EP0658228B1 - Mixtures of paper sizing agents - Google Patents

Mixtures of paper sizing agents Download PDF

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Publication number
EP0658228B1
EP0658228B1 EP93919142A EP93919142A EP0658228B1 EP 0658228 B1 EP0658228 B1 EP 0658228B1 EP 93919142 A EP93919142 A EP 93919142A EP 93919142 A EP93919142 A EP 93919142A EP 0658228 B1 EP0658228 B1 EP 0658228B1
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EP
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Prior art keywords
mixture
paper
weight
paper size
sizing
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EP93919142A
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German (de)
French (fr)
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EP0658228A1 (en
Inventor
Arnold De Clercq
Roland Ettl
Carlos Alberto Goncalves
Lothar Hoehr
Andreas Hohmann
Ulrich Riebeling
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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
    • D21H21/16—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
    • D21H17/03—Non-macromolecular organic compounds
    • D21H17/05—Non-macromolecular organic compounds containing elements other than carbon and hydrogen only
    • D21H17/17—Ketenes, e.g. ketene dimers
    • 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
    • D21H17/24—Polysaccharides
    • D21H17/28—Starch
    • D21H17/29—Starch cationic

Definitions

  • the invention relates to paper sizing mixtures of C 14 to C 22 alkyl diketene emulsions and glue-acting, finely divided, aqueous polymer dispersions, and to the use of the paper sizing mixtures as mass and surface sizing agents for paper.
  • alkyldiketenes having at least 6 carbon atoms in the molecule can be emulsified in water in the presence of cationic starch.
  • the relatively low concentrated alkyl diketene emulsions thus obtainable are used as bulk sizing agents for paper. Papers that are sized with these emulsions do not develop full sizing directly after the paper drying process, but only after the papers have been stored for one or more days at room temperature. In practice, however, sizing agents are required which fully develop the full sizing effect immediately after the sized paper has dried.
  • aqueous emulsions of fatty alkyl diketenes in a mixture with cationic condensates as sizing agents.
  • Suitable cationic condensates are, for example, reaction products of condensates of dicyandiamide or cyanamide and a bisaminopropylpiperazine crosslinked with epichlorohydrin or condensation products of epichlorohydrin and bisaminopropylpiperazine.
  • the cationic condensates cause an accelerated formation of the size of fatty alkyl diketenes, but they have the disadvantage that they adversely affect the paper whiteness.
  • Stabilized aqueous alkyldiketene emulsions are known from EP-A-0 437 764, which can contain up to 60% by weight of alkyldiketene emulsified and which contain long-chain fatty acid esters and / or urethanes as stabilizers.
  • a paper auxiliary which increases the strength of paper and at the same time sizes the paper.
  • This paper aid is based on a dispersion of a graft copolymer of styrene with alkyl acrylates on starch.
  • the graft copolymers are obtained by polymerizing styrene and an acrylic ester in an aqueous medium at from 20 to 100 ° C. to form an aqueous dispersion.
  • the degraded starches have viscosities ⁇ i of 0.04 - 0.50 dl / g.
  • EP-B-0 051 144 discloses finely divided, aqueous polymer dispersions which are a sizing agent for paper and are produced by a 2-stage polymerization.
  • a low molecular weight prepolymer is first prepared from a nitrogen-containing monomer, a nonionic, hydrophobic ethylenically unsaturated monomer and an ethylenically unsaturated carboxylic acid or maleic anhydride.
  • This prepolymer serves as a protective colloid for the subsequent second stage of the polymerization, in which nonionic, hydrophobic, ethylenically unsaturated monomers are polymerized in the manner of an emulsion polymerization in the presence of conventional amounts of water-soluble polymerization initiators.
  • cationic sizing agents for paper which are obtained by copolymerizing acrylonitrile and acrylic acid and / or methacrylic acid esters or monomer mixtures of styrene, acrylic acid and / or methacrylic acid esters and optionally acrylonitrile and / or methacrylonitrile can be obtained as an emulsifier in an aqueous solution of a cationic copolymer.
  • the cationic emulsifier is a terpolymer of N, N-dimethylaminoethyl acrylate and / or methacrylate, styrene and acrylonitrile.
  • paper sizing mixtures consist of emulsions of C 14 to C 20 dialkyl ketene and finely divided polymer dispersions containing copolymerized nitrogen-containing monomers, which are known from EP-B-0 051 144 mentioned above.
  • These sizing mixtures are prepared by combining a fatty alkyl diketene emulsion with the aqueous fine-particle polymer dispersion or are only formed in the paper stock before sheet formation by adding the emulsified fatty alkyl diketene and the fine-particle aqueous dispersion to the paper stock at the same time and thoroughly mixing the system.
  • Mere mixtures of fatty alkyl diketene emulsions and the cationic, finely divided aqueous polymer dispersions are not sufficiently stable in storage.
  • the invention has for its object to provide an improved paper sizing agent containing fatty alkyl diketenes, which results in sufficient instant sizing when used as a mass sizing agent and which does not impair the whiteness of the paper.
  • the object is achieved according to the invention with paper size mixtures if they are prepared by mixing an aqueous suspension of a digested cationic starch with finely divided, aqueous polymer dispersions which are a size for paper and emulsifying C 14 -C 22 -alkyldiketenes in this mixture at temperatures of at least 70 ° C.
  • the alkyldiketenes can optionally also be emulsified in the presence of fatty acid esters and urethanes, which are stabilizers for alkyldiketene emulsions.
  • Alkyldiketenes are known and commercially available. They are produced, for example, from the corresponding carboxylic acid chlorides by splitting off hydrogen chloride with tertiary amines.
  • the fatty alkyl diketenes can be characterized, for example, using the following formula: in which the substituents R 1 and R 2 are C 4 - to C 20 -alkyl.
  • the above-described alkyl diketenes or mixtures of the alkyl diketenes are emulsified in a mixture consisting of an aqueous suspension of digested cationic starch and finely divided aqueous polymer dispersions which are usually used alone as sizing agents for paper.
  • Suitable cationic starches are commercially available and are commonly used as protective colloids for the emulsification of alkyldiketenes.
  • Suitable cationic starches are known, for example, from US-A-3 130 118 given above. Based on fatty alkyl diketene, 1 to 20, preferably 2 to 7% by weight of protective colloid, preferably cationic starch, is usually required.
  • the compounds of formula I are known.
  • suitable compounds of the formula I with the meaning for R 1 and R 2 given above under (1) are stearic acid behenyl ester, behenic acid stearyl ester, myristic acid stearyl ester, myristic acid behenyl ester, palmitic acid behenyl ester and stearic acid isododecyl ester.
  • R 3 -O-CO-R 4 (II) are also suitable as stabilizers.
  • the substituents R 3 and R 4 mean either the same or different alkyl or alkenyl radicals, with at least one of the substituents R 3 and R 4 having at least 6 carbon atoms. These substituents can contain 2 to 22 carbon atoms. If the substituents R 3 and R 4 are alkenyl, the alkenyl group preferably contains at least 6 carbon atoms.
  • Examples of compounds of formula II are carbonic acid oleyl stearyl ester, carbonic acid behenyl oleylester, carbonic acid ethyl oleylester, carbonic acid diol ester, carbonic acid behenyl stearyl ester and carbonic acid (2-hexyldecanyl) oley ester.
  • the substituents R 5 , R 6 and R 7 are either the same or different. They can have 2 to 22 carbon atoms and stand for an alkyl or alkenyl group, at least one of the substituents R 5 , R 6 and R 7 containing at least 12 carbon atoms. If these substituents represent alkenyl groups, the number of carbon atoms in the alkenyl groups is generally at least 12.
  • Examples of compounds of the formula III are oleyl-N, N-distearyl urethane, palmityl-N, N-distearyl urethane, oleyl-N-palmityl N-stearyl urethane and behenyl-N, N-distearyl urethane.
  • the stabilizers are used in amounts of 0.1 to 20, preferably 3 to 6,% by weight, based on fatty alkyldiken.
  • a solution copolymer is first prepared in which the monomers of groups (1) and (2) and optionally (3) are copolymerized in a water-miscible organic solvent.
  • Suitable solvents are, for example, C 1 to C 3 carboxylic acids, such as formic acid, acetic acid and propionic acid, or C 1 to C 4 alcohols, such as methanol, ethanol, n-propanol or isopropanol, and ketones such as acetone.
  • the group (1) monomers used are preferably dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, dimethylaminopropyl methacrylate and dimethylaminopropyl acrylate.
  • the monomers of group (1) are preferably used in protonated or quaternized form. Suitable quaternizing agents are, for example, methyl chloride, dimethyl sulfate or benzyl chloride.
  • the group (2) monomers used are nonionic, hydrophobic, ethylenically unsaturated compounds which, when polymerized on their own, form hydrophobic polymers.
  • styrene methylstyrene
  • C 1 - to C 18 -alkyl esters of acrylic acid or methacrylic acid for example methyl acrylate, ethyl acrylate, N-propyl acrylate, isopropyl acrylate, n-butyl acrylate, tert-butyl acrylate and isobutyl acrylate as well as isobutyl methacrylate, n-butyl methacrylate and n-butyl methacrylate .
  • Acrylonitrile, methacrylonitrile, vinyl acetate, vinyl propionate and vinyl butyrate are also suitable.
  • the solution copolymers used as emulsifiers can optionally also contain copolymerized monomers of group (3), for example monoethylenically unsaturated C 3 to C 5 carboxylic acids or their anhydrides, for example acrylic acid, methacrylic acid, itaconic acid, maleic acid, maleic anhydride or itaconic anhydride.
  • group (3) for example monoethylenically unsaturated C 3 to C 5 carboxylic acids or their anhydrides, for example acrylic acid, methacrylic acid, itaconic acid, maleic acid, maleic anhydride or itaconic anhydride.
  • the molar ratio of (1): (2): (3) is 1: 2.5 to 10: 0 to 1.5.
  • the copolymer solutions obtained in this way are diluted with water and in this form serve as a protective colloid for the polymerization of the above-mentioned monomer mixtures of components (a) and (b) and, if appropriate, (c).
  • Monomers of group (a) are styrene, acrylonitrile, methacrylonitrile or mixtures of styrene and acrylonitrile or of styrene and methacrylonitrile.
  • the monomers of group (b) used are acrylic acid and / or methacrylic acid esters of C 1 to C 18 alcohols and / or vinyl esters of saturated C 2 to C 4 carboxylic acids. This group of monomers corresponds to the monomers of group (2), which has already been described above.
  • Preferably used as the monomer of group (b) are butyl acrylate and butyl methacrylate, for example isobutyl acrylate, n-butyl acrylate and isobutyl methacrylate.
  • Monomers of group (c) are, for example, C 3 -C 5 -monoethylenically unsaturated carboxylic acids, acrylamidomethylpropanesulfonic acid, sodium vinyl sulfonate, vinylimidazole, N-vinylformamide, acrylamide, methacrylamide and N-vinylimidazoline.
  • 1 to 32 parts by weight of a monomer mixture of components (a) to (c) are used per 1 part by weight of the copolymer.
  • the monomers of components (a) and (b) can be copolymerized in any ratio, for example in the molar ratio 0.1: 1 to 1: 0.1.
  • the monomers of group (c) are used to modify the properties of the copolymers.
  • the degraded starches act as emulsifiers in the copolymerization of the monomers (a) to (c) in an aqueous medium in the manner of an emulsion polymerization.
  • the monomers are copolymerized in an aqueous solution which contains 1 to 21, preferably 3 to 15% by weight of degraded starch. In 100 parts by weight of such a solution, 10 to 140, preferably 40 to 100 parts by weight of the monomer mixture of (a) and (b) and optionally (c) are usually polymerized.
  • the diameter of the dispersed polymer particles is 50 to 350, preferably 100 to 250 nm.
  • Also suitable as monomer of group (b) are vinyl esters of C 2 - to C 4 -saturated carboxylic acids.
  • Suitable monomers of group (c) are, for example, acrylamide, methacrylamide, stearyl acrylate, stearyl methacrylate, palmitylacrylate, acrylic acid, methacrylic acid, maleic acid, maleic anhydride, itaconic acid, vinylsulfonic acid, acrylamidopropanesulfonic acid and acrylic and methacrylic acid esters of amino alcohols, for example dimethylaminoethylamylamethylataminate, dimethylaminoethyl amyl acrylate dimethyl methylethyl amyl acrylate dimethyl methylethyl amyl acrylate,
  • the paper sizing agent mixtures according to the invention are prepared by first mixing an aqueous suspension of a digested cationic starch with at least one of the abovementioned fine-particle aqueous polymer dispersion, which is a sizing agent for paper.
  • a sizing agent for paper One can, for example, start from a 0.5 to 5% by weight aqueous suspension of a cationic starch, which is converted in a known manner into a water-soluble form, for example by heating to the gelatinization temperature or by heating in the presence of an acid, for example Sulfuric acid.
  • the aqueous solution obtained is then mixed with the finely divided aqueous polymer dispersion or a mixture of such dispersions and heated to a temperature of at least 70 ° C.
  • the temperature of the mixture can be raised to the boiling point of the mixture.
  • C 14 -C 22 -Alkyldiketenes are then emulsified into the mixture of digested cationic starch and finely divided aqueous polymer suspension heated to at least 70 ° C.
  • the alkyldiketenes are added in molten form to the mixture of digested starch and aqueous polymer dispersions and emulsified under the action of shear forces, for example the emulsification is carried out in so-called homogenizers which work according to the high pressure relaxation principle.
  • particularly stable storage sizing mixtures are obtained if the solid fatty alkyl diketene and one of the stabilizers indicated above, e.g. Stearic acid behenyl ester or behenyl acid oleylester, mixed and added in the form of a melt to a finely divided, aqueous polymer dispersion heated to 75 to 95 ° C., which is a sizing agent for paper and which contains a digested cationic starch, and homogenizes this mixture under the action of shear forces. After the homogenization step, the paper sizing mixture obtained is cooled to ambient temperature.
  • the stabilizers indicated above e.g. Stearic acid behenyl ester or behenyl acid oleylester
  • the pH of the alkyl diketene emulsion / polymer dispersion mixture is usually in the range from 2.0 to 4.0 and is preferably 3.0. In the preparation of this mixture it is possible, if appropriate, to add further auxiliaries, such as lignin sulfonate, formalin or propionic acid.
  • the finished paper size mixtures contain 10 to 80, preferably 30 to 60% by weight of fatty alkyl diketene.
  • the content of the paper sizing agent mixtures in finely divided, aqueous polymer dispersions is 20 to 90, preferably 30 to 70, in each case based on the solids.
  • the paper sizing mixtures described above are used as pulp and surface sizing for paper, with use as a bulk sizing agent being preferred.
  • the aqueous polymer sizing mixtures diluted by adding water to concentrations of 0.08 to 0.5% by weight, based on alkyldiketene.
  • the paper sizing agent mixtures according to the invention are stable on storage, while mixtures which are merely by combining finely divided aqueous polymer dispersions which are sizing agents for paper with emulsions of fatty alkyldiketenes which have been emulsified as protective colloids with the aid of digested cationic starch do not have sufficient stability.
  • the latter mixtures either tend to segregate or are stored after a short storage, e.g. after 8 days, solid and are then no longer usable for the intended purpose.
  • the parts given in the examples are parts by weight, the percentages relate to the weight of the emulsions produced. They have been chosen so that the amount of alkyl diketene added is constant in relation to atro material.
  • the degree of sizing of the papers was determined using the Cobb value according to DIN 53 132.
  • the following material model was used to test the sizing effect:
  • the sheets are dried on a steam-heated drying cylinder at 90 ° C to a residual moisture of 10-15%;
  • the final sizing test is carried out 1 day after the sheets have been produced and dried at 90 ° C. to a residual moisture of approx. 6% and then stored at 23 ° C. in a relative air humidity of 50%.
  • the papers produced have a basis weight of 80 g / m 2 and an ash content of approx. 17%.
  • the whiteness of the papers was determined according to DIN 53 145.
  • Starch A is a degraded cationic potato starch with a viscosity ⁇ i of 0.47 dl / g, a degree of substitution of 0.015-COOH and 0.027 N mol / mol glucose units and a solids content of 83%.
  • Starch B is a degraded, cationic potato starch with a viscosity ⁇ i of 1.16, a degree of substitution of 0.07 N mol / mol glucose units and a solids content of 83%.
  • a mixture of 20 parts (1.92 mol) of styrene, 7 parts (0.41 mol) of dimethylaminopropyl methacrylamide, 3.5 parts (0.486 mol) of acrylic acid and 10 parts of acetic acid was pumped into a 90 ° C. over the course of 1 hour C pumped heated kettle. Simultaneously and also within 1 hour, 2 parts of azoisobutyronitrile and 10 parts of acetic acid were added using another metering device. The mixture was heated to a temperature of 90 ° C. for 30 minutes and then dissolved in 180 parts of water.
  • a 2.36% aqueous suspension of a commercially available cationic starch (degree of substitution 0.02) is prepared by suspending the required amount of starch in water and then adding enough sulfuric acid that the pH is 2.5. The starch suspension is then heated to a temperature of 95 ° C. within 1 hour, the reaction mixture is stirred at this temperature for 1 hour and the aqueous solution thus obtained is allowed to cool.
  • Example 1 is repeated with the exception that polymer dispersion 1 is grafted with ethyleneimine and with a bifunctional crosslinker by a condensation product of adipic acid and diethylenetriamine known as a promoter for alkyldiketene is implemented, which is obtainable by reaction of epichlorohydrin with 34 ethylene oxide units containing polyethylene glycol.
  • Example 1 was repeated with the changes that a 2.66% aqueous suspension of a commercial cationic starch (degree of substitution 0.02) was prepared, to 80 parts of the above-described 2.66% aqueous starch suspension, 20 parts of polymer dispersion 1 were added and the mixture was stirred at 85 ° C for 10 minutes. This unlocked the strength.
  • Example 1 was repeated with the changes that a 5.13% strength aqueous suspension of a commercially available cationic starch (degree of substitution 0.02) was prepared, 50 parts of this suspension, 50 parts of polymer dispersion 1 were added, and the starch was added for 10 minutes Heat in a mixture with polymer dispersion 1 at a temperature of 85 ° C.
  • Example 1 was repeated with the changes that a 5.13% strength aqueous suspension of a commercially available cationic starch (degree of substitution 0.02) was prepared, mixed with 50 parts of polymer dispersion 2 and the starch was heated by heating the mixture to 85 ° C. for a total Unlocked 10 minutes. A mixture of 20 parts of stearyl diketene and 2 parts of stearic acid oleate ester and then heated to 90 ° C. was then added to 78 parts of the mixture of digested starch and polymer dispersion 2 thus obtained emulsified the melt therein as indicated in Example 1.
  • Example 1 78 parts of a 2.56% strength aqueous solution of a digested commercially available cationic starch (degree of substitution 0.02) was heated to a temperature of 85 ° C. and at this temperature with a melt of 20 parts of stearyl diketene and 2 parts of stearic acid oleate ester according to that in Example 1 specified method brought together and thereby emulsified.
  • the size mixture thus obtained was tested for its effectiveness on the fabric model described above. Based on dry paper stock, 0.5% of the sizing agent was used. Table 2 shows the value for the final sizing obtained.

