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EP0948677A1 - Method for producing paper - Google Patents

Method for producing paper

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Publication number
EP0948677A1
EP0948677A1 EP97952902A EP97952902A EP0948677A1 EP 0948677 A1 EP0948677 A1 EP 0948677A1 EP 97952902 A EP97952902 A EP 97952902A EP 97952902 A EP97952902 A EP 97952902A EP 0948677 A1 EP0948677 A1 EP 0948677A1
Authority
EP
European Patent Office
Prior art keywords
cationic
paper
agents
retention
aids
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.)
Granted
Application number
EP97952902A
Other languages
German (de)
French (fr)
Other versions
EP0948677B1 (en
Inventor
Werner Auhorn
Dietmar MÖNCH
Rainer Dyllick-Brenzinger
Rainer Scholz
Rainer Blum
Hubert Meixner
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Publication of EP0948677A1 publication Critical patent/EP0948677A1/en
Application granted granted Critical
Publication of EP0948677B1 publication Critical patent/EP0948677B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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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 process for the production of paper by dewatering 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 are fed to the paper machine wire via a headbox, the proportion of which in the total headbox feed 5 to 35 vol. % is.
  • the paper machines usually only have a single stream for feeding the paper stock to the headbox.
  • the paper stock contains process chemicals such as fixatives, drainage aids, retention aids and flocculants, and optionally sizing agents, dry and wet strength agents, dyes and fillers.
  • the process chemicals can be metered into the paper stock by various methods described in the literature. For example, from Schublatt für Textilfabrikation, Volume 13, 493-502 (1979) the use of cationic polyelectrolytes in combination with bentonite is known, with bentonite first being added to the paper stock and then the cationic polyelectrolytes being added, the paper stock possibly being subjected to a shear rate can.
  • EP-B-0 235 893 it is known to first add a synthetic cationic polymer with a molecular weight of more than 500,000 to a paper stock, so that flakes are formed which are then comminuted into microflakes in a subsequent shearing step. Then bentonite is then added and the paper stock containing the processing aids is dewatered.
  • two different water-soluble, cationic polymers are added to the paper stock in succession.
  • a low-molecular cationic polymer is first metered in as a fixative.
  • the object of the invention is to provide a process for the production of paper, an increase in the retention, in particular the fiber and fine material retention and, if appropriate, the filler retention being achieved compared to the known processes, and at the same time obtaining papers with a uniform formation transverse profile .
  • the object is achieved according to the invention with a process for the production of paper by dewatering a process chemical and optionally filler-containing paper stock on a paper machine, in which a main stream of the paper stock and a dilution stream consisting of white water, the proportion of which in the total headbox feed, are fed to the paper machine screen via a headbox 5 to 35 vol .-% is, if one doses at least 5 wt .-% of the process chemicals in the dilution stream.
  • the papers produced in this way have a uniform formation cross profile and surprisingly contain a very good qualitative bond between the fine and fillers to the long fiber material, so that these papers practically do not dust or to a non-disturbing extent.
  • the contaminants mostly contained in the white water such as wood constituents, sticky contaminants from the paper line in recycled fibers or when using waste paper are almost quantitatively fixed to the paper stock and thereby rendered harmless for the paper manufacturing process and later paper recycling.
  • a headbox with a main and a dilution stream which is fed to the individual sections of the headbox via metering valves in order to set the stock density cross profile.
  • the dilution stream consists of white water. It is well known that white water contains fine substances and fiber fragments from the cellulose or wood pulp fibers used in paper production. These fines are usually difficult to get out of the cycle. If papers containing filler are produced, the white water contains at least twice as much filler as the main stream, based on the fiber.
  • the proportion of the dilution stream consisting of the white water in the total headbox feed is, for example, 5 to 35% by volume, preferably 7 to 15% by volume.
  • Suitable process chemicals are, for example, fixing agents, drainage aids, retention aids, flocculants alone, in a mixture with one another or in combination with bentonite and / or colloidal silica, dyes, bulk sizing agents, dry setting agents and / or wet setting agents.
  • Polymers such as polymers containing vinylamine units, for example, can simultaneously act as fixing agents, drainage aids, retention aids and as a flocculant, 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 fixatives are used to eliminate contaminants that interfere with the effectiveness of retention aids, wet and dry strength agents and bulk sizing agents. Such contaminants are, for example, lignosulfonates or Hu acids.
  • Cationic fixing agents which can be used are, for example, polyethyleneimines, polymers containing vinylamine units and / or poly (diallyldimethylammonium chlorides) with a molecular weight 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 in
  • 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 polymerized 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 polyacrylamides which contain, for example, copolymerized acrylic acid or methacrylic acid, and amphoteric polyacrylamides as drainage aids, retention aids and flocculants.
  • Cationic, nonionic, amphoteric or anionic polymers, which are used as drainage aids, retention aids and flocculants have an improved effectiveness, for example in combination with bentonite and / or colloidal silica. This is particularly the case if a cationic fixative is also used. This is illustrated by the prior art specified in the introduction to the description.
  • Process auxiliaries which are also used are, for example, water-soluble polymers which are selected from polyethylene iines, reaction products of polyethyleneimines with at least bifunctional crosslinkers, anionic polyacrylamides, cationic polyacrylamides, amphoteric polyacrylamides, reaction products from polyamidoamines grafted with ethyleneimine and with at least two functional groups having crosslinkers - nylformamide units and / or vinylamine unit-containing polymers and poly (diallyldimethylammonium halides).
  • polyethyleneimines are produced, for example, by polymerizing ethyleneimine in an aqueous medium in the presence of traces of acids or compounds which split off acids.
  • water-soluble polymeric reaction products containing amino groups which are obtainable by reacting Michael addition products of polyalkylene polyamines, polyamidoamines, polyamidoamines grafted with ethyleneimine and mixtures of the compounds mentioned and monoethylenically unsaturated carboxylic acids, salts, esters, amides or nitriles with at least bifunctional crosslinkers.
  • reaction products are, for example, from the WO-A-94/184743 known.
  • halogen-free crosslinkers such as glycidyl ethers of polyalkylene glycols, are particularly suitable for their preparation.
  • the monobasic carboxylic acids have, for example, 1 to 28, preferably 8 to 18, carbon atoms and can optionally contain one or more ethylenic double bonds, e.g. Oleic acid or linolenic acid.
  • the molar masses of the polyethyleneimines in question can be up to 2 million and are preferably in the range from 1000 to 50,000.
  • the polyethyleneimines are partially amidated with monobasic carboxylic acids, so that, for example, 0.1 to 90, preferably 1 up to 50% of the amidatable nitrogen atoms in the polyethyleneimines is present as an amide group.
  • Suitable crosslinkers containing at least two functional double bonds are mentioned above. Halogen-free crosslinkers are preferably used.
  • crosslinking agents for example, 0.001 to 10, preferably 0.01 to 3 parts by weight of at least one crosslinking agent are used per 1 part by weight of a compound containing amino groups.
  • 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 MO 6 .
  • the polyethyleneimines and the quaternized polyethyleneimines can optionally be reacted with a crosslinker containing at least two functional groups.
  • the quaternization of the polyethyleneimines can, for example, with alkyl halides such as methyl chloride, ethyl chloride, hexyl chloride, benzyl chloride or lauryl chloride and, for example, with dimethyl sulfate.
