CA1326313C - Aqueous dispersion blends of polyesters and polyurethane materials and printing inks therefrom - Google Patents

Abstract

Abstract of the Disclosure Compositions useful as printing inks or as dry or wet concentrates for the preparation of inks, comprising substantially homogenous blends of from about 0.1 to about 50.0 wt. % water dispersible polyurethane, and conversely from about 99.9 to about 50.0 wt. % water dispersible polyester, and preferably containing from about 1.0 to about 95.0 wt. % of a solvent system comprising water or water admixed with cosolvent, the cosolvent comprising up to about 30.0 wt. % of the solvent system. These blends show exceptionally marked improvements in certain physical properties such as:
stability of viscosity to ambient and process conditions; linearity of viscosity change with water dilution; consistency of viscosity for a great variety of pigments; and greatly improved shelf-life (no significant polymer segregation or layering).
Such properties greatly enhance the utility of these blends for use in pigmented or dyed printing inks and in other substrate coating formulations which may or may not contain colorants. Also disclosed is a process useful for the preparation of such compositions.

Description

~ ~ 326313 .~ .

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AQUEOUS DISPERSION BLENDS OF POLYESTERS AND
POLYURETHANE MATERIALS AND PRINTING INKS THEREFROM
r - Field of Invention This invention concerns substantially homogenous < aqueous dispersion blends of certain polyester and polyurethane materials wherein the polymers are water dispersible, water soluble or water dissipatable, all ~ hereinafter termed "water dispersible". These blends -1 10 have substantial utility in the printing ink and . substrate coatings fields, for example, as extenders.
The present invention also concerns a process for the manufacture of such blends.
, Backqround of the Invention j In the field of coatings, and in particular in the field of water-based coatings such as in printing :1 inks and the like, wherein the coatings employ water dispersible polyester material as the ink varnish or binder, with or without colorants, problems associated with viscosity are commonly encountered and affect formulation and preparation of the coating compositions, their use, and the coated product . appearance. For example, in the manufacture and use .; 25 of conventional water-based, polyester containing :l printing inks, one is confronted in many instances with such problems as: limited viscosity range obtainable with such inks; substantial changes in viscosity of the ink compositions, e.g., during processing, particularly during operations wherein , heating and/or shearing occurs, including printing, in particular, when thixotropic phenomena are present ~ which reduce the shear viscosity of the polymer . ~ .
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dispersion to a point where proper dispersal of the desired amounts of colorant therein by typical mixing apparatus becomes virtuslly impossible in that adequate shear is not developed to separate the s plgment agglomerate; non-linear ~nd unpredictable viscosity changes of the aqueous ink compositions with respect to polyester concentration;
, unpredictable build in viscosity of the ink ` compositions with time; difficulty in developing full pigment color during processing, as in milling operations wherein adequate viscosities of the compositions have not been achieved; and hazing and diminished gloss of the dried films such as occurs with conventional viscosity modifiers.
., SummarY of the Inventlon Principal ob~ects of the present invention are:
to eliminate one or more and prefer~bly all of the above viscosity related problems in a cost effective and efficient manner whereby negative effects on the coating compositions are minimal or nonexi~tent; to y provide me2ns to quickly and essily extend the lnk ,'~ varnish or colorant (reduce color density) at press side without employing large amounts of polyester, and to provide a process for the rapid prepar~tion of pigmented or otherwise colored substantially homogeneous systems containing water dispersible polyesters whlch normally exhiblt thixotropic behavior.
Accordingly, the pre~ent invention i~ directed to '~ compositions useful as inks or as dry or wet concentrates for the preparation of inks, comprising substantially homogenous blends of from about 0.1 to ~$ about 50.0 wt. % water dispersible polyurethane, and 35 conversely from about 99.9 to about 50.0 wt. ~ water dlspersible polye~ter, end preferably containlng from ':, ., .. . . .

-~ ~326313 . - 3 -''''' about 1.0 to about 95.0 wt. ~ of a solvent system comprising water or water admixed with cosolvent, said cosolvent comprising up to about 30.0 wt. ~ of said solvent system.
The present invention iQ also directed to a process for preparing colored, aqueous inks or ink concentrates containing ~ubstantial iRmounts of water dispersible polymeric (i.e., polyester) material which normally exhibits thixotropic behavior.
.j - 10 More specifically~ the process of the present invention comprises blending a mixture comprising:
(A) a water dispersible polyester material which normally exhibits thixotrophic behavior, (B) a colorant, which is essentially in~oluble in the polyester material, in the form of aggregates, and (C) an effective amount of water dispersible polyurethane material, ; under sufficient blending conditions such that ,~ 20 the size of said aggregates is reduced.
In such process it is preferred that said mixture i~, comprises (A) from about 3 to about 60 weight ~ of said water dispersible polyester material, (B) from about 0.1 to about 85 weight ~ of said colorant, i (C) from about 0.1 to about 20 weight % of said !~ water dispersible polyurethane material, and (D) from 0 to about 75 weight ~ of a solvent comprislng water.
The mixture of such process is preferably a stock 1 mixture which i8 either a separate premix of the ', polymers and pigment, with or without wster, or which is a mixture of these materials which have been fed ~ 35 separately or in any combination to a suitable ;1 blender.

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`. - 4 -As used herein, "normally exhibits thixotropic behavior" means that the water dispersible polyester material exhibits thixotropic behavior in the absence or substantial absence of water dispersible .~ 5 polyurethane material; "thixotropic behavior" means ; that a reduction in viscosity takes place with ;~ continuing shear at the same ~hear rate to some minimum value, and on termination of the shearing stress, an immediate or gradual recovery of the viscosity loss take~ place; ~'effective amount" means : that amount of water dispersible polyurethane material effective to result in the size of colorant aggregates to become reduced under sufficient .. blending conditions; and "sufficient blending : 15 conditions" includes those conditions that have ' forces that are the same or greater than those forces ; present in a high speed discspercer (i.e., disc ;. cavitation mixer or high speed disk impeller) . oper~ted at a peripheral or tip speed of about 1,000 feetlmlnute; preferred is a tip speed of about .. 4,000 to about 6,000 feet~minute.
':',, Petailed DescriPtion of the Invention The blends of the invention show exceptlonally marked improvement~ in certaln physicfil properties such as: stability of viscosity to ambient and process conditions; linearity of viscosity change with water dilution; consistency of viscosity for a great variety of pigments; and greatly improved shelf-life (no significant polymer segregatlon or ;~ layering). Such properties greatly enhance the utility of these blends for use in plgmented or dyed printing inks and in other Qubstrate coating formulations which may or may not contain colorants, particularly since the polyurethsne component is highly compatible with such systems and shows no ., ~ : , .
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- adverse effects on such properties as film blocking, adhesion, gloss, haze or the like. In this regard, these blends are extremely u~eful as extenders for various pigmented or dye colored systems such as printing inks in that viscosity of the ink can be decreased, increased, or retained by the addition of -the present extenders, without markedly increasing, if at all, the polyester levels.
By way of the process of this invention the - 10 colorant (pigment, disperse dye, etc.) aggregates (or agglomerates) are very rapidly reduced in size since ~- the viscosity of the system under sufficient blending conditions is maintained. This rapid and effective aggregate reduction achieves two principal objectives.
i 15 The first is that the stock mixture can be formulated, e.g., for low pigment loading which would normally produce ineffective pigment reduction, but which, by virtue of the polyurethane material now promotes , excellent pigment reduction. The second is that in high pigment content formulations, the viscosities under sufficient blending conditions do not tend to . ~, : diminish to ineffective levels and the resulting rapid pigment reduction gives a flowable, pumpable material .. very quickly and avoids such problems as filter or pump clogging.
, The blending equipment useful for carrying out the present process should be capable of stirring, milling or otherwise mixing to achieve sufficient ~ blending conditions. Such blending equipment ;~ 30 includes dispersion equipment requiring: very high ' viscosity such as two-roll rubber mills, and Banbury ,~ ~sigma blade) mills; high viscosity such as three-~ roll paint mills; medium viscosity such as high-speed 1 stone mills and high speed disk impellers, for example, ` 35 a Hockmeyer High Speed Discperser (trademark) ~ (Model 2HL) or a Cowles mixer; and low viscosity such ~ , ,,,.~ , ,., ., "' ' ' ' : . ' :

