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WO2014204779A1 - Dispersions de copolymère et leur utilisation dans des formulations de couchage de papier - Google Patents

Dispersions de copolymère et leur utilisation dans des formulations de couchage de papier Download PDF

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Publication number
WO2014204779A1
WO2014204779A1 PCT/US2014/042123 US2014042123W WO2014204779A1 WO 2014204779 A1 WO2014204779 A1 WO 2014204779A1 US 2014042123 W US2014042123 W US 2014042123W WO 2014204779 A1 WO2014204779 A1 WO 2014204779A1
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Prior art keywords
acid
dispersion
monomer
linking
paper
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English (en)
Inventor
Argiri TSAMI-SCHULTE
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Celanese Sales Germany GmbH
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Celanese Emulsions GmbH
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    • 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
    • C08F218/00—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 acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid
    • C08F218/02—Esters of monocarboxylic acids
    • C08F218/04—Vinyl esters
    • C08F218/08—Vinyl acetate
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H23/00—Processes or apparatus for adding material to the pulp or to the paper
    • D21H23/02—Processes or apparatus for adding material to the pulp or to the paper characterised by the manner in which substances are added
    • D21H23/22—Addition to the formed paper
    • D21H23/32—Addition to the formed paper by contacting paper with an excess of material, e.g. from a reservoir or in a manner necessitating removal of applied excess material from the paper
    • D21H23/34—Knife or blade type coaters
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H25/00—After-treatment of paper not provided for in groups D21H17/00 - D21H23/00
    • D21H25/08—Rearranging applied substances, e.g. metering, smoothing; Removing excess material
    • D21H25/10—Rearranging applied substances, e.g. metering, smoothing; Removing excess material with blades

Definitions

  • the present invention relates to copolymer dispersions comprising vinyl ester/ethylene copolymers and their use in paper coating formulations.
  • Pigmented paper coating formulations generally comprise an aqueous synthetic polymer binder dispersion and pigment and may contain other additives typically used in the paper coating art.
  • Illustrative of the polymer binders used in these formulations are vinyl acetate copolymers and interpolymers, including vinyl acetate/ethylene (VAE) and vinyl acetate/alkyl acrylate copolymers and interpolymers, as well as styrene/butadiene and styrene/acrylate copolymers.
  • Such copolymers and interpolymers can also contain other co- monomers such as, for example, a copolymerized ethylenically unsaturated mono- or dicarboxylic acid or other unsaturated co-monomers which can function as cross-linking agents.
  • U.S. Patent No. 4,395,499 discloses high strength pigment binders for paper coatings having increased water retention and stability.
  • the coating compositions contain an aqueous synthetic polymer latex comprising a dispersed interpolymer of a vinyl ester; a polyethylenically unsaturated co-monomer which can be triallyl cyanurate, triallyl isocyanurate, diallyl maleate, diallyl fumarate, divinyl benzene or diallyl phthalate; an ethylenically unsaturated mono- or dicarboxylic acid co-monomer or half ester thereof; and optionally an alkyl acrylate co-monomer.
  • U.S. Patent No. 4,503,185 discloses aqueous vinyl ester/ethylene emulsion copolymers demonstrating enhanced dry pick strength and gloss in paper coating formulations.
  • the copolymers comprise a vinyl ester/ethylene copolymer colloidally dispersed in an aqueous medium, the copolymer consisting essentially of (a) a vinyl ester of a C 1 -C 12 alkanoic acid, (b) about 0.5 to 15 wt% ethylene, (c) 0.1 to 10 wt% of an ethylenically unsaturated C 3 -C 10 mono- or dicarboxylic acid or half ester of such dicarboxylic acid with a C ds alkanol, (d) 0.05 to 10 wt% of a dicyclopentadienyl acrylate, and (e) 0-50 wt% of an alkyl acrylate.
  • VAE vinyl ester/ethylene
  • the invention resides in a copolymer dispersion, comprising:
  • copolymer is dispersed in an aqueous medium comprising a stabilizer and all percentages are by weight based on the total weight of the monomers (a), (b) and, where present, (c).
  • the first, ethylenically unsaturated cross-linking co-monomer (d) monomer is selected from the group consisting of allyl glycidyl ether, methacryloyl glycidyl ether, butadiene monoepoxides, 1 ,2-epoxy-5-hexene, 1 ,2-epoxy-7-octene, 1 ,2- epoxy-9-decene, 8-hydroxy-6,7-epoxy-1 -octene, 8-acetoxy-6,7-epoxy-1 -octene, N-(2,3- epoxypropyl)acrylamide, N-(2,3-epoxypropyl)methacrylamide, 4-acrylamidophenyl glycidyl ether, 3-acrylamidophenyl glycidyl ether, 4-methacrylamidophenyl glycidyl ether, 3- methacrylamidophenyl ether, 3- methacryla
  • the second, ethylenically unsaturated cross-linking co- monomer is selected from the group consisting of acrylic acid, vinyl acetic acid, crotonic acid, methacrylic acid, tiglic acid, maleic acid, fumaric acid, itaconic acid, maleic acid, citraconic acid, hydromusonic acid, and allylmolonic acid, mono(2-ethylhexyl) maleate, monoethyl maleate, monobutyl maleate and mixtures thereof.