  • alkyl halides such as methyl chloride, ethyl chloride, hexyl chloride, benzyl chloride or lauryl chloride and, for example, with dimethyl sulfate.
  • Other suitable polymers containing amino groups are phosphonomethylated polyethyleneimines and alkoxylated polyethyleneimines, which are obtainable, for example, by reacting polyethyleneimine with ethylene oxide and / or propylene oxide.
  • the phosphonomethylated and the alkoxylated polyethyleneimines can optionally be reacted with a crosslinker containing at least two functional groups.
  • the alkoxylated polyethyleneimines contain 1 to 100, preferably 2 to 20, alkylene oxide units per NH group.
  • the molecular weight of the polyethyleneimines can be up to 2 million.
  • Polyethyleneimines with molar masses of 1000 to 50,000 are preferably used for the alkoxylation.
  • Other suitable water-soluble retention aids or fixatives are reaction products of
  • Polyethyleneimines with diketenes e.g. of polyethyleneimines with a molecular weight of 1,000 to 50,000 with distearyl diketene. Products of this type can also, if appropriate, be reacted with a crosslinker containing at least two functional groups.
  • Reaction products made from ethyleneimine-grafted polyamidoamines with at least two functional groups containing crosslinkers are known from DE-B-2 434 816.
  • Suitable crosslinkers are, for example, ⁇ , ⁇ -bis (chlorohydrin) ethers of polyalkylene oxides having 1 to 100 alkylene oxide units.
  • the resulting resins - measured at 20 ° C in 20 wt .-% aqueous solution - have a viscosity of more than 300 mPas.
  • Other process chemicals for papermaking are reaction products of polyalkylene polyamines, dimethylamine, diethylamine or ethylenediamine with epichlorohydrin or dichloroethane or other at least bifunctional crosslinkers. Reaction products of this type are known, for example, from EP-A-0 411 400 and DE-A-2 162 567.
  • the preferred drainage aids, retention aids and flocculants are 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 .
  • 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,
  • finely divided inorganic solids include such as 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 with / 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 ⁇ .
  • a procedure is particularly preferred in which a cationic fixing agent is additionally used in the amounts customary for this.
  • All paper grades, cardboard and cardboard can be produced by the process according to the invention, for example papers for newspaper printing, so-called medium-fine writing and printing papers, gravure printing papers and also lightweight coating base papers.
  • wood pulp, thermo-mechanical material (TMP), chemo-thermomechanical material (CTMP), pressure grinding (PGW) and sulphite and sulphate pulp can be used.
  • Pulp and wood pulp can also be used as raw materials for the production of the pulp.
  • these materials are further processed into paper in a more or less moist form without prior thickening or drying. Due to the impurities that have not been completely removed from them, these fiber materials still contain substances which severely disrupt the normal paper production process.
  • pulps containing interfering substances can also be easily processed in the method according to the invention.
  • filler-free and filler-containing papers can be produced by the process according to the invention.
  • the filler content in paper can be up to a maximum of 40% by weight and is preferably in the range from 5 to 25% by weight.
  • Suitable fillers are, for example, clay, kaolin, native and precipitated chalk, titanium dioxide, talc, calcium sulfate, barium sulfate, aluminum oxide, satin white or mixtures of the fillers mentioned.
  • the consistency of the pulp is, for example, 0.1 to
  • 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 stage, which, for. B. in one or more cleaning, mixing and pumping stages or a pulper, classifier or even 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 micro flakes 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 ⁇ , the platelet thickness is approximately 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 reloaded and sheared paper materials. This results in optimal flocculation in the paper stock.
  • the process chemicals are metered into the dilution stream.
  • retention aid systems made of cationic polymers and fine Partial solids
  • all of the cationic polymers can be added completely to the main stream and the finely divided solids can only be added to the dilution stream consisting of white water.
  • a method of working in which defoamers are introduced into the dilution stream has proven particularly useful.
  • Dyes, mass sizing agents (in particular alkyldiketene dispersions, resin glue, alkenylsuccinimide dispersions or glue-acting polymer dispersions) and solidifying agents (e.g. polyamidoamines crosslinked with epichlorohydrin) can optionally only be metered into the headbox via the dilution stream. Preferably 5 to 40% by weight of the process chemicals are introduced into the dilution stream.
  • Example 3 a polyamidoamine is prepared by condensing adipic acid with diethylenetriamine and then grafted in aqueous solution with sufficient ethyleneimine that the polyamidoamine per basic nitrogen grouping is 6.7 ethyleneimine. Contains units grafted on. A 10% aqueous solution of the polymer has a viscosity of 22 mPas.
  • the polyamidoamine grafted with ethyleneimine is then crosslinked by reaction with a bis-glycidyl ether of a polyethylene glycol having an average molecular weight of 2000 as described in Example 3 of DE-B-2 434 816.
  • a polymer containing ethyleneimine units and having a viscosity of 120 mPas (determined in a 10% strength aqueous solution at 20 ° C. and pH 10) is obtained.
  • the concentration of the aqueous solution is 12.5%
  • Cationic copolymer of acrylamide and dimethylaminoethyl acrylate which is quaternized with methyl chloride with a content 5 of acrylamide of 84 mol% and a molar mass of approx. 10 million.
  • the charge density of the copolymer is 1.7 meq / g at pH 4.5 .
  • Cross-linked 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 supercalendered paper
  • SC paper was based on a composition of materials comprising 35 parts of ground wood, 17 parts of deinked waste paper, 19 parts of long-fiber sulfate pulp,
  • 25 contained 25 parts scrap and 25 parts clay.
  • This paper stock was processed on an SC paper machine which was equipped with a module jet headbox from Voith-Sulzer. 0.29% of polymer 1 was metered into the main stream of paper stock before the vertical sorter and 0.024% after the vertical sorter
  • a dilution stream of white water was fed to the paper machine sieve via the module jet headbox, to which 0.03% polymer 1, based on dry paper, was metered.
  • the volume ratio of the main stream to the dilution stream was 9: 1.
  • the ash retention was 29.5%, the fiber and fine
  • the paper contains the fine and fillers in a very well bound form and has a very good formation cross profile and an excellent ash distribution.
  • Example 1 was repeated with the exception that the paper stock described above was fed and dewatered from the SC paper machine in a single stream without a module jet system using the process auxiliaries indicated.
  • the retention of ashes was 27.8%, the retention of fibers and fines 60.3%.
  • Example 2
  • Example 1 was repeated with the only exception that 0.38% of polymer 4 was now metered into the dilution stream instead of polymer 1. Ash retention was 33.6%, fiber and fines retention 63.6%. The paper has an excellent uniform formation cross profile.
  • a composition of 40 parts of wood pulp, 40 parts of bleached pine sulfate pulp and 20 parts of coated scrap was processed into paper on a paper machine for wood-containing coating base papers.
  • the paper machine was equipped with a Dilution Head Box from Valmet. With the help of this device, a dilution stream consisting of white water could be fed to the headbox.
  • the ratio of the main stream to the dilution stream was 9: 1.
  • 0.05% of polymer 2 based on dry paper, was metered into the main stream upstream of the vertical sorter.
