EP1819877B1 - Method for producing high dry strength paper, paperboard or cardboard - Google Patents

Method for producing high dry strength paper, paperboard or cardboard Download PDF

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Publication number
EP1819877B1
EP1819877B1 EP05811227A EP05811227A EP1819877B1 EP 1819877 B1 EP1819877 B1 EP 1819877B1 EP 05811227 A EP05811227 A EP 05811227A EP 05811227 A EP05811227 A EP 05811227A EP 1819877 B1 EP1819877 B1 EP 1819877B1
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mol
units
monoethylenically unsaturated
process according
polymer
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German (de)
French (fr)
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EP1819877A1 (en
Inventor
Anton Esser
Hans-Joachim HÄHNLE
Martin Rübenacker
Norbert Schall
Jacques Dupuis
Josef Neutzner
Manfred Niessner
Berthold Sturm
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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
    • D21H21/14—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 characterised by function or properties in or on the paper
    • D21H21/18—Reinforcing agents
    • 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
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/33—Synthetic macromolecular compounds
    • D21H17/46—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H17/54—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen
    • D21H17/55—Polyamides; Polyaminoamides; Polyester-amides
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/33—Synthetic macromolecular compounds
    • D21H17/46—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H17/54—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen
    • D21H17/56—Polyamines; Polyimines; Polyester-imides

Definitions

  • the invention relates to a process for the production of paper, paperboard and cardboard with high dry strength by separately adding a polymer containing vinylamine units and a polymeric anionic compound to a pulp, dewatering the pulp and drying the paper products.
  • a method for the production of paper with high dry strength is known in which the paper stock is first a water-soluble cationic polymer, z.
  • a water-soluble cationic polymer such as a hydrolyzed polyacrylamide
  • the anionic polymers contain up to 30 mol% of copolymerized acrylic acid.
  • From the DE-A 35 06 832 discloses a process for the production of paper with high dry strength, in which one adds to the stock first a water-soluble cationic polymer and then a water-soluble anionic polymer.
  • Suitable anionic polymers are, for example, homopolymers or copolymers of ethylenically unsaturated C 3 -C 5 -carboxylic acids.
  • the copolymers contain at least 35 wt .-% of an ethylenically unsaturated C 3 - C 5 carboxylic acid (eg acrylic acid) in copolymerized form.
  • polyethyleneimine polyvinylamine, polydiallyldimethylammonium chloride and epichlorohydrin crosslinked condensation products of adipic acid and diethylenetriamine are described.
  • the use of partially hydrolyzed homo- and Copolymers of N-vinylformamide have been considered.
  • the degree of hydrolysis of the N-vinylformamide polymers is at least 30 mol% and is preferably 50 to 100 mol%.
  • the JP-A 1999-140787 relates to a process for the production of corrugated board, wherein to improve the strength properties of a paper product to the pulp 0.05 to 0.5 wt .-%, based on dry pulp, of a polyvinylamine obtained by hydrolysis of polyvinylformamide having a degree of hydrolysis of 25 to 100 %, in combination with an anionic polyacrylamide, the pulp is then dewatered and dried.
  • a paper product having improved strength properties obtainable by applying to the surface of a paper product a polyvinylamine and a polymeric anionic compound which can form a polyelectrolyte complex with polyvinylamine, or a polymeric compound having aldehyde functions such as aldehyde group-containing polysaccharides.
  • a polyvinylamine and a polymeric anionic compound which can form a polyelectrolyte complex with polyvinylamine or a polymeric compound having aldehyde functions such as aldehyde group-containing polysaccharides.
  • WO 04/061235 a method for the production of paper, especially tissue, with particularly high wet and / or dry strengths is known, in which one first admits to the paper a water-soluble cationic polymer that contains at least 1.5meq / g polymer of primary amino functionalities and a molecular weight of at least 10,000 daltons. Particular emphasis is placed here partially and fully hydrolyzed homopolymers of N-vinylformamide. Subsequently, a water-soluble anionic polymer is added which contains anionic and / or aldehydic groups.
  • the advantage of this method is mainly the variability of the two-component systems described in terms of various paper properties, including wet and dry strength, exposed.
  • EP-A 438 744 is the use of copolymers of, for example, N-vinylformamide and acrylic acid, methacrylic acid and / or maleic acid having a K value of 8 to 50 (determined according to H. Fikentscher in 1% aqueous solution at pH 7 and 25 ° C) and the from them by partial or complete removal of formyl groups from the copolymerized vinylformamide with the formation of vinylamine units polymers available as anti-scale agents in water-bearing systems such as boilers or pipes, known.
  • copolymers obtainable by copolymerizing N-vinylcarboxamides, monoethylenically unsaturated carboxylic acids and optionally other ethylenically unsaturated monomers and subsequent hydrolysis of the vinylcarboxylic acid units contained in the copolymers to the corresponding amine or ammonium units are used as additives in papermaking to paper stock to increase the drainage rate and the retention and the dry and wet strength of the paper can use, see. EP-B 672 212 ,
  • the present invention has for its object to provide a further process for the production of paper with high dry strength and lowest possible wet strength available.
  • the increase in dry strength, in particular in packaging papers (for example testliner) should be further improved compared with the previously known processes.
  • the wet strength or the ratio of wet to dry strength should be further minimized.
  • Examples of monomers of group (a) are N-vinylformamide, N-vinyl-N-methylformamide, N-vinylacetamide, N-vinyl-N-methylacetamide, N-vinyl-N-ethylacetamide, N-vinyl-N-methylpropionamide and N -Vinylpropionamid.
  • the monomers of group (a) may be used alone or in admixture in the copolymerization with the monomers of the other groups.
  • Suitable monomers of group (b) are, in particular, monoethylenically unsaturated carboxylic acids having 3 to 8 carbon atoms and the water-soluble salts of these carboxylic acids.
  • This group of monomers includes, for example, acrylic acid, methacrylic acid, dimethacrylic acid, ethacrylic acid, maleic acid, fumaric acid, itoconic acid, mesaconic acid, citraconic acid, methylenemalonic acid, allylacetic acid, vinylacetic acid and crotonic acid.
  • monomers of group (b) are monomers containing sulfo groups, such as vinylsulfonic acid, acrylamido-2-methylpropanesulfonic acid and styrenesulfonic acid and vinylphosphonic acid.
  • the monomers of this group can be used alone or in admixture with each other, in partially or completely neutralized form in the copolymerization.
  • neutralization for example, alkali metal or alkaline earth metal bases, ammonia, amines and / or alkanolamines are used.
  • the monomers of group (b) are preferably used in the copolymerization in partially neutralized form.
  • the copolymers may optionally contain monomers of group (c) in copolymerized form, for example esters of ethylenically unsaturated C 3 to C 5 carboxylic acids such as methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, isobutyl methacrylate, methyl methacrylate, ethyl methacrylate and vinyl esters such as vinyl acetate or Vinyl propionate, or other monomers such as N-vinylpyrrolidone, N-vinylimidazole, acrylamide and / or methacrylamide.
  • esters of ethylenically unsaturated C 3 to C 5 carboxylic acids such as methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, isobutyl methacrylate, methyl methacrylate, ethyl methacrylate and vinyl est
  • copolymers (d) which contain at least two double bonds in the molecule, for example methlenebisacrylamide, glycol diacrylate, glycol dimethacrylate, glyceryl triacrylate, triallylamine, pentaerythritol triallyl ether, esterified at least twice with acrylic acid and / or methacrylic acid
  • polyalkylene glycols or polyols such as pentaerythritol, Sobit or glucose. If at least one monomer of group (d) is used in the copolymerization, the amounts used are up to 2 mol%, for example 0.001 to 1 mol%.
  • the copolymerization of the monomers takes place in a known manner in the presence of free-radical polymerization initiators and optionally in the presence of polymerization regulators, cf. EP-B 672 212 , Page 4, lines 13 - 37 or EP-A 438 744 , Page 2, line 26 to page 8, line 18.
  • the hydrolysis of the anionic copolymers can be carried out in the presence of acids or bases or else enzymatically.
  • the vinylamine groups formed from the vinylcarboxamide units are present in salt form.
  • the hydrolysis of vinylcarboxylic acid amide copolymers is described in U.S. Pat EP-A 438 744 , Page 8, line 20 to page 10, line 3, described in detail. The remarks made there apply correspondingly to the preparation of the amphoteric polymers to be used according to the invention.
  • the average molecular weights M.sub.w of the anionic or amphoteric polymers are, for example, 30,000 D to 10 million D, preferably 100,000 D to 1 million D.
  • These polymers have, for example, K values (determined according to H. Fikentscher in 5% aqueous sodium chloride solution pH 7, a polymer concentration of 0.5% by weight and a temperature of 25 ° C) in the range of 20 to 250, preferably 50 to 150.
  • a polymeric cationic component which is exclusively polymer containing vinylamine units is first added to the paper stock. All polymers suitable for this purpose, for example those cited in the prior art, are suitable for this purpose WO 04/061235 , Page 12, line 28 to page 13, line 21 and in Figure 1 are indicated.
  • the molecular weight M w of the polymers containing vinylamine units is, for example, 1000 to 5 million, and is usually in the range of 5,000 to 500,000, preferably 40,000 D to 400,000 D.
  • R 1 , R 2 H or C 1 - to C 6 -alkyl
  • amidine units can form from vinylamine units and adjacent vinylsamide units.
  • the indication of vinylamine units comprises the sum of vinylamine and amidine units in the polymer.
  • polymer containing vinylamine units for example, a homopolymer of N-vinylformamide hydrolyzed to at least 10 mol% is used.
  • Polyvinylamine and / or at least 50 mol% of hydrolyzed homopolymers of N-vinylformamide are preferably used in the inventive method as a cationic component.
  • This group of polymers contains, for example, up to a maximum of 35 mol%, preferably up to a maximum of 10 mol%, of at least one acid group-containing monomer of group (b).
  • 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.
  • 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.
  • the method according to the invention has particular significance for the production of paper and board from waste paper, because it significantly increases the strength properties of the recycled fibers.
  • the pH of the stock suspension is, for example, in the range of 4.5 to 8, most 6 to 7.5.
  • an acid such as sulfuric acid or aluminum sulphate.
  • the polymers comprising vinylamine units, ie the cationic component of the polymers to be metered into the paper stock, are added in the method according to the invention to the thick stock or preferably to a thin stock.
  • the point of addition is preferably in front of the screens, but may also be between a shearing stage and a screen or afterwards.
  • the anionic component is usually only after addition of the cationic component added to the pulp, but can also be dispensed simultaneously but separately from the cationic component to the pulp. Furthermore, it is also possible first to add the anionic and subsequently the cationic component.
  • the vinylamine units-containing polymer and the polymeric anionic compound are used, for example, each in an amount of 0.1 to 2.0 wt .-%, preferably 0.3 to 1 wt .-%, based on dry pulp.
  • the ratio of vinylamine units-containing polymer to polymeric anionic compound is, for example, 5: 1 to 1: 5, and is preferably in the range of 2: 1 to 1: 2.
  • the process according to the invention gives paper products which, compared with the processes of the prior art, have a higher level of dry strength with simultaneously low wet strength.
  • the parts given in the following examples are parts by weight, the percentages are based on the weight of the substances.
  • the K value of the polymers was determined by Fikentscher, Cellulose-Chemie, Vol. 13, 58-64 and 71-74 (1932 ) at a temperature of 20 ° C in 5 wt .-% aqueous saline solutions at a pH of 7 and a polymer concentration of 0.5%.
  • K k * 1000.
  • a 0.5% aqueous pulp suspension was prepared.
  • the pH of the suspension was 7.1, the freeness of the substance 50 ° Schopper-Riegler (° SR).
  • the stock suspension was then divided into 36 equal parts and processed into sheets of a basis weight of 120 g / m 2 in Comparative Examples 1 to 26 and Examples 27 to 36 under the following conditions.

