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WO1996003467A1 - Ink and coating compositions containing a blend of water-dispersible polyester and carboxylic acids - Google Patents

Ink and coating compositions containing a blend of water-dispersible polyester and carboxylic acids Download PDF

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Publication number
WO1996003467A1
WO1996003467A1 PCT/US1995/008830 US9508830W WO9603467A1 WO 1996003467 A1 WO1996003467 A1 WO 1996003467A1 US 9508830 W US9508830 W US 9508830W WO 9603467 A1 WO9603467 A1 WO 9603467A1
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Prior art keywords
pigment
mole
component
acid
weight
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PCT/US1995/008830
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French (fr)
Inventor
Gary Lynn Bond
William Christopher Hickman
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Eastman Chemical Company
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Publication of WO1996003467A1 publication Critical patent/WO1996003467A1/en

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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
    • C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
    • C09D167/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • 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

Definitions

  • the field of the invention relates to blends of water—dispersible polyesters or polyamides and carboxylic acids and their use in ink and coating compositions.
  • Inks containing a water—dissipatable polyester or polyesteramide are well known in the art (see, for example, U.S. Patents 4,704,309, 4,738,785 and 4,340,519). Inks containing such a polymeric material have many desirable properties such as good adhesion to a variety of substrates and a wide viscosity range.
  • the water— dissipatable polyester material as described herein when blended with one or more carboxylic acids will provide to ink compositions good and immediate wet—rub resistance without concomitant substantial sacrifice of the advantages obtained by use of the water—dissipatable polyester material alone.
  • This polymer blend can be used to prepare water—based inks, ink overprints and ink primers, which shall be referred to herein collectively as "ink compositions.”
  • the ink compositions may be in dry form (dry ink compositions) or in wet form (aqueous ink compositions) .
  • the present invention is directed to a polymer blend
  • a polymer blend comprising: (a) a polyester, component (A) , consisting essentially of repeat units from a 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 containing substantially equimolar proportions of acid equivalents (100 mole %) to hydroxy and a ino equivalents (100 mole %) , the polymer comprising the reaction products of reactants selected from the following components (1), (2), (3), and (4), or the ester forming or esteramide forming derivatives thereof, as follows, wherein all stated mole percentages are
  • At least one difunctional reactant selected from a glycol or a mixture of a glycol and diamine having two —NRH groups, the glycol containing two —C(R) 2 —OH groups, and
  • each R in the (3) and (4) reactants is a hydrogen atom or an alkyl group of 1 to
  • water-dissipatable polyester refers to component (A) described hereinabove
  • carboxylic acid refers to component (B) described hereinabove
  • styrene/hydroxyethyl acrylate or styrene/hydroxyethyl methacrylate copolymer refers to component (C) described herein
  • styrene copolymer refers to component (D) described hereinbelow.
  • Polymer blend refers to a blend of component (A) and component (B) , and, optionally, components (C) or (D) .
  • water-dissipatable or “water-dispersible”
  • water-dispersible refers to the activity of a water or aqueous solution on the polymer. The term is specifically intended to cover those situations wherein the solution dissolves and/or disperses the polyester material therein and/or therethrough.
  • the invention provides a polymer blend comprising: (a) a polyester, component (A) , consisting essentially of repeat units from a linear water—dissipatible polymer having carbonyloxy linking groups in the linear molecular structure wherein up to 80% of the linking groups are carbonyla ido 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 containing substantially equimolar proportions of acid equivalents (100 mole %) to hydroxy and amino equivalents (100 mole %) , the polymer comprising the reaction products of reactants selected from the following components (1) , (2) , (3) , and (4) , or the ester forming or esteramide forming derivatives thereof, as follows, wherein all stated mole percentages are based on the total of all acid
  • the polyester contains repeating units of a poly(ethylene glycol) of the formula H-(OCH 2 -CH 2 ) n —OH wherein n is an integer of 2 to 500.
  • n is preferably from between about 2 to about 20.
  • the values of n and the mole percent of poly(ethylene glycol) in the polyester, if used, are adjusted such that the mole percent of poly(ethylene glycol) within the stated range is inversely proportional to the quantity of n within the stated ranges. Thus, when the mole percent is high, the value of n is low.
  • the weight percent (product of mole percent and molecular weight) of the poly(ethylene glycol) is an important consideration because the water dissipatability of the copolyester decreases as the weight percent poly(ethylene glycol) in the copolyester decreases. For example, if the weight of poly(ethylene glycol) is too low, the water dissipatability of the copolyester may be inadequate.
  • the weight percent of poly(ethylene glycol) is preferably adjusted such that it is inversely proportional to the mole percent of the difunctional sulfomonomer because the water dissipatability of the copolyester is a function of both the mole percent sulfomonomer and the weight percent polyethylene glycol.
  • suitable poly(ethylene glycols) include relatively high molecular weight polyethylene glycols, some of which are available commercially under the designation "Carbowax", a product of Union Carbide. Diethylene glycol is also especially suitable.
  • glycols for preparing copolyester may consist of aliphatic, alicyclic and arylalkyl glycols.
  • these glycols include ethylene glycol; propylene glycol; 1,3-propanediol; 2, -dimethyl-2- ' ethylhexane 1,3-diol; 2,2—dimethyl-1,3-propanediol; 2—ethyl-2—butyl-1,3-propanediol; 2—ethyl-2-isobutyl- .1,3—propanediol; 1,3— utanediol, 1,4—butanediol, ⁇ ,5-pentanediol, 1,6-hexanediol, 2,2,4-trimethyl-l,6- hexanediol; thiodiethanol.
  • the dicarboxylie acid component of the polyester are selected from aliphatic dicarboxylic acids, alicyclic dicarboxylic acids, aromatic dicarboxylic acids, or mixtures of two or more of these acids. Examples of such dicarboxylic acids, include succinic; glutaric; adipic; azelaic; sebacic;
  • Terephthalic acid and isophthalic acid are preferred as the carboxylic acid component of the polyester.
  • Cyclohexanedicarboxylic acid is also preferred. It should be understood that use of the corresponding acid anhydrides, esters, and acid chlorides of these acids is included in the term "dicarboxylic acid.”
  • Other suitable acids are disclosed in U.S. Patent 3,779,993.
  • the difunctional sulfomonomer component of the polyester may advantageously be a dicarboxylic acid or an ester thereof containing a metal sulfonate group, a glycol containing a metal sulfonate group or a hydroxy acid containing a metal sulfonate group.
  • the metal ion of the sulfonate salt may be a monovalent metal such as Na+, Li+, K+ and the like.
  • Advantageous difunctional sulfomonomer components are those wherein the sulfonate salt group is attached to an aromatic acid nucleus such as benzene, naphthalene, diphenyl, oxydiphenyl, sulfonyldiphenyl or methylenediphenyl nucleus.
  • Preferred results are obtained through the use of sulfophthalic acid, sulfoterephthalic acid, sulfoisophthalic acid, 4-sulfonaphthalene—2,7—dicarboxylic acid, and their esters, or metallosulfoaryl sulfonate as described in U.S. Patent 3,779,993.
  • the difunctional sulfomonomer component is 5—sodiosulfo— isophthalic acid or its esters
  • the glycol is a mixture of ethylene glycol or 1, —cyclohexanedimethanol with diethylene glycol.
  • the non etallic portion of the nonmetallic sulfonate group is a nitrogen—based cation derived from nitrogen—containing bases which may be aliphatic, cycloaliphatic or aromatic basic compounds that have lonization constants in water at 25°C of 10 —3 to 10—10, preferably 10 —5 to 10—8.
  • nitrogen—containing bases are ammonia, dimethylethanolamine, diethanolamine, triethanolamine, pyridine, morpholine, and piperidine.
  • nitrogen—containing bases and cations derived therefrom are described in U.S. Patent 4,304,901, incorporated herein by reference.
  • the polyester or polyesteramide should contain at least 4 mole % of said monomer based on total acid content, with more than 8 mole % given particularly advantageous results.
  • reactant (4) is employed, that at least about 70 mol percent of reactant (3) is glycol, and that at least about 70 mol percent of all the hydroxy equivalents is present in the glycol. It is also preferred that a substantial portion of reactant (3) is a cycloaliphaticdimethanol, e.g., up to 50 mole percent of a cycloaliphaticdimethanol such as
  • the polyester has an inherent viscosity of from about 0.28 to about 0.38, an acid moiety of from about 75 to about 91, preferably about 75 to about 84, mole % isophthalic acid and conversely from about 25 to about 9, preferably about 25 to about 16, mole % 5-sodiosulfoisophthalic acid, and a glycol moiety of from about 45 to about 80, preferably about 45 to about 60, mole % diethylene glycol and conversely from about 55 to about 20, preferably about 55 to 40, mole % 1,4—cyclohexanedimethanol or ethylene glycol or mixtures thereof.
  • the polyester comprises an acid moiety comprising from about 88 to about 93 mole % isophthalic acid and conversely from about 12 to about 7 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.
  • the polyester comprises (a) component (A) consisting essentially of a linear, water-dissipatable polyester having an inherent viscosity of at least about 0.1 as measured in a 60/40 parts by weight solution of phenol tetrachloroethane at 25*C and at a concentration of 0.5 gram of polyester in 100 ml of solvent, the polyester containing substantially equimolar proportions of acid moiety repeating units (100 mole %) to hydroxy moiety repeating units (100 mole %) , the polyester comprising repeating units of components (1) , (2), (3) and (4), as follows wherein all stated mole percentages are based on the total of all acid and hydroxy moiety repeating units being equal to 200 mole %: (1) about 90 to about 97 mole % isophthalic acid. (2) about 3 to about 10 mole % 5—sulfoiso- phthalic acid,
  • component (B) comprising a carboxylic acid.
  • component (B) comprising a carboxylic acid.
  • component (B) comprising a carboxylic acid.
  • component (B) comprising a carboxylic acid.
  • a monovalent alkali metal ion is used, the resulting polyesters are less readily dissipated by cold water and more readily dissipated by hot water.
  • a divalent or a trivalent metal ion is used the resulting polyesters are not ordinarily easily dissipated by cold water but are more readily dissipated in hot water.
  • the difunctional monomer component may also be referred to the difunctional sulfomonomer and is further described hereinbelow.
  • the inherent viscosities (I.V.) of the particular water-dissipatable polymeric materials useful herein range from about 0.1 to about 1.0 determined according to ASTM D2857—70 procedure, in a Wagner Visco eter 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 at 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
  • additives can be emulsion stabilizers, surfactants, dispersants, antimicrobials or biocides, pH stabilizers, and the like.
  • the additives described herein as suitable for use in the ink compositions are also suitable for use with the mixture of acrylic polymer and aqueous solution.
  • the polyester material can be dispersed in water or aqueous solution using the techniques described herein or known in the art and then blended with an aqueous dispersion or emulsion of acrylic polymer prepared by similar techniques, or blended with an aqueous emulsion or dispersion of acrylic polymer in a form commercially available.
  • the following procedure can be used for dispersing the polyester in water:
