CA2154352A1 - Water-dissipatable polyesters and amides containing near infrared fluorescent compounds copolymerized therein - Google Patents

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

Info

Publication number
CA2154352A1
CA2154352A1 CA002154352A CA2154352A CA2154352A1 CA 2154352 A1 CA2154352 A1 CA 2154352A1 CA 002154352 A CA002154352 A CA 002154352A CA 2154352 A CA2154352 A CA 2154352A CA 2154352 A1 CA2154352 A1 CA 2154352A1
Authority
CA
Canada
Prior art keywords
alkyl
near infrared
monomer residues
diol
aryl
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Abandoned
Application number
CA002154352A
Other languages
French (fr)
Inventor
James John Krutak Sr.
Michael Roy Cushman
William Whitfield Parham
Clarence Alvin Coates Jr.
Max Allen Weaver
Gabor Patonay
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Eastman Chemical Co
Original Assignee
Individual
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Individual filed Critical Individual
Publication of CA2154352A1 publication Critical patent/CA2154352A1/en
Abandoned legal-status Critical Current

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00Inks
    • C09D11/02Printing inks
    • C09D11/10Printing inks based on artificial resins
    • C09D11/102Printing inks based on artificial resins containing macromolecular compounds obtained by reactions other than those only involving unsaturated carbon-to-carbon bonds
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/68Polyesters containing atoms other than carbon, hydrogen and oxygen
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/44Polyester-amides
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09BORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B69/00Dyes not provided for by a single group of this subclass
    • C09B69/10Polymeric dyes; Reaction products of dyes with monomers or with macromolecular compounds
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D167/00Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
    • C09D167/02Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • DTEXTILES; PAPER
    • D21PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21HPULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H19/00Coated paper; Coating material
    • D21H19/10Coatings without pigments
    • D21H19/14Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12
    • D21H19/24Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12 comprising macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H19/28Polyesters
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/29Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/31504Composite [nonstructural laminate]
    • Y10T428/31786Of polyester [e.g., alkyd, etc.]
    • Y10T428/3179Next to cellulosic

Abstract

Provided are water-dissipatable, sulfo-containing polyesters and polyester-amides having copolymerized therein thermally stable near infrared fluorophoric 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 fluorophoric ink or coating compositions.

Description

WO94/19387 21~ ~ 3 S ~ PCT~S94/01381 WATER-DISSIPATABLE POLYESTERS AND AMIDES
CONTAINING NEAR INFRARED FLUORESCENT
COMPOUNDS COPOLYMERIZED THEREIN

This invention belongs to the field of organic chemistry. In particular, this invention relates to certain water-dissipatable polyester or polyester-amide polymers which contain thermally stable, near infrared fluorescing compounds copolymerized therein. The novel polymers have are useful as inks, paints, film forming compositions, etc. for marking various items for subsequent detection~identification.
It is known (U.S. Patent 4,540,595) that one may mark documents such as bank checks by the use of inks that fluoresce in the near infrared region , i.e., generally between 650 and 800 nm, for automatic identification. Fluorescent phenoxazine dyes of the formula (Rl)2N~ ~ ~ ~N~ ~ ~.
i1 i ~.~ ~O ~- N(R)2X

wherein Rl and R are alkyl and X~ is an anion are shown to be effective near-infrared fluorescing compounds for this purpose. Attempts to use these compounds to impart fluorescence in the near infrared by adding them to water dissipatable polymers have failed because of poor thermal stability.
It has been proposed (G. Patonay, Analytical Chemistry, Vol. 63, No. 6, l99l, pp 321-327) to use near infrared fluorescent compounds for fluorogenic labels for biomolecules; however, the disclosed fluorescent compounds have poor thermal stability and are not W094/19387 4 ~ ~ 2 PCT~594/01381 -suitable for adding to water-dissipatable polymers during preparation.
This present invention, as described below, relates to water-dissipatable (i.e., dispersible) pol~ eric compositions which are useful in the formu ~tion of near infrared fluorescent inks, paints and film~forming compositions. The polymeric compositions are unique in that the near infrared fluorophores (NIRF's) are copolymerized therein and thus are not extractable, exudable, sublimable or leachable from the polymeric composition. Also, since the NIRF is bound to polymer chain by covalent bonds or incorporated into the back-bone of the polymer by covalent bonds, toxicological concerns are minimized because of low potential for exposure to humans. The inks, paints and film forming compositions prepared from the polymeric compositions of this invention are especially useful in "marking" or "tagging" various items, e.g. security documents, bank checks and other printed or coated materials where subsequent detection or identification is desired.
The present invention provides certain water-dissipatable (i.e., dispersible) polymeric compositions which have near infrared fluorophoric (NIRF) moieties copolymerized therein. Such compositions are useful as coatings or inks, when an invisible identification mark is desired on an article. For example, such composi-tions can be applied to the outside surface of rigid or flexible polymeric containers, thus providing a method for identification of the containers by polymeric class.
Figure l depicts an apparatus useful for practicing the present invention for identification of the near infrared (NIR) marker in the polymer described herein.
This arrangement will be understood to be an application of commercially available fluorometers. As may be seen WO 94/19387 215 ~ 3 5 2 ~PCT~S94/01381 r from Figure l, there is present a light source (l) capable of emitting radiation in the visible and NIR
region which illuminates the polymer sample (2) through a wavelength selector (3) e.g., monochromator or interference filter. A wavelength selector (4) and a NIR sensitive photodetector (5) is placed at 9O or less angle. It may be seen from Figure l that light source (l), wavelength selector (3 & 4) and photodetector(5) are all arranged on two sides of a triangle to minimize scattered light entering the detector. The light source (l) in Figure l may be replaced with lasers, preferably semiconductor lasers. The output of photodetector (5) is provided to level adjustment amplifier (6), the output of which is provided to an integrated circuit digital multimeter(7). The output of the digital multimeter is connected to a computer display so as to provide a numeral and graphical indication of the amount of luminous flux at the predetermined wavelength (preferably at the emission maxima) emitted by the substance contained in the polymer.
Figure 2 shows a preferred apparatus useful for practice of the present invention which will be under-stood to be a specialized arrangement for performing the tests of the present invention. As may be seen from Figure 2, there is present a laser diode light source (l) capable of emitting radiation in the NI~ region which is collimated through a collimating lens (2), and illuminates the NIRF-marked article (4) through an optical filter (3). A focusing lens (5) and a beam compressor are placed at 30 degrees or less angle. It may be seen from Figure 2 that the laser diode light source and the collimating lens are arranged to m;n;m;ze scattered light from entering the detector. An optical filter (6) is placed between the compressor lenses (7 &

WO94/19387 ¢ PCT~S94/01381 -
2~5~2 8) to select the wavelength of fluorescence of the tagging molecule which is focused on the photodet~ector.
A current-to-voltage converter is connected to the photodetector t9) to amplify the detector signàl. The arrangement and the electronic circuitry of the current-to-voltage amplifier (10) is widely known an~d the routines of amplifying and processing the photodetector signal are also well-known. The signal from the current-to-voltage converter circuit is detected by a threshold detector (11). The threshold level of the threshold detector is set at the level required to minimize any interference from untagged articles. The presence of tagged articles in front of the preferred apparatus is indicated by the light-emitting diode (LED) indicator (12).
Figures 1 and 2 are more fully described below.
The present invention provides 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 cont~;~;ng 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:

WO94/19387 PCT~S94/01381 ~154~S~

(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 O.l ppm by weight to about 10% by weight of a thermally stable near infrared flouorphoric compound copolymerized therein.
In a preferred embodiment of the present invention, 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 -(OCH2CH2) n - where n is 2 to about 20, or (b) about O.l 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 - (OCH2CH2) n - where n is 2 to about 500, provided that the mole percent of such residues is inversely proportional to the value of n.

Some of the compounds useful in the practice-of this invention are known tGB 1,537,375; U. S . Patent Nos.
4,606,859 and 4,904,567; U.K. Pat. Appl. GB 2,168,372;
JACS, 1984, 106, pp 7404 - 7410; Jap. Pat. 61,215,663 (CA
Vol. 114: 196445p); Jap. Pat. 90,187,391 (CA Vol. 114:

W094/19387 PCT~S94/01381 -~ al5~35~

.
196418g)]; however, the compounds are used for optical recording devices, liquid crystal displays, electro-. . ~, .
chemical chemiluminescence and as colorants.
The preferred near infrared fluorescent~c~mpounds useful in the practice of this invention are.~escribedin copending U.S. Serial No. 07~789,570, ent~itled "Method for Tagging Thermoplastic Materials With Near Infrared Fluorophores", incorporated herein by reference.
The preferred near infrared fluorescent compounds useful in the practice of the invention are selected from the classes of phthalocyanines, naphthalocyanines and squaraines (derivatives of squaric acid) and correspond to Formulae II, III and IV:

tPc]~ [Nc]~
(X-R)m (X-R) (II) (III) l~---~
~ ~ ~H3 ~ ~2 .~ ~._!~ CH3 ~ 3~f 3 ~ / ~CH=-~ ~/--CH=- ~ -IV

wherein Pc and Nc represent the phthalocyanine and naphthalocyanine moieties of Formulae IIa and IIIa, Phthalocyanine 2,3-Naphthalocyanine ~ WO94/19387 21 S ~ 3 5 2 PCT~S94/01381 .~ ~.
~-~ 25 I ~-~ 2~ -~ 32 3~ 36 ~!~ ~-4 22Il~ 26"N~ 2~ 2~ ~! 4 27 ~ 33~N~35~!~ ~! 5 N~ ~ ~ 6 25 N~ 7, 7 11~ ~l 15 13 i~ 1l 23~ ~l5~ il9 ~-19 13-~

IIa IIIa respectively, covalently bonded to hydrogen or to various metals, halometals, organometallic groups, and oxymetals including AlCl, AlBr, AlF, AlOH, AlOR5, AlSR5, Ca, Co, CrF, Fe, Ge, Ge(OR6), Ga, InCl, Mg, Mn, Ni, Pb, , ~ SiCl2~ SiF2~ SnCl2, Sn(OR6)2, Si(oR6)2, Sn(SR6)2 Si(SR6)2, Sn, Tio~ VO or Zn, wherein R5 and R6 are selected from hydrogen, alkyl, aryl, heteroaryl, lower alkanoyl, trifluoroacetyl, groups of the formulae 5 0 ~7 ~ 7 ~7 ~R7 R7 OR7 ~n R8, ~n OR8, Si R8, -Si-oR8, -Ge-R8, or -r-e-oR8;
9 R9 9 Rg Rg ORg R7, R8 and Rg are independently selected from 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-Rlo, wherein Rlo is hydrogen, cycloalkyl, alkyl, acyl, alkylsulfonyl, or WO94/19387 PCT~S94/01381 -215 ~3~2 aryl or R1o 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 unsubstituted or substituted alkyl,alkenyl, alkynyl, ~7 C3 - C8 cycloalkyl, aryl, heteroaryl, alkylene -~i-R or alkylene -~i-oR8; or ORg -(X-R)m is alkylsulfonylamino, arylsulfonylamino, or a group selected from the formulae -X(C2H4O)zRl, ~7 1OR7 ~7 OR7 ~ R8, Sn OR8, -Si-R8, or -~i-oR8, Rg ORg ~9 Rg 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 ~ 1 wherein each xl is independently selected from -O-, -S-, or -N-R1o and A is selected from ethylene; propylene;

~ WO94119387 21 S ~ 3 ~ ~ PCT~S94/01381 _ g _ trimethylene; and such groups substituted with Cl-C4 alkyl, Cl-C4 alkoxy, aryl and cycloalkyl; l,2-phenylene and l,2-phenylene contA;n;ng l-3 substituents selected from Cl-C4 alkyl, Cl-C4 alkoxy or halogen;

Rl and R2 are independently selected from 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, IR7 ~R7 ~7 ~R7 ~ R8, Sn-OR8, -Si-R8, or -~i-OR8;
Rg ~Rg Rg ~Rg R3 and R4 are independently selected from hydrogen, lower alkyl, alkenyl or aryl; n is an integer from O-12;
nl is an integer from O-24, m is an integer from 4-16;
ml is an integer from O-16, provided that the sums of n+m and nl+ml are 16 and 24, respectively.