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Description

Die Erfindung betrifft ein Verfahren zur Herstellung von Papier, Pappe und Karton mit hoher Trockenfestigkeit durch getrennte Zugabe eines Vinylamineinheiten enthaltenden Polymers und einer polymeren anionischen Verbindung zu einem Papierstoff, Entwässern des Papierstoffs und Trocknen der Papierprodukte.The invention relates to a process for the production of paper, paperboard and cardboard with high dry strength by separately adding a polymer containing vinylamine units and a polymeric anionic compound to a pulp, dewatering the pulp and drying the paper products.

Zur Herstellung von Papier mit hoher Trockenfestigkeit ist es bekannt, auf die Oberfläche von bereits getrocknetem Papier verdünnte wässrige Lösungen von gekochter Stärke oder von synthetischen Polymerisaten aufzutragen, die jeweils als Trockenverfestiger wirken. Die Mengen an Trockenverfestigungsmittel betragen in der Regel 0,1 bis 6 Gew.-%, bezogen auf trockenes Papier. Da die Trockenverfestiger einschließlich der Stärke in einer wässrigen verdünnten Lösung aufgetragen werden - im allgemeinen beträgt die Polymer- bzw. Stärkekonzentration der wässrigen Präparationslösung zwischen 1% und 10 Gew.% - ist bei dem darauf folgenden Trocknungsprozess eine beträchtliche Menge an Wasser zu verdampfen. Der Trocknungsschritt ist daher sehr energieaufwendig. Die Kapazität der üblichen Trocknungseinrichtungen an Papiermaschinen ist aber in vielen Fällen nicht so groß, dass man bei der maximal möglichen Produktionsgeschwindigkeit der Maschine fahren könnte. Die Produktionsgeschwindigkeit der Papiermaschine muß vielmehr zurückgenommen werden, damit das Papier in ausreichendem Maße getrocknet wird.For the production of paper with high dry strength, it is known to apply to the surface of already dried paper diluted aqueous solutions of cooked starch or synthetic polymers, each acting as a dry strength. The amounts of dry strength agent are usually 0.1 to 6 wt .-%, based on dry paper. Since the dry strength agents, including the starch, are applied in an aqueous dilute solution - generally the polymer or starch concentration of the aqueous preparation solution is between 1% and 10% by weight - a considerable amount of water is to be evaporated in the subsequent drying process. The drying step is therefore very energy consuming. However, the capacity of the usual drying devices on paper machines is in many cases not so great that one could drive at the maximum possible production speed of the machine. Rather, the production speed of the paper machine must be reduced so that the paper is sufficiently dried.

Aus dem CA-Patent 1 110 019 ist ein Verfahren zur Herstellung von Papier mit hoher Trockenfestigkeit bekannt, bei dem man zum Papierstoff zunächst ein wasserlösliches kationisches Polymerisat, z. B. Polyethylenimin, zugibt und danach ein wasserlösliches anionisches Polymerisat, z.B. ein hydrolysiertes Polyacrylamid, zufügt und den Papierstoff auf der Papiermaschine unter Blattbildung entwässert. Die anionischen Polymerisate enthalten bis zu 30 Mol% Acrylsäure einpolymerisiert.From the CA patent 1 110 019 a method for the production of paper with high dry strength is known in which the paper stock is first a water-soluble cationic polymer, z. As polyethyleneimine, adding and then adding a water-soluble anionic polymer, such as a hydrolyzed polyacrylamide, and drained the paper stock on the paper machine with formation of sheets. The anionic polymers contain up to 30 mol% of copolymerized acrylic acid.

Aus der DE-A 35 06 832 ist ein Verfahren zur Herstellung von Papier mit hoher Trockenfestigkeit bekannt, bei dem man zum Papierstoff zunächst ein wasserlösliches kationisches Polymerisat und anschließend ein wasserlösliches anionisches Polymerisat zugibt. Als anionische Polymerisate kommen beispielsweise Homo- oder Copolymerisate von ethylenisch ungesättigten C3 - C5-Carbonsäuren in Betracht. Die Copolymerisate enthalten mindestens 35 Gew.-% einer ethylenisch ungesättigten C3 - C5-Carbonsäure (z.B. Acrylsäure) einpolymerisiert. Als kationische Polymerisate werden in den Beispielen Polyethylenimin, Polyvinylamin, Polydiallyldimethylammoniumchlorid und mit Epichlorhydrin vernetzte Kondensationsprodukte aus Adipinsäure und Diethylentriamin beschrieben. Auch die Verwendung von partiell hydrolysierten Homo- und Copolymerisaten des N-Vinylformamids ist in Betracht gezogen worden. Der Hydrolysegrad der N-Vinylformamidpolymeren beträgt dabei mindestens 30 mol-% und beträgt vorzugsweise 50 bis 100 Mol-%.From the DE-A 35 06 832 discloses a process for the production of paper with high dry strength, in which one adds to the stock first a water-soluble cationic polymer and then a water-soluble anionic polymer. Suitable anionic polymers are, for example, homopolymers or copolymers of ethylenically unsaturated C 3 -C 5 -carboxylic acids. The copolymers contain at least 35 wt .-% of an ethylenically unsaturated C 3 - C 5 carboxylic acid (eg acrylic acid) in copolymerized form. As cationic polymers in the examples polyethyleneimine, polyvinylamine, polydiallyldimethylammonium chloride and epichlorohydrin crosslinked condensation products of adipic acid and diethylenetriamine are described. The use of partially hydrolyzed homo- and Copolymers of N-vinylformamide have been considered. The degree of hydrolysis of the N-vinylformamide polymers is at least 30 mol% and is preferably 50 to 100 mol%.

Die JP-A 1999-140787 betrifft ein Verfahren zur Herstellung von Wellpappe, wobei man zur Verbesserung der Festigkeitseigenschaften eines Papierprodukts zum Papierstoff 0,05 bis 0,5 Gew.-%, bezogen auf trockenen Papierstoff, eines Polyvinylamins, das durch Hydrolyse von Polyvinylformamid mit einem Hydrolysegrad von 25 bis 100% zugänglich ist, in Kombination mit einem anionischen Polyacrylamid zugibt, den Papierstoff dann entwässert und trocknet.The JP-A 1999-140787 relates to a process for the production of corrugated board, wherein to improve the strength properties of a paper product to the pulp 0.05 to 0.5 wt .-%, based on dry pulp, of a polyvinylamine obtained by hydrolysis of polyvinylformamide having a degree of hydrolysis of 25 to 100 %, in combination with an anionic polyacrylamide, the pulp is then dewatered and dried.

Aus der WO 03/052206 ist ein Papierprodukt mit verbesserten Festigkeitseigenschaften bekannt, dass dadurch erhältlich ist, dass man auf die Oberfläche eines Papierprodukts ein Polyvinylamin und eine polymere anionische Verbindung, die mit Polyvinylamin einen Polyelektrolytkomplex bilden kann, oder eine polymere Verbindung mit Aldehydfunktionen wie Aldehydgruppen enthaltende Polysaccharide aufbringt. Man erhält nicht nur eine Verbesserung der Trocken- und Nassfestigkeit des Papiers, sondern beobachtet auch eine Leimungswirkung der Behandlungsmittel.From the WO 03/052206 For example, there is known a paper product having improved strength properties obtainable by applying to the surface of a paper product a polyvinylamine and a polymeric anionic compound which can form a polyelectrolyte complex with polyvinylamine, or a polymeric compound having aldehyde functions such as aldehyde group-containing polysaccharides. Not only does the paper improve its dry and wet strength, it also observes a sizing effect of the treating agents.

Aus WO 04/061235 ist ein Verfahren zur Herstellung von Papier, insbesondere Tissue, mit besonders hohen Naß- und/oder Trockenfestigkeiten bekannt, bei dem man zum Papierstoff zunächst ein wasserlösliches kationisches Polymerisat zugibt, dass mindestens 1,5meq/g Polymer an primären Aminofunktionalitäten enthält und ein Molekulargewicht von wenigstens 10.000 Dalton aufweist. Besonders hervorgehoben werden hierbei partiell- und vollhydrolysierte Homopolymerisate des N-Vinylformamids. Anschließend wird ein wasserlösliches anionisches Polymerisat zugegeben, dass anionische und/oder aldehydische Gruppen enthält. Als Vorteil dieses Verfahrens wird vor allem die Variabilität der beschriebenen Zweikomponentensysteme im Hinblick auf verschiedene Papiereigenschaften, darunter Naß- und Trockenfestigkeit, herausgestellt.Out WO 04/061235 a method for the production of paper, especially tissue, with particularly high wet and / or dry strengths is known, in which one first admits to the paper a water-soluble cationic polymer that contains at least 1.5meq / g polymer of primary amino functionalities and a molecular weight of at least 10,000 daltons. Particular emphasis is placed here partially and fully hydrolyzed homopolymers of N-vinylformamide. Subsequently, a water-soluble anionic polymer is added which contains anionic and / or aldehydic groups. The advantage of this method is mainly the variability of the two-component systems described in terms of various paper properties, including wet and dry strength, exposed.