Abstract

Mixtures of paper sizing agents are produced by mixing an aqueous suspension of a hydrolyzed cationic starch with fine particle aqueous polymer dispersions which constitute a paper sizing agent, and by emulsifying C14-C22-alkyl diketens in said mixture at temperatures of at least 70 °C. The mixtures are used for paper beater and surface sizing.

Description

Die Erfindung betrifft Papierleimungsmittelmischungen aus C14- bis C22-Alkyldiketenemulsionen und leimend wirkenden feinteiligen, wäßrigen Polymerdispersionen sowie die Verwendung der Papierleimungsmittelmischungen als Masse- und Oberflächenleimungsmittel für Papier.The invention relates to paper sizing mixtures of C 14 to C 22 alkyl diketene emulsions and glue-acting, finely divided, aqueous polymer dispersions, and to the use of the paper sizing mixtures as mass and surface sizing agents for paper.

Aus der US-A-3 130 118 ist bekannt, daß man Alkyldiketene mit mindestens 6 Kohlenstoffatomen im Molekül in Gegenwart von kationischer Stärke in Wasser emulgieren kann. Die so erhältlichen relativ niedrig konzentrierten Alkyldiketenemulsionen werden als Masseleimungsmittel für Papier verwendet. Papiere, die mit diesen Emulsionen in der Masse geleimt sind, entwickeln die volle Leimung nicht direkt nach dem Papiertrocknungsprozeß, sondern erst nach einer ein- oder mehrtägigen Lagerung der Papiere bei Raumtemperatur. In der Praxis werden jedoch Leimungsmittel gefordert, die die volle Leimungswirkung unmittelbar nach dem Trocknen des geleimten Papiers vollständig ausbilden.From US-A-3 130 118 it is known that alkyldiketenes having at least 6 carbon atoms in the molecule can be emulsified in water in the presence of cationic starch. The relatively low concentrated alkyl diketene emulsions thus obtainable are used as bulk sizing agents for paper. Papers that are sized with these emulsions do not develop full sizing directly after the paper drying process, but only after the papers have been stored for one or more days at room temperature. In practice, however, sizing agents are required which fully develop the full sizing effect immediately after the sized paper has dried.

Aus der DE-A-3 000 502 ist bekannt, wäßrige Emulsionen von Fettalkyldiketenen in Mischung mit kationischen Kondensaten als Leimungsmittel zu verwenden. Geeignete kationische Kondensate sind beispielsweise mit Epichlorhydrin vernetzte Umsetzungsprodukte von Kondensaten aus Dicyandiamid oder Cyanamid und einem Bisaminopropylpiperazin oder Kondensationsprodukte aus Epichlorhydrin und Bisaminopropylpiperazin. Die kationischen Kondensate bewirken zwar eine beschleunigte Ausbildung der Leimung von Fettalkyldiketenen, jedoch haben sie den Nachteil, daß sie die Papierweiße nachteilig beeinflussen.From DE-A-3 000 502 it is known to use aqueous emulsions of fatty alkyl diketenes in a mixture with cationic condensates as sizing agents. Suitable cationic condensates are, for example, reaction products of condensates of dicyandiamide or cyanamide and a bisaminopropylpiperazine crosslinked with epichlorohydrin or condensation products of epichlorohydrin and bisaminopropylpiperazine. The cationic condensates cause an accelerated formation of the size of fatty alkyl diketenes, but they have the disadvantage that they adversely affect the paper whiteness.

