EP2297251A1

EP2297251A1 - Aqueous suspensions of fine-particulate fillers, method for the manufacture thereof and use thereof for the manufacture of fluid-containing papers

Info

Publication number: EP2297251A1
Application number: EP09772428A
Authority: EP
Inventors: Jürgen Schmidt-Thümmes; Anton Esser; Jörg NIEBERLE
Original assignee: BASF SE
Current assignee: BASF SE
Priority date: 2008-07-03
Filing date: 2009-06-30
Publication date: 2011-03-23
Also published as: JP5389166B2; JP2011526658A; CN102083916A; US8449721B2; KR20110052597A; US20110100575A1; WO2010000728A1; CA2729498A1

Abstract

Aqueous suspensions of fine-particulate fillers that are at least partially lined with anionic lattices, wherein the suspensions are obtained from the treatment of aqueous suspensions of fine-particulate fillers with at least one anionic latex comprising at least one polymerized monomer containing a phosphonic or phosphoric acid group, preparation of the aqueous suspensions and use thereof as additives to paper materials in the production of paper containing fillers, carton containing fillers or corrugated cardboard containing fillers by de-watering the paper materials.

Description

Aqueous slurries of finely divided fillers, process for their preparation and their use for the production of filler-containing papers

description

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.

In the production of filler-containing papers, 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.

Moreover, if the filler is cheaper than the pulp, the addition or increased addition of filler can lead to a reduction of the fiber content and thus to a reduction in the production cost of the paper. 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. As a result, the paper machine can be operated faster and with lower steam consumption, which both increases productivity and lowers costs.

However, the filler addition to the fiber suspension also entails disadvantages which can only be partially compensated by the addition of further paper auxiliaries. For a given basis weight, 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. Likewise, synthetic dry and wet strength agents are used, for example, based on cationic or anionic polyacrylamides. However, the amount of addition and the strengthening effect are limited in most cases. To the same extent is also the compensatory effect in relation to Limits the loss of strength by increasing the filler and thus the ever realizable filler increase. In addition, 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, on the other hand, usually has a very strong negative impact on continuing work.

Other important properties are the thickness and stiffness of the paper. 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.

It is known from DE-B-25 16 097 that 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. However, 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. In this process, 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. However, the cationic starting materials are always used in such an amount that the finely divided fillers carry a cationic charge. From 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. In this process, 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. However, such dispersions always contain polymeric emulsifiers, for example degraded starches or synthetic polymers.

In WO-A-03/074786 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.

It is an object of the present invention to provide further aqueous slurries of fine-particle fillers which, in papermaking, give papers with an improved breaking length and printability in comparison with the known slurries. In addition, the papers produced by the process according to the invention should have a high filler content and high dry strength.

The object is achieved according to the invention with 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.

The term 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.

According to the invention, anionic latices are used which comprise at least one monomer containing phos- pho- and / or phosphoric acid groups in copolymerized form. In the context of the present invention, 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.

To name a few are z. B. (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.

In particular, 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, α- and p-methylstyrene, α-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. To name as vinyl ethers of alcohols containing 1 to 10 carbon atoms are, for. As 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).

In addition to the main monomers (a), 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.

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. Examples of 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-cyclohexanediol divinyl ether, divinylbenzene, allyl acrylate, allyl methacrylate , Methallyl acrylate, methallyl methacrylate, (meth) acrylic acid but-3-en-2-yl ester, (meth) acrylic acid but-2-en-1-yl ester,

(Meth) acrylic acid 3-methylbut-2-en-1-yl ester, ester of (meth) acrylic acid with geraniol, citronellol, cinnamyl alcohol, glycerol mono- or diallyl ether, trimethylolpropane mono-or diallyl ether, ethylene glycol monoallyl ether, diethylene glycol monoallyl ether, propy - Lenglykolmonoallylether, Dipropylenglykolmonoallylether, 1, 3-Propandiolmonoallylether, 1, 4-Butandiolmonoallylether and also Itaconsäurediallylester. Preference is given to allyl acrylate, divinylbenzene, 1,4-butanediol diacrylate and 1,6-hexanediol diacrylate. In addition, 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.

