EP0723482A1 - Copolymeres utiles comme milieu de suspension pour encres d'impression - Google Patents

Copolymeres utiles comme milieu de suspension pour encres d'impression

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Publication number
EP0723482A1
EP0723482A1 EP94920292A EP94920292A EP0723482A1 EP 0723482 A1 EP0723482 A1 EP 0723482A1 EP 94920292 A EP94920292 A EP 94920292A EP 94920292 A EP94920292 A EP 94920292A EP 0723482 A1 EP0723482 A1 EP 0723482A1
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EP
European Patent Office
Prior art keywords
polymer
carbon atoms
weight
group
formula
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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EP94920292A
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German (de)
English (en)
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EP0723482A4 (fr
Inventor
Steven P. Boucher
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Henkel Corp
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Henkel Corp
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Publication of EP0723482A1 publication Critical patent/EP0723482A1/fr
Publication of EP0723482A4 publication Critical patent/EP0723482A4/fr
Withdrawn legal-status Critical Current

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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
    • C09D125/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Coating compositions based on derivatives of such polymers
    • C09D125/02—Homopolymers or copolymers of hydrocarbons
    • C09D125/04—Homopolymers or copolymers of styrene
    • C09D125/08—Copolymers of styrene
    • C09D125/14—Copolymers of styrene with unsaturated esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1808—C8-(meth)acrylate, e.g. isooctyl (meth)acrylate or 2-ethylhexyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1812—C12-(meth)acrylate, e.g. lauryl (meth)acrylate

