EP2744940B1 - Sauces de couchage aqueuses à base d'urée, composants de sauces de couchage aqueux à base d'urée et leur utilisation - Google Patents

Sauces de couchage aqueuses à base d'urée, composants de sauces de couchage aqueux à base d'urée et leur utilisation Download PDF

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EP2744940B1
EP2744940B1 EP12751311.7A EP12751311A EP2744940B1 EP 2744940 B1 EP2744940 B1 EP 2744940B1 EP 12751311 A EP12751311 A EP 12751311A EP 2744940 B1 EP2744940 B1 EP 2744940B1
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weight
parts
acid
monomers
ethylenically unsaturated
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German (de)
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EP2744940A2 (fr
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Thomas Steinmacher
Norbert Gispert
Jens Utecht
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BASF SE
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BASF SE
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Classifications

    • 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
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/03—Non-macromolecular organic compounds
    • D21H17/05—Non-macromolecular organic compounds containing elements other than carbon and hydrogen only
    • D21H17/07—Nitrogen-containing compounds
    • 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
    • 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
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/21—Macromolecular organic compounds of natural origin; Derivatives thereof
    • D21H17/24—Polysaccharides
    • D21H17/28—Starch
    • 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
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/33—Synthetic macromolecular compounds
    • D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H17/35—Polyalkenes, e.g. polystyrene
    • 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
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/33—Synthetic macromolecular compounds
    • D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H17/36—Polyalkenyalcohols; Polyalkenylethers; Polyalkenylesters
    • 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
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/33—Synthetic macromolecular compounds
    • D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H17/37—Polymers of unsaturated acids or derivatives thereof, e.g. polyacrylates
    • 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
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/63—Inorganic compounds
    • D21H17/67—Water-insoluble compounds, e.g. fillers, pigments
    • 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
    • D21H19/54—Starch
    • 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

Definitions

  • the invention relates to the use of urea to reduce the amount of energy required for drying paper coated with aqueous paper coating slip and / or to reduce the viscosity of paper coating slips, as well as aqueous compositions suitable for this use in the form of aqueous paper coating slips and urea-containing aqueous paper coating color components, each with one certain content of urea H2N-CO-NH2.
  • the manufacture of paper is a very energy-intensive process. For example, around 2300 to 2600 kWh of energy are required to produce one ton of paper. In paper finishing, a considerable part of the amount of energy required is used to dry the paper coated with an aqueous paper coating color. Manufacturers try to produce paper coating colors with the lowest possible water content, i.e. to use with the highest possible solids content in order to keep the required drying energy as low as possible. 500 tons of coating color with an initial solids content of 66% are processed every day, the increase in solids content by as little as 1% means that 7.5 tons less water have to be removed through drying. The drying energy saved (at 100% efficiency) is then approx. 5 MWh / day.
  • the US 2007/0082212 teaches special paper based on a non-acidic base paper that has been coated with a paper coating slip that contains clay as a pigment. It also contains additives which can also be rheological aids.
  • the invention is based on the object of enabling greater energy efficiency in the production of coated paper or of providing aqueous paper coating slips and aqueous compositions for the production of paper coating slips which enable the formulation of paper coating slips with an increased solids content without the Viscosity increases or the viscosity is even decreased.
  • the applicability of paper coating slips and the quality of the coated paper, in particular the smoothness should be improved as much as possible, and the calcium ion stability should be improved.
  • urea especially when it is used in larger amounts, preferably in an amount of up to 100% of the maximum amount soluble in the respective composition, can be used to increase the solids content to reduce the amount required for drying
  • the quality of the coated paper, especially the smoothness can be increased.
  • the aqueous compositions are preferably suitable for use to reduce the amount of energy required for drying paper coated with aqueous paper coating slip and / or to reduce the viscosity of paper coating slips and / or to increase the smoothness of coated paper.
  • the comparison standard is the corresponding urea-free composition.
  • Preferred aqueous binder dispersions contain urea H2N-CO-NH2 in an amount of 1 to 100% or 20 to 100% or 50 to 100% or 70 to 100% or 90 to 100% of the maximum amount soluble in the composition.
  • the solids content of the aqueous binder dispersions is preferably at least 50% by weight or at least 60% by weight
  • the polymers which can be used as binders in the coating slips and binder dispersions can be prepared as emulsion polymers by free-radically initiated emulsion polymerization from one or more ethylenically unsaturated, free-radically polymerizable monomers, the monomers being polymerized in the presence of a molecular weight regulator composition.
  • the polymeric binders have a glass transition temperature Tg of less than 50.degree. C., preferably less than 30.degree.
  • the glass transition temperature can be determined by differential scanning calorimetry (ASTM D 3418-08, so-called “midpoint temperature”).
