WO1987007289A1

WO1987007289A1 - Ink composition

Info

Publication number: WO1987007289A1
Application number: PCT/US1987/001132
Authority: WO
Inventors: Charles Herbert Coney; Theron Edward Parsons, Iii; Gary Thomas Clark; Hazel Rebecca Stockl; Frank Joseph Tortorici
Original assignee: Eastman Kodak Company
Priority date: 1986-05-20
Filing date: 1987-05-19
Publication date: 1987-12-03
Also published as: JP2563419B2; JPH01503071A; AU7480587A; EP0325581A1; CA1323126C; AU599672B2

Abstract

A water dispersible composition useful in printing inks exemplified as comprising: (A) one or more polyester materials having an acid component of from about 75 to about 84 mole % isophthalic acid and conversely from about 25 to about 16 mole % 5-sodio-sulfoisophthalic acid, and having a glycol component of from about 45 to about 60 mole % diethylene glycol and conversely from about 55 to about 40 mole % 1,4-cyclohexanedimethanol or ethylene glycol or mixtures thereof, and; (B) pigment material in a weight ratio with respect to total polyester material of from about 1/1000 to about 10/1 blended with said polyester material.

Description

INK COMPOSITION

This application is a continuation—in— art of Application Serial No. 864,996 filed May 20, 1986. This invention concerns pigmented, aqueous inks and concentrates for the preparation thereof wherein the pigment carrier or binder comprises water dispersible polyester material. No organic solvents or other property modifiers are necessary in the ink system for achieving markedly superior printed coatings by greatly simplified ink preparation and printing methods; however, such solvents and property modifiers as well as conventional dispersing aids, defoamers and the like may be used if desired. The present inks find special utility for letter press, intaglio, gravure, flexographic and other printing processes adaptable to the use of aqueous inks. The term dispersible as used herein encompasses the phenomena of solubilization, dissipation, suspension and the like of the polyester in the aqueous system. The printing industry* in general is a high priortiy field for the use of water—based inks and overprint varnishes as a means of meeting increas¬ ingly stringent solvent effluent regulations. Present—day water—based inks often fail to satisfy these regulations as well as the necessary print- ability, stability, and performance properties required for commercial inks. For example, the various ethylene-acrylic acid copolymer salts of U.S. Patent 3,607,813, the disclosure of which is incor¬ porated herein by reference (for the printing process descriptions therein), in addition to requiring complex polymer and ink preparations, lack in performance on certain substrates. Other such aqueous or semi—aqueous systems proposed for printing inks contain polymers such as styrene—butadiene or polyacrylate latex systems but these systems also have serious drawbacks including being non-water dispersible after short drying periods which compli¬ cates equipment clean up. Other water soluble or dispersible polymers suggested for printing ink use are discussed in U.S. Patent 4,072,644.

The present invention provides vast improve¬ ments in the preparation, stability, and performance of water—based inks for printing and coating. The invention in its broad embodiment is defined as a water dispersible composition useful in printing inks comprising:

(A) polymeric material of at least one linear water-dispersible polymer having carbonyloxy linking groups in the linear molecular structure wherein up to 80% of the linking groups may be carbonylamido linking groups, the polymer having an inherent viscosity of from about 0.1 to about 1.0, preferably from about 0.1 to about 0.5 measured in a 60/40 parts by weight solution of phenol/tetrachloro— ethane at 25°C and at a concentration of 0.25 gram of polymer in 100 ml of the solvent, the polymer containing substantially equimolar proportions of acid equivalents (100 mole percent) to hydroxy and amino equivalents (100 mole percent), the polymer comprising the reaction products of (a), (b), (c), and (d) from the following components or ester forming or ester—amide forming derivatives thereof; (a) at least one difunctional dicarboxylic acid; (b) from about 4 to about 25 mole percent, based on a total of all acid, hydrox 1 and amino equivalents being equal to 200 mole percent, of at least one difunctional sulfomonomer containing at least one metal cationic group attached to an aromatic or cycloaliphatic nucleus wherein the functional groups are hydroxy, carboxyl or amino; (c) at least one difunctional reactant selected from a glycol or a mixture of a glycol and diamine having two -NRH groups, the glycol containing two -CH--OH groups of which

(1) at least 15 mole percent, based on the total mole percent of hydroxy or hydroxy and amino equivalents, is a poly(ethylene glycol) having the structural formula