Definitions

  • the present invention relates to copolymers and to their use as printing vehicles. More particularly, it relates to alkyl acrylate copolymers and their use in printing inks or varnishes particularly suited for use flexographic or gravure printing processes.
  • Alkyl acrylate and methacrylate polymers are generally known in the art. see e.g. "Acrylic and Methacrylic Ester Polymers", Encyclopedia of Polymer Science and Engineering, vol. 1 , pp. 236-299 (John Wiley & Sons, Inc. N.Y., N.Y., 1985). For example, the effect of the choice of alkyl group on the chemical and mechanical properties of homopolymers of the alkyl acrylate and methacrylate monomers is discussed at pages 256-261 .
  • the predominant raw materials are the butyl and 2-ethylhexyl esters of acrylic acid.
  • One formulation for a general purpose pressure-sensitive adhesive is a copolymer of 97% by weight 2-ethylhexyl acrylate and 3% by weight of acrylic acid.
  • Another formulation is a copolymer of 63% by weight 2- ethylhexyl acrylate and 30% by weight of vinyl acetate and 2% by weight acrylamide.
  • U.S. Patent No. 5,196,470 discloses an alcohol based, water soluble binder composition for nonwoven material made from water swellable, water soluble or water sensitive fibers and related substances is provided comprising a substantially anhydrous solution of an acrylic polymeric resin, and an alcohol diluent.
  • the resin is a synthetic polymer which may be synthesized from an acrylic acid ester, methacrylic acid ester, or both, in combination with a polymerizable alpha, beta ethylenically unsaturated carboxylic acid.
  • U.S. Pat. No. 4,230,613 discloses a lacquer composition for coating a substrate, comprising acrylic polymers such as methyl methacrylate/butyl acrylate/acrylic acid terpolymers, a volatile solvent such as a mixture of toluene and isopropanol, and a tertiary amine activator.
  • the water-based inks containing the blend of these polymers as a binder can significantly improve ink film properties such as alcohol resistance, block resistance and water resistance as compared to use of water-dispersible polyester alone.
  • the polymer blends were also employed to prepare ink primers and overprint varnishes. It is stated that these polymer blends were prepared by mixing an aqueous polyester dispersion with an acrylic emulsion which contains surfactants and other additives and that the presence of surfactants in the ink formulations creates several problems related to ink stability, printing process and print quality of the ink film.
  • U. S. Patent No. 5,075,364 discloses a blend of a water-dissipatable polyester material, an acrylic polymer and a water-dissipatable vinyl polymer. It is stated that the acrylic polymer and the vinyl polymer must be compatible with the polyester which has a particular composition. It is stated that the polymer blends are useful for preparing ink compositions having improved block resistance, water resistance, and alcohol resistance.
  • R 2 R 4 R 6 wherein R 1 is an aromatic group having from 6 to 10 carbon atoms, R 3 is a fatty alkyl group having from 12 to 22 carbon atoms, and R 5 is a hardening alkyl group having from 1 to 4 carbon atoms, R 2 , R 4 , and R 6 are each independently hydrogen or methyl, and y is effective in relation to x and z to improve the alkali resistance of a film of said polymer.
  • the subscripts x, y, and z represent the mole ratios of the monomeric units. Thus, the subscripts will be integers for a mono-disperse polymer composition and will be average values when expressed in relation to a poly-disperse polymer composition.
  • a preferred class of polymers within the scope of this invention have the formula set forth above wherein R 1 is phenyl, R 3 is a straight chain alkyl group selected from the group consisting of tetradecyl, hexadecyl and octadecyl, R 5 is methyl, the ratio of x:y:z is chosen such that the polymer is comprised of monomeric units of formula A in an amount from about 25% to about 45% by weight, monomeric units of formula B in an amount from about 25% to about 45% by weight, and monomeric units of formula C in an amount from about 25% to about 45% by weight, and the sum of x, y, and z is chosen such that the polymer has a molecular weight of from about 150,000 to about 300,000.
  • This invention also relates to a method of coating a substrate comprising (i) contacting a surface of a substrate with a composition comprising a polymer as defined above, and (ii) drying said surface to form a film of said polymer in contact with said surface.
  • said polymer in aqueous dispersion is supplied to said surface by a hydrophilic cylindrical transfer roll.
  • This invention relates to novel polymers of this invention, e.g. polymers having the formula set forth above, to printing ink vehicles which contain these novel polymers, and to methods which employ these novel polymers.
  • These polymers are at least terpolymers, i.e. they have repeating units derived from a vinyl aromatic monomer and two different alkyl acrylates. The precise identity of each monomer and the amount of each monomer affect properties of the polymer which are important to its utility in a printing ink vehicle
  • the starting materials for preparing the novel polymers of this invention are vinyl aromatic. compounds and alkyl esters of acrylic acid and methacrylic acid. Vinyl aromatic compounds are discussed in "Styrene Polymers" Encyclopedia of Polymer Science and Engineering, vol. 16, pp.
