EP0438707A1 - Process for making paper and board - Google Patents

Process for making paper and board Download PDF

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Publication number
EP0438707A1
EP0438707A1 EP90124067A EP90124067A EP0438707A1 EP 0438707 A1 EP0438707 A1 EP 0438707A1 EP 90124067 A EP90124067 A EP 90124067A EP 90124067 A EP90124067 A EP 90124067A EP 0438707 A1 EP0438707 A1 EP 0438707A1
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EP
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Prior art keywords
vinylformamide
paper
hydrolysis
degree
hydrolyzed
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EP90124067A
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German (de)
French (fr)
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EP0438707B1 (en
Inventor
Werner Auhorn
Friedrich Dr. Linhart
Primoz Dr. Lorencak
Michael Dr. Kroener
Norbert Dr. Sendhoff
Walter Denzinger
Heinrich Dr. Hartmann
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BASF SE
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BASF SE
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    • 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

Definitions

  • US Pat. No. 4,421,602 discloses the use of partially hydrolyzed homopolymers of N-vinylformamide as retention aids, drainage aids and flocculants in the manufacture of paper.
  • anionic compounds accumulate in the returned water, which severely impair the effectiveness of cationic polymeric process chemicals in the dewatering of paper stock and the retention of fillers and fibers.
  • the procedure in practice is to additionally dewater these paper materials in the presence of a fixing agent.
  • condensates made from dicyandiamide and formaldehyde or condensates made from dimethylamine and epichlorohydrin are used as fixatives, cf. Tappi Journal, August 1988, pages 131 to 134.
  • the object of the present invention is to provide products which are more effective than the previously used fixing agents and which, in combination with cationic retention agents, have an improved retention, flocculation and drainage effect than combinations previously used.
  • the object is achieved according to the invention with a process for the production of paper, cardboard and cardboard by dewatering a paper material containing impurities in the presence of fixing agents and cationic retention agents if the fixing agent is hydrolyzed homo- and / or copolymers of N-vinylformamide with a degree of hydrolysis of at least Uses 60%.
  • paper materials are dewatered, for their production all fiber qualities, either alone or in Mixture among themselves.
  • water is used for the production of the paper stock, which is at least partially or completely returned from the paper machine. These are either clarified or unclarified white water and mixtures of such water qualities.
  • the returned water contains more or less large amounts of so-called contaminants, which are known to have a very severe effect on the effectiveness of the cationic retention and drainage agents.
  • the content of such contaminants in the paper stock can be characterized, for example, with the sum parameter chemical oxygen demand (COD value).
  • the COD values of such paper stock are 300-30,000, preferably 1,000-20,000 mg oxygen / kg of the aqueous phase of the paper stock.
  • wood pulp includes wood pulp, thermomechanical material (TMP), chemo-thermomechanical material (CTMP), pressure grinding, semi-pulp, high-yield pulp and refiner mechanical pulp (RMP).
  • TMP thermomechanical material
  • CMP chemo-thermomechanical material
  • RMP refiner mechanical pulp
  • suitable pulps are sulfate, sulfite and sodium pulps.
  • the unbleached pulps which are also referred to as unbleached kraft pulp, are preferably used.
  • Suitable annual plants for the production of paper materials are, for example, rice, wheat, sugar cane and kenaf. Waste paper is also used to produce the pulps, either alone or in a mixture with other fibrous materials.
  • Pulps of the type described above contain more or less large amounts of interfering substances which, as already explained above, can be determined using the COD value or also using the so-called cationic requirement.
  • the cationic requirement is the amount of a cationic polymer that is necessary to bring a defined amount of white water to the isoelectric point. Since the cationic requirement is very much dependent on the composition of the cationic retention agent used for the determination, a polyamidoamine obtained from example 3 of DE-PS 2 434 816 from adipic acid and diethylenetriamine was used for the standardization, which was grafted with ethyleneimine and crosslinked with polyethylene glycol dichlorohydrin ether was, cf. the polymer I described below.
  • the pulps containing impurities have the COD values given above and have a cationic requirement of more than 50 mg polymer I / l white water.
  • the fixing agent for paper materials containing impurities is hydrolyzed homo- and / or copolymers of N-vinylformamide with a degree of hydrolysis of at least 60%.
  • Polymers of this type are known, for example, from EP application 0 216 387.
  • N-vinylformamide is polymerized and formyl groups are split off from the polymer by hydrolysis in the presence of acids or bases. The cleavage of the formyl group from the polymers containing N-vinylformamide units in copolymerized form leads to the formation of vinylamine units in the polymer.
  • the degree of hydrolysis of the polymerized N-vinylformamide is at least 60, preferably 70-100 mol%.
  • the cleavage of the formyl groups can, however, also be carried out with the exclusion of water with hydrogen chloride or hydrogen bromide.
  • an N-formyl group of the copolymer forms an amino group with elimination of carbon monoxide.
  • acids or bases act on copolymers of N-vinylformamide and acrylonitrile, methacrylonitrile, N-vinylpyrrolidone and C1- to C4-alkyl vinyl ethers, the comonomers of N-vinylformamide are hardly changed chemically, while the copolymerized N-vinylformamide is at least partially hydrolyzed.
  • copolymers of N-vinylformamide with vinyl acetate and / or Vinyl propionate is obtained, for example, under the action of hydrochloric acid at a temperature of 50 ° C., in which the copolymerized vinyl acetate or vinyl propionate is not hydrolyzed, whereas the copolymerized N-vinylformamide is at least 60%.
  • copolymers of N-vinylformamide and vinyl acetate or vinyl propionate are treated with sodium hydroxide solution at a temperature of 50 ° C.
  • the formyl groups from the polymerized N-vinylformamide and the acetyl or propionyl groups from the polymerized vinyl acetate or vinyl propionate are approximately the same Split off the dimensions of the copolymer.
  • the degree of hydrolysis of the polymers depends mainly on the amount of acid or base used and the temperature during the hydrolysis.
  • the homo- and copolymers of N-vinylformamide with a degree of hydrolysis of at least 60% have K values according to Fikentscher (measured in 5% aqueous saline solution at a polymer concentration of 0.5% by weight and a temperature of 25 ° C) of 30-150, preferably 60-90.
