CA2073016A1

CA2073016A1 - Aqueous inks having improved resistance to blocking

Info

Publication number: CA2073016A1
Application number: CA 2073016
Authority: CA
Inventors: Kenneth R. Barton; Bobby J. Sublett
Original assignee: Individual
Current assignee: Eastman Chemical Co
Priority date: 1989-11-06
Filing date: 1990-10-26
Publication date: 1991-05-07
Also published as: WO1991006608A1; EP0500677A1; JPH05501428A

Abstract

Disclosed are aqueous inks containing a water-dissipatable polyester that have improved properties such as blocking resistance.
The polyesters of the inks contain 12 to 25 mole % (based on the total of all acid and hydroxyl equivalents being equal to 200 mole %) of at least one difunctional ester-forming sulfomonomer. The glycol portion of the polyester is an aliphatic, alicyclic, or aralkyl glycol.

Description

W~91/06608 PCT/US90/06257 3 0 ~ 6 AQUEOUS_INKS HAVING IMPROVED_RESISTANCE TO BLOCKING

Field of Invention This invention concerns aqueous inks having improved resistance to blocking which contain certain water-dissipatable polyesters.
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Backqround of the Invention Water-dispersible polyesters containing a metal sulfonate group attached to an aromatic nucleus are described in U.S. Patents ~,546,008; 3,734,874;
3,779,993; 4,233,196; and 4,427,557. In all of these disclosures, it is taught that a certain minimum amount of a polyethylene glycol, i.e., H(OCH2CH2)nOH, where n >2, is required for adequate water dispersibility ~see U.S. 4,233,196, Col. 3, Lines 4-14) or for improved soil resistance properties (per U.S. 4,427,557, Col. 1, Lines 36-65). In none of the references cited above is it recognized that certain water-dispersible sulfo polyesters containing no diethylene glycol or polyethylene glycols are useful for inks.
U.S. 4,052,368 claims certain water-dispersible hot melt adhesives based on sulfo polyesters that contain from 0 to 10 mol % polyoxyalkylene glycols and/or from 0 to 100 mol % ethylene glycol. This disclosure did not recognize that any of the sulfo polyesters described might have utility in printing inks or overprints.
U.S. 4,340,519 discloses an aqueous dispersion of -at least,two sulfo polyesters useful for printing inks.
At least one sulfo polyester must be crystalline and at least one sulfo polyester must be non-crystalline. To obtain an;a~ueous dispersion of the sulfo polyesters from 2 to 66% of a water-soluble organic compound is required-because of the low (< 10 mol %) sulfo substitution level in the claimed polyesters.

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i PCT/US90/06257 U.S. Patents 4,704,309 and 4,847,316 disclose printing processes employing water-dispersible inks based on sulfo polyesters containing at least 0.1 mol %
of a polyethylene glycol. These patents do not recognize that improved inks or overprints can also be prepared from certain sulfo polyesters containing no polyethylene glycols.

Summary of the Invention The present invention is directed to certain ink and overprint compositions that have improved properties, especially block resistance, as compared to prior art compositions. The ink compositions of the p~esent invention contain polyesters which have certain levels of sulfomonomer and certain types of glycols.
More specifically, the present invention is directed to a composition useful as an ink, overprint, or concentrate thereof comprising:

(A) about 1 to about 35 weight percent of at least one amorphous, linear, water-dissipata~le polyester having an inherent viscosity of at least about 0.1 dL/g measured iD a 60/40 parts by weight solution of phenol/tetrachloroethane at 25C and at:a concentration of 0.5 gram of polymer in 100-ml of solvent and having a glass transition temperature (Tg) as measured by differential scanning calorimetry (DSC) of greater than about 60C, the polyester co~taining substantially equimolar proportions -of acid.equivalents-(100 mole~) to hydroxyl equivalents (100 mole ~ the polyester -- consisting essentially of the reaction -products of reactants selected from (1), (2), (3), and (4) or the ester forming derivatives :

WO9t/06608 P~T/US90/06257 2~73~

thereof, as follows, wherein all stated percentages are based on the total of all acid and hydroxyl equivalents being equal to 200 mole %:
(1~ at least o~e aromatic dicarboxylic acidi (2) from 0 to about 30 mole ~ of at least one aliphatic or cycloaliphatic dicarboxylic acid;

(3) from about 12 to about 25 mole % of at least one difunctional ester-forming sulfomonomer containing at least one sulfonate group attached to an aromatic ..
ring; and (4) at least one aliphatic, cycloaliphatic or aralkyl glycol;
(B) 0 to about 50 weight % of at least one colorant;

. (C) about 15 to about 99 weight % of water; and (D) 0 to about 5 weight ~ (based on the weight of total dry wax solids~ of an emulsified, dispers~d, powdered or micronized wax.
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Detailed Description of the Invention .The.advantages of.this invention.are achieved by incorporating the.amorphous water-dispersible polyesters deiscribed herein into water-borne ink compositions. As ~ :
used herein, unless otherwise indicated, the term "ink composition" and like terms will be used in its broad :::

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WO91/06608 PCT/US~0/06257 2~ 3 ~ ~6 _ 4 sense, that is, to include concentrates thereof, primers, and overprints or overprint varnishes.
Overprints typically have low levels of colorant or no colorant. The polyesters useful in the present invention have the feature of containing certain levels of a sulfomonomer having a sulfonate group attached to an aromatic nucleus and the additional feature of containing no diethylene glycol or higher polyethylene glycol residues in the polymer chain. Some of the advantages of aqueous ink compositions made according to the present invention are (1) greater blocking resistance, especially in warm, humid climates, (2) the simplicity of a single polyester binder polymer, and (3) the reduction or elimination of organic solvent emissions during drying of the ink.
In the ink compositions of the present invention, component (A) preferably comprises from about 2 to about 25 weight percent, more preferably from about 5 to about 20 weight percent.
In overprints, component (B) preferably comprises 0 to 35 weight percent. In finished inks or concentrates thereof, component ~B) preferably comprises about 0.5 to about 50 weight percent, more preferably about 0.5 to about 35 weight percent and most preferably about 5 to 2S about 35 weight percent.
In the ink compositions of the present invention, component (C) preferably comprises about 50 to about 90 weight percent.
In the ink compositions of the present invention, component (D) usually comprises from about 0.01 to about 5 weight percent, preferably-about 0.01 to~about 3 weight percent, more preferabIy about 0.1:to about 3 weight percent, and most preferably about 0.2 to about 2 weight percent. The wax can be incorporated into inks in either a dry form or non-dry form (e.g., emulsified);

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WO9l/06608 PC~tUS90/06257 2 ~ 7 3 however, the amount of wax (i.e., eomponent (D)) in the ink composition is based on the welght of the dry wax solids.
If the ink composition of the invention is a finished ink or concentrate thereof, such composition will contain at least one colorant. Such compositions have at least about 0.5 weight percent of colorant.
More typically, in such ink compositions, at least about 5 weight percent of eolorant is present. If the ink lQ eomposition contains an organic pigment, typically such an organic pigment is present in an amount of about 17.5 weight percent or less of the total composition. If the ink eomposition contains an inorganie pigment, typically such inorganic pigment is present in an amount of about 50 weight percent or less of the total eomposition.
The glycol eomponent of the polyester of ~he present invention is an aliphatic, alicyclic ! or aralkyl glycol. These glycols are distinguishable from the glycols used to prepare certain prior art polyesters in that they do not contain an oxygen atom in the backbone of the molecule (i.e., no ether linkage).
It is preferred that the glyeol (i.e., component (A)(4)) is an aliphatie glyeol containing 2 to 8 carbon atoms, an alicyclic glyeol containing 6 to 12 earbon atoms or a mixture thereof.
Examples of suitable glycols (component (A)(4)) inelude ethylene glyeol, propylene glyeol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,3-butanediol, 2,2-dimethyl- ~ -1,3-propanediol,-1,2-cyclohexanedLmethanol, 1,4-eyclo-hexanedimethanol, p-xylenediol,:or a mixture thereof.
The most preferred glycols are 1,4-cyclohexane-dimethanol; 1,3-cyclohexanedimethanol-; 2,2-dimethyl-1,3-pxopanediol; p-xylenediol, and ethylene glyeol.

