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
  • D21H17/63—Inorganic compounds
  • D21H17/67—Water-insoluble compounds, e.g. fillers, pigments
  • D21H17/69—Water-insoluble compounds, e.g. fillers, pigments modified, e.g. by association with other compositions prior to incorporation in the pulp or paper
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
  • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
  • C09C1/02—Compounds of alkaline earth metals or magnesium
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
  • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
  • C09C1/02—Compounds of alkaline earth metals or magnesium
  • C09C1/021—Calcium carbonates
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
  • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
  • C09C1/40—Compounds of aluminium
  • C09C1/42—Clays
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
  • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
  • C09C3/10—Treatment with macromolecular organic 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
  • 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
• • 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
• • 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
  • D21H3/00—Paper or cardboard prepared by adding substances to the pulp or to the formed web on the paper-making machine and by applying substances to finished paper or cardboard (on the paper-making machine), also when the intention is to impregnate at least a part of the paper body
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
  • C01P2004/00—Particle morphology
  • C01P2004/60—Particles characterised by their size
  • C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
• • 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
  • D21H17/10—Phosphorus-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
  • 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
  • D21H17/20—Macromolecular organic compounds
  • D21H17/33—Synthetic macromolecular compounds
  • D21H17/46—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
  • D21H17/54—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen
  • D21H17/55—Polyamides; Polyaminoamides; Polyester-amides
• • 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
  • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
  • D21H21/06—Paper forming aids
  • D21H21/10—Retention agents or drainage improvers
• • 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 invention relates to aqueous slurries of finely divided fillers which are at least partially coated with polymers, processes for their preparation and their use as additives to the paper stock in the production of filler-containing paper, board containing filler and filler-containing cardboard with high dry strength.
• the slurry of slurry is added to the fiber suspension prior to passing it to the former of the paper machine.
• a retention aid or retention aid system is typically added to the filler / pulp suspension to retain as much filler as possible in the paper sheet.
• the addition of the filler to the paper gives the papermaker the opportunity to achieve numerous improvements in sheet properties. These include properties such as opacity, whiteness, feel and printability.
• filler-containing papers or papers with a particularly high filler content are easier to dry than non-filler papers or papers with a lower filler content.
• the paper machine can be operated faster and with lower steam consumption, which both increases productivity and lowers costs.
• the filler addition to the fiber suspension also entails disadvantages which can only be partially compensated by the addition of further paper auxiliaries.
• the amount of filler that can be used there are limits to the amount of filler that can be used.
• the strength properties of the paper are usually the most important parameters that limit the amount of filler in the paper.
• Other factors, such as filler retention, dewatering of the pulp suspension, and possibly increased need for chemicals in retention and sizing may also play a role here.
• the loss of strength properties of papers can in some cases be compensated in whole or in part by the use of dry and wet strength agents.
• a common procedure is the addition of cationic starch as dry strength in the pulp.
• synthetic dry and wet strength agents are used, for example, based on cationic or anionic polyacrylamides.
• the amount of addition and the strengthening effect are limited in most cases.
• the compensatory effect in relation to Limits the loss of strength by increasing the filler and thus the ever realizable filler increase.
• not all strength properties are increased to the same extent and in some cases only insufficiently by the use of dry strength agents.
• An important example of this is the further work, which is only slightly influenced by the use of starch or synthetic dry strength agents in comparison to other strength parameters.
• the increase in the filler content in paper usually has a very strong negative impact on continuing work.
• the increase in the filler content leads to an increase in paper density and a decrease in the thickness of the paper sheet at the same basis weight.
• the latter leads to a significant decrease in paper stiffness. In many cases, this reduction in paper stiffness can not be compensated for by the use of dry strength agents alone. Frequently, additional measures such as the reduction of mechanical pressure in the press section in the calenders, in calenders or in the dryer section of the paper machine are necessary. The latter compensates the thickness loss by increasing the filler in whole or in part.