HfOCH₂-CH₂7-_nOH, n being an integer of from 2 to about 20, or (2) of which from about 0.1 to less than about, 15 mole percent, based on the total mole percent of hydroxy or hydroxy and amino equivalents, is a poly(ethylene glycol) having the structural formula

Ht^CH₂-CH_{2 n}OH, n being an integer of between 2 and about 500, and with the proviso that the mole percent of said poly(ethylene glycol) within said range is inversely proportional to the quantity of n within said range; and (d) from none to at least one difunctional reactant selected from a hydroxycarboxylic acid having one -C(R)_-OH group, an aminocarboxylic acid having one -NRH group, and an amino—alcohol having one -C(R)₂-OH group and one -NRH group, or mixtures of said difunctional reactants; wherein each R in the (c) or (d) reactants is a H atom or an alkyl group of 1 to 4 carbon atoms, and; (B) pigment material dispersed in said polymeric material in a weight ratio of pigment to total polymeric material of from about 1/1000 to about 10/1, preferably from about 1/100 to about 5/1, and most preferably from about 1/20 to about 3/1.

In the above polyester material it is preferred that very minor, e.g., less than about 10 mol % based on all reactants, of reactant (d) is employed, that at least about 70 mol % of reactant (c) is glycol, and that at least about 70 mol % of all the hydroxy equivalents is present in the glycol.

In preferred embodiments of the invention: the polymeric material comprises an acid component (moiety) of from about 75 to about 84 mole % isophthalic acid and conversely from about 25 to about 16 mole % 5—sodiosulfoisophth'alic acid, and a glycol component (moiety) of from about 45 to about 60 mole % diethylene glycol and conversely from about 55 to about 40 mole % 1,4—cyclohexanedimethanol or ethylene glycol (the term "moiety" as used herein designates the residual portion of the reactant acid or glycol which actually enters into or onto the polymer chain during the condensation or polyconden— sation reaction); the pigment material is dispersed in the polymeric material in a weight ratio with respect to the total of the polymeric material, of from about 1/100 to about 5/1; the inherent viscosity of the polymeric material is from about 0.28 to about 0.35, the said acid component (moiety) comprises from about 80 to about 83 mole % isophthalic acid and conversely from about 20 to about 17 mole % 5-sodiosulfoisophthalic acid, and the said glycol component (moiety) comprises from about 52 to about 56 mole % diethylene glycol and conversely from about 48 to about 44 mole % 1, —cyclohexanedimethanol;

_ 5 _

the pigment is one or a mixture of the following color index materials according to their generic names: C.I. Pigment Yellow 17, C.I. Pigment Blue 27, C.I. Pigment Red 49:2, C.I. Pigment Red 81:1, C.I. Pigment Red 81:3, C.I. Pigment Red 81:x, C.I. Pigment Yellow 83, C.I. Pigment Red 57:1, C.I. Pigment Red 49:1, C.I. Pigment Violet 23, C.I. Pigment Green 7, C.I. Pigment Blue 61, C.I. Pigment Red 48:1, C.I. Pigment Red 52:1, C.I. Pigment Violet 1, C.I. Pigment White 6, C.I. Pigment Blue 15, C.I. Pigment Yellow 12, C.I. Pigment Blue 56, C.I. Pigment Orange 5, C.I. Pigment Black 7, C.I. Pigment Yellow 14, C.I. Pigment Red 48:2, C.I. Pigment Blue 15:3; the polymeric material is dispersed in water and comprises from about 1 to about 50% by weight of the total aqueous dispersion, preferably from about 10 to about 40% by weight of the total aqueous dispersion; the aqueous dispersion is coated or printed onto a substrate selected from metal foil, newsprint, bleached and unbleached Kraft paper, clay coated paper, glass, calendered paper, stainless paper, paper board, and films or other substrates of poly¬ ester, polycarbonate, cellulose ester, regenerated cellulose, poly(vinylidene cholride), polyamide or polystyrene; and said coating or print comprises any of the above compositions wherein a substantial portion of the initial metal cations of the water solubilizing sulfonate groups of the polymeric material has been replaced with an ihsolubllizing polyvalent metal

+3 i r cation, such as Al , Ca , or the like as disclosed and in the manner described in U.S. Patent

4,145,469, the disclosure of which is incorporated herein by reference. As stated therein, generally, based on the weight of the polymeric material, 0.05% to about 2.0% by weight solids of the polyvalent metal cation are required for effective insolubili- zation.