, i 13263~3 as sand mills, ball and pebble mills, attritors and vibratroy mills, and kinetic dispersion mills.
In the preferred process of the present invention .; it is more preferred that the weight ~ of component (A) is from about 5% to about 40%, the weight % of component (B) is from about 10% to about 75%, the weight % of component (C) is from about 0.2% to about 15%, and the weight percent of component (D) is from about 1% to about 40%.
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- 10 It is also preferred that the present process is carried out at a temperature of from about 0C to about 100C for about 1 minute to about 1 hour.
, In the process of the invention it is typical that the average size of said aggregates before blending is greater than about lOO microns in diameter and the , average size of said aggregates after blending is less than about 50 microns in diameter, preferably less than about 1 micron in diameter.
To break down the colorant aggregates sufficient , 20 forces must be exerted by one or more means to overcome the forces holding the aggregate together such as:
-~ (1) by physical impact, (2) by particle-particle attrition, and/or (3) by shear transmitted through an intermediate fluid layer. Usually most of the size -~ 25 reduction is accomplished by shear transmitted through the fluid layer surrounding the aggregate or by ,~, impingement of the aggregate against a hard surface~
When a high speed discspercer is operated at a peripheral speed of between 1,000 and 4,000 feet/minute for a typical starting mixture, typically the forces present will include a high ~ shear rate of greater than about 3,000 sec. 1, '~ preferably greater than or equal to about 10,000 ~l sec. 1 For example, typical forces of a '~' ,' `; ~r .j j .
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- Cowles mixer operated at such a peripheral speed range for a typical starting mixture may include a shear rate of about 20,000 sec. 1 and a shear stress of about 6 pounds/inches2. As appreciated by a skilled artisan, for any given type of blending equipment under any given set of conditions, the effective amount of water dispersible polyurethane material can vary and can be determined using conventional blending technology.
The polyurethanes useful in the compositions and process of the present invention include those disclosed in U.S. Patents: 4,180,491; 4,155,892; and 4,079,028. In these polymers, as stated in 4,079,028, the polyether segments have molecular weights of at least 1500 (preferably 3000-20,000), the polymers contain, on the average, at least three hydrophobic . groups and at least two water soluble polyether segments ; linking the hydrophobes, the sum of the carbon atoms in - the hydrophobic groups being at least 20, preferably at .. j ~ least 30, and the total molecular weight is about Jj 20 10,000-200,000, preferably 12,000-150,000. The optimum polyether content will d0pend, of course, on the bulk and distribution of the hydrophobic groups in the polymer. Whereas a total polyether molecular weight of 4000-5000 may be suitable when the polymer contains small external and internal hydrophobes, the polyether j content may have to be substantially increased when heavier and/or more extensively branched hydrophobic groups are to be built into the polymer, such as long :! chain fatty polyols or amines. About 200 carbon atoms in the hydrophobic portion is the practical upper limit ~, although it will be understood that it is a relative matter since the proportion of polyether may be increased to offset increased hydrophobicity.
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' However, as total molecular we~ght increase~ the viscosity increases and ease of handlin~ decreases, :~ and therefore the economic usefulness of the products is substantially diminished.
The water dispersible polyester materials usefu;
-~ in the compositiuns and process of the present invention are non-polyurethane polymers which comprise at lea~t one linear, water dissipatable . polymer having carbonyloxy (i~e., ester) linking groups in the linear molecular structure wherein up to 80% of the linking groups may be carbonylamido (i.e., amide) linking groups, the polymer hsving an inherent viscosity of from about 0 1 to about 1.0 measured ln a 60/40 parts by weight solution of phenol/tetrachloroethane at 25C and at a concentration of 0.25 gram of polymer in 100 mL of the solvent, the polymer comprising the condensation reaction products of (a), (b), (c) and (d) from the following components or the ester forming or : 20 egteramide forming derivatives thereof;

:, (a) at least one difunctlonal dicarboxylic acid ~.. which i~ not a sulfomonomer;
,;:;, (b) from about 4 to about 25 mole percent, based on a total of all acid, hydroxyl and amino equivalents belng equal to 200 mole percent, l of at least one difunctional qulfomonomer ;. containing at lesst one metallic sulfonate group attached to an aromatic hydrocarbon .. ~ nucleus or cycloaliphatic nucleus wherein the functlonal 8rouPs are hydroxy, carboxyl .~ or amino;

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, . , , :,. ~ : - , . g (c) at least one dlfunctional reactant which is not a culfomonomer selected from a glycol or : a mixture of a glycol and diamine having two -NRH group~, the glycol containing two -CH2-OH groups of which (1) at least 15 mole percent, based on 100 mole percent of hydroxy or hydroxy And amino equivalents, is a ~: 10 poly(ethylene glycol) havin& the .~ structural formula HtOCH2--CH2~ OH, ;¦ n being an inte8er of from 2 to about 20, or (2) of which from about 0.1 to less than ' ebout 15 mole percent, ba~ed on 100 mole percent of hydroxy or hydroxy ; 20 and amino equivslents, ls a . poly(ethylene glycol) having the . structural formula H~ocH2~H2tnoH
~I n being an lnteger of between 2 and about 500, and with the proviso that the mole percent of said poly(ethylene , glycol) within said ran8e i9 inversely :~ proportional to the quantlty of n within said range; and l (d) from none to at least one dlfunctional - reactsn~ selected from a hydroxycarboxyllc acid having one -C(R)2-OH group, an smlnocarboxyllc acid having one -NRH group, and an amino-alcohol havlng one -C(R)2-OH
group and one -NRH group, or mlxtures of sald dlfunctional reactants;
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wherein each R in the (c) or (d) reactants is a H
atom or an alkyl group of 1 to 4 carbon atoms.
~ , 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 hydroxy equivalents is present in the glycol.
In preferred embodiments of the present invention:

., (a) water comprises at least about 90.0 wt. % of ; all the solvent system;
: .', (b) the cosolvent is selected from diethylene glycol monomethyl ether, propylene glycol, , ethylene glycol, diethylene glycol, n-propyl alcohol, isopropyl alcohol, ethyl alcohol, glycerin, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol " 3 monoethyl ether, diethylene glycol monopropyl ' ether, and diethylene glycol monobutyl ether;

. a 5 (c) from about 1.0 wt. % to about 20.0 wt. % of ;~ colorant based on total weight of the f press-ready ink, is present therein; and (d) the n value of reactant (c) (2) is between about 2 and about 200.
.j The pigment type colorants useful in the present ,~ invention, in addition to those specifically identified :~ below, include those described in NPIRI
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Raw Materials Data, Vol. 4, Pigments, Copyright 1983. The dye type colorants useful in the present invention include those classified by the Colour Index as disperse colors. They may be of any chemical class such as ezo, anthraquinone, methine, and disazo, which are characteri~ed by the absence of any pendant water solubilizing groups such as a sulfonic acid group or a salt thereof. Such dyes also include those u~eful for hest transfer printing uses exemplified by C. I. Disperse Yellow 3, Disper-~e Yellow 85, Disperse Yellow 23, Disperse Oran~e 25, Disperse Red 60, Disperse Red 4, Disperse Red 78, Disperse Violet 1, Disperse Violet 27, Disperse Blue 3, Disperse Blue 14, and Dlsperse Blue 35.
15One or more of these disperse dyé~, which slso may be blended with pigments, may be blended in the seme resin, if desired, to produce a resultant color, ; provlded that no adver~e chemical reaction between the dyes or the resin occurs at the dye dissolution ~'3 20 temperature. Conventlonal disper~ing aids, biocides, defoamers and the like may be used in the preQent ink3 if desired for their Xnown ef~ect-~.
In further preferred embodiments of the invention, the water dispersible polymeric m~terial comprises (a) an acld component (moiety) of from about 75 to about 84 mole ~ isophthalic acid and conversely from about 25 to about 16 mole S
, 5-sodiosulfoisophthalic ~cld, and (b) a glycol ; component (moiety) of from about 45 to about 60 mole ~ diethylene glycol and conversely from about 55 to ~4 about 40 mole % 1,4-cyclohexanedimethanol or ethylene glycol or mixtures thereof, and wherein the weight ratio of pigment material to tot~l polymeric material (polye~ter and polyurethane) is from about 1l10 to i 35 about 2/1. With re8ard to the polyester material, the term "moiety" as used hereln designates the , - .
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residual portion of the reactant acid or ~lycol which actually enters into or onto the polyme~ chain during : the condensation or polycondensation reaction.
Additional preferred embodiments of the invention are as follows:

(a) the inherent viscosity of the water-dispersible polymeric material is from :; about 0.28 to about 0.38, the said acid . 10 component (moiety) comprise 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 .~ 15 about 52 to about 56 mole ~ diethylene glycol and conversely from about 48 to about 44 mole ~ 1,4-cyclohexanedimethanol;

