EP1727938B1 - Method for producing paper, paperboard and cardboard - Google Patents

Method for producing paper, paperboard and cardboard Download PDF

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Publication number
EP1727938B1
EP1727938B1 EP05716030A EP05716030A EP1727938B1 EP 1727938 B1 EP1727938 B1 EP 1727938B1 EP 05716030 A EP05716030 A EP 05716030A EP 05716030 A EP05716030 A EP 05716030A EP 1727938 B1 EP1727938 B1 EP 1727938B1
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Prior art keywords
stock
consistency
polymers
paper
mol
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German (de)
French (fr)
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EP1727938A1 (en
Inventor
Anton Esser
Rainer Blum
Joachim Kuhn
Marc Leduc
Ralf Hemel
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BASF SE
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BASF SE
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Classifications

    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • 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
    • D21H21/02—Agents for preventing deposition on the paper mill equipment, e.g. pitch or slime control
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/33—Synthetic macromolecular compounds
    • D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21F—PAPER-MAKING MACHINES; METHODS OF PRODUCING PAPER THEREON
    • D21F13/00—Making discontinuous sheets of paper, pulpboard or cardboard, or of wet web, for fibreboard production
    • 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

Definitions

  • the invention relates to a process for the production of paper, paperboard and cardboard by dewatering a pulp containing contaminants in the presence of polymers containing vinylamine units and having an average molecular weight M w of at least 1 million.
  • From the EP-A-0 438 707 is a process for the production of paper, paperboard and cardboard by dewatering a contaminant-containing stock in the presence of hydrolyzed homo- and / or copolymers of N-vinylformamide having a degree of hydrolysis of at least 60% known as fixing agents and cationic retention agents.
  • the polymers used as fixing agents have Fikentscher K values of 30 to 150 (measured in 5% strength aqueous sodium chloride solution at a polymer concentration of 0.5% by weight and a temperature of 25 ° C.).
  • the hydrolyzed polymers are used as dehydrating, retention and flocculating agents a thin material (density of, for example, 0.4 or 0.5 wt .-%) in amounts of 0.002 to 0.1 wt .-%, each based on dry pulp, used.
  • WO-A-98/48112 discloses a process for the production of paper, paperboard and paperboard, wherein a contaminant-containing pulp in the presence of a fixing agent from a 25 to 55% hydrolyzed homo- or copolymer of N-vinylformamide having a K value of Fikentscher of 30 to 150 (Determined in 1 wt .-% aqueous solution at 25 ° C) and a retention agent dehydrated.
  • polymers containing vinylamine units disclosed in the above references are good fixers or dewatering, flocculation and retention aids, in practice, in the processing of pulp containing contaminants such as coated broke, still deposition problems in the wire, press and Drying section of the paper machine. The paper machine must then be turned off and cleaned.
  • the invention has the object of minimizing or eliminating the abovementioned deposition problems in the paper machine in the processing of pulp-containing paper materials, in particular in the reuse of coated broke.
  • the object is achieved by a method for the production of paper, cardboard and paperboard by dewatering a contaminant-containing paper stock molecular weight M w of at least 1 million, if you first prepare a thick stock, at least one vinylamine units containing polymer having an average molecular weight M w of dosed at least 1 million and a degree of hydrolysis of 1 to 20 mol% in the thick material, diluted the thick matter by adding water to a thin material and dehydrated the thin.
  • the consistency of the thick material is for example more than 2 wt .-%, based on dry pulp.
  • the degree of hydrolysis of the polymers is in most cases from 3 to 15 mol%.
  • Preference is given to a thick material with a consistency of 3.0 to 6.0 wt .-%, based on dry pulp, and vinylamine units containing polymers having a degree of hydrolysis of 5 to 12 mol% of.
  • the consistency of the thick material is preferably 3.5 to 4.5 wt .-%, based on dry pulp.
  • the thick matter is converted by adding water into a so-called thin material which has a substance concentration below 1.5% by weight, based on dry paper stock. In most cases, the substance concentration of the thin material is below 1.2% by weight, for example 0.5 to 1.1% by weight, preferably 0.6 to 0.9% by weight, in each case based on dry paper stock.
  • paper stocks are used, for the production of which all fiber qualities or mixtures of fibers come into consideration.
  • water is usually used in practice, which is at least partially, in most cases even completely, returned from the paper machine. These are either clarified or unclarified white water as well as mixtures of such water qualities.
  • the recycled water therefore contains more or less large amounts of so-called impurities, which are known to affect the effectiveness of the cationic retention and dehydration agents or the "runnability" of the paper machine very much, see. HL Baumgarten, The Paper, Volume 38, Issue 10 A, pp. V121 to V125 (1984 ).
  • Soluble impurities are e.g. Humic acids, lignosulfonate, silicas or wood extracts.
  • Insoluble, lipophilic / hydrophobic impurities - so-called stickies or white pitch - are derived, for example, from process chemicals used in paper production, binders for paper and board blending, and adhesives for paper processing. These may be, for example, pressure-sensitive adhesives, dispersion adhesives or hot-melt adhesives, or else printing ink binders or paper processing materials. Problems with the "runnability" of the paper machine occur in particular in the use of waste paper and in the return of coated broke. In the preparation of these stocks, larger particles, e.g.
  • Wood pulp includes, for example, groundwood, thermomechanical pulp (TMP), chemo-thermo-mechanical pulp (CTMP), pressure groundwood, semi-pulp, high yield pulp, and refiner mechanical pulp (RMP).
  • TMP thermomechanical pulp
  • CMP chemo-thermo-mechanical pulp
  • RMP refiner mechanical pulp
  • pulp for example, sulphate, sulphite and soda pulps come into consideration.
  • unbleached pulp also referred to as unbleached kraft pulp
  • Suitable annual plants for the production of pulps are, for example, rice, wheat, sugar cane and kenaf.
  • pulps waste paper is usually used, which is used either alone or in admixture with other pulps or one starts from fiber blends of a primary material and recycled coated broke, e.g. bleached pine sulfate mixed with recycled coated board.
  • polymers containing vinylamine units which are obtainable by hydrolysis of homopolymers and / or copolymers of N-vinylcarboxamides are metered into the thick stock.
  • vinylamine units containing polymers hydrolyzed homopolymers of N-vinylformamide having a degree of hydrolysis of 1 to 20 mol% used.
  • the polymers in question have an average molecular weight M w of at least 1 million, usually from 1 to 10 million daltons, preferably 1.5 to 3.5 million daltons.
  • the polymers have for example a charge density of 0.5 to 5.0, preferably 1.5 to 3.5 meq / g.
  • Polymers containing vinylamine units are known in the art, cf. especially EP-A-0 438 755 , Page 3, line 15 to page 4, line 20, US-A-4,421,602 such as EP-A-0 231 901 ,
  • the polymers are obtainable by homopolymerization or copolymerization of N-vinylcarboxamides such as N-vinylformamide, N-vinylacetamide, N-ethyl-N-vinylformamide, N-ethyl-N-vinylacetamide, N-methyl-N-vinylformamide, N-methyl-N vinylacetamide and N-vinylpropionamide.