  • 0.03% of polymer 3 based on dry paper, and 0.1% bentonite, also based on dry paper, were added to the dilution stream before the vertical sorter.
  • Ash retention was 30.5%, fiber and fines retention 69.5%.
  • the paper had a uniform 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 exceptions that, based in each case on dry paper, 0.02% polymer 2 was metered into the dilution stream of the dilution head box before the vertical sorter and 0.1% bentonite after the vertical sorter and 0.04 into the main stream % Polymer 2 before passing through the vertical sorter. Ash retention was 30.1%, fiber and fines retention 69.7%. The paper had an excellent ash distribution and an even formation cross profile. Comparative Example 3
  • Example 4 was repeated without dilution head box dosing.
  • 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

Verfahren zur Herstellung von PapierProcess for making paper
Beschreibungdescription
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 Verdünnungsström zuführt, dessen Anteil an der GesamtstoffauflaufZuführung 5 bis 35 Vol.-% beträgt .The invention relates to a process for the production of paper by dewatering 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 are fed to the paper machine wire via a headbox, the proportion of which 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 her- stellen. Die nach diesem Verfahren erhältlichen Papiere neigen jedoch zum Stauben.The method described above is known in the specialist literature under the module jet concept, cf. Das Papier, Issue 10A, Pages V 99-V 105 (1995) and Wochenblatt für Papierfabrikation, Volume 122, 485-491 (1994). With the help of this special headbox you can Manufacture highly filled, supercalendered papers (SC papers) with a uniform formation at a high level. However, the papers obtainable by this process tend to become dusty.
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 Poly- elektrolyten 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 a single stream 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 optionally sizing agents, dry and wet strength agents, dyes and fillers. The process chemicals can be metered into the paper stock by various methods described in the literature. For example, from Wochenblatt für Papierfabrikation, Volume 13, 493-502 (1979) the use of cationic polyelectrolytes in combination with bentonite is known, with bentonite first being added to the paper stock and then the cationic polyelectrolytes being added, the paper stock possibly being subjected to a shear rate can.
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 Fixier- mittel 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.From EP-B-0 235 893 it is known to first add a synthetic cationic polymer with a molecular weight of more than 500,000 to a paper stock, so that flakes are formed which are then comminuted into microflakes in a subsequent shearing step. Then bentonite is then added and the paper stock containing the processing aids is dewatered. In the process for producing paper known from EP-A-0 335 575, two different water-soluble, cationic polymers are added to the paper stock in succession. Here, a low-molecular cationic polymer is first metered in as a fixative. medium and then a high molecular weight cationic polymer as a flocculant, then subjects the paper stock to a shear step to form microflakes, adds bentonite and then dewatered it. However, the formation profile of the papers produced in this way is in need of improvement.
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 Füll- stoffretention erzielt und gleichzeitig Papiere mit einem gleichmäßigen Formationsquerprofil erhält.The object of the invention is to provide a process for the production of paper, an increase in the retention, in particular the fiber and fine material retention and, if appropriate, the filler retention being achieved compared to the known processes, and at the same time obtaining papers with a uniform formation transverse profile .
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 Verdünnungsström 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 according to the invention with a process for the production of paper by dewatering a process chemical and optionally filler-containing paper stock on a paper machine, in which a main stream of the paper stock and a dilution stream consisting of white water, the proportion of which in the total headbox feed, are fed to the paper machine screen via a headbox 5 to 35 vol .-% is, if one doses at least 5 wt .-% of the process chemicals in the dilution stream. The papers produced in this way have a uniform formation cross profile and surprisingly contain a very good qualitative bond between the fine and fillers to the long fiber material, so that these papers practically do not dust or to a non-disturbing extent. In addition, the contaminants mostly contained in the white water such as wood constituents, sticky contaminants from the paper line in recycled fibers or when using waste paper are almost quantitatively fixed to the paper stock and thereby rendered harmless for the paper manufacturing process and later paper recycling.
Bei dem erfindungsgemäßen Verfahren hat man einen Stoffauflauf mit einem Haupt- und einem Verdünnungsström, der über Dosierven- tile den einzelnen Sektionen des Stoffauflaufs zur Einstellung des Stoffdichtequerprofils zugeführt wird. Der Verdünnungsström besteht aus Siebwasser. Das Siebwasser enthält bekanntlich Feinstoffe und Faserbruchstücke von den bei der Papierherstellung eingesetzten Zellstoffen oder Holzstoffasern. Diese Feinstoffan- teile 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 fed to the individual sections of the headbox via metering valves in order to set the stock density cross profile. The dilution stream consists of white water. It is well known that white water contains fine substances and fiber fragments from the cellulose or wood pulp fibers used in paper production. These fines are usually difficult to get out of the cycle. If papers containing filler are produced, the white water contains at least twice as much filler as the main stream, based on the fiber. The proportion of the dilution stream consisting of the white water in the total headbox feed is, for example, 5 to 35% by volume, preferably 7 to 15% by volume. Suitable constructions for carrying out the method according to the invention are in the references cited above for the prior art "Das Papier" and in "Wochenblatt für Papierfabrikation".
Als Prozeßchemikalien kommen beispielsweise Fixiermittel, Entwäs- serungshilfsmittel, 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 enthal- tende Polymere, können beispielsweise gleichzeitig als Fixiermittel, Entwässerungshilfsmittel, Retentionsmittel und als Flok- kungsmittel 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-, Ent- wässerungs- oder Flockungsmittel in den Hauptstrom. Der pH-Wert der StoffSuspension beträgt beispielsweise 4,5 bis 9, vorzugs- weise 6 bis 8. So benutzt man beispielsweise kationische Fixiermittel, um Störstoffe zu eliminieren, die die Wirksamkeit von Re- tentionsmitteln, Naß- und Trockenverfestiger sowei Masseleimungsmittel stören. Solche Störstoffe sind beispielsweise Ligninsulfo- nate oder Hu insäuren. 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 aids, flocculants alone, in a mixture with one another or in combination with bentonite and / or colloidal silica, dyes, bulk sizing agents, dry setting agents and / or wet setting agents. Polymers such as polymers containing vinylamine units, for example, can simultaneously act as fixing agents, drainage aids, retention aids and as a flocculant, 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 fixatives are used to eliminate contaminants that interfere with the effectiveness of retention aids, wet and dry strength agents and bulk sizing agents. Such contaminants are, for example, lignosulfonates or Hu acids. Cationic fixing agents which can be used are, for example, polyethyleneimines, polymers containing vinylamine units and / or poly (diallyldimethylammonium chlorides) with a molecular weight 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 Reten- tionsmittel und kationische Flockungsmittel allein oder inProcess chemicals which can be used are, for example, cationic fixatives, cationic drainage aids, cationic retention agents and cationic flocculants, alone or in
Mischung untereinander einsetzen. Als Retentions- und Flockungsmittel besonders geeignet sind beispielsweise kationische Poly- acrylamide mit hoher Molmasse, z.B. mit Molmassen Mw von mindestens 4000000.Use mixture with each other. 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 herge- stellt. Geeignete kationische Monomere sind beispielsweise die Ester von ethylenisch ungesättigten C3- bis C5-Carbonsäuren mit Aminoalkoholen, wie Dimethylaminoethylacrylat, Diethylaminoethyl- acrylat, Dimethylaminoethylmethacrylat , Diethylaminoethylmeth- acrylat 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 quatemi- sierter Form bei der Copolymerisation eingesetzt werden. Die kationischen Polyacrylamide enthalten beispielsweise 5 bis 40, vorzugsweise 10 bis 40 Gew.-% an kationischen Monomeren in einpoly- merisierter 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 polymerized 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, it is also possible to use anionic polyacrylamides, which contain, for example, copolymerized acrylic acid or methacrylic acid, and amphoteric polyacrylamides as drainage aids, retention aids and flocculants. Cationic, nonionic, amphoteric or anionic polymers, which are used as drainage aids, retention aids and flocculants, have an improved effectiveness, for example in combination with bentonite and / or colloidal silica. This is particularly the case if a cationic fixative is also used. This is illustrated by the prior art specified in the introduction to the description.