  • Suitable ethylenically unsaturated, radically polymerizable monomers can be selected from the group consisting of vinyl aromatic compounds, conjugated aliphatic dienes, ethylenically unsaturated acids, ethylenically unsaturated carboxamides, ethylenically unsaturated carboxylic acid nitriles, vinyl esters of saturated C 1 - to C 20 -carboxylic acids, esters of acrylic acid or of methacrylic acid with monohydric C 1 - to C 20 -alcohols, allyl esters of saturated carboxylic acids, vinyl ethers, vinyl ketones, dialkyl esters of ethylenically unsaturated dicarboxylic acids, N-vinylpyrrolidone, N-vinylpyrrolidine, N-vinylformamide, N, N-dialkylaminoalkylacrylamides, N, N-dialkylaminoalkyl acrylamides, N, N-dialkylamino
  • the emulsion polymer consists preferably of at least 40% by weight, more preferably at least 60% by weight, particularly preferably at least 80% by weight, of so-called main monomers.
  • the main monomers are selected from C1-C20 alkyl (meth) acrylates, vinyl esters of carboxylic acids containing up to 20 carbon atoms, vinyl aromatics with up to 20 carbon atoms, ethylenically unsaturated nitriles, vinyl halides, vinyl ethers containing 1 to 10 carbon atoms Alcohols, aliphatic hydrocarbons with 2 to 8 carbon atoms and one or two double bonds or mixtures of these monomers. To be mentioned are z. B.
  • (Meth) acrylic acid alkyl esters with a C1-C10-alkyl radical such as methyl methacrylate, methyl acrylate, n-butyl acrylate, ethyl acrylate and 2-ethylhexyl acrylate. Mixtures of the (meth) acrylic acid alkyl esters are also particularly suitable.
  • Vinyl esters of carboxylic acids with 1 to 20 carbon atoms are, for. B. vinyl laurate, vinyl stearate, vinyl propionate, Versatic acid vinyl ester and vinyl acetate.
  • Vinyl aromatic compounds are vinyl toluene, alpha- and p-methylstyrene, alpha-butylstyrene, 4-n-butylstyrene, 4-n-decylstyrene and preferably styrene are suitable.
  • nitriles are acrylonitrile and methacrylonitrile.
  • the vinyl halides are ethylenically unsaturated compounds substituted with chlorine, fluorine or bromine, preferably vinyl chloride and vinylidene chloride.
  • vinyl ethers are such.
  • Vinyl ethers of alcohols containing 1 to 4 carbon atoms are preferred. Hydrocarbons with 2 to 8 carbon atoms and one or two olefinic double bonds include ethylene, propylene, butadiene, isoprene and chloroprene.
  • Preferred main monomers are C1-C10-alkyl (meth) acrylates and mixtures of alkyl (meth) acrylates with vinyl aromatics, in particular styrene (collectively also referred to as polyacrylate binders) or hydrocarbons with 2 double bonds, in particular butadiene, or mixtures of such hydrocarbons with Vinyl aromatics, especially styrene (also referred to collectively as polybutadiene binders).
  • the weight ratio of butadiene to vinyl aromatics (especially styrene) can be e.g. B. 10:90 to 90:10, preferably 20:80 to 80:20.
  • Polybutadiene binders are particularly preferred.
  • the polymer can contain other monomers, e.g. B. monomers with carboxylic acid, sulfonic acid or phosphonic acid groups. Carboxylic acid groups are preferred.
  • the content of ethylenically unsaturated acids in the emulsion polymer is generally less than or equal to 10% by weight.
  • Other monomers are e.g. B. also hydroxyl-containing monomers, in particular C1-C10-hydroxyalkyl (meth) acrylates, or amides such as (meth) acrylamide.
  • the polymer is at least 60% by weight of butadiene or mixtures of butadiene and styrene or at least 60% by weight of C1 to C20 alkyl (meth) acrylates or mixtures of C1 to C20 alkyl (meth) acrylates and Styrene built up.
  • Preferred polymeric binders are
  • Suitable monomers of group (A1) or (A2) are vinyl aromatic compounds, for example styrene, ⁇ -methylstyrene and / or vinyl toluene and mixtures thereof. From this group of monomers, styrene is preferably used. 100 parts by weight of the total in the polymerization
  • the monomer mixtures used contain, for example, 19.8 to 80 parts by weight and preferably 25 to 70 parts by weight of at least one monomer from group (A1) or (A2).
  • Monomers of group (B1) are, for example, 1,3-butadiene, isoprene, 1,3-pentadiene, 1,3-dimethylbutadiene and cyclopentadiene. From this group of monomers, preference is given to using 1,3-butadiene and / or isoprene.
  • 100 parts by weight of the monomer mixtures used in total in the emulsion polymerization contain, for example, 19.8 to 80 parts by weight, preferably 25 to 70 parts by weight and in particular 25 to 60 parts by weight of at least one monomer of the group (B1).
