AU599672B2 - Polyester printing ink - Google Patents

Description

AU-AI-74805/87 P T WORLD INTELLECTUAL PROPERTY ORGANIZA N P C T WO LInternatio V urgEw g N O A INTERNATIONAL APPLICATION PUBLISHED UN R. E OE ENCO ERATION TREATY (PCT) (51) International Patent Classification 4 (11) International Publication Number: WO 87/ 07289 C09D 11/10, C08G 63/68 A l (43) International Publication Date: 3 December 1987 (03.12.87) (21) International Application Number: PCT/US87/01132 (74) Agent: HEATH, William, Jr.; 343 State Street, Rochester, NY 14650 (US).

(22) International Filing Date: 19 May 1987 (19.05.87) (81) Designated States: AU, BE (European patent), DE (Eu- (31) Priority Application Numbers: 864,996 ropean patent), FR (European patent), GB (Euro- 050,452 pean patent), IT (European patent), JP, NL (European patent), SE (European patent).

(32) Priority Dates: 20 May 1986 (20.05.86) 18 May 1987 (18.05.87) Published (33) Priority Country: US With international search report.

Before the expiration of the time limit for amending the claims and to be republished in the event of the receipt (71) Applicant: EASTMAN KODAK COMPANY [US/US]; of amendments.

343 State Street, Rochester, NY 14650 (US).

(72) Inventors: CONEY, Charles, Herbert 2008 Canterbury P 4 FEB 988 Road, Kingsport, TN 37660 PARSONS, Theron, Edward, III; 1245 Watauga Street, Kingsport, TN 37664 CLARK, Gary, Thomas Route 13, 513 AUSTRALAN Montezuma Road, Kingsport, TN 37664 (US).

STOCKL, Hazel, Rebecca 1138 Catawba Street, 2 2 DEC 1987 Kingsport, TN 37660 TORTORICI, Frank, Joseph 3832 Lochwood Road, Kingsport, TN 37660 PATENT OFFICE

(US).

(54) Title: INK COMPOSITION (57) Abstract A water dispersible composition useful in printing inks exemplified as comprising: one or more polyester materials having an acid component of from about 75 to about 84 mole isophthalic acid and conversely from about 25 to about 16 mole 5-sodio-sulfoisophthalic acid, and having a glycol component of from about 45 to about 60 mole diethylene glycol and'conversely from about 55 to about 40 mole 1,4-cyclohexanedimethanol or ethylene glycol or mixtures thereof, and; pigment material in a weight ratio with respect to total polyester material of from about 1/1000 to about 10/1 blended with said polyester material.

'u d Jocurent contains ttw artendaenrus xadoe and Section 49.

and is corncct for priotlng.

SWO, 87/07289 PCT/US87/01132 4 -1- INK COMPOSITION This application is a continuation-in-part of Application Serial No. 864,996 filed May 20, 1986.

This invention concerns pigmented, aqueous inks and concentrates for the preparation thereof wherein the pigment carrier or binder comprises water dispersible polyester material. No organic solvents or other property modifiers are necessary in the ink system for achieving markedly superior printed coatings by greatly simplified ink preparation and printing methods; however, such solvents and property modifiers as well as conventional dispersing aids, defoamers and the like may be used if desired. The present inks find special utility for letter press, intaglio, gravure, flexographic and other printing processes adaptable to the use of aqueous inks. The term dispersible as used herein encompasses the phenomena of solubilization, dissipation, suspension and the like of the polyester in the aqueous system.

The printing industry in general is a high priortiy field for the use of water-based inks and overprint varnishes as a means of meeting increasingly stringent solvent effl,ent regulations.

Present-day water-based inks often fail to satisfy these regulations as well as the necessary printability, stability, and performance properties required for commercial inks. For example, the various ethylene-acrylic acid copolymer salts of U.S.

Patent 3,607,813, the disclosure of which is incorporated herein by reference (for the printing process descriptions therein), in addition to requiring complex polymer and ink preparations, lack in performance on certain substrates. Other such aqueous or semi-aqueous systems proposed for printing inks contain polymers such as styrene-butadiene or polyacrylate latex systems but these systems also PCT/US87/01,132.