Als Prozeßhilfsmittel werden außerdem beispielsweise wasserlösliche Polymere eingesetzt, die ausgewählt sind unter Polyethylen- i inen, Umsetzungsprodukten von Polyethyleniminen mit mindestens bifunktioneilen Vernetzern, anionischen Polyacrylamiden, kationischen Polyacrylamiden, amphoteren Polyacrylamiden, Reaktionsprodukten aus mit Ethylenimin gepfropften Polyamidoaminen mit mindestens zwei funktionelle Gruppen aufweisenden Vernetzern, Vi- nylformamid-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 ab- spaltenden 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-94/184743 bekannt. Zu ihrer Herstellung kommen außer halogenhal igen Vernetzern besonders halogenfreie Vernetzer in Betracht, wie Glycidylether von Polyalkylenglykolen.Process auxiliaries which are also used are, for example, water-soluble polymers which are selected from polyethylene iines, reaction products of polyethyleneimines with at least bifunctional crosslinkers, anionic polyacrylamides, cationic polyacrylamides, amphoteric polyacrylamides, reaction products from polyamidoamines grafted with ethyleneimine and with at least two functional groups having crosslinkers - nylformamide units and / or vinylamine unit-containing polymers and poly (diallyldimethylammonium halides). The above classes of compounds are known. Polyethyleneimines are produced, for example, by polymerizing ethyleneimine in an aqueous medium in the presence of traces of acids or compounds which split off acids. Also suitable are water-soluble polymeric reaction products containing amino groups, which are obtainable by reacting Michael addition products of polyalkylene polyamines, polyamidoamines, polyamidoamines grafted with ethyleneimine and mixtures of the compounds mentioned and monoethylenically unsaturated carboxylic acids, salts, esters, amides or nitriles with at least bifunctional crosslinkers. Such reaction products are, for example, from the WO-A-94/184743 known. In addition to halogen-containing crosslinkers, halogen-free crosslinkers, such as glycidyl ethers of polyalkylene glycols, are particularly suitable for their preparation.
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 durchAnother 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
- Reaktion von Polyethyleniminen mit einbasischen Carbonsäuren oder ihren Estern, Anhydriden, Säurechloriden oder Säure- amiden unter Amidbildung und- Reaction of polyethyleneimines with monobasic carboxylic acids or their esters, anhydrides, acid chlorides or acid amides with the formation of amides and
Umsetzung der amidierten Polyethylenimine mit mindestens zwei funktioneile Gruppen enthaltenden Vernetzern.Reaction of the amidated polyethyleneimines with at least two functional 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 contain one or more ethylenic double bonds, e.g. Oleic acid or linolenic acid. To produce these modified polyethyleneimines, the molar masses of the polyethyleneimines in question can be up to 2 million and are preferably in the range from 1000 to 50,000. The polyethyleneimines are partially amidated with monobasic carboxylic acids, so that, for example, 0.1 to 90, preferably 1 up to 50% of the amidatable nitrogen atoms in the polyethyleneimines is present as an amide group. Suitable crosslinkers containing at least two functional double bonds are mentioned above. Halogen-free crosslinkers are preferably 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 amino group-containing compounds with crosslinking agents, for example, 0.001 to 10, preferably 0.01 to 3 parts by weight of at least one crosslinking agent are used per 1 part by weight of a compound containing amino groups.
Andere Aminogruppen enthaltende Additionsprodukte sind quaterni- sierte Polyethylenimine. Es kommen hierfür z.B. sowohl Homopoly- merisate von Ethylenimin als auch Polymere in Betracht, die beispielsweise Ethylenimin aufgepfropft enthalten. Die so er- hältlichen Polyethylenimine haben eine breite Molmassenverteilung und Molmassen von beispielsweise 129 bis 2-106, vorzugsweise 430 bis MO6.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 MO 6 .
Die Polyethylenimine und die quaternisierten Polyethylenimine können gegebenenfalls mit einem mindestens zwei funktioneile Gruppen enthaltenden Vernetzer umgesetzt sein. Die Quaterni- sierung der Polyethylenimine kann beispielsweise mit Alkyl- halogeniden 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 funktioneile 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 Mol- massen von 1000 bis 50000. Weitere geeignete wasserlösliche Re- tentionsmittel bzw. Fixiermittel sind Umsetzungsprodukte vonThe polyethyleneimines and the quaternized polyethyleneimines can optionally be reacted with a crosslinker containing at least two functional groups. The quaternization of the polyethyleneimines can, for example, with alkyl halides such as methyl chloride, ethyl chloride, hexyl chloride, benzyl chloride or lauryl chloride and, for example, with dimethyl sulfate. Other suitable polymers containing amino groups are phosphonomethylated polyethyleneimines and alkoxylated polyethyleneimines, which are obtainable, for example, by reacting polyethyleneimine with ethylene oxide and / or propylene oxide. The phosphonomethylated and the alkoxylated polyethyleneimines can optionally be reacted with a crosslinker containing at least two functional groups. The alkoxylated polyethyleneimines contain 1 to 100, preferably 2 to 20, alkylene oxide units per NH group. The molecular weight of the polyethyleneimines can be up to 2 million. Polyethyleneimines with molar masses of 1000 to 50,000 are preferably used for the alkoxylation. Other suitable water-soluble retention aids or fixatives are reaction products of
Polyethyleniminen mit Diketenen, z.B. von Polyethyleniminen einer Molmasse von 1000 bis 50000 mit Distearyldiketen. Auch solche Produkte können gegebenenfalls mit einem mindestens zwei funktio- nelle Gruppen enthaltenden Vernetzer umgesetzt sein.Polyethyleneimines with diketenes, e.g. of polyethyleneimines with a molecular weight of 1,000 to 50,000 with distearyl diketene. Products of this type can also, if appropriate, be reacted with a crosslinker containing at least two functional groups.
Reaktionsprodukte aus mit Ethylenimin gepfropften Polyamidoaminen mit mindestens zwei funktioneile 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 made from ethyleneimine-grafted polyamidoamines with at least two functional groups containing crosslinkers are known from DE-B-2 434 816. Suitable crosslinkers are, for example, α, ω-bis (chlorohydrin) ethers of polyalkylene oxides having 1 to 100 alkylene oxide units. The resulting resins - measured at 20 ° C in 20 wt .-% aqueous solution - have a viscosity of more than 300 mPas. Other process chemicals for papermaking are reaction products of polyalkylene polyamines, dimethylamine, diethylamine or ethylenediamine with epichlorohydrin or dichloroethane or other at least bifunctional crosslinkers. Reaction products of this type are known, for example, from EP-A-0 411 400 and DE-A-2 162 567.
