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EP0948677B1 - Method for producing paper - Google Patents

Method for producing paper Download PDF

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Publication number
EP0948677B1
EP0948677B1 EP97952902A EP97952902A EP0948677B1 EP 0948677 B1 EP0948677 B1 EP 0948677B1 EP 97952902 A EP97952902 A EP 97952902A EP 97952902 A EP97952902 A EP 97952902A EP 0948677 B1 EP0948677 B1 EP 0948677B1
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EP
European Patent Office
Prior art keywords
cationic
paper
retention
agents
polyethyleneimines
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP97952902A
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German (de)
French (fr)
Other versions
EP0948677A1 (en
Inventor
Werner Auhorn
Dietmar MÖNCH
Rainer Dyllick-Brenzinger
Rainer Scholz
Rainer Blum
Hubert Meixner
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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
    • D21H23/00—Processes or apparatus for adding material to the pulp or to the paper
    • D21H23/02—Processes or apparatus for adding material to the pulp or to the paper characterised by the manner in which substances are added
    • D21H23/22—Addition to the formed paper
    • D21H23/24—Addition to the formed paper during paper manufacture
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21F—PAPER-MAKING MACHINES; METHODS OF PRODUCING PAPER THEREON
    • D21F1/00—Wet end of machines for making continuous webs of paper
    • D21F1/08—Regulating consistency
    • 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
    • D21H17/46—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
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/06—Paper forming aids
    • D21H21/10—Retention agents or drainage improvers