WO 87/07289 2 have serious drawbacks including being non-water dispersible after short drying periods which complicates equipment clean up. Other water soluble or dispersible polymers suggested for printing ink use are discussed in U.S. Patent 4,072,644.

The present invention provides vast improvements in the preparation, stability, and performance of water-based inks for printing and coating. The invention in its broad embodiment is defined as a water dispersible composition useful in printing inks comprising: polymeric material of at least one linear water-dispersible polymer having carbonyloxy linking groups in the linear molecular structure wherein up to 80% of the linking groups may be carbonylamido linking groups, the polymer having an inherent viscosity of from about 0.1 td about preferably from about 0.1 to about 0.5 measured in a 60/40 parts by weight solution of phenol/tetrachloroethane at 25 0 C and at a concentration of 0.25 gram of polymer in 100 ml of the solvent, the polymer containing substantially equimolar proportions of acid equivalents (100 mole percent) to hydroxy and amino equivalents (100 mole percent), the polymer comprising the reaction products of and from the following components or ester forming or ester-amide forming derivatives thereof; at least one difunctional dicarboxylic acid; 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 metal cationic group attached to an aromatic or cycloaliphatic nucleus wherein the functional groups are hydroxy, carboxyl or amino; W87/07289 PCT/US87/01132 WO 87/07289 -3at least one difunctional reactant 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 at least 15 mole percent, based on the total mole percent of hydroxy or hydroxy and amino equivalents, is a poly(ethylene glycol) having the structural formula

H(OCH

2 -CH2 nOH, n being an integer of from 2 to about or of which from about 0.1 to less than about 15 mole percent, based on the total mole percent of hydroxy or hydroxy and amino equivalents, is a poly(ethylene glycol) having the structural formula HtOCH 2 -CH2tnOH, 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 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 or reactants is a H atom or an alkyl group of 1 to 4 carbon atoms, and; ll i' WO 87/07289 PCT/US87/01132 -4pigment material dispersed in said polymeric material in a weight ratio of pigment to total polymeric material of from about 1/1000 to about 10/1, preferably from about 1/100 to about 5/1, and most preferably from about 1/20 to about 3/1.

In the above polyester material it is preferred that very minor, less than about 10 mol based on all reactants, of reactant is employed, that at least about 70 mol I& of reactant is glycol, and that at least about 70 mol of all the hydroxy equivalents is present in the glycol.

In preferred embodiments of the invention: the polymeric material comprises an acid component (moiety) of from about 75 to about 84 mole isophthalic acid and conversely from about 25 to about 16 mole 5-sodiosulfoisophthalic acid, and a glycol component (moiety) of from about 45 to about mole diethylene glycol and conversely from about to about 40 mole 1 1,4-cyclohexanedimethanol or ethylene glycol (the term "moiety" as used herein designates the residual portion of the reactant acid or glycol which actually enters into or onto the polymer chain during the condensation or polycondensation reaction); the pigment material is dispersed in the polymeric material in a weight ratio with respect to the total of the polymeric material, of from about 1/100 to about 5/1; the inherent viscosity of the polymeric material is from about 0.28 to about 0.35, the said acid component (moiety) comprises from about 80 to about 83 mole isophthalic acid and conversely from about to about 17 mole 5-sodiosulfoisophthalic acid, and the said glycol component (moiety) comprises from about 52 to about 56 mole diethylene glycol and conversely from about 48 to about 44 mole 1,4-cyclohexanedimethanol; WQ 87/07289 PCT/US87/01132 the pigment is one or a mixture of the following color index materials according to their generic names: C.I. Pigment Yellow 17, C.I. Pigment Blue 27, C.I. Pigment Red 49:2, C.I. Pigment Red 81:1, C.I.

Pigment Red 81:3, C.I. Pigment Red 81:x, C.I. Pigment Yellow 83, C.I. Pigment Red 57:1, C.I. Pigment Red 49:1, C.I. Pigment Violet 23, C.I. Pigment Green 7, C.I. Pigment Blue 61, C.I. Pigment Red 48:1, C.I.