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WO9t/06608 PCT/US90/06257 2Q~3~ 6 -When eLhylene glycol is included, the polymeriz~-tion mixture must be buffered with, for example, sodium acetate, to help prevent the in situ formation of diethylene glycol and higher polyethylene glycols, which would then b~ incorporated into the polymer and could result in undesirable properties such as reduced blocking resistance.
Suitable dicarboxylic acids, or esters thereof (components (A)(1) and (A)(2)), and difunctional sulfo monomers (component (A)(3)) are given in U.S. Patents 3,734,874 and 3,779,993, incorporated herein by reference in their entirety. The aromatic dicarboxylic acids (component (A)(1)) preferably contain 8 to 14 carbon atoms and the aliphatic or cycloaliphatic dicarboxylic acids preferably contain 4 to 20 carbon atoms.
As is obvious to a skilled artisan, components (A)(l) and (A)(2) do not contain a sulfomonomer.
Examples of component (A)(1~ include terephthalic acid, isophthalic acid, orthophthalic acid, 2,6-naphthalene dicarboxylic acid, or a mixture thereof.
Examples of component (A)~2) include glutaric acid, succinic acid, adipic acid, trimethyladipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, 1,4-cyclohexanedicarboxylic acid, or a mixture thereof.
The most preferred dicarboxylic acids are isophthalic acid and terephthalic acid.
It is preferred that component (A)(3) is a metal 30 -- or ammonium salt of a sulfoaromatic dicarboxylic acid.
Examples of the metal of the metal salt include lithium, sodiumj potassium, magnesium, calcium, copper, or iron.
Preferred are sodium and lithium with sodium being most preferred. It is preferred th&t the sulfomonomer contains 8 to 14 carbon atoms.

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- 7 - 2~3~6 Examples of suitable sulfomonomers (component (A)(3)) include a metal salt of sulfo-terephthalic acid, 5-sulfoisophthalic acid, 4-sulfophthalic acid, 4-sulfonaphthalene-2,7-dicarboxylic acid, 5-(4-sulfophenoxy)isophthalic acid, or a mixture thereof.
The preferr~d sulfomonomers are 5-sodiosulfoiso-phthalic acid and 5-lithiosulfoisophthalic acid or the dimethyl esters thereof.
Preferred polyesters of the present invention are wherein component (A)(2) is isophthalic acid, terephthalic acid, or a mixture thereof, component (A)(2) is not present (i.e., 0 mole %), component (A)(3) is 5-sodiosulfoisophthalic acid, 5-lithiosulfoisophthalic acid, or a mixture thereof, and component (A)(4) is 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 2,2-dimethyl-1,3-propanediol, ethylene glycol, p-xylenediol, or a mixture thereof. It is more preferred wherein component (A)(l) is about 35 to 85 mole % isophthalic acid, 0 to about 35 mole %
2,6-naphthalene dicarboxylic acid, and 0 to about 45 mole % terephthalic acid, component (A)(3) is about 18-22 mole % 5-sodiosulfoisophthalic acid, and component (A)(4) is 0-100 mole ~, 1,4-cyclohexane-dimethanol, 0-100 mole % 2,2-dimethyl-1,3-propanediol, and 0-100 mole % ethylene glycol.
The following table lists specific polymers believed to be novel which have been found to be particularly useful in the present invention.
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WO91~06608 PCT/US90/0625~ _ ~,3~6 - 8 -Mol ~
Polymer Composition of No. _ Polyester I.V.
I About 50 Isophthalic Acid About 0.2 to About 0.3 About 30 2,6-Naphthalene Dicarboxylic Acid About 20 5-Sodiosulfoiso-phthalic Acid About lO0 l,4-Cyclohexane-dimethanol II About 40 Isophthalic Acid About 0.2 to About 0.3 About 40 Terephthalic Acid About 20 5-Sodiosulfoiso-phthalic Acid About lO0 l,4-Cyclohexane-dimethanol III About 80 Isophthalic Acid About O.l to About 0.2 About 20 5-Sodiosulfoiso-phthalic Acid About lO0 2,2-Dimethyl-l,3-propanediol IV About 81 Isophthalic Acid About 0.2 to About 0.3 About l9 5-Sodiosulfoiso- --~:~ phthalic Acid : ~ ~ 40 About lO0 Ethylene Glycol V About 80 Isophthalic Acid About 0.2 to : - - - About 0.3, .
~ About 20 5-Sodiosulfoiso-phthalic Acid . .
About 80 1,4-Cyclohexane- ~ ¦
dimethanol About 20 Ethylene Glycol , , WO91/06608 PCr/US90/06257 - 9 - 2~730 1 fi Glass transition temperature (Tg) of the sulfo polyesters is determined by heating a small sample of finely divided polymer to about 130C (well above the expected Tg), quenching the sample with liquid nitrogen, then reheating at a rate of 20C/min in a Du Pont Instruments Model 912 Differential Scanning Calorimeter.
The Tg is taken as the mid-point of an abrupt base line shift in a plot of heat flow versus sample temperature. `
The Tg is greater than about 60C, preferred is gr~ater than about 70C.
It is preferred, concerning block resistance, that the ink compositions of the present invention when printed on a substrate do not block below about 100F
(37.78C); more preferably do not block below about 120 to 220F (48.89 to 104.44C), when heated for 5 seconds on a Sentinel Heat Sealer at 40 psi (275.79 kilopascal).
An improvement provided by inks of this invention is an increased resistance to blocking of printed matter. Both ink-to-ink and ink-to-paper blocking i5 reduced. This improvement is especially beneficial when printed matter is exposed to warm humid climates. The ~
inks and o~erprints of this invention are superior to -those described by Coney et al (U.S. 4,704,309), in that the sulfo polyesters of this invention contain no 25 diethylene glycol or polyethylene glycol residues. It ~-is not desired to be bound by any particular theory or mechanism; however, it is believed that the presence of these hydrophilic glycols residues in sulfo polyesters increases the tendency of inks prepared therefrom to i~
block as relative humidity increases. On the other hand,-the easy press clean up and~rewet propertiés-of the inks descxibed by Coney et al, Col. 1, Lines 15-38, are substantially-retained by the inks of the present lnvention.

