EP2744940A2 - 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

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Publication number
EP2744940A2
EP2744940A2 EP12751311.7A EP12751311A EP2744940A2 EP 2744940 A2 EP2744940 A2 EP 2744940A2 EP 12751311 A EP12751311 A EP 12751311A EP 2744940 A2 EP2744940 A2 EP 2744940A2
Authority
EP
European Patent Office
Prior art keywords
weight
parts
urea
acid
monomers
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Granted
Application number
EP12751311.7A
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German (de)
English (en)
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EP2744940B1 (fr
Inventor
Thomas Steinmacher
Norbert Gispert
Jens Utecht
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BASF SE
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BASF SE
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Publication of EP2744940A2 publication Critical patent/EP2744940A2/fr
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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 for reducing the amount of energy required for the drying of paper coated with aqueous paper coating and / or for reducing 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 components each with a specific content of urea H2N-CO-NH2.
  • the invention has for its object to enable a higher energy efficiency in the production of coated paper or to provide aqueous paper coatings and aqueous compositions for the production of paper coating colors, which allow the formulation of paper coatings with an increased solids content, without that Viscosity increases or wherein the viscosity is even lowered.
  • the application of paper coating colors and the quality of the coated paper, Rus / sm 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 particular composition, can be used to increase the solids content to reduce the drying of With paper coated with aqueous paper coated paper required amount of energy and / or to reduce the viscosity of paper coating colors. At the same time, the quality of the coated paper, in particular the smoothness, can be increased.
  • aqueous compositions containing urea H2N-CO-NH2 in an amount of preferably 1-100%, in particular 50-100% of the maximum amount soluble in the respective composition are selected from
  • aqueous paper coating slivers having a solids content of at least 72% by weight, preferably of at least 75% by weight
  • a content of inorganic pigments of at least 60 wt .-%, based on the
  • aqueous, pigment-free binder dispersions for paper coating slivers having a solids content of at least 21, preferably at least 40% by weight, particularly preferably at least 50%,
  • aqueous, binder-free pigment slurries having a solids content of at least 60% by weight, preferably at least 70 or at least 80% by weight, a content of at least 60% by weight or at least 70% by weight of inorganic pigments and
  • aqueous non-pigmented starch solutions heated above the gelation point of the starch containing at least 8% by weight, preferably at least 20 or at least 30% by weight of starch and preferably at least 10% by weight of the urea.
  • the aqueous compositions are preferably suitable for use in reducing the amount of energy required to dry papers coated with aqueous paper coating ink and / or reducing the viscosity of paper coating colors and / or increasing the smoothness of coated paper.
  • the comparison standard in each case 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 compositionally soluble amount.
  • 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 colors and binder dispersions can be prepared as emulsion polymers by free-radically initiated emulsion polymerization of one or more ethylenically unsaturated, radically polymerizable monomers, wherein the polymerization of the monomers can be carried out in the presence of a molecular weight regulator composition.
  • the polymeric binders have a glass transition temperature Tg of less than 50 ° C, preferably less than 30 ° C. The glass transition temperature can be determined by differential scanning calorimetry (ASTM D 3418-08, so-called "midpoint temperature").
  • Suitable ethylenically unsaturated, free-radically polymerizable monomers may be selected from the group consisting of vinylaromatic compounds, conjugated aliphatic dienes, ethylenically unsaturated acids, ethylenically unsaturated carboxylic acid amides, ethylenically unsaturated carbonitriles, 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, allylic 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-dialkylaminoalkylmethacrylamides, N, N-dialkylaminoalkyl
  • the emulsion polymer is preferably at least 40% by weight, preferably at least 60% by weight, particularly preferably at least 80% by weight, of so-called main monomers.
  • the main monomers are selected from C 1 -C 20 -alkyl (meth) acrylates, vinyl esters of carboxylic acids containing up to 20 carbon atoms, vinylaromatics having up to 20 carbon atoms, ethylenically unsaturated nitriles, vinyl halides, vinyl ethers having from 1 to 10 carbon atoms Alcohols, aliphatic hydrocarbons having 2 to 8 carbon atoms and one or two double bonds or mixtures of these monomers. To name a few are z. B.