(b) the pigment i~ one or a mixture of the following color index materials according to ', their generic names: C.I. Pigment Yellow ;~ 17; C.I. Plgment 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.
.,. ~5 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. Pi~ment Red 48:1; C.I. Pigment Red ~ 52:1; C.I. Pigment Violet l; C.I. Pigment -; 30 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 Red 53:1; C.I. Pi8ment Yellow 42; C.I. Plgment Brown 6; C.I. Pigment Red 101; and C.I.
., Pigment Black 11;
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.~ - 13 -.~ (c~ the aqueous ink 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 polyester, polycarbonate, cellulose ester, regenerated ;.~ cellulose, poly(vinylidene chloride), polyamide, polyolefin, or polystyrene;
,~,', 10 (d) the polyurethane has a molecular weight of at least 10,000 and at least three hydrophobic branching groups, the hydrophobic :;~ groups containing a total of at least 20 -j~ 15 carbon atoms and being linked through hydrophilic polyether segments of from about . 3,000 to about 20,000 molecular weight each;
wherein the polyurethane thickener is selected from the following reaction products :i 20 wherein reactant (a) is at least one water :~ soluble polyether polyol containing at least . three hydroxyl groups, reactant (b) is at ;' least one water insoluble organic ~. diisocyanate, reactant (c) is at least one ,~. 25 water insoluble organic polyisocyanate ~, containing at least three isocyanate groups, ~ reactant (d) is at least one hydrophobic : organic monofunctional active hydrogen compound, reactant (e) is at least one ~ 30 hydrophobic organic monoisocyanate, and ;~ reactant (~ is at least one polyhydric d alcohol or polyhydric alcohol ether containing three or more hydroxyl groups:

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. (I) reaction products of reactants (a) and (e), (II) reaction products of reactants (a), (c) and (d), . 5 (III) reaction products of reactants (a), (b), (d) and tf), :.; (IV) reaction products of reactants (a), , (b)~ (e) and (f)~
. (V) reaction products of reactants (a), ~ 10 (b), ~c) and (d), J' (VI) reaction products of reactants (b), (e) and (f), (VII) reaction products of reactants (a), : (c) and (e), ; 15 (VIII) reaction products of reactants (b), (d) and (f), and , (e) the polyurethane is selected from a ;:~ trimethylol propane/ethylene oxide adduct ;, 20 capped with octyldecyl isocyanate, a dipentaerythritol/ethylene oxide adduct ~ capped with octyldecyl isocyanate, a .:l, trimethylol propane/ethylene oxide adduct , reacted with a tolylene diisocyanate . I
.:, 25 polyethylene glycol condensate and capped ., with octadecanol, a trimethylol ., propane/ethylene oxide/C36 dimer acid diisocyanate/polyethylene glycol condensate . capped with octadeayl isocyanate, a . .~ .
`~ 30 polyethylene glycol/4,4'-methylenebis ~r (isocyanatocyclohexane)/triisocyanate adduct of trimethylol propane and tolylene dissocyanate capped with hexadecanol, a polyethylene glycol/methylenedi-p-phenylene diisocyanate/triisocyanate adduct of , trimethylol propane and tolylene 1~. e, .
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: ' - 15 -diisocyanate condensate capped wlth eicosanol, a polyethylene glycolltolylene . diisocyanate/polymethylene .~ polyphenylisocyanate condensate capped with .. 5 octadecanol, a polyethylene ~; glycol/trimethylol propane/tolylene . diisocyanate condenqate capped with ;; octadecanol, a polyethylene glycol/tolylene ~; diisocyanate/dipentacrythritol condensate : lO capped with octadecanol, and a polyethylene glycol/trimethylol propane/tolylene diisocy~nate condensate capped with perfluorododecanol.
., The complete chemical definitlons of the above .~ C.I. plgment3 re glven ln the Eollowlng t-ble:

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", PiRments Generic Name C.A. IndexlChemical Name C.I. P~gment Yellow 17 Butanamide, 2,2'-[(3,3'-dichloro[l,l'-biphenyl]
,~ 5 4,4'-diyl)bi~(azo)bic[N-(2-me~hoxyphenyl)-3-oxo-C.I. Pigment Blue 27 Ferrate (4-1), hexakis (cyano-C)-ammonium iron (3+)(1:1:1) ; 10 C.I. Pigment Red 49:2 l-Naphthalenesulfonic acid, 2-[(2-hydroxy-1-naphthalenyl)azo]-, . calcium salt (2:1) : C.I. Pigment Red 81:1 Benzoic acid, 2,-[6-ethyl-; amino)-3-(ethylimino)-2,7-N~ dimethyl-3H-x~nthen-9-yl]-, .-~ 15 ethyl ester, wlmolybdenum :, tungsten hydroxide oxide phosphate . , . C.I. Pigment Red 81:3 Benzoic acid, 2-[6-ethyl-, amino)-3-ethyllmino)-2,7-,,. dimethyl-3H-xanthen-9-yl]-, ethyl ester, molybd~te-C.I. Pigment Red 81:x Benzolc acid, 2-t6-(ethyl-. amino)-3-(ethylimino)-2,7-. dimethyl-3H-xanthen-9-yl]-u ethyl e~ter, molybdate-.~ 25 pho-~phate .~ C.I. Pigment Yellow 83 Butanamlde, 2,2'-[(3,3'-.~ dichloro[l,l'-biphenyl]-4,4'-diyl)bis(azo)bis[N-(4-chloro-2,5-dimethoxy-~ phenyl)-3-oxo-., 30 C.I. Pigment Red 57:1 2-Naphthalenecarboxylic .. acid, 3-hydroxy-4-[(4-.. methyl-2-sulfophenyl)azo]-, .l calcium salt (1:1) ,1 C.I. Pigment Red 49:1 l-Naphthalene~ulfonic acid, 2-[(2-hydroxy-1-.. , naphthalenyl)azo]-, ~ 35 barium salt (2:1) , ~, .
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Generic Name C.A. Index/Chemical Name C.I. Pigment Violet 23 Diindolo~3,3',2'ml triphenodioxazine, 8,18-:.................. dichloro-5,15-diethyl-5,15-dihydro-C.I. Pigment Green ~ C.I. Pigment Green 7 C.I. Pigment Blue 61 Benzenesulfonic acid, [[4-[~4-phenylsmino)phenyl]-[4-(phenylimino)-2,5-cyclo-. hexadien-l-ylidene]methyl]-. 10 phenyl]amino]-: C.I. Pigment Red 48:1 2-Naphthalenecarboxylic j acid, 4-[(5-chloro-4-.~ methyl-2- ulfophenyl)azo]-.. -¦ 3-hydroxy-, barium salt (1:1) .~ 15 C.I. Pigment Red 52:1 2-Naphthalenecarboxylic acid, 4-[(4-chloro-5-. methyl-2-sulfophenyl)azo]-i 3-hydroxy-, calcium ~alt (1:1) : C.I. Pigment Violet 1 Ethansminium, N-[g-(2-.~ 24 carboxyphenyl)-6-(diethyl-.~ smino)-3H-xanthen-3-: ylidene]~N-ethyl-, molyb-datetungstatephosphate C.I. Pigment White 6 Titanium oxide (TiO2) :/1 25 ; 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'-dlchloro[l,l'-blphenyl]-4,4'-dlyl)bls(szo)]bis[3-.~ oxo-N-phenyl-C.I. Plgment Blue 56 Benzenesulfonic scld, 2-methyl-4-[[4-~[4-[(3-methylphenyl)smino]phenyl]-~ [4-[(3-methylphenyl)-''! 35 imlno]-2,5-cyclohexa-: dien-l-ylidene]methyl]-phenyl]amino]-. .~

