EP0223223A1 - Process for the production of paper and cardboard - Google Patents

Process for the production of paper and cardboard Download PDF

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Publication number
EP0223223A1
EP0223223A1 EP86115915A EP86115915A EP0223223A1 EP 0223223 A1 EP0223223 A1 EP 0223223A1 EP 86115915 A EP86115915 A EP 86115915A EP 86115915 A EP86115915 A EP 86115915A EP 0223223 A1 EP0223223 A1 EP 0223223A1
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EP
European Patent Office
Prior art keywords
weight
paper
acrylamide
paper stock
pulp
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EP86115915A
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German (de)
French (fr)
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EP0223223B1 (en
Inventor
Rudolf Lorz
Friedrich Dr. Linhart
Werner Auhorn
Manfred Matz
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BASF SE
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BASF SE
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Classifications

    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/63—Inorganic compounds
    • D21H17/67—Water-insoluble compounds, e.g. fillers, pigments
    • D21H17/68—Water-insoluble compounds, e.g. fillers, pigments siliceous, e.g. clays
    • 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
    • D21H17/375—Poly(meth)acrylamide
    • 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
    • D21H17/41—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups
    • D21H17/44—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups cationic
    • D21H17/45—Nitrogen-containing groups
    • D21H17/455—Nitrogen-containing groups comprising tertiary amine or being at least partially quaternised
    • 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
    • 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
    • D21H17/56—Polyamines; Polyimines; Polyester-imides
    • 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
    • D21H23/00—Processes or apparatus for adding material to the pulp or to the paper
    • D21H23/76—Processes or apparatus for adding material to the pulp or to the paper characterised by choice of auxiliary compounds which are added separately from at least one other compound, e.g. to improve the incorporation of the latter or to obtain an enhanced combined effect
    • D21H23/765—Addition of all compounds to the pulp

Definitions

  • the present invention has for its object to provide a process for the production of paper and cardboard, according to which one can produce papers with good formation and surface quality and which are well printable.
  • All paper grades can be produced using these processes, e.g. Papers for newspaper printing (high-pressure / offset printing), so-called medium-fine writing and printing papers, gravure printing papers and also lightweight coating base papers. Wood pulp, thermomechanical material (TMP), chemo-thermomechanical material (CTMP), pressure sanding (PGW), and sulphite and sulphate pulp, which can be short or long fibers, are used as the main raw material components for the production of such papers.
  • TMP thermomechanical material
  • CTMP chemo-thermomechanical material
  • PGW pressure sanding
  • sulphite and sulphate pulp which can be short or long fibers
  • an aqueous slurry of fiber and filler is first prepared.
  • the concentration of the aqueous pulp is initially 2.5 to 5% by weight and comprises both the content of fibrous materials, fine materials and fillers.
  • a pulp whose substance concentration is in the range from 2.5 to 5% by weight is added in process section a) from 0.1 to 2% by weight, preferably from 0.5 to 1.5% by weight. an activated bentonite. Then the paper stock concentration is adjusted to a value of 0.3 to 2% by weight by dilution with water.
  • the activated bentonite is added to the aqueous pulp, based on dry paper stock, in an amount of 0.1 to 2, preferably 0.5 to 1.5% by weight.
  • the bentonite can be added either in solid form or, preferably, in the form of an aqueous slurry.
  • the cationic polyelectrolytes of component b) have a high charge density.
  • These compounds are, for example, the following polymers: polyethyleneimines, polyamines with a molecular weight of more than 50,000, polyamidoamines modified by grafting ethyleneimine, polyamidoamines, polyetheramines, polyvinylamines, modified polyvinylamines, polyalkylamines, polyvinylimidazoles, polyvinylpyridines, polyvinylimidazolines, Polyvinyltetrahydropyridines, polydialkylaminoalkyl vinyl ethers, polydialkylaminoalkyl (meth) acrylates, polydialkylaminoalkyl (meth) acrylamides in protonated or quaternized form.
  • Other suitable compounds of this type are polydiallyldialkylammonium halides, in particular polydiallyldimethylammonium chloride.
  • the polyelectrolytes are
  • component b) are also suitable as component b) are the condensation products known from DE-AS 17 71 814, which are crosslinking products of polyamidoamines with bifunctional crosslinking agents.
  • Cationic polyelectrolytes with a high charge density are also obtained by condensation of di- and polyamines, such as ethylenediamine, diethylenetriamine, triethylenetetramine and the higher homologues with crosslinking agents, such as dichloroethane, epichlorohydrin, and the reaction products of polyethylene glycols and epichlorohydrin in a molar ratio of 1: at least 2 or by Reaction of primary and secondary amines, such as methylamine or dimethylamine with epichlorohydrin, dichloroethane, dichloropropane or dichlorobutane.
  • di- and polyamines such as ethylenediamine, diethylenetriamine, triethylenetetramine and the higher homologues with crosslinking agents, such as dichloroethane, epichlorohydrin
  • crosslinking agents such as dichloroethane, epichlorohydrin
  • crosslinking agents such as dichloroethane, epichlorohydrin
  • Polyvinylamines are prepared by polymerizing N-vinylformamide and hydrolyzing the resulting polymers by the action of acids or bases, the formyl groups being split off from the polymer. Those polymers which contain copolymerized N-vinylformamide and vinylamine units are also very effective. Such polymers are produced by partial hydrolysis of polyvinylformamides.
  • cationic polyelectrolytes b) di-C1 to C3-alkylamino-C2 to C6-alkyl (meth) acrylates, di-C1-to C3-alkylamino-C2 to C6-alkyl (meth) acrylamides and dialkylaminoalkyl vinyl ether.
  • Another class of compounds belonging to component b) are polymerized diallyldi-C1-C3-alkylammonium halides, in particular polydi-allyldimethylammonium chloride.
  • Preferably used as compounds of component b) are polyethyleneimine, water-soluble crosslinked condensation products based on polyamidoamines, polyvinylamines, polydiallylammonium chloride and / or at least 10 mol% of hydrolyzed poly-N-vinylformamides.
  • the molecular weight of the cationic polyelectrolytes of component b) is in the range from 50,000 to 3,000,000, preferably 200,000 to 2,000,000. Polymers of this type are known and the majority are commercially available.
  • the charge density of the cationic polyelectrolytes at pH 4.5 is preferably in the range from 5 to 20 meq / g polyelectrolyte.
  • the pulp as component c) is metered in with a high molecular weight polymer based on acrylamide or methacrylamide.
  • This polymer is also mixed with the paper stock, which is then dewatered in the usual way on a sieve. Based on dry paper stock, 0.003 to 0.03, preferably 0.005 to 0.015,% by weight of a high molecular weight polymer of component c) is used.
  • This group of polymers includes the homopolymers of acrylamide and methacrylamide and the copolymers of the two monomers with anionic or cationic monomers.
  • the homopolymers and copolymers have an average mass molecular weight (determined by the light scattering method) of 1 million to 20 million.
  • Anionically modified polymers of acrylamide or methacrylamide are obtained by copolymerizing acrylamide or methacrylamide with monoethylenically unsaturated C3- to C5-carboxylic acids, which may or may not be partially or completely neutralized, or by partial hydrolysis of the amide groups of an acrylamide or methacrylamide homopolymer.
  • the anionically modified polyacrylamides mainly the copolymers of acrylamide and acrylic acid are used.
  • the copolymerized acrylic acid content in the copolymer can be 5 to 80% by weight.
  • cationic modification of the (meth) acrylamide polymers use is made, for example, of the C1- to C2-alkylamino-C2- to C6-alkyl (meth) acrylates, for example diethylaminoethyl acrylate, dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, dimethylaminopropyl acrylate, dimethylaminobutyl acrylate and methacrylate, dimethylacrylate, dimethyl acrylate, dimethyl acrylate, dimethyl acrylate, Monomers in the form of the salt with hydrochloric acid or sulfuric acid or in quaternized form, for example quaternized by reaction with methyl chloride, dimethyl sulfate or benzyl chloride, are subjected to the copolymerization.
  • the C1- to C2-alkylamino-C2- to C6-alkyl (meth) acrylates for example diethylamino
  • Suitable cationic monomers for modifying the (meth) acrylamide polymers are dialkylaminoalkyl (meth) acrylamides, dialkylaminoalkyl vinyl ethers, N-vinylimidazoles, N-vinylpyridine and diallyldimethylammonium chloride.
  • polyacrylamide, copolymers of acrylamide and acrylic acid, copolymers of acrylamide and dimethylaminoethyl acrylate, copolymers of acrylamide and diethylaminoethyl acrylate, copolymers of acrylamide and N-vinylimidazoline, copolymers of acrylamide and 2-methyl-1-vinylimidazoline are preferably used for the process according to the invention and copolymers of acrylamide and 2-phenyl-1-vinylimidazoline.
  • the cationic monomers are used in neutralized or quaternized form.
  • the two classes of compounds then differ in that the compounds c) have a molecular weight which is at least 1 million higher than the molecular weight of the compounds b).
  • Another distinguishing feature of the two connection classes b) and c) lies in the charge density.
  • the compounds c) - if they are cationically modified - have a charge density of at most 3.5 meq / g polyelectrolyte (measured at pH 4.5).
  • Vinylsulfonic acid, acrylamidopropanesulfonic acids and / or their alkali metal, ammonium or amine salts can also be used for the anionic modification of the polyacrylamides.
  • the starting point is an aqueous pulp, the concentration of which is 2.5 to 5% by weight.
  • the activated bentonite is added in the amounts indicated above.
  • the bentonite is preferably added in the form of a 3 to 6% aqueous dispersion.
  • the pulp containing the bentonite is then diluted with water.
  • the white water is preferably used for this in the production plant.
  • At least one compound according to b) is then metered into the diluted stock suspension, for example into the line at the outlet of the mixing pump, in the amount specified above. Due to the flow conditions in the line system, there is sufficient mixing of the cationic polymer with the paper stock.
  • the high molecular weight polymer of component c) can be added.
  • compounds c) are added before the headbox, advantageously at a point between the pressure sorter and the headbox.
  • the polymers b) and c) are preferably metered in in the form of dilute aqueous solutions. Due to the auxiliary system used, paper production can take place in closed water cycles. Paper with good printability is obtained which also has good printability in the offset process.
  • Determination of the dewatering time 1 l of the pulp slurry to be tested is dewatered in a Schopper-Riegler test device. The time that is determined for different outlet volumes is evaluated as a criterion for the drainage rate of the substance suspension examined in each case. The drainage times were determined in all cases specified here after the passage of 150, 200 and 250 ml of water.
  • the retention was checked by determining the solids content in 250 ml of a filtrate obtained by dewatering the fiber slurry to be tested in a Schopper-Riegler device.
  • Polyelectrolyte 1 (component b) This was a polyamidoamine from adipic acid and diethylenetriamine, which was grafted with ethyleneimine and crosslinked with a polyalkylene oxide, the terminal OH groups of which had been reacted with epichlorohydrin.
  • Such a product is known from Example 1 of DE-PS 24 34 816, it has a charge density of 12.2 meq / g (measured at pH 4.5).
  • thermomechanical substance TMP
  • concentration of 3.2% is produced in a 20 l container.
  • the pH of the stock suspension is 5.7.
  • the paper fiber suspension prepared in this way is stirred and mixed with a 5% strength aqueous slurry of a commercially available sodium bentonite, so that the amount of bentonite, based on paper stock, is 0.5%. After homogenization, the substance is diluted to a concentration of 0.85% by adding water.
  • the headbox concentration is 6.84 g / l
  • the white water contains 2.32 g / l solids.
  • the First Pass Retention (FPR) is 66.1%.
  • the production speed is 577 m / min. You get 6.8 t of paper per hour.
  • Example 1 is repeated with the exception that the polyelectrolyte 1 is omitted.
  • the paper flocculates so strongly that perfect sheet formation is not guaranteed.
  • the formation and surface quality of the sheet is insufficient for the printing requirements.