Definitions

  • the invention relates to a method for producing paper by dewatering a pulp containing process chemicals on a paper machine in which the paper machine sieve a main stream of paper stock via a headbox and feeds a dilution stream consisting of white water, whose share in the total headbox feed 5 to 35 vol .-% is.
  • the paper machines usually only have one Electricity for feeding the paper stock to the headbox.
  • the paper stock contains Process chemicals such as fixatives, drainage aids, Retention aids and flocculants and, if appropriate, sizing agents, Dry and wet strength agents, dyes and fillers.
  • the dosage of the process chemicals to the paper stock can be various methods described in the literature become. So from weekly paper manufacturing, Volume 13, 493-502 (1979) the use of cationic polyelectrolytes known in combination with bentonite, whereby the First paper bentonite and then the cationic Adds polyelectrolytes, the paper stock optionally can be subjected to a shear gradient.
  • EP-B-0 235 893 discloses a paper stock first a synthetic cationic polymer with a molecular weight of to add more than 500,000 flakes that are formed then crushed into microflakes in a subsequent shear step become. Then bentonite is added and the Process material containing dewatered. With that processes known from EP-A-0 335 575 for the production of paper the paper stock is successively treated with two different water-soluble cationic polymers added. Here you dose initially a low molecular weight cationic polymer as a fixative and then a high molecular weight cationic polymer as Flocculant, then subjects the pulp to form of micro flakes at a shear level, bentonite clogs and drains then him. The formation profile of the papers so produced is in need of improvement, however.
  • the invention has for its object a method for manufacturing of paper to provide, facing one the known methods an increase in retention, in particular fiber and fines retention as well as filler retention, if applicable achieved and at the same time papers with a uniform Formation cross profile receives.
  • the object is achieved with a method for Manufacture of paper by dewatering a process chemical and optionally filler-containing paper stock on a Paper machine, in which the paper machine sieve over one Headbox a main stream of paper stock and one out White water supplies existing dilution stream, the proportion of which the total headbox feed is 5 to 35 vol .-% if one at least 5% by weight of the process chemicals in the dilution stream dosed.
  • the papers produced in this way are uniform Formation cross profile and surprisingly contain one very good qualitative binding of the fine and fillers to the Long fiber material, so that these papers practically not or in dust to a non-disturbing degree.
  • most of the time Impurities contained in the white water such as wood constituents, adhesive Impurities from the paper line on recycled fibers or when using waste paper almost quantitatively to the Paper stock fixed and thus for the paper manufacturing process and made the later paper recycling harmless.
  • a headbox with a main and a dilution stream which is via metering valves the individual sections of the headbox for adjustment of the consistency cross section is fed.
  • the dilution stream consists of white water. It is well known that white water contains fine substances and fiber fragments from those used in papermaking used cellulose or wood pulp fibers. These fines are usually difficult to get out of the cycle. If filler-containing papers are made, contains the white water, based on fiber, at least one twice as much filler as the main stream.
  • the Share of the dilution stream consisting of the white water the total headbox feed is, for example, 5 to 35 vol%, preferably 7 to 15 vol%. Suitable constructions for carrying out the method according to the invention are described in the references cited above for the prior art "Das Paper "and in” Kliblatt für Textilfabrikation ".
  • Suitable process chemicals are, for example, fixing agents, drainage aids, retention agents, flocculants alone, in a mixture with one another or in combination with bentonite and / or colloidal silica, dyes, mass sizing agents, dry strength agents and / or wet strength agents.
  • Polymers such as polymers containing vinylamine units, for example, can simultaneously act as fixing agents, drainage aids, retention aids and as a flocculating agent, and as dry and wet strength agents.
  • the process chemicals are therefore added to the paper stock in the usual manner and in the same way as in the known paper production, so that reference can be made in this regard to the known prior art for paper production.
  • cationic fixing agents are used to eliminate interfering substances which interfere with the effectiveness of retention agents, wet and dry strength agents and bulk sizing agents. Such contaminants are, for example, lignin sulfonates or humic acids.
  • Cationic fixing agents which can be used are, for example, polyethyleneimines, polymers containing vinylamine units and / or poly (diallyldimethylammonium chlorides) with a molar mass M w of 10,000 to 2,000,000 each.
  • Polymers containing vinylamine units are known to be prepared by homo- or copolymerization of N-vinylformamide and subsequent hydrolysis of the polymers with acids or bases, cf. EP-B-0 071 050 and EP-B-0 216 387.
  • Process chemicals which can be used are, for example, cationic fixatives, cationic drainage aids, cationic retention agents and cationic flocculants, alone or as a mixture with one another.
  • Cationic polyacrylamides with a high molecular weight, for example with molecular weights M w of at least 4000000, are particularly suitable as retention and flocculants.
  • the high molecular weight cationic polyacrylamides are produced by polymerizing acrylamide with cationic monomers.
  • Suitable cationic monomers are, for example, the esters of ethylenically unsaturated C 3 to C 5 carboxylic acids with amino alcohols, such as dimethylaminoethyl acrylate, diethylaminoethyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate and di-n-propylaminoethyl acrylate.
  • Suitable cationic monomers that can be copolymerized with acrylamide are N-vinylimidazole, N-vinylimidazoline and basic acrylamides such as dimethylaminoethylacrylamide.
  • the basic monomers can be used in the form of the free bases, as salts or in quaternized form in the copolymerization.
  • the cationic polyacrylamides contain, for example, 5 to 40, preferably 10 to 40% by weight of cationic monomers in copolymerized form.
  • the molecular weights M w of the cationic polyacrylamides are at least 4,000,000 and in most cases are above 5,000,000, for example in the range from 5,000,000 to 1,500,000.
  • anionic ones can also be used Polyacrylamides, for example acrylic acid or methacrylic acid polymerized contain, as well as amphoteric polyacrylamides Drainage aids, retention aids and flocculants deploy.
  • Cationic, nonionic, amphoteric or anionic Polymers used as drainage aids, retention aids and Flocculants are used, for example, in Combination with bentonite and / or colloidal silica improved effectiveness. This is particularly the case if you also use a cationic fixative. The State of the art specified in the introduction to the description clarifies this.
  • Water-soluble for example, are also used as process aids
  • Polymers used which are selected from polyethyleneimines, Reaction products of polyethyleneimines with at least bifunctional crosslinkers, anionic polyacrylamides, cationic Polyacrylamides, amphoteric polyacrylamides, reaction products from polyamidoamines grafted with ethyleneimine at least two crosslinkers containing functional groups, vinylformamide units and / or containing vinylamine units Polymers and poly (diallyldimethylammonium halides).
  • Polyethyleneimines are, for example, by polymerizing ethyleneimine in aqueous medium in the presence of traces of acids or acids Connections established.
  • water-soluble, Polymeric reaction products containing amino groups which are available through the implementation of Michael addition products from polyalkylene polyamines, polyamidoamines, with ethyleneimine grafted polyamidoamines and mixtures of the above Compounds and monoethylenically unsaturated carboxylic acids, salts, Esters, amides or nitriles with at least bifunctional ones Networkers.
  • Such reaction products are, for example, from the WO-A-94/14873 known. To make them come out halogen - containing crosslinkers especially halogen - free crosslinkers in Consider how glycidyl ethers of polyalkylene glycols.
  • the monobasic carboxylic acids have, for example, 1 to 28, preferably 8 to 18 carbon atoms and can optionally have one or contain several ethylenic double bonds, e.g. Oleic acid or Linolenic acid.
  • modified polyethyleneimines can the molecular weights of the polyethyleneimines in question up to 2 million and are preferably in the range from 1000 to 50000.
  • the polyethyleneimines become partial amidated with monobasic carboxylic acids, so that, for example, 0.1 to 90, preferably 1 to 50% of the amidatable nitrogen atoms is present as an amide group in the polyethyleneimines.
  • Suitable, at least crosslinkers containing two functional double bonds are mentioned above. Halogen-free crosslinkers are preferred used.
  • crosslinkers In the reaction of compounds containing amino groups with Crosslinkers are, for example, based on 1 part by weight of one Compound containing amino groups 0.001 to 10, preferably 0.01 to 3 parts by weight of at least one crosslinker.
  • polyethyleneimines are quaternized polyethyleneimines. Both homopolymers of ethyleneimine and polymers which contain, for example, ethyleneimine grafted on are suitable for this purpose.
  • the polyethyleneimines obtainable in this way have a broad molar mass distribution and molar masses of, for example, 129 to 2 ⁇ 10 6 , preferably 430 to 1 ⁇ 10 6 .
  • the polyethyleneimines and the quaternized polyethyleneimines can optionally with at least two functional Crosslinkers containing groups can be implemented.
  • the quaternization the polyethyleneimines can, for example, with alkyl halides such as methyl chloride, ethyl chloride, hexyl chloride, Benzyl chloride or lauryl chloride and with, for example Dimethyl sulfate can be made.
  • alkyl halides such as methyl chloride, ethyl chloride, hexyl chloride, Benzyl chloride or lauryl chloride and with, for example Dimethyl sulfate can be made.
  • Other suitable amino groups containing polymers are phosphonomethylated polyethyleneimines and alkoxylated polyethyleneimines, for example by reaction of polyethyleneimine with ethylene oxide and / or propylene oxide are available.
  • the phosphonomethylated and the alkoxylated Polyethyleneimines can optionally be combined with at least two crosslinkers containing functional groups.
  • the alkoxylated polyethyleneimines contain 1 to 100 per NH group, preferably 2 to 20 alkylene oxide units.
  • the molecular weight of the Polyethyleneimines can be up to 2 million.
  • Preferably polyethyleneimines with molar masses are used for the alkoxylation from 1000 to 50000.
  • Other suitable water-soluble retention agents or fixatives are reaction products of Polyethyleneimines with diketenes, e.g. of polyethyleneimines one Molar mass from 1000 to 50000 with distearyl diketene. Even those Products can optionally be functional with at least two Crosslinkers containing groups can be implemented.
  • Reaction products from polyamidoamines grafted with ethyleneimine with at least two crosslinkers having functional groups are known from DE-B-2 434 816.
  • a crosslinker for example ⁇ , ⁇ -bis (chlorohydrin) ether of polyalkylene oxides with 1 to 100 alkylene oxide units into consideration.
  • the resulting Resins have - measured at 20 ° C in 20 wt .-% aqueous Solution - a viscosity of more than 300 mPas.
  • Other process chemicals are reaction products for papermaking of polyalkylene polyamines, dimethylamine, diethylamine or Ethylenediamine with epichlorohydrin or dichloroethane or others at least bifunctional crosslinkers.
  • Reaction products of this Art are for example from EP-A-0 411 400 and DE-A-2 162 567 known.
  • Another preferred retention system consists of combinations of cationic synthetic polymers and / or cationic starch with finely divided organic or inorganic solids. Such systems are specified in the prior art described at the outset and in references EP-B-0 041 056, EP-B-0 080 986 and EP-B-0 218 674.
  • Fine-particle inorganic solids come for this retention agent system Bentonite, colloidal silica, microcrystalline talc, precipitated calcium carbonate, precipitated gypsum and / or calcined clay.
  • the amount of finely divided solids is, for example, 0.01 to 2.0% by weight, based on dry paper. It is particularly preferred to use the above-mentioned retention agent systems composed of cationic synthetic retention agents and / or cationic starch in combination with bentonite, which can optionally be activated in an alkaline or acidic manner or colloidal silica.
  • Bentonite and silica, as well as the other finely divided inorganic substances that are considered, are preferably used in amounts of 0.02 to 0.5% by weight, based on dry paper.
  • the inorganic, finely divided solids for example, have an inner surface area of 5 to 1000 m 2 / g (determined according to BET with nitrogen).
  • finely divided organic particles can be considered, for example crosslinked polyacrylic acid or modified lignin sulfonate.
  • the finely divided organic solids also increase retention.
  • Such a system is known for example from WO-A-96/26220 for the combination of cationically modified cellulose particles with polyacrylamides.
  • the other retention and flocculation agents mentioned above can also be combined with these cellulose particles to form an effective retention agent system.
  • the particle size of the inorganic and organic solids in the application, ie when introduced into the aqueous medium, is in the range, for example, from 10 nm to 10 ⁇ m.
  • All paper grades, Cardboard and cardboard are made, for example Papers for newspaper printing, so-called medium-fine writing and printing papers, gravure papers and also lightweight Coating base papers.
  • Pulp also comes as raw materials for the production of the pulp and wood pulp into consideration. These substances are mainly used in the so-called integrated factories in more or less humid Form directly without further thickening or drying Paper processed. Because of the not completely removed from it These fiber materials still contain impurities Fabrics that severely disrupt the usual paper manufacturing process. To However, the method according to the invention can also contain contaminants containing pulps can be processed easily.
  • both filler-free as well as filler-containing papers can be up to a maximum of 40% by weight and is preferably in the range of 5 to 25% by weight.
  • Suitable Fillers are, for example, clay, kaolin, native and precipitated Chalk, titanium dioxide, talc, calcium sulfate, barium sulfate, Alumina, satin white or mixtures of the above Fillers.
  • the consistency of the pulp is, for example, 0.1 to 15% by weight.
  • at least one cationic polymer is first added as a fixing agent to the fiber slurry and then at least one cationic polymer which acts as a retention agent is added. This addition causes a strong flocculation of the paper stock.
  • the z. B. in one or more cleaning, mixing and pumping stages or a pulper, classifier or also in a refiner or sieve through which the pre-flocked paper stock is passed, the so-called "hard giant flakes" present in the flocked system are destroyed . Bentonite, colloidal silica or calcined clay are preferably added after the shear stage, so-called soft microflakes are formed.
  • the amounts of bentonite, colloidal silica or calcined clay are 0.01 to 2, preferably 0.02 to 0.5% by weight, based on dry paper stock.
  • Bentonite is a layered aluminum silicate based on montmorillonite that occurs naturally. It is mostly used after the calcium ions have been replaced by sodium ions.
  • bentonite in an aqueous slurry is treated with sodium hydroxide solution. This makes it fully swellable in water and forms highly viscous thixotropic gel structures.
  • the platelet diameter of the bentonite is, for example, 1 to 2 ⁇ m, the platelet thickness is approximately 1 nm (10 ⁇ ).
  • the bentonite has a specific surface area of 60 to 800 m 2 / g. Due to the large inner surface and the outwardly negative excess charges on the surface, such inorganic polyanions can be used for adsorptive collection effects of cationically charged and sheared paper materials. This results in optimal flocculation in the paper stock.
  • Dyes, mass sizing agents (especially alkyldiketene dispersions, Resin glue, alkenyl succinimide dispersions or glue polymer dispersions) and solidifying agents (e.g. with Epichlorohydrin crosslinked polyamidoamines) can optionally dosed exclusively into the headbox via the dilution stream become.
  • the figures mean in percent Percent by weight, the parts are parts by weight.
  • the molecular weights were determined by light scattering.
  • Example 3 is made by condensing adipic acid with diethylenetriamine prepared a polyamidoamine and then in aqueous Grafted solution with so much ethyleneimine that the polyamidoamine per basic nitrogen grouping 6.7 ethyleneimine units grafted contains.
  • a 10% aqueous solution of the polymer has a viscosity of 22 mPas.
  • the polyamidoamine grafted with ethyleneimine is then by reaction with a bis-glycidyl ether of a polyethylene glycol the average molecular weight of 2000 according to the information in Example 3 of DE-B-2 434 816 networked.
  • An ethyleneimine unit is obtained containing polymer with a viscosity of 120 mPas (determined in 10% aqueous solution at 20 ° C and pH 10). The Concentration of the aqueous solution is 12.5%, the pH is 10.
  • Cationic copolymer of acrylamide and dimethylaminoethyl acrylate that is quaternized with methyl chloride with a content of acrylamide of 84 mol% and a molar mass of approximately 10 million Charge density of the copolymer is 1.7 mEq / g at pH 4.5.
  • Crosslinked polyethyleneimine with an average molecular weight Mw of 1.4 million and a charge density of 20.4 mEq / g (measured at pH 4.5).
  • Crosslinked polyethyleneimine with an average molecular weight of 1 million and a charge density of 14.7 mEq / g (measured at pH 4.5).
  • SC paper super calendered paper
  • This paper stock was on an SC paper machine with a module jet headbox from Voith-Sulzer was processed.
  • the main stream of paper stock was metered in front of the vertical sorter 0.29% polymer 1 and after the vertical sorter 0.024% Polymer 2.
  • Over the module jet headbox was the paper machine screen a dilution stream of white water is supplied to which 0.03% of polymer 1, based on dry paper, was metered in.
  • the Volume ratio of main stream to dilution stream was 9: 1.
  • the ash retention was 29.5%, the fiber and fines retention 62.4%.
  • the paper contains the fine and fillers in a very well bound form and has a very good formation cross profile and excellent ash distribution.
  • Example 1 was repeated with the exception that the above described paper stock of the SC paper machine in a single Electricity without a module jet system with the specified process aids fed and drained.
  • the ash retention was 27.8%, fiber and fines retention 60.3%.
  • Example 1 was repeated with the only exception that in the dilution stream instead of polymer 1 now 0.38% polymer 4 dosed.
  • the ash retention was 33.6%, the fiber and Fineness retention 63.6%.
  • the paper exhibits an excellent uniform formation cross profile.
  • a fabric composition of 40 parts wood pulp, 40 parts bleached pine sulfate pulp and 20 parts coated Committee was on a paper machine for wood-containing coating base papers processed into paper.
  • the paper machine was with a Dilution Head Box from Valmet. With help this device could make the headbox an existing of white water Dilution stream are supplied.
  • the ratio of Main stream to dilution stream was 9: 1 0.05% polymer 2, based on dry paper, in the main stream in front of the vertical sorter.
  • the dilution stream was added in each case in front of the vertical sorter 0.03% polymer 3, based on dry paper, and 0.1% bentonite, also based on dry Paper.
  • the ash retention was 30.5%, the fiber and Fineness retention 69.5%.
  • the paper was even Formation cross profile.
  • Example 3 was then repeated without a dilution head box.
  • the ash retention was 26.8% and the fiber and fines retention 64.6%.
  • Example 3 was repeated with the exception that one, each based on dry paper, in the dilution stream of the dilution Head box 0.02% polymer 2 in front of the vertical sorter and 0.1% bentonite dosed after the vertical sorter and into the Main stream 0.04% polymer 2 before passing through the vertical sorter gave.
  • the ash retention was 30.1%, the fiber and Fineness retention 69.7%.
  • the paper showed an excellent Ash distribution and had a uniform formation cross profile.
  • Example 4 was repeated without dilution head box dosing. Here the ash retention was 25.7% and the fiber and fines retention 63.7%.