• aqueous suspensions of inorganic particles which have a positive zeta potential are mixed with an anionic latex of a resin, the equilibrium of the negative and positive charges of the particles of the inorganic substance in the suspension and the resin in the latex when mixing is adjusted so that substantially all the resin particles are bonded to the surface of the particles of the inorganic substance and the thus obtained coated particles have a zeta potential of substantially zero.
• treatment of the inorganic particles with a latex requires that the inorganic particles be pretreated with a cationic agent, such as cationic starch, to have a positive zeta potential.
• the aqueous Sus pensions are added to the stock in the production of filler-containing paper.
• EP-B-0 573 458 discloses a process for the preparation of aqueous slurries of finely divided fillers, which are at least partially coated with polymers, for the production of filler-containing papers.
• an aqueous slurry of fillers is first added with a cationic solidifier for paper followed by a non-ionic and / or anionic strength agent for paper or else a non-ionic or anionic sizing agent for paper.
• the cationic starting materials are always used in such an amount that the finely divided fillers carry a cationic charge.
• DE-A-198 21 089 another process for the preparation of aqueous slurries of finely divided fillers is known, which are at least partially coated with polymers.
• an aqueous slurry of fillers is treated in the absence of cationic strengtheners for paper with at least one polymer sizing agent in the form of an aqueous dispersion.
• such dispersions always contain polymeric emulsifiers, for example degraded starches or synthetic polymers.
• aqueous slurries of finely divided fillers are disclosed, which are at least partially coated with polymers.
• These polymers are binders for paper coating slivers whose glass transition temperature is in the range of -40 to +50 0 C and preferably below 6 0 C.
• the binders for paper-coating paints disclosed therein are free of phosphine- and / or phosphoric acid-group-containing monomers.
• the papers produced by the process according to the invention should have a high filler content and high dry strength.
• aqueous slurries of finely divided fillers which are at least partially coated with anionic latices, the slurries being obtainable by treating aqueous slurries of finely divided fillers with at least one anionic latex having at least one phosphonic and / or phosphoric acid groups Containing monomer in copolymerized contains.
• the aqueous slurries according to the invention contain, for example, 1 to 70% by weight, preferably 5 to 50% by weight, particularly preferably 10 to 40% by weight, of at least one finely divided filler.
• the amount of latex is for example 0.01 to 10 wt .-%, preferably 0.1 to 5 wt .-%, particularly preferably 0.2 to 3 wt .-%, based on the filler.
• the invention further provides a process for the preparation of the aqueous slurries, wherein 0.01 to 10% by weight of at least one anionic latex, based on filler, is added to an aqueous slurry of at least one finely divided filler or the aqueous slurry is at least finely divided.
• Filler enters into an aqueous dispersion of an anionic latex and mixing the components each.
• Another object of the invention is the use of the above-described aqueous slurries as an additive to the paper stock in the production of filler-containing paper, filler-containing cardboard or filler-containing cardboard with high dry strength by dewatering of the paper stock.
• latex in the context of the present invention is understood as meaning water-insoluble copolymers which are preferably used in the form of dispersions or emulsions.
• anionic latices are used which comprise at least one monomer containing phos- pho- and / or phosphoric acid groups in copolymerized form.
• phosphonic and / or phosphoric acid group-containing monomers are understood as meaning both those having a free acid group and their salts, esters and anhydrides.
• the latex is preferably at least 40 wt .-%, preferably at least 60 wt .-%, more preferably at least 80 wt .-% of so-called main monomers (a).
• the main monomers (a) 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 of from 1 to 10 ° C -Atome-containing alcohols, aliphatic hydrocarbons having 2 to 8 carbon atoms and one or two double bonds or mixtures of these monomers.
• (meth) acrylic acid alkyl ester having a Ci-Cio-alkyl radical such as methyl methacrylate, methyl acrylate, n-butyl acrylate, isobutyl acrylate, ethyl acrylate and 2-ethylhexyl acrylate.
• mixtures of (meth) acrylic acid alkyl esters are also suitable.
• Vinyl esters of carboxylic acids having 1 to 20 carbon atoms are, for. As vinyl laurate, stearate, vinyl propionate, vinyl versatate and vinyl acetate.