Aus EP-A 438 744 ist die Verwendung von Copolymerisaten aus beispielsweise N-Vinylformamid und Acrylsäure, Methacrylsäure und/oder Maleinsäure mit einem K-Wert von 8 bis 50 (bestimmt nach H. Fikentscher in 1 %-iger wässriger Lösung bei pH 7 und 25°C) sowie den daraus durch partielle oder vollständige Abspaltung von Formylgruppen aus dem einpolymerisierten Vinylformamid unter Bildung von Vinylamineinheiten erhältlichen Polymerisaten als Belagsverhinderer in wasserführenden Systemen wie Kesseln oder Rohren, bekannt.Out EP-A 438 744 is the use of copolymers of, for example, N-vinylformamide and acrylic acid, methacrylic acid and / or maleic acid having a K value of 8 to 50 (determined according to H. Fikentscher in 1% aqueous solution at pH 7 and 25 ° C) and the from them by partial or complete removal of formyl groups from the copolymerized vinylformamide with the formation of vinylamine units polymers available as anti-scale agents in water-bearing systems such as boilers or pipes, known.

Außerdem ist bekannt, dass man Copolymerisate, die durch Copolymerisieren von N-Vnylcarbonsäureamiden, monoethylenisch ungesättigten Carbonsäuren und gegebenenfalls anderen ethylenisch ungesättigten Monomeren und anschließende Hydrolyse der in den Copolymeren enthaltenden Vinylcarbonsäureeinheiten zu den entsprechenden Amin- bzw. Ammoniumeinheiten erhältlich sind, bei der Papierherstellung als Zusatz zum Papierstoff zur Erhöhung der Entwässerungsgeschwindigkeit und der Retention sowie der Trocken- und Nassfestigkeit des Papiers einsetzen kann, vgl. EP-B 672 212 .In addition, it is known that copolymers obtainable by copolymerizing N-vinylcarboxamides, monoethylenically unsaturated carboxylic acids and optionally other ethylenically unsaturated monomers and subsequent hydrolysis of the vinylcarboxylic acid units contained in the copolymers to the corresponding amine or ammonium units are used as additives in papermaking to paper stock to increase the drainage rate and the retention and the dry and wet strength of the paper can use, see. EP-B 672 212 ,

Der vorliegenden Erfindung liegt die Aufgabe zugrunde, ein weiteres Verfahren zur Herstellung von Papier mit hoher Trockenfestigkeit und möglichst niedriger Nassfestigkeit zur Verfügung zu stellen. Dabei soll jedoch gegenüber den bisher bekannten Verfahren die Steigerung der Trockenfestigkeit, insbesondere in Verpackungspapieren (z.B. Testliner), noch weiter verbessert werden. Darüber hinaus soll die Nassfestigkeit bzw. das Verhältnis von Nass- zu Trockenfestigkeit weiter minimiert werden.The present invention has for its object to provide a further process for the production of paper with high dry strength and lowest possible wet strength available. In this case, however, the increase in dry strength, in particular in packaging papers (for example testliner), should be further improved compared with the previously known processes. In addition, the wet strength or the ratio of wet to dry strength should be further minimized.

Die Aufgabe wird erfindungsgemäß gelöst mit einem Verfahren zur Herstellung von Papier, Pappe und Karton mit hoher Trockenfestigkeit durch getrennte Zugabe eines Vinylamineinheiten enthaltenden Polymeren und einer polymeren anionischen Verbindung zu einem Papierstoff, Entwässern des Papierstoffs und Trocknen der Papierprodukte, wenn man als polymere anionische Verbindung mindestens ein Copolymerisat einsetzt, das erhältlich ist durch Copolymerisieren von

  • (a) mindestens eines N-Vinylcarbonsäureamids der Formel
    Figure imgb0001
     in der R1, R2 = H oder C1- bis C6-Alkyl bedeuten,
  • (b) mindestens eines Säuregruppen enthaltenden monoethylenisch ungesättigten Monomeren und/oder deren Alkalimetall-, Erdalkalimetall- oder Ammoniumsalzen und gegebenenfalls
  • (c) anderen monoethylenisch ungesättigten Monomeren, und gegebenenfalls
  • (d) Verbindungen, die mindestens zwei ethylenisch ungesättigte Doppelbindungen im Molekül aufweisen.
The object is achieved according to the invention by a process for the production of paper, paperboard and cardboard with high dry strength by separate addition of a polymer containing vinylamine units and a polymeric anionic compound to a pulp, dewatering of the pulp and drying of the paper products, if at least as a polymeric anionic compound a copolymer obtainable by copolymerizing
  • (a) at least one N-vinylcarboxamide of the formula
    Figure imgb0001
     in which R 1 , R 2 = H or C 1 - to C 6 -alkyl,
  • (B) at least one acid group-containing monoethylenically unsaturated monomer and / or their alkali metal, alkaline earth metal or ammonium salts and optionally
  • (c) other monoethylenically unsaturated monomers, and optionally
  • (d) compounds having at least two ethylenically unsaturated double bonds in the molecule.

Vorzugsweise setzt man als polymere anionische Verbindung ein Copolymerisat ein, das erhältlich ist durch Copolymerisieren von

  • (a) N-Vinylformamid,
  • (b) Acrylsäure, Methacrylsäure und/oder deren Alkali- oder Ammoniumsalzen und gegebenenfalls
  • (c) anderen monoethylenisch ungesättigten Monomeren.
Preferably used as the polymeric anionic compound is a copolymer obtainable by copolymerizing
  • (a) N-vinylformamide,
  • (b) acrylic acid, methacrylic acid and / or their alkali or ammonium salts and optionally
  • (c) other monoethylenically unsaturated monomers.

Die polymere anionische Verbindung enthält beispielsweise

  • (a) 10 bis 95 Mol-% Einheiten der Formel I
  • (b) 5 bis 90 Mol-% Einheiten einer monoethylenisch ungesättigten Carbonsäure mit 3 bis 8 C-Atomen im Molekül und/oder deren Alkalimetall-, Erdalkalimetall- oder Ammoniumsalze und
  • (c) 0 bis 30 Mol-% Einheiten mindestens eines anderen monoethylenisch ungesättigten Monomeren.
The polymeric anionic compound contains, for example
  • (a) 10 to 95 mol% of the units of the formula I.
  • (B) 5 to 90 mol% of units of a monoethylenically unsaturated carboxylic acid having 3 to 8 carbon atoms in the molecule and / or their alkali metal, alkaline earth metal or ammonium salts and
  • (c) 0 to 30 mol% of units of at least one other monoethylenically unsaturated monomer.

Diese Verbindungen können dahingehend modifiziert sein, dass sie zusätzlich noch mindestens eine Verbindung mit mindestens zwei ethylenish ungesätigten Doppelbindungen im Molekül einpolymerisiert enthalten. Wenn man die Monomeren (a) und (b) oder (a), (b) und (c) in Gegenwart einer solchen Verbindung copolymerisiert, erhält man verzweigte Copolymerisate. Dabei sind die Mengenverhältnisse und Reaktionsbedingungen so zu wählen, dass noch wasserlösliche Polymere erhalten werden. Unter Umständen kann es dazu notwendig sein, Polymerisationsregler einzusetzen. Verwendung finden können alle bekannten Regler wie z.B. Thiole, sec. Alkohole, Sulfite, Phosphite, Hypophosphite, Thiosäuren, Aldehyde usw. (nähere Angaben findet man z.B. in EP-A 438 744 , Seite 5, Zeilen 7-12). Die verzweigten Copolymerisate enthalten beispielsweise

  • (a) 10 bis 95 Mol-% Einheiten der Formel I
  • (b) 5 bis 90 Mol-% Einheiten eines Säuregruppen enthaltenden monoethylenisch ungesättigten Monomeren und/oder deren Alkalimetall-, Erdalkalimetall- oder Ammoniumsalzen,
  • (c) 0 bis 30 Mol-% Einheiten mindestens eines anderen monoethylenisch ungesättigten Monomeren und
  • (d) 0 bis 2 Mol-%, vorzugsweise 0,001 bis 1 Mol-% mindestens einer Verbindung mit mindestens zwei ethylenisch ungesättigten Doppelbindungen
einpolymerisiert.These compounds may be modified so that they additionally contain at least one compound having at least two ethylenically unsaturated double bonds in the molecule in copolymerized form. When the monomers (a) and (b) or (a), (b) and (c) are copolymerized in the presence of such a compound, branched copolymers are obtained. The proportions and reaction conditions are to be chosen so that water-soluble polymers are still obtained. Under certain circumstances it may be necessary to use polymerization regulators. All known regulators can be used, such as, for example, thiols, sec. Alcohols, sulfites, phosphites, hypophosphites, thioacids, aldehydes, etc. (for details, see, for example, in US Pat EP-A 438 744 , Page 5, lines 7-12). The branched copolymers contain, for example
  • (a) 10 to 95 mol% of the units of the formula I.
  • (b) 5 to 90 mol% of units of an acid group-containing monoethylenically unsaturated monomer and / or their alkali metal, alkaline earth metal or ammonium salts,
  • (c) 0 to 30 mol% of units of at least one other monoethylenically unsaturated monomer and
  • (D) 0 to 2 mol%, preferably 0.001 to 1 mol% of at least one compound having at least two ethylenically unsaturated double bonds
in copolymerized form.

Beispiele für Monomere der Gruppe (a) sind N-Vinylformamid, N-Vinyl-N-methylformamid, N-Vinylacetamid, N-Vinyl-N-methylacetamid, N-Vinyl-N-ethylacetamid, N-Vinyl-N-methylpropionamid und N-Vinylpropionamid. Die Monomeren der Gruppe (a) können allein oder in Mischung bei der Copolymerisation mit den Monomeren der anderen Gruppen eingesetzt werden.Examples of monomers of group (a) are N-vinylformamide, N-vinyl-N-methylformamide, N-vinylacetamide, N-vinyl-N-methylacetamide, N-vinyl-N-ethylacetamide, N-vinyl-N-methylpropionamide and N -Vinylpropionamid. The monomers of group (a) may be used alone or in admixture in the copolymerization with the monomers of the other groups.