  • (meth) acrylic acid alkyl ester having a C 1 -C 10 -alkyl radical such as methyl methacrylate, methyl acrylate, n-butyl acrylate, ethyl acrylate and 2-ethylhexyl acrylate.
  • C 1 -C 10 -alkyl radical such as methyl methacrylate, methyl acrylate, n-butyl acrylate, ethyl acrylate and 2-ethylhexyl acrylate.
  • (Meth) acrylic acid alkyl ester suitable Vinyl esters of carboxylic acids having 1 to 20 carbon atoms are, for. As vinyl laurate, vinyl stearate, vinyl propionate, vinyl versatate and vinyl acetate.
  • As a vinyl Aromatic compounds are vinyltoluene, alpha- and p-methylstyrene, alpha-butylstyrene, 4-n-butylstyrene, 4-n-decylstyrene and preferably styrene. Examples of nitriles are acrylonitrile and methacrylonitrile.
  • the vinyl halides are chloro, fluoro or bromo substituted ethylenically unsaturated compounds, preferably vinyl chloride and vinylidene chloride.
  • vinyl ether are, for.
  • hydrocarbons having 2 to 8 carbon atoms and one or two olefinic double bonds may be mentioned ethylene, propylene, butadiene, isoprene and chloroprene.
  • Preferred main monomers are C 1 -C 10 -alkyl (meth) acrylates and mixtures of the alkyl (meth) acrylates with vinylaromatics, in particular styrene (collectively also referred to as polyacrylate binder) or hydrocarbons having 2 double bonds, in particular butadiene, or mixtures of such hydrocarbons with Vinylaromatics, especially styrene (collectively referred to as polybutadiene binder).
  • Particularly preferred are polybutadiene binders.
  • the polymer may contain other monomers, for.
  • the content of ethylenically unsaturated acids in the emulsion polymer is generally less than or equal to 10% by weight.
  • Other monomers are z.
  • 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 Built up styrene.
  • Preferred polymeric binders are
  • acrylate monomer selected from C1 to C10 alkylacrylates
  • (D1) 0 to 20 parts by weight, preferably 0.1 to 15 parts by weight, of at least one other monoethylenically unsaturated monomer other than the monomers (A1) to (C1)
  • (B2) 19.8 to 80 parts by weight, preferably 25 to 70 parts by weight, of at least one monomer selected from C1 to C18 alkyl esters of acrylic acid and C1 to C18 alkyl esters of methacrylic acid,
  • (D2) 0 to 20 parts by weight, preferably 0.1 to 15 parts by weight, of at least one other monoethylenically unsaturated monomer other than the monomers (A2) to (C2)
  • Suitable monomers of group (A1) or (A2) are vinylaromatic compounds, e.g. Styrene, ⁇ -methylstyrene and / or vinyltoluene and mixtures thereof. From this group of monomers, styrene is preferably used. 100 parts by weight of the monomer mixtures used in the polymerization as a whole 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 (A1) or (A2).
  • Monomers of group (B1) are, for example, butadiene-1,3, isoprene, pentadiene-1,3, dimethylbutadiene-1,3, and cyclopentadiene. From this group of monomers it is preferred to use butadiene-1, 3 and / or isoprene.
  • 100 parts by weight of the monomer mixtures used in the emulsion polymerization in total contain, for example, 19.8 to 80 parts by weight, preferably 25 to 70 parts by weight, and more preferably 25 to 60 parts by weight, of at least one monomer of the group (B1).
  • Monomers of the 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 .alpha.,. Beta.-monoethylenically unsaturated mono- and dicarboxylic acids having from 3 to 6 carbon atoms in the molecule. Examples of these are acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, crotonic acid, vinylacetic acid and vinyllactic acid.
  • Suitable ethylenically unsaturated sulfonic acids are, for example, vinylsulfonic acid, styrenesulfonic acid, acrylamidomethylpropanesulfonic acid, sulfopropyl acrylate and sulfopropyl methacrylate. Particularly preferred are acrylic acid and methacrylic acid, especially acrylic acid.
  • the acid group-containing monomers of group (C1) or (C2) can be used in the form of the free acids as well as partially or completely neutralized with suitable bases in the polymerization. Sodium hydroxide solution, potassium hydroxide solution or ammonia are preferably used as 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).
  • Suitable monomers of group (B2) are esters of acrylic acid and of 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.