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Generlc Name C.A. Index/Chemical Name C.I. Pigment Orange 5 2-Naphthalenol, 1-[(2,4-dinitrophenyl)a20]-C.I. Pigment Black 7 Carbon black C.I. Pigment Yellow 14 Butanamide, 2,2'-[(3,3'-dichloro[l,l'-biphenyl]-4,4'-diyl)bis(azo)]bis-[N-(2-methylphenyl)-3-oxo-10 C.I. Pigment Red 48 2 2-Naphthalenecarboxylic acid, 4-[(5-chloro-4-methyl-2-sulfophenyl)-azo~-3-hydroxy-, calcium salt (1:1) C.I. Pigment Blue 15:3 Copper, [29H, 31H--, phthalocyaninato (~-)-N29, N30, N31 N 2]_, (SP-4-1)-,:
C.I. Pigment Red 53:1 Benzenesulfonic acid, 5-chloro-2-[(2-hydroxy-1-naphthalenyl)azo]-4-methyl, ".`f barium salt I 20 C.I. Pigment Yellow 42 Iron oxide (Fe203)-: $ hydrate ;~ C.I. Pigment Brown 6 Iron oxlde (Fe203) ~3~ C.I. Pigment Red 101 Iron oxide (Fe203) 25 C.I. Pigment Black 11 Iron oxide (FeO-Fe203) ;~ The inherent viscosities (I.V.) of the particular ;? polyester materials useful herein ran8e from about ~, 30 0.1 to about 1.0 determined Rccording to ASTM
D2857-70 procedure, in a Wagner Viscometer of Lab G1B88~ Inc. of Vineland, New Jersey, having 8 1/2 mL.
capillary bulb, using a polymer concentration about ~ 0.25% by welght in 60/40 by welght o~
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~ 35 phenol/tetrachloroethane. The procedure is carried ;~ out by heating the polymer/solvent system at 120C
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132~313 ,, , :: -- 19 --measuring the time of flow at 25C. The I.V. is calculated from the equation t ( n) 25C. = ln ts 0.50% o C
where:
(n) = inherent viscosity at 25C et a polymer concentration of 0.25 g/100 mL of qolvent;
ln = natural loRarithm;
ts = sample flow tlme;
to = solvent-blank flow tlme; ~nd C = concentratlon of polymer ln grams per 100 mL of solvent = 0.25.
The unlts of the ~nherent vlscoslty throughout thls appllcatlon are ln declllters/gram. It 19 noted that hi8her concentrations of polymer, e.8., 0-50 8 :~!
of polymer/lO0 mL solvent may be employed for more precise I.V. determinatlons.
In general, the water disperslble polye~ter - materlals useful ln the present inventlon and blends thereof are excellent fllm formers for water based prlntlng lnks. The polymers form stable dlsperslons 25 ln water and produce tough, flexible films on drying. Films wlll form at temperaturec down to ~ust above the fteezlng point of water. The polymers in dlsperslon form may be plastlclzed lf nece~sery, for example, with certain water lmmisclble phthalate 30 esters to hi8h degrees of flexiblllty. Prlntlng lnks prepared from the present concentrates are readily further water reduclble (dllutlon) and the finlshed or pre~s-resdy lnks typically comprlse ln S by welght, from about 55% to about 90~ water, preferably from about 65% to sbout 75%, from about 4~ to about J 30% water dlssipatable polymer, preferably from about ,, `
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10% to about 25~, and from about 1~ to about 20%
pigment, preferably from about 8% to about 15~.
` Various types of modifiers may be used such as up to . about 10.0% polyvinyl alcohol or the like. The inks dry rapidly upon printing, wet surfaces exceptionally - well and have excellent adhesion to many plastic films and metal foil as well as to paper, glass, polyethylene and many other substrates. Both the 100% solids, water dissipatable polymers and the corresponding aqueous dispersions thereof may be pigmented by conventional techniques. The use of deionized water in the present invention is preferred in order to prevent premature ion , exchange.
The aforedescribed polyester material is prepared :
15 according to the polyester preparation technology described in U.S. Patents: 3,734,874; 3,779,993; and 4,233,196, 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 ;~ 20 acid reactants such as the dimethyl esters thereof as employed in the preparations set out in these patents.
.~I Among the preferred sulfo-monomers are those wherein the sulfonate group is attached to an aromatic nucleus such 3 as benzene, naphthalene, diphenyl, or the like, or 25 wherein the nucleus is cycloaliphatic such as in ~ 1,4-cyclohexanedicarboxylic acid.
i~ Dispersal of the present polyester material and concentrate materials in water may be done, for example, at preheated water temperature of about a 180 to 30 about 200~F and the polymer added as pellets to the ,~
,:~ vortex under high shear stirring. A Cowles Dissolver, Waring ~trademark) blender, or similar equipment may be used. Once water is heated to temperature, addi-tional heat input is not required. Depending .'.
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upon the volume prepared, dlspersal of the pellets by stirring should be complete within 15 to 30 minutes.
Continued agitation with cooling may be deslrable to prevent thickening at the surface due to water evaporation. Viscosities of the dispersions remain low up to nonvolatile levels of about 25S-30~, but generally increa~e sharply above these levels.
Viscosities of the dispersions will be influenced by the degree of polymer dispersion (fineness) obtained which is affected by the dispersing temperature, shear, and time.
; The present concentrates and inks may also be prepared by milling, e.g., two-roll milling the polymers themselve-~ into a blend, or by milling the finely comminuted, polymer insoluble pigment or other colorsnt into the solid polyester and polyurethane mater~al, and for the aqueous inks and semi-aqueous ; concentrates, thereafter dispersing the milled materlal in water in a manner generally similar to the procedure described in U.S. Patent 4,148,779 for -~olubilizing organic disperse textile dyes in - polyester for subsequent dispersal in water.
Dispersions can also be made by adding the pigment or ; other colorant at high speed agitation to the ~` 25 polymers previously dispersed in water and then ;~; grinding in a ball mill or sand mill to further .~. .
reduce pigment slze ln accordance wlth the process of ~ the pre-~ent inventlon.
:~ The viscosltles of the lnks may, of course, ran8e wldely, e.g., from about 15 to about 60 seconds as ~i measured ln a #2 ~ahn cup accordlng to ASTM
i D-4212-82. The higher viscosities, e.g. from about 22 to about 60 seconds snd lower water levels, e.g.
~ç from about 20 to about 55 wt. % represent '; 35 seml-aqueous concentrated forms of the present lnks.
~ In thls regard, in order to reduce the viscoslties of `,,'' -: ~
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- these inks when necessary for certain printlng apparatus and processes, varying amounts of water are added. In this water addition, the ink viscosity may be reduced up to about 60~ of its origlnal concentrate value, and the press-ready ink viscosity preferably ranges between about 15 and 30 seconds in a number 2 Zahn cup.
The weight percentages of the polyester (P Est.), polyurethane (PU), solvent, and pigment will of course vary depending on whether it is desired to produce an essentially dry concentrate, an aqueous ' concentrate, or a finished, press-ready, aqueous ink. Typical ranges for broad and preferred of these percentages (dry wt. ~) are given in the following ' 15 table.

;~, prv Concentrate ~¦ Broad Preferred ; P E~t. 15-60 20-40 ~i !
'~, 20 Pigment 40-85 50-75 ,i PU 0.5 20 1 8 531 Aqueous Concentrate Broad Preferred P Est. 10-40 15-35 Pigment 30-75 35-65 ; PU 0.2-15 0.5-12 Solvent1.0-40 5-25 Press-Rea~y Ink Broad Preferred ~, P Est. 3-30 10-18 Pigment0.1-40 20-35 PU 0.1-10 0.5-5 Solvent 40-75 45-60 ,..~) .:
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It is noted that the solvent in the above ranges is, of course, mostly w~ter. However, up to sbout 30 wt. ~ of the water may be replaced with ml~cible cosolvents such a~ diethylene glycol monomethyl ether, propylene glycol, ethylene glycol, diethylene glycol, n-propyl alcohol, iYopropyl alcohol, ethyl alcohol, glycerin, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, and diethylene glycol monobutyl ether, or mixtures thereof.
The following exsmples will further illu~trate practice of the invention.

Exam~le A - PolYester PreParation A mixture of 79.5 g (0.41 mole) of dimethyl isophthalate, 26.6 g (0.09 mole) of dimethyl-5-sodlosulfoisophthalate, 54.1 g (0.51 mole) of diethylene glycol, 37.4 g (0.26 mole) of i 20 1,4-cyclohexanedlmethanol, 1.4 mL of a l.OS (based on i; Tl) catalyst solutlon of tltanlum tetrai~opropoxlde, i and 0.74 8 (0.009 mole) of sodium acetate buffer is stlrred and heated for two hours at 200-220C. The temperature ls then ralsed to 275C and a vacuum of 0.3 mm 18 applled. He~tlng and stlrrlng is continued for 1 hour under these condltlons. After cooling, the polymer obtalned has an I.V. of 0.36 and is tough and rubbery and 15 dissipatable ln hot water to the , extent of about 25 wt. % to glve a clear, ~llghtly v 30 vl~couq solutlon. The composltion o$ the acld ~' moieties of this polye~ter material is analyzed to be 82 mole % lsophthallc acld resldue and 18 mole %
5-Yodiosulfol~ophthallc acld re~ldue, and of the 1 81ycol moleties ls analyzed to be 54 mole 35 dlethylene glycol and 46 mole ~
1,4-cyclohexanedlmethanol. Thls materlal ls , deqlgnated herelnafter a~ "Polymer-A".
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~ - 24 -- Example B
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) q. moles Dimethyl Isophthalate (IPA) 0.415 Dimethyl-5-Sodiosulfoisophthalate (SIP) 0.085 1,4-Cyclohexanedimethanol (CHDM) 0.520 Carbowax (trademark) 1000 0.0237 ; polyethylene glycol (CW 1000) ; Sodium Acetate 0.0085 Irganox (trademark) 1010 antioxidant 0.0085 The Carbowax 1000 polyethylene glycol has the '~ structure H~OCH2-CH2t~0H wherein n is about 22. The , polymer analyzed by NMR contains (in reacted form) ;:i about 83 mole % IPA, about 17 mole % SIP, about `1 20 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 ' 25 Dimethyl-5-Sodiosulfoisophthalate 0.072 1,4-Cyclohexanedimethanol 0.442 ~; Carbowax 400 polyethylene glycol (n=10) 0.058 ~:~ Sodium Acetate 0.0072 .;~ .
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.