Abstract

Paper and cardboard are produced by draining a paper stock by a method in which a stock having a consistency of from 2.5 to 5% by weight is used as a starting material, and (a) from 0.1 to 2% by weight of an activated bentonite are added and the stock consistency is then brought to 0.3-2% by weight by dilution with water, after which (b) from 0.01 to 0.1% by weight of a cationic polyelectrolyte having a charge density of not less than 4 meq/g of polyelectrolyte is added and distributed therein, and, after thorough mixing (c) from 0.003 to 0.3% by weight of a high molecular weight polymer based on acrylamide or methacrylamide is metered in and mixed with the paper stock, the percentages in each case being based on dry paper stock, and the resulting pulp is drained on a wire. The paper obtained is distinguished in particular by good printing properties in the offset printing process.

Description

Aus der DE-OS 2 262 906 ist bekannt, daß man bei der Herstellung von Papier und Karton Mischungen aus Bentonit und Polyamidoaminen, Polyether­aminen oder Polyethyleniminen als Entwässerungshilfsmittel von Störstoffe enthaltenden Pulpen bei der Herstellung von Papier und Karton verwenden kann. Die mit diesem Hilfsstoffsystem erreichbaren Papiermaschinenge­schwindigkeiten sind jedoch noch verbesserungsbedürftig. Außerdem erhält man nach diesem Verfahren Papierqualitäten, deren Bedruckbarkeit nicht zufriedenstellend ist.From DE-OS 2 262 906 it is known that mixtures of bentonite and polyamidoamines, polyetheramines or polyethyleneimines can be used as drainage aids for pulps containing impurities in the production of paper and cardboard in the production of paper and cardboard. However, the paper machine speeds that can be achieved with this auxiliary system still need to be improved. This process also gives paper grades whose printability is unsatisfactory.

Aus der US-PS 3 052 595 ist ein Verfahren zur Herstellung von insbeson­dere Füllstoffe enthaltenden Papieren bekannt, bei dem man den Papier­stoff in Gegenwart von Bentonit und Polyacrylamiden entwässert. Dadurch wird zwar eine erhöhte Füllstoffretention im Papier erreicht, jedoch bewirken selbst die geringen Polyacrylamidmengen eine zu starke Flockung im Papierstoff, so daß es zu Ungleichmäßigkeiten im Papier und an der Oberfläche des Papiers kommt. Diese Papiere sind schlecht bedruckbar.US Pat. No. 3,052,595 discloses a process for the production of papers containing fillers in particular, in which the paper stock is dewatered in the presence of bentonite and polyacrylamides. Although this results in increased filler retention in the paper, even the small amounts of polyacrylamide cause too much flocculation in the paper stock, so that there are non-uniformities in the paper and on the surface of the paper. These papers are difficult to print on.

Aus der EP-PS 17 353 ist ein Verfahren zur Herstellung von Papier oder Katon aus einer wäßrigen Suspension von Cellulosefasern bekannt, bei dem man eine praktisch füllstoff-freie Stoffsuspension unter Verwendung einer Mischung aus wasserlöslichen, hochmolekularen, im wesentlichen nichtioni­schen Polymerisaten und eines Bentonit-artigen Tons unter Blattbildung entwässert. Als Polymerisate kommen im wesentlichen Polyacrylamide in Betracht. Auch in einem praktisch füllstoff-freien System bewirken die Polyacrylamide bereits im Papierstoff eine starke Flockung, die die Qualität der Papiere beeinträchtigt. Die Formation und Oberflächenbe­schaffenheit der so hergestellten Papiere genügt nicht den Anforderungen, die an die Bedruckbarkeit der Papiere gestellt werden. Beim Bedrucken solcher Papiere nach dem Offset-Verfahren werden aus der Papieroberfläche Fasern und Feinstoffe abgelöst.From EP-PS 17 353 a process for the production of paper or Katon from an aqueous suspension of cellulose fibers is known, in which a practically filler-free substance suspension using a mixture of water-soluble, high molecular weight, essentially non-ionic polymers and a bentonite dewy clay under leaf formation. Polyacrylamides are essentially suitable as polymers. Even in a practically filler-free system, the polyacrylamides cause strong flocculation in the paper stock, which affects the quality of the paper. The formation and surface properties of the papers produced in this way do not meet the requirements placed on the printability of the papers. When printing on such papers using the offset process, fibers and fines are removed from the paper surface.