• Suitable vinylaromatic compounds having up to 20 carbon atoms are vinyltoluene, ⁇ - and p-methylstyrene, ⁇ -butylstyrene, 4-n-butylstyrene, 4-n-decylstyrene and preferably styrene.
• Examples of ethylenically unsaturated nitriles are acrylonitrile and methacrylonitrile.
• the vinyl halides are chloro, fluoro or bromo substituted ethylenically unsaturated compounds, preferably vinyl chloride and vinylidene chloride.
• vinyl ethers of alcohols containing 1 to 10 carbon atoms are, for.
• vinyl methyl ether or vinyl isobutyl ether Preference is given to vinyl ethers of alcohols containing from 1 to 4 carbon atoms.
• Ethylene, propylene, butadiene, isoprene and chloroprene are mentioned as aliphatic hydrocarbons having 2 to 8 carbon atoms and one or two olefinic double bonds.
• Preferred main monomers (a) are C 1 -C 20 -alkyl (meth) acrylates and mixtures of the alkyl (meth) acrylates with vinylaromatics, in particular styrene (also referred to as polyacrylate latex) or hydrocarbons having 2 double bonds, in particular butadiene, or mixtures of these Hydrocarbons with vinyl aromatics, especially styrene (collectively referred to as polybutadiene latex).
• vinylaromatics in particular styrene (also referred to as polyacrylate latex) or hydrocarbons having 2 double bonds, in particular butadiene, or mixtures of these Hydrocarbons with vinyl aromatics, especially styrene (collectively referred to as polybutadiene latex).
• the latex may contain other monomers (b), e.g. B. hydroxyl-containing monomers, in particular C 1 -C 10 hydroxyalkyl (meth) acrylates, and monomers having alkoxy groups, as they are obtainable by alkoxylation of hydroxyl-containing monomers with alkoxides, in particular ethylene oxide or propylene oxide.
• B hydroxyl-containing monomers, in particular C 1 -C 10 hydroxyalkyl (meth) acrylates, and monomers having alkoxy groups, as they are obtainable by alkoxylation of hydroxyl-containing monomers with alkoxides, in particular ethylene oxide or propylene oxide.
• Further monomers (b) are compounds which have at least two free-radically polymerizable double bonds, preferably 2 to 6, particularly preferably 2 to 4, very particularly preferably 2 to 3 and in particular 2. Such compounds are also referred to as crosslinkers.
• the at least two free-radically polymerizable double bonds of the crosslinkers (b) can be selected from the group consisting of (meth) acrylic, vinyl ether, vinyl ester, allyl ether and allyl ester groups.
• crosslinkers (b) are 1, 2-ethanediol di (meth) acrylate, 1, 3-propanediol di (meth) acrylate, 1, 2-propanediol di (meth) acrylate, 1, 4-butanediol di (meth) acrylate, 1, 6 Hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, trimethylolpropane trioldi (meth) acrylate, pentaerythritol tetra (meth) acrylate, 1,4-butanediol divinyl ether, 1,6-hexanediol divinyl ether, 1,4-cyclohex
• the anionic latex may contain other monomers (c), e.g. As monomers with carboxylic acid groups, their salts or anhydrides. Called z. For example, acrylic acid, methacrylic acid, itaconic acid, maleic acid or fumaric acid and aconitic acid.
• the content of ethylenically unsaturated acids in the latex is generally less than 10% by weight.
• the proportion of these monomers (c) is for example at least 1 wt .-%, preferably at least 2 wt .-% and particularly preferably at least 3 wt .-%.
• the acid groups of the latex may optionally be at least partially neutralized prior to later use. Preferably, at least 30 mol%, particularly preferably 50-100 mol% of the acid groups are neutralized.
• Suitable bases are volatile bases such as ammonia or non-volatile bases such as alkali metal hydroxides, in particular sodium hydroxide solution.
• the anionic latex comprises at least one monomer containing phosphonated and / or phosphoric acid groups in copolymerized form, which may be both monomers having a free acid group and their salts, esters and / or anhydrides.