  • the third, polyethylenically unsaturated cross-linking co- monomer is selected from the group consisting of triallyl cyanurate, triallyl isocyanurate, diallyl maleate, diallyl fumarate, diallyl phthalate, divinyladipate, divinyl benzene, 1 ,4- butanedioldiacrylate, and mixtures thereof.
  • the invention resides in a paper coating composition
  • a paper coating composition comprising any of the copolymer dispersions described herein and one or more pigments.
  • the pigment may be selected from the group consisting of clay, calcium carbonate, titanium dioxide, plastic pigments and combinations thereof.
  • the present invention relates to aqueous, stabilized, copolymer dispersions that demonstrate excellent pick strength when such dispersions are incorporated into coating compositions, and in particular into coating compositions for paper products.
  • the primary copolymer contained in the present dispersions is a copolymer formed from a monomer mixture comprising, as main monomers, (a) a vinyl ester monomer, (b) ethylene and, optionally, (c) an alkyl or hydroxyalkyi acrylate or methacrylate having 2 to 10 carbon atoms in the alkyl portion thereof.
  • copolymer comprises at least three cross-linking co- monomers.
  • the first of these cross-linking co-monomers comprises at least one ethylenically unsaturated cross-linking co-monomer comprising an epoxy group and/or a silane group
  • the second cross-linking co-monomer comprises at least one ethylenically unsaturated mono- or dicarboxylic acid and/or monoester of an ethylenically unsaturated dicarboxylic acid.
  • the third cross-linking co-monomer comprises at least one polyethylenically unsaturated cross-linking co-monomer.
  • the resultant copolymer is dispersed in an aqueous medium comprising a stabilizer, preferably a surfactant stabilizer.
  • the dispersion may be formulated, with a pigment and/or filler, for example, into a coating composition for coating paper or paperboard substrates.
  • a coating composition for coating paper or paperboard substrates for example, into a coating composition for coating paper or paperboard substrates.
  • Substrates coated with the inventive coating compositions advantageously have excellent picking and wet rub characteristics, making them particularly well suited for paper and paperboard coating applications.
  • Exemplary vinyl ester monomers for forming the present copolymer include vinyl acetate, vinyl formate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl valerate, vinyl- 2-ethyl-hexanoate, vinyl isooctanoate, vinyl nonate, vinyl decanoate, vinyl pivalate, vinyl versatate, and mixtures thereof.
  • vinyl acetate is readily availability and low cost.
  • the vinyl ester may be present in the monomer mixture in an amount ranging from 60 to 90 %, such as from 75 to 90%, by weight based on the total weight of the main monomers (a), (b) and (c).
  • the monomer mixture preferably comprises ethylene in an amount from 2 to 20 %, such as, from 10 to 20 %, by weight based on the total weight of the main monomers (a), (b) and (c).
  • An optional component of the present copolymer comprises an alkyl or hydroxyalkyl acrylate or methacrylate having 2 to 10 carbon atoms in the alkyl portion thereof. Examples include 2-ethyhexyl acrylate, butyl acrylate, hydroxyethyl methacrylate, hydroxyethyl acrylate and mixtures thereof.
  • the alkyl or hydroxyalkyl (meth)acrylate may be present in the monomer mixture in an amount ranging from 0 to 30 %, such as from 0 to 20%, by weight based on the total weight of the main monomers (a), (b) and (c).
  • the first cross-linking co-monomer comprises an ethylenically unsaturated monomer comprising an epoxy group and/or a silane group.
  • suitable epoxy-containing monomers include ally I glycidyl ether, methacryloyl glycidyl ether, butadiene monoepoxides, 1 ,2-epoxy-5-hexene, 1 ,2-epoxy-7- octene, 1 ,2-epoxy-9-decene, 8-hydroxy-6,7-epoxy-1 -octene, 8-acetoxy-6,7-epoxy-1 -octene, N-(2,3-epoxypropyl)acrylamide, N-(2,3-epoxypropyl)methacrylamide, 4-acrylamidophenyl glycidyl ether, 3-acrylamidophenyl glycidyl ether, 4-methacrylamidophenyl glycidyl ether, 3- methacrylamidophenyl glycidyl ether, N-glycidyloxymethylacrylamide, N- glycidyloxymethyl
  • silane-containing monomers includes compounds of the general formula I:
  • R denotes an organic radical olefinically unsaturated in the ⁇ -position
  • R 1 , R 2 and R 3 which may be identical or different, denote halogen, chlorine, or the group -OZ, with Z denoting hydrogen or primary or secondary alkyl or acyl radicals optionally substituted by alkoxy groups.
