EP1530659A1 - Use of polymers containing vinylamine units as promoters for alkyldiketene glueing - Google Patents

Use of polymers containing vinylamine units as promoters for alkyldiketene glueing

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Publication number
EP1530659A1
EP1530659A1 EP03793630A EP03793630A EP1530659A1 EP 1530659 A1 EP1530659 A1 EP 1530659A1 EP 03793630 A EP03793630 A EP 03793630A EP 03793630 A EP03793630 A EP 03793630A EP 1530659 A1 EP1530659 A1 EP 1530659A1
Authority
EP
European Patent Office
Prior art keywords
acid
polymers containing
vinylamine units
vinyl
paper
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Application number
EP03793630A
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German (de)
French (fr)
Inventor
Simon Champ
Roland Ettl
Rainer Dyllick-Brenzinger
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BASF SE
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BASF SE
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Publication date
Application filed by BASF SE filed Critical BASF SE
Publication of EP1530659A1 publication Critical patent/EP1530659A1/en
Withdrawn legal-status Critical Current

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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
    • D21H23/00—Processes or apparatus for adding material to the pulp or to the paper
    • D21H23/02—Processes or apparatus for adding material to the pulp or to the paper characterised by the manner in which substances are added
    • D21H23/04—Addition to the pulp; After-treatment of added substances in the pulp

Definitions

  • the invention relates to the use of polymers as promoters for the mass sizing of paper with alkyldiketenes.
  • Aqueous alkyldiketene dispersions which are stabilized with cationic starch or with anionic emulsifiers are commercially available bulk sizes for paper.
  • the full sizing effect of the papers glued with alkyldiketene dispersions only develops when the glued papers are stored.
  • Such papers cannot therefore be processed immediately after the paper production, e.g. finished with coating colors, or printed. Rather, they must be stored for at least 24 hours until a sufficient power effect develops.
  • a sizing mixture which contains a hydrophobic, cellulose-reactive sizing agent such as alkyl ketene dimers, and a cationic polymer such as, for example, a condensation product of epichlorohydrin and bis-aitiinopropylpiperazine.
  • the cationic polymers increase the rate of sizing formation, i.e. they act as promoters.
  • aqueous dispersion of a reactive sizing agent for cellulose which contains a cationic organic compound with a molecular weight of less than 10,000 and an anionic stabilizer.
  • WO-A-00/23651 discloses aqueous, anionically sized sizing agent dispersions which can be obtained by dispersing a reactive sizing agent such as alkyldiketene or alkenylsuccinic anhydride in the presence of an anionic dispersing agent in water.
  • a reactive sizing agent such as alkyldiketene or alkenylsuccinic anhydride
  • examples of dispersants are condensation products from naphthalenesulfonic acid and formaldehyde or condensation products from phenol, phenolsulfonic acid and formaldehyde or amphiphilic copolymers from hydrophobic monoethylenically unsaturated monomers and hydrophilic monomers used with an anionic group.
  • the dispersants can be in the form of the free acids, the alkali metal, alkaline earth metal and / or the ammonium salts.
  • the sizing agent dispersions are added to the paper stock, where appropriate the dewatering, flocculation and retention agents and fixing agents normally used in paper production can also be used. The full sizing of the paper does not occur immediately even when using anionic alkyldiketene dispersions, but also - as with the sizing of paper with cationically dispersed alkyldiketene dispersions - only after the sized paper has been stored for a long time.
  • EP-A-0 438 707 relates to a process for the production of paper, cardboard and cardboard from a paper material containing impurities, wherein hydrolyzed homo- and copolymers of N-vinylformamide with a degree of hydrolysis of at least 60% are used as fixing agents for impurities. used. These polymers are preferably used in combination with a cationic retention agent.
  • WO-A-97/05330 discloses the use of synthetic cationic polymers such as polyvinylamines and polyvinylamine hydrochlorides, as promoters for the mass sizing of paper with alkenylbernoic acid anhydrides.
  • the object of the present invention is to provide further promoters for the mass sizing of paper with alkyldiketenes.
  • the object is achieved according to the invention with the use of polymers containing vinylamine units with a K value (determined in 5% aqueous sodium chloride solution at 25 ° C., a pH value of 7 and a polymer concentration of 0.5% by weight) of 30 up to 150 as a promoter for the mass sizing of paper with alkyl diketenes.
  • a K value determined in 5% aqueous sodium chloride solution at 25 ° C., a pH value of 7 and a polymer concentration of 0.5% by weight
  • wood fibers for the production of paper, cardboard and cardboard all common types can be considered, for example cellulose fibers made from wood pulp and all fibers grown from ear plants.
  • wood pulp includes wood pulp, thermomechanical material (TMP), chemothermomechanical material (CTMP), pressure sanding, semi-pulp, high-yield pulp and refiner mechanical pulp (RMP) as well as waste paper.
  • pulps that can be used in bleached or unbleached form. Examples of these are sulfate, sulfite and sodium pulps.
  • Unbleached pulps which are also used as unbleached kraft pulp, are preferably used be designated.
  • the fibers mentioned can be used alone or in a mixture.
  • Sizing agents for the preparation of the aqueous alkyldiketene dispersions are, for example, fatty alkyldiketenes which can be obtained from long-chain saturated or ethylenically unsaturated carboxylic acid chlorides by splitting off hydrogen chloride with tertiary amines.
  • the alkyldiketenes preferably contain 12 to 22 carbon atoms in the alkyl group.
  • Suitable alkyldiketenes are, for example, tetradecyldiketene, palmityldiketene, oleyldiketene, stearyldiketene and behenyldiketene.
  • alkyldiketenes with different alkyl groups such as stearyl palmityldiketene, behenylstearyldiketene, behenyloleyl diketene or palmitylbehenyldiketene are suitable. It is preferred to use stearyl dikets, palmityldikets, behenyl dikets or mixtures of behenyl dikets and stearyl dikets.
  • the fatty alkyl diketenes are processed into aqueous dispersions by first melting them and the melt under the action of shear forces, e.g. with the aid of an Ultraturrax device, dispersed in water in the presence of cationic starch as a stabilizer.
  • Anionic compounds can also be used as stabilizers.
  • Processes for the preparation of anionically adjusted aqueous dispersions of alkyldiketenes are e.g. known from WO-A-00/23651, cf. Pages 2 to 12.
  • the alkyldiketenes are usually heated to a temperature above their melting point and emulsified in molten form in water under the action of shear forces. For this you use e.g. Homogenizers.
  • a cationic starch or at least one anionic dispersant from the group of the condensation products is used
  • the anionic dispersants can be in the form of the free acids, the alkali metal, alkaline earth metal and / or the ammonium salts.
  • the ammonium salts can be derived from ammonia as well as from primary, secondary and tertiary amines, for example the ammonium salts of dimethylamine are suitable, Trimethylamine, hexylamine, cyclohexylamine, dicyclohexylamine, ethanolamine, diethanolamine and triethanolamine.
  • the condensation products described above are known and commercially available. They are produced by condensing the constituents mentioned, it being possible to use the corresponding alkali metal, alkaline earth metal or ammonium salts instead of the free acids.
  • Acids such as sulfuric acid, p-toluenesulfonic acid and phosphoric acid are suitable as catalysts in the condensation.
  • Naphthalenesulfonic acid or its alkali metal salts are preferably condensed with formaldehyde in a molar ratio of 1: 0.1 to 1: 2 and mostly in a molar ratio of 1: 0.5 to 1: 1.
  • the molar ratio for the production of condensates from phenol, phenolsulfonic acid and formaldehyde is also in the range given above, using any mixtures of phenol and phenolsulfonic acid instead of naphthalenesulfonic acid in the condensation with formaldehyde.
