EP0777692B1 - Paper-sizing agents containing aqueous, solvent-free dispersions of cationic polymers and method of preparing sized paper by using these agents - Google Patents

Paper-sizing agents containing aqueous, solvent-free dispersions of cationic polymers and method of preparing sized paper by using these agents Download PDF

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Publication number
EP0777692B1
EP0777692B1 EP95929873A EP95929873A EP0777692B1 EP 0777692 B1 EP0777692 B1 EP 0777692B1 EP 95929873 A EP95929873 A EP 95929873A EP 95929873 A EP95929873 A EP 95929873A EP 0777692 B1 EP0777692 B1 EP 0777692B1
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Prior art keywords
paper
copolymerizate
mole
sizing agents
meth
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EP95929873A
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German (de)
French (fr)
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EP0777692A1 (en
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Kurt Dahmen
Richard Mertens
Thomas Müller
Johann Schulte
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Stockhausen GmbH and Co KG
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Stockhausen GmbH and Co KG
Chemische Fabrik Stockhausen GmbH
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    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • 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
    • D21H21/16—Sizing or water-repelling 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

Definitions

  • the invention relates to compositions for the mass and / or surface sizing of paper, which contain aqueous, solvent-free dispersions of cationic polymers and a method for sizing paper using these agents.
  • Sizing is used in the manufacture of ink-resistant papers and printing papers of the papers on the surface or in bulk in order to improve the wettability of the cellulose and the absorption of water or aqueous liquids through the capillary system of the Reduce paper sheet and the inclusion of printing inks, the white and to improve the opacity and the mechanical properties of the paper sheet.
  • sizing process and the means usually used here in Ullmann's Encyclopedia, Volume 17 (1979) on pages 585 - 587 and on p. 599 described.
  • cationic polymers in the sizing process, which is characterized by It is known to have a high substantivity towards the cellulose fibers.
  • the Japanese Patent JP-A-04 108 196 describes cationic sizing agents based on of rosin and cationic polymers.
  • Japanese publication JP-A-04 091 290, JP-A-63 270 893 and JP-A-59 159 198 describe sizing agents made from alkyl ketene dimers and cationic polymers are formed.
  • DE 37 37 615 C2 sizing agents which are modified with carboxylic acids, represent so-called reinforced resins, which are caused by portions of cationic copolymers be dispersed.
  • the cationic copolymers are Solution polymerization shown and the preparation of the dispersed sizing agent happens from the anionically modified resins and the cationic copolymers in a complex procedure with removal of the solvent by distillation the copolymer, melting of the modified resin and dispersion in Water with the partial use of surfactants.
  • the Resin parts not bound in the paper pulp must contain the process water and, if necessary be removed using other tools.
  • DE 38 26 825 C2 describes cationic sizing agents which are derived from Methyl (meth) acrylate, butyl (meth) acrylate, acrylic acid and 10-30% by weight of N, N dimethylaminoethyl (meth) acrylate are formed and isopropanol or other organic Contain solvents.
  • the sizing agents described are unstable when stored and not sufficiently effective when used.
  • EP 416 427 B1 describes sizing agents based on aqueous, cationic polymer dispersions described, the polymer content from 2-20% by weight of a salt-forming, water-soluble monomer with alkylammonium, alkylsulfonium or alkylphosphonium groups are formed, which, however, always with cationic Polymers such as retention aids and protective colloids (poly-DADMAC) are used, so that these polymers are used in total in a relatively large amount will.
  • the dispersions described also contain emulsifiers and especially non-ionic surfactants, which in addition to the water-soluble retention aids Paper can impair the sizing effect and can pollute the process water.
  • the object of the invention was therefore to include the known cationic sizing agents To avoid avoiding their disadvantages, in particular to provide sizing agents, which can be manufactured more economically and environmentally friendly, are stable in storage and can be used alone as sizing agents without the use of further components and also have an improved effect.
  • the monomers of group a) are in an amount of 30-70 mol% in the copolymer available. If these limits are undershot, unstable dispersions are usually obtained, while a proportion of more than 70 mol% significantly worsens the sizing effect. A proportion of 40-60 mol% of these monomers is preferably used in the copolymer.
  • the monomers of group b) are hydrophobic esters or amides of acrylic acid and / or methacrylic acid. They essentially ensure the sizing effect. Suitable monomers are, for example, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, isononyl (meth) acrylate, decyl (meth) acrylate, lauryl (meth) acrylate, isotridecyl (meth) acrylate, myristyl (meth) acrylate , Stearyl (meth) acrylate, C 18-22 (meth) acrylate, 2-ethylhexyl (meth) acrylamide, n-octyl (meth) acrylamide, isononyl (meth) acrylamide, decyl (meth) acrylamide, lauryl (meth) acrylamide, Isotridecyl (meth) acrylamide
  • Some of the monomers of group b) can be replaced by long-chain monoolefins. Suitable for this purpose are, for example, octene-1, decene-1, dodecene-1, tetradecene-1, hexadecene-1, octadecen-1, eicosen-1 and C 20-24 or C 30+ alpha-olefin sections. These monomers are also commercially available. They can be used in an amount of 0.001 to 1: 1 in relation to the monomer group b). Octadecene-1 and C 20-24 -alpha-olefin mixtures are preferably used.
  • beta unsaturated monomers are present.
  • Styrenes are suitable, for example, Vinyl esters, vinyl ethers, (meth) acrylic acid and / or (meth) acrylamide.
  • the sizing agents preferably used according to the invention contain copolymers, those with the rejection of organic solvents by bulk polymerization in on be made in a known manner.
  • the polymerization is carried out at temperatures of 20 to 200 ° C., preferably 60 to 160 ° C. carried out. It is initiated thermally, photochemically or redox-catalytically, preferably with the help of peroxo and / or azo compounds.
  • oil-soluble initiators such as, for example 2,2'-azobis (isobutyronitrile) (AIBN), 2,2'-azobis (2-methylbutyronitrile), 4,4'-azo (4-cyanopentanoic acid), 2,2'-azobis (2,4-dimethylvaleronitrile), di-tert-butyl peroxide, Dibenzoyl peroxide or tert-butyl peroxy-2-ethylhexanoate is preferred.
  • AIBN 2,2'-azobis (isobutyronitrile)
  • 2,2'-azobis (2-methylbutyronitrile) 2,2'-azobis (2-methylbutyronitrile)
  • 4,4'-azo (4-cyanopentanoic acid 4,4'-azo (4-cyanopentanoic acid
  • 2,2'-azobis (2,4-dimethylvaleronitrile di-tert-butyl peroxide
  • the number average molecular weight of the copolymers is 1000 to 100,000 g / mol.
  • the molar mass is preferably regulated by using known regulators such as, for example Mercaptoethanol or dodecyl mercaptan.
  • part or all of the amount of Monomers submitted at a suitable temperature, the initiator in whole or in part added to the polymerization mixture and the further reaction under adiabatic Conditions made, the resulting heat of polymerization Reaction batch warmed.
  • the copolymer is neutralized directly with dilute acid and emulsified in water.
  • the amount of acid is chosen so that in End product sets a pH of 8 to 3.
  • Both are inorganic for neutralization Acids such as hydrochloric acid or sulfuric acid, as well as organic acids in particular Carboxylic acids such as formic acid or acetic acid are suitable.
  • the initiator can be added again after neutralization or emulsification to reduce the residual monomer content.
  • oil-soluble and water-soluble initiator systems are then suitable.
  • copolymers are used whose Amino groups partially or completely with a suitable quaternizing agent be implemented.
  • suitable quaternizing agents are methyl chloride, Benzyl chloride, dimethyl sulfate and / or epichlorohydrin.
  • the amount of quaternizing agent is chosen so that a degree of quaternization of 1-100 mol% is preferred 5 to 50 mol%.
  • the reaction takes place in a molar ratio of amino group to Quaternizing agent from 100: 1 to 1: 1, or in one Molar ratio of amino group to epichlorohydrin of 50: 1 to 1: 1.
  • the solids content of the polymer dispersions to be used according to the invention is 10-60% by weight, preferably 20-50% by weight, particularly preferably 30-40 % By weight.
  • copolymer dispersions to be used according to the invention are surprisingly distinguished despite their production without any additional aids, due to good dispersion stability so that even after several weeks of storage at 50 ° C none Separation or coagulation of the polymer can be observed.
  • hydrophobizing sizing of papers especially writing and Suitable for printing papers.
  • they can be used for both mass gluing and Surface sizing agents are used.
  • the invention further relates to a method for paper sizing using the inventive Medium, both for mass and surface sizing.
  • the polymer dispersions are added to the thick or thin material with 0.1 - 3.0% active substance (based on dry substance), while with surface sizing 0.1 - 5.0 g active substance per m 2 onto the paper after Drying section is applied.
  • the polymer dispersions can be used to achieve an immediate sizing, ie the desired hydrophobization of the paper is achieved immediately after the manufacturing process.
  • the disadvantageous process of aging the freshly sized papers which is often necessary when using the sizes currently used to achieve hydrophobic effects and the associated paper properties, can therefore largely be dispensed with.
  • the amount of cationic polymer dispersions used can be outstanding Way to set a graded degree of sizing of the papers, which both acidic as well as reproducible in neutral or alkaline paper production is. Further aids are advantageously not required for the sizing.
  • Solvents and optionally regulators are in the same reactor as in regulation A. submitted and gassed with nitrogen. The mixture is then heated to the intended polymerization temperature and then leaves the from different inlets at the same time Monomers and the initiator (optionally diluted with further solvent) run over the intended response time. After the feed has ended, 2 React for hours. The polymer is then as in Preparation A neutralized and emulsified with dilute acid. The solvent becomes the solvent largely distilled off.
  • paper sheets with a basis weight of approx. 100 g / m 2 were produced in a Rapid-Koethen sheet former.
  • Short fiber pulp (birch sulfate) or waste paper (newspaper printing) or wood pulp were used as raw materials.
  • the sizing agent to be tested was added to the substance / water mixture and 15 Seconds mixed.
  • the sheet was then formed in the sheet former and in a vacuum dryer of the Rapid-Köthen device dried at 92 ° C for 10 minutes.
  • Table 1 shows that very good instant sizing can be achieved with the copolymers to be used according to the invention.
  • the comparative example shows no immediate sizing and, even after 24 hours, gives significantly worse values than the examples according to the invention.
  • Table 2 shows that when the copolymers are used according to the invention, an advantage over known solvents can also be found at lower use concentrations.