  • the monomeric unit A is derived from a vinyl aromatic compound.
  • the vinyl aromatic compounds comprise monovinyl aromatic hydrocarbons containing from 8 to 12 carbon atoms and halogenated derivatives thereof having halo-substituted aromatic moieties. Examples include styrene, alpha-methylstyrene, vinyl toluene (e.g.
  • meta-methylstyrene and para-methylstyrene meta-methylstyrene
  • meta-methylstyrene para- methylstyrene
  • para-ethylstyrene para-n-propylstyrene
  • para- isopropylstyrene para-tert-butylstyrene
  • ortho-chlorostyrene para- chlorostyrene
  • alpha-methyl-meta-methylstyrene alpha-methyl-para- methylstyrene, tert-butyl styrene, alpha-methyl-ortho-chlorostyrene, and alpha-methyl-para-chlorostyrene.
  • the monomeric unit B is derived from acrylate or methacrylate esters of fatty alcohols which give rise to the R 3 in the polymer.
  • the group R 3 is selected so that the unit derived from that monomer will provide alkali resistance to a film of the polymer.
  • R 3 is, thus, selected from fatty alkyl groups having from 12 to 22 carbon atoms. Examples of such fatty alkyl groups include n-dodecyl (e.g. lauryl), n-tridecyl, n-tetradecyl (e.g. myristyl), n-pentadecyl, n-hexadecyl (e.g.
  • n-heptadecyl e.g. margaryl
  • n-octadecyl e.g. stearyl
  • n-nonadecyl e.g. arachidyl
  • docosanyl e.g. behenyl
  • alkyl radicals having from 14 to 18 carbon atoms, most preferably straight chain alkyl radicals, and more preferably from natural sources such that the group will have an even number of carbon atoms.
  • R 3 is a lauryl, myristyl, palmityl or stearyl group, or monomers derived from mixtures of fatty alcohols. It is the fatty alcohol groups of the B monomeric unit that are believed to be responsible for the enhanced alkali resistance of films of the polymer. It should be noted, however that enhanced alkali resistance is only one facet of the important properties of the polymer and that stability of the polymer emulsion in an aqueous medium is important as well. Therefore, the amount of the B monomeric unit should be adjusted to obtain the desired degrees of both alkali resistance and emulsion stability. This amount will generally be a minor amount, e.g.
  • the monomeric unit C is derived from acrylate or methacrylate esters of alcohols which give rise to the R 5 in the polymer.
  • R 5 groups examples include methyl, ethyl, isopropyl, isobutyl, sec-butyl, t- butyl, isoamyl, and t-amyl.
  • the precise identity and amount of the R 3 monomer will depend upon the desired degree of hardness which, in turn, depends at least in part on the identity and amounts of the other monomeric units.
  • R ⁇ R 5 , x and z are selected so that the polymer will have sufficient hardness and sufficient susceptibility to emulsification in the polymer emulsion.
  • the mechanical properties contributed to the polymer by the R 2 through R 4 and R 6 groups may require the selection of an R 1 and/or R 5 group that has a relatively greater hardening effect (e.g. phenyl for R 1 and methyl or t-butyl for R 5 ) than other others (e.g. ethyl or isobutyl).
  • a measure of the hardening effect of the R 5 group can be found by examining the glass transition temperature of a homopolymer of the monomer.
  • R 5 will be selected such that a homopolymer of the monomer will exhibit a glass transition temperature (T a ) of greater than about 50°C
  • the values of x and z should be sufficient in relation to y to yield a polymer that is sufficiently susceptible to emulsification such that a stable polymer emulsion is formed. If the polymer is not sufficiently susceptible to emulsion, observable polymer coagulum may form in the emulsion during either the polymerization or the intended shelf life of the aqueous emulsion or printing vehicle prepared therefrom. Monomeric units derived from other alkyl acrylates or methacrylates may also be present in the polymer.
  • esters examples include the acrylate or methacrylate esters methyl, ethyl, n- propyl, isopropyl, n-butyl, isobutyl, sec-butyl, n-amyl, isoamyl, t-amyl, n- hexyl, 2-ethylbutyl, cyclohexyl, 2-heptyl, n-octyl, 2-ethylhexyl, n-decyl, and n-undecyl.
  • a potential utility of such monomers is the ability of one of ordinary skill, in possession of this disclosure, to use such monomers to optimize the hardness of the polymer.
  • a measure of their utility will depend upon the desired degree of hardness of the polymer which, in turn, depends at least in part, on the identity and amounts of the other monomeric units.
  • a measure of the plasticizing effect of a monomer can be found by examining the glass transition temperature of a homopolymer of the monomer. Generally, a plasticizing monomer will be such that a homopolymer of the monomer will exhibit a glass transition temperature (T g ) of less than about -30°C.
  • T g glass transition temperature
  • acrylates of a straight chain alkyl having from 3 to 1 1 carbon atoms or a branched chain alkyl having from 5 to 1 1 carbon atoms may generally be useful for plasticizing the polymer. Because of the relatively high T g of poly(t-butyl acrylate), the use of a monomer t- butyl acrylate is unlikely to be advantageous.
  • alkyl acrylates and methacrylates described above are preferably employed without additional comonomers for preparing ink vehicles of this invention