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 minde- stens 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,The preferred drainage aids, retention aids and flocculants are 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 . 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 und EP-B-0 218 674. Für dieses Rententionsmittel- System kommen als feinteilige anorganische Feststoffe beispiels- weise 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 Retentionsmit eln 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 fein- teiligen 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 Polyacryl- säure 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 μ .EP-B-0 080 986 and EP-B-0 218 674. For this pension system, finely divided inorganic solids include such as 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 with / 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 μ.
Besonders bevorzugt ist eine Verfahrensweise, bei der man zusätzlich ein kationisches Fixiermittel in den dafür üblichen Mengen einsetzt.A procedure is particularly preferred in which a cationic fixing agent is additionally used in the amounts customary for this.
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, thermo- mechanischen Stoff (TMP) , chemo-thermomechanisehen 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 can be produced by the process according to the invention, for example papers for newspaper printing, so-called medium-fine writing and printing papers, gravure printing papers and also lightweight coating base papers. For example, wood pulp, thermo-mechanical material (TMP), chemo-thermomechanical material (CTMP), pressure grinding (PGW) and sulphite and sulphate pulp can be used. Pulp and wood pulp can also be used as raw materials for the production of the pulp. In the so-called integrated factories in particular, these materials are further processed into paper in a more or less moist form without prior thickening or drying. Due to the impurities that have not been completely removed from them, these fiber materials still contain substances which severely disrupt the normal paper production process. To However, pulps containing interfering substances can also be easily processed in the method according to the invention.
Nach dem erfindungsgemäßen Verfahren können sowohl füllstoff- freie 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 prä- zipitierte Kreide, Titandioxid, Talkum, Kalziumsulfat, Barium- sulfat, Aluminiumoxid, Satinweiß oder Mischungen der genannten Füllstoffe.Both filler-free and filler-containing papers can be produced by the process according to the invention. The filler content in paper can be up to a maximum of 40% by weight and is preferably in the range from 5 to 25% by weight. Suitable fillers are, for example, clay, kaolin, native and precipitated chalk, titanium dioxide, talc, calcium sulfate, barium sulfate, aluminum oxide, satin white or mixtures of the fillers mentioned.
Die Stoffdichte der Pulpe beträgt beispielsweise 0,1 bisThe consistency of the pulp is, for example, 0.1 to
15 Gew.-%. Man gibt z.B. zunächst mindestens ein kationisches Po- lymer 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 Kiesel- säure oder calcinierten Clay zu, wodurch sogenannte weiche Mikro- flocken 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 μ , die Plättchendicke ca. 10 Ä. 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 Sammel- effekte von kationisch umgeladenen und einer Scherbehandlung unterworfenen Papierstoffen verwenden. Man erreicht dadurch eine optimale Flockung im Papierstoff.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 stage, which, for. B. in one or more cleaning, mixing and pumping stages or a pulper, classifier or even 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 micro flakes 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 μ, the platelet thickness is approximately 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 reloaded 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 Verdünnungsström dosiert man mindestens 5 Gew.-% der Prozeßchemikalien in den Verdünnungsstrom. Bei Re- tentionsmittelsystemen aus kationischen Polymeren und fein- teiligen 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 Hauptström 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 Verdünnungsström einbringt.Due to the above-mentioned division of the headbox into a main stream and a dilution stream, at least 5% by weight of the process chemicals are metered into the dilution stream. For retention aid systems made of cationic polymers and fine Partial solids, for example, preferably all of the cationic polymers can be added completely to the main stream and the finely divided solids can only be added to the dilution stream consisting of white water. However, it is also possible, for example, to add 60 to 95% by weight of this retention agent system to the main stream in a conventional manner and to meter the rest of the mixture through the white water. A method of working in which defoamers are introduced into the dilution stream has proven particularly useful.
Farbstoffe, Masseleimungsmittel (insbesondere Alkyldiketen-Dis- persionen, Harzleim, Alkenylsuccinimid-Dispersionen oder leimend wirkende Polymerdispersionen) sowie Verfestigungsmittel (z.B. mit Epichlorhydrin vernetzte Polyamidoamine) können gegebenenfalls ausschließlich über den Verdünnungsström in den Stoffauflauf do- siert werden. Vorzugsweise werden 5 bis 40 Gew.-% der Prozeßchemikalien in den Verdünnungsström eingebracht.Dyes, mass sizing agents (in particular alkyldiketene dispersions, resin glue, alkenylsuccinimide dispersions or glue-acting polymer dispersions) and solidifying agents (e.g. polyamidoamines crosslinked with epichlorohydrin) can optionally only be metered into the headbox via the dilution stream. Preferably 5 to 40% by weight of the process chemicals are 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 percentages by weight and 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 Diethylentri- amin 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 specification given in DE-B-2 434 816, Example 3, a polyamidoamine is prepared by condensing adipic acid with diethylenetriamine and then grafted in aqueous solution with sufficient ethyleneimine that the polyamidoamine per basic nitrogen grouping is 6.7 ethyleneimine. Contains units grafted on. 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 Polyethylen- glykols 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 pH = 10. Polymer 2The polyamidoamine grafted with ethyleneimine is then crosslinked by reaction with a bis-glycidyl ether of a polyethylene glycol having an average molecular weight of 2000 as described in Example 3 of DE-B-2 434 816. A polymer containing ethyleneimine units and having a viscosity of 120 mPas (determined in a 10% strength aqueous solution at 20 ° C. and pH 10) is obtained. The concentration of the aqueous solution is 12.5%, the pH is pH = 10. Polymer 2
Kationisches Copolymerisat aus Acrylamid und Dimethylaminoethyl- acrylat, das mit Methylchlorid quaternisiert ist mit einem Gehalt 5 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, which is quaternized with methyl chloride with a content 5 of acrylamide of 84 mol% and a molar mass of approx. 10 million. The charge density of the copolymer is 1.7 meq / g at pH 4.5 .
Polymer 3Polymer 3
10 Vernetztes Polyethylenimin mit einer mittleren Molmasse Mw von 1,4 Millionen und einer Ladungsdichte von 20,4 mEq/g (gemessen bei pH 4,5) .10 Cross-linked 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 4 15Polymer 4 15
Vernetztes Polyethylenimin mit einer mittleren Molmasse von 1 Million und einer Ladungsdichte von 14,7 mEq/g (gemessen bei pH 4,5) .Cross-linked polyethyleneimine with an average molecular weight of 1 million and a charge density of 14.7 mEq / g (measured at pH 4.5).