In a preferred embodiment of this aspect of the present invention m is from 4 to 12; ml is from O-8;
provided that in the definitions of the substituents (Y)n, (Y)nl and (-X-R)ml that these substituents are not present when n, nl and ml are zero, respectively.
Substituents (X-R)m and (Y)n are present in compounds IIa on the peripheral carbon atoms, i.e. in positions l, 2, 3, 4, 8, 9, lO, ll, 15, 16, 17, 18, 22, 23, 24, 25 and substituents (X-R)ml and (Y)nl are present on the peripheral carbon atoms of III, i.e. in positions l, 2, W094/19387 PCT~S94/01381 ~
3, 4, 5, 9, 10, 11, 12, 13, 14, 18, 19, 20, 21, 22, 23, 27, 28, 29, 30, 31, 32 and 36.
In the above definitions, the term alkyl is used to designate a straight or branched chained hydrocarbon radical contA;n;ng 1-12 carbons. ~ ~
In the terms lower alkyl, lower ai~oxy, lower alkyl-thio, lower alkoxycarbonyl, lower alkanoyl and lower alkanoyloxy the alkyl portion of the groups contains 1-6 carbons and may be a straight or branched chain.
The term "cycloalkyl" is used to represent a cyclic aliphatic hydrocarbon radical cont~;n;ng 3-8 carbons, preferably 5 to 7 carbons.
The alkyl and lower alkyl portions of the previously defined groups may contain as further substituents one or more groups selected from hydroxy, halogen, carboxy, cyano, Cl-C4-alkoxy, aryl, C1-C4-alkylthio, arylthio, aryloxy, Cl-C4-alkoxycarbonyl or Cl-C4-alkanoyloxy.
The term "aryl" includes carbocyclic aromatic radicals containing 6-18 carbons, preferably phenyl and naphthyl, and such radicals substituted with one or more substituents selected from lower alkyl, lower alkoxy, halogen, lower alkylthio, Ntlower alkyl)2, trifluro-methyl, carboxy, lower alkoxycarbonyl, hydroxy, lower alkanoylamino, lower alkylsulfonylamino, arylsulfonyl-amino, cycloalkylsulfonylamino, lower alkanoyloxy, cyano, phenyl, phenylthio and phenoxy.
The term "heteroaryl" is used to represent mono or bicyclic hetero aromatic radicals con~A;n;ng at least one "hetero" atom selected from oxygen, sulfur and nitrogen or a combination of these atoms. Examples of suitable heteroaryl groups include: ~hiazolyl, benzo-thiazolyl, pyrazolyl, pyrrolyl, thienyl, furyl, thia-diazolyl, oxadiazolyl, benzoxazolyl, benzimidazolyl, ~ W094/19387 215 ~ 3 5 2 PCT~S94/01381 pyridyl, pyrimidinyl and triazolyl. These heteroaryl radicals may contain the same substituents listed above as possible substituents for the aryl radicals. The term triazolyl also includes structure V and mixed isomers thereof, N- ~ 1 ~ /
(V) wherein Rl1 is hydrogen or selected from lower alkyl and lower alkyl substituted with one or two groups selected from hydroxy, halogen, carboxy, lower alkoxy, aryl, cyano, cycloalkyl, lower alkanoyloxy or lower alkoxy-carbonyl.
The terms "alkenyl and alkynyl" are used to denote aliphatic hydrocarbon moiety having 3-8 carbons and containing at least one carbon-carbon double bond and one carbon-carbon triple bond, respectively.
The term halogen is used to include bromine, chlorine, fluorine and iodine.
The term "substituted alkyl" is used to denote a straight or branched chain hydrocarbon radical cont~;n;ng 1-12 carbon atoms and containing as substituents 1 or 2 groups selected from hydroxy, halogen, carboxy, cyano, Cl-C4 alkoxy, aryl, Cl-C4 alkylthio, arylthio, aryloxy, Cl-C4 alkoxycarbonyl, or C1-C4 alkanoyloxy.
The term "substituted carbamoyl" is used to denote a radical having the formula -CONR12R13, wherein R12 and R13 are selected from unsubstituted or substituted alkyl, alkenyl, alkynyl, cycloalkyl, aryl, or heteroaryl.

WO94/19387 PCT~S94/01381 -~5~35~ ~

The term "substituted sulfamoyl" is used to denote a radical having the formula -S02NR12Rl3, wherein R12 R13 are as defined above.
The term "alkylene" refers to a divalent Cl-C12 aliphatic hydrocarbon moiety, either straight or branched-chain, and either unsubstituted or substituted with one or more groups selected from lower alkoxy, halogen, aryl, or aryloxy.
The term "acyl" refers to a group of the formula RC(0)-O-, wherein R is preferably a Cl-C10 alkyl moiety. The term "alkyl sulfonyl" refers to a group of the formula RS02-, wherein R is as defined for acyl.
Preferred -X-R groups include those listed in Table I below.
In the compounds above, it should be recognized that the structures must bear at least one polyester reactive group to allow the compound to be incorporated into the polymeric composition and to ~e bound by covalent bonds.
The water-dissipatable polymers, without the near infrared fluorescent compounds incorporated therein, are described in U.S. Patents 3,734,874; 3,779,993;
3,828,010; 3,546,008; 4,233,196; and 4,335,220, incorporated herein by reference.
The polymers of the present invention are, for the most part, water-dispersible because they form electrostatically-stabilized colloids when mixed with water. The colloid particle size varies with the polymer composition but has been shown by light diffraction studies and tr~nC~;ssion electron microscopy (on fresh films) to be mostly 200-800 A in diameter.
The aqueous colloid dispersions exhibit a minimum precipitation of solid material with time, in the temperature range of 0.1-99.9C because the relationship WO94/19387 21 S 4 3 5 2 PCT~S94/01381 between the particle densities and viscosities (very similar to those of water when concentrations are less than 30 weight percent) are such that thermal energy expressed as Brownian motion is sufficient to keep the particles suspended in water.
The water-dispersible polyesters have an inherent viscosity of at least O.l dL~g, preferably about 0.28-0.38 dL~g, when determined at 25C using 0.25 g polymer per lO0 ml of a solvent consisting of 60 parts by weight phenol and 40 parts by weight tetrachloro-ethane.
The sulfonate-con~A;n;ng, water-dispersible, linear polymers thus comprise polyesters, including polyester-amides, consisting of repeating, alternating residues of (l) one or more dicarboxylic acids and (2) one or more diols or a combination of one or more diols and one or more diamines where, in the preceding definition, the mole percentages are based on lO0 mole percent dicarboxylic acid residues and lO0 mole percent diol or diol and diamine residues. Alternatively, the polymers may include residues of monomers having mixed functionality such as hydroxycarboxylic acids, aminocarboxylic acids and~or aminoalkanols. The near infrared flourophoric (NIRF) compounds can thus be incorporated into the polyester, so long as the NIRF has one, or preferably two, polyester reactive groups (e.g., hydroxy, carboxy, etc.) present.
The residues of component (i) may be derived from one or more dicarboxylic acids or their ester-forming derivatives such as dialkyl esters, bis(hydroxyalkyl) esters, acid chlorides or, in some cases, anhydrides.
The sulfonate group of component (ii) may be an alkali metal sulfonic salt such as lithium, potassium or, WO94/19387 PCT~S94/01381 -z~S ~3$2 preferably, sodium sulfonate groups, or an ammonium or substituted ammonium sulfonate.
The preferred water-dispersib~.polymers have an inherent viscosity of about 0.28 to `b .38 dL~g and are comprised of:

(i) diacid monomer residues comprising about 75 to 84 mole percent isophthalic acid monomer residues and about 16 to 25 mole percent 5-sodiosulfoisophthalic acid monomer residues; and (ii) diol monomer residues comprising about 45 to 60 mole percent diethylene glycol monomer residues and about 40 to 55 mole percent ethylene glycol, 1,4-cycloh~ne~imethanol monomer residues or mixtures thereof.

Specific embodiments of these water-dispersible polymers are available from Eastman Chemical Products, Inc., a subsidiary of Eastman Kodak CO~AnY, in the form of pellets (EASTMAN AQ 29S Polymer, EASTMAN 38S Polymer and EASTMAN 55S Polymer) and in the form of aqueous dispersions (EASTMAN A~ 29D Polymer, EASTMAN 38D Polymer and EASTMAN 55D Polymer). These polyesters have been shown to disperse in water due to the presence of 5-sodiosulfoisophthalic acid residues.
Preferably, the water dispersible polyester above contains some poly(ethylene glycol) to aid in its water dispersibility. When some poly(ethylene glycol) is used, the content of the sulfomonomer can be lower, which aids in flexibility of formulating the polyester.
The water dispersibility of the po~yester is related to the weight percent of poly(ethylene glycol) and mole percent of sulfomonomer. Therefore, if the 21S~352 WO94/19387 ^ PCT~S94/01381 content of either is relatively low, the other should be relatively high to maintain adequate dispersibility.
The poly(ethylene glycol) need not be present in the initial reaction charge, because poly(ethylene glycol) may form in situ from decomposition products and be incorporated into the polyester chain. It is well known, for example, that diethylene glycol is formed in situ in such reactions.
In the preferred form of the present invention, the polyester contains repeating units of a poly(ethylene glycol) of the formula H-(OCH2-CH2)n-OH wherein n is an integer of 2 to 500. The value of n is preferably from between about 2 to about 20. The values of n and the mole percent of poly(ethylene glycol) in the polyester, if used, are adjusted such that the mole percent of poly(ethylene glycol) within the stated range is inversely proportional to the quantity of n within the stated ranges. Thus, when the mole percent is high, the value of n is low. On the other hand, if the mole percent is low, the value of n is high. It is apparent, therefore, that the weight percent (product of mole percent and molecular weight) of the poly(ethylene glycol) is an important consideration because the water dissipatability of the copolyester decreases as the weight percent poly(ethylene glycol) in the copolyester decreases. For example, if the weight of poly(ethylene glycol) is too low, the water dissipatability of the copolyester may be inadequate. Furthermore, the weight percent of poly(ethylene glycol) is preferably adjusted 30 such that it is inversely proportional to the mole percent of the difunctional sulfomonomer because the - water dissipatability of the copolyester is a function of both the mole percent sulfomonomer and the weight percent polyethylene glycol.