Abstract

PCT No. PCT/EP95/03232 Sec. 371 Date Feb. 25, 1997 Sec. 102(e) Date Feb. 25, 1997 PCT Filed Aug. 16, 1995 PCT Pub. No. WO96/06119 PCT Pub. Date Feb. 29, 1996The present invention relates to agents for the pulp and/or surface sizing of paper, which comprise aqueous, solventless dispersions of cationic polymers, and to a process for sizing paper by using said agent. The sizing agents according to the present invention which can be used both in pulp and surface sizing obtain as active substance copolymers of a) 30-70 mole-% of a monomer I with b) 70-30 mole-% of a monomer II, and optionally c) 0-20 mole-% of C8-C30 monoolefins, and d) 0-10 mole-% of further monomers copolymerizable with a), b), and optionally c), the sum of monomers a), b), c), and d) amounting to 100 mole-%.

Description

Die Erfindung betrifft Mittel für die Masse- und /oder Oberflächenleimung von Papier, die wäßrige, lösungsmittelfreie Dispersionen von kationischen Polymerisaten enthalten sowie ein Verfahren zur Leimung von Papier unter Verwendung dieser Mittel.The invention relates to compositions for the mass and / or surface sizing of paper, which contain aqueous, solvent-free dispersions of cationic polymers and a method for sizing paper using these agents.

Bei der Herstellung von tintenfesten Papieren und Druckpapieren erfolgt eine Leimung der Papiere an der Oberfläche oder in der Masse, um die Benetzbarkeit der Cellulose und die Aufnahme von Wasser oder wäßrigen Flüssigkeiten durch das Kapillarsystem des Papierblattes zu vermindern sowie um die Aufnahme von Druckfarben, die Weiße und die Opazität sowie die mechanischen Eigenschaften des Papierblattes zu verbessern. Der schon bekannte Leimungsprozeß und die hierbei üblicherweise verwendeten Mittel sind in Ullmanns Enzyklopädie, Band 17 (1979) auf den Seiten 585 - 587 sowie auf S. 599 beschrieben.Sizing is used in the manufacture of ink-resistant papers and printing papers of the papers on the surface or in bulk in order to improve the wettability of the cellulose and the absorption of water or aqueous liquids through the capillary system of the Reduce paper sheet and the inclusion of printing inks, the white and to improve the opacity and the mechanical properties of the paper sheet. Of the already known sizing process and the means usually used here in Ullmann's Encyclopedia, Volume 17 (1979) on pages 585 - 587 and on p. 599 described.

Auch die Verwendung kationischer Polymerisate beim Leimungsprozeß, die sich durch eine große Substantivität gegenüber den Cellulosefasern auszeichnen, ist bekannt. Die japanische Patentschrift JP-A-04 108 196 beschreibt kationische Leimungsmittel auf der Basis von Kollophonium und kationischen Polymerisaten. Die japanischen Schriften JP-A-04 091 290, JP-A-63 270 893 und JP-A-59 159 198 beschreiben Leimungsmittel die aus Alkylketen-Dimeren und kationischen Polymerisaten gebildet werden.The use of cationic polymers in the sizing process, which is characterized by It is known to have a high substantivity towards the cellulose fibers. The Japanese Patent JP-A-04 108 196 describes cationic sizing agents based on of rosin and cationic polymers. Japanese publication JP-A-04 091 290, JP-A-63 270 893 and JP-A-59 159 198 describe sizing agents made from alkyl ketene dimers and cationic polymers are formed.

Aus der DE 37 37 615 C2 sind Leimungsmittel bekannt, die mit Carbonsäuren modifizierte, sogenannte verstärkte Harze darstellen, die durch Anteile von kationischen Copolymerisaten dispergiert werden. Hierbei werden die kationischen Copolymerisate durch Lösungspolymerisation dargestellt und die Herstellung des dispergierten Leimungsmittels aus den anionisch modifizierten Harzen und den kationischen Copolymerisaten geschieht in aufwendiger Verfahrensweise unter destillativer Abtrennung des Lösungsmittels aus dem Copolymerisat, Aufschmelzen des modifizierten Harzes sowie Dispergierung in Wasser unter teilweiser Verwendung von Tensiden. Bei der Anwendung belasten die nicht in der Papiermasse gebundenen Harzanteile das Prozeßwasser und müssen gegebenenfalls unter Einsatz weiterer Hilfsmittel entfernt werden. DE 37 37 615 C2 sizing agents are known which are modified with carboxylic acids, represent so-called reinforced resins, which are caused by portions of cationic copolymers be dispersed. Here, the cationic copolymers are Solution polymerization shown and the preparation of the dispersed sizing agent happens from the anionically modified resins and the cationic copolymers in a complex procedure with removal of the solvent by distillation the copolymer, melting of the modified resin and dispersion in Water with the partial use of surfactants. When using the Resin parts not bound in the paper pulp must contain the process water and, if necessary be removed using other tools.

In der DE 38 26 825 C2 werden kationische Leimungsmittel beschrieben, die aus Metyl(meth)acrylat, Butyl(meth)acrylat, Acrylsäure und 10-30 Gew. %-Anteile N,N Dimethylaminoethyl(meth)acrylat gebildet werden und Isopropanol oder andere organische Lösungsmittel enthalten. Die beschriebenen Leimungsmittel sind bei Lagerung instabil und bei der Anwendung nicht ausreichend wirksam.DE 38 26 825 C2 describes cationic sizing agents which are derived from Methyl (meth) acrylate, butyl (meth) acrylate, acrylic acid and 10-30% by weight of N, N dimethylaminoethyl (meth) acrylate are formed and isopropanol or other organic Contain solvents. The sizing agents described are unstable when stored and not sufficiently effective when used.