  • phenolsulfonic acid instead of phenolsulfonic acid, one can also use the alkali metal and ammonium salts of phenolsulfonic acid.
  • the condensation of the starting materials specified above can optionally also be carried out in the presence of urea.
  • urea based on naphthalenesulfonic acid or on the mixture of phenol and phenolsulfonic acid, 0.1 to 5 moles of urea are used per mole of naphthalenesulfonic acid or per mole of the mixture of phenol and phenolsulfonic acid.
  • the condensation products have, for example, molar masses in the range from 800 to 100,000, preferably 1,000 to 30,000 and in particular 4,000 to 25,000.
  • the anionic dispersants used are preferably salts which are obtained, for example, by neutralizing the condensation products with lithium hydroxide, sodium hydroxide, Potassium hydroxide or ammonia.
  • the pH of the salts is, for example, in the range from 7 to 10.
  • Amphiphilic copolymers are also suitable as anionic dispersants
  • hydrophilic monomers with an anionic group such as monoethylenically unsaturated carboxylic acids, monoethylenically unsaturated sulfonic acids, monoethylenically unsaturated phosphonic acids or mixtures thereof.
  • anionic group such as monoethylenically unsaturated carboxylic acids, monoethylenically unsaturated sulfonic acids, monoethylenically unsaturated phosphonic acids or mixtures thereof.
  • (a) are, for example, olefins having 2 to 150 carbon atoms, styrene, ⁇ -methylstyrene, ethylstyrene, 4-methylstyrene, acrylonitrile, methacrylonitrile, esters of monoethylenically unsaturated C 3 to Cs carboxylic acids and monohydric alcohols, amides of acrylic acid or methacrylic acid with Ci to C 2 alkyl amines, Vinylester of saturated monocarboxylic acids having 2 to 24 carbon atoms, diesters of maleic acid or fumaric acid with monohydric term C ⁇ ⁇ -C 2 -alcohols, vinyl ethers of alcohols having 3 to 24 C-atoms or mixtures of the compounds mentioned.
  • amphiphilic copolymers contain as hydrophilic monomers
  • Aqueous size dispersions which comprise amphiphilic copolymers as an anionic dispersant are particularly preferred
  • Preferred anionic dispersants are copolymers of maleic anhydride with C 1 -C 8 -olefins, particularly preferably Cs-olefins such as octene-1 and diisobutene. Diisobutene is particularly preferred.
  • the molar ratio between maleic anhydride and olefin is, for example, in the range 0.9: 1 to 3: 1, preferably from 0.95: 1 to 1.5: 1.
  • These copolymers are preferably used in hydrolyzed form as an aqueous solution or dispersions, where the anhydride group is open and the carboxyl groups are preferably partially or completely neutralized.
  • alkali metal bases such as sodium hydroxide, potassium hydroxide, Sodium carbonate, potassium carbonate, alkaline earth salts such as calcium hydroxide, calcium carbonate, magnesium hydroxide, ammonia, primary, secondary or tertiary amines such as triethylamine, triethanolamine, diethanolamine, ethanolamine, morpholine etc.
  • amphiphilic copolymers are not sufficiently water-soluble in the form of the free acid, they are used in the form of water-soluble salts, for example using the corresponding alkali metal, alkaline earth metal and ammonium salts.
  • the molar mass M w of the amphiphilic copolymers is, for example, 800 to 250,000, mostly 1,000 to 100,000 and is preferably in the range from 3,000 to 20,000, in particular from 1,500 to 10,000.
  • the acid numbers of the amphiphilic copolymers are, for example, 50 to 500, preferably 150 to 300 mg KOH / g polymer.
  • the amphiphilic copolymers are e.g. in amounts of 0.05 to 20, preferably 0.5 to 10% by weight, based on the reactive size, used as an anionic dispersant for the production of the size dispersions.
  • the amphiphilic copolymers are preferably used in amounts of 0.1 to 2, in particular 0.6 to 1,% by weight, based on the sizing agent to be dispersed. If only amphiphilic copolymers are used as dispersants, aqueous size dispersions are obtained which are formaldehyde-free and stable in storage.
  • aqueous, anionic sizing agent dispersions for example, an aqueous solution of at least one condensation product or at least one amphiphilic copolymer can be introduced and the sizing agent dispersed therein at temperatures of, for example, 20 to 100, preferably 40 to 90 ° C.
  • the sizing agent is preferably added in the form of a melt and dispersed with vigorous stirring or shearing. The resulting dispersion is cooled in each case.
  • aqueous, anionically sized sizing agent dispersions which contain 6 to 65% by weight of an alkyldiketene in dispersed form as a sizing agent.
  • Preference is given to highly concentrated sizing agent dispersions which, for example, comprise 25 to 60% by weight of an alkyldiketene as sizing agent in the presence of 0.1 to 5.0% by weight of a condensation product
  • Naphthalenesulfonic acid and formaldehyde or at least one condensation product from (b), (c) and / or (d) dispersed are further preferred size dispersions.
  • Further preferred size dispersions contain 25 to 60% by weight of an alkyl diketene as a size and 0.1 to 5.0% by weight of an amphiphilic copolymer
  • Such highly concentrated sizing agent dispersions have a relatively low viscosity, e.g. in the range of 20 to
  • the pH is, for example, 2 to 8 and is preferably in the range from 3 to 4.
  • Aqueous, anionically sized sizing agent dispersions having an average particle size of the sizing agents in the range of 0.1 are obtained to 3, preferably 0.5 to 1.5 microns.
  • the anionically adjusted alkyldiketene dispersions can optionally be made cationic by adding a sufficient amount of cationic starch.
  • At least one polymer containing vinylamine units is used as a promoter for alkyldiketene sizing agents.
  • the amount of cationic polymers is, for example, 0.01 to 2.0% by weight, preferably 0.01 to 0.1% by weight, based on dry cellulose fibers.
  • Polymers containing vinylamine units are known, cf. US-A-4,421,602, US-A-5, 334, 287, EP-A-0 216 387, US-A-5, 981, 689, WO-A-00/63295 and US-A-6, 121, 409. They are prepared by hydrolysis of open-chain polymers containing N-vinylcarboxamide units. These polymers are e.g. obtainable by polymerizing N-vinylformamide, N-vinyl-N-methylformamide, N-vinyl acetamide, N-vinyl-N-methylacetamide, N-vinyl-N-ethylacetamide and N-vinyl propionamide. The monomers mentioned can be polymerized either alone or together with other monomers.
  • All compounds which can be copolymerized therewith come into consideration as monoethylenically unsaturated monomers which are copolymerized with the N-vinylcarboxamides.
  • Examples include vinyl esters of saturated carboxylic acids of 1 to 6 carbons.
  • Substance atoms such as vinyl formate, vinyl acetate, vinyl propionate and vinyl butyrate and vinyl ethers such as C ⁇ ⁇ to Cg alkyl vinyl ether, such as methyl or ethyl vinyl ether.
  • Suitable comonomers are esters, amides and nitriles of ethylenically unsaturated C 3 - to C ⁇ carboxylic acids, for example methyl acrylate, methyl methacrylate, ethyl acrylate and ethyl methacrylate, acrylamide and methacrylamide, and acrylonitrile and methacrylonitrile.
  • carboxylic acid esters are derived from glycols or polyalkylene glycols, only one OH group being esterified in each case, e.g. Hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, hydroxypropyl methacrylate, hydroxybutyl ethacrylate and acrylic acid monoesters of polyalkylene glycols with a molecular weight of 500 to 10,000.