  • the water should be preheated to about 180°F (82.22°C) to about 200°F (93.33°C) and the polyester in pellet form is added rapidly to the vortex under high shear stirring.
  • a Cowles Dissolver, Waring Blender, or similar equipment may be used. Once the water is heated to the desired temperature, additional heat input may not be required.
  • dispersion of the pellets should be complete within 15 to 30 minutes stirring. Continued agitation with cooling may be desirable to prevent thickening at the surface due to water evaporation. Viscosities of the dispersions remain low up to polyester levels of 25 percent to 34 percent and viscosities increase sharply above these levels. Viscosities of the dispersions will be influenced by the degree of polymer dispersion obtained which is affected by the dispersing temperature, shear, and time.
  • Dispersibility of the polyester can be improved when the levels of sodiosulfoisophthalic acid are low by either the addition of solvents such as n—propyl alcohol, isopropyl alcohol, propylene glycol, ethylene glycol monobutyl ether, or ethylene glycol or by the addition of hydantoin compounds as described herein.
  • solvents such as n—propyl alcohol, isopropyl alcohol, propylene glycol, ethylene glycol monobutyl ether, or ethylene glycol
  • the ink compositions of this invention can be for any of the typical ink applications such as flexographic, gravure, letterpress, ink—jet, or screen—process printing applications.
  • the ink compositions of the present invention have excellent adhesion to a wide variety of substrates including plastic films such as polyester, polyethylene or polypropylene; aluminum foil; glass; and paper.
  • the ink compositions of the present invention should have a pH of about 8.2 or lower; preferred is a pH of about 7 to 8. If the pH is higher than about 8.2, there is a danger of the polymer(s) hydrolyzing which may result in gelling of the system.
  • the flexographic and gravure inks of this invention contain, in addition to the base polymers and additives as described above, a minor amount of a carboxylic acid to blend with the polyester of the general formula XCR 1 R YC00H wherein Y represents a chain of from 0 to 4 carbon atoms which may be substituted with hydrogen, lower alkyl, hydroxyl or carboxyl groups wherein R 1 and R 2 are selected from the group consisting of hydrogen and alkyl having from about 1 to about 10 carbon atoms and wherein X is selected from the group consisting of hydrogen, lower alkyl having from about l to about 10 carbon atoms, hydroxyl and one or more carboxyl groups.
  • X is H0-, and either R 1 or R 2 or both may be hydrogen or lower alkyl.
  • the fragment XCR ⁇ -R 2 constitutes a carboxyl group, HOOC—.
  • Y contains either one or no carbon atoms. It is also preferred that the carbon atom attached to the X is substituted with either or both of an -OH of —COOH group.
  • acids of this group are, for example, oxalic, tartaric, glycolic, phthalic, (ethylenedinitrilo) tetraacetic acid, glutaric, malic, and citric acids.
  • Preferred acids of this group are those in which Y contains no carbon atoms or in which it contains one carbon atom optionally substituted with H0- or HOOC- or both.
  • Citric acid a member of this latter class, is especially preferred. *
  • carboxylic acids which are within the scope of the invention .are c—phthalic and o—hexahydrophthalic acids and such well—known chelating agents as (ethylenedinitrilo) tetraacetic acid. (Ethylene dinitrilo) tetracetic acid is preferred.
  • carboxylic acid to be blended with the polyester be water—soluble.
  • Water— solubility means “the extent to which a substance mixes with water to produce a homogenous solution”.
  • Component (B) is typically blended with the final product of any blends or aqueous dispersions made using component (A) and optional component (C) or (D) .
  • component (C) is also useful within the context of this invention.
  • component (C) refers to a polymer having repeat units from
  • a preferred aqueous dispersion of the invention contains about 95—60% of said component (C) and about 5—40% of said component (A) , both said percentages being based on the combined weight of (A) and (C) .
  • Component (C) provides high solids aqueous polymer compositions. However, the preferred concentrations are 90-75% component (C) and 10—25% component (A) .
  • a blend of the invention would typically comprise component (A) , component (B) and component (C) as described herein.
  • the polyester, component (A) has repeat units from isophthalic acid, sodiosulfoisc— phthalic acid, diethylene glycol, and another glycol selected from at least one of ethylene glycol and 1,4—cyclohexanedimethanol, and another polymer con ⁇ taining at least 20% by weight of repeat units from styrene or one or more derivatives of styrene, and 15% by weight of hydroxyalkyl (meth)acrylate.
  • component (A) has a solids content of about 5 to 40 weight %, preferably about 10 to about 30 weight %, based on dry solids. It is preferred that the aqueous dispersion has a solids content of about 25 to about 45 weight % based on the total weight of said dispersion.
  • the styrene or styrene derivative(s) and the hydroxyalkyl (meth)acrylate of component (C) may be mixed with additional monomers which are copolymerizable with the styrene or styrene derivatives, hydroxyalkyl (meth)acrylate.
  • the comonomers may be present in amounts from 0 to about 60 weight percent.
  • Polymer blends in which component (C) contains from about 35 to about 100% of a combination of the weight percents of styrene or styrene derivatives and hydroxyalkyl (meth)acrylate as described herein are preferred.
  • the preferred total amount of comonomers is approximately about 0—40 weight percent.
  • esters are acrylic and methacrylic esters.
  • Acrylic and methacrylic acid esters having from 1 to about 20 carbon atoms in the alcohol moiety are commercially available or can be easily prepared by known esterification processes.
  • Preferred esters are the methyl, ethyl, butyl, 2—ethylhexyl and lauryl esters.
  • the acrylic and methacrylic acid esters may contain additional functional groups of the alcohol moiety, such as for example, hydroxyl, amine, halogen, ester, carboxylic acid, amide, nitrile and alkyl groups.
  • Functionalized monomers such as blocked isocyanate acrylates and ethacrylates may also be used to provide crosslinking sites for the preparation of curable systems.
  • C 1-4 diesters of maleic and fumaric acids e.g., dibutyl maleate
  • styrene or styrene derivatives may be used in copolymers with styrene or styrene derivatives and hydroxyalkyl (meth)acrylate or hydroxyalkylacrylate as described herein.
  • comonomers include acrylonitrile, acrylic acid, maleic anhydride, fumaric acid, methacrylic acid, acetoacetoxyethyl methacrylate and the corresponding acrylate, and halogenated vinyl monomers such as vinyl chloride and vinylidene chloride. These monomers may be used individually or may be used as mixtures to provide the desired properties. The preferred ratios of the various monomers can be readily determined by one skilled in the art and are dependent upon the particular application and desired properties of the water-dispersible polyester blend.
  • component (C) comprise repeat units from 0 to about 80 weight % of one or more comonomers selected from the group consisting of ethylene, acrylic acid, methacrylic acid, acrylic and methacrylic acid esters, acryla ides, unsaturated dicarboxylic acid diesters, vinyl chloride and maleic anhydride.
  • component (C) comprise repeat units from at least 20% by weight of one or more comonomers selected from styrene, methylmethacrylate, ethylhexylacrylate and butylacrylate.
  • Component (D) of the invention comprises about 25 to 95 weight % of a styrene copolymer comprising: (a) about 30 to 100 weight % of repeating units from at least one styrene compound.
  • Component (A) is also present at about 5 to about 75 weight %. It is preferred that the styrene polymer of component (D) of the invention also comprise (b) up to about 70 weight % of repeating units from at least one (meth)acrylate compound.
  • component (A) is present in a preferred blend of the invention in an amount of about 15 to about 50 weight %, component (D) is present in an amount of about 50 to about 98 weight %; and component (D) comprises about 50 to about 100 weight % of component (D) (a) and 0 to about 50 weight % of component (D) (b) .
  • a preferred polymer blend of the invention is wherein component (A) is present in an amount of about 20 to about 40 weight %, component (D) is present in an amount of about 60 to about 80 weight %; and component (D) comprises about 70 to 100 weight % of component (D) (a) and 0 to about 30 weight % of component (D) (b) .
  • component (A) is present in a preferred blend of the invention in an amount of about 30 to about 99.5 weight %, preferably about 20 to about 40 weight % and component (B) is present in an amount of about 0.1 to about 20 weight %, preferably about 0.5 to about 15 weight %.
  • the styrene monomer useful for component (D) herein is preferably of the structure wherein R 3 is H or methyl, R 4 is a lower alkyl group of
  • m 1 to 6 carbon atoms
  • m is an integer of 0 to 2.
  • R 4 is methyl.
  • the most preferable styrene monomers for component (D) are styrene, ⁇ —methyl styrene, 4—methyl styrene, 3—methyl styrene, t—butyl styrene, and mixtures thereof.
  • the meth(acrylate) monomer for component (D) useful herein preferably is of the structure
  • R 3 is H or an alkyl group of 1 to 10 carbon atoms, optionally substituted with one or two sub— stituents selected from the group consisting of C j —C 6 alkoxy, hydroxy, epoxy, acetoacetoxy and halogen, and R 1 has the same meaning as previously defined.
  • the (meth)acrylate monomer for component (D) is selected from the group consisting of butyl acrylate, ethyl acrylate, propyl acrylate, 2—ethylhexyl acrylate, methyl methacrylate, hydroxyethyl methacrylate, glycidyl (meth)acrylate, acetoacetoxyethyl methacrylate, and mixtures thereof.
  • component (D) it is preferred that the monomers are polymerized in the presence of the sulfonate—group containing polymer (i.e., the polyester or polyesteramide).
  • the sulfonate—group containing polymer i.e., the polyester or polyesteramide.
  • compositions of the present invention are prepared in aqueous dispersions.
  • the monomers are generally added to an aqueous dispersion of the water- dispersible polyester and polymerized by free radical initiation in conventional emulsion or suspension polymerization processes.
  • the preferred ratio of polyester to monomer in the dispersion prior to polymerization will vary widely and depends on the intended application.
  • the polymerization can be initiated by a water- soluble or water—dispersible free radical initiator known in the art such as sodium persulfate, or by an oil—soluble initiator such as benzoyl peroxide.
  • a water- soluble or water—dispersible free radical initiator known in the art such as sodium persulfate, or by an oil—soluble initiator such as benzoyl peroxide.
  • Other useful initiators include redox initiators such as sodium or potassium persulfate, ammonium persulfate, sodium or potassium roetabisulfite, and sodium or potassium formaldehyde sulfoxylate/Fe/hydrogen peroxide.
  • the concentration of the initiator will generally range from about 0.01% to about 0.5% based on total reaction weight.
  • a typical temperature range for the polymeriza ⁇ tion reaction is about 20 ⁇ C to about 90 ⁇ C with about 50 ⁇ C to about 80°C being preferred.
  • the sulfonate-group containing polyesters which are used in the present invention typically become very viscous at concentrations above the 34 percent total solids.
  • the reaction typically is begun with a polyester or polyesteramide dispersion that is about 30 percent total solids or less.
  • the water- dispersible polyester blend dispersions are prepared at final total solids levels of up to about 20 percent to 60 percent for blends containing components (A) , (B) , and (D) .
  • a total solids content of about 10 percent to 50 percent for blends containing components (A) , (B) , and (D) is preferred.
  • the water—dispersible polyester blend dispersions are prepared at final total solids levels of up to about 10 percent to about 50 percent.
  • a total solids level of about 10 percent to about 25 percent is preferred.