Aus der DE-A-3 316 179 ist bekannt, Emulsionen von Fettalkyldiketenen zusammen mit Polyethyleniminen und/oder wasserlöslichen Kondensationsprodukten auf Basis wasserlöslicher mit Ethylenimin gepfropfter und anschließend mit Epichlorhydrin vernetzter Polyamidoamine als Leimungsmittel für Papier zu verwenden. Auch bei Verwendung dieser Leimungsmittelmischungen bildet sich die Diketenleimung innerhalb kurzer Zeit aus. Die kationischen Leimungsmittelbeschleuniger für Fettalkyldiketene reagieren jedoch sehr empfindlich auf Störstoffe, die sich bei dem Papierherstellungsprozeß in den Papierfabriken aufgrund der teilweise oder vollständig geschlossenen Wasserkreisläufe anreichern. Zudem haben sie einen nachteiligen Einfluß auf die Papierweiße.From DE-A-3 316 179 it is known to use emulsions of fatty alkyl diketenes together with polyethyleneimines and / or water-soluble condensation products based on water-soluble polyamidoamines grafted with ethyleneimine and then crosslinked with epichlorohydrin as paper sizing agents. When using these sizing mixtures, the diketene sizing is formed within a short time. However, the cationic sizing accelerators for fatty alkyl diketenes are very sensitive to contaminants that accumulate in the paper manufacturing process in the paper mills due to the partially or completely closed water cycles. They also have an adverse impact on paper whiteness.

Aus der EP-A-0 437 764 sind stabilisierte wäßrige Alkyldiketenemulsionen bekannt, die bis zu 60 Gew.-% Alkyldiketen emulgiert enthalten können und die als Stabilisator langkettige Fettsäureester und/oder Urethane enthalten.Stabilized aqueous alkyldiketene emulsions are known from EP-A-0 437 764, which can contain up to 60% by weight of alkyldiketene emulsified and which contain long-chain fatty acid esters and / or urethanes as stabilizers.

Aus der JP-A-58/115 196 ist ein Papierhilfsmittel bekannt, daß die Festigkeit von Papier erhöht und gleichzeitig das Papier leimt. Dieses Papierhilfsmittel beruht auf einer Dispersion eines Pfropfcopolymerisates von Styrol mit Alkylacrylaten auf Stärke. Die Pfropfcopolymerisate werden dadurch erhalten, daß man Styrol und einen Acrylester in wäßrigem Medium bei Temperaturen von 20 bis 100°C unter Bildung einer wäßrigen Dispersion polymerisiert.From JP-A-58/115 196 a paper auxiliary is known which increases the strength of paper and at the same time sizes the paper. This paper aid is based on a dispersion of a graft copolymer of styrene with alkyl acrylates on starch. The graft copolymers are obtained by polymerizing styrene and an acrylic ester in an aqueous medium at from 20 to 100 ° C. to form an aqueous dispersion.

Aus der EP-B-0 257 412 sowie der EP-B-0 267 770 sind Leimungsmittel für Papier auf Basis feinteiliger, wäßriger Dispersionen von Copolymerisaten bekannt, die durch Copolymerisieren von

  • (a) 20 bis 65 Gew.-% Acrylnitril und/oder Methacrylnitril,
  • (b) 80 bis 35 Gew.-% eines Acrylsäureesters eines einwertigen, gesättigten C3- bis C8-Alkohols und
  • (c) 0 bis 10 Gew.-% anderen monoethylenisch ungesättigten copolymerisierbaren Monomeren
EP-B-0 257 412 and EP-B-0 267 770 disclose sizing agents for paper based on finely divided, aqueous dispersions of copolymers which are obtained by copolymerizing
  • (a) 20 to 65% by weight of acrylonitrile and / or methacrylonitrile,
  • (b) 80 to 35% by weight of an acrylic acid ester of a monohydric, saturated C 3 to C 8 alcohol and
  • (c) 0 to 10% by weight of other monoethylenically unsaturated copolymerizable monomers

nach Art einer Emulsionspolymerisation in einer wäßrigen Lösung, die eine abgebaute Stärke enthält, in Gegenwart von Peroxidgruppen enthaltenden Initiatoren erhältlich sind. Die abgebauten Stärken haben Viskositäten ηi von 0,04 - 0,50 dl/g.can be obtained in the manner of an emulsion polymerization in an aqueous solution which contains a degraded starch in the presence of initiators containing peroxide groups. The degraded starches have viscosities η i of 0.04 - 0.50 dl / g.

Aus der EP-B-0 051 144 sind feinteilige, wäßrige Polymerdispersionen bekannt, die ein Leimungsmittel für Papier sind und durch eine 2-stufige Polymerisation hergestellt werden. In der 1. Stufe der Polymerisation wird zunächst ein niedrigmolekulares Vorpolymerisat aus einem stickstoffhaltigen Monomeren, einem nichtionischen, hydrophoben ethylenisch ungesättigten Monomeren und einer ethylenisch ungesättigten Carbonsäure oder Maleinsäureanhydrid hergestellt. Dieses Vorpolymerisat dient als Schutzkolloide für die nachfolgende 2. Stufe der Polymerisation, in der man nichtionische hydrophobe ethylenisch ungesättigte Monomere nach Art einer Emulsionspolymerisation in Gegenwart üblicher Mengen wasserlöslicher Polymerisationsinitiatoren polymerisiert.EP-B-0 051 144 discloses finely divided, aqueous polymer dispersions which are a sizing agent for paper and are produced by a 2-stage polymerization. In the first stage of the polymerization, a low molecular weight prepolymer is first prepared from a nitrogen-containing monomer, a nonionic, hydrophobic ethylenically unsaturated monomer and an ethylenically unsaturated carboxylic acid or maleic anhydride. This prepolymer serves as a protective colloid for the subsequent second stage of the polymerization, in which nonionic, hydrophobic, ethylenically unsaturated monomers are polymerized in the manner of an emulsion polymerization in the presence of conventional amounts of water-soluble polymerization initiators.

Aus der EP-A-0 058 313 und der EP-A-0 150 003 sind kationische Leimungsmittel für Papier bekannt, die durch Copolymerisieren von Acrylnitril und Acrylsäure- und/oder Methacrylsäureestern oder von Monomergemischen aus Styrol, Acrylsäure- und/oder Methacrylsäureestern und ggf. Acrylnitril und/oder Methacrylnitril in einer wäßrigen Lösung eines kationischen Copolymerisats als Emulgator erhalten werden. Der kationische Emulgator ist dabei ein Terpolymerisat aus N,N-Dimethylaminoethylacrylat und/oder -methacrylat, Styrol und Acrylnitril.From EP-A-0 058 313 and EP-A-0 150 003 cationic sizing agents for paper are known which are obtained by copolymerizing acrylonitrile and acrylic acid and / or methacrylic acid esters or monomer mixtures of styrene, acrylic acid and / or methacrylic acid esters and optionally acrylonitrile and / or methacrylonitrile can be obtained as an emulsifier in an aqueous solution of a cationic copolymer. The cationic emulsifier is a terpolymer of N, N-dimethylaminoethyl acrylate and / or methacrylate, styrene and acrylonitrile.

Die oben beschriebene feinteiligen, wäßrigen Polymerdispersionen haben bei Verwendung als Leimungsmittel zwar eine ausgezeichnete Sofortleimung, jedoch sind die erforderlichen anzuwendenden Mengen für eine Volleimung des Papiers erheblich höher als bei Leimungsmitteln, die aus Fettalkyldiketenemulsionen bestehen oder Fettalkyldiketene in emulgierter Form enthalten.Although the finely divided, aqueous polymer dispersions described above have excellent instant sizing when used as sizing agents, the amounts required for fully sizing the paper are considerably higher than for sizing agents which consist of fatty alkyl diketene emulsions or contain fatty alkyl diketenes in emulsified form.

Aus der DE-A-3 235 529 sind Papierleimungsmittelmischungen bekannt, die aus Emulsionen aus C14- bis C20-Dialkylketenen und feinteiligen, stickstoffhaltigen Monomere einpolymerisiert enthaltenden Polymerdispersionen bestehen, die aus der obengenannten EP-B-0 051 144 bekannt sind. Diese Leimungsmittelmischungen werden durch Vereinigen einer Fettalkyldiketenemulsion mit der wäßrigen feinteiligen Polymerdispersion hergestellt oder erst im Papierstoff vor der Blattbildung dadurch gebildet, daß man das emulgierte Fettalkyldiketen und die feinteilige wäßrige Dispersion gleichzeitig zum Papierstoff zugibt und das System gut durchmischt. Bloße Mischungen aus Fettalkyldiketenemulsionen und den kationischen feinteiligen wäßrigen Polymerdispersionen sind nicht ausreichend lagerstabil.From DE-A-3 235 529 paper sizing mixtures are known which consist of emulsions of C 14 to C 20 dialkyl ketene and finely divided polymer dispersions containing copolymerized nitrogen-containing monomers, which are known from EP-B-0 051 144 mentioned above. These sizing mixtures are prepared by combining a fatty alkyl diketene emulsion with the aqueous fine-particle polymer dispersion or are only formed in the paper stock before sheet formation by adding the emulsified fatty alkyl diketene and the fine-particle aqueous dispersion to the paper stock at the same time and thoroughly mixing the system. Mere mixtures of fatty alkyl diketene emulsions and the cationic, finely divided aqueous polymer dispersions are not sufficiently stable in storage.

Der Erfindung liegt die Aufgabe zugrunde, ein verbessertes Papierleimungsmittel mit einem Gehalt an Fettalkyldiketenen zur Verfügung zu stellen, das bei der Anwendung als Masseleimungsmittel eine ausreichende Sofortleimung ergibt und das nicht zu einer Beeinträchtigung der Weiße des Papiers führt.The invention has for its object to provide an improved paper sizing agent containing fatty alkyl diketenes, which results in sufficient instant sizing when used as a mass sizing agent and which does not impair the whiteness of the paper.

Die Aufgabe wird erfindungsgemäß mit Papierleimungsmittelmischungen gelöst, wenn man sie herstellt durch Mischen einer wäßrigen Suspension einer aufgeschlossenen kationischen Stärke mit feinteiligen, wäßrigen Polymerdispersionen, die ein Leimungsmittel für Papier sind und Emulgieren von C14- bis C22-Alkyldiketenen in dieser Mischung bei Temperaturen von mindestens 70°C. Das Emulgieren der Alkyldiketene kann ggf. zusätzlich noch in Gegenwart von Fettsäureestern und Urethanen erfolgen, die Stabilisatoren für Alkyldiketenemulsionen sind.The object is achieved according to the invention with paper size mixtures if they are prepared by mixing an aqueous suspension of a digested cationic starch with finely divided, aqueous polymer dispersions which are a size for paper and emulsifying C 14 -C 22 -alkyldiketenes in this mixture at temperatures of at least 70 ° C. The alkyldiketenes can optionally also be emulsified in the presence of fatty acid esters and urethanes, which are stabilizers for alkyldiketene emulsions.

Alkyldiketene sind bekannt und im Handel erhältlich. Sie werden beispielsweise aus den entsprechenden Carbonsäurechloriden durch Abspaltung von Chlorwasserstoff mit tertiären Aminen hergestellt.Alkyldiketenes are known and commercially available. They are produced, for example, from the corresponding carboxylic acid chlorides by splitting off hydrogen chloride with tertiary amines.

Die Fettalkyldiketene können beispielsweise mit Hilfe folgender Formel charakterisiert werden:

Figure imgb0001
in der die Substituenten R1 und R2 für C4- bis C20-Alkyl stehen.The fatty alkyl diketenes can be characterized, for example, using the following formula:
Figure imgb0001
 in which the substituents R 1 and R 2 are C 4 - to C 20 -alkyl.