Der vorliegenden Erfindung liegt die Aufgabe zugrunde, ein Verfahren zur Herstellung von Papier und Karton zur Verfügung zu stellen, gemäß dem man Papiere mit guter Formation und Oberflächenbeschaffenheit herstellen kann und die gut bedruckbar sind.The present invention has for its object to provide a process for the production of paper and cardboard, according to which one can produce papers with good formation and surface quality and which are well printable.

Die Aufgabe wird erfindungsgemäß gelöst mit einem Verfahren zur Herstel­lung von Papier und Karton durch Entwässern eines Papierstoffs, der Ben­tonit und Polyelektrolyte enthält, auf einem Sieb, wenn man zu einer wäß­rigen Pulpe, deren Stoffkonzentration 2,5 bis 5 Gew.% beträgt, jeweils bezogen auf trockenen Papierstoff,

  • a) 0,1 bis 2 Gew.% eines aktivierten Bentonits zusetzt, danach die Papierstoffkonzentration durch Verdünnen mit Wasser auf 0,3 bis 2 Gew.% einstellt,
  • b) 0,001 bis 0,1 Gew.% eines kationischen Polyelektrolyten mit einer Ladungsdichte von mindestens 4 mVal/g Polyelektrolyt zufügt, darin verteilt und nach der Durchmischung
  • c) 0,003 bis 0,03 Gew.% eines hochmolekularen Polymerisats auf Basis von Acrylamid oder Methacrylamid zudosiert, mit dem Papierstoff mischt und die so erhaltene Pulpe auf einem Sieb entwässert.
The object is achieved according to the invention with a process for the production of paper and cardboard by dewatering a paper stock which contains bentonite and polyelectrolytes on a sieve, if one is based in each case on an aqueous pulp whose substance concentration is 2.5 to 5% by weight on dry paper stock,
  • a) 0.1 to 2% by weight of an activated bentonite is added, then the pulp concentration is adjusted to 0.3 to 2% by weight by dilution with water,
  • b) 0.001 to 0.1% by weight of a cationic polyelectrolyte with a charge density of at least 4 meq / g polyelectrolyte is added, distributed therein and after mixing
  • c) 0.003 to 0.03% by weight of a high molecular weight polymer based on acrylamide or methacrylamide are metered in, mixed with the paper stock and the pulp thus obtained is dewatered on a sieve.

Nach diesen Verfahren können sämtliche Papierqualitäten hergestellt wer­den, z.B. Papiere für den Zeitungsdruck (Hochdruck/Offset-Druck), soge­nannte mittelfeine Schreib- und Druckpapiere, Naturtiefdruckpapiere und auch leichtgewichtige Streichrohpapiere. Zur Herstellung solcher Papiere verwendet man als Hauptrohstoffkomponente Holzschliff, thermomechanischen Stoff (TMP), chemo-thermomechanischen Stoff (CTMP), Druckschliff (PGW), sowie Sulfit- und Sulfatzellstoff, die jeweils kurz- bzw. langfaserig sein können. Als Rohstoffe für die Herstellung der Pulpe kommt auch Zell­stoff und Holzstoff in Betracht, der in den sogenannten integrierten Fabriken in mehr oder weniger feuchter Form direkt ohne vorherige Ein­dickung bzw. Trocknung weiter zu Papier verarbeitet wird und aufgrund der nicht vollständig entfernten Verunreinigungen vom Aufschluß her noch Stoffe enthält, die den üblichen Papierherstellprozeß stark stören. Nach dem erfindungsgemäßen Verfahren können sowohl füllstoff-freie als auch füllstoff-haltige Papiere hergestellt werden. Der Füllstoffgehalt im Papier kann bis maximal 30 Gew.% betragen und liegt vorzugsweise in dem Bereich von 5 bis 25 Gew.% Füllstoff. Geeignete Füllstoffe sind bei­spielsweise Clay, Kaolin, Kreide, Talkum, Titandioxid, Kalziumsulfat, Bariumsulfat, Aluminiumoxid, Satinweiß oder Mischungen der genannten Füllstoffe. Sofern füllstoff-enthaltende Papiere hergestellt werden, stellt man zunächst eine wäßrige Anschlämmung von Faserstoff und Füll­stoff her. Die Stoffkonzentration der wäßrigen Pulpe beträgt zunächst 2,5 bis 5 Gew.% und umfaßt sowohl den Gehalt an Faserstoffen, Feinstoffen und Füllstoffen. Bei dem erfindungsgemäßen Verfahren gibt man zu einer Pulpe, deren Stoffkonzentration in dem Bereich von 2,5 bis 5 Gew.% beträgt, im Verfahrenabschnitt a) 0,1 bis 2 Gew.%, vorzugsweise 0,5 bis 1,5 Gew.% eines aktivierten Bentonits. Danach wird erst die Papierstoffkonzentra­tion durch Verdünnen mit Wasser auf einen Wert von 0,3 bis 2 Gew.% ein­gestellt.All paper grades can be produced using these processes, e.g. Papers for newspaper printing (high-pressure / offset printing), so-called medium-fine writing and printing papers, gravure printing papers and also lightweight coating base papers. Wood pulp, thermomechanical material (TMP), chemo-thermomechanical material (CTMP), pressure sanding (PGW), and sulphite and sulphate pulp, which can be short or long fibers, are used as the main raw material components for the production of such papers. Also suitable as raw materials for the production of pulp are pulp and wood pulp, which in the so-called integrated factories are further processed in paper in a more or less moist form directly to paper without prior thickening or drying, and due to the incomplete removal of impurities from the pulp Contains substances that severely disrupt the usual paper manufacturing process. Both filler-free and filler-containing papers can be produced by the process according to the invention. The filler content in the paper can be up to a maximum of 30% by weight and is preferably in the range from 5 to 25% by weight of filler. Suitable fillers are, for example, clay, kaolin, chalk, talc, titanium dioxide, calcium sulfate, barium sulfate, aluminum oxide, satin white or mixtures of the fillers mentioned. If filler-containing papers are produced, an aqueous slurry of fiber and filler is first prepared. The concentration of the aqueous pulp is initially 2.5 to 5% by weight and comprises both the content of fibrous materials, fine materials and fillers. In the process according to the invention, a pulp whose substance concentration is in the range from 2.5 to 5% by weight is added in process section a) from 0.1 to 2% by weight, preferably from 0.5 to 1.5% by weight. an activated bentonite. Then the paper stock concentration is adjusted to a value of 0.3 to 2% by weight by dilution with water.

Unter Bentonit werden allgemein Schichtsilikate verstanden, die in Wasser quellbar sind. Es handelt sich hierbei in erster Linie um das Tonmineral Montmorillonit sowie ähnliche Tonmineralien, z.B. Nontronit, Hectorit, Saponit, Volkonskoit, Sauconit, Beidellit, Allevardit, Illit, Halloysit, Attapulgit und Sepiolit. Das Schichtsilikat muß dabei in Wasser quellbar sein und durch diese Quellung im Extremfall in seine Elementarschichten zerfallen können. Sollte diese Eigenschaft nicht von Natur aus gegeben sein, so muß das Schichtsilikat vor der Anwendung aktiviert werden, d.h. in seine mit Wasser quellbare Natrium-, Kalium-, Ammonium- oder Hydroxo­niumform überführt worden sein. Eine derartige Aktivierung der Bentonite wird erreicht, indem man die Schichtsilikate mit den entsprechenden Basen oder Soda bzw. Pottasche behandelt. Vorzugsweise wird für die erfindungs­gemäße Anwendung ein Natriumbentonit verwendet.Bentonite is generally understood to mean layered silicates which are swellable in water. This is primarily the clay mineral Montmorillonite and similar clay minerals, eg nontronite, hectorite, saponite, Volkonskoit, sauconite, beidellite, allevardite, illite, halloysite, attapulgite and sepiolite. The layered silicate must be swellable in water and, in extreme cases, be able to disintegrate into its elementary layers through this swelling. If this property is not inherent, the layered silicate must be activated before use, ie converted into its water-swellable sodium, potassium, ammonium or hydroxonium form. Such activation of the bentonites is achieved by treating the layered silicates with the appropriate bases or soda or potash. A sodium bentonite is preferably used for the application according to the invention.