  • the increase in solids level is achieved during polymerization by controlling the amount of water, if any, which is added along with the monomer. By decreasing the amount of water added during the polymerization, increased total solids contents up to about 30 percent to 55 percent, preferably 35 percent to 45 percent, are possible. This increase in solids level can offer significant benefits for the use of the water— dispersible polyesters of the present invention.
  • the copolymerization of the styrene and acrylate monomer(s) in the presence of water—dispersible polyester for component (C) may be conducted batchwise, semi—batch or in a continuous manner.
  • the sulfonate group- containing polyester is prepared, generally by melt phase polymerization techniques which are well known in the art.
  • the polymers are extended into rods and chopped into pellets. These pellets can later be dispersed in hot blend of water with an organic cosolvent if desired.
  • a mixture of one or more monomers and the polymerization initiators may then be added to the aqueous dispersion of the polyester and polymerization initiated to produce an aqueous dispersion.
  • the polymerizations are generally conducted at temperatures of about 70 ⁇ C to about 90°C.
  • a small amount of initiator is added toward the end of the copolymeriza ⁇ tion in order to react as much of the styrene and hydroxyethyl (meth)acrylate or hydroxypropylacrylate monomers as possible.
  • the aqueous dispersion of component (C) can be prepared with total solids contents from about 10 percent to about 55 percen .
  • component (C) In another mode of operation for the preparation of component (C) , some of the aqueous polyester dispersion is added to the reaction vessel while the vinyl monomers and initiator are dispersed in another portion of the polyester dispersion. After heating the reaction mixture to the desired temperature, the portion containing polyester, vinyl monomers and initiator is gradually added with stirring. The translucent latexes obtained have virtually no coagulum.
  • the total solids content of the aqueous dispersion is controlled by the relative amounts of polymers which are used in the polymerization reaction and by the amount of water added during polymerization.
  • dispersions of sulfonate group-containing polymers can practically be prepared only at total solids contents up to about 34 percent. Above 34 percent, these dispersions become highly viscous and difficult to process. Higher total solids contents can be obtained by increasing the amount of monomer and decreasing the amount of polyester which are used in the polymerization reaction.
  • component (A) and component (C) can be chosen by one skilled in the art depending on the specific monomers, the desired total solids content and the application for which the aqueous dispersion is intended.
  • Aqueous dispersions for component (C) can be formulated by those skilled in the art so that excellent wet block resistance in overprint varnish applications as well as excellent printability, adhesion, and water- resistance in ink applications for paper, film and foil results.
  • these properties are dependent on latex composition, particularly on the composition of the styrene/(meth)acrylate co— or terpoly er.
  • the particle size of these aqueous polymer blends, component (C) generally range from ⁇ 300 nm, and more preferably from about 40 nm to about 200 nm. It is believed that the hydroxyethyl (meth)acrylate or hydroxypropyl acrylate monomers are responsible for providing polymer blends with these small particle sizes.
  • the hydroxyethyl (meth)acrylate or hydroxypropyl acrylate serves as a reactive cosolvent which lowers the interfacial tension between the monomer droplets and the aqueous phase, thereby lowering the monomer droplet size and consequently reducing the final particle size.
  • the hydrophilic hydroxyethyl (meth)- acrylate or hydroxypropyl acrylate may also react with the hydrophobic styrene and/or (meth)acrylate monomer units to form oligomeric surfactant molecules in situ.
  • the dispersions or blends according to this invention may be used by applying them as a coating to a substrate such as paper followed by drying to leave a residue of solids in the form of a coating.
  • a second substrate can be applied prior to drying to form a bond between the substrates.
  • a method of preparing an aqueous polymer dispersion which comprises forming an aqueous dispersion having the components of polyester (A) and component (C) as described herein and polymerizing components b(l) , b(2) and b(3) of component (C) in the aqueous dispersion, to thereby obtain an aqueous dispersion of a blend of polymers with a total solids content of up to about 60%.
  • component (B) of the invention is present in an amount of about 0.1% to about 20% by weight, preferably 0.5% to 15% by weight, and that components (A) , (C) or (D) are present in an amount of about 99.5 to about 25% by weight, that about 0.00% to about 45% by weight of a colorant is present, that about 0% to 15.0% by weight of an organic, polar solvent, preferably about 0 to about 10% by weight, such as 1- or 2-propanol, ethanol, 2-butoxyethanol, 2—ethoxyethanol is present, and that water satisfies any remaining percentage by weight so that the total percentage by weight of all of the components is equal to 100%.
  • an organic, polar solvent preferably about 0 to about 10% by weight, such as 1- or 2-propanol, ethanol, 2-butoxyethanol, 2—ethoxyethanol is present, and that water satisfies any remaining percentage by weight so that the total percentage by weight of all of the components is equal to 100%.
  • the ink is a finished ink, it is preferred that at least about 0.5 weight percent of colorant is present. More typically, in inks, .at least about 15 weight percent of colorant is present. ' If the ink composition contains an organic pigment, typically such an organic pigment is present in an amount of about
  • the ink composition contains an inorganic pigment, typically such inorganic pigment is present in an amount of about 30 weight percent or less of the total composi- tion. However, for some pigments such as titanium dioxide, the pigment can be present in an amount as high as about 60 percent.
  • additives such as waxes, clays, surfactants, defoamers, viscosity modifiers, etc.
  • the ink compositions can optionally contain up to about 20 weight percent, preferably up to about 10 weight percent, more preferably up to about 5 weight percent, of one or more such additives.
  • Such additives include waxes such as Jonwax 26, Jonwax 120 (available from S. C.
  • Vanwax 35 available from Vantage, Garfield, New Jersey 07026) ; surfactants such as Surfynol 104 and Surfynol 440 (available from Air Products and Chemicals, Allentown, Pennsylvania 18105) ; modifiers (for example, defoamers) such as WBT—409, Resolv (available from Vantage) , Carbowet 990 (available from Vantage) , Aerosol OT—70 (available from Mclntyre, Chicago, Illinois 60632) , Foamaster 111 (available from Henkel Corporation, Morristown, New Jersey 07960) ; alcohols such as n—propyl alcohol, isopropyl alcohol, propylene glycol, ethylene glycol monobutyl ether, or ethylene glycol; biocides; pH stabilizers; dispersants; thickeners such as Acrysol RM—825 (available from Rohm & Haas, Philadelphia,
  • the ink compositions of the present invention should have a pH of about 8.2 or lower; preferred is a pH of about 3 to 7. If the pH is higher than about 8.2, there is a possibility of the polymer(s) hydrolyzing which may result in gelling of the system.
  • the ink compositions of this invention can be for any of the typical ink applications such as flexo— graphic, gravure, letterpress, ink-jet, or screen- process printing applications.
  • the ink compositions of the present invention have excellent adhesion to a wide variety of substrates including plastic films such as polyester, polyethylene or polypropylene; aluminum foil; glass; and paper.
  • the inks, overprints, and primers of this invention can be prepared, for example, as disclosed in U.S. Patent 4,148,779, which is incorporated herein by reference in its entirety.
  • the present invention is not limited to any type of dye, pigment, filler, or the like, all of which are hereinafter included in the term "colorant,” and can accommodate any colorant which can be dispersed, milled, mixed, blended or dissolved in any manner in either the polymer blend, water or aqueous polymer system.
  • a feed stream is fed continuously to a two—stage stainless steel reactor zone such that the composition of the stream is: 45.3% Component A 15.7% Component B 38.7% Component C 0.2% Component D 0.1% Component E
  • A is isophthalic acid
  • B is a slurry of the diethylene glycol diester of 5—sodiosulfoisophthalie acid at 46.5 weight percent in diethylene glycol
  • C is 1,4—cyclohexanedimethanol
  • D is a solution of titanium tetraisopropoxide in n—butanol at 2.54 weight percent titanium
  • E is anhydrous sodium acetate.
  • the feed rate of the stream and the size of the reactor are such that the stream is under nitrogen at atmospheric pressure at 255°C for one hour and under nitrogen at less than 4,000 microns pressure at 285°C for 0.5 hour.
  • the product is extruded from the stage II reactor into a chilled water bath and mechanically chopped into pellets. The pellets are then dried in a rotary cone dryer at 65"C until less than 1% moisture remains.
  • Polymer B was made using similar reaction conditions but varying the ratio of the components.
  • compositions for the polyester polymers A and B are as follows P Poollvvmmeerr A A P Pjolymer B 9 911 8 822 mole % isophthalic acid
  • Tekta er 38LV Thiadiazine biocide from Calgon Co.
  • Wax Mixed polyethylene S—232 wax from Shamrock
  • Alcogum L1228 Ammonium acrylate copolymer which is a viscosity modifier from Alco Chemical
  • Surfynol 104PA acetylenic diol surfactant from Air
  • the polymer dispersions and millbase are prepared as follows:
  • Polyester Polymer A Dispersion with 2% n-propyl alcohol: 5 67.9% Deionized water
  • Draw-downs are made with a #0 RK rod from Paul N. Gardner Company, Inc. , Pampano Beach FL 33060 on a polyethylene coated board using an RK laboratory coater.
  • the experimental ink and the control ink are drawn down side by side.
  • the coated board is allowed to dry for approximately 20 seconds while the coating rod is removed and rinsed.
  • the coated polyethylene board is then placed in a 100°C oven for 3 seconds.
  • the coated board is then removed and allowed to cool at room temperature.
  • a stop watch is used to mark the time the coated board was removed from the oven. During the cooling period, the polyethylene coated board is cut into two-samples that have been identified on the back for testing.
  • the two samples of coated board are placed under the demineralized water tap for approximately 5 seconds to thoroughly wet them, then the samples are rubbed face to face against each other with 20 back and forth strokes between the thumb and index finger.
  • the experimental sample is rubbed against the experimental and the control against the control.
  • a paper tissue is used to remove the excess water from the samples.
  • the control blue flexo ink has a rating of 2 and the experimental a rating of 5.
  • citric acid is replaced by each of the following acids: oxalic acid; tartaric acid; glycolic acid; phthalic acid; and (ethylenedinitrilo) tetraacetic acid.
  • the polymer dispersions were prepared as described in Example 1. Polymer dispersions and pigment millbase were formulated as follows: Polyester Polymer A Dispersion with 10% n-propyl alcohol 59.9% Deionized water 30.0% Polyester polymer A pellets 10.0% n—propyl alcohol 0.1% Tektamer 38LV Polyester Polymer B Dispersion with 0% n—propyl alcohol 33.0% Polyester polymer B pellets 66.7% deionized water 0.3% Tektamer 38LV Red Millbase 33.0% Polyester Polymer B Dispersion with 0% n-propyl alcohol 26.8% deionized water 40.0% C. I.
  • EXAMPLE 3 Yellow Flexograohic Ink Yellow millbase is prepared as follows:
  • the ink is evaluated in the same way as in the preceding examples.
  • the control ink has a wet rub resistance of 1;
  • the experimental ink which contains 5% of a 10% solution of citric acid, has a rating of 3.
  • a gravure ink formulation for metallized paper was prepared as follows:
  • the inks are evaluated by a standard water drop test as follows: 1. The inks are applied to the foil laminated paper using an applicator bar creating a draw down. 2. The draw down is then placed in an oven at 100°C for five seconds to simulate an oven on a printing press.