Um Papierleimungsmittelmischungen gemäß Erfindung herzustellen, werden die obenbeschriebenen Alkyldiketene oder Mischungen der Alkyldiketene in einer Mischung emulgiert, die aus einer wäßrigen Suspension einer aufgeschlossenen kationischen Stärke und feinteiligen wäßrigen Polymerdispersionen besteht, die üblicherweise allein als Leimungsmittel für Papier verwendet werden. Geeignete kationische Stärken sind im Handel erhältlich und werden üblicherweise als Schutzkolloid für das Emulgieren von Alkyldiketenen verwendet. Geeignete kationische Stärken sind beispielsweise aus der obenangegebenen US-A-3 130 118 bekannt. Bezogen auf Fettalkyldiketen benötigt man üblicherweise 1 bis 20, vorzugsweise 2 bis 7 Gew.-% an Schutzkolloid, vorzugsweise kationischer Stärke.To produce paper sizing mixtures according to the invention, the above-described alkyl diketenes or mixtures of the alkyl diketenes are emulsified in a mixture consisting of an aqueous suspension of digested cationic starch and finely divided aqueous polymer dispersions which are usually used alone as sizing agents for paper. Suitable cationic starches are commercially available and are commonly used as protective colloids for the emulsification of alkyldiketenes. Suitable cationic starches are known, for example, from US-A-3 130 118 given above. Based on fatty alkyl diketene, 1 to 20, preferably 2 to 7% by weight of protective colloid, preferably cationic starch, is usually required.

Um besonders hoch konzentrierte Alkyldiketenemulsionen in der Mischung aus Stärke und feinteiligen, wäßrigen Polymerdispersionen, die Leimungsmittel für Papier sind, herzustellen, führt man das Emulgieren der Alkyldiketene zusätzlich in Gegenwart von Stabilisatoren durch. Geeignete Stabilisatoren sind aus der EP-A-0 437 764 bekannt. Hierbei handelt es sich beispielsweise um Ester der Formel

Figure imgb0002
in der R1 und R2

  • (1) C14- bis C22-Alkyl bedeuten, wobei sich R1 und R2 um mindestens 4 C-Atome in der Alkylkette unterscheiden,
  • (2)

            R1 = C14- bis C22-Alkyl



            R2 = C14- bis C22-Akenyl

  • (3)

            R1 = C14- bis C22-Alkenyl



            R2 = C14- bis C22-Akyl oder

  • (4) R1 und R2 gleiche oder verschiedene C14- bis C22-Alkenyl bedeuten.
In order to produce particularly highly concentrated alkyldiketene emulsions in the mixture of starch and finely divided, aqueous polymer dispersions which are sizing agents for paper, the alkyldiketenes are additionally emulsified in the presence of stabilizers. Suitable stabilizers are known from EP-A-0 437 764. These are, for example, esters of the formula
Figure imgb0002
 in the R 1 and R 2
  • (1) C 14 -C 22 -alkyl, where R 1 and R 2 differ by at least 4 C atoms in the alkyl chain,
  • (2)

    R 1 = C 14 to C 22 alkyl



    R 2 = C 14 to C 22 akenyl

  • (3)

    R 1 = C 14 to C 22 alkenyl



    R 2 = C 14 to C 22 alkyl or

  • (4) R 1 and R 2 are identical or different C 14 to C 22 alkenyl.

Die Verbindungen der Formel I sind bekannt. Beispiele für geeignete Verbindungen der Formel I mit der oben unter (1) angegebenen Bedeutung für R1 und R2 sind Stearinsäurebehenylester, Behensäurestearylester, Myristinsäurestearylester, Myristinsäurebehenylester, Palmitinsäurebehenylester und Stearinsäurisododecylester.The compounds of formula I are known. Examples of suitable compounds of the formula I with the meaning for R 1 and R 2 given above under (1) are stearic acid behenyl ester, behenic acid stearyl ester, myristic acid stearyl ester, myristic acid behenyl ester, palmitic acid behenyl ester and stearic acid isododecyl ester.

Als Stabilisatoren eignen sich außerdem Verbindungen der Formel R3-O-CO-R4 (II). Die Substituenten R3 und R4 bedeuten entweder gleiche oder verschiedene Alkyl- oder Alkenylreste, wobei mindestens einer der Substituenten R3 und R4 mindestens 6 C-Atome aufweist. Diese Substituenten können 2 bis 22 C-Atome enthalten. Sofern die Substituenten R3 und R4 Alkenyl bedeuten, enthält die Alkenylgruppe vorzugsweise mindestens 6 C-Atome. Beispiele für Verbindungen der Formel II sind Kohlensäureoleylstearylester, Kohlensäurebehenyloleylester, Kohlensäureethyloleylester, Kohlensäuredioleylester, Kohlensäurebehenylstearylester und Kohlensäure-(2-hexyldecanyl)-oleylester.Compounds of the formula R 3 -O-CO-R 4 (II) are also suitable as stabilizers. The substituents R 3 and R 4 mean either the same or different alkyl or alkenyl radicals, with at least one of the substituents R 3 and R 4 having at least 6 carbon atoms. These substituents can contain 2 to 22 carbon atoms. If the substituents R 3 and R 4 are alkenyl, the alkenyl group preferably contains at least 6 carbon atoms. Examples of compounds of formula II are carbonic acid oleyl stearyl ester, carbonic acid behenyl oleylester, carbonic acid ethyl oleylester, carbonic acid diol ester, carbonic acid behenyl stearyl ester and carbonic acid (2-hexyldecanyl) oley ester.

Auch die Verbindungen der Formel

Figure imgb0003
sind bekannte Stoffe. Die Substituenten R5, R6 und R7 sind entweder gleich oder verschieden. Sie können 2 bis 22 C-Atome aufweisen und stehen für eine Alkyl- oder Alkenylgruppe, wobei mindestens einer der Substitutenten R5, R6 und R7 mindestens 12 C-Atome enthält. Sofern diese Substituenten für Alkenylgruppen stehen, beträgt die Anzahl der C-Atome der Alkenylgruppen im allgemeinen mindestens 12. Beispiele für Verbindugnen der Formel III sind Oleyl-N,N-distearylurethan, Palmityl-N,N-distearylurethan, Oleyl-N-palmityl-N-stearylurethan und Behenyl-N,N-distearylurethan.Also the compounds of the formula
Figure imgb0003
 are known substances. The substituents R 5 , R 6 and R 7 are either the same or different. They can have 2 to 22 carbon atoms and stand for an alkyl or alkenyl group, at least one of the substituents R 5 , R 6 and R 7 containing at least 12 carbon atoms. If these substituents represent alkenyl groups, the number of carbon atoms in the alkenyl groups is generally at least 12. Examples of compounds of the formula III are oleyl-N, N-distearyl urethane, palmityl-N, N-distearyl urethane, oleyl-N-palmityl N-stearyl urethane and behenyl-N, N-distearyl urethane.

Die Stabilisatoren werden, bezogen auf Fettalkyldiken in Mengen von 0,1 bis 20, vorzugsweise 3 bis 6 Gew.-% eingesetzt.The stabilizers are used in amounts of 0.1 to 20, preferably 3 to 6,% by weight, based on fatty alkyldiken.

Feinteilige, wäßrige Polymerdispersionen, die ein Leimungsmittel für Papier sind, sind beispielsweise aus der EP-B-0 051 144, der EP-B-0 257 412, der EP-B-0 276 770, der EP-B-0 058 313 und der EP-B-0 150 003 bekannt. Solche als Papierleimungsmittel wirkenden Polymerdispersionen sind beispielsweise dadurch erhältlich, daß man 1 bis 32 Gew.-Teile einer Mischung aus

  • (a) Styrol, Acrylnitril und/oder Methacrylnitril,
  • (b) Acrylsäure- und/oder Methacrylsäureester von C1- bis C18-Alkoholen und/oder Vinylester von gesättigtem C2- bis C4-Carbonsäuren und ggf.
  • (c) anderen monoethylenisch ungesättigten copolymerisierbaren Monomeren
in wäßriger Lösung in Gegenwart von 1 Gew.-Teil eines Lösungscopolymerisats aus
  • (1) Di-C1- bis C4-Alkylamino-C2- bis C4-Alkyl(meth)acrylaten, die ggf. protoniert oder quaterniert sein können,
  • (2) nichtionischen, hydrophoben, ethylenisch ungesättigten Monomeren, bei diesen Monomeren, wenn sie für sich alleine polymerisiert werden, hydrophobe Polymerisate bilden und ggf.
  • (3) monoethylenisch ungesättigten C3- bis C5-Carbonsäuren oder ihren Anhydriden, wobei das Molverhältnis von (1) : (2) : (3) = 1 : 2,5 bis 10 : 0 bis 1,5 beträgt, copolymerisiert.
Fine-particle, aqueous polymer dispersions which are a sizing agent for paper are, for example, from EP-B-0 051 144, EP-B-0 257 412, EP-B-0 276 770, EP-B-0 058 313 and EP-B-0 150 003. Such polymer dispersions which act as paper sizing agents can be obtained, for example, by mixing 1 to 32 parts by weight of a mixture
  • (a) styrene, acrylonitrile and / or methacrylonitrile,
  • (b) acrylic and / or methacrylic acid esters of C 1 to C 18 alcohols and / or vinyl esters of saturated C 2 to C 4 carboxylic acids and optionally
  • (c) other monoethylenically unsaturated copolymerizable monomers
in aqueous solution in the presence of 1 part by weight of a solution copolymer
  • (1) di-C 1 -C 4 -alkylamino-C 2 -C 4 -alkyl (meth) acrylates, which can optionally be protonated or quaternized,
  • (2) nonionic, hydrophobic, ethylenically unsaturated monomers, in the case of these monomers, if they are polymerized on their own, form hydrophobic polymers and, if appropriate,
  • (3) monoethylenically unsaturated C 3 to C 5 carboxylic acids or their anhydrides, the molar ratio of (1): (2): (3) = 1: 2.5 to 10: 0 to 1.5 being copolymerized.

Man stellt zunächst ein Lösungscopolymerisat her, in dem man die Monomeren der Gruppen (1) und (2) sowie ggf. (3) in einem mit Wasser mischbaren organischen Lösemittel copolymerisiert. Geeignete Lösemittel sind beispielsweise C1- bis C3-Carbonsäuren, wie Ameisensäure, Essigsäure und Propionsäure oder C1- bis C4-Alkohole, wie Methanol, Ethanol, n-Propanol oder Isopropanol und Ketone wie Aceton. Als Monomere der Gruppe (1) verwendet man vorzugsweise Dimethylaminoethylacrylat, Dimethylaminoethylmethacrylat, Dimethylaminopropylmethacrylat und Dimethylaminopropylacrylat. Die Monomeren der Gruppe (1) werden vorzugsweise in protonierter oder in quaternierter Form eingesetzt. Geeignete Quaternierungsmittel sind beispielsweise Methylchlorid, Dimethylsulfat oder Benzylchlorid.A solution copolymer is first prepared in which the monomers of groups (1) and (2) and optionally (3) are copolymerized in a water-miscible organic solvent. Suitable solvents are, for example, C 1 to C 3 carboxylic acids, such as formic acid, acetic acid and propionic acid, or C 1 to C 4 alcohols, such as methanol, ethanol, n-propanol or isopropanol, and ketones such as acetone. The group (1) monomers used are preferably dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, dimethylaminopropyl methacrylate and dimethylaminopropyl acrylate. The monomers of group (1) are preferably used in protonated or quaternized form. Suitable quaternizing agents are, for example, methyl chloride, dimethyl sulfate or benzyl chloride.

Als Monomere der Gruppe (2) verwendet man nichtionische, hydrophobe, ethylenisch ungesättigte Verbindungen, die, wenn sie für sich allein polymerisiert werden, hydrophobe Polymerisate bilden.The group (2) monomers used are nonionic, hydrophobic, ethylenically unsaturated compounds which, when polymerized on their own, form hydrophobic polymers.