  • suitable comonomers are esters of ethylenically unsaturated
  • Carboxylic acids with amino alcohols such as dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl acrylate, diethylaminoethyl methacrylate, dimethylaminopropyl acrylate, dimethylaminopropyl methacrylate, diethylaminopropyl acrylate, dimethylaminobutyl acrylate and diethylaminobutyl acrylate.
  • the basic acrylates can be used in the form of the free bases, the salts with mineral acids such as hydrochloric acid, sulfuric acid or nitric acid, the salts with organic acids such as formic acid, acetic acid, propionic acid or the sulfonic acids or in quaternized form.
  • Suitable quaternizing agents are, for example, diethyl sulfate, diethyl sulfate, methyl chloride, ethyl chloride or benzyl chloride.
  • Suitable comonomers are amides of ethylenically unsaturated carboxylic acids such as acrylamide, methacrylamide and N-alkyl mono- and diamides of monoethylenically unsaturated carboxylic acids with alkyl residues of 1 to 6 carbon atoms, e.g. N-methyl acrylamide, N, N-dimethyl acrylamide, N-methyl methacrylamide, N-ethyl acrylamide, N-propylacrylamide and tert.
  • Butylacrylamide and basic (meth) acrylic amides e.g.
  • N-vinylpyrrolidone N-vinylcaprolactam
  • acrylonitrile methacrylonitrile
  • N-vinylimidazole and substituted N-vinylimidazoles such as N-vinyl-2-methylimidazole, N-vinyl-4-methylimidazole, N-vinyl -5-methylimidazole, N-vinyl-2-ethylimidazole and N-vinylimidazolines
  • N-vinylimidazoline N-vinyl-2-methylimidazoline and N-vinyl-2-ethylimidazoline.
  • N-Vinylidazole and N-Vinylimidazoline are except in the form of free bases are also used in neutralized or in quaternized form with mineral acids or organic acids, the quaternization preferably being carried out with dimethyl sulfate, diethyl sulfate, methyl chloride or benzyl chloride.
  • Diallyldialkylammonium halides such as diallyldimethylammonium chloride, are also suitable.
  • copolymers contain, for example
  • the comonomers are preferably free from acid groups.
  • vinylamine unit-containing polymers it is preferable to start from homopolymers of N-vinylformamide or from copolymers which are obtained by copolymerizing
  • the degree of hydrolysis being e.g. Is 1 to 100 mol%, preferably 70 to 100 mol%.
  • the degree of hydrolysis is in particular 80 to 100 mol%.
  • the polymers described above are hydrolysed by known processes by the action of acids, bases or enzymes. When acids are used as hydrolysis agents, the vinylamine units of the polymers are in the form of the ammonium salt, while the free amino groups are formed in the hydrolysis with bases.
  • the polymers containing vinylamine units can be used in the form of the free bases, the ammonia salts or also in uaternized form as a promoter.
  • the degree of hydrolysis of the homopolymers and copolymers used is 90 to 95 mol%.
  • the degree of hydrolysis of the homopolymers is synonymous with the vinylamine units in the polymers.
  • the N-vinyl formamide units undergo hydrolysis of the ester groups to form vinyl alcohol units. This is particularly the case if the copolymers are hydrolysed in the presence of sodium hydroxide solution.
  • Polymerized acrylonitrile 5 is also chemically modified during hydrolysis. This creates, for example, amide groups or carboxyl groups.
  • the homo- and copolymers containing vinylamine units can optionally contain up to 20% by weight of amidine units, which can be obtained, for example, by reacting formic acid with two adjacent amino groups.
  • the molar masses M w of the polymers containing vinylamine units are, for example, 500 to 10 million, preferably 1000 to 5 million (determined by light scattering).
  • This molar mass range corresponds, for example, to K values of 30 to 150, preferably 60 to 90 (determined according to H. Fikentscher in 5% aqueous saline solution at 25 ° C., a pH of 7 and a polymer concentration of 0.5% by weight). %). Cationic polymers with a K value of 85 to are particularly preferred
  • the average molecular weights M w of the polymers containing vinylamine units are, for example, 8000 to 2 million, preferably 70,000 to 240,000.
  • the polymers containing vinylamine units are preferably used in salt-free form.
  • Salt-free aqueous solutions of polymers containing vinylamine units can, for example, from the salt-containing polymer solutions described above
  • Derivatives of polymers containing vinylamine units can also be used as cationic polymers.
  • suitable derivatives from the polymers containing vinylamine units by amidation, alkylation, sulfonamide formation, urea formation, thiourea formation, carbamate formation, acylation, carboxymethylation, phosphonomethylation or Michael addition 40 of the amino groups of the polymer.
  • the polymers containing vinylamine units also include hydrolyzed graft polymers of, for example, N-vinylformamide on polyalkylene glycols, polyvinyl acetate, polyvinyl alcohol, polyvinylformamides, polysaccharides such as starch, oligosaccharides or monosaccharides.
  • the graft polymers can be obtained by free-radically polymerizing, for example, N-vinylformamide in an aqueous medium in the presence of at least one of the graft bases mentioned, together with copolymerizable other monomers, and then hydrolyzing the grafted vinylformamide units to vinylamine units in a known manner.
  • Polymers which preferably come into consideration as vinylamine units are vinylamine homopolymers, 10 to 95% hydrolyzed polyvinylformamides, partially or completely, preferably 90-95% hydrolyzed copolymers of vinylformamide and vinyl acetate, vinyl alcohol, vinylpyrrolidone or acrylamide, each with a K value of 30 up to 150, in particular 60 to 90.
  • Paper, cardboard and cardboard are usually produced by dewatering a slurry of cellulose fibers.
  • the use of kraft pulp is particularly preferred.
  • the use of TMP and CTMP is also of particular interest.
  • the pH of the cellulose fiber slurry is, for example, 4 to 8, preferably 6 to 8.
  • the paper stock can be dewatered discontinuously or continuously on a paper machine.
  • the order of addition of cationic polymer, bulk sizing agent and retention agent can be chosen arbitrarily.
  • a procedure is preferred in which a mixture of an aqueous alkyldiketene dispersion and at least one compound containing vinylamine units or first the cationic polymer, preferably polyvinylamine, and then at least one alkylketene dimer, or a mixture of Add alkylketene dimers. Then at least one retention aid is preferably metered in. According to another embodiment of the invention, at least one alkyl diketene is metered in first, then the retention agent and finally the polymer containing vinylamine units.
  • Alkyl ketene dimers are used, for example, in amounts of 0.01 to 2% by weight, preferably 0.01 to 0.2% by weight, in each case based on dry paper stock, in the mass sizing of paper. If the aqueous dispersion of the alkyl ketene dimers already contains at least one polymer containing vinylamine units to be used as a promoter. hold, for example, based on alkyl ketene dimer, 0.0001% to 2%, preferably 0.001% to 1% by weight of the promoter is used.
  • mass-sized paper products such as paper, cardboard or cardboard are obtained with a basis weight of e.g. 20 to 400 g / m2, preferably 40 to 220 g / m2.
  • the paper stock is preferably additionally dewatered in the presence of a retention agent.
  • a retention agent in addition to anionic retention aids or nonionic retention aids such as polyacrylamides, cationic polymers are preferably used as retention aids and as drainage aids. This leads to a significant improvement in the runnability of the paper machines.
