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WO1987007289A1 - Composition d'encre - Google Patents

Composition d'encre Download PDF

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Publication number
WO1987007289A1
WO1987007289A1 PCT/US1987/001132 US8701132W WO8707289A1 WO 1987007289 A1 WO1987007289 A1 WO 1987007289A1 US 8701132 W US8701132 W US 8701132W WO 8707289 A1 WO8707289 A1 WO 8707289A1
Authority
WO
WIPO (PCT)
Prior art keywords
pigment
mole
acid
glycol
hydroxy
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/US1987/001132
Other languages
English (en)
Inventor
Charles Herbert Coney
Theron Edward Parsons, Iii
Gary Thomas Clark
Hazel Rebecca Stockl
Frank Joseph Tortorici
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Eastman Kodak Co
Original Assignee
Eastman Kodak Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Eastman Kodak Co filed Critical Eastman Kodak Co
Publication of WO1987007289A1 publication Critical patent/WO1987007289A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • C09D11/102—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions other than those only involving unsaturated carbon-to-carbon bonds
    • C09D11/104—Polyesters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
    • C08G63/688—Polyesters containing atoms other than carbon, hydrogen and oxygen containing sulfur
    • C08G63/6884—Polyesters containing atoms other than carbon, hydrogen and oxygen containing sulfur derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/6886—Dicarboxylic acids and dihydroxy compounds