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Abstract

PCT No. PCT/EP97/06857 Sec. 371 Date Jan. 27, 1999 Sec. 102(e) Date Jan. 27, 1999 PCT Filed Dec. 9, 1997 PCT Pub. No. WO98/29603 PCT Pub. Date Jul. 9, 1998Paper is produced by draining a paper stock containing process chemicals on a paper machine, a main stream of the paper stock and a dilution stream which consists of white water, contains at least 5% by weight of the process chemicals and amounts to 5-35% by volume of the total head box feed being fed via a head box to the paper machine wire. The papers thus produced have an excellent formation profile and an outstanding ash distribution.

Description

Die Erfindung betrifft ein Verfahren zur Herstellung von Papier durch Entwässern eines Prozeßchemikalien enthaltenden Papierstoffs auf einer Papiermaschine, in der man dem Papiermaschinensieb über einen Stoffauflauf einen Hauptstrom des Papierstoffs und einen aus Siebwasser bestehenden Verdünnungsstrom zuführt, dessen Anteil an der Gesamtstoffauflaufzuführung 5 bis 35 Vol.-% beträgt.The invention relates to a method for producing paper by dewatering a pulp containing process chemicals on a paper machine in which the paper machine sieve a main stream of paper stock via a headbox and feeds a dilution stream consisting of white water, whose share in the total headbox feed 5 to 35 vol .-% is.

Das oben beschriebene Verfahren ist in der Fachliteratur unter Modul-Jet-Konzept bekannt, vgl. Das Papier, Heft 10A, Seiten V 99-V 105 (1995) und Wochenblatt für Papierfabrikation, Band 122, 485-491 (1994). Mit Hilfe dieses speziellen Stoffauflaufs kann man u.a. hochgefüllte, superkalandrierte Papiere (SC-Papiere) mit einer gleichmäßigen Formation auf hohem Niveau herstellen. Die nach diesem Verfahren erhältlichen Papiere neigen jedoch zum Stauben.The procedure described above is in the specialist literature under Module jet concept known, cf. The paper, booklet 10A, pages V 99-V 105 (1995) and Wochenblatt für Papierfabrikation, Volume 122, 485-491 (1994). With the help of this special headbox one can highly filled, supercalendered papers (SC papers) with a uniform formation at a high level. The papers that can be obtained by this procedure tend however for dusting.

Die Papiermaschinen verfügen üblicherweise nur über einen einzigen Strom für die Zuführung des Papierstoffs zum Stoffauflauf. Der Papierstoff enthält außer den in Wasser suspendierten Fasern Prozeßchemikalien wie Fixiermittel, Entwässerungshilfsmittel, Retentions- und Flockungsmittel sowie gegebenenfalls Leimungsmittel, Trocken- und Naßverfestiger, Farbstoffe und Füllstoffe. Die Dosierung der Prozeßchemikalien zum Papierstoff kann nach verschiedenen in der Literatur beschriebenen Verfahren vorgenommen werden. So ist aus Wochenblatt für Papierfabrikation, Band 13, 493-502 (1979) die Verwendung von kationischen Polyelektrolyten in Kombination mit Bentonit bekannt, wobei man dem Papierstoff zunächst Bentonit und anschließend den kationischen Polyelektrolyten zusetzt, wobei der Papierstoff gegebenenfalls einem Schergefälle unterworfen werden kann.The paper machines usually only have one Electricity for feeding the paper stock to the headbox. In addition to the fibers suspended in water, the paper stock contains Process chemicals such as fixatives, drainage aids, Retention aids and flocculants and, if appropriate, sizing agents, Dry and wet strength agents, dyes and fillers. The dosage of the process chemicals to the paper stock can be various methods described in the literature become. So from weekly paper manufacturing, Volume 13, 493-502 (1979) the use of cationic polyelectrolytes known in combination with bentonite, whereby the First paper bentonite and then the cationic Adds polyelectrolytes, the paper stock optionally can be subjected to a shear gradient.

Aus der EP-B-0 235 893 ist bekannt, einem Papierstoff zunächst ein synthetisches kationisches Polymer mit einer Molmasse von mehr als 500.000 zuzusetzen, daß Flocken gebildet werden, die dann in einem anschließenden Scherschritt zu Mikroflocken zerkleinert werden. Danach wird dann Bentonit zugegeben und der die Prozeßhilfsmittel enthaltende Papierstoff entwässert. Bei dem aus der EP-A-0 335 575 bekannten Verfahren zur Herstellung von Papier wird der Papierstoff nacheinander mit zwei verschiedenen wasserlöslichen, kationischen Polymeren versetzt. Hierbei dosiert man zunächst ein niedrigmolekulares kationisches Polymer als Fixiermittel und danach ein hochmolekulares kationisches Polymer als Flockungsmittel, unterwirft den Papierstoff dann unter Bildung von Mikroflocken einer Scherstufe, setzt Bentonit zu und entwässert ihn dann. Das Formationsprofil der so hergestellten Papiere ist jedoch verbesserungsbedürftig.EP-B-0 235 893 discloses a paper stock first a synthetic cationic polymer with a molecular weight of to add more than 500,000 flakes that are formed then crushed into microflakes in a subsequent shear step become. Then bentonite is added and the Process material containing dewatered. With that processes known from EP-A-0 335 575 for the production of paper the paper stock is successively treated with two different water-soluble cationic polymers added. Here you dose initially a low molecular weight cationic polymer as a fixative and then a high molecular weight cationic polymer as Flocculant, then subjects the pulp to form of micro flakes at a shear level, bentonite clogs and drains then him. The formation profile of the papers so produced is in need of improvement, however.

Der Erfindung liegt die Aufgabe zugrunde, ein Verfahren zur Herstellung von Papier zur Verfügung zu stellen, wobei man gegenüber den bekannten Verfahren eine Erhöhung der Retention, insbesondere der Faser- und Feinstoffretention sowie gegebenenfalls der Füllstoffretention erzielt und gleichzeitig Papiere mit einem gleichmäßigen Formationsquerprofil erhält.The invention has for its object a method for manufacturing of paper to provide, facing one the known methods an increase in retention, in particular fiber and fines retention as well as filler retention, if applicable achieved and at the same time papers with a uniform Formation cross profile receives.

Die Aufgabe wird erfindungsgemäß gelöst mit einem Verfahren zur Herstellung von Papier durch Entwässern eines Prozeßchemikalien und gegebenenfalls Füllstoffe enthaltenden Papierstoffs auf einer Papiermaschine, in der man dem Papiermaschinensieb über einen Stoffauflauf einen Hauptstrom des Papierstoffs und einem aus Siebwasser bestehenden Verdünnungsstrom zuführt, dessen Anteil an der Gesamtstoffauflaufzuführung 5 bis 35 Vol.-% beträgt, wenn man mindestens 5 Gew.-% der Prozeßchemikalien in den Verdünnungsstrom dosiert. Die so hergestellten Papiere weisen ein gleichmäßiges Formationsquerprofil auf und enthalten überraschenderweise eine qualitativ sehr gute Bindung der Fein- und Füllstoffe an den Langfaserstoff, so daß diese Papiere praktisch nicht oder in einem nicht störenden Maß stauben. Außerdem werden die meistens im Siebwasser enthaltenen Störstoffe wie Holzinhaltssstoffe, klebende Verunreinigungen aus dem Papierstrich bei recyclierten Fasern oder beim Einsatz von Altpapier nahezu quantitativ an den Papierstoff fixiert und dadurch für den Papierherstellungsprozeß und das spätere Papier-Recycling unschädlich gemacht.The object is achieved with a method for Manufacture of paper by dewatering a process chemical and optionally filler-containing paper stock on a Paper machine, in which the paper machine sieve over one Headbox a main stream of paper stock and one out White water supplies existing dilution stream, the proportion of which the total headbox feed is 5 to 35 vol .-% if one at least 5% by weight of the process chemicals in the dilution stream dosed. The papers produced in this way are uniform Formation cross profile and surprisingly contain one very good qualitative binding of the fine and fillers to the Long fiber material, so that these papers practically not or in dust to a non-disturbing degree. Besides, most of the time Impurities contained in the white water such as wood constituents, adhesive Impurities from the paper line on recycled fibers or when using waste paper almost quantitatively to the Paper stock fixed and thus for the paper manufacturing process and made the later paper recycling harmless.