  • Monomers of group (C1) or (C2) are, for example, ethylenically unsaturated carboxylic acids, ethylenically unsaturated sulfonic acids and vinylphosphonic acid and salts of these acids.
  • the ethylenically unsaturated carboxylic acids used are preferably ⁇ , ⁇ -monoethyienically unsaturated mono- and dicarboxylic acids having 3 to 6 carbon atoms in the molecule. Examples are acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, crotonic acid, vinyl acetic acid and vinyl lactic acid.
  • ethylenically unsaturated sulfonic acids are vinyl sulfonic acid, styrene sulfonic acid, acrylamidomethylpropanesulfonic acid, sulfopropyl acrylate and sulfopropyl methacrylate.
  • Acrylic acid and methacrylic acid, in particular acrylic acid, are particularly preferred.
  • the monomers of group (C1) or (C2) containing acid groups can be used in the polymerization in the form of the free acids and in a form partially or completely neutralized with suitable bases. Sodium hydroxide solution, potassium hydroxide solution or ammonia are preferably used as the neutralizing agent.
  • 100 parts by weight of the monomer mixtures used in the emulsion polymerization contain, for example, 0.1 to 15 parts by weight, preferably 0.1 to 10 parts by weight or 1 to 8 parts by weight of at least one monomer of the group (C1) or (C2).
  • Monomers of group (B2) include esters of acrylic acid and methacrylic acid with monohydric C 1 to C 18 alcohols such as methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, n-butyl acrylate, n -Butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, sec-butyl acrylate.
  • 100 parts by weight of the total monomer mixtures used in the polymerization contain, for example, 19.8 to 80 parts by weight and preferably 25 to 70 parts by weight of at least one monomer of group (B2).
  • ethylenically unsaturated compounds come into consideration as monomers of group (D2).
  • examples of these are ethylenically unsaturated carboxamides such as, in particular, acrylamide and methacrylamide, and ethylenically unsaturated carboxamides such as in particular Acrylonitrile and methacrylonitrile, vinyl esters of saturated C 1 to C 18 carboxylic acids, preferably vinyl acetate, allyl esters of saturated carboxylic acids, vinyl ethers, vinyl ketones, dialkyl esters of ethylenically unsaturated dicarboxylic acids, N-vinylpyrrolidone, N-vinylpyrrolidine, N-vinylformamide, N, N-dialyl acylamides N, N-dialkylaminoalkyl methacrylamides, N, N-dialkylaminoalkyl acrylates, N, N-dialkylaminoalkyl methacrylates, vinyl chloride and vinylidene
  • the monomers of group (D1) are the monomers of group (D2) and also esters of acrylic acid and methacrylic acid with monohydric C 1 to C 18 alcohols such as methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, Isopropyl acrylate, isopropyl methacrylate, n-butyl acrylate, n-butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, sec-butyl acrylate.
  • the further monomers (D1) and (D2) are used in amounts of 0.1-15 parts by weight each;
  • the vinyl aromatic compound is selected from styrene, methyl styrene and mixtures thereof;
  • the conjugated aliphatic diene is selected from 1,3-butadiene, isoprene and mixtures thereof;
  • the ethylenically unsaturated acid is selected from one or more compounds from the group consisting of acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, crotonic acid, vinyl acetic acid, vinyl lactic acid, vinyl sulfonic acid, styrenesulfonic acid, acrylamidomethylpropanesulfonic acid, sulfopropyl acrylate, sulfopropyl methacrylate, and salzenphosphonic acid.
  • initiators are usually used which form free radicals under the reaction conditions.
  • the initiators are used, for example, in amounts of up to 2% by weight, preferably at least 0.9% by weight, for example from 1.0 to 1.5% by weight, based on the monomers to be polymerized.
  • Suitable polymerization initiators are, for example, peroxides, hydroperoxides, hydrogen peroxide, sodium or potassium persulfate, redox catalysts and azo compounds such as 2,2-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2-azo-bis (2,4-dimethylvaleronitrile) and 2,2-azobis (2-amidinopropane) dihydrochloride.
  • initiators examples include dibenzoyl peroxide, tert-butyl perpivalate, tert-butyl per-2-ethyl hexanoate, di-tert-butyl peroxide, diamyl peroxide, dioctanoyl peroxide, didecanoyl peroxide, dilauroyl peroxide, bis (o-toluyl) peroxide, succinyl peroxide , tert-butyl peracetate, tert-butyl permaleate, tert-butyl perisobutyrate, tert-butyl perpivalate, tert-butyl peroctoate, tert-butyl perbenzoate, tert-butyl hydroperoxide, azo-bis-isobutyronitrile, 2,2'-azo-bis - (2-methylbutyronitrile), 2,2'-azobis (2,4-dimethylvaleron
  • initiators are selected from the group of peroxodisulfates, peroxosulfates, azo initiators, organic peroxides, organic hydroperoxides and hydrogen peroxide.