Hierzu gehören beispielsweise Styrol, Methylstyrol, C1- bis C18-Alkylester von Acrylsäure oder Methacrylsäure, beispielsweise Methylacrylat, Ethylacrylat, N-Propylacrylat, Isopropylacrylat, n-Butylacrylat, tert.Butylacrylat und Isobutylacrylat sowie Isobutylmethacrylat, n-Butylmethacrylat und tert.Butylmethacrylat. Außerdem eignen sich Acrylnitril, Methacrylnitril, Vinylacetat, Vinylpropionat und Vinylbutyrat. Man kann auch Mischungen der Monomeren der Gruppe 2 bei der Copolymerisation einsetzen, z.B. Mischungen aus Styrol und Isobutylacrylat. Die als Emulgator dienenden Lösungscopolymerisate können ggf. noch Monomeren der Gruppe (3) einpolymerisiert enthalten, z.B. monoethylenisch ungesättigte C3- bis C5-Carbonsäuren oder ihre Anhydride, z.B. Acrylsäure, Methacrylsäure, Itakonsäure, Maleinsäure, Maleinsäureanhydrid oder Itakonsäureanhydrid. Das Molverhältnis von (1) : (2) : (3) beträgt 1 : 2,5 bis 10 : 0 bis 1,5. Die so erhaltenen Copolymerisatlösungen werden mit Wasser verdünnt und dienen in dieser Form als Schutzkolloid für die Polymerisation der obenangegebenen Monomermischungen aus den Komponenten (a) und (b) und ggf. (c). Als Monomere der Gruppe (a) kommen Styrol, Acrylnitril, Methacrylnitril oder Mischungen aus Styrol und Acrylnitril oder aus Styrol und Methacrylnitril in Betracht. Als Monomere der Gruppe (b) verwendet man Acrylsäure- und/oder Methacrylsäureester von C1- bis C18-Alkoholen und/oder Vinylester von gesättigten C2- bis C4-Carbonsäuren. Diese Gruppe von Monomeren entspricht den Monomeren der Gruppe (2), die oben bereits beschrieben wurde. Vorzugsweise verwendet man als Monomer der Gruppe (b) Acrylsäurebutylester und Methacrylsäurebutylester, z.B. Acrylsäureisobutylacrylat, Acrylsäure-n-butylacrylat und Methacrylsäureisobutylacrylat. Monomere der Gruppe (c) sind beispielsweise C3- bis C5-monoethylenisch ungesättigte Carbonsäuren, Acrylamidomethylpropansulfonsäure, Natriumvinylsulfonat, Vinylimidazol, N-Vinylformamid, Acrylamid, Methacrylamid und N-Vinylimidazolin. Pro 1 Gew.-Teil des Copolymerisates verwendet man 1 bis 32 Gew.-Teile einer Monomermischung aus den Komponenten (a) bis (c). Die Monomeren der Komponenten (a) und (b) können dabei in einem beliebigen Verhältnis copolymerisiert werden, z.B. im Molverhältnis 0,1 : 1 bis 1 : 0,1.These include, for example, styrene, methylstyrene, C 1 - to C 18 -alkyl esters of acrylic acid or methacrylic acid, for example methyl acrylate, ethyl acrylate, N-propyl acrylate, isopropyl acrylate, n-butyl acrylate, tert-butyl acrylate and isobutyl acrylate as well as isobutyl methacrylate, n-butyl methacrylate and n-butyl methacrylate . Acrylonitrile, methacrylonitrile, vinyl acetate, vinyl propionate and vinyl butyrate are also suitable. Mixtures of the group 2 monomers can also be used in the copolymerization, for example mixtures of styrene and isobutyl acrylate. The solution copolymers used as emulsifiers can optionally also contain copolymerized monomers of group (3), for example monoethylenically unsaturated C 3 to C 5 carboxylic acids or their anhydrides, for example acrylic acid, methacrylic acid, itaconic acid, maleic acid, maleic anhydride or itaconic anhydride. The molar ratio of (1): (2): (3) is 1: 2.5 to 10: 0 to 1.5. The copolymer solutions obtained in this way are diluted with water and in this form serve as a protective colloid for the polymerization of the above-mentioned monomer mixtures of components (a) and (b) and, if appropriate, (c). Monomers of group (a) are styrene, acrylonitrile, methacrylonitrile or mixtures of styrene and acrylonitrile or of styrene and methacrylonitrile. The monomers of group (b) used are acrylic acid and / or methacrylic acid esters of C 1 to C 18 alcohols and / or vinyl esters of saturated C 2 to C 4 carboxylic acids. This group of monomers corresponds to the monomers of group (2), which has already been described above. Preferably used as the monomer of group (b) are butyl acrylate and butyl methacrylate, for example isobutyl acrylate, n-butyl acrylate and isobutyl methacrylate. Monomers of group (c) are, for example, C 3 -C 5 -monoethylenically unsaturated carboxylic acids, acrylamidomethylpropanesulfonic acid, sodium vinyl sulfonate, vinylimidazole, N-vinylformamide, acrylamide, methacrylamide and N-vinylimidazoline. 1 to 32 parts by weight of a monomer mixture of components (a) to (c) are used per 1 part by weight of the copolymer. The monomers of components (a) and (b) can be copolymerized in any ratio, for example in the molar ratio 0.1: 1 to 1: 0.1.

Die Monomeren der Gruppe (c) werden im Bedarfsfalls zur Modifizierung der Eigenschaften der Copolymerisate verwendet.If necessary, the monomers of group (c) are used to modify the properties of the copolymers.

Vorzugsweise werden die als Leimungsmittel für Papier beschriebenen feinteiligen, wäßrigen Dispersionen eingesetzt, die aus der EP-0 257 412 und der EP-B-0 276 770 bekannt sind. Diese Dispersionen werden durch Copolymerisieren von

  • (a) 20 bis 65 Gew.-% Styrol, Acrylnitril und/oder Methacrylnitril,
  • (b) 80 bis 35 Gew.-% Acrylsäure- und/oder Methacrylsäureestern von einwertigen gesättigten C3- bis C8-Alkoholen und
  • (c) 0 bis 10 Gew.-% anderen monoethylenisch ungesättigten copolymerisierbaren Monomeren
in Gegenwart von Radikale bildenden Initiatoren nach Art einer Emulsionspolymerisation in einer wäßrigen Lösung einer abgebauten Stärke als Schutzkolloid hergestellt. Die abgebaute Stärke hat vorzugsweise Viskositäten ηi = 0,04 bis 0,50 dl/g. Diese Stärken sind einem oxidativen, thermischen, azidolytischem oder einem enzymatischen Abbau unterworfen worden. Für diesen Abbau können sämtliche nativen Stärken eingesetzt werden, z.B. Stärken aus Kartoffeln, Weizen, Reis, Tapioka und Mais. Außerdem sind chemisch modifizierte Stärken einsetztbar, wie Hydroxyethyl-, Hydroxypropyl- oder quaternisierter Aminoalkylgruppen enthaltende Stärken mit Viskositäten in dem obenangegebenen Bereich. Besonders geeignet sind oxidativ abgebaute Kartoffelstärken, kationisierte, abgebaute Kartoffelstärken oder Hydroxyethylstärke. Die Mischung aus leimend wirkender Copolymerisatdispersion und einer nicht aufgeschlossenen Stärke wird vorzugsweise mindestens 10 Minuten bei 85°C gerührt. Dadurch wird die Stärke aufgeschlossen.The finely divided, aqueous dispersions described as sizing agents for paper, which are known from EP-0 257 412 and EP-B-0 276 770, are preferably used. These dispersions are obtained by copolymerizing
  • (a) 20 to 65% by weight of styrene, acrylonitrile and / or methacrylonitrile,
  • (b) 80 to 35% by weight of acrylic acid and / or methacrylic acid esters of monohydric saturated C 3 to C 8 alcohols and
  • (c) 0 to 10% by weight of other monoethylenically unsaturated copolymerizable monomers
prepared in the presence of free radical initiators in the manner of an emulsion polymerization in an aqueous solution of a degraded starch as a protective colloid. The degraded starch preferably has viscosities η i = 0.04 to 0.50 dl / g. These starches have been subjected to oxidative, thermal, acidolytic or enzymatic degradation. All native starches can be used for this degradation, for example starches from potatoes, wheat, rice, tapioca and corn. In addition, chemically modified starches can be used, such as starches containing hydroxyethyl, hydroxypropyl or quaternized aminoalkyl groups with viscosities in the range given above. Oxidatively degraded potato starches, cationized, degraded potato starches or hydroxyethyl starch are particularly suitable. The mixture of size-acting copolymer dispersion and an undigested starch is preferably stirred at 85 ° C. for at least 10 minutes. This unlocks the strength.

Die abgebauten Stärken wirken als Emulgatoren bei der Copolymerisation der Monomeren (a) bis (c) in wäßrigem Medium nach Art einer Emulsionspolymerisation. Die Monomeren werden in einer wäßrigen Lösung copolymerisiert, die 1 bis 21, vorzugsweise 3 bis 15 Gew.-% abgebaute Stärke enthält. In 100 Gew.-Teilen einer solchen Lösung polymerisiert man üblicherweise 10 bis 140, vorzugsweise 40 bis 100 Gew.-Teile der Monomermischung aus (a) und (b) und ggf. (c). Der Durchmesser der dispergierten Polymerteilchen beträgt 50 bis 350, vorzugsweise 100 bis 250 nm. Als Monomer der Gruppe (b) kommen außerdem noch Vinylester von C2- bis C4-gesättigten Carbonsäuren in Betracht. Geeignete Monomere der Gruppe (c) sind beispielsweise Acrylamid, Methacrylamid, Stearylacrylat, Stearylmethacrylat, Palmitylacrylat, Acrylsäure, Methacrylsäure, Maleinsäure, Maleinsäureanhydrid, Itakonsäure, Vinylsulfonsäure, Acrylamidopropansulfonsäure und Acrylsäure- und Methacrylsäureester von Aminoalkoholen, z.B. Dimethylaminoethylacrylat, Dimethylaminoethylmethacrylat, Dimethylaminopropylacrylat und Dimethylaminomethacrylat.The degraded starches act as emulsifiers in the copolymerization of the monomers (a) to (c) in an aqueous medium in the manner of an emulsion polymerization. The monomers are copolymerized in an aqueous solution which contains 1 to 21, preferably 3 to 15% by weight of degraded starch. In 100 parts by weight of such a solution, 10 to 140, preferably 40 to 100 parts by weight of the monomer mixture of (a) and (b) and optionally (c) are usually polymerized. The diameter of the dispersed polymer particles is 50 to 350, preferably 100 to 250 nm. Also suitable as monomer of group (b) are vinyl esters of C 2 - to C 4 -saturated carboxylic acids. Suitable monomers of group (c) are, for example, acrylamide, methacrylamide, stearyl acrylate, stearyl methacrylate, palmitylacrylate, acrylic acid, methacrylic acid, maleic acid, maleic anhydride, itaconic acid, vinylsulfonic acid, acrylamidopropanesulfonic acid and acrylic and methacrylic acid esters of amino alcohols, for example dimethylaminoethylamylamethylataminate, dimethylaminoethyl amyl acrylate dimethyl methylethyl amyl acrylate dimethyl methylethyl amyl acrylate,