  • Suitable silane compounds of the formula I include those in which the radical R in the formula represents an ⁇ -unsaturated alkenyl of 2 to 10 carbon atoms, particularly of 2 to 4 carbon atoms, or an ⁇ -unsaturated carboxylic acid ester formed from unsaturated carboxylic acids of up to 4 carbon atoms and alcohols carrying the Si group of up to 6 carbon atoms.
  • Suitable radicals R 1 , R 2 , R 3 may be the group -OZ, Z representing primary and/or secondary alkyl radicals of up to 10 carbon atoms, for example, up to 4 carbon atoms, or alkyl radicals substituted by alkoxy groups, for example, of up to 3 carbon atoms, or acyl radicals of up to 6 carbon atoms, for example, of up to 3 carbon atoms, or hydrogen.
  • Exemplary unsaturated silane co-monomers include vinyl trialkoxy silanes.
  • Exemplary silane compounds of the formula I include vinyltrichlorosilane, vinylmethyldichlorosilane, Y-methacryloxypropyltris(2-methoxyethoxy)silane, vinylmethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyldiethoxysilanol, vinylethoxysilanediol, allyltriethoxysilane, vinyltripropoxysilane, vinyltriisopropoxysilane, vinyltributoxysilane, vinyltriacetoxysilane, trimethylglycolvinylsilane, ⁇ - methacryloxypropyltrimethylglycolsilane, ⁇ -acryloxypropyltriethoxysilane and ⁇ - methacryloxypropyltrimethoxysilane.
  • the first cross-linking co-monomer may be present in the copolymer in an amount from 0.1 to 5 % based on the total weight of the main monomers (a), (b) and (c).
  • the second cross-linking co-monomer employed in the present copolymer comprises at least one ethylenically unsaturated mono- or dicarboxylic acid and/or monoester of an ethylenically unsaturated dicarboxylic acid.
  • Suitable examples include acrylic acid, vinyl acetic acid, crotonic acid, methacrylic acid, tiglic acid, maleic acid, fumaric acid, itaconic acid, maleic acid, citraconic acid, hydromusonic acid, and allylmolonic acid, mono(2-ethylhexyl) maleate, monoethyl maleate, monobutyl maleate and mixtures thereof.
  • the second cross-linking co-monomer may be present in the copolymer in an amount from 0.1 to 5 % based on the total weight of the main monomers (a), (b) and, where present, (c).
  • the third cross-linking co-monomer agent comprises at least one polyethylenically unsaturated cross-linking co-monomer, such as triallyl cyanurate, triallyl isocyanurate, diallyl maleate, diallyl fumarate, diallyl phthalate, divinyladipate, divinyl benzene, 1 ,4-butanedioldiacrylate, and mixtures thereof.
  • polyethylenically unsaturated cross-linking co-monomer such as triallyl cyanurate, triallyl isocyanurate, diallyl maleate, diallyl fumarate, diallyl phthalate, divinyladipate, divinyl benzene, 1 ,4-butanedioldiacrylate, and mixtures thereof.
  • the third cross-linking co-monomer may be present in the copolymer in an amount from 0.1 to 5 % based on the total weight of the main monomers (a), (b) and, where present, (c).
  • copolymers described herein may also include monomer units derived from monomers in addition to the vinyl ester, ethylene, and the cross-linking co-monomers.
  • Auxiliary monomers useful for optionally being incorporated into the presently disclosed copolymer dispersions include ethylenically unsaturated sulfonic acids, ethylenically unsaturated phosphonic acids and salts thereof.
  • Suitable ethylenically unsaturated sulfonic acids include those having 2-8 carbon atoms, such as vinylsulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, 2-acryloyloxyethanesulfonic acid and 2-methacryloyloxyethanesulfonic acid, 2- acryloyloxy- and 3-methacryloyloxypropanesulfonic acid, as well as salts of such acids, such as sodium vinyl sulfonate.
  • suitable ethylenically unsaturated phosphonic acids include vinylphosphonic acid. Where present, these auxiliary momoners are generally added in an amount from 0.2 to 1 weight %, based on the total weight of the monomers (a), (b) and (c).
  • auxiliary monomers that can be incorporated into the presently disclosed copolymer dispersions include ethylenically unsaturated 1 ,3-dicarbonyl compounds and N- methylol compounds.