  • N-vinylformamide Preferably starting from N-vinylformamide.
  • the polymers containing copolymerized units of N-vinylcarboxamides are partially hydrolyzed.
  • the degree of hydrolysis of the vinylcarboxylic acid amide polymers is preferably from 3 to 15, and more preferably from 5 to 12, mol%.
  • the degree of hydrolysis corresponds to the content of the polymers of vinylamine groups in mol%.
  • the hydrolysis is preferably carried out in the presence of an acid or a base. However, the polymers can also be hydrolyzed enzymatically.
  • the corresponding ammonium salts of the polymers while in the hydrolysis with bases the vinylamine units of the polymers are present in the form of the free bases , the copolymerized in the copolymer vinyl ester units are partially or completely converted into vinyl alcohol units.
  • the vinylamine units of the polymers may optionally be modified by converting them into the quaternization products in a known manner, e.g. by reaction of the polymers with dimethyl sulfate.
  • the polymers containing vinylamine units are metered into the thick material in the production of paper, for example in an amount of 0.002 to 0.1% by weight, based on dry paper stock.
  • the invention also provides the use of hydrolyzed homo- or copolymers of N-vinylcarboxamides having a degree of hydrolysis of 1 to 20 mol% and an average molecular weight M w of at least 1 million in the production of paper, paperboard or cardboard as an additive to a Heavy material containing impurities for reducing deposits in the wire, press and dryer sections of paper machines.
  • At least one retention agent is metered into the thin material.
  • a retention agent all polymeric substances described here can be used. So you can, for example, from the US-A-4,421,602 known partially hydrolyzed homopolymers of N-vinylformamide used as a retention agent. The degree of hydrolysis of the copolymerized N-vinylformamide units may be 1 to 100%. However, it is also possible to use unhydrolysed polymers of N-vinylformamide as retention agent. Such polymers have for example K values of at least 160, preferably 180 to 300 (determined according to H. Fikentscher in 5% strength aqueous sodium chloride solution at 25 ° C. and a polymer concentration of 0.5% by weight).
  • retention aids are, for example, polyacrylamides which can be used in unmodified form or in cationically or anionically modified form.
  • Copolymers of acrylamide or methacrylamide are cationically modified, for example, by copolymerization with dialkylaminoethyl acrylates or dialkylaminoethyl methacrylates.
  • retention aids are copolymers of acrylamide and N, N-dimethylaminoethyl acrylate or copolymers of acrylamide and N, N-diethylaminoethyl acrylate.
  • the basic acrylates are contained, for example, in amounts of from 5 to 70, preferably from 8 to 40, mol% in the copolymers and are preferably present in acids neutralized or in quaternized form.
  • the quaternization can be carried out, for example, with methyl chloride or dimethyl sulfate.
  • Acrylamide and methacrylamide can also be anionically modified by copolymerizing with monoethylenically unsaturated carboxylic acids.
  • High molecular weight copolymers of, for example, acrylamide and acrylic acid are known retention aids.
  • the content of anionic comonomers in the copolymers is for example 5 to 50, preferably 10 to 40 wt .-%.
  • the cationically or anionically modified poly (meth) acrylamides have, for example, K values of at least 180 (determined according to H. Fikentscher in 5% strength aqueous sodium chloride solution at 25 ° C. and a polymer concentration of 0.5% by weight).
  • cationic retention aids are polyethyleneimines, polyamines having molar masses of more than 50,000, polyamidoamines, optionally by grafting with ethyleneimine and subsequent crosslinking with, for example, polyethylene glycol dichlorohydrin ethers according to the teaching of US Pat DE-C-24 34 816 or are crosslinked with epichlorohydrin, polyetheramines, polyvinylimidazoles, polyvinylimidazoles, polyvinyltetrahydropyridines, polydialkylaminoalkyl vinyl ethers, polydialkylaminoalkyl (meth) acrylates in protonated or quaternized form, polydiallyldialkylammonium halides, in particular polydiallyldimethylammonium chloride.
  • Particularly preferred retention aids are those specified above DE-C-24 34 816 known polyamidoamines grafted with ethyleneimine and subsequently crosslinked.
  • a retention agent it is also possible to use the microparticle systems of high molecular weight polyacrylamides and bentonite known from the literature, initially adding a high molecular weight cationic polyacrylamide to the paper stock, subjecting the paper stock to shear, and then metering in bentonite.
  • Such methods are for example the subject of EP-A-0 235 893 and the EP-A-0 335 575 .
  • Another order of dosing of polymeric retention aid and inorganic particles such as bentonite is out DE-A-102 36 252 known. It is preferable to use cationic retention aids.
  • the retention agents are usually used in an amount of from 0.01 to 0.2% by weight, based on dry paper stock, applied.
  • the ratio of polymers to be used according to the invention containing 1 to 20 mol% of vinylamine units with molar masses of> 1 million to retention agent is, for example, 1: 2 to 5: 1.
  • the process according to the invention it is possible to add further customary products in the customary amounts to the thin material, e.g. Sizing agents, strength agents (wet and dry strength agents), biocides and / or dyes.
  • Sizing agents e.g. Sizing agents, strength agents (wet and dry strength agents), biocides and / or dyes.
  • Wood-free base paper with a basis weight of 150 g / cm 2 was continuously produced on a paper machine.
  • the composition of the pulp in the mixing chest consisted of 14% bleached pine sulfate, 34% bleached birch sulphite, 21% coated broke and 31% ground calcium carbonate, the pulp concentration being 4% based on dry pulp.
  • the capacity of the paper machine was 20 t / h.
  • the finished paper contained about 18% ground calcium carbonate.
  • the fibers were fed to the mixing chest in separate strands.
  • the one in the mixer 4% stock was diluted by feeding water from the paper machine circuit to a 0.8% concentration of dry stock.
  • the machine ran flawlessly. After a period of one month, the machine was routinely shut down and cleaned. However, the deposits on the machine were not so serious that you should have turned off the machine.
  • Example 1 was repeated with the sole exception that, instead of PVAm 3, 400 g / t of polyaluminum chloride in the form of an 18% aqueous solution were now metered into the strand in which the coated broke was transported.
  • the running characteristics of the machine and the quality of the paper produced are unsatisfactory.
  • the paper production had to be interrupted after a running time of the machine of 3 days to remove interfering deposits on the wire, press and dryer section of the machine.
  • Example 1 was repeated with the sole exception that, instead of PVAm 3, 400 g / t of PVAm 1 were now metered into the strand in which the coated broke was transported. Although the running properties of the machine and the quality of the paper produced are improved compared to Comparative Example 1, the paper production also had to be interrupted after a running time of the machine of 3 days to remove disturbing deposits on the screen, press and dryer section of the machine.
  • Example 1 was repeated with the sole exception that instead of PVAm 3, 400 g / t of PVAm 2 were now metered into the strand in which the coated broke was transported. Although the running characteristics of the machine and the quality of the produced paper are improved over Comparative Example 1, the paper production had to be interrupted after a running time of the machine of 4 days to remove disturbing deposits on the screen, press and dryer section of the machine.