Pigment Red 52:1, C.I. Pigment Violet 1, C.I. Pigment White 6, C.I. Pigment Blue 15, C.I. Pigment Yellow 12, C.I. Pigment Blue 56, C.I. Pigment Orange 5, C.I.

Pigment Black 7, C.I. Pigment Yellow 14, C.I. Pigment Red 48:2, C.I. Pigment Blue 15:3; the polymeric material is dispersed in water and comprises from about 1 to about 50% by weight of the total aqueous dispersion, preferably from about 10 to about 40% by weight of the total aqueous dispersion; the aqueous dispersion is coated or printed onto a substrate selected from metal foil, newsprint, bleached and unbleached Kraft paper, clay coated paper, glass, calendered paper, stainless paper, paper board, and films or other substrates of polyester, polycarbonate, cellulose ester, regenerated cellulose, poly(vinylidene cholride), polyamide or polystyrene; and said coating or print comprises any of the above compositions wherein a substantial portion of the initial metal cations of the water solubilizing sulfonate groups of the polymeric material has been replaced with an insolubilizing polyvalent metal +3 cation, such as Al Ca or the like as disclosed and in the manner described in U.S. Patent 4,145,469, the disclosure of which is incorporated herein by reference. As stated therein, generally, based on the weight of the polymeric material, 0.05% to about 2.0% by weight solids of the polyvalent r- PCT/US87/0 1132, WO 87/07289 -6 metal cation are required for effective insolubilizat ion.

The complete chemical definitions of the above C.I. pigments are given in the following table: Pigments Generic Name C.I. Pigment Yellow 17 C.I. Pigment Blue 27 C.I. Pigment Red 49:2 C.X. Pigment Red 81:1 C.A. Index/Chemical Name, Butanamide, dichloro( 1 '-biphenyll- 4,4 '-di y1) b is (azo )b is[N- (2-me choxyphenyl )-3-oxo- Ferrate hexakis (cyano-C)-ammonium iron 1:1) I-Naphthalenesulfonic acid, (2-hydroxy-1naphthalenyl )azo 3-, calcium salt (2;1) Benzoic acid, 2,-[6-ethylamino )-3-(ethylimino 7dimethyl-3H-xanthen-9-yl 3-, ethyl ester, w/molybdenux tungs ten hydroxide oxide phosphate Benzoic acid, 2-[6-ethylamino)-3-ethylimino)-2, 7dimethyl-3H-xanthen-9-yl 3-, ethyl ester, molybdatesilicate Benzoic acid, 2-(6-(ethylamino)-3-(ethylimino)-2,7dimethyl-3H-xanthen-9-yl 3 ethyl ester, molybdatephosphate Butanamide, dichloro( 1 '-biphenyl 4,4 '-diyl)bis(azo)bis[N- (4--chloro-2, phenyl )-3--oxo- C.I. Pigment Red 81:3 C.I. Pigment Red 81:x C.I. Pigment Yellow 83

V--

PCT/US87/0 1132 IWQ 87/07289 -7 Generic Name 0.1. Pigment Red 57:1 0.I. Pigment Red 49:1 C.A. Index/Chemical Name 2-Naphthalenecarboxyl ic acid, 3-hydroxy-4-[ (4methyl-2--sulfophenyl )azo]-, calcium salt (1:1) l-Naphthalenesulfonic acid, (2--hydroxy-1naphthalenyl )azo 1-, barium salt (2:1) Diindolo[3,3' ,21m] triphenodioxazine, 8 ,18- ,15-die thyl-5 d ihydro- 0.1. Pigment Violet 23 0.1. Pigment Green 7 0.1. Pigment Blue 61 0.1. Pigment Green 7 0.1. Pigment Red 48:1 C.I. Pigment Red 52:1 .4 Benzenesulfonic acid, [[4-phenylamino)phenyl V- [4-(phenyliminu)-2, hexadien-l-ylidene]methyl 3phenyl ]amino I- 2-Naphthalenecarboxyl ic acid, (5-c-rhloro-4methyl-2-sulfophenyl )azo]- 3-hydroxy-, barium salt (1:1) 2--Naphthaleriecarboxylic acid, methyl-2-sulfopheny'l )azo 3- 3-hydroxy-, calcium salt (1:1) Ethanaminium, carboxyphenyl )-6-(diethylamino )-3H-xanthen-3ylidene]-N--ethyl-, molybdatetungs tatephosphate Titanium oxide (TiO2) Copper, [29H, 31Hphthalocyaninato

