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WO2010058087A1 - Composition de polymère - Google Patents

Composition de polymère Download PDF

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Publication number
WO2010058087A1
WO2010058087A1 PCT/FI2009/050947 FI2009050947W WO2010058087A1 WO 2010058087 A1 WO2010058087 A1 WO 2010058087A1 FI 2009050947 W FI2009050947 W FI 2009050947W WO 2010058087 A1 WO2010058087 A1 WO 2010058087A1
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WO
WIPO (PCT)
Prior art keywords
dry coating
binder
vinyl
monomers
acid
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/FI2009/050947
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English (en)
Inventor
Jonni Ahlgren
Nina Bruun
Vesa Nuutinen
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Kemira Oyj
Original Assignee
Kemira Oyj
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Kemira Oyj filed Critical Kemira Oyj
Priority to RU2011125948/04A priority Critical patent/RU2011125948A/ru
Priority to US13/130,876 priority patent/US20110236572A1/en
Priority to CA2744373A priority patent/CA2744373A1/fr
Priority to CN2009801464778A priority patent/CN102224174A/zh
Priority to EP09827238A priority patent/EP2358763A4/fr
Publication of WO2010058087A1 publication Critical patent/WO2010058087A1/fr
Anticipated expiration legal-status Critical
Ceased 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
    • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
    • 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
    • C08F212/00—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 aromatic carbocyclic ring
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/06—Hydrocarbons
    • C08F212/08—Styrene
    • 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
    • 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
    • C09D133/00—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 only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09D133/08—Homopolymers or copolymers of acrylic acid esters
    • 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
    • C09D135/00—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 a carboxyl radical, and containing at least another carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D135/06—Copolymers with vinyl aromatic monomers
    • 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
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/03—Powdery paints
    • 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
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/03—Powdery paints
    • C09D5/033—Powdery paints characterised by the additives
    • C09D5/035—Coloring agents, e.g. pigments
    • 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • 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
    • D21H19/00—Coated paper; Coating material
    • D21H19/10—Coatings without pigments
    • D21H19/14—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12
    • D21H19/24—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12 comprising macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • 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
    • D21H19/00—Coated paper; Coating material
    • D21H19/36—Coatings with pigments
    • D21H19/44—Coatings with pigments characterised by the other ingredients, e.g. the binder or dispersing agent
    • D21H19/56—Macromolecular organic compounds or oligomers thereof obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H19/58—Polymers or oligomers of diolefins, aromatic vinyl monomers or unsaturated acids or derivatives thereof
    • 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
    • D21H27/00—Special paper not otherwise provided for, e.g. made by multi-step processes
    • D21H27/30—Multi-ply
    • D21H27/42—Multi-ply comprising dry-laid paper
    • 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
    • C08F220/04—Acids; Metal salts or ammonium salts thereof
    • C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
    • 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
    • C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]