  • Water-soluble initiators are particularly preferably used, e.g. B. sodium persulfate, potassium persulfate, ammonium persulfate, sodium peroxodisulfate, potassium peroxodisulfate and / or ammonium peroxodisulfate.
  • the polymerization can also be initiated with the aid of high-energy rays such as electron beams or by exposure to UV light.
  • the amount of molecular weight regulators is, for example, 0.01 to 5, preferably 0.1 to 1% by weight, based on the monomers used in the polymerization.
  • the regulators are preferably metered in together with the monomers. However, they can also be partially or completely present in the template. They can also be metered in incrementally offset from the monomers.
  • the protective colloids and / or emulsifiers customarily used as dispersants can be used.
  • suitable protective colloids can be found in Houben-Weyl, Methods of Organic Chemistry, Volume XIV / 1, Macromolecular Materials, Georg-Thieme-Verlag, Stuttgart, 1961, pages 411 to 420 .
  • Suitable emulsifiers are surface-active substances whose number average molecular weight is usually below 2000 g / mol or preferably below 1500 g / mol, while the number average molecular weight of the protective colloids is above 2000 g / mol, for example from 2000 to 100000 g / mol , in particular from 5000 to 50,000 g / mol.
  • Suitable emulsifiers are, for example, ethoxylated C 8 to C 36 fatty alcohols with a degree of ethoxylation of 3 to 50, ethoxylated mono-, di and tri C 4 - to C 12 -alkylphenols with a degree of ethoxylation of 3 to 50, alkali metal salts of dialkyl esters Sulphosuccinic acid, alkali metal and ammonium salts of C 8 to C 12 alkyl sulphates, alkali metal and ammonium salts of C 12 to C 18 alkyl sulphonic acids and alkali metal and ammonium salts of C 8 to C 18 alkylarylsulphonic acids.
  • Cation-active emulsifiers are, for example, compounds with at least one amino or ammonium group and at least one C8-C22-alkyl group. If emulsifiers and / or protective colloids are also used as auxiliaries for dispersing the monomers, the amounts used thereof are, for example, 0.1 to 5% by weight, based on the monomers.
  • Suitable protective colloids are, for example, degraded starch, in particular maltodextrin.
  • All native starches such as starches from corn, wheat, oats, barley, rice, millet, potatoes, peas, tapioca, sorghum or sago are suitable as starting starches for the production of the degraded starches.
  • Natural starches with a high amylopectin content such as waxy maize starch and waxy potato starch, are also of interest. The amylopectin content of these starches is above 90%, mostly 95 to 100%.
  • Chemically too Starches modified by etherification or esterification can be used to prepare the polymer dispersions according to the invention. Such products are known and are commercially available.
  • Degraded native starches are particularly preferred, in particular native starches degraded to maltodextrin. Further suitable starches are cationically modified starches, ie starch compounds which have amino groups or ammonium groups.
  • the degraded starches have, for example, an intrinsic viscosity ⁇ i of less than 0.07 dl / g or less than 0.05 dl / g.
  • the intrinsic viscosity ⁇ i of the degraded starches is preferably in the range from 0.02 to 0.06 dl / g.
  • the intrinsic viscosity ⁇ i is determined according to DIN EN1628 at a temperature of 23 ° C.
  • the emulsion polymerization takes place in the presence of seed particles.
  • the template then contains polymer seeds, in particular a polystyrene seeds, i.e. an aqueous dispersion of finely divided polymer, preferably polystyrene, with a particle diameter of 20 to 40 nm.
  • the emulsion polymerization takes place in an aqueous medium.
  • This can e.g. be completely deionized water or mixtures of water and a miscible solvent such as methanol, ethanol or tetrahydrofuran.
  • metering in of the monomers begins. For example, they can be pumped continuously into the reactor within, for example, 60 minutes to 10 hours, usually within 2 to 4 hours.
  • the reaction mixture in the initial charge is preferably heated to the required temperature at which the polymerization takes place. These temperatures are, for example, from 80 to 130.degree.
  • the polymerization can also be carried out under pressure, e.g. at pressures up to 15 bar, e.g. at 2 to 10 bar.
  • the monomer can be fed in as a batch process, continuously or in stages.
  • further initiator can optionally be added to the reaction mixture and post-polymerization can be carried out at the same, lower or higher temperature as in the main polymerization.
  • post-polymerization can be carried out at the same, lower or higher temperature as in the main polymerization.
  • the pH during the polymerization can be, for example, 1 to 5.
  • the pH is adjusted to a value between 6 and 7, for example.
  • An aqueous polymer dispersion is obtained whose dispersed particles have an average particle diameter of preferably 80 to 200 nm.