Der aktivierte Bentonit wird der wäßrigen Pulpe, bezogen auf trockenen Papierstoff, in einer Menge von 0,1 bis 2, vorzugsweise 0,5 bis 1,5 Gew.% zugesetzt. Die Zugabe des Bentonits kann entweder in fester Form oder bevorzugt in Form einer wäßrigen Aufschlämmung erfolgen.The activated bentonite is added to the aqueous pulp, based on dry paper stock, in an amount of 0.1 to 2, preferably 0.5 to 1.5% by weight. The bentonite can be added either in solid form or, preferably, in the form of an aqueous slurry.

Der Pulpe, die einen aktivierten Bentonit in den oben angegebenen Mengen enthält, werden dann 0,01 bis 0,1, vorzugsweise 0,03 bis 0,06 Gew.%, be­zogen auf trockenen Papierstoff, eines kationischen Polyelektrolyten zu­gesetzt, der bei pH 4,5 eine Ladungsdichte von mindestens 4 mVal/g Poly­elektrolyt besitzt. Die Ladungsdichte wird bestimmt nach D. Horn, Poly­ethylenimine/Physicochemical Properties and Application (IUPAC) Polymeric Amines and Ammonium Salts, Pergamon Press Oxford and New York, 1980, Seite 333 bis 355.0.01 to 0.1, preferably 0.03 to 0.06% by weight, based on dry paper stock, of a cationic polyelectrolyte, which is present at pH 4, is then added to the pulp, which contains an activated bentonite in the amounts specified above , 5 has a charge density of at least 4 meq / g polyelectrolyte. The charge density is determined according to D. Horn, Polyethylenimine / Physicochemical Properties and Application (IUPAC) Polymeric Amines and Ammonium Salts, Pergamon Press Oxford and New York, 1980, pages 333 to 355.

Die kationischen Polyelektrolyte der Komponente b) haben eine hohe La­dungsdichte. Es handelt sich bei diesen Verbindungen beispielsweise um folgende Polymerisate: Polyethylenimine, Polyamine mit einem Molekularge­wicht von mehr als 50 000, Polyamidoamine, die durch Aufpfropfen von Ethylenimin modifiziert sind, Polyamidoamine, Polyetheramine, Polyvinyl­amine, modifizierte Polyvinylamine, Polyalkylamine, Polyvinylimidazole, Polyvinylpyridine, Polyvinylimidazoline, Polyvinyltetrahydropyridine, Polydialkylaminoalkylvinylether, Polydialkylaminoalkyl(meth)acrylate, Polydialkylaminoalkyl(meth)acrylamide in protonierter oder quaternisier­ter Form. Weitere geeignete Verbindungen dieses Typs sind Polydiallyl­dialkylammoniumhalogenide, insbesondere Polydiallyldimethylammoniumchlo­rid. Die Polyelektrolyte sind in Wasser löslich und werden in Form der wäßrigen Lösungen eingesetzt.The cationic polyelectrolytes of component b) have a high charge density. These compounds are, for example, the following polymers: polyethyleneimines, polyamines with a molecular weight of more than 50,000, polyamidoamines modified by grafting ethyleneimine, polyamidoamines, polyetheramines, polyvinylamines, modified polyvinylamines, polyalkylamines, polyvinylimidazoles, polyvinylpyridines, polyvinylimidazolines, Polyvinyltetrahydropyridines, polydialkylaminoalkyl vinyl ethers, polydialkylaminoalkyl (meth) acrylates, polydialkylaminoalkyl (meth) acrylamides in protonated or quaternized form. Other suitable compounds of this type are polydiallyldialkylammonium halides, in particular polydiallyldimethylammonium chloride. The polyelectrolytes are soluble in water and are used in the form of aqueous solutions.

Polyethylenimine werden beispielsweise durch Polymerisieren von Ethylen­imin in wäßriger Lösung unter Einwirkung von sauren Katalysatoren nach bekannten Verfahren hergestellt. Modifizierte Polyethylenimine erhält man, indem man Polyethylenimine in einem Maße vernetzt, daß die entste­ henden Polymerisate noch wasserlöslich sind. Als Vernetzer eignen sich beispielsweise Epichlorhydrin, Dichlorethan oder Xylylendichlorid.Polyethyleneimines are prepared, for example, by polymerizing ethyleneimine in aqueous solution under the action of acidic catalysts by known processes. Modified polyethyleneimines are obtained by crosslinking polyethyleneimines to such an extent that the first polymers are still water-soluble. Suitable crosslinkers are, for example, epichlorohydrin, dichloroethane or xylylene dichloride.