Definitions

  • the present invention is in the field of paper coating materials.
  • the invention relates to a binder composition comprising copolymer particles.
  • the present invention further concerns the use of the binder composition in coating powders suitable for dry coating systems.
  • Conventional paper coatings are applied on a paper substrate as water containing coating colors. These coating formulations are prepared by mixing solids of suitable properties, such as inorganic pigments, binders and additives, with water.
  • the conventional coating mixes are applied on the surface of the paper web as water-based slurry, the water carried over to the web by the coating mix must be removed and therefore effective drying is needed after coating.
  • WO 2004/044323 discloses a method for coating a web of paper by a dry coating powder. The method comprises the step of applying the coating powder to at least one side of the moving web.
  • the coating powders include inorganic materials and polymeric binder material.
  • US 2005/0006041 discloses a composite compositions of co-structured or co-adsorbed fillers containing at least two different types of minerals or organic pigments and their use in papermaking for the coating.
  • This composition contains at least one pigment having a surface with at least one hydrophilic site and at least one pigment having at least one organophilic site.
  • the binder of this composition is selected from the group containing acrylic polymers, vinyl polymers, their copolymers, their polycondensates, or the polyaddition products, in their free acid state or partially neutralized, or totally neutralized, of at least one of the monomers acrylic acid, methacrylic acid etc.
  • WO 01/00712 discloses dry pigment granulates for paper coating, especially for fine paper.
  • the pigment granulate comprises 95-99.5 wt- % of organic polymer pigment, 0-94.5 wt-% of inorganic pigment and 0.5-5 wt- % of a binder or a mixture of binders and the particle size of the granulate is 4- 400 ⁇ m.
  • Polyvinyl alcohol, polyvinylacetate, styrene-butadiene latex, polyethylene glycol, and similar compounds are mentioned as examples of suitable binders. This publication does not contain any teaching regarding the particle size of the binder before mixing with the pigment.
  • WO 2006/050873 discloses a paper coating slip containing at least one inorganic pigment, in particular white pigments, and, in relation to 100 weight parts of the inorganic pigments, less than 40 weight parts of organic polymers, and less than 25 weight parts of water or other solvents with a boiling point lower than 150 °C at 1 bar.
  • the paper coating slips should have as low content as possible of water or solvents and they should adhere well to paper.
  • the binder used in the slip can be a polymer prepared by emulsion polymerization, such as Acronal ® S 728, which is an aqueous dispersion of a styrene/butyl acrylate copolymer.
  • Hayes discloses that a decrease in the particle size of a styrene-butadiene or styrene-acrylic latex will produce an increase in coating strength. This is assumed to be the result of an increase in the total number of latex particles available in a given formulation. Further, Hayes discloses that the strongest styrene-butadiene binders have a small particle size and optimized gel content, glass transition temperature (T 9 ), and acid content.
  • One of the problems related to the coating by the dry surface treatment process is the behavior of the polymeric binder material during the process.
  • synthetic paper coating binders have a particle size between 100-150 nm and the glass transition temperature (T 9 ) is from -35 °C to +35 °C.
  • the binder dosage being typically between 10-15 parts per 100 parts inorganic pigment.
  • coatings are produced by mixing the pigments and binder together with water. The resulting mixture is then dried and dry ground to produce a dry coating powder. The use of these known coating powders results in coatings having a quality that is unacceptable for high speed printing.
  • Pick is the name commonly given to damage to the paper surface occurring during the printing operation.
  • the ink exerts on the paper a force, which increases with increasing viscosity and tack of the ink and with increasing printing speed.
  • This force exceeds a critical value, which depends on the paper, the surface of the paper is damaged.
  • the minimum printing speed at which pick occurs is a measure of the pick resistance of the paper.
  • Pick velocity [m/s] is the velocity at which pick of the surface on the printed paper begins under the conditions defined in the International standard ISO 3783 (IGT type tester). This pick resistance measurement can be used to describe the surface strength of the paper.
  • An object of the present invention is thus to provide a binder material so as to alleviate the above disadvantages.