20 Beispiel 120 Example 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,The production of SC paper (supercalendered paper) was based on a composition of materials comprising 35 parts of ground wood, 17 parts of deinked waste paper, 19 parts of long-fiber sulfate pulp,
25 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 %25 contained 25 parts scrap and 25 parts clay. This paper stock was processed on an SC paper machine which was equipped with a module jet headbox from Voith-Sulzer. 0.29% of polymer 1 was metered into the main stream of paper stock before the vertical sorter and 0.024% after the vertical sorter
30 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 Verdünnungsström betrug 9 : 1. Die Ascheretention betrug 29,5 %, die Faser- und Fein-30 polymer 2. A dilution stream of white water was fed to the paper machine sieve via the module jet headbox, to which 0.03% polymer 1, based on dry paper, was metered. The volume ratio of the main stream to the dilution stream was 9: 1. The ash retention was 29.5%, the fiber and fine
35 stoffretention 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.35 fabric 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 an excellent ash distribution.
40 Vergleichsbeispiel 140 Comparative 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 Prozeßhilfs- 45 mittein zuführte und entwässerte. Die Aseheretention betrug 27,8 %, die Faser- und Feinstoffretention 60,3 %. Beispiel 2Example 1 was repeated with the exception that the paper stock described above was fed and dewatered from the SC paper machine in a single stream without a module jet system using the process auxiliaries indicated. The retention of ashes was 27.8%, the retention of fibers and fines 60.3%. Example 2
Beispiel 1 wurde mit der einzigen Ausnahme wiederholt, daß man in den Verdünnungsström anstelle von Polymer 1 jetzt 0,38 % Poly- mer 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 0.38% of polymer 4 was now metered into the dilution stream instead of polymer 1. Ash retention was 33.6%, fiber and fines retention 63.6%. The paper has 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 Verdünnungsström betrug 9 : 1. Man dosierte 0,05 % Polymer 2, bezogen auf trockenes Papier, in den Hauptstrom vor den Vertikalsortierer. In den Verdünnungsström gab man jeweils vor den Vertikalsortierer 0,03 % Polymer 3, bezogen auf trockenes Papier, und 0,1 % Bentonit, ebenfalls bezogen auf trok- kenes Papier. Die Ascheretention betrug 30,5 %, die Faser- und Feinstoffretention 69,5 %. Das Papier hatte ein gleichmäßiges Formationsquerprofil.A composition of 40 parts of wood pulp, 40 parts of bleached pine sulfate pulp and 20 parts of coated scrap was processed into paper on a paper machine for wood-containing coating base papers. The paper machine was equipped with a Dilution Head Box from Valmet. With the help of this device, a dilution stream consisting of white water could be fed to the headbox. The ratio of the main stream to the dilution stream was 9: 1. 0.05% of polymer 2, based on dry paper, was metered into the main stream upstream of the vertical sorter. 0.03% of polymer 3, based on dry paper, and 0.1% bentonite, also based on dry paper, were added to the dilution stream before the vertical sorter. Ash retention was 30.5%, fiber and fines retention 69.5%. The paper had a uniform 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 Verdünnungsström der Dilution Head Box 0,02 % Polymer 2 vor den Vertikalsortierer und 0,1 % Bentonit nach dem Vertikalsortierer dosierte und in den Hauptström 0,04 % Polymer 2 vor dem Durchgang durch den Vertikal- Sortierer gab. Die Ascheretention betrug 30,1 %, die Faser- und Feinstoffretention 69,7 %. Das Papier wies eine hervorragende Ascheverteilung auf und hatte ein gleichmäßiges Formationsquerprofil. Vergleichsbeispiel 3Example 3 was repeated with the exceptions that, based in each case on dry paper, 0.02% polymer 2 was metered into the dilution stream of the dilution head box before the vertical sorter and 0.1% bentonite after the vertical sorter and 0.04 into the main stream % Polymer 2 before passing through the vertical sorter. Ash retention was 30.1%, fiber and fines retention 69.7%. The paper had an excellent ash distribution and an even formation cross profile. Comparative Example 3
Beispiel 4 wurde ohne Dilution Head Box Dosierung wiederholt. Dabei betrug die Ascheretention 25,7 % und die Faser- und Feinstof- fretention 63,7 %. Example 4 was repeated without dilution head box dosing. The ash retention was 25.7% and the fiber and fines retention 63.7%.

Claims

Patentansprüche claims
1. 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 Verdünnungsström zuführt, dessen Anteil an der Gesamtstoffauflaufzuführung 5 bis 35 Vol.-% beträgt, dadurch gekennzeichnet, daß man mindestens 5 Gew.-% der Prozeßchemikalien in den Verdünnungsstrom dosiert.1. A process for the production of paper by dewatering 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 are fed to the paper machine screen via a headbox, the proportion of which in the total headbox feed is 5 to 35% by volume , characterized in that at least 5 wt .-% of the process chemicals are metered into the dilution stream.
2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß man als Prozeßchemikalien Fixiermittel, Entwässerungshilfsmittel, Retentionsmittel, Flockungsmittel allein, in Mischung untereinander oder in Kombination mit Bentonit und/oder kolloidaler Kieselsäure, Farbstoffe, Masseleimungsmittel, Trockenver- festigungsmittel und/oder Naßverfestigungsmittel einsetzt.2. The method according to claim 1, characterized in that fixing agents, drainage aids, retention aids, flocculants are used alone, as 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.
3. Verfahren nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß man als Prozeßchemikalien kationische Fixiermittel, kationische Entwässerungshilfsmittel, kationische Retentionsmittel und kationische Flockungsmittel allein oder in Mischung untereinander einsetzt.3. The method according to claim 1 or 2, characterized in that the process chemicals used are cationic fixing agents, cationic drainage aids, cationic retention agents and cationic flocculants alone or in a mixture with one another.
4. Verfahren nach den Ansprüchen 1 bis 3, dadurch gekennzeichnet, daß man kationische oder anionische Polymere, die als Entwässerungshilfsmittel, Retentionsmittel und Flockungsmittel wirken, in Kombination mit Bentonit und/oder kolloidaler Kieselsäure einsetzt.4. Process according to claims 1 to 3, characterized in that cationic or anionic polymers, which act as drainage aids, retention aids and flocculants, are used in combination with bentonite and / or colloidal silica.
5. Verfahren nach Anspruch 4, dadurch gekennzeichnet, daß man zusätzlich ein kationisches Fixiermittel einsetzt.5. The method according to claim 4, characterized in that one additionally uses a cationic fixing agent.
6. Verfahren nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, daß man als Prozeßhilfsmittel wasserlösliche Polymere einsetzt, die ausgewählt sind unter Polyethyleniminen, Umsetzungsprodukten von Polyethyleniminen mit mindestens bifunktionellen Vernetzern, anionischen Polyacryl- amiden, kationischen Polyacrylamiden, amphoteren Polyacrylamiden, Reaktionsprodukten aus mit Ethylenimin gepfropften Polyamidoaminen mit mindestens zwei funktioneile Gruppen aufweisenden Vernetzern, Vinylformamideinheiten und/oder Vinyl- amineinheiten enthaltenden Polymeren und Poly (diallyldi e- thylammmoniumhalogeniden) . 6. The method according to any one of claims 1 to 5, characterized in that water-soluble polymers are used as process aids, which are selected from polyethyleneimines, reaction products of polyethyleneimines with at least bifunctional crosslinking agents, anionic polyacrylamides, cationic polyacrylamides, amphoteric polyacrylamides, reaction products with Ethyleneimine-grafted polyamidoamines with at least two functional crosslinkers, vinylformamide units and / or vinylamine unit-containing polymers and poly (diallyldi ethylammmonium halides).
