Water-dissipatable polyesters and amides containing near infrared fluorescent compounds copolymerized therein

• US 5,292,855 A
• Filed: 02/18/1993
• Issued: 03/08/1994
• Est. Priority Date: 02/18/1993
• Status: Expired due to Term

• Current Assignee: Authentix, Inc.
• Original Assignee: Eastman Kodak Company
• Inventors: Patonay, Gabor, Krutak, James J., Cushman, Michael R., Weaver, Max A., Parham, William W., Coates, Clarence A.
• Primary Examiner(s): Acquah, Samuel A.
• Application Number:
  US08/019,535
• Time in Patent Office: 383 Days
• Field of Search: 528/272, 528/275, 528/278, 528/279, 528/280, 528/281, 528/282, 528/283, 528/284, 528/285, 528/288, 528/289, 528/290, 528/293, 528/295, 528/298, 528/299, 528/300, 528/301 , 528/302, 528/303, 528/307, 528/308, 528/308.6, 528/392, 528/395, 528/422, 528/26, 528/28, 528/29, 528/36, 528/40, 528/42, 528/43, 252/301.16, 252/301.35
• US Class Current: 528/289
• CPC Class Codes: C08G 63/68 Polyesters containing atoms other than carbon, hydrogen and oxygen C08G63/64 takes precedence
• CPC Class Codes: C08G 69/44 Polyester-amides
• CPC Class Codes: C09B 69/10 Polymeric dyes; Reaction products of dyes with monomers or with macromolecular compounds addition products of alkylene oxide to dyes, C09B69/00; dyeing with polymeric dyes D06P1/0056
• CPC Class Codes: C09D 11/102 containing macromolecular compounds obtained by reactions other than those only involving unsaturated carbon-to-carbon bonds
• CPC Class Codes: Y10T 428/29 Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
• CPC Class Codes: Y10T 428/3179 Next to cellulosic

Abstract

Provided are water-dissipatable, sulfo-containing polyesters and polyester-amides having copolymerized therein thermally stable near infrared flourophoric compounds. The polymers are useful in coating or ink compositions, which are in turn useful for marking articles for identification/authentication purposes. Also provided is a method for invisibly marking such articles and a method for detecting and sorting articles by utilizing the near infrared flourophoric ink or coating compositions.

Claims

1. A water-dissipatable polymer 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 sulfo monomer containing at least one sulfonate group bonded to an aromatic ring where the functional groups are hydroxy, carboxyl or amino;

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

optionally

(iv) monomer residues of at least one difunctional monomer reactant selected from hydroxycarboxylic acids, aminocarboxylic 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 flouorphoric compound copolymerized therein.

2. The polyester of claim 1, wherein component (iii) is comprised of

(a) at least 15 mole percent, based on the total mole percent of diol monomer residues or diol and diamine monomer residues, of a diol having the formula --(OCH₂ CH₂)_n -- where n is 2 to about 20, or

(b) about 0.1 to less than about 15 mole percent, based on the total mole percent of diol monomer residues or diol and diamine monomer residues, of monomer residues of a poly(ethylene glycol) having the formula --(OCH₂ CH₂)_n -- where n is 2 to about 500, provided that the mole percent of such residues is inversely proportional to the value of n.

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

##STR33## wherein Pc and Nc represent the phthalocyanine and 2,3-naphthalocyanine moieties of Formulae IIa and IIIa, ##STR34## respectively, 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, Ca, Co, CrF, Fe, Ge, Ga, InCl, Mg, Mn, Ni, Pb, Pt, Pd, SiCl₂, SiF₂, SnCl₂, Sn(OR₆)₂, Si(OR₆)₂, Sn(SR₆)₂, Si(SR₆)₂, Sn, VO, TiO, or Zn,

wherein R₅ and R₆ are selected from hydrogen, C₁ -C₁₂ alkyl, phenyl, lower alkanoyl, trifluoroacetyl or groups of the formulae ##STR35## R₇, R₈ and R₉ are independently selected from C₁ -C₁₂ alkyl, phenyl or phenyl substituted with lower alkyl, lower alkoxy or halogen;

X is selected from oxygen, sulfur, selenium, tellurium or a group of the formula --N--R₁₀, wherein R₁₀ is hydrogen, C₃ -C₈ cycloalkyl, C₁ -C₁₂ alkyl, C₁ -C₁₀ acyl, C₁ -C₁₂ 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 C₁ -C₁₂ alkyl, phenyl, halogen and hydrogen;

R is selected from unsubstituted or substituted C₁ -C₁₂ alkyl, C₃ -C₈ alkenyl or alkynyl,

C₃ -C₈ cycloalkyl, phenyl, heteroaryl, ##STR36## --(X--R)_m is alkylsulfonylamino, arylsulfonylamino, or a group selected from the formulae --X(C₂ H₄ O)_Z R¹, ##STR37## 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 ##STR38## wherein each X¹ is independently selected from --O--, --S--, or --N--R₁₀ and A is selected from 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 C₁ -C₄ alkyl, C₁ -C₄ alkoxy or halogen;

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

arylsulfonyl;

lower alkylsulfonylamino, arylsulfonylamino, cycloalkysulfonylamino, carboxy, unsubstituted and substituted carbamoyl and sulfamoyl, lower alkoxycarbonyl, hydroxy, lower alkanoyloxy, ##STR39## R₃ and R₄ are independently selected from 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.

4. The polyester of claim 1, wherein the near infrared fluorescing compound is a squaraine compound of Formula IV, wherein R₁ and R₂ are independently carboxy or lower alkoxycarbonyl.

5. The polyester of claim 1, 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.

6. The polyester of claim 1, 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.

7. The polyester of claim 1, 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.