Als Monomere der Gruppe (b) kommen insbesondere monoethylenisch ungesättigte Carbonsäuren mit 3 bis 8 C-Atomen sowie die wasserlöslichen Salze dieser Carbonsäuren in Betracht. Zu dieser Gruppe von Monomeren gehören beispielsweise Acrylsäure, Methacrylsäure, Dimethacrylsäure, Ethacrylsäure, Maleinsäure, Fumarsäure, Itoconsäure, Mesaconsäure, Citraconsäure, Methylenmalonsäure, Allylessigsäure, Vinylessigsäure und Crotonsäure. Als Monomere der Gruppe (b) eignen sich außerdem Sulfogruppen enthaltende Monomere wie Vinylsulfonsäure, Acrylamido-2-methyl-propansulfonsäure und Styrolsulfonsäure sowie Vinylphosphonsäure. Die Monomeren dieser Gruppe können allein oder in Mischung miteinander, in teilweise oder in vollständig neutralisierter Form bei der Copolymerisation eingesetzt werden. Zur Neutralisation verwendet man beispielsweise Alkalimetall- oder Erdalkalimetallbasen, Ammoniak, Amine und/oder Alkanolamine. Beispiele hierfür sind Natronlauge, Kalilauge, Soda, Pottasche, Natriumhydrogencarbonat, Magnesiumoxid, Calciumhydroxid, Calciumoxid, Triethanolamin, Ethanolamin, Morpholin, Diethylentriamin oder Tetraethylenpentamin. Die monomeren der Gruppe (b) werden bei der Copolymerisation vorzugsweise in teilweise neutralisierter Form eingesetzt.Suitable monomers of group (b) are, in particular, monoethylenically unsaturated carboxylic acids having 3 to 8 carbon atoms and the water-soluble salts of these carboxylic acids. This group of monomers includes, for example, acrylic acid, methacrylic acid, dimethacrylic acid, ethacrylic acid, maleic acid, fumaric acid, itoconic acid, mesaconic acid, citraconic acid, methylenemalonic acid, allylacetic acid, vinylacetic acid and crotonic acid. Also suitable as monomers of group (b) are monomers containing sulfo groups, such as vinylsulfonic acid, acrylamido-2-methylpropanesulfonic acid and styrenesulfonic acid and vinylphosphonic acid. The monomers of this group can be used alone or in admixture with each other, in partially or completely neutralized form in the copolymerization. For neutralization, for example, alkali metal or alkaline earth metal bases, ammonia, amines and / or alkanolamines are used. Examples of these are sodium hydroxide solution, potassium hydroxide solution, soda, potash, sodium bicarbonate, magnesium oxide, calcium hydroxide, calcium oxide, triethanolamine, ethanolamine, morpholine, diethylenetriamine or tetraethylenepentamine. The monomers of group (b) are preferably used in the copolymerization in partially neutralized form.

Die Copolymerisate können zur Modifizierung gegebenenfalls Monomere der Gruppe (c) in einpolymerisierter Form enthalten z.B. Ester von ethylensich ungesättigten C3-bis C5-Carbonsäuren wie Methylacrylat, Ethylacrylat, n-Butylacrylat, Isobutylacrylat, Isobutylmethacrylat, Methylmethacrylat, Ethylmethacrylat sowie Vinylester z.B. Vinylacetat oder Vinylpropionat, oder andere Monomere wie N-Vinylpyrrolidon, N-Vinylimidazol, Acrylamid und/oder Methacrylamid.The copolymers may optionally contain monomers of group (c) in copolymerized form, for example esters of ethylenically unsaturated C 3 to C 5 carboxylic acids such as methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, isobutyl methacrylate, methyl methacrylate, ethyl methacrylate and vinyl esters such as vinyl acetate or Vinyl propionate, or other monomers such as N-vinylpyrrolidone, N-vinylimidazole, acrylamide and / or methacrylamide.

Eine weitere Modifizierung der Copolymerisate ist dadurch möglich, dass man bei der Copolymerisation Monomere (d) einsetzt, die mindestens zwei Doppelbindungen im Molekül enthalten, z.B. Methlenbisacrylamid, Glykoldiacrylat, Glykoldimethacrylat, Gylcerintriacrylat, Triallylamin, Pentaerythrittriallylether, mindestens zweifach mit Acrylsäure und/oder Methacrylsäure veresterte Polyalkylenglykole oder Polyole wie Pentaerythrit, Sobit oder Glukose. Falls mindestens ein Monomer der Gruppe (d) bei der Copolymerisation eingesetzt wird, so betragen die angewendeten Mengen bis zu 2 Mol-%, z.B. 0,001 bis 1 Mol-%.A further modification of the copolymers is possible by using in the copolymerization monomers (d) which contain at least two double bonds in the molecule, for example methlenebisacrylamide, glycol diacrylate, glycol dimethacrylate, glyceryl triacrylate, triallylamine, pentaerythritol triallyl ether, esterified at least twice with acrylic acid and / or methacrylic acid Polyalkylene glycols or polyols such as pentaerythritol, Sobit or glucose. If at least one monomer of group (d) is used in the copolymerization, the amounts used are up to 2 mol%, for example 0.001 to 1 mol%.

Die Copolymerisation der Monomeren erfolgt in bekannter Weise in Gegenwart von radikalischen Polymerisationsinitiatoren und gegebenenfalls in Gegenwart von Polymerisationsreglem, vgl. EP-B 672 212 , Seite 4, Zeilen 13 - 37 oder EP-A 438 744 , Seite 2, Zeile 26 bis Seite 8,Zeile 18.The copolymerization of the monomers takes place in a known manner in the presence of free-radical polymerization initiators and optionally in the presence of polymerization regulators, cf. EP-B 672 212 , Page 4, lines 13 - 37 or EP-A 438 744 , Page 2, line 26 to page 8, line 18.

Als polymere anionische Verbindung kommen auch amphotere Copolymerisate in Betracht, die erhältlich sind durch Copolymerisieren von

  • (a) mindestens einem N-Vinylcarbonsäureamid der Formel
    Figure imgb0002
     in der R1, R2 = H oder C1- bis C6-Alkyl bedeuten,
  • (b) mindestens einer monoethylenisch ungesättigten Carbonsäure mit 3 bis 8 C-Atomen im Molekül und/oder deren Alkalimetall-, Erdalkalimetall- oder Ammoniumsalzen und gegebenenfalls
  • (c) anderen monoethylenisch ungesättigten Monomeren, und gegebenenfalls
  • (d) Verbindungen, die mindestens zwei ethylenisch ungesättigte Doppelbindungen im Molekül aufweisen,
und anschließende teilweise Abspaltung von Gruppen -CO-R1 aus den in das Copolymerisat einpolymerisierten Monomeren der Formel I unter Bildung von Aminogruppen, wobei der Gehalt an Aminogruppen im Copolymerisat mindestens 5 Mol-% unter dem Gehalt an einpolymerisierten Säuregruppen der Monomere (b) beträgt. Bei der Hydrolyse von N-Vinylcarbonsäureamidpolymeren entstehen in einer sekundären Reaktion Amidineinheiten, indem Vinylamineinheiten mit einer benachbarten Vinylformamideinheit reagieren. Im Folgenden bedeutet die Angabe von Vinylamineinheiten in den amphoteren Copolymerisaten immer die Summe aus Vinylamin- und Amidineinheiten.Suitable polymeric anionic compounds are also amphoteric copolymers obtainable by copolymerizing
  • (a) at least one N-vinylcarboxamide of the formula
    Figure imgb0002
     in which R 1 , R 2 = H or C 1 - to C 6 -alkyl,
  • (B) at least one monoethylenically unsaturated carboxylic acid having 3 to 8 carbon atoms in the molecule and / or their alkali metal, alkaline earth metal or ammonium salts and optionally
  • (c) other monoethylenically unsaturated monomers, and optionally
  • (d) compounds which have at least two ethylenically unsaturated double bonds in the molecule,
and subsequent partial cleavage of groups -CO-R 1 from the copolymerized in the copolymer monomers of formula I to form amino groups, wherein the content of amino groups in the copolymer at least 5 mol% below the content of copolymerized acid groups of the monomers (b) , In the hydrolysis of N-vinylcarboxamide polymers, amidine units are formed in a secondary reaction by reacting vinylamine units with an adjacent vinylformamide unit. In the following, the indication of vinylamine units in the amphoteric copolymers always means the sum of vinylamine and amidine units.

Die so erhältlichen amphoteren Verbindungen enthalten beispielsweise

  • (a) 10 bis 95 Mol-% Einheiten der Formel I
  • (b) 5 bis 90 Mol-% Einheiten eines Säuregruppen enthaltenden monoethylenisch ungesättigten Monomeren und/oder deren Alkalimetall-, Erdalkalimetall- oder Ammoniumsalzen,
  • (c) 0 bis 30 Mol-% Einheiten mindestens eines anderen monoethylenisch ungesättigten Monomeren,
  • (d) 0 bis 2 Mol-% mindestens einer Verbindung, die mindestens zwei ethylenisch ungesättigte Doppelbindungen in Molekül aufweist, und
  • (e) 0 bis 42 Mol-% Vinylamineinheiten einpolymerisiert enthält, wobei der Gehalt an Aminogruppen im Copolymerisat mindestens 5 Mol-% unter dem Gehalt an einpolymerisierten Säuregruppen enthaltenden Monomeren (b) beträgt.
The amphoteric compounds thus obtained contain, for example
  • (a) 10 to 95 mol% of the units of the formula I.
  • (b) 5 to 90 mol% of units of an acid group-containing monoethylenically unsaturated monomer and / or their alkali metal, alkaline earth metal or ammonium salts,
  • (c) 0 to 30 mol% of units of at least one other monoethylenically unsaturated monomer,
  • (d) 0 to 2 mol% of at least one compound having at least two ethylenically unsaturated double bonds in molecule, and
  • (e) 0 to 42 mol% of vinylamine units in copolymerized form, wherein the content of amino groups in the copolymer is at least 5 mol% below the content of copolymerized acid group-containing monomers (b).