In EP 416 427 B1 werden Leimungsmittel auf der Basis von wäßrigen, kationischen Polymerisatdispersionen beschrieben, deren Polymerisatanteil zwar nur aus 2-20 Gew. % eines salzbildenen, wasserlöslichen Monomeren mit Alkylammonium-, Alkylsulfonium- oder Alkylphosphoniumgruppen gebildet werden, die jedoch zusätzlich immer mit kationischen Polymerisaten, wie Retentionsmitteln und Schutzkolloiden (Poly-DADMAC) verwendet werden, so daß diese Polymerisate insgesamt in doch größerer Menge eingesetzt werden. Weiterhin enthalten die beschriebenen Dispersionen auch Emulgatoren und insbesondere nichtionogene Tenside, die neben den wasserlöslichen Retentionsmitteln im Papier die Leimungswirkung beeinträchtigen und die Prozeßwässer belasten können.EP 416 427 B1 describes sizing agents based on aqueous, cationic polymer dispersions described, the polymer content from 2-20% by weight of a salt-forming, water-soluble monomer with alkylammonium, alkylsulfonium or alkylphosphonium groups are formed, which, however, always with cationic Polymers such as retention aids and protective colloids (poly-DADMAC) are used, so that these polymers are used in total in a relatively large amount will. The dispersions described also contain emulsifiers and especially non-ionic surfactants, which in addition to the water-soluble retention aids Paper can impair the sizing effect and can pollute the process water.

Aufgabe der Erfindung war es daher, die bekannten kationischen Leimungsmittel unter Vermeidung ihrer Nachteile zu verbessern, insbesondere Leimungsmittel bereitzustellen, die sich wirtschaftlicher und umweltfreundlicher herstellen lassen, lagerstabil sind und ohne die Verwendung weiterer Komponenten allein als Leimungsmittel verwendbar sind sowie darüber hinaus eine verbesserte Wirkung aufweisen.The object of the invention was therefore to include the known cationic sizing agents To avoid avoiding their disadvantages, in particular to provide sizing agents, which can be manufactured more economically and environmentally friendly, are stable in storage and can be used alone as sizing agents without the use of further components and also have an improved effect.

Diese Aufgabe wird gelöst durch die Verwendung von wäßrigen, lösungsmittelfreien Dispersionen von kationischen Polymerisaten als Leimungsmittel, wobei die kationischen Polymerisate durch radikalische Polymerisation in Lösung oder Dispersion, vorzugsweise in Substanz aus

  • a) 30 - 70 Mol% wenigstens eines Monomeren der allgemeinen Formel H2C=CR1-CO-X-R2-N(R3)2 in der
  • R1 = H,CH3
  • R2 = eine C2 - C4-Alkylengruppe
  • R3 = H, eine C1-C4-Alkylguppe und
  • X = O, NH bedeuten
    • mit
  • b) 70 - 30 Mol % wenigstens eines Monomeren der Formel H2C=CR1-CO-X-R4 in der
  • R1 und X die bei Verbindung I genannte Bedeutung haben und
  • R4 = eine C8-C30-Alkylgruppe bedeuten
    • sowie gegebenenfalls
  • c) 0 - 20 Mol% wenigstens eines C8-C30-Monoolefins
    und
  • d) 0 - 10 Mol% wenigstens eines weiteren, mit a), b) und ggf. c) copolymerisierbaren Monomeren,
    • anschließender Neutralisation und gegebenenfalls Quaternierung der Copolymerisate sowie Dispergierung in Wasser oder wäßrigen Flüssigkeiten erhalten werden, wobei die Summe der Monomeren a), b), c) und d) 100 Mol% beträgt.This object is achieved by the use of aqueous, solvent-free dispersions of cationic polymers as sizing agents, the cationic polymers by radical polymerization in solution or dispersion, preferably in bulk
  • a) 30-70 mol% of at least one monomer of the general formula H 2 C = CR 1 -CO-XR 2 -N (R 3 ) 2 in the
  • R 1 = H, CH 3
  • R 2 = a C 2 -C 4 alkylene group
  • R 3 = H, a C 1 -C 4 alkyl group and
  • X = O, NH mean
    • With
  • b) 70-30 mol% of at least one monomer of the formula H 2 C = CR 1 -CO-XR 4 in the
  • R 1 and X have the meaning given for compound I and
  • R 4 = a C 8 -C 30 alkyl group
    • and if necessary
  • c) 0-20 mol% of at least one C 8 -C 30 monoolefin
    and
  • d) 0-10 mol% of at least one further monomer which can be copolymerized with a), b) and optionally c),
    • subsequent neutralization and optionally quaternization of the copolymers and dispersion in water or aqueous liquids are obtained, the sum of the monomers a), b), c) and d) being 100 mol%.

    Die Monomeren der Gruppe a) umfassen Acryl- und/oder Methacrylderivate mit einer Aminfunktion. Sie sind einerseits für die Fixierung an die Cellulosefaser erforderlich und sorgen andererseits in ihrer teilweise oder vollständig neutralisierten Form für die Dispergierbarkeit des Polymeren in Wasser. Als geeignete Monomere seien genannt

  • N,N-Dimethylaminoethyl(meth)acrylat, N,N-Dimethylaminopropyl(meth)acrylat,
  • N,N-Dimethylaminoethyl(meth)acrylamid und
  • N,N-Dimethylaminopropyl(meth)acrylamid. Bevorzugt Verwendung finden
  • N,N-Dimethylaminoethylacrylat und N,N-Dimethylaminopropylacrylamid.
    • The monomers of group a) include acrylic and / or methacrylic derivatives with an amine function. On the one hand, they are necessary for fixation to the cellulose fiber and, on the other hand, in their partially or completely neutralized form, they ensure the dispersibility of the polymer in water. Suitable monomers are mentioned
  • N, N-dimethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate,
  • N, N-dimethylaminoethyl (meth) acrylamide and
  • N, N-dimethylaminopropyl (meth) acrylamide. Find preferred use
  • N, N-dimethylaminoethyl acrylate and N, N-dimethylaminopropylacrylamide.

    • Die Monomeren der Gruppe a) sind in einer Menge von 30 - 70 mol% im Copolymerisat vorhanden. Bei Unterschreitung dieser Grenzen erhält man in der Regel instabile Dispersionen, während ein Anteil von mehr als 70 mol % den Leimungseffekt erheblich verschlechtert. Bevorzugt verwendet wird ein Anteil von 40 - 60 mol % dieser Monomeren im Copolymerisat.The monomers of group a) are in an amount of 30-70 mol% in the copolymer available. If these limits are undershot, unstable dispersions are usually obtained, while a proportion of more than 70 mol% significantly worsens the sizing effect. A proportion of 40-60 mol% of these monomers is preferably used in the copolymer.

