EP1999314B1 - Method for producing paper, paperboard and cardboard having high dry strength - Google Patents

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

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Publication number
EP1999314B1
EP1999314B1 EP07712497.2A EP07712497A EP1999314B1 EP 1999314 B1 EP1999314 B1 EP 1999314B1 EP 07712497 A EP07712497 A EP 07712497A EP 1999314 B1 EP1999314 B1 EP 1999314B1
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EP
European Patent Office
Prior art keywords
units
cationic polymer
process according
acid
paper
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EP07712497.2A
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German (de)
French (fr)
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EP1999314A1 (en
Inventor
Martin Rübenacker
Norbert Schall
Ellen KRÜGER
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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
    • D21H17/21—Macromolecular organic compounds of natural origin; Derivatives thereof
    • D21H17/23—Lignins
    • 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
    • D21H17/41—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups
    • D21H17/42—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups anionic
    • 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
    • D21H17/41—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups
    • D21H17/42—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups anionic
    • D21H17/43—Carboxyl groups or derivatives thereof

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. As polyethyleneimine, and then adding a water-soluble anionic polymer, eg. As a hydrolyzed polyacrylamide, added and dehydrated the pulp on the paper machine with sheet formation.
  • 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% by weight of an ethylenically unsaturated C 3 -C 5 -carboxylic acid (for example 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 has also been considered.
  • the degree of hydrolysis The N-vinylformamide polymer 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.
  • WO 03/052206 discloses 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.
  • the EP 672 212 discloses the sole use of hydrolyzed copolymers of N-vinylcarboxamides and monoethylenically unsaturated carboxylic acids as an additive to the paper stock.
  • EP 362 770 and EP 723,047 each disclose combinations of polyacrylamides and lignosulfonate, which are previously prepared as a polyelectrolyte complex and added as such to the stock.
  • both documents each disclose the addition of alum, which causes an increase in pH. It is known to the person skilled in the art that alum is used as fixing agent in order to fix the polyelectrolyte and lignosulphonate polyelectrolyte complex on the fiber.
  • 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 obtained 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 available, can be used in papermaking as an additive to the paper stock to increase the rate of dewatering and retention and the dry and wet strength of the paper, 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 dry strength in particular in packaging papers (for example, wave from waste paper, Fluting) should be further improved compared to the previously known methods.
  • a polymer comprising vinylamine units is added to the paper stock as the polymeric cationic component.
  • These compounds are preferably used as the sole cationic component. However, they may optionally be substituted by up to 50% by weight of other cationic polymers such as cationic poly (meth) acrylamides, polydiallyldimethylammonium chlorides, condensates of dimethylamine and epichlorohydrin or polydialkyl (meth) acrylamides.
  • Suitable cationic polymers containing vinylamine units are all polymers which are cited, for example, in the prior art 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.
  • the indication of vinylamine units comprises the sum of vinylamine and amidine units in the polymer.
  • a polymer containing at least 1 mol% of N-vinylformamide homopolymer is used as the polymer containing vinylamine units.
  • 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 which are amphoteric and which have a total of more cationic than anionic groups contains, for example, up to a maximum of 35 mol%, preferably up to 10 mol%, of at least one acid group-containing monomer of group (b) in copolymerized form.
  • lignosulfonic acid and / or a lignosulfonate into consideration. Further details of these products can be found for example in the above reference Römpp, 9th edition, G. Thieme Verlag Stuttgart, 1990, page 2511 and in Ullmann's Encyclopedia of Industrial Chemistry, 5th Completely Revised Edition, Volume A15, pages 311-314 , Lignosulfonic acid is formed in cellulose production by sulphite digestion of wood, whereby lignin reacts with sulphurous acid. It is sulfonated here on the C 3 side chains of the phenylpropane units.
  • lignin sulphonic acid or lignin sulphonates are formed, for example, the sodium, potassium, ammonium, magnesium or calcium salts of lignosulphonic acid.
  • Lignosulfonic acid and the salts of lignosulfonic acid mentioned are soluble in water.
  • the molecular weight of the lignosulfonic acid is, for example 10,000 to 200,000 g / mol.
  • Lignosulfonates are z. B. obtained from the sulfite waste liquors (black liquor) of cellulose production.
  • Lignosulfonic acid and / or lignin sulfonate are used, for example, in an amount of from 0.1 to 10% by weight, preferably from 0.2 to 5% by weight and in particular from 0.5 to 2% by weight, based on dry paper stock.
  • Vinylamine units containing polymer and lignosulfonic acid and / or lignin sulfonate be used in the inventive method, for example in a weight ratio of 5: 1 to 1: 5, preferably in a weight ratio of 2: 1 to 1: 2.
  • 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, itaconic 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 also 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
  • 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.
  • monomers (d) which contain at least two double bonds in the molecule
  • methylenebisacrylamide glycol diacrylate, glycol dimethacrylate, Gylcerintriacrylat, triallylamine, Pentaerythrittriallylether, at least twice with acrylic acid and / or methacrylic acid esterified polyalkylene glycols or polyols such as pentaerythritol, soba or glucose.
  • the amounts used are up to 2 mol%, z. B. 0.001 to 1 mol%.
  • the copolymerization of the monomers is carried out 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 average molecular weights M W of the anionic polymers (ii) 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.
  • the invention further provides the use of a polymeric anionic compound according to the invention as an additive to the paper stock in the production of paper, paperboard and cardboard in the presence of at least one vinylamine units containing cationic polymers to increase the dry strength.
  • 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, or a waste paper 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 fibers or it is based on fiber blends of a primary material and recycled coated Committee, z. Bleached pine sulfate in admixture with recycled coated broke.
  • the dewatering of the stock usually takes place on the wire of a paper machine.
  • 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 vinylamine unit-containing polymer i. the cationic component of the polymer to be metered to the paper stock is added in the inventive method, for example to the thick material or preferably to a thin material.
  • 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 preferably dosed to the thin.
  • first lignosulfonic acid or lignin sulfonate is metered in, thereafter as the sole cationic component a polymer containing vinylamine groups and subsequently an anionic polymer of vinylformamide.
  • the sole cationic component a polymer containing vinylamine groups and subsequently an anionic polymer of vinylformamide.
  • the cationic component (vinylamine units-containing polymer as the sole cationic component) to the paper stock and to meter the anionic component simultaneously but separately from the cationic component to the paper stock.
  • the vinylamine units-containing polymer is used, for example, in an amount of 0.05 to 2.0 wt .-%, preferably 0.1 to 1 wt .-%, based on dry pulp.
  • the ratio of cationic component (polymer containing vinylamine units) to polymeric anionic component (ligninsulfonic acid and / or ligninsulfonate or combination of ligninsulfonic acid and / or ligninsulfonate with at least one anionic polymer of vinylformamide) is for example 5: 1 to 1: 5 and is preferably in 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.
  • these papers have a high CMT value compared with known paper products.
  • 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 after H. Fikentscher, Cellulose Chemistry, 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.
  • Example 1 in each case one sample of the above-described paper stock was first metered into the quantities of lignosulfonate indicated in Table 1, the sample was mixed, then the cationic polymer (PVAm 1) was added after a residence time of 20 seconds and the mixture was mixed In turn, after a 20 second residence time, the anionic polymer 1 was added, the mixed stock was mixed, and then dewatered on a Rapid-Kothen sheet former.
  • the values for the dry burst pressure, the SCT value and the CMT value converted to sheets having a basis weight of 120 g / m 2 are given in Table 1. Table 1 Comp.