  • other monoethylenically unsaturated polymerizable monomers useful in minor proportion (e.g. less than 10% by weight of the total monomer composition) as comonomers with acrylic monomers may be useful in preparing the polymers of this invention, particularly for uses other than in ink vehicles.
  • These monomers include the vinylidene halides, vinyl halides, acrylonitrile, methacrylonitrile, vinyl esters such as vinyl formate, vinyl acetate and vinyl propionate, and mixtures of ethylene and such vinyl esters, acrylic and methacrylic acid esters of alcohol ethers such as diethylene glycol monoethyl or monobutyl ether methacrylate, ⁇ -C ⁇ alky!
  • Additional monoethylenically unsaturated polymerizable comonomers that may be useful in preparing the polymer of the invention include hydroxy functional vinyl monomers such as 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, 3-hydroxypropyl methacrylate, butanediol acrylate, 3-chloro-2-hydroxypropyl acrylate, 2-hydroxypropyl acrylate, and 2-hydroxypropyl methacrylate.
  • Further examples of useful monomers include the partial esters of unsaturated aliphatic dicarboxylic acids and particularly the alkyl half esters of such acids.
  • partial esters examples include the alkyl half esters of itaconic acid, fumaric acid and maleic acid wherein the alkyl group contains 1 to 6 carbon atoms.
  • Representative members of this group of compounds include methyl acid itaconic, butyl acid itaconic, ethyl acid fumarate, butyl acid fumarate, and methyl acid maleate.
  • Minor amounts of other comonomers, such as adhesion promoting comonomers, may also be used. These monomers may be copolymerized with acrylic monomers to yield the polymer.
  • alpha, beta-ethylenically unsaturated carboxylic acids which may also be useful as comonomers to prepare the polymer of the invention include acrylic acid, beta- acryloxypropionic acid and higher oligomers of acrylic acid and mixtures thereof, methacrylic acid, itaconic acid, aconitic acid, crotonic acid, citraconic acid, maleic acid, fumaric acid, alpha-chloroacrylic acid, cinnamic acid, mesaconic acid and mixtures thereof.
  • ethylenically unsaturated monomer having at least two sites of ethylenic unsaturation, that is, di- or multi-ethylenically unsaturated monomer
  • allyl methacrylate or divinyl benzene may be used.
  • the initial latex polymer may be prepared from a monomer mixture containing from about 0.005 to 2 percent by weight, based on the weight of the total solids of the polymer, of monomer containing at least two sites of ethylenic unsaturation. However, it is preferred to employ no multi-ethylenically unsaturated monomer.
  • the polymer be prepared by emulsion polymerization of monomers comprising: (a) a first minor amount by weight (e.g. from about 25% to 45% by weight, based on the total weight of the polymer) of vinyl aromatic monomer having less than twelve carbon atoms, and mixtures thereof,
  • a second minor amount by weight e.g. from about 25% to 45% percent by weight, based on the total weight of the polymer
  • a third minor amount by weight e.g. from about 25% to 45% percent by percent by weight, based on the total weight of the polymer
  • a third minor amount by weight e.g. from about 25% to 45% percent by percent by weight, based on the total weight of the polymer
  • Conventional emulsion polymerization techniques may be used to prepare the aqueous dispersion of polymers of this invention.
  • monomers may be emulsified with an anionic, cationic or nonionic dispersing agent, using for example from about 0.05% to 10% by weight of dispersing agent on the weight of total monomers.
  • an anionic, cationic or nonionic dispersing agent such as hydroxy ethyl cellulose, methyl cellulose and polyvinyl alcohol may be used as emulsion stabilizers and protective colloids, as may polyelectrolytes such as polyacrylic acid .
  • Cationic dispersion agents include lauryl-pyridinium chlorides, cetyldimethyl amine acetate, and alkyldimethylbenzylammonium chlorides in which the alkyl group has from 8 to 18 carbon atoms.
  • Anionic dispersing agents include, for example, the higher fatty alcohol sulfates, such as sodium lauryl sulfate, and the like; alkylaryl sufonates such as sodium or potassium isopropylbenzene sulfonates or isopropyl napththalene sulfonates, and the like; alkali metal higher alkyl sulfosuccinates, such as sodium octyl sulfosuccinate, sodium N-methyl-N-palmitoyltaurate, sodium oleyl isothionate, and the like; and alkali metal salts of alkylarylpolyethoxyethanol sulfates or sulfonates, such as sodium
  • Suitable non-ionic dispersing agents include alkylphenoxy- polyethoxyethanols having alkyl groups of from about 7 to 18 carbon atoms and from about 6 to about 60 oxyethylene units, such as heptylphenoxypolyethoxyethanols, methyloctylphenoxypolyethoxyethanols, and the like; polyethoxyethanol derivatives of methylene-linked alkyl phenols; sulfur-containing agents such as those made by condensing from about 6 to about 60 moles of ethylene oxide with nonyl mercaptan, dodecyl mercaptan, and the like, or with alkylthiophenols wherein the alkyl groups contain from 6 to 16 carbon atoms; ethylene oxide derivatives of long-chained carboxylic acids, such as lauric acid, myristic acid, palmitic acid, oleic acid, and the like, or mixtures of acids such as those found in tall oil containing from 6 to 60 oxethylene units per molecule;