Definitions

  • This application is a continuation—in— art of Application Serial No. 864,996 filed May 20, 1986.
  • This invention concerns pigmented, aqueous inks and concentrates for the preparation thereof wherein the pigment carrier or binder comprises water dispersible polyester material.
  • No organic solvents or other property modifiers are necessary in the ink system for achieving markedly superior printed coatings by greatly simplified ink preparation and printing methods; however, such solvents and property modifiers as well as conventional dispersing aids, defoamers and the like may be used if desired.
  • the present inks find special utility for letter press, intaglio, gravure, flexographic and other printing processes adaptable to the use of aqueous inks.
  • dispersible encompasses the phenomena of solubilization, dissipation, suspension and the like of the polyester in the aqueous system.
  • the printing industry* in general is a high priortiy field for the use of water—based inks and overprint varnishes as a means of meeting increas ⁇ ingly stringent solvent effluent regulations.
  • Present—day water—based inks often fail to satisfy these regulations as well as the necessary print- ability, stability, and performance properties required for commercial inks.
  • Patent 3,607,813 the disclosure of which is incor ⁇ porated herein by reference (for the printing process descriptions therein), in addition to requiring complex polymer and ink preparations, lack in performance on certain substrates.
  • Other such aqueous or semi—aqueous systems proposed for printing inks contain polymers such as styrene—butadiene or polyacrylate latex systems but these systems also have serious drawbacks including being non-water dispersible after short drying periods which compli ⁇ cates equipment clean up.
  • Other water soluble or dispersible polymers suggested for printing ink use are discussed in U.S. Patent 4,072,644.
  • the present invention provides vast improve ⁇ ments in the preparation, stability, and performance of water—based inks for printing and coating.
  • the invention in its broad embodiment is defined as a water dispersible composition useful in printing inks comprising:
  • HfOCH 2 -CH 2 7- n OH HfOCH 2 -CH 2 7- n 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 the total mole percent of hydroxy or hydroxy and amino equivalents, is a poly(ethylene glycol) having the structural formula
  • the polymeric material comprises an acid component (moiety) of from about 75 to about 84 mole % isophthalic acid and conversely from about 25 to about 16 mole % 5—sodiosulfoisophth'alic acid, and a glycol component (moiety) of from about 45 to about 60 mole % diethylene glycol and conversely from about 55 to about 40 mole % 1,4—cyclohexanedimethanol or ethylene glycol (the term "moiety” as used herein designates the residual portion of the reactant acid or glycol which actually enters into or onto the polymer chain during the condensation or polyconden— sation reaction); the pigment material is dispersed in the polymeric material in a weight ratio with respect to the total of the polymeric material, of from about 1/100 to about 5/1; the inherent viscosity of the polymeric material is from about 0.28 to about 0.35, the said acid component (moiety) comprises from about 80 to about 83 mofetil, aroyl
  • 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.
  • the polymeric material is dispersed in water and comprises from about 1 to about 50% by weight of the total aqueous dispersion, preferably from about 10 to about 40% by weight of the total aqueous dispersion;
  • the aqueous dispersion is coated or printed onto a substrate selected from metal foil, newsprint, bleached and unbleached Kraft paper, clay coated paper, glass, calendered paper, stainless paper, paper board, and films or other substrates of poly ⁇ ester, polycarbonate, cellulose ester, regenerated cellulose, poly(vinylidene cholride), polyamide or polystyrene; and said coating or print comprises any of the above compositions wherein a substantial portion of the initial metal cations of the water solubilizing sulfonate groups of the polymeric material
  • +3 i r cation such as Al , Ca , or the like as disclosed and in the manner described in U.S. Patent
  • the inherent viscosities (I.V.) of the particular polyester materials useful herein range from about 0.1 to about 1.0 determined according to ASTM D2857-70 procedure, in a Wagner Viscometer of Lab Glass, Inc. of Vineland, New Jersey, having a 1/2 ml. capillary bulb, using a polymer concentration about 0.25% by weight in 60/40 by weight of phenol/- tetrachloroethane.
  • the procedure is carried out by heating the polymer/solvent system ar 120°C for 15 minutes, cooling the solution to 25°C and measuring the time of flow at 25°C.
  • the I.V. is calculated from the equation - 9 -
  • the present polyester materials are excellent film formers for water—based printing inks.
  • the polymers form stable dispersions in water and produce tough, flexible films on drying. No solvents are required, and films will form at temperatures just above the freezing point of water.
  • the polymers in dispersion form may be plasticized if necessary, for example, with certain water immiscible phthalate esters to high degrees of flexibility.
  • Printing inks prepared from the aqueous dispersed polymers are water reducible and require no organic solvents or wetting agents although such may be employed. The inks dry rapidly upon printing but have long "open" times in containers exposed to the atmosphere, such as a printing press fountain.
  • the inks wet surfaces well and have excellent adhesion to many plastic films and metal foil as well as to paper, glass and many other substrates.
  • Both the 100% solid polymers and the corresponding aqueous dispersions thereof may be pigmented by conventional techniques, and high gloss prints may be obtained.
  • the prints have moderate water resistance upon heating and may be post—treated to produce films with excellent resistance to water, for example, with an aqueous alum solution or the like cation.