Die Hydrolyse der anionischen Copolymerisate kann in Gegenwart von Säuren oder Basen oder auch enzymatisch durchgeführt werden. Bei der Hydrolyse mit Säuren liegen die aus den Vinylcarbonsäureamideinheiten entstehenden Vinylamingruppen in Salzform vor. Die Hydrolyse von Vinylcarbonsäureamidcopolymerisaten ist in der EP-A 438 744 , Seite 8, Zeile 20 bis Seite 10, Zeile 3, ausführlich beschrieben. Die dort gemachten Ausführungen gelten entsprechend für die Herstellung der erfindungsgemäß einzusetzenden amphoteren Polymeren.The hydrolysis of the anionic copolymers can be carried out in the presence of acids or bases or else enzymatically. In the case of hydrolysis with acids, the vinylamine groups formed from the vinylcarboxamide units are present in salt form. The hydrolysis of vinylcarboxylic acid amide copolymers is described in U.S. Pat EP-A 438 744 , Page 8, line 20 to page 10, line 3, described in detail. The remarks made there apply correspondingly to the preparation of the amphoteric polymers to be used according to the invention.

Als polymere anionische Verbindung setzt man vorzugsweise ein Copolymerisat ein, das

  1. (a) 50 bis 90 Mol-% N-Vinylformamid,
  2. (b) 10 bis 50 Mol-% Acrylsäure, Methacrylsäure und/oder deren Alkali- oder Ammoniumsalze und gegebenenfalls
  3. (c) 0 bis 30 Mol-% mindestens eines anderen monoethylenisch ungesättigten Monomeren einpolymerisiert enthält.
As the polymeric anionic compound is preferably used a copolymer which
  1. (a) 50 to 90 mol% N-vinylformamide,
  2. (B) 10 to 50 mol% of acrylic acid, methacrylic acid and / or their alkali metal or ammonium salts and optionally
  3. (C) 0 to 30 mol% of at least one other monoethylenically unsaturated monomer in copolymerized form.

Die mittleren Molmassen Mw der anionischen bzw. amphoteren Polymeren betragen beispielsweise 30 000 D bis 10 Millionen D, vorzugsweise 100 000 D bis 1 Million D. Diese Polymeren haben beispielsweise K-Werte (bestimmt nach H. Fikentscher in 5%iger wässriger Kochsalzlösung bei pH 7, einer Polymerkonzentration von 0,5 Gew.-% und einer Temperatur von 25°C) in dem Bereich von 20 bis 250, vorzugsweise 50 bis 150.The average molecular weights M.sub.w of the anionic or amphoteric polymers are, for example, 30,000 D to 10 million D, preferably 100,000 D to 1 million D. These polymers have, for example, K values (determined according to H. Fikentscher in 5% aqueous sodium chloride solution pH 7, a polymer concentration of 0.5% by weight and a temperature of 25 ° C) in the range of 20 to 250, preferably 50 to 150.

Bei dem erfindungsgemäßen Verfahren wird dem Papierstoff zunächst eine polymere kationische Komponente zugesetzt, bei der es sich ausschließlich um Vinylamineinheiten enthaltende Polymere handelt. Hierfür sind sämtliche Polymere geeignet, die beispielsweise in der zum Stand der Technik zitierten WO 04/061235 , Seite 12, Zeile 28 bis Seite 13, Zeile 21 sowie in Figur 1 angegeben sind. Die Molmasse Mw der Vinylamineinheiten enthaltenden Polymeren beträgt beispielsweise 1000 bis 5 Millionen und liegt meistens in dem Bereich von 5 000 bis 500 000, vorzugsweise 40 000 D bis 400 000 D.In the process according to the invention, a polymeric cationic component which is exclusively polymer containing vinylamine units is first added to the paper stock. All polymers suitable for this purpose, for example those cited in the prior art, are suitable for this purpose WO 04/061235 , Page 12, line 28 to page 13, line 21 and in Figure 1 are indicated. The molecular weight M w of the polymers containing vinylamine units is, for example, 1000 to 5 million, and is usually in the range of 5,000 to 500,000, preferably 40,000 D to 400,000 D.

Die andere Gruppe von Polymeren, nämlich Vinylamineinheiten enthaltende Polymere, sind beispielsweise erhältlich durch Polymerisieren mindestens eines Monomeren der Formel

Figure imgb0003
in der R1, R2 = H oder C1- bis C6-Alkyl bedeuten,
und anschließende teilweise oder vollständige Abspaltung der Gruppen -CO-R1 aus den in das Polymerisat einpolymerisierten Einheiten der Monomeren I unter Bildung von Aminogruppen. Wie oben bereits dargelegt, können sich in einer sekundären Reaktion aus Vinylamineinheiten und benachbarten Vnylformamideinheiten Amidineinheiten bilden. Auch für die hier beschriebenen kationischen Polymeren umfasst die Angabe von Vinylamineinheiten die Summe aus Vinylamin- und Amidineinheiten im Polymeren. Als Vinylamineinheiten enthaltendes Polymer setzt man beispielsweise ein zu mindestens 10 Mol-% hydrolysiertes Homopolymerisat von N-Vinylformamid ein. Polyvinylamin und/oder zu mindestens 50 Mol-% hydrolysierte Homopolymerisate des N-Vinylformamids werden bei dem erfindungsgemäßen Verfahren bevorzugt als kationische Komponente eingesetzt.The other group of polymers, namely polymers containing vinylamine units, are obtainable, for example, by polymerizing at least one monomer of the formula
Figure imgb0003
 in which R 1 , R 2 = H or C 1 - to C 6 -alkyl,
and subsequent partial or complete cleavage of the groups -CO-R 1 from the units of the monomers I copolymerized in the polymer to form amino groups. As stated above, in a secondary reaction, amidine units can form from vinylamine units and adjacent vinylsamide units. Also for the cationic polymers described herein, the indication of vinylamine units comprises the sum of vinylamine and amidine units in the polymer. As polymer containing vinylamine units, for example, a homopolymer of N-vinylformamide hydrolyzed to at least 10 mol% is used. Polyvinylamine and / or at least 50 mol% of hydrolyzed homopolymers of N-vinylformamide are preferably used in the inventive method as a cationic component.

Bei dem erfindungsgemäßen Verfahren kann man als kationische Komponente auch amphotere Copolymerisate verwenden, sofern sie mindestens 10 Mol-% mehr kationische als anionische Gruppen aufweisen. Solche amphoteren Polymerisate sind beispielsweise erhältlich durch Copolymerisation

  • (a) mindestens eines N-Vinylcarbonsäureamids der Formel
    Figure imgb0004
     in der R1, R2 = H oder C1- bis C6-Alkyl bedeuten,
  • (b) mindestens eines Säuregruppen enthaltenden monoethylenisch ungesättigten Monomeren und/oder deren Alkalimetall-, Erdalkalimetall- oder Ammoniumsalalzen und gegebenenfalls
  • (c) anderen monoethylenisch ungesättigten Monomeren, und gegebenenfalls
  • (d) Verbindungen, die mindestens zwei ethylenisch ungesättigte Doppelbindungen im Molekül aufweisen
und anschließende teilweise oder vollständige Abspaltung der Gruppen -CO-R1 aus den in das Polymerisat einpolymerisierten Einheiten der Monomeren I unter Bildung von Aminogruppen, wobei der Anteil der Aminogruppen im Copolymerisat um mindestens 10 Mol-% größer ist als der Anteil der Einheiten an Säuregruppen enthaltenden monoethylenisch ungesättigten Monomeren.In the process according to the invention, it is also possible to use amphoteric copolymers as the cationic component, provided that they have at least 10 mol% more cationic than anionic groups. Such amphoteric polymers are obtainable, for example, by copolymerization
  • (a) at least one N-vinylcarboxamide of the formula
    Figure imgb0004
     in which R 1 , R 2 = H or C 1 - to C 6 -alkyl,
  • (B) at least one acid group-containing monoethylenically unsaturated monomer and / or their alkali metal, alkaline earth metal or ammonium salts and optionally
  • (c) other monoethylenically unsaturated monomers, and optionally
  • (d) compounds having at least two ethylenically unsaturated double bonds in the molecule
and subsequent partial or complete cleavage of the groups -CO-R 1 from the polymerized into the polymer units of the monomers I to form amino groups, wherein the proportion of amino groups in the copolymer by at least 10 mol% greater than the proportion of units of acid groups containing monoethylenically unsaturated monomers.

Diese Polymeren sind nach dem selben Verfahren zugänglich wie die oben beschriebenen amphoteren Polymeren, die erfindungsgemäß als anionische Komponente eingesetzt werden, jedoch ist hier lediglich das Verhältnis von kationischen zu anionischen Gruppen anders, so dass man jetzt kationische Polymere erhält. Diese Gruppe von Polymeren enthält beispielsweise bis maximal 35 Mol-%, vorzugsweise bis maximal 10 Mol-% mindestens eines Säuregruppen enthaltenden Monomers der Gruppe (b).These polymers are accessible by the same method as the amphoteric polymers described above, which are used according to the invention as anionic component, but here only the ratio of cationic to anionic groups is different, so that one now obtains cationic polymers. This group of polymers contains, for example, up to a maximum of 35 mol%, preferably up to a maximum of 10 mol%, of at least one acid group-containing monomer of group (b).

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 Kiefemsulfat in Mischung mit zurückgeführtem gestrichenem Ausschuß. Das erfindungsgemäße Verfahren hat insbesondere Bedeutung für die Herstellung von Papier und Pappe aus Altpapier, weil es die Festigkeitseigenschaften der zurückgeführten Fasern deutlich erhöht.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. The method according to the invention has particular significance for the production of paper and board from waste paper, because it significantly increases the strength properties of the recycled fibers.

Der pH-Wert der Stoffsuspension liegt beispielsweise in dem Bereich von 4,5 bis 8, meisten bei 6 bis 7,5. Zur Einstellung des pH-Wertes kann man beispielsweise eine Säure wie Schwefelsäure oder Aluminiumsulfat verwenden.The pH of the stock suspension is, for example, in the range of 4.5 to 8, most 6 to 7.5. To adjust the pH, it is possible to use, for example, an acid, such as sulfuric acid or aluminum sulphate.