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: - 25 -~ q. moles Dimethyl Isophthalate 0.41 Dimethyl-5-Sodiosulfoisophthalate 0.09 1,4-Cyclohexanedimethanol 0.55 : 5 Carbowax 4000 polyethylene glycol (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, 10 about 99.9 mole % CHDM and about 0.1 mole % CW 4000, and has an I.V. of about 0.16.
':
(d) g. moles Dimethyl Isophthalate 0.205 15 Dimethyl-5-Sodiosulfoisophthalate 0.045 Ethylene Glycol (EG) 0.9638 Carbowax 2000 polyethylene glycol (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.
r,',In such polymers containing the Carbowax .~25 polyethylene glycol, the n value is preferably between about 6 and 150.
Mixing or blending of the polyester with the polyurethane can be done at any stage prior to making ~of the finished coating formulation. Typical mixing ~30 techniques are (1) melt-phase or roll-milling of the polymers, (2) codispersion in water or water-solvent blends, (3) mixing of predispersed polyester and predispersed polyurethane by simple agitation, of :~(4) any suitable combination of those techniques.
; 35 The amounts of polyester and polyurethane in the ii ~ aqueous blends is dictated by desired end-use ,~;.

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~ - 26 -, properties. For certain water-based ink-Q, ~queous : ink concentrates, clear extenders, and over-print varnishes, the polyester concentration bssed on total blend weight is typically 5.0 - 40 wt. %, while the polyurethane is typically 0.1 - 15 wt. ~.
The increase in viscosity achieved through the use of the polyurethane depends on the rat1os of H20/polyester/polyurethane, and can range from no increase to an increase of many thousand centipoise ' 10 (gelled state). This flexibility is important for many reasons. For example, the thixotropic nature of ~, the polyester systems is mostly eliminated through blending with the polyurethane, which makes possible the formulatlon of flowable, very high viscosity pigment concentrates, which do not thin in the high shear, high temperature milling processes, thereby .~;
; improving milling efficiency (pigment development) and reducing mill wear. Also, the blend~ng allows j better correlation of the ~tatic vlscosity measurements used by pressmen for convenience (Zahn or Shell cups representing the actual viscosity ;, created by the higher shear conditions on the press) thereby giving better print quality control and reproducibility. Also, because inkq made with only ',~A'i 25 the polyester tend to be very thin, the increased viscoslty given by the blends more readily enables the inks to be used in applications where the hlgher , vi3coslties are required.
Moreover, the present blends increase the economy of the lnks since the polymer weight level cen be reduced, for some applicRtions, for example, by as much as about 75~ while maintainin8 or exceeding the i original ink quality. The following examples ~ demonstrate the invention.

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-''' : An aqueous master batch was made containing 14.0 dry wt. ~ of finely ground C.I. Pigment Red 57:1, 13.6 dry wt. % Polymer -A, and 7.2 wt. % normal propyl alcohol. The blending was done by mixing with low shear agitation, a finely ground pigment concentrate (28 wt. % aqueous mix) into a water/n-propanol dispersion of Polymer -A.
' A. The above master batch was then let down with a water dispersion of Polymer -A into a press-ready ink comprised of 7.0 dry wt. %
C.I. Pigment Red-57, 20.0 dry wt. %
Polymer -A, 5.0 wt. % normal propyl alcohol, and 68.0 wt. % water. This ink had a viscosity of 18.5 seconds on a No. 2 Zahn cup .

B. To the ink of A above was added with low shear mixing 1.5 wt. % of 25% active ~, polyurethane material. This ink had a ' viscosity of 30.5 seconds on a No. 2 Zahn cup. The 25% active polyurethane material '~ comprised about 24-26 wt. % polyurethane, ~,~i 25 about 18-19 wt. % diethylene glycol monobutyl ether, and about 56-57 wt. % water and is sold by Rohm and Haas Company under the i Trademark ACRYSOL RN-825. This material is y described in the Trade Sales Coatings ~ 30 brochure entitled "Polymers, Resins and 'i Monomer~, ACRYSOL~ RN-825 Rheology Nodifier For Coatings" c Rohm and Haas Company, 1985.
:~, j3 35 Both inks A and B were then drawn down on ,~ .,s Pen-o-Pac paper stock with a No. 6 RD rod. By . . ~ , . . .

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132631~
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comparison, the addition of ACRYSOL RM-825 boosted the -; viscosity to a more desirable printing level while maintaining gloss, shade, print quality, and the like.

.~ Two viscosity modifiers as described below were l added to a press-ready ink consisting of 22.4 dry wt. %
Polymer -A, 7.0 dry wt. % C.I. Pigment Red-57, 0.5 wt. %
; Tektamer (trademark) 38AD biocide (~ 25% active), 0.2 wt. % of Surfynol (trademark) 104E wetting agent (~
50~ active), and 6.2 wt. % normal propyl alcohol.
:.
A. A water solution of Kelzan S (trademark), a :
sodium salt of xanthan gum, was stirred into the press-ready ink at 0.06 dry wt. %
yielding a viscosity of 31.0 seconds on a No. 2 Zahn cup.
.'Z
''.''~, B. ACRYSOL RM-825 (~ 25% active) was stirred into the press-ready ink at 2.0 wt. %, yielding a viscosity of 32.0 seconds on a No. 2 Zahn cup.
''' Inks A and B were then drawn down in essentially the same manner as in Example 1. Results showed that ink A had yellowed in shade, although the gloss was ~i similar to the control. The ACRYSOL RM-825 containing ~ ink B performed essentially the same as observed for s ink B of Example 1.
j 30 l The experiment in Example 2 was repeated using ACRYSOL RM-825 versus partially hydrolyzed polyvinyl g alcohol [Vinol (trademark) 540] described in the sales brochure of Air Products and Chemicals, Inc., titled "VINOLTM POLYVINYL ALCOHOLS", No. 152-901.
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A. ACRYSOL RM-825 at 1.5 wt. ~ (@ 25% active) was incorporated into the press-ready ink to give a viscosity of 27.0 seconds on a No. 2 Zahn cup.
~ 5 - B. Polyvinyl alcohol ~PVA) at 1.5 wt. % (~ 25%
active) was incorporated into the press-ready ink to give a viscosity of 53.5 seconds on a No. 2 Zahn cup. The PVA is described in "MATERIAL SAFETY DATA SHEET" entitled ` "POLYVINYL ALCOHOL, Standard Grades" of Air ~; Products and Chemicals, Inc., c Air ; ,.
. Products and Chemicals, Inc., 1979, - Revision 1, January 1, 1980.

Inks A and B were then drawn down in essentially , , the same manner as in Example 1. Results showed the PVA ink B to exhibit a severe loss of gloss with some shade change, while the ACRYSOL RM-825 ink A results were essentially the same as observed for ink B of Example 1.
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The same experiment as in Example 2 was repeated using ACRYSOL G-110 of Rohm and Haas Company, versus .~ ACRYSOL RM-825 in a press-ready ink formulation.
., " ~ , ~.~ A. The ACRYSOL G-110 ink had a viscosity of 28.0 ''`'J, seconds on a No. 2 Zahn cup. This material is described in the Trade Sales Coatings brochure of Rohm and Haas Co. entitled "ACRYSOL~ G-110 THICKENER FOR LATEX
PAINTS", c Rohm and Haas Co., 1982.
,'' B. The ACRYSOL RM-825 ink had a viscosity of ' 27.0 seconds on a No. 2 Zahn cup.
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, -~ - 30 -Inks A and B were then drawn down in essentially .~ the same manner as in Examples 1-3. The ACRYSOL G-110 ink was hazy with low gloss and transparency while the ; ACRYSOL RM-825 ink was essentially the same as observed for B of Example 1.
:i - The experiment in Example ~' was repeated using ACRYSOL RM-825 versus Hydroxyethyl Cellulose, a Nonionic water soluble ether of cellulose from Union Carbide Corp. described in Product Specification, September 4, 1986, 1-44c.QP100MH-lh, 1904900.
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A. A water solution of Hydroxyethyl Cellulose at ,~ 15 0.5 ~t. % (dry) was incorpoxated into a press ready ink and gave a 62.0 second viscosity on a No. 2 Zahn cup.
'' B. ACRYSOL RM-825 at 1.5 wt. % (@ 25% active) i 20 was incorporated into the same press-ready ink and gave a 27.0 second viscosity on a No. 2 Zahn cup.
,,, Inks A and B were then drawn down in essentially ~J 25 the same manner as in Example 1, showing the Hydroxyethyl Cellulose containing ink to have changed markedly in shade. The ACRYSOL RM-825 containing ink was essentially the same as observed for B of Example l.

