the organic solvent soluble polyester and near infrared fluorophore.

21. The composition of claim 20 wherein the amount of said near infrared fluorophore copolymerized with said polyester is from about 1,000 ppm by weight to about 5% by weight.

22. The composition of claim 21 wherein said near infrared fluorophore monomer includes two functional groups which are reactive under polyester forming conditions which allow copolymerization of said near infrared fluorophore into said at least one organic solvent soluble polyester.

23. The composition of claim 18 wherein said near infrared fluorophores are selected from the group consisting of phthalocyanines, naphthalocyanines and squaraines corresponding to Formulae I, II and III:

##STR16## wherein Pc and Nc represent the phthalocyanine and naphthalocyanine moieties of Formulae Ia and IIa, ##STR17## respectively, covalently bonded to hydrogen or metals selected from the group consisting of AlCl, AlBr, AlF, AlOH, AlOR₅, AlSR₅, Ca, Co, CrF, Cu, Fe, Ge, Ge(OR₆), Ga, InCl, Mg, Mn, Ni, Pb, Pt, Pd, SiCl₂, SiF₂, SnCl₂, Sn(OR₆)₂, Si(OR₆)₂, Sn(SR₆)₂, Si(SR₆)₂, Sn, TiO, VO and Zn,

wherein R₅ and R₆ are selected from the group consisting of hydrogen, alkyl, aryl, heteroaryl, lower alkanoyl, trifluoroacetyl, and groups of the formulae;

##STR18## R₇, R₈ and R₉ are independently selected from alkyl, phenyl, phenyl substituted with lower alkyl, phenyl substituted with lower alkoxy or halogen;

X is selected from oxygen, sulfur, selenium, tellurium or a group of the formula --N(R₁₀)--, wherein R₁₀ is selected from hydrogen, cycloalkyl, alkyl, acyl, lower 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 alkyl, aryl, halogen or hydrogen;

R is selected from alkyl, alkenyl, alkynyl, cycloalkyl, aryl, heteroaryl, ##STR19## (X--R) is selected from alkylsulfonylamino, arylsulfonylamino, or a group selected from the formulae --X(C₂ H₄ O)_z R'"'"', ##STR20## wherein R'"'"' is selected from hydrogen or R as defined above;

z is an integer of from 1-4;

or two (X--R) groups can be taken together to form divalent substituents of the formula ##STR21## wherein each X¹ is independently selected from --O--, --S--, or --N(R₁₀)-- and A is selected from the group consisting of ethylene;

propylene;

trimethylene; and

such 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 C₁ -C₄ alkyl, C₁ -C₄ alkoxy or 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, lower alkanoylamino, arylsulfonylamino, cycloalkylsulfonylamino, carboxy, unsubstituted and substituted carbamoyl and sulfamoyl, lower alkoxycarbonyl, hydroxy, lower alkanoyloxy, ##STR22## R₃ and R₄ are independently selected from hydrogen, lower alkyl, alkenyl or aryl;

n is an integer from 0-16;

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

m₁ is an integer from 0-24;

provided that the sums of n+m and n₁ +m₁ are 16 and 24, respectively.

24. The composition of claim 23 wherein said near infrared fluorophore compound is a squaraine compound of Formula III, wherein R₁ and R₂ are independently carboxy, or lower alkoxycarbonyl.

25. The composition of claim 23 wherein said near infrared fluorophore compound is a 2,3-naphthalocyanine compound of Formula II, wherein Y is hydrogen, n₁ is 24 and m₁ is 0.

26. The composition of claim 23 wherein said near infrared fluorophore compound is a 2,3-naphthalocyanine compound of Formula II, wherein the naphthalocyanine moiety is bonded to SiCl₂, Si(OH)₂, or Si(OR₆)₂.

27. The composition of claim 23 wherein said near infrared fluorophore compound is a phthalocyanine compound of Formula II, wherein X is oxygen or sulfur, 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.

28. The composition of claim 18 wherein said corrosion inhibitor is 1H-benzotriazole.

29. The composition of claim 18 wherein said electrolytes are selected from alkali metal salts of thiocyanic or ammonium salts of sulfuric acid.

30. The composition of claim 29 wherein said electrolytes are selected from sodium thiocyanate, potassium thiocyanate, tetrabutylammonium hydrogen sulfate or tetrabutylammonium sulfate.

31. A method for detecting an article having a fluorescing ink printed thereon, said ink having detectable fluorescence when exposed to near infrared radiation, said method comprising the steps of:

a) applying to a surface of said article a fluorescing ink comprising;

i) between about 1 and about 10 weight percent of at least one non-sulfo containing, organic soluble polyester having from about 0.1 ppm by weight to about 10% by weight of at least one thermally stable near infrared fluorophore copolymerized therein;

ii) between about 1 and about 5 weight percent of an organic solvent polymeric binder resin selected from the group consisting of condensed phenolic, polyketones, polyamides and polyurethanes;

iii) between about 0.01 and about 0.5 weight percent of a corrosion inhibitor;

iv) between about 0.50 and about 1.0 weight percent of an organic soluble electrolyte;

v) the remainder of said ink consisting of an organic solvent comprising at least 40 weight percent of at least one lower aliphatic alcohol and up to 60 weight percent of at least one compound selected from the group consisting of a C₃ -C₆ aliphatic ketone, a C₃ -C₆ aliphatic ester and mixtures thereof, with all of the weight percentages in a-d being based on the total weights of components a-e;

b) using an excitation means to subject said fluoresceing ink to an excitation radiation whereby said fluorescing ink produces a detectable fluorescence; and

c) using a detection means to detect said detectable fluorescence.

32. The method of claim 31 wherein said article has porous surface characteristics.

33. The method of claim 31 wherein said article has non-porous surface characteristics.