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6 PCT/US90/06257 _ Waxes (i.e., component (D)) of many chemical types are preferably incorporated into printing inks and overprint varnishes of the present invention to impart improved properties such as mar-resistance, improved slip and water repellency properties. Waxes are normally introduced to inks and overprint varnishes in one of two ways: (1) wax of a controlled fine particle size, i.e., powdered or micronized, is mixed or ground into the ink or overprint along with pigments, if any, or (2) waxes are dispersed, emulsified or dissQlved in the ink medium (i.e., in water in the case of the water-borne inks and overprint varnishes of the present invention) and added to the ink or overprint varnish formulation. These methods are well-known to those skilled in the art.
On a chemical basis, waxes are usually divided into three broad classifications: synthetic waxes, petroleum waxes and natural waxes. Although waxes vary in their efficacy in the inks and overprints of this invention, useful examples of waxes are found in all three classifications. In general, synthetic waxes, such as polyethylene waxes, both as fine powders (micronized form) and as emulsions in water, are preferred. Also preferred are polytetrafluoroethylene waxes in powder form. These and other useful waxes are des~ribed in !'The Printing Ink Manual", Third Edition, edited by D. E.
Bisset et al., Van Nostrand Reinhold (UK) Co., Ltd., Berkshire, England, 1979, pages 28~-295. Useful wax levels in the inks and overprints of this invention range from about 0.01 weight % to about 5 weight (based on the weight of dr~ wax in the formulation).
~ Higher levels of wax can be used but the gloss of the ink or oYerprint is usuaIly adversely~affected.
Specific examples of commercially available waxes useful in this invention include Jonwax (trademark) 26 and - 11 2~730l6 Jonwax 120 [available from S. C. Johnson and Sons, Inc., Racine, Wisconsin 43403 (U.S.A. ) ], Vanwax (trademark) 35 [available from Vantage, Garfield, New Jersey 07026 (U.S.A.)] and Epolene (trademark) E
waxes [available from Eastman Chemical Products, Inc., Kingsport, Tennessee 37662 (U.S.A.)]. Of course, it is understood that two or more waxes ca~ be combined for special effects, if desired.
The ink compositions can optionally contain up to about 15 weight percent, preferably up to about 3 weight percent of one or more other additives. Such additives include surfactants such as Surfynol (trademark) 104 and Surfonyl 440 (available from Air Products and Chemicals, Allentown, Pennsylvania 18105); modifiers (for example, defoamers) such as Resolv (trademark) (available from Vantage), Foamaster (trademark) 111 (available from Henkel Corporation, Morristown, New Jersey 07960);
alcohols such as n-propyl alcohol, isopropyl alcohol, ethanol, methanol or glycol ethers derived from reaction `
of alcohols or glycols with ethylene oxide and/or propylene oxide such as ethylene glycol, propylene glycol, ethylene glycol monobutyl ether or propylene glycol monobutyl ether; biocides; pH stabilizers;
dispersants; thickeners such as Acrysol (trademark) RM-825 (available from Rohm & Haas, Philadelphia, Pennsylvania 19105); and the like.
Typically, it is desirable to add a small amount of -one or more pH stabilizers to the ink compositions to keep the pH within a desired range. For example, it is common to add about 0;1 weight percent sodium acetate to an ink~or aqueous solution/dispersion of polymèr.
More typical amounts of certai~ additives in ink ~
compositions of the present invention are set forth in the following table.

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WO9l/06608 PCr/USgO/06257 ._.

Component Wei2ht Percent Surfactanta 0.0 - 3.0 Modifierb 0.0 - 2.0 Alcohol 0.0 - 8.0 be.g., Surfynol 104,440 ce.g., wsT-4o9~ Resolv, Carbowet 990, Foamaster 111 e.g., n-Propyl Alcohol, Isopropyl Alcohol, Ethanol, Methanol, Propylene Glycol, Ethylene Glycol Monobutyl Ether Preferred amounts of an alcohol are about 0.1 to about 10 weight percent, more preferred is about 0.5 to about 8 weight percent. The presence of one or more alcohols is particularly advantageous to enhance surface wetting properties. -It is preferred that the ink composition of the invention is 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 polyester, polycarbonate, cellulose ester, regenerated cellulose, poly(vinylidene chloride), polyamide polypropylene, polyethylene or polystyrene.
It is also preferred that after the ink composition is printed a substantial portion of the initial metal 30 cations of the water solubilizing sulfonate groups of .
the water-dissipatable polyester material has been replaced with an insolubili~ing polyvalen~ metal cation, such as A1 3, Ca , or the like as disclosed and in the manner described in U.S. Patents 4,145,469, and 35~ 4,704,309, the disclosures of which are incorporated herein by reference in their entirety. As statéd therein, generally, based on the weight of the polymeric material, 0.05 percent to about 2.0 percent by weight solids of the polyvalent metal cation are required for effective insolubilization.

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- 13 2 ~ 73 0 ~ 6 The inherent viscosities (I.V.) of the particular water-dissipatable polyesters useful herein are at least 0.1 dL/g and preferably range from about 0.1 to about 1.0 dL/g, most preferably from about 0.2 to about S 0.4 dL/g, 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 0.5% by weight in 60/40 by weight of phenol/tetrachloroethane. Depending on the specific polymer prepared, the procedure is carried out by heating the polymer/solvent system at 120C for 15 minutes, cooling the solution to 25C and measuring the time of flow at 25C. The I.V. is calculated from the equation :
t ln ts :
(11) = o C ~, where: ~:
(~) = inherent viscosity at 25C at a polymer : concentration of 0.5 g/100 mL of solvent;
:~. :.:
ln = natural logarithm; ~ :
- ~:
ts = sample flow time;
.. - . .,. . : ~-to = solvent~-blank flow time; and .
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~C - ~concentration of polymer in-grams per .. .100.mL-of solYent.= O.5..-. . - -, ~ . , " . . , . - .-- - - -- . .
The units of .the inherent viscosity throughout : .
this application are in deciliters/gram.
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PCT/US~0/06257 ~o~3~ ~ 14 -As appr~ciated in the art, the exact components and properties of components desired for any given ink application can vary, and, therefore, routine experimentation may be required to determine the optional components and proportions of component~ for a given application and desired properties.
The ink compositions of this invention can be for any of the typical ink applications such as flexo-graphic, gravure, letterpress, ink-jet, or screen-process printing applications. The ink compositions of the present invention have excellent adhesion to a wide variety of substrates including plastic films such as polyester, polyethylene or polypropylene; aluminum foil;
glass; and paper.
The ink compositions of the present invention should have a pH of about 8.2 or lower; preferred is a pH of about 7 to 8. If the'pH is higher than about 8.2, there is a danger of the polymer(s) hydrolyzing which may result in gelling of the system.
The polyesters of this invention can be dispersed in water for ink preparation by the procedure given in U.S. 4,704,309, Col. 3, Line 52 to Col. 4, Line 6.
For example, the following procedure can be used for dispersing the polyester in water: The water should be preheated to about 180F (82.22C) to about 200F
(93.33C) and the polyester in pellet form is added '' rapidly to the vortex under high shear stirring. A
Cowles Dissolver, Waring (trademark) blender, or similar equipment may be used. Once the water is heated to the desired'temperature, additional heat'input is notrequired. Depending~upon''the volume prepared, dispersion o~ the pellets should be complete within 15 to 30 minutes stirring; Continued agitation with cooling may be desirable to prevent thickening at the surface due to water evaporation. Viscosities of the WO9~/06608 PCT/US90/06257 - 15 - 2~ 7301 6 dispersions remain low up to polyester levels of 25 percent to 30 percent and viscosities increase sharply above these le~els. Viscosities of the dispersions will be influenced by the degree of polymer dispersion obtained which is affected by the dispersing temperature, shear, and time. The polyester content typically may range from about 15 percent to about 40 percent by weight of the aqueous dispersion with the preferred for most applications being from about 20 percent to about 35 percent.
The inks, overprints, and primers of this invention can be prepared, for example, as disclosed in U.S. Patents 4,148,779 and 4,704,309, which are incorporated herein by reference in their entirety.
For example, the printing ink, overprint, or primer may be prepared as follows: The colorant is added to the polymer blend dispersion and, at a properly adjusted -viscosity, dispersed thereinto with ball mill, sand mill, high~shear fluid flow mill, Cowles Dissolvex, Katy ~ill or the like. The colorants also may be dispersed directly in the polymer by milling on a heated two-roll mill at about 220 to 360F (104.44 to 182.22C) and using processing aids as desired, such as solvents or plasticizers. The viscosity and printing characteristics of the ink composition may be modified further by addition of water, solvents, plasticizers, sequestered wax, surfactants and the lik~ to suit the particular printing needs. The amounts and nature of these optional additives have been previously described herei~.
The present invention is not limited to any type of dye, pigment, filler, or the like, all of which are hereinafter included in the term "colorant," and can accommodate any colorant which can be dispersed, milled, ' ~ ' WO91~06608 PCT/US90/06257 .