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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, and then adding a water-soluble anionic polymer, eg. As a hydrolyzed polyacrylamide, added and dehydrated the pulp on the paper machine with sheet formation. 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% by weight of an ethylenically unsaturated C 3 -C 5 -carboxylic acid (for example 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 has also been considered. The degree of hydrolysis The N-vinylformamide polymer 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, das 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 discloses 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.

DE 195 370 88 offenbart ein Verfahren zur Herstellung von trockenfest und naßfest ausgerüstetem Papier durch Zugabe von Kombinationen aus hydrophil modifizierten Polyisocyanaten und Vinylamineinheiten enthaltenden Polymerisaten. DE 195 370 88 discloses a process for producing dry-strength and wet-strength finished paper by adding combinations of hydrophilically modified polyisocyanates and polymers containing vinylamine units.

Die EP 672 212 offenbart die alleinige Verwendung von hydrolysierten Copolymerisaten aus N-Vinylcarbonsäureamiden und monoethylenisch ungesättigten Carbonsäuren als Zusatz zum Papierstoff.The EP 672 212 discloses the sole use of hydrolyzed copolymers of N-vinylcarboxamides and monoethylenically unsaturated carboxylic acids as an additive to the paper stock.

Die EP 362 770 und EP 723 047 offenbaren jeweils Kombinationen von Polyacrylamiden und Ligninsulfonat, die zuvor als Polyelektrolytkomplex hergestellt werden und als solcher dem Papierstoff zugesetzt werden. Darüber hinaus offenbaren beide Dokumente jeweils den Zusatz von Alum, welches eine Steigerung es pH-Werts verursacht. Dem Fachmann ist bekannt, dass Alum als Fixiermittel eingesetzt wird, um den Polelektrolytkomplex aus Polyacrylamid und Ligninsulfonat auf der Faser zu fixieren.The EP 362 770 and EP 723,047 each disclose combinations of polyacrylamides and lignosulfonate, which are previously prepared as a polyelectrolyte complex and added as such to the stock. In addition, both documents each disclose the addition of alum, which causes an increase in pH. It is known to the person skilled in the art that alum is used as fixing agent in order to fix the polyelectrolyte and lignosulphonate polyelectrolyte complex on the fiber.

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, das 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, das 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 is a process for the production of paper, especially tissue, with particularly high wet and / or dry strengths known, in which one first adds to the paper a water-soluble cationic polymer which 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. As an advantage of this method is used In particular, the variability of the two-component systems described with regard to various paper properties, including wet and dry strength, highlighted.

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-Vinylcarbonsäureamiden, 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 obtained 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 available, can be used in papermaking as an additive to the paper stock to increase the rate of dewatering and retention and the dry and wet strength of the paper, see. EP-B 672 212 ,

Aus der älteren DE-Anmeldung 10 2004 056 551.1 ist ein 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 bekannt. Hierbei wird als polymere anionische Verbindung mindestens ein Copolymerisat eingesetzt, das erhältlich ist durch Copolymerisieren von

  1. (a) mindestens eines N-Vinylcarbonsäureamids der Formel
    Figure imgb0001
     in der R1, R2 = H oder C1- bis C6-Alkyl bedeuten,
  2. (b) mindestens eines Säuregruppen enthaltenden monoethylenisch ungesättigten Monomeren und/oder deren Alkalimetall-, Erdalkalimetall- oder Ammoniumsalzen und gegebenenfalls
  3. (c) anderen monoethylenisch ungesättigten Monomeren, und gegebenenfalls
  4. (d) Verbindungen, die mindestens zwei ethylenisch ungesättigte Doppelbindungen im Molekül aufweisen.
From the older one DE application 10 2004 056 551.1 discloses a process for producing high dry strength paper, board and paperboard by separately adding a vinylamine unit-containing polymer and a polymeric anionic compound to a stock, dewatering the stock and drying the paper products. In this case, the polymeric anionic compound used is at least one copolymer obtainable by copolymerizing
  1. (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,
  2. (B) at least one acid group-containing monoethylenically unsaturated monomer and / or their alkali metal, alkaline earth metal or ammonium salts and optionally
  3. (c) other monoethylenically unsaturated monomers, and optionally
  4. (d) compounds having at least two ethylenically unsaturated double bonds in the molecule.

Außerdem ist bekannt, Ligninsulfonsäure und Ligninsulfonate als Dispergiermittel in Zement- und Gipsmörteln, als Flotationsmittel, als Zusatz bei der Futtermittelpelettierung, als Formsandbindemittel und als Agglomerierungsmittel bei der Erzverhüttung einzusetzen, vgl. Römpp, 9. Auflage, Georg Thieme Verlag Stuttgart, 1990, Seite 2511 .It is also known to use lignosulfonic acid and lignosulfonates as dispersants in cement and gypsum mortars, as flotation agents, as an additive in feed paving, as molding sand binders and as agglomerating agents in ore smelting, cf. Römpp, 9th edition, Georg Thieme Verlag Stuttgart, 1990, page 2511 ,

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 gegenüber den bisher bekannten Verfahren die Trockenfestigkeit, insbesondere in Verpackungspapieren (z.B. Welle aus Altpapier, Fluting), weiter verbessert 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, the dry strength, in particular in packaging papers (for example, wave from waste paper, Fluting) should be further improved compared to the previously known methods.