  • cationic retention agents can be used as cationic retention agents. These are, for example, cationic polyacrylamides, polydiallyldimethylammonium chlorides, high molecular weight polyvinylamines, high molecular weight polyvinylamines with K values of more than 150, polyethyleneimines, polyamines with a molecular weight of more than 50,000, modified polyamines grafted with ethyleneimine and optionally grafted are networked, polyetheramides, polyvinylimidazoles, polyvinylpyrrolidines, polyvinylimidazolines, polyvinyltetrahydropyrins, poly (dialkylaminoalkyl vinyl ethers), poly (dialkylaminoalkyl (meth) acrylates) in protonated or in quaternized form, and also polyamidoamines from a dicarboxylic acid alkylene such as adipic acid and polyamine such as diethylenetriamine, which are grafted with ethylene
  • the cationic polymers that are used as retention agents have, for example, K values according to Fikentscher of more than 150 (determined in 5% strength aqueous saline solution at a polymer concentration of 0.5% by weight and a temperature of 25 ° C and a pH of 7). They are preferably used in amounts of 0.01 to 0.3% by weight, based on dry cellulose fibers.
  • the percentages in the examples mean percent by weight.
  • the K values were determined according to H. Fikentscher, Cellulose-Chemie, Vol. 13, 58-64 and 71-74 (1932) in 5% aqueous saline solution at a temperature of 25 ° C. and a pH of 7 at a Polymer concentration of 0.5 wt .-% determined.
  • the molecular weights Mw of the polymers were measured by light scattering.
  • Determination was carried out in accordance with DIN 53 132 by storing the paper sheets in water for a period of 60 seconds.
  • the water absorption is given in g / m2.
  • the HST values were determined using the Hercules Size Tester in accordance with TAPPI test method T530 pm-89.
  • Aqueous dispersion with a solids content of 12% stearyl diketene and 2% cationic starch is aqueous dispersion with a solids content of 12% stearyl diketene and 2% cationic starch.
  • the sheet was then dried on a steam-heated drying cylinder at a temperature of 90 ° C to a water content of 7%. Immediately after drying, the Cobb value and the HST value of the leaves were determined. The leaves were then stored for 24 hours at 25 ° C and 50% relative humidity. The measurements were then repeated. The results obtained are given in Tables 1 and 2.
  • Test Nos. 1 and 2 are comparative examples, and Tests 3 to 7 are examples according to the invention. Table 2
  • Test Nos. 8 and 9 are comparative examples, Tests 10 to 14 are examples according to the invention.

Abstract

The invention relates to the use of polymers containing vinylamine units having a K-value (determined in 5 % of an aqueous sodium chloride solution and at a temperature of 25 %, having a pH-value of 7, and a polymer concentration of 0.5 wt.%) of 30 - 150 as promoters for mass glueing of paper with alkyldiketenes.

Description

Verwendung von Vinylamineinheiten enthaltenden Polymeren als Promoter für die AlkyldiketenleimungUse of polymers containing vinylamine units as promoters for alkyldiketene sizing
Beschreibungdescription
Die Erfindung betrifft die Verwendung von Polymeren als Promoter für die Masseleimung von Papier mit Alkyldiketenen .The invention relates to the use of polymers as promoters for the mass sizing of paper with alkyldiketenes.
Wäßrige Alkyldiketendispersionen, die mit kationischer Stärke oder mit anionischen Emulgatoren stabilisiert sind, sind handelsübliche Masseleimungsmittel für Papier. Die volle Leimungswirkung der mit Alkyldiketendispersionen geleimten Papiere entwik- kelt sich erst bei der Lagerung der geleimten Papiere. Solche Pa- piere können daher nicht unmittelbar im Anschluß an die Papierherstellung weiterverarbeitet, z.B. mit Streichfarben veredelt, oder bedruckt werden. Sie müssen vielmehr mindestens 24 Stunden gelagert werden, bis sich eine ausreichende Lei ungswirkung ausbildet.Aqueous alkyldiketene dispersions which are stabilized with cationic starch or with anionic emulsifiers are commercially available bulk sizes for paper. The full sizing effect of the papers glued with alkyldiketene dispersions only develops when the glued papers are stored. Such papers cannot therefore be processed immediately after the paper production, e.g. finished with coating colors, or printed. Rather, they must be stored for at least 24 hours until a sufficient power effect develops.
Aus der US-A-4, 317 , 756 ist eine Leimungsmittelmischung bekannt, die ein hydrophobes, gegenüber Cellulose reaktives Leimungsmittel wie Alkylketendimere , und ein kationisch.es Polymer wie beispielsweise ein Kondensationsprodukt aus Epichlorhydrin und Bis- aitiinopropylpiperazin enthalten. Die kationischen Polymeren erhöhen die Geschwindigkeit der Ausbildung der Leimung, d.h. sie wirken als Promoter.From US-A-4, 317, 756 a sizing mixture is known which contains a hydrophobic, cellulose-reactive sizing agent such as alkyl ketene dimers, and a cationic polymer such as, for example, a condensation product of epichlorohydrin and bis-aitiinopropylpiperazine. The cationic polymers increase the rate of sizing formation, i.e. they act as promoters.
Eine schnellere Ausbildung des Leimungseffektes von wäßrigen Al- kyldiketendispersionen wird gemäß der US-A-4, 784, 727 mit Hilfe von Terpolymeren erreicht, die Styrol, N,N, -Dimethylaminoe- thyl (meth) acrylat und Acrylnitril einpolymerisiert enthalten.A faster development of the sizing effect of aqueous alkyldiketene dispersions is achieved according to US Pat. No. 4,784,727 with the aid of terpolymers which contain copolymerized styrene, N, N, dimethylaminoethyl (meth) acrylate and acrylonitrile.
Aus der WO-A-98/33979 ist eine wäßrige Dispersion eines Reaktiv- leimungsmittels für Cellulose bekannt, die eine kationische organische Verbindung mit einer Molmasse von weniger als 10000 und einen anionischen Stabilisator enthält.From WO-A-98/33979 an aqueous dispersion of a reactive sizing agent for cellulose is known which contains a cationic organic compound with a molecular weight of less than 10,000 and an anionic stabilizer.
Aus der WO-A-00/23651 sind wäßrige, anionisch eingestellte Lei- mungsmitteldispersionen bekannt, die durch Dispergieren eines Re- aktivleimungsmittels wie Alkyldiketen oder Alkenylbernsteinsäu- reanhydrids in Gegenwart eines anionischen Dispergiermittels in Wasser erhältlich sind. Als Dispergiermittel werden beispielsweise Kondensationsprodukte aus Naphthalinsulfonsäure und Formal- dehyd oder Kondensationsprodukte aus Phenol, Phenolsulfonsäure und Formaldehyd oder amphiphile Copolymerisate aus hydrophoben monoethylenisch ungesättigten Monomeren und hydrophilen Monomeren mit einer anionischen Gruppe verwendet. Die Dispergiermittel können in Form der freien Säuren, der Alkalimetall-, Erdalkalimetall- und/oder der Ammoniumsalze vorliegen. Die Leimungsmittel- dispersionen werden dem Papierstoff zugesetzt, wobei man gegebe- nenfalls die üblicherweise bei der Papierherstellung eingesetzten Entwässerungs-, Flockungs- und Retentionsmittel sowie Fixiermittel mitverwenden kann. Die volle Leimung des Papiers tritt auch bei Verwendung von anionischen Alkyldiketendispersionen nicht sofort ein, sondern ebenfalls - wie bei der Leimung von Papier mit kationisch dispergierten Alkyldiketendispersionen - erst nach längerer Lagerung des geleimten Papiers .WO-A-00/23651 discloses aqueous, anionically sized sizing agent dispersions which can be obtained by dispersing a reactive sizing agent such as alkyldiketene or alkenylsuccinic anhydride in the presence of an anionic dispersing agent in water. Examples of dispersants are condensation products from naphthalenesulfonic acid and formaldehyde or condensation products from phenol, phenolsulfonic acid and formaldehyde or amphiphilic copolymers from hydrophobic monoethylenically unsaturated monomers and hydrophilic monomers used with an anionic group. The dispersants can be in the form of the free acids, the alkali metal, alkaline earth metal and / or the ammonium salts. The sizing agent dispersions are added to the paper stock, where appropriate the dewatering, flocculation and retention agents and fixing agents normally used in paper production can also be used. The full sizing of the paper does not occur immediately even when using anionic alkyldiketene dispersions, but also - as with the sizing of paper with cationically dispersed alkyldiketene dispersions - only after the sized paper has been stored for a long time.