According to the invention, 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.

Preference is given to using 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. Particular preference is given to 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)

H- [X] _n -P (O) (OH) ₂ (I)

are available in which

X is a straight-chain or branched C 2 -C 6 -alkylene oxide unit and n is an integer from 0 to 20

mean.

Preference is given to using monoalkoxylated phosphoric acids of the formula (I) in which 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.

Of course, 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. Preference is given to using mixtures of monoalkoxylated phosphoric acids of the formula (I) which contain the same alkylene oxide unit, preferably propylene oxide, but have a different degree of alkoxylation, preferably degree of propoxylation. Particularly preferred mixtures of monoalkoxylated phosphoric acids contain 5 to 15 units of propylene oxide, ie n is an integer between 5 and 15.

For the preparation of the monomers containing phosphonic and / or phosphoric acid groups, 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.

Of course, 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. However, preference is given to using only one monoethylenically unsaturated carboxylic acid, for example acrylic acid or methacrylic acid.

Preferred anionic latexes are, for example, aqueous dispersions

a) 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.

Particularly preferred are aqueous dispersions of anionic latices

(1) styrene and / or acrylonitrile,

(2) acrylic esters of C 1 to C 4 alcohols, and optionally

(3) 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. For example, 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. Butyl acrylate, 0-5% by weight of acrylic acid and 0.1-5% by weight of (meth) acrylic acid esters of monoalkoxylated phosphoric acids of the formula (I) in which X is a propylene oxide unit, and n is an integer between 5 and 15 is.

Typically, 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).

According to Fox (TG Fox, Bull. Am. Phys Soc., 1956 [Ser. II] 1, page 123 and according to LJII- Mann's Encyclopedia of Industrial Chemistry, Vol. 19, page 18, 4th edition, Verlag Chemie, Weinheim, 1980) applies to the glass transition temperature of at most weakly crosslinked copolymers in a good approximation:

1 / Tg = XVTg ¹ + X ² / T _g ² + .... X "/ V,

where x ¹ , x ² , .... x ⁿ the mass fractions of the monomers 1, 2, .... n and T ₉ ¹ , T ₉ ² , .... T ₉ "the glass transition temperatures of each of only one of Monomers 1, 2, .... n are the polymers prepared in degrees Kelvin The T ₉ values for the homopolymers of most monomers are known and are described, for example, in Ullmann's Encyclopedia of Industrial Chemistry, Vol. A21, page 169, VCH Weinheim, 1992. Other sources of glass transition temperatures of homopolymers include, for example, J. Brandrup, EH Immergut, Polymer Handbook, Ist Ed., J. Wiley, New York, 1966, 2nd Ed ., J. Wiley, New York, 1975, and 3rd Ed., J. Wiley, New York, 1989.

The latices are generally prepared by 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).

In the emulsion polymerization for the preparation of latices, 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. For example, ammonium and alkali metal salts of peroxodisulfuric, z. For example, sodium peroxodisulfate, hydrogen peroxide or organic peroxides, eg. B. tert-butyl hydroperoxide. Also suitable are so-called reduction-oxidation (red-ox) initiator systems.

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.

In the 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, Thioglycolsäureethylacrylester, mercaptoethynol, mercaptopropyltrimethoxysilane or tert-dodecylmercaptan or regulator without thiol, in particular z. B. terpinolene.

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. Is preferred the 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. In 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.

To remove the residual monomers is usually after the end of the actual emulsion polymerization, d. H. after a conversion of the monomers of at least 95%, initiator added.

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.

Following the copolymerization, 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.

In the emulsion polymerization, 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. In order to prepare aqueous slurries of the other fillers, 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 Füllstoffanschlämmungen. 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.