WO94/19387 PCT~S94/01381 -215~352 Examples of suitable poly(ethylene glycols) include relatively high molecular weight polyeth~ene glycols, some of which are available commercia~ly under the designation CARB0WAX, a product of Union Carbide.
Diethylene glycol is also especially suitable.
Other useful glycols for preparing copolyesters include aliphatic, alicyclic and aralkyl glycols.
Examples of these glycols include ethylene glycol;
propylene glycol; l,3-propanediol; 2,4-dimethyl-2-ethylhexane-l,3-diol; 2,2-dimethyl-l,3-propanediol;
2-ethyl-2-butyl-l,3-propanediol; 2-ethyl-2-isobutyl-l,3-propanediol; l,3-butanediol, l,4-butanediol, l,5-pentanediol, l,6-hexanediol, 2,2,4-trimethyl-l,6-hexanediol; thiodiethanol. l,2-cyclohexanedimethanol, l,3-cyclohe~n~imethanol; l,4-cyclohexanedimethanol;
2,2,4,4-tetramethyl-l,3-cyclobutanediol; and p-xylylenediol.
The dicarboxylic acid component of the polyesters are preferably selected from aliphatic dicarboxylic acids, alicyclic dicarboxylic acids, aromatic dicarboxylic acids, or mixtures of two or more of these acids. Examples of such dicarboxylic acids, include succinic; glutaric; adipic; azelaic; sebacic;
l,4-cyclohexanedicarboxylic; phthalic; terephthalic and isophthalic acid. Terephthalic acid and isophthalic acid are preferred as the carboxylic acid component of the polyester.
It should be understood that use of the corresponding acid anhydrides, esters, and acid chlorides of these acids is included in the term "dicarboxylic acid."
The difunctional ulfomonomer component of the polyester may advantageously be a dicarboxylic acid or an ester thereof cont~;n;ng a metal sulfonate group, a wog4/1s387 PCT~S94/01381 21~3S2 . .

o glycol containing a metal sulfonate group or a hydroxy acid containing a metal sulfonate group. The metal ion of the sulfonate salt may be Na+, Li+, K+ and the like.
When a monovalent alkali metal ion is used, the resulting polyesters are less readily dissipated by cold water and more readily dissipated by hot water. When a divalent or a trivalent metal ion is used the resulting polyesters are not ordinarily easily dissipated by cold water but are more readily dissipated in hot water. It is possible to prepare the polyester using, for example, a sodium sulfonate salt and latex and by ion-exchange replace this ion with a different ion, and thus alter the characteristics of the polymer. The difunctional monomer component may also be referred to the difunctional sulfomonomer and is further described herein below.
Advantageous difunctional sulfomonomer components are those wherein the sulfonate salt group is attached to an aromatic acid nucleus such as benzene, naphthalene, diphenyl, oxydiphenyl, sulfonyldiphenyl or methylenediphenyl nucleus. Preferred results are obtained through the use of sulfophthalic acid, sulfoterephthalic acid, sulfoisophthalic acid,
4-sulfonaphthalene-2,7-dicarboxylic acid, and their esters.
Particularly superior results are achieved when the difunctional sulfomonomer component is 5-sodiosulfo-isophthalic acid or its esters, and the glycol is a mixture of ethylene glycol or l,4-cyclohexanedimethanol with diethylene glycol.
Thus, this invention provides water-dissipatable, sulfo-containing polyesters and amides having copolymerized therein at about O.lppm by weight to about 10% by weight, based on the final weight of the polymer, -WO94/19387 ;. PCT~S94/01381 -. ,. .

2~S 43~2 ^ - 18 -of a thermally stable, near infrared fluorescent compound. In a preferred embodiment, the near infrared fluorescent compound is present at about lppm to about l,OOOppm. ~;`
The polymeric composition of this invention allows the preparation of stable aqueous solutions~dispersions which are useful in forming films when dried, said films having the valuable property of being fluorescent when exposed to infrared radiation. The emitted light is detected by a near infrared radiation detector, thus allowing the "marking" or "tagging" of items to which the film forming polymeric composition has been applied.
The near infrared fluorescent polymeric composition may be formulated into inks, paints or various coating compositions; such compositions can be applied to various objects by conventional processes.
It is advantageous that the polymeric compositions of this invention can produce essentially "colorless" films when applied and yet can be detected by conventional near infrared sensitive detector units. This property allows the items or objects to which the polymeric compositions are applied to be marked "invisibly", since when added at low levels, many of the near infrared compounds used in this invention absorb little, if any, visible light.
Thus, as a further aspect of the present invention, there is provided a coating composition comprising (I) about 20 weight percent to about 35 weight percent of a water-dissipatable polyester comprising:

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

~ WO94/19387 PCT~S94/01381 (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 comprising:

(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 -(OCH2CH2)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 -(OCH2CH2) n -where n is 2 to about 500, provided that the mole percent of such residues is inversely proportional to the value of n; and optionally, (iv) monomer residues of at least one difunctional monomer reactant selected from hydroxycarboxylic acids, aminocarboxylic acids and aminoalkanols;

W094/19387 PCT~S94/01381 ~
2,1543~

provided that at least 20 percent of the groups linking the monomeric units are ester linkages;
said water dissipatable polyester.~hav~ng from about O.l ppm by weight to about 10% b~weight of a s thermally stable near i~frared flouorphoric residue copolymerized therein; and (II) about 65 weight percent to about 80 weight percent of water.
As as a further aspect of the present invention, there is provided a method for invisibly marking, for identification purposes, an article with the water-dispersible polymers of the present invention, wherein said polymers have from about O.l to about lO.0 ppm of a residue of a near infrared flourescing compound copolymerized therein, which comprises applying to said article a composition comprising (I) about 20 weight percent to about 35 weight percent of a 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 sulfo monomer cont~;ning at least one sulfonate group bonded to an aromatic ring where the functional groups are hydroxy, carboxyl or amino;

~ WO94119387 215 ~ 3 5 2 PCT~S94/01381 (iii) monomer residues of at least one diol or a mixture of a diol and a diamine comprising:

(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 -(OCH2CH2)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 -(OCH2CH2) n -where n is 2 to about 500, provided that the mole percent of such residues is inversely proportional to the value of n; 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 residue copolymerized therein; and WO94/19387 PCT~S94/01381 ~
2~S ~3~2 (II) about 65 weight percent to about 80 weight percent of water. ~
. ..
As a further aspect of the present invention, there is provided a method for detecting and separating articles, said articles coated with the coating composi-tion above, said composition having detectible fluorescence when exposed to near infrared radiation, which comprises the following steps:
(a) exposure of a mixture of articles to near infrared radiation having wavelengths of about 670-2,500 nm, with the provision that at least one of said articles is coated with a water-dissipatable, sulfo-contA;n;ng polyester or polyester-amide having copolymerized therein at about O.l ppm by weight to about 10% by weight, based on the weight of the polymer, of a thermally stable, near infrared fluorescent compound, said polyester or polyester-amide being present in sufficient ~uantity to impart fluorescence when exposed to radiation having wavelengths of about 670-2,5000 nm, said radiation provided by light sources;

(b) detection of the emitted fluorescent light via near infrared light detection means; and (c) separating the fluorescing articles from the non-fluorescing articles or articles fluorescing at a detectibly different wave-length or wavelengths by mech~nical means.

~ W094/19387 ~ 215 4 3 S 2 PCT~S94/01381 - In a preferred embodiment of this aspect of the invention the preferred coating compositions as described above are utilized.
In the above method, preferred articles include containers, papers, including commercially significant documents, or trademarked goods of any sort, wherever there is a need or desire to easily and quickly authenticate the origin of the article, by its invisible identifying near infrared (NIR) flourophoric marking or coating.
As noted above, one apparatus useful for practicing the present invention for identification of the NIRF
marker in the polymer described hereinabove is shown in the drawing Figure 1 wherein like numerals reference like parts. Figure 1 is a pictorial diagram of the first preferred embodiment of the apparatus useful in the present invention. This arrangement will be under-stood to be an application of commercially available fluorometers for example currently manufactured by SLM
Aminco of Urbana, IL. This arrangement is for performing the tests of the present invention one at a time. It will be apparent that in using this apparatus, it will be necessary to perform calculations for the concentration ratio of the markers externally. As may be seen from Figure 1, there is present a light source (1) capable of emitting radiation in the visible and NIR
region which illuminates the polymer sample (2) through a wavelength selector (3) e.g., monochromator or interference filter. A wavelength selector (4) and a 30 NIR sensitive photodetector (5) is placed at 90 or less angle. It may be seen from Figure 1 that light source (1), wavelength selectors (3 & 4) and photodetector (5) are all arranged on two sides of a triangle to minimize scattered light entering the detector. The arrangement WO94/19387 PCT~S94/01381 ~
2~$ ~3~

of the light source, wavelength selector and detector to m;n;m;ze scattered light entering the detector is known to those skilled in the art and-the routines of obt~;n;ng fluorescence signalJa~e not considered novel ~er se. The light source (l) in Figure l may be replaced with lasers, preferably semiconductor lasers.
The output of photodetector (5) is provided to level adjustment amplifier (6), the output of which is provided to an integrated circuit digital multimeter.
In the preferred embodiment, digital multimeter (7) is embodied by a computerized unit currently manufactured by SLM Aminco of Urbana, IL. The output of the digital multimeter is connected to a computer display so as to provide a numeral and graphical indication of the amount of luminous flux at the predetermined wavelength (preferably at the emission maxima) emitted by the substance contained in polymer. It is of course apparent that level adjustment amplifier (6) should be adjusted to provide an output appropriately scaled to suit digital multimeter (7).
Figure 2 shows a preferred embodiment of the apparatus useful for practice of the present invention which will be understood to be a specialized arrangement for performing the tests of the present invention. As may be seen from Figure 2, there is present a laser diode light source (l) capable of emitting radiation in the NIR region which is collimated through a collimating lense (2), and illuminates the article (4) through an optical filter (3). A focusing lens (5) and a beam compressor are placed at 30 degrees or less angle. It may be seen from Figure 2 that the laser diode light source and the collimating lens are arranged to minimize scattered light from entering the detector. An optical filter (6) is placed between the compressor lenses W094/19387 215 4 3 5 2 PCT~S94/01381 ~ (7 & 8) to select the wavelength of fluorescence of the tagging molecule which is focused on the photodetector.
A current-to-voltage converter is connected to the photodetector (9) to amplify the detector signal. The arrangement and the electronic circuitry of the current-to-voltage amplifier (lO) is widely known and the routines of amplifying and processing the photodetector signal are also well-known. The signal from the current-to-voltage converter circuit is detected by a threshold detector (ll). The threshold level of the threshold detector is set at the level required to minimize any interference from untagged articles. The presence of tagged articles in front of the preferred apparatus is indicated by the LED indicator (12). The LED indicator may be replaced with appropriate mechanical or electronic actuators for physical sorting of the articles to be sorted such as air jets for moving indicated articles from one conveyor to another.
For identification of more than one type of article or category of articles, the use of more than one marker is necessary. In other words, one fluorophore can be used to mark polyester containers, another to mark high density polypropylene containers, another to mark polycarbonate containers, etc. In another application of the present invention, one marker can be used to authenticate commercial documents from one banking institution, and another can be used to identify another, and so on. In these instances, the use of more than one unit of the preferred apparatus as shown in Figure 2 is nec~ss~ry. The choice of markers is dependent on their spectral properties, wherein the absorption and fluorescence maxima are sufficiently separated from each other to allow for identification of the individual markers (e.g., about 20nm or more). The WO94/19387 PCT~S94/01381 -~S ~35~

multiplexing and computing apparatus which is programmed to calculate ratios of fluorescence signal of the markers present in the polymer is within the ability of one of ordinary skill in the art.
The dispersions or blends according to this invention may be used by applying them as a coating or ink to an article or substrate such as paper, metal foil, clay coated paper, paperboard, or thermoplastic or thermosetting polymers such as polyesters, polyolefins, polyamides, polyimides, polyvinyl chloride, poly-vinylidene chloride, polyurethAn~s, polycarbonates, cellulose esters, polyacrylates, polyvinylesters, polyester-amides, polystyrene, acrylonitrile-butadiene-styrene, and styrene-acrylonitrile, followed by drying to leave a residue of solids in the form of a coating.
Alternately, a second substrate can be applied prior to drying to form a bond between the substrates.
In the coating compositions of the present invention, it is preferred that component (I) be present in about 25 to about 30 weight percent relative to the component (II) water. Further, the compositions may contain up to about l0 weight percent of one or more additives commonly found in ink compositions, for example, waxes such as JONWAX 26, JONWAX 120 (available from S.C. Johnson and Sons, Inc., Racine, Wisconsin, 43403; U.S.A.), or VANWAX 35 (available from Vantage, Garfield, New Jersey, 07026); surfactants such as SURFYNOL ~04 and SURFYNOL 440, available from Air Products and Chemicals, Allentown, Pa. 1810~); modifiers (e.g., defoamers) such as WBT-409, RESOLV (available from Vantage), CARBOWET 990 (available from Vantage), OT-70 aerosol (available from McIntyre, Chicago, Ill.
60632), FOAMASTER lll (available from Henkel Corporation, Morristown, N.J., 07960); alcohols such as WO94/19387 215 4 ~ S 2 PCT~S94101381 n-propanol, isopropanol, propylene glycol, ethylene glycol monobutyl ether, or ethylene glycol; biocides; pH
stabilizers; dispersants; thickeners such as ACRYSOL
RM-825 (available from Rohm & Haas, Philadelphia, Pa.
19105); wetting agents, e.g., FLOURAD FC-430 and FC-431, from 3M Company; and the like.
Typically, it is desireable to add a small amount of one or more pH stabilizers to the ink or coating composition to keep the pH within a desired range. For example, it is preferred to add about 0.1 weight percent sodium acetate to an ink or aqueous solution~dispersion of the polymer~water composition.
Preferred amounts of certain additives in the ink or coating compositions of the present invention are set forth in the following table:

Com~onent Weiqht Percent Waxa 0.0-3.0 Surfactantb o.o-3.0 ModifierC 0.0-2.0 Alcohold 0.0-8.0 (a) e.g., JONWAX 26, 120, VANWAX 35 (b) e g., SURFYNOL 104, 440 (C) e.g., WBT-409, RESOLV, CARBOWET 990, Aerosol OT-70, (d) e.g., n-propanol; isopropanol; propylene glycol;
ethylene glycol monobutyl ether Other description of possible additives, formula-tion, and use of such coating or ink compositions can be W094/19387 PCT~S94/01381 -. 2~S ~3~?.

found in U. S. Patent No. 4,996,252, inc4rporated herein by reference.
., The practice of the invention is illustrated further by the following examples:

Ex~erimental Section Exam~le l A mixture of methyl l,l,2-trimethyl-lH-benz[e3-indole-7-carboxylate (tautomer is methyl l,-dihydro-2-methylene-l, l-dimethyl-lH-benz [e] indole-7-carboxylate), 2.67 g (O.Ol M) (see U.S. Pat. 5,030,708), squaric acid (0.57 g, 0.005 M) and 2-ethoxyethanol (40 g) was heated at reflux under nitrogen for 16 hours.

The reaction mixture was cooled with an ice bath and the green solid collected by filtration, washed with isopropanol and dried in air. Recrystallization from 2-ethoxyethanol (20 mL), collection of the solid by filtration, washing of the solid with isopropanol and drying gave the pure product. Mass spectrometry indicated mostly the following structure plus a small amount CH32C~ ~-~ ~ ~ ~C02CH3 i~ ~ \ \- ~ H~

Amax = 690 nm (CH2Cl2) of the mono 2-ethoxyethyl ester which had been produced by transesterification. In methylene chloride an WO94/19387 21~ ~ 3 5 2 PCT~S94/01381 absorption maxi~um (~ max) was observed in the visible-near infrared absorption spectrum at 690 nm (~-214,287).

Example 2 A 300 mL 3-neck round-bottom flask was equipped with a magnetic stirrer, thermometer and gas inlet tube.
Methanol (50 mL) was added followed by sodium metal (0.66 g, 0.029 mole) with stirring to facilitate reaction and solution, with a slow nitrogen purge applied. To this solution was added 12.54 g (0.058 mole) of 4-phenoxyphthalonitrile (A. W. Snow and J. R.
Griffith, Macromolecules, 1984, 17, 1614-24), followed by additional methanol (50 mL). Anhydrous ammonia was bubbled in under the surface, giving an exotherm to 45C
and total solution. The ammonia addition was continued until no more starting material was evident by thin-layer chromatography. The solution was clarified by filtering through a pad of Dicalite filter aid which had a small layer of charcoal on it and the filtrate drowned into water. The oily product layer thus produced was washed by decantation with 500 mL portions of water (4-5 times or until pH reached about 7-8). After the final wash water was decanted off, methanol was added to dissolve the product, which crystallized upon stirring overnight at room temperature. After being collected by filtration, the gr~n;~h-yellow solid was washed with methylene chloride and dried in air. The yield was 13.75 g, 91.1% of the theoretical yield. Mass spectrometry showed the product to consist largely of the desired 5-phenoxy-1,3-diiminoisoindoline.

WO94/19387 PCT~S94/01381 -3~2 ExamPle 3 A mixture of 5-phenoxy-l,3-diiminoisoindoline (3.68 g, 0.016 m) (from Example 2), 1j-2,3,4-tetrahydronaphtha-S lene (20 mL) and tri-n-butylaffline (lO mL) was stirred under a nitrogen sweep. Aluminum chloride (3.l9 g, 0.024 m) was added to give a slurry. After the reaction mixture was heated at about 180C for 4 hours, it was allowed to cool to room temperature and diluted with methanol to enhance solubility to facilitate transfer into about 500 mL of ice-water mixture containing lO mL
HCl. The somewhat "greasy" solid product was collected by filtration and washed with dilute HCl. The filter cake was washed on the filter with cycloheY~ne and finally washed thoroughly with ethyl acetate and dried in air. Mass spectrometry indicated good quality 2(3), 9(10), 16(17), 23(24)-tetraphenoxy-Pc-Al-Cl (Pc =
phthalocyanine moiety) having the desired molec~ r weight of 942 (l.S6 g, 41.4% of the theoretical yield).
Example 4 A reaction mixture of tetraphenoxy-chloroaluminum phthalocyanine (0.94 g) of Example 3, dimethyl-3-hydroxyisophthalate (0.24 g) and pyridine (20 g) was heated at reflux for 24 hours and allowed to cool to room temperature. Isopropanol (20 mL) was added and then precipitated, by the addition of water, the phthalocyanine product, which was collected by filtration, washed with water and dried in air (yield -0.90 g). In methylene chloride, absorption maxima were observed at 696 nm (104,585), 626 nm (3~,882) and 343 nm (64,090) in the ultraviolet, visible and near infrared absorption spectra.

W094/19387 _ 21 ~ ~ ~ 5 2 PCT~S94/01381 Example 5 Preparation of Sulfo-Containing Polyester Having Near Infrared Fluorescinq ComPound CoPolYmerized Therein Components I-VII were added to a 500 mL round bottom flask which was fitted with a vacuum outlet, stirrer, condensate take off and nitrogen inlet.

I 79.54g (0.41 m) dimethyl terephthalate II 26.64g (0.09 m) dimethyl 5-sodiosulfo-isophthalate 15 III 54.06g (0.51 m) ethylene glycol IV 37.44g (0.26 m) 1,4-cyclohexanedimethanol V 0.74g (o.oos m) anhydrous sodium acetate VI 100 ppm Ti catalyst as titanium isopropoxide VII 0.0138g (1.24 x 10 5 m) infrared fluorescent compound t(C6H5O) 4 PCAlOC6H~--3, 4--diC02CH3 (Pc = phthalocyanine) - Compound of Example 4 above]

The flask and contents were immersed in a Belmont metal bath at 200OC with a nitrogen sweep over the reaction mixture and the temperature increased to 220C
over two hours. To complete the polycondensation, the temperature of the reaction mixture was increased to 250C, vacuum was applied to lower the pressure to about 0.5 mmHg, and heating at 250C continued for about 20 minutes. This gave a water-dissipatable polymer which contained about 100 ppm of the near infrared fluorescing compound. The polymer was extruded and pelletized.

WO94/19387 PCT~S94/01381 -35~

ExamPle 6 The procedure of Example 5 was repeated using the same conditions and reactants except that the infrared fluorescing compound which was used was the compound of Example l above.

ExamPle 7 A portion (20.0g) of the sulfo-containing water-dispersible polymer from Example 5 was added to distilled water (80.0g) at about 80-85C. Good dispersion of the polymer was achieved by stirring and heating to 100C. Upon cooling, a portion (50g) of the aqueous dispersion was combined with l.Sg of a solution which was prepared by combining l part of isopropanol with 1 part of FLORAD FC-430 (a nonionic fluorochemical wetting agent from 3M Industrial Chemical Products Division). The infrared fluorescent ink was then coated on an uncirculated $1 bill by using a K-coater with a #2RK drawdown rod (RK Print - Coat Instruments Ltd.) to give a wet coating approximately .0005 in. in thickness and allowed to dry. When a portion of the coated $1 bill was exposed to infrared light generated by a laser diode source and having a wavelength of about 672 nm, a broad band fluorescence was detected over the wavelength range of about 675-730 nm, yet the coating was invisible to the human eye.

Exam~le 8 Example 7 was repeated exactly the water-dispersible polymer of Example 6 was used. The coated $1 bill had similar fluorescence properties as that -WO94/19387 PCT~S94/01381 produced in Example 7 when exposed to infrared light having wavelengths of about 680 nm.

Additional examples of compounds having Formulae II, III and IV are presented in Tables 3, 4 and 2, respectively.

~3~?~

EXE2~IPLARY --X--R Groups --X--R --X--R

--OCH 1~ ~ ~.
3 ~S~ ~-~

~ ~
~C4Hg--n --S--II~N~ i 3 ~C ( CH3 ) 3 S

~C12H25 --S--~N~ H

.~ ~.
-SCH -S-~ '! !
3 ~O~ ~-~

SC2H4 --S_1~\~/

8 17 S ~ ~ ~ ~ OCH3 S

WO94/19387 21~ ~ 3 5 2 PCT~S94/01381 (Continued) EXEMPLARY -X-R Groups -X-R -X-R

CH2CH(C2H5)C4Hg n -S-~ -CO2CH3 -OCH2CH=CH2 -OCH2CH=CH-CH3 ~ _ ~ 3 .-.
2 6H5 -Se--~ ~-ScH2cH(OH)cH2oH 2 6 4 4 COOH
-OCH2C=CH -OC6H4-4-CH COOH

-N(C2H5)2 -OCH2CH2CO2CH3 N(CH3)C6H5 --O--C6F5 75 ( 2 4 )2 6 4 4 Cl WO94/19387 PCT~S94/01381 -?.~$ 43~

TABLE 1 ..~`
(Con ~ ed) EXEMPLARY -X-R Groups -X-R -X-R

{~-~ ~-H 6Hll ~ ~
~ _ ~--O~

_ ~
~._.4 -OC6H5 -O(CH2cH2O)2H

-OC6H -4-COOH -s(cH2cH2o)2H

SC6H4 4 COOH -O(CH2CH2O)4H

OC6H3-3,5-diCooH _o(cH2cH2o)3cH3 -oc6H3-3,5-dicO2cH3 -o(cH2cH2o)2c6H5 -SC6H4-2-COOH -NH(cH2cH2o)2H

-SC6H4-3-cO2CH3 WO94/19387 2 1 5 ~
3 5 ~ PCT~S94/01381 (Continued) EXEMPLARY -X-R Groups -X-R -X-R

WO 94119387 2~5 4352 ~ PCT/US94/01381 ~

.=~ ,.

0= - ~ o d t~

. .

. .
~ ~ / d' ~
_ a: o t.) o N _ p~l N ~i o~ o ~ D

=.
~ ! .

~o ~ o ~
o=-\ /- rO C~)~

~. !~ o o ~, ~ u u X zl WO 94/19387 21~ 4 3 5 2 PCT/US94/01381 . _ . .
~= .
:C~ +~
1 U ~ U U

0=- --0 \ ~

al U ~ ~U 5 , ~ ~
o U :~
~, t U
3 o O, , 1 ~.D I ~ _ U. U
U
C) C) C.) U
P~<; \P:l Z Z 2 Z N
O ~ ~ O O O

3~ 1 )Z~;
~---1 o Oc ~ Io u~
\ / 'I 5~D I ^ U
~ VD ~, ~D N U u V U U
Z Z Z
~_._! + ~I z z z z y Ul I Ul /

.~ ~._.~ . .
-I ~ / X O o _l ~ ~ ~ ~ ~D
P: =- ~ Z , . ~ ~ ~ ~ ~

, `--~, .=. .
r~ I +~ ....