  • the mean particle diameter of the polymer particles can be determined by dynamic light scattering on a 0.005 to 0.01% strength by weight aqueous polymer dispersion at 23 ° C. using an IIC Autosizer from Malvern Instruments, England. The information relates in each case to the mean diameter of the cumulant evaluation (cumulant z-average) of the measured autocorrelation function according to IOS standard 13321.
  • the urea-containing binder dispersion can be produced by dissolving the desired amount of urea (preferably 50-100% of the maximum soluble amount) in a urea-free binder dispersion. However, some or all of the urea can also be added before the monomers are polymerized. In a preferred embodiment, at least some of the urea is added during the polymerization. This method has the advantage that, due to the enthalpy of dissolution of urea in water, heat of reaction is withdrawn from the reaction medium and the expenditure for external cooling can accordingly be reduced.
  • the pigments and any mixtures thereof are dispersed in the pigment slurries in water.
  • White pigments are particularly suitable.
  • Suitable pigments are, for example, metal salt pigments such as calcium sulfate, calcium aluminate sulfate, barium sulfate, magnesium carbonate and calcium carbonate, of which carbonate pigments, in particular calcium carbonate, are preferred.
  • the calcium carbonate can be ground calcium carbonate (GCC, natural ground calcium carbonate), precipitated calcium carbonate (PCC, precipitated calcium carbonate), lime or chalk.
  • Suitable calcium carbonate pigments are available, for example, as Covercarb® 60, Hydrocarb® 60 or Hydrocarb® 90 ME.
  • Suitable pigments are, for example, silicas, aluminum oxides, aluminum hydrate, silicates, titanium dioxide, zinc oxide, kaolin, alumina, talc or silicon dioxide.
  • Suitable further pigments are available, for example, as Capim® MP 50 (clay), Hydragloss® 90 (clay) or Talcum C10.
  • the pigments are preferably selected from the group consisting of calcium sulfate, calcium aluminate sulfate, Barium sulfate, magnesium carbonate, calcium carbonate, silicic acids, aluminum oxides, aluminum hydrate, silicates, titanium dioxide, zinc oxide, kaolin, clay, talc and silicon dioxide.
  • the aqueous pigment slurry can be produced by grinding the pigments together with at least part of the urea or by introducing the urea into a urea-free aqueous pigment slurry.
  • starch is to be understood as meaning any native, modified or degraded starch.
  • Native starches can consist of amylose, amylopectin or their mixtures.
  • Modified starches can be oxidized starches, starch esters or starch ethers. The molecular weight of the starch can be reduced by hydrolysis (degraded starch). Oligosaccharides or dextrins come into consideration as degradation products.
  • Preferred starches are cereal, corn and potato starch. Grain starch and corn starch are particularly preferred, and grain starch is very particularly preferred.
  • the aqueous starch composition can be prepared by heating the starch in water in the presence of at least part of the urea above the gelation point of the starch or by introducing urea into a urea-free, aqueous starch composition which has been heated above its gelation point.
  • Preferred aqueous paper coating slips contain urea H2N-CO-NH2 in an amount of 50 to 100% or 70 to 100% or 90 to 100% of the maximum amount soluble in the composition.
  • the paper coating slips preferably contain at least 5 parts by weight or at least 10 parts by weight of the urea, based on 100 parts by weight of pigment.
  • paper coating slips In addition to water, paper coating slips generally contain pigments, one or more binders and, optionally, auxiliaries such as one or more thickeners for setting the required rheological properties, one or more fluorescent or phosphorescent dyes, especially as optical brighteners and other auxiliaries, e.g. B. fillers, leveling agents or other dyes.
  • the paper coating slips according to the invention contain at least one of the above-described binders for paper coating slips suitable polymers with a glass transition temperature Tg of less than 50 ° C or less than 30 ° C.
  • binders in paper coating slips are to bond the pigments to the paper and the pigments to one another and to partially fill voids between pigment particles.
  • a mixture of the above-mentioned synthetic binders with the above-mentioned starch can be used as the binder.
  • the urea-containing binder dispersions according to the invention or the urea-containing aqueous starch compositions described above can advantageously be used.
  • the proportion of starch can be 1 to 99% by weight, particularly preferably 10 to 90% by weight, and very particularly preferably 30 to 80% by weight, based on the total weight of synthetic binder and starch.
  • the paper coating slip contains at least 3 parts by weight of starch, e.g. 3 to 18 or 3 to 12 parts by weight, based on 100 parts by weight of pigments.
  • the paper coating slip contains the abovementioned inorganic pigments in an amount of at least 60% by weight, preferably at least 80% by weight, e.g. 80 to 95% by weight or 80 to 90% by weight, based on the total solids content.
  • natural-based thickeners in particular celluloses, preferably carboxymethyl cellulose, are also suitable as thickeners.