  • the fixing agents are used in customary amounts, ie of 0.02-2, preferably 0.05-0.5% by weight, based on dry paper stock.
  • All commercially available products for this purpose can be used as cationic retention agents. These are, for example, polyethyleneimines, polyamines with a molecular weight of more than 50,000, polyamidoamines which may have been modified by grafting on ethyleneimine, polyetheramines, polyvinylimidazoles, polyvinylpyrrolidines, polyvinylimidazolines, polyvinyltetrahydropyridines, polydialkylaminoalkylvinylethers, polydialkylamate alkylated (acrylated) acrylated (acrylated) methacrylate (acrylated) methacrylate (methacrylate) acrylate (or methylated) acrylated (acrylated) methacrylate (methoxylated) acrylate (methoxylated) acrylate (methoxylated) acrylate (acrylated) methacrylate (methacrylate) formated .
  • polyethyleneimines polyamines with a molecular weight of more than 50,000
  • Suitable compounds are, for example, polydiallyldialkylammonium halides, in particular polydiallyldimethylammonium chloride.
  • Particularly preferred retention aids are polyamidoamines from adipic acid and polyalkylene polyamines, such as diethylenetriamine, which are grafted with ethyleneimine and crosslinked with polyethylene glycol dichlorohydrin ethers according to the teaching of DE-PS 2 434 816 or with epichlorohydrin, and commercially available polyethyleneimines and copolymers of acrylamide or methamyl acrylate or methamyl acrylate and methamyl acrylate or methacrylamide and acrylamyl acrylate or methacrylamide and acrylamyl acrylate or methacrylamide and acrylamyl acrylate or methacrylamide and acrylamyl acrylate or methacrylamide and acrylamyl acrylate or methacrylamide and acrylamyl acrylate or methacrylamide and
  • Basic acrylates are preferably in neutralized or quaterized form with acids.
  • the quaternization can take place, for example, with methyl chloride or dimethyl sulfate.
  • the cationic retention agents have K values according to Fikentscher (determined in 5% aqueous saline solution at a polymer concentration of 0.5% by weight and a temperature of 25 ° C) of at least 180.
  • dehydration-containing paper materials are dewatered in the presence of hydrolyzed N-vinylformamide polymers as fixing agents and the commonly used cationic retention agents. It is preferable to add the fixing agent to the paper stock first and then the retention agent. However, they can also be added to the paper stock at the same time. It is only essential that the paper stock is dewatered in the presence of fixative and retention aid.
  • the retention aids are used in an amount of 0.01 to 0.2% by weight, based on dry paper stock.
  • the ratio of fixative to retention aid is generally 1: 2 to 5: 1. Compared to conventional combinations of fixatives and cationic retention aids, improved retention and accelerated dewatering of the paper stock are obtained by the process according to the invention.
  • the chemical oxygen demand, COD value was determined according to DIN 38 409.
  • the light transmission of the white water was measured with the Zeiss PM 7 spectrophotometer. It is a measure of the retention of fine and fillers. It is given in percent. The higher the value for the light transmittance, the better the retention.
  • the end point was determined with the aid of polyelectrolyte titration according to D. Horn, Progr. Colloid & Polym. Sci. Vol. 65, 251-264 (1978).
  • Polymer I polyamidoamine from adipic acid and diethylenetriamine, which was grafted with ethyleneimine and crosslinked with polyethylene glycol dichlorohydrin ether as described in Example 3 of DE-PS 2 434 816.
  • Polymer II polyamidoamine from adipic acid and diethylenetriamine, which was grafted with ethyleneimine and crosslinked with epichlorohydrin.
  • Polymer III Commercial high molecular weight polyethyleneimine which was adjusted to a pH of 7.5 with formic acid.
  • Polymer IV copolymer of 70% acrylamide and 30% N-dimethylaminoethyl acrylate in the form of methochloride with a K value of 220.
  • Polymer A Hydrolyzed homopolymer of N-vinylformamide with a degree of hydrolysis of 96% and a K value of 75.
  • Polymer B Hydrolyzed copolymer 70% N-vinylformamide and 30% vinyl acetate, in which 96% of the formyl groups of the polymerized N-vinylformamide and 68% of the polymerized vinyl acetate groups had been hydrolyzed.
  • the K value of the hydrolyzed copolymer was 75.
  • Polymer C Commercial condensate of dicyandiamide and formaldehyde as a comparison with the prior art.
  • Polymer D Commercial homopolymer of diallyldimethylammonium chloride with a K value of 100 as a comparison.
  • the material model used was a wood and kaolin-containing newsprint with a density of 2 g / l with a pH of 7 and a degree of paint of 68 ° SR.
  • the paper stock also contained 3% sodium lignin sulfonate as a contaminant.
  • the amounts of fixing agent given in Table 2 and then 0.06% of polymer 1 as the cationic retention agent were added to samples of this paper stock.
  • the dewatering time was first determined in a Schopper-Riegler test device and the light transmittance was determined on the filtrate obtained.
  • sheets with a basis weight of 70 g / m2 were formed on the Rapid-Köthen device and their ash content was determined. The amounts used in each case and the results obtained therewith are given in Table 2.
  • a paper stock with a consistency of 5 g / l from 75% wood pulp, 25% pine sulfate pulp, 35% china clay with a degree of grinding of 25 ° SR and a pH of 7 was turned into paper on a test paper machine at a machine speed of 80 m / minute processed with a basis weight of 60 g / m2.
  • the paper stock contained 0.2% of the sodium salt of humic acid and 0.2% of polymer 1 as a retention agent. Under these conditions, the dewatering time was 124 seconds and the ash retention was 57.4%.
  • the polymers described in Table 3 were added to the paper stock described above. The results obtained are given in Table 3.
  • a wood and kaolin-containing newsprint with a consistency of 2 g / l and a pH value of 7 and a degree of paint of 68 ° SR was used as the model substance.
  • 3% sodium lignin sulfonate was added as an interfering substance.
  • the paper stock thus obtained was dewatered in a Schopper-Riegler device.
  • the results obtained without the addition of a retention and drainage agent are shown in Table 4, as are the results obtained by adding 0.2% of the polymers mentioned in the table as a fixing agent and then adding 0.06% polymer 1 were obtained as a retention aid.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Paper (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

In a process for making paper, paperboard and cardboard, a paper pulp containing interfering materials is dehydrated in the presence of a hydrolysed homopolymer and/or copolymer of N-vinylformamide having a degree of hydrolysis of at least 60%, and of cationic retention agents. As compared with the use of known fixing agents, a higher dehydration rate and improved retention are obtained according to the invention.