7. Verfahren nach einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, daß man als kationische Fixiermittel Polyethylenimine, Vinylamineinheiten enthaltende Polymerisate und/oder Poly (diallyldimethylammmoniumchloriden) mit einer Molmasse Mw von jeweils 10.000 bis 2 Millionen einsetzt.7. The method according to any one of claims 1 to 6, characterized in that the cationic fixing agent used are polyethyleneimines, vinylamine unit-containing polymers and / or poly (diallyldimethylammmonium chlorides) with a molecular weight Mw of 10,000 to 2 million each.
8. Verfahren nach einem der Ansprüche 1 bis 7, dadurch gekennzeichnet, daß man als Entwässerungshilfsmittel, Retentionsund Flockungsmittel wasserlösliche kationische Polyacrylamide mit einer mittleren Molmasse Mw von mindestens 500.000 und/ oder die wasserlöslichen Reaktionsprodukte einsetzt, die durch Umsetzung von Polyamidoaminen, die mit Ethylenimin gepfropft sind, mit mindestens bifunktionellen Vernetzern erhältlich sind.8. The method according to any one of claims 1 to 7, characterized in that water-soluble cationic polyacrylamides with an average molecular weight Mw of at least 500,000 and / or the water-soluble reaction products are used as drainage aids, retention aids and flocculants, which are grafted with ethyleneimine by reaction of polyamidoamines are available with at least bifunctional crosslinkers.
9. Verfahren nach den Ansprüchen 1 bis 8, dadurch gekennzeichnet, daß man als Prozeßchemikalien Kombinationen aus kationischen Polymeren und/oder kationischer Stärke mit feinteiligen organischen oder anorganischen Feststoffen einsetzt.9. Process according to claims 1 to 8, characterized in that combinations of cationic polymers and / or cationic starch with finely divided organic or inorganic solids are used as process chemicals.
10. Verfahren nach Anspruch 9, dadurch gekennzeichnet, daß man als einteilige anorganische Feststoffe Bentonit, kolloidale Kieselsäure, mikrokristallines Talkum, präzipitiertes Calciumcarbonat, präzipitierten Gips und/oder calcinierten Clay einsetzt.10. The method according to claim 9, characterized in that bentonite, colloidal silica, microcrystalline talc, precipitated calcium carbonate, precipitated gypsum and / or calcined clay are used as one-piece inorganic solids.
11. Verfahren nach den Ansprüchen 1 bis 10, dadurch gekennzeichnet, daß die Menge an feinteiligen Feststoffen 0,01 bis11. The method according to claims 1 to 10, characterized in that the amount of finely divided solids 0.01 to
2,0 Gew.-%, bezogen auf trockenes Papier, beträgt.2.0% by weight, based on dry paper.
12. Verfahren nach den Ansprüchen 1 bis 11, dadurch gekennzeichnet, daß der Papierstoff mindestens einen Füllstoff enthält. 12. The method according to claims 1 to 11, characterized in that the paper stock contains at least one filler.
EP97952902A 1996-12-27 1997-12-09 Method for producing paper Expired - Lifetime EP0948677B1 (en)

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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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Families Citing this family (63)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6346169B1 (en) 1998-01-13 2002-02-12 Kao Corporation Paper bulking promoter
US6846384B2 (en) * 2000-08-07 2005-01-25 Akzo Nobel N.V. Process for sizing paper
US6673205B2 (en) * 2001-05-10 2004-01-06 Fort James Corporation Use of hydrophobically modified polyaminamides with polyethylene glycol esters in paper products
CA2447136A1 (en) * 2001-06-11 2002-12-19 Basf Aktiengesellschaft Wet-strength finishing agents for paper
US6855672B2 (en) * 2001-11-07 2005-02-15 Baker Hughes Incorporated Copolymers useful for gelling acids
AU2003227212A1 (en) * 2002-03-28 2003-10-13 Nippon Paper Industries, Co., Ltd. Bulky paper
MXPA04009754A (en) * 2002-04-08 2004-12-13 Ciba Spec Chem Water Treat Ltd White pitch deposit treatment.
DE10237911A1 (en) * 2002-08-14 2004-02-26 Basf Ag Use of polymers comprising vinylamine units as promoters for bulk sizing of paper with alkyl diketenes
US20040084162A1 (en) 2002-11-06 2004-05-06 Shannon Thomas Gerard Low slough tissue products and method for making same
US7258764B2 (en) * 2002-12-23 2007-08-21 Sca Hygiene Products Gmbh Soft and strong webs from highly refined cellulosic fibres
ZA200508659B (en) * 2003-05-09 2007-03-28 Akzo Nobel Nv A process for the production of paper
EP1626866A1 (en) * 2003-05-16 2006-02-22 Basf Aktiengesellschaft Packaging material consisting of an at least double-layered composite material for producing containers for packing liquids
DE10333524A1 (en) * 2003-07-23 2005-02-17 Voith Paper Patent Gmbh Method and device for producing a fibrous web, in particular SC-A or SC-B paper web
WO2005042843A1 (en) * 2003-10-24 2005-05-12 National Gypsum Properties, Llc Process for making abrasion resistant paper and paper and paper products made by the process
JP2005171411A (en) * 2003-12-10 2005-06-30 Seiko Pmc Corp Filler-containing paper and method for producing filler-containing paper
US7641766B2 (en) * 2004-01-26 2010-01-05 Nalco Company Method of using aldehyde-functionalized polymers to enhance paper machine dewatering
DE102004013007A1 (en) * 2004-03-16 2005-10-06 Basf Ag Process for the production of paper, cardboard and cardboard
US20050236123A1 (en) * 2004-04-26 2005-10-27 Mcnamara Bruce A Retention and drainage in the manufacture of paper
DE102004044379B4 (en) * 2004-09-10 2008-01-10 Basf Ag Process for the production of paper, paperboard and cardboard and use of a retention agent combination
DE102004056551A1 (en) * 2004-11-23 2006-05-24 Basf Ag Process for the production of paper, cardboard and cardboard with high dry strength
CA2590489C (en) * 2004-12-17 2015-02-10 Basf Aktiengesellschaft Papers with a high filler material content and high dry strength
US7955473B2 (en) * 2004-12-22 2011-06-07 Akzo Nobel N.V. Process for the production of paper
US20060142431A1 (en) * 2004-12-29 2006-06-29 Sutman Frank J Retention and drainage in the manufacture of paper
US8932433B2 (en) * 2004-12-29 2015-01-13 Solenis Technologies, L.P. Retention and drainage in the manufacture of paper
AU2011213761B2 (en) * 2004-12-29 2012-07-12 Solenis Technologies Cayman, L.P. Improved retention and drainage in the manufacture of paper
US8308902B2 (en) 2004-12-29 2012-11-13 Hercules Incorporated Retention and drainage in the manufacture of paper