Abstract

A process for the production of paper, board and cardboard by draining a paper stock containing interfering substances in the presence of polymers which contain vinylamine units and which have an average molar mass Mw of at least 1 million, a high-consistency stock first being prepared, at least one polymer containing vinylamine units and having an average molar mass Mw of at least 1 million and a degree of hydrolysis of from 1 to 20 mol % being metered into the high-consistency stock, the high-consistency stock being diluted to a low-consistency stock by adding water, and the low-consistency stock being drained, the polymers being hydrolyzed homo- or copolymers of N-vinylcarboxamides additives for reducing deposits in the wire part, press section and drying section of paper machines.

Description

Die Erfindung betrifft ein Verfahren zur Herstellung von Papier, Pappe und Karton durch Entwässern eines Störstoffe enthaltenden Papierstoffs in Gegenwart von Polymerisaten, die Vinylamineinheiten enthalten und die eine mittlere Molmasse Mw von mindestens 1 Million haben.The invention relates to a process for the production of paper, paperboard and cardboard by dewatering a pulp containing contaminants in the presence of polymers containing vinylamine units and having an average molecular weight M w of at least 1 million.

Aus der EP-A-0 438 707 ist ein Verfahren zur Herstellung von Papier, Pappe und Karton durch Entwässern eines Störstoffe enthaltenden Papierstoffs in Gegenwart von hydrolysierten Homo- und/oder Copolymerisaten des N-Vinylformamids mit einem Hydrolysegrad von mindestens 60 % als Fixiermittel und kationischen Retentionsmitteln bekannt. Die als Fixiermittel eingesetzten Polymeren haben K-Werte nach Fikentscher von 30 bis 150 (gemessen in 5 %iger wässriger Kochsalzlösung bei einer Polymerkonzentration von 0,5 Gew.-% und einer Temperatur von 25°C).From the EP-A-0 438 707 is a process for the production of paper, paperboard and cardboard by dewatering a contaminant-containing stock in the presence of hydrolyzed homo- and / or copolymers of N-vinylformamide having a degree of hydrolysis of at least 60% known as fixing agents and cationic retention agents. The polymers used as fixing agents have Fikentscher K values of 30 to 150 (measured in 5% strength aqueous sodium chloride solution at a polymer concentration of 0.5% by weight and a temperature of 25 ° C.).

Nach dem aus der EP-A-0 438 755 bekannten Verfahren stellt man Papier, Pappe und Karton durch Entwässern eines Störstoffe enthaltenden Papierstoffs in Gegenwart von Polymerisaten her, die Vinylformamid- und Vinylamineinheiten enthalten und die K-Werte nach Fikentscher von mindestens 130 (bestimmt in 5 gew.-%iger wässriger Kochsalzlösung bei 25°C und einer Polymerkonzentration von 0,1 Gew.-%) haben. Die mittlere Molmasse Mw der in den Beispielen eingesetzten Polymeren liegt oberhalb von 1 Million. Die Polymeren sind beispielsweise durch Hydrolyse von Homopolymerisaten des N-Vinylformamids zugänglich. Der Hydrolysegrad der Polymeren beträgt weniger als 10 mol-%. Die hydrolysierten Polymeren werden als Entwässerungs-, Retentions- und Flockungsmittel einem Dünnstoff (Stoffdichte von beispielsweise 0,4 bzw. 0,5 Gew.-%) in Mengen von 0,002 bis 0,1 Gew.-%, jeweils bezogen auf trockenen Papierstoff, eingesetzt.After the out of the EP-A-0 438 755 Known methods to produce paper, cardboard and paperboard by dewatering a contaminant-containing stock in the presence of polymers containing vinylformamide and vinylamine units and the Fikentscher K values of at least 130 (determined in 5 wt .-% aqueous saline at 25 ° C and a polymer concentration of 0.1 wt .-%) have. The average molecular weight M w of the polymers used in the examples is above 1 million. The polymers are accessible, for example, by hydrolysis of homopolymers of N-vinylformamide. The degree of hydrolysis of the polymers is less than 10 mol%. The hydrolyzed polymers are used as dehydrating, retention and flocculating agents a thin material (density of, for example, 0.4 or 0.5 wt .-%) in amounts of 0.002 to 0.1 wt .-%, each based on dry pulp, used.

Aus der WO-A-98/48112 ist ein Verfahren zur Herstellung von Papier, Pappe und Karton bekannt, wobei man einen Störstoffe enthaltenden Papierstoff in Gegenwart eines Fixiermittels aus einem zu 25 bis 55 % hydrolysierten Homo- oder Copolymerisat des N-Vinylformamids mit einem K-Wert nach Fikentscher von 30 bis 150 (bestimmt in 1 gew.-%iger wässriger Lösung bei 25°C) und einem Retentionsmittel entwässert.From the WO-A-98/48112 discloses a process for the production of paper, paperboard and paperboard, wherein a contaminant-containing pulp in the presence of a fixing agent from a 25 to 55% hydrolyzed homo- or copolymer of N-vinylformamide having a K value of Fikentscher of 30 to 150 (Determined in 1 wt .-% aqueous solution at 25 ° C) and a retention agent dehydrated.

Obwohl die in den obengenannten Schriften offenbarten Vinylamineinheiten enthaltenden Polymeren gute Fixiermittel bzw. Entwässerungs-, Flockungs- und Retentionsmittel sind, treten in der Praxis bei der Verarbeitung von störstoffhaltigen Papierstoffen wie gestrichenem Ausschuß, immer noch Ablagerungsprobleme in der Sieb-, Pressen- und Trockenpartie der Papiermaschine auf. Die Papiermaschine muß dann abgestellt und gereinigt werden.Although the polymers containing vinylamine units disclosed in the above references are good fixers or dewatering, flocculation and retention aids, in practice, in the processing of pulp containing contaminants such as coated broke, still deposition problems in the wire, press and Drying section of the paper machine. The paper machine must then be turned off and cleaned.

Der Erfindung liegt die Aufgabe zugrunde, die genannten Ablagerungsprobleme in der Papiermaschine bei der Verarbeitung von störstoffhaltigen Papierstoffen, insbesondere bei der Wiederverwendung von gestrichenem Ausschuß, zu minimieren bzw. zu beseitigen.The invention has the object of minimizing or eliminating the abovementioned deposition problems in the paper machine in the processing of pulp-containing paper materials, in particular in the reuse of coated broke.

Die Aufgabe wird erfindungsgemäß gelöst mit einem Verfahren zur Herstellung von Papier, Pappe und Karton durch Entwässern eines Störstoffe enthaltenden Papierstoffs Molmasse Mw von mindestens 1 Million haben, wenn man zunächst einen Dickstoff bereitet, mindestens ein Vinylamineinheiten enthaltendes Polymer mit einer mittleren Molmasse Mw von mindestens 1 Million und einem Hydrolysegrad von1 bis 20 mol-% in den Dickstoff dosiert, den Dickstoff durch Zufügen von Wasser zu einem Dünnstoff verdünnt und den Dünnstoff entwässert.The object is achieved by a method for the production of paper, cardboard and paperboard by dewatering a contaminant-containing paper stock molecular weight M w of at least 1 million, if you first prepare a thick stock, at least one vinylamine units containing polymer having an average molecular weight M w of dosed at least 1 million and a degree of hydrolysis of 1 to 20 mol% in the thick material, diluted the thick matter by adding water to a thin material and dehydrated the thin.

Die Stoffdichte des Dickstoffs beträgt beispielsweise mehr als 2 Gew.-%, bezogen auf trockenen Papierstoff. Der Hydrolysegrad der Polymeren liegt in den meisten Fällen bei 3 bis 15 mol-%. Vorzugsweise geht man von einem Dickstoff mit einer Stoffdichte von 3,0 bis 6,0 Gew.-%, bezogen auf trockenen Papierstoff, und von Vinylamineinheiten enthaltenden Polymeren mit einem Hydrolysegrad von 5 bis 12 mol-% aus. Die Stoffdichte des Dickstoffs beträgt vorzugsweise 3,5 bis 4,5 Gew.-%, bezogen auf trockenen Papierstoff. Nach dem Zusatz mindestens eines Vinylamineinheiten enthaltenden Polymeren wird der Dickstoff durch Zuführen von Wasser in einen sog. Dünnstoff überführt, der eine Stoffkonzentration unterhalb von 1,5 Gew.-%, bezogen auf trockenen Papierstoff, hat. Meistens liegt die Stoffkonzentration des Dünnstoffs unterhalb von 1,2 Gew.-%, beispielsweise bei 0,5 bis 1,1 Gew.-%, vorzugsweise 0,6 bis 0,9 Gew.-%, jeweils bezogen auf trockenen Papierstoff.The consistency of the thick material is for example more than 2 wt .-%, based on dry pulp. The degree of hydrolysis of the polymers is in most cases from 3 to 15 mol%. Preference is given to a thick material with a consistency of 3.0 to 6.0 wt .-%, based on dry pulp, and vinylamine units containing polymers having a degree of hydrolysis of 5 to 12 mol% of. The consistency of the thick material is preferably 3.5 to 4.5 wt .-%, based on dry pulp. After the addition of at least one polymer comprising vinylamine units, the thick matter is converted by adding water into a so-called thin material which has a substance concentration below 1.5% by weight, based on dry paper stock. In most cases, the substance concentration of the thin material is below 1.2% by weight, for example 0.5 to 1.1% by weight, preferably 0.6 to 0.9% by weight, in each case based on dry paper stock.