Bei dem erfindungsgemäßen Verfahren hat man einen Stoffauflauf mit einem Haupt- und einem Verdünnungsstrom, der über Dosierventile den einzelnen Sektionen des Stoffauflaufs zur Einstellung des Stoffdichtequerprofils zugeführt wird. Der Verdünnungsstrom besteht aus Siebwasser. Das Siebwasser enthält bekanntlich Feinstoffe und Faserbruchstücke von den bei der Papierherstellung eingesetzten Zellstoffen oder Holzstoffasern. Diese Feinstoffanteile sind üblicherweise nur schwierig aus dem Kreislauf herauszuholen. Falls füllstoffhaltige Papiere hergestellt werden, enthält das Siebwasser, bezogen auf Faserstoffe, einen mindestens doppelt so hohen Anteil an Füllstoff wie der Hauptstrom. Der Anteil des aus dem Siebwasser bestehenden Verdünnungsstroms an der Gesamtstoffauflaufzuführung beträgt beispielsweise 5 bis 35 Vol-%, vorzugsweise 7 bis 15 Vol-%. Geeignete Konstruktionen für die Durchführung des erfindungsgemäßen Verfahrens werden in den oben zum Stand der Technik angegebenen Literaturstellen "Das Papier" sowie in "Wochenblatt für Papierfabrikation" beschrieben.In the method according to the invention, there is a headbox with a main and a dilution stream, which is via metering valves the individual sections of the headbox for adjustment of the consistency cross section is fed. The dilution stream consists of white water. It is well known that white water contains fine substances and fiber fragments from those used in papermaking used cellulose or wood pulp fibers. These fines are usually difficult to get out of the cycle. If filler-containing papers are made, contains the white water, based on fiber, at least one twice as much filler as the main stream. The Share of the dilution stream consisting of the white water the total headbox feed is, for example, 5 to 35 vol%, preferably 7 to 15 vol%. Suitable constructions for carrying out the method according to the invention are described in the references cited above for the prior art "Das Paper "and in" Wochenblatt für Papierfabrikation ".

Als Prozeßchemikalien kommen beispielsweise Fixiermittel, Entwässerungshilfsmittel, Retentionsmittel, Flockungsmittel allein, in Mischung untereinander oder in Kombination mit Bentonit und/oder kolloidaler Kieselsäure, Farbstoffe, Masseleimungsmittel, Trockenverfestigungsmittel und/oder Naßverfestigungsmittel in Betracht. Polymere wie beispielsweise Vinylamin-Einheiten enthaltende Polymere, können beispielsweise gleichzeitig als Fixiermittel, Entwässerungshilfsmittel, Retentionsmittel und als Flokkungsmittel sowie als Trocken- und Naßverfestiger wirken. Die Prozeßchemikalien werden daher wie bei der bekannten Papierherstellung dem Papierstoff in üblicher Weise und Menge zugesetzt, so daß diesbezüglich auf den bekannten Stand der Technik für die Papierherstellung verwiesen werden kann. Bezogen auf trockenes Papier dosiert man z.B. 0,005 bis 1,0 Gew.-% an Retentions-, Entwässerungs- oder Flockungsmittel in den Hauptstrom. Der pH-Wert der Stoffsuspension beträgt beispielsweise 4,5 bis 9, vorzugsweise 6 bis 8. So benutzt man beispielsweise kationische Fixiermittel, um Störstoffe zu eliminieren, die die Wirksamkeit von Retentionsmitteln, Naß- und Trockenverfestiger sowei Masseleimungsmittel stören. Solche Störstoffe sind beispielsweise Ligninsulfonate oder Huminsäuren. Als kationische Fixiermittel kann man beispielsweise Polyethylenimine, Vinylamin-Einheiten enthaltende Polymerisate und/oder Poly(diallyldimethylammoniumchloride) mit einer Molmasse Mw von jeweils 10000 bis 2000000 einsetzen. Vinylamin-Einheiten enthaltende Polymerisate werden bekanntlich durch Homo- oder Copolymerisation von N-Vinylformamid und anschließende Hydrolyse der Polymerisate mit Säuren oder Basen hergestellt, vgl. EP-B-0 071 050 und EP-B-0 216 387.Suitable process chemicals are, for example, fixing agents, drainage aids, retention agents, flocculants alone, in a mixture with one another or in combination with bentonite and / or colloidal silica, dyes, mass sizing agents, dry strength agents and / or wet strength agents. Polymers such as polymers containing vinylamine units, for example, can simultaneously act as fixing agents, drainage aids, retention aids and as a flocculating agent, and as dry and wet strength agents. The process chemicals are therefore added to the paper stock in the usual manner and in the same way as in the known paper production, so that reference can be made in this regard to the known prior art for paper production. Based on dry paper, for example, 0.005 to 1.0% by weight of retention, drainage or flocculant is metered into the main stream. The pH of the stock suspension is, for example, 4.5 to 9, preferably 6 to 8. For example, cationic fixing agents are used to eliminate interfering substances which interfere with the effectiveness of retention agents, wet and dry strength agents and bulk sizing agents. Such contaminants are, for example, lignin sulfonates or humic acids. Cationic fixing agents which can be used are, for example, polyethyleneimines, polymers containing vinylamine units and / or poly (diallyldimethylammonium chlorides) with a molar mass M w of 10,000 to 2,000,000 each. Polymers containing vinylamine units are known to be prepared by homo- or copolymerization of N-vinylformamide and subsequent hydrolysis of the polymers with acids or bases, cf. EP-B-0 071 050 and EP-B-0 216 387.

Als Prozeßchemikalien kann man beispielsweise kationische Fixiermittel, kationische Entwässerungshilfsmittel, kationische Retentionsmittel und kationische Flockungsmittel allein oder in Mischung untereinander einsetzen. Als Retentions- und Flockungsmittel besonders geeignet sind beispielsweise kationische Polyacrylamide mit hoher Molmasse, z.B. mit Molmassen Mw von mindestens 4000000.Process chemicals which can be used are, for example, cationic fixatives, cationic drainage aids, cationic retention agents and cationic flocculants, alone or as a mixture with one another. Cationic polyacrylamides with a high molecular weight, for example with molecular weights M w of at least 4000000, are particularly suitable as retention and flocculants.

Polymerisate dieser Art werden in der zum Stand der Technik genannten EP-A-335 575 beschrieben. Sie sind im Handel erhältlich. Die hochmolekularen kationischen Polyacrylamide werden durch Polymerisieren von Acrylamid mit kationischen Monomeren hergestellt. Geeignete kationische Monomere sind beispielsweise die Ester von ethylenisch ungesättigten C3- bis C5-Carbonsäuren mit Aminoalkoholen, wie Dimethylaminoethylacrylat, Diethylaminoethylacrylat, Dimethylaminoethylmethacrylat, Diethylaminoethylmethacrylat und Di-n-propylaminoethylacrylat. Weitere geeignete kationische Monomere, die mit Acrylamid copolymerisiert werden können, sind N-Vinylimidazol, N-Vinylimidazolin und basische Acrylamide wie Dimethylaminoethylacrylamid. Die basischen Monomeren können in Form der freien Basen, als Salze oder in quaternisierter Form bei der Copolymerisation eingesetzt werden. Die kationischen Polyacrylamide enthalten beispielsweise 5 bis 40, vorzugsweise 10 bis 40 Gew.-% an kationischen Monomeren in einpolymerisierter Form. Die Molmassen Mw der kationischen Polyacrylamide betragen mindestens 4000000 und liegen in den meisten Fällen oberhalb von 5000000, z.B. in dem Bereich von 5000000 bis 15000000.Polymers of this type are described in EP-A-335 575 cited in the prior art. They are commercially available. The high molecular weight cationic polyacrylamides are produced by polymerizing acrylamide with cationic monomers. Suitable cationic monomers are, for example, the esters of ethylenically unsaturated C 3 to C 5 carboxylic acids with amino alcohols, such as dimethylaminoethyl acrylate, diethylaminoethyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate and di-n-propylaminoethyl acrylate. Other suitable cationic monomers that can be copolymerized with acrylamide are N-vinylimidazole, N-vinylimidazoline and basic acrylamides such as dimethylaminoethylacrylamide. The basic monomers can be used in the form of the free bases, as salts or in quaternized form in the copolymerization. The cationic polyacrylamides contain, for example, 5 to 40, preferably 10 to 40% by weight of cationic monomers in copolymerized form. The molecular weights M w of the cationic polyacrylamides are at least 4,000,000 and in most cases are above 5,000,000, for example in the range from 5,000,000 to 1,500,000.

Außer den kationischen Polyacrylamiden kann man auch anionische Polyacrylamide, die beispielsweise Acrylsäure oder Methacrylsäure einpolymerisiert enthalten, sowie amphotere Polyacrylamide als Entwässerungshilfsmittel, Retentionsmittel und Flockungsmittel einsetzen. Kationische, nichtionische, amphotere oder anionische Polymere, die als Entwässerungshilfsmittel, Retentionsmittel und Flockungsmittel eingesetzt werden, entfalten beispielsweise in Kombination mit Bentonit und/oder kolloidaler Kieselsäure eine verbesserte Wirksamkeit. Dies ist insbesondere dann der Fall, wenn man zusätzlich ein kationisches Fixiermittel einsetzt. Der in der Beschreibungseinleitung angegebene Stand der Technik verdeutlicht dies.In addition to the cationic polyacrylamides, anionic ones can also be used Polyacrylamides, for example acrylic acid or methacrylic acid polymerized contain, as well as amphoteric polyacrylamides Drainage aids, retention aids and flocculants deploy. Cationic, nonionic, amphoteric or anionic Polymers used as drainage aids, retention aids and Flocculants are used, for example, in Combination with bentonite and / or colloidal silica improved effectiveness. This is particularly the case if you also use a cationic fixative. The State of the art specified in the introduction to the description clarifies this.