0=-/ ~
5~j )z;~s V ~.=.
.
/--- o / \ /\ ~ N

0: ¦ N N N N N

=.
._ "'1' ~r U

Z~ o _l WO 94/19387 21~ 4 3 5 2 PCT/US94/01381 U ~ -- ~ N
U

0=-/ ~-~ I

~ T ~1 ~ U
~z~

U o m ~
E-~ U = = = z tq ~C~ N

Ul T

U_._.

U I o N ~
U U u 71 ~" T ~ I T ~ r r~

xZ~

WO 94/19387 ~ ~3$~ PCT/US94/01381 , ~ -i-+~
U~

p~l ~ ~ ~U
:C' i ~
U ~.=.

C f O

U~ I ~ :C C O

.=-U--._.
~/ $

0=-~ ~--0 r~
.T+ ~ o ol U . Z ~

X O al o li3 Z ~

WO 94/19387 21 5 ~ 3 5 ~ PCT/US94/01381 ~ + ~
,_.~

O= --o \ ~

~D

:Z~

~ ,~-.-~

a C o~ o~
V ~
Z Z
8 o o~ o~ N ~
~ ~ ~ Y I I I I I
t` :C ~` t` 1~ t` 1`
=.

~.--.
~/ 11 C~ I

Oz-/ ~--O

u ~ u u u ~ ._! + ~;1 8 o~ o~

U ,.=.

X O ~ o ~1 =- ~ Z ~ ~ In u~

2~S~3s2 , 0=-/ ~--0 .7 r~ i _ / \
~.=./ 0~

~ c) I r~ r c~
p .=. ~ _ 1 o~ O

t~ t~

7 ~~
c~ ~

o=-/ ~- o ~D
~! + ~~ o~ o~

u /.=.

~ ~- x z;l ~

~ WO 94/19387 215 9 3 5 2 PCTIUS94/01381 C.) U
N N
O O
U
d' N O
~r ~ ~
N
U U
~ C~ V~ VJ _I
V N ~
U ~ H ~,) - 1 I r4 ~4 r4 1 1 1 ~4 ~4 '7; X X X X X X X X X
O O O O O O O O O
O ~ C
H S S S S S S S S S
Z ~ ~ ~:4 ~ ~ ~ ~ ~ ~ ~
C~ U J ~ J ~
r ~ J
C ~ C~ _ _ ~ _ _ _ Z, p,, p N N N N N N N N
~ O -- -- -- -- ---- -- _ _ E~ " ~4 ~ ~ ~ ~ ~ ~ ~ ~ ~
N N N N N N N N N
~1 o O
-- -- -- -- -- -- _ _ _ _ O O O O O O O O O
_ _ X O In ~D t` 00 a~ O --1 N ~
1~ Z

WO 94/19387 2~ 43~2 PCT/US94101381 ~

.~ ~
~ C -CJ --I o ~' O,.~ , t) U C
r~ ô O
X X X X ---- -- S .C
o o o o ~ :~
C ~ X X X --I --O
.C S .C S
a ~ ~ o : ~ X~X1 X~ ~ ~
Z ~ ~ ~ ..~ o o o O z , J ) ,~
~ c a ~ ~ ~I N -- -- _ _ _ ~ X' ` ` ' ~ N ~ t~ t~
P~ O^ ~ _ _~ ,1 ,.1,1 _ _ _ _ _ O O O O
~ _ o O O O O
_ ~_ _ _ _ _ _ _ -x o~ o WO 94/19387 21 5 4 3 5 ~ PCT/US94/01381 t~
O
~r a ~J ~ ~
O ~ ~r ~/al ~ t~ u U
t~!~t~ C O O
U O -- -- ~
C ~ C
tq tl~ tq r~t,~ I ~
,) C)t,)t) O O O P~ r4 r4 r4 .,~ .,1 .~1 1 1 1 .C ~ -- -- -- _ _ _ _ I X X X X X X X
~ ~ ~ O O O O O O O
1:aC)aC~ ~C ~: ~C ~aC~aC~ C
U ~ ~ S ~ ,C .
tn ~

w ~ I I I I I I I I a u ~ , J
C ~ _ _ _ _ _ _ _ _ _ _ o------------____ E-~ ~ t' t1 ~ ~ t' l ~ ~ ~ t') ) ~ ~ 8 ~ __________ t,`t,`t,` t,` t,` I~t` t,` t,` t,`

O O O O O O O O O O

_ ~ ~ t'- t~tr~ ~t' t`~ ~ t'-x o~ t` Ot~ a~ O
W Z ~o x oococo 01~

WO 94/19387 PCT/US94/01381 ~
2~ ~3~

U ` ~ ~ . U
o ~`
U
O ~~ 4r'~ O
L4 r4 ~4 r4 r4~ o 7 ~ ~
.~ ~ s c ~ ~7 ~ ~ Z ~
p ~J Z U ~ ~ ~ ~ ~ ~ ~ ~ ~
u U ~ J
O E-~ a ~,, 8 t~ ~` ,.... .. ..

, , ,1 , , , I , ,~ , o o o o o o o o ~, _ _ _ _ _ _ _ _ _ _ _ _ . . o,~ ~
~ ol ~ ~ u~ t~ o o o WO 94/19387 ~ 2 I 5 ~ 3 5 2 PCT/US94/01381 u S
~ ~1 ,_ ' -- J N

~D Ut.:
U ~ ~ ~ ~ V
V 1 0 ~ 2S
O
S O ~1 rq S
3 rq,~ S ~ 4 O r~ O
tn :) x I I ~ ~ ~
) 4 0 0 0 3 X ~1 X X S S
O ~ >1 N _I N N t`

Z ~ Q U ,~ ,4 4 ~ ~ C J J J ~ ' ~ ' ' J

~, ~4 ~ N N N N N N N N
~ ~ -- -- -- ---- _ _ _ ~
: _ N N N N N N N N
U
` ` ` ` ` ` ` `

O
O O O O O O O O ~1 ~ r,r~ r,~7 ~ ~ ~ ~ ~

X O O O O O O O O ~1 ~1 Z ~

WO 94tl9387 ~ 2 l 5 ~ 3 5 ~ PCTIUS94/01381 ~

, ,, i , .~
N ~7 ~4 N
_ U
r, N Nc~ C
~ ^--I O UJ
L 'r~
V U _UJ ~ l:4 o ~ ~2 ~
-~t ~1 _ N O I O
Z ~q o ~-- O ) C
U .) -,1 U C

a ~ c ~ ~ c9' " "
Z ~ C ~ ~ X
1 1 1 o Z U~ o ~
~æ ~ ~ U ~ r r rL ~ Z ~ S~ I I ~ ~ ~ ~ _ P ~ ~ U ~ _, ~ ~ ~ ~ ~
r~r~
U~ ~ I I I l l I
,~, '2 ~N N N N N N~I N
~ 1l ~, N N N N N N N N
~ u 8 `
, , ,, ,,,, ,, , , ~O ~ W ~D ~ ~~O ~
,. . .. .. . . .. .

o o o o o o o o I Nt~7 d' If) ~Dt~ Cl~
x l WO 94/19387 ~ 3 ~ 2 PCT/US94/01381 O C~ iJ
O
O
:C U U U U
O ~ ~ ~ ~
~: ~ O o --I U C O O
r ~
r r .C .. C
~ -- ~ U U
H O
U ~,i ~ _ ~ ~
,~ U ~ U U
~ T ~ l l ~1 N~ ~ ~r ~ ~
X ~ C ~1 N N N
o u a~
C~ S ~ ~ ~ ~
~ N N N N
r ~~1 X t` t` t`
XXO C
U~ ~ O~
a ~
o ~ ~ ~

H ~N d' ' C ~ C J~ ~ X X X X
,) ~ II I C C C ,C
E~ Z ~ ~ ~ ~ ~
C D N N N a~
O ~-- _ ~ ,~
U U U U
~ U ~0 NN N I T l l ) ~ If) In ~ ~ O N
N N N N
U
I NN N N
NN N N ~ I
O
,1~i ~1 o~oo CO O C
O _~
OO O ~ ~i .C C
--I 'I --I ` ` ` ~ U f ~ r ~ X X
~ ~ ` ` Q~ Q) ¦ O~I N ~ ~ 1~
X O NN N N~1 N N N N

WO 94/19387 ~,~5 435?, PCTIUS94/01381 ~
-:

,_ ~D
U U
~4 o r~
U ~.C
a ~ I ~ ~ u'D
z ~ o xa~ ~ o ~ r.~ ~ o o ~ _ .~ ~ ~ ~ ~ .
4 Z u~ ~ rl~ ~D O O ~ r/~
~c~ O z ~ l O '~ r4 ~" o U H o '3 o x _ -- r~ .~ o ~ u Z ~ r~ X ~ ~ ~ 0 ~4 41 ,C
E- O ~ C 4 0 ~ a) ~ h S~
C .C I O E~ O
U ~ 1 o ~~ ~
~ C ~ Z o~
~ ~ ~ ~ tr.~ tr~ t t~ t~ tr~ 1 aJ
~1l 2 ~ u u c~ ~ u u J U
4 Cu~ C~ l I Cl~ ~ ol l ~ T
.. C t,~ t~t,'~l t,'~l N t,'~l t,~ t~l r~ t,~ t,`l t,~ t,~ r~) r~ ~ t'~
t,~ t.~ t.~l t~ t,~ t,~ t~ t,~l t~t~D t~O r ~ I~ t~ I`

tr ,1,1 _I,i O O O O
,ot~ t~t~ a tn a~ t~
r~ t~ t,~ tr~
~ t,~ t,~ t~ t,~

X O ~ r.~ t~t~ t~ t~ r,'~ r,~ t~
W Z _I ,1,1 ~ ~ ~ _~ ,/ ,i WO 94/19387 215`~ ~ 5 2 PCT/US94/01381 8 ~ ~ ~ ,~
L ~1 ~
3 ~
N
~ -- '¢ O O O `O
O ~ ~ ' ' '~ Y ~
~ O ~ C1 û -~
,_' Ul ~ r~
_ o ___:C ` G
Z X ~ X I ~ o _ o o C ~ I XO O 0 ~
~ O
1~ C ~ ;~ ~ ~ ~ r~~ r., ".~
H c ~ Xo S ~ ~ S ~ C
C Z ~ I ~ X ~ ~ _l o _~
0 ~ ~ o u ~ a~ o Q~
C 0~ C
a ~ ~ ~ ~ ~.c ~, r 4 u u U U U U U U O ~ tJ U ~ U
c ~: T T l l l T l o G O ~ O
N N N N N ~ N N N
t~ tqt~ ~1 N N N N N
N N N N N N N N N

O O O O

N N N N ~

¦ 00 01 O ~/ N ~ ~ In ~o X O ~ t~

WO 94/19387 ~';!, PCT/US94/01381 _I
~¢ V
1 0 ~ r~
u 1 8 ~
~ 8 ~ 1 8 8 o I I Ln X ~ :C
u ~ 1~ o ~ c U ~ U ~ ~

a , a 9' ~ ~ O C 3 N N N C

~ ~ _ _ _ ~
00 ~ 'I 'I ~i ~ o o o --l ~ ~ - - - ~
~ - - - ~

I t` co ~ o ,~
zl ~ u~

WO 94/19387 ~ 215 4 ~ 5 2 ~ PCT/US94/01381 O ~ J _l O O C~) U ~ ~ ~ ~ O t~5 '1:5 , u uu u u Z T Z Z Z Z