Bei dem erfindungsgemäßen Verfahren werden Papierstoffe eingesetzt, für deren Herstellung sämtliche Faserqualitäten oder Mischungen von Fasern in Betracht kommen. Für die Herstellung des Papierstoffs wird in der Praxis meistens Wasser verwendet, das zumindest teilweise, meistens sogar vollständig von der Papiermaschine zurückgeführt wird. Es handelt sich hierbei entweder um geklärtes oder auch ungeklärtes Siebwasser sowie um Mischungen solcher Wasserqualitäten. Das zurückgeführte Wasser enthält daher mehr oder weniger größere Mengen an sogenannten Störstoffen, die bekanntlich die Wirksamkeit der kationischen Retentions- und Entwässerungsmittel oder die "runnability" der Papiermaschine sehr stark beeinträchtigen, vgl. H.L. Baumgarten, Das Papier, Band 38, Heft 10 A, S. V121 bis V125 (1984 ).In the method according to the invention, paper stocks are used, for the production of which all fiber qualities or mixtures of fibers come into consideration. For the production of the paper stock, water is usually used in practice, which is at least partially, in most cases even completely, returned from the paper machine. These are either clarified or unclarified white water as well as mixtures of such water qualities. The recycled water therefore contains more or less large amounts of so-called impurities, which are known to affect the effectiveness of the cationic retention and dehydration agents or the "runnability" of the paper machine very much, see. HL Baumgarten, The Paper, Volume 38, Issue 10 A, pp. V121 to V125 (1984 ).

Diese Störstoffe kommen sowohl in löslicher als auch in unlöslicher und in kolloidaler Form vor. Lösliche Störstoffe sind dabei z.B. Huminsäuren, Ligninsulfonat, Kieselsäuren oder Holzextrakte. Unlösliche, lipophil/hydrophobe Störstoffe - sogenannte Stickies oder white-pitch - stammen beispielsweise aus Prozeßchemikatien, die bei der Papiererzeugung verwendet werden, aus Bindemitteln für das Streichen von Papier und Karton, aus Klebstoffen für die Papierverarbeitung. Beispielsweise kann es sich hierbei um Haftklebstoffe, Dispersionsklebstoffe oder um Schmelzklebstoffe handeln oder auch um Druckfarbenbindemittel oder aus Werkstoffen der Papierverarbeitung. Probleme mit der "runnability" der Papiermaschine treten insbesondere beim Einsatz von Altpapier und bei der Rückführung von gestrichenem Ausschuß auf. Bei der Aufbereitung dieser Papierstoffe werden größere Teilchen, z.B. Teilchen mit einem Durchmesser oberhalb von 50 µm, mit Hilfe mechanischer Verfahren abgetrennt. In einem geschlossenen Wasserkreislauf einer Papiermaschine können jedoch aus kleineren Teilchen, die einen Durchmesser von unterhalb 50 µm haben und die mit Hilfe mechanischer Verfahren nicht abgetrennt werden können, infolge von Akkumulation größere Teilchen bilden. Diese sogenannte Sekundärstickybildung führt im Papierherstellungsprozeß zu störenden Ablagerungen auf der Sieb-, Pressen- und Trockenpartie der Papiermaschine.These contaminants occur in both soluble and insoluble and in colloidal form. Soluble impurities are e.g. Humic acids, lignosulfonate, silicas or wood extracts. Insoluble, lipophilic / hydrophobic impurities - so-called stickies or white pitch - are derived, for example, from process chemicals used in paper production, binders for paper and board blending, and adhesives for paper processing. These may be, for example, pressure-sensitive adhesives, dispersion adhesives or hot-melt adhesives, or else printing ink binders or paper processing materials. Problems with the "runnability" of the paper machine occur in particular in the use of waste paper and in the return of coated broke. In the preparation of these stocks, larger particles, e.g. Particles with a diameter above 50 microns, separated by mechanical methods. However, in a closed water cycle of a papermaking machine smaller particles that are less than 50 microns in diameter and that can not be separated by mechanical means may form larger particles due to accumulation. This so-called Sekundärstickybildung leads to disturbing deposits on the wire, press and dryer section of the paper machine in the papermaking process.

Als Faserstoffe zur Herstellung der Pulpen kommen sämtliche dafür gebräuchlichen Qualitäten in Betracht, z.B. Holzstoff, gebleichter und ungebleichter Zellstoff sowie Papierstoffe aus allen Einjahrespflanzen. Zu Holzstoff gehören beispielsweise Holzschliff, thermomechanischer Stoff (TMP), chemo-thermomechanischer Stoff (CTMP), Druckschliff, Halbzellstoff, Hochausbeute-Zellstoff und Refiner Mechanical Pulp (RMP). Als Zellstoff kommen beispielsweise Sulfat-, Sulfit- und Natronzellstoffe in Betracht. Vorzugsweise verwendet man ungebleichten Zellstoff, der auch als ungebleichter Kraftzellstoff bezeichnet wird. Geeignete Einjahrespflanzen zur Herstellung von Papierstoffen sind beispielsweise Reis, Weizen, Zuckerrohr und Kenaf. Zur Herstellung der Pulpen wird meistens Altpapier verwendet, das entweder allein oder in Mischung mit anderen Faserstoffen eingesetzt wird oder man geht von Fasermischungen aus einem Primärstoff und zurückgeführtem gestrichenem Ausschuß aus, z.B. gebleichtes Kiefernsulfat in Mischung mit zurückgeführtem gestrichenem Ausschuß.As pulps for the production of the pulps, all qualities which are customary for this purpose can be considered, e.g. Pulp, bleached and unbleached pulp and pulps from all annual plants. Wood pulp includes, for example, groundwood, thermomechanical pulp (TMP), chemo-thermo-mechanical pulp (CTMP), pressure groundwood, semi-pulp, high yield pulp, and refiner mechanical pulp (RMP). As pulp, for example, sulphate, sulphite and soda pulps come into consideration. Preferably, unbleached pulp, also referred to as unbleached kraft pulp, is used. Suitable annual plants for the production of pulps are, for example, rice, wheat, sugar cane and kenaf. For the production of the pulps waste paper is usually used, which is used either alone or in admixture with other pulps or one starts from fiber blends of a primary material and recycled coated broke, e.g. bleached pine sulfate mixed with recycled coated board.