Als Prozeßhilfsmittel werden außerdem beispielsweise wasserlösliche Polymere eingesetzt, die ausgewählt sind unter Polyethyleniminen, Umsetzungsprodukten von Polyethyleniminen mit mindestens bifunktionellen Vernetzern, anionischen Polyacrylamiden, kationischen Polyacrylamiden, amphoteren Polyacrylamiden, Reaktionsprodukten aus mit Ethylenimin gepfropften Polyamidoaminen mit mindestens zwei funktionelle Gruppen aufweisenden Vernetzern, Vinylformamid-Einheiten und/oder Vinylamin-Einheiten enthaltenden Polymeren und Poly(diallyldimethylammoniumhalogeniden). Die oben genannten Klassen von Verbindungen sind bekannt. Polyethylenimine werden beispielsweise durch Polymerisieren von Ethylenimin in wäßrigem Medium in Gegenwart von Spuren an Säuren oder Säuren abspaltenden Verbindungen hergestellt. Außerdem eignen sich wasserlösliche, Aminogruppen enthaltende polymere Reaktionsprodukte, die erhältlich sind durch Umsetzung von Michaeladditionsprodukten aus Polyalkylenpolyaminen, Polyamidoaminen, mit Ethylenimin gepfropften Polyamidoaminen sowie Mischungen der genannten Verbindungen und monoethylenisch ungesättigten Carbonsäuren, Salzen, Estern, Amiden oder Nitrilen mit mindestens bifunktionellen Vernetzern. Solche Reaktionsprodukte sind beispielsweise aus der WO-A-94/14873 bekannt. Zu ihrer Herstellung kommen außer halogenhaltigen Vernetzern besonders halogenfreie Vernetzer in Betracht, wie Glycidylether von Polyalkylenglykolen.Water-soluble, for example, are also used as process aids Polymers used which are selected from polyethyleneimines, Reaction products of polyethyleneimines with at least bifunctional crosslinkers, anionic polyacrylamides, cationic Polyacrylamides, amphoteric polyacrylamides, reaction products from polyamidoamines grafted with ethyleneimine at least two crosslinkers containing functional groups, vinylformamide units and / or containing vinylamine units Polymers and poly (diallyldimethylammonium halides). The above classes of compounds mentioned are known. Polyethyleneimines are, for example, by polymerizing ethyleneimine in aqueous medium in the presence of traces of acids or acids Connections established. In addition, water-soluble, Polymeric reaction products containing amino groups, which are available through the implementation of Michael addition products from polyalkylene polyamines, polyamidoamines, with ethyleneimine grafted polyamidoamines and mixtures of the above Compounds and monoethylenically unsaturated carboxylic acids, salts, Esters, amides or nitriles with at least bifunctional ones Networkers. Such reaction products are, for example, from the WO-A-94/14873 known. To make them come out halogen - containing crosslinkers especially halogen - free crosslinkers in Consider how glycidyl ethers of polyalkylene glycols.

Eine weitere Klasse von Ethylenimin-Einheiten enthaltenden Polymeren ist aus der WO-A-94/12560 bekannt. Es handelt sich hierbei um wasserlösliche, vernetzte, teilweise amidierte Polyethylenimine, die erhältlich sind durch

  • Reaktion von Polyethyleniminen mit einbasischen Carbonsäuren oder ihren Estern, Anhydriden, Säurechloriden oder Säureamiden unter Amidbildung und
  • Umsetzung der amidierten Polyethylenimine mit mindestens zwei funktionelle Gruppen enthaltenden Vernetzern.
Another class of polymers containing ethyleneimine units is known from WO-A-94/12560. These are water-soluble, crosslinked, partially amidated polyethyleneimines, which are obtainable from
  • Reaction of polyethyleneimines with monobasic carboxylic acids or their esters, anhydrides, acid chlorides or acid amides with the formation of amides and
  • Reaction of the amidated polyethyleneimines with at least two functional groups containing crosslinkers.

Die einbasischen Carbonsäuren haben beispielsweise 1 bis 28, vorzugsweise 8 bis 18 C-Atome und können gegebenenfalls eine oder mehrere ethylenische Doppelbindungen enthalten, z.B. Ölsäure oder Linolensäure. Zur Herstellung dieser modifizierten Polyethylenimine können die Molmassen der in Betracht kommenden Polyethylenimine bis zu 2 Mio. betragen und liegen vorzugsweise in dem Bereich von 1000 bis 50000. Die Polyethylenimine werden partiell mit einbasischen Carbonsäuren amidiert, so daß beispielsweise 0,1 bis 90, vorzugsweise 1 bis 50 % der amidierbaren Stickstoffatome in den Polyethyleniminen als Amidgruppe vorliegt. Geeignete, mindestens zwei funktionelle Doppelbindungen enthaltende Vernetzer sind oben genannt. Vorzugsweise werden halogenfreie Vernetzer eingesetzt.The monobasic carboxylic acids have, for example, 1 to 28, preferably 8 to 18 carbon atoms and can optionally have one or contain several ethylenic double bonds, e.g. Oleic acid or Linolenic acid. For the production of these modified polyethyleneimines can the molecular weights of the polyethyleneimines in question up to 2 million and are preferably in the range from 1000 to 50000. The polyethyleneimines become partial amidated with monobasic carboxylic acids, so that, for example, 0.1 to 90, preferably 1 to 50% of the amidatable nitrogen atoms is present as an amide group in the polyethyleneimines. Suitable, at least crosslinkers containing two functional double bonds are mentioned above. Halogen-free crosslinkers are preferred used.

Bei der Reaktion von Aminogruppen enthaltenden Verbindungen mit Vernetzern setzt man beispielsweise auf 1 Gewichtsteil einer Aminogruppen enthaltenden Verbindung 0,001 bis 10, vorzugsweise 0,01 bis 3 Gewichtsteile mindestens eines Vernetzers ein.In the reaction of compounds containing amino groups with Crosslinkers are, for example, based on 1 part by weight of one Compound containing amino groups 0.001 to 10, preferably 0.01 to 3 parts by weight of at least one crosslinker.

Andere Aminogruppen enthaltende Additionsprodukte sind quaternisierte Polyethylenimine. Es kommen hierfür z.B. sowohl Homopolymerisate von Ethylenimin als auch Polymere in Betracht, die beispielsweise Ethylenimin aufgepfropft enthalten. Die so erhältlichen Polyethylenimine haben eine breite Molmassenverteilung und Molmassen von beispielsweise 129 bis 2·106, vorzugsweise 430 bis 1·106.Other addition products containing amino groups are quaternized polyethyleneimines. Both homopolymers of ethyleneimine and polymers which contain, for example, ethyleneimine grafted on are suitable for this purpose. The polyethyleneimines obtainable in this way have a broad molar mass distribution and molar masses of, for example, 129 to 2 · 10 6 , preferably 430 to 1 · 10 6 .

Die Polyethylenimine und die quaternisierten Polyethylenimine können gegebenenfalls mit einem mindestens zwei funktionelle Gruppen enthaltenden Vernetzer umgesetzt sein. Die Quaternisierung der Polyethylenimine kann beispielsweise mit Alkylhalogeniden wie Methylchlorid, Ethylchlorid, Hexylchlorid, Benzylchlorid oder Laurylchlorid sowie mit beispielsweise Dimethylsulfat vorgenommen werden. Weitere geeignete Aminogruppen enthaltende Polymere sind phosphonomethylierte Polyethylenimine und alkoxylierte Polyethylenimine, die beispielsweise durch Umsetzung von Polyethylenimin mit Ethylenoxid und/oder Propylenoxid erhältlich sind. Die phosphonomethylierten und die alkoxylierten Polyethylenimine können gegebenenfalls mit einem mindestens zwei funktionelle Gruppen enthaltenden Vernetzer umgesetzt sein. Die alkoxylierten Polyethylenimine enthalten pro NH-Gruppe 1 bis 100, vorzugsweise 2 bis 20 Alkylenoxid-Einheiten. Die Molmasse der Polyethylenimine kann bis zu 2 Millionen betragen. Vorzugsweise verwendet man für die Alkoxylierung Polyethylenimine mit Molmassen von 1000 bis 50000. Weitere geeignete wasserlösliche Retentionsmittel bzw. Fixiermittel sind Umsetzungsprodukte von Polyethyleniminen mit Diketenen, z.B. von Polyethyleniminen einer Molmasse von 1000 bis 50000 mit Distearyldiketen. Auch solche Produkte können gegebenenfalls mit einem mindestens zwei funktionelle Gruppen enthaltenden Vernetzer umgesetzt sein.The polyethyleneimines and the quaternized polyethyleneimines can optionally with at least two functional Crosslinkers containing groups can be implemented. The quaternization the polyethyleneimines can, for example, with alkyl halides such as methyl chloride, ethyl chloride, hexyl chloride, Benzyl chloride or lauryl chloride and with, for example Dimethyl sulfate can be made. Other suitable amino groups containing polymers are phosphonomethylated polyethyleneimines and alkoxylated polyethyleneimines, for example by reaction of polyethyleneimine with ethylene oxide and / or propylene oxide are available. The phosphonomethylated and the alkoxylated Polyethyleneimines can optionally be combined with at least two crosslinkers containing functional groups. The alkoxylated polyethyleneimines contain 1 to 100 per NH group, preferably 2 to 20 alkylene oxide units. The molecular weight of the Polyethyleneimines can be up to 2 million. Preferably polyethyleneimines with molar masses are used for the alkoxylation from 1000 to 50000. Other suitable water-soluble retention agents or fixatives are reaction products of Polyethyleneimines with diketenes, e.g. of polyethyleneimines one Molar mass from 1000 to 50000 with distearyl diketene. Even those Products can optionally be functional with at least two Crosslinkers containing groups can be implemented.