    Bei den Monomeren der Gruppe b) handelt es sich um hydrophobe Ester oder Amide der Acrylsäure und/oder der Methacrylsäure. Sie sorgen im wesentlichen für den Leimungseffekt. Geeignete Monomere sind zum Beispiel 2-Ethylhexyl(meth)acrylat, n-Octyl(meth)acrylat, Isononyl(meth)acrylat, Decyl(meth)acrylat, Lauryl(meth)acrylat, Isotridecyl(meth)acrylat, Myristyl(meth)acrylat, Stearyl(meth)acrylat, C18-22(meth)acrylat, 2-Ethylhexyl(meth)acrylamid, n-Octyl(meth)acrylamid, Isononyl(meth)acrylamid, Decyl(meth)acrylamid, Lauryl(meth)acrylamid, Isotridecyl(meth)acrylamid, Myristyl(meth)acrylanrid, Stearyl(meth)acrylamid und C18-22-(meth)acrylamid. Die Monomeren werden in bekannter Weise aus den hydrophoben Alkoholen oder Aminen und der (Meth)acrylsäure bzw. reaktiven Derivaten hiervon hergestellt. Viele dieser Monomere sind kommerziell erhältlich. Bevorzugt Verwendung findet aus dieser Gruppe Stearylmethacrylat.The monomers of group b) are hydrophobic esters or amides of acrylic acid and / or methacrylic acid. They essentially ensure the sizing effect. Suitable monomers are, for example, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, isononyl (meth) acrylate, decyl (meth) acrylate, lauryl (meth) acrylate, isotridecyl (meth) acrylate, myristyl (meth) acrylate , Stearyl (meth) acrylate, C 18-22 (meth) acrylate, 2-ethylhexyl (meth) acrylamide, n-octyl (meth) acrylamide, isononyl (meth) acrylamide, decyl (meth) acrylamide, lauryl (meth) acrylamide, Isotridecyl (meth) acrylamide, myristyl (meth) acrylamide, stearyl (meth) acrylamide and C 18-22 - (meth) acrylamide. The monomers are prepared in a known manner from the hydrophobic alcohols or amines and the (meth) acrylic acid or reactive derivatives thereof. Many of these monomers are commercially available. Stearyl methacrylate is preferably used from this group.

    Ein Teil der Monomeren der Gruppe b) kann durch langkettige Monoolefine ersetzt werden. Geeignet für diesen Zweck sind beispielsweise Octen-1, Decen-1, Dodecen-1, Tetradecen-1, Hexadecen-1, Octadecen-1, Eicosen-1 sowie C20-24 bzw. C30+-alpha-Olefin-Schnitte. Auch diese Monomeren sind kommerziell zugänglich. Sie können im Verhältnis zur Monomerengruppe b) in einer Menge von 0,001 bis 1 : 1 eingesetzt werden. Bevorzugt verwendet werden Octadecen-1 sowie C20-24-alpha-Olefingemische.Some of the monomers of group b) can be replaced by long-chain monoolefins. Suitable for this purpose are, for example, octene-1, decene-1, dodecene-1, tetradecene-1, hexadecene-1, octadecen-1, eicosen-1 and C 20-24 or C 30+ alpha-olefin sections. These monomers are also commercially available. They can be used in an amount of 0.001 to 1: 1 in relation to the monomer group b). Octadecene-1 and C 20-24 -alpha-olefin mixtures are preferably used.

    Gegebenenfalls können zur Erzielung spezieller Eigenschaften im Polymerisationsansatz bis zu 10 mol % weitere, mit den Monomeren der Gruppen a), b) und ggf. c) copolymerisierbare alpha,beta-ungesättigte Monomere vorliegen. Bedingung für ihre Verwendung ist, daß sie sich mit den vorgenannten Monomeren zu einer homogenen Mischung gegebenenfalls bei höherer Temperatur verarbeiten lassen. Geeignet sind beispielsweise Styrole, Vinylester, Vinylether, (Meth)acrylsäure und/oder (Meth)acrylamid.If necessary, to achieve special properties in the polymerization approach up to 10 mol% of further copolymerisable with the monomers of groups a), b) and optionally c) Alpha, beta unsaturated monomers are present. Condition for their use is that they combine with the aforementioned monomers to form a homogeneous mixture if necessary Have it processed at a higher temperature. Styrenes are suitable, for example, Vinyl esters, vinyl ethers, (meth) acrylic acid and / or (meth) acrylamide.

    Die erfindungsgemäß bevorzugt verwendeten Leimungsmittel enthalten Copolymerisate, die unter Ausschuß von organischen Lösungsmitteln durch Substanzpolymerisation in an sich bekannter Weise hergestellt werden. The sizing agents preferably used according to the invention contain copolymers, those with the rejection of organic solvents by bulk polymerization in on be made in a known manner.

    Die Polymerisation wird bei Temperaturen von 20 bis 200°C, bevorzugt 60 bis 160°C durchgeführt. Sie wird thermisch, photochemisch oder redoxkatalytisch initiiert, vorzugsweise unter Zuhilfenahme von Peroxo- und/oder Azoverbindungen. Aufgrund der überwiegend hydrophoben Natur der Monomeren sind öllösliche Initiatoren wie beispielsweise 2,2'-Azobis(isobutyronitril) (AIBN), 2,2'-Azobis(2-methylbutyronitril), 4,4'-Azo(4-cyanopentansäure), 2,2'-Azobis(2,4-dimethylvaleronitril), Di-tert-Butylperoxid, Dibenzoylperoxid oder tert-Butylperoxy-2-ethylhexanoat bevorzugt.The polymerization is carried out at temperatures of 20 to 200 ° C., preferably 60 to 160 ° C. carried out. It is initiated thermally, photochemically or redox-catalytically, preferably with the help of peroxo and / or azo compounds. Due to the The predominantly hydrophobic nature of the monomers are oil-soluble initiators such as, for example 2,2'-azobis (isobutyronitrile) (AIBN), 2,2'-azobis (2-methylbutyronitrile), 4,4'-azo (4-cyanopentanoic acid), 2,2'-azobis (2,4-dimethylvaleronitrile), di-tert-butyl peroxide, Dibenzoyl peroxide or tert-butyl peroxy-2-ethylhexanoate is preferred.

    Das Zahlenmittel der Molmasse der Copolymerisate beträgt 1000 bis 100.000 g/mol. Die Regelung der Molmasse erfolgt vorzugsweise durch Einsatz bekannter Regler wie beispielsweise Mercaptoethanol oder Dodecylmercaptan.The number average molecular weight of the copolymers is 1000 to 100,000 g / mol. The The molar mass is preferably regulated by using known regulators such as, for example Mercaptoethanol or dodecyl mercaptan.

    In weiter bevorzugten Ausführungsformen wird ein Teil oder die gesamte Menge der Monomeren vorgelegt, bei einer geeigneten Temperatur der Initiator ganz oder in Teilmengen zur Polymerisationsmischung gegeben und die weitere Reaktion unter adiabatischen Bedingungen vorgenommen, wobei die entstehende Polymerisationswärme den Reaktionsansatz erwärmt.In more preferred embodiments, part or all of the amount of Monomers submitted, at a suitable temperature, the initiator in whole or in part added to the polymerization mixture and the further reaction under adiabatic Conditions made, the resulting heat of polymerization Reaction batch warmed.

    Nach der Polymerisation wird das Copolymerisat direkt mit verdünnter Säure neutralisiert und in Wasser emulgiert. Die Menge an Säure wird hierbei so gewählt, daß sich im Endprodukt ein pH-Wert von 8 bis 3 einstellt. Zur Neutralisation sind sowohl anorganische Säuren, wie Salzsäure oder Schwefelsäure, als auch organische Säuren insbesondere Carbonsäuren, wie Ameisensäure oder Essigsäure geeignet.After the polymerization, the copolymer is neutralized directly with dilute acid and emulsified in water. The amount of acid is chosen so that in End product sets a pH of 8 to 3. Both are inorganic for neutralization Acids such as hydrochloric acid or sulfuric acid, as well as organic acids in particular Carboxylic acids such as formic acid or acetic acid are suitable.

    Sofern erforderlich kann nach der Neutralisation oder Emulgierung eine erneute Initiatorzugabe zur Reduzierung des Restmonomergehaltes vorgenommen werden. Hierzu eignen sich dann sowohl öllösliche als auch wasserlösliche Initiatorsysteme.If necessary, the initiator can be added again after neutralization or emulsification to reduce the residual monomer content. For this Both oil-soluble and water-soluble initiator systems are then suitable.