In order to prepare the aqueous slurries of finely divided fillers according to the invention, aqueous slurries of optionally anionically dispersed finely divided fillers are treated with 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. When the finely divided fillers are combined with anionic latices, 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. In most cases the components are mixed at the respective room temperature up to a temperature of 40 ⁰ C. 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.

Particularly preferred are 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. For the production of such papers, for example, the main raw material components used are groundwood, thermomechanical (TMP), chemo-thermomechanical (CTMP), pressure ground (PGW) and sulphite and sulphate pulp. By using the aqueous slurries according to the invention, the filler content of the paper can be significantly increased with virtually unchanged strength properties. Such papers have strength properties comparable to those of conventional low solids papers.

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. In addition to the treated fillers and pulps, the overall fabric may contain other conventional paper additives. These include, for example, 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. In addition, 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. In order to achieve a high filler retention, the addition is recommended of such retention agents, which can be added to the thick material but also to the thin material, for example.

The invention will be explained in more detail by means of the following non-limiting examples.

Examples

The percentages in the examples are by weight unless otherwise indicated in the context.

Polymer 1

424.2 g of demineralized water, 14.5 g of a polystyrene seed (solids content 33%, average particle size 29 nm) and 1.4 g of a 45% strength by weight solution of dodecylphenoxybenzene diurea were placed in a 4 l planoidal vessel equipped with anchor stirrer. sulfonic acid sodium salt (Dowfax ^® 2A1, Dow Chemicals) and 15.4 g of a 7% strength by weight solution of sodium peroxydisulfate submitted. About a controlled, external oil bath, the reaction vessel was heated to 93 ⁰ C with stirring. After reaching the temperature, a previously prepared monomer emulsion consisting of 534.2 g of demineralized water, 22.4 g of a 15 wt .-% solution of sodium laurylsulfat (Disponil ^® SDS 15, Cognis), 8 g of a 45 wt .-% solution of Dodecylphenoxybenzoldisulfonsäure sodium salt (Dowfax ^® 2A1, Dow Chemicals), 12 g of a 10 wt .-% solution of sodium hydroxide, 6 g of a methacrylic acid ester with an esterified with phosphoric acid esterified oligopropylene oxide (Sipomer ^® PAM 200: CH ₂ = C (CHS) -COO- (CH ₂ CH (CH ₃ ) O) ₈ -IO-P (O) (OH) ₂ , Rhodia), 30 g of acrylic acid, 168 g of styrene, 828 g n-butyl acrylate and 168 g of acrylonitrile are added uniformly over 2 hours. In parallel, 49.7 g of a 7 wt .-% solution of sodium peroxydisulfate were added. The mixture was stirred while keeping the temperature constant for a further 45 minutes. Subsequently, 78 g of a 10 wt .-% solution of sodium hydroxide was added, and the reaction contents cooled to 60 ⁰ C. Subsequently, two feeds consisting of a) 24 g of a 10% strength by weight solution of tert-butyl hydroperoxide and b) 33 g of a 13% strength by weight solution containing the addition product of 2.67 g of sodium disulfite and 1.62 g were added in parallel Acetone added within 30 minutes. The reactor contents were cooled to room temperature.

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.

Polymer 3

Polymer 3 was prepared analogously to polymer 1, but in the preparation of the monomer emulsion a monomer mixture of 12 g of an acrylic ester with an esterified with phosphoric acid oligopropylene oxide (Sipomer ^® PAM 300: CH ₂ = CH-COO- (CH ₂ CH (CH ₃ ) O) ₈ -IO-P (O) (OH) ₂ , Rhodia), 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.

example 1

To 150 g of a 20% by weight 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.

Example 2

To 150 g of a 20% by weight 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 2). 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. Example 3

To 150 g of a 20% by weight 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.