Um Ablagerungen auf der Papiermaschine zu vermeiden und um die Runnability der Papiermaschine zu verbessern, dosiert man Vinylamineinheiten enthaltenden Polymere, die durch Hydrolyse von Homo- und/oder Copolymerisaten von N-Vinylcarbonsäureamiden erhältlich sind, in den Dickstoff. Vorzugsweise verwendet man als Vinylamineinheiten enthaltende Polymere hydrolysierte Homopolymerisate von N-Vinylformamid mit einem Hydrolysegrad von 1 bis 20 mol-% einsetzt. Die in Betracht kommenden Polymeren haben eine mittlere Molmasse Mw von mindestens 1 Million, meistens von 1 bis 10 Millionen Dalton, vorzugsweise 1,5 bis 3,5 Millionen Dalton. Die Polymeren haben beispielsweise eine Ladungsdichte von 0,5 bis 5,0, vorzugsweise 1,5 bis 3,5 meq/g. Vinylamineinheiten enthaltende Polymere sind aus dem Stand der Technik bekannt, vgl. insbesondere EP-A-0 438 755 , Seite 3, Zeile 15 bis Seite 4, Zeile 20, US-A-4 421 602 sowie EP-A-0 231 901 . Die Polymerisate sind erhältlich durch Homopolymerisation oder Copolymerisation von N-Vinylcarbonsäureamiden wie N-Vinylformamid, N-Vinylacetamid, N-Ethyl-N-vinylforrnamid, N-Ethyl-N-vinylacetamid, N-Methyl-N-vinylformamid, N-Methyl-N-vinylacetamid und N-Vinylpropionamid. Vorzugsweise geht man von N-Vinylformamid aus.In order to avoid deposits on the paper machine and to improve the runnability of the paper machine, polymers containing vinylamine units which are obtainable by hydrolysis of homopolymers and / or copolymers of N-vinylcarboxamides are metered into the thick stock. Preferably used as vinylamine units containing polymers hydrolyzed homopolymers of N-vinylformamide having a degree of hydrolysis of 1 to 20 mol% used. The polymers in question have an average molecular weight M w of at least 1 million, usually from 1 to 10 million daltons, preferably 1.5 to 3.5 million daltons. The polymers have for example a charge density of 0.5 to 5.0, preferably 1.5 to 3.5 meq / g. Polymers containing vinylamine units are known in the art, cf. especially EP-A-0 438 755 , Page 3, line 15 to page 4, line 20, US-A-4,421,602 such as EP-A-0 231 901 , The polymers are obtainable by homopolymerization or copolymerization of N-vinylcarboxamides such as N-vinylformamide, N-vinylacetamide, N-ethyl-N-vinylformamide, N-ethyl-N-vinylacetamide, N-methyl-N-vinylformamide, N-methyl-N vinylacetamide and N-vinylpropionamide. Preferably starting from N-vinylformamide.

Als Comonomere für die Herstellung von Copolymerisaten des N-Vinylformamids eignen sich insbesondere Vinylformiat, Vinylacetat, Vinylpropionat, C1- bis C4-Alkylvinylether, N-Vinylpyrrolidon, Ester, Nitrile und Amide von monoethylenisch ungesättigten C3- bis C5-Carbonsäuren, insbesondere von Acrylsäure oder von Methacrylsäure sowie monoethylenisch ungesättigte C3- bis C5-Carbonsäuren. Die Ester der Acrylsäure und Methacrylsäure leiten sich beispielsweise von Alkoholen mit 1 bis 6 Kohlenstoffatomen ab. Die Copolymerisate enthalten vorzugsweise 95 bis 10 Mol-% N-Vinylformamid und 5 bis 90 Mol-% mindestens eines anderen ethylenisch ungesättigten Monomeren. Bevorzugt werden hydrolysierte Polymerisate eingesetzt, die erhältlich sind durch Polymerisieren von

  1. (a) 100 bis 10 Mol-% N-Vinylformamid und
  2. (b) 0 bis 90 Mol-% Vinylformiat, Vinylacetat, Vinylpropionat, Methylacrylat, Ethylacrylat, Methylmethacrylat und/oder Maleinsäuredimethylester
und wobei aus diesen Polymeren im Anschluß an die Polymerisation 1 bis 20 mol-% der einpolymerisierten Vinylformamid-Einheiten unter Bildung von Vinylamin-Einheiten abgespalten werden. Ganz besonders bevorzugt werden bei dem erfindungsgemäßen Verfahren hydrolysierte Homopolymerisate des N-Vinylformamids mit einem Hydrolysegrad von 1 bis 20 mol-% und einer mittleren Molmasse Mw von mindestens 1 Million eingesetzt. Die Polymerisation der Monomeren wird üblicherweise in Gegenwart von Radikale bildenden Polymerisationsinitiatoren durchgeführt. Man kann die Polymeren nach allen bekannten Verfahren polymerisieren, z.B. erhält man sie durch Lösungspolymerisation in Wasser, Alkoholen, Ethern oder Dimethylformamid oder in Gemischen aus verschiedenen Lösemitteln, durch Fällungspolymerisation, umgekehrte Suspensionspolymerisation (Polymerisieren einer Emulsion einer monomerhaltigen wässrigen Phase in einer Ölphase) und Polymerisieren einer Wasser-in-Wasser-Emulsion, beispielsweise bei der man eine wässrige Monomerlösung in einer wässrigen Phase löst oder emulgiert und unter Bildung einer wässrigen Dispersion eines wasserlöslichen Polymeren polymerisiert, wie beispielsweise in WO 00/27893 beschrieben.Suitable comonomers for the preparation of copolymers of N-vinylformamide are in particular vinyl formate, vinyl acetate, vinyl propionate, C 1 -C 4 -alkyl vinyl ethers, N-vinylpyrrolidone, esters, nitriles and amides of monoethylenically unsaturated C 3 - to C 5 -carboxylic acids, in particular of acrylic acid or methacrylic acid and monoethylenically unsaturated C 3 - to C 5 -carboxylic acids. The esters of acrylic acid and methacrylic acid are derived, for example, from alcohols having 1 to 6 carbon atoms. The copolymers preferably contain 95 to 10 mol% of N-vinylformamide and 5 to 90 mol% of at least one other ethylenically unsaturated monomer. Preference is given to using hydrolyzed polymers obtainable by polymerizing
  1. (a) 100 to 10 mol% of N-vinylformamide and
  2. (b) 0 to 90 mol% of vinyl formate, vinyl acetate, vinyl propionate, methyl acrylate, ethyl acrylate, methyl methacrylate and / or dimethyl maleate
and from these polymers after the polymerization 1 to 20 mol% of the polymerized vinyl formamide units are cleaved to form vinylamine units. Very particular preference is given to using hydrolyzed homopolymers of N-vinylformamide having a degree of hydrolysis of from 1 to 20 mol% and an average molar mass M w of at least 1 million in the process according to the invention. The polymerization of the monomers is usually carried out in the presence of radical-forming polymerization initiators. The polymers can be polymerized by all known methods, for example by solution polymerization in water, alcohols, ethers or dimethylformamide or in mixtures of various solvents, by precipitation polymerization, reverse suspension polymerization (polymerizing an emulsion of a monomer-containing aqueous phase in an oil phase) and polymerizing a water-in-water emulsion, for example, in which an aqueous monomer solution is dissolved or emulsified in an aqueous phase and polymerized to form an aqueous dispersion of a water-soluble polymer, such as in WO 00/27893 described.