  • polyester material is prepared according to the polyester preparation technology described in U.S. Patents 3,734,874 and 3,779,993, the disclosures of which are incorporated herein by reference, and the use of the term "acid" in the above description and in the appended claims includes the various ester forming or condensable derivatives of the acid reactants such as the dimethyl esters thereof as employed in the preparations set out in these patents.
  • Dispersal of the present polyester material in water is preferably done at preheated water tempera— ture of about a 180° to about 200°F and the polymer added rapidly as pellets to the vortex under high shear stirring.
  • a Cowles Dissolver, Waring Blender, or similar equipment may be used. Once water is heated to temperature, additional heat input is not required.
  • dispersal of the pellets by stirring should be complete within 15 to 30 minutes. Continued agitation with cooling may be desirable to prevent thickening at the surface due to water evaporation. Viscosities of the dispersions remain low up to nonvolatile levels of about 25—30%, but generally increase sharply above these levels.
  • Viscosities of the dispersions will be influenced by the degree of polymer dispersion (fineness) obtained which is affected by the dispers— ing temperature, shear, and time.
  • a nonvolatile limit for most applications is about 38% for the present preferred polyester material.
  • the present pig ented polyester material and inks may also be prepared by two— oll milling the finely comminuted, nonpolymer soluble pigment into the solid polyester material and thereafter dispersing the pigmented material in water in a manner generally similar to the procedure described in U.S. Patent 4,148,779 for solubilizing organic disperse textile dyes in polyester for subsequent dispersal in water.
  • Dispersions can also be made by adding the pigment at high speed agitation to the polyester material previously dispersed in water and then grinding in a ball mill or sand mill to further reduce pigment size.
  • the preferred pH of the present inks is from about 5.0 to about 7.5.
  • the pigments useful in the present invention include those described in NP1RI Raw Materials Data, Vol. 4, Pigments, Copyright 1983.
  • the polymer obtained After cooling, the polymer obtained has an I.V. of 0.36 and is tough and rubbery. It is dissipatable in hot water to the extent of about 25 weight percent to give a clear, slightly viscous solution.
  • the composition of the acid moieties of this polyester material is analyzed to be 82 mole % isophthalic acid residue and 18 mole % 5-sodiosulfoisophthalic acid residue, and of the glycol moieties is analyzed to be 54 mole % diethylene glycol and 46 mole % 1,4-cyclohexanedimethanol.
  • Example 1A Polyesters designated (a), (b), (c) and (d) were prepared essentially in accordance with Example 1 of the aforementioned U.S. Patent 4,233,196 from the following materials:
  • IPA Dimethyl Isophthalate
  • SIP Dimethyl-5-Sodiosulfoisophthalate
  • the Carbowax 1000 has the structure H OCH 2 -CH 2 ⁇ -OH wherein n is about 22.
  • 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.
  • 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.
  • 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.
  • 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.
  • the n value is preferably between about 6 and 150.
  • inks prepared from the above polyester material have been found to be unexpectedly superior over prior aqueous inks in one or more of such properties as pigment wetting, pigment stability, temperature stability (heat and freeze—thaw), non-settling for extended periods of time, nonpolluting with respect to odor and volatile organics, nonflocculating, long "open" time in the press fountain, wide viscosity range inks, adhesion to a variety of substrates, hardness, gloss, drying rate on substrates, film—forming properties at low temperatures without organic co—solvents, resistance to grease, water and scuff, compatibility with other water—based inks, wet rub resistance, ink mileage characteristics (considerable water dilution allowable at the press), ink press stability in general, printability (clean, sharp transfer without “stringing or misting"), trapping, easy clean up, nonplugging of printing plates, flexibility, redispersibility or rewetting, crinkle resistance, high pigment loading, solvent resistance,
  • the solid polymer (32 parts) is dispersed in 68 parts of deionized water at 85°C to 95°C and 0.2 parts of biocide added. To 90 parts of this dispersion is
  • Example 3 ( ⁇ about 3.0) NPIRI grind gauge.
  • the resulting ink has a pH of about 5.85 and a viscosity of 27-30 seconds on a #2 Zahn cup determined according to ASTM D-4212-82.
  • This procedure yields a fluid ink which is nonsettling for extended periods, does not flocculate or agglomerate, and can be reduced in viscosity with deionized water.
  • the ink has virtually no odor and can be readily cleaned from printing equipment with warm deionized water. Tenacious, dried films of this ink can be cleaned from printing equipment with small amounts of detergents (5—10%) added to warm (80—90°F.) deionized water.
  • the ink dries rapidly upon printing yet remains "open" in a container exposed to the atmosphere, such as a printing press reservoir.
  • Example 3 Example 3
  • Example 2 The ink of Example 2 was reduced (diluted) with deionized water to a press ready viscosity of 24 seconds measured in a #2 Zahn cup and proofs prepared therefrom with a flexographic or gravure hand proofer employing a 180 line screen anilox roll on aluminum foil, newsprint, bleached white Kraft paper, 60# clay coated paper, and Mylar film.
  • the target yellow-gold color, ease of printing and adhesion to all substrates was good to excellent.
  • the hand proofer employed provides reasonable facsimiles of prints obtained by the gravure or flexographic printing processes as discussed in the aforesaid U.S. Patent 3,607,813, and is typically used to prepare roll-outs or proofs for laboratory testing on a wide variety of substrates.
  • the wire— ound rod is typically used to prepare draw-downs of inks on a variety of substrates. These rods apply a uniform wet—film thickness to the substrate, and after drying, the draw-downs are ready for testing. Typically 2.5—8 number wire wound draw—down rods are employed.
  • 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.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)
  • Polyamides (AREA)
  • Polyesters Or Polycarbonates (AREA)