  • Suitable monomers of group (D2) are other monoethylenically unsaturated compounds.
  • these are ethylenically unsaturated carboxylic acid amides such as, in particular, acrylamide and methacrylamide, ethylenically unsaturated carboxylic acid nitriles, in particular acrylonitrile and methacrylonitrile, vinyl esters of saturated C 1 to C 20 -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-dialkylaminoalkylacrylamides, ⁇ , ⁇ -dialkylaminoalkylmethacrylamides, N, N-dialkylaminoalkyl acrylates, ⁇ , ⁇ -dialkylamin
  • Monomers of group (D1) are the monomers of group (D2) and furthermore esters of acrylic acid and of 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.
  • Group of monomers is optionally used to modify the polymers. Contain 100 parts by weight of the monomer mixtures used in the emulsion polymerization for example 0 to 20 parts by weight, or 0.1 to 15 parts by weight and in particular 0.5 to 10 parts by weight of at least one monomer of group (D1) or (D2).
  • the further monomers (D1) and (D2) are used in amounts of 0.1 to 15 parts by weight;
  • the vinyl aromatic compound is selected from styrene, methyl styrene and their mixture;
  • the conjugated aliphatic diene is selected from 1,3-butadiene, isoprene and their mixture;
  • the ethylenically unsaturated acid is selected from one or more compounds of the group consisting of acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, crotonic acid, vinylacetic acid, vinylmicacid, vinylsulfonic acid, styrenesulfonic acid, acrylamidomethylpropanesulfonic acid, sulfopropyl acrylate, sulfopropyl methacrylate, vinylphosphonic acid and Salts of these acids.
  • initiators which form 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-azobis (2,4-azobis). dimethylvaleronitrile) and 2,2-azobis (2-amidinopropane) dihydrochloride.
  • initiators examples include dibenzoyl peroxide, tert-butyl perpivalate, tert-butyl per-2-ethylhexanoate, di-tert-butyl peroxide, diamyl peroxide, dioctanoyl peroxide, didecanoyl peroxide, dilauroperoxide, bis (o-toluyl) peroxide , succinyl, tert-Butalperacetat, tert-Butylpermaleinat, tert-butyl perisobutyrate, tert-butyl perpivalate, tert-butyl peroctoate, tert-butyl perbenzoate, tert-butyl hydroperoxide, azo-bis-isobutyronitrile, 2,2 'azobis bis- (2-methylbutyronitrile), 2,2'-azobis (2,4-di methylvaleronitrile), and
  • initiators selected from the group of peroxodisulfates, peroxosulfates, azo initiators, organic peroxides, organic hydroperoxides and hydrogen peroxide.
  • Particular preference is given to using water-soluble initiators, eg. For example, sodium persulfate, potassium persulfate, ammonium persulfate, sodium peroxodisulfate, potassium peroxodisulfate and / or ammonium peroxodisulfate.
  • the amount of molecular weight regulators is for example 0.01 to 5, preferably 0.1 to 1 wt .-%, based on the monomers used in the polymerization.
  • the regulators are preferably metered in together with the monomers. However, they may also be present partially or completely in the template. You can also be gradually added to the monomers added.
  • protective colloids In order to assist the dispersion of the monomers in the aqueous medium, it is possible to use the protective colloids and / or emulsifiers customarily used as dispersants.
  • suitable protective colloids can be found in Houben-Weyl, Methods of Organic Chemistry, Volume XIV / 1, Macromolecular substances, Georg Thieme Verlag, Stuttgart, 1961, pages 41 1 to 420.
  • Emulsifiers are surface-active substances into consideration, 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
  • Suitable emulsifiers are, for example, ethoxylated Cs to C36 fatty alcohols having a degree of ethoxylation of from 3 to 50, ethoxylated mono-, di- and tri-C 4 - to C 12 -alkylphenols having a degree of ethoxylation of from 3 to 50, alkali metal salts of dialkyl esters of sulfosuccinic acid , Alkali metal and ammonium salts of Cs to Ci2 alkyl sulfates, alkali metal and ammonium salts of C12 to Cis alkyl sulfonic acids and alkali metal and ammonium salts of C9 to Cis alkylaryl sulfonic acids.