Die erfindungsgemäßen Papierleimungsmittelmischungen werden dadurch hergestellt, daß man zunächst eine wäßrige Suspension einer aufgeschlossenen kationischen Stärke mit mindestens einer der obengenannten feinteiligen, wäßrigen Polymerdispersion, die ein Leimungsmittel für Papier ist, mischt. Man kann beispielsweise von einer 0,5 bis 5-gew.%igen wäßrigen Suspension einer kationischen Stärke ausgehen, die in bekannter Weise in eine in Wasser lösliche Form überführt wird, z.B. durch Erhitzen auf die Verkleisterungstemperatur oder durch Erhitzen in Gegenwart einer Säure, z.B. Schwefelsäure. Die dabei erhaltene wäßrige Lösung wird dann mit der feinteiligen wäßrigen Polymerdispersion oder auch einer Mischung solcher Dispersionen gemischt und auf eine Temperatur von mindestens 70°C erhitzt. Die Temperatur der Mischung kann bis zum Siedepunkt der Mischung gesteigert werden. In die auf mindestens 70°C erhitzte Mischung aus aufgeschlossener kationischer Stärke und feinteiliger wäßriger Polymersuspension werden dann C14- bis C22-Alkyldiketene einemulgiert. Die Alkyldiketene werden in geschmolzender Form zu der Mischung aus aufgeschlossener Stärke und wäßrigen Polymerdispersionen zudosiert und unter Einwirkung von Scherkräften emulgiert, z.B. erfolgt das Emulgieren in sogenannten Homogenisatoren, die nach dem Hochdrukkentspannungsprinzip arbeiten.The paper sizing agent mixtures according to the invention are prepared by first mixing an aqueous suspension of a digested cationic starch with at least one of the abovementioned fine-particle aqueous polymer dispersion, which is a sizing agent for paper. One can, for example, start from a 0.5 to 5% by weight aqueous suspension of a cationic starch, which is converted in a known manner into a water-soluble form, for example by heating to the gelatinization temperature or by heating in the presence of an acid, for example Sulfuric acid. The aqueous solution obtained is then mixed with the finely divided aqueous polymer dispersion or a mixture of such dispersions and heated to a temperature of at least 70 ° C. The temperature of the mixture can be raised to the boiling point of the mixture. C 14 -C 22 -Alkyldiketenes are then emulsified into the mixture of digested cationic starch and finely divided aqueous polymer suspension heated to at least 70 ° C. The alkyldiketenes are added in molten form to the mixture of digested starch and aqueous polymer dispersions and emulsified under the action of shear forces, for example the emulsification is carried out in so-called homogenizers which work according to the high pressure relaxation principle.

Erfindungsgemäß erhält man dann besonders lagerstabile Leimungsmittelmischungen, wenn man das feste Fettalkyldiketen und einen der oben angegebenen Stabilisatoren, z.B. Stearinsäurebehenylester oder Behenylsäureoleylester, mischt und in Form einer Schmelze zu einer auf 75 bis 95°C erwärmten feinteiligen, wäßrigen Polymerdispersion zugibt, die ein Leimungsmittel für Papier ist und die eine aufgeschlossene kationische Stärke enthält, und diese Mischung unter Einwirkung von Scherkräften homogenisiert. Nach dem Homogenisierschritt wird die erhaltene Papierleimungsmittelmischung auf Umgebungstemperatur abgekühlt. Der pH-Wert der Alkyldiketenemulsion/Polymerdispersion-Mischung liegt üblicherweise in dem Bereich von 2,0 bis 4,0 und beträgt vorzugsweise 3,0. Bei der Herstellung dieser Mischung kann man ggf. noch weitere Hilfsstoffe, wie Ligninsulfonat, Formalin oder Propionsäure zusetzen.According to the invention, particularly stable storage sizing mixtures are obtained if the solid fatty alkyl diketene and one of the stabilizers indicated above, e.g. Stearic acid behenyl ester or behenyl acid oleylester, mixed and added in the form of a melt to a finely divided, aqueous polymer dispersion heated to 75 to 95 ° C., which is a sizing agent for paper and which contains a digested cationic starch, and homogenizes this mixture under the action of shear forces. After the homogenization step, the paper sizing mixture obtained is cooled to ambient temperature. The pH of the alkyl diketene emulsion / polymer dispersion mixture is usually in the range from 2.0 to 4.0 and is preferably 3.0. In the preparation of this mixture it is possible, if appropriate, to add further auxiliaries, such as lignin sulfonate, formalin or propionic acid.

Die fertigen Papierleimungsmittelmischungen enthalten 10 bis 80, vorzugsweise 30 bis 60 Gew.-% an Fettalkyldiketen. Der Gehalt der Papierleimungsmittelmischungen an feinteiligen, wäßrigen Polymerdispersionen beträgt 20 bis 90, vorzugsweise 30 bis 70, jeweils auf die Feststoffe bezogen. Die oben beschriebenen Papierleimungsmittelmischungen werden als Masse und Oberflächenleimungsmittel für Papier verwendet, wobei die Verwendung als Masseleimungsmittel bevorzugt ist. Hierfür werden die wäßrigen Polymerleimungsmittelmischungen durch Zugabe von Wasser auf Konzentrationen von 0,08 bis 0,5 Gew.-%, bezogen auf Alkyldiketen, verdünnt.The finished paper size mixtures contain 10 to 80, preferably 30 to 60% by weight of fatty alkyl diketene. The content of the paper sizing agent mixtures in finely divided, aqueous polymer dispersions is 20 to 90, preferably 30 to 70, in each case based on the solids. The paper sizing mixtures described above are used as pulp and surface sizing for paper, with use as a bulk sizing agent being preferred. For this, the aqueous polymer sizing mixtures diluted by adding water to concentrations of 0.08 to 0.5% by weight, based on alkyldiketene.

Die erfindungsgemäßen Papierleimungsmittelmischungen sind lagerstabil, während Mischungen, die lediglich durch Vereinigen von feinteiligen wäßrigen Polymerdispersionen, die Leimungsmittel für Papier sind, mit Emulsionen von Fettalkyldiketenen, die mit Hilfe von aufgeschlossener kationischer Stärke als Schutzkolloid emulgiert wurden, keine ausreichende Stabilität aufweisen. Die zuletzt genannten Mischungen neigen entweder zum Entmischen oder werden nach kurzer Lagerung, z.B. nach 8 Tagen, fest und sind dann nicht mehr für den vorgesehenen Einsatzzweck brauchbar.The paper sizing agent mixtures according to the invention are stable on storage, while mixtures which are merely by combining finely divided aqueous polymer dispersions which are sizing agents for paper with emulsions of fatty alkyldiketenes which have been emulsified as protective colloids with the aid of digested cationic starch do not have sufficient stability. The latter mixtures either tend to segregate or are stored after a short storage, e.g. after 8 days, solid and are then no longer usable for the intended purpose.

Die in den Beispielen angegebenen Teile sind Gewichtsteile, die Angaben in Prozent beziehen sich jeweils auf das Gewicht der hergestellten Emulsionen. Sie sind so gewählt worden, daß die Alkyldiketen-Zugabemenge bezogen auf atro Stoff konstant ist.The parts given in the examples are parts by weight, the percentages relate to the weight of the emulsions produced. They have been chosen so that the amount of alkyl diketene added is constant in relation to atro material.

Der Leimungsgrad der Papiere wurde mit Hilfe des Cobb-Wertes nach DIN 53 132 bestimmt. Für die Prüfung der Leimungswirkung wurde folgendes Stoffmodell verwendet:The degree of sizing of the papers was determined using the Cobb value according to DIN 53 132. The following material model was used to test the sizing effect:

100 % gebl. Birkensulfat mit Mahlgrad 35°SR (Schopper-Riegler), 40 % Kreide und als Retentionsmittel 0,025 % eines hochmolekularen Polyacrylamids. Gelegentlich wird 1 Gew.-% einer kationischen Stärke dem Papierstoff zugegeben.100% blown Birch sulfate with a freeness of 35 ° SR (Schopper-Riegler), 40% chalk and 0.025% of a high molecular weight polyacrylamide as a retention agent. Occasionally, 1% by weight of a cationic starch is added to the paper stock.

Für die Sofortleimung werden die Blätter auf einem dampfbeheizten Trockenzylinder bei 90°C bis zur Restfeuchte von 10-15 % getrocknet; die Prüfung der Endleimung wird 1 Tag nach Herstellung der Blätter und Trocknen bei 90°C bis zur Restfeuchte von ca. 6 % und anschließend Lagern bei 23°C in einer relativen Luftfeuchte von 50 % durchgeführt.For immediate sizing, the sheets are dried on a steam-heated drying cylinder at 90 ° C to a residual moisture of 10-15%; The final sizing test is carried out 1 day after the sheets have been produced and dried at 90 ° C. to a residual moisture of approx. 6% and then stored at 23 ° C. in a relative air humidity of 50%.

Die hergestellten Papiere haben ein Flächengewicht von 80 g/m2 und einen Aschegehalt von ca. 17 %.The papers produced have a basis weight of 80 g / m 2 and an ash content of approx. 17%.

Die Weiße der Papiere wurde bestimmt nach DIN 53 145.The whiteness of the papers was determined according to DIN 53 145.

In den Beispielen wurden folgende feinteilige wäßrige Polymerdispersionen, die üblicherweise als Leimungsmittel für Papier eingesetzt werden, verwendet:The following finely divided aqueous polymer dispersions, which are usually used as sizing agents for paper, were used in the examples:

Polymerdispersion 1Polymer dispersion 1

In einem 1 1 Vierhalskolben, der mit Rührer, Rückflußkühler, Dosiervorrichtung und einer Einrichtung zum Arbeiten unter Stickstoffatmosphäre ausgestattet ist, werden 34,0 g Stärke A sowie 8,4 g Stärke B in 148 g Wasser suspendiert und unter Rühren auf 85°C erhitzt.In a 1 1 four-necked flask equipped with a stirrer, reflux condenser, metering device and a device for working under a nitrogen atmosphere, 34.0 g of starch A and 8.4 g of starch B are suspended in 148 g of water and heated to 85 ° C. with stirring .

Stärke A ist eine abgebaute kationische Kartoffelstärke mit einer Viskosität ηi von 0,47 dl/g, einem Substitutionsgrad von 0,015-COOH- und 0,027 N Mol/Mol Glucoseeinheiten und einem Feststoffgehalt von 83 %.Starch A is a degraded cationic potato starch with a viscosity η i of 0.47 dl / g, a degree of substitution of 0.015-COOH and 0.027 N mol / mol glucose units and a solids content of 83%.

Stärke B ist eine abgebaute, kationische Kartoffelstärke mit einer Viskosität ηi von 1,16, einem Substitutionsgrad von 0,07 N Mol/Mol Glucoseeinheiten und einem Feststoffgehalt von 83 %.Starch B is a degraded, cationic potato starch with a viscosity η i of 1.16, a degree of substitution of 0.07 N mol / mol glucose units and a solids content of 83%.