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Abstract

This invention relates to a polymer blend comprising: a) component (A) consisting essentially of a linear, water-dissipatable polyester having an inherent viscosity of at least about 0.1 as measured in a 60/40 parts by weight solution of phenol/tetrachloroethane at 25 °C and at a concentration of 0.5 gram of polyester in 100 ml of solvent, the polyester containing substantially equimolar proportions of acid moiety repeating units (100 mole %) to hydroxy moiety repeating units (100 mole %), the polyester comprising repeating units of components (1, 2, 3 and 4), as follows wherein all stated mole percentages are based on the total of all acid and hydroxy moiety repeating units being equal to 200 mole %: 1) about 90 to about 97 mole % isophthalic acid, 2) about 3 to about 10 mole % 5-sulfoisophthalic acid, 3) about 70 to about 85 mole % 1,4-cyclohexanedimethanol, and 4) about 15 to about 30 mole % diethylene glycol, and b) component (B) comprising a carboxylic acid.

Description

INK AND COATING COMPOSITIONS CONTAINING A BLEND OF WATER-DISPE SIBLE POLYESTER AND CARBOXYLIC ACIDS
Field of the Invention
The field of the invention relates to blends of water—dispersible polyesters or polyamides and carboxylic acids and their use in ink and coating compositions.
Background of the Invention Inks containing a water—dissipatable polyester or polyesteramide are well known in the art (see, for example, U.S. Patents 4,704,309, 4,738,785 and 4,340,519). Inks containing such a polymeric material have many desirable properties such as good adhesion to a variety of substrates and a wide viscosity range.
Although existing inks are satisfactory with regard to wet—rub fastness after adequate drying, either at ambient temperature or at elevated temperatures, the immediate wet—rub resistance is not good enough to permit shipment of the printed material to the packaging customer as soon as it comes off of the press. It would be highly desirable to have a material that imparts good immediate wet—rub resistance so that shipment of the printed material to the packaging customer can occur as soon as it comes off the press while maintaining the other advantages associated with the use of the water— dissipatable polyester. Summary of the Invention
It has now been discovered that the water— dissipatable polyester material as described herein, when blended with one or more carboxylic acids will provide to ink compositions good and immediate wet—rub resistance without concomitant substantial sacrifice of the advantages obtained by use of the water—dissipatable polyester material alone. This polymer blend can be used to prepare water—based inks, ink overprints and ink primers, which shall be referred to herein collectively as "ink compositions." The ink compositions may be in dry form (dry ink compositions) or in wet form (aqueous ink compositions) . More specifically, the present invention is directed to a polymer blend comprising: (a) a polyester, component (A) , consisting essentially of repeat units from a 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 containing substantially equimolar proportions of acid equivalents (100 mole %) to hydroxy and a ino equivalents (100 mole %) , the polymer comprising the reaction products of reactants selected from the following components (1), (2), (3), and (4), or the ester forming or esteramide forming derivatives thereof, as follows, wherein all stated mole percentages are based on the total of all acid, hydroxyl and amino equivalents being equal to 200 mole %: (1) at least one difunctional dicarboxylic acid;
(2) from about 2 to about 25 mole % of at least one difunctional sulfomono er containing at least one metallic sulfonate group or nitrogen—containing non— etallic sulfonate group attached to an aromatic or cycloaliphatic nucleus wherein the functional groups are hydroxy, carboxy1 or amino;
(3) at least one difunctional reactant selected from a glycol or a mixture of a glycol and diamine having two —NRH groups, the glycol containing two —C(R)2—OH groups, and
(4) from none to about 40 mole % of difunctional reactant selected from hydroxycarboxylic acids having one
—C(R)2—OH group, aminocarboxylic acids having one —NRH group, and amino—alcohols having one —C(R)2-OH group and one —NRH group, or mixtures of said difunctional reactants; wherein each R in the (3) and (4) reactants is a hydrogen atom or an alkyl group of 1 to
4 carbons; and (b) a carboxylic acid, component (B) . Advantages of this invention for inks and coatings include good water resistance and wet-rub fastness or resistance.
Detailed Description of the Preferred Embodiments As used herein, the term "water-dissipatable polyester", "water-dissipatable polyester material", "polyester material", or "polyester" refers to component (A) described hereinabove, "carboxylic acid" refers to component (B) described hereinabove, "styrene/hydroxyethyl acrylate or styrene/hydroxyethyl methacrylate copolymer" refers to component (C) described herein, and "styrene copolymer" refers to component (D) described hereinbelow. "Polymer blend" refers to a blend of component (A) and component (B) , and, optionally, components (C) or (D) .
Whenever the term "water-dissipatable" or "water-dispersible" is used in this description, it will be understood to refer to the activity of a water or aqueous solution on the polymer. The term is specifically intended to cover those situations wherein the solution dissolves and/or disperses the polyester material therein and/or therethrough.
The invention provides a polymer blend comprising: (a) a polyester, component (A) , consisting essentially of repeat units from a linear water—dissipatible polymer having carbonyloxy linking groups in the linear molecular structure wherein up to 80% of the linking groups are carbonyla ido 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 containing substantially equimolar proportions of acid equivalents (100 mole %) to hydroxy and amino equivalents (100 mole %) , the polymer comprising the reaction products of reactants selected from the following components (1) , (2) , (3) , and (4) , or the ester forming or esteramide forming derivatives thereof, as follows, wherein all stated mole percentages are based on the total of all acid, hydroxy1 and amino equivalents being equal to 200 mole %: (1) at least one difunctional dicarboxylic acid; (2) from about 2 to about 25 mole % of at least one difunctional sulfomono er containing at least one metallic sulfonate group or nitrogen—contained non—metallic sulfonate group attached to an aromatic or cycloaliphatic nucleus wherein the functional groups are hydroxy, carboxy1 or amino; (3) at least one difunctional reactant selected from a glycol or a mixture of a glycol and diamine having two —NRH groups, the glycol containing two —C(R)2—OH groups, and (4) from none to about 40 mole % of difunctional reactant selected from hydroxycarboxylic acids having one —C(R)2—OH group, aminocarboxylic acids having one —NRH group, and amino-alcohols having one —C(R)2—OH group and one —NRH group, or mixtures of said difunctional reactants; wherein each R in the (3) and (4) reactants is a hydrogen atom or an alkyl group of 1 to 4 carbons; and
(b) a car oxylie acid, component (B) . In the preferred form of the present inventfon, the polyester contains repeating units of a poly(ethylene glycol) of the formula H-(OCH2-CH2)n—OH wherein n is an integer of 2 to 500. The value of n is preferably from between about 2 to about 20. The values of n and the mole percent of poly(ethylene glycol) in the polyester, if used, are adjusted such that the mole percent of poly(ethylene glycol) within the stated range is inversely proportional to the quantity of n within the stated ranges. Thus, when the mole percent is high, the value of n is low. On the other hand, if the mole percent is low, the value of n is high. It is apparent, therefore, that the weight percent (product of mole percent and molecular weight) of the poly(ethylene glycol) is an important consideration because the water dissipatability of the copolyester decreases as the weight percent poly(ethylene glycol) in the copolyester decreases. For example, if the weight of poly(ethylene glycol) is too low, the water dissipatability of the copolyester may be inadequate. Furthermore, the weight percent of poly(ethylene glycol) is preferably adjusted such that it is inversely proportional to the mole percent of the difunctional sulfomonomer because the water dissipatability of the copolyester is a function of both the mole percent sulfomonomer and the weight percent polyethylene glycol.
Examples of suitable poly(ethylene glycols) include relatively high molecular weight polyethylene glycols, some of which are available commercially under the designation "Carbowax", a product of Union Carbide. Diethylene glycol is also especially suitable.
Other useful glycols for preparing copolyester may consist of aliphatic, alicyclic and arylalkyl glycols. Examples of these glycols include ethylene glycol; propylene glycol; 1,3-propanediol; 2, -dimethyl-2- ' ethylhexane 1,3-diol; 2,2—dimethyl-1,3-propanediol; 2—ethyl-2—butyl-1,3-propanediol; 2—ethyl-2-isobutyl- .1,3—propanediol; 1,3— utanediol, 1,4—butanediol, ι,5-pentanediol, 1,6-hexanediol, 2,2,4-trimethyl-l,6- hexanediol; thiodiethanol. l,2—cyclohexanedimethanol, 1,3-cyclohexandimethanol; l,4—cyclohexanedimethanol; 2,2,4,4—tetra ethyl—1,3—cyclobutanediol; and p-xylylenediol. The dicarboxylie acid component of the polyester are selected from aliphatic dicarboxylic acids, alicyclic dicarboxylic acids, aromatic dicarboxylic acids, or mixtures of two or more of these acids. Examples of such dicarboxylic acids, include succinic; glutaric; adipic; azelaic; sebacic;
1,4—cyclohexanedicarboxylic; phthalic; terephthalic; naphthalenedicarboxylic; and isophthalic acid. Terephthalic acid and isophthalic acid are preferred as the carboxylic acid component of the polyester. Cyclohexanedicarboxylic acid is also preferred. It should be understood that use of the corresponding acid anhydrides, esters, and acid chlorides of these acids is included in the term "dicarboxylic acid." Other suitable acids are disclosed in U.S. Patent 3,779,993.
The difunctional sulfomonomer component of the polyester may advantageously be a dicarboxylic acid or an ester thereof containing a metal sulfonate group, a glycol containing a metal sulfonate group or a hydroxy acid containing a metal sulfonate group. The metal ion of the sulfonate salt may be a monovalent metal such as Na+, Li+, K+ and the like.
Advantageous difunctional sulfomonomer components are those wherein the sulfonate salt group is attached to an aromatic acid nucleus such as benzene, naphthalene, diphenyl, oxydiphenyl, sulfonyldiphenyl or methylenediphenyl nucleus. Preferred results are obtained through the use of sulfophthalic acid, sulfoterephthalic acid, sulfoisophthalic acid, 4-sulfonaphthalene—2,7—dicarboxylic acid, and their esters, or metallosulfoaryl sulfonate as described in U.S. Patent 3,779,993.
Particularly superior results are achieved when the difunctional sulfomonomer component is 5—sodiosulfo— isophthalic acid or its esters, and the glycol is a mixture of ethylene glycol or 1, —cyclohexanedimethanol with diethylene glycol.
The non etallic portion of the nonmetallic sulfonate group is a nitrogen—based cation derived from nitrogen—containing bases which may be aliphatic, cycloaliphatic or aromatic basic compounds that have lonization constants in water at 25°C of 10 —3 to 10—10, preferably 10 —5 to 10—8. Especially preferred nitrogen containing bases are ammonia, dimethylethanolamine, diethanolamine, triethanolamine, pyridine, morpholine, and piperidine. Such nitrogen—containing bases and cations derived therefrom are described in U.S. Patent 4,304,901, incorporated herein by reference.
When the sulfonate—containing difunctional monomer is an acid or its ester, the polyester or polyesteramide should contain at least 4 mole % of said monomer based on total acid content, with more than 8 mole % given particularly advantageous results.
In the water-dissipatable polymer it is preferred that very minor, e.g., less than about 10 mol percent based on all reactants, of reactant (4) is employed, that at least about 70 mol percent of reactant (3) is glycol, and that at least about 70 mol percent of all the hydroxy equivalents is present in the glycol. It is also preferred that a substantial portion of reactant (3) is a cycloaliphaticdimethanol, e.g., up to 50 mole percent of a cycloaliphaticdimethanol such as
1,4—cyclohexanedimethanol.
More preferably the polyester has an inherent viscosity of from about 0.28 to about 0.38, an acid moiety of from about 75 to about 91, preferably about 75 to about 84, mole % isophthalic acid and conversely from about 25 to about 9, preferably about 25 to about 16, mole % 5-sodiosulfoisophthalic acid, and a glycol moiety of from about 45 to about 80, preferably about 45 to about 60, mole % diethylene glycol and conversely from about 55 to about 20, preferably about 55 to 40, mole % 1,4—cyclohexanedimethanol or ethylene glycol or mixtures thereof. Even more preferably, the polyester comprises an acid moiety comprising from about 88 to about 93 mole % isophthalic acid and conversely from about 12 to about 7 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.
Even more preferably, the polyester comprises (a) component (A) consisting essentially of a linear, water-dissipatable polyester having an inherent viscosity of at least about 0.1 as measured in a 60/40 parts by weight solution of phenol tetrachloroethane at 25*C and at a concentration of 0.5 gram of polyester in 100 ml of solvent, the polyester containing substantially equimolar proportions of acid moiety repeating units (100 mole %) to hydroxy moiety repeating units (100 mole %) , the polyester comprising repeating units of components (1) , (2), (3) and (4), as follows wherein all stated mole percentages are based on the total of all acid and hydroxy moiety repeating units being equal to 200 mole %: (1) about 90 to about 97 mole % isophthalic acid. (2) about 3 to about 10 mole % 5—sulfoiso- phthalic acid,