    In einer weiteren bevorzugten Ausführungsform werden Copolymerisate verwendet, deren Aminogruppen teilweise oder vollständig mit einem geeigneten Quaternierungsmittel umgesetzt werden. Beispiele für geeignete Quaternisierungsmittel sind Methylchlorid, Benzylchlorid, Dimethylsulfat und/oder Epichlorhydrin. Die Menge des Quaternierungsmittels wird so gewählt, daß sich ein Quaternisierungsgrad von 1 - 100 mol %, bevorzugt 5 bis 50 mol% einstellt.In a further preferred embodiment, copolymers are used whose Amino groups partially or completely with a suitable quaternizing agent be implemented. Examples of suitable quaternizing agents are methyl chloride, Benzyl chloride, dimethyl sulfate and / or epichlorohydrin. The amount of quaternizing agent is chosen so that a degree of quaternization of 1-100 mol% is preferred 5 to 50 mol%.

    Die Umsetzung erfolgt dabei im Molverhältnis von Aminogruppe zu Quaternierungsmittel von 100:1 bis 1:1, oder aber in einem Molverhältnis von Aminogruppe zu Epichlorhydrin von 50 : 1 bis 1 : 1. The reaction takes place in a molar ratio of amino group to Quaternizing agent from 100: 1 to 1: 1, or in one Molar ratio of amino group to epichlorohydrin of 50: 1 to 1: 1.

    Der Feststoffgehalt der erfindungsgemäß zu verwendenen Polymerisatdispersionen beträgt 10 - 60 Gew.%, vorzugsweise 20 - 50 Gew.%, besonders bevorzugt 30 - 40 Gew.%.The solids content of the polymer dispersions to be used according to the invention is 10-60% by weight, preferably 20-50% by weight, particularly preferably 30-40 % By weight.

    Die erfindungsgemäß zu verwendeten Copolymerisatdispersionen zeichnen sich überraschenderweise trotz ihrer Herstellung ohne weitere Hilfsmittel durch eine gute Dispersionsstabilität aus, sodaß selbst nach mehreren Wochen der Lagerung bei 50°C keine Auftrennung bzw. Koagulation von Polymerisat zu beobachten ist. Weiterhin zeichnen sie sich in an sich nicht zu erwartender Weise durch eine gute Leimungswirkung aus und sind daher zur hydrophobierenden Leimung von Papieren, insbesondere von Schreib- und Druckpapieren geeignet. Hierbei können sie sowohl bei der Masseleimung als auch als Oberflächenleimungsmittel eingesetzt werden.The copolymer dispersions to be used according to the invention are surprisingly distinguished despite their production without any additional aids, due to good dispersion stability so that even after several weeks of storage at 50 ° C none Separation or coagulation of the polymer can be observed. Continue drawing it is not to be expected in itself by a good sizing effect and are therefore for the hydrophobizing sizing of papers, especially writing and Suitable for printing papers. Here they can be used for both mass gluing and Surface sizing agents are used.

    Die Erfindung betrifft ferner ein Verfahren zur Papierleimung unter Verwendung der erfindungsgemäßen Mittel, und zwar sowohl zur Masse- als auch zur Oberflächenleimung.The invention further relates to a method for paper sizing using the inventive Medium, both for mass and surface sizing.

    Bei der Masseleimung werden die Polymerdispersionen dem Dick- oder Dünnstoff mit 0,1 - 3,0% Wirksubstanz (bezogen auf atro Stoff) zugesetzt, während bei der Oberflächenleimung 0,1 - 5,0 g Wirksubstanz pro m2 auf das Papier nach der Trockenpartie aufgetragen wird. in den meisten Fällen läßt sich mit den Polymerdispersionen eine Sofortleimung erzielen, das heißt die gewünschte Hydrophobierung des Papiers wird sofort nach dem Herstellungsprozeß erreicht. Der nachteilige Vorgang der Alterung der frisch geleimten Papiere der bei der Verwendung der mit derzeit eingesetzten Leimungsmittel zur Erreichung hydrophober Effekte und der damit verbundenen Papiereigenschaften oft notwendig ist, kann daher weitgehend entfallen.In bulk sizing, the polymer dispersions are added to the thick or thin material with 0.1 - 3.0% active substance (based on dry substance), while with surface sizing 0.1 - 5.0 g active substance per m 2 onto the paper after Drying section is applied. In most cases, the polymer dispersions can be used to achieve an immediate sizing, ie the desired hydrophobization of the paper is achieved immediately after the manufacturing process. The disadvantageous process of aging the freshly sized papers, which is often necessary when using the sizes currently used to achieve hydrophobic effects and the associated paper properties, can therefore largely be dispensed with.

    Weiterhin läßt sich über die Einsatzmenge der kationischen Polymerdispersionen in hervorragender Weise ein abgestufter Leimungsgrad der Papiere einstellen, der sowohl bei der sauren als auch bei der neutralen oder alkalischen Papierherstellung reproduzierbar ist. Weitere Hilfsmittel werden für die Leimung vorteilhafter Weise nicht benötigt.Furthermore, the amount of cationic polymer dispersions used can be outstanding Way to set a graded degree of sizing of the papers, which both acidic as well as reproducible in neutral or alkaline paper production is. Further aids are advantageously not required for the sizing.

    Allerdings können gegebenenfalls inerte Füllstoffe, Pigmente und andere Farbstoffe zugemischt werden.However, inert fillers, pigments and others may be used Dyes are added.

    Die Erfindung wird in den folgenden Beispielen dargestellt.The invention is illustrated in the following examples.

    Allgemeine Herstellvorschrift AGeneral manufacturing instructions A

    In einem Reaktor mit mechanischem Rührer, Rückflußkühler und Innenthermometer werden die Monomeren und ggf. Regler vorgelegt und 30 Minuten mit Stickstoffgas durchspült. Sodann wird auf die vorgesehene Starttemperatur aufgeheizt. Anschließend gibt man den Initiator zu. Durch die einsetzende Polymerisation kommt es zu einer Temperaturerhöhung. Nach Überschreiten des Temperaturmaximums rührt man noch drei Stunden bei der vorgesehenen Polymerisationstemperatur weiter. Anschließend gibt man verdünnte Säure zur Neutralisation hinzu und rührt weitere 30 Minuten bei 60 - 90°C, gegebenenfalls nach einer eventuellen erneuten Initiatorzugabe. Man läßt unter Rühren auf 30-40°C abkühlen und füllt das Produkt ab.In a reactor with mechanical stirrer, reflux condenser and internal thermometer the monomers and, if necessary, regulators are introduced and 30 minutes with nitrogen gas rinsed through. Then it is heated to the intended starting temperature. Subsequently you add the initiator. The onset of polymerization leads to an increase in temperature. After the maximum temperature has been exceeded, three more are stirred Hours at the intended polymerization temperature. Then you give dilute acid for neutralization and stir for a further 30 minutes at 60 - 90 ° C, if necessary after a new initiator addition. The mixture is left under stirring Cool to 30-40 ° C and fill the product.

    Allgemeine Herstellvorschrift B:General manufacturing instructions B:

    Im gleichen Reaktor wie in Vorschrift A werden Lösungsmittel und gegebenenfalls Regler vorgelegt und mit Stickstoff begast. Anschließend heizt man auf die vorgesehene Polymerisationstemperatur auf und läßt dann aus verschiedenen Zuläufen gleichzeitig die Monomeren und den Initiator (gegebenenfalls verdünnt mit weiterem Lösungsmittel) über die vorgesehene Reaktionszeit zulaufen. Nach Beendigung des Zulaufes läßt man 2 Stunden nachreagieren. Anschließend wird das Polymerisat wie in Herstellvorschrift A mit verdünnter Säure neutralisiert und emulgiert. Aus der Emulsion wird das Lösungsmittel weitestgehend abdestilliert.Solvents and optionally regulators are in the same reactor as in regulation A. submitted and gassed with nitrogen. The mixture is then heated to the intended polymerization temperature and then leaves the from different inlets at the same time Monomers and the initiator (optionally diluted with further solvent) run over the intended response time. After the feed has ended, 2 React for hours. The polymer is then as in Preparation A neutralized and emulsified with dilute acid. The solvent becomes the solvent largely distilled off.