  • the objects of the invention are achieved by a dry coating binder, a dry coating composition and coating process, which are characterized by what is stated in the independent claims.
  • the preferred embodiments of the invention are disclosed in the dependent claims.
  • the invention is based on the realization that by the right selection of polymeric binder for coating powder the final coating quality (surface strength) can be improved.
  • surface strength surface strength
  • the particle size of the binder is a determinant factor of the final surface strength of the coating.
  • a bigger particle size than normally used gave better surface strength.
  • the present invention provides a binder comprising a synthetic polymer and having a specific particle size.
  • the lower limit of the particle size is 200 nm, but in some embodiments of the invention the lower limit of the particle size may be 220 nm, 240 nm or even 250 nm.
  • the upper limit of the particle size is 400 nm, but in some embodiments of the invention the upper limit of the particle size may be 350 nm, 320 nm or 300 nm. It should be clear for a person skilled in the art that the binder may contain some small portions of fine particles having a particle size below 200 nm, but that the binder of the present invention comprises substantially only particles within the above-mentioned particle size limits.
  • the particle size should not be too large because then the dispersion does not maintain stability as well as when the upper limit of the particle size is set to 400 nm.
  • the big particles sediment more easily and they also may form agglomerates, which would increase the sedimentation.
  • the binder of the invention is especially useful in dry coating powder compositions for coating a web of paper.
  • the inventors have surprisingly found out that particle size of the binder has a great impact on the IGT surface strength of dry coated papers.
  • synthetic paper coating binders have particle size between 50-150 nm and the glass transition temperature (T 9 ) is from -35 °C to +35 °C.
  • T 9 glass transition temperature
  • the excellent results of the present invention were obtained with binders having bigger particle size than typically.
  • particle size is meant the mean particle size of the polymerized particles.
  • the dry coating binder of the present invention is characterized by the particle size of the binder, which is between 200-400 nm, preferably between 220-350 nm, and more preferably between 250-350 nm.
  • Suitable binders are synthetic polymers, in particular polymers which are obtainable by free radical polymerization of ethylenically unsaturated compounds (monomers).
  • the polymers are prepared by emulsion polymerization, and an emulsion polymer is therefore involved.
  • Other possible preparation methods include suspension polymerization and subsequent dispersing in water.
  • the dry coating binder of the present invention is a polymer which comprises at least 80% by weight of so-called main monomers. In some embodiments the amount of main monomers can be at least 90% by weight or at least 95% by weight.
  • the main monomers are selected from C- ⁇ -C 2 o-alkyl (meth)acrylates, d- C- 20 -hydroxy alkyl (meth)acrylates, Ci-C 2 o-alkyl (meth)acrylamides, C 1 -C 2O - hydroxy alkyl (meth)acrylamides, vinyl esters of carboxylic acids comprising up to 20 carbon atoms, vinyl aromatics having up to 20 carbon atoms, ethylenically unsaturated nitriles, vinyl ethers of alcohols comprising 1 to 10 carbon atoms, aliphatic hydrocarbons having 2 to 8 carbon atoms and one or two double bonds, or mixtures of these monomers.
  • alkyl (meth)acrylates having a Ci-Ci O -alkyl radical such as methyl methacrylate, methyl acrylate, butyl acrylate, ethyl acrylate, and 2-ethylhexyl acrylate, may be mentioned.
  • mixtures of the alkyl (meth)acrylates are suitable.
  • Vinyl esters of carboxylic acids having 1 to 20 carbon atoms are, for example, vinyl laurate, vinyl stearate, vinyl propionate, vinyl versatate, and vinyl acetate.
  • vinyl esters have been hydrolyzed to alcohols in the final polymer, thus forming polyalcohols.
  • Suitable vinyl aromatic compounds are styrene, vinyltoluene, ⁇ - and p-methylstyrene, ⁇ -butylstyrene, 4-n-butylstyrene, and 4-n-decylstyrene, styrene being a preferred main monomer.
  • nitriles are acrylonitrile and methacrylonitrile.
  • vinyl methyl ether or vinyl isobutyl ether may be mentioned as vinyl ethers.
  • Vinyl ethers of alcohols comprising 1 to 4 carbon atoms are preferred.
  • Ethylene, propylene, butadiene, isoprene and chloroprene may be mentioned as examples of hydrocarbons having 2 to 8 carbon atoms and one or two olefinic double bonds.
  • Preferred main monomers are C-i-C-io-alkyl (meth)acrylates, in particular butyl acrylate, and mixtures of the alkyl(meth)acrylates with vinyl aromatics, in particular styrene, or, alternatively, hydrocarbons having 2 double bonds, in particular butadiene, or mixtures of such hydrocarbons with vinyl aromatics, in particular styrene.