The complete chemical definitions of the above C.I. pigments are given in the following table:

Pigments

Generic Name C.A. Index/Chemical Name

C.I. Pigment Yellow 17 Butanamide, 2,2'-[(3,3'- dichloro[l,1'-biphenyl]- 4,4^»-diyl)bis(azo)bis[N- (2—methoxypheny1)—3-oxo-

C.I. Pigment Blue 27 Ferrate (4-1), hexakis (cyano-C)—ammonium iron (3+)(l:l:l)

C.I. Pigment Red 49:2 1-Naphthalenesulfonic acid, 2-[(2-hydroxy-l- naphthalenyl)azo]—, calcium salt (2:1)

C.I. Pigment Red 81:1 Benzoic acid, 2,—[6—ethyl— •amino)—3—(ethylimino)—2,7— dimethyl-3H-xanthen-9-yl]-, ethyl ester, w/molybdenum tungsten hydroxide oxide phosphate

C.I. Pigment Red 81:3 Benzoic acid, 2—[6—ethyl— amino)—3—ethylimino)—2,7— dimethyl-3H-xanthen-9-yl]-, ethyl ester, molybdate— silicate

C.I. Pigment Red 81:x Benzoic acid, 2—[6—(ethyl— amino)—3—(ethy1imino)—2,7- dimethyl-3H-xanthen-9-yl] ethyl ester, molybdate— phosphate

C.I. Pigment Yellow 83 Butanamide, 2,2'-[(3,3'- dichloro[l,l*—biphenyl]— 4,4'-diyl)bis(azo)bis[N- ( —ch1oro-2,5—dimethoxy— pheny1)—3—oxo— Generic Name C.A. Index/Chemical Name C.I. Pigment Red 57:1 2-Naphthalenecarboxylic acid, 3-hydroxy~4-[(4- methyl—2—sulfophenyl)azo]—, calcium salt (1:1)

C.I. Pigment Red 49:1 1-Naphthalenesulfonic acid, 2-[(2-hydroxy-l— naphthalenyl)azo]-, barium salt (2:1)

C.I. Pigment Violet 23 Diindolo[3,3^,,2^,m] triphenodioxazine, 8,18— dichloro-5,15-diethyl-5,15- dihydro—

C.I. Pigment Green 7 C.I. Pigment Green 7

C.I. Pigment Blue 61 Benzenesulfonic acid, [[4— [[4—phenylamino)phenyl]— [4-(phenylimino)—2,5-cyclo- hexadien—1-ylidene]methyl]- phenyl]amino]—

C.I. Pigment Red 48:1 2-Naphthaienecarboxylie acid, 4—[(5—chloro— — methyl—2—sul ophenyl)azo]— 3-hydroxy—, barium salt (1:1)

C.I. Pigment Red 52:1 2-Naphtha1enecarbox 1ic acid, 4—[(4—chloro-5— methyl—2—sulfophenyl)azo]— 3-hydroxy—, calcium salt (1:1)

C.I. Pigment Violet 1 Ethanaminium, N-[9-(2- carboxyphenyl)—6-(diethyl- amino)—3H—xanthen—3— ylidene]-N—ethyl-, molyb— datetungstatephosphate

C.I. Pigment White 6 Titanium oxide (Tiθ2)

C.I. Pigment Blue 15 Copper, [29H, 31H- phthalocyaninato (2—)— _N29, _N30, N31,

N³²]-, (Sp-4-1)- Generic Name C.A. Index/Chemical Name C.I. Pigment Yellow 12 Butanamide, 2,2'-[(3,3'- dichloro[l,1*-biphenyl]— 4,4'-diyl)bis(azo)]bis[3- oxo-N— henyl—

C.I. Pigment Blue 56 Benzenesulfonic acid, 2- methyl-4-[[4-[[4-[(3- methylphenyl)amino]phenyl]- [4-[(3-methylphenyl)- imino]—2,5-cyclohexa- dien-l-ylidene]methyl]- phenyl]amino]—

C.I. Pigment Orange 5 2-Naphthalenol, l-[(2,4- dinitrophenyl)azo]—

C.I. Pigment Black 7 Carbon black

C.I. Pigment Yellow 14 Butanamide, 2,2'-[(3,3'- dichloro[1,1'-biphenyl]- 4,4^,-diyl)bis(azo)]bis- [N—(2-methylphenyl)—3-oxo-