Reaktionsprodukte aus mit Ethylenimin gepfropften Polyamidoaminen mit mindestens zwei funktionelle Gruppen aufweisenden Vernetzern sind aus der DE-B-2 434 816 bekannt. Als Vernetzer kommen beispielsweise α,ω-Bis(chlorhydrin)ether von Polyalkylenoxiden mit 1 bis 100 Alkylenoxid-Einheiten in Betracht. Die dabei entstehenden Harze haben - gemessen bei 20°C in 20 gew.-%iger wäßriger Lösung - eine Viskosität von mehr als 300 mPas. Weitere Prozeßchemikalien für die Papierherstellung sind Reaktionsprodukte von Polyalkylenpolyaminen, Dimethylamin, Diethylamin oder Ethylendiamin mit Epichlorhydrin oder Dichlorethan oder anderen mindestens bifunktionellen Vernetzern. Reaktionsprodukte dieser Art sind beispielsweise aus der EP-A-0 411 400 und der DE-A-2 162 567 bekannt.Reaction products from polyamidoamines grafted with ethyleneimine with at least two crosslinkers having functional groups are known from DE-B-2 434 816. Come as a crosslinker for example α, ω-bis (chlorohydrin) ether of polyalkylene oxides with 1 to 100 alkylene oxide units into consideration. The resulting Resins have - measured at 20 ° C in 20 wt .-% aqueous Solution - a viscosity of more than 300 mPas. Other process chemicals are reaction products for papermaking of polyalkylene polyamines, dimethylamine, diethylamine or Ethylenediamine with epichlorohydrin or dichloroethane or others at least bifunctional crosslinkers. Reaction products of this Art are for example from EP-A-0 411 400 and DE-A-2 162 567 known.

Bevorzugt setzt man als Entwässerungshilfsmittel, Retentions- und Flockungsmittel wasserlösliche kationische Polyacrylamide mit einer mittleren Molmasse Mw von mindestens 500000 und/oder die wasserlöslichen Reaktionsprodukte ein, die durch Umsetzung von Polyamidoaminen, die mit Ethylenimin gepfropft sind, mit mindestens bifunktionellen Vernetzern erhältlich sind. Ein weiteres bevorzugtes Retentionssystem besteht aus Kombinationen aus kationischen synthetischen Polymeren und/oder kationischer Stärke mit feinteiligen organischen oder anorganischen Feststoffen. Solche Systeme sind in dem eingangs beschriebenen Stand der Technik angegeben sowie in den Literaturstellen EP-B-0 041 056, EP-B-0 080 986 und EP-B-0 218 674. Für dieses Retentionsmittel-System kommen als feinteilige anorganische Feststoffe beispielsweise Bentonit, kolloidale Kieselsäure, microkristallines Talkum, präzipitiertes Kalziumcarbonat, präzipitierter Gips und/oder calcinierter Clay in Betracht. Die Menge an feinteiligen Feststoffen beträgt beispielsweise 0,01 bis 2,0 Gew.-%, bezogen auf trockenes Papier. Besonders bevorzugt ist die Verwendung der oben genannten Retentionsmittelsysteme aus kationischen synthetischen Retentionsmitteln und/oder kationischer Stärke in Kombination mit Bentonit, der gegebenenfalls alkalisch oder sauer aktiviert sein kann oder kolloidaler Kieselsäure. Bentonit und Kieselsäure sowie die anderen in Betracht kommenden feinteiligen anorganischen Stoffe werden vorzugsweise in Mengen von 0,02 bis 0,5 Gew.-%, bezogen auf trockenes Papier, eingesetzt. Die anorganischen feinteiligen Feststoffe haben beispielsweise eine innere Oberfläche von 5 bis 1000 m2/g (bestimmt nach BET mit Stickstoff). Außer den genannten anorganischen Teilchen können feinteilige organische Teilchen in Betracht kommen, beispielsweise vernetzte Polyacrylsäure oder modifiziertes Ligninsulfonat. Auch die feinteiligen organischen Feststoffe bewirken eine Erhöhung der Retention. Ein solches System ist beispielsweise aus der WO-A-96/26220 für die Kombination von kationisch modifizierten Cellulosepartikeln mit Polyacrylamiden bekannt. Auch die anderen oben genannten Retentions- und Flockungsmittel können mit diesen Cellulosepartikeln zu einem wirksamen Retentionsmittelsystem kombiniert werden. Die Teilchengröße der anorganischen und organischen Feststoffe liegt bei der Anwendung, d.h. beim Einbringen in das wäßrige Medium in dem Bereich von beispielsweise 10 nm bis 10 µm.Preference is given to using water-soluble cationic polyacrylamides with an average molecular weight M w of at least 500,000 and / or the water-soluble reaction products which can be obtained by reacting polyamidoamines grafted with ethyleneimine with at least bifunctional crosslinking agents as drainage aids, retention aids and flocculants. Another preferred retention system consists of combinations of cationic synthetic polymers and / or cationic starch with finely divided organic or inorganic solids. Such systems are specified in the prior art described at the outset and in references EP-B-0 041 056, EP-B-0 080 986 and EP-B-0 218 674. Fine-particle inorganic solids, for example, come for this retention agent system Bentonite, colloidal silica, microcrystalline talc, precipitated calcium carbonate, precipitated gypsum and / or calcined clay. The amount of finely divided solids is, for example, 0.01 to 2.0% by weight, based on dry paper. It is particularly preferred to use the above-mentioned retention agent systems composed of cationic synthetic retention agents and / or cationic starch in combination with bentonite, which can optionally be activated in an alkaline or acidic manner or colloidal silica. Bentonite and silica, as well as the other finely divided inorganic substances that are considered, are preferably used in amounts of 0.02 to 0.5% by weight, based on dry paper. The inorganic, finely divided solids, for example, have an inner surface area of 5 to 1000 m 2 / g (determined according to BET with nitrogen). In addition to the inorganic particles mentioned, finely divided organic particles can be considered, for example crosslinked polyacrylic acid or modified lignin sulfonate. The finely divided organic solids also increase retention. Such a system is known for example from WO-A-96/26220 for the combination of cationically modified cellulose particles with polyacrylamides. The other retention and flocculation agents mentioned above can also be combined with these cellulose particles to form an effective retention agent system. The particle size of the inorganic and organic solids in the application, ie when introduced into the aqueous medium, is in the range, for example, from 10 nm to 10 μm.

Besonders bevorzugt ist eine Verfahrensweise, bei der man zusätzlich ein kationisches Fixiermittel in den dafür üblichen Mengen einsetzt.A procedure in which one additionally a cationic fixative in the usual amounts starts.

Nach dem erfindungsgemäßen Verfahren können sämtliche Papierqualitäten, Pappe und Karton hergestellt werden, beispielsweise Papiere für den Zeitungsdruck, sogenannte mittelfeine Schreib- und Druckpapiere, Naturtiefdruckpapiere und auch leichtgewichtige Streichrohpapiere. Man kann beispielsweise Holzschliff, thermomechanischen Stoff (TMP), chemo-thermomechanischen Stoff (CTMP), Druckschliff (PGW) sowie Sulfit- und Sulfatzellstoff einsetzen. Als Rohstoffe für die Herstellung der Pulpe kommen auch Zellstoff und Holzstoff in Betracht. Diese Stoffe werden vor allem in den sogenannten integrierten Fabriken in mehr oder weniger feuchter Form direkt ohne vorherige Eindickung bzw. Trocknung weiter zu Papier verarbeitet. Aufgrund der nicht vollständig daraus entfernten Verunreinigungen enthalten diese Fasermaterialien noch Stoffe, die den üblichen Papierherstellprozeß stark stören. Nach dem erfindungsgemäßen Verfahren können jedoch auch Störstoffe enthaltende Pulpen ohne weiteres verarbeitet werden.All paper grades, Cardboard and cardboard are made, for example Papers for newspaper printing, so-called medium-fine writing and printing papers, gravure papers and also lightweight Coating base papers. One can, for example, ground wood, thermomechanical Fabric (TMP), chemo-thermomechanical fabric (CTMP), Use pressure grinding (PGW) as well as sulfite and sulfate pulp. Pulp also comes as raw materials for the production of the pulp and wood pulp into consideration. These substances are mainly used in the so-called integrated factories in more or less humid Form directly without further thickening or drying Paper processed. Because of the not completely removed from it These fiber materials still contain impurities Fabrics that severely disrupt the usual paper manufacturing process. To However, the method according to the invention can also contain contaminants containing pulps can be processed easily.

Nach dem erfindungsgemäßen Verfahren können sowohl füllstofffreie als auch füllstoffhaltige Papiere hergestellt werden. Der Füllstoffgehalt in Papier kann bis zu maximal 40 Gew.-% betragen und liegt vorzugsweise in dem Bereich von 5 bis 25 Gew.-%. Geeignete Füllstoffe sind beispielsweise Clay, Kaolin, native und präzipitierte Kreide, Titandioxid, Talkum, Kalziumsulfat, Bariumsulfat, Aluminiumoxid, Satinweiß oder Mischungen der genannten Füllstoffe.According to the method of the invention, both filler-free as well as filler-containing papers. The Filler content in paper can be up to a maximum of 40% by weight and is preferably in the range of 5 to 25% by weight. Suitable Fillers are, for example, clay, kaolin, native and precipitated Chalk, titanium dioxide, talc, calcium sulfate, barium sulfate, Alumina, satin white or mixtures of the above Fillers.