The experiment in Example 2 was repeated using ~i ACRYSOL RM-825 versus EMA (trademark), an Ethylene ~ Maleic Anhydride copolymer described in Technical ;~ 35 Bulletin No. lC/FP-7 entitled "EMA~", of Monsanto `1 Company.

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A. ACRYSOL RM-825 at 1.5 wt. % 5@ 25% active) -~ was incorporated into a press-ready ink and ~: yielded a viscosity of 27.0 seconds on a ;~ No. 2 Zahn cup.
: 5 ~
- B. EMA at 0.25 dry wt. % was incorporated into the same press-ready ink and yielded a viscosity of 21.0 seconds on a No. 2 Zahn ~, cup.
''::' 10 :, Inks A and B were then drawn down in essentially : the same manner as in Example 1. The EMA ink showed a great loss of gloss, and very poor print quality. The ;~ ACRYSOL RM-825 ink results were essentially the same as observed for B of Example 1.
.:~
~i EXAMPLE 7 "5 The experiment in Example 2 was repeated using ',~ ACRYSOL RM-825 versus Stymer S (trademark), a sodium salt of a polystyrene/maleia anhydride copolymer marketed by Monsanto Company and described in the ;~, accompanying brochure titled "Stymer S~ Resin For Warp . A, Sizing , Pub. No. 5013C.
,~
5~ 25 A. ACRYSOL RM-825 at 1.5 wt. % (@ 25% active) ~ was incorporated into the press-ready ink and .,l yielded 27.0 seconds on a No. 2 Zahn cup.
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B. Stymer S at 1.5 wt. % was incorporated into ,3 30 the same press-ready ink and yielded over '3 60.0 seconds on a No. 2 Zahn cup.
., '''7 Inks A and B were then drawn down in essentially ~ the same manner as in Example 1 showing the Stymer ink `~ 35 to be hazy with low gloss and transparency, The ,~, :
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~- - 32 -'-' ACRYSOL RM-825 ink was essentially the same as observed - for B of Example 1.

In this example two ink formulations, (1) which was a control, and (2) representing the present invention, each containing fairly high pigment loadings were processed on the same equipment under essentially the same conditions. Formulation (1), the control, , 10 contained the following ingredients in % by weight:
33.3% Carbon Beads (Raven 1020) 43.3~ AQ 55 (33% Polymer in Water) 2.3% NPA (n-Propyl Alcohol) 2.8% Surfynol 104E (Dispersant-Surfactant-Antifoa~) 0.8% Merpol (trademark) LFH (Low Cloud Pt.Polyether Surfactant) - 17.5% H2O (Additional) Formulation (2) of the present invention is the same as (1) except for -0.91% Acrysol RM-825 (25% Active) and 16.59% H2O (Additional) l The 25% active polyurethane material comprises about 'j 24-26 wt. % polyurethane, about 18-19 wt. % diethylene ~i~ 25 glycol monobutyl ether, and about 56-57 wt. % water and is sold by Rohm and Haas Company under the Trademark ACRYSOL RM-825. This material is described in the Trade i Sales Coatings brochure entitled "Polymers, Resins and .~ Monomers, ACRYSOL~ RM-825 Rheology Modifier For 30 Coatings" Rohm and Haas Company, 1985.
s The premixing conditions for each of these 3 formulations was 10 minutes at 4,000 rpm (gauge) and . 3 minutes at 6,000 rpm (gauge) on a Hockmeyer mixer.
The subsequent milling was done on a Dynomill 35 Horizontal Mill (85% filled with 0.5-0.8 mm SAZ beads ~d r (zirconium silicate) at a feed rate of about A
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.:, 0.25 lb/minute. The exact procedures were a~
, follows:
Control-Formulation (1) The liquid ingredients, except the additional 5 water, were placed in a mixing bucket for a Hockmeyer ;~ Discperser and the carbon black beads were added over a 10-minute period at 1,000 rpm. The additional water was not added in order to optimize viscosity.
After mixing, the batch was disper~ed in the Hockmeyer Discper~er at 6,000 rpm for 3 minutes and ,~ at 4,000 rpm (machine gauge reading) for 10 minutes.
The resulting temperature was 27C. The additional ~ water was then added. This premix was then j transferred to the mill feed funnel of the Dynomill , 15 mill and milled at a rate of about 0.25 lb/mlnute.
'~ After about 5 minutes, the gear pump ~ammed with , undi~persed pigment beads. A portion of the premix and milled sample were saved, but about three ~ quarters of the batch could not be milled because of s, 20 insufficient premixing.
~ Fomulation (2) ;, Premixed as with the control except all of the " additional water was sdded inltially. The premix maximum temperature was about 60C, reflecting the 25 increase in heat generated by the higher viscosity.
The premix was milled at a rate of 0.277 lb/minute with a feed outlet temperature of 50C. No settling ~, of undispersed beads or pump plugging, or other ; problem~ were encountered because the beads were ~, 30 broken adequately in the premix.
The following properties of the two blends were determined:

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, ~h ~ of PiRment Retained on 325 Mesh Screen (~ 42 Microns~
Formulation (1~ Formulation (2) ',' On Wt. TotPl On Wt._PiRment On Wt. TotAl On Wt. Pi~ment , 31.1~ 93.4~ 7.6% 22.8~
., S
Ph~sical AP~earence Formulation (1) Formulation (2~
' Very thin, many unbroken Very thick, smooth, no beads which settled. settling.
,'10 S Solids in Milled Material Formulation (1) , Formulation (2 , 44.1~ (From Beads Settling 49.3~ (Predicted "~ and Being Held Up Theoretical ,-~ 15 in Pump) Solidi~i = 49.8%) ,,, : ;' j Milled Results '~ The Formulstion (1) besds were not broken ,,j 20 sufficiently to feed properly. After only a few " moments running time, the 8eAr pump ~ammed, snd the ', run was discontinued. No problems were encountered '~ , with the Formulation (2) ssmple.
j ,.,~
-1, 25 Milled Psrtlcle Size in Mlcrons Determined on Leed~ and Northrup Instrument ;, Formulation (1~ Formulstlon (2) ess Thsn Les~ Thsn ~, 18~50% 84~ 18~ 50~ 84 'i, 30 0.28~ 0.52~ 0.88~ 0.28~ 0.43~ 0.78~
. ~ , Surfsce Area of Mllled Partlcles Formul~tlon (1) _ For,mulstion (2) ','1 14.627 m2/g 15.255 m2/g '"i ~, t~
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13263:L3 . - 35 -`~
:~Ink Strenqth -Formulation (1) was much weaker (- 25~ less) than Formulation (2) because of loss of pigment (bead :~settling) and because of lower surface area.

.:Brookfield Model RVT (trademark) Viscositv of Premix .~ Formulation (1)Formulation (2) SPindle 3 SPindle 7 20 rpm 50 rpm 20 rpm 50 rpm 75 cps 54 cps 92,800 cps 63,000 cps , . .
Brookfield Model RVT ViscositY of Milled Material . Formulation (1)Formulation (2 SPindle 3 SPindle 7 , 15 20 rpm 50 rpm 100 rpm 20 rpm 50 rpm 100 rpm . 1~ 635 874 564 60,000 42,000 29,200 ',: cps cps cps cps cps cps t,!
The millbase was diluted as follows:
. 15 ~ millbase ; 69.3~ of polymer extender containing 32.5 polymer, 5~ n-propyl alcohol in H2O.
15.7% H2O
;' 25 Both inks were then drawn down on Pen-o-Pac paper stock with a No. 6 RD rod. By comparison, Formulation ~2) showed increased viscosity which gave a :~ more desirable printing level while maintaining gloss, shade, print quality, and the like when compared to ;i Formulation (1). The ink strength of the control.
~Formula 1) was - 25% less because of pigment loss :l caused by settling in the premix.
' In acaordance with the present invention, inks ~, 35 prepared from the present blends, with or without various property modifiers such as polyvinyl alcohol, i~, e~ ., ,'~ I
.