  • Cationic emulsifiers are, for example, compounds having at least one amino or ammonium group and at least one C 8 -C 22 -alkyl group. If emulsifiers and / or protective colloids are used as auxiliaries for dispersing the monomers, the amounts used thereof are, for example, from 0.1 to 5% by weight, based on the monomers.
  • Suitable protective colloids are, for example, degraded starch, in particular maltodextrin.
  • Suitable starches for the production of degraded starches are all native starches such as starches from corn, wheat, oats, barley, rice, millet, potatoes, peas, tapioca, sorghum or sago.
  • those natural starches which have a high amylopectin content such as waxy maize starch and waxy potato starch.
  • the amylopectin content of these starches is above 90%, usually 95 to 100%.
  • chemically modified by etherification or esterification starches can be used to prepare the polymer dispersions of the invention. Such products are known and commercially available.
  • starches are prepared, for example, by esterification of native starch or degraded native starch with inorganic or organic acids, their anhydrides or chlorides.
  • inorganic or organic acids their anhydrides or chlorides.
  • phosphated and acetylated degraded starches are phosphated and acetylated degraded starches.
  • the most common method of etherifying starches is to treat starch with organic halogen compounds, epoxies or sulfates in aqueous alkaline solution.
  • Known starch ethers are alkyl ethers, hydroxyalkyl ethers, carboxyalkyl ethers and allyl ethers.
  • the reaction products of starches with 2,3-Epoxipropyltri- methylammoniumchlorid are.
  • degraded native starches in particular native starches degraded to maltodextrin.
  • suitable starches are cationically modified starches, i. Starch compounds which have amino groups or ammonium groups.
  • the degraded starches have an intrinsic viscosity ⁇ of less than 0.07 dl / g or less than 0.05 dl / g.
  • the intrinsic viscosity ⁇ of the degraded starches is preferably in the range of 0.02 to 0.06 dl / g.
  • the intrinsic viscosity ⁇ is determined according to DIN EN 1628 at a temperature of 23 ° C.
  • the emulsion polymerization takes place in the presence of seed particles.
  • the template then contains polymer seed, in particular a polystyrene seed, ie an aqueous dispersion of finely divided polymer, preferably polystyrene, having a particle diameter of 20 to 40 nm.
  • the emulsion polymerization takes place in an aqueous medium. This may be, for example, completely desalinated water or mixtures of water and a miscible solvent such as methanol, ethanol or tetrahydrofuran.
  • the reaction mixture is heated in the template to the required temperature at which the polymerization proceeds. These temperatures are for example 80 to 130 ° C, preferably 85 to 120 ° C.
  • the polymerization can also be carried out under pressure, for example at pressures up to 15 bar, for example at 2 to 10 bar.
  • the monomer feed can be carried out as a batch process, continuously or stepwise.
  • the pH may be, for example, 1 to 5 in the polymerization. After the polymerization, 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 average 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.degree. C. with the aid of an Autosizers NC from Malvern Instruments, England.
  • the data relate 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 preparation of the urea-containing binder dispersion can be carried out by dissolving the desired amount of urea (preferably 50-100% of the maximum soluble amount) in a urea-free binder dispersion.
  • the urea can also be added in whole or in part even before the polymerization of the monomers.
  • at least a portion of the urea is added during the polymerization.
  • Preferred aqueous binder-free pigment slurries contain urea H2N-CO-NH2 in an amount of 1 to 100% or 50 to 100% or 70 to 100% or 90 to 100% of the maximum compositionally soluble amount.
  • the solids content of the aqueous pigment slurries is preferably at least 80% by weight.
  • the pigments and any mixtures thereof are dispersed in the pigment slurries in water.
  • Particularly suitable are white pigments.
  • suitable pigments are metal salt pigments such as, for example, 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 may be ground calcium carbonate (GCC), precipitated calcium carbonate (PCC), lime or chalk.
  • Suitable calcium carbonate pigments are available, for example, as Covercarb® 60, Hydrocarb® 60 or Hydrocarb® 90 ME. Further suitable pigments are, for example, silicic acids, 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 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 silica.
  • the preparation of the aqueous pigment slurry can be accomplished by milling the pigments together with at least a portion of the urea, or by incorporating the urea into a urea-free aqueous pigment slurry.