Gegenstand der EP-A-0 438 707 ist ein Verfahren zur Herstellung von Papier, Pappe und Karton aus einem Störstoffe enthaltenden Papierstoff, wobei man als Fixiermittel für Störstoffe hydroly- sierte Homo- und Copolymerisate des N-Vinylformamids mit einem Hydrolysegrad von mindestens 60% verwendet. Diese Polymeren werden vorzugsweise in Kombination mit einem kationischen Retentionsmittel eingesetzt.EP-A-0 438 707 relates to a process for the production of paper, cardboard and cardboard from a paper material containing impurities, wherein hydrolyzed homo- and copolymers of N-vinylformamide with a degree of hydrolysis of at least 60% are used as fixing agents for impurities. used. These polymers are preferably used in combination with a cationic retention agent.
Aus der WO-A-97/05330 ist die Verwendung von synthetischen kationischen Polymeren wie Polyvinylaminen und Polyvinylaminhydrochlo- riden, als Promoter für die Masseleimung von Papier mit Alkenylb- ernsteinsäureanhydriden bekannt.WO-A-97/05330 discloses the use of synthetic cationic polymers such as polyvinylamines and polyvinylamine hydrochlorides, as promoters for the mass sizing of paper with alkenylbernoic acid anhydrides.
Der vorliegenden Erfindung liegt die Aufgabe zugrunde, weitere Promotoren für die Masseleimung von Papier mit Alkyldiketenen zur Verfügung zu stellen.The object of the present invention is to provide further promoters for the mass sizing of paper with alkyldiketenes.
Die Aufgabe wird erfindungsgemäß gelöst mit der Verwendung von Vinylamineinheiten enthaltenden Polymeren mit einem K-Wert (bestimmt in 5%iger wäßriger Kochsalzlösung bei 25°C, einem pH-Wert von 7 und einer Polymerkonzentration von 0,5 Gew.-%) von 30 bis 150 als Promoter für die Masseleimung von Papier mit Alkyldikete- nen.The object is achieved according to the invention with the use of polymers containing vinylamine units with a K value (determined in 5% aqueous sodium chloride solution at 25 ° C., a pH value of 7 and a polymer concentration of 0.5% by weight) of 30 up to 150 as a promoter for the mass sizing of paper with alkyl diketenes.
Als Cellulosefasern für die Herstellung von Papier, Pappe und Karton kommen sämtliche dafür gängigen Typen in Betracht, z.B. Cellulosefasern aus Holzstoff und allen Ein ahrespflanzen gewon- nen Fasern in Betracht. Zu Holzstoff gehören beispielsweise Holzschliff, thermomechanischer Stoff (TMP) , chemothermomechanischer Stoff (CTMP) , Druckschliff, Halbzellstoff, Hochausbeutezellstoff und Refiner Mechanical Pulp (RMP) sowie Altpapier. Außerdem eigenen sich Zellstoffe, die in gebleichter oder in ungebleichter Form verwendet werden können. Beispiele hierfür sind Sulfat-, Sulfit- und Natronzellstoffe. Vorzugsweise verwendet man ungebleichte Zellstoffe, die auch als ungebleichter Kraftzellstoff bezeichnet werden. Die genannten Faserstoffe können allein oder in Mischung verwendet werden.As cellulose fibers for the production of paper, cardboard and cardboard, all common types can be considered, for example cellulose fibers made from wood pulp and all fibers grown from ear plants. For example, wood pulp includes wood pulp, thermomechanical material (TMP), chemothermomechanical material (CTMP), pressure sanding, semi-pulp, high-yield pulp and refiner mechanical pulp (RMP) as well as waste paper. Also suitable are pulps that can be used in bleached or unbleached form. Examples of these are sulfate, sulfite and sodium pulps. Unbleached pulps, which are also used as unbleached kraft pulp, are preferably used be designated. The fibers mentioned can be used alone or in a mixture.
Als Leimungsmittel zur Herstellung der wäßrigen Alkyldiketendis- persionen kommen beispielsweise Fettalkyldiketene in Betracht, die aus langkettigen gesättigten oder ethylenisch ungesättigten Carbonsäurechloriden durch Abspaltung von Chlorwasserstoff mit tertiären Aminen erhältlich sind. Die Alkyldiketene enthalten vorzugsweise 12 bis 22 C-Atome in der Alkylgruppe. Geeignete Al- kyldiketene sind beispielsweise Tetradecyldiketen, Palmityldiketen, Oleyldiketen, Stearyldiketen und Behenyldiketen. Außerdem eigenen sich Alkyldiketene mit unterschiedlichen Alkylgruppen wie Stearylpalmityldiketen, Behenylstearyldiketen, Behenyloleyldike- ten oder Palmitylbehenyldiketen. Verzugsweise verwendet man Stea- ryldiketen, Palmityldiketen, Behenyldiketen oder Mischungen aus Behenyldiketen und Stearyldiketen.Sizing agents for the preparation of the aqueous alkyldiketene dispersions are, for example, fatty alkyldiketenes which can be obtained from long-chain saturated or ethylenically unsaturated carboxylic acid chlorides by splitting off hydrogen chloride with tertiary amines. The alkyldiketenes preferably contain 12 to 22 carbon atoms in the alkyl group. Suitable alkyldiketenes are, for example, tetradecyldiketene, palmityldiketene, oleyldiketene, stearyldiketene and behenyldiketene. In addition, alkyldiketenes with different alkyl groups such as stearyl palmityldiketene, behenylstearyldiketene, behenyloleyl diketene or palmitylbehenyldiketene are suitable. It is preferred to use stearyl dikets, palmityldikets, behenyl dikets or mixtures of behenyl dikets and stearyl dikets.
Die Fettalkyldiketene werden zu wäßrigen Dispersionen verarbeitet, indem man sie zunächst schmilzt und die Schmelze unter Ein- Wirkung von Scherkräften z.B. mit Hilfe eines Ultraturrax-Gerä- tes, in Wasser in Gegenwart von kationischer Stärke als Stabilisator dispergiert. Als Stabilisator können auch anionische Verbindungen eingesetzt werden. Verfahren zur Herstellung anionisch eingestellter wäßriger Dispersionen von Alkyldiketenen sind z.B. aus der WO-A-00/23651 bekannt, vgl. Seiten 2 bis 12. Zur Herstellung von Leimungsmittel-Dispersionen werden die Alkyldiketene üblicherweise auf eine Temperatur oberhalb ihres Schmelzpunkts erhitzt und in geschmolzener Form in Wasser unter Einwirkung von Scherkräften emulgiert. Hierfür benutzt man z.B. Homoge- nisatoren. Um die dispergierten Leimungsmittel in der wäßrigen Phase zu stabilisieren, verwendet man entweder eine kationische Stärke oder mindestens ein anionisches Dispergiermittel aus der Gruppe der Kondensationsprodukte ausThe fatty alkyl diketenes are processed into aqueous dispersions by first melting them and the melt under the action of shear forces, e.g. with the aid of an Ultraturrax device, dispersed in water in the presence of cationic starch as a stabilizer. Anionic compounds can also be used as stabilizers. Processes for the preparation of anionically adjusted aqueous dispersions of alkyldiketenes are e.g. known from WO-A-00/23651, cf. Pages 2 to 12. To produce size dispersions, the alkyldiketenes are usually heated to a temperature above their melting point and emulsified in molten form in water under the action of shear forces. For this you use e.g. Homogenizers. In order to stabilize the dispersed sizing agents in the aqueous phase, either a cationic starch or at least one anionic dispersant from the group of the condensation products is used
(a) Naphthalinsulfonsäure und Formaldehyd,(a) naphthalenesulfonic acid and formaldehyde,
(b) Phenol, Phenolsulfonsäure und Formaldehyd,(b) phenol, phenolsulfonic acid and formaldehyde,
(c) Naphthalinsulfonsäure, Formaldehyd und Harnstoff sowie(c) naphthalenesulfonic acid, formaldehyde and urea and
(d) Phenol, Phenolsulfonsäure, Formaldehyd und Harnstoff.(d) phenol, phenol sulfonic acid, formaldehyde and urea.