O Z ~ ~ r~~ r ~

z ~ a ~ ~s H
Z C~ ~J ~ ) ) J J

C r~
3 'q ~~7~ ~~r7 _ _ _ _ _ O ~a~
Z 11 C~
~___________ Z ~ ~~ N ~ ~ ~ ~ ~ ~'3 ~
_ O OO O O O O O O O O

_ _ _ _ X O u~ ~u710In U')1~') ~D~D~O ~D

WO 94/19387 ~,~S ~3~3~ PCT/US94/01381 .
~ N
V
N ~'1 O :C
t~ U

8 ~ c~
C~ N t`'7 t`l I ~ _ ~D C~ ~' ~ '~D t~ CJ O
CJ tJ O O
C C ~
O
Z
a ~ z ~ Z ~ ~ ~ ~ I X --U ~ ~ V V V

-- _ _ _ _ _ C E~ a o O O O O O O

N N N N N N N
Z 11 oX
N N N N N N N
_ O O O O O O O
N N N N N N N
_ N N N N N N N

- - - - - - - o ~ ~
t~l N N N N N N Z Z Z

. . ~ In .o ~` co a~ o _I N ~
X O ~D U~ D ~D ~D ~D t` t` l` I`

~ WO 94/19387 215 4 3 5 2 PCTIUS94/01381 ~: _ C~
,1 o ~
o O o o _. ~, ,1 O
U
U~ t) C) U t) C~t) O Z
Z~ Zl Zl Z~ , X~
Z ~ X X X X X X o D D V ~ , , C
O
U C~
~ a o o o o O O O O
~ :~ p ~ ~ ~ ~ ~ ~
~C Z ~ ~ N
~ 11 ~0 Z C,~ _ _ _ _ _ _ _ _ Z ~ ~ ~ ~ ~ ~ ~ ~
O O O O O O O O
' ' ' ' ' ' _ C~
U~ ~-- _ -- -- _ _ _ _ C.~O------------__ Z z ~ N t~

X O I` t` I` t` r~ I` OD O~ 0~ CO
Z ~

~S 43~
WO 94/19387~' PCT/US94101381 C ~ -- _ f _~ ~J O
l' ~ O O
Z
O
''I ~ V~ V~
S -~ 0 3 0 ~ u ~ z F o ~
~ V~ V~
V~ ` _ _ O
V, I I 1 1 ~ O ~ V
C~ ~ t` r a _ ~ s s z o r ~ a a, ;~; ~ s O Z ~ E~ U ~ O ~ ~ O

c ~ Z 8 s ~ ~ 3 c O ~ Z C
U U 3;
-- C ~ o Z, ~ 'q /~ a~ G
~ P~ ~ ~ ~ ~ ~ ~ ~I C~ N
Z 11 0 ` _ ~

_ O O O O O O O O O

N ~
_ _ _ _ _ _ ~ ~ ~I ~t'~l N ~ ~I N

x l ~ ~ oo x ~ WO 94119387 215 1 3 5 2 PCTIUS94/01381 _, , . U
u .
In I,,, ::
o O ~ g o I

Zl ~ V
U ~ _ U
Z X ~ ~ I t u. X s z Zl -2 ~ ' ~ C ~ o z s~ .~ Po .,1 G
~0 Z 'I S~ ~ N . ~ ,~
H

~ VZ ~ ~ ~ J J J ~ _I X X
E~ 0~` ~ 4 '-I 4 '--I 4 S .~
C E~ a o r~t~ ~ tr) tO t tt~
p _ _ _ _ _ ~ z t~ ol cl~ ol cl~
Z U _ _ _ _ _ t~ t~ t~ tr~
Z ~ ~t~l N tN t~ t,'~l t~ t,~
t~ t~ t~ tr~
O O O O O
t~t.~ t.~ N t~ ~ 1` t` l~
t,~l t,~ t~ t~
t'~ t~ ~ t'~
t~t"J t,~t~ t,~ t,~ t~ t,~ N

-- t~ 0 t t ~ ~ ~ er tr~ t~tt~ t~ tr~ t~ t~ t~ tJ~
t,~ t~ t.~t~ t~ ~ I

I t~ o ~ t~D t~ O _~
X I t5~ tJ~tJ~t~ tJ~ tJ~ tJ~ O O
1~ Z ~ I t~ t~

2~S43S?~ --. ` ~

o C) o o Z
-- t~ O Z :1 o ~ ~ ~ Z
,~, D -- -- A O u C Z U ~ g o u U F~ N
~ ~ ~ a o o ~ ~ Q ,~ _ _ , ~ r ~; Z p~ l l l l ~ l ~: 11 0 ~ o o o o o o o Z O C,) tr~ t l 7 t~ tr.
Z ~ t~
o o ~ ~ ~ ~ N t~ t~
tr~ O O o o o o o t~ ~ ~ ~ t~ 3 t~ ~ ~ ~

'7 ~ t~ ~ t~ ~ ~7 t1 In ~ t~ t~l ~ ~ t~ ~ ~ ~

x ol o o o o o o o o ~
~ zl ~I t~ t~ ~ r,'~ ~ N ~ ~1 ~ WO 94/19387 215 4 3 5 2 PCT/}JS94/01381 ~: - O
O
O O -- O
CJ V~
~--1 N ~ Vl '¢C`
V.~ I U -- C~
v~ Zo ~ I T z a- c z 1 3 3 o 2 Z ~ ~, ~c , ,, X ~ ~ c .~

o v z c v " ~ ~ ~ T

-- C E-~ ~r N ~
a _ ~ ô o o o u u u u u u ~, ~ a~ a ~ I S~ l l l l ~ N N N
U C ) ~ ~ ~ ~ ~ ~ ~ ^
Z cn o~ N N
N N N N N N N
O O O
~1 ~I N N
N N N N N N N
O O O O O O O _ _ _ N N N N N N N N N N
N N N N N N N

N N N N N N N N N N

x o ~
~I Z N N N N N N N N N N

WO 94/19387 ~ S ~3$~ PCT/US94/01381 _ ? o ,~
a~ -- O ~ O
~, -,~ -- u~ -- ~ cn ~
0 ,1 ~ O ~ ~
~ o u~ ~ cn o ~ ~ u -- ~-- o ~ o -- ~ _ --Cq ~~1 Cq u~ a) u~ ~ 'J
b'I z T I ~
Or I 5Fi I cn I I cn T 1' ~ O N t) C) n I ~1~ ~ cln I C ~; ~
C) U~ ~C~ -- O Ul Z ~ O C~
~ _ I I ,I ~ ~ C,) C) U ~ U~ ~ U~
~ I C~ I ,~ ~1 U~
a ~ ~, ul~ 1~ ul~ ul~ 1~ ul~
Z C o ~ _~ 7 _ o ~ ~ _ o Z ~ ~ ~ ~ ~ ~ ' ~ ~ ~' ~) C~ ~ V ~ ~ U
C) H
_~ J
o ~ c ~ . 3 o~ ~ I I I I I I I I I _ V E-~
,~ ~, Z -- -- _ _ _ _ _ _ _ _ ~z O ~ ~ ~ ~ ~ ~ ~ ~ l N
~4 W t~l t~ ~ ~ N ~ N
Z _ _ _ _ _ _ _ _ _ _ O O O O O O O O O O

N ~ t~ ~
- _ _ _ _ _ _ ~ ~ N ~ ~ N

X O ~ ~ ~ ~ ~ ~C~
1~ Z ~I ~ t~ ~ ~ ~ ~ t~ ~ ~1 ~15~352 -I`
O
_I
,1 ~
C~ C) O Z
I
r _. t) U~ O
~ O
-- ~J
Z ~1 ~ I
~ _ ~r U~ ~ O
O CJ

U
~ C. ~ ~ ~ Z Z U~
5 3 -- ^ u~ I I
~ V C~
-- O Z
C,~ H '~

C ~i C ~ I C~ i i i U CJ j~ o o ~ -- _ _ Z -- --:C--' O
I
11 ~ ' O
Z ~ ~ a~
- - - ~ - - -o o ~`~
- - o ~ ~ N ~ ~ ~r C~

~i _ _ ' _, ~ _ _ _ X O ~7 ~ ~ ~ ~ t ~3 Z ~ ~ ~ ~

Claims (16)

Claims We claim:
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 -(OCH2CH2)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 -(OCH2CH2)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 or 2, 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:

(II) (III) IV

wherein Pc and Nc represent the phthalocyanine and 2,3-naphthalocyanine moieties of Formulae IIa and IIIa, IIa IIIa 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, alkyl, aryl, lower alkanoyl, trifluoroacetyl or groups of the formulae , , , , , or ;

R7, R8 and R9 are independently selected from 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, 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 alkyl, aryl, halogen or hydrogen;

R is selected from unsubstituted or substituted alkyl, alkenyl, alkynyl, C3-C8 cycloalkyl, aryl, heteroaryl, or ; or -(X-R)m is alkylsulfonylamino, arylsulfonylamino, or a group selected from the formulae -X(C2H4O)zR1, , , , or , 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 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; aryl-sulfonyl; lower alkylsulfonylamino, arylsulfonyl-amino, cycloalkylsulfonylamino, carboxy, unsubstituted and substituted carbamoyl and sulfamoyl, lower alkoxycarbonyl, hydroxy, lower alkanoyloxy, , , , or , 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 any one of claims 1 to 3, 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.
5. The polyester of any one of claims 1 to 3, 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.
6. A coating composition comprising (I) about 20 weight percent to about 35 weight percent of a 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 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, 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 flouorphoric compound copolymerized therein; and (II) about 65 weight percent to about 80 weight percent of water.
7. The coating composition of claim 6, 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 -(OCH2CH2)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 -(OCH2CH2)n- where n is 2 to about 500, provided that the mole percent of such residues is inversely proportional to the value of n.
8. The coating composition of claim 6 or 7, wherein the near infrared flourescing compound is selected from the classes of phthalocyanines, 2,3-naphthalo-cyanines and squaraines and correspond to Formulae II, III and IV:

(II) (III) IV

wherein Pc and Nc represent the phthalocyanine and 2,3-naphthalocyanine moieties of Formulae IIa and IIIa, IIa IIIa 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, alkyl, aryl, lower alkanoyl, trifluoroacetyl or groups of the formulae , , , , , or ;

R7, R8 and R9 are independently selected from 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, 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 alkyl, aryl, halogen or hydrogen;

R is selected from unsubstituted or substituted alkyl, alkenyl, alkynyl, C3-C8 cycloalkyl, aryl, heteroaryl, or ; or -(X-R)m is alkylsulfonylamino, arylsulfonylamino, or a group selected from the formulae -X(C2H4O)zR1, , , , or , 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 wherein each xl 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; aryl-sulfonyl; lower alkylsulfonylamino, arylsulfonyl-amino, cycloalkylsulfonylamino, carboxy, unsubstituted and substituted carbamoyl and sulfamoyl, lower alkoxycarbonyl, hydroxy, lower alkanoyloxy, , , , or , 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.
9. The coating composition of any one of claims 6-8, 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.
10. The coating composition of any one of claims 6-8, 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.
11. 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 (I) about 20 weight percent to about 35 weight percent of a 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 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, 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 flouorphoric residue copolymerized therein; and (II) about 65 weight percent to about 80 weight percent of water.
12. The method of claim 11, wherein the near infrared fluorescing compound is a 2,3-naphthalocyanine compound of Formula III, wherein the naphthalo-cyanine moiety is bonded to SiCl2, Si(OH)2, or Si(OR6)2.
13. The method of claim 11, 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.
14. A method for detecting and separating articles, said articles coated with the coating composition of Claim 6, said composition having detectible fluorescence when exposed to near infrared radiation, which comprises the following steps:

(a) exposure of a mixture of articles to near infrared radiation having wavelengths of about 670-2,500 nm, with the provision that at least one of said articles is coated with a water-dissipatable, sulfo-containing polyester or polyester-amide having copolymerized therein at about 0.1 ppm by weight to about 10% by weight, based on the weight of the polymer, of a thermally stable, near infrared fluorescent compound, said polyester or polyester-amide being present in sufficient quantity to impart fluorescence when exposed to radiation having wavelengths of about 670-2,5000 nm, said radiation provided by light sources;

(b) detection of the emitted fluorescent light via near infrared light detection means; and (c) separating the fluorescing articles from the non-fluorescing articles or articles fluorescing at a detectibly different wave-length or wavelengths by mechanical means.
15. An article coated with the coating composition of claim 6.
16. The article of claim 15, wherein the article is paper.
CA002154352A 1993-02-18 1994-02-07 Water-dissipatable polyesters and amides containing near infrared fluorescent compounds copolymerized therein Abandoned CA2154352A1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US08/019,535 US5292855A (en) 1993-02-18 1993-02-18 Water-dissipatable polyesters and amides containing near infrared fluorescent compounds copolymerized therein
US08/019,535 1993-02-18
PCT/US1994/001381 WO1994019387A1 (en) 1993-02-18 1994-02-07 Water-dissipatable polyesters and amides containing near infrared fluorescent compounds copolymerized therein

Publications (1)

Publication Number Publication Date
CA2154352A1 true CA2154352A1 (en) 1994-09-01

Family

ID=21793719

Family Applications (1)

Application Number Title Priority Date Filing Date
CA002154352A Abandoned CA2154352A1 (en) 1993-02-18 1994-02-07 Water-dissipatable polyesters and amides containing near infrared fluorescent compounds copolymerized therein

Country Status (9)

Country Link
US (2) US5292855A (en)
EP (1) EP0684963B1 (en)
JP (1) JP3241732B2 (en)
KR (1) KR960701121A (en)
AT (1) ATE169045T1 (en)
CA (1) CA2154352A1 (en)
DE (1) DE69412071T2 (en)
TW (1) TW266218B (en)
WO (1) WO1994019387A1 (en)

Families Citing this family (98)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
SG47881A1 (en) * 1991-11-08 1998-04-17 Eastman Chem Co Method for tagging thermoplastic materials with near infrared fluorophores
US6766953B1 (en) 1992-05-01 2004-07-27 Hewlett-Packard Development Company, L.P. Tape indicia on clear film media
DE4403664A1 (en) * 1994-02-07 1995-08-10 Basf Ag Use of compounds that absorb and fluoresce in the IR range as crack test agents
EP0931823A3 (en) 1994-03-17 2000-06-21 Hitachi Maxell, Ltd. Fluorescent substance, fluorescent composition, fluorescent mark carrier and optical reader therefor
US5525516B1 (en) * 1994-09-30 1999-11-09 Eastman Chem Co Method for tagging petroleum products
DE69520644T2 (en) * 1994-10-21 2001-11-22 Hitachi Maxell Fluorescent label composition and label obtained
US5843783A (en) * 1994-11-04 1998-12-01 Amoco Corporation Tagging hydrocarbons for subsequent identification
US5723338A (en) * 1994-11-04 1998-03-03 Amoco Corporation Tagging hydrocarbons for subsequent identification
US5710046A (en) * 1994-11-04 1998-01-20 Amoco Corporation Tagging hydrocarbons for subsequent identification
GB9516371D0 (en) * 1995-08-10 1995-10-11 Zeneca Ltd Compositions
US5614008A (en) * 1995-10-23 1997-03-25 Escano; Nelson Z. Water based inks containing near infrared fluorophores
US7253557B2 (en) * 1996-02-08 2007-08-07 Bright Solutions, Inc. Light source provided with a housing enclosing voltage regulator means and method of manufacturing thereof
US6590220B1 (en) * 1996-02-08 2003-07-08 Bright Solutions, Inc. Leak detection lamp
US6174400B1 (en) 1997-03-04 2001-01-16 Isotag Technology, Inc. Near infrared fluorescent security thermal transfer printing and marking ribbons
US6232124B1 (en) 1996-05-06 2001-05-15 Verification Technologies, Inc. Automated fingerprint methods and chemistry for product authentication and monitoring
US5959296A (en) * 1996-06-24 1999-09-28 Eastman Chemical Company Scanners for reading near infrared fluorescent marks
JP2001501661A (en) 1996-10-01 2001-02-06 ゼネカ・リミテッド Composition
CN1232481A (en) 1996-10-01 1999-10-20 曾尼卡有限公司 Aqueous ink compositions
JP2001501246A (en) 1996-10-01 2001-01-30 ゼネカ・リミテッド Composition
US5990197A (en) * 1996-10-28 1999-11-23 Eastman Chemical Company Organic solvent based ink for invisible marking/identification
US5851243A (en) * 1997-04-30 1998-12-22 Eastman Kodak Company Radiographic elements capable of rapid access processing modified to reduce red light transmission
US5744294A (en) * 1997-04-30 1998-04-28 Eastman Kodak Company Radiographic element modified to provide protection from visual fatigue
US6585341B1 (en) 1997-06-30 2003-07-01 Hewlett-Packard Company Back-branding media determination system for inkjet printing
US6036298A (en) 1997-06-30 2000-03-14 Hewlett-Packard Company Monochromatic optical sensing system for inkjet printing
US6557965B2 (en) 1997-06-30 2003-05-06 Hewlett-Packard Company Shortcut media determination system for inkjet printing
US6561643B1 (en) 1997-06-30 2003-05-13 Hewlett-Packard Co. Advanced media determination system for inkjet printing
US6325505B1 (en) 1997-06-30 2001-12-04 Hewlett-Packard Company Media type detection system for inkjet printing
US6685313B2 (en) 1997-06-30 2004-02-03 Hewlett-Packard Development Company, L.P. Early transparency detection routine for inkjet printing
US6425650B1 (en) 1997-06-30 2002-07-30 Hewlett-Packard Company Educatable media determination system for inkjet printing
US6386669B1 (en) 1997-06-30 2002-05-14 Hewlett-Packard Company Two-stage media determination system for inkjet printing
US5922782A (en) * 1997-07-23 1999-07-13 Eastman Chemical Company Foamable copolyesters prepared from divalent metal containing co-ionomers
US6006991A (en) * 1997-10-31 1999-12-28 Psc Inc. Method and apparatus for reading both of standard and fluorescent bar codes
US6138913A (en) * 1997-11-05 2000-10-31 Isotag Technology, Inc. Security document and method using invisible coded markings
US6103006A (en) * 1998-01-28 2000-08-15 Day-Glo Color Corporation Fluorescent polymeric pigments
US6106910A (en) * 1998-06-30 2000-08-22 Ncr Corporation Print media with near infrared fluorescent sense mark and printer therefor
US6060426A (en) * 1998-06-30 2000-05-09 Ncr Corporation Thermal paper with security features
US6432715B1 (en) 1998-02-24 2002-08-13 Isotag Technology, Inc. Method for marking items for identification
US6150494A (en) * 1998-04-30 2000-11-21 Eastman Chemical Company Polymers containing optical brightener compounds copolymerized therein and methods of making and using therefor
US6217794B1 (en) 1998-06-01 2001-04-17 Isotag Technology, Inc. Fiber coating composition having an invisible marker and process for making same
US6406668B1 (en) 1998-08-03 2002-06-18 University Of Iowa Research Foundation Sensing array and sensor structure
US6036885A (en) * 1998-09-15 2000-03-14 Eastman Chemical Company Method for making cellulose esters incorporating near-infrared fluorophores
US6165937A (en) * 1998-09-30 2000-12-26 Ncr Corporation Thermal paper with a near infrared radiation scannable data image
US6149719A (en) 1998-10-28 2000-11-21 Hewlett-Packard Company Light sensitive invisible ink compositions and methods for using the same
US6644764B2 (en) 1998-10-28 2003-11-11 Hewlett-Packard Development Company, L.P. Integrated printing/scanning system using invisible ink for document tracking
US6613403B2 (en) 1998-12-21 2003-09-02 Ncr Corporation Ink with near infrared fluorophores and U.V. absorbers
US6490030B1 (en) 1999-01-18 2002-12-03 Verification Technologies, Inc. Portable product authentication device
US5993237A (en) * 1999-04-12 1999-11-30 Aines Manufacturing Corp. Modular telephone plug
US6162869A (en) * 1999-06-22 2000-12-19 Eastman Chemical Company Waterborne acrylic polymers containing polymeric fluorescent compounds
US6221279B1 (en) 1999-06-24 2001-04-24 Isotag Technology, Inc. Pigment particles for invisible marking applications
US6512580B1 (en) 1999-10-27 2003-01-28 Verification Technologies, Inc. Method and apparatus for portable product authentication
US6969549B1 (en) 1999-11-19 2005-11-29 Hewlett-Packard Development Company, L.P. Techniques to prevent leakage of fluorescing signals through print media or indicia tape
US6386671B1 (en) 1999-12-29 2002-05-14 Hewlett-Packard Company Orientation independent indicia for print media
GB0000788D0 (en) 2000-01-14 2000-03-08 Willett Int Ltd Apparatus
US20030112423A1 (en) * 2000-04-24 2003-06-19 Rakesh Vig On-line verification of an authentication mark applied to products or product packaging
US20040000787A1 (en) * 2000-04-24 2004-01-01 Rakesh Vig Authentication mark for a product or product package
WO2002002301A1 (en) 2000-06-30 2002-01-10 Verification Technologies Inc. Copy-protected optical media and method of manufacture thereof
US7124944B2 (en) * 2000-06-30 2006-10-24 Verification Technologies, Inc. Product packaging including digital data
US6638593B2 (en) 2000-06-30 2003-10-28 Verification Technologies, Inc. Copy-protected optical media and method of manufacture thereof
US7660415B2 (en) * 2000-08-03 2010-02-09 Selinfreund Richard H Method and apparatus for controlling access to storage media
US6962670B1 (en) 2000-08-16 2005-11-08 Eastman Chemical Company Determination of layer thickness or non-uniformity of layer thickness based on fluorophore additives
AU2001295025A1 (en) * 2000-09-08 2002-03-22 Isotag Technology, Inc. Monomeric dye inkjet printing ink formulations for invisible marking/identification
US6562755B1 (en) 2000-10-31 2003-05-13 Ncr Corporation Thermal paper with security features
US7122248B2 (en) * 2001-02-21 2006-10-17 Honeywell International Inc. Security articles
US6725207B2 (en) 2001-04-23 2004-04-20 Hewlett-Packard Development Company, L.P. Media selection using a neural network
US6893489B2 (en) 2001-12-20 2005-05-17 Honeywell International Inc. Physical colored inks and coatings
US6803344B2 (en) * 2001-12-21 2004-10-12 Ncr Corporation Thermal paper with preprinted indicia
US20050084645A1 (en) * 2002-02-07 2005-04-21 Selinfreund Richard H. Method and system for optical disc copy-protection
US20040023397A1 (en) * 2002-08-05 2004-02-05 Rakesh Vig Tamper-resistant authentication mark for use in product or product packaging authentication
CA2497645A1 (en) * 2002-09-26 2004-04-08 Verification Technologies, Inc. Authentication of items using transient optical state change materials
US20060203700A1 (en) * 2003-02-06 2006-09-14 Verification Technologies, Inc. Method and system for optical disk copy-protection
US7687143B2 (en) * 2003-06-19 2010-03-30 Eastman Chemical Company Water-dispersible and multicomponent fibers from sulfopolyesters
US20110139386A1 (en) * 2003-06-19 2011-06-16 Eastman Chemical Company Wet lap composition and related processes
US20040260034A1 (en) 2003-06-19 2004-12-23 Haile William Alston Water-dispersible fibers and fibrous articles
US8513147B2 (en) 2003-06-19 2013-08-20 Eastman Chemical Company Nonwovens produced from multicomponent fibers
US7892993B2 (en) 2003-06-19 2011-02-22 Eastman Chemical Company Water-dispersible and multicomponent fibers from sulfopolyesters
DE102004046618A1 (en) * 2004-09-25 2006-03-30 Robert Bosch Gmbh Circuit arrangement for analog / digital conversion
US7645719B2 (en) * 2004-10-13 2010-01-12 Ncr Corporation Thermal paper with security features
US7635745B2 (en) * 2006-01-31 2009-12-22 Eastman Chemical Company Sulfopolyester recovery
EE200600004A (en) * 2006-03-03 2007-10-15 O� Raidenil Infrared sensitive composite material
US20070287822A1 (en) * 2006-06-13 2007-12-13 Eastman Chemical Company Light absorbing compositions
US20080064621A1 (en) * 2006-09-07 2008-03-13 Daniel Alan Jervis Optically brightened aqueous compositions
US20080160859A1 (en) * 2007-01-03 2008-07-03 Rakesh Kumar Gupta Nonwovens fabrics produced from multicomponent fibers comprising sulfopolyesters
US8512519B2 (en) 2009-04-24 2013-08-20 Eastman Chemical Company Sulfopolyesters for paper strength and process
CN102812093B (en) * 2010-03-02 2014-01-15 新日铁住金化学株式会社 Squarylium dye, dye-sensitized solar cell using the dye, and photoelectric conversion element using the dye
US20120183861A1 (en) 2010-10-21 2012-07-19 Eastman Chemical Company Sulfopolyester binders
US8403223B2 (en) 2011-02-11 2013-03-26 Ut-Battelle, Llc Invisible-fluorescent identification tags for materials
TW201335295A (en) * 2011-11-30 2013-09-01 西克帕控股公司 Marked coating composition and method for its authentication
WO2013110166A1 (en) 2012-01-26 2013-08-01 S. A. Armstrong Limited Method and system for selecting a device from a graphical interface
US8882963B2 (en) 2012-01-31 2014-11-11 Eastman Chemical Company Processes to produce short cut microfibers
US9303357B2 (en) 2013-04-19 2016-04-05 Eastman Chemical Company Paper and nonwoven articles comprising synthetic microfiber binders
US9605126B2 (en) 2013-12-17 2017-03-28 Eastman Chemical Company Ultrafiltration process for the recovery of concentrated sulfopolyester dispersion
US9598802B2 (en) 2013-12-17 2017-03-21 Eastman Chemical Company Ultrafiltration process for producing a sulfopolyester concentrate
WO2016025620A1 (en) 2014-08-12 2016-02-18 Georgia State University Research Foundation, Inc. Near infrared absorbing fluorescent compositions
US10119071B2 (en) 2015-06-10 2018-11-06 Ut-Battelle, Llc Enhanced invisible-fluorescent identification tags for materials
CN105061294A (en) * 2015-08-07 2015-11-18 常州大学 Benzindole squarylium cyanine colorimetric probe, preparation method therefor and application thereof
WO2017146187A1 (en) * 2016-02-25 2017-08-31 株式会社日本触媒 Oxocarbon compound, resin composition, and ink composition
US10309901B2 (en) 2017-02-17 2019-06-04 International Business Machines Corporation Water-sensitive fluorophores for moisture content evaluation in hygroscopic polymers
US20210214567A1 (en) * 2020-01-14 2021-07-15 Xerox Corporation Ink composition and method of printing ink