Description

Aus der EP-Anmeldung 0216387 ist bekannt, daß man Copolymerisate aus 95 - 10 mol-% N-Vinylformamid und 5 - 90 mol-% eines ethylenisch ungesättigten Monomeren aus der Gruppe Vinylacetat, Vinylpropionat, der C₁- bis C₄-Alkylvinylether, N-Vinylpyrrolidon, der Ester, Nitrile und Amide von Acrylsäure und Methacrylsäure in zumindest partiell hydrolysierter Form, bei der 30 - 100 mol-% der Formylgruppen aus dem Copolymerisat abgespalten sind, in Mengen von 0, 1 - 5 Gew.-%, bezogen auf trockene Fasern, dem Papierstoff vor der Blattbildung als Naß- und Trockenverfestigungsmittel für Papier zusetzt.From EP application 0216387 it is known that copolymers of 95-10 mol% N-vinylformamide and 5-90 mol% of an ethylenically unsaturated monomer from the group vinyl acetate, vinyl propionate, the C₁ to C₄ alkyl vinyl ether, N- Vinyl pyrrolidone, the esters, nitriles and amides of acrylic acid and methacrylic acid in at least partially hydrolyzed form, in which 30-100 mol% of the formyl groups have been split off from the copolymer, in amounts of 0.1-5% by weight, based on dry Fibers to which paper stock is added as a wet and dry strength agent for paper before sheet formation.

Aus der US-PS 4 421 602 ist die Verwendung von partiell hydrolysierten Homopolymerisaten des N-Vinylformamid als Retentions-, Entwässerungs- und Flockungsmittel bei der Herstellung von Papier bekannt. Da in den Papierfabriken die Wasserkreisläufe immer stärker eingeengt werden, reichern sich im zurückgeführten Wasser anionische Verbindungen an, die die Wirksamkeit kationischer polymerer Prozeßchemikalien bei der Entwässerung von Papierstoff und die Retention von Füll- und Faserstoffen stark beeinträchtigen. Zur Entwässerung von Störstoffe enthaltenden Papierstoffen mit den kationischen Polymeren geht man in der Praxis daher so vor, daß man die Entwässerung dieser Papierstoffe zusätzlich in Gegenwart eines Fixiermittels durchführt. Als Fixiermittel verwendet man beispielsweise Kondensate aus Dicyandiamid und Formaldehyd oder Kondensate aus Dimethylamin und Epichlorhydrin, vgl. Tappi Journal, August 1988, Seiten 131 bis 134.US Pat. No. 4,421,602 discloses the use of partially hydrolyzed homopolymers of N-vinylformamide as retention aids, drainage aids and flocculants in the manufacture of paper. As the water cycles in the paper mills are increasingly restricted, anionic compounds accumulate in the returned water, which severely impair the effectiveness of cationic polymeric process chemicals in the dewatering of paper stock and the retention of fillers and fibers. In order to dewater paper materials containing impurities with the cationic polymers, the procedure in practice is to additionally dewater these paper materials in the presence of a fixing agent. For example, condensates made from dicyandiamide and formaldehyde or condensates made from dimethylamine and epichlorohydrin are used as fixatives, cf. Tappi Journal, August 1988, pages 131 to 134.

Der vorliegenden Erfindung liegt die Aufgabe zugrunde, gegenüber den bisher gebräuchlichen Fixiermitteln wirksamere Produkte zur Verfügung zu stellen, die in Kombination mit kationischen Retentionsmitteln eine verbesserte Retentions-, Flockungs- und Entwässerungswirkung haben als bisher gebräuchliche Kombinationen.The object of the present invention is to provide products which are more effective than the previously used fixing agents and which, in combination with cationic retention agents, have an improved retention, flocculation and drainage effect than combinations previously used.

Die Aufgabe wird erfindungsgemäß gelöst mit einem Verfahren zur Herstellung von Papier, Pappe und Karton durch Entwässern eines Störstoffe enthaltenden Papierstoffs in Gegenwart von Fixiermitteln und kationischen Retentionsmitteln, wenn man als Fixiermittel hydrolysierte Homo- und/oder Copolymerisate des N-Vinylformamids mit einem Hydrolysegrad von mindestens 60 % einsetzt.The object is achieved according to the invention with a process for the production of paper, cardboard and cardboard by dewatering a paper material containing impurities in the presence of fixing agents and cationic retention agents if the fixing agent is hydrolyzed homo- and / or copolymers of N-vinylformamide with a degree of hydrolysis of at least Uses 60%.

Bei dem erfindungsgemäßen Verfahren werden Papierstoffe entwässert, für deren Herstellung sämtliche Faserqualitäten, entweder allein oder in Mischung untereinander in Betracht kommen. Für die Herstellung des Papierstoffs wird in der Praxis Wasser verwendet, das zumindest teilweise oder vollständig von der Papiermaschine zurückgeführt wird. Es handelt sich hierbei entweder um geklärtes oder ungeklärtes Siebwasser sowie um Mischungen solcher Wasserqualitäten. Das zurückgeführte Wasser enthält mehr oder weniger größere Mengen an sogenannten Störstoffen, die bekanntlich die Wirksamkeit der kationischen Retentions- und Entwässerungsmittel sehr stark beeinträchtigen. Der Gehalt des Papierstoffs an solchen Störstoffen kann beispielsweise mit dem Summen-Parameter chemischer Sauerstoffbedarf (CSB-Wert) charakterisiert werden. Die CSB-Werte solcher Papierstoffe betragen 300 - 30.000, vorzugsweise 1.000 - 20.000 mg Sauerstoff/kg der wäßrigen Phase des Papierstoffs. Diese Mengen an Störstoffen führen zu einer starken Beeinträchtigung der Wirksamkeit üblicher kationischer Entwässerungs- und Retentionsmittel, solange sie in Abwesenheit von Fixiermitteln bei der Papierherstellung eingesetzt werden.In the method according to the invention, paper materials are dewatered, for their production all fiber qualities, either alone or in Mixture among themselves. In practice, water is used for the production of the paper stock, which is at least partially or completely returned from the paper machine. These are either clarified or unclarified white water and mixtures of such water qualities. The returned water contains more or less large amounts of so-called contaminants, which are known to have a very severe effect on the effectiveness of the cationic retention and drainage agents. The content of such contaminants in the paper stock can be characterized, for example, with the sum parameter chemical oxygen demand (COD value). The COD values of such paper stock are 300-30,000, preferably 1,000-20,000 mg oxygen / kg of the aqueous phase of the paper stock. These amounts of contaminants severely impair the effectiveness of conventional cationic drainage and retention agents as long as they are used in the absence of fixatives in papermaking.