  • Preferred paper coating slips are characterized in that the pigments are selected from the group consisting of calcium sulfate, calcium aluminate sulfate, barium sulfate, magnesium carbonate, calcium carbonate, silicas, aluminum oxides, aluminum hydrate, silicates, titanium dioxide, zinc oxide, kaolin, clay, talc and silicon dioxide and that the paper coating slips additionally contain at least one additive selected from the group consisting of thickeners, other polymeric binders, co-binders, optical brighteners, fillers, leveling aids, dispersants, surfactants, lubricants (e.g. calcium stearate and waxes), neutralizing agents (e.g.
  • Optical brighteners are, for example, fluorescent or phosphorescent dyes, in particular stilbenes.
  • the pH of the paper coating slip is preferably adjusted to values of 6 to 10, in particular 7 to 9.5.
  • the paper coating color is preferably applied to uncoated base papers or uncoated cardboard.
  • the amount is generally 1 to 50 g, preferably 5 to 30 g (solid, i.e. without water or other solvents which are liquid at 21 ° C, 1 bar) per square meter.
  • the coating can be carried out by conventional application methods, e.g. using a size press, film press, blade coater, air brush, squeegee, curtain coating or spray coater.
  • the paper coating colors can be used for the base coat and / or for the top coat.
  • paper coating slips with a particularly high solids content can be produced which, due to their low viscosities and high shear, can be easily processed on industrial paper coating plants.
  • Coated papers are characterized by a particularly high level of smoothness. They can be easily printed in the usual printing processes, such as letterpress, gravure, offset printing, digital printing, inkjet printing, flexographic printing, newspaper printing, letterpress printing, sublimation printing, laser printing, electrophotographic printing or a combination of these printing processes.
  • the use of urea in binder dispersions also leads to improved calcium ion stability.
  • paper coating inks with a high urea content have the additional advantages of being able to reduce chemicals (binders and starch) without any loss of quality.
  • the solids contents are determined by drying a defined amount of the respective aqueous polymer dispersion (approx. 5 g) at 140 ° C. in a drying cabinet to constant weight. Two separate measurements are carried out each time and the mean value is calculated.
  • Example 1 Viscosity of aqueous binder dispersions
  • Aqueous binder dispersions were prepared with the constituents indicated in Table 1 and the viscosity was measured (Brookfield measurement method, 100 rpm, 23 ° C., spindle number 2).
  • Table 1 Aqueous binder dispersions No. Dispersion Urea additive [parts by weight] Solids content [%] Viscosity [mPa s] 1 D1 - 54.2 387 2 D1 30th 65.4 108 3 D1 45 69.1 83 4th D2 - 48.9 106 5 D2 30th 61.5 63 6th D2 50 66.3 73 7th D3 - 50.5 116 8th D3 30th 62.2 74 9 D3 50 67.2 63 10 D4 - 48.8 122 11 D4 30th 60.6 71 12 D4 50 64.4 56 13 D5 - 49 74 14th D5 30th 61.3 52 15th D5 50 66.3 47 16 D6 - 49.6 230 17th D6 30th 62 91 18th D6 50
  • Aqueous pigment suspensions were prepared with the constituents indicated in Table 2 and the viscosity was measured (Brookfield measurement method, 100 rpm, 23 ° C., spindle No. 2).
  • Table 2 Aqueous pigment slurries No. pigment Urea additive [parts by weight] Solids content [%] Viscosity [mPa s] 1 Hydrocarb 60 GU - 77.3 195 2 Hydrocarb 60 GU 1 77.5 170 3 Hydrocarb 60 GU 2 77.6 159 4th Hydrocarb 60 GU 5 78.1 135 5 Hydrocarb 60 GU 10 79.1 109 6th Hydrocarb 60 GU 20th 80.3 89 7th Hydrocarb 90 GU - 78 417 8th Hydrocarb 90 GU 1 78.1 323 9 Hydrocarb 90 GU 2 78.2 273 10 Hydrocarb 90 GU 5 78.6 201 11 Hydrocarb 90 GU 10 79.8 143 12 Hydrocarb 90 GU 20th 80.2 110 13 Hydro
  • Example 3 Viscosity of aqueous starch compositions
  • Aqueous starch compositions were prepared with the ingredients indicated in Table 3 and the viscosity was measured (Brookfield measurement method, 100 rpm, 23 ° C., spindle no. 4 or 5, depending on the viscosity).
  • Cargill C-Film 7311 was used as the starch. The starch was boiled in a water bath at 95 ° C for 30 minutes. The urea was added after boiling.
  • Table 3 Aqueous starch compositions No. Strength Urea additive [parts by weight] Solids content [%] Viscosity [mPa s] Temperature [° C] 1 C-movie 7311 0 31.8 456 81.2 2 C-movie 7311 0 41.2 3480 75.2 3 C-movie 7311 5 40.8 2230 74.8 4th C-movie 7311 10 40.4 1980 70.3 5 C-movie 7311 20th 39.7 1060 71.3
  • C-film 7311 corn starch
  • starch preparations When using urea, starch preparations can be obtained which have a reduced viscosity compared to compositions with a comparable solids content.
