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WO1996003467A1 - Composition d'encres et de revetements contenant un melange de polyester et d'acides carboxyliques dispersables dans l'eau - Google Patents

Composition d'encres et de revetements contenant un melange de polyester et d'acides carboxyliques dispersables dans l'eau 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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WIPO (PCT)
Prior art keywords
pigment
mole
component
acid
weight
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PCT/US1995/008830
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English (en)
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/fr

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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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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)
  • Paints Or Removers (AREA)

Abstract

L'invention concerne un mélange polymère comprenant: a) une composante A consistant pour l'essentiel en un polyester linéaire pouvant se dissiper dans l'eau et qui présente une viscosité inhérente d'au moins 0,1 environ, mesurée dans une solution à 60/40 parties en poids de phénol/tétrachloroéthane à 25 °C et à une concentration de 0,5 g de polyester pour 100 ml de solvant, ce polyester contenant des proportions sensiblement équimolaires d'unités récurrentes d'une fraction acide (100 moles %) par rapport à des unités récurrentes d'une fraction hydroxy (100 moles %), ce polyester contenant aussi des unités récurrentes des composants (1, 2, 3 et 4) comme indiqué ci-dessous où tous les pourcentages molaires sont basés sur l'ensemble des unités récurrentes des fractions acides et hydroxy valant 200 moles %: 1) environ 90 à 97 moles % d'acide isophtalique, 2) environ 3 à 10 moles % d'acide 5-sulfo-isophtalique, 3) environ 70 à 80 moles % de 1,4-cyclohexanediméthanol, et 4) environ 15 à 30 moles % de diéthylène glycol; et b) un composant (B) comprenant un acide carboxylique.
PCT/US1995/008830 1994-07-25 1995-07-14 Composition d'encres et de revetements contenant un melange de polyester et d'acides carboxyliques dispersables dans l'eau WO1996003467A1 (fr)

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Application Number Priority Date Filing Date Title
US28002394A 1994-07-25 1994-07-25
US280,023 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 (fr) * 1996-10-01 1998-04-09 Zeneca Limited Compositions d'encres aqueuses
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 (fr) * 2019-04-26 2023-01-18 Kao Corporation Résine soluble dans l'eau pour impression

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AT337847B (de) * 1974-12-18 1977-07-25 Stolllack Ag Einbrennlack
WO1991016382A2 (fr) * 1990-04-24 1991-10-31 Eastman Kodak Company Encre d'imprimerie aqueuse ayant des caracteristiques de gel et degel ameliorees

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AT337847B (de) * 1974-12-18 1977-07-25 Stolllack Ag Einbrennlack
WO1991016382A2 (fr) * 1990-04-24 1991-10-31 Eastman Kodak Company Encre d'imprimerie aqueuse ayant des caracteristiques de gel et degel ameliorees

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1998014524A1 (fr) * 1996-10-01 1998-04-09 Zeneca Limited Compositions d'encres aqueuses
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 (fr) * 2019-04-26 2023-01-18 Kao Corporation Résine soluble dans l'eau pour impression

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