~`~ 1326313 .. .
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Pluronics (trademark) copolymers, or the like, have been found to be unexpectedly superior as stated above over prior aqueous inks, and also with respect to one or more of such properties as flow-out or printability, 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, wide viscosity range inks, adhesion to a variety of substrates, hardness, gloss, drying rate on substrates, 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, dry-rate, and no offset on the printing press (coating, e.g., on tension rollers).
The invention has been described in detail with , 25 particular reference to preferred embodiments thereof, `~. but it will be understood that variations and modifications can be effected within the spirit and scope of the invention.
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Claims (38)

1. A composition comprising a substantially homogenous blend of water dispersible polyester material and water dispersible polyurethane, the weight ratio of the polyester to the polyurethane being from about 0.5 to about 900, wherein the polyurethane has at least 3 hydrophobic branching groups and a molecular weight of at least 10,000, and wherein the polyester material comprises at least one linear, water-dissipatable 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/tetrachloro-ethane at 25°C and at a concentration of 0.25 gram of polymer in 100 mL of the solvent, the polymer comprising the condensation reaction products of (a), (b), (c) and (d) from the following reactants or ester forming or esteramide forming derivatives thereof;

(a) at least one difunctional dicarboxylic acid which is not a sulfomonomer;

(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 difunctional sulfomonomer containing at least one metallic sulfonate group attached to an aromatic hydrocarbon nucleus or cycloaliphatic nucleus wherein the functional groups are hydroxy, carboxyl or amino;

(c) at least one difunctional reactant which is not a sulfomonomer selected from a glycol or a mixture of a glycol and diamine having two -NRH groups, the glycol containing two -CH2-OH groups of which (1) at least 15 mole percent based on 100 mole percent of hydroxy or hydroxy and amino equivalents, is a poly(ethylene glycol) having the structural formula H?OCH2-CH2?OH, 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 100 mole percent of hydroxy or hydroxy and amino equivalents, is a poly(ethylene glycol) having the structural formula H?OCH2-CH2?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)2-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.

2. A dispersion of the composition of Claim 1 in a solvent system comprising water or water admixed with water miscible cosolvent which comprises up to about 30.0 wt. % of said solvent system, said solvent system comprising from about 1.0 to about 95.0 wt. % of the total dispersion weight.

3. The dispersion of Claim 2 wherein the solvent system comprises from about 30 to about 90 wt. %
of the total dispersion weight.

4. The dispersion of Claim 2 wherein the weight % of the polyester is from about 5.0 to about 33.0, the % of the polyurethane is from about 0.01 to about 10.0, the weight % of the solvent system is from about 30.0 to about 90.0, and said dispersion further comprises a colorant and the weight % of colorant is from 0 to about 25Ø

5. The dispersion of Claim 2 wherein the cosolvent is selected from diethylene glycol monomethyl ether, propylene glycol, ethylene glycol, diethylene glycol, n propyl alcohol, isopropyl alcohol, ethyl alcohol, glycerin, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, and diethylene glycol monobutyl ether or mixtures thereof.

6. The composition of Claim 1 containing from about 1.0 to about 80.0 wt. % colorant.

7. The composition of Claim 1 wherein from none to about 60 wt. % of pigment material based on total polymer weight is present admixed into the composition.

8. The dispersion of Claim 2 wherein from none to about 60 wt. % of pigment material based on total polymer weight is present admixed into the composition.

9. The dispersion of Claim 3 wherein from none to about 60 wt. % of pigment material based on total polymer weight is present admixed into the composition.

10. The composition of Claim 7 wherein the n value of reactant (c) (2) is between 2 and about 200.

11. The composition of Claim 7 wherein the polyester materials have an inherent viscosity of from about 0.28 to about 0.38, an acid moiety of from about 75 to about 84 mole % isophthalic acid and conversely from about 25 to about 16 mole %
5-sodiosulfoisophthalic 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 the pigment material is present in a weight ratio with respect to total polyester materials of from about 1/10 to about 2/1.

12. The dispersion of Claim 8 wherein the polyester materials have an inherent viscosity of from about 0.28 to about 0.38, an acid moiety of from about 75 to about 84 mole % isophthalic acid and conversely from about 25 to about 16 mole %
5-sodiosulfoisophthalic 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 the pigment material is present in a weight ratio with respect to total polyester materials of from about 1/10 to about 2/1.

13. The composition of Claim 7 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-cyclohexanedimethanol.

14. The dispersion of Claim 8 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.

15. The composition of Claim 7 wherein the polyurethane is selected from a trimethylol propane/ethylene oxide adduct capped with octyldecyl isocyanate, a dipentaerythritol/
ethylene oxide adduct capped with octyldecyl isocyanate, a trimethylol propane/ethylene oxide adduct reacted with a tolylene diisocyanate polyethylene glycol condensate and capped with octadecanol, a trimethylol propane/ethylene oxide/C36 dimer acid diisocyanate/polyethylene glycol condensate capped with octadecyl isocyanate, a polyethylene glycol/4,4'methylene-bis(isocyanatocyclohexane)/triisocyanate adduct of trimethylol propane and tolylene dissocyanate capped with hexadecanol, a polyethylene glycol/methylenedi-p-phenylene diiso-cyanate/triisocyanate adduct of trimethylol propane and tolylene diisocyanate condensate capped with eicosanol, a polyethylene glycol/
tolylene diisocyanate/polymethylene polyphenyl-isocyanate condensate capped with octadecanol, a polyethylene glycol/trimethylol propane/tolylene diisocyanate condensate capped with octadecanol, a polyethylene glycol/tolylene diisocyanate/dipent-acrythritol condensate capped with octadecanol, and a polyethylene glycol/trimethylol propane/tolylene diisocyanate condensate capped with perfluorododecanol.

16. The dispersion of Claim 8 wherein the polyurethane is selected from a trimethylol propane/ethylene oxide adduct capped with octyldecyl isocyanate, a dipentaerythritol/ethylene oxide adduct capped with octyldecyl isocyanate, a trimethylol propane/ethylene oxide adduct reacted with a tolylene diisocyanate polyethylene glycol condensate and capped with octadecanol, a trimethylol propane/ethylene oxide/C36 dimer acid diisocyanate/polyethylene glycol condensate capped with octadecyl isocyanate, a polyethylene glycol/4,4'methylenebis(isocyanatocyclo-hexane)/triisocyanate adduct of trimethylol propane and tolylene dissocyanate capped with hexadecanol, a polyethylene glycol/methylenedi-p-phenylene diisocyanate/triisocyanate adduct of trimethylol propane and tolylene diisocyanate condensate capped with eicosanol, a polyethylene glycol/tolylene diisocyanate/polymethylene polyphenylisocyanate condensate capped with octadecanol, a polyethylene glycol/trimethylol propane/tolylene diisocyanate condensate capped with octadecanol, a polyethylene glycol/tolylene diisocyanate/dipentacrythritol condensate capped with octadecanol, and a polyethylene glycol/trimethylol propane/tolylene diisocyanate condensate capped with perfluorododecanol.

17. The dispersion of Claim 4 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; and C.I.
Pigment Red 53:1; C.I. Pigment Yellow 42; C.I.

Pigment Brown 6; C.I. Pigment Red 101; and C.I.
Pigment Black 11.

18. The dispersion of Claim 4 wherein the polyester material comprises from about 10 to about 20 weight %, the pigment material comprises from about 3.0 to about 15.0 weight %, the water comprises from about 20 to about 70 weight %, and the polyurethane comprises from about 0.5 to about 5.0 weight %.

19. The dispersion of Claim 4 wherein the polyester comprises from about 15 to about 18 weight %, the colorant material comprises from about 5.0 to about 10.0 weight %, the water comprises from about 70 to about 80 weight %, and the polyurethane comprises from about 1.0 to about 5.0 weight %.

20. 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(vinylidiene chloride), polyamide, polyolefin, or polystyrene.