(3) about 70 to about 85 mole % 1,4-cyclohexanedimethanol, and (4) about 15 to about 30 mole % diethylene glycol, and (b) component (B) comprising a carboxylic acid. When a monovalent alkali metal ion is used, the resulting polyesters are less readily dissipated by cold water and more readily dissipated by hot water. When a divalent or a trivalent metal ion is used the resulting polyesters are not ordinarily easily dissipated by cold water but are more readily dissipated in hot water. The difunctional monomer component may also be referred to the difunctional sulfomonomer and is further described hereinbelow.
It is possible to prepare other salts of the polyester using, for example, a sodium sulfonate salt of the polyester and an appropriate ion—exchange resin. The inherent viscosities (I.V.) of the particular water-dissipatable polymeric materials useful herein range from about 0.1 to about 1.0 determined according to ASTM D2857—70 procedure, in a Wagner Visco eter 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 at 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
In r^
,n\ 25°c _ ° { Ω ) 0.50% ~~ where :
(n) = inherent viscosity at 25°C at a polymer concentration of 0.25 g/10 mL of solvent;
In = natural logarithm;
ts = sample flow time;
tQ = solvent-blank flow time; and
= 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, e.g., 0.50 g of polymer/100 mL solvent may be employed for more precise I.V. determinations.
Such additives can be emulsion stabilizers, surfactants, dispersants, antimicrobials or biocides, pH stabilizers, and the like. The additives described herein as suitable for use in the ink compositions are also suitable for use with the mixture of acrylic polymer and aqueous solution.
The polyester material can be dispersed in water or aqueous solution using the techniques described herein or known in the art and then blended with an aqueous dispersion or emulsion of acrylic polymer prepared by similar techniques, or blended with an aqueous emulsion or dispersion of acrylic polymer in a form commercially available. The following procedure can be used for dispersing the polyester in water: The water should be preheated to about 180°F (82.22°C) to about 200°F (93.33°C) and the polyester in pellet form is added rapidly to the vortex under high shear stirring. A Cowles Dissolver, Waring Blender, or similar equipment may be used. Once the water is heated to the desired temperature, additional heat input may not be required. Depending upon the volume prepared, dispersion of the pellets should be complete within 15 to 30 minutes stirring. Continued agitation with cooling may be desirable to prevent thickening at the surface due to water evaporation. Viscosities of the dispersions remain low up to polyester levels of 25 percent to 34 percent and viscosities increase sharply above these levels. Viscosities of the dispersions will be influenced by the degree of polymer dispersion obtained which is affected by the dispersing temperature, shear, and time. Dispersibility of the polyester can be improved when the levels of sodiosulfoisophthalic acid are low by either the addition of solvents such as n—propyl alcohol, isopropyl alcohol, propylene glycol, ethylene glycol monobutyl ether, or ethylene glycol or by the addition of hydantoin compounds as described herein.
The ink compositions of this invention can be for any of the typical ink applications such as flexographic, gravure, letterpress, ink—jet, or screen—process printing applications. The ink compositions of the present invention have excellent adhesion to a wide variety of substrates including plastic films such as polyester, polyethylene or polypropylene; aluminum foil; glass; and paper.
The ink compositions of the present invention should have a pH of about 8.2 or lower; preferred is a pH of about 7 to 8. If the pH is higher than about 8.2, there is a danger of the polymer(s) hydrolyzing which may result in gelling of the system. The flexographic and gravure inks of this invention contain, in addition to the base polymers and additives as described above, a minor amount of a carboxylic acid to blend with the polyester of the general formula XCR1R YC00H wherein Y represents a chain of from 0 to 4 carbon atoms which may be substituted with hydrogen, lower alkyl, hydroxyl or carboxyl groups wherein R1 and R2 are selected from the group consisting of hydrogen and alkyl having from about 1 to about 10 carbon atoms and wherein X is selected from the group consisting of hydrogen, lower alkyl having from about l to about 10 carbon atoms, hydroxyl and one or more carboxyl groups. If none of the carbon atoms of the fragment Y in the above formula contains H0-, or H00C— groups, X is H0-, and either R1 or R2 or both may be hydrogen or lower alkyl. Alternatively, the fragment XCR^-R2 constitutes a carboxyl group, HOOC—.
It is preferred for Y to contain either one or no carbon atoms. It is also preferred that the carbon atom attached to the X is substituted with either or both of an -OH of —COOH group.
Representative acids of this group are, for example, oxalic, tartaric, glycolic, phthalic, (ethylenedinitrilo) tetraacetic acid, glutaric, malic, and citric acids. Preferred acids of this group are those in which Y contains no carbon atoms or in which it contains one carbon atom optionally substituted with H0- or HOOC- or both. Citric acid, a member of this latter class, is especially preferred. *
Another class of carboxylic acids which are within the scope of the invention .are c—phthalic and o—hexahydrophthalic acids and such well—known chelating agents as (ethylenedinitrilo) tetraacetic acid. (Ethylene dinitrilo) tetracetic acid is preferred.
It is also preferred that the carboxylic acid to be blended with the polyester be water—soluble. "Water— solubility" as used herein means "the extent to which a substance mixes with water to produce a homogenous solution".
It should be understood that the named acids are for purposes of illustration and it is not intended to limit the scope of the invention to those compounds.
Component (B) is typically blended with the final product of any blends or aqueous dispersions made using component (A) and optional component (C) or (D) .
Component (C) is also useful within the context of this invention. The term "component (C)" refers to a polymer having repeat units from
(1) about 20 to about 80% by weight of a polymer comprising repeat units from styrene or one or more derivatives of styrene; (2) about 15 to about 50% by weight, preferably about 15 to about 40%, more preferably about 20 to about 30%, of hydroxyalkyl (meth)- acrylate; and (3) about 0 to about 60% by weight of alkyl (meth)acrylate.
A preferred aqueous dispersion of the invention contains about 95—60% of said component (C) and about 5—40% of said component (A) , both said percentages being based on the combined weight of (A) and (C) . Component (C) provides high solids aqueous polymer compositions. However, the preferred concentrations are 90-75% component (C) and 10—25% component (A) . A blend of the invention would typically comprise component (A) , component (B) and component (C) as described herein. It is preferred that the polyester, component (A) , has repeat units from isophthalic acid, sodiosulfoisc— phthalic acid, diethylene glycol, and another glycol selected from at least one of ethylene glycol and 1,4—cyclohexanedimethanol, and another polymer con¬ taining at least 20% by weight of repeat units from styrene or one or more derivatives of styrene, and 15% by weight of hydroxyalkyl (meth)acrylate.
It is also preferred in the aqueous dispersion that component (A) has a solids content of about 5 to 40 weight %, preferably about 10 to about 30 weight %, based on dry solids. It is preferred that the aqueous dispersion has a solids content of about 25 to about 45 weight % based on the total weight of said dispersion. If desired, the styrene or styrene derivative(s) and the hydroxyalkyl (meth)acrylate of component (C) , as described herein, may be mixed with additional monomers which are copolymerizable with the styrene or styrene derivatives, hydroxyalkyl (meth)acrylate. The comonomers may be present in amounts from 0 to about 60 weight percent. Polymer blends in which component (C) contains from about 35 to about 100% of a combination of the weight percents of styrene or styrene derivatives and hydroxyalkyl (meth)acrylate as described herein are preferred. The preferred total amount of comonomers is approximately about 0—40 weight percent.
One class of suitable comonomers are acrylic and methacrylic esters. Acrylic and methacrylic acid esters having from 1 to about 20 carbon atoms in the alcohol moiety are commercially available or can be easily prepared by known esterification processes. Preferred esters are the methyl, ethyl, butyl, 2—ethylhexyl and lauryl esters.
The acrylic and methacrylic acid esters may contain additional functional groups of the alcohol moiety, such as for example, hydroxyl, amine, halogen, ester, carboxylic acid, amide, nitrile and alkyl groups. Functionalized monomers such as blocked isocyanate acrylates and ethacrylates may also be used to provide crosslinking sites for the preparation of curable systems.
Also, particularly useful as comonomers are lower alkyl diesters of unsaturated dicarboxylic acids. For example, C1-4 diesters of maleic and fumaric acids, e.g., dibutyl maleate, may be used in copolymers with styrene or styrene derivatives and hydroxyalkyl (meth)acrylate or hydroxyalkylacrylate as described herein.
Other useful comonomers include acrylonitrile, acrylic acid, maleic anhydride, fumaric acid, methacrylic acid, acetoacetoxyethyl methacrylate and the corresponding acrylate, and halogenated vinyl monomers such as vinyl chloride and vinylidene chloride. These monomers may be used individually or may be used as mixtures to provide the desired properties. The preferred ratios of the various monomers can be readily determined by one skilled in the art and are dependent upon the particular application and desired properties of the water-dispersible polyester blend. It is preferred that component (C) comprise repeat units from 0 to about 80 weight % of one or more comonomers selected from the group consisting of ethylene, acrylic acid, methacrylic acid, acrylic and methacrylic acid esters, acryla ides, unsaturated dicarboxylic acid diesters, vinyl chloride and maleic anhydride.
It is more preferred that component (C) comprise repeat units from at least 20% by weight of one or more comonomers selected from styrene, methylmethacrylate, ethylhexylacrylate and butylacrylate. Component (D) of the invention comprises about 25 to 95 weight % of a styrene copolymer comprising: (a) about 30 to 100 weight % of repeating units from at least one styrene compound. Component (A) is also present at about 5 to about 75 weight %. It is preferred that the styrene polymer of component (D) of the invention also comprise (b) up to about 70 weight % of repeating units from at least one (meth)acrylate compound. It is preferred that component (A) is present in a preferred blend of the invention in an amount of about 15 to about 50 weight %, component (D) is present in an amount of about 50 to about 98 weight %; and component (D) comprises about 50 to about 100 weight % of component (D) (a) and 0 to about 50 weight % of component (D) (b) .
A preferred polymer blend of the invention is wherein component (A) is present in an amount of about 20 to about 40 weight %, component (D) is present in an amount of about 60 to about 80 weight %; and component (D) comprises about 70 to 100 weight % of component (D) (a) and 0 to about 30 weight % of component (D) (b) .
It is also preferred that component (A) is present in a preferred blend of the invention in an amount of about 30 to about 99.5 weight %, preferably about 20 to about 40 weight % and component (B) is present in an amount of about 0.1 to about 20 weight %, preferably about 0.5 to about 15 weight %. The styrene monomer useful for component (D) herein is preferably of the structure
Figure imgf000020_0001
wherein R3 is H or methyl, R4 is a lower alkyl group of
1 to 6 carbon atoms, and m is an integer of 0 to 2. Preferably m is 0 or 1, and R4 is methyl.
The most preferable styrene monomers for component (D) are styrene, α—methyl styrene, 4—methyl styrene, 3—methyl styrene, t—butyl styrene, and mixtures thereof. The meth(acrylate) monomer for component (D) useful herein preferably is of the structure
Figure imgf000020_0002
wherein R3 is H or an alkyl group of 1 to 10 carbon atoms, optionally substituted with one or two sub— stituents selected from the group consisting of Cj—C6 alkoxy, hydroxy, epoxy, acetoacetoxy and halogen, and R1 has the same meaning as previously defined.
Most preferably the (meth)acrylate monomer for component (D) is selected from the group consisting of butyl acrylate, ethyl acrylate, propyl acrylate, 2—ethylhexyl acrylate, methyl methacrylate, hydroxyethyl methacrylate, glycidyl (meth)acrylate, acetoacetoxyethyl methacrylate, and mixtures thereof.
In the process of preparing component (D) , it is preferred that the monomers are polymerized in the presence of the sulfonate—group containing polymer (i.e., the polyester or polyesteramide).
The compositions of the present invention are prepared in aqueous dispersions. The monomers are generally added to an aqueous dispersion of the water- dispersible polyester and polymerized by free radical initiation in conventional emulsion or suspension polymerization processes. The preferred ratio of polyester to monomer in the dispersion prior to polymerization will vary widely and depends on the intended application.