~ 6 16 -mixed, blended or dissolved in any manner in either the polymer blend, water or aqueous polymer system.
Exemplary useful C.I. pigments for use in the present invention are given in the following table:

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PCT/US90/06257 :

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Pigments Generic Name C A. Index/Chemical Name C.I. Pigment Yellow 17 Butanamide, 2,2'-[(3,3'-dichloro[1,1'-biphenyl]
4,4'-diyl)bis(azo)bis [N-(2-methoxyphenyl)-3-oxo :
C.I. Pigment Blue 27 Ferrate (4-1), hexakis (cyano-C)-ammonium iron (3+)(1 15 C.I. Pigment Red 49:2 1-Naphthalenesulfonic acid, 2-[(2-hydroxy~
naphthalenyl)azo]-, .
. calcium salt (2:1) C.I. Pigment Red 81:1 Benzoic acid, 2,-[6-ethyl-amino)-3-(ethylim$no)-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-(ethylimino)-2,7-dimethyl-3H-xanthen-9-yl]-, . :.
: ethyl ester, molybdate-phosphate : , -C.I. Pigment Yellow 83 Butanamide, 2,2'-[(3,3'-40- ~ dichloro[l,l'-biphenyl]- ..
-~ ~` - 4,4'-diyl)bis~azo)bis[N-: - . (4-chloro-2,5-dimethoxy-. phenyl)-3-oxo-WO91/06608 6 PCTtUS90/06257 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 l-Naphthalenesulfonic acid, 2-[(2-hydroxy-1-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 20 C.I. Pigm~nt Blue 61 Benzenesulfonic acid, [[4-[[4-phenylamino)-phenyl]-[4-(phenylimlno)-2,5-cyclohexadien-1-ylidene]methyl]-phenyl]
amino]-C.I. Pigment Red 48:1 2-Naphthalenecarboxylic acid, 4-[(5-chloro-4-methyl-2-sulfophenyl)azo]-30 3-hydroxy-, barium salt (1:1) , C.I. Pigment Red 52:1 2-Naphthalenecarboxylic acid, 4-~(4-chloro-5- ~ :
methyl-2-sulfophenyl)azo]- :
3-hydroxy-, calcium salt (1:1) . - ,-C.I. Pigment Violet l Ethanaminium, N-~9-(2-. carboxyphenyl)-6-(diethyl amino)-3H-xanthen-3-ylide~e]-N-ethyl , molybdatetungstate-phosphate C.I. Pigment White 6 Titani~m oxide (TiO2) -, - .. ,,.. ~. , -.:

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W09l~6608 2~73016 - 19 - .
_ Generic Name C.A. Index/Chemical Name C.I. Pigment Blue 15 Copper, [29H, 31H- .
N29 N30 N31 ( ) .
N32]-, (Sp-4-1)-C.I. Pigment Yellow 12 Butanamide, 2,2'-[(3,3'-dichloro[l,l'-biphenyl]-4,4'-diyl)bis(azo)]bis[3-oxo-N-phenyl- :
C.I. Pigment Blue 56 Benzenesulfonic acid, 2-methyl-4-[[4-[[4-[(3-methylphenyl)amino]
phenyl]-[4-[(3-methyl-phenyl)-imino]-2-5-cyclohexadien-l-ylidene]methyl]-phenyl]
aminoJ- .
C.I. Pigment Orange 5 2-Naphthalenol, 1-[(2,4-dinitrophenyl)azo]-25 C.I. Pigment Black 7 Carbon black , C.I. Pigment Yellow 14 Butanamide, 2~2'-[(3,3'- .
dichloro[l,1'-biphenyl]-4,4'-diyl)bis(azo)]bis- .
[N-(2-methylphenyl)-3-oxo- : -C.I. Pigment Red 48:2 2-Naphthalenecarboxylic :
acid, 4-[(5-chloro-4-. methyl-2-sulfophenyl)-. azo]-3-hydroxy-, calcium salt (1~
C.I. Pigment Blue 15:3 Copper, [29H, 31H- -- . phthalocyaninato ' ' - ' - - ` - (2-)-N29, N30, N31, N32]-~ . (SP-4-1)- : :
C.I. Pigment Yellow 1 Butanamide, 2-[(4-methyl ~ 2-nitrophenyl)azo]-3-oxo-N-phenyl- - .

. --.. . . .

W~91~06608 PCT/US~0/06257 _Generic Name __ C.A In~ex~Chemical Name_ C.I. Pigment Yellow 3 Butanamide, 2-[(4-chloro-2-nitrophenyl) azo]-N-(2-chlorophenyl) -3-oxo-C.I.Pigment Yellow 13 Butanamide, 2,2'-[(3,3'-dichloro~1,1'-biphenyl]-4,4'-diyl)bis(azo)]bis [N-(2,4-dimethylphenyl)-B-oxo -C.I. Pigment Orange 16 Butanamide, 2,2'-[(3,3'-dimethoxy[1,1'-biphenyl]-4,4'-diyl)bis(azo)]bis [3-oxo-N-phenyl-C.I. Pigment Yellow 55 Butanamide, 2,2'-[(3,3'-0 dichloro[1,1'-biphenyl]
4~4~-diyl)bis(azo:)]bis [N-(4-methylphenyl)-3- :
oxo- : , C.I. Pigment Red 41 3H-Pyrazol-3-one,4,4'-[(3,3'-dimethoxy[l,1'-biphenyl]-4,4'-diyl)~is (azo)]bis[2,4-dihydro-5- :.
methyl-2-phenyl-C.I. Pigment Orange 34 3H-Pyrazol-3-one,4,4'-[(3,3'-dich~oro[1,1'-biphenyl]-4,4'-diyl)bis (azo)]bis[2,4-dihydro-5-methyl-2-(4-methylphenyl)-C.I. Pigment Blue 62 4,4'-Bis(diethylamino) :
benzophenone condensed ~: with N-ethyl-1-naphthyl-. - amine in toluene with : phosphorous oxychloride and converted to the . copper ferrocyanide salt ~PTMA salt in P.Blue 1) . .
~21~2~73gl~
_ Generic Name ~ Name_ C.I. Pigment Violet 1 Ethanaminium, N-[9-(2-carboxyph~nyl)-6-(diethylami.no)-3H-xanthen-3-ylidene]-N~
ethyl-, molybdatetung-statephosphate lO C.I. Pigment Red 22 2-Naphthalenecarboxamide, 3-hydroxy-4-[(2-methyl-5- ~ -nitrophenyl)azo3-N~phenyl-C.I. Pigment Red 170 2-NaphthalPnecarboxamide, 4-~[(4-(aminocarbonyl) phenyl]azo]-N-(2-ethoxy phenyl)-3-hydroxy-C.I. Pigment Red 88 Benzo[b]thiophen-3(2H)-one, 4,7-dichloro-2-(4,7- ~:.
dichloro-3-oxobenzo[b]-thien-2(3H)-ylidene)-,:
C.I. Pigment Yellow 151 A diazotized aniline derivative coupled with an acetoacetyl derivative of ~ 5-aminobenzimidazolone C.I. Pigment Violet 23 Diindolo[3,3',2'm]tri-phenodioxazine, 8-18-dichloro-5,15-diethyl-5,15-dihydro-. C.I. Pigment Red 184 A diazotized substituted ~ aniline coupled with a derivative of 3-hydroxy- :
2-naphthanilide C.I. Pigment Blue 1:2 Ethanaminium, N-[4-[[4- :-- ~ (diethylamino)phenyl] - :
4-(ethylamino)-1-1 naphthalenyl]methylene]-2,5-cyclohexadi~n-1- .
ylidene]-N-ethyl-, [orthosilicato(4-)]
hexatriacontaoxo-dodecamolybdate(4)-(4:1 . . ~ . . . ., . - ., :,, , ~ : ., ,,.. , . ,,:, ,., , ., . ,., . ; , , " , - , ........... . . .