Im Anschluß an die Polymerisation werden die Polymeren, die einpolymerisierte Einheiten von N-Vinylcarbonsäureamiden enthalten, partiell hydrolysiert. Der Hydrolysegrad der Vinylcarbonsäureamidpolymeren beträgt vorzugsweise 3 bis 15 und insbesondere 5 bis 12 mol%. Der Hydrolysegrad entspricht dem Gehalt der Polymeren an Vinylamingruppen in mol-%. Die Hydrolyse wird vorzugsweise in Gegenwart einer Säure oder einer Base durchgeführt. Man kann die Polymeren jedoch auch enzymatisch hydrolysieren. Bei der Hydrolyse mit Säuren (z.B. Mineralsäuren wie Schwefelsäure, Salzsäure oder Phosphorsäure, Carbonsäuren wie Ameisensäure oder Essigsäure, bzw. Sulfonsäuren oder Phosphonsäuren) entstehen die entsprechenden Ammoniumsalze der Polymeren, während bei der Hydrolyse mit Basen die Vinylamineinheiten der Polymeren in Form der freien Basen vorliegen. Bei der Hydrolyse von Copolymerisaten des N-Vinylformamids mit Vinylestern werden die in das Copolymerisat einpolymerisierten Vinylester-Einheiten partiell oder vollständig in Vinylalkohol-Einheiten überführt. Die Vinylamineinheiten der Polymeren können gegebenenfalls dadurch modifiziert werden, dass man sie in bekannter Weise in die Quaternierungsprodukte umwandelt, z.B. durch Umsetzung der Polymeren mit Dimethylsulfat.Following the polymerization, the polymers containing copolymerized units of N-vinylcarboxamides are partially hydrolyzed. The degree of hydrolysis of the vinylcarboxylic acid amide polymers is preferably from 3 to 15, and more preferably from 5 to 12, mol%. The degree of hydrolysis corresponds to the content of the polymers of vinylamine groups in mol%. The hydrolysis is preferably carried out in the presence of an acid or a base. However, the polymers can also be hydrolyzed enzymatically. In the hydrolysis with acids (eg, mineral acids such as sulfuric acid, hydrochloric acid or phosphoric acid, carboxylic acids such as formic acid or acetic acid, or sulfonic acids or phosphonic acids), the corresponding ammonium salts of the polymers, while in the hydrolysis with bases the vinylamine units of the polymers are present in the form of the free bases , In the hydrolysis of copolymers of N-vinylformamide with vinyl esters, the copolymerized in the copolymer vinyl ester units are partially or completely converted into vinyl alcohol units. The vinylamine units of the polymers may optionally be modified by converting them into the quaternization products in a known manner, e.g. by reaction of the polymers with dimethyl sulfate.

Die Vinylamineinheiten enthaltenden Polymeren werden erfindungsgemäß bei der Herstellung von Papier beispielsweise in einer Menge von 0,002 bis 0,1 Gew.-%, bezogen auf trockenen Papierstoff, in den Dickstoff dosiert.The polymers containing vinylamine units are metered into the thick material in the production of paper, for example in an amount of 0.002 to 0.1% by weight, based on dry paper stock.

Gegenstand der Erfindung ist außerdem die Verwendung von hydrolysierten Homo- oder Copolymerisaten von N-Vinylcarbonsäureamiden mit einem Hydrolysegrad von 1 bis 20 mol-% und einer mittleren Molmasse Mw von mindestens 1 Million bei der Herstellung von Papier, Pappe oder Karton als Zusatz zu einem Störstoffe enthaltendem Dickstoff zur Verringerung von Ablagerungen in der Sieb-, Pressen- und Trockenpartie von Papiermaschinen.The invention also provides the use of hydrolyzed homo- or copolymers of N-vinylcarboxamides having a degree of hydrolysis of 1 to 20 mol% and an average molecular weight M w of at least 1 million in the production of paper, paperboard or cardboard as an additive to a Heavy material containing impurities for reducing deposits in the wire, press and dryer sections of paper machines.

Bei dem erfindungsgemäßen Verfahren wird vorteilhafterweise mindestens ein Retentionsmittel zum Dünnstoff dosiert. Als Retentionsmittel können alle hierfür beschriebenen polymeren Stoffe eingesetzt werden. So kann man beispielsweise die aus der US-A-4 421 602 bekannten partiell hydrolysierten Homopolymerisate des N-Vinylformamids als Retentionsmittel einsetzen. Der Hydrolysegrad der einpolymerisierten N-Vinylformamideinheiten kann 1 bis 100 % betragen. Man kann jedoch auch nicht hydrolysierte Polymerisate von N-Vinylformamid als Retentionsmittel verwenden. Solche Polymeren haben beispielsweise K-Werte von mindestens 160, vorzugsweise 180 bis 300 (bestimmt nach H. Fikentscher in 5 %iger wäßriger Kochsalzlösung bei 25°C und einer Polymerkonzentration von 0,5 Gew.-%).In the method according to the invention, advantageously at least one retention agent is metered into the thin material. As a retention agent all polymeric substances described here can be used. So you can, for example, from the US-A-4,421,602 known partially hydrolyzed homopolymers of N-vinylformamide used as a retention agent. The degree of hydrolysis of the copolymerized N-vinylformamide units may be 1 to 100%. However, it is also possible to use unhydrolysed polymers of N-vinylformamide as retention agent. Such polymers have for example K values of at least 160, preferably 180 to 300 (determined according to H. Fikentscher in 5% strength aqueous sodium chloride solution at 25 ° C. and a polymer concentration of 0.5% by weight).

Weitere geeignete Retentionsmittel sind beispielsweise Polyacrylamide, die in nicht modifizierter Form oder in kationisch oder anionisch modifizierter Form eingesetzt werden können. Copolymerisate aus Acrylamid oder Methacrylamid werden beispielsweise durch Copolymerisieren mit Dialkylaminoethylacrylaten oder Dialkylaminoethylmethacrylaten kationisch modifiziert. Von besonderem Interesse als Retentionsmittel sind hierbei Copolymerisate aus Acrylamid und N,N-Dimethylaminoethylacrylat oder Copolymerisate aus Acrylamid und N,N-Diethylaminoethylacrylat. Die basischen Acrylate sind beispielsweise in Mengen von 5 bis 70, vorzugsweise 8 bis 40 Mol-% in den Copolymerisaten enthalten und liegen vorzugsweise in mit Säuren neutralisierter oder in quaternisierter Form vor. Die Quaternisierung kann beispielsweise mit Methylchlorid oder Dimethylsulfat erfolgen. Acrylamid und Methacrylamid können durch Copolymerisieren mit monoethylenisch ungesättigten Carbonsäuren auch anionisch modifiziert werden. Hochmolekulare Copolymerisate aus beispielsweise Acrylamid und Acrylsäure sind bekannte Retentionsmittel. Der Gehalt an anionischen Comonomeren in den Copolymerisaten beträgt beispielsweise 5 bis 50, vorzugsweise 10 bis 40 Gew.-%. Die kationisch bzw. anionisch modifizierten Poly(meth)acrylamide haben beispielsweise K-Werte von mindestens 180 (bestimmt nach H. Fikentscher in 5 %iger wäßriger Kochsalzlösung bei 25°C und einer Polymerkonzentration von 0,5 Gew.-%).Further suitable retention aids are, for example, polyacrylamides which can be used in unmodified form or in cationically or anionically modified form. Copolymers of acrylamide or methacrylamide are cationically modified, for example, by copolymerization with dialkylaminoethyl acrylates or dialkylaminoethyl methacrylates. Of particular interest as retention aids are copolymers of acrylamide and N, N-dimethylaminoethyl acrylate or copolymers of acrylamide and N, N-diethylaminoethyl acrylate. The basic acrylates are contained, for example, in amounts of from 5 to 70, preferably from 8 to 40, mol% in the copolymers and are preferably present in acids neutralized or in quaternized form. The quaternization can be carried out, for example, with methyl chloride or dimethyl sulfate. Acrylamide and methacrylamide can also be anionically modified by copolymerizing with monoethylenically unsaturated carboxylic acids. High molecular weight copolymers of, for example, acrylamide and acrylic acid are known retention aids. The content of anionic comonomers in the copolymers is for example 5 to 50, preferably 10 to 40 wt .-%. The cationically or anionically modified poly (meth) acrylamides have, for example, K values of at least 180 (determined according to H. Fikentscher in 5% strength aqueous sodium chloride solution at 25 ° C. and a polymer concentration of 0.5% by weight).