Nach 30 Minuten bei 85°C werden 2,6 g einer wäßrigen 10%igen Calciumacetatlösung und 10 g einer 1%igen Enzymlösung (a-Amylase A) zugefügt. Nach weiteren 20 Minuten bei 85°C wird der enzymatische Stärkeabbau durch Zugabe von 1,5 g Eisessig abgestoppt. Anschließend weren 16,5 g einer 1%igen Eisen(II)sulfatlösung und 1,75 g 30%iges Wasserstoffperoxid zugesetzt. Nach 20 Minuten ist das Wasserstoffperoxid zersetzt und der oxidative Stärkeabbau beendet. Die Intrinsic-Viskosität der Stärkemischung beträgt dann 0,08 dl/g. Dann gibt man 1,8 g 30%iges Wasserstoffperoxid zu und beginnt sofort damit, eine Emulsion, die aus 93,7 g Acrylnitril, 76,4 g n-Butylacrylat und einer Lösung von 0,2 g Na-C14-alkylsulfonat in 50 g Wasser besteht, gleichmäßig innerhalb von 1 Stunde sowie gleichzeitig separat davon 50 g einer 3,12 %igen Wasserstoffperoxidlösung innerhalb von 1,75 Stunden zuzufügen. Während dieser Zeit und noch 60 Minuten nach dem Ende der Monomerdosierung wird die Temperatur des Reaktionsgemisches auf 85°C gehalten. Man erhält eine Dispersion mit einem Feststoffgehalt von 41,0 % und einem Teilchendurchmesser (ohne Stärkehülle) von 100 - 150 nm. Die Dispersion wird durch Zugabe von Wasser auf einen Feststoffgehalt von 33 % verdünnt.After 30 minutes at 85 ° C., 2.6 g of an aqueous 10% calcium acetate solution and 10 g of a 1% enzyme solution (a-amylase A) are added. After a further 20 minutes at 85 ° C, the enzymatic starch breakdown is stopped by adding 1.5 g of glacial acetic acid. Then 16.5 g of a 1% iron (II) sulfate solution and 1.75 g of 30% hydrogen peroxide are added. After 20 minutes the hydrogen peroxide has decomposed and the oxidative starch degradation has ended. The intrinsic viscosity of the starch mixture is then 0.08 dl / g. Then 1.8 g of 30% hydrogen peroxide are added and an emulsion is immediately started which consists of 93.7 g of acrylonitrile, 76.4 g of n-butyl acrylate and a solution of 0.2 g of Na-C 14 -alkylsulfonate 50 g of water consist, add 50 g of a 3.12% hydrogen peroxide solution evenly within 1 hour and simultaneously separately within 1.75 hours. During this time and 60 minutes after the end of the monomer metering, the temperature of the reaction mixture is kept at 85 ° C. A dispersion with a solids content of 41.0% and a particle diameter (without starch shell) of 100-150 nm is obtained. The dispersion is diluted to a solids content of 33% by adding water.

Polymerdispersion 2Polymer dispersion 2

Eine Mischung aus 20 Teilen (1,92 Mol) Styrol, 7 Teilen (0,41 Mol) Dimethylaminopropylmethacrylamid, 3,5 Teilen (0,486 Mol) Acrylsäure und 10 Teilen Essigsäure wurde innerhalb von 1 Stunde mit Hilfe einer Pumpe in einen auf 90°C erhitzten Kessel gepumpt. Gleichzeitig und ebenfalls innerhalb 1 Stunde fügte man mit Hilfe einer anderen Dosiervorrichtung 2 Teile Azoisobuttersäuredinitril und 10 Teile Essigsäure zu. Das Gemisch wurde 30 min auf eine Temperatur von 90°C erhitzt und danach in 180 Teilen Wasser gelöst. Dann setzte man 0,01 Teile Eisensulfat zu und polymerisierte bei einer Temperatur von 85°C darin eine Mischung von 32 Teilen Styrol und 32 Teilen Isobutylacrylat. Separat davon gab man 33 Teile einer 6%igen Wasserstoffperoxidlösung kontinuierlich innerhalb von 2 Stunden zum Vorpolymerisat zu. Nach 1stündiger Nachpolymerisation bei einer Temperatur von 85°C resultierte eine feinteilige Dispersion mit einem Feststoffgehalt von 31,4 % und einem Teilchendurchmesser von 150 - 250 nm. Die Dispersion wird durch Zugabe von Wasser auf einen Feststoffgehalt von 20 % verdünnt.A mixture of 20 parts (1.92 mol) of styrene, 7 parts (0.41 mol) of dimethylaminopropyl methacrylamide, 3.5 parts (0.486 mol) of acrylic acid and 10 parts of acetic acid was pumped into a 90 ° C. over the course of 1 hour C pumped heated kettle. Simultaneously and also within 1 hour, 2 parts of azoisobutyronitrile and 10 parts of acetic acid were added using another metering device. The mixture was heated to a temperature of 90 ° C. for 30 minutes and then dissolved in 180 parts of water. Then 0.01 part of iron sulfate was added and a mixture of 32 parts of styrene and 32 parts of isobutyl acrylate was polymerized therein at a temperature of 85 ° C. Separately, 33 parts of a 6% hydrogen peroxide solution were added continuously to the prepolymer over the course of 2 hours. After post-polymerization for 1 hour at a temperature of 85 ° C., a finely divided dispersion with a solids content of 31.4% and a particle diameter of 150-250 nm resulted. The dispersion is diluted to a solids content of 20% by adding water.

Beispiel 1example 1

Man stellt eine 2,36-%ige wäßrige Suspension einer handelsüblichen kationischen Stärke her (Substitutionsgrad 0,02), indem man die erforderliche Menge an Stärke in Wasser suspendiert und danach soviel Schwefelsäure zusetzt, daß der pH-Wert 2,5 beträgt. Danach erhitzt man die Stärkesuspension innerhalb von 1 Stunde auf eine Temperatur von 95°C, rührt das Reaktionsgemisch 1 Stunde bei dieser Temperatur und läßt die so erhaltene wäßrige Lösung abkühlen.A 2.36% aqueous suspension of a commercially available cationic starch (degree of substitution 0.02) is prepared by suspending the required amount of starch in water and then adding enough sulfuric acid that the pH is 2.5. The starch suspension is then heated to a temperature of 95 ° C. within 1 hour, the reaction mixture is stirred at this temperature for 1 hour and the aqueous solution thus obtained is allowed to cool.

Zu 90 Teilen der obenbeschriebenen 2,36-%igen wäßrigen Stärkesuspension, die eine Temperatur von 85°C hat, gibt man 10 Teile der Polymerdispersion 1 zu. Diese Mischung wird 10 Minuten bei 85°C gerührt.10 parts of polymer dispersion 1 are added to 90 parts of the 2.36% strength aqueous starch suspension described above, which has a temperature of 85 ° C. This mixture is stirred at 85 ° C for 10 minutes.

Zu 94 Teilen dieser Mischung aus Stärke und Polymerdispersion 1 gibt man 6 Teile einer auf 90°C erhitzten Schmelze von Stearyldiketen und behandelt die Mischung 3 Minuten mit dem Turrax. Anschließend wird die Emulsion bei einer Temperatur von 70°C und einem Druck von 150 bar zweimal in einem Lab 100 homogenisiert und danach auf Raumtemperatur abgekühlt. Man erhält eine stabile, 6-%ige wäßrige Stearyldiketenemulsion, die außerdem 2 % Stärke und 3,1 % Polymerdispersion 1 enthält. Die Leimungsmittelmischung war nach Lagerung von 30 Tagen bei 25°C noch immer stabil. Ein Aufrahmen oder ein Festwerden wurde nicht beobachtet.6 parts of a melt of stearyldiketene heated to 90 ° C. are added to 94 parts of this mixture of starch and polymer dispersion 1 and the mixture is treated with the Turrax for 3 minutes. The emulsion is then homogenized twice in a Lab 100 at a temperature of 70 ° C. and a pressure of 150 bar and then cooled to room temperature. A stable, 6% strength aqueous stearyl diketene emulsion is obtained which also contains 2% starch and 3.1% polymer dispersion 1. The size mixture was still stable after storage for 30 days at 25 ° C. No creaming or solidification was observed.

Vergleichsbeispiel 1Comparative Example 1

Beispiel 1 wird mit der Ausnahme wiederholt, daß man die Polymerdispersion 1 durch ein als Promotor für Alkyldiketen bekanntes Kondensationsprodukt aus Adipinsäure und Diethylentriamin, das mit Ethylenimin gepfropft und mit einem bifunktionellen Vernetzer umgesetzt ist, der durch Reaktion von Epichlorhydrin mit 34 Ethylenoxideinheiten enthaltendem Polyethylenglykol erhältlich ist.Example 1 is repeated with the exception that polymer dispersion 1 is grafted with ethyleneimine and with a bifunctional crosslinker by a condensation product of adipic acid and diethylenetriamine known as a promoter for alkyldiketene is implemented, which is obtainable by reaction of epichlorohydrin with 34 ethylene oxide units containing polyethylene glycol.

Zu 94 Teilen dieser Stärke-Promotormischung gab man anschließend 6 Teile einer auf 90°C erhitzten Schmelze von Stearyldiketen. Man erhielt eine stabile, 6-%ige wäßrige Emulsion von Stearyldiketen. Die Leimungsmittelmischungen gemäß Beispiel 1 und Vergleichsbeispiel 1 wurden jeweils auf ihre Leimungswirkung mit dem obenbeschriebenen Papierstoffmodell getestet. Die Zugabe an Leimungsmittel, berechnet auf Feststoffe, betrug jeweils 2 %, bezogen auf trocknem Papierstoff. Man erhielt die in Tabelle 1 angegebenen Ergebnisse.6 parts of a stearyldiketene melt heated to 90 ° C. were then added to 94 parts of this starch-promoter mixture. A stable, 6% aqueous emulsion of stearyl diketene was obtained. The sizing agent mixtures according to Example 1 and Comparative Example 1 were each tested for their sizing effect using the paper stock model described above. The addition of sizing agent, calculated on solids, was 2% in each case, based on dry paper stock. The results given in Table 1 were obtained.

Beispiel 2Example 2

Beispiel 1 wurde mit den Änderungen wiederholt, daß man eine 2,66 %ige wäßrige Suspension einer handelsüblichen kationischen Stärke (Substitutionsgrad 0,02) herstellte, zu 80 Teilen der obenbeschriebenen 2,66-%igen wäßrigen Stärkesuspension, 20 Teile der Polymerdispersion 1 zugab und die Mischung 10 Minuten bei 85°C rührte. Dadurch wurde die Stärke aufgeschlossen.Example 1 was repeated with the changes that a 2.66% aqueous suspension of a commercial cationic starch (degree of substitution 0.02) was prepared, to 80 parts of the above-described 2.66% aqueous starch suspension, 20 parts of polymer dispersion 1 were added and the mixture was stirred at 85 ° C for 10 minutes. This unlocked the strength.

Zu 94 Teilen dieser Mischung aus aufgeschlossener Stärke und Polymerdispersion 1 gab man anschließend 6 Teile einer auf 90°C erhitzten Schmelze von Steryldiketen. Man erhielt eine stabile, 6-%ige wäßrige Steryldiketenemulsion, die außer Steryldiketen 2 % Stärke und 6,2 % Polymerdispersion 1 enthielt, jeweils bezogen auf die Feststoffe. Die Emulsion war nach einer Lagerung von 30 Tagen bei 25°C noch immer stabil. Ein Aufrahmen oder Festwerden der Leimungsmittelmischung wurde nicht beobachtet.6 parts of a melt of steryl diketene heated to 90 ° C. were then added to 94 parts of this mixture of digested starch and polymer dispersion 1. A stable, 6% strength aqueous steryl diketene emulsion was obtained which, in addition to steryl diketene, contained 2% starch and 6.2% polymer dispersion 1, based in each case on the solids. The emulsion was still stable after storage for 30 days at 25 ° C. No creaming or solidification of the sizing mixture was observed.