N

29

N

30 j3l,

N

32 (Sp-4-l)- 125 0.1. Pigment Violet 1 C.I. Pigment White 6 0.1. Pigment Blue 15 WO 87/07289 PCT/US87/0 1132 8- Generic Name 0.1. Pigment Yellow 12 C.I. Pigment Blue 56 C.A. Index/Chemical Name Butanamide, dichloro[ 1 '-bipheriyl]- 4,4 -diyl)bis(azo) ]bis[3ox a-N-ph eny 1- Benzenesulfonic acid, 2methyl--4-[ (3methylphenyl )amino]phenyl]- (3-methylphenyl imino]-2, dien-1-ylidenejjmethyl]phenyl Iamino]- 2-Naphthalenol, dinitrophenyl )azo]- 0.1. Pigment orange 5 0.1. Pigment Black 7 0.1. Pigment Yellow 14 Carbon black C.I. Pigment Red 48:2 Butanamide, 2,21-[(3,31dichloro[ 1,1 '-biphenyl I- 4,4 '-diyl )bis(azo) ibis-.

(N-(2-miethylphenyl )-3--oxo- 2-Naphthalenecarboxyl ic acid, 4-[(5-chloro-4methyl-2-sulfophenyl azo]-3--hydroxy-, calcium salt (1:1) Copper, [29H, 31Hphthalocyaninato 29

N

30

N

31

N

3 2 (Sp-4-1)- 0.1. Pigment Blue 15:3 The inherent viscosities of the particular polyester materials useful herein range from about 0.1 to about 1.0 determined according to ASTM D2857-70 procedure, in a Wagner Viscometer of Lab Glass, Inc. of Vineland, New Jersey, having a 1/2 ml. capillary bulb, using a polymer concentration about 0.257% by weight in 60/40 by weight of phenol/tetrachloroethane. The procedure is carried out by heating the polymer/solvent system ar 1200C for cooling the solution to 250C and measuring the time of flow at 2500. The I.V. is calculated from the equation Wq 87/07289 PCT/US87/01132 -9n) 25°C. In 0.50% o_

C

where: inherent viscosity at 25 0 C at a polymer concentration of 0.25 g/100 ml. of solvent; In natural logarithm; t sample flow time; to solvent-blank flow time; and C concentration of polymer in grams per 100 ml. of solvent 0.25.

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

In general, the present polyester materials are excellent film formers for water-based printing inks.

The polymers form stable dispersions in water and produce tough, flexible films on drying. No solvents are required, and films will form at temperatures just above the freezing point of water. The polymers in dispersion form may be plasticized if necessary, for example, with certain water immiscible phthalate esters to high degrees of flexibility. Printing inks prepared from the aqueous dispersed polymers are water reducible and require no organic solvents or wetting agents although such may be employed. The inks dry rapidly upon printing but have long "open" times in containers exposed to the atmosphere, such as a printing press fountain. The inks wet surfaces well and have excellent adhesion to many plastic films and metal foil as well as to paper, glass and many other substrates. Both the 100% solid polymers and the U;I~jiiip51~1~-- WO 87/07289 PT/US87/01132' WO 87/07289 10 corresponding aqueous dispersions thereof may be pigmented by conventional techniques, and high gloss, prints may be obtained. The prints have moderate water resistance upon heating and may be post-treated to produce films with excellent resistance to water, for example, with an aqueous alum solution or the like cation.