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

  1. (i) Ligninsulfonsäure und/oder ein Ligninsulfonat und
  2. (ii) mindestens ein Copolymerisat einsetzt, das erhältlich ist durch Copolymerisieren von
    1. (a) mindestens eines N-Vinylcarbonsäureamids der Formel
      Figure imgb0002
       in der R1, R2 = H oder C1- bis C6-Alkyl bedeuten,
    2. (b) mindestens eines Säuregruppen enthaltenden monoethylenisch ungesättigten Monomeren und/oder deren Alkalimetall-, Erdalkalimetall- oder Ammoniumsalzen und gegebenenfalls
    3. (c) anderen monoethylenisch ungesättigten Monomeren, und gegebenenfalls
    4. (d) Verbindungen, die mindestens zwei ethylenisch ungesättigte Doppelbindungen im Molekül aufweisen
einsetzt.The object is achieved according to the invention by a process for producing paper, paperboard and cardboard with high dry strength by separate addition of a vinylamine units containing cationic polymers and a polymeric anionic compound to a pulp, dewatering of the pulp and drying of paper products, when used as a polymeric anionic compound
  1. (I) lignosulfonic acid and / or a lignosulfonate and
  2. (ii) at least one copolymer obtainable by copolymerizing
    1. (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,
    2. (B) at least one acid group-containing monoethylenically unsaturated monomer and / or their alkali metal, alkaline earth metal or ammonium salts and optionally
    3. (c) other monoethylenically unsaturated monomers, and optionally
    4. (d) compounds having at least two ethylenically unsaturated double bonds in the molecule
starts.

Bei dem erfindungsgemäßen Verfahren wird dem Papierstoff als polymere kationische Komponente ein Vinylamineinheiten enthaltendes Polymer zugesetzt. Diese Verbindungen werden vorzugsweise als alleinige kationische Komponente eingesetzt. Man kann sie jedoch gegebenenfalls bis zu einem Anteil von 50 Gew.-% durch andere kationische Polymere wie kationische Poly(meth)acrylamide, Polydiallyldimethylammoniumchloride, Kondensate aus Dimethylamin und Epichlorhydrin oder Polydialkyl(meth)acrylamide ersetzen.In the process according to the invention, a polymer comprising vinylamine units is added to the paper stock as the polymeric cationic component. These compounds are preferably used as the sole cationic component. However, they may optionally be substituted by up to 50% by weight of other cationic polymers such as cationic poly (meth) acrylamides, polydiallyldimethylammonium chlorides, condensates of dimethylamine and epichlorohydrin or polydialkyl (meth) acrylamides.

Als Vinylamineinheiten enthaltende kationische Polymere eignen sich sämtliche Polymere, 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.Suitable cationic polymers containing vinylamine units are all polymers which are cited, for example, in the prior art 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.

Vinylamineinheiten enthaltende kationische Polymere sind beispielsweise erhältlich durch Polymerisieren mindestens eines Monomeren der Formel

Figure imgb0003
in der R1, R2 = H oder C1- bis C6-Alkyl bedeuten,Cationic 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,

und anschließende teilweise oder vollständige Abspaltung der Gruppen -CO-R1 aus den in das Polymerisat einpolymerisierten Einheiten der Monomeren I unter Bildung von Aminogruppen. Bei der Herstellung dieser Polymeren können sich bekanntlich in einer sekundären Reaktion aus Vinylamineinheiten und benachbarten Vinylformamideinheiten Amidineinheiten bilden. 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 1 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 verwendet.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. In the preparation of these polymers, it is known that amidine units can be formed in a secondary reaction from vinylamine units and adjacent vinylformamide units. For the cationic polymers described herein, the indication of vinylamine units comprises the sum of vinylamine and amidine units in the polymer. For example, a polymer containing at least 1 mol% of N-vinylformamide homopolymer is used as the polymer containing vinylamine units. 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 einsetzen, die Vinylamineinheiten enthalten und die mindestens 10 Mol-% mehr kationische als anionische Gruppen aufweisen. Solche amphoteren Polymerisate sind beispielsweise erhältlich durch Copolymerisation

  1. (a) mindestens eines N-Vinylcarbonsäureamids der Formel
    Figure imgb0004
     in der R1, R2 = H oder C1- bis C6-Alkyl bedeuten,
  2. (b) mindestens eines Säuregruppen enthaltenden monoethylenisch ungesättigten Monomeren und/oder deren Alkalimetall-, Erdalkalimetall- oder Ammoniumsalzen und gegebenenfalls
  3. (c) anderen monoethylenisch ungesättigten Monomeren, und gegebenenfalls
  4. (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 method according to the invention can be used as a cationic component and amphoteric copolymers containing Vinylamineinheiten and at least 10 mol% more cationic than anionic groups. Such amphoteric polymers are obtainable, for example, by copolymerization
  1. (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,
  2. (B) at least one acid group-containing monoethylenically unsaturated monomer and / or their alkali metal, alkaline earth metal or ammonium salts and optionally
  3. (c) other monoethylenically unsaturated monomers, and optionally
  4. (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 Gruppe von Polymeren, die amphoter sind und die insgesamt mehr kationische als anionische Gruppen aufweisen, enthält beispielsweise bis maximal 35 Mol-%, vorzugsweise bis maximal 10 Mol-% mindestens eines Säuregruppen enthaltenden Monomers der Gruppe (b) einpolymerisiert.This group of polymers which are amphoteric and which have a total of more cationic than anionic groups contains, for example, up to a maximum of 35 mol%, preferably up to 10 mol%, of at least one acid group-containing monomer of group (b) in copolymerized form.

Als polymere anionische Verbindung kommt erfindungsgemäß Ligninsulfonsäure und/oder ein Ligninsulfonat in Betracht. Nähere Angaben zu diesen Produkten findet man beispielsweise in der obengenannten Literaturstelle Römpp, 9. Auflage, G. Thieme Verlag Stuttgart, 1990, Seite 2511 und in Ullmann's Encyclopedia of Industrial Chemistry, 5. Completely Revised Edition, Volume A15, Seiten 311 bis 314 . Ligninsulfonsäure entsteht bei der Celluloseherstellung durch Sulfitaufschluß von Holz, wobei Lignin mit schwefliger Säure reagiert. Es wird hierbei an den C3-Seitenketten der Phenylpropaneinheiten sulfoniert. In Abhängigkeit von den beim Aufschluß des Holzes eingesetzten Chemikalien entstehen dabei Ligninsulfonsäure oder Lingninsulfonate beispielsweise die Natrium-, Kalium-, Ammonium-, Magnesium- oder Calciumsalze der Ligninsulfonsäure. Ligninsulfonsäure sowie die genannten Salze der Ligninsulfonsäure sind in Wasser löslich. Die Molmasse der Ligninsulfonsäure beträgt beispielsweise 10 000 bis 200 000 g/mol. Ligninsulfonate werden z. B. aus den Sulfitablaugen (Schwarzlauge) der Celluloseherstellung gewonnen.As a polymeric anionic compound comes according to the invention lignosulfonic acid and / or a lignosulfonate into consideration. Further details of these products can be found for example in the above reference Römpp, 9th edition, G. Thieme Verlag Stuttgart, 1990, page 2511 and in Ullmann's Encyclopedia of Industrial Chemistry, 5th Completely Revised Edition, Volume A15, pages 311-314 , Lignosulfonic acid is formed in cellulose production by sulphite digestion of wood, whereby lignin reacts with sulphurous acid. It is sulfonated here on the C 3 side chains of the phenylpropane units. Depending on the chemicals used in the digestion of the wood, lignin sulphonic acid or lignin sulphonates are formed, for example, the sodium, potassium, ammonium, magnesium or calcium salts of lignosulphonic acid. Lignosulfonic acid and the salts of lignosulfonic acid mentioned are soluble in water. The molecular weight of the lignosulfonic acid is, for example 10,000 to 200,000 g / mol. Lignosulfonates are z. B. obtained from the sulfite waste liquors (black liquor) of cellulose production.