  • Preferred aqueous starch solutions 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 compositionally soluble amount.
  • the solids content of the aqueous starch compositions is preferably at least 45 or at least 50 or at least 55% by weight.
  • Strength should be understood in this context to mean any native, modified or degraded starch.
  • Native starches may consist of amylose, amylopectin or mixtures thereof.
  • Modified starches may be oxidized starch, starch esters or starch ethers. Hydrolysis can reduce the molecular weight of the starch (degraded starch). The degradation products are oligosaccharides or dextrins into consideration.
  • Preferred starches are corn, corn and potato starch. Particularly preferred are corn and corn starch, most preferably cereal starch.
  • the aqueous starch composition may be prepared by heating the starch in water in the presence of at least a portion of the urea above the gelation point of the starch, or introducing urea into a urea-free aqueous starch composition that has been heated above its gel 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 compositionally soluble amount. Based on 100 parts by weight of pigment, the paper coating slivers preferably contain at least 5 parts by weight or at least 10 parts by weight of the urea.
  • paper coating slips generally contain pigments, one or more binders and optional auxiliaries, for example one or more thickeners for adjusting the required rheological properties, one or more fluorescence or phosphorescent dyes, in particular as optical brightener and further auxiliaries, eg. As fillers, flow control agents or other dyes.
  • the paper coating slips according to the invention comprise at least one of the polymers described above, suitable as binders for paper coating slivers, having a glass transition temperature Tg of less than 50 ° C. or of less than 30 ° C.
  • the most important tasks of binders in paper coating slips are to join the pigments to the paper and the pigments and to partially fill voids between pigment particles.
  • from 1 to 50 parts by weight, preferably from 1 to 25 parts by weight, or from 5 to 20 parts by weight of an organic binder (solid, ie without water or otherwise at 21 ° C.) are used per 100 parts by weight of pigments. 1 bar of liquid solvent).
  • the binder in particular, a mixture of the above-mentioned synthetic binders having the above-mentioned strength can be used.
  • the proportion of the starch can be from 1 to 99% by weight, more preferably from 10 to 90% by weight, and most preferably from 30 to 80% by weight, based on the total weight of synthetic binder and starch.
  • the paper coating color 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 above-mentioned inorganic pigments in an amount of at least 60% by weight, preferably at least 80% by weight, e.g. 80 to 95 wt.% Or 80 to 90 wt.%, Based on the total solids content.
  • Suitable thickeners apart from synthetic polymers, preferably crosslinked polyacrylate, are also natural-based thickeners, in particular celluloses, preferably carboxymethylcellulose.
  • 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, silicic acids, aluminum oxides, aluminum hydrate, silicates, titanium dioxide, zinc oxide, kaolin, alumina, talc and silicon dioxide and that the Paper coating in addition contain at least one additive selected from the group consisting of thickeners, other polymeric binders, co-binders, optical brighteners, fillers, flow control agents, dispersants, surfactants, lubricants (eg calcium stearate and waxes), neutralizing agents (eg NaOH or ammonium hydroxide ) for pH adjustment, defoamers, deaerators, preservatives (eg biocides), and dyes (in particular especially soluble dyes).
  • 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 invention also relates to a paper or board coated with a paper coating paint according to the invention and to a method for painting paper or cardboard, wherein
  • the paper coating is applied to at least one surface of paper or cardboard and then dried.
  • the paper coating color is preferably applied to uncoated base paper or uncoated cardboard.
  • the amount is generally 1 to 50 g, preferably 5 to 30 g (solid, i.e. without water or other at 21 ° C, 1 bar liquid solvent) per square meter.
  • the coating can be done 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 line and / or for the top coat.
  • Coated papers are characterized by a particularly high smoothness. They are well printable in the usual printing processes, such as letterpress, gravure, offset, digital, inkjet, flexo, newspaper, letterpress, sublimation, laser, electrophotographic, or a combination of these.
  • the use of urea in binder dispersions also leads to improved calcium ion stability.
  • the indication of a content refers to the content in aqueous solution or dispersion.
  • the solids contents are determined by adding a defined amount of the respective aqueous polymer dispersion (about 5 g) at 140 ° C. in a drying oven to constant weight. is dried. In each case, two separate measurements are carried out and the mean value is formed.