21. The dispersion of Claim 4 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, polyolefin, or polystyrene.

22. A process comprising blending a mixture comprising:

(A) a water dispersible polyester material which normally exhibits thixotrophic behavior, (B) a colorant, which is essentially insoluble in the polyester material, in the form of aggregates, and (C) an effective amount of a water dispersible polyurethane material, under sufficient conditions such that the size of said aggregates is reduced, wherein the polyurethane has at least 3 hydrophobic branching groups and a molecular weight of at least 10,000, and wherein the polyester material comprises at least one linear, water-dissipatable 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 concentration of 0.25 gram of polymer in 100 mL
of the solvent, the polymer comprising the condensation reaction products of (a), (b), (c) and (d) from the following reactants or ester forming or esteramide forming derivatives thereof;
(a) at least one difunctional dicarboxylic acid which is not a sulfomonomer;

(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 difunctional sulfomonomer containing at least one metallic sulfonate group attached to an aromatic hydrocarbon nucleus or cycloaliphatic nucleus wherein the functional groups are hydroxy, carboxyl or amino;

(c) at least one difunctional reactant which is not a sulfomonomer selected from a glycol or a mixture of a glycol and diamine having two -NRH groups, the glycol containing two -CH2-OH groups of which (1) at least 15 mole percent based on 100 mole percent of hydroxy or hydroxy and amino equivalents, is a poly(ethylene glycol) having the structural formula H?OCH2-CH2?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 100 mole percent of hydroxy or hydroxy and amino equivalents, is a polyethylene glycol) having the structural formula H?OCH2 - CH2?nOH, 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)2-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.

23. The process of Claim 22 wherein said mixture comprises (A) from about 3 to about 60 weight % of said water dispersible polyester material, (B) from about 0.1 to about 85 weight % of said colorant, (C) from about 0.1 to about 20 weight % of said water dispersible polyurethane material, and (D) from 0 to about 75 weight % of a solvent comprising water.

24. The process of Claim 23 wherein the solvent comprises from about 5 to about 60 weight % of said mixture.

25. The process of Claim 23 wherein the weight % of component (A) is from about 5% to about 40%, the weight % of component (B) is from about 10% to about 75%, the weight % of component (C) is from about 0.2% to about 15%, and the weight percent of component (D) is from about 1% to about 40%.

26. The process of Claim 22 carried out at a temperature of from about 0°C to about 100°C.

27. The process of Claim 22 carried out under forces that are the same or greater than those present in a high speed discperser operated at a peripheral speed of about 1,000 feet/minute.

28. The process of Claim 27 wherein said peripheral speed is between about 4,000 and about 6,000 feet/minute, and said blending occurs for about 1 minute to about 1 hour.

29. The process of Claim 22 wherein the average size of said aggregates before blending is greater than about 100 microns in diameter and the average size of said aggregates after blending is less than about 50 microns in diameter.

30. The process of Claim 29 wherein the average size of said aggregate after blending is less than about 1 micron in diameter.

31. The process of Claim 22 wherein the solvent comprises water plus a cosolvent which is selected from diethylene glycol monomethyl ether, propylene, glycol, ethylene glycol, diethylene glycol, n-propyl alcohol, isopropyl alcohol, ethyl alcohol, glycerin, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, and diethylene glycol monobutyl ether or mixtures thereof.

32. The process of Claim 23 wherein the solvent comprises water plus a cosolvent which is selected from diethylene glycol monomethyl ether, propylene glycol, ethylene glycol, diethylene glycol, n-propyl alcohol, isopropyl alcohol, ethyl alcohol, glycerin, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, and diethylene glycol monobutyl ether or mixtures thereof.

33. The process of Claim 22 wherein the n value of reactant (c) (2) is between 2 and about 200.

34. The process of Claim 22 wherein the polyester material has an inherent viscosity of from about 0.28 to about 0.38, an acid moiety of from about 75 to about 84 mole % isophthalic acid and conversely from about 25 to about 16 mole %
5-sodiosulfoisophthalic 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.

35. The process of Claim 22 wherein said water dispersible polymeric material comprise an acid moiety and a glycol moiety 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.

36. The process of Claim 22 wherein the polyurethane is selected from a trimethylol propane/ethylene oxide adduct capped with octyldecyl isocyanate, a dipentaerythritol/ethylene oxide adduct capped with octyldecyl isocyanate, a trimethylol propane/ethylene oxide adduct reacted with a tolylene diisocyanate polyethylene glycol condensate and capped with octadecanol, a trimethylol propane/ethylene oxide/C36 dimer acid diisocyanate/polyethylene glycol condensate capped with octadecyl isocyanate, a polyethylene glycol/4,4'methylenebis(isocyanatocyclohexane)/
triisocyanate adduct of trimethylol propane and tolylene diisocyanate capped with hexadecanol, a polyethylene glycol/methylenedi-p-phenylene diisocyanate/triisocyanate adduct of trimethylol propane and tolylene diisocyanate condensate capped with eicosanol, a polyethylene glycol/tolylene diisocyanate/polymethylene polyphenylisocyanate condensate capped with octadecanol, a polyethylene glycol/trimethylol propane/tolylene diisocyanate condensate capped with octadecanol, a polyethylene glycol/tolylene diisocyanate/dipentacrythritol condensate capped with octadecanol, and a polyethylene glycol/trimethylol propane/tolylene diisocyanate condensate capped with perfluorododecanol.

37. The process of Claim 22 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; and C.I.
Pigment Red 53:1; C.I. Pigment Yellow 42; C.I.
Pigment Brown 6; C.I. Pigment Red 101; and C.I.
Pigment Black 11.

38. A process comprising blending a mixture comprising:

(A) from about 10 to about 40 weight percent of a water dispersible polyester material comprising at least one linear, water-dissipatable 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 concentration of 0.25 gram of polymer in 100 mL of the solvent, the polymer comprising the condensation reaction products of (a), (b), (c) and (d) from the following reactants or ester forming or esteramide forming derivatives thereof:

(a) at least one difunctional dicarboxylic acid which is not a sulfomonomer;

(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 difunctional sulfomonomer containing at least one metallic sulfonate group attached to an aromatic hydrocarbon nucleus or cycloaliphatic nucleus wherein the functional groups are hydroxy, carboxyl or amino;

(c) at least one difunctional reactant which is not a sulfomonomer selected from a glycol or a mixture of a glycol and diamine having two -NRH groups, the glycol containing two -CH2-OH groups of which (1) at least 15 mole percent based on 100 mole percent of hydroxy or hydroxy and amino equivalents, is a poly(ethylene glycol) having the structural formula H?OCH2 - CH2?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 100 mole percent of hydroxy or hydroxy and amino equivalents, is a poly(ethylene glycol) having the structural formula H?OCH2 - CH2?nOH, 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)2-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, (B) from about 30 to about 75 weight percent of a colorant wherein said 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; and C.I. Pigment Red 53:1; C.I.
Pigment Yellow 42; C.I. Pigment Brown 6; C.I.
Pigment Red 101; and C.I. Pigment Black 11, said colorant being in the form of aggregates, (C) from about 0.2 to about 15 weight percent of a water dispersible polyurethane material wherein said polyurethane material is one or a mixture of the following materials:

a trimethylol propane/ethylene oxide adduct capped with octyldecyl isocyanate, a dipentaerythritol/ ethylene oxide adduct capped with octyldecyl isocyanate, a trimethylol propane/ethylene oxide adduct reacted with a tolylene diisocyanate poly-ethylene glycol condensate and capped with octadecanol, a trimethylol propane/ ethylene oxide/C36 dimer acid diisocyanate/polyethylene glycol condensate capped with octadecyl isocyanate, a polyethylene glycol/4,4'-methylenebis(isocyanatocyclohexane)/tri-isocyanate adduct of trimethylol propane and tolylene diisocyanate capped with hexadecanol, a polyethylene glycol/methylenedi-p-phenylene diisocyanate/triisocyanate adduct of trimethylol propane and tolylene diisocyanate condensate capped with eicosanol, a polyethylene glycol/tolylene diisocyanate/
polymethylene polyphenylisocyanate condensate capped with octadecanol, a polyethylene glycol/trimethylol propane/ tolylene diisocyanate condensate capped with octadecanol, a polyethylene glycol/ tolylene diisocyanate/dipentacrythritol condensate capped with octadecanol, and a polyethylene glycol/trimethylol propane/ tolylene diisocyanate condensate capped with perfluorododecanol, and (D) from about 1 to about 40 weight percent of a solvent comprising water plus a cosolvent which is one or a mixture of the following cosolvents:

diethylene glycol monomethyl ether, propylene glycol, ethylene glycol, diethylene glycol, n-propyl alcohol, isopropyl alcohol, ethyl alcohol, glycerin, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, and diethylene glycol monobutyl ether, at a temperature of from about 0° to about 100°C, for about 1 minute to about 1 hour, under forces that are the same or greater than those present in a high speed discperser operated at a peripheral speed of between about 4,000 and ahout 6,000 feet/minute, such that the average size of said aggregates before blending is greater than about 100 microns in diameter and the average size of said aggregates after blending is less than about 1 micron in diameter.