C.I. Pigment Red 48:2 2-Naphthaienecarboxylie acid, 4—[(5-chloro-4— methyl—2—sul ophenyl)— azo]—3-hydroxy—, calcium salt (1:1)

C.I. Pigment Blue 15:3 Copper, [29H, 31H- phthalocyaninato (2-)-N²*, _N30, „31, N³²]-, (SP-4-1)-

The inherent viscosities (I.V.) of the particular polyester materials useful herein range from about 0.1 to about 1.0 determined according to ASTM D2857-70 procedure, in a Wagner Viscometer of Lab Glass, Inc. of Vineland, New Jersey, having a 1/2 ml. capillary bulb, using a polymer concentration about 0.25% by weight in 60/40 by weight of phenol/- tetrachloroethane. The procedure is carried out by heating the polymer/solvent system ar 120°C for 15 minutes, cooling the solution to 25°C and measuring the time of flow at 25°C. The I.V. is calculated from the equation - 9 -

s

( n) 25°C. In 0.50%

where:

(n) =■ inherent viscosity at 25°C at a polymer concentration of 0.25 g/100 ml. of solvent;

In =* natural logarithm; t_s =•* sample flow time; t_Q =» solvent-blank flow time; and

C = concentration of polymer in grams per 100 ml. of solvent - 0.25.

The units of the inherent viscosity throughout this application are in decili ers/gram. It is noted that higher concentrations of polymer, e.g., 0.50 g of polymer/100 ml solvent may be employed for more precise I.V. determinations.

In general, the present polyester materials are excellent film formers for water—based printing inks. The polymers form stable dispersions in water and produce tough, flexible films on drying. No solvents are required, and films will form at temperatures just above the freezing point of water. The polymers in dispersion form may be plasticized if necessary, for example, with certain water immiscible phthalate esters to high degrees of flexibility. Printing inks prepared from the aqueous dispersed polymers are water reducible and require no organic solvents or wetting agents although such may be employed. The inks dry rapidly upon printing but have long "open" times in containers exposed to the atmosphere, such as a printing press fountain. The inks wet surfaces well and have excellent adhesion to many plastic films and metal foil as well as to paper, glass and many other substrates. Both the 100% solid polymers and the corresponding aqueous dispersions thereof may be pigmented by conventional techniques, and high gloss prints may be obtained. The prints have moderate water resistance upon heating and may be post—treated to produce films with excellent resistance to water, for example, with an aqueous alum solution or the like cation.

The aforedescribed polyester material is prepared according to the polyester preparation technology described in U.S. Patents 3,734,874 and 3,779,993, the disclosures of which are incorporated herein by reference, and the use of the term "acid" in the above description and in the appended claims includes the various ester forming or condensable derivatives of the acid reactants such as the dimethyl esters thereof as employed in the preparations set out in these patents.

Dispersal of the present polyester material in water is preferably done at preheated water tempera— ture of about a 180° to about 200°F and the polymer added rapidly as pellets to the vortex under high shear stirring. A Cowles Dissolver, Waring Blender, or similar equipment may be used. Once water is heated to temperature, additional heat input is not required. Depending upon the volume prepared, dispersal of the pellets by stirring should be complete within 15 to 30 minutes. Continued agitation with cooling may be desirable to prevent thickening at the surface due to water evaporation. Viscosities of the dispersions remain low up to nonvolatile levels of about 25—30%, but generally increase sharply above these levels. Viscosities of the dispersions will be influenced by the degree of polymer dispersion (fineness) obtained which is affected by the dispers— ing temperature, shear, and time. A nonvolatile limit for most applications is about 38% for the present preferred polyester material. The present pig ented polyester material and inks may also be prepared by two— oll milling the finely comminuted, nonpolymer soluble pigment into the solid polyester material and thereafter dispersing the pigmented material in water in a manner generally similar to the procedure described in U.S. Patent 4,148,779 for solubilizing organic disperse textile dyes in polyester for subsequent dispersal in water. Dispersions can also be made by adding the pigment at high speed agitation to the polyester material previously dispersed in water and then grinding in a ball mill or sand mill to further reduce pigment size. The preferred pH of the present inks is from about 5.0 to about 7.5. The pigments useful in the present invention, in addition to those specifically identified above, include those described in NP1RI Raw Materials Data, Vol. 4, Pigments, Copyright 1983.