Wasserlösliche, Ethylenimin einkondensiert enthaltende Kondensationspro­dukte werden beispielsweise dadurch hergestellt, daß man zunächst 1 Mol einer Dicarbonsäure mit 4 bis 10 Kohlenstoffatomen mit 1 bis 2 Mol eines Polyalkylenpolyamins, das 3 bis 10 basische Stickstoffatome im Molekül aufweist, zu Polyamidoaminen kondensiert, dann Ethylenimin auf die Kon­densationsprodukte aufpfropft und die Ethylenimin modifizierten Polyami­doamine mit einem Vernetzer umsetzt, so daß wasserlösliche Kondensations­produkte erhalten werden. Als Vernetzer eignen sich beispielsweise Epi­chlorhydrin, vgl. DE-PS 18 02 435 und Polyalkylenoxide mit 8 bis 100 Alkylenoxideinheiten, die an den endständigen OH-Gruppen mit mindestens äquivalenten Mengen Epichlorhydrin umgesetzt worden sind, vgl. DE-PS 24 34 816. Außerdem eignen sich als Komponente b) die Kondensa­tionsprodukte, die aus der DE-AS 17 71 814 bekannt sind, bei denen es sich um Vernetzungsprodukte von Polyamidoaminen mit bifunktionellen Ver­netzern handelt. Kationische Polyelektrolyte mit einer hohen Ladungs­dichte erhält man auch durch Kondensation von Di- und Polyaminen, wie Ethylendiamin, Diethylentriamin, Triethylentetramin und den höheren Homo­logen mit Vernetzern, wie Dichlorethan, Epichlorhydrin, und den Umset­zungsprodukten aus Polyethylenglykolen und Epichlorhydrin im Molverhält­nis 1: mindestens 2 oder durch Umsetzung von primären und sekundären Aminen, wie Methylamin oder Dimethylamin mit Epichlorhydrin, Dichlor­ethan, Dichlorpropan oder Dichlorbutan. Polyvinylamine werden herge­stellt, indem man N-Vinylformamid polymerisiert und die erhaltenen Poly­merisate durch Einwirkung von Säuren oder Basen hydrolysiert, wobei die Formylgruppen aus dem Polymerisat abgespalten werden. Sehr wirksam sind auch diejenigen Polymerisate, die N-Vinylformamid- und Vinylamin-einhei­ten einpolymerisiert enthalten. Solche Polymerisate werden durch partiel­le Hydrolyse von Polyvinylformamiden hergestellt. Die Polymerisate von Vinylheterocyclen werden erhalten, indem man die diesen Polymerisaten zugrundeliegenden Monomeren der Polymerisation unterwirft, z.B. polymeri­siert man N-Vinylimidazol oder dessen Derivate, z.B. 2-Methyl-1-vinyl­imidazol oder 2-Benzyl-1-vinylimidazol, N-Vinylpyridin oder dessen Deri­vate sowie N-Vinylimidazoline, z.B. 2-Methyl-1-vinyl-imidazolin, 2-Phe­nyl-1-vinyl-imidazolin oder 2-Benzyl-1-vinyl-imidazolin. Die heterocycli­schen kationischen Monomeren werden vorzugsweise in neutralisierter oder quaternisierter Form bei der Polymerisation eingesetzt. Außerdem eigenen sich als kationische Polyelektrolyte b) Di-C₁-bis C₃-alkylamino-C₂-bis C₆-alkyl(meth)acrylate, Di-C₁-bis C₃-alkylamino-C₂-bis C₆-alkyl(meth)­acrylamide und Dialkylaminoalkylvinylether. Eine weitere Verbindungsklas­se, die zu der Komponente b) gehört, sind polymerisierte Diallyldi-C₁-­C₃-alkylammoniumhalogenide, insbesondere Polydi-allyldimethylammonium­ chlorid. Außerdem eignen sich Polymerisate, die durch eine polymeranaloge Umsetzung von Polyacrylamid mit Formaldehyd und sekundären Aminen, z.B. Dimethylamin erhältlich sind. Vorzugsweise verwendet man als Verbindungen der Komponente b) Polyethylenimin, wasserlösliche, Ethylenimin einkonden­siert enthaltende vernetzte Kondensationsprodukte auf Basis von Polyami­doaminen, Polyvinylamine, Polydiallylammoniumchlorid und/oder zuminde­stens 10 Mol.% hydrolysierte Poly-N-vinylformamide. Das Molekulargewicht der kationischen Polyeleketrolyte der Komponente b) liegt in dem Bereich von 50 000 bis 3 000 000, vorzugsweise 200 000 bis 2 000 000. Polymeri­sate dieser Art sind bekannt und größtenteils im Handel erhältlich. Die Ladungsdichte der kationischen Polyelektrolyte liegt bei pH 4,5 vorzugs­weise in dem Bereich von 5 bis 20 mVal/g Polyelektrolyt.Water-soluble condensation products containing condensed ethyleneimine are prepared, for example, by firstly condensing 1 mol of a dicarboxylic acid having 4 to 10 carbon atoms with 1 to 2 mols of a polyalkylene polyamine which has 3 to 10 basic nitrogen atoms in the molecule into polyamidoamines, then ethyleneimine onto the condensation products grafted and the ethyleneimine-modified polyamidoamines reacted with a crosslinking agent, so that water-soluble condensation products are obtained. Suitable crosslinkers are, for example, epichlorohydrin, cf. DE-PS 18 02 435 and polyalkylene oxides with 8 to 100 alkylene oxide units which have been reacted at the terminal OH groups with at least equivalent amounts of epichlorohydrin, cf. DE-PS 24 34 816. Also suitable as component b) are the condensation products known from DE-AS 17 71 814, which are crosslinking products of polyamidoamines with bifunctional crosslinking agents. Cationic polyelectrolytes with a high charge density are also obtained by condensation of di- and polyamines, such as ethylenediamine, diethylenetriamine, triethylenetetramine and the higher homologues with crosslinking agents, such as dichloroethane, epichlorohydrin, and the reaction products of polyethylene glycols and epichlorohydrin in a molar ratio of 1: at least 2 or by Reaction of primary and secondary amines, such as methylamine or dimethylamine with epichlorohydrin, dichloroethane, dichloropropane or dichlorobutane. Polyvinylamines are prepared by polymerizing N-vinylformamide and hydrolyzing the resulting polymers by the action of acids or bases, the formyl groups being split off from the polymer. Those polymers which contain copolymerized N-vinylformamide and vinylamine units are also very effective. Such polymers are produced by partial hydrolysis of polyvinylformamides. The polymers of vinyl heterocycles are obtained by subjecting the monomers on which these polymers are based to the polymerization, for example polymerizing N-vinylimidazole or its derivatives, for example 2-methyl-1-vinylimidazole or 2-benzyl-1-vinylimidazole, N-vinylpyridine or the like Derivatives and N-vinylimidazolines, for example 2-methyl-1-vinyl-imidazoline, 2-phenyl-1-vinyl-imidazoline or 2-benzyl-1-vinyl-imidazoline. The heterocyclic cationic monomers are preferably used in the polymerization in neutralized or quaternized form. Also suitable as cationic polyelectrolytes b) di-C₁ to C₃-alkylamino-C₂ to C₆-alkyl (meth) acrylates, di-C₁-to C₃-alkylamino-C₂ to C₆-alkyl (meth) acrylamides and dialkylaminoalkyl vinyl ether. Another class of compounds belonging to component b) are polymerized diallyldi-C₁-C₃-alkylammonium halides, in particular polydi-allyldimethylammonium chloride. Also suitable are polymers which are obtainable by polymer-analogous reaction of polyacrylamide with formaldehyde and secondary amines, for example dimethylamine. Preferably used as compounds of component b) are polyethyleneimine, water-soluble crosslinked condensation products based on polyamidoamines, polyvinylamines, polydiallylammonium chloride and / or at least 10 mol% of hydrolyzed poly-N-vinylformamides. The molecular weight of the cationic polyelectrolytes of component b) is in the range from 50,000 to 3,000,000, preferably 200,000 to 2,000,000. Polymers of this type are known and the majority are commercially available. The charge density of the cationic polyelectrolytes at pH 4.5 is preferably in the range from 5 to 20 meq / g polyelectrolyte.

Nach einer Durchmischung der Komponente b) mit dem Papierstoff wird der Pulpe als Komponente c) ein hochmolekulares Polymerisat auf Basis von Acrylamid oder Methacrylamid zudosiert. Auch dieses Polymerisat wird mit dem Papierstoff gemischt, der dann in üblicher Weise auf einem Sieb ent­wässert wird. Bezogen auf trockenen Papierstoff verwendet man 0,003 bis 0,03, vorzugsweise 0,005 bis 0,015 Gew.% eines hochmolekularen Polymeri­sats der Komponente c). Zu dieser Gruppe von Polymerisaten gehören die Homopolymerisate von Acrylamid und Methacrylamid sowie die Copolymerisate der beiden Monomeren mit anionischen oder kationischen Monomeren. Die Homo- und Copolymerisate haben ein mittleres Massenmolekulargewicht (be­stimmt nach der Lichtstreuungsmethode) von 1 Million bis 20 Millionen. Anionisch modifizierte Polymerisate des Acrylamids bzw. Methacrylamids erhält man durch Copolymerisieren von Acrylamid oder Methacrylamid mit monoethylenisch ungesättigten C₃- bis C₅-Carbonsäuren, die gegebenenfalls teilweise oder vollständig neutralisiert sein können, oder durch teil­weise Hydrolyse der Amidgruppen eines Acrylamid- oder Methacrylamidhomo­polymerisats. Von den anionisch modifizierten Polyacrylamiden verwendet man hauptsächlich die Copolymerisate aus Acrylamid und Acrylsäure. Der Gehalt an einpolymerisierter Acrylsäure im Copolymerisat kann dabei 5 bis 80 Gew.% betragen.After component b) has been mixed with the paper stock, the pulp as component c) is metered in with a high molecular weight polymer based on acrylamide or methacrylamide. This polymer is also mixed with the paper stock, which is then dewatered in the usual way on a sieve. Based on dry paper stock, 0.003 to 0.03, preferably 0.005 to 0.015,% by weight of a high molecular weight polymer of component c) is used. This group of polymers includes the homopolymers of acrylamide and methacrylamide and the copolymers of the two monomers with anionic or cationic monomers. The homopolymers and copolymers have an average mass molecular weight (determined by the light scattering method) of 1 million to 20 million. Anionically modified polymers of acrylamide or methacrylamide are obtained by copolymerizing acrylamide or methacrylamide with monoethylenically unsaturated C₃- to C₅-carboxylic acids, which may or may not be partially or completely neutralized, or by partial hydrolysis of the amide groups of an acrylamide or methacrylamide homopolymer. Of the anionically modified polyacrylamides, mainly the copolymers of acrylamide and acrylic acid are used. The copolymerized acrylic acid content in the copolymer can be 5 to 80% by weight.