. . .

WO9l/06608 , ~ PCT/US~0/06257 _~

_ Generlc Name _ _ C.A. Ind~Chemical Name C.I. Pigment Red 3 2-Naphthalenol, 1-[(4-methyl-2-nitro-phenyl~azo]-C.I. Pigment Blue 15:1 Copper,[29H,32H-p2h9haloocy3alninato(2-) N32]-,(Sp-4-l)-or Copper,[chloro-29H, 31H-phthalocvaninato (2-l)-N29/N3~)/N3l N32]_ 15 C.I. Pigment Red 23 2-Naphthalenecarboxamide, - 3-hydroxy-4-[(2-methoxy-5-nitrophenyl)azo]-N-(3-nitrophenyl)-20 C.I. Pigment Red 112 2-Naphthalenecarboxamide, 3-hydroxy-N-(2-methyl-phenyl)-4-[(2,4,5-tri-chlorophenyl)azo]-25 C.I. Pigment Yellow 126 A tetrazotized derivative ~:
of 3,3-dichlorobenzidene coupled with a derivative of acetoacetanilide 30 C.I. Pigment Red 169 3-Ethylamino-p-cresol condensed with phthalic anhydride, esterified with ethanol and a mineral -acid, and converted to the copper ferrocyanide complex (chloride salt is C.I. Basic Red 1, PTMA
salt is P.Red 81:1).
40 C.I. Pigment Orange 5 2-Naphthalenol, - 1-[~2,4-dinitro- ~ .
~' phenyl)azo]-, - 23 - 2~730~
Generic Name C.A. Index/Chemical Name C.I. Pigment Orange 13 3H-Pyrazol-3-one, 4,4'-[(3,3'-dichloro [1,1'-biphenyl]-4,4'-diyl)bis(azo)]bis[2,4-dihydro-5-methyl-2-phenyl-C.I. Pigment Orange 34 3H-Pyrazol-3-one, :
4,4'-[(3,3'-dichloro [1,1'-biphenyl]-4,4'-diyl)~is(azo)]bis[2,4-dihydro-5-methyl-2-(4-methylphenyl)-C.I. Pigment Red 10 2-Naphthalenecarboxamide, 4-[(2,5-dichlorophenyl) azo]-3-hydroxy-N-(4- :
methylphenyl)-C.I. Pigment Blue l:X Ethanaminium, N-[4-[[4-(diethylamino)phenyl]
[4-(ethylamino)-1-naphtha-lenyl]methylene]-2,5- .
cyclohexadien-1-ylidene]-N-ethyl-, molybdate-~ phosphate C.I. Pigment Yellow 42 Iron oxide (Fe2O3) hydrate C.I. Pigment Red 101 Iron oxide (Fe~O3) C.I. Pigment Brown 6 Iron oxide (Fe2O3), some FeO and Fe203 ~2 C.I. Pigment Brown 7 Iron oxide (Fe2O3) plus ~arying amounts of clay C.I. Pigment Brown 7:X Fe203 x MnO2 with varying amounts of clay C.I. Pigment-Black 11 FeO-Fe2O3 -C.I. Pigment Metal 1 Alumi~um C.I. Pigment-Metal 2 Copper, zinc .

. " , . .- . . , : . , , , . . . . : : " , .. . :

, . ; . , : , . .; , : : . , - : , , ~ PC~/US90/06257 3~ ~

In accordance with the present in~ention, ink compositions disclosed herein may be superior o~er prior aqueous ink compositions 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, non-flocculating, long "open" time in the press fountain, wide ~iscosity 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 (consider- ..
able 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, 20 solvent resistance, alkali, chemical and detergent :
resistance, blocking resistance, lightfastness, heat resistance, slip angle, coefficient of friction, toughness, substrate wetting, hold-out, opacity, .:
dry-rate, and no offset on the printing press (coating : .
e.g. on tension rollers).
The following examples are to illustrate the invention but should not be interpreted as a limitation thereon. All percentages are by weight unless otherwise indicated .
Exa ~ ration of_Sulfo PolYester A 500-mL round-bottom flask equipped with an agitator shaft, nitrogen inlet and distillation sidearm is charged with 78.6 g (0.405 mol) of dimethyl isophthalate, 28.1 g (0.0950 mol) of dimethyl ~ . .

, : . ,: . : :. . ;: . :. : .

WO91/06608 2 ~ 7 3 o 1 PCT/Usgo/06257 5-sodiosulfoisophthalate, 79.2 g (0.550 mol) 1,4-cyclohexanedimethanol, 0.078 g sodium acetate (buffer) and about 100 ppm (based on final polymer weight) titanium catalyst as titanium tetraisopropoxide.
The flask is immersed in a Belmont metal bath at 200C
for two hours with stirring under a nitrogen sweep. -.
Approximately 1.0 mol of methanol, the ester interchange reaction product, is removed through the distillation sidearm. The temperature of the bath is then increased stepwise over a period of about 45 minutes to 285C.
The reaction flask and sidearm are rigged for operation under vacuum. Pressure in the flask is gradually -reduced over a period of about 30 minutes to less than 0.5 torr. During this time the viscosity of the reaction mixture increases as the polymer molecular weight increases. The flask is removed from the molten metal bath and dry nitrogen gas is bled into the flask.
When cooled to room temperature, the polymer is removed from the flask and ground into a coarse powder. The I.V. of the polymer is 0.22 dL/g, the second cycle Tg of the polymer (after quenching from the melt) is 84C and the sulfur content of the polymer is 1.93%.

Example 2. Dispersion of Sulfo PolYester Fifty grams of the coarse-ground polymer from Example 1 is sifted into 150 g of demineralized water in a 3-necked flask equipped with a-stirrer, and a temperature controlled heating mantle. After 15 minutes at room temperature, the temperature of the flask is ; increased stepwise to g5C over a period of 30 minutes.
The polymer particles became highly~swollen and gradually disperse over a period of ahout 1 hour. The flask is cooled to about 60C, at which point the dispersion is filtered to remove a small fxaction of undispersed particles. The resulting dispersion has a ~_ _ . . ' .. __ __ , . .. . .: ., .. ,,, ,, , . , . . , . , " , ~ , . . . .. . . . .