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

Dispersal of the present polyester material in water is preferably done at preheated water temperail v ture of about a 1800 to about 200 0 F and the polymer added rapidly as pellets to the vortex under high shear stirring. A Cowles Dissolver, Waring Blender, or similar equipment may be used. Once water is heated to temperature, additional heat input is not required. Depending upon the volume prepared, dispersal of the pellets by stirring should be complete within 15 to 30 minutes. Continued agitation .'with cooling may be desirable to prevent thickening at the surface due to water evaporation. Viscosities of the dispersions remain low up to nonvolatile levels of about 25-30%, but generally increase sharply above these levels. Viscosities of the dispersions will be influenced by the degree of polymer dispersion (fineness) obtained which is affected by the dispersing temperature, shear, and time. A nonvolatile limit for most applications is about 38% for the present preferred polyester material.

tion of 0.25 gram of polymer in 100 ml of the solvent, the polymer containing substantially equimolar proportions of acid equivalents (100 mole percent) to hydroxy and amino I/ 2

I

WO,87/07289 PCT/US87/01132 11 The present pigmented polyester material and inks may also be prepared by two-roll milling the finely comminuted, nonpolymer soluble pigment into the solid polyester material and thereafter dispersing the pigmented material in water in a manner generally similar to the procedure described in U.S. Patent 4,148,779 for solubilizing organic disperse textile dyes in polyester for subsequent dispersal in water.

SDispersions can also be made by adding the pigment at high speed agitation to the polyester material previously dispersed in water and then grinding in a ball mill or sand mill to further reduce pigment size. The preferred pH of the present inks is from about 5.0 to about The pigments useful in the present invention, in addition to those specifically identified above, include those described in NP1RI Raw Materials Data, Vol. 4, Pigments, Copyright 1983.

The following examples will further illustrate practice of the invention.

Polyester Preparation Example 1 A mixture of 79.5 g (0.41 mole) of dimethyl isophthalate, 26.6 g (0.09 mole) of dimethyl-5- sodiosulfoisophthalate, 54.1 g (0.51 mole) of diethylene glycol, 37.4 g (0.26 mole) of 1,4-cyclohexanedimethanol, 1.4 ml of a 1.0% (based on Ti) catalyst solution of titanium tetraisopropoxide, and 0.74 g (0.009 mole) of sodium acetate buffer is stirred and heated for two hours at 200-220 0 C. The temperature is then raised to 275"C and a vacuum of 0.3 mm is applied. Heating and stirring is continued for 1 hour under these conditions. After cooling, the polymer obtained has an I.V. of 0.36 and is tough and rubbery. It is dissipatable in hot water to the te equivalents, is a poly(ethylene glycol) having the structural formula ./o -i

-V

S87/07289 WO 87/07289 PCT/US87/0 132' 12 extent of about 25 weight percent to give a clear, slightly viscous solution. The composition of the acid moieties of this polyester material is analyzed to be 82 mole isophthalic acid residue and 18 mole 5-sodiosulfoisophthalic acid residue, and of the glycol moieties is analyzed to be 54 mole diethylene glycol and 46 mole I 1,4-cyclohexanedimethanol.

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

(SIP)

1,4-Cyclohexanedimethanol (CHDM) Carbowax 1000 (CW 1000) Sodium Acetate Irganox 1010 g. moles 0.415 0.085 0.520 0.0237 0.0085 0.0085 The Carbowax 1000 has the structure HfOCH 2

-CH

2 -OH wherein n is about 22. The polymer analyzed by NMR contains (in reacted form) about 83 mole IPA, about 17 mole SIP, about 94.5 mole CHDM, and about 5.5 mole of CW 1000, and has an I.V. of about 0.39.

Dimethyl Isophthalate 1,4-Cyclohexanedimethanol Carbowax 400 (n=10) Sodium Acetate R. moles 0.328 0.072 0.442 0.058 0.0072 L- ii L rrurw~nmra~-~; I 1 1; WQO87/07289 PCT/US87/01132 13 The polymer as analyzed by NMR contains (in reacted form) about 82 mole IPA, about 18 mole SIP, about 85.5 mole CHDM and about 14.5 mole CW 400, and has an I.V. of about 0.46.

rr, Dimethyl Isophthalate 1,4-Cyclohexanedimethanol Carbowax 4000 (n=90) Sodium Acetate g. moles 0.41 0.09 0.55 0.0005 0.009 The polymer as analyzed by NMR contains (in reacted from) about 82 mole IPA, about 18 mole SIP, about 99.9 mole CHDM and about 0.1 mole CW 4000, and has an I.V. of about 0.16.