Die Stoffdichte der Pulpe beträgt beispielsweise 0,1 bis 15 Gew.-%. Man gibt z.B. zunächst mindestens ein kationisches Polymer als Fixiermittel zur Faserstoffaufschlämmung und setzt danach mindestens ein kationisches Polymer, das als Retentionsmittel wirkt, zu. Dieser Zusatz bewirkt eine starke Flockung des Papierstoffs. In mindestens einer anschließenden Scherstufe, die z. B. in einem oder mehreren Reinigungs-, Misch- und Pumpstufen bzw. einem Pulper, Sichter oder auch in einem Refiner oder Sieb bestehen können, durch die der vorgeflockte Papierstoff durchgeleitet wird, werden die in dem geflockten System vorliegenden sogenannten "harten Riesenflocken" zerstört. Vorzugsweise im Anschluß an die Scherstufe setzt man Bentonit, kolloidale Kieselsäure oder calcinierten Clay zu, wodurch sogenannte weiche Mikroflocken gebildet werden. Die Mengen an Bentonit, kolloidaler Kieselsäure bzw. calciniertem Clay betragen 0,01 bis 2, vorzugsweise 0,02 bis 0,5 Gew.-%, bezogen auf trockenen Papierstoff. Bentonit ist ein Aluminiumschichtsilikat auf Basis Montmorillonit, der in der Natur vorkommt. Er wird meistens nach einem Ersatz der Kalziumionen durch Natriumionen eingesetzt. Beispielsweise behandelt man Bentonit in wäßriger Aufschlämmung mit Natronlauge. Er wird dadurch voll in Wasser quellbar und bildet hochviskose thixotrope Gelstrukturen. Der Plättchendurchmesser des Bentonits beträgt beispielsweise 1 bis 2 µm, die Plättchendicke ca. 1 nm (10 Å). Je nach Typ und Aktivierung hat der Bentonit eine spezifische Oberfläche von 60 bis 800 m2/g. Aufgrund der großen inneren Oberfläche und der nach außenhin negativen Überschußladungen an der Oberfläche kann man solche anorganischen Polyanionen für adsorptive Sammeleffekte von kationisch umgeladenen und einer Scherbehandlung unterworfenen Papierstoffen verwenden. Man erreicht dadurch eine optimale Flockung im Papierstoff.The consistency of the pulp is, for example, 0.1 to 15% by weight. For example, at least one cationic polymer is first added as a fixing agent to the fiber slurry and then at least one cationic polymer which acts as a retention agent is added. This addition causes a strong flocculation of the paper stock. In at least one subsequent shear step, the z. B. in one or more cleaning, mixing and pumping stages or a pulper, classifier or also in a refiner or sieve through which the pre-flocked paper stock is passed, the so-called "hard giant flakes" present in the flocked system are destroyed . Bentonite, colloidal silica or calcined clay are preferably added after the shear stage, so-called soft microflakes are formed. The amounts of bentonite, colloidal silica or calcined clay are 0.01 to 2, preferably 0.02 to 0.5% by weight, based on dry paper stock. Bentonite is a layered aluminum silicate based on montmorillonite that occurs naturally. It is mostly used after the calcium ions have been replaced by sodium ions. For example, bentonite in an aqueous slurry is treated with sodium hydroxide solution. This makes it fully swellable in water and forms highly viscous thixotropic gel structures. The platelet diameter of the bentonite is, for example, 1 to 2 μm, the platelet thickness is approximately 1 nm (10 Å). Depending on the type and activation, the bentonite has a specific surface area of 60 to 800 m 2 / g. Due to the large inner surface and the outwardly negative excess charges on the surface, such inorganic polyanions can be used for adsorptive collection effects of cationically charged and sheared paper materials. This results in optimal flocculation in the paper stock.

Aufgrund der oben angegebenen Aufteilung des Stoffauflaufs in einen Haupt- und einen Verdünnungsstrom dosiert man mindestens 5 Gew.-% der Prozeßchemikalien in den Verdünnungsstrom. Bei Retentionsmittelsystemen aus kationischen Polymeren und feinteiligen Feststoffen kann man z.B. vorzugsweise die kationischen Polymeren vollständig dem Hauptstrom und die feinteiligen Feststoffe ausschließlich dem aus Siebwasser bestehenden Verdünnungsstrom zusetzen. Man kann jedoch auch z.B. 60 bis 95 Gew.-% dieses Retentionsmittelsystems dem Hauptstrom in üblicher Weise zufügen und den Rest der Mischung über das Siebwasser dosieren. Besonders bewährt hat sich eine Arbeitsweise, bei der man Entschäumer in den Verdünnungsstrom einbringt.Due to the division of the headbox into a main and a dilution stream are dosed at least 5% by weight of the process chemicals in the dilution stream. With retention aid systems made of cationic polymers and fine particles Solids can e.g. preferably the cationic Polymers completely the main stream and the finely divided solids only the dilution stream consisting of white water clog. However, one can also e.g. 60 to 95% by weight of this Add the retention aid system to the main stream in the usual way and dose the rest of the mixture over the white water. Especially A method of working in which defoamers in introduces the dilution stream.

Farbstoffe, Masseleimungsmittel (insbesondere Alkyldiketen-Dispersionen, Harzleim, Alkenylsuccinimid-Dispersionen oder leimend wirkende Polymerdispersionen) sowie Verfestigungsmittel (z.B. mit Epichlorhydrin vernetzte Polyamidoamine) können gegebenenfalls ausschließlich über den Verdünnungsstrom in den Stoffauflauf dosiert werden. Vorzugsweise werden 5 bis 40 Gew.-% der Prozeßchemikalien in den Verdünnungsstrom eingebracht.Dyes, mass sizing agents (especially alkyldiketene dispersions, Resin glue, alkenyl succinimide dispersions or glue polymer dispersions) and solidifying agents (e.g. with Epichlorohydrin crosslinked polyamidoamines) can optionally dosed exclusively into the headbox via the dilution stream become. Preferably 5 to 40 wt .-% of the process chemicals introduced into the dilution stream.

Falls nicht anders angegeben, bedeuten die Angaben in Prozent Gew.-Prozent, die Teile sind Gewichtsteile. Die Molmassen wurden durch Lichtstreuung bestimmt.Unless stated otherwise, the figures mean in percent Percent by weight, the parts are parts by weight. The molecular weights were determined by light scattering.

BeispieleExamples Polymer 1Polymer 1

Nach der in der DE-B-2 434 816, Beispiel 3, angegebenen Vorschrift wird durch Kondensieren von Adipinsäure mit Diethylentriamin ein Polyamidoamin hergestellt und anschließend in wäßriger Lösung mit soviel Ethylenimin gepfropft, daß das Polyamidoamin pro basischer Stickstoffgruppierung 6,7 Ethylenimin-Einheiten aufgepfropft enthält. Eine 10 %ige wäßrige Lösung des Polymeren hat eine Viskosität von 22 mPas.According to the instructions given in DE-B-2 434 816, Example 3 is made by condensing adipic acid with diethylenetriamine prepared a polyamidoamine and then in aqueous Grafted solution with so much ethyleneimine that the polyamidoamine per basic nitrogen grouping 6.7 ethyleneimine units grafted contains. A 10% aqueous solution of the polymer has a viscosity of 22 mPas.

Das mit Ethylenimin gepfropfte Polyamidoamin wird anschließend durch Umsetzung mit einem Bis-Glycidylether eines Polyethylenglykols der mittleren Molmasse von 2000 gemäß den Angaben in Beispiel 3 der DE-B-2 434 816 vernetzt. Man erhält ein Ethylenimin-Einheiten enthaltendes Polymer mit einer Viskosität von 120 mPas (bestimmt in 10 %iger wäßriger Lösung bei 20°C und pH 10). Die Konzentration der wäßrigen Lösung beträgt 12,5 %, der pH-Wert liegt bei 10. The polyamidoamine grafted with ethyleneimine is then by reaction with a bis-glycidyl ether of a polyethylene glycol the average molecular weight of 2000 according to the information in Example 3 of DE-B-2 434 816 networked. An ethyleneimine unit is obtained containing polymer with a viscosity of 120 mPas (determined in 10% aqueous solution at 20 ° C and pH 10). The Concentration of the aqueous solution is 12.5%, the pH is 10.

Polymer 2Polymer 2

Kationisches Copolymerisat aus Acrylamid und Dimethylaminoethylacrylat, das mit Methylchlorid quaternisiert ist mit einem Gehalt von Acrylamid von 84 Mol-% und einer Molmasse von ca. 10 Mio. Die Ladungsdichte des Copolymerisats beträgt 1,7 mEq/g bei pH 4,5.Cationic copolymer of acrylamide and dimethylaminoethyl acrylate, that is quaternized with methyl chloride with a content of acrylamide of 84 mol% and a molar mass of approximately 10 million Charge density of the copolymer is 1.7 mEq / g at pH 4.5.

Polymer 3Polymer 3

Vernetztes Polyethylenimin mit einer mittleren Molmasse Mw von 1,4 Millionen und einer Ladungsdichte von 20,4 mEq/g (gemessen bei pH 4,5).Crosslinked polyethyleneimine with an average molecular weight Mw of 1.4 million and a charge density of 20.4 mEq / g (measured at pH 4.5).

Polymer 4Polymer 4

Vernetztes Polyethylenimin mit einer mittleren Molmasse von 1 Million und einer Ladungsdichte von 14,7 mEq/g (gemessen bei pH 4,5).Crosslinked polyethyleneimine with an average molecular weight of 1 million and a charge density of 14.7 mEq / g (measured at pH 4.5).

Beispiel 1example 1

Zur Herstellung von SC-Papier (superkalandriertem Papier) ging man von einer Stoffzusammensetzung aus, die 35 Teile Holzschliff, 17 Teile deinktes Altpapier, 19 Teile Langfaser-Sulfatzellstoff, 25 Teile Ausschuß und 25 Teile Clay enthielt. Dieser Papierstoff wurde auf einer SC-Papiermaschine, die mit einem Module-Jet-Stoffauflauf der Fa. Voith-Sulzer ausgerüstet war, verarbeitet. In den Hauptstrom des Papierstoffs dosierte man vor den Vertikalsortierer 0,29 % Polymer 1 und nach dem Vertikalsortierer 0,024 % Polymer 2. Über den Module-Jet-Stoffauflauf wurde dem Papiermaschinensieb ein Verdünnungsstrom aus Siebwasser zugeführt, zu dem man 0,03 % Polymer 1, bezogen auf trockenes Papier, dosierte. Das Volumenverhältnis von Hauptstrom zu Verdünnungsstrom betrug 9 : 1. Die Ascheretention betrug 29,5 %, die Faser- und Feinstoffretention 62,4 %. Das Papier enthält die Fein- und Füllstoffe in qualitativ sehr gut gebundener Form und hat ein sehr gutes Formationsquerprofil und eine hervorragende Ascheverteilung.It went to the production of SC paper (super calendered paper) one starts from a material composition that contains 35 parts of wood pulp, 17 parts deinked waste paper, 19 parts long fiber sulfate pulp, Contained 25 parts scrap and 25 parts clay. This paper stock was on an SC paper machine with a module jet headbox from Voith-Sulzer was processed. The main stream of paper stock was metered in front of the vertical sorter 0.29% polymer 1 and after the vertical sorter 0.024% Polymer 2. Over the module jet headbox was the paper machine screen a dilution stream of white water is supplied to which 0.03% of polymer 1, based on dry paper, was metered in. The Volume ratio of main stream to dilution stream was 9: 1. The ash retention was 29.5%, the fiber and fines retention 62.4%. The paper contains the fine and fillers in a very well bound form and has a very good formation cross profile and excellent ash distribution.