' .: ' - . . ' ' . ' ` ' , ' , :, ~ , . ~ : ` ' . .

W O 91~06608 PC~r/US90/06257 ~ 9~6 ~ - 26 -viscosity of 120 cP (Brookfield Viscometer, Model RVT, Spindle No. 3, 100 rpm) and is found to contain 25.2%
nonvolatile matter.

Example 3. Preparatlon of Ink Based on Sulfo PolYester An aqueous ink suitable for printing on paper, film or foil substrates is prepared by blending the following components in a high speed mixer:
Ink Formula 120 parts dispersion from Example 2 (25~ solids) 2.0 parts ethylene glycol monobutyl ether 8.0 parts n-propanol 2.6 parts acrylic thickener (Acrysol RM825 from Rohm & Haas) 4.0 parts pigment blue 15:3 mill base (Colour Index 74160), 20% solids 0.25 parts emulsified low-density polyethylene wax (20% solids in water- Epolene E-14 polyethylene from Eastman Chemical Products, Inc.) Ink viscosity is adjusted to 25 seconds, No. 3 Zahn cup, for printing by addition of water and/or n-propanol as required.
To prepare an overprint, the pigment is omitted from the formulation.

Example 4. Determination of Ink Blockin~_Temperature ~Strips of 60-lb. (27.22-kg) clay-coated paper r5 in. x 14 in. (12.7 cm x 35.56 cm)] are coated with 2-in. t5.08-cm) bands of the ink from Example 3 by draw-down with a No. 3 RK wire-wound rod (RK Print-Coat Instruments, Ltd., Litlington, Royston, Herts, UK)-. -35 ~--After drying at room temperature for 24 hours, the ink -draw-downs arèiplaced in a constant-humiidity (70%
relative humidity) storaye cabinet-to condition at room temperature for-7 days. At the end of the conditioning period, the paper strips are removed one by one from the constant humidity cabinet and tested for blocking WO9~/06608 PCT/US90/06257 -2Q73Ol6 temperature as follows: The paper strip is folded so that ink film-to-ink film contact is made. This fold is inserted in between the pre-heated (100F, 37.78~C) platens of a Sentinel Heat Sealer (Packaging Industries, Inc., Hyannis, Mass., Model 12 ASL). The heat sealer is activated to compress the folded paper strip between the heated platens for 5 seconds at 40 psi (275.79 kilopascal). After remo~al from the sealer and cooling, the fold is carefully opened to inspect for ink-to-ink sticking or blocking. If no blocking is detected, the temperature of the platens is increased in 10F (5.56C) increments and the test is repeated until blocking occurs. The lowest temperature at which ink film sticking results in paper tear is taken as the blocking temperature of the ink. In this way, the blocking temperature of the ink from Example 3 is determined to be 140F (60C).

Examples 5-10 In the same or similar manner as described in Examples 1-4, the water-dispersible polyesters listed in Table 1 were prepared, dispersed, formulated into inks -and tested for ink blocking temperature. The sulfo polyesters of Examples S-9 are illustrative of the present invention, i.e., they oontain no diethylene glycol or polyethylene glycols. Ink blocking temperature for all of these polyesters is well above 100F (37.78C~. In contrast, the ink blocking temperature of the sulfo polyester of Example 10 (an ~-example from the prior art) is less than 100F
(37.78C). ; - ``

~ . . .

WO91/06608 PCT/US90/~6257 3~ - 28 -Table 1 Mol % Ink slocking 5 Ex. Composition of Tg, Temperature No. Polyester I.V. C F (C) 50 Isophthalic Acid0.24 105 150 (65.56J
30 2,6-Naphthalene Dicarboxylic Acid 20 5-Sodiosulfo-isophthalic Acid :
lO0 1,4-Cyclohexane-dimethanol 6 40 Isophthalic Acid0.25 90 150 (65.56) 40 Terephthalic Acid 20 5-Sodiosulfo-isophthalic Acid 100 1,4-Cyclohexane-dimethanol 7 80 Isophthalic Acid0.15 78 120 (48.89) 20 5-Sodiosulfo-isophthalic Acid ~ .
100 2,2-Dimethyl-1,3-propanediol 8 81 Isophthalic Acid0.19 80 130 (54.44) ::
19 5-Sodiosulfo-isophthalic Acid 100 Ethylene Glycol ~ :
- .... ~ ., .

9 80 Isophthalic Acid0.24 85. 140 (60.00) ::.
20 5-Sodiosulfo- :
-- isophthalic Acid 80 1,4-Cyclohexane-dimethanol 20 Ethylene Glycol .. .. . .. .. .. . . ..

WO9l/06608 ~1 3~

Table 1 (Continued) 5 Ex. Mol % Tg, Ink Blocking No. Polyester I.V. C F (C) _ -10* 88 Isophthalic Acid 0.35 32 90 (32.22) 12 5-Sodiosulfo-isophthalic Acid 92 Diethylene Glycol 8 Ethylene Glycol *Polyester of U.S. 4,704,309; Col. 4, Lines 42-46.

: .

, . - - ., ~ - , . ... . . i , .

'` . " . ' ' . - ' .' , , ., ~ . ' ' . . . ' . , ~ j ' , ,. , . , , . , , . ' ' ` ~ . ., ~ '` ',, . ` ' .', ' ' ' . ' ' ' ' . ' " . ~ . ' . , ' ' ' . ', ' . " ' ' ' '

Claims

We claim:

1. A composition useful as an ink or concentrate thereof comprising:

(A) 1 to 35 weight percent of at least one amorphous, linear, water-dissipatable polyester having an inherent viscosity of at least 0.1 dL/g measured in a 60/40 parts by weight solution of phenol/tetrachloroethane at 25°C and at a concentration of 0.5 gram of polymer in 100 ml of solvent and having a Tg as measured by DSC of greater than 60°C, the polyester containing substantially equimolar proportions of acid equivalents (100 mole %) to hydroxyl equivalents (100 mole %), the polyester consisting essentially of the reaction products of reactants selected from (1), (2), (3), and (4) or the ester forming derivatives thereof, as follows, wherein all stated percentages are based on the total of all acid and hydroxyl equivalents being equal to 200 mole %:

(1) at least one aromatic dicarboxylic acid;

(2) from 0 to 30 mole % of at least one aliphatic or cycloaliphatic dicarboxylic acid;

(3) from 12 to 25 mole % of at least one difunctional ester-forming sulfomonomer containing at least one sulfonate group attached to an aromatic ring; and (4) at least one aliphatic cyclo-aliphatic or aralkyl glycol;

(B) 0 to 50 weight % of at least one colorant;

(C) 15 to 99 weight % of water; and (D) 0.01 to 5 weight % of an emulsified, dispersed, powdered, or micronized wax.

2. A composition useful as an ink or concentrate thereof comprising:

(A) 1 to 35 weight percent of at least one amorphous, linear, water-dissipatable polyester having an inherent viscosity of at least 0.1 dL/g measured in a 60/40 parts by weight solution of phenol/tetrachloroethane at 25°C and at a concentration of 0.5 gram of polymer in 100 ml of solvent and having a Tg as measured by DSC of greater than 60°C, the polyester containing substantially equimolar proportions of acid equivalents (100 mole %) to hydroxyl equivalents (100 mole %), the polyester consisting essentially of the reaction products of reactants selected from (1), (2), (3), and (4) or the ester forming derivatives thereof, as follows, wherein all stated percentages are based on the total of all acid and hydroxyl equivalents being equal to 200 mole %:

(1) at least one difunctional dicarboxylic acid;

(2) from 0 to 30 mole % of at least one aliphatic or cycloaliphatic dicarboxylic acid;

(3) from 12 to 25 mole % of at least one difunctional ester-forming sulfomonomer containing at least one sulfonate group attached to an aromatic ring; and (4) at least one aliphatic cyclo-aliphatic or aralkyl glycol;

(B) 0.5 to 50 weight % of at least one colorant;

(C) 15 to 99 weight % of water; and (D) 0 to 5 weight % of an emulsified, dispersed, powdered, or micronized wax.