Beispiele für kationische Retentionsmittel sind Polyethylenimine, Polyamine mit Molmassen von mehr als 50.000, Polyamidoamine, die gegebenenfalls durch Pfropfen mit Ethylenimin und anschließende Vernetzung mit beispielsweise Polyethylenglykoldichlorhydrinethern gemäß der Lehre der DE-C-24 34 816 oder mit Epichlorhydrin vernetzt sind, Polyetheramine, Polyvinylimidazole, Polyvinylimidazole, Polyvinyltetrahydropyridine, Polydialkylaminoalkylvinylether, Polydialkylaminoalkyl(meth)acrylate in protonierter oder quartemisierter Form, Polydiallyldialkylammoniumhalogenide wie insbesondere Polydiallyldimethylammoniumchlorid. Besonders bevorzugte Retentionsmittel sind die aus der oben angegebenen DE-C-24 34 816 bekannten mit Ethylenimin gepfropften und anschließend vernetzten Polyamidoamine.Examples of cationic retention aids are polyethyleneimines, polyamines having molar masses of more than 50,000, polyamidoamines, optionally by grafting with ethyleneimine and subsequent crosslinking with, for example, polyethylene glycol dichlorohydrin ethers according to the teaching of US Pat DE-C-24 34 816 or are crosslinked with epichlorohydrin, polyetheramines, polyvinylimidazoles, polyvinylimidazoles, polyvinyltetrahydropyridines, polydialkylaminoalkyl vinyl ethers, polydialkylaminoalkyl (meth) acrylates in protonated or quaternized form, polydiallyldialkylammonium halides, in particular polydiallyldimethylammonium chloride. Particularly preferred retention aids are those specified above DE-C-24 34 816 known polyamidoamines grafted with ethyleneimine and subsequently crosslinked.

Als Retentionsmittel kann man auch die aus der Literatur bekannten Mikropartikel-Systeme aus hochmolekularen Polyacrylamiden und Bentonit verwenden, wobei man dem Papierstoff zunächst ein hochmolekulares kationisches Polyacrylamid zusetzt, den Papierstoff einer Scherung unterwirft und danach Bentonit dosiert. Verfahren dieser Art sind beispielsweise Gegenstand der EP-A-0 235 893 und der EP-A-0 335 575 . Eine andere Reihenfolge der Dosierung von polymerem Retentionsmittel und anorganischen Partikeln wie Bentonit, ist aus DE-A-102 36 252 bekannt. Vorzugsweise setzt man kationische Retentionsmittel ein. Die Retentionsmittel werden üblicherweise in einer Menge von 0,01 bis 0,2 Gew.-%, bezogen auf trockenen Papierstoff, angewendet. Das Verhältnis von erfindungsgemäß zu verwendendem 1 bis 20 mol-% Vinylamineinheiten enthaltenden Polymeren mit Molmassen von > 1 Million zu Retentionsmittel beträgt beispielsweise 1:2 bis 5:1.As a retention agent, it is also possible to use the microparticle systems of high molecular weight polyacrylamides and bentonite known from the literature, initially adding a high molecular weight cationic polyacrylamide to the paper stock, subjecting the paper stock to shear, and then metering in bentonite. Such methods are for example the subject of EP-A-0 235 893 and the EP-A-0 335 575 , Another order of dosing of polymeric retention aid and inorganic particles such as bentonite is out DE-A-102 36 252 known. It is preferable to use cationic retention aids. The retention agents are usually used in an amount of from 0.01 to 0.2% by weight, based on dry paper stock, applied. The ratio of polymers to be used according to the invention containing 1 to 20 mol% of vinylamine units with molar masses of> 1 million to retention agent is, for example, 1: 2 to 5: 1.

Außer mindestens einem Retentionsmittel kann man bei der Herstellung von Papier, Pappe und Karton nach dem erfindungsgemäßen Verfahren weitere übliche Produkte in den gebräuchlichen Mengen zum Dünnstoff zugeben, z.B. Leimungsmittel, Verfestiger (Naß- und Trockenverfestigungsmittel), Biozide und/oder Farbstoffe.Apart from at least one retention agent, in the production of paper, paperboard and cardboard by the process according to the invention, it is possible to add further customary products in the customary amounts to the thin material, e.g. Sizing agents, strength agents (wet and dry strength agents), biocides and / or dyes.

Sofern nichts anderes angegeben ist, bedeuten die Prozentangaben in den Beispielen Gewichtsprozent. Die Molmassen wurden durch statische Lichtstreuung bestimmt.Unless otherwise indicated, percentages in the examples are percent by weight. The molecular weights were determined by static light scattering.

BeispieleExamples

Folgende Polymere wurden verwendet:

PVAm 1:
Polyvinylamin mit einer Molmasse von 400 000 D (hergestellt durch Hydrolyse von Poly-N-vinylformamid, Hydrolysegrad 95 mol-%)
PVAm 2:
Polymer aus 30 mol-% Vinylamineinheiten und 70 mol-% N-Vinylformamideinheiten mit einer Molmasse von 400 000 D (hergestellt durch partielle Hydrolyse von Poly-N-vinylformamid)
PVAm 3:
Polymer aus 10 mol-% Vinylamineinheiten und 90 mol-% N-Vinylformamideinheiten mit einer Molmasse von 2 Millionen D (hergestellt durch partielle Hydrolyse aus Poly-N-vinylformamid)
The following polymers were used:
PVAm 1:
Polyvinylamine with a molecular weight of 400 000 D (prepared by hydrolysis of poly-N-vinylformamide, degree of hydrolysis 95 mol%)
PVAm 2:
Polymer of 30 mol% of vinylamine units and 70 mol% of N-vinylformamide units having a molecular weight of 400,000 D (prepared by partial hydrolysis of poly-N-vinylformamide)
PVAm 3:
Polymer of 10 mol% of vinylamine units and 90 mol% of N-vinylformamide units with a molecular weight of 2 million D (prepared by partial hydrolysis of poly-N-vinylformamide)

Beispiel 1example 1

Auf einer Papiermaschine wurde kontinuierlich holzfreies Streichrohpapier mit einem Flächengewicht von 150 g/cm2 hergestellt. Die Zusammensetzung des Papierstoffs in der Mischbütte bestand aus 14% gebleichtem Kiefernsulfat, 34% gebleichtem Birkensulfit, 21% gestrichenem Ausschuß und 31% gemahlenem Calciumcarbonat, die Konzentration des Papierstoffs betrug 4%, bezogen auf trockenen Papierstoff. Die Kapazität der Papiermaschine betrug 20 t/h. Das fertige Papier enthielt ca. 18% gemahlenes Calciumcarbonat.Wood-free base paper with a basis weight of 150 g / cm 2 was continuously produced on a paper machine. The composition of the pulp in the mixing chest consisted of 14% bleached pine sulfate, 34% bleached birch sulphite, 21% coated broke and 31% ground calcium carbonate, the pulp concentration being 4% based on dry pulp. The capacity of the paper machine was 20 t / h. The finished paper contained about 18% ground calcium carbonate.