Das Vinylamineinheiten enthaltende Polymere, d.h. die kationische Komponente der zum Papierstoff zu dosierenden Polymeren, wird bei dem erfindungsgemäßen Verfahren zum Dickstoff oder vorzugsweise zu einem Dünnstoff zugegeben. Die Zugabestelle liegt vorzugsweise vor den Sieben, kann jedoch auch zwischen einer Scherstufe und einem Screen oder danach liegen. Die anionische Komponente wird meistens erst nach der Zugabe der kationischen Komponente zum Papierstoff zugegeben, kann aber auch gleichzeitig, jedoch getrennt von der kationischen Komponente zum Papierstoff dosiert werden. Weiterhin ist es auch möglich zuerst die anionische und nachfolgend die kationische Komponente zuzugeben. Das Vinylamineinheiten enthaltende Polymer und die polymere anionische Verbindung werden beispielsweise jeweils in einer Menge von 0,1 bis 2,0 Gew.-%, vorzugsweise 0,3 bis 1 Gew.-%, bezogen auf trockenen Papierstoff, eingesetzt. Das Verhältnis von Vinyamineinheiten enthaltendem Polymer zu polymerer anionischer Verbindung beträgt beispielsweise 5 : 1 bis 1 : 5 und liegt vorzugsweise in dem Bereich von 2 : 1 bis 1 : 2.The polymers comprising vinylamine units, ie the cationic component of the polymers to be metered into the paper stock, are added in the method according to the invention to the thick stock or preferably to a thin stock. The point of addition is preferably in front of the screens, but may also be between a shearing stage and a screen or afterwards. The anionic component is usually only after addition of the cationic component added to the pulp, but can also be dispensed simultaneously but separately from the cationic component to the pulp. Furthermore, it is also possible first to add the anionic and subsequently the cationic component. The vinylamine units-containing polymer and the polymeric anionic compound are used, for example, each in an amount of 0.1 to 2.0 wt .-%, preferably 0.3 to 1 wt .-%, based on dry pulp. The ratio of vinylamine units-containing polymer to polymeric anionic compound is, for example, 5: 1 to 1: 5, and is preferably in the range of 2: 1 to 1: 2.

Nach dem erfindungsgemäßen Verfahren erhält man Papierprodukte, die gegenüber den Verfahren des Standes der Technik ein höheres Trockenfestigkeitsniveau bei gleichzeitig niedriger Nassfestigkeit aufweisen.The process according to the invention gives paper products which, compared with the processes of the prior art, have a higher level of dry strength with simultaneously low wet strength.

Die in den folgenden Beispielen angegebenen Teile sind Gewichtsteile, die Prozentangaben beziehen sich auf das Gewicht der Stoffe. Der K-Wert der Polymerisate wurde nach Fikentscher, Cellulose-Chemie, Band 13, 58 - 64 und 71 -74 (1932 ) bei einer Temperatur von 20°C in 5 gew.-%igen wässrigen Kochsalzlösungen bei einem pH-Wert von 7 und einer Polymerkonzentration von 0,5% bestimmt. Dabei bedeutet K=k*1000.The parts given in the following examples are parts by weight, the percentages are based on the weight of the substances. The K value of the polymers was determined by Fikentscher, Cellulose-Chemie, Vol. 13, 58-64 and 71-74 (1932 ) at a temperature of 20 ° C in 5 wt .-% aqueous saline solutions at a pH of 7 and a polymer concentration of 0.5%. Where K = k * 1000.

Für die einzelnen Tests wurden in Laborversuchen Blätter in einem Rapid-Köthen-Laborblattbildner hergestellt. Die Trockenreißlänge wurde gemäß DIN 53 112, Blatt 1 und die Nassreißlänge gemäss DIN 53 112, Blatt 2 bestimmt. Die Ermittlung des CMT-Wertes erfolgte nach DIN 53 143, der Trockenberstdruck wurde nach DIN 53 141 ermittelt.For the individual tests, sheets were produced in laboratory tests in a Rapid-Köthen laboratory sheet former. The dry breaking length was determined according to DIN 53 112, sheet 1 and the wet breaking length according to DIN 53 112, sheet 2. The determination of the CMT value was carried out according to DIN 53 143, the dry burst pressure was determined according to DIN 53 141.

BeispieleExamples

Aus 100% gemischtem Altpapier wurde eine 0,5%ige wässrige Stoffsuspension hergestellt. Der pH-Wert der Suspension betrug 7,1, der Mahlgrad des Stoffs 50° Schopper-Riegler (°SR). Die Stoffsuspension wurde dann in 36 gleiche Teile geteilt und in den Vergleichsbeispielen 1 bis 26 und in den Beispielen 27 bis 36 unter folgenden Bedingungen zu Blättern einer Flächenmasse von 120 g/qm verarbeitet.From 100% mixed waste paper, a 0.5% aqueous pulp suspension was prepared. The pH of the suspension was 7.1, the freeness of the substance 50 ° Schopper-Riegler (° SR). The stock suspension was then divided into 36 equal parts and processed into sheets of a basis weight of 120 g / m 2 in Comparative Examples 1 to 26 and Examples 27 to 36 under the following conditions.

Vergleichsbeispiel 1Comparative Example 1

Aus der oben beschriebenen Stoffsuspension wurde ohne weitere Zusätze ein Blatt gebildet.From the stock suspension described above, a sheet was formed without further additions.

Vergleichsbeispiele 2 - 6 gemäß DE-A 35 06 832Comparative Examples 2 to 6 according to DE-A 35 06 832

Zu weiteren Proben der oben beschriebenen Stoffsuspension gab man, bezogen auf trockenen Faserstoff, zunächst die in Tabelle 1 angegebenen Mengen eines Polyvinylamins (PVAm 1) mit einem K-Wert von 110 (hergestellt durch Hydrolyse von Polyvinylformamid, Hydrolysegrad 95%) und nach einer Verweilzeit von 5 Minuten, die ebenfalls in Tabelle 1 angegebenen Mengen eines Copolymerisats aus 60% Acrylsäure und 40% Acrylnitril (Copolymerisat 1) zu. Das Copolymer lag in Form des Natriumsalzes vor und hatte einen K-Wert von 130. Nach einer Einwirkungszeit von 1 Minute wurde der in dieser Weise jeweils behandelte Papierstoff unter Blattbildung entwässert. Tabelle 1 Vergleichsbeispiel PVAm 1 [%] Copolymerisat 1 [%] 1 0 0 2 0,25 0,25 3 0,5 0,5 4 0,5 1 5 1 0,5 6 1 1 For further samples of the stock suspension described above, based on dry fiber, first the amounts of a polyvinylamine (PVAm 1) with a K value of 110 (prepared by hydrolysis of polyvinylformamide, degree of hydrolysis 95%) and a residence time are given in Table 1 of 5 minutes, the amounts of a copolymer of 60% of acrylic acid and 40% of acrylonitrile (copolymer 1) also shown in Table 1. The copolymer was in the form of the sodium salt and had a K value of 130. After an exposure time of 1 minute, the paper stock thus treated in each case was dewatered to form a sheet. Table 1 Comparative example PVAm 1 [%] Copolymer 1 [%] 1 0 0 2 0.25 0.25 3 0.5 0.5 4 0.5 1 5 1 0.5 6 1 1

Vergleichsbeispiele 7-11 gemäß DE-A 35 06 832Comparative Examples 7-11 according to DE-A 35 06 832

Zu weiteren Proben der oben beschriebenen Stoffsuspension gab man, bezogen auf trockenen Faserstoff, die in Tabelle 2 angegebenen Mengen eines Polyethylenimins, das in 10%-iger wässriger Lösung eine Viskosität von 30 mPas hatte. Nach einer Einwirkungszeit von 5 Minuten fügte man, bezogen auf trockenen Faserstoff, die ebenfalls in Tabelle 2 angegebenen Mengen eines Copolymerisats aus 50% Acrylsäure und 50% Acrylnitril (Copolymerisat 2) zu. Das Copolymer lag in Form des Natriumsalzes vor und hatte einen K-Wert von 120. Nach einer Einwirkungszeit von 1 Minute wurde auch der in dieser Weise behandelte Papierstoff unter Blattbildung entwässert. Tabelle 2 Nr. Polyethylenimin [%] Copolymerisat 2 [%] 7 0,25 0,25 8 0,5 0,5 9 0,5 1 10 1 0,5 11 1 1 For further samples of the stock suspension described above, the amounts of a polyethyleneimine indicated in Table 2, based on dry pulp, which had a viscosity of 30 mPas in 10% strength aqueous solution were given. After an exposure time of 5 minutes, the amounts of a copolymer of 50% of acrylic acid and 50% of acrylonitrile (copolymer 2), likewise indicated in Table 2, were added, based on dry pulp. The copolymer was in the form of the sodium salt and had a K value of 120. After an exposure time of 1 minute, the stock treated in this manner was also dewatered with foliar formation. Table 2 No. Polyethyleneimine [%] Copolymer 2 [%] 7 0.25 0.25 8th 0.5 0.5 9 0.5 1 10 1 0.5 11 1 1

Vergleichsbeispiele 12-16 gemäß WO 04/061235Comparative Examples 12-16 according to WO 04/061235

Zu weiteren Proben der oben beschriebenen Stoffsuspension gab man, bezogen auf trockenen Faserstoff, die in Tabelle 3 angegebenen Mengen eines Polyvinylamins (PVAm 2) mit einem K-Wert von 90 (Catiofast® PR 8106 von BASF, hergestellt durch Hydrolyse von Polyvinylformamid, Hydrolysegrad 90%). Nach einer Verweilzeit von 5 Minuten wurden die ebenfalls in Tabelle 3 angegebenen Mengen eines glyoxylierten kationischen Polyacrylamids (kationisches Copolymer 1, vertrieben von Bayer AG unter der Bezeichnung Parez® 631 NC) zu der Papierstoffsuspension zugegeben. Nach einer Einwirkungszeit von 1 Minute wurde der in dieser Weise behandelte Papierstoff jeweils unter Blattbildung entwässert. Tabelle 3 Nr. PVAm 2 [%] Kationisches Copolymer 1 [%] 12 0,25 0,25 13 0,5 0,5 14 0,5 1 15 1 0,5 16 1 1 For further samples of the stock suspension described above, the amounts of a polyvinylamine (PVAm 2) with a K value of 90 (Catiofast® PR 8106 from BASF, prepared by hydrolysis of polyvinylformamide, degree of hydrolysis of 90, based on dry pulp, stated in Table 3 were added %). After a residence time of 5 minutes, the amounts of a glyoxylated cationic polyacrylamide (cationic copolymer 1, sold by Bayer AG under the name Parez® 631 NC) also shown in Table 3 were added to the paper stock suspension. After an exposure time of 1 minute, the stock treated in this manner was dewatered each time with sheet formation. Table 3 No. PVAm 2 [%] Cationic copolymer 1 [%] 12 0.25 0.25 13 0.5 0.5 14 0.5 1 15 1 0.5 16 1 1