3. The composition of Claim 1 comprising 2 to 25 weight percent of component (A), 0 to 35 weight percent of component (B), and 0.1 to 3 weight percent of component (D).

4. The composition of Claim 1 comprising 5 to 20 weight percent of component (A), 0.5 to 35 weight percent of component (B), 50 to 90 weight percent of component (C), and 0.2 to 2 weight percent of component (D).

5. The composition of Claim 1 comprising 0.5 to 50 weight percent of component (B).

6. The composition of Claim 2 comprising 2 to 25 weight percent of component (A), and 0.5 to 35 weight percent of component (B).

7. The composition of Claim 2 comprising 5 to 20 weight percent of component (A), 5 to 35 weight percent of component (B), and 50 to 90 weight percent of component (C).

8. The composition of Claim 1 wherein component (A)(4) is an aliphatic glycol containing 2 to 8 carbon atoms, an alicyclic glycol containing 6 to 12 carbon atoms or a mixture thereof.

9. The composition of Claim 2 wherein component (A)(4) is an aliphatic glycol containing 2 to 8 carbon atoms, an alicyclic glycol containing 6 to 12 carbon atoms or a mixture thereof.

10. The composition of Claim 1 wherein component (A)(4) is selected from the group consisting of ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,3-butanediol, 2,2-dimethyl-1,3-propanediol, 1,2-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, p-xylenediol, and a mixture thereof.

11. The composition of Claim 2 wherein component (A)(4) is selected from the group consisting of ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,3-butanediol, 2,2-dimethyl-1,3-propanediol, 1,2-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, p-xylenediol, and a mixture thereof.

12. The composition of Claim 1 wherein component (A)(1) is selected from the group consisting of terephthalic acid, isophthalic acid, orthophthalic acid, 2,6-naphthalene dicarboxylic acid and a mixture thereof; and component (A)(2) is selelcted from the group consisting of glutaric acid, succinic acid, adipic acid, trimethyladipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, 1,4-cyclohexanedicarboxylic acid, and a mixture thereof.

13. The composition of Claim 2 wherein component (A)(1) is selected from the group consisting of terephthalic acid, isophthalic acid, orthophthalic acid, 2,6-naphthalene dicarboxylic acid and a mixture thereof; and component (A)(2) is selected from the group consisting of glutaric acid, succinic acid, adipic acid, trimethyladipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, 1,4-cyclohexanedicarboxylic acid, and a mixture thereof.

14. The composition of Claim 1 wherein component (A)(3) is a metal salt of a sulfoaromatic dicarboxylic acid.

15. The composition of Claim 14 wherein the metal of the salt is lithium, sodium, potassium, magnesium, calcium, copper, or iron.

16. The composition of Claim 2 wherein component (A)(3) is a metal salt of a sulfoaromatic dicarboxylic acid.

17. The composition of Claim 16 wherein the metal of the salt is lithium, sodium, potassium, magnesium, calcium, copper, or iron.

18. The composition of Claim 1 wherein component (A)(3) is a metal salt of a compound selected from the group consisting of sulfoterephthalic acid, 5-sulfoisophthalic acid, 4-sulfophthalic acid, 4-sulfonaphthalene-2,7-dicarboxylic acid, 5-(4-sulfo-phenoxy)isophthalic acid, and a mixture thereof.

19. The composition of Claim 2 wherein component (A)(3) is a metal salt of a compound selected from the group consisting of sulfoterephthalic acid, 5-sulfoisophthalic acid, 4-sulfophthalic acid, 4-sulfonaphthalene-2,7-dicarboxylic acid, 5-(4-sulfophenoxy)isophthalic acid, and a mixture thereof.

20. The composition of Claim 1 wherein component (A)(1) is isophthalic acid, terephthalic acid, or a mixture thereof, component (A)(2) is not present, component (A)(3) is 5-sulfoisophthalic acid, 5-lithiosulfoisophthalic acid, or a mixture thereof, and component (A)(4) is 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 2,2-dimethyl-3-propanediol, ethylene glycol, p-xylenediol, or a mixture thereof.

21. The composition of Claim 2 wherein component (A)(1) is isophthalic acid, terephthalic acid, or a mixture thereof, component (A)(2) is not present, component (A)(3) is 5-sulfoisophthalic acid, 5-lithio-sulfoisophthalic acid, or a mixture thereof, and component (A)(4) is 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 2,2-dimethyl-3-propanediol, ethylene glycol, p-xylenediol, or a mixture thereof.

22. The composition of Claim 1 wherein component (A)(1) is 35 to 85 mole % isophthalic acid, 0 to 35 mole % 2,6-naphthalene dicarboxylic acid, and 0 to 45 mole % terephthalic acid, component (A)(2) is not present, component (A)(3) is 18-22 mole % 5-sodiosulfo-isophthalic acid, and component (A)(4) is 0-100 mole %, 1,4-cyclohexanedimethanol, 0-100 mole % 2,2-dimethyl-1,3-propanediol, and 0-100 mole % ethylene glycol.

23. The composition of Claim 2 wherein component (A)(1) is 35 to 85 mole % isophthalic acid, 0 to 35 mole % 2,6-naphthalene dicarboxylic acid, and 0 to 45 mole % terephthalic acid, component (A)(2) is not present, component (A)(3) is 18-22 mole % 5-sodiosulfo-isophthalic acid, and component (A)(4) is 0-100 mole %, 1,4-cyclohexanedimethanol, 0-100 mole % 2,2-dimethyl-1,3-propanediol, and 0-100 mole % ethylene glycol.

24. The composition of Claim 2 wherein the colorant 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, C.I. Pigment Yellow 1, C.I. Pigment Yellow 3, C.I. Pigment Yellow 13, C.I.
Pigment Orange 16, C.I. Pigment Yellow 55, C.I. Pigment Red 41, C.I. Pigment Orange 34, C.I. Pigment Blue 62, C.I. Pigment Violet l, C.I. Pigment Red 22, C.I. Pigment Orange 16, C.I. Pigment Red 170, C.I. Pigment Red 88, C.I. Pigment Yellow 151, C.I. Pigment Violet 23:, C.I.
Pigment Red 184, C.I. Pigment Blue 1:2, C.I. Pigment Red 3, C.I. Pigment Blue 15:1, C.I. Pigment Red 23, C.I.
Pigment Red 112, C.I. Pigment Yellow 126, C.I. Pigment Red 169, C.I. Pigment Orange 5, C.I. Pigment Orange 13, C.I. Pigment Orange 34, C.I. Pigment Red 1-10, 12, C.I.
Pigment Blue 1:X, C.I. Pigment Black 7, C.I. Pigment White 6, C.I. Pigment Blue 27, C.I. Pigment Yellow 42, C.I. Pigment Red 101, C.I. Pigment Brown 6, C.I. Pigment Brown 7, C.I. Pigment Brown 7:X, C.I. Pigment Black 11, C.I. Pigment Metal 1, or C.I. Pigment Metal 2.