  • the ratio may be, for example, from 10:90 to 90:10, in particular from 20:80 to 80:20.
  • the polymer may comprise monomers having at least one acid group, for example monomers having carboxylic, sulfonic or phosphonic acid groups.
  • Carboxylic groups are preferred.
  • acrylic acid, methacrylic acid, itaconic acid, maleic acid, crotonic acid, fumaric acid, 2- acrylamido-2-methyl propanesulfonic acid (AMPS), vinyl sulfonic acid, and vinyl phosphonic acid may be mentioned.
  • the acids may be also in the corresponding salt form.
  • monomers over and above these are, for example, monomers comprising hydroxyl groups, in particular C-i-C-io-hydroxyalkyl (meth)acrylates, and (meth)acrylamide.
  • the main monomers preferably comprise acid monomers as comonomers, preferably in an amount of from 1 % to 6% by weight.
  • the dry coating binder is a styrene/butyl acrylate/acrylic acid copolymer (S/BA/AA).
  • Said S/BA/AA copolymer has been preferably polymerized with the following monomer ratio: a) 34 to 90 parts, more preferably 60 to 75 parts by weight styrene, b) 5 to 65 parts, more preferably 15 to 35 parts by weight butyl acrylate, and c) 1 to 5 parts, more preferably 2 to 4 parts by weight acrylic acid.
  • ionic and/or nonionic emulsifiers and/or protective colloids can be used as stabilizers.
  • the surface- active substances are used in amounts of from 1 % to 5% by weight, based on the monomers to be polymerized. It is an advantage of the present invention that the amount of surface-active substances may be decreased. In some embodiments of the present invention, it is advantageous that the amount of surface-active substances is less than 1 % or less than 0.5 % or even less than 0.2 % and preferably less than 0.15 % by weight based on the monomers to be polymerized.
  • surface active substance is sodium dodecyl sulfate (SDS)
  • SDS sodium dodecyl sulfate
  • other examples of possible surface active substances are, but not limited to, sodium dodecanoate, sodium tetradecanoate, sodium hexadecanoate, sodium octadecanoate, sodium tetradecyl sulfate, sodium hexadecyl sulfate, sodium octadecyl sulfate, sodium dodecyl sulfonate, sodium dodecyl benzene sulfonate, sodium dialkyl sulfosuccinates, polyoxyethylene dodecyl ethers, and polyoxythylene nonyl phenyl ethers.
  • protective colloids such as polyvinylalcohol (PVA), starch or carboxymethyl cellulose (CMC).
  • Water-soluble initiators for the emulsion polymerization are, for example, ammonium and alkali metal salts of peroxodisulfuric acid, e.g. potassium persulfate (K 2 S 2 O 8 ), sodium persulfate (Na 2 S 2 O 8 ), hydrogen peroxide or organic peroxides, e.g. tert-butyl hydroperoxide. So-called reduction-oxidation (redox) initiator systems are also suitable. The amount of the initiators is in general from
  • Chain length regulators can be used in the polymerization, for example in amounts of from 0 to 0.8 part by weight, based on 100 parts by weight of the monomers to be polymerized, the molar mass being reduced by the said regulators.
  • compounds having a thiol group such as tert-butyl mercaptan, thioglycolic acid, mercaptoethanol, mercaptopropyltrimethoxysilane or tert-dodecyl mercaptan, are suitable.
  • the emulsion polymerization is effected, as a rule, at from 30 °C to 130°C, preferably from 50 °C to 90 °C.
  • the polymerization medium may consist either only of water or of mixtures of water with liquids miscible therewith, such as methanol. Preferably, only water is used.
  • the emulsion polymerization can be carried out both as a batch process and in the form of a feed process, including a step or gradient procedure.
  • a part of the polymerization batch is initially taken, heated to polymerization temperature and partly polymerized and then the remainder of the polymerization batch is fed to the polymerization zone, usually via a plurality of spatially separate feeds, one or more of which comprises the monomers in pure or in emulsified form, continuously, stepwise or with superposition of a concentration gradient, while maintaining the polymerization, is preferred.
  • a polymer seed may also be initially taken, for example for better adjustment of the particle size.
  • the manner in which the initiator is added to the polymerization vessel in the course of the free radical aqueous emulsion polymerization is known to the average person skilled in the art. It can either be completely initially taken in the polymerization vessel or used continuously or stepwise at the rate of its consumption in the course of the free radical aqueous emulsion polymerization. Specifically, this depends on the chemical nature of the initiator system and on the polymerization temperature. Preferably, a part is initially taken and the remainder is fed to the polymerization zone at the rate of consumption.
  • the initiator is usually also added after the end of the actual emulsion polymerization, i.e. after a conversion of at least 95% of the monomers.