Die anionischen Dispergiermittel können sowohl in Form der freien Säuren, der Alkalimetall-, Erdalkalimetall- und/oder der Ammoniumsalze vorliegen. Die Ammoniumsalze können sich sowohl von Ammoniak als auch von primären, sekundären und tertiären Aminen ableiten, z.B. eignen sich die Ammoniumsalze von Dimethylamin, Trimethylamin, Hexylamin, Cyclohexyla in, Dicyclohexylamin, Ethanolamin, Diethanolamin und Triethanolamin. Die oben beschriebenen Kondensationsprodukte sind bekannt und im Handel erhältlich. Sie werden durch Kondensieren der genannten Bestandteile hergestellt, wobei man anstelle der freien Säuren auch die entsprechenden Alkalimetall-, Erdalkalimetall- oder Ammoniumsalze einsetzen kann. Als Katalysator bei der Kondensation eignen sich beispielsweise Säuren wie Schwefelsäure, p-Toluolsulfonsäure und Phosphorsäure. Naphthalinsulfonsäure oder deren Alkalimetallsalze werden mit Formaldehyd vorzugsweise im Molverhältnis 1 : 0,1 bis 1 : 2 und meistens im Molverhältnis 1 : 0,5 bis 1 : 1 kondensiert. Das Molverhältnis für die Herstellung von Kondensaten aus Phenol, Phenolsulfonsäure und Formaldehyd liegt ebenfalls in dem oben angegebenen Bereich, wobei man beliebige Mischungen von Phenol und Phenolsulfonsäure anstelle von Naphthalinsulfonsäure bei der Kondensation mit Formaldehyd einsetzt. Anstelle von Phenolsulfonsäure kann man auch die Alkalimetall- und Ammoniumsalze der Phenolsulfonsäure verwenden. Die Kondensation der oben angegebenen Ausgangsstoffe kann gegebenenfalls zusätzlich in Gegenwart von Harnstoff durchgeführt werden. Beispielsweise verwendet man, bezogen auf Naphthalinsulfonsäure oder auf die Mischung von Phenol und Phenolsulfonsäure 0,1 bis 5 Mol Harnstoff pro Mol Naphthalinsulfonsäure beziehungsweise pro Mol der Mischung aus Phenol und Phenolsulfonsäure .The anionic dispersants can be in the form of the free acids, the alkali metal, alkaline earth metal and / or the ammonium salts. The ammonium salts can be derived from ammonia as well as from primary, secondary and tertiary amines, for example the ammonium salts of dimethylamine are suitable, Trimethylamine, hexylamine, cyclohexylamine, dicyclohexylamine, ethanolamine, diethanolamine and triethanolamine. The condensation products described above are known and commercially available. They are produced by condensing the constituents mentioned, it being possible to use the corresponding alkali metal, alkaline earth metal or ammonium salts instead of the free acids. Acids such as sulfuric acid, p-toluenesulfonic acid and phosphoric acid are suitable as catalysts in the condensation. Naphthalenesulfonic acid or its alkali metal salts are preferably condensed with formaldehyde in a molar ratio of 1: 0.1 to 1: 2 and mostly in a molar ratio of 1: 0.5 to 1: 1. The molar ratio for the production of condensates from phenol, phenolsulfonic acid and formaldehyde is also in the range given above, using any mixtures of phenol and phenolsulfonic acid instead of naphthalenesulfonic acid in the condensation with formaldehyde. Instead of phenolsulfonic acid, one can also use the alkali metal and ammonium salts of phenolsulfonic acid. The condensation of the starting materials specified above can optionally also be carried out in the presence of urea. For example, based on naphthalenesulfonic acid or on the mixture of phenol and phenolsulfonic acid, 0.1 to 5 moles of urea are used per mole of naphthalenesulfonic acid or per mole of the mixture of phenol and phenolsulfonic acid.
Die Kondensationsprodukte haben beispielsweise Molmassen in dem Bereich von 800 bis 100 000, vorzugsweise 1 000 bis 30 000 und insbesondere von 4 000 bis 25 000. Vorzugsweise setzt man als anionische Dispergiermittel Salze ein, die man beispielsweise durch Neutralisieren der Kondensationsprodukte mit Lithiumhydroxid, Natriumhydroxid, Kaliumhydroxid oder Ammoniak erhält. Der pH-Wert der Salze liegt beispielsweise in dem Bereich von 7 bis 10.The condensation products have, for example, molar masses in the range from 800 to 100,000, preferably 1,000 to 30,000 and in particular 4,000 to 25,000. The anionic dispersants used are preferably salts which are obtained, for example, by neutralizing the condensation products with lithium hydroxide, sodium hydroxide, Potassium hydroxide or ammonia. The pH of the salts is, for example, in the range from 7 to 10.
Als anionische Dispergiermittel eignen sich außerdem amphiphile Copolymerisate ausAmphiphilic copolymers are also suitable as anionic dispersants
(i) hydrophoben monoethyleniseh ungesättigten Monomeren und(i) hydrophobic monoethylenically unsaturated monomers and
(ii) hydrophilen Monomeren mit einer anionischen Gruppe wie mono- ethylenisch ungesättigten Carbonsäuren, monoethylenisch ungesättigten Sulfonsäuren, monoethylenisch ungesättigten Phosphonsäuren oder deren Mischungen. Geeignete hydrophobe monoethylenisch ungesättigte Monomere(ii) hydrophilic monomers with an anionic group such as monoethylenically unsaturated carboxylic acids, monoethylenically unsaturated sulfonic acids, monoethylenically unsaturated phosphonic acids or mixtures thereof. Suitable hydrophobic monoethylenically unsaturated monomers
(a) sind beispielsweise Olefine mit 2 bis 150 C-Atomen, Styrol, α-Methylstyrol, Ethylstyrol, 4-Methylstyrol, Acrylnitril, Me- thacrylnitril, Ester aus monoethylenisch ungesättigten C3- bis Cs-Carbonsäuren und einwertigen Alkoholen, Amide der Acrylsäure oder Methacrylsäure mit Ci- bis C2 -Alkylaminen, Vinylester von gesättigten Monocarbonsäuren mit 2 bis 24 C- Atomen, Diester der Maleinsäure oder Fumarsäure mit einwer- tigen Cι~ bis C2 -Alkoholen, Vinylether von Alkoholen mit 3 bis 24 C-Atomen oder Mischungen der genannten Verbindungen.(a) are, for example, olefins having 2 to 150 carbon atoms, styrene, α-methylstyrene, ethylstyrene, 4-methylstyrene, acrylonitrile, methacrylonitrile, esters of monoethylenically unsaturated C 3 to Cs carboxylic acids and monohydric alcohols, amides of acrylic acid or methacrylic acid with Ci to C 2 alkyl amines, Vinylester of saturated monocarboxylic acids having 2 to 24 carbon atoms, diesters of maleic acid or fumaric acid with monohydric term Cι ~ -C 2 -alcohols, vinyl ethers of alcohols having 3 to 24 C-atoms or mixtures of the compounds mentioned.