Vergleichsbeispiele 17-21 gemäß WO 04/061235Comparative Examples 17-21 according to WO 04/061235

Zu weiteren Proben der oben beschriebenen Stoffsuspension gab man jeweils, bezogen auf trockenen Faserstoff, die in Tabelle 4 angegebenen Mengen eines Polyvinylamins (PVAm 2) mit einem K-Wert von 90 (hergestellt durch Hydrolyse von Polyvinylformamid, Hydrolysegrad 90%). Nach einer Verweilzeit von 5 Minuten wurden jeweils die in Tabelle 4 angegebenen Mengen eines Copolymerisats aus 80% Acrylsäure und 20% Acrylamid (Copolymerisat 4) zugegeben. Das Copolymer lag in Form des Natriumsalzes vor und hatte einen K-Wert von 120. Nach einer Einwirkungszeit von 1 Minute wurde der jeweils in dieser Weise behandelte Papierstoff unter Blattbildung entwässert. Tabelle 4 Nr. PVAm [%] Copolymerisat 4 [%] 17 0,25 0,25 18 0,5 0,5 19 0,5 1 20 1 0,5 21 1 1 For further samples of the stock suspension described above, in each case based on dry pulp, the amounts of a polyvinylamine (PVAm 2) with a K value of 90 (prepared by hydrolysis of polyvinylformamide, degree of hydrolysis 90%) indicated in Table 4 were added. After a residence time of 5 minutes were respectively the amounts of a copolymer of 80% acrylic acid and 20% acrylamide (copolymer 4) given in Table 4 were added. The copolymer was in the form of the sodium salt and had a K value of 120. After an exposure time of 1 minute, the paper stock thus treated was dewatered to form sheets. Table 4 No. PVAm [%] Copolymer 4 [%] 17 0.25 0.25 18 0.5 0.5 19 0.5 1 20 1 0.5 21 1 1

Vergleichsbeispiele 22 -26 gemäß WO 04/061235Comparative Examples 22-26 according to WO 04/061235

Zu weiteren Proben der oben beschriebenen Stoffsuspension gab man, bezogen auf trockenen Faserstoff, jeweils die in Tabelle 5 angegebenen Mengen eines Polyvinylamins (PVAm 2) mit einem K-Wert von 90 (Catiofast® PR 8106, hergestellt durch Hydrolyse aus Polyvinylformamid, Hydrolysegrad 90%) zu. Nach einer Verweilzeit von 5 Minuten wurden dann jeweils die in Tabelle 5 angegebenen Mengen eines anionischen glyoxylierten Copolymerisats aus Acrylsäure und Acrylamid zugegeben (Copolymerisat 3, erhältlich unter der Bezeichnung Parez® von Bayer AG). Nach einer Einwirkungszeit von 1 Minute wurde auch der jeweils in dieser Weise behandelte Papierstoff unter Blattbildung entwässert. Tabelle 5 Nr. PVAm 2 [%] Copolymerisat 3 [%] 22 0,25 0,25 23 0,5 0,5 24 0,5 1 25 1 0,5 26 1 1 For further samples of the stock suspension described above, in each case based on dry pulp, the amounts of a polyvinylamine (PVAm 2) with a K value of 90 (Catiofast® PR 8106, prepared by hydrolysis from polyvinylformamide, degree of hydrolysis 90% in Table 5 ) too. After a residence time of 5 minutes, the quantities of an anionic glyoxylated copolymer of acrylic acid and acrylamide indicated in Table 5 were then added in each case (copolymer 3, obtainable under the name Parez® from Bayer AG). After an exposure time of 1 minute, the paper stock treated in this way was also dewatered with foliar formation. Table 5 No. PVAm 2 [%] Copolymer 3 [%] 22 0.25 0.25 23 0.5 0.5 24 0.5 1 25 1 0.5 26 1 1

Beispiele 1-5 gemäß ErfindungExamples 1-5 according to the invention

Zu weiteren Proben der oben beschriebenen Stoffsuspension gab man, bezogen auf trockenen Faserstoff, jeweils die in Tabelle 6 angegebenen Mengen eines Polyvinylamins PVAm 3) mit einem K-Wert von 90 (hergestellt durch Hydrolyse von Polyvinylformamid, Hydrolysegrad 50%) zu. Nach einer Verweilzeit von 5 Minuten wurden dann jeweils die ebenfalls in Tabelle 6 angegebenen Mengen eines Copolymerisats aus 30% Acrylsäure und 70% Vinylformamid (Copolymerisat 4) zugegeben. Das Copolymer lag in Form des Natriumsalzes vor und hatte einen K-Wert von 90. Nach einer Einwirkungszeit von 1 Minute wurde dann jeweils auch der in dieser Weise behandelte Papierstoff unter Blattbildung entwässert. Die Testergebnisse sind in Tabelle 8 zusammengestellt. Tabelle 6 Beispiel Nr. Test Nr. PVAm 3 [%] Copolymerisat 4 [%] 1 27 0,25 0,25 2 28 0,5 0,5 3 29 0,5 1 4 30 1 0,5 5 31 1 1 For further samples of the stock suspension described above, based on dry pulp, in each case the amounts of a polyvinylamine PVAm 3) given in Table 6 with a K value of 90 (prepared by hydrolysis of polyvinylformamide, degree of hydrolysis 50%) were added. After a residence time of 5 minutes, the amounts of a copolymer of 30% of acrylic acid and 70% of vinylformamide (copolymer 4), also indicated in Table 6, were then added in each case. The copolymer was in the form of the sodium salt and had a K value of 90. After an exposure time of 1 minute, the paper stock treated in this way was then dewatered to form sheets. The test results are summarized in Table 8. Table 6 Example no. Test no. PVAm 3 [%] Copolymer 4 [%] 1 27 0.25 0.25 2 28 0.5 0.5 3 29 0.5 1 4 30 1 0.5 5 31 1 1

Beispiele 6-10 gemäß ErfindungExamples 6-10 according to the invention

Zu weiteren Proben der oben beschriebenen Stoffsuspension gab man, bezogen auf trockenen Faserstoff, jeweils die in Tabelle 7 angegebenen Mengen eines Polyvinylamins (PVAm 4) mit einem K-Wert von 90 (zu 30%. hydrolysiertes Polyvinylformamid). Nach einer Verweilzeit von 5 Minuten wurden dann jeweils die in Tabelle 7 angegebenen Mengen eines Copolymerisats aus 30% Acrylsäure und 70% Vinylformamid (Copolymerisat 4) zugegeben. Das Copolymer lag in Form des Natriumsalzes vor und hatte einen K-Wert von 90. Nach einer Einwirkungszeit von 1 Minute wurde dann jeweils der in dieser Weise behandelte Papierstoff unter Blattbildung entwässert. Die Testergebnisse sind in Tabelle 8 zusammengestellt. Tabelle 7 Beispiel Nr. Test Nr. PVAm 4[%] Copolymerisat 4 [%] 6 32 0,25 0,25 7 33 0,5 0,5 8 34 0,5 1 9 35 1 0,5 10 36 1 1 For further samples of the stock suspension described above, based on dry pulp, in each case the amounts of a polyvinylamine (PVAm 4) with a K value of 90 (30% hydrolysed polyvinylformamide) given in Table 7 were added. After a residence time of 5 minutes, the amounts indicated in Table 7 of a copolymer of 30% acrylic acid and 70% vinylformamide (copolymer 4) were then added. The copolymer was in the form of the sodium salt and had a K value of 90. After an exposure time of 1 minute, the pulp treated in this way was then dewatered to form sheets. The test results are summarized in Table 8. Table 7 Example no. Test no. PVAm 4 [%] Copolymer 4 [%] 6 32 0.25 0.25 7 33 0.5 0.5 8th 34 0.5 1 9 35 1 0.5 10 36 1 1

Die in den Vergleichsbeispielen 1-26 und in den Beispielen 1 bis 10 jeweils hergestellten Papierblätter wurden auf Trocken- und Naßreißlänge, CMT-Wert und Trockenberstdruck nach den oben angegebenen Methoden geprüft. Die Ergebnisse der Prüfungen, die an den jeweils gebildeten Blättern vorgenommen wurden, sind in Tabelle 8 unter Test Nm. 1 bis 36 angegeben. Die Test Nummern 27 - 36 sind Beispiele gemäß Erfindung.The paper sheets respectively prepared in Comparative Examples 1-26 and Examples 1 to 10 were tested for dry and wet tear length, CMT value and dry bursting pressure according to the methods given above. The results of the tests made on the respective sheets formed are shown in Table 8 under Test Nm. 1 to 36 indicated. Test Nos. 27-36 are examples according to the invention.