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 Zellstoffe kommen beispielsweise Sulfat-, Sulfit- und Natronzellstoffe in Betracht. Vorzugsweise verwendet man die ungebleichten Zellstoffe, die auch als ungebleichter Kraftzellstoff bezeichnet werden. Geeignete Einjahrespflanzen zur Herstellung von Papierstoffen sind beispielsweise Reis, Weizen, Zuckerrohr und Kenaf. Zur Herstellung der Pulpen wird auch Altpapier verwendet, entweder allein oder in Mischung mit anderen Faserstoffen.As fiber materials for the production of the pulps, all the usual qualities are possible, e.g. Wood pulp, bleached and unbleached pulp and paper pulp from all annual plants. For example, wood pulp includes wood pulp, thermomechanical material (TMP), chemo-thermomechanical material (CTMP), pressure grinding, semi-pulp, high-yield pulp and refiner mechanical pulp (RMP). Examples of suitable pulps are sulfate, sulfite and sodium pulps. The unbleached pulps, which are also referred to as unbleached kraft pulp, are preferably used. Suitable annual plants for the production of paper materials are, for example, rice, wheat, sugar cane and kenaf. Waste paper is also used to produce the pulps, either alone or in a mixture with other fibrous materials.

Pulpen der oben beschriebenen Art enthalten mehr oder weniger größere Mengen an Störstoffen, die, wie bereits oben erläutert, mit Hilfe des CSB-Werts erfaßt werden können oder auch mit Hilfe des sogenannten kationischen Bedarfs. Unter dem kationischen Bedarf wird diejenige Menge eines kationischen Polymeren verstanden, die notwendig ist, um eine definierte Menge des Siebwassers zum isoelektrischen Punkt zu bringen. Da der kationische Bedarf sehr stark von der Zusammensetzung des jeweils für die Bestimmung verwendeten kationischen Retentionsmittels verantwortlich ist, wurde zur Standardisierung ein gemäß Beispiel 3 der DE-PS 2 434 816 erhaltenes Polyamidoamin aus Adipinsäure und Diethylentriamin eingesetzt, das mit Ethylenimin gepfropft und mit Polyethylenglykoldichlorhydrinether vernetzt war, vgl. das unten beschriebene Polymer I. Die Störstoffe enthaltenden Pulpen haben die oben angegebenen CSB-Werte und weisen einen kationischen Bedarf von mehr als 50 mg Polymer I/l Siebwasser auf.Pulps of the type described above contain more or less large amounts of interfering substances which, as already explained above, can be determined using the COD value or also using the so-called cationic requirement. The cationic requirement is the amount of a cationic polymer that is necessary to bring a defined amount of white water to the isoelectric point. Since the cationic requirement is very much dependent on the composition of the cationic retention agent used for the determination, a polyamidoamine obtained from example 3 of DE-PS 2 434 816 from adipic acid and diethylenetriamine was used for the standardization, which was grafted with ethyleneimine and crosslinked with polyethylene glycol dichlorohydrin ether was, cf. the polymer I described below. The pulps containing impurities have the COD values given above and have a cationic requirement of more than 50 mg polymer I / l white water.

Gemäß Erfindung verwendet man als Fixiermittel für Störstoffe enthaltende Papierstoffe hydrolysierte Homo- und/oder Copolymerisate des N-Vinylformamids mit einem Hydrolysegrad von mindestens 60 % Polymerisate dieser Art sind beispielsweise aus der EP-Anmeldung 0 216 387 bekannt. Zu ihrer Herstellung polymerisiert man beispielsweise N-Vinylformamid und spaltet aus dem Polymeren durch Hydrolysieren in Gegenwart von Säuren oder Basen Formylgruppen ab. Die Abspaltung der Formylgruppe aus den N-Vinylformamid-Einheiten einpolymerisiert enthaltenden Polymerisaten führt zur Bildung von Vinylamin-Einheiten im Polymerisat. Der Hydrolysegrad des einpolymerisierten N-Vinylformamids beträgt mindestens 60, vorzugsweise 70 - 100 mol-%.According to the invention, the fixing agent for paper materials containing impurities is hydrolyzed homo- and / or copolymers of N-vinylformamide with a degree of hydrolysis of at least 60%. Polymers of this type are known, for example, from EP application 0 216 387. For their preparation, for example, N-vinylformamide is polymerized and formyl groups are split off from the polymer by hydrolysis in the presence of acids or bases. The cleavage of the formyl group from the polymers containing N-vinylformamide units in copolymerized form leads to the formation of vinylamine units in the polymer. The degree of hydrolysis of the polymerized N-vinylformamide is at least 60, preferably 70-100 mol%.

Die als Fixiermittel in Betracht kommenden Copolymerisate leiten sich von Copolymerisaten ab, die 95 - 10 mol-% N-Vinylformamid und 5 - 90 mol- % eines ethylenisch ungesättigten Monomeren aus der Gruppe Vinylacetat, Vinylpropionat, der C₁- bis C₄-Alkylvinylether, N-Vinylpyrrolidon, der Ester, Nitrile und Amide von Acrylsäure und Methacrylsäure einpolymerisiert enthalten, wobei die Formylgruppen im Copolymerisat zu mindestens 60, vorzugsweise 70 bis 100 % hydrolysiert sind und somit als Aminogruppen vorliegen. Die Ester der Acrylsäure und Methacrylsäure leiten sich von Alkoholen mit 1 - 6 Kohlenstoffatomen ab. Bevorzugt ist der Einsatz von hydrolysierten Polymerisaten, die erhältlich sind durch Polymerisieren von

  • a) 100 - 10 mol-% Vinylformamid und
  • b) 0 - 90 mol-% Vinylacetat und/oder Vinylpropionat und

aus denen im Anschluß an die Polymerisation 60 - 100 % der Formylgruppen aus den einpolymerisierten Einheiten a) und 60 - 100 % der Acetyl- und/oder Propionylgruppen aus den einpolymerisierten Einheiten b) des Copolymerisats abgespaltet sind. Die Abspaltung der Formylgruppen aus den Copolymerisaten erfolgt vorzugsweise mit Salzsäure oder Natronlauge und kann in dem Temperaturbereich von beispielsweise 20 - 100°C durchgeführt werden.The copolymers which are suitable as fixatives are derived from copolymers which contain 95-10 mol% of N-vinylformamide and 5-90 mol% of an ethylenically unsaturated monomer from the group of vinyl acetate, vinyl propionate, the C₁- to C₄-alkyl vinyl ether, N. -Vinylpyrrolidon, the esters, nitriles and amides of acrylic acid and methacrylic acid copolymerized, wherein the formyl groups in the copolymer are at least 60, preferably 70 to 100% hydrolyzed and thus exist as amino groups. The esters of acrylic acid and methacrylic acid are derived from alcohols with 1-6 carbon atoms. Preference is given to using hydrolyzed polymers which can be obtained by polymerizing
  • a) 100-10 mol% vinylformamide and
  • b) 0 - 90 mol% vinyl acetate and / or vinyl propionate and

from which 60-100% of the formyl groups from the copolymerized units a) and 60-100% of the acetyl and / or propionyl groups from the copolymerized units b) of the copolymer are split off after the polymerization. The cleavage of the formyl groups from the copolymers is preferably carried out using hydrochloric acid or sodium hydroxide solution and can be carried out in the temperature range from 20 to 100 ° C., for example.