    Herstellung der Copolymerisate:Preparation of the copolymers:

    In den folgenden Beispielen sind die nach obigen Vorschriften hergestellten Copolymer-dispersionen aufgeführt. Die angeführten Zahlen bedeuten Gewichtsteile. Die verwendeten Abkürzungen haben folgende Bedeutung: ACP 4,4'-Azo(4-cyanopentansäure) AIBN 2,2'-Azobis(isobutyronitril) DIMAPA N,N-Dimethylaminopropylacrylamid DM Dodecylmercaptan DMAEA N,N-Dimethylaminoethylacrylat DMS Dimethylsulfat ECH Epichlorhydrin EHMa Ethylhexylmethacrylat HAc Essigsäure ME Mercaptoethanol StMA Stearylmethacrylat TS Trockensubstanz In the following examples, the copolymer dispersions prepared according to the above regulations are listed. The numbers given mean parts by weight. The abbreviations used have the following meaning: ACP 4,4'-azo (4-cyanopentanoic acid) AIBN 2,2'-azobis (isobutyronitrile) DIMAPA N, N-dimethylaminopropylacrylamide DM Dodecyl mercaptan DMAEA N, N-dimethylaminoethyl acrylate DMS Dimethyl sulfate ECH Epichlorohydrin EHMa Ethylhexyl methacrylate HAc acetic acid ME Mercaptoethanol StMA Stearyl methacrylate TS Dry matter

    Die Lagerstabilität wurde bei Raumtemperatur und bei 50°C beurteilt. Als stabil gilt eine Dispersion, die wenigstens während 7 Tage Lagerung bei 50°C und während 1 Monat Lagerung bei Raumtemperatur nicht auftrennt. Die Viskositäten wurden jeweils bei Raumtemperatur mit einem Brookfield Rotationsviskosimeter gemessen.

    Copolymerisat A:
    Methode A, 60 DIMAPA, 100 StMa, 1,5 ME, TStart 80°C, 1,0 AIBN, 1,5 Std. bei 90-150°C, 38,0 HCl (37%), 410 H2O demin., Helle, stabile Emulsion, TS 30 %, 460 mPas, pH(10% in H2O) 2,9
    Copolymerisat B:
    Methode A, 60 DIMAPA, 100 StMa, 7,5 ME, TStart 80°C, 5,0 ACP, 1,5 Std. bei 90-120°C, 35,7 HCl (37%), 127 H2O demin. Helle, stabile Emulsion, TS 50 %, 900 mPas, pH(10% in H2O) 3,8
    Copolymerisat C:
    Methode A, 50 DIMAPA, 100 StMa, 1,5 ME, TStart 80°C, 1,0 AIBN, 1,5 Std. bei 90-150°C, 31,5 HCI (37%), 265 H2O demin., Nachinitiierung mit 1,0 H2O2 (30%) und 0,1 ME Helle, stabile Emulsion, TS 35 %, 34.000 mPas, pH(10% in H2O) 3,2
    Copolymerisat D:
    Methode A, 50 DIMAPA, 110 StMa, 1,5 ME, TStart 80°C, 1,0 AIBN, 90 Min bei 90-150°C, 31,5 HCl (37%), 400 H2O demin Nachinitiierung mit 0,2 ABAH in 5 H2O demin. Helle, stabile Emulsion, TS 30 %, 740 mPas, pH(10% in H2O) 3,1
    Copolymerisat E:
    Methode A, 50 DIMAPA, 110 StMa, 1,5 ME, TStart 80°C, 1,0 AIBN, 2 Std. bei 90-140°C, 31,5 HCl (37%), 400 H2O demin. Helle, stabile Emulsion, TS 30 %, 1680 mPas, pH(10% in H2O) 3,1
    Copolymerisat F:
    Methode A, 50 DIMAPA, 100 StMa, 1,5 ME, TStart 80°C, 1,0 AIBN, 1,5 Std. bei 90-150°C, 18,8 HAc, 500 H2O demin. Nachbehandlung mit 14,8 ECH, 5 Std. 30°C Helle, stabile Emulsion, TS 26%, 150 mPas, pH(10% in H2O) 5,7
    Copolymerisat G:
    wie Copolymerisat F, jedoch Nachbehandlung mit 1,48 ECH, 5 Std. 80°C Helle, stabile Emulsion, TS 26 %, 280 mPas, pH(10% in H2O) 5,2
    Copolymerisat H:
    wie Copolymerisat F, jedoch Nachbehandlung mit 20,2 DMS, 5 Std. 80°C Helle, stabile Emulsion, TS 26%, 120 mPas, pH(10% in H2O) 4,4
    Copolymerisat I:
    Methode B, 100 Isopropanol, 1,5 ME, 50 DIMAPA, 100 StMa 2,0 ACP in 20 Isopropanol, 1 Std. bei 75-80°C zudosieren, 5 Std. 90°C, 30,0 HCl (37%), 250 H2O demin., 1 Std. bei 80°C, anschließend Isopropanol abdestilliert Helle, stabile Emulsion, TS 35 %, 250 mPas, pH(10% in H2O) 4,3
    Copolymerisat J:
    Methode A, 50 DIMAPA, 95 StMa, 5 EHMa, 1,5 ME, TStart 80°C 1,0 AIBN, 1,5 Std. 80-155°C, 31,5 HCl (37%), 265 H2O demin., Nachinitiierung mit 0,2 ABAH in 5 H2O demin., 1 Std. 90°C Helle, stabile Emulsion, TS 35 %, 750 mPas, pH(10% in H2O) 5,9
    Copolymerisat K:
    Methode A, 72 DMAEA, 165 StMa, 1,5 ME, 1,0 AIBN, 1,5 Std. 80-135°C, 49,2 HCI (37%), 1030 H2O demin., Nachinitiierung mit 0,2 ABAH in 5 H2O demin., 1 Std. 90°C Helle, stabile Emulsion, TS 20 %, 480 mPas, pH(10% in H2O) 3,0
    Vergleichsprodukt:
    nach Beispiel 4 aus DE 38 26 825 C2 Weiße Emulsion, schichtet nach 3 Tagen bei Raumtemperatur TS 16 %, 30 mPas, pH(10% in H2O) 3,2
    The storage stability was assessed at room temperature and at 50 ° C. A dispersion is considered stable if it does not separate at least for 7 days at 50 ° C. and for 1 month at room temperature. The viscosities were measured in each case at room temperature using a Brookfield rotary viscometer.
    Copolymer A:
    Method A, 60 DIMAPA, 100 StMa, 1.5 ME, T start 80 ° C, 1.0 AIBN, 1.5 hours at 90-150 ° C, 38.0 HCl (37%), 410 H 2 O demin., Bright, stable emulsion, TS 30%, 460 mPas, pH (10% in H 2 O) 2.9
    Copolymer B:
    Method A, 60 DIMAPA, 100 StMa, 7.5 ME, T start 80 ° C, 5.0 ACP, 1.5 hours at 90-120 ° C, 35.7 HCl (37%), 127 H 2 O demin. Bright, stable emulsion, TS 50%, 900 mPas, pH (10% in H 2 O) 3.8
    Copolymer C:
    Method A, 50 DIMAPA, 100 StMa, 1.5 ME, T start 80 ° C, 1.0 AIBN, 1.5 hours at 90-150 ° C, 31.5 HCl (37%), 265 H 2 O demin., post-initiation with 1.0 H 2 O 2 (30%) and 0.1 ME Bright, stable emulsion, TS 35%, 34,000 mPas, pH (10% in H 2 O) 3.2
    Copolymer D:
    Method A, 50 DIMAPA, 110 StMa, 1.5 ME, T start 80 ° C, 1.0 AIBN, 90 min at 90-150 ° C, 31.5 HCl (37%), 400 H 2 O demin after initiation 0.2 ABAH in 5 H 2 O demin. Bright, stable emulsion, TS 30%, 740 mPas, pH (10% in H 2 O) 3.1
    Copolymer E:
    Method A, 50 DIMAPA, 110 StMa, 1.5 ME, T start 80 ° C, 1.0 AIBN, 2 hours at 90-140 ° C, 31.5 HCl (37%), 400 H 2 O demin. Bright, stable emulsion, TS 30%, 1680 mPas, pH (10% in H 2 O) 3.1
    Copolymer F:
    Method A, 50 DIMAPA, 100 StMa, 1.5 ME, T start 80 ° C, 1.0 AIBN, 1.5 hours at 90-150 ° C, 18.8 HAc, 500 H 2 O demin. Aftertreatment with 14.8 ECH, 5 hours at 30 ° C. Bright, stable emulsion, TS 26%, 150 mPas, pH (10% in H 2 O) 5.7
    Copolymer G:
    Like copolymer F, but aftertreatment with 1.48 ECH, 5 hours at 80 ° C. Bright, stable emulsion, TS 26%, 280 mPas, pH (10% in H 2 O) 5.2
    Copolymer H:
    as copolymer F, but aftertreatment with 20.2 DMS, 5 hours at 80 ° C. Bright, stable emulsion, TS 26%, 120 mPas, pH (10% in H 2 O) 4.4
    Copolymer I:
    Method B, 100 isopropanol, 1.5 ME, 50 DIMAPA, 100 StMa 2.0 ACP in 20 isopropanol, metered in for 1 hour at 75-80 ° C, 5 hours 90 ° C, 30.0 HCl (37%) , 250 H 2 O demin., 1 hour at 80 ° C., then isopropanol distilled off. Bright, stable emulsion, TS 35%, 250 mPas, pH (10% in H 2 O) 4.3
    Copolymer J:
    Method A, 50 DIMAPA, 95 StMa, 5 EHMa, 1.5 ME, T Start 80 ° C 1.0 AIBN, 1.5 hours 80-155 ° C, 31.5 HCl (37%), 265 H 2 O demin., Post-initiation with 0.2 ABAH in 5 H 2 O demin., 1 hour 90 ° C. Bright, stable emulsion, TS 35%, 750 mPas, pH (10% in H 2 O) 5.9
    Copolymer K:
    Method A, 72 DMAEA, 165 StMa, 1.5 ME, 1.0 AIBN, 1.5 hours 80-135 ° C, 49.2 HCl (37%), 1030 H 2 O demin., Post-initiation with 0, 2 ABAH in 5 H 2 O demin., 1 h 90 ° C Bright, stable emulsion, TS 20%, 480 mPas, pH (10% in H 2 O) 3.0
    Comparative product:
    according to Example 4 from DE 38 26 825 C2 White emulsion, layered after 3 days at room temperature TS 16%, 30 mPas, pH (10% in H 2 O) 3.2