Dimethyl Isophthalate Dimethyl-5-Sodiosulfoisophthalate Ethylene Glycol (EG) Carbowax 2000 (n=45) Sodium Acetate R. moles 0.205 0.045 0.9638 0.03625 0.0045 The polyner as analyzed by NMR contains (in reacted from) about 82 mole IPA, about 18 mole I SIP, about 85.5 mole EG and about 14.5 mole CW 2000, and has an I.V. of about 0.34.

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

In accordance with the present invention, inks prepared from the above polyester material have been found to be unexpectedly superior over prior aqueous inks in one or more of such properties as pigment wetting, pigment stability, temperature stability WO 87/07289 PCT/US87/01132 WO 87/07289 14- (heat and freeze-thaw), non-settling for extended periods of time, nonpolluting with respect to odor and volatile organics, nonflocculating, long "open" time in the press fountain, wide viscosity range inks, adhesion to a variety of substrates, hardness, gloss, drying rate on substrates, film-forming properties at low temperatures without organic co-solvents, resistance to grease, water and scuff, compatibility with other water-based inks, wet rub resistance, ink mileage characteristics (considerable water dilution allowable at the press), ink press stability in general, printability (clean, sharp transfer without "stringing or misting"), trapping, easy clean up, nonplugging of printing plates, flexibility, redispersibility or rewetting, crinkle resistance, high pigment loading, solvent resistance, alkali, chemical and detergent resistance, blocking resistance, lightfastness, toughness, substrate wetting, hold-out, opacity, dry-rate, and no offset on the printing press (coating e.g. on tension rollers).

Ink Preparation Example 2 7 Ink Ingredients by Weight Deionized water 61.0 Polymer of Example 1 28.8 C.I. Pigment Yellow 83 10.0 Biocide, Tektamer 38 AD 0.2 The solid polymer (32 parts) is dispersed in 68 parts of deionized water at 85 0 C to 95 0 C and 0.2 parts of biocide added. To 90 parts of this dispersion is Lii PCL JL U L UIII O V I L u ll IA a u W aqueous or semi-aqueous systems proposed for printing inks contain polymers such as styrene-butadiene or polyacrylate latex systems but these systems also i WQ 87/07289 PCT/US87/01132 15 added 10 parts of the yellow pigment at high speed agitation for five minutes on a Waring Blender. The mixture is then milled in an Eiger mill operated at about 5,000 rpm for about 7.5 minutes to further reduce the pigment for a grind approaching "0" (<about 3.0) NPIRI grind gauge. The resulting ink has a pH of about 5.85 and a viscosity of 27-30 seconds on a #2 Zahn cup determined according to ASTM D-4212-82.

This procedure yields a fluid ink which is nonsettling for extended periods, does not flocculate or agglomerate, and can be reduced in viscosity with deionized water. The ink has virtually no odor and can be readily cleaned from printing equipment with warm deionized water. Tenacious, dried films of this ink can be cleaned from printing equipment with small amounts of detergents added to warm (80-90°F.) deionized water. The ink dries rapidly upon printing yet remains "open" in a container exposed to the atmosphere, such as a printing press reservoir.

Example 3 The ink of Example 2 was reduced (diluted) with deionized water to a press ready viscosity of 24 seconds measured in a #2 Zahn cup and proofs prepared therefrom with a flexographic or gravure hand proofer employing a 180 line screen anilox roll on aluminum foil, newsprint, bleached white Kraft paper, 60# clay S coated paper, and Mylar film. The target yellow-gold color, ease of printing and adhesion to all substrates was good to excellent. The hand proofer employed provides reasonable facsimiles of prints obtained by the gravure or flexographic printing processes as discussed in the aforesaid U.S. Patent 3,607,813, and is typically used to prepare roll-outs or proofs for laboratory testing on a wide variety of substrates.