  • the individual components can be added to the reactor from above, at the side or from below through the reactor bottom.
  • aqueous dispersions of the polymer generally having solids contents of from 15 to 75% by weight, typically from 40 to 55% by weight, are obtained.
  • the T 9 changes.
  • the T 9 of the polymer is between -25 °C to 95 °C.
  • Variation of T 9 can be used to optimize the binder.
  • the T 9 of the binder may be adjusted within the predetermined limits.
  • the lower limit of the T 9 of the binder according to the present invention may be -25 °C, 0°C, 1 O 0 C, 15 0 C, 20 °C, or 25 °C
  • the upper limit of the T 9 of the binder according to the present invention may be 95 °C, 80 °C, 70 °C, 60 °C, 50 °C, or 40 °C.
  • X 1 , X 2 ,..., X s denote the proportions by weight of monomers 1 , 2, . . . , s, and T 9 1 , T 9 2 , . . . , T 9 S denotes the glass transition temperatures of the respective polymers built up only from one of the monomers 1 , 2, . . . , s, in Kelvin.
  • the glass transition temperatures of some of the monomers are essentially known and are listed, for example, in Emulsion Polymerization and Emulsion Polymers, ed. Lovell and Al-Aasser, p. 622.
  • regulators such as sodium dodecyl sulfate (SDS) can be used in the polymerization to adjust the mean particle size.
  • SDS sodium dodecyl sulfate
  • the amount of SDS is preferably from 0.05 wt-% to 0.5 wt-% based on the monomers to be polymerized.
  • the particle size changes depending on how much SDS is charged to the reactor, but also the speed of the agitator affects the particle size. Higher agitator speed degreases the mean particle size.
  • the binder of the present invention is preferably a styrene/butyl aery I ate/acrylic acid copolymer (S/BA/AA), containing 60 to 76 parts by weight styrene, 15 to 35 parts by weight butyl acrylate, and 2 to 4 parts by weight acrylic acid.
  • the solid content is preferably 40 wt-% to 45 wt-%, and as the initiator potassium persulfate (K 2 S 2 O 8 ) is used in an amount of 0.25 wt-% to 0.5 wt-% based on the monomers to be polymerized.
  • T 9 and particle size of the binder By changing T 9 and particle size of the binder it is possible to find out the binder with the substantially improved properties.
  • the surface strength of the coated paper is very good when using the binder of the present invention having the mean particle size between 250 nm and 350 nm.
  • the present invention provides the use of the binder composition according to the invention in a paper or board coating composition.
  • the paper coating composition is in powder form and is applied on the paper using dry coating technology.
  • the present invention provides a coating composition comprising inorganic particles and the binder of the present invention.
  • a coating composition may contain inorganic particles, such as crystalline or amorphous aluminum hydroxides, natural or synthetic calcium carbonate, for example chalk, calcite, marble or any other form of calcium carbonate, natural or synthetic precipitated silicates, calcium sulfate, titanium dioxide, satin white, talcs, micas, clays, calcined clays, zinc oxide and mixtures thereof.
  • the composition may comprise a mixture of mineral and plastic pigments. In one embodiment of the invention the amount of the plastic pigment is 0.1 - 20% by weight of the amount of the inorganic particles.
  • the coating composition may also comprise coloring pigments and/or carbon black.
  • the coating composition may be produced by mixing the binder with inorganic particles.
  • the binder dosage is between 5- 20 parts per 100 parts inorganic particles and typically being between 10-15 parts per 100 parts inorganic particles.
  • the mixing can be performed with or without additional water.
  • After mixing the obtained mixture is dried by a convenient manner such as spray drying or freeze drying.
  • the dry mixture is then ground for example with a jet mill and then the coating composition is recovered in dry powder form.
  • the obtained coating powder can be used for coating a paper substrate in a dry coating method.
  • the coating composition may also comprise other additives, such as optical brightening agent or antiblocking agent.
  • the present invention provides a process for coating a web of paper by a dry coating powder, the process being characterized in that it comprises a step of applying a coating composition of the invention to at least one side of the web using known dry coating methods.
  • Thermoplastic binders according to the invention were emulsion polymerized. Polymerizations were made in a 700 ml glass reactor. Nitrogen was fed into the reactor during polymerization. A glass agitator with 3 blades was used. The reactor was placed in a water bath. The temperature of the bath was 80 °C. All the binder samples were polymerized in this reactor. The polymerization time was 6 hours. After this the water was removed from the bath. Then during 3 hours the sample in the reactor was cooled to room temperature, after this the agitation was stopped. The agitation speed during cooling was the same as during polymerization from 4h30min to 6h.