Die in Tabelle 8 verwendeten Abkürzungen haben folgende Bedeutung:
X: eingesetzte Menge an kationischer Komponente
Y: eingesetzte Menge an anionischer Komponente
TRL: Trockenreißlänge
NRL: Naßreißlänge
Rel. NRL: relative Naßreißlänge Tabelle 8 Test Nr. X [%] Y [%] Berstdruck [kPa] TRL [m] NRL [m] CMT30 [N] Rel.NRL [%] 1 0 0 339 3971 156 152 3,93 2 0,25 0,25 394 4587 617 184 13,45 3 0,5 0,5 423 4712 656 194 13,92 4 0,5 1 409 4918 678 204 13,76 5 1 0,5 431 5134 729 189 14,20 6 1 1 451 5094 712 208 13,97 7 0,25 0,25 379 4601 691 181 15,02 8 0,5 0,5 412 4799 734 201 15,29 9 0,5 1 429 4894 746 187 15,24 10 1 0,5 434 4765 775 209 16,26 11 1 1 445 4943 821 202 16,61 12 0,25 0,25 365 4425 728 147 16,45 13 0,5 0,5 403 4877 838 171 17,18 14 0,5 1 414 4933 856 186 17,35 15 1 0,5 407 4861 876 181 18,02 16 1 1 421 4929 899 189 18,24 17 0,25 0,25 387 4416 692 161 15,67 18 0,5 0,5 411 4779 789 187 16,51 19 0,5 1 405 4634 767 179 16,55 20 1 0,5 413 4729 802 183 16,96 21 1 1 402 4743 812 192 17,12 22 0,25 0,25 371 4367 699 151 16,01 23 0,5 0,5 405 4823 782 168 16,23 24 0,5 1 416 4934 828 173 16,78 25 1 0,5 407 4912 803 176 16,34 26 1 1 422 5013 845 183 16,85 27 0,25 0,25 406 4626 547 172 11,83 28 0,5 0,5 488 5443 625 229 11,48 29 0,5 1 474 5278 600 226 11,36 30 1 0,5 471 5223 624 216 11,96 31 1 1 496 5511 638 232 11,57 32 0,25 0,25 399 4589 435 179 9,49 33 0,5 0,5 444 5321 515 224 9,68 34 0,5 1 459 5181 484 222 9,34 35 1 0,5 467 5229 525 217 10,04 36 1 1 483 5412 531 233 9,82 The abbreviations used in Table 8 have the following meaning:
X: amount of cationic component used
Y: amount of anionic component used
TRL: Dry tear length
NRL: wet tear length
Rel. NRL: relative wet tear length Table 8 Test no. X [%] Y [%] Burst pressure [kPa] TRL [m] NRL [m] CMT 30 [N] Rel.NRL [%] 1 0 0 339 3971 156 152 3.93 2 0.25 0.25 394 4587 617 184 13,45 3 0.5 0.5 423 4712 656 194 13.92 4 0.5 1 409 4918 678 204 13.76 5 1 0.5 431 5134 729 189 14,20 6 1 1 451 5094 712 208 13.97 7 0.25 0.25 379 4601 691 181 15.02 8th 0.5 0.5 412 4799 734 201 15.29 9 0.5 1 429 4894 746 187 15.24 10 1 0.5 434 4765 775 209 16.26 11 1 1 445 4943 821 202 16.61 12 0.25 0.25 365 4425 728 147 16.45 13 0.5 0.5 403 4877 838 171 17.18 14 0.5 1 414 4933 856 186 17.35 15 1 0.5 407 4861 876 181 18,02 16 1 1 421 4929 899 189 18.24 17 0.25 0.25 387 4416 692 161 15.67 18 0.5 0.5 411 4779 789 187 16.51 19 0.5 1 405 4634 767 179 16.55 20 1 0.5 413 4729 802 183 16.96 21 1 1 402 4743 812 192 17.12 22 0.25 0.25 371 4367 699 151 16,01 23 0.5 0.5 405 4823 782 168 16.23 24 0.5 1 416 4934 828 173 16.78 25 1 0.5 407 4912 803 176 16.34 26 1 1 422 5013 845 183 16.85 27 0.25 0.25 406 4626 547 172 11.83 28 0.5 0.5 488 5443 625 229 11.48 29 0.5 1 474 5278 600 226 11.36 30 1 0.5 471 5223 624 216 11.96 31 1 1 496 5511 638 232 11.57 32 0.25 0.25 399 4589 435 179 9.49 33 0.5 0.5 444 5321 515 224 9.68 34 0.5 1 459 5181 484 222 9.34 35 1 0.5 467 5229 525 217 10.04 36 1 1 483 5412 531 233 9.82

Wie aus Tabelle 8 ersichtlich ist, wird mit den erfindungsgemäßen Kombinationen Test Nm. 27 -36 gegenüber den Vergleichsbeispielen Test Nummern 1 bis 26 das höchste Trockenfestigkeitsniveau bei gleichzeitig niedrigster Nassfestigkeit erreicht. Hervorzuheben ist auch das signifikant niedrigere Niveau der Nassverfestigung bei Verwendung eines Polyvinylamins mit relativ niedrigem Hydrolysegrad als kationische Komponente (vgl. Beispiele 6 bis 10).As can be seen from Table 8, with the combinations according to the invention test Nm. 27-36 compared to the comparative examples test numbers 1 to 26 reaches the highest dry strength level with the lowest wet strength. Also to be emphasized is the significantly lower level of wet strength when using a polyvinylamine with a relatively low degree of hydrolysis as a cationic component (see Examples 6 to 10).

Claims (14)

  1. A process for producing paper, board and cardboard of high dry strength by separately adding a polymer comprising vinylamine units and a polymeric anionic compound to a paper pulp, dewatering the pulp and drying the paper products, which comprises using as polymeric anionic compound at least one copolymer obtainable by copolymerizing
    (a) at least one N-vinylcarboxamide of the formula
    Figure imgb0009
     in which R1 and R2 are H or C1- to C6 alkyl,
    (b) at least one monoethylenically unsaturated monomer comprising acid groups, and/or the alkali metal, alkaline earth metal or ammonium salts thereof, and optionally
    (c) other monoethylenically unsaturated monomers, and optionally
    (d) compounds having at least two ethylenically unsaturated double bonds in their molecule.
  2. The process according to claim 1, wherein a copolymer is used which is obtainable by copolymerizing
    (a) N-vinylformamide,
    (b) acrylic acid, methacrylic acid and/or the alkali metal or ammonium salts thereof, and optionally
    (c) other monoethylenically unsaturated monomers.
  3. The process according to claim 1 or 2, wherein the polymeric anionic compound comprises in copolymerized form
    (a) 10 to 95 mol% of units of the formula I
    (b) 5 to 90 mol% of units of a monoethylenically unsaturated carboxylic acid having 3 to 8 carbon atoms in its molecule, and/or the alkali metal, alkaline earth metal or ammonium salts thereof, and
    (c) 0 to 30 mol% of units of at least one other monoethylenically unsaturated monomer.
  4. The process according to claim 4, wherein the polymeric anionic compound comprises in copolymerized form
    (a) 10 to 95 mol% of units of the formula I
    (b) 5 to 90 mol% of units of a monoethylenically unsaturated monomer comprising acid groups, and/or the alkali metal, alkaline earth metal or ammonium salts thereof,
    (c) 0 to 30 mol% of units of at least one other monoethylenically unsaturated monomer, and
    (d) 0 to 2 mol%, preferably 0.001 to 1 mol%, of at least one compound having at least two ethylenically unsaturated double bonds.
  5. The process according to any one of claims 1 to 4, wherein the polymeric anionic compound is obtainable by copolymerizing
    (a) at least one N-vinylcarboxamide of the formula
    Figure imgb0010
     in which R1 and R2 are H or C1- to C6 alkyl,
    (b) at least one monoethylenically unsaturated carboxylic acid having 3 to 8 carbon atoms in its molecule, and/or the alkali metal, alkaline earth metal or ammonium salts thereof, and optionally
    (c) other monoethylenically unsaturated monomers, and optionally
    (d) compounds having at least two ethylenically unsaturated double bonds in their molecule,
    and then partly eliminating groups -CO-R1 from the monomers of the formula I copolymerized in the copolymer, to form amino groups, the amount of amino groups in the copolymer being at least 5 mol% below the amount of copolymerized monomers (b) comprising acid groups.
  6. The process according to any one of claims 1 to 5, wherein the polymeric anionic compound comprises in copolymerized form
    (a) 10 to 95 mol% of units of the formula I
    (b) 5 to 90 mol% of units of a monoethylenically unsaturated monomer comprising acid groups, and/or the alkali metal, alkaline earth metal or ammonium salts thereof,
    (c) 0 to 30 mol% of units of at least one other monoethylenically unsaturated monomer,
    (d) 0 to 2 mol% of units of at leaste one compound having at least two ethylenically unsaturated double bonds in its molecule, and
    (e) 0 to 42 mol% of vinylamine units, the amount of amino groups in the copolymer being at least 5 mol% below the amount of copolymerized monomers (b) comprising acid groups.
  7. The process according to any one of claims 1 to 6, wherein the polymeric anionic compound comprises in copolymerized form
    (a) 50 to 90 mol% of N-vinylformamide,
    (b) 10 to 50 mol% of acrylic acid, methacrylic acid and/or the alkali metal or ammonium salts thereof, and optionally
    (c) 0 to 30 mol% of at least one other monoethylenically unsaturated monomer.
  8. The process according to any one of claims 1 to 7, wherein as polymer comprising vinylamine units at least one compound is used which is obtainable by polymerizing at least one monomer of the formula
    Figure imgb0011
     in which R1 and R2 are H or C1- to C6 alkyl,
    and then partly or completely eliminating the groups -CO-R1
    from the monomer I units copolymerized in the polymer, to form amino groups.
  9. The process according to any one of claims 1 to 8, wherein as polymer comprising vinylamine units an at least 10 mol% hydrolyzed homopolymer of N-vinylformamide is used.
  10. The process according to any one of claims 1 to 9, wherein as polymer comprising vinylamine unites a copolymer is used which is obtainable by copolymerizing
    a) at least one N-vinylcarboxamide of the formula
    Figure imgb0012
     in which R1 and R2 are H or C1- to C6 alkyl,
    b) at least once monoethylenically unsaturated monomer comprising acid groups, and/or the alkali metal, alkaline earth metal or ammonium salts thereof, and optionally
    c) other monoethylenically unsaturated monomers, and optionally
    d) compound heaving at least two ethylenically unsaturated double bonds in their molecule,
    and then partly or completely eliminating the groups -CO-R1
    from the monomer I units copolymerized in the polymer, to form amino groups, the fraction of amino groups in the copolymer bering greater by at least 10 mol% than the fraction of units of monoethylenically unsaturated monomers (b) comprising acid groups.
  11. The process according to any once of claims 1 to 10, wherein as polymer comprising vinylamine units polyvinylamine and/or at least 50 mol% hydrolyzed homopolymers of N-vinylformamide are used.
  12. The process according to any one of claims 1 to 11, whereon the polymer comprising vinylamine units and the polymeric anionic compound are each used in an amount of 0.1 to 2.0% by weight, based on dry paper pulp.
  13. The process according to any one of claims 1 to 12, wherein the ratio of polymer comprising vinylamine units to polymeric anionic compound is 5 : 1 to 1 : 5.
  14. The process according to any one of claims 1 to 13, wherein the ratio of polymer comprising vinylamine units to polymeric anionic compound is 2 : 1 to 1 : 2.
EP05811227A 2004-11-23 2005-11-21 Method for producing high dry strength paper, paperboard or cardboard Active EP1819877B1 (en)

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CN101065538A (en) 2007-10-31
ES2400189T3 (en) 2013-04-08
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US20090145566A1 (en) 2009-06-11
BRPI0518485A2 (en) 2008-11-18
DE102004056551A1 (en) 2006-05-24
EP1819877A1 (en) 2007-08-22
US8349134B2 (en) 2013-01-08
PT1819877E (en) 2013-03-12
JP2008520844A (en) 2008-06-19
JP4778521B2 (en) 2011-09-21
PL1819877T3 (en) 2013-05-31

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