Die Wirksamkeit dieser Leimungsmittelmischung wurde an dem obenangegebenen Stoffmodell getestet. Die Ergebnisse sind in Tabelle 1 angegeben. Gegenüber dem Stand der Technik wird bei gleicher Endleimung eine deutlich verbesserte Sofortleimung erhalten. Tabelle 1 Leimungsmittel hergestellt nach Sofortleimung [Cobb] Endleimung [Cobb] Weiße des Papiers Beispiel 1 110 27 80,2 Vergleichsbeispiel 1 120 27 78,6 Beispiel 2 65 27 79,8 The effectiveness of this sizing mixture was tested on the fabric model given above. The results are shown in Table 1. Compared to the prior art, significantly improved instant sizing is obtained with the same final sizing. Table 1 Sizing agent made after Immediate Sizing [Cobb] Final Sizing [Cobb] Whiteness of the paper example 1 110 27 80.2 Comparative Example 1 120 27 78.6 Example 2 65 27 79.8

Beispiel 3Example 3

Beispiel 1 wurde mit den Änderungen wiederholt, daß man eine 5,13-%ige wäßrige Suspension einer handelsüblichen kationischen Stärke (Substitutionsgrad 0,02) herstellte, zu 50 Teilen dieser Suspension, 50 Teile der Polymerdispersion 1 zugab und die Stärke durch 10-minütiges Erhitzen in Mischung mit der Polymerdispersion 1 auf eine Temperatur von 85°C aufschloß.Example 1 was repeated with the changes that a 5.13% strength aqueous suspension of a commercially available cationic starch (degree of substitution 0.02) was prepared, 50 parts of this suspension, 50 parts of polymer dispersion 1 were added, and the starch was added for 10 minutes Heat in a mixture with polymer dispersion 1 at a temperature of 85 ° C.

Zu 78 Teile der Mischung aus der aufgeschlossenen Stärke und der Polymerdispersion (1) gab man eine auf 90°C erhitzte Schmelze aus 20 Teilen Stearyldiketen und 2 Teilen Stearinsäureoleylester und homogenisierte die Mischung anschließend wie in Beispiel 1 beschrieben. Man erhielt eine stabile, 20-%ige wäßrige Stearyldiketenemulsion, die außer Stearyldiketen 2 % Stärke, 2 % Stearinsäureoleylester als Stabilisator und 12,9 % der Polymerdispersion 1 enthielt. Die Emulsion war nach einer Lagerung von 30 Tagen bei 25°C noch immer stabil. Ein Aufrahmen oder ein Festwerden wurden innerhalb dieser Zeit nicht beobachtet. Die Wirksamkeit dieser Papierleimungsmittelmischung wurde anhand des obenangegebenen Stoffmodells getestet. Die Ergebnisse sind in Tabelle 2 angegeben.A melt of 20 parts of stearyldiketene and 2 parts of stearic acid ethyl ester, heated to 90 ° C., was added to 78 parts of the mixture of the digested starch and the polymer dispersion (1), and the mixture was then homogenized as described in Example 1. A stable, 20% strength aqueous stearyl diketene emulsion was obtained which, in addition to stearyl diketene, contained 2% starch, 2% stearic acid oleate ester as stabilizer and 12.9% of polymer dispersion 1. The emulsion was still stable after storage for 30 days at 25 ° C. No creaming or solidification was observed during this time. The effectiveness of this paper sizing mixture was tested using the material model given above. The results are shown in Table 2.

Vergleichsbeispiel 2Comparative Example 2

78 Teile einer 2,5-%igen wäßrigen Lösung einer aufgeschlossenen handelsüblichen kationischen Stärke (Substitutionsgrad 0,02) wurden auf eine Temperatur von 85°C erhitzt und mit einer auf 90°C erhitzten Schmelze aus 20 Teilen Steryldiketen und 2 Teilen Stearinsäureoleylester zugegeben und wie in Beispiel 1 beschrieben darin emulgiert. Anschließend wurde die so erhaltene Dispersion sowie die gemäß Beispiel 3 hergestellte Papierleimungsmittelmischung bezüglich ihrer Wirksamkeit anhand des obenangegebenen Papierstoffs geprüft. Bei einer Zugabe von 0,5 % Feststoff, bezogen auf trockenen Papierstoff, wurden die in Tabelle 2 jeweils angegebenen Werte erhalten.78 parts of a 2.5% aqueous solution of a digested commercial cationic starch (degree of substitution 0.02) were heated to a temperature of 85 ° C. and added with a melt of 20 parts of steryl diketene and 2 parts of stearic acid oleate ester to 90 ° C. and emulsified therein as described in Example 1. The dispersion obtained in this way and the paper sizing mixture prepared according to Example 3 were then tested for their effectiveness using the paper stock specified above. With the addition of 0.5% solids, based on dry paper stock, the values given in Table 2 were obtained.

Beispiel 4Example 4

Beispiel 1 wurde mit den Änderungen wiederholt, daß man eine 5,13 %ige wäßrige Suspension einer handelsüblichen kationischen Stärke (Substitutionsgrad 0,02) herstellte, mit 50 Teilen der Polymerdispersion 2 mischte und die Stärke durch Erhitzen der Mischung auf 85°C für insgesamt 10 Minuten aufschloß. Zu 78 Teilen der so erhaltenen Mischung aus aufgeschlossener Stärke und Polymerdispersion 2 gab man dann eine auf 90°C erhitzte Schmelze aus 20 Teilen Stearyldiketen und 2 Teilen Stearinsäureoleylester und emulgierte die Schmelze darin wie in Beispiel 1 angegeben. Man erhielt eine stabile 20-%ige wäßrige Stearyldiketenemulsion, die außer Stearyldiketen noch 2 % Stärke, 2 % Stearinsäureoleylester und 7,8 % der Polymerdispersion 2 enthielt. Die Papierleimungsmittelmischung war nach einer Lagerung von 30 Tagen bei 35°C noch immer stabil. Sie wurde innerhalb dieser Zeit nicht fest und rahmte auch nicht auf. Die damit erzielbare Endleimung ist in Tabelle 2 angegeben.Example 1 was repeated with the changes that a 5.13% strength aqueous suspension of a commercially available cationic starch (degree of substitution 0.02) was prepared, mixed with 50 parts of polymer dispersion 2 and the starch was heated by heating the mixture to 85 ° C. for a total Unlocked 10 minutes. A mixture of 20 parts of stearyl diketene and 2 parts of stearic acid oleate ester and then heated to 90 ° C. was then added to 78 parts of the mixture of digested starch and polymer dispersion 2 thus obtained emulsified the melt therein as indicated in Example 1. A stable 20% strength aqueous stearyl diketene emulsion was obtained which, in addition to stearyl diketene, also contained 2% starch, 2% stearic acid olylester and 7.8% of polymer dispersion 2. The paper sizing mixture was still stable after storage for 30 days at 35 ° C. It did not become firm within this time and did not cream. The final sizing that can be achieved is given in Table 2.

Vergleichsbeispiel 3Comparative Example 3

78 Teile einer 2,56-%igen wäßrigen Lösung einer aufgeschlossenen handelsüblichen kationischen Stärke (Substitutionsgrad 0,02) wurde auf eine Temperatur von 85°C erwärmt und bei dieser Temperatur mit einer Schmelze aus 20 Teilen Stearyldiketen und 2 Teilen Stearinsäureoleylester nach der in Beispiel 1 angegebenen Methode zusammengebracht und dadurch emulgiert. Die so erhaltene Leimungsmittelmischung wurde auf ihre Wirksamkeit an dem obenbeschriebenen Stoffmodell getestet. Bezogen auf trocknen Papierstoff setzte man 0,5 % des Leimungsmittels ein. In Tabelle 2 ist der Wert für die erhaltene Endleimung angegeben. Wie daraus ersichtlich ist, ist die Endleimung bei Einsatz der Leimungsmittelmischung nach Beispiel 4 deutlich höher als die Leimung, die mit dem Mittel nach Vergleichsbeispiel 3 erhältlich ist. Tabelle 2 Leimungsmittel hergestellt nach Endleimung [Cobb] Beispiel Vergleichsbeispiel 3 - 35 - 2 62 4 - 31 - 3 62 78 parts of a 2.56% strength aqueous solution of a digested commercially available cationic starch (degree of substitution 0.02) was heated to a temperature of 85 ° C. and at this temperature with a melt of 20 parts of stearyl diketene and 2 parts of stearic acid oleate ester according to that in Example 1 specified method brought together and thereby emulsified. The size mixture thus obtained was tested for its effectiveness on the fabric model described above. Based on dry paper stock, 0.5% of the sizing agent was used. Table 2 shows the value for the final sizing obtained. As can be seen from this, the final sizing when using the sizing agent mixture according to Example 4 is significantly higher than the sizing that can be obtained with the agent according to Comparative Example 3. Table 2 Sizing agent made after Final Sizing [Cobb] example Comparative example 3rd - 35 - 2nd 62 4th - 31 - 3rd 62

Claims (5)

  1. A paper size mixture which is prepared by mixing an aqueous suspension of a digested cationic starch with a finely divided, aqueous 0.5-5% strength by weight polymer dispersion which is a paper size and emulsifying a C14-C22-alkyldiketene in this mixture at not less than 70°C.
  2. A paper size mixture as claimed in claim 1, wherein emulsification of the C14-C22-alkyldiketene is additionally effected in the presence of fatty esters and urethanes which are stabilizers for alkyldiketene emulsions.
  3. A paper size mixture as claimed in claim 1 or 2, wherein a copolymer obtainable by copolymerizing
    (a) from 20 to 65% by weight of styrene, acrylonitrile and/or methacrylonitrile,
    (b) from 80 to 35% by weight of an acrylate and/or methacrylate of a monohydric saturated C3-C8-alcohol and
    (c) from 0 to 10% by weight of other monoethylenically unsaturated copolymerizable monomers
    in the presence of a free radical initiator by an emulsion polymerization method in an aqueous solution of a degraded starch as a protective colloid is used as the polymer dispersion which is the paper size.
  4. A paper size mixture as claimed in claim 1 or 2, wherein a copolymer which is obtainable by copolymerizing from 1 to 32 parts by weight of a mixture of
    (a) styrene, acrylonitrile and/or methacrylonitrile and
    (b) an acrylate and/or methacrylate of C1-C18-alcohol and/or a vinyl ester of a saturated C2-C4-carboxylic acid, with or without
    (c) other monoethylenically unsaturated copolymerizable monomers
    in aqueous solution in the presence of 1 part by weight of a solution copolymer of
    (1) a di-C1-C4-alkylamino-C2-C4-alkyl (meth)acrylate which may be protonated or quaternized and
    (2) nonionic, hydrophobic, ethylenically unsaturated monomers which, when polymerized alone, form hydrophobic polymers, with or without
    (3) a monoethylenically unsaturated C3-C5-carboxylic acid or an anhydride thereof,
    the molar ratio of (1) : (2) : (3) being 1 : 2.5-10 : 0-1.5,
    is used as the polymer dispersion which is the paper size.
  5. Use of a paper size mixture as claimed in any of claims 1 to 4 as an engine or surface size for paper.
EP93919142A 1992-09-01 1993-08-23 Mixtures of paper sizing agents Expired - Lifetime EP0658228B1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE4229142A DE4229142A1 (en) 1992-09-01 1992-09-01 Paper sizing mixtures
DE4229142 1992-09-01
PCT/EP1993/002259 WO1994005855A1 (en) 1992-09-01 1993-08-23 Mixtures of paper sizing agents

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EP0658228B1 true EP0658228B1 (en) 1996-07-10

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DE19505751A1 (en) * 1995-02-20 1996-08-22 Basf Ag Aqueous alkyldiketene dispersions and their use as sizing agents for paper
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FI933829A0 (en) 1993-09-01
US5498648A (en) 1996-03-12
NO933099D0 (en) 1993-08-31
NO933099L (en) 1994-03-02
AU4951693A (en) 1994-03-29
DE4229142A1 (en) 1994-03-03
ES2089839T3 (en) 1996-10-01
NO300699B1 (en) 1997-07-07
FI933829A (en) 1994-03-02
EP0658228A1 (en) 1995-06-21
DE59303206D1 (en) 1996-08-14

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