Für die kationische Modifizierung der (Meth)acrylamidpolymerisate ver­wendet man beispielsweise die C₁- bis C₂-Alkylamino-C₂- bis C₆-Alkyl­(meth)acrylate, z.B. Diethylaminoethylacrylat, Dimethylaminoethylacrylat, Dimethylaminoethylmethacrylat, Dimethylaminopropylacrylat, Dimethylamino­butylacrylat, Dimethylaminoneopentylacrylat sowie die entsprechenden Methacrylate, wobei diese Monomeren in Form des Salzes mit Salzsäure oder Schwefelsäure bzw. in quaternisierter Form, z.B. quaternisiert durch Um­setzung mit Methylchlorid, Dimethylsulfat oder Benzylchlorid der Copoly­merisation unterworfen werden. Weitere geeignte kationische Monomere zur Modifizierung der (Meth)acrylamidpolymerisate sind Dialkylaminoalkyl­ (meth)acrylamide, Dialkylaminoalkylvinylether, N-Vinylimidazole, N-Vinyl­pyridin und Diallyldimethylammoniumchlorid. Als Komponente c) verwendet man für das erfindungsgemäße Verfahren vorzugsweise Polyacrylamid, Co­polymerisate aus Acrylamid und Acrylsäure, Copolymerisate aus Acrylamid und Dimethylaminoethylacrylat, Copolymerisate aus Acrylamid und Diethyl­aminoethylacrylat, Copolymerisate aus Acrylamid und N-Vinylimidazolin, Copolymerisate aus Acrylamid und 2-Methyl-1-vinylimidazolin und Copoly­merisate aus Acrylamid und 2-Phenyl-1-vinylimidazolin. Die kationischen Monomeren werden dabei in neutralisierter bzw. quaternisierter Form ein­gesetzt.For the cationic modification of the (meth) acrylamide polymers, use is made, for example, of the C₁- to C₂-alkylamino-C₂- to C₆-alkyl (meth) acrylates, for example diethylaminoethyl acrylate, dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, dimethylaminopropyl acrylate, dimethylaminobutyl acrylate and methacrylate, dimethylacrylate, dimethyl acrylate, dimethyl acrylate, Monomers in the form of the salt with hydrochloric acid or sulfuric acid or in quaternized form, for example quaternized by reaction with methyl chloride, dimethyl sulfate or benzyl chloride, are subjected to the copolymerization. Other suitable cationic monomers for modifying the (meth) acrylamide polymers are dialkylaminoalkyl (meth) acrylamides, dialkylaminoalkyl vinyl ethers, N-vinylimidazoles, N-vinylpyridine and diallyldimethylammonium chloride. As component c), polyacrylamide, copolymers of acrylamide and acrylic acid, copolymers of acrylamide and dimethylaminoethyl acrylate, copolymers of acrylamide and diethylaminoethyl acrylate, copolymers of acrylamide and N-vinylimidazoline, copolymers of acrylamide and 2-methyl-1-vinylimidazoline are preferably used for the process according to the invention and copolymers of acrylamide and 2-phenyl-1-vinylimidazoline. The cationic monomers are used in neutralized or quaternized form.

Sofern bei dem erfindungsgemäßen Verfahren chemisch ähnliche Verbindungen b) und c) eingesetzt werden, so unterscheiden sich die beiden Verbin­dungsklassen dann dadurch, daß die Verbindungen c) ein Molekulargewicht aufweisen, das um mindestens 1 Million höher ist als das Molekulargewicht der Verbindungen b). Ein weiteres Unterscheidungsmerkmal der beiden Ver­bindungsklassen b) und c) liegt in der Ladungsdichte. Die Verbindungen c) haben - sofern sie kationisch modifiziert sind - eine Ladungsdichte von höchstens 3,5 mVal/g Polyelektrolyt (gemessen bei pH 4,5). Zur anioni­schen Modifizierung der Polyacrylamide können außerdem Vinylsulfonsäure, Acrylamidopropansulfonsäuren und/oder deren Alkali-, Ammonium- bzw. Aminsalze eingesetzt werden.If chemically similar compounds b) and c) are used in the process according to the invention, the two classes of compounds then differ in that the compounds c) have a molecular weight which is at least 1 million higher than the molecular weight of the compounds b). Another distinguishing feature of the two connection classes b) and c) lies in the charge density. The compounds c) - if they are cationically modified - have a charge density of at most 3.5 meq / g polyelectrolyte (measured at pH 4.5). Vinylsulfonic acid, acrylamidopropanesulfonic acids and / or their alkali metal, ammonium or amine salts can also be used for the anionic modification of the polyacrylamides.

Bei der Herstellung von Papier geht man zunächst von einer wäßrigen Pulpe aus, deren Stoffkonzentration 2,5 bis 5 Gew.% beträgt. Hierzu gibt man den aktivierten Bentonit in den oben angegebenen Einsatzmengen. Der Bentonit wird vorzugsweise in Form einer 3- bis 6 %igen wäßrigen Disper­sion zugegeben. Die Pulpe, die den Bentonit enthält, wird dann mit Wasser verdünnt. Hierfür verwendet man im Produktionsbetrieb vorzugsweise das Siebwasser. In die verdünnte Stoffsuspension wird dann, z.B. in die Lei­tung am Ausgang der Mischpumpe, mindestens eine Verbindung gemäß b) in der oben angegebenen Menge zudosiert. Aufgrund der Strömungsverhältnisse in dem Leitungssystem kommt es zu einer ausreichenden Vermischung des kationischen Polymeren mit dem Papierstoff. Sobald die Komponenten aus­reichend miteinander vermischt sind, kann das hochmolekulare Polymerisat der Komponente c) zugeführt werden. Die Zugabe der Verbindungen c) er­folgt in jedem Fall vor dem Stoffauflauf, zweckmäßigerweise an einer Stelle zwischen Drucksortierer und dem Stoffauflauf. Die Polymerisate b) und c) werden vorzugsweise in Form verdünnter wäßriger Lösungen zudo­siert. Aufgrund des verwendeten Hilfsstoffsystems kann die Papierproduk­tion in geschlossenen Wasserkreisläufen erfolgen. Man erhält Papier mit guter Bedruckbarkeit, das auch im Offset-Verfahren eine gute Bedruckbar­keit aufweist.In the production of paper, the starting point is an aqueous pulp, the concentration of which is 2.5 to 5% by weight. To do this, the activated bentonite is added in the amounts indicated above. The bentonite is preferably added in the form of a 3 to 6% aqueous dispersion. The pulp containing the bentonite is then diluted with water. The white water is preferably used for this in the production plant. At least one compound according to b) is then metered into the diluted stock suspension, for example into the line at the outlet of the mixing pump, in the amount specified above. Due to the flow conditions in the line system, there is sufficient mixing of the cationic polymer with the paper stock. As soon as the components have been mixed sufficiently, the high molecular weight polymer of component c) can be added. In any case, compounds c) are added before the headbox, advantageously at a point between the pressure sorter and the headbox. The polymers b) and c) are preferably metered in in the form of dilute aqueous solutions. Due to the auxiliary system used, paper production can take place in closed water cycles. Paper with good printability is obtained which also has good printability in the offset process.

Die in den Beispielen angegebenen Teile sind Gewichtsteile. Die Angaben in Prozent beziehen sich auf das Gewicht der Stoffe. Die Ladungsdichte und die Molekulargewichte (Lichtstreuung) wurden nach D. Horn, Polyethy­lenimine/Physicochemical Properties and Application (IUPAC) Polymeric Amines and Ammonium Salts, Pergamon Press Oxford and New York, 1980, Seite 333 bis 355 bestimmt.The parts given in the examples are parts by weight. The percentages relate to the weight of the fabrics. Charge density and molecular weights (light scattering) were determined according to D. Horn, Polyethylenimine / Physicochemical Properties and Application (IUPAC) Polymeric Amines and Ammonium Salts, Pergamon Press Oxford and New York, 1980, pages 333 to 355.

Bestimmung der Entwässerungszeit: 1 l der zu prüfenden Faserstoffauf­schlämmung wird jeweils in einem Schopper-Riegler-Testgerät entwässert. Die Zeit, die für verschiedene Auslaufvolumina ermittelt wird, wird als Kriterium für die Entwässerungsgeschwindigkeit der jeweils untersuchten Stoffsuspension gewertet. Die Entwässerungszeiten wurden in allen hier angegebenen Fällen nach dem Durchlauf von 150, 200 und 250 ml Wasser ermittelt.Determination of the dewatering time: 1 l of the pulp slurry to be tested is dewatered in a Schopper-Riegler test device. The time that is determined for different outlet volumes is evaluated as a criterion for the drainage rate of the substance suspension examined in each case. The drainage times were determined in all cases specified here after the passage of 150, 200 and 250 ml of water.

Die Retention wurde geprüft, indem man jeweils den Feststoffgehalt in 250 ml eines Filtrats bestimmte, das durch Entwässern der zu prüfenden Faseraufschlämmung in einem Schopper-Riegler-Gerät erhalten wurde.The retention was checked by determining the solids content in 250 ml of a filtrate obtained by dewatering the fiber slurry to be tested in a Schopper-Riegler device.