The polymerization can be initiated by a water- soluble or water—dispersible free radical initiator known in the art such as sodium persulfate, or by an oil—soluble initiator such as benzoyl peroxide. Other useful initiators include redox initiators such as sodium or potassium persulfate, ammonium persulfate, sodium or potassium roetabisulfite, and sodium or potassium formaldehyde sulfoxylate/Fe/hydrogen peroxide. The concentration of the initiator will generally range from about 0.01% to about 0.5% based on total reaction weight. A typical temperature range for the polymeriza¬ tion reaction is about 20βC to about 90βC with about 50βC to about 80°C being preferred.
The sulfonate-group containing polyesters which are used in the present invention typically become very viscous at concentrations above the 34 percent total solids. Thus, the reaction typically is begun with a polyester or polyesteramide dispersion that is about 30 percent total solids or less. However, the water- dispersible polyester blend dispersions are prepared at final total solids levels of up to about 20 percent to 60 percent for blends containing components (A) , (B) , and (D) . A total solids content of about 10 percent to 50 percent for blends containing components (A) , (B) , and (D) is preferred.
For blends containing components (A) , (B) and (C) , the water—dispersible polyester blend dispersions are prepared at final total solids levels of up to about 10 percent to about 50 percent. For blends containing components (A) , (B) and (C) , a total solids level of about 10 percent to about 25 percent is preferred.
The increase in solids level is achieved during polymerization by controlling the amount of water, if any, which is added along with the monomer. By decreasing the amount of water added during the polymerization, increased total solids contents up to about 30 percent to 55 percent, preferably 35 percent to 45 percent, are possible. This increase in solids level can offer significant benefits for the use of the water— dispersible polyesters of the present invention.
The copolymerization of the styrene and acrylate monomer(s) in the presence of water—dispersible polyester for component (C) may be conducted batchwise, semi—batch or in a continuous manner.
In a preferred embodiment, the sulfonate group- containing polyester is prepared, generally by melt phase polymerization techniques which are well known in the art. The polymers are extended into rods and chopped into pellets. These pellets can later be dispersed in hot blend of water with an organic cosolvent if desired. An aqueous dispersion containing about 5—40 weight %, preferably from about 10 percent to 34 percent total solids, is prepared from the polyester directly. A mixture of one or more monomers and the polymerization initiators may then be added to the aqueous dispersion of the polyester and polymerization initiated to produce an aqueous dispersion. When using a persulfate initiator, for example, the polymerizations are generally conducted at temperatures of about 70βC to about 90°C. For component (C) , usually a small amount of initiator is added toward the end of the copolymeriza¬ tion in order to react as much of the styrene and hydroxyethyl (meth)acrylate or hydroxypropylacrylate monomers as possible. For component (C) , it is desirable to have less than 100 ppm of unreacted vinyl/acrylic monomer(s) in the final product and preferably less than 50 ppm unreacted monomer(s) . The aqueous dispersion of component (C) can be prepared with total solids contents from about 10 percent to about 55 percen .
In another mode of operation for the preparation of component (C) , some of the aqueous polyester dispersion is added to the reaction vessel while the vinyl monomers and initiator are dispersed in another portion of the polyester dispersion. After heating the reaction mixture to the desired temperature, the portion containing polyester, vinyl monomers and initiator is gradually added with stirring. The translucent latexes obtained have virtually no coagulum.
The total solids content of the aqueous dispersion is controlled by the relative amounts of polymers which are used in the polymerization reaction and by the amount of water added during polymerization. As noted above, dispersions of sulfonate group-containing polymers can practically be prepared only at total solids contents up to about 34 percent. Above 34 percent, these dispersions become highly viscous and difficult to process. Higher total solids contents can be obtained by increasing the amount of monomer and decreasing the amount of polyester which are used in the polymerization reaction.
The specific amounts of component (A) and component (C) can be chosen by one skilled in the art depending on the specific monomers, the desired total solids content and the application for which the aqueous dispersion is intended.
Aqueous dispersions for component (C) can be formulated by those skilled in the art so that excellent wet block resistance in overprint varnish applications as well as excellent printability, adhesion, and water- resistance in ink applications for paper, film and foil results. However, these properties are dependent on latex composition, particularly on the composition of the styrene/(meth)acrylate co— or terpoly er. The particle size of these aqueous polymer blends, component (C) , generally range from <300 nm, and more preferably from about 40 nm to about 200 nm. It is believed that the hydroxyethyl (meth)acrylate or hydroxypropyl acrylate monomers are responsible for providing polymer blends with these small particle sizes. It is also believed that the hydroxyethyl (meth)acrylate or hydroxypropyl acrylate serves as a reactive cosolvent which lowers the interfacial tension between the monomer droplets and the aqueous phase, thereby lowering the monomer droplet size and consequently reducing the final particle size. The hydrophilic hydroxyethyl (meth)- acrylate or hydroxypropyl acrylate may also react with the hydrophobic styrene and/or (meth)acrylate monomer units to form oligomeric surfactant molecules in situ. Such an interaction would allow a low emulsion particle size to be maintained even with a reduction in the amount of the water—dispersible polyester (i.e., primary surfactant) present in the latex. Finally, the presence of the hydroxyethyl (meth)acrylate or hydroxypropyl acrylate reduces the amount of coagulum formed during latex preparation.
The dispersions or blends according to this invention may be used by applying them as a coating to a substrate such as paper followed by drying to leave a residue of solids in the form of a coating. Alternately, a second substrate can be applied prior to drying to form a bond between the substrates.
Also preferred is a method of preparing an aqueous polymer dispersion which comprises forming an aqueous dispersion having the components of polyester (A) and component (C) as described herein and polymerizing components b(l) , b(2) and b(3) of component (C) in the aqueous dispersion, to thereby obtain an aqueous dispersion of a blend of polymers with a total solids content of up to about 60%.
In the ink compositions of the present invention, it is preferred that component (B) of the invention is present in an amount of about 0.1% to about 20% by weight, preferably 0.5% to 15% by weight, and that components (A) , (C) or (D) are present in an amount of about 99.5 to about 25% by weight, that about 0.00% to about 45% by weight of a colorant is present, that about 0% to 15.0% by weight of an organic, polar solvent, preferably about 0 to about 10% by weight, such as 1- or 2-propanol, ethanol, 2-butoxyethanol, 2—ethoxyethanol is present, and that water satisfies any remaining percentage by weight so that the total percentage by weight of all of the components is equal to 100%. If the ink is a finished ink, it is preferred that at least about 0.5 weight percent of colorant is present. More typically, in inks, .at least about 15 weight percent of colorant is present. ' If the ink composition contains an organic pigment, typically such an organic pigment is present in an amount of about
20 weight percent or less of the total composition. If the ink composition contains an inorganic pigment, typically such inorganic pigment is present in an amount of about 30 weight percent or less of the total composi- tion. However, for some pigments such as titanium dioxide, the pigment can be present in an amount as high as about 60 percent.
Clearly, other additives, such as waxes, clays, surfactants, defoamers, viscosity modifiers, etc., may be added to the ink to modify or enhance end—use properties. The ink compositions can optionally contain up to about 20 weight percent, preferably up to about 10 weight percent, more preferably up to about 5 weight percent, of one or more such additives. Such additives include waxes such as Jonwax 26, Jonwax 120 (available from S. C. Johnson and Sons, Inc., Racine, Wisconsin 43403; U.S.A.), or Vanwax 35 (available from Vantage, Garfield, New Jersey 07026) ; surfactants such as Surfynol 104 and Surfynol 440 (available from Air Products and Chemicals, Allentown, Pennsylvania 18105) ; modifiers (for example, defoamers) such as WBT—409, Resolv (available from Vantage) , Carbowet 990 (available from Vantage) , Aerosol OT—70 (available from Mclntyre, Chicago, Illinois 60632) , Foamaster 111 (available from Henkel Corporation, Morristown, New Jersey 07960) ; alcohols such as n—propyl alcohol, isopropyl alcohol, propylene glycol, ethylene glycol monobutyl ether, or ethylene glycol; biocides; pH stabilizers; dispersants; thickeners such as Acrysol RM—825 (available from Rohm & Haas, Philadelphia, Pennsylvania 19105); and the like.
The ink compositions of the present invention should have a pH of about 8.2 or lower; preferred is a pH of about 3 to 7. If the pH is higher than about 8.2, there is a possibility of the polymer(s) hydrolyzing which may result in gelling of the system.
The ink compositions of this invention can be for any of the typical ink applications such as flexo— graphic, gravure, letterpress, ink-jet, or screen- process printing applications. The ink compositions of the present invention have excellent adhesion to a wide variety of substrates including plastic films such as polyester, polyethylene or polypropylene; aluminum foil; glass; and paper. The inks, overprints, and primers of this invention can be prepared, for example, as disclosed in U.S. Patent 4,148,779, which is incorporated herein by reference in its entirety. The present invention is not limited to any type of dye, pigment, filler, or the like, all of which are hereinafter included in the term "colorant," and can accommodate any colorant which can be dispersed, milled, mixed, blended or dissolved in any manner in either the polymer blend, water or aqueous polymer system.
As appreciated in the art, the exact components and properties of components desired for any given ink application can vary, and, therefore, routine experi¬ mentation may be required to determine the optional components and proportions of components for a given application and desired properties.
Exemplary useful C.I. pigments and solvent dyes for use in the present invention are given in the following table:
Piσments and Solvent Dyes Generic Name C.A. Index/Chemical Name
C.I. Pigment Yellow 17 Butanamide, 2,2'-[(3,3'- dichloro[1,1'-bipheny1] 4, '—diyl)bis(azo)bis [N—(2—methoxypheny1)—3- oxo—
C.I. Pigment Blue 27 Ferrate (4—1) , hexakis (cyano—C)—ammonium iron (3+) (l:l:l)
C.I. Pigment Red 49:2 1—Naphthalenesulfonic acid, 2—[ (2—hydroxy—l- naphthalenyl)azo]-, calcium salt (2:1)
C.I. Pigment Red 81:1 Benzoic acid, 2,-[6—ethyl- amino)—3—(ethylimino)—2,7— dimethyl—3H—xanthen—9—yl]—, ethyl ester, w/molybdenum tungsten hydroxide oxide phosphate
C.I. Pigment Red 81:3 Benzoic acid, 2—[6—ethyl— amino)—3—ethylimino)—2,7— dimethyl—3H—xanthen—9—y1]-, ethyl ester, molybdate— silicate
C.I. Pigment Red 81:x Benzoic acid, 2—[6—(ethyl- amino)-3-(ethylimino)-2,7- dimethyl-3H-xanthen-9-yl]-, ethyl ester, molybdate— phosphate
C.I. Pigment Yellow 83 Butanamide, 2,2'-[(3,3'- dichloro[1,1'-bipheny1]- 4,4'-diyl)bis(azo)bis[N- (4—chloro—2,5—dimethoxy— pheny1)—3—oxo— Generic Name C.A. Index/Chemical Name
C.I. Pigment Red 57:1 2-Naphthalenecarboxylic acid, 3-hydroxy-4-[ (4- methyl-2-sulfophenyl)azo]-, calcium salt (1:1)
C.I. Pigment Red 49:1 1-Naphthalenesulfonic acid, 2-[ (2-hydroxy-l- naphthalenyl)azo]—, barium salt (2:1)
C.I. Pigment Green 7 C.I. Pigment Green 7 C.I. Pigment Blue 61 Benzenesulfonic acid,. [ [4—[ [4—phenylamino)- phenyl]—[4-(phenylimino)- 2,5—cyclohexadien—1— ylidene]methylJ-pheny1] amino]—
C.I. Pigment Red 48:1 2—Naphtha1enecarboxylie acid, 4-[ (5-chlorc—4- methyl-2—sulfophenyl)azo]- 3—hydroxy—, barium salt (1:1)
C.I. Pigment Red 52:1 2—Naphthalenecarboxylie acid, 4—[ (4—chloro—5— methyl—2—sulfophenyl)azo]— 3—hydroxy—, calcium salt (1:1)
C.I. Pigment Violet l Ethanaminium, N—[9—(2— carboxypheny1)—6-(diethy1- amino)—3H—xanthen-3- ylidene]— -ethy1-, molybdatetungstate— phosphate
C.I. Pigment White 6 Titanium oxide (Ti02) Generic Name C.A. Index/Chemical Name
C.I. Pigment Blue 15 Copper, [29H, 31H- phthalocyaninato (2-)- N29, N30, N31, N32]-, (Sp-4-1)-
C.I. Pigment Yellow 12 Butanamide, 2,2'-[(3,3'- dichloro[1,1'-bipheny1]- 4,4'-diyl)bis(azo) ]bis[3- oxo—N—phenyl—
C.I. Pigment Blue 56 Benzenesulfonic acid, 2- methyl-4-[ [4-[ [4-[ (3- methyIpheny1)amino] phenyl]—[4—[ (3—methyl- pheny1)—imino]—2—5— cyclohexadien—1— ylidene]methyl]-phenyl] amino]—
C.I. Pigment Black 7 Carbon black C.I. Pigment Yellow 14 Butanamide, 2,2'—[(3,3'— dichloro[1,1'—bipheny1]- 4,4'—diyl)bis(azo) ]bis— [N-(2-methyIpheny1)-3—oxo-