25. The composition of Claim 21 wherein the colorant is 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, C.I. Pigment Yellow 1, C.I. Pigment Yellow 3, C.I. Pigment Yellow 13, C.I.
Pigment Orange 16, C.I. Pigment Yellow 55, C.I. Pigment Red 41, C.I. Pigment Orange 34, C.I. Pigment Blue 62, C.I. Pigment Violet 1, C.I. Pigment Red 22, C.I. Pigment Orange 16, C.I. Pigment Red 170, C.I. Pigment Red 88, C.I. Pigment Yellow 151, C.I. Pigment Violet 23, C.I.
Pigment Red 184, C.I. Pigment Blue 1:2, C.I. Pigment Red 3, C.I. Pigment Blue 15:1, C.I. Pigment Red 23, C.I.
Pigment Red 112, C.I. Pigment Yellow 126, C.I. Pigment Red 169, C.I. Pigment Orange 5, C.I. Pigment Orange 13, C.I. Pigment Orange 34, C.I. Pigment Red 1-10, 12, C.I.
Pigment Blue 1:X, C.I. Pigment Black 7, C.I. Pigment White 6, C.I. Pigment Blue 27, C.I. Pigment Yellow 42, C.I. Pigment Red 101, C.I. Pigment Brown 6, C.I. Pigment Brown 7, C.I. Pigment Brown 7:X, C.I. Pigment Black 11, C.I. Pigment Metal 1, or C.I. Pigment Metal 2.

26. The composition of Claim 23 wherein the colorant 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, C.I. Pigment Yellow 1, C.I. Pigment Yellow 3, C.I. Pigment Yellow 13, C.I.
Pigment Orange 16, C.I. Pigment Yellow 55, C.I. Pigment Red 41, C.I. Pigment Orange 34, C.I. Pigment Blue 62, C.I. Pigment Violet 1, C.I. Pigment Red 22, C.I. Pigment Orange 16, C.I. Pigment Red 170, C.I. Pigment Red 88, C.I. Pigment Yellow 151, C.I. Pigment Violet 23, C.I.
Pigment Red 184, C.I. Pigment Blue 1:2, C.I. Pigment Red 3, C.I. Pigment Blue 15:1, C.I. Pigment Red 23, C.I.
Pigment Red 112, C.I. Pigment Yellow 126, C.I. Pigment Red 169, C.I. Pigment Orange 5, C.I. Pigment Orange 13, C.I. Pigment Orange 34, C.I. Pigment Red 1-10, 12, C.I.
Pigment Blue 1:X, C.I. Pigment Black 7, C.I. Pigment White 6, C.I. Pigment Blue 27, C.I. Pigment Yellow 42, C.I. Pigment Red 101, C.I. Pigment Brown 6, C.I. Pigment Brown 7, C.I. Pigment Brown 7:X, C.I. Pigment Black 11, C.I. Pigment Metal 1, or C.I. Pigment Metal 2.

27. The composition of Claim 1 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(vinylidene chloride), polyamide, polypropylene, polyethylene or polystyrene.

28. The composition of Claim 2 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(vinylidene chloride), polyamide, polypropylene, polyethylene or polystyrene.

29. The composition of Claim 22 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(vinylidene chloride), polyamide, polypropylene, polyethylene or polystyrene.

30. The composition of Claim 23 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(vinylidene chloride), polyamide, polypropylene, polyethylene or polystyrene.

31. The composition of Claim 26 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(vinylidene chloride), polyamide, polypropylene, polyethylene or polystyrene.

32. A substantially water-insoluble coating or print, on a substrate according to Claim 27 wherein substantially all water has evaporated and a substantial portion of the metal portion of the metal salt of the sulfomonomer of the polymeric material has been replaced with an in-solubilizing cation.

33. A substantially water-insoluble coating of print, on a substrate according to Claim 28 wherein substantially all water has evaporated and a substantial portion of the metal portion of the metal salt of the sulfomonomer of the polymeric material has been replaced with an in-solubilizing cation.

34. A linear water-dissipatable polyester having an inherent viscosity of 0.2 to 0.3 dL/g measured in a 60/40 parts by weight solution of phenol/tetrachloroethane at 25°C and at a concentration of 0.5 grams of polymer in 100 ml of solvent and having a Tg as measured by DSC of 105°C, the polyester consisting essentially of the reactants, (a), (b), (c), and (d) as follows, wherein all stated percentages are based on the total of all acid and hydroxyl equivalents being equal to 200 mole %:

(a) 50 mole % isophthalic acid (b) 30 mole % 2,6-naphthalene dicarboxylic acid, (c) 20 mole % 5-sodiosulfoisophthalic acid, and (d) 100 mole % 1,4-cyclohexanedimethanol.

35. A linear water-dissipatable polyester having an inherent viscosity of 0.2 to 0.3 dL/g measured in a 60/40 parts by weight solution of phenol/tetrachloro-ethane at 25°C and at a concentration of 0.5 grams of polymer in 100 ml of solvent and having a Tg as measured by DSC of 90°C, the polyester consisting essentially of the reactants, (a), (b), (c), and (d) as follows, wherein all stated percentages are based on the total of all acid and hydroxyl equivalents being equal to 200 mole %:

(a) 40 mole % isophthalic acid (b) 40 mole % terephthalic acid, (c) 20 mole % 5-sodiosulfoisophthalic acid, and (d) 100 mole % 1,4-cyclohexanedimethanol.

36. A linear water-dissipatable polyester having an inherent viscosity of 0.1 to 0.2 dL/g measured in a 60/40 parts by weight solution of phenol/tetrachloro-ethane at 25°C and at a concentration of 0.5 grams of polymer in 100 ml of solvent and having a Tg as measured by DSC of 78°C, the polyester consisting essentially of the reactants, (a), (b), and (c) as follows, wherein all stated percentages are based on the total of all acid and hydroxyl equivalents being equal to 200 mole %:

(a) 80 mole % isophthalic acid (b) 20 mole % 5-sodiosulfoisophthalic acid, and (c) 100 mole % 2,2-dimethyl-1,3-propanediol.

37. A linear water-dissipatable polyester having an inherent viscosity of 0.2 to 0.3 dL/g measured in a 60/40 parts by weight solution of phenol/tetrachloro-ethane at 25°C and at a concentration of 0.5 grams of polymer in 100 ml of solvent and having a Tg as measured by DSC of 80°C, the polyester consisting essentially of the reactants, (a), (b), and (c) as follows, wherein all stated percentages are based on the total of all acid and hydroxyl equivalents being equal to 200 mole %:

(a) 80 mole % isophthalic acid, (b) 20 mole % 5-sodiosulfoisophthalic acid, and (c) 100 mole % ethylene glycol.

38. A linear water-dissipatable polyester having an inherent viscosity of 0.2 to 0.3 dL/g measured in a 60/40 parts by weight solution of phenol/tetrachloro-ethane at 25°C and at a concentration of 0.50 grams of polymer in 100 ml of solvent and having a Tg as measured by DSC of 85°C, the polyester consisting essentially of the reactants, (a), (b), (c) and (d) as follows, wherein all stated percentages are based on the total of all acid and hydroxyl equivalents being equal to 200 mole %:

(a) 80 mole % isophthalic acid, (b) 20 mole % 5-sodiosulfoisophthalic acid, (c) 80 mole % 1,4-cyclohexanedimethanol, and (d) 20 mole % ethylene glycol.