Family Cites Families (47)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3734874A (en) * 1970-02-27 1973-05-22 Eastman Kodak Co Polyesters and polyesteramides containing ether groups and sulfonate groups in the form of a metallic salt
US3779993A (en) * 1970-02-27 1973-12-18 Eastman Kodak Co Polyesters and polyesteramides containing ether groups and sulfonate groups in the form of a metallic salt
US3828010A (en) * 1973-06-04 1974-08-06 Eastman Kodak Co Water-dissipatable polyesteramides
DE2506153A1 (en) * 1975-02-14 1976-08-26 Basf Ag SOLUBLE COPPER PHTHALOCYANINE DYES AND THEIR APPLICATION
US4231133A (en) * 1979-03-19 1980-11-04 Deep Steam Extraction (1974) Ltd. Wet vacuum machine
US4250078A (en) * 1979-03-19 1981-02-10 Eastman Kodak Company Thermoplastic polyester molding compositions
US4420581A (en) * 1979-03-19 1983-12-13 Eastman Kodak Company Thermoplastic polyester molding compositions
US4233196A (en) * 1979-04-30 1980-11-11 Eastman Kodak Company Polyester and polyesteramide compositions
US4321133A (en) * 1979-12-31 1982-03-23 Occidental Research Corporation Sorting of limestone ores using fluorescent compounds
US4335220A (en) * 1981-04-06 1982-06-15 Eastman Kodak Company Sequestering agents and compositions produced therefrom
US4423814A (en) * 1981-06-05 1984-01-03 Occidental Research Corporation Separation or concentration of magnesium-bearing minerals by induced fluorescence
US4540595A (en) * 1982-02-01 1985-09-10 International Business Machines Corporation Article identification material and method and apparatus for using it
US4408004A (en) * 1982-02-24 1983-10-04 The Goodyear Tire & Rubber Company High clarity, low haze polyesters having reduced infrared heat-up times
US4476272A (en) * 1982-02-24 1984-10-09 The Goodyear Tire & Rubber Company High clarity, low haze polyesters having reduced infrared heat-up times
US4535118A (en) * 1982-02-24 1985-08-13 The Goodyear Tire & Rubber Company High clarity, low haze polyesters having reduced infrared heat-up times
US4541438A (en) * 1983-06-02 1985-09-17 The Johns Hopkins University Localization of cancerous tissue by monitoring infrared fluorescence emitted by intravenously injected porphyrin tumor-specific markers excited by long wavelength light
AU565143B2 (en) * 1983-10-31 1987-09-03 Institut Obschei I Neorganicheskoi Khimii Imeni N.S. Kurnakova Akademii Nauk Sssr, Et Al Polymer material for coating hot greenhouses
DE3576823D1 (en) * 1984-03-21 1990-05-03 Ici Plc INFRARED ABSORBER.
DD227520A1 (en) * 1984-09-27 1985-09-18 Schwerin Plastverarb Veb METHOD FOR SORTING USED PLASTIC PARTS
GB8431446D0 (en) * 1984-12-13 1985-01-23 Secr Defence Alkoxyphthalocyanines
US4704309A (en) * 1985-06-07 1987-11-03 Eastman Kodak Company Printing processes employing water dispersible inks
US4904567A (en) * 1985-08-13 1990-02-27 Mitsubishi Kasei Corporation Optical recording member
US4816386A (en) * 1986-01-13 1989-03-28 Toray Industries, Inc. Near-infrared sensitive phthalocyanine-polymer compositions
US4649064A (en) * 1986-03-10 1987-03-10 Eastman Kodak Company Rapid-drying recording element for liquid ink marking
US4738785A (en) * 1987-02-13 1988-04-19 Eastman Kodak Company Waste treatment process for printing operations employing water dispersible inks
GB8705575D0 (en) * 1987-03-10 1987-04-15 Ici Plc Substituted phthalocyanine
US4883714A (en) * 1987-05-18 1989-11-28 Eastman Kodak Company Ink compositions and preparation
US4804719A (en) * 1988-02-05 1989-02-14 Eastman Kodak Company Water-dissipatable polyester and polyester-amides containing copolymerized colorants
DE68926129T2 (en) * 1988-03-07 1996-08-14 Kanebo Ltd Molded polyamide articles and process for their manufacture
US4915827A (en) * 1988-05-19 1990-04-10 Trebor Industries, Inc. Method and apparatus for optical sorting of materials using near infrared absorbtion criteria
US4910292A (en) * 1988-10-14 1990-03-20 Eastman Kodak Company Water-dissipatable polyester resins and coatings prepared therefrom
US4983817A (en) * 1989-03-01 1991-01-08 Battelle Memorial Institute Background compensating bar code readers
DE3908458A1 (en) * 1989-03-16 1990-09-20 Basf Ag NEW POLYMERS AND ITS USE
US4992204A (en) * 1989-08-22 1991-02-12 Miliken Research Corporation Irradiation detection and identification method and compositions useful therein
US5169881A (en) * 1989-10-24 1992-12-08 Eastman Kodak Company Process for treating pigments
US5055500A (en) * 1989-10-24 1991-10-08 Eastman Kodak Company Process for treating pigments
US5260052A (en) * 1989-10-24 1993-11-09 Eastman Kodak Company Process for treating pigments
US4975220A (en) * 1989-11-09 1990-12-04 Nalco Chemical Company Polyamide-polyester fluorescent pigments
US5006598A (en) * 1990-04-24 1991-04-09 Eastman Kodak Company Water-dispersible polyesters imparting improved water resistance properties to inks
DE4024130A1 (en) * 1990-07-30 1992-02-06 Folkerts Karl Heinz Prof Dr Re Separating mixed plastic materials - by producing each type with its own markings, irradiating mixt., analysing characteristic emissions and using them to control sorting
US5093147A (en) * 1990-09-12 1992-03-03 Battelle Memorial Institute Providing intelligible markings
DE4029167A1 (en) * 1990-09-14 1992-03-19 Bayer Ag METHOD FOR IDENTIFYING PLASTICS
US5143671A (en) * 1990-10-31 1992-09-01 Eastman Kodak Company Fluidized bed process for treating pigments
EP0484027B1 (en) * 1990-11-02 1996-12-18 Zeneca Limited Polysubstituted phthalocyanines
US5102980A (en) * 1990-11-13 1992-04-07 Eastman Kodak Company Colored polyester compositions
US5030708A (en) * 1990-12-17 1991-07-09 Eastman Kodak Company Colored polyester compositions
US5218042A (en) * 1991-09-25 1993-06-08 Thauming Kuo Water-dispersible polyester resins and process for their preparation

Also Published As

Publication number Publication date
US5292855A (en) 1994-03-08
EP0684963B1 (en) 1998-07-29
EP0684963A1 (en) 1995-12-06
TW266218B (en) 1995-12-21
US5336714A (en) 1994-08-09
DE69412071T2 (en) 1998-12-03
JP3241732B2 (en) 2001-12-25
DE69412071D1 (en) 1998-09-03
WO1994019387A1 (en) 1994-09-01
KR960701121A (en) 1996-02-24
JPH08507317A (en) 1996-08-06
ATE169045T1 (en) 1998-08-15

Similar Documents

Publication Publication Date Title
CA2154352A1 (en) Water-dissipatable polyesters and amides containing near infrared fluorescent compounds copolymerized therein
US5423432A (en) Water-dissipatable polyesters and amides containing near infrared fluorescent compounds copolymerized therein
CA2121507C (en) Method for tagging thermoplastic materials with near infrared fluorophores
EP0857197B1 (en) Water based inks containing near infrared fluorophores
EP0934370B1 (en) Organic solvent based ink for invisible marking/identification
US5525516A (en) Method for tagging petroleum products
US6150494A (en) Polymers containing optical brightener compounds copolymerized therein and methods of making and using therefor
EP1794136B1 (en) Aryl-ureido benzoxazinone compounds
WO2016025620A1 (en) Near infrared absorbing fluorescent compositions
US6221279B1 (en) Pigment particles for invisible marking applications
US20080305243A1 (en) Method for identifying articles and process for maintaining security
MXPA98003148A (en) Water based inks containing infrared fluoroforos proxi

Legal Events

Date Code Title Description
EEER Examination request
FZDE Discontinued