Bei dem erfindungsgemäßen Verfahren dosiert man z. B. zu einem Papierstoff nacheinander Ligninsulfonsäure und/oder mindestens ein Ligninsulfonat und danach mindestens ein Vinylamineinheiten enthaltendes Polymer. Man kann jedoch auch zunächst ein Vinylamineinheiten enthaltendes Polymer und anschließend Ligninsulfonsäure und/oder ein Ligninsulfonat zu einem Papierstoff geben und ihn dann unter Blattbildung entwässern. Wesentlich ist lediglich, dass man kationisches Polymer und die anionische Komponente getrennt voneinander dosiert. Ligninsulfonsäure und/oder Ligninsulfonat werden beispielsweise in einer Menge von 0,1 bis 10 Gew.-%, vorzugsweise 0,2 bis 5 Gew.-% und insbesondere 0,5 bis 2 Gew.-%, bezogen auf trockenen Papierstoff, eingesetzt.In the method according to the invention are metered z. B. to a pulp successively lignosulfonic acid and / or at least one lignosulfonate and then at least one vinylamine units containing polymer. However, it is also possible first to add a polymer containing vinylamine units and subsequently lignosulphonic acid and / or a lignosulphonate to a paper stock and then dewater it with sheet formation. All that is essential is that one doses cationic polymer and the anionic component separately. Lignosulfonic acid and / or lignin sulfonate are used, for example, in an amount of from 0.1 to 10% by weight, preferably from 0.2 to 5% by weight and in particular from 0.5 to 2% by weight, based on dry paper stock.

Als Ligninsulfonat werden beispielsweise die wasserlöslichen Natrium-, Kalium-, Ammonium-, Calcium-, Magnesiumsalze oder deren Mischungen eingesetzt. Vorzugsweise verwendet man die Natrium-, Ammonium- und Calciumsalze.As lignosulfonate, for example, the water-soluble sodium, potassium, ammonium, calcium, magnesium salts or mixtures thereof are used. Preferably, the sodium, ammonium and calcium salts are used.

Vinylamineinheiten enthaltendes Polymer und Ligninsulfonsäure und/oder Ligninsulfonat werden bei dem erfindungsgemäßen Verfahren beispielsweise im Gewichtsverhältnis 5 : 1 bis 1 : 5, vorzugsweise im Gewichtsverhältnis 2 : 1 bis 1 : 2 eingesetzt.Vinylamine units containing polymer and lignosulfonic acid and / or lignin sulfonate be used in the inventive method, for example in a weight ratio of 5: 1 to 1: 5, preferably in a weight ratio of 2: 1 to 1: 2.

Erfindungsgemäß setzt man Ligninsulfonsäure und/oder Ligninsulfonat zusammen mit einem anionischen Copolymerisat eines N-Vinylcarbonsäureamids ein. Die Dosierung dieser beiden Komponenten kann dabei getrennt oder auch als Mischung erfolgen. Vorzugsweise dosiert man jedoch zunächst Ligninsulfonat und anschließend das anionionische Polymer, man kann die Dosierreihenfolge dieser Verbindungen jedoch auch umkehren. So verwendet man erfindungsgemäß beispielsweise als polymere anionische Verbindung

  1. (i) Ligninsulfonsäure und/oder ein Ligninsulfonat und
  2. (ii) mindestens ein Copolymerisat, das erhältlich ist durch Copolymerisation von
    1. (a) mindestens eines N-Vinylcarbonsäureamids der Formel
      Figure imgb0005
       in der R1, R2 = H oder C1- bis C6-Alkyl bedeuten,
    2. (b) mindestens eines Säuregruppen enthaltenden monoethylenisch ungesättigten Monomeren und/oder deren Alkalimetall-, Erdalkalimetall- oder Ammoniumsalzen und gegebenenfalls
    3. (c) anderen monoethylenisch ungesättigten Monomeren, und gegebenenfalls
    4. (d) Verbindungen, die mindestens zwei ethylenisch ungesättigte Doppelbindungen im Molekül aufweisen.
According to the invention, lignin sulfonic acid and / or lignin sulfonate are used together with an anionic copolymer of an N-vinylcarboxamide. The dosage of these two components can be done separately or as a mixture. However, it is preferable first to meter lignosulfonate and then the anionic polymer, but it is also possible to reverse the dosing order of these compounds. For example, according to the invention, it is used as a polymeric anionic compound
  1. (I) lignosulfonic acid and / or a lignosulfonate and
  2. (ii) at least one copolymer obtainable by copolymerization of
    1. (a) at least one N-vinylcarboxamide of the formula
      Figure imgb0005
       in which R 1 , R 2 = H or C 1 - to C 6 -alkyl,
    2. (B) at least one acid group-containing monoethylenically unsaturated monomer and / or their alkali metal, alkaline earth metal or ammonium salts and optionally
    3. (c) other monoethylenically unsaturated monomers, and optionally
    4. (d) compounds having at least two ethylenically unsaturated double bonds in the molecule.

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

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

Die polymere anionische Verbindung (ii) enthält beispielsweise

  1. (a) 10 bis 95 Mol-% Einheiten der Formel I
  2. (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
  3. (c) 0 bis 30 Mol-% Einheiten mindestens eines anderen monoethylenisch ungesättigten Monomeren.
The polymeric anionic compound (ii) contains, for example
  1. (a) 10 to 95 mol% of the units of the formula I.
  2. (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
  3. (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 ethylenisch 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

  1. (a) 10 bis 95 Mol-% Einheiten der Formel I
  2. (b) 5 bis 90 Mol-% Einheiten eines Säuregruppen enthaltenden monoethylenisch ungesättigten Monomeren und/oder deren Alkalimetall-, Erdalkalimetall- oder Ammoniumsalzen,
  3. (c) 0 bis 30 Mol-% Einheiten mindestens eines anderen monoethylenisch ungesättigten Monomeren und
  4. (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 copolymerized form in the molecule. 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
  1. (a) 10 to 95 mol% of the units of the formula I.
  2. (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,
  3. (c) 0 to 30 mol% of units of at least one other monoethylenically unsaturated monomer and
  4. (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, Itaconsäure, Mesaconsäure, Citraconsäure, Methylenmalonsäure, Allylessigsäure, Vinylessigsäure und Crotonsäure. Als Monomere der Gruppe (b) eignen sich außerdem Sulfogruppen enthaltende Monomere wie Vinylsulfonsäure, Acrylamido-2-methylpropansulfonsäure 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, itaconic 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 also 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. Methylenbisacrylamid, 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. As methylenebisacrylamide, glycol diacrylate, glycol dimethacrylate, Gylcerintriacrylat, triallylamine, Pentaerythrittriallylether, at least twice with acrylic acid and / or methacrylic acid esterified polyalkylene glycols or polyols such as pentaerythritol, soba or glucose. If at least one monomer of group (d) is used in the copolymerization, the amounts used are up to 2 mol%, z. B. 0.001 to 1 mol%.