  • polymerizable 1 ,3-dicarbonyl compounds include acetoacetoxyethyl acrylate, acetoacetoxypropyl methacrylate, acetoacetoxyethyl methacrylate, acetoacetoxybutyl methacrylate, 2,3-di(acetoacetoxy)propyl methacrylate, and allyl acetoacetate.
  • polymerizable N-methylol compounds include N- methylolacrylamide (NMA), N-methylolmethacrylamide, N-methylolallyl carbamate, alkyl ethers and esters such as the isobutoxy ethers or esters of N-methylolacrylamide, of N- methylolmethacrylamide, and of N-methylolallyl carbamate.
  • NMA N-methylolacrylamide
  • N-methylolmethacrylamide N-methylolallyl carbamate
  • alkyl ethers and esters such as the isobutoxy ethers or esters of N-methylolacrylamide, of N- methylolmethacrylamide, and of N-methylolallyl carbamate.
  • Such additional auxiliary monomers may be present in an amount from 0 to 5 weight %, based on the total weight of the monomers (a), (b) and (c).
  • the respective monomers can be polymerized in an aqueous medium at temperatures from 20 °C to 150 °C, preferably from 50 °C to 120 °C under pressures not more than 150 bar, preferably not more than 120 bar or not more than 100 bar, in the presence of an initiator and at least one stabilizer.
  • the aqueous system can be maintained by a suitable buffering agent at a pH of from 2 to 6 or from 4 to 6, with the catalyst being added incrementally or continuously.
  • the co- polymerization process may be run as a batch, semi-batch, or continuous process with periodic or continuous addition of one or more of the monomers during the polymerization process.
  • an initial charge of vinyl ester, ethylene and stabilizer is made, followed by subsequent periodic charges of initiator and additional vinyl ester and/or ethylene.
  • the first, second and third cross-linking co-monomers may be charged, together or separately, with the initial charge and/or in subsequent charging steps, although it is preferred that the cross-linking co-monomers are added shortly after polymerization has begun.
  • the cross-linking co-monomers can be added separately or in admixture.
  • a further, preferably chemical after- treatment especially with redox catalysts, for example combinations of the abovementioned oxidizing agents and reducing agents, may follow to reduce the level of residual unreacted monomer on the product.
  • residual monomer can be removed in known manner, for example by physical demonomerization, i.e. distillative removal, especially by means of steam distillation, or by stripping with an inert gas.
  • a particularly efficient combination is one of physical and chemical methods, which permits lowering of the residual monomers to very low contents ( ⁇ 1000 ppm, preferably ⁇ 100 ppm).
  • Suitable initiators for use in the present polymerization process include any of the water-soluble free-radical-formers generally used in emulsion polymerization, such as hydrogen peroxide, sodium persulfate, potassium persulfate and ammonium persulfate, as well as tert-butyl hydroperoxide, preferably in amounts between 0.01 % and 3% by weight, for example, 0.01 % and 1 % by weight, based on the total weight of the dispersion.
  • reducing agents such as sodium formaldehyde-sulfoxylate, ferrous salts, sodium dithionite, sodium hydrogen sulfite, sodium sulfite, sodium thiosulfate, as redox catalysts in amounts of 0.01 % to 3% by weight, for example, 0.01 % to 1 % by weight, based on the total amount of the dispersion.
  • the free-radical-formers can be charged in the aqueous emulsifier solution or can be added during the polymerization in doses.
  • the reducing agent Bruggolite FF6TM is employed in the polymerization process.
  • FF6 comprises three sulfur-based reducing agents: (i) 2-Hydroxy-S-Sulfinatoacetic acid, di-sodium salt (50-60%); (ii) sodium sulfite (30-35%); and (iii) 2-Hydroxy-2- sulfonatoacetic acid, di-sodium salt (10-15%).
  • the total amount of initiator system prefferably, however, a portion of the initiator is included in the initial charge, and the remainder is added after the polymerization has commenced, in one or more steps or continuously.
  • the present emulsion polymerization process is carried out in the presence of a stabilization system which comprises one or more stabilizers selected from protective colloids, anionic and/or non-ionic surfactants and mixtures thereof.
  • a stabilization system which comprises one or more stabilizers selected from protective colloids, anionic and/or non-ionic surfactants and mixtures thereof.
  • the stabilizer(s) are present in the aqueous polymerization mixture in an amount between 0.5 and 15 % by weight based on the total weight of monomer(s) in the mixture.
  • Suitable protective colloids for use as one or more of the further stabilizer(s) include polyvinyl alcohols, polyvinyl pyrrolidones, methylcelluloses, hydroxyethyl- and propylcelluloses, and also sodium carboxymethylcelluloses, gelatin, casein, starch, gum arabic, hydroxy ethyl starches and sodium alginates.
  • a preferred protective colloid is polyvinyl alcohol.
  • surfactant stabilizers are preferred.