Folgende Einsatzstoffe wurden verwendet:
Polyelektrolyt 1 (Komponente b)
Hierbei handelte es sich um ein Polyamidoamin aus Adipinsäure und Diethylentriamin, das mit Ethylenimin gepfropft und mit einem Polyalky­lenoxid, dessen endständige OH-Gruppen mit Epichlorhydrin umgesetzt sind, vernetzt ist. Ein derartiges Produkt ist aus Beispiel 1 der DE-PS 24 34 816 bekannt, es hat eine Ladungsdichte von 12,2 mVal/g (gemessen bei pH 4,5).The following ingredients were used:
Polyelectrolyte 1 (component b)
This was a polyamidoamine from adipic acid and diethylenetriamine, which was grafted with ethyleneimine and crosslinked with a polyalkylene oxide, the terminal OH groups of which had been reacted with epichlorohydrin. Such a product is known from Example 1 of DE-PS 24 34 816, it has a charge density of 12.2 meq / g (measured at pH 4.5).

Hochmolekulares Polymerisat 1 (Komponente c):
Man verwendet ein Homopolymerisat des Acrylamids vom Molekulargewicht 3,5 Millionen.High molecular polymer 1 (component c):
A homopolymer of acrylamide with a molecular weight of 3.5 million is used.

Beispiel 1example 1

In einem 20 l fassenden Gefäß wird eine Stoffsuspension aus thermomecha­nischem Stoff (TMP) mit einer Konzentration von 3,2 % hergestellt. Der pH-Wert der Stoffsuspension beträgt 5,7. Die so hergestellte Papierfaser­suspension wird gerührt und mit einer 5 %igen wäßrigen Anschlämmung eines handelsüblichen Natrium-Bentonits versetzt, so daß die Bentonitmenge, bezogen auf Papierstoff, 0,5 % beträgt. Nach dem Homogenisieren wird der Stoff auf eine Konzentration von 0,85 % durch Zugabe von Wasser verdünnt.A suspension of thermomechanical substance (TMP) with a concentration of 3.2% is produced in a 20 l container. The pH of the stock suspension is 5.7. The paper fiber suspension prepared in this way is stirred and mixed with a 5% strength aqueous slurry of a commercially available sodium bentonite, so that the amount of bentonite, based on paper stock, is 0.5%. After homogenization, the substance is diluted to a concentration of 0.85% by adding water.

Im Versuch

  • a) werden von dieser Stoffmischung die Entwässerungszeiten sowie die Retention gemessen. Die dafür ermittelten Werte sind in Tabelle 1 angegeben.
  • b) Zu der gemäß a) erhaltenen Papierstoffsuspension gibt man, bezogen auf trockenen Papierstoff, 0,06 % des oben angegebenen Polyelektrolyten 1. Nach dem Durchmischen wird die Entwässerungszeit gemessen und die Reten­tion bestimmt. Bei der visuellen Prüfung des Flockungszustandes konnte nur eine geringe Flockung festgestellt werden. Die Ergebnisse sind in Tabelle 1 angegeben.
  • c) Zu der gemäß a) erhaltenen Stoffsuspension gibt man 0,02 % des oben an­gegebenen hochmolekularen Polymerisats 1, und bestimmt nach dem Durch­mischen die Entwässerungszeit, die Retention und Flockung. Die Ergebnisse sind in Tabelle 1 angegeben. Bemerkenswert ist hierbei vor allem, daß es zu einer starken Flockung kommt.
  • d) - Beispiel gemäß Erfindung
    Zu 1 l der gemäß a) erhaltenen Bentonit-haltigen Stoffsuspension gibt man zunächst 0,06 % des Polyelektrolyten 1 und rührt die Mischung 1 Minute. Danach fügt man 0,02 % des hochmolekularen Polymerisats 1 zu, rührt die Mischung wiederum 1 Minute und prüft nach der oben angegebenen Vorschrift die Entwässerung und die Retention. Das System weist bemerkenswerterweise nur eine geringe Flockung auf.
Figure imgb0001
 In the attempt
  • a) the dewatering times and the retention are measured from this mixture of substances. The values determined for this are given in Table 1.
  • b) 0.06% of the above-mentioned polyelectrolyte 1, based on dry paper stock, is added to the paper stock suspension obtained according to a). After mixing, the dewatering time is measured and the retention is determined. Only a slight flocculation was found during the visual inspection of the flocculation state. The results are shown in Table 1.
  • c) 0.02% of the high molecular weight polymer 1 mentioned above is added to the stock suspension obtained according to a), and the dewatering time, retention and flocculation are determined after mixing. The results are shown in Table 1. It is particularly noteworthy that there is strong flocculation.
  • d) - Example according to the invention
    0.01% of the polyelectrolyte 1 is first added to 1 l of the bentonite-containing stock suspension obtained according to a) and the mixture is stirred for 1 minute. Then 0.02% of the high molecular weight polymer 1 is added, the mixture is stirred again for 1 minute and the drainage and the retention are checked in accordance with the above-mentioned instructions. The system is remarkably low in flocculation.
Figure imgb0001

Beispiel 2Example 2

Auf einer Papiermaschine wird füllstoff-freies Zeitungsdruckpapier in Offset-Qualität mit einem Flächengewicht von 52 g/m² aus 100 % gebleich­tem TMP (thermomechanischem Stoff) hergestellt. Man geht dabei zunächst von einer Stoffkonzentration von 2,95 % aus und gibt dazu im kontinuier­lichen Betrieb 0,7 % Natrium-Bentonit in Form einer 5 %igen wäßrigen Anschlämmung zu. Dann verdünnt man den Papierstoff in der Mischpumpe mit Siebwasser auf eine Konzentration von 0,75 % und dosiert am Ausgang der Mischpumpe in die Leitung, bezogen auf trockenen Papierstoff, 0,05 % des oben angegebenen Polyelektrolyten 1 und nach dem Durchmischen zwischen Drucksortierer und Stoffauflauf, 0,01 % des hochmolekularen Polymeri­sats 1. Nach Einstellung des Systemgleichgewichts ermittelt man die Werte für Stoffauflauf, Siebwasser und errechnet daraus die Werte für die First Pass Retention (FPR). Als weiteren Parameter ermittelt man die Maschinen­geschwindigkeit und die Papierproduktion pro Zeiteinheit.Filler-free newsprint in offset quality with a basis weight of 52 g / m² is made from 100% bleached TMP (thermomechanical fabric). It is initially assumed that the substance concentration is 2.95% and 0.7% sodium bentonite in the form of a 5% aqueous slurry is added in continuous operation. Then the paper stock in the mixing pump is diluted with white water to a concentration of 0.75% and metered into the line at the outlet of the mixing pump, based on dry paper stock, 0.05% of the above-mentioned polyelectrolyte 1 and after mixing between the pressure sorter and the headbox , 0.01% of the high molecular weight polymer 1. After adjusting the system balance, the values for headbox, white water are determined and the values for the first pass retention (FPR) are calculated. The machine speed and the paper production per unit of time are determined as a further parameter.

Die Konzentration des Stoffauflaufs beträgt 6,84 g/l, das Siebwasser ent­hält 2,32 g/l Feststoffe. Die First Pass Retention (FPR) liegt bei 66,1 %. Die Produktionsgeschwindigkeit beträgt 577 m/min. Pro Stunde er­hält man 6,8 t Papier.The headbox concentration is 6.84 g / l, the white water contains 2.32 g / l solids. The First Pass Retention (FPR) is 66.1%. The production speed is 577 m / min. You get 6.8 t of paper per hour.

Vergleichsbeispiel 2Comparative Example 2

Das Beispiel 1 wird mit der Ausnahme wiederholt, daß man den Polyelektro­lyten 1 fortläßt. In diesem Fall flockt der Papierstoff derart stark, daß eine einwandfreie Blattbildung nicht gewährleistet ist. Die Formation und Oberflächenbeschaffenheit des Blattes ist für die gestellten Druckanfor­derungen unzureichend.Example 1 is repeated with the exception that the polyelectrolyte 1 is omitted. In this case, the paper flocculates so strongly that perfect sheet formation is not guaranteed. The formation and surface quality of the sheet is insufficient for the printing requirements.