    Zur Prüfung der Leimungswirkung der Polymerdispersionen wurden in einem Rapid-Köthen Blattbildner Papierblätter mit einem Flächengewicht von ca. 100 g/m2 hergestellt. Als Rohstoffe wurden ein Kurzfaserzellstoff (Birke-Sulfat) oder ein Altpapier (Zeitungsdruck) oder ein Holzschliff verwendet.To test the sizing effect of the polymer dispersions, paper sheets with a basis weight of approx. 100 g / m 2 were produced in a Rapid-Koethen sheet former. Short fiber pulp (birch sulfate) or waste paper (newspaper printing) or wood pulp were used as raw materials.

    Das zu prüfende Leimungsmittel wurde dem Stoff/Wasser-Gemisch zugegeben und 15 Sekunden vermischt. Anschließend wurde das Blatt im Blattbildner gebildet und im Vakuumtrockner des Rapid-Köthen Gerätes bei 92°C 10 Minuten getrocknet.The sizing agent to be tested was added to the substance / water mixture and 15 Seconds mixed. The sheet was then formed in the sheet former and in a vacuum dryer of the Rapid-Köthen device dried at 92 ° C for 10 minutes.

    Die Leimungswerte, die nach DIN 53132 "Wasseraufnahme nach Cobb" gemessen wurden, wurden direkt nach der Herstellung, nach einer zusätzlichen Trocknung bei 110°C für 10 Minuten sowie nach 24 Stunden bestimmt. Die Ergebnisse sind in den folgenden Tabellen zusammengefaßt. Beispiel Copolymerisat Menge in % Papierstoff Cobb-Wert (g/m2) nach Herstellung nach Zusatztrocknung nach 24 h 1 A 2,0 Zellstoff 36 31 26 2 B 2,0 Zellstoff 88 28 18 3 C 2,0 Zellstoff 28 21 20 4 D 2,0 Zellstoff 53 30 28 5 E 2,0 Zellstoff 68 25 19 6 H 2,0 Zellstoff 28 25 23 7 I 2,0 Zellstoff n.b. 61 36 8 J 2,0 Zellstoff 86 21 19 9 K 2,0 Zellstoff n.b. 58 34 Vergl.- Vergl- 2,0 Zellstoff 155 54 51 Beisp. 1 Prod. The sizing values, which were measured according to DIN 53132 "Cobb water absorption", were determined directly after production, after an additional drying at 110 ° C. for 10 minutes and after 24 hours. The results are summarized in the following tables. example Copolymer amount in % Paper stock Cobb value (g / m 2 ) after manufacture after additional drying after 24 h 1 A 2.0 cellulose 36 31 26 2nd B 2.0 cellulose 88 28 18th 3rd C. 2.0 cellulose 28 21 20th 4th D 2.0 cellulose 53 30th 28 5 E 2.0 cellulose 68 25th 19th 6 H 2.0 cellulose 28 25th 23 7 I. 2.0 cellulose nb 61 36 8th J 2.0 cellulose 86 21 19th 9 K 2.0 cellulose nb 58 34 Compare Compare 2.0 cellulose 155 54 51 Ex. 1 Prod.

    Die Tabelle 1 zeigt, daß mit den erfindungsgemäß zu verwendenen Copolymerisaten eine sehr gute Sofortleimung erzielt werden kann. Das Vergleichsbeispiel zeigt keine Sofortleimung und ergibt auch nach 24 Stunden deutlich schlechtere Werte als die erfindungsgemäßen Beispiele. Copolymerisat Menge in % Papierstoff Cobb-Wert (g/m2) nach Herstellung nach Zusatztrocknung nach 24 h 10 B 0,50 Zellstoff - 211 49 1,00 Zellstoff 175 34 18 11 C 0,50 Zellstoff - 126 40 1,00 Zellstoff 114 38 22 12 F 0,25 Zellstoff - 110 101 0,50 Zellstoff 91 19 19 13 G 0,50 Zellstoff n.b. 50 43 1,00 Zellstoff 58 24 22 14 H 1,00 Zellstoff 66 38 33 Vergl.- Vergl- 0,50 Zellstoff - 169 112 Beisp. 2 Prod. 1,00 Zellstoff 157 75 65 Table 1 shows that very good instant sizing can be achieved with the copolymers to be used according to the invention. The comparative example shows no immediate sizing and, even after 24 hours, gives significantly worse values than the examples according to the invention. Copolymer amount in % Paper stock Cobb value (g / m 2 ) after manufacture after additional drying after 24 h 10th B 0.50 cellulose - 211 49 1.00 cellulose 175 34 18th 11 C. 0.50 cellulose - 126 40 1.00 cellulose 114 38 22 12th F 0.25 cellulose - 110 101 0.50 cellulose 91 19th 19th 13 G 0.50 cellulose nb 50 43 1.00 cellulose 58 24th 22 14 H 1.00 cellulose 66 38 33 Compare Compare 0.50 cellulose - 169 112 Ex. 2 Prod. 1.00 cellulose 157 75 65