  • Suitable nonionic surfactants which can be used as stabilizers in the present process include polyoxyethylene condensates, although it is generally preferred to minimize the use of ethoxylated nonionics based on alkylphenols (APEs).
  • APEs alkylphenols
  • dispersions and coating compositions are considered to be substantially free of APEs if they contain less than 500 wppm of alkylphenol ethoxylates.
  • Exemplary polyoxyethylene condensates that can be used include polyoxyethylene aliphatic ethers, such as polyoxyethylene lauryl ether and polyoxyethylene oleyl ether; polyoxyethylene alkaryl ethers, such as polyoxyethylene nonylphenol ether and polyoxyethylene octylphenol ether; polyoxyethylene esters of higher fatty acids, such as polyoxyethylene laurate and polyoxyethylene oleate, as well as condensates of ethylene oxide with resin acids and tall oil acids; polyoxyethylene amide and amine condensates such as N-polyoxyethylene lauramide, and N-lauryl-N-polyoxyethylene amine and the like; and polyoxyethylene thio- ethers such as polyoxyethylene n-dodecyl thio-ether.
  • polyoxyethylene aliphatic ethers such as polyoxyethylene lauryl ether and polyoxyethylene oleyl ether
  • polyoxyethylene alkaryl ethers such as polyoxyethylene nonylphenol
  • Nonionic surfactants that can be used also include a series of surface active agents available from BASF under the PluronicTM and TetronicTM trade names.
  • Pluronic surfactants are ethylene oxide (EO)/Propylene oxide (PO)/ethylene oxide block copolymers that are prepared by the controlled addition of PO to the two hydroxyl groups of propylene glycol. EO is then added to sandwich this hydrophobe between two hydrophilic groups, controlled by length to constitute from 10% to 80% (w/w) of the final molecule.
  • PO/EO/PO block copolymers also available under the trade name Pluronic and are prepared by adding EO to ethylene glycol to provide a hydrophile of designated molecular weight.
  • Tetronic surfactants are tetra-functional block copolymers derived from the sequential addition of PO and EO to ethylene-diamine. Tetronic surfactants are produced by the sequential addition of EO and PO to ethylene-diamine. In addition, a series of ethylene oxide adducts of acetyleneic glycols, sold commercially by Air Products under the SurfynolTM trade name, are suitable as nonionic surfactants.
  • nonionic surfactants include DisponilTM A 3065 (alcohol ethoxylate), EmulsogenTM EPN 407 (alkyl polyglycol ether with 40 EO), and EmulsogenTM EPN 287 (alkyl polyglycol ether with 28 EO).
  • Suitable anionic surfactants that can be used as emulsifiers in the binder latex components of the coating compositions, e.g., paper coating compositions, described herein include alkyl aryl sulfonates, alkali metal alkyl sulfates, sulfonated alkyl esters and fatty acid soaps.
  • Specific examples include sodium dodecylbenzene sulfonate, sodium butylnaphthalene sulfonate, sodium lauryl sulfate, disodium dodecyl diphenyl ether disulfonate, N-octadecyl sulfosuccinate and dioctyl sodiumsulfosuccinate.
  • the particle size of the dispersion can be regulated by the quantity of non-ionic or anionic surfactants employed. To obtain smaller particles sizes, greater amounts of surfactants are used. As a general rule, the greater the amount of the surfactant employed, the smaller the average particle size.
  • the copolymer has an average particle size greater than 80 and less than 260 nm, e.g., greater than 100 and less than 200 nm or greater than 120 and less than 180 nm, as determined by Laser Aerosol Spectroscopy. A detailed description of the method is published in Dr. J. Paul Fischer, Kunststoffharz septen 28, "Characterization and quality assurance of polymer dispersions," October 1992.
  • a Nd:YV04 Laser (Millenia II), Spectra Physics with a power of 2 W and a wavelength of 532 nm is used.
  • Polymer particles are spray dried before entering the analyzer. Light scattered by the particles is registered in an angle of 40 °C and the signal is analyzed with a 1024 channel multi channel analyzer from TMCA.
  • TMCA 1024 channel multi channel analyzer
  • 0.2 ml of dispersion are diluted in highly purified water with a specific conductivity of 18.2 [iS/m. The sample is sprayed via a Beckman nozzle and dried with nitrogen.
  • the resulting single particles are neutralized by irradiation (Kr-85 source) and analyzed via the single particle scattering experiment. From the recorded data are calculated the number and weight average distribution curves in a range from 80 to 550 nm as well as the corresponding average particle size diameters (dn, dw and dz as well as dw/dn).
  • the solids content of the resulting dispersion can be adjusted to the level desired by the addition of water or by the removal of water by distillation.
  • the desired level of polymeric solids content is from about 40 wt.% to about 70 wt.% based on the total weight of the respective dispersion, from about 40 wt.% to about 60 wt.% or from about 45 to about 57 wt.%.