  • the speed of the agitator can be varied depending on the desired mean particle size.
  • the agitation speed was 175 rpm during the first 4h 30 min from the beginning of the polymerization, and 250 rpm during the next 1.5 hours (from 4h 30min to 6 h) for all the polymerizations except for Sample 01 1 for which the agitation speeds were 220 rpm and 310 rpm respectively.
  • the monomers were: styrene, n-butyl acrylate and acrylic acid.
  • the formulation of the polymerized binders is disclosed in Table 1. The amount of styrene varied from 59.8 wt-% to 71 wt-%, the amount of n-butyl acrylate varied from 27 wt-% to 38.2 wt-%, and the amount of acrylic acid varied from 2 wt-% to 4 wt-%.
  • the solid content was 42.5 wt-% in all polymerizations.
  • SDS Sodium dodecyl sulfate
  • K 2 S 2 O 8 Initiator potassium persulfate
  • Sample 002 was polymerized in the 700 ml reactor. Nitrogen was fed into reactor during polymerization. Following chemicals were added into the reactor: styrene 6.1 g, n-butyl acrylate 2.3 g and acrylic acid 0.17 g, SDS 0.25 g (0.12 wt-%) and water 248.2 g, Potassium persulfate 0.20 g and water 8.8 g. The polymerization was continued for 10 minutes. Then the addition of following chemicals into the reactor was started and continued during 300 minutes:
  • the sample was filtered through a filter cloth 50 ⁇ m.
  • the quantity of the lumped polymers that was carried on the filter was weighted.
  • the mean particle size and the T 9 were analyzed. The particle size changes depending on how much SDS is charged to the reactor, but also the speed of the agitator affects the particle size. By changing the ratio of monomers in the formulation the T 9 changes.
  • the obtained polymers from Example 1 were used together with pigments in coating powders.
  • the polymers obtained were neutralized with ammonium hydroxide before mixing with pigments.
  • the coating powders were used in paper dry coating.
  • Table 1 the coating powders (Table 1 ) were formed from the raw materials. This was done by mixing 15 parts of experimental binders with 100 parts GCC pigment (particle size: 90% less than 2 microns) in water state.
  • the mixtures were freeze dried and micronized in a fluidized bed jet mill of the type Alpine AFG 100. Powders thus obtained having a particle size D90 2,5 - 5,5 ⁇ m were applied on paper substrate (base paper 37 g/m 2 ) using Nordson Versa Spray Il manual spray gun. The coat weights varied between 5 - 1 1 g/m 2 .
  • the fixing of coating powder on a base paper was done by thermo-mechanical treatment using a laboratory calender (DT Paper Science; heated steel roll, polymer covered backing roll). In fixing each sample was run through four calender nips with the following condition. The first three nips: the calendering speed 4 m/min, the temperature of the heated roll was 150°C and the nip load 64 kN/m. Siliconised baking paper was used to prevent sticking onto the hot calender roll. The last fixing nip was done without siliconised baking paper in the calendering speed 4 m/min, the temperature of the heated roll was 150°C and the nip load 164 kN/m.
  • the coating quality (IGT surface strength) of the dry coated papers was then analyzed.
  • the experimental binders were styrene/n-butylacrylate/acrylic acid copolymers (S/BA/AA) with varied particle size and glass transition temperature (T g ) as shown in Table 1.
  • IGT Pick velocity [m/s], the velocity at which pick of the surface on the printed paper begins under the conditions defined in the International standard ISO 3783 (IGT type tester). Test performed using IGT AIC2-5T2000 by IGT Testing Systems with low viscosity oil.
  • SDS The amount of Sodium dodecyl sulfate based on the monomers to be polymerized. Particle sizes were measured using photon correlation spectroscopy with a Zetamaster device (Malvern Instruments, Finland). The accuracy of the device was tested using the following polystyrene standards: Duke Scientific Corporation, 3020 A (20 nm) and 3100 A (100nm).
  • the glass transition (T 9 ) determinations were carried out according to the ASTM E1356-03 Standard Test Method for Assignment of the Glass Transition Temperatures by Differential Scanning Calorimetry using Mettler Toledo DSC821 instrument, calibrated against indium and zinc.
  • the temperature range of the dynamic experiment was heating from 0°C to 100°C at the rate of 5°C/min and then after cooling back to 0°C the heating was repeated.
  • the glass transition temperature was determined by the second heating curve.
  • Aluminum crucibles and sample weights of about 20 mg were used.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Inorganic Chemistry (AREA)
  • Paper (AREA)
  • Paints Or Removers (AREA)