  • the emulsion may contain one or more suspending aids.
  • Preferred compositions contain an acrylic resin having a substantial acid number as a suspending aid. (By "substantial” is meant an acid number sufficient to impart the desired degree of resolubility to the polymers of in the ink or varnish, as discussed below.)
  • Such resins become and contribute to the polymer film prepared from the emulsion, but do not have acceptable properties, e.g. alkali resistance, by themselves.
  • Such suspending aid resins do, however, affect the resolubility of the polymer blend in the ink vehicle.
  • resolubility is meant that the polymer will redisperse in the ink vehicle while still in a wet state so that there will not be an unacceptable build up of the polymer on a transfer roll used to apply the polymer to a substrate.
  • a suspending aid polymer with a relatively higher acid number.
  • Use of such a polymer will tend to decrease the alkali resistance of a film of the polymer, but should improve the resolubility of the polymer in the ink or varnish, and thus, tend to prevent deposition of the polymer on a transfer rolls used to apply the ink or varnish to a printing substrate.
  • resolubility is not as important a factor for a given ink composition or varnish, or for a given printing apparatus, it may be desirable to minimize the acid number of the suspending aid resin and, thus, obtain superior alkali resistance.
  • Preferred carboxylate polymers are vinyl aromatic/acrylic copolymers (e.g. styrene/acrylic copolymers) having a substantial acid number (typically 150-250, and preferably 180-220) and a moderate molecular weight (e.g. 6,000 to 10,000). Vinyl aromatic compounds are discussed in "Styrene Polymers” Encyclopedia of Polymer Science and Engineering, vol. 16, pp. 1 -
  • the vinyl aromatic compounds comprise monovinyl aromatic hydrocarbons containing from 8 to 12 carbon atoms and halogenated derivatives thereof having halo-substituted aromatic moieties. Examples include styrene, alpha-methylstyrene, vinyl toluene (e.g.
  • meta-methylstyrene and para-methylstyrene meta-methylstyrene, meta-methylstyrene, para-methylstyrene, para-ethylstyrene, para-n-propylstyrene, para-isopropylstyrene, para-tert-butylstyrene, ortho-chlorostyrene, para- chlorostyrene, alpha-methyl-meta-methylstyrene, alpha-methyl-para- methylstyrene, tert-butyl styrene, alpha-methyl-ortho-chlorostyrene, and alpha-methyl-para-chlorostyrene.
  • At least a portion of the acrylic units of the polymer will bear free carboxyl or carboxylate groups (the carboxyl or carboxylate form depending upon the pH of the aqueous emulsion).
  • This carboxylate functionality is solvated by the aqueous polymerization medium and, thus, contributes to the stability of the polymer suspension.
  • the aqueous composition should be essentially free of species which can react with or form a complex with such carboxylate functionality. Such freedom will ensure that the carboxylate functionality remains solvated by the aqueous polymerization medium and/or that the carboxylate polymer will not engage in measurable crosslinking, either in the aqueous polymerization medium or the films prepared therewith.
  • emulsion stabilizers i.e. water soluble polymers such as water-soluble polyalkylene oxides, may be useful.
  • a preferred emulsion stabilizer is a polypropylene glycol having a molecular weight in the range of 1 ,000 to 1 ,500.
  • a polymerization initiator of the free radical type such as ammonium or potassium persulfate
  • a redox system which also includes a reducing component such as potassium metabisulfite, sodium thiosulfate or sodium formaldehyde sulfoxylate.
  • the reducing component is frequently referred to as an accelerator.
  • the initiator and accelerator commonly referred to as catalyst, catalyst system or redox system, may be used in proportion from about 0.01 % or less to 3% each, based on the weight of monomers to be copolymerized.
  • redox catalyst systems examples include t-butyl hydroperoxide/sodium formaldehyde sulfoxylate/Fe(ll), and ammonium persulfate/sodium bisulfite/sodium hydrosulfite/Fe(ll).
  • the polymerization temperature may be from room temperature to 90°C., or more, and may be optimized for the catalyst system employed, as is conventional.
  • Emulsion polymerization may be seeded or unseeded. Seeded polymerization is preferred and tends to yield aqueous dispersions of latex polymer having more uniform physical properties than unseeded polymerization.
  • Chain transfer agents including mercaptans, polymercaptans and polyhalogen compounds are sometimes desirable in the polymerization mixture to moderate polymer molecular weight.
  • chain transfer agents which may be used include long chain alkyl mercaptans such as t-dodecyl mercaptans, alcohols such as isopropanol, isobutanol, lauryl alcohol or t-octyl alcohol, carbon tetrachloride, tetrachloroethylene and trichlorobromoethane. Generally from about 0 to 3% by weight, based on the weight of the monomer mixture, may be used.
  • the polymerization process may be a thermal or redox type; that is, free radicals may be generated solely by the thermal dissociation of an initiator species or a redox system may be used.
  • a monomer emulsion containing all or some portion of the monomers to be polymerized may be prepared using the monomers, water and emulsifiers.