  • the actual paper coating compositions of the invention comprise the copolymer dispersion, described above, optionally together with pigments, such as, for example, one or more of (kaolin) clay, titanium dioxide and/or calcium carbonate, talc, and the usual paper coating additives, which may include, for example, rheology modifiers such as CMC (carboxymethyl cellulose), sodium polyacrylates or sodium alginates; lubricants; cross- linkers; optical brighteners; biocides; dispersants; or other co-binders, such as polyvinyl alcohol, protein, e.g., casein or soy protein, or starch, as is well known to those skilled in the art.
  • the coating compositions herein may also contain sufficient alkali to maintain the pH of the coating composition between 6 and 10, for example, between 7 and 9.
  • the pigment used in coating compositions herein may be any of those conventionally employed. Frequently, some or all of the pigment comprises clay and for this portion any of the clays customarily used for paper coating, including the hydrous aluminum silicates of kaolin group clays, hydrated silica clays, and the specific types of clays recommended in Chapters 10-16 of "Kaolin Clays and their Industrial Uses," by J. M. Huber Corp. (1949), New York, N.Y. may be employed.
  • the coating composition may further comprise a pigment selected from the group consisting of clay, calcium carbonate, titanium dioxide, plastic pigments and combinations thereof.
  • optical brighteners and/or paper pigments may also be utilized, such as, for example, calcium carbonate, titanium dioxide, or other coating pigments including plastic pigments, for example, polystyrene.
  • the pigments, in particular calcium carbonate may be present, for example, in amounts up to 50 wt.%, up to 75 wt.% or up to 97 wt.%, based on the total weight of the coating composition.
  • the composition may also contain other additives such as zinc oxide and/or a small amount of a dispersing or stabilizing agent such as sodium polyacrylate or tetrasodium polyphosphate (TSPP).
  • the amount of binder (dispersion) in the paper coating composition may vary, but can range from 2.5 to 25 parts per 100 parts dry pigment, e.g., from 3.5 to 18 parts per 100 parts dry pigment.
  • the coating composition of the invention may also comprise one or more external cross-linkers.
  • Suitable external cross-linkers include carbonates such as ammonium zirconium carbonate (AZC) and potassium zirconium carbonate (KZC). If present, the external cross-linker may comprise from 0.1 to 10 wt.%, e.g., from 0.5 to 5 wt.%, of the total weight of the coating composition.
  • the paper coating compositions of the invention may be applied to various substrates including paper such as freesheet and groundwood grades; paper board; labels; paper products used for newspapers, advertisements, poster, books or magazines; and building substrates such as wall paper, wall board, or ceiling tile.
  • the paper coating composition can be used to coat paper intended for rotogravure printing.
  • the amount of the paper coating composition applied to the substrate is generally in the range of about 1 to 40 g/m 2 , for example, in the range of 3 to 12 g/m 2 or 15 to 25 g/m 2 .
  • the paper coating composition may be applied in a single step or by using two or more steps to build the final coat weight. Further, the paper coating composition may also be applied to the second side of the substrate either simultaneously or as a separate coating step.
  • the paper coating composition may be applied to the substrate by techniques well known to those in the art.
  • the paper coating composition may be applied with a roll applicator such as a metered size press; a blade coater such as a short dwell time applicator; air knife coater; slot die coater; jet applicator; curtain coater or brush.
  • Coating methods for high speed application include the use of a blade coater, a metered size press or a film press.
  • the paper coating compositions of the present invention which contain the particular copolymer dispersions described above, provide highly desirable binding characteristics when applied as a coating to paper substrates of the type described above.
  • the binding performance can be quantified by the IGT dry and wet pick values of the paper coating.
  • a measure of dry binding strength is provided by the IGT dry pick test pursuant to TAPPI Useful Method UM 591 , Surface Strength of Paper, the entirety of which is incorporated herein by reference.
  • the IGT dry pick strength measures the speed, in cm/sec, required to lift the paper coating off of the surface of a paper substrate strip when printed using an ink roller and standard conditions as described in UM 591 . Higher IGT dry pick numbers indicate better resistance of the coated substrate to picking and hence higher strength coating performance.
  • the present coating composition has an IGT Dry Pick Value of at least 50, such as at least 90, for example at least 130 cm/s.
  • pick strength values may vary based on the substrate used, pick strength may also be characterized relative to a control.
  • %IGT and % dry IGT refer to such values relative to a control based on a similarly formed copolymer, but without the first, second and third cross-linking co-monomers.
  • the coating compositions of the invention may provide a %IGT dry pick value greater than 100%, greater than 120 % or greater than 170 %, relative to such a control.