Die Abspaltung der Formylgruppen kann jedoch auch unter Ausschluß von Wasser mit Chlorwasserstoff oder Bromwasserstoff durchgeführt werden. Hierbei entsteht aus einer N-Formylgruppe des Copolymerisats unter Abspaltung von Kohlenmonoxid eine Aminogruppe. Bei der Einwirkung von Säuren oder Basen auf Copolymerisate aus N-Vinylformamid und Acrylnitril, Methacrylnitril, N-Vinylpyrrolidon und C₁- bis C₄-Alkylvinylethern werden die Comonomeren des N-Vinylformamids chemisch kaum verändert, während das einpolymerisierte N-Vinylformamid zumindest partiell hydrolysiert wird. Bei Copolymerisaten des N-Vinylformamids mit Vinylacetat und/oder Vinylpropionat erhält man beispielsweise bei der Einwirkung von Salzsäure bei einer Temperatur von 50°C hydrolysierte Produkte, bei denen das einpolymerisierte Vinylacetat bzw. Vinylpropionat nicht hydrolysiert ist, dagegen das einpolymerisierte N-Vinylformamid zu mindestens 60 %. Behandelt man Copolymerisate aus N-Vinylformamid und Vinylacetat bzw. Vinylpropionat bei einer Temperatur von 50°C mit Natronlauge, so werden die Formylgruppen aus dem einpolymerisierten N-Vinylformamid als auch die Acetyl- bzw. Propionylgruppen aus den einpolymerisierten Vinylacetat bzw. Vinylpropionat in etwa gleichem Maße aus dem Copolymerisat abgespalten. Der Hydrolysegrad der Polymerisate hängt hauptsächlich von der eingesetzten Menge an Säure oder Base und der Temperatur bei der Hydrolyse ab.The cleavage of the formyl groups can, however, also be carried out with the exclusion of water with hydrogen chloride or hydrogen bromide. Here, an N-formyl group of the copolymer forms an amino group with elimination of carbon monoxide. When acids or bases act on copolymers of N-vinylformamide and acrylonitrile, methacrylonitrile, N-vinylpyrrolidone and C₁- to C₄-alkyl vinyl ethers, the comonomers of N-vinylformamide are hardly changed chemically, while the copolymerized N-vinylformamide is at least partially hydrolyzed. In the case of copolymers of N-vinylformamide with vinyl acetate and / or Vinyl propionate is obtained, for example, under the action of hydrochloric acid at a temperature of 50 ° C., in which the copolymerized vinyl acetate or vinyl propionate is not hydrolyzed, whereas the copolymerized N-vinylformamide is at least 60%. If copolymers of N-vinylformamide and vinyl acetate or vinyl propionate are treated with sodium hydroxide solution at a temperature of 50 ° C., the formyl groups from the polymerized N-vinylformamide and the acetyl or propionyl groups from the polymerized vinyl acetate or vinyl propionate are approximately the same Split off the dimensions of the copolymer. The degree of hydrolysis of the polymers depends mainly on the amount of acid or base used and the temperature during the hydrolysis.

Die Homo- und Copolymerisate des N-Vinylformamids mit einem Hydrolysegrad von mindestens 60 % haben K-Werte nach Fikentscher (gemessen in 5 %iger wäßriger Kochsalzlösung bei einer Polymerkonzentration von 0,5 Gew.-% und einer Temperatur von 25°C) von 30 - 150, vorzugsweise 60 - 90. Die Fixiermittel werden bei dem erfindungsgemäßen Verfahren in üblichen Mengen, d.h. von 0,02 - 2, vorzugsweise 0,05 - 0,5 Gew.- %, bezogen auf trockenen Papierstoff, eingesetzt.The homo- and copolymers of N-vinylformamide with a degree of hydrolysis of at least 60% have K values according to Fikentscher (measured in 5% aqueous saline solution at a polymer concentration of 0.5% by weight and a temperature of 25 ° C) of 30-150, preferably 60-90. In the process according to the invention, the fixing agents are used in customary amounts, ie of 0.02-2, preferably 0.05-0.5% by weight, based on dry paper stock.