The following examples will further illustrate practice of the invention.

Polyester Preparation Example 1

A mixture of 79.5 g (0.41 mole) of dimethyl isophthalate, 26.6 g (0.09 mole) of dimethyl-5- sodio- sulfoisophthalate, 54.1 g (0.51 mole) of diethylene glycol, 37.4 g (0.26 mole) of 1,4—cyclohexane¬ dimethanol, 1.4 ml of a 1.0% (based on Ti) catalyst solution of titanium tetraisopropoxide, and 0.74 g (0.009 mole) of sodium acetate buffer is stirred and heated for two hours at 200-220°C. The temperature is then raised to 275°C and a vacuum of 0.3 mm is applied. Heating and stirring is continued for 1 hour under these conditions. After cooling, the polymer obtained has an I.V. of 0.36 and is tough and rubbery. It is dissipatable in hot water to the extent of about 25 weight percent to give a clear, slightly viscous solution. The composition of the acid moieties of this polyester material is analyzed to be 82 mole % isophthalic acid residue and 18 mole % 5-sodiosulfoisophthalic acid residue, and of the glycol moieties is analyzed to be 54 mole % diethylene glycol and 46 mole % 1,4-cyclohexanedimethanol.

Example 1A Polyesters designated (a), (b), (c) and (d) were prepared essentially in accordance with Example 1 of the aforementioned U.S. Patent 4,233,196 from the following materials:

(a) g. moles

Dimethyl Isophthalate (IPA) 0.415 Dimethyl-5-Sodiosulfoisophthalate (SIP) 0.085

1,4-Cyclohexanedimethanol (CHDM) 0.520

Carbowax 1000 (CW 1000) 0.0237

Sodium Acetate 0.0085

Irganox 1010 0.0085

The Carbowax 1000 has the structure H OCH₂-CH₂^-OH wherein n is about 22. The polymer

analyzed by NMR contains (in reacted form) about 83 mole % IPA, about 17 mole % SIP, about 94.5 mole % CHDM, and about 5.5 mole % of CW 1000, and has an I.V. of about 0.39.

(b) g. moles

Dimethyl Isophthalate 0.328

Dimethyl—5-Sodiosulfoisophthalate 0.072

1.4—Cyclohexanedimethanol 0.442 Carbowax 400 (n=10) 0.058

Sodium Acetate 0.0072

- 13 -

The polymer as analyzed by NMR contains (in reacted form) about 82 mole % IPA, about 18 mole % SIP, about 85.5 mole % CHDM and about 14.5 mole % CW 400, and has an I.V. of about 0.46.

(c) g. moles

Dimethyl Isophthalate 0. .41 Dimethyl-5—Sodiosulfoisophthalate 0. .09 1» -Cyclohexanedimethanol 0. .55 Carbowax 4000 (n-90) 0. .0005 Sodium Acetate 0, .009

The polymer as analyzed by NMR contains (in reacted from) about 82 mole % IPA, about 18 mole % SIP, about 99.9 mole % CHDM and about 0.1 mole % CW 4000, and has an I.V. of about 0.16.

LsΩ. g. moles

Dimethyl Isophthalate 0.205

Dimethy1-5-Sodiosulfoisophthalate 0.045

Ethylene Glycol (EG) 0.9638

Carbowax 2000 (n=»45) 0.03625

Sodium Acetate 0.0045

The polymer as analyzed by NMR contains (in reacted from) about 82 mole % IPA, about 18 mole % SIP, about 85.5 mole % EG and about 14.5 mole % CW 2000, and has an I.V. of about 0.34.

In such polymers containing the Carbowax material, the n value is preferably between about 6 and 150.