  • wet pick Water on the paper may also cause the paper to not accept ink due to the fact that the water did not completely penetrate into the paper. This is referred to as wet repellence.
  • Wet pick and wet repellence may be ascertained as described in IGT Information leaflet W32, July 2002, published by IGT Testing Systems b.v., the entirety of which is incorporated herein by reference.
  • the present coating compositions may provide IGT wet pick values less than 100 %, such as less than 35 %, for example less than 20 %.
  • the wet rub resistance is Another method to measure the strength between the coating and the paper substrate under wet conditions.
  • the coated substrate is fixed to a rotating plate and, following the addition of 40ml of deionized water, the substrate is abraded with rub rollers for at least 5 rotations. Afterwards the liquid is collected in a 100 ml cylinder, and the plate is then washed again with a certain amount of water and wash water is collected in the cylinder. The cylinder is then filled up to 100 ml. The suspension is transferred into a cuvette and the light transmission through the suspension is measured with a spectrophotometer at 490 nm wave length. A high transmission value is indicative of a good wet rub resistance.
  • the present coating compositions may provide wet rub resistance values of at least 15%, such as at least 30%, for example, at least 40%.
  • the binder and paper-coating compositions of the present invention may or may not comply with U.S. Food & Drug Administration (FDA) regulations concerning paper products that can be used in contact with food.
  • FDA regulations embodied in 21 CFR ⁇ 176.170 and 21 CFR ⁇ 176.180 indicate the types of paper coating composition components, including components of polymers used in such compositions, which can be utilized to coat paper for eventual use with food products.
  • the copolymer dispersions described herein can also be used in other coating compositions, such as paints.
  • copolymer dispersions of the present invention and the performance of such dispersions in the paper coating compositions herein, are illustrated by way of the following non-limiting Examples.
  • feed (1 ) was dosed at a constant rate from 0 to 300 min;
  • feed (3) was dosed at a constant rate from 0 to 150 min and
  • feed (1 ) was dosed at a constant rate from 0 to 300 min;
  • feed (3) was dosed at a constant rate from 0 to 150 min and
  • feed (2) was dosed at a constant rate from 150 to 300 min.
  • the resulting emulsion had a solids content of 50.7%, a viscosity of 296 mPas and an average particle size of 138 nm.
  • the temperature was increased to 80 °C for another 10 minutes, then the mixture was cooled to 50 °C and treated with 93 g tert-butyl hydroperoxide solution (1 1 .3%) and 126 g of Bruggolite®FF6 M solution (7.4%) inclusive 0.21 g ammonium iron (II) sulfate.
  • the resulting emulsion had a solids content of 50.7%, a viscosity of 183 mPas and an average particle size of 143 nm.
  • the temperature was increased to 80 °C for another 10 minutes, then the mixture cooled to 50 °C and treated with 94 g tert-butyl hydroperoxide solution (1 1 .3%) and 128 g of Bruggolite®FF6 M solution (7.4%) inclusive 0.22 g ammonium iron (II) sulfate.
  • the resulting emulsion had a solids content of 50.2%, a viscosity of 227 mPas and an average particle size of 140 nm.
  • the temperature was increased to 80 °C for another 10 minutes, then the mixture cooled to 50 °C and treated with 93 g tert-butyl hydroperoxide solution (1 1 .3%) and 126 g of Bruggolite®FF6 M solution (7.4%) inclusive 0.21 g ammonium iron (II) sulfate.
  • the resulting emulsion had a solids content of 50.6%, a viscosity of 199 mPas and an average particle size of 134 nm.
  • the temperature was increased to 80 °C for another 10 minutes, then the mixture was cooled to 50 °C and treated with 94 g tert-butyl hydroperoxide solution (1 1 .3%) and 128 g of Bruggolite®FF6 M solution (7.4%) inclusive 0.22 g ammonium iron (II) sulfate.
  • the resulting emulsion had a solids content of 50.2%, a viscosity of 227 mPas and an average particle size of 133 nm.
  • the resulting emulsion had a solids content of 49.95%, a viscosity of 376 mPas and an average particle size of 193 nm.
  • the temperature was increased to 80 °C for another 10 minutes, then the mixture cooled to 50 °C and treated with 94 g tert-butyl hydroperoxide solution (1 1 .3%) and 128 g of Bruggolite®FF6 M solution (7.4%) inclusive 0.22 g ammonium iron (II) sulfate.
  • the resulting emulsion had a solids content of 49.75%, a viscosity of 179 mPas and an average particle size of 137 nm.
  • Paper coating compositions as detailed in Table 3 were formulated from each of the copolymer dispersion Samples A to K and from Mowilith PE 292 (a commercial VAE dispersion) and DE 517 (a commercial SBR styrene/butadiene dispersion) as external benchmarks. The formulations were modified by water addition to a target solids content of 68 wt.%.