Abstract

La présente invention porte sur un liant de couchage à sec comprenant un polymère qui contient au moins 80 % en poids de monomères principaux. Les monomères principaux sont choisis parmi les (méth)acrylates d'alkyle en C1-C20, les (méth)acrylates d'hydroxyalkyle en C1-C20, les esters vinyliques d'acides carboxyliques comprenant jusqu'à 20 atomes de carbone, les aromatiques vinyliques comportant jusqu'à 20 atomes de carbone, les nitriles à insaturation éthylénique, les éthers de vinyle et d'alcools comprenant 1 à 10 atomes de carbone, les hydrocarbures aliphatiques comportant de 2 à 8 atomes de carbone et une ou deux doubles liaisons ou les mélanges de ces monomères et la taille des particules du liant est comprise entre 200 et 400 nm. En outre, la présente invention porte sur l'utilisation dudit liant de revêtement à sec. Un autre aspect de l'invention porte sur une composition de couchage à sec.
PCT/FI2009/050947 2008-11-24 2009-11-23 Composition de polymère Ceased WO2010058087A1 (fr)

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RU2011125948/04A RU2011125948A (ru) 2008-11-24 2009-11-23 Полимерная композиция
US13/130,876 US20110236572A1 (en) 2008-11-24 2009-11-23 Polymer composition
CA2744373A CA2744373A1 (fr) 2008-11-24 2009-11-23 Composition de polymere
CN2009801464778A CN102224174A (zh) 2008-11-24 2009-11-23 聚合物组合物
EP09827238A EP2358763A4 (fr) 2008-11-24 2009-11-23 Composition de polymère

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FI20086122A FI20086122A7 (fi) 2008-11-24 2008-11-24 Polymeerikoostumus

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WO2012084775A1 (fr) * 2010-12-22 2012-06-28 Basf Se Carton recyclé ou gris et ses procédés de fabrication
CN103044623A (zh) * 2011-10-17 2013-04-17 中国石油天然气股份有限公司 一种包覆剂及其在粉末橡胶制备中的应用
EP2370631B1 (fr) 2008-12-18 2017-11-08 Kemira OYJ Composition de sauce de couchage et papier ou carton revêtu de celle-ci
EP3755753B1 (fr) * 2018-02-21 2022-07-27 Basf Se Procédé de production d'articles enduits d'adhésifs

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WO2014122031A1 (fr) * 2013-02-06 2014-08-14 Basf Se Latex hybride comprenant des particules polymères ayant une structure cœur-coque et son procédé de préparation
CA2906958A1 (fr) * 2013-03-15 2014-09-18 Kemira Oyj Polymeres reduisant les frottements
US20140323659A1 (en) * 2013-04-26 2014-10-30 Canon Kabushiki Kaisha Method for producing resin composition and resin composition
KR102028439B1 (ko) * 2015-03-19 2019-10-04 동우 화인켐 주식회사 자발광 감광성 수지 조성물, 이를 포함하는 컬러필터 및 화상표시장치

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WO2004099261A1 (fr) * 2003-05-06 2004-11-18 Nuplex Resins B.V. Procede de polymerisation par emulsion, dispersion polymerique et composition filmogene
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Cited By (7)

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Publication number Priority date Publication date Assignee Title
EP2370631B1 (fr) 2008-12-18 2017-11-08 Kemira OYJ Composition de sauce de couchage et papier ou carton revêtu de celle-ci
WO2012084775A1 (fr) * 2010-12-22 2012-06-28 Basf Se Carton recyclé ou gris et ses procédés de fabrication
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CN103044623B (zh) * 2011-10-17 2016-09-07 中国石油天然气股份有限公司 一种包覆剂及其在粉末橡胶制备中的应用
EP3755753B1 (fr) * 2018-02-21 2022-07-27 Basf Se Procédé de production d'articles enduits d'adhésifs

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US20110236572A1 (en) 2011-09-29
CN102224174A (zh) 2011-10-19
CA2744373A1 (fr) 2010-05-27
RU2011125948A (ru) 2012-12-27
EP2358763A1 (fr) 2011-08-24
EP2358763A4 (fr) 2012-12-05
FI20086122L (fi) 2010-05-25
FI20086122A7 (fi) 2010-05-25
FI20086122A0 (fi) 2008-11-24

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