C.I. Pigment Red 48:2 2—Naphthalenecarboxylie acid, 4—[ (5—chloro— — methyl—2—sulfophenyl)— azo]—3—hydroxy—, calcium salt (1:1) C.I. Pigment Blue 15:3 Copper, [29H, 31H- phthalocyaninato (2-)-N29, N30, N31, N32]-, (SP-4-1)- C.I. Pigment Yellow 1 Butanamide, 2-[ (4-methyl —2—nitrophenyl)azo]—3—oxo- N—phenyl— Generic Name C.A. Index/Chemical Name
C.I. Pigment Yellow 3 Butanamide, 2—[ (4- chlorc—2-nitropheny1) azo]—N-(2—chlorophenyl) —3—oxo—
C.I.Pigment Yellow 13 Butanamide, 2,2'-[(3,3'- dichloro[1,1'-bipheny1]- 4,4'-diyl)bis(azo) ]bis [N-(2,4-dimethylphenyl)-B- oxo—
C.I. Pigment Orange 16 Butanamide, 2,2'—[(3,3'— dimethoxy[1,1'—bipheny1]- 4,4'—diyl)bis(azo) ]bis [3—oxo—N-pheny1-
C.I. Pigment Yellow 55 Butanamide, 2,2'—[(3,3'— dichloro[1,1'—bipheny1] -4,4'-diyl)bis(azo) ]bis [N-(4-methyIpheny1)-3- oxo— C.I. Pigment Red 41 3H-Pyrazol-3-one,4,4'- [ (3,3'-dimethoxy[l,l'- biphenyl]—4,4'—diyl)bis (azo) ]bis[2,4—dihydro-5- ethyl—2—phenyl—
C.I. Pigment Orange 34 3H—Pyrazol—3—one,4,4'— [ (3,3'-dichloro[l,l'- biphenyl]—4,4'—diyl)bis (azo) ]bis[2,4—dihydro-5- methyl—2—(4—methyIpheny1)—
C.I. Pigment Blue 62 4,4'—Bis(diethylamino) benzophenone condensed with N—ethyl-l-naphthyl- amine in toluene with phosphorous oxychloride and converted to the copper ferrocyanide salt (PTMA salt in P.Blue 1) Generic Name C.A. Index/Chemical Name
C.I. Pigment Red 22 2-Naphthalenecarboxamide, 3-hydroxy-4-[ (2-methy1-5- nitrophenyl)azo]-N-pheny1-
C.I. Pigment Red 170 2-Naphthalenecarboxamide, 4-[ [ (4—(aminocarbonyl) pheny1]azo]-N-(2—ethoxy- pheny1)-3-hydroxy-
C.I. Pigment Red 88 Benzo[b]thiophen-3 (2H)-one, 4,7-dichloro-2-(4,7- dichloro—3—oxobenzo[b]— thien-2(3H)-ylidene)-.
C.I. Pigment Yellow 151 A diazotized aniline derivative coupled with an acetoacetyl derivative of 5— minobenzimidazolone
C.I. Pigment Violet 23 Diindolo[3,3' ,2'm]tri- phenodioxazine, 8—18— dichloro—5, 15—diethyl— 5,15—dihydro-
C.I. Pigment Red 184 A diazotized substituted aniline coupled with a derivative of 3—hydroxy— 2—naphthanilide
C.I. Pigment Blue 1:2 Ethanaminium, N—[ —[ [4— (diethylamino)phenyl] [4—(ethyla ino)—1—1 naphtha1eny1]methy1ene]— 2,5—cyclohexadien—1— y1idene]—N—ethy1—, [orthosilicato(4-) ] hexatriacontaoxo— dodecamolybdate(4)—( :1) Generic Name C.A. Index/Chemical Name
C.I. Pigment Red 3 2-Naphthalenol, 1—[ (4—methyl—2—nitro¬ phenyl)azo]-
C.I. Pigment Blue 15:1 Copper, [29H,32H- phthalocyaninato(2-)-
N29,N30,N31,
N32]-, (SP-4-1)- or Copper, [chloro—29H,
31H—phthalocyaninato
(2-l)-N29,N3 ,N31, N32]- C.I. Pigment Red 23 2-Naphthalenecarboxamide, 3—hydroxy-4-[ (2-methoxy- 5—nitrophenyl)azo]—N— (3-nitrophenyl)- C.I. Pigment Red 112 2-Naphthalenecarboxamide, 3—hydroxy—N-(2—methy1- phenyl)-4-[ (2,4,5-tri- chlorophenyl)azo]- C.I. Pigment Yellow 126 A tetrazotized derivative of 3,3—dichlorobenzidene coupled with a derivative of acetoacetanilide C.I. Pigment Red 169 3—Ethylamino—p—cresol condensed with phthalic anhydride, esterified with ethanol and a mineral acid, and converted to the copper ferrocyanide complex (chloride salt is C.I. Basic Red 1, PTMA salt is P.Red 81:1) . C.I. Pigment Orange 13 3H-Pyrazol-3-one, 4,4'-[(3,3'-dichloro [1,1'-bipheny1]-4 ,4'- diyl)bis(azo) ]bis[2,4- dihydro-5-methy1-2-pheny1- Generic Name C.A. Index/Chemical Name
C.I. Pigment Red 10 2-Naphthalenecarboxamide, 4-[ (2,5-dichloropheny1) azo]—3—hydroxy—N—(4— methyIpheny1)—
C.I. Pigment Blue l:X Ethanaminium, N—[4—
[ [4-(diethylamino)phenyl]
[4—(ethylamino)—1—naphtha— lenyl]methylene]—2,5— cyclohexadien—1—ylidene]—
N—ethyl—, molybdate— phosphate
C.I. Pigment Yellow 42 Iron oxide (Fe203) hydrate C.I. Pigment Yellow 74 C.I. Pigment Red 101 Iron oxide (Fe203) C.I. Pigment Brown 6 Iron oxide (Fe203) , some FeO and Fe 03Η20
C.I. Pigment Brown 7 Iron oxide (Fe203) plus varying amounts of clay
C.I. Pigment Brown 7:X Fe203- x Mn02 with varying amounts of clay
C.I. Pigment Black 11 FeO-Fe203
C.I. Pigment Metal l Aluminum
C.I. Pigment Metal 2 Copper, zinc
C.I. Solvent Yellow 135
C.I. Basic Red 1
C.I. Basic Violet 11
C.I. Solvent Blue 44
C.I. Solvent Blue 38 Generic Name C.A. Index/Chemical Name
C.I. Solvent Black 45
C.I. Solvent Orange 41
C.I. Solvent Red 124
C.I. Solvent Red 127
C.I. Solvent Yellow 48
C.I. Solvent Blue 45
C.I. Solvent Yellow 83:1
C.I. Basic Yellow 40 and 42
This invention can be further illustrated by the following examples of preferred embodiments thereof, although it will be understood that these examples are included merely for purposes of illustration and are not intended to limit the scope of the invention unless otherwise specifically indicated. The starting materials are commercially available unless otherwise described. All percentages are by weight unless otherwise described.
EXAMPLES
Preparation of the Polyester Polv er Resins Continuous Process for Polymer A
A feed stream is fed continuously to a two—stage stainless steel reactor zone such that the composition of the stream is: 45.3% Component A 15.7% Component B 38.7% Component C 0.2% Component D 0.1% Component E where A is isophthalic acid; B is a slurry of the diethylene glycol diester of 5—sodiosulfoisophthalie acid at 46.5 weight percent in diethylene glycol; C is 1,4—cyclohexanedimethanol; D is a solution of titanium tetraisopropoxide in n—butanol at 2.54 weight percent titanium; and E is anhydrous sodium acetate.
The feed rate of the stream and the size of the reactor are such that the stream is under nitrogen at atmospheric pressure at 255°C for one hour and under nitrogen at less than 4,000 microns pressure at 285°C for 0.5 hour. The product is extruded from the stage II reactor into a chilled water bath and mechanically chopped into pellets. The pellets are then dried in a rotary cone dryer at 65"C until less than 1% moisture remains. Polymer B was made using similar reaction conditions but varying the ratio of the components.
The compositions for the polyester polymers A and B are as follows P Poollvvmmeerr A A P Pjolymer B 9 911 8 822 mole % isophthalic acid
9 18 mole % sodiosulfoisophthalie acid
75 46 mole % 1,4—cyclohexanedielethanol
25 54 mole % diethylene glycol The commercial additives referred to in the following examples are identified as follows:
Tekta er 38LV: Thiadiazine biocide from Calgon Co. Wax: Mixed polyethylene S—232 wax from Shamrock
Technologies Alcogum L1228: Ammonium acrylate copolymer which is a viscosity modifier from Alco Chemical
Surfynol 104PA: acetylenic diol surfactant from Air
Products Co. Acrysol RM825: polyurethane resin from Rohn Haas Co. ,^ Λ„ PCTΛJS95/08830 6/03467
- 35 -
EXAMPLE l - Blue Flexograohic Ink
The polymer dispersions and millbase are prepared as follows:
Polyester Polymer A Dispersion with 2% n-propyl alcohol: 5 67.9% Deionized water
30.0% Polymer A polyester pellets 2.0% n—propyl alcohol 0.1% Tektamer 38LV Polymer A was dispersed in water with a n—propanol 0 cosolvent and heated to reflux at about 88°C (3:1 water:n—propanol) , the azeotrope was removed to give a lower percent alcohol and higher percent solids.
Polyester Polymer B dispersion with 10% n—propyl alcohol: 5 60.7% deionized water 10.0% n—propyl alcohol
29.0% Polyester Polymer B polymer pellets 0.3% Tektamer 38LV Polymer B was dispersed in water at about 82βC. The 0 n-propanol was added to the dispersion after cooling. Blue Millbase:
49.0% Polymer B polyester dispersion with 10% n-propyl alcohol 15.5% Water 5 34.9% C. I. Pigment Blue 15:3
0.4% Acrysol RM-825 0.2% Tektamer 38LV The above pigment was milled until the color was developed and until the particles were small enough to be used in 0 ink formulations.
These are combined as follows to prepare a Blue Flexo Ink: 60.9% Polyester polymer A dispersion with 2% n—propanol 30.0% Blue 15:3 Millbase 4.0% Polyethylene wax - S 232 4.0% Propylene glycol
1.0% Viscosity modifier - Alcogum L1228 0.1% Surfactant - Surfynol 104PA An experimental ink is prepared identically to the control, except for the addition of 5% by weight of a 10% solution of citric acid.
EVALUATION AND TEST PROCEDURE
Draw-downs are made with a #0 RK rod from Paul N. Gardner Company, Inc. , Pampano Beach FL 33060 on a polyethylene coated board using an RK laboratory coater. The experimental ink and the control ink are drawn down side by side. The coated board is allowed to dry for approximately 20 seconds while the coating rod is removed and rinsed. The coated polyethylene board is then placed in a 100°C oven for 3 seconds. The coated board is then removed and allowed to cool at room temperature. A stop watch is used to mark the time the coated board was removed from the oven. During the cooling period, the polyethylene coated board is cut into two-samples that have been identified on the back for testing. After the coated board has been allowed to cool for 2 minutes, the two samples of coated board are placed under the demineralized water tap for approximately 5 seconds to thoroughly wet them, then the samples are rubbed face to face against each other with 20 back and forth strokes between the thumb and index finger. The experimental sample is rubbed against the experimental and the control against the control. A paper tissue is used to remove the excess water from the samples. The samples are rated visually for loss of color for wet rub resistance, using the following rating scale: 1 = Very Poor Approx. 100% removal of ink from substrate
2 = Poor Approx. 75% removal of ink from substrate 3 = Fair Approx. 50% removal of ink from substrate
4 = Good Approx. 25% removal of ink from substrate
5 = Excellent Approx. 0% removal of ink from substrate
The control blue flexo ink has a rating of 2 and the experimental a rating of 5.
In order to determine the effectiveness of other acids on the wet-rub performance of this ink formulation, the citric acid is replaced by each of the following acids: oxalic acid; tartaric acid; glycolic acid; phthalic acid; and (ethylenedinitrilo) tetraacetic acid.
A significant improvement in the wet—rub performance of the draw—downs was noted in each case. In contrast, there was no improvement in the wet-rub test over the control when citric acid was replaced by boric or acetic acids. In similar work, ammonium citrate was added to the blue ink instead of the citric acid or ammonium hydroxide was added to the citric acid containing ink and tested. These inks also had an improvement in wet—rub test performance compared to the control.
EXAMPLE 2 - Red Flexographic Ink
The polymer dispersions were prepared as described in Example 1. Polymer dispersions and pigment millbase were formulated as follows: Polyester Polymer A Dispersion with 10% n-propyl alcohol 59.9% Deionized water 30.0% Polyester polymer A pellets 10.0% n—propyl alcohol 0.1% Tektamer 38LV Polyester Polymer B Dispersion with 0% n—propyl alcohol 33.0% Polyester polymer B pellets 66.7% deionized water 0.3% Tektamer 38LV Red Millbase 33.0% Polyester Polymer B Dispersion with 0% n-propyl alcohol 26.8% deionized water 40.0% C. I. Pigment Red 170 0.2% Tektamer 38LV These were combined into a Red Flexo Ink Formulation: 10.0% Polyester polymer A Dispersion with 10% n—propyl alcohol 50.9% Polyester polymer A Dispersion with 2% n—propyl alcohol 30.0% Red 170 millbase
4.0% polyethylene wax - S-232 4.0% propylene glycol
1.0% viscosity modifier — Alcogum L-1228 0.1% Surfynol 104PA surfactant Experimental and control inks are identical, except that the experimental ink contains 5% of a 10% solution of citric acid.
The inks are evaluated as in the previous example. The control sample has a rub resistance rating of 2, while the rating of the experimental sample, in which the ink contained citric acid, was 5. EXAMPLE 3 - Yellow Flexograohic Ink Yellow millbase is prepared as follows:
56.9% Polyester polymer B Dispersion with 10% n—propyl alcohol (Example 1) 10.3% Deionized water
32.5% C. I. Pigment Yellow 74 0.3% Tektamer 38LV Yellow Flexographic Ink
60.9% Polyester polymer A Dispersion with 2% n-propyl alcohol (Example 1)
30 % Yellow 74 millbase 4 % Polyethylene wax, S—232 4 % Propylene glycol 1 % Viscosity modifier, Alcogum L1228 0.1% Surfynol 104PA surfactant
The ink is evaluated in the same way as in the preceding examples. The control ink has a wet rub resistance of 1; the experimental ink, which contains 5% of a 10% solution of citric acid, has a rating of 3.
EXAMPLE 4 - Gravure Printing Ink
A gravure ink formulation for metallized paper was prepared as follows:
68.9% Polyester Polymer A Dispersion with 2% n-propyl alcohol (see Example 1)
28.6% Blue 15:3 Millbase (see Example 1) 2.5% Water or 2.5% of 10% citric acid solution Control and experimental inks are prepared in each case; the inks are identical except that the experimental ink contains 2.5% citric acid solution (10% citric acid in water.)
The inks are evaluated by a standard water drop test as follows: 1. The inks are applied to the foil laminated paper using an applicator bar creating a draw down. 2. The draw down is then placed in an oven at 100°C for five seconds to simulate an oven on a printing press.
3. Immediately after removing the draw down from the oven, water drops are placed on the surface and the time is noted.
4. After one, three, and five minutes the water drops are wiped with a tissue. Any removal of the ink film to the tissue, or distortion of the printed surface is registered as a failure. In all cases, the control ink, which contained no citric acid washed from the surface of the foil, leaving voids in the printing. In contrast, the experimental ink which contained citric acid at any of the levels between 0.25% and 1.0% showed essentially no removal of the ink film.
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. Moreover, all patents, patent applications (published or unpublished, foreign or domestic) , literature references or other publications noted above are incorporated herein by reference for any disclosure pertinent to the practice of this invention.