  • a catalyst solution containing catalyst in water may be separately prepared.
  • the monomer emulsion and catalyst solution may be co-fed into the polymerization vessel over the course of the emulsion polymerization.
  • the reaction vessel itself may initially contain water.
  • the reaction vessel may also additionally contain seed emulsion and further may additionally contain an initial charge of polymerization catalyst.
  • the temperature of the reaction vessel during the emulsion polymerization may be controlled by cooling to remove heat generated by the polymerization reaction or by heating the reaction vessel.
  • Several monomer emulsions may be simultaneously co-fed into the reaction vessel. When multiple monomer emulsions are co-fed, they may be of different monomer composition. The sequence and rates at which the diverse monomer emulsions are co-fed may be altered during the emulsion polymerization process.
  • the polymerization reaction mixture may be chased (e.g. with t-butyl hydroperoxide and or sodium ascorbate) to minimize the concentrations of unreacted monomer and unreacted polymerization catalyst species.
  • the pH of the contents of the reaction vessel may also be altered during the course of the emulsion polymerization process. Both thermal and redox polymerization processes may be employed. While the preferred use of the preferred polymers of this invention is in a printing ink vehicle, e.g. as a binder resin or a varnish, the polymer can be used in a wide variety of end-use applications. For example, it can be used in leather finishes and coatings, clear and pigmented coatings for wood and other architectural substrates, caulks, and sealants and as a binder for an exterior coating composition, such as those used to protect sprayed-in-place polyurethane foam roofing (roof mastics).
  • a printing ink vehicle e.g. as a binder resin or a varnish
  • the polymer can be used in a wide variety of end-use applications. For example, it can be used in leather finishes and coatings, clear and pigmented coatings for wood and other architectural substrates, caulks, and sealants and as a
  • the polymer can be used in coating in general.
  • the aqueous dispersions of the present invention can, thus, be applied to a variety of substrates to form a coating thereon.
  • substrates include, for example, porous stock such as paper and cardboard, wood and wood products, metals such as aluminum, copper, steel, and plastics e.g. films such as polyolefins (low density polyethylene, linear low density polyethylene, polypropylene), polyesters, (e.g. polyethylene terephthalate), polyamides, polycarbonates, acrylics and the like.
  • the compositions are applied by methods such as spraying, rollcoating, flexo and gravure processes onto a selected substrate.
  • the resulting coated substrate is typically allowed to dry before further processing.
  • the coating compositions may optionally include other substances such as pigments, resins, monomers and additives such as anti-oxidants and rheological modifiers.
  • pigments such as pigments, resins, monomers and additives such as anti-oxidants and rheological modifiers.
  • the ink and varnish compositions of this invention can be for any of the typical ink or varnish 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 and varnish compositions of the present invention should have a pH greater than 8, e.g. typically 8.2 to 9.0.
  • the inks, overprints, and primers of this invention can be prepared, for example, as disclosed in U.S. Pat. No. 4,148,779, which is incorporated herein by reference in its entirety.
  • the printing ink, overprint, or primer may be prepared as follows.
  • the colorant is added to the polymer blend dispersion and, at a properly adjusted viscosity, dispersed thereinto with ball mill, sand mill, high-shear fluid flow mill, Cowles Dissolver, Katy Mill or the like.
  • the colorants also may be dispersed directly in the polymer by milling on a heated two-roll mill at about 220°F to 360°F.
  • the viscosity and printing characteristics of the ink composition may be modified further by addition of water, solvents, plasticizers, sequestered wax, surfactants and the like to suit the particular printing needs.
  • the ink compositions of the present invention are 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.
  • the aqueous emulsions of this invention are particularly useful in preparing inks or varnishes that are, in turn, particularly useful in the printing of packaging substrates, e.g. non-woven cellulosic substrates.
  • non-woven cellulosic substrates are sheets or other continuous webs of cellulosic fibers formed by deposition of the fibers from a suspension in such a way that the fibers are intermeshed to form a thin but compact whole.
  • these substrates can be characterized as paper. Examples of paper stocks include letter stock, bag stock, carton stock, newsprint, and so on.
  • the inks and varnishes of this invention are particularly useful in printing packaging papers, such as bag stock and carton stock.
  • the printing processes most advantageously used with the inks or varnishes are the flexographic and/or gravure printing processes.
  • One characteristic of such printing processes is that the aqueous dispersion of ink or varnish is supplied to said surface by a hydrophilic cylindrical transfer roll.