Abstract

Une composition dispersible dans l'eau utile dans des encres d'impression comprend: (A) un ou plusieurs matériaux polyester ayant un constituant acide d'environ 75 à environ 84 moles % d'acide isophtalique et inversement d'environ 25 à environ 16 moles % d'acide 5-sodio-sulfoisophtalique, et ayant un constituant de glycol d'environ 45 à environ 60 moles % de glycole diéthylène et inversement d'environ 55 à environ 40 moles % de 1,4-cyclohéxanediméthanol ou éthylène glycol ou des mélanges de ceux-ci, et (B) un matériau de pigmentation dans un rapport pondéral calculé sur le matériau polyester total d'environ 1/1000 à environ 10/1, mélangé avec le matériau polyester.
PCT/US1987/001132 1986-05-20 1987-05-19 Composition d'encre Ceased WO1987007289A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US86499686A 1986-05-20 1986-05-20
US864,996 1986-05-20
US5045287A 1987-05-18 1987-05-18
US050,452 1987-05-18

Publications (1)

Publication Number Publication Date
WO1987007289A1 true WO1987007289A1 (fr) 1987-12-03

Family

ID=26728288

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1987/001132 Ceased WO1987007289A1 (fr) 1986-05-20 1987-05-19 Composition d'encre

Country Status (5)

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EP (1) EP0325581A1 (fr)
JP (1) JP2563419B2 (fr)
AU (1) AU599672B2 (fr)
CA (1) CA1323126C (fr)
WO (1) WO1987007289A1 (fr)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1990004006A1 (fr) * 1988-10-11 1990-04-19 Eastman Kodak Company Composition d'encre contenant un melange d'un polyester, d'un polymere acrylique et d'un polymere vinylique
EP0290359A3 (en) * 1987-05-06 1990-05-02 Eastman Kodak Company (A New Jersey Corporation) Aqueous dispersion blends of polyesters and polyurethane materials and printing inks therefrom
WO1991006607A1 (fr) * 1989-10-24 1991-05-16 Eastman Kodak Company Procede de traitement de pigments
WO1991006608A1 (fr) * 1989-11-06 1991-05-16 Eastman Kodak Company Encres aqueuses avec meilleure resistance a l'adherence de contact
WO1992007912A1 (fr) * 1990-10-31 1992-05-14 Eastman Kodak Company Procede de traitement de pigments avec lit fluidise

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA1322805C (fr) * 1986-06-02 1993-10-05 Charles Herbert Coney Encre a base d'alcool

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3734874A (en) * 1970-02-27 1973-05-22 Eastman Kodak Co Polyesters and polyesteramides containing ether groups and sulfonate groups in the form of a metallic salt
FR2311820A1 (fr) * 1975-05-22 1976-12-17 Eastman Kodak Co Compositions de colorants et de matieres thermoplastiques pouvant etre dispersees dans l'eau et leur application a l'impression par report thermique
US4145469A (en) * 1977-10-11 1979-03-20 Basf Wyandotte Corporation Water-insoluble treated textile and processes therefor

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5710663A (en) * 1980-06-20 1982-01-20 Toyobo Co Ltd Aqueous printing ink

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3734874A (en) * 1970-02-27 1973-05-22 Eastman Kodak Co Polyesters and polyesteramides containing ether groups and sulfonate groups in the form of a metallic salt
FR2311820A1 (fr) * 1975-05-22 1976-12-17 Eastman Kodak Co Compositions de colorants et de matieres thermoplastiques pouvant etre dispersees dans l'eau et leur application a l'impression par report thermique
US4145469A (en) * 1977-10-11 1979-03-20 Basf Wyandotte Corporation Water-insoluble treated textile and processes therefor

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0290359A3 (en) * 1987-05-06 1990-05-02 Eastman Kodak Company (A New Jersey Corporation) Aqueous dispersion blends of polyesters and polyurethane materials and printing inks therefrom
WO1990004006A1 (fr) * 1988-10-11 1990-04-19 Eastman Kodak Company Composition d'encre contenant un melange d'un polyester, d'un polymere acrylique et d'un polymere vinylique
EP0365388A1 (fr) * 1988-10-11 1990-04-25 Eastman Chemical Company Composition d'encre contenant un mélange d'un polyester, d'un polymère acrylique et d'un polymère vinylique
WO1991006607A1 (fr) * 1989-10-24 1991-05-16 Eastman Kodak Company Procede de traitement de pigments
US5055500A (en) * 1989-10-24 1991-10-08 Eastman Kodak Company Process for treating pigments
WO1991006608A1 (fr) * 1989-11-06 1991-05-16 Eastman Kodak Company Encres aqueuses avec meilleure resistance a l'adherence de contact
WO1992007912A1 (fr) * 1990-10-31 1992-05-14 Eastman Kodak Company Procede de traitement de pigments avec lit fluidise
US5143671A (en) * 1990-10-31 1992-09-01 Eastman Kodak Company Fluidized bed process for treating pigments

Also Published As

Publication number Publication date
EP0325581A1 (fr) 1989-08-02
JPH01503071A (ja) 1989-10-19
AU7480587A (en) 1987-12-22
AU599672B2 (en) 1990-07-26
JP2563419B2 (ja) 1996-12-11
CA1323126C (fr) 1993-10-12

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