Claims

CLAIMSWe claim:
1. A polymer blend comprising:
(a) component (A) consisting essentially of a linear, water-dissipatable polyester having an inherent viscosity of at least about 0.1 as measured in a 60/40 parts by weight solution of phenol/tetrachloroethane at 25βC and at a concentration of 0.5 gram of polyester in 100 ml of solvent, the polyester containing substantially equimolar proportions of acid moiety repeating units (100 mole %) to hydroxy moiety repeating units (100 mole %) , the polyester comprising repeating units of components (1) , (2), (3) and (4), as follows wherein all stated mole percentages are based on the total of all acid and hydroxy moiety repeating units being equal to 200 mole %:
(1) about 90 to about 97 mole % isophthalic acid,
(2) about 3 to about 10 mole %' 5-sulfoisc— phthalic acid, (3) about 70 to about 85 mole %
1,4—cyclohexanedimethanol, and (4) about 15 to about 30 mole % diethylene glycol, and
(b) component (B) comprising a carboxylic acid.
2. The polymer blend of Claim 1 wherein component (B) is present in the amount of about 0.1 to about 20 weight % based on the total weight of components (A) and (B) and wherein component (A) is an aqueous dispersion.
3. The polymer blend of Claim l wherein either or both of components (A) and (B) additionally comprises up to 50 weight percent of one or more additives.
4. The polymer blend of Claim 3 wherein either or both of components (A) or (B) additionally comprises about 0.05 to about 30 weight percent of one or more additives selected from the group consisting of an emulsion stabilizer, a surfactant, a dispersant, a biocide, and a pH stabilizer.
5. The polymer blend of Claim 1 wherein either or both of components (A) and (B) additionally comprises up to 25 weight percent of one or more additives.
6. The polymer blend of Claim 5 wherein either or both of components (A) and (B) additionally comprises about 1 to about 20 weight percent of one or more additives selected from the group consisting of an emulsion stabilizer, a surfactant, a dispersant, a biocide, and a pH stabilizer.
7. The polymer blend of Claim 1 wherein component (B) is selected from the group consisting of oxalic, tartaric, glycolic, phthalic, (ethylenedinitrilo) tetraacetic, glutaric, malic, and citric acids.
8. The polymer blend of Claim 1 wherein component (B) is a carboxylic acid of the formula XCR1R2YCOOH where Y represents a chain of from about o to about 4 carbon atoms which may be substituted with hydrogen, lower alkyl, hydroxyl or carboxyl groups wherein R1 and R2 are selected from the group consisting of hydrogen and lower alkyl having from about l to about 10 carbon atoms and X is selected from the group consisting of hydrogen, lower alkyl having from about l to about 10 carbon atoms, hydroxyl or one or more carboxyl groups.
9. The polymer blend of Claim 8 wherein X is OH and either or both of R1 and R2 is hydrogen or lower alkyl having 1 to 10 carbon atoms and where none of the carbon atoms of Y contain -OH or —COOH groups.
10. The polymer blend of Claim 8 wherein the fragment XCRαR2 is a carboxyl group.
11. The polymer blend of Claim 8 wherein Y contains no carbon atoms.
12. The polymer blend of Claim 8 wherein Y contains one carbon atom.
13. The polymer blend of Claim 8 wherein the carbon atom attached to said X is substituted with either or both of an —OH or —COOH group.
14. The polymer blend of Claim 8 wherein said component (B) is selected from the group consisting of oxalic, tartaric, glycolic, phthalic, (ethylene- dinitrilo) tetraacetic, glutaric, malic, and citric acids.
15. The polymer blend of Claim 1 wherein said carboxylic acid is a polyfunctional carboxylic acid.
16. The polymer blend of Claim 1 wherein said carboxylic acid is water—soluble.
17. The polymer blend of Claim 15 wherein said component (B) is citric acid.
18. The polymer blend of Claim 15 wherein said component (B) is selected from the group consisting of c—(ethylenedinitrilo)tetraacetic acid.
19. An ink composition comprising about 3 to about 40 weight % of (I) a polymer blend comprising:
(a) about 3.0 to about 40% by weight of component (A) consisting essentially of repeat units from a linear water—dissipatible polymer having carbonyloxy linking groups in the linear molecular structure wherein up to 80% of the linking groups are 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 containing substantially equimolar proportions of acid equivalents (100 mole %) to hydroxy and amino equivalents (100 mole %) , the polymer comprising the reaction products of reactants selected from the following components (1) , (2) , (3) , and (4) , or the ester forming or esteramide forming derivatives thereof, as follows, wherein all stated mole percentages are based on the total of all acid, hydroxyl and amino equivalents being equal to 200 mole %: (1) about 90 to about 97 mole % isophthalic acid,
(2) about 3 to about 10 mole % 5-sulfc— isophthalic acid, (3) about 70 to about 85 mole %
1,4—eyelohexanedimethano1, and (4) about 15 to about 30 mole % diethylene glycol, and (b) about 0.1 to about 15% by weight of component (B) comprising a carboxylic acid based on the total weight of components (A) and (B) and wherein component (A) is an aqueous polyester dispersion, (II) up to about 45 weight % of a pigment material or solvent dye, (III) about 40 to about 90 weight % of water, and (IV) 0 to about 15 weight % of an alcohol.
20. The ink composition of Claim 19 wherein said pigment material of component (II) is one or a mixture of the following color index materials: C.I. Pigment Yellow 17, C.I. Pigment Blue 27, C.I. Pigment Red 49:2, C.I. Pigment Red 81:1, C.I. Pigment Red 81:3, C.I. Pigment Red 81:x, C.I. Pigment Yellow 83, C.I. Pigment Red 57:1, C.I. Pigment Red 49:1, C.I. Pigment Violet 23, C.I. Pigment Green 7, C.I. Pigment Blue 61, C.I. Pigment Red 48:1, C.I. Pigment Red 52:1, C.I. Pigment Violet 1, C.I. Pigment White 6, C.I. Pigment Blue 15, C.I. Pigment Yellow 12, C.I. Pigment Blue 56, C.I. Pigment Orange 5, C.I. Pigment Black 7, C.I. Pigment Yellow 14, C.I. Pigment Red 48:2, C.I. Pigment Blue 15:3, C.I. Pigment Yellow l, c.I. Pigment Yellow 3, C.I. Pigment Yellow 13, C.I. Pigment Yellow 74, C.I. PC17US95/08830
- 46 -
Pigment Orange 16, C.I. Pigment Yellow 55, C.I. Pigment Red 41, C.I. Pigment Orange 34, C.I. Pigment Blue 62, C.I. Pigment Red 22, C.I. Pigment Red 170, C.I. Pigment Red 88, C.I. Pigment Yellow 151, C.I. Pigment Red 184, C.I. Pigment Blue 1:2, C.I. Pigment Red 3, C.I. Pigment Blue 15:1, C.I. Pigment Red 23, C.I. Pigment Red 112, C.I. Pigment Yellow 126, C.I. Pigment Red 169, C.I. Pigment Orange 13, C.I. Pigment Red 1—10, 12, C.I. Pigment Blue 1:X, C.I. Pigment Yellow 42, C.I. Pigment Red 101, C.I. Pigment Brown 6, c.I. Pigment Brown 7, c.I. Pigment Brown 7:X, C.I. Pigment Black 11, C.I. Pigment Metal 1, or C.I. Pigment Metal 2.
21. The ink composition of Claim 19 wherein said solvent dye is one or a mixture of the following: C.I. Solvent Yellow 135, C.I. Basic Red 1, C.I. Basic Violet 11, C.I. Solvent Blue 44, C.I. Solvent Blue 38, C.I. Solvent Black 45, C.I. Solvent Orange 41, C.I. Solvent Red 124, C.I. Solvent Red 127, C.I. Solvent Yellow 48, C.I. Solvent Blue 45, C.I. Solvent Yellow 83:1, or C.I. Basic Yellow 40 and 42.
22. The ink composition of Claim 45 additionally comprising up to 10 weight % of at least one additional additive selected from the group consisting of a wax, a biocide, a surfactant, a transfer agent, a coalescence aid, and an antifoam.
PCT/US1995/008830 1994-07-25 1995-07-14 Ink and coating compositions containing a blend of water-dispersible polyester and carboxylic acids WO1996003467A1 (en)

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US28002394A 1994-07-25 1994-07-25

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1998014524A1 (en) * 1996-10-01 1998-04-09 Zeneca Limited Aqueous ink compositions
US6200371B1 (en) 1996-10-01 2001-03-13 Zeneca Limited Aqueous ink compositions
US6235096B1 (en) 1996-10-01 2001-05-22 Zeneca Limited Aqueous ink compositions
EP3960819A4 (en) * 2019-04-26 2023-01-18 Kao Corporation WATER SOLUBLE RESIN FOR PRINTING

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AT337847B (en) * 1974-12-18 1977-07-25 Stolllack Ag BAKING-IN LACQUER
WO1991016382A2 (en) * 1990-04-24 1991-10-31 Eastman Kodak Company Aqueous printing inks having improved freeze-thaw properties

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AT337847B (en) * 1974-12-18 1977-07-25 Stolllack Ag BAKING-IN LACQUER
WO1991016382A2 (en) * 1990-04-24 1991-10-31 Eastman Kodak Company Aqueous printing inks having improved freeze-thaw properties

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1998014524A1 (en) * 1996-10-01 1998-04-09 Zeneca Limited Aqueous ink compositions
US6200371B1 (en) 1996-10-01 2001-03-13 Zeneca Limited Aqueous ink compositions
US6235096B1 (en) 1996-10-01 2001-05-22 Zeneca Limited Aqueous ink compositions
US6344497B1 (en) 1996-10-01 2002-02-05 Avecia Limited Aqueous ink compositions
EP3960819A4 (en) * 2019-04-26 2023-01-18 Kao Corporation WATER SOLUBLE RESIN FOR PRINTING

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