Vergleichsbeispiel 1Comparative Example 1

Beispiel 1 wurde mit der Ausnahme wiederholt, daß man den oben beschriebenen Papierstoff der SC-Papiermaschine in einem einzigen Strom ohne Module-Jet-System mit den angegebenen Prozeßhilfsmitteln zuführte und entwässerte. Die Ascheretention betrug 27,8 %, die Faser- und Feinstoffretention 60,3 %. Example 1 was repeated with the exception that the above described paper stock of the SC paper machine in a single Electricity without a module jet system with the specified process aids fed and drained. The ash retention was 27.8%, fiber and fines retention 60.3%.

Beispiel 2Example 2

Beispiel 1 wurde mit der einzigen Ausnahme wiederholt, daß man in den Verdünnungsstrom anstelle von Polymer 1 jetzt 0,38 % Polymer 4 dosierte. Die Ascheretention betrug 33,6 %, die Faser- und Feinstoffretention 63,6 %. Das Papier weist ein ausgezeichnetes gleichmäßiges Formationsquerprofil auf.Example 1 was repeated with the only exception that in the dilution stream instead of polymer 1 now 0.38% polymer 4 dosed. The ash retention was 33.6%, the fiber and Fineness retention 63.6%. The paper exhibits an excellent uniform formation cross profile.

Beispiel 3Example 3

Eine Stoffzusammensetzung aus 40 Teilen Holzschliff, 40 Teilen gebleichtem Kiefernsulfatzellstoff und 20 Teilen gestrichenem Ausschuß wurde auf einer Papiermaschine für holzhaltige Streichrohpapiere zu Papier verarbeitet. Die Papiermaschine war mit einer Dilution Head Box der Fa. Valmet ausgerüstet. Mit Hilfe dieser Vorrichtung konnte dem Stoffauflauf ein aus Siebwasser bestehender Verdünnungsstrom zugeführt werden. Das Verhältnis von Hauptstrom zu Verdünnungsstrom betrug 9 : 1. Man dosierte 0,05 % Polymer 2, bezogen auf trockenes Papier, in den Hauptstrom vor den Vertikalsortierer. In den Verdünnungsstrom gab man jeweils vor den Vertikalsortierer 0,03 % Polymer 3, bezogen auf trockenes Papier, und 0,1 % Bentonit, ebenfalls bezogen auf trokkenes Papier. Die Ascheretention betrug 30,5 %, die Faser- und Feinstoffretention 69,5 %. Das Papier hatte ein gleichmäßiges Formationsquerprofil.A fabric composition of 40 parts wood pulp, 40 parts bleached pine sulfate pulp and 20 parts coated Committee was on a paper machine for wood-containing coating base papers processed into paper. The paper machine was with a Dilution Head Box from Valmet. With help this device could make the headbox an existing of white water Dilution stream are supplied. The ratio of Main stream to dilution stream was 9: 1 0.05% polymer 2, based on dry paper, in the main stream in front of the vertical sorter. The dilution stream was added in each case in front of the vertical sorter 0.03% polymer 3, based on dry paper, and 0.1% bentonite, also based on dry Paper. The ash retention was 30.5%, the fiber and Fineness retention 69.5%. The paper was even Formation cross profile.

Vergleichsbeispiel 2Comparative Example 2

Beispiel 3 wurde anschließend ohne Dilution Head Box wiederholt. Dabei betrug die Ascheretention 26,8 % und die Faser- und Feinstoffretention 64,6 %.Example 3 was then repeated without a dilution head box. The ash retention was 26.8% and the fiber and fines retention 64.6%.

Beispiel 4Example 4

Beispiel 3 wurde mit den Ausnahmen wiederholt, daß man, jeweils bezogen auf trockenes Papier, in den Verdünnungsstrom der Dilution Head Box 0,02 % Polymer 2 vor den Vertikalsortierer und 0,1 % Bentonit nach dem Vertikalsortierer dosierte und in den Hauptstrom 0,04 % Polymer 2 vor dem Durchgang durch den Vertikalsortierer gab. Die Ascheretention betrug 30,1 %, die Faser- und Feinstoffretention 69,7 %. Das Papier wies eine hervorragende Ascheverteilung auf und hatte ein gleichmäßiges Formationsquerprofil. Example 3 was repeated with the exception that one, each based on dry paper, in the dilution stream of the dilution Head box 0.02% polymer 2 in front of the vertical sorter and 0.1% bentonite dosed after the vertical sorter and into the Main stream 0.04% polymer 2 before passing through the vertical sorter gave. The ash retention was 30.1%, the fiber and Fineness retention 69.7%. The paper showed an excellent Ash distribution and had a uniform formation cross profile.

Vergleichsbeispiel 3Comparative Example 3

Beispiel 4 wurde ohne Dilution Head Box Dosierung wiederholt. Dabei betrug die Ascheretention 25,7 % und die Faser- und Feinstoffretention 63,7 %.Example 4 was repeated without dilution head box dosing. Here the ash retention was 25.7% and the fiber and fines retention 63.7%.

Claims (12)

  1. A process for the production of paper by draining a paper stock containing process chemicals on a paper machine in which a main stream of the paper stock and a dilution stream consisting of white water and amounting to 5 - 35 % by volume of the total head box feed are fed via a head box to the paper machine wire, wherein at least 5 % by weight of the process chemicals are metered into the dilution stream.
  2. A process as claimed in claim 1, wherein the process chemicals used are fixing agents, drainage aids, retention aids, flocculants alone, as a mixture with one another or in combination with bentonite or colloidal silica, dyes, engine sizes, dye strength agents or wet strength agents.
  3. A process as claimed in claim 1 or 2, wherein the process chemicals used are cationic fixing agents, cationic drainage aids, cationic retention aid and cationic flocculants alone or as a mixture with one another.
  4. A process as claimed in any of claims 1 to 3, wherein cationic or anionic polymers which act as drainage aids, retention aids and flocculants are used in combination with bentonite or colloid silica.
  5. A process as claimed in claim 4, wherein a cationic fixing agent is additionally used.
  6. A process as claimed in any of claims 1 to 5, wherein the process chemicals used are water-soluble polymers which are selected from polyethyleneimines, reaction products of polyethyleneimines with at least bifunctional crosslinking agents, anionic polyacrylamides, cationic polyacrylamides, amphoteric polyacrylamides, reaction products of ethyleneimine-grafted polyamidoamines with crosslinking agents having at least two functional groups, polymers containing vinylformamide units or vinylamine units and poly(diallyldimethylammonium halides).
  7. A process as claimed in any of claims 1 to 6, wherein the cationic fixing agents used are polyethyleneimines, polymers containing vinylamine units or poly(diallyldimethylammonium chlorides) having a molecular mas Mw of in each case from 10.000 to 2 million.
  8. A process as claimed in any of claims 1 to 7, wherein the drainage aids, retention aids and flocculants used are water-soluble cationic polyacrylamides having an average molar mass Mw of at least 500.000 or the water-soluble reaction products which are obtainable by reacting polyamidoamines, which are grafted with ethyleneimine, with at least bifunctional crosslinking agents.
  9. A process as claimed in any of claims 1 to 8, wherein the process chemicals used are combinations of cationic polymers or cationic starch with finely divided organic or inorganic solids.
  10. A process as claimed in claim 9, wherein the finely divided inorganic filler used is bentonite, colloidal silica, microcrystalline talc, precipitated calcium carbonate, precipitated gypsum or calcined clay.
  11. A process as claimed in any of claims 1 to 10, wherein the amount of finely divided solids is from 0.01 to 2.0 % by weight, based on dry paper.
  12. A process as claimed in any of claims 1 to 11, wherein the paper stock contains at least one filler.
EP97952902A 1996-12-27 1997-12-09 Method for producing paper Expired - Lifetime EP0948677B1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19654390A DE19654390A1 (en) 1996-12-27 1996-12-27 Process for making paper
DE19654390 1996-12-27
PCT/EP1997/006857 WO1998029603A1 (en) 1996-12-27 1997-12-09 Method for producing paper

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EP0948677A1 EP0948677A1 (en) 1999-10-13
EP0948677B1 true EP0948677B1 (en) 2000-08-30

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JP (1) JP2001508137A (en)
AT (1) ATE195985T1 (en)
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DE (2) DE19654390A1 (en)
ES (1) ES2151296T3 (en)
PT (1) PT948677E (en)
WO (1) WO1998029603A1 (en)

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PT948677E (en) 2001-01-31
WO1998029603A1 (en) 1998-07-09
CA2256431A1 (en) 1998-07-09
ES2151296T3 (en) 2000-12-16
JP2001508137A (en) 2001-06-19
CA2256431C (en) 2005-11-08
DE59702299D1 (en) 2000-10-05
DE19654390A1 (en) 1998-07-02
US6083348A (en) 2000-07-04
EP0948677A1 (en) 1999-10-13
ATE195985T1 (en) 2000-09-15

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