Comparative Example (VB) 1 (according to WO-A-03/074786)

To 150 g of a 20 wt .-% aqueous slurry of precipitated calcium carbonate (PCC) 8 g of a 50 wt .-% aqueous dispersion of a binder for paper coating slips (Acro nal ^® S 504, BASF SE were under gentle stirring at room temperature for 1, ) mixed. 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.

Example 4

2.7 g of a 50% by weight dispersion of an anionic latex (polymer 1) were mixed with gentle stirring at room temperature to 150 g of a 30% by weight aqueous slurry of a commercially available kaolin clay. 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.

Example 5

2.7 g of a 50% strength by weight dispersion of an anionic latex (polymer 2) were mixed with gentle stirring at room temperature to 150 g of a 30% by weight aqueous slurry of a commercially available kaolin clay. 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.

Example 6

To 150 g of a 30% strength by weight aqueous slurry of a commercially available kaolin clay, with gentle stirring at room temperature, 2.7 g of a 50 wt.

% dispersion of an anionic latex (polymer 3) mixed. During the addition and afterward, the mixture was stirred at 1000 rpm using a Heiltof stirrer. stirred per minute (rpm). The pH of the mixture was then adjusted to 8.5.

Example 7

2.7 g of a 50% by weight dispersion of an anionic latex (polymer 2) was diluted with 150 ml of water. The strongly diluted dispersion was then added at room temperature to a commercially available kaolin clay in powder form. The solids concentration of the slurry after the addition of the kaolin clay was 30%. 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.

Comparative Example (VB) 2 (according to WO-A-03/074786)

To 150 g of a 30 wt .-% aqueous slurry of a commercially available kaolin clay 2.7 g of a 50 wt% dispersion of a binder for paper coating slips were under gentle stirring at room temperature (Acronal ^® S 504, BASF SE) are mixed. 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.

Production of filler-containing paper

Type A papers

Examples 8-16 Comparative Examples 3 - 8

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 .-%. To determine the behavior of the aqueous filler slurries described above in the manufacture of filler-containing paper, was placed 500 ml of the paper stock suspension before and in each case the pulp treated according to the examples, slurries, as well as a cationic polyacrylamide (as retention aids poly min ^® KE 440, BASF SE). 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.

Subsequently, sheets were formed with the above-described pretreated fillers (Examples 8-16 and Comparative Examples 3-5). The amount of filler used was adjusted so that the filler contents were about 20%, 30% and 40%, respectively. In the case of the pretreated fillers, the amount of slurry used, which must be used to achieve a specific target value, always lower than in the case of the untreated fillers.

To the pretreated type of filler, comparative examples were also carried out with untreated filler (Comparative Examples 6-8). For this purpose, the amount of untreated stock slurry was first determined in preliminary experiments, which is necessary to set a filler content of about 20%, 30% and 40%. Subsequently, leaves were formed with the untreated fillers.

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.

Type B papers

Examples 17-28 Comparative Examples 9-14

A mixture of TMP (thermo-mechanical pulp) and 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 .-%.

In order to determine the behavior of the above-described 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.

Subsequently, sheets were formed with the above-described pretreated fillers (Examples 17-28 and Comparative Examples 9-1.1). The amount of filler used was adjusted so that the filler contents were about 20%, 30% and 40%, respectively. In the case of the pretreated fillers, the amount of slurry used, which must be used to achieve a specific target value, always lower than in the case of the untreated fillers.

In addition, to the pretreated type of filler, comparative examples were carried out with untreated filler (Comparative Examples 12-14). For this purpose, the amount of untreated filler slurry was first determined in preliminary experiments, which is necessary to set a filler content of about 20%, 30% and 40%. Subsequently, sheets were formed with the untreated filler.

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.

Testing of type A paper sheets

After a storage time in a climate chamber at constant 23 ⁰ C and 50% humidity for 12 hours, the dry breaking length of the sheets were determined according to DIN 54540, the inner strength according to DIN 54516 and the flexural strength according to DIN 53121. The results are shown in Table 1. The slurries according to the comparative examples or the comparative examples with the paper sheets produced therefrom are marked with the addition (VB). The other examples are examples according to the invention.