Die Copolymerisation der Monomeren erfolgt in bekannter Weise in Gegenwart von radikalischen Polymerisationsinitiatoren und gegebenenfalls in Gegenwart von Polymerisationsreglern, 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 is carried out 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 (ii) 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 Am moniumsalze und gegebenenfalls
  3. (c) 0 bis 30 Mol-% mindestens eines anderen monoethylenisch ungesättigten Monomeren einpolymerisiert enthält.
As the polymeric anionic compound (ii) 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 Polymeren (ii) 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 W of the anionic polymers (ii) 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.

Gegenstand der Erfindung ist außerdem die Verwendung von einer erfindungsgemäßen polymeren anionischen Verbindung als Zusatz zum Papierstoff bei der Herstellung von Papier, Pappe und Karton in Gegenwart mindestens eines Vinylamineinheiten enthaltenden kationischen Polymeren zur Erhöhung der Trockenfestigkeit.The invention further provides the use of a polymeric anionic compound according to the invention as an additive to the paper stock in the production of paper, paperboard and cardboard in the presence of at least one vinylamine units containing cationic polymers to increase the dry strength.

In einer bevorzugten Ausführungsform der Erfindung dosiert man zunächst Ligninsulfonsäure und/oder Linginsulfonat zum Papierstoff, fügt dann das Vinylamineinheiten enthaltende Polymer zu und entwässert anschließend den Papierstoff. Besonders bevorzugt ist eine Ausführungsform des erfindungsgemäßen Verfahrens, wobei man nach Zusatz von Ligninsulfonsäure und/oder Ligninsulfonat und mindestens eines Vinylamineinheiten enthaltenden Polymeren zum Papierstoff noch ein anionisches Vinylcarbonsäureamideinheiten enthaltendes Copolymerisat zusetzt, das erhältlich ist durch Copolymerisieren von

  1. (a) mindestens eines N-Vinylcarbonsäureamids der Formel
    Figure imgb0006
     in der R1, R2 = H oder C1- bis C6-Alkyl bedeuten,
  2. (b) mindestens eines Säuregruppen enthaltenden monoethylenisch ungesättigten Monomeren und/oder deren Alkalimetall-, Erdalkalimetall- oder Ammoniumsalzen und gegebenenfalls
  3. (c) anderen monoethylenisch ungesättigten Monomeren, und gegebenenfalls
  4. (d) Verbindungen, die mindestens zwei ethylenisch ungesättigte Doppelbindungen im Molekül aufweisen.
In a preferred embodiment of the invention, lignosulfonic acid and / or lingosulfonate are first metered into the paper stock, then the polymer containing vinylamine units is added and the paper stock is subsequently dehydrated. Particular preference is given to an embodiment of the process according to the invention wherein, after the addition of lignin sulfonic acid and / or lignin sulfonate and at least one polymer containing vinylamine units to the paper stock, an anionic vinylcarboxamide unit is still present containing copolymer obtained by copolymerizing
  1. (a) at least one N-vinylcarboxamide of the formula
    Figure imgb0006
     in which R 1 , R 2 = H or C 1 - to C 6 -alkyl,
  2. (B) at least one acid group-containing monoethylenically unsaturated monomer and / or their alkali metal, alkaline earth metal or ammonium salts and optionally
  3. (c) other monoethylenically unsaturated monomers, and optionally
  4. (d) compounds having at least two ethylenically unsaturated double bonds in the molecule.

Danach wird der Papierstoff entwässert.Thereafter, the pulp is dewatered.

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 oder einen Papierstoff aus Altpapier. Geeignete Einjahrespflanzen zur Herstellung von Papierstoffen sind beispielsweise Reis, Weizen, Zuckerrohr und Kenaf. Zur Herstellung der Pulpen wird meistens Altpapier verwendet, das entweder allein oder in Mischung mit anderen Faserstoffen eingesetzt wird oder man geht von Fasermischungen aus einem Primärstoff und zurückgeführtem gestrichenem Ausschuß aus, z. B. gebleichtes Kiefernsulfat in Mischung mit zurückgeführtem gestrichenem Ausschuß. Die Entwässerung des Papierstoffs erfolgt üblicherweise auf dem Sieb einer Papiermaschine. 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 fibrous materials for the production of pulps all conventional qualities come into consideration, for. B. wood 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. It is preferred to use unbleached pulp, also referred to as unbleached kraft pulp, or a waste paper pulp. Suitable annual plants for the production of pulps are, for example, rice, wheat, sugar cane and kenaf. To produce the pulps waste paper is usually used, which is used either alone or in admixture with other fibers or it is based on fiber blends of a primary material and recycled coated Committee, z. Bleached pine sulfate in admixture with recycled coated broke. The dewatering of the stock usually takes place on the wire of a paper machine. 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 beispielsweise 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. Auch die anionische Komponente wird vorzugsweise zum Dünnstoff dosiert.The vinylamine unit-containing polymer, i. the cationic component of the polymer to be metered to the paper stock is added in the inventive method, for example to the thick material or preferably to a thin material. The point of addition is preferably in front of the screens, but may also be between a shearing stage and a screen or afterwards. Also, the anionic component is preferably dosed to the thin.