• phosphonic and / or phosphoric acid group-containing monomers which are obtainable by esterification of monoethylenically unsaturated C 3 -C 8 -carboxylic acids with optionally monoalkoxylated phosphonic and / or phosphoric acids.
• monoalkoxylated phosphoric acid group-containing monomers which are obtained by esterification of monoethylenically unsaturated Cs-Cs-carboxylic acids with optionally monoalkoxylated phosphoric acids of the general formula (I)
• X is a straight-chain or branched C 2 -C 6 -alkylene oxide unit and n is an integer from 0 to 20
• X is a straight-chain or branched C 2 -C 3 -alkylene oxide unit, and n is an integer between 5 and 15.
• X is preferably an ethylene or propylene oxide unit, particularly preferably a propylene oxide unit.
• any mixtures of different optionally monoalkoxylated phosphonic acids and optionally monoalkoxylated phosphoric acids of the formula (I) for the esterification with a monoethylenically unsaturated C3- Cs-carboxylic acid can be used.
• Particularly preferred mixtures of monoalkoxylated phosphoric acids contain 5 to 15 units of propylene oxide, ie n is an integer between 5 and 15.
• monoethylenically unsaturated carboxylic acids having 3 to 8 carbon atoms are esterified with the abovementioned optionally monoalkoxylated phosphonic and / or phosphoric acids, preferably with the optionally monoalkoxylated phosphoric acids of the general formula (I).
• Such monoethylenically unsaturated C 3 -C 8 -carboxylic acids are, for example, acrylic acid, methacrylic acid, dimethylacrylic acid, ethacrylic acid, maleic acid, citraconic acid, methylenemalonic acid, crotonic acid, fumaric acid, mesaconic acid and itaconic acid, maleic acid. Preference is given to using acrylic acid and methacrylic acid.
• mixtures of monoethylenically unsaturated C3-Cs carboxylic acids for esterification with optionally monoalkoxylated phosphonic and / or phosphoric acids, preferably with optionally monoalkoxylated phosphoric acids of the formula (I) are used.
• Preferred anionic latexes are, for example, aqueous dispersions
• styrene and / or acrylonitrile or methacrylonitrile b) acrylic acid esters and / or methacrylic acid esters of C 1 - to C 10 -alcohols, and optionally c) acrylic acid, methacrylic acid, maleic acid and / or itaconic acid, and d) (meth) acrylic acid esters of optionally monoalkoxylated phosphoric acids of formula (I) wherein X and n are as defined above.
• aqueous dispersions of anionic latices are particularly preferred.
• acrylic acid and (4) (meth) acrylic esters of monoalkoxylated phosphoric acids of the formula (I) wherein X is a propylene oxide unit, and n is an integer between 5 and 15.
• such particularly preferred polyacrylate latexes contain 2-25% by weight of styrene, 2-25% by weight of acrylonitrile, 50-95% by weight of C 1 -C 4 -alkyl acrylates, preferably C 4 acrylates such as n-butyl acrylate, isobutyl acrylate and / or part.
• the glass transition temperature (measured by DSC) of the anionic latices in the range of -40 to +50 0 C.
• anionic latexes are preferred with a glass transition temperature of -20 to +20 0 C and more preferably from -10 to +10 0 C in the aqueous slurries of finely divided fillers according to the invention are used.
• the person skilled in the art is familiar with the literature mentioned below, as by selecting the monomers anionic latices are obtained with the appropriate glass transition temperature.
• the glass transition temperature T 9 is generally known to the person skilled in the art. This means the limit value of the glass transition temperature, which according to G. Kanig (Kolloid-Zeitschrift & Zeitschrift fur Polymere, Vol. 190, page 1, equation 1) tends to increase with increasing molecular weight.
• the glass transition temperature is determined by the DSC method (differential scanning calorimetry, 20 K / min, midpoint measurement, DIN 53765).
• the latices are generally prepared by emulsion polymerization, which is therefore an emulsion polymer.
• emulsion polymerization which is therefore an emulsion polymer.
• the preparation of aqueous polymer dispersions by the process of free-radical emulsion polymerization is on known (see Houben-Weyl, Methods of Organic Chemistry, Volume XIV, Makromolekulare substances, loc cit, pages 133ff).