  • Example 4 Calcium ion stability of aqueous binder dispersions
  • Aqueous binder dispersions were prepared with the components indicated in Table 4 and the calcium ion stability was measured.
  • the calcium ion stability of the respective binder dispersion can be significantly improved by adding urea.
  • Aqueous paper coating slips with the components indicated in Table 5 were produced.
  • the coating color is prepared in a stirring unit into which the individual components are fed one after the other.
  • the pigments are added in predispersed form (slurry).
  • the other components are added after the pigments, the sequence corresponding to the sequence in the coating slip recipe given.
  • the final solids content is adjusted by adding water.
  • Table 5 Compositions of the coating colors tested Coating color 1 2 3 pigment 100 100 100 binder 10 10 10 Thickener 1 1 1 urea 0 4th 10 Ca stearate 0.1 0.1 0.1 Pigment: natural Ca carbonate, particle size 60% ⁇ 2 ⁇ m
  • the coating slips are applied to wood-free paper at a speed of 1000 m / min with a coating weight of 12 g / m 2 with stiff blade mode (applicator roller with blade leveling).

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Claims (10)

  1. Composition aqueuse sous la forme d'un lait aqueux de couchage de papier ayant une teneur en solides d'au moins 72 % en poids, contenant :
    - au moins un polymère approprié en tant que liant pour laits de couchage de papier ayant une température de transition vitreuse Tg de moins de 50 °C,
    - au moins 60 % en poids de pigments inorganiques par rapport à la teneur totale en solides,
    - au moins 5 parties en poids d'urée, par rapport à 100 parties en poids de pigment et éventuellement d'additifs supplémentaires.
  2. Composition selon la revendication 1 sous la forme d'un lait de couchage de papier, caractérisée en ce que le liant est un polymère, qui peut être fabriqué par polymérisation en émulsion initiée radicalairement à partir d'un ou de plusieurs monomères éthyléniquement insaturés, polymérisables radicalairement, les monomères éthyléniquement insaturés, polymérisables radicalairement, étant choisis dans le groupe constitué par les composés aromatiques de vinyle, les diènes aliphatiques conjugués, les acides éthyléniquement insaturés, les amides d'acides carboxyliques éthyléniquement insaturés, les nitriles d'acides carboxyliques éthyléniquement insaturés, les esters de vinyle d'acides carboxyliques en C1 à C20 saturés, les esters de l'acide acrylique ou de l'acide méthacrylique avec des alcools en C1 à C20 monovalents, les esters allyliques d'acides carboxyliques saturés, les éthers de vinyle, les vinylcétones, les esters dialkyliques d'acides dicarboxyliques éthyléniquement insaturés, la N-vinylpyrrolidone, la N-vinylpyrrolidine, le N-vinylformamide, les N,N-dialkylaminoalkylacrylamides, les N,N-dialkylaminoalkylméthacrylamiden, les acrylates de N,N-dialkylaminoalkyle, les méthacrylates de N,N-dialkylaminoalkyle, les halogénures de vinyle, les hydrocarbures aliphatiques contenant 2 à 8 atomes C et une ou deux doubles liaisons ou les mélanges de ces monomères.
  3. Composition selon l'une quelconque des revendications précédentes sous la forme d'un lait de couchage de papier, caractérisée en ce que le liant est choisi parmi :
    (a) les copolymères de (a1) 19,9 à 80 parties en poids d'au moins un composé aromatique de vinyle, (a2) 19,9 à 80 parties en poids d'au moins un diène aliphatique conjugué, (a3) 0,1 à 10 parties en poids d'au moins un acide éthyléniquement insaturé, et (a4) 0 à 20 parties en poids d'au moins un autre monomère monoéthyléniquement insaturé, la somme des parties en poids des monomères (a1) à (a4) étant de 100,
    (b) les copolymères de (b1) 19,9 à 80 parties en poids d'au moins un composé aromatique de vinyle, (b2) 19,9 à 80 parties en poids d'au moins un monomère acrylate choisi parmi les acrylates d'alkyle en C1 à C10 et les méthacrylates d'alkyle en C1 à C10, (b3) 0,1 à 10 parties en poids d'au moins un acide éthyléniquement insaturé et (b4) 0 à 20 parties en poids d'au moins un autre monomère monoéthyléniquement insaturé, la somme des parties en poids des monomères (b1) à (b4) étant de 100,
    (c) les copolymères d'acétate de vinyle et d'au moins un monomère (méth)acrylate, choisi parmi les acrylates d'alkyle en C1 à C10 et les méthacrylates d'alkyle en C1 à C10, et
    (d) les copolymères d'éthylène/acétate de vinyle.