In accordance with the present invention, inks prepared from the above polyester material have been found to be unexpectedly superior over prior aqueous inks in one or more of such properties as pigment wetting, pigment stability, temperature stability (heat and freeze—thaw), non-settling for extended periods of time, nonpolluting with respect to odor and volatile organics, nonflocculating, long "open" time in the press fountain, wide viscosity range inks, adhesion to a variety of substrates, hardness, gloss, drying rate on substrates, film—forming properties at low temperatures without organic co—solvents, resistance to grease, water and scuff, compatibility with other water—based inks, wet rub resistance, ink mileage characteristics (considerable water dilution allowable at the press), ink press stability in general, printability (clean, sharp transfer without "stringing or misting"), trapping, easy clean up, nonplugging of printing plates, flexibility, redispersibility or rewetting, crinkle resistance, high pigment loading, solvent resistance, alkali, chemical and detergent resistance, blocking resistance, lightfastness, toughness, substrate wetting, hold-out, opacity, dry—rate, and no offset on the printing press (coating e.g. on tension rollers).

Ink Preparation

Example 2

Ink Ingredients % by Weight

Deionized water 61 . 0 Polymer of Example 1 28.8

C.I. Pigment Yellow 83 10. 0 Biocide, Tektamer 38 AD 0.2

The solid polymer (32 parts) is dispersed in 68 parts of deionized water at 85°C to 95°C and 0.2 parts of biocide added. To 90 parts of this dispersion is

- 15 -

added 10 parts of the yellow pigment at high speed agitation for five minutes on a Waring Blender. The mixture is then milled in an Eiger mill operated at about 5,000 rpm for about 7.5 minutes to further reduce the pigment for a grind approaching "0"

(<about 3.0) NPIRI grind gauge. The resulting ink has a pH of about 5.85 and a viscosity of 27-30 seconds on a #2 Zahn cup determined according to ASTM D-4212-82. This procedure yields a fluid ink which is nonsettling for extended periods, does not flocculate or agglomerate, and can be reduced in viscosity with deionized water. The ink has virtually no odor and can be readily cleaned from printing equipment with warm deionized water. Tenacious, dried films of this ink can be cleaned from printing equipment with small amounts of detergents (5—10%) added to warm (80—90°F.) deionized water. The ink dries rapidly upon printing yet remains "open" in a container exposed to the atmosphere, such as a printing press reservoir. Example 3

The ink of Example 2 was reduced (diluted) with deionized water to a press ready viscosity of 24 seconds measured in a #2 Zahn cup and proofs prepared therefrom with a flexographic or gravure hand proofer employing a 180 line screen anilox roll on aluminum foil, newsprint, bleached white Kraft paper, 60# clay coated paper, and Mylar film. The target yellow-gold color, ease of printing and adhesion to all substrates was good to excellent. The hand proofer employed provides reasonable facsimiles of prints obtained by the gravure or flexographic printing processes as discussed in the aforesaid U.S. Patent 3,607,813, and is typically used to prepare roll-outs or proofs for laboratory testing on a wide variety of substrates. The wire— ound rod is typically used to prepare draw-downs of inks on a variety of substrates. These rods apply a uniform wet—film thickness to the substrate, and after drying, the draw-downs are ready for testing. Typically 2.5—8 number wire wound draw—down rods are employed. For exemplary details of such proofer equipment and use, see the publication "Gardco 1983-1984 Handbook of Paint Testing, Corrosion Control and Laboratory Instruments" of the Paul N. Gardner Company, Inc., 218 D Commercial Blvd., Suite 205 Lauderdale by the Sea, Florida 33308-4491, a copy of which accompanies this application.

Proofs are allowed to "age" at ambient tempera¬ ture (74°F) for one hour and rub resistance tests are then conducted thereon with a Sutherland Rub Tester employing a 2 lb. weight at 100 cycles. The rub resistance of the above proofs were good to excellent. The invention has been described in detail with particular reference to preferred embodiments thereof, but it will be understood that variations and modifi— cations can be effected within the spirit and scope of the invention.

Claims

Claims We Claim: 1. A water dispersible composition useful in printing inks comprising: (A) polymeric material of at least one linear, water—dispersible polymer having carbonyloxy linking groups in the linear molecular structure wherein up to 80% of the linking groups may be carbonylamido linking groups, the polymer having an inherent viscosity of from about 0.1 to about 1.0 measured in a 60/40 parts by weight solution of phenol/— tetrachloroethane at 25°C and at a concentra¬ tion of 0.25 gram of polymer in 100 ml of the solvent, the polymer containing substantially equimolar proportions of acid equivalents (100 mole percent) to hydroxy and amino equivalents (100 mole percent), the polymer comprising the reaction products of (a), (b), (c) and (d) from the following components or ester forming or estera ide forming derivatives thereof;