In einer besonders bevorzugten Ausführungsform des erfindungsgemäßen Verfahrens dosiert man zunächst Ligninsulfonsäure bzw. Ligninsulfonat, danach als alleinige kationische Komponente ein Vinylamingruppen enthaltendes Polymer und anschließend ein anionisches Polymerisat von Vinylformamid. Man kann jedoch auch zuerst die kationische Komponente (Vinylamineinheiten enthaltendes Polymer als alleinige kationische Komponente) zum Papierstoff zugeben und die anionische Komponente gleichzeitig, jedoch getrennt von der kationischen Komponente zum Papierstoff dosieren. Das Vinylamineinheiten enthaltende Polymer wird beispielsweise in einer Menge von 0,05 bis 2,0 Gew.-%, vorzugsweise 0,1 bis 1 Gew.-%, bezogen auf trockenen Papierstoff, eingesetzt. Das Verhältnis von kationischer Komponente (Vinylamineinheiten enthaltendem Polymer) zu polymerer anionischer Komponente (Ligninsulfonsäure und/oder Ligninsulfonat bzw. Kombination von Ligninsulfonsäure und/oder Ligninsulfonat mit mindestens einem anionischen Polymerisat von Vinylformamid) beträgt beispielsweise 5 : 1 bis 1 : 5 und liegt vorzugsweise in dem Bereich von 2 : 1 bis 1 : 2.In a particularly preferred embodiment of the process according to the invention, first lignosulfonic acid or lignin sulfonate is metered in, thereafter as the sole cationic component a polymer containing vinylamine groups and subsequently an anionic polymer of vinylformamide. However, it is also possible first to add the cationic component (vinylamine units-containing polymer as the sole cationic component) to the paper stock and to meter the anionic component simultaneously but separately from the cationic component to the paper stock. The vinylamine units-containing polymer is used, for example, in an amount of 0.05 to 2.0 wt .-%, preferably 0.1 to 1 wt .-%, based on dry pulp. The ratio of cationic component (polymer containing vinylamine units) to polymeric anionic component (ligninsulfonic acid and / or ligninsulfonate or combination of ligninsulfonic acid and / or ligninsulfonate with at least one anionic polymer of vinylformamide) is for example 5: 1 to 1: 5 and is preferably in 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. Diese Papiere weisen, verglichen mit bekannten Papierprodukten, insbesondere einen hohen CMT-Wert auf.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. In particular, these papers have a high CMT value compared with known paper products.

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 H. 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 after H. Fikentscher, Cellulose Chemistry, 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 Nassreißlänge wurde gemäss DIN 53 112, Blatt 2 bestimmt. Die Ermittlung des CMT-Wertes erfolgte nach DIN 53 143, der Streifenstauchwiderstand (SCT-Wert) wurde nach DIN 54518 und der Trockenberstdruck nach DIN 53 141 gemessen.For the individual tests, sheets were produced in laboratory tests in a Rapid-Köthen laboratory sheet former. The wet tear length was determined according to DIN 53 112, sheet 2. The determination of the CMT value was carried out according to DIN 53 143, the strip crush resistance (SCT value) was measured according to DIN 54518 and the dry burst pressure according to DIN 53 141.

BeispieleExamples

Aus 100% gemischtem Altpapier wurde zunächst eine 4%ige wässrige Stoffsuspension hergestellt, die dann auf eine Stoffdichte von 0,4% verdünnt wurde. Der pH-Wert der Suspension betrug 7,1, der Mahlgrad des Stoffs 40° Schopper-Riegler (°SR). Die Stoffsuspension enthielt 0,27% eines handelsüblichen Entschäumers (Afranil® SLO). Sie wurde dann in 9 gleiche Teile geteilt und gemäß Vergleichsbeispiel 1 bzw. gemäß den Beispielen 1 bis 8 in Gegenwart der in Tabelle 1 angegebenen Polymeren auf einem Rapid-Köthen-Blattbildner zu Blättern einer Flächenmasse von 120 bis 130 g/m2 verarbeitet. Um die Ergebnisse miteinander vergleichen zu können, wurden die einzelnen Messwerte auf Blätter eines Flächengewichts von 120 g/m2 umgerechnet. Die so erhaltenen Ergebnisse sind in Tabelle 1 angegeben.From 100% mixed waste paper, first a 4% aqueous pulp suspension was prepared, which was then diluted to a consistency of 0.4%. The pH of the suspension was 7.1, the freeness of the substance 40 ° Schopper-Riegler (° SR). The stock suspension contained 0.27% of a commercially available defoamer (Afranil® SLO). It was then divided into 9 equal parts and processed according to Comparative Example 1 or according to Examples 1 to 8 in the presence of the polymers indicated in Table 1 on a Rapid-Köthen sheet former to sheets having a basis weight of 120 to 130 g / m 2 . In order to be able to compare the results with each other, the individual measured values were converted to sheets of a basis weight of 120 g / m 2 . The results thus obtained are shown in Table 1.

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.

Beispiele 1 bis 8Examples 1 to 8

Folgende Polymere wurden verwendet:

  • Als Ligninsulfonat wurde eine handelsübliche 54,69 %ige wässrige Lösung des Calciumsalzes von Ligninsulfonsäure eingesetzt.
  • PVAm 1: Als kationisches Polymer wurde ein zu 50% hydrolysiertes Homopolymerisat von N-Vinylformamid in Form einer 13 %igen wässrigen Lösung eingesetzt. Das Polymer hatte eine Molmasse Mw von 400 000.
  • Anionisches Polymer 1: Copolymerisat aus 70 % N-Vinylformamid und 30% Natriumacrylat einer Molmasse Mw von 400 000.
The following polymers were used:
  • The lignosulfonate used was a commercially available 54.69% strength aqueous solution of the calcium salt of lignosulfonic acid.
  • PVAm 1: The cationic polymer used was a 50% hydrolysed homopolymer of N-vinylformamide in the form of a 13% strength aqueous solution. The polymer had a molecular weight M w of 400,000.
  • Anionic polymer 1: copolymer of 70% N-vinylformamide and 30% sodium acrylate of molecular weight M w of 400,000.