Als kationische Retentionsmittel können sämtliche dafür im Handel erhältliche Produkte verwendet werden. Hierbei handelt es sich beispielsweise um Polyethylenimine, Polyamine mit einem Molekulargewicht von mehr als 50.000, Polyamidoamine, die gegebenenfalls durch Aufpfropfen von Ethylenimin modifiziert sind, Polyetheramine, Polyvinylimidazole, Polyvinylpyrrolidine, Polyvinylimidazoline, Polyvinyltetrahydropyridine, Polydialkylaminoalkylvinylether, Polydialkylaminoalkyl(meth)acrylate in protonierter oder quaternisierter Form. Weitere geeignete Verbindungen sind beispielsweise Polydiallyldialkylammoniumhalogenide, insbesondere Polydiallyldimethylammoniumchlorid. Besonders bevorzugte Retentionsmittel sind Polyamidoamine aus Adipinsäure und Polyalkylenpolyaminen, wie Diethylentriamin, die mit Ethylenimin gepfropft und mit Polyethylenglykoldichlorhydrinethern gemäß der Lehre der DE-PS 2 434 816 oder mit Epichlorhydrin vernetzt sind, sowie handelsübliche Polyethylenimine und Copolymerisate aus Acrylamid oder Methacrylamid und Dialkylaminoethylacrylaten oder -methacrylaten, z.B. Copolymerisate aus Acrylamid und N,N-Dimethylaminoethylacrylat oder Copolymerisate aus Acrylamid und N,N-Diethylaminoethylacrylat. Basische Acrylate liegen vorzugsweise in mit Säuren neutralisierter oder in quaterisierter Form vor. Die Quaternisierung kann beispielsweise mit Methylchlorid oder Dimethylsulfat erfolgen. Die kationischen Retentionsmittel haben K-Werte nach Fikentscher (bestimmt in 5 %iger wäßriger Kochsalzlösung bei einer Polymerkonzentration von 0,5 Gew.-% und einer Temperatur von 25°C) von mindestens 180.All commercially available products for this purpose can be used as cationic retention agents. These are, for example, polyethyleneimines, polyamines with a molecular weight of more than 50,000, polyamidoamines which may have been modified by grafting on ethyleneimine, polyetheramines, polyvinylimidazoles, polyvinylpyrrolidines, polyvinylimidazolines, polyvinyltetrahydropyridines, polydialkylaminoalkylvinylethers, polydialkylamate alkylated (acrylated) acrylated (acrylated) methacrylate (acrylated) methacrylate (methacrylate) acrylate (or methylated) acrylated (acrylated) methacrylate (methoxylated) acrylate (methoxylated) acrylate (acrylated) methacrylate (methacrylate) formated . Other suitable compounds are, for example, polydiallyldialkylammonium halides, in particular polydiallyldimethylammonium chloride. Particularly preferred retention aids are polyamidoamines from adipic acid and polyalkylene polyamines, such as diethylenetriamine, which are grafted with ethyleneimine and crosslinked with polyethylene glycol dichlorohydrin ethers according to the teaching of DE-PS 2 434 816 or with epichlorohydrin, and commercially available polyethyleneimines and copolymers of acrylamide or methamyl acrylate or methamyl acrylate and methamyl acrylate or methacrylamide and acrylamyl acrylate or methacrylamide and acrylamyl acrylate or methacrylamide and acrylamyl acrylate or methacrylamide and acrylamyl acrylate or methacrylamide and acrylamyl acrylate or methacrylate or acrylamyl acrylate or methacrylate and acrylamide or methacrylamide and acrylamyl acrylate or methacrylamide and acrylamyl acrylate or methacrylamide and acrylamyl acrylate or methacrylamide and acrylate or methacrylamide and acrylate or acrylate methacrylate or acrylate or methacrylamide type , for example copolymers of acrylamide and N, N-dimethylaminoethyl acrylate or copolymers of acrylamide and N, N-diethylaminoethyl acrylate. Basic acrylates are preferably in neutralized or quaterized form with acids. The quaternization can take place, for example, with methyl chloride or dimethyl sulfate. The cationic retention agents have K values according to Fikentscher (determined in 5% aqueous saline solution at a polymer concentration of 0.5% by weight and a temperature of 25 ° C) of at least 180.

Erfindungsgemäß erfolgt die Entwässerung störstoffhaltiger Papierstoffe in Gegenwart von hydrolysiertem N-Vinylformamid-Polymerisaten als Fixiermittel und den üblicherweise verwendeten kationischen Retentionsmitteln. Vorzugsweise setzt man den Papierstoff zuerst das Fixiermittel und danach das Retentionsmittel zu. Sie können jedoch auch gleichzeitig dem Papierstoff zugefügt werden. Wesentlich ist lediglich, daß die Entwässerung des Papierstoffs in Gegenwart von Fixiermittel und Retentionsmittel erfolgt. Die Retentionsmittel werden in einer Menge von 0,01 bis 0,2 Gew.-%, bezogen auf trockenen Papierstoff, angewendet. Das Verhältnis von Fixiermittel zu Retentionsmittel beträgt im allgemeinen 1 : 2 bis 5 : 1. Gegenüber herkömmlichen Kombinationen aus Fixiermitteln und kationischen Retentionsmitteln erhält man nach dem erfindungsgemäßen Verfahren eine verbesserte Retention und eine beschleunigte Entwässerung des Papierstoffs.According to the invention, dehydration-containing paper materials are dewatered in the presence of hydrolyzed N-vinylformamide polymers as fixing agents and the commonly used cationic retention agents. It is preferable to add the fixing agent to the paper stock first and then the retention agent. However, they can also be added to the paper stock at the same time. It is only essential that the paper stock is dewatered in the presence of fixative and retention aid. The retention aids are used in an amount of 0.01 to 0.2% by weight, based on dry paper stock. The ratio of fixative to retention aid is generally 1: 2 to 5: 1. Compared to conventional combinations of fixatives and cationic retention aids, improved retention and accelerated dewatering of the paper stock are obtained by the process according to the invention.

Die in den Beispielen angegebenen Teile sind Gewichtsteile, die Angaben in Prozent beziehen sich auf das Gewicht der Stoffe.The parts given in the examples are parts by weight, the percentages relate to the weight of the substances.

Bestimmung der Entwässerungszeit:Determining the drainage time:

1 Liter der zu prüfenden Faserstoffaufschlämmung wird jeweils in einem Schopper-Riegler-Testgerät entwässert. Die Zeit, in der 700 ml Wasser aus dem Schopper-Riegler-Testgerät ausliefen, wurde als Entwässerungszeit angegeben.1 liter of the pulp slurry to be tested is dewatered in a Schopper-Riegler test device. The time during which 700 ml of water ran out of the Schopper-Riegler test device was given as the drainage time.

Der chemische Sauerstoffbedarf, CSB-Wert, wurde nach DIN 38 409 bestimmt.The chemical oxygen demand, COD value, was determined according to DIN 38 409.

Die Lichtdurchlässigkeit des Siebwassers wurde mit dem Zeiss-Spektralfotometer PM 7 gemessen. Sie ist ein Maß für die Retention von Fein- und Füllstoffen. Sie wird in Prozent angegeben. Je höher der Wert für die Lichtdurchlässigkeit ist, desto besser ist die Retention.The light transmission of the white water was measured with the Zeiss PM 7 spectrophotometer. It is a measure of the retention of fine and fillers. It is given in percent. The higher the value for the light transmittance, the better the retention.

Kationischer Bedarf:Cationic need:

Die Menge an Polymer I, die notwendig ist, um ein Liter Siebwasser zum isoelektrischen Punkt zu bringen. Die Endpunktbestimmung erfolgte mit Hilfe der Polyelektrolyttitration nach D. Horn, Progr. Colloid & Polym. Sci. Bd. 65, 251 - 264 (1978).The amount of polymer I needed to get one liter of white water to the isoelectric point. The end point was determined with the aid of polyelectrolyte titration according to D. Horn, Progr. Colloid & Polym. Sci. Vol. 65, 251-264 (1978).

Der K-Wert der Polymerisate wurde nach H. Fikentscher, Cellulose-Chemie Band 13, 48 - 64 und 71 - 74 (1932) in 5 %iger wäßriger Kochsalzlösung bei einer Temperatur von 25°C und einer Polymerkonzentration von 0,5 Gew.-% gemessen. Dabei bedeutet K=k·10³.The K value of the polymers was determined according to H. Fikentscher, Cellulose-Chemie Vol. 13, 48-64 and 71-74 (1932) in 5% aqueous saline solution at a temperature of 25 ° C. and a polymer concentration of 0.5 wt. -% measured. K = k · 10³.