  • Example 1 Viscosity of aqueous binder dispersions
  • Aqueous binder dispersions having the constituents stated in Table 1 were prepared and the viscosity was measured (measuring method Brookfield, 100 rpm, 23 ° C., spindle no. 2).
  • Table 1 Aqueous binder dispersions
  • Example 2 Viscosity of aqueous pigment slurries
  • Aqueous pigment slurries having the ingredients shown in Table 2 were prepared and the viscosity was measured (Brookfield measuring method, 100 rpm, 23 ° C., spindle no. 2).
  • Hydrocarb 60 GU natural CaCO 3; 60% ⁇ 2 ⁇
  • Hydrocarb 90 GU natural CaCO 3; 90% ⁇ 2 ⁇
  • Hydrocarb 95 ME natural CaCO 3; 95% ⁇ 2 ⁇
  • Covercarb 60 ME natural CaCO 3; 60% ⁇ 1 ⁇ ; narrow particle size distribution
  • Covercarb 75 ME natural CaCO 3; 75% ⁇ 1 ⁇ ; narrow particle size distribution
  • Hydragloss 90 kaolin fine; 96-100% ⁇ 2 ⁇
  • Capim SP kaolin
  • Example 3 Viscosity of Aqueous Starch Compositions Aqueous starch compositions having the ingredients shown in Table 3 were prepared and the viscosity was measured (Brookfield measuring method, 100 rpm, 23 ° C., spindle no. 4 or 5, depending on the viscosity).
  • the starch used was Cargill C-Film 731 1.
  • the starch was boiled in a water bath at 95 ° C for 30 minutes.
  • the addition of urea was carried out after boiling.
  • Table 3 Aqueous starch compositions
  • C-Film 731 1 Corn starch When using urea, starch preparations can be obtained which have a reduced viscosity compared to compositions with comparable solids content.
  • Example 4 Calcium Ion Stability of Aqueous Binder Dispersions Aqueous binder dispersions having the constituents given in Table 4 were prepared and the calcium ion stability was measured.
  • Measurement results include the titration consumption of the CaCb solution up to the first flocculation and the titration consumption until the closing of the stirring cone (instability of the dispersion).
  • the results are summarized in Table 4.
  • Table 4 Ca-ion stability of aqueous binder dispersions
  • D8 50% dispersion of 45% styrene / 45% butadiene / 10% acrylonitrile
  • D9 50% dispersion of 60% styrene / 40% butadiene
  • the Ca ion stability of the respective binder dispersion can be significantly improved.
  • Aqueous paper coating pastes having the constituents stated in Table 5 were prepared.
  • the coating composition is prepared in a stirring unit into which the individual components are fed in succession.
  • the pigments are added in predispersed form (slurry).
  • the other components are added after the pigments, with the order of the order in the given coating color recipe.
  • the final solids content is adjusted by the addition of water.
  • Pigment natural Ca carbonate, particle size 60% ⁇ 2 ⁇
  • the coating colors are applied at a speed of 1000 m / min with a coating weight of 12 g / m 2 with Stiffblademodus (application roller with Bladeegalmaschine) on wood-free paper.

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Abstract

L'invention concerne l'utilisation d'urée pour réduire la quantité d'énergie nécessaire pour sécher un papier enduit d'une sauce de couchage aqueuse et/ou pour réduire la viscosité des sauces de couchage. L'invention concerne également des compositions aqueuses adaptées à une utilisation conformément à la revendication 1, sous forme de sauces de couchage aqueuses, dispersions aqueuses de liants sans pigments, suspensions aqueuses de pigments sans liants et solutions aqueuses d'amidon sans pigments avec une teneur en urée H2N-CO-NH2 dans une quantité comprise de préférence entre 1 et 100 % respectivement de la quantité maximale soluble dans la composition correspondante.
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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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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US201161525211P 2011-08-19 2011-08-19
EP11178067 2011-08-19
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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EP2744940A2 true EP2744940A2 (fr) 2014-06-25
EP2744940B1 EP2744940B1 (fr) 2020-11-04

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IT202100033104A1 (it) * 2021-12-30 2023-06-30 Lamberti Spa Metodo per migliorare le proprieta’ di barriera di un substrato di carta

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WO2013026788A2 (fr) 2013-02-28
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