In den Beispielen 1 bis 8 dosierte man in jeweils eine Probe des oben beschriebenen Papierstoffs zunächst die in Tabelle 1 jeweils angegebenen Mengen an Ligninsulfonat, durchmischte die Probe, gab dann nach einer Verweilzeit von 20 Sekunden das kationische Polymer (PVAm 1) zu, durchmischte die Probe wiederum, fügte nach einer Verweilzeit von 20 Sekunden das anionische Polymer 1 zu, durchmischte den so erhaltenen Papierstoff und entwässerte ihn anschließend auf einem Rapid-Köthen-Blattbildner. Die auf Blätter mit einem Flächengewicht von 120 g/m2 umgerechneten Werte für den Trockenberstdruck, den SCT-Wert und den CMT-Wert sind in Tabelle 1 angegeben. Tabelle 1 Vergleichsbsp. 1 Beispiel 1 2 3 4 5 6 7 8 Ligninsulfonat [%] - 0,5 1,0 1,5 1,0 2,0 3,0 0,5 1,0 PVAm 1 [%] - 0,5 0,5 0,5 1,0 1,0 1,0 0,5 0,5 Anionisches Polymer [%] - - - - - - - 0,5 0,5 Trockenberstdruck [kPa] 318,0 358,8 357,6 357,8 394,2 376,8 388,5 417,7 415,6 Steigerung [%] 0 13 12 13 24 18 22 31 31 SCT-Wert [kN/m] 1,88 2,09 2,11 2,09 2,22 2,36 2,21 2,48 2,42 Steigerung [%] 0 11 12 11 18 26 17 32 29 CMT-Wert [N] 116,5 156,83 158,6 150,24 166,8 171,6 175,2 170,3 182,2 Steigerung [%] 0 35 36 29 43 47 50 46 56 In Examples 1 to 8, in each case one sample of the above-described paper stock was first metered into the quantities of lignosulfonate indicated in Table 1, the sample was mixed, then the cationic polymer (PVAm 1) was added after a residence time of 20 seconds and the mixture was mixed In turn, after a 20 second residence time, the anionic polymer 1 was added, the mixed stock was mixed, and then dewatered on a Rapid-Kothen sheet former. The values for the dry burst pressure, the SCT value and the CMT value converted to sheets having a basis weight of 120 g / m 2 are given in Table 1. Table 1 Comp. 1 example 1 2 3 4 5 6 7 8th Lignosulfonate [%] - 0.5 1.0 1.5 1.0 2.0 3.0 0.5 1.0 PVAm 1 [%] - 0.5 0.5 0.5 1.0 1.0 1.0 0.5 0.5 Anionic polymer [%] - - - - - - - 0.5 0.5 Dry burst pressure [kPa] 318.0 358.8 357.6 357.8 394.2 376.8 388.5 417.7 415.6 Increase [%] 0 13 12 13 24 18 22 31 31 SCT value [kN / m] 1.88 2.09 2.11 2.09 2.22 2.36 2.21 2.48 2.42 Increase [%] 0 11 12 11 18 26 17 32 29 CMT value [N] 116.5 156.83 158.6 150.24 166.8 171.6 175.2 170.3 182.2 Increase [%] 0 35 36 29 43 47 50 46 56

Claims (13)

  1. A process for the production of paper, board and cardboard having high dry strength by separate addition of a cationic polymer comprising vinylamine units and of a polymeric anionic compound to a paper stock, draining of the paper stock and drying of the paper products, wherein
    (i) ligninsulfonic acid and/or a ligninsulfonate and
    (ii)at least one copolymer which is obtainable by copolymerization of
    (a) at least one N-vinylcarboxamide of the formula
    Figure imgb0011
     where R1, R2 is 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 which have at least two ethylenically unsaturated double bonds in the molecule
    are used as the polymeric anionic compound.
  2. The process according to claim 1, wherein at least one compound which is obtainable by polymerization of at least one monomer of the formula
    Figure imgb0012
     where R1, R2 are H or C1- to C6-alkyl,
    and subsequent partial or complete elimination of the -CO-R1 groups from those units of the monomers I which are incorporated as polymerized units in the polymer with formation of amino groups is used as the cationic polymer comprising vinylamine units.
  3. The process according to claim 1 or 2, wherein an N-vinylformamide homopolymer having a degree of hydrolysis of at least 1 mol% is used as the cationic polymer comprising vinylamine units.
  4. The process according to any of claims 1 to 3, wherein a copolymer which is obtainable by copolymerization of
    (a) at least one N-vinylcarboxamide of the formula
    Figure imgb0013
     where R1, 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 which have at least two ethylenically unsaturated double bonds in the molecule
    and subsequent partial or complete elimination of the -CO-R1
    groups from those units of the monomers I which are incorporated in the polymer in the form of polymerized units with formation of amino groups, the proportion of the amino groups in the copolymer being at least 10 mol% greater than the proportion of the units of monoethylenically unsaturated monomers comprising acid groups, is used as the cationic polymer comprising vinylamine units.
  5. The process according to any of claims 1 to 4, wherein polyvinylamine and/or an N-vinylformamide homopolymer having a degree of hydrolysis of at least 50 mol% is used as the cationic polymer comprising vinylamine units.
  6. The process according to any of claims 1 to 5, wherein the water-soluble sodium, potassium, ammonium, calcium or magnesium salts or mixtures thereof are used as the ligninsulfonate.
  7. The process according to any of claims 1 to 6, wherein the cationic polymer comprising vinylamine units is used in an amount of from 0.05 to 2.0% by weight, based on dry paper stock.
  8. The process according to any of claims 1 to 7, wherein the cationic polymer comprising vinylamine units and ligninsulfonic acid and/or ligninsulfonate are used in the weight ratio of from 5:1 to 1:5.
  9. The process according to any of claims 1 to 8, wherein the cationic polymer comprising vinylamine units and ligninsulfonic acid and/or ligninsulfonate are used in the weight ratio of from 2:1 to 1:2.
  10. The process according to any of claims 1 to 9, wherein first ligninsulfonic acid and/or ligninsulfonate is metered into the paper stock, then the cationic polymer comprising vinylamine units is added and then the paper stock is drained.
  11. The process according to any of claims 1 to 9, wherein first the cationic polymer comprising vinylamine units is metered into the paper stock, then ligninsulfonic acid and/or ligninsulfonate is added and then the paper stock is drained.
  12. The process according to claim 10, wherein, after addition of ligninsulfonic acid and/or ligninsulfonate and at least one cationic polymer comprising vinylamine units to the paper stock, an anionic co-polymer comprising vinyl carboxamide units, which is obtainable by copolymerization of
    (a) at least one N-vinylcarboxamide of the formula
    Figure imgb0014
     where R1, 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 which have at least two ethylenically unsaturated double bonds in the molecule
    is also added.
  13. The use of a polymeric anionic compound according to claim 1 as an additive to the paper stock in the production of paper, board and cardboard in the presence of at least one cationic polymer comprising vinylamine units for increasing the dry strength.
EP07712497.2A 2006-03-16 2007-03-09 Method for producing paper, paperboard and cardboard having high dry strength Not-in-force EP1999314B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP07712497.2A EP1999314B1 (en) 2006-03-16 2007-03-09 Method for producing paper, paperboard and cardboard having high dry strength

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP06111267 2006-03-16
PCT/EP2007/052238 WO2007104716A1 (en) 2006-03-16 2007-03-09 Method for producing paper, paperboard and cardboard having high dry strength
EP07712497.2A EP1999314B1 (en) 2006-03-16 2007-03-09 Method for producing paper, paperboard and cardboard having high dry strength

Publications (2)

Publication Number Publication Date
EP1999314A1 EP1999314A1 (en) 2008-12-10
EP1999314B1 true EP1999314B1 (en) 2017-02-22

Family

ID=38325364

Family Applications (1)

Application Number Title Priority Date Filing Date
EP07712497.2A Not-in-force EP1999314B1 (en) 2006-03-16 2007-03-09 Method for producing paper, paperboard and cardboard having high dry strength