Verwendete kationische RetentionsmittelCationic retention agents used

Polymer I: Polyamidoamin aus Adipinsäure und Diethylentriamin, das mit Ethylenimin gepfropft und mit Polyethylenglykoldichlorhydrinether vernetzt wurde gemäß den Angaben in Beispiel 3 der DE-PS 2 434 816.Polymer I: polyamidoamine from adipic acid and diethylenetriamine, which was grafted with ethyleneimine and crosslinked with polyethylene glycol dichlorohydrin ether as described in Example 3 of DE-PS 2 434 816.

Polymer II: Polyamidoamin aus Adipinsäure und Diethylentriamin, das mit Ethylenimin gepfropft und Epichlorhydrin vernetzt wurde.Polymer II: polyamidoamine from adipic acid and diethylenetriamine, which was grafted with ethyleneimine and crosslinked with epichlorohydrin.

Polymer III: Handelsübliches hochmolekulares Polyethylenimin, das mit Ameisensäure auf einen pH-Wert von 7,5 eingestellt war.Polymer III: Commercial high molecular weight polyethyleneimine which was adjusted to a pH of 7.5 with formic acid.

Polymer IV: Copolymerisat aus 70 % Acrylamid und 30 % N-Dimethylaminoethylacrylat in Form des Methochlorids vom K-Wert 220.Polymer IV: copolymer of 70% acrylamide and 30% N-dimethylaminoethyl acrylate in the form of methochloride with a K value of 220.

Als Fixiermittel wurden eingesetzt:The following were used as fixatives:

Polymer A: Hydrolysiertes Homopolymerisat von N-Vinylformamid mit einem Hydrolysegrad von 96 % und einem K-Wert von 75.Polymer A: Hydrolyzed homopolymer of N-vinylformamide with a degree of hydrolysis of 96% and a K value of 75.

Polymer B: Hydrolysiertes Copolymerisat 70 % N-Vinylformamid und 30 % Vinylacetat, bei dem 96 % der Formylgruppen des einpolymerisierten N-Vinylformamids und 68 % der einpolymerisierten Vinylacetatgruppen hydrolysiert waren. Der K-Wert des hydrolysierten Copolymerisats betrug 75.Polymer B: Hydrolyzed copolymer 70% N-vinylformamide and 30% vinyl acetate, in which 96% of the formyl groups of the polymerized N-vinylformamide and 68% of the polymerized vinyl acetate groups had been hydrolyzed. The K value of the hydrolyzed copolymer was 75.

Polymer C: Handelsübliches Kondensat aus Dicyandiamid und Formaldehyd als Vergleich mit dem Stand der Technik.Polymer C: Commercial condensate of dicyandiamide and formaldehyde as a comparison with the prior art.

Polymer D: Handelsübliches Homopolymerisat des Diallyldimethylammoniumchlorids vom K-Wert 100 als Vergleich.Polymer D: Commercial homopolymer of diallyldimethylammonium chloride with a K value of 100 as a comparison.

Beispiel 1example 1

Man stellte mehrere Proben von Störstoffe enthaltenden Papierstoffen her, indem man jeweils zu einem Liter eines holz- und kaolinhaltigen Zeitungspapierstoffs der Stoffdichte 2 g/l mit einem pH-Wert von 7 und einem Malgrad von 68°SR (Schopper-Riegler) jeweils 0,2 % des Natriumsalzes der Huminsäure als Störstoff hinzugab. Dann dosierte man jeweils die in Tabelle 1 angegebenen Mengen von Polymer A bzw. Polymer C in den Störstoffe enthaltenden Papierstoff, gab danach jeweils 0,06 % der in Tabelle 1 angegebenen Retentionsmittel hinzu und bestimmte die Entwässerungszeit. Die dabei erhaltenen Ergebnisse sind ebenfalls in Tabelle 1 angegeben.

Figure imgb0001
Several samples of paper materials containing interfering substances were prepared by adding 2 g / l to a liter of a wood and kaolin-containing newsprint with a pH of 7 and a degree of 68 ° SR (Schopper-Riegler). 2% of the sodium salt of humic acid added as a contaminant. Then you dosed each in Amounts of polymer A and polymer C given in the paper stock containing impurities, respectively, then added 0.06% of the retention agents given in table 1 and determined the drainage time. The results obtained are also shown in Table 1.
Figure imgb0001

Beispiel 2Example 2

Als Stoffmodell verwendete man einen holz- und kaolinhaltigen Zeitungspapierstoff der Dichte 2 g/l mit einem pH-Wert von 7 und einem Malgrad von 68°SR. Der Papierstoff enthielt außerdem 3 % Natriumligninsulfonat als Störstoff. Zu Proben dieses Papierstoffs gab man jeweils die in Tabelle 2 angegebenen Mengen an Fixiermittel und danach 0,06 % Polymer 1 als kationisches Retentionsmittel zu. Man bestimmte zunächst in einem Schopper-Riegler-Testgerät die Entwässerungszeit und an dem dabei erhaltenen Filtrat die Lichtdurchlässigkeit. Außerdem wurden auf dem Rapid-Köthen-Gerät Blätter mit einem Flächengewicht von 70 g/m² gebildet und deren Aschegehalt bestimmt. Die jeweils angewendeten Mengen sowie die damit erhaltenen Ergebnisse sind in Tabelle 2 angegeben.

Figure imgb0002
The material model used was a wood and kaolin-containing newsprint with a density of 2 g / l with a pH of 7 and a degree of paint of 68 ° SR. The paper stock also contained 3% sodium lignin sulfonate as a contaminant. The amounts of fixing agent given in Table 2 and then 0.06% of polymer 1 as the cationic retention agent were added to samples of this paper stock. The dewatering time was first determined in a Schopper-Riegler test device and the light transmittance was determined on the filtrate obtained. In addition, sheets with a basis weight of 70 g / m² were formed on the Rapid-Köthen device and their ash content was determined. The amounts used in each case and the results obtained therewith are given in Table 2.
Figure imgb0002

Beispiel 3Example 3

Ein Papierstoff mit einer Stoffdichte von 5 g/l aus 75 % Holzschliff, 25 % Kiefernsulfatzellstoff, 35 % China-Clay vom Mahlgrad 25°SR mit einem pH-Wert von 7 wurde auf einer Versuchspapiermaschine bei einer Maschinengeschwindigkeit von 80 m/Minute zu Papier mit einem Flächengewicht von 60 g/m² verarbeitet. Der Papierstoff enthielt als Störstoff 0,2 % des Natriumsalzes der Huminsäure und 0,2 % Polymer 1 als Retentionsmittel. Unter diesen Bedingungen betrug die Entwässerungszeit 124 sec. und die Asche-Retention 57,4 % In weiteren Versuchen setzte man dem oben beschriebenen Papierstoff die in in Tabelle 3 angegebenen Polymeren zu. Die jeweils erhaltenen Ergebnisse sind in Tabelle 3 angegeben.