Testing of type B paper sheets

After a storage time in a climate chamber at constant 23 ⁰ C and 50% humidity for 12 hours, the dry breaking length of the sheets were determined according to DIN 54540 and the internal strength according to DIN 54516. The dry pick resistance of the papers was determined by the IGT printability tester (ISO 3783). The results are shown in Table 2. The slurries according to the comparative examples or the comparative examples with the paper sheets produced therefrom are marked with the addition (VB). The other examples are examples according to the invention. Table 1 (Type A paper sheet test)

Table 2 (Examination of type B paper sheets

Claims

Aqueous slurries of finely divided fillers, process for their preparation and their use for the production of filler-containing papers Patent claims

1. Aqueous slurries of finely divided fillers, which are at least partially coated with anionic latices, characterized in that the slurries are obtainable by treating aqueous slurries of finely divided fillers with at least one anionic latex containing at least one phosphonic and / or phosphoric acid group-containing monomer incorporated in copolymerized form.

2. Aqueous slurry according to claim 1, characterized in that phosphoric acid group-containing monomers are used which are obtained by esterification of monoethylenically unsaturated Cs-Cs-carboxylic acids with optionally monoalkoxylated phosphoric acids of the general formula (I)

H- [X] _n -P (O) (OH) ₂ (I)

are available in which

mean.

3. Aqueous slurry according to claim 2, characterized in that one uses monoalkoxylated phosphoric acids of the formula (I), in which X is a straight-chain or branched C 2 -C 3 -alkylene oxide unit, and n is an integer between 5 and 15.

4. Aqueous slurry according to claim 2 or 3, characterized in that one uses mixtures of monoalkoxylated phosphoric acids of the formula (I) with 5 to 15 units of propylene oxide.

5. Aqueous slurry according to claim 2, characterized in that it is acrylic acid, methacrylic acid, dimethylacrylic acid, ethacrylic acid, maleic acid, citraconic acid, methylenemalonic acid, crotonic acid, fumaric acid, mesaconic acid, itaconic acid and / or maleic acid in the monoethylenically unsaturated Cs-Cs carboxylic acid ,

6. Aqueous slurry according to claim 5, characterized in that it is the monoethylenically unsaturated Cs-Cs carboxylic acid is acrylic acid and methacrylic acid.

7. An aqueous slurry according to any one of the preceding claims, characterized in that the anionic latexes

a) 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 the formula (I) in which X and n have the abovementioned meaning,

consist.

8. Aqueous slurry according to claim 7, characterized in that the anionic latexes from 2-25 wt .-% styrene, 2-25 wt .-% acrylonitrile, 50 -

95% by weight of C 1 -C ₄ -alkyl acrylates, 0-5% by weight of acrylic acid and 0.1-5% by weight of (meth) acrylic acid esters of monoalkoxylated phosphoric acids of the formula (I) in which X is a propylene oxide unit, and n is an integer between 5 and 15.

Aqueous slurry according to any one of the preceding claims, characterized in that it contains from 1 to 70% by weight of at least one finely divided filler and from 0.01 to 10% by weight, relative to the filler, of at least one anionic latex.

10. A process for preparing an aqueous slurry according to any one of the preceding claims, characterized in that one adds to an aqueous slurry of at least one finely divided filler 0.01 to 10 wt .-%, based on the filler, of at least one anionic latex, or aqueous slurry of a finely divided filler is introduced into an aqueous dispersion of an anionic latex and the components are each mixed, or the finely divided filler is introduced firmly into an aqueous dispersion of an anionic latex.

1 1. Use of the aqueous slurries according to one of claims 1 to 9 as an additive to the paper stock in the production of filler-containing paper, filler-containing cardboard or filler-containing cardboard by dewatering of the paper.