The wire-wound rod is typically used to prepare least one metal cationic group attached to an aromatic or cycloaliphatic nucleus wherein the functional groups are hydroxy, carboxyl or amino; WO 87/07289 PCT/US87/01132 16 draw-downs of inks on a variety of substrates. These rods apply a uniform wet-film thickness to the substrate, and after drying, the draw-downs are ready for testing. Typically 2.5-8 number wire wound draw-down rods are employed. For exemplary details of such proofer equipment and use, see the publication "Gardco 1983-1984 Handbook of Paint Testing, Corrosion Control and Laboratory Instruments" of the Paul N.

Gardner Company, Inc., 218 D Commercial Blvd., Suite 205 Lauderdale by the Sea, Florida 33308-4491, a copy of which accompanies this application.

Proofs are allowed to "age" at ambient temperature (74 0 F) for one hour and rub resistance tests are then conducted thereon with a Sutherland Rub Tester employing a 2 lb. weight at 100 cycles. The rub resistance of the above proofs were good to excellent.

The invention has been described in detail with particular reference to preferred embodiments thereof, but it will be understood that variations and modifications can be effected within the spirit and scope of the invention.

Claims (8)

1. A water dispersible composition useful in printing inks comprising: polymeric material of at least one linear, water-dispersible polymer having carbonyloxy linking groups in the linear molecular structure wherein up to 80% of the linking groups may be carbonylamido linking groups, the polymer having an inherent viscosity of from about 0.1 to abtoxt 1.0 measured in a 60/40 parts by weight solution of phenol/- tetrachloroethane at 25 0 C and at a concentra- tion of 0.25 gram of polymer in 100 ml of the solvent, the polymer containing substantially equimolar proportions of acid equivalents (100 mole percent) to hydroxy and amino equivalents (100 mole percent), the polymer comprising the reaction products of and from the following components or ester forming or esteramide forming derivatives thereof; at least one difunctional dicarboxylic acid; from a~tt 4 to abatt 25 mole percent, based on a total of all acid, hydroxyl and amino equivalents being equal to 200 mole percent, of at least one difunc- tional sulfomonomer containing at least onekcationic -ufonte- group attached ,to an aromatic or cycloaliphatic nucleus wherein the functional groups are hydroxy, carboxyl or amino; at least one difunctional reactant selected from a glycol or a mixture of a glycol and diamine having two -NRH RA I. Q? C i i r~jlii~~ WO 87/07289 PCT/US87/0I-132, 18 groups, the glycol containing two -CH2-OH groups of which at least 15 mole percent, based on the total mole percent of hydroxy or hydroxy and amino equivalents, is a poly(ethylene glycol) having the structural formula HOCH 2 -CH2 nOH, n being an integer of from 2 to abort 20, or of which from about 0.1 to less than about 15 mole percent, based on the total mole percent of hydroxy or hydroxy and amino equivalents, is a poly(ethylene glycol) having the structural formula HfOCH 2 -CH 2 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 propor- tional to the quantity of n within said range; and from none to at least one difunctional reactant selected from a hydroxy- carboxylic acid having one -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 or reactants SRis a H atom or an alkyl group of 1 to 4 S I carbon atoms, and; A WQ 87/07289 PCT/US87/01132 19 pigment material dispersed in said polymeric material in a weight ratio with respect to the total of said polymeric material of from -about 1/1000 to-about 10/1.

2. A water dispersible composition of claim 1 wherein the polymeric material comprises: one or more polyesters having an inherent viscosity of from about 0.28 to about 0.35, an acid moiety of from about 75 to about 84 mole isophthalic acid and conversely from ahout 25 to about 16 mole isophthalic acid, and a glycol moiety of from about 45 to about 60 mole diethylene glycol and conversely from about 55 to 'about 44 mole 1,4-cyclohexanedimethanol or ethylene glycol or mixtures thereof, and; pigment material in a weight ratio with respect to total polymeric material of from abot 1/100 to about 5/1 blended with said polyester materials.