Country Status (8)

Country Link
US (1) US7922867B2 (en)
EP (1) EP1999314B1 (en)
JP (1) JP5156650B2 (en)
CN (1) CN101405457B (en)
CA (1) CA2644348C (en)
ES (1) ES2625622T3 (en)
PT (1) PT1999314T (en)
WO (1) WO2007104716A1 (en)

Families Citing this family (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102004056551A1 (en) * 2004-11-23 2006-05-24 Basf Ag Process for the production of paper, cardboard and cardboard with high dry strength
EP2288750B1 (en) * 2008-05-15 2012-09-05 Basf Se Method for producing paper, paperboard and cardboard with a high dry strength
WO2010145956A1 (en) * 2009-06-16 2010-12-23 Basf Se Method for increasing the dry strength of paper, paperboard, and cardboard
JP5571014B2 (en) * 2011-02-21 2014-08-13 Ｋｊ特殊紙株式会社 Electromagnetic wave suppression sheet
TWI511999B (en) * 2011-07-11 2015-12-11 Ind Tech Res Inst Electronic element, conductive polymer composition, and method for fabricating the same
EP2748373B1 (en) 2011-08-25 2024-02-21 Solenis Technologies Cayman, L.P. Method for increasing the advantages of strength aids in the production of paper and paperboard
US9816233B2 (en) 2012-09-28 2017-11-14 Kimberly-Clark Worldwide, Inc. Hybrid fiber compositions and uses in containerboard packaging
US9908680B2 (en) 2012-09-28 2018-03-06 Kimberly-Clark Worldwide, Inc. Tree-free fiber compositions and uses in containerboard packaging
US9562326B2 (en) * 2013-03-14 2017-02-07 Kemira Oyj Compositions and methods of making paper products
CN104452455B (en) 2013-09-12 2019-04-05 艺康美国股份有限公司 The method that paper making auxiliary agent composition and increase are stayed at paper ash code insurance
CN104452463B (en) 2013-09-12 2017-01-04 艺康美国股份有限公司 Papermaking process and compositions
EP3122937B1 (en) * 2014-03-28 2019-01-02 Basf Se Method for producing corrugated cardboard
CN106930142B (en) * 2015-12-31 2020-03-24 艺康美国股份有限公司 Dry strength agent composition and method for improving dry strength of paper
JP6999162B2 (en) * 2017-12-22 2022-02-10 国立研究開発法人産業技術総合研究所 Ion composite material containing lignin sulfonic acid and cationic polymer
US11846074B2 (en) 2019-05-03 2023-12-19 First Quality Tissue, Llc Absorbent structures with high strength and low MD stretch
WO2023031667A1 (en) * 2021-08-30 2023-03-09 Ecolab Usa Inc. Use of modified lignin as a wet end strength additive

Family Cites Families (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2721140A (en) * 1952-09-19 1955-10-18 Hercules Powder Co Ltd Paper of high wet strength and process therefor
US3448005A (en) * 1965-01-04 1969-06-03 Weyerhaeuser Co Process of forming wet strength paper containing a cationic resin and fumarated unsaturated oil
SE443818B (en) 1978-04-24 1986-03-10 Mitsubishi Chem Ind PROCEDURE FOR MAKING PAPER WITH IMPROVED DRY STRENGTH
JPS57191394A (en) * 1981-05-19 1982-11-25 Rei Tech Inc Papermaking method using lignin like substance and cationic polymer
DE3506832A1 (en) * 1985-02-27 1986-08-28 Basf Ag, 6700 Ludwigshafen METHOD FOR PRODUCING PAPER WITH HIGH DRY RESISTANCE
DE3534273A1 (en) * 1985-09-26 1987-04-02 Basf Ag METHOD FOR PRODUCING VINYLAMINE UNITS CONTAINING WATER-SOLUBLE COPOLYMERISATS AND THE USE THEREOF AS WET AND DRY-FASTENING AGENTS FOR PAPER
JPH01183598A (en) * 1988-01-18 1989-07-21 Showa Denko Kk Production of paper and paperboard
KR0159921B1 (en) * 1988-10-03 1999-01-15 마이클 비. 키한 A composition comprising cathionic and anionic polymer process thereof
DE4001808A1 (en) 1990-01-23 1991-07-25 Basf Ag Water sol co-polymer for water treatment - from unsatd. carboxylic acid and vinyl:amide deriv.
US5630907A (en) * 1992-12-07 1997-05-20 Basf Aktiengesellschaft Use of hydrolyzed copolymers of N-vinylcarboxamides and monoethylenically unsaturated carboxylic acids in papermaking
DE4241117A1 (en) * 1992-12-07 1994-06-09 Basf Ag Use of hydrolyzed copolymers of N-vinylcarboxamides and monoethylenically unsaturated carboxylic acids in papermaking
JPH06184983A (en) * 1992-12-21 1994-07-05 Sumitomo Chem Co Ltd Production of paper and paperboard
US6228217B1 (en) 1995-01-13 2001-05-08 Hercules Incorporated Strength of paper made from pulp containing surface active, carboxyl compounds
DE19530788C1 (en) * 1995-08-22 1996-08-01 Leica Ag Measurement rod for geodetic measurements with bar coded measurement scale
DE19537088A1 (en) * 1995-10-05 1997-04-10 Basf Ag Process for the production of dry and wet strength paper
US6315824B1 (en) * 1996-02-02 2001-11-13 Rodrigue V. Lauzon Coacervate stabilizer system
JP3151427B2 (en) * 1997-11-06 2001-04-03 株式会社トキワ Method for manufacturing corrugated cardboard
US6824650B2 (en) 2001-12-18 2004-11-30 Kimberly-Clark Worldwide, Inc. Fibrous materials treated with a polyvinylamine polymer
US20040118540A1 (en) 2002-12-20 2004-06-24 Kimberly-Clark Worlwide, Inc. Bicomponent strengtheninig system for paper
DE102004056551A1 (en) 2004-11-23 2006-05-24 Basf Ag Process for the production of paper, cardboard and cardboard with high dry strength

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
None *

Also Published As

Publication number Publication date
US7922867B2 (en) 2011-04-12
WO2007104716A1 (en) 2007-09-20
EP1999314A1 (en) 2008-12-10
PT1999314T (en) 2017-05-26
CA2644348A1 (en) 2007-09-20
CA2644348C (en) 2014-06-10
CN101405457B (en) 2011-08-17
JP5156650B2 (en) 2013-03-06
US20100108279A1 (en) 2010-05-06
CN101405457A (en) 2009-04-08
ES2625622T3 (en) 2017-07-20
JP2009530504A (en) 2009-08-27

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