  4. Composition sous la forme d'un lait de couchage de papier selon l'une quelconque des revendications précédentes, caractérisée en ce que le liant est un polymère, qui est formé à hauteur d'au moins 60 % en poids à partir de butadiène ou de mélanges de butadiène et de styrène ou à hauteur d'au moins 60 % en poids à partir de (méth)acrylates d'alkyle en C1 à C20 ou de mélanges de (méth)acrylates d'alkyle en C1 à C20 et de styrène.
  5. Composition selon l'une quelconque des revendications précédentes sous la forme d'un lait de couchage de papier, caractérisée en ce que, pour la fabrication du liant,
    (A1) 19,8 à 80 parties en poids d'au moins un composé aromatique de vinyle,
    (B1) 19,8 à 80 parties en poids d'au moins un diène aliphatique conjugué,
    (C1) 0,1 à 15 parties en poids d'au moins un acide éthyléniquement insaturé et
    (D1) 0 à 20 parties en poids d'au moins un monomère monoéthyléniquement insaturé supplémentaire, différent des monomères (A1) à (C1) ;
    ou
    (A2) 19,8 à 80 parties en poids d'au moins un composé aromatique de vinyle,
    (B2) 19,8 à 80 parties en poids d'au moins un monomère choisi parmi les esters alkyliques en C1 à C18 de l'acide acrylique et les esters alkyliques en C1 à C18 de l'acide méthacrylique,
    (C2) 0,1 à 15 parties en poids d'au moins un acide éthyléniquement insaturé, et
    (D2) 0 à 20 parties en poids d'au moins un monomère monoéthyléniquement insaturé supplémentaire, différent des monomères (A2) à (C2),
    sont utilisés en tant que monomères, la somme des parties en poids des monomères (A1) à (D1) ou (A2) à (D2) étant à chaque fois de 100.
  6. Composition selon la revendication précédente, caractérisée en ce que les monomères supplémentaires (D1) et (D2) sont utilisés en quantités respectives de 0,1 à 15 parties en poids ; le composé aromatique de vinyle est choisi parmi le styrène, le méthylstyrène et leur mélange ; le diène aliphatique conjugué est choisi parmi le 1,3-butadiène, l'isoprène et leur mélange ; et l'acide éthyléniquement insaturé est choisi parmi un ou plusieurs composés du groupe constitué par l'acide acrylique, l'acide méthacrylique, l'acide itaconique, l'acide maléique, l'acide fumarique, l'acide crotonique, l'acide vinylacétique, l'acide vinyllactique, l'acide vinylsulfonique, l'acide styrène-sulfonique, l'acide acrylamidométhylpropanesulfonique, l'acrylate de sulfopropyle, le méthacrylate de sulfopropuyle, l'acide vinylphosphonique et les sels de ces acides.
  7. Composition selon l'une quelconque des revendications précédentes sous la forme d'un lait de couchage de papier, caractérisée en ce que les pigments sont choisis dans le groupe constitué par le sulfate de calcium, l'aluminate-sulfate de calcium, le sulfate de baryum, le carbonate de magnésium, le carbonate de calcium, les silices, les oxydes d'aluminium, l'hydrate d'aluminium, les silicates, le dioxyde de titane, l'oxyde de zinc, le kaolin, les alumines, le talc et le dioxyde de silicium et contient en outre au moins un additif, choisi dans le groupe constitué par les épaississants, les liants polymères supplémentaires, les co-liants, les azurants optiques, les charges, les adjuvants de nivellement, les dispersants, les tensioactifs, les lubrifiants, les agents neutralisants, les agents antimousses, les agents d'aération, les agents conservateurs et les colorants.
  8. Composition selon l'une quelconque des revendications précédentes sous la forme d'un lait de couchage de papier, caractérisée en ce que la teneur de l'urée est d'au moins 10 parties en poids, par rapport à 100 parties en poids de pigment.
  9. Procédé de couchage de papier ou de carton, dans lequel
    - un lait de couchage de papier selon l'une quelconque des revendications 1 à 8 est mis à disposition ; et
    - le lait de couchage de papier est appliqué sur au moins une surface de papier ou de carton, puis séché.
  10. Papier ou carton revêtu avec un lait de couchage de papier selon l'une quelconque des revendications 1 à 8.
EP12751311.7A 2011-08-19 2012-08-17 Sauces de couchage aqueuses à base d'urée, composants de sauces de couchage aqueux à base d'urée et leur utilisation Active EP2744940B1 (fr)

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US201161525211P 2011-08-19 2011-08-19
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PCT/EP2012/066077 WO2013026788A2 (fr) 2011-08-19 2012-08-17 Sauces de couchage aqueuses à base d'urée, composants de sauces de couchage aqueux à base d'urée et leur utilisation
EP12751311.7A EP2744940B1 (fr) 2011-08-19 2012-08-17 Sauces de couchage aqueuses à base d'urée, composants de sauces de couchage aqueux à base d'urée et leur utilisation

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