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

4. A composition of any one of claims 1, 2 or 3 wherein the pigment is one or a mixture of the following color index materials: C.I. Pigment Yellow 17, C.I. Pigment Blue 27, C.I. Pigment Red t 49:2, C.I. Pigment Red 81:1, C.I. Pigment Red -r; L.CI- 4Q~ 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. Pigm.'nt 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. An aqueous dispersion comprising the composition of any one of claims 1, 2, 3 or 4 dispersed in water wherein the polymeric material comprises from 1 to 50% by weight thereof.

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

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

8. An aqueous dispersion as claimed in claim 1, substantially as hereinbefore described with reference to any one of the examples. DATED: 11 April, 1990 PHILLIPS ORMONDE FITZPATRICK Attorneys for: ~EASTMAN KODAK COMPANY S 3866N Lr.-r .1 metal roll as well as to paper, glass and many other substrates. Both the 100% solid polymers and the L- I.I I~r ir- r 1. CF INTERNATIONAL SEARCH REPORT International Apolication No PCT/US 87/01132 .ASSIFICATION OF SUBJECT MATTER (if several classification symbols apply, indicate all) i According to international Patent Classification (IPC) or to both National Classification and IPC IPC4: C 09 D 11/10; C 08 G 63/68 II. FIELDS SEARCHED Minimum Documentation Searched I Classification System Classification Symbols 4 IPC C 09 D Documentation Searched other than Minimum Documentatlon to the Extent that such Documents are Included In the Fields Searched I III. DOCUMENTS CONSIDERED TO BE RELEVANT' Category I Citation of Document, it with Indication, where appropriate, of the relevant passages 1 Relevant to Claim No. X FR, A, 2311820 (EASTMAN KODAK) 17 December 1976 see claims 1,5 1 A US, A, 3734874 (CHARLES J. KIBLER) 22 May 1973 see abstract (cited in the application) A US, A, 4145469 (DAVID D. NEWKIRK) March 1979 see abstract 7 (cited in the application) Special categories of cited documents: o1 later document published after the International filing date document defining the general atate of the art which is not or priority date and not in conflict with the application but considered to be of particular relevance inventionderstand t rinciple or theory underlyng the invention earlier document but published on or after the international fi ling data document of particular relevance: the claimed invention cannot be considered novel or cannot be considered to document which may throw doubts on priority claim(s) or Involve an inventive step which io cited to eb li h the publication dat of another document of particular relevance; the claimed invention cannot be considered to involve an inventive step when the document referring to an oral disclosure, use, exhibition or document is combined with one or more other such docu- other means ments, such combination being obvioua to a person skilled document published prior to the international filing date but In the art. 'later than the priority date claimed document member of the same I, t family IV. CERTIFICATION Date of the Actual Completion of the International Search Date of Mailing of this International Search Report 27th August 1987 -6 OCT 1987 international Searching Authority Signature of Authorized Offcer EUROPEAN PATENT OFFICE L. ROSSI Form PCTIISA210 (second sheet) (January 1985) *r _i 1 j ANNEX TO THE INTERNATIONAL SEARCH REPORT ON INTERNATIONAL APPLICATION NO. PCT/US 87/01132 (SA 17329) This Annex lists the patent family members relating to the patent documents cited in the above-mentioned international search report. The members are as contained in the European Patent Office EDP file on 17/09/87 The European Patent Office is in no way liable for these particulars which are merely given for the purpose of information. Patent document cited in search report Publication date Patent family member(s) Publication date FR-A- 2311820 17/12/76 BE-A- 842114 22/11/76 DE-A- 2621988 02/12/76 AT-D- 372776 15/10/77 CH-A- 603777 31/08/78 GB-A- 1526337 27/09/78 AT-B- 343768 12/06/78 US-A- 4148779 10/04/79 JP-A- 51146905 16/12/76 US-A- 3734874 22/05/73 US-A- 3779993 18/12/73 US-A- 4145469 20/03/79 CA-A- 1104761 14/07/81 US-4- 4145469 20/03/79 CA-A- 1104761 14/07/81 For more details about this annex see Official Journal of the European Patent Office, No. 12/82 t-