• ionic and / or nonionic emulsifiers and / or protective colloids or stabilizers are used as surface-active compounds.
• the surface-active substance is usually used in amounts of from 0.1 to 10% by weight, in particular from 0.2 to 3% by weight, based on the monomers to be polymerized.
• Common emulsifiers are z. B. ammonium or alkali metal salts of higher fatty alcohol sulfates, such as Na-n-lauryl sulfate, fatty alcohol phosphates, ethoxylated Cs to Cio-alkylphenols having a degree of ethoxylation of 3 to 30 and ethoxylated Cs to C25 fatty alcohols having a degree of ethoxylation of 5 to 50 are conceivable also mixtures of nonionic and ionic emulsifiers. Also suitable are phosphate- or sulfate-containing, ethoxylated and / or propoxylated alkylphenols and / or fatty alcohols. Further suitable emulsifiers are listed in Houben-Weyl, Methods of Organic Chemistry, Volume XIV, Macromolecular Materials, Georg Thieme Verlag, Stuttgart, 1961, pages 192 to 209.
• Water-soluble initiators for the emulsion polymerization for the preparation of latices are, for.
• so-called reduction-oxidation (red-ox) initiator systems are also suitable.
• the amount of initiators is generally 0.1 to 10 wt .-%, preferably 0.5 to 5 wt .-%, based on the monomers to be polymerized. It is also possible to use a plurality of different initiators in the emulsion polymerization.
• emulsion polymerization regulators can be used, for. B. in amounts of 0 to 3 parts by weight, based on 100 parts by weight of the monomers to be polymerized, by which the molecular weight is reduced. Suitable z.
• B. Compounds with a thiol group such as tert-butylmercaptan, Thioglycolklareethylacrylester, mercaptoethynol, mercaptopropyltrimethoxysilane or tert-dodecylmercaptan or regulator without thiol, in particular z.
• the emulsion polymerization for the preparation of the latexes is generally carried out at 30 to 130 0 C, preferably at 50 to 100 0 C.
• the polymerization medium may consist either of water alone or of mixtures of water and water-miscible liquids such as methanol th exist. 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 stepwise or gradient procedure.
• feed process in which one submits a portion of the polymerization, heated to the polymerization temperature, and then polymerized the remainder of the polymerization mixture, usually over several spatially separate feeds, one or more of the monomers in pure or in emulsified form, continuously, stepwise or with superposition of a concentration gradient while maintaining the polymerization of the polymerization zone supplies.
• the polymerization can also z. B. be presented for better adjustment of the particle size of a polymer seed.
• 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 one of ordinary skill in the art. It can be introduced both completely into the polymerization vessel, or used continuously or in stages according to its consumption in the course of the free radical aqueous emulsion polymerization. In detail, this depends on the chemical nature of the initiator system as well as on the polymerization temperature. Preferably, a part is initially charged and the remainder supplied according to the consumption of the polymerization.
• the individual components can be added to the reactor in the feed process from above, in the side or from below through the reactor bottom.
• the acid groups contained in the latex can still be at least partially neutralized.
• This can be done, for example, with oxides, hydroxides, carbonates or bicarbonates of alkali metals or alkaline earth metals, preferably with hydroxides to which any one or more counterions may be associated, eg Li + , Na + , K + , Cs + , Mg 2+ , Ca 2 + or Ba 2+ .
• Also suitable for neutralization are ammonia or amines. Preference is given to aqueous ammonium hydroxide, sodium hydroxide or potassium hydroxide solutions.
• aqueous dispersions of the latex are generally obtained with solids contents of from 15 to 75% by weight, preferably from 40 to 75% by weight.
• the particle size of the latices is preferably in the range of 10 to 1000 nm, more preferably in the range of 50 to 300 nm (measured using a Malvern ® Au tosizer 2 C).
• the aqueous dispersions of at least one latice are used according to the invention for the treatment of finely divided fillers.