Die amphiphilen Copolymerisate enthalten als hydrophile MonomereThe amphiphilic copolymers contain as hydrophilic monomers
(b) z.B. C3- bis Cιo~ monoethylenisch ungesättigte Carbonsäuren oder deren Anhydride, 2-Acrylamido-2-methylpropansulfonsäure,(b) for example C 3 -C 1 -C 1 -monoethylenically unsaturated carboxylic acids or their anhydrides, 2-acrylamido-2-methylpropanesulfonic acid,
Vinylsulfonsäure, Styrolsulfonsäure, Vinylphosphonsäure, Salze der genannten Monomeren oder deren Mischungen als hydrophile Monomere mit einer anionischen GruppeVinylsulfonic acid, styrenesulfonic acid, vinylphosphonic acid, salts of the monomers mentioned or mixtures thereof as hydrophilic monomers with an anionic group
einpolymerisiert . Besonders bevorzugt sind wäßrige Leimungsmittel-Dispersionen, die als anionisches Dispergiermittel amphiphile Copolymerisate auspolymerized. Aqueous size dispersions which comprise amphiphilic copolymers as an anionic dispersant are particularly preferred
(a) -Olefinen mit 4 bis 12 C-Atomen, Styrol oder deren Mischungen als hydrophobe Monomere und(a) olefins with 4 to 12 carbon atoms, styrene or mixtures thereof as hydrophobic monomers and
(b) Maleinsäure, Acrylsäure, Methacrylsäure, Halbester aus Maleinsäure und Alkoholen mit 1 bis 25 C-Atomen oder Alkoxy- lierungsprodukten solcher Alkohole, Halbamide der Malein- säure, Salze der genannten Monomeren oder Mischungen dieser Verbindungen als hydrophile Monomere mit einer anionischen Gruppe(b) Maleic acid, acrylic acid, methacrylic acid, half esters of maleic acid and alcohols with 1 to 25 carbon atoms or alkoxylation products of such alcohols, half amides of maleic acid, salts of the monomers mentioned or mixtures of these compounds as hydrophilic monomers with an anionic group
einpolymerisiert enthalten und eine Molmasse Mw von 1 500 bis 100 000 haben.contain polymerized and have a molecular weight M w of 1,500 to 100,000.
Bevorzugt werden als anionische Dispergiermittel Copolymerisate aus Maleinsäureanhydrid mit C - bis Cι -0lefinen, besonders bevorzugt Cs-Olefine wie Octen-1 und Diisobuten. Ganz besonders bevor- zugt ist Diisobuten. Das molare Verhältnis zwischen Maleinsäureanhydrid und Olefin liegt z.B. im Bereich 0,9 : 1 bis 3 : 1, bevorzugt von 0,95 : 1 bis 1,5 : 1. Diese Copolymerisate werden bevorzugt in hydrolysierter Form als wäßrige Lösung oder Dispersionen eingesetzt, wobei die Anhydridgruppe geöffnet vor- liegt und die Carboxylgruppen vorzugsweise zum Teil oder ganz neutralisiert sind. Zur Neutralisation werden folgende Basen eingesetzt: Alkalimetallbasen, wie Natriumhydroxid, Kaliumhydroxid, Natriumcarbonat , Kaliumcarbonat, Erdalkalisalze wie Calcium- hydroxid, Calciumcarbonat, Magnesiumhydroxid, Ammoniak, primäre, sekundäre oder tertiäre Amine wie Triethylamin, Triethanolamin, Diethanolamin, Ethanolamin, Morpholin etc..Preferred anionic dispersants are copolymers of maleic anhydride with C 1 -C 8 -olefins, particularly preferably Cs-olefins such as octene-1 and diisobutene. Diisobutene is particularly preferred. The molar ratio between maleic anhydride and olefin is, for example, in the range 0.9: 1 to 3: 1, preferably from 0.95: 1 to 1.5: 1. These copolymers are preferably used in hydrolyzed form as an aqueous solution or dispersions, where the anhydride group is open and the carboxyl groups are preferably partially or completely neutralized. The following bases are used for neutralization: alkali metal bases, such as sodium hydroxide, potassium hydroxide, Sodium carbonate, potassium carbonate, alkaline earth salts such as calcium hydroxide, calcium carbonate, magnesium hydroxide, ammonia, primary, secondary or tertiary amines such as triethylamine, triethanolamine, diethanolamine, ethanolamine, morpholine etc.
Sofern die amphiphilen Copolymerisate in Form der freien Säure nicht ausreichend wasserlöslich sind, werden sie in Form von wasserlöslichen Salzen eingesetzt, z.B. verwendet man die entsprechenden Alkalimetall-, Erdalkalimetall- und Ammoniumsalze. Die Molmasse Mw der amphiphilen Copolymerisate beträgt beispielsweise 800 bis 250 000, meistens 1 000 bis 100 000 und liegt vorzugsweise in dem Bereich von 3000 bis 20000, insbesondere von 1 500 bis 10 000. Die Säurezahlen der amphiphilen Copolymerisate betragen beispielsweise 50 bis 500, vorzugsweise 150 bis 300 mg KOH/g Polymer.If the amphiphilic copolymers are not sufficiently water-soluble in the form of the free acid, they are used in the form of water-soluble salts, for example using the corresponding alkali metal, alkaline earth metal and ammonium salts. The molar mass M w of the amphiphilic copolymers is, for example, 800 to 250,000, mostly 1,000 to 100,000 and is preferably in the range from 3,000 to 20,000, in particular from 1,500 to 10,000. The acid numbers of the amphiphilic copolymers are, for example, 50 to 500, preferably 150 to 300 mg KOH / g polymer.
Die amphiphilen Copolymeren werden z.B. in Mengen von 0,05 bis 20, vorzugsweise 0,5 bis 10 Gew.-%, bezogen auf das Reaktivlei- mungsmittel, als anionisches Dispergiermittel zur Herstellung der Leimungsmittel-Dispersionen eingesetzt. Vorzugsweise verwendet man die amphiphilen Copolymerisate in Mengen von 0,1 bis 2, insbesondere 0,6 bis 1 Gew.-%, bezogen auf das zu dispergierende Leimungsmittel . Bei alleiniger Verwendung von amphiphilen Copoly- erisaten als Dispergiermittel erhält man wäßrige Leimungsmittel- Dispersionen, die formaldehydfrei und lagerstabil sind.The amphiphilic copolymers are e.g. in amounts of 0.05 to 20, preferably 0.5 to 10% by weight, based on the reactive size, used as an anionic dispersant for the production of the size dispersions. The amphiphilic copolymers are preferably used in amounts of 0.1 to 2, in particular 0.6 to 1,% by weight, based on the sizing agent to be dispersed. If only amphiphilic copolymers are used as dispersants, aqueous size dispersions are obtained which are formaldehyde-free and stable in storage.