Vergleichsbeispiel 3Comparative Example 3

Das Beispiel 2 wird mit der Ausnahme wiederholt, daß man das hochmole­kulare Polymerisat 1 fortläßt. In diesem Fall bekommt man zwar eine gute Formation, aber die Entwässerung des Papierstoffs ist schlecht, so daß die Maschine nur mit geringerer Geschwindigkeit laufen kann.Example 2 is repeated with the exception that the high molecular weight polymer 1 is omitted. In this case you get a good formation, but the drainage of the paper stock is bad, so that the machine can only run at a lower speed.

Claims (5)

1. Verfahren zur Herstellung von Papier und Karton durch Entwässern eines Papierstoffs, der Bentonit und Polyelektrolyte enthält, auf einem Sieb, dadurch gekennzeichnet, daß man zu einer wäßrigen Pulpe, deren Stoffkonzentration 2,5 bis 5 Gew.% beträgt, jeweils bezogen auf trockenen Papierstoff, a) 0,1 bis 2 Gew.% eines aktivierten Bentonits zusetzt, danach die Papierstoffkonzentration durch Verdünnen mit Wasser auf 0,3 bis 2 Gew.% einstellt, b) 0,01 bis 0,1 Gew.% eines kationischen Polyelektrolyten mit einer Ladungsdichte von mindestens 4 mVal/g Polyelektrolyt (gemessen bei pH 4,5) zufügt, darin verteilt und nach der Durchmischung c) 0,003 bis 0,03 Gew.% eines hochmolekularen Polymerisats auf Basis von Acrylamid oder Methacrylamid zudosiert, mit dem Papierstoff mischt und die so erhaltene Pulpe auf einem Sieb entwässert. 1. A process for the production of paper and cardboard by dewatering a paper stock containing bentonite and polyelectrolytes on a sieve, characterized in that an aqueous pulp, the concentration of which is 2.5 to 5% by weight, based in each case on dry Paper stock, a) 0.1 to 2% by weight of an activated bentonite is added, then the pulp concentration is adjusted to 0.3 to 2% by weight by dilution with water, b) 0.01 to 0.1% by weight of a cationic polyelectrolyte with a charge density of at least 4 meq / g polyelectrolyte (measured at pH 4.5) is added, distributed therein and after mixing c) 0.003 to 0.03% by weight of a high molecular weight polymer based on acrylamide or methacrylamide are metered in, mixed with the paper stock and the pulp thus obtained is dewatered on a sieve. 2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß man als Kom­ponente b) Polyethylenimine, wasserlösliche, Ethylenimin einkonden­siert enthaltende vernetzte Kondensationsprodukte auf Basis von Polyamidoaminen, Polyamidoamine, Polyetheramine, Polyvinylamine, Polydiallylammmoniumchlorid und/oder zu mindestens 10 Mol.% hydrolisierte Poly-N-vinylformamide einsetzt.2. The method according to claim 1, characterized in that as component b) polyethyleneimines, water-soluble, ethyleneimine condensed containing crosslinked condensation products based on polyamidoamines, polyamidoamines, polyetheramines, polyvinylamines, polydiallylammmonium chloride and / or at least 10 mol.% Hydrolyzed poly-N uses vinylformamide. 3. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß man als Kom­ponente (c) Homopolymerisate des Acrylamid und Methacrylamids ein­setzt, die ein mittleres Massen-Molekulargewicht von 1 000 000 bis 20 000 000 haben.3. The method according to claim 1, characterized in that one uses as component (c) homopolymers of acrylamide and methacrylamide, which have an average mass molecular weight of 1,000,000 to 20,000,000. 4. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß man als Kom­ponente c) Copolymerisate aus Acrylamid und mindestens einem anio­nischen Monomeren aus der Gruppe der ethylenisch ungesättigten C₃-­bis C₅-Carbonsäuren, Vinylsulfonsäure, Acrylamidopropansulfonsäuren und/oder deren Alkali-, Ammonium- bzw. Aminsalze einsetzt.4. The method according to claim 1, characterized in that copolymers of acrylamide and at least one anionic monomer from the group of ethylenically unsaturated C₃ to C₅ carboxylic acids, vinylsulfonic acid, acrylamidopropanesulfonic acids and / or their alkali metal, ammonium or Uses amine salts. 5. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß man als Kom­ponente c) Copolymerisate aus Acrylamid und mindestens einem katio­nischen Monomeren aus der Gruppe der Di-C₁- bis C₂-alkylamino-C₂- bis C₆-alkyl(meth)acrylate, Di-C₁- bis C₂-alkylamino-C₂-bis C₆-alkyl­(meth)acrylamide, N-Vinylimidazole, N-Vinylpyridine und N-Vinylimida­zoline gegebenenfalls in quaternisierter Form oder als Salze sowie Diallyldi-C₁- bis C₂-alkylammoniumhalogenide einsetzt.5. The method according to claim 1, characterized in that as component c) copolymers of acrylamide and at least one cationic monomer from the group of di-C₁ to C₂-alkylamino-C₂ to C₆-alkyl (meth) acrylates, di- C₁- to C₂-alkylamino-C₂ to C₆-alkyl (meth) acrylamides, N-vinylimidazoles, N-vinylpyridines and N-vinylimidazolines optionally in quaternized form or as salts and diallyldi-C₁ to C₂-alkylammonium halides.
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EP0335575A3 (en) * 1988-03-28 1990-12-12 Allied Colloids Limited Production of paper and paper board
EP0335575A2 (en) * 1988-03-28 1989-10-04 Ciba Specialty Chemicals Water Treatments Limited Production of paper and paper board
EP0468558A2 (en) * 1990-07-03 1992-01-29 Laporte Industries Limited Production of paper and paperboard
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EP0608986A1 (en) * 1993-01-26 1994-08-03 Ciba Specialty Chemicals Water Treatments Limited Production of filled paper
US5501774A (en) * 1993-01-26 1996-03-26 Allied Colloids Limited Production of filled paper
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GB2309280A (en) * 1996-01-16 1997-07-23 Monroe Auto Equipment Co Shock absorber
WO1997033040A1 (en) * 1996-03-08 1997-09-12 Allied Colloids Limited Activation of swelling clays and processes of using the activated clays
WO1997033041A1 (en) * 1996-03-08 1997-09-12 Allied Colloids Limited Clay compositions and their use in paper making
WO1998001623A1 (en) * 1996-07-09 1998-01-15 Basf Aktiengesellschaft Process for producing paper and cardboard
WO2001034910A1 (en) * 1999-11-08 2001-05-17 Ciba Specialty Chemicals Water Treatments Limited Manufacture of paper and paperboard
EP1529133A1 (en) 2002-08-07 2005-05-11 Basf Aktiengesellschaft Method for the production of paper, paperboard, and cardboard
US7306701B2 (en) 2002-08-07 2007-12-11 Basf Aktiengesellschaft Production of paper, board and cardboard
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US7998314B2 (en) 2004-12-22 2011-08-16 Basf Aktiengesellschaft Method for the production of paper, cardboard and card
DE102008000811A1 (en) 2007-03-29 2008-10-09 Basf Se Preparing paper, paperboard and cardboard, comprises shearing the paper material, adding ultrasound treated microparticle system and fine-particle inorganic component to the paper material and dewatering the paper material to form sheets
WO2010020551A1 (en) * 2008-08-18 2010-02-25 Basf Se Method for increasing the dry strength of paper, paperboard and cardboard
US8404083B2 (en) 2008-08-18 2013-03-26 Basf Se Process for increasing the dry strength of paper, board and cardboard

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NO168593C (en) 1992-03-11
CA1278403C (en) 1991-01-02
FI864294A0 (en) 1986-10-23
AU578404B2 (en) 1988-10-20
FI85397B (en) 1991-12-31
NO168593B (en) 1991-12-02
JPS62125098A (en) 1987-06-06
DE3669336D1 (en) 1990-04-12
DE3541163A1 (en) 1987-05-27
NO864644D0 (en) 1986-11-20
US4749444A (en) 1988-06-07
NZ217951A (en) 1988-10-28
EP0223223B1 (en) 1990-03-07
FI85397C (en) 1992-04-10
JPH0159399B2 (en) 1989-12-18
FI864294A (en) 1987-05-22
NO864644L (en) 1987-05-22
ATE50814T1 (en) 1990-03-15
AU6397786A (en) 1987-05-28

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