(a) at least one difunctional dicarboxylic acid; (b) from about 4 to about 25 mole percent, based on a total of all acid, hydroxyl and amino equivalents being equal to 200 mole percent, of at least one difunc¬ tional sulfomonomer containing at least one cationic sulfonate group attached to an aromatic or cycloaliphatic nucleus wherein the functional groups are hydroxy, carboxyl or amino; (c) at least one difunctional reactant selected from a glycol or a mixture of a glycol and diamine having two -NRH groups, the glycol containing two -CH -OH groups of which

HfOCH₂-CH_{2 n}OH, n being an integer of from 2 to

10 about 20, or

(2) of which from about 0.1 to less than about 15 mole percent, based on the total mole percent of hydroxy or hydroxy and amino

15 equivalents, is a poly(ethylene glycol) having the structural formula

H OCH₂-CH_{2 n}OH,

20 n being an integer of between 2 and about 500, and with the proviso that the mole percent of said pol (ethylene glycol) within said range is inversely propor¬

25 tional to the quantity of n within said range; and (d) from none to at least one difunctional reactant selected from a hydroxy— carboxylic acid having one —C(R)~-OH

30 group, an aminocarboxylic acid having one —NRH group, and an amino—alcohol having one -C(R)₂-0H group and one -NRH group, or mixtures of said difunctional reactants;

35 wherein each R in the (c) or (d) reactants is a H atom or an alkyl group of ϊ to 4 carbon atoms, and; (B) pigment material dispersed in said polymeric material in a weight ratio with respect to the total of said polymeric material of from about 1/1000 to about 10/1.

2. A water dispersible composition of claim 1 wherein the polymeric material comprises:

(A) one or more polyesters having an inherent viscosity of from about 0.28 to about 0.35, an acid moiety of from about 75 to about 84 mole % isophthalic acid and conversely from about 25 to about 16 mole % 5-sodiosulfo— isophthalic acid, and a glycol moiety of from about 45 to about 60 mole % diethylene glycol and conversely from about 55 to about

44 mole % 1,4-cyclohexanedimethanol or ethylene glycol or mixtures thereof, and;

(B) pigment material in a weight ratio with respect to total polymeric material of from about 1/100 to about 5/1 blended with said polyester materials.

3. A composition of claim 2 wherein said acid moiety comprises from about 80 to about 83 mole % isophthalic acid and conversely from about 20 to about 17 mole % 5-sodiosulfoisophthalic acid, and said glycol moiety comprises from about 52 to about 56 mole % diethylene glycol and conversely from about 48 to about 44 mole % 1,4-cyclohexane— dimethanol.

4. A composition of any one of claims 1, 2 or 3 wherein the pigment is one or a mixture of the following color index materials: C.I. Pigment Yellow 17, C.I. Pigment Blue 27, C.I. Pigment Red 49:2, C.I. Pigment Red 81:1, C.I. Pigment Red 81:3, C.I. Pigment Red 81:x, C.I. Pigment Yellow 83, C.I. Pigment Red 57:1, C.I. Pigment Red 49:1, C.I. Pigment Violet 23, C.I. Pigment Green 7, C.I. Pigment Blue 61, C.I. Pigment Red 48:1, C.I. Pigment Red 52:1, C.I. Pigment Violet 1, C.I. Pigment White 6, C.I. Pigment Blue 15, C.I. Pigment Yellow 12, C.I. Pigment Blue 56, C.I. Pigment Orange 5, C.I. Pigment Black 7, C.I.

Pigment Yellow 14, C.I. Pigment Red 48:2, C.I. Pigment Blue 15:3.

5. An aqueous dispersion of the composition of any one of claims 1, 2, 3 or 4 wherein the polymeric material comprises from about 1 to about 50% by weight thereof.

6. An aqueous dispersion of claim 5 coated onto a substrate selected from metal foil, newsprint, bleached and unbleached Kraft paper, clay coated paper, glass, calendered paper, stainless paper, paper board, and films or other substrates of polyester, polycarbonate, cellulose ester, regenerated cellulose, poly(vinylidiene chloride), polyamide or polystyrene.

7. A substantially water—insoluble coating or print on a substrate, said coating or print comprising a composition of any one of claims 1, 2 or 3 wherein a substantial portion of the initial metal cations of the water solubilizing sulfonate groups of the polymeric material has been replaced with an insolubilizing cation.