    Die Tabelle 2 verdeutlicht, daß bei erfindungsgemäßer Verwendung der Copolymerisate auch bei niedrigeren Einsatzkonzentrationen ein Vorteil gegenüber bekannten Lösungsmitteln festzustellen ist. Beispiel Copolymerisat Menge in % Papierstoff Cobb-Wert (g/m2) nach Herstellung nach Zusatztrocknung nach 24 h 15 F 0,5 Holzschliff - 109 88 1,0 Holzschliff 186 37 24 2,0 Holzschliff 33 26 17 16 G 1,0 Holzschliff n.b. 69 61 2,0 Holzschliff 48 39 31 17 H 1,0 Holzschliff - - 62 2,0 Holzschliff - 44 31 Beispiel Copolymerisat Menge in % Papierstoff Cobb-Wert (g/m2) nach Herstellung nach Zusatztrocknung nach 24 h 18 B 2,0 Altpapier - 171 81 19 D 2,0 Altpapier - 172 95 20 F 0,5 Altpapier - 142 141 1,0 Altpapier - 54 38 2,0 Altpapier 89 23 18 21 G 2,0 Altpapier 112 48 42 Vergl.- Vergl- 1,0 Altpapier - 166 157 Beisp. 3 Prod. 2,0 Altpapier - 116 109 Table 2 shows that when the copolymers are used according to the invention, an advantage over known solvents can also be found at lower use concentrations. example Copolymer Quantity in% Paper stock Cobb value (g / m 2 ) after manufacture after additional drying after 24 h 15 F 0.5 Wood sanding - 109 88 1.0 Wood sanding 186 37 24th 2.0 Wood sanding 33 26 17th 16 G 1.0 Wood sanding nb 69 61 2.0 Wood sanding 48 39 31 17th H 1.0 Wood sanding - - 62 2.0 Wood sanding - 44 31 example Copolymer amount in % Paper stock Cobb value (g / m 2 ) after manufacture after additional drying after 24 h 18th B 2.0 Waste paper - 171 81 19th D 2.0 Waste paper - 172 95 20th F 0.5 Waste paper - 142 141 1.0 Waste paper - 54 38 2.0 Waste paper 89 23 18th 21 G 2.0 Waste paper 112 48 42 Compare Compare 1.0 Waste paper - 166 157 Ex. 3 Prod. 2.0 Waste paper - 116 109

    Die in Tab. 4 dargestellten Ergebnisse zeigen, daß auch bei nur sehr schwierig zu hydrophobierendem Altpapier erfindungsgemäß gegenüber dem Vergleichsprodukt eine deutlich verbesserte Sofortleimung erreicht wird, die nach 24 h Lagerung weiter verbessert ist.The results shown in Table 4 show that even with very difficult to hydrophobize Waste paper according to the invention compared to the comparative product significantly improved instant sizing is achieved, which continues after 24 h of storage is improved.

    Claims (9)

    1. Cationic, aqueous, solvent-free dispersions of paper sizing agents containing cationic polymerizates, characterized by a content of cationic polymerizates, obtained by free-radical polymerization in solution or dispersion, preferably in substance, using
      a) 30-70 mole-% of at least one monomer of general formula H2C=CR1-CO-X-R2-N(R3)2 wherein
      R1 represents H, CH3,
      R2 represents a C2-C4 alkylene group,
      R3 represents H, a C1-C4 alkyl group, and
      X represents O, NH,
      with
      b) 70-30 mole-% of at least one monomer of formula H2C=CR1-CO-X-R4 wherein
      R1 and X have the meanings indicated for compound (I), and R4 represents a C8-C30 alkyl group,
      and optionally
      c) 0-20 mole-% of at least one C8-C30 monoolefin,
      and
      d) 0-10 mole-% of at least one further monomer copolymerizable with a), b) and optionally c),
      subsequent neutralization and optionally quaternization of the copolymerizates, and dispersion in water or aqueous liquids, the sum of monomers a), b), c), and d) being 100 mole-%.
    2. The paper sizing agents according to claim 1, characterized in that the aqueous copolymerizate dispersions contain N,N-dimethylaminopropyl(meth)acrylamide and/or N,N-dimethylaminoethyl (meth)acrylate, preferably N,N-dimethylaminopropylacrylamide and/or N,N-dimethylaminoethyl acrylate as group a) monomers, and stearyl (meth)acrylate as group b) monomer.
    3. The paper sizing agents according to one of claims 1 or 2, characterized by a content of a copolymerizate which, following polymerization, is neutralized with inorganic and/or organic acids, preferably carboxylic acids, and emulsified with water, the pH value in the final product ranging from 3.0 to 8.0 and optionally, the amino groups of the group a) monomers being reacted with a quaternizing agent at a molar ratio of amino groups to quaternizing agents of from 100:1 to 1:1.
    4. The paper sizing agents according to one of claims 1 to 3, characterized by a content of copolymerizate quaternized with epichlorohydrin at a molar ratio of amino groups to epichlorohydrin of from 50:1 to 1:1.
    5. The paper sizing agents according to one of claims 1 to 4, characterized by a solids content of from 10 to 60 wt.-% of polymerizate.
    6. The paper sizing agents according to claim 5, characterized by a solids content of from 20 to 50 wt.-% of polymerizate.
    7. The paper sizing agents according to claim 6, characterized by a solids content of from 30 to 40 wt.-% of polymerizate.
    8. A process for the production of pulp-sized paper using a cationic copolymerizate dispersion, characterized in that an aqueous copolymerizate dispersion according to claims 1-7 is used as pulp sizing agent, which is mixed with intense stirring into the thick matter or the thin matter using an amount of from 0.1% to 3.0% of copolymerizate relative to abs. dry matter, optionally together with inert fillers, pigments and other colorants, and other auxiliary agents, and the sized paper is isolated and dried.
    9. A process for the production of surface-sized paper, wherein a cationic copolymerizate dispersion is used, characterized in that an aqueous copolymerizate dispersion according to claims 1-7 is used as surfacesizing agent, with 0.1 - 5.0 g of copolymerizate per m2 of paper being applied after the drying section.
    EP95929873A 1994-08-25 1995-08-16 Paper-sizing agents containing aqueous, solvent-free dispersions of cationic polymers and method of preparing sized paper by using these agents Expired - Lifetime EP0777692B1 (en)

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    DE4430069 1994-08-25
    DE4430069A DE4430069A1 (en) 1994-08-25 1994-08-25 Aqueous, solvent-free dispersions of paper sizing agents containing cationic polymers and process for the production of size paper using these agents
    PCT/EP1995/003232 WO1996006119A1 (en) 1994-08-25 1995-08-16 Paper-sizing agents containing aqueous, solvent-free dispersions of cationic polymers and method of preparing sized paper by using these agents

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    EP0777692B1 true EP0777692B1 (en) 1998-04-01

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    DE19851024A1 (en) 1998-11-05 2000-05-11 Basf Ag Aqueous dispersions of water-soluble polymers of N-vinylcarboxamides, processes for their preparation and their use
    DE19909653A1 (en) 1999-03-05 2000-09-07 Stockhausen Chem Fab Gmbh Powdery, crosslinked, aqueous liquids and blood-absorbing polymers, processes for their preparation and their use
    US6572736B2 (en) 2000-10-10 2003-06-03 Atlas Roofing Corporation Non-woven web made with untreated clarifier sludge
    US6488812B2 (en) * 2000-12-14 2002-12-03 Kimberly-Clark Worldwide, Inc. Soft tissue with improved lint and slough properties
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    FI119250B (en) * 2002-05-29 2008-09-15 Upm Kymmene Corp Procedure for the production of release paper
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    ATE164599T1 (en) 1998-04-15
    NO970833D0 (en) 1997-02-24
    DE4430069A1 (en) 1996-02-29
    WO1996006119A1 (en) 1996-02-29
    US5954921A (en) 1999-09-21
    FI970770A0 (en) 1997-02-24
    FI970770A (en) 1997-02-24
    CA2194602A1 (en) 1996-02-29
    NO970833L (en) 1997-02-24
    EP0777692A1 (en) 1997-06-11
    DE59501788D1 (en) 1998-05-07

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