US7718035B2 (en) * 2005-03-15 2010-05-18 Georgia-Pacific Consumer Products Lp Phosphoric acid quenched creping adhesive
US20060254464A1 (en) 2005-05-16 2006-11-16 Akzo Nobel N.V. Process for the production of paper
JP4891601B2 (en) * 2005-12-02 2012-03-07 ハリマ化成株式会社 Paperboard manufacturing method
KR101242490B1 (en) 2005-12-30 2013-03-12 아크조 노벨 엔.브이. A process for the production of paper
US8273216B2 (en) * 2005-12-30 2012-09-25 Akzo Nobel N.V. Process for the production of paper
JP4868282B2 (en) * 2006-09-15 2012-02-01 星光Ｐｍｃ株式会社 Dirt prevention method
GB0702248D0 (en) * 2007-02-05 2007-03-14 Ciba Sc Holding Ag Manufacture of Filled Paper
GB0702249D0 (en) * 2007-02-05 2007-03-14 Ciba Sc Holding Ag Manufacture of paper or paperboard
FI122734B (en) * 2007-05-21 2012-06-15 Kemira Oyj Process chemical for use in the manufacture of paper or board
US8088250B2 (en) * 2008-11-26 2012-01-03 Nalco Company Method of increasing filler content in papermaking
US9752283B2 (en) 2007-09-12 2017-09-05 Ecolab Usa Inc. Anionic preflocculation of fillers used in papermaking
JP2009144272A (en) * 2007-12-12 2009-07-02 Daio Paper Corp Paper and method for producing paper
US9249240B2 (en) * 2007-12-20 2016-02-02 Basf Se Graft polymers having oligoalkylenimine side chains, process for their preparation and their use
US20100132522A1 (en) * 2008-09-19 2010-06-03 Peterson Michael E Trimmer
JP5289882B2 (en) * 2008-09-30 2013-09-11 日本製紙株式会社 Paper manufacturing method
DE102009001731A1 (en) * 2009-03-23 2010-09-30 Voith Patent Gmbh Method for adjusting a basis weight cross-section of a fibrous or nonwoven web and machine for producing a fibrous or nonwoven web
JP5570004B2 (en) * 2009-05-28 2014-08-13 ハイモ株式会社 Paper making method
WO2010145990A1 (en) * 2009-06-16 2010-12-23 Basf Se Method for reducing deposits in the drying section in the manufacture of paper, paperboard, and cardboard
US8288502B2 (en) 2009-12-18 2012-10-16 Nalco Company Aldehyde-functionalized polymers with enhanced stability
BR112012025330B1 (en) 2010-04-07 2020-12-08 Solenis Technologies Cayman, L.P. polyvinylamine compositions with cationic starch and the process of making paper or cardboard products
CA2801736C (en) * 2010-06-11 2018-07-10 Imerys Talc America, Inc. Method for contaminant removal in paper production
JP5961619B2 (en) 2010-10-29 2016-08-02 バックマン・ラボラトリーズ・インターナショナル・インコーポレーテッドＢｕｃｋｍａｎ Ｌａｂｏｒａｔｏｒｉｅｓ Ｉｎｔｅｒｎａｔｉｏｎａｌ Ｉｎｃｏｒｐｏｒａｔｅｄ Method for producing paper using ionic crosslinked polymer fine particles and product produced by the method
US8840759B2 (en) 2010-11-02 2014-09-23 Ecolab Usa Inc. Method of using aldehyde-functionalized polymers to increase papermachine performance and enhance sizing
US8709207B2 (en) 2010-11-02 2014-04-29 Nalco Company Method of using aldehyde-functionalized polymers to increase papermachine performance and enhance sizing
JP5900844B2 (en) * 2011-06-08 2016-04-06 丸住製紙株式会社 Colored paper manufacturing method and colored paper
CA2918468A1 (en) * 2013-08-09 2015-05-07 Solenis Technologies Cayman, L.P. Polyethylene oxide treatment for drainage agents and dry strength agents
WO2015070012A1 (en) * 2013-11-08 2015-05-14 Solenis Technologies, L.P. Surfactant based brown stock wash aid treatment for papermachine drainage and dry strength agents
US9567708B2 (en) 2014-01-16 2017-02-14 Ecolab Usa Inc. Wet end chemicals for dry end strength in paper
US9702086B2 (en) 2014-10-06 2017-07-11 Ecolab Usa Inc. Method of increasing paper strength using an amine containing polymer composition
US9920482B2 (en) 2014-10-06 2018-03-20 Ecolab Usa Inc. Method of increasing paper strength
US10006170B2 (en) 2015-08-06 2018-06-26 Ecolab Usa Inc. Aldehyde-functionalized polymers for paper strength and dewatering
WO2017197380A1 (en) 2016-05-13 2017-11-16 Ecolab Usa Inc. Tissue dust reduction
CN109844220A (en) * 2016-09-16 2019-06-04 索理思科技公司 The water filtering performance of paper manufacturing systems is improved using microfibrillated cellulose
CN111406136B (en) * 2017-10-03 2022-12-30 索理思科技公司 Chemical efficiency enhancement in papermaking process
US11926966B2 (en) 2017-10-03 2024-03-12 Solenis Technologies, L.P. Method of increasing efficiency of chemical additives in a papermaking system
CN114150527B (en) * 2021-12-17 2023-04-25 杭州绿邦科技有限公司 Retention and filter aid
CN116103954B (en) * 2023-02-23 2024-05-03 山东金蔡伦纸业有限公司 Quaternized polyethylenimine-lignin nanosphere retention and drainage aid system for papermaking of cultural paper

Family Cites Families (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2262906A1 (en) * 1972-03-30 1973-10-11 Sandoz Ag Dewatering of paper - accelerated by polyamide amines polyether amines and polyethylene imines, with addn of bentonite
US3933966A (en) * 1973-06-14 1976-01-20 A. Alhstrom Osakeyhtio Method and device for spraying fluid into a headbox
DE3514554C3 (en) * 1984-09-19 1998-01-08 Escher Wyss Gmbh Headbox device for a paper machine and method for its operation
GB8602121D0 (en) * 1986-01-29 1986-03-05 Allied Colloids Ltd Paper & paper board
GB8711330D0 (en) * 1987-05-14 1987-06-17 Beloit Corp Headbox
US4795531A (en) * 1987-09-22 1989-01-03 Nalco Chemical Company Method for dewatering paper
DE3741603A1 (en) * 1987-12-09 1989-06-22 Voith Gmbh J M FABRIC DRAIN FOR A PAPER MACHINE OR THE LIKE.
EP0335575B2 (en) * 1988-03-28 2000-08-23 Ciba Specialty Chemicals Water Treatments Limited Production of paper and paper board
US4940512A (en) * 1988-08-18 1990-07-10 E. I. Du Pont De Nemours And Co.Ny Cross-directional distribution of additives in synthetic papers
US5147509A (en) * 1990-06-25 1992-09-15 Beloit Corporation Headbox for a papermaking machine with distribution tubes
US5196091A (en) * 1991-10-29 1993-03-23 Beloit Technologies, Inc. Headbox apparatus with stock dilution conduits for basis weight control
DE69429693T2 (en) * 1993-07-01 2002-08-08 Metso Paper, Inc. Method and device for controlling a headbox
US5560807A (en) * 1995-03-29 1996-10-01 Beloit Technologies, Inc. Headbox additive injection system
FI98938C (en) * 1996-06-20 1997-09-10 Valmet Corp Apparatus for combining the dilution flow with the pulp flow from the paper / board divider

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9829603A1 *

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

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