Figure imgb0003
A paper stock with a consistency of 5 g / l from 75% wood pulp, 25% pine sulfate pulp, 35% china clay with a degree of grinding of 25 ° SR and a pH of 7 was turned into paper on a test paper machine at a machine speed of 80 m / minute processed with a basis weight of 60 g / m². The paper stock contained 0.2% of the sodium salt of humic acid and 0.2% of polymer 1 as a retention agent. Under these conditions, the dewatering time was 124 seconds and the ash retention was 57.4%. In further experiments, the polymers described in Table 3 were added to the paper stock described above. The results obtained are given in Table 3.
Figure imgb0003

Beispiel 4Example 4

Als Modellsubstanz diente ein holz- und kaolinhaltiger Zeitungspapierstoff der Stoffdichte 2 g/l mit einem pH-Wert von 7 und einem Malgrad von 68°SR. Dazu gab man 3 % Natriumligninsulfonat als Störstoff. Der so erhaltene Papierstoff wurde in einem Schopper-Riegler-Gerät entwässert. Die Ergebnisse, die ohne Zusatz eines Retentions- und Entwässerungsmittels erhalten wurden, sind in Tabelle 4 angegeben, ebenso die Ergebnisse, die durch jeweiligen Zusatz von 0,2 % der in der Tabelle genannten Polymeren als Fixiermittel und anschließende Zugabe von 0,06 % Polymer 1 als Retentionsmittel erhalten wurden.

Figure imgb0004
A wood and kaolin-containing newsprint with a consistency of 2 g / l and a pH value of 7 and a degree of paint of 68 ° SR was used as the model substance. In addition, 3% sodium lignin sulfonate was added as an interfering substance. The paper stock thus obtained was dewatered in a Schopper-Riegler device. The results obtained without the addition of a retention and drainage agent are shown in Table 4, as are the results obtained by adding 0.2% of the polymers mentioned in the table as a fixing agent and then adding 0.06% polymer 1 were obtained as a retention aid.
Figure imgb0004

Claims (5)

Verfahren zur Herstellung von Papier, Pappe und Karton durch Entwässern eines Störstoffe enthaltenden Papierstoffs in Gegenwart von Fixiermitteln und kationischen Retentionsmitteln, dadurch gekennzeichnet, daß man als Fixiermittel hydrolysierte Homo- und/oder Copolymerisate des N-Vinylformamids mit einem Hydrolysegrad von mindestens 60 % einsetzt.Process for the production of paper, cardboard and cardboard by dewatering a paper material containing impurities in the presence of fixing agents and cationic retention agents, characterized in that hydrolyzed homo- and / or copolymers of N-vinylformamide with a degree of hydrolysis of at least 60% are used as fixing agents. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß man als Fixiermittel hydrolysierte Homopolymerisate des N-Vinylformamids mit einem Hydrolysegrad von 70 bis 100 % einsetzt.Process according to Claim 1, characterized in that hydrolyzed homopolymers of N-vinylformamide with a degree of hydrolysis of 70 to 100% are used as fixing agents. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß man als Fixiermittel hydrolysierte Copolymerisate des N-Vinylformamids einsetzt, die bis zu 90 mol-% ethylenisch ungesättigte Monomere aus der Gruppe Vinylacetat, Vinylpropionat, der C₁- bis C₄-Alkylvinylether, N-Vinylpyrrolidon, der Ester, Nitrile und Amide von Acrylsäure oder Methacrylsäure einpolymerisiert enthalten, und bei denen der Hydrolysegrad der einpolymerisierten N-Vinylformamid-Einheiten 70 bis 100 % beträgt.Process according to Claim 1, characterized in that the fixing agent used is hydrolysed copolymers of N-vinylformamide which contain up to 90 mol% of ethylenically unsaturated monomers from the group consisting of vinyl acetate, vinyl propionate, the C₁- to C₄-alkyl vinyl ether, N-vinylpyrrolidone, the Contain esters, nitriles and amides of acrylic acid or methacrylic acid copolymerized, and in which the degree of hydrolysis of the polymerized N-vinylformamide units is 70 to 100%. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß man hydrolysierte Polymerisate einsetzt, die erhältlich sind durch Polymerisieren von (a) 100 bis 10 mol-% N-Vinylformamid und (b) 0 bis 90 mol-% Vinylacetat und/oder Vinylpropionat und anschließende Abspaltung von 60 bis 100 % der Formylgruppen aus den einpolymerisierten Einheiten (a) und 60 bis 100 % der Acetyl- und/oder Propionylgruppen aus den einpolymerisierten Einheiten (b) des Copolymerisats.Process according to Claim 1, characterized in that hydrolyzed polymers are used which can be obtained by polymerizing (a) 100 to 10 mol% N-vinylformamide and (b) 0 to 90 mol% vinyl acetate and / or vinyl propionate and subsequent elimination of 60 to 100% of the formyl groups from the copolymerized units (a) and 60 to 100% of the acetyl and / or propionyl groups from the copolymerized units (b) of the copolymer. Verwendung von hydrolysierten Homo- und/oder Copolymerisaten des N-Vinylformamids mit einem Hydrolysegrad von mindestens 60 % der einpolymerisierten N-Vinylformamid-Einheiten als Fixiermittel in Kombination mit einem kationischen Retentionsmittel bei der Herstellung von Papier, Pappe und Karton durch Entwässern eines Störstoffe enthaltenden Papierstoffs.Use of hydrolyzed homopolymers and / or copolymers of N-vinylformamide with a degree of hydrolysis of at least 60% of the polymerized N-vinylformamide units as fixatives in combination with a cationic retention agent in the manufacture of paper, cardboard and cardboard by dewatering a paper material containing impurities .
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FI910206A (en) 1991-07-17
FI102687B (en) 1999-01-29
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CA2034135A1 (en) 1991-07-17
US5145559A (en) 1992-09-08
FI102687B1 (en) 1999-01-29
ES2046658T3 (en) 1994-02-01
FI910206A0 (en) 1991-01-15
EP0438707B1 (en) 1993-12-15
JPH05106193A (en) 1993-04-27
DE59003890D1 (en) 1994-01-27
DE4001045A1 (en) 1991-07-18

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