  • Printing processes are described by T. Sulzberg et al., "Printing Ink Vehicles", Encyclopedia of Polymer Science and Engineering, vol. 13, pp. 368-398 (John Wiley & Sons, Inc., N.Y, N.Y., 1988), the disclosure of which is incorporated herein by reference.
  • this invention relates to a method of printing comprising applying a first portion of an aqueous dispersion comprised of the polymer of this invention to a first essentially impervious printing surface, said surface having recesses therein which define a resolvable image, contacting said surface with a printable substrate, and repeating said applying and said contacting with a second portion of said aqueous dispersion and a second printable surface.
  • This method may be a letterpress printing method (wherein said recesses define raised portions of the surface which carry the aqueous dispersion to the substrate, e.g. flexography) or a gravure printing method (wherein said recesses carry the aqueous dispersion to the substrate).
  • flexographic printing in particular, an aqueous dispersion comprised of the polymer of this invention is applied to a flexible plate mounted on a plate cylinder. The flexible plate is then contacted with a printable substrate by rotation of the plate cylinder.
  • the aqueous dispersion is applied to the flexible plate with a hydrophilic cylindrical transfer roll which is rotated to successively take up and then apply successive portions of the aqueous dispersion.
  • a hydrophilic cylindrical transfer roll which is rotated to successively take up and then apply successive portions of the aqueous dispersion.
  • ink or varnish compositions prepared from the above polymer blends may be superior over prior aqueous ink or varnish compositions in one or more of such properties as pigment wetting, pigment stability, temperature stability (heat and freeze-thaw), nonsettling for extended periods of time, nonpolluting with respect to odor and volatile organics, nonflocculating, long "open" time in the press fountain, wide viscosity range inks, adhesion to a variety of substrates, hardness, gloss, drying rate on substrates, film-forming properties at low temperatures without organic co-solvents, resistance to grease, water and scuff, compatibility with other water-based inks, wet rub resistance, ink mileage characteristics (considerable water dilution allowable at the press), ink press stability in general, printability (clean, sharp transfer without “stringing or misting"), trapping, easy clean up, nonplugging of printing plates, flexibility, redispersibility or rewetting, crinkle resistance, solvent resistance, alkal
  • Suspending aid resin styrenated acrylic resin at 31 .68
  • the polymers were then prepared by the following steps. Blanket the reactor with nitrogen and add charge 1 . Heat Charge 1 in the reactor to 85°C. Pump 10% of Charge 3 from monomer tank into the reactor. Add Charge 2 to the reactor and continue mixing. Meter the remaining Charge 3 from the monomer tank into the reactor over a 105 minute period at 83 °C and mix for 1 hour. Add Charge 5 to the reactor and mix for 1 hour at 84°C. Cool to 49°C. Pump Charge 6 into reactor over 60 minutes and mix for 15 minutes.
  • Varnish Preparation All of the polymers were used to prepare a varnish by simple mixing of 91 parts by weight of the product of the polymerization with a 9 parts by weight of a coalescent agent, ethylene glycol propyl ether.
  • the varnishes were diluted with water to a composition having a viscosity of 21 to 23 seconds on a #2 Zahn cup and the diluted composition was printed with a #8 wound wire rod on an uncoated Leneta chart. The coatings were then allowed to dry overnight.
  • the coatings were tested for alkali resistance with an alkali drop test.
  • the coatings were evaluated for gloss by conventional means, i.e. simply measuring the percent of visible light reflected from the surface at the same angle as the incident angle of the light. The values expressed below are the percent of light reflected.
  • Polymers were prepared by the procedure set forth above using a monomer blend of styrene (STY), methyl methacrylate (MMA), 2-ethylhexyl acrylate (EHA) and hexadecyl acrylate (HDA) in the amounts (in parts by weight) shown in Table 1 A.
  • STY styrene
  • MMA methyl methacrylate
  • EHA 2-ethylhexyl acrylate
  • HDA hexadecyl acrylate
  • a polymer was prepared by the procedure set forth above from 15 parts by weight of styrene, 12 parts by weight of methyl methacrylate, 4 parts by weight of 2-ethylhexyl acrylate, and 4 parts by weight of dodecyl acrylate.
  • the polymer was made into a varnish, printed, and the printed film was evaluated, all as set forth above.
  • the alkali resistance rating was 5.7, difference of -4% from Comparative Example A, and the gloss was 69.4%.
  • Example 1 Polymers were prepared as set forth for Example 1 , but a suspending aid resin having less free acid groups (i.e. one less susceptible to being redissolved in a printing ink or varnish) was used.
  • the suspending aid resin had the percentage reduction by weight of free acid groups shown in Table 3 and printed films thereof exhibited the alkali resistance and gloss shown in Table 3, wherein the " ⁇ %" value under alkali resistance is the percent difference in the alkali rating from the value of Example 1 .