• Suitable fillers are all pigments of inorganic material customarily used in the paper industry, for example calcium carbonate, which can be used in the form of ground lime (GCC), chalk, marble or precipitated calcium carbonate (PCC), talc, kaolin, bentonite, satin white, Calcium sulfate, barium sulfate or titanium dioxide. It is also possible to use mixtures of two or more pigments, but preference is given to using a pigment.
• the average particle diameter is for example in the range of 0.5 to 30 microns, preferably between 1 and 10 microns.
• Another object of the present invention is a process for preparing the aqueous slurry of particulate fillers.
• the fillers are processed, for example, by introducing into water to form an aqueous slurry.
• Precipitated calcium carbonate is usually slurried in water in the absence of dispersants.
• an anionic dispersant for example polyacrylic acids having a molecular weight M w of, for example, 1,000 to 40,000, is generally used. If an anionic dispersant is used, for example, from 0.01 to 0, 5 wt .-%, preferably 0.2 to 0.3 wt .-% for the preparation of the aqueous Grestoffanschlämmieux.
• the finely divided fillers dispersed in water in the presence of anionic dispersants are anionic.
• the aqueous slurries particularly preferably contain 10 to 40% by weight of at least one filler.
• aqueous slurries of optionally anionically dispersed finely divided fillers are treated with at least one anionic latex.
• at least one anionic latex For example, from 0.01 to 10% by weight, based on the filler, of an anionic latex, or an aqueous slurry of a finely divided filler into an aqueous dispersion of an anionic latex, may be added to a 1- to 70% by weight aqueous slurry containing at least one finely divided filler Add anionic latices and mix the components. It is also possible that the finely divided filler is introduced firmly into an aqueous dispersion of an anionic latex.
• the treatment of the aqueous slurries of finely divided fillers with the anionic latices can be carried out continuously or batchwise.
• the fillers are at least partially coated or impregnated with anionic latices.
• the mixing of the components takes place, for example, in a shear field. In most cases, it is sufficient to stir the components after being brought into contact or to treat them in a shear field of an Ultraturrax device.
• the contacting and mixing of the components of the aqueous slurries can be carried out, for example, in US Pat Temperature range of 0 0 C to 95 ° C, preferably 10 to 70 0 C take place.
• the pH of the treated with anionic latices aqueous slurries of fillers is for example 5 to 1 1, preferably 6 to 9, wherein the pH of calcium carbonate containing slurries is preferably more than 6.5.
• aqueous slurries of precipitated calcium carbonate free of dispersants and ground calcium carbonate obtainable by milling particulate calcium carbonate or marble in the presence of anionic polymeric dispersants such as polyacrylic acids having molecular weights of from 1,000 to 15,000.
• Another object of the invention is the use of the aqueous Anschläm- ments as an additive to the paper stock in the production of filler-containing paper, filler-containing cardboard or filler-containing paperboard by dewatering of the pulp.
• the aqueous pigment slurries treated with an anionic latex according to the invention can be used to prepare all filler-containing paper grades, e.g. Newspaper printing, SC paper (supercalendered paper), wood-free or wood-containing writing and printing papers.
• the main raw material components used are groundwood, thermomechanical (TMP), chemo-thermomechanical (CTMP), pressure ground (PGW) and sulphite and sulphate pulp.
• the aqueous slurries of finely divided fillers according to the invention are added to the pulp in papermaking so as to form the total paper stock.
• the overall fabric may contain other conventional paper additives.
• sizing agents such as alkylketene dimers (AKD), alkenylsuccinic anhydrides (ASA), rosin size, wet strength agents, cationic or anionic retention agents based on synthetic polymers.
• Suitable retention agents are, for example, anionic microparticles (colloidal silicic acid, bentonite), anionic polyacrylamides, cationic polyacrylamides, cationic starch, cationic polyethylenimine or cationic polyvinylamine.
• any combinations thereof are conceivable, for example dual systems consisting of a cationic polymer with an anionic microparticle or an anionic polymer with a cationic microparticle.
• the addition is recommended of such retention agents, which can be added to the thick material but also to the thin material, for example.