Um wäßrige, anionische Leimungsmittel-Dispersionen herzustellen, kann man beispielsweise eine wäßrige Lösung mindestens eines Kondensationsprodukts oder mindestens eines amphiphilen Copolymeri- sats vorlegen und darin bei Temperaturen von beispielsweise 20 bis 100, vorzugsweise 40 bis 90°C das Leimungsmittel dispergieren. Das Leimungsmittel wird dabei vorzugsweise in Form einer Schmelze zugegeben und unter starkem Rühren bzw. Scheren dispergiert. Die entstehende Dispersion wird jeweils gekühlt. Auf diese Weise kann man beispielsweise wäßrige, anionisch eingestellte Leimungsmittel-Dispersionen herstellen, die 6 bis 65 Gew.-% eines Alkyldi- ketens als Leimungsmittel dispergiert enthalten. Bevorzugt sind hochkonzentrierte Leimungsmittel-Dispersionen, die beispielsweise 25 bis 60 Gew.-% eines Alkyldiketens als Leimungsmittel in Gegen- wart von 0,1 bis 5,0 Gew.-% eines Kondensationsprodukts ausIn order to prepare aqueous, anionic sizing agent dispersions, for example, an aqueous solution of at least one condensation product or at least one amphiphilic copolymer can be introduced and the sizing agent dispersed therein at temperatures of, for example, 20 to 100, preferably 40 to 90 ° C. The sizing agent is preferably added in the form of a melt and dispersed with vigorous stirring or shearing. The resulting dispersion is cooled in each case. In this way it is possible, for example, to prepare aqueous, anionically sized sizing agent dispersions which contain 6 to 65% by weight of an alkyldiketene in dispersed form as a sizing agent. Preference is given to highly concentrated sizing agent dispersions which, for example, comprise 25 to 60% by weight of an alkyldiketene as sizing agent in the presence of 0.1 to 5.0% by weight of a condensation product
Naphthalinsulfonsäure und Formaldehyd oder mindestens eines Kondensationsprodukts aus (b) , (c) und/oder (d) dispergiert enthalten. Weitere bevorzugt in Betracht kommende Leimungsmittel-Dispersionen enthalten 25 bis 60 Gew.-% eines Alkyldiketens als Leimungs- mittel und 0,1 bis 5,0 Gew.-% eines amphiphilen Copolymerisats ausNaphthalenesulfonic acid and formaldehyde or at least one condensation product from (b), (c) and / or (d) dispersed. Further preferred size dispersions contain 25 to 60% by weight of an alkyl diketene as a size and 0.1 to 5.0% by weight of an amphiphilic copolymer
(i) 95 bis 50 Gew.-% Isobuten, Diisobuten, Styrol oder deren Mischungen und(i) 95 to 50% by weight of isobutene, diisobutene, styrene or mixtures thereof and
(ii) 5 bis 50 Gew.-% Acrylsäure, Methacrylsäure, Maleinsäure, Halbester von Maleinsäure oder deren Mischungen(ii) 5 to 50% by weight of acrylic acid, methacrylic acid, maleic acid, half esters of maleic acid or mixtures thereof
oder eines wasserlöslichen Salzes eines solchen Copolymerisats.or a water-soluble salt of such a copolymer.
Solche hochkonzentrierten Leimungsmittel-Dispersionen haben eine relativ geringe Viskosität, z.B. in dem Bereich von 20 bisSuch highly concentrated sizing agent dispersions have a relatively low viscosity, e.g. in the range of 20 to
100 mpas (gemessen mit einem Brookfield Viskosimeter und einer Temperatur von 20°C) . Bei der Herstellung der wäßrigen Dispersionen beträgt der pH-Wert beispielsweise 2 bis 8 und liegt vorzugsweise in dem Bereich von 3 bis 4. Man erhält wäßrige, an- ionisch eingestellte Leimungsmittel-Dispersionen mit einer mittleren Teilchengröße der Leimungsmittel in dem Bereich von 0,1 bis 3, vorzugsweise 0,5 bis 1,5 μm.100 mpas (measured with a Brookfield viscometer and a temperature of 20 ° C). In the preparation of the aqueous dispersions, the pH is, for example, 2 to 8 and is preferably in the range from 3 to 4. Aqueous, anionically sized sizing agent dispersions having an average particle size of the sizing agents in the range of 0.1 are obtained to 3, preferably 0.5 to 1.5 microns.
Die anionisch eingestellten Alkyldiketendispersionen können gege- benenfalls durch Zugabe einer ausreichenden Menge an kationischer Stärke kationisch eingestellt werden.The anionically adjusted alkyldiketene dispersions can optionally be made cationic by adding a sufficient amount of cationic starch.
Erfindungsgemäß wird mindestens ein Vinylamineinheiten enthaltendes Polymer als Promotor für Alkyldiketenleimungsmittel verwen- det. Die Menge an kationischen Polymeren beträgt beispielsweise 0,01 bis 2,0 Gew.-%, vorzugsweise 0,01 bis 0,1 Gew.-%, bezogen auf trockene Cellulosefasern.According to the invention, at least one polymer containing vinylamine units is used as a promoter for alkyldiketene sizing agents. The amount of cationic polymers is, for example, 0.01 to 2.0% by weight, preferably 0.01 to 0.1% by weight, based on dry cellulose fibers.
Vinylamineinheiten enthaltende Polymere sind bekannt, vgl. US-A-4,421,602, US-A-5 , 334, 287 , EP-A-0 216 387, US-A-5, 981, 689 , WO-A-00/63295 und US-A-6 , 121 , 409. Sie werden durch Hydrolyse von offenkettigen N-Vinylcarbonsäureamideinheiten enthaltenden Polymeren hergestellt. Diese Polymeren sind z.B. erhältlich durch Po- ly erisieren von N-Vinylformamid, N-Vinyl-N-methylformamid, N-Vi- nylacetamid, N-Vinyl-N-methylacetamid, N-Vinyl-N-ethylacetamid und N-Vinylpropionamid. Die genannten Monomeren können entweder allein oder zusammen mit anderen Monomeren polymerisiert werden.Polymers containing vinylamine units are known, cf. US-A-4,421,602, US-A-5, 334, 287, EP-A-0 216 387, US-A-5, 981, 689, WO-A-00/63295 and US-A-6, 121, 409. They are prepared by hydrolysis of open-chain polymers containing N-vinylcarboxamide units. These polymers are e.g. obtainable by polymerizing N-vinylformamide, N-vinyl-N-methylformamide, N-vinyl acetamide, N-vinyl-N-methylacetamide, N-vinyl-N-ethylacetamide and N-vinyl propionamide. The monomers mentioned can be polymerized either alone or together with other monomers.
Als monoethylenisch ungesättigte Monomere, die mit den N-Vinyl- carbonsäureamiden copolymerisiert werden, kommen alle damit copolymerisierbaren Verbindungen in Betracht. Beispiele hierfür sind Vinylester von gesättigten Carbonsäuren von 1 bis 6 Kohlen- stoffatomen wie Vinylformiat, Vinylacetat, Vinylpropionat und Vinylbutyrat und Vinylether wie Cχ~ bis Cg-Alkylvinylether, z.B. Methyl- oder Ethylvinylether . Weitere geeignete Comonomere sind Ester, A ide und Nitrile von ethylenisch ungesättigten C3- bis Cς-Carbonsäuren, beispielsweise Methylacrylat, Methylmethacrylat, Ethylacrylat und Ethylmethacrylat , Acrylamid und Methacrylamid sowie Acrylnitril und Methacrylnitril .All compounds which can be copolymerized therewith come into consideration as monoethylenically unsaturated monomers which are copolymerized with the N-vinylcarboxamides. Examples include vinyl esters of saturated carboxylic acids of 1 to 6 carbons. Substance atoms such as vinyl formate, vinyl acetate, vinyl propionate and vinyl butyrate and vinyl ethers such as Cχ ~ to Cg alkyl vinyl ether, such as methyl or ethyl vinyl ether. Other suitable comonomers