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

Abstract

L'invention concerne des polymères ayant la formule (A, B, C). Dans cette formule, R1 est un groupe aromatique ayant de 6 à 10 atomes de carbone, R3 est un groupe alkyle provenant d'un acide gras ayant de 12 à 22 atomes de carbone et R5 est un groupe alkyle de durcissement ayant de 1 à 4 atomes de carbone, R?2, R4 et R6¿ sont chacun d'une manière indépendante un hydrogène ou un méthyle et y est choisi en fonction de x et de z pour qu'un film dudit polymère ait une résistance améliorée aux milieux alcalins. L'invention concerne également un procédé pour appliquer un revêtement sur un substrat consistant: (i) à mettre en contact une surface d'un substrat avec une composition de dispersion aqueuse contenant un polymère comme défini ci-dessus et (ii) à sécher ladite surface pour former un film dudit polymère en contact avec ladite surface. Dans les procédés préférés, ledit polymère en dispersion aqueuse est appliqué sur ladite surface par un rouleau de transfert cylindrique hydrophile. Ces polymères sont particulièrement utiles comme liants pour une composition d'encre ou un vernis à surimpression, car ils ont une bonne résistance aux milieux alcalins.
EP94920292A 1993-07-01 1994-06-23 Copolymeres utiles comme milieu de suspension pour encres d'impression Withdrawn EP0723482A4 (fr)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
US8782393A 1993-07-01 1993-07-01
US87823 1993-07-01
US16726493A 1993-12-14 1993-12-14
US167264 1993-12-14
PCT/US1994/007002 WO1995001228A1 (fr) 1993-07-01 1994-06-23 Copolymeres utiles comme milieu de suspension pour encres d'impression

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EP0723482A1 true EP0723482A1 (fr) 1996-07-31
EP0723482A4 EP0723482A4 (fr) 1997-10-01

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EP (1) EP0723482A4 (fr)
AU (1) AU7114494A (fr)
CA (1) CA2166412A1 (fr)
WO (1) WO1995001228A1 (fr)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5554705A (en) * 1995-03-17 1996-09-10 Henkel Corporation Polymers useful as printing vehicles
EP0890621B1 (fr) * 1997-07-08 2005-12-21 Arkema Revêtement

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4162997A (en) * 1978-03-02 1979-07-31 Hercules Incorporated Heat-fusible pastes for printing inks, adhesives and moldings
DE3447713A1 (de) * 1983-12-28 1985-07-11 Sakata Shokai Ltd., Osaka Waessrige ueberzugsmasse und ihre verwendung in einem druckverfahren
JPH0381371A (ja) * 1989-08-23 1991-04-05 Nippon Synthetic Chem Ind Co Ltd:The 艶消し塗料用樹脂の製造法
EP0460973A2 (fr) * 1990-06-07 1991-12-11 Nippon Paint Co., Ltd. Revêtement multicouche durable
EP0469484A2 (fr) * 1990-07-26 1992-02-05 Mita Industrial Co. Ltd. Développateur électrophotographique

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4814373A (en) * 1984-12-20 1989-03-21 Rohm And Haas Company Modified latex polymer composition
US5075364A (en) * 1988-10-11 1991-12-24 Eastman Kodak Company Ink composition containing a blend of a polyester, an acrylic polymer and a vinyl polymer

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4162997A (en) * 1978-03-02 1979-07-31 Hercules Incorporated Heat-fusible pastes for printing inks, adhesives and moldings
DE3447713A1 (de) * 1983-12-28 1985-07-11 Sakata Shokai Ltd., Osaka Waessrige ueberzugsmasse und ihre verwendung in einem druckverfahren
JPH0381371A (ja) * 1989-08-23 1991-04-05 Nippon Synthetic Chem Ind Co Ltd:The 艶消し塗料用樹脂の製造法
EP0460973A2 (fr) * 1990-06-07 1991-12-11 Nippon Paint Co., Ltd. Revêtement multicouche durable
EP0469484A2 (fr) * 1990-07-26 1992-02-05 Mita Industrial Co. Ltd. Développateur électrophotographique

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
PATENT ABSTRACTS OF JAPAN vol. 015, no. 252 (C-0844), 26 June 1991 & JP 03 081371 A (NIPPON SYNTHETIC CHEM IND CO LTD:THE), 5 April 1991, *
See also references of WO9501228A1 *

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CA2166412A1 (fr) 1995-01-12
EP0723482A4 (fr) 1997-10-01
WO1995001228A1 (fr) 1995-01-12
AU7114494A (en) 1995-01-24

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