• a virtually coagulate-free polymer dispersion having a solids content of 50.1% by weight, a pH of 7.1 and a particle size of 183 nm measured by dynamic light scattering (Malvern HPPS) was obtained.
• the polymer had a DSC (Mettler DSC 820) measured glass transition temperature of +3 0 C.
• Polymer 2 Polymer 2 was prepared similarly to Polymer 1, but 168 g of styrene, 828 g of n-butyl acrylate and 168 g of acrylonitrile, in the preparation of the monomer emulsion a monomer mixture of 12 g of Sipomer PAM 200 ®, 24 g of acrylic acid, are used.
• a practically coagulate-free polymer dispersion having a solids content of 50.0% by weight, a pH of 6.7 and a particle size of 181 nm measured by dynamic light scattering (Malvern HPPS) was obtained.
• the polymer had a DSC-measured particle size Glass transition temperature of +4 0 C on.
• 24 g of acrylic acid 168 g of styrene, 828 g of n-butyl acrylate and 168 g of acrylonitrile.
• a practically coagulate-free polymer dispersion having a solids content of 50.0% by weight, a pH of 6.8 and a particle size of 193 nm measured by dynamic light scattering (Malvern HPPS) was obtained DSC measured glass transition temperature of +6 0 C.
• aqueous precipitated calcium carbonate (PCC) slurry was mixed, while stirring gently at room temperature, 1.8 g of a 50% by weight anionic latex dispersion (Polymer 1). During the addition and then the mixture was stirred by means of a Heiltof stirrer at 1000 revolutions per minute (rpm). The pH of the mixture was then adjusted to 8.5.
• PCC aqueous precipitated calcium carbonate
• aqueous precipitated calcium carbonate (PCC) slurry was mixed, while stirring gently at room temperature, 1.8 g of a 50% by weight dispersion of an anionic latex (Polymer 3). During the addition and then the mixture was stirred by means of a Heiltof stirrer at 1000 revolutions per minute (rpm). The pH of the mixture was then adjusted to 8.5.
• PCC aqueous precipitated calcium carbonate
• a mixture of bleached birch sulphate and bleached pine sulphite was blotted open in a ratio of 70/30 at a solids concentration of 4% in the laboratory pulper until a freeness of 30-35 was reached.
• the opened substance is an optical brightener (Blankophor PSG ®, Bayer AG) and a cationic starch (HICAT ® 5163 A) were then added.
• the digestion of the cationic starch was carried out as a 10 wt .-% starch slurry in a jet cooker at 130 0 C and 1 minute residence time.
• the metered amount of the optical brightener was 0.5% by weight of commercial product, based on the solids content of the paper stock suspension.
• the dosage of the cationic starch was 0.5 wt .-% of starch, based on the solids content of the pulp suspension.
• the pH of the substance was in the range between 7 and 8.
• the milled material was then diluted by addition of water to a solids concentration of 0.35 wt .-%.
• the metered amount of the retention agent in each case in each case 0.01 wt .-% polymer, based on the solids content of the pulp suspension.
• the paper sheets were each fabricated on a Rapid-Köthen sheet former according to ISO 5269/2 with a sheet weight of 70 g / m 2 and then dried for 7 minutes at 90 0 C.
• TMP thermo-mechanical pulp
• groundwood was whisk-free in a ratio of 70/30 at a solids concentration of 4% in the laboratory pulper until a grinding degree of 35 was reached.
• the pH of the substance was in the range between 7 and 8.
• the milled substance was then diluted by addition of water to a solids concentration of 0.35 wt .-%.
• aqueous filler slurries in the production of filler-containing paper, 500 ml of the stock suspension were introduced and the slurries treated according to the examples were metered into this pulp and a cationic polyacrylamide as retention agent (polymer). min® KE 440, BASF SE). The dosage of the retention agent was in all cases in each case 0.01% by weight of polymer, based on the solids content of the paper stock suspension.
• the paper sheets were each produced on a Rapid-Köthen sheet former according to ISO 5269/2 with a sheet weight of 80 g / m, then dried for 7 minutes at 90 0 C and then calendered with a line pressure of 200 N / cm.

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