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  • Health & Medical Sciences (AREA)
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Abstract

L'invention concerne une dispersion de copolymère aqueuse stabilisée qui comprend un copolymère de : (a) de 60 à 90 % d'un ester vinylique d'un acide alcanoïque ayant de 1 à 13 atomes de carbone ; (b) de 2 à 20 % d'éthylène ; (c) de 0 à 30 % d'un acrylate ou méthacrylate d'alkyle ou d'hydroxyalkyle ayant 2 à 10 atomes de carbone dans leur partie alkyle ; (d) de 0,1 à 5 % d'un premier comonomère de réticulation éthyléniquement insaturé comprenant un groupe époxy et/ou un groupe silane ; (e) de 0,1 à 5 % d'un deuxième comonomère de réticulation éthyléniquement insaturé choisi parmi un acide monocarboxylique, un acide dicarboxylique et/ou un monoester d'un acide dicarboxylique ; et (f) de 0,1 à 5 % d'un troisième comonomère de réticulation polyéthyléniquement insaturé, tous les pourcentages étant en poids sur la base du poids total des monomères (a), (b) et, si présent, (c).
PCT/US2014/042123 2013-06-18 2014-06-12 Dispersions de copolymère et leur utilisation dans des formulations de couchage de papier Ceased WO2014204779A1 (fr)

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US201361836293P 2013-06-18 2013-06-18
US61/836,293 2013-06-18
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US61/915,623 2013-12-13

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Cited By (4)

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Publication number Priority date Publication date Assignee Title
WO2015146876A1 (fr) * 2014-03-27 2015-10-01 Ｋｊケミカルズ株式会社 (méth)acrylamide contenant un groupe glycidyle
CN114134753A (zh) * 2021-10-26 2022-03-04 苏州吉谷新材料有限公司 用于新闻用纸的涂层材料及其制备方法、转印纸生产工艺
US11401639B2 (en) 2016-09-06 2022-08-02 Owens Corning Intellectual Capital, Llc Corrosion-resistant non-woven for pipe liner pultrusion applications
WO2022223884A1 (fr) * 2021-04-21 2022-10-27 Daito Kasei Europe Sas Polymère réticulé obtenu par polymérisation d'au moins un monomère éthylénique dicarboxylique particulier en présence d'un agent de réticulation particulier de type diester avec deux insaturations.

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US4503185A (en) 1984-06-22 1985-03-05 Air Products And Chemicals, Inc. Vinyl acetate/ethylene copolymer emulsions for paper coating compositions
EP0699692A2 (fr) * 1994-09-02 1996-03-06 Hoechst Aktiengesellschaft Dispersions aqueuses pour adhésifs
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US4395499A (en) 1982-09-13 1983-07-26 National Starch And Chemical Corporation High strength pigment binders for paper coatings containing carboxylated vinyl ester alkyl acrylic interpolymers
US4503185A (en) 1984-06-22 1985-03-05 Air Products And Chemicals, Inc. Vinyl acetate/ethylene copolymer emulsions for paper coating compositions
EP0699692A2 (fr) * 1994-09-02 1996-03-06 Hoechst Aktiengesellschaft Dispersions aqueuses pour adhésifs
US5849389A (en) 1997-03-10 1998-12-15 National Starch And Chemical Investment Holding Corporation Carpet coating compositions

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015146876A1 (fr) * 2014-03-27 2015-10-01 Ｋｊケミカルズ株式会社 (méth)acrylamide contenant un groupe glycidyle
JPWO2015146876A1 (ja) * 2014-03-27 2017-04-13 Ｋｊケミカルズ株式会社 グリシジル基含有（メタ）アクリルアミド
US11401639B2 (en) 2016-09-06 2022-08-02 Owens Corning Intellectual Capital, Llc Corrosion-resistant non-woven for pipe liner pultrusion applications
US11970801B2 (en) 2016-09-06 2024-04-30 Owens Corning Intellectual Capital, Llc Corrosion-resistant non-woven for pipe liner pultrusion applications
WO2022223884A1 (fr) * 2021-04-21 2022-10-27 Daito Kasei Europe Sas Polymère réticulé obtenu par polymérisation d'au moins un monomère éthylénique dicarboxylique particulier en présence d'un agent de réticulation particulier de type diester avec deux insaturations.
FR3122180A1 (fr) * 2021-04-21 2022-10-28 Daito Kasei Europe Sas Polymère réticulé obtenu par polymérisation d'au moins un monomère éthylénique dicarboxylique particulier en présence d'un agent de réticulation particulier de type diester avec deux insaturations.
CN114134753A (zh) * 2021-10-26 2022-03-04 苏州吉谷新材料有限公司 用于新闻用纸的涂层材料及其制备方法、转印纸生产工艺

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