Die Faserstoffe wurden der Mischbütte in getrennten Strängen zugeführt. In den Strang, in dem der gestrichene Ausschuß transportiert wurde, dosierte man nach dem Entstipper 400 g/t PVAm 3, bezogen auf gestrichenen Ausschuß. Der in der Mischbütte befindliche Papierstoff mit einer Stoffkonzentration von 4% wurde durch Zuführen von Wasser aus dem Papiermaschinenkreislauf zu einem Dünnstoff mit einer Konzentration von 0,8%, bezogen auf trockenen Papierstoff, verdünnt. Der Dünnstoff wurde nach Durchlaufen des Vertikalsichters kurz vor dem Stoffauflauf mit einem Retentionssystem aus 5 kg/t einer handelsüblichen kationischen Stärke (Substitutionsgrad DS = 0,03) und 800 g/t Polyaluminiumchlorid in Form einer 18%igen wässrigen Lösung versetzt. Die Maschine lief einwandfrei. Nach einer Laufzeit von einem Monat wurde die Maschine routinemäßig abgestellt und gereinigt. Die Ablagerungen auf der Maschine waren jedoch nicht so gravierend, dass man die Maschine hätte abstellen müssen.The fibers were fed to the mixing chest in separate strands. In the strand in which the coated committee was transported, metered after the Entstipper 400 g / t PVAm 3, based on coated Committee. The one in the mixer 4% stock was diluted by feeding water from the paper machine circuit to a 0.8% concentration of dry stock. The thin material was treated after passing through the vertical sight just before the headbox with a retention system of 5 kg / t of a commercial cationic starch (degree of substitution DS = 0.03) and 800 g / t of polyaluminum chloride in the form of an 18% aqueous solution. The machine ran flawlessly. After a period of one month, the machine was routinely shut down and cleaned. However, the deposits on the machine were not so serious that you should have turned off the machine.

Vergleichsbeispiel 1Comparative Example 1

Beispiel 1 wurde mit der einzigen Ausnahme wiederholt, dass man anstelle von PVAm 3 jetzt 400 g/t Polyaluminiumchlorid in Form einer 18%igen wässrigen Lösung in den Strang dosierte, in dem der gestrichene Ausschuß transportiert wurde. Die Laufeigenschaften der Maschine und die Qualität des hergestellten Papiers sind unbefriedigend. Die Papierproduktion musste nach einer Laufzeit der Maschine von 3 Tagen unterbrochen werden, um störende Ablagerungen auf Sieb-, Pressen- und Trockenpartie der Maschine zu entfernen.Example 1 was repeated with the sole exception that, instead of PVAm 3, 400 g / t of polyaluminum chloride in the form of an 18% aqueous solution were now metered into the strand in which the coated broke was transported. The running characteristics of the machine and the quality of the paper produced are unsatisfactory. The paper production had to be interrupted after a running time of the machine of 3 days to remove interfering deposits on the wire, press and dryer section of the machine.

Vergleichsbeispiel 2Comparative Example 2

Beispiel 1 wurde mit der einzigen Ausnahme wiederholt, dass man anstelle von PVAm 3 jetzt 400 g/t PVAm 1 in den Strang dosierte, in dem der gestrichene Ausschuß transportiert wurde. Die Laufeigenschaften der Maschine und die Qualität des hergestellten Papiers sind zwar gegenüber dem Vergleichsbeispiel 1 verbessert, jedoch musste die Papierproduktion ebenfalls nach einer Laufzeit der Maschine von 3 Tagen unterbrochen werden, um störende Ablagerungen auf Sieb-, Pressen- und Trockenpartie der Maschine zu entfernen.Example 1 was repeated with the sole exception that, instead of PVAm 3, 400 g / t of PVAm 1 were now metered into the strand in which the coated broke was transported. Although the running properties of the machine and the quality of the paper produced are improved compared to Comparative Example 1, the paper production also had to be interrupted after a running time of the machine of 3 days to remove disturbing deposits on the screen, press and dryer section of the machine.

Vergleichsbeispiel 3Comparative Example 3

Beispiel 1 wurde mit der einzigen Ausnahme wiederholt, dass man anstelle von PVAm 3 jetzt 400 g/t PVAm 2 in den Strang dosierte, in dem der gestrichene Ausschuß transportiert wurde. Die Laufeingenschaften der Maschine und die Qualität des hergestellten Papiers sind zwar gegenüber dem Vergleichsbeispiel 1 verbessert, jedoch mußte die Papierproduktion nach einer Laufzeit der Maschine von 4 Tagen unterbrochen werden, um störende Ablagerungen auf Sieb-, Pressen- und Trockenpartie der Maschine zu entfernen.Example 1 was repeated with the sole exception that instead of PVAm 3, 400 g / t of PVAm 2 were now metered into the strand in which the coated broke was transported. Although the running characteristics of the machine and the quality of the produced paper are improved over Comparative Example 1, the paper production had to be interrupted after a running time of the machine of 4 days to remove disturbing deposits on the screen, press and dryer section of the machine.

Claims (9)

  1. A process for the production of paper, board and cardboard by draining a paper stock comprising interfering substances in the presence of polymers which comprise vinylamine units and which have an average molar mass Mw of at least 1 million, wherein a high-consistency stock is first prepared, at least one polymers comprising vinylamine units and having an average molar mass Mw of at least 1 million and a degree of hydrolysis of from 1 to 20 mol% is metered into the high-consistency stock, the high-consistency stock is diluted to a low-consistency stock by adding water, and the low-consistency stock is drained.
  2. The process according to claim 1, wherein the consistency of the high-consistency stock is more than 2% by weight, based on dry paper stock, and the degree of hydrolysis of the polymers is from 3 to 15 mol%.
  3. The process according to claim 1 or 2, wherein the consistency of the high-consistency stock is from 3.0 to 6.0% by weight, based on dry paper stock, and the degree of hydrolysis of the polymers is from 5 to 12 mol%.
  4. The process according to any of claims 1 to 3, wherein the consistency of the high-consistency stock is from 3.5 to 4.5% by weight, based on dry paper stock, and wherein the consistency of the low-consistency stock is brought to a concentration below 1.5% by weight, based on dry paper stock.
  5. The process according to any of claims 1 to 4, wherein polymers comprising vinylamine units and are obtainable by hydrolysis of homo- and/or copolymers of N-vinylcarboxamides are used.
  6. The process according to claim 5, wherein hydrolyzed homopolymers of N-vinylformamide having a degree of hydrolysis of from 1 to 20 mol% are used as polymers comprising vinylamine units.
  7. The process according to any of claims 1 to 6, wherein at least one retention aid is metered into the low-consistency stock.
  8. The process according to any of claims 1 to 7, wherein the amount of the polymers comprising vinylamine units and metered into the high-consistency stock is from 0.002 to 0.1% by weight, based on dry paper stock.
  9. The use of hydrolyzed homo- or copolymers of N-vinylcarboxamides having a degree of hydrolysis of from 1 to 20 mol% and an average molar mass Mw of at least 1 million in the production of paper, board or cardboard as an additive to a high-consistency stock comprising interfering substances, for reducing deposits in the wire part, press section and drying section of paper machines.
EP05716030A 2004-03-16 2005-03-14 Method for producing paper, paperboard and cardboard Active EP1727938B1 (en)

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DE102004013007A DE102004013007A1 (en) 2004-03-16 2004-03-16 Process for the production of paper, cardboard and cardboard
PCT/EP2005/002685 WO2005090678A1 (en) 2004-03-16 2005-03-14 Method for producing paper, paperboard and cardboard

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CN (1) CN1934315B (en)
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JP2013508568A (en) * 2009-10-20 2013-03-07 ビーエーエスエフ ソシエタス・ヨーロピア Method for producing paper, board and cardboard having high dry strength
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CN105399897B (en) * 2015-12-30 2017-08-25 中国石油化工股份有限公司 Temperature-tolerant anti-salt polyacrylamide is birdsed of the same feather flock together compound and preparation method thereof

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CN1934315A (en) 2007-03-21
EP1727938A1 (en) 2006-12-06
KR20070011377A (en) 2007-01-24
DE502005003567D1 (en) 2008-05-15
CA2558277A1 (en) 2005-09-29
ZA200608558B (en) 2008-06-25
US8337665B2 (en) 2012-12-25
KR101136290B1 (en) 2012-04-24
BRPI0508262A (en) 2007-07-31
ATE391207T1 (en) 2008-04-15
US8486227B2 (en) 2013-07-16
CA2558277C (en) 2013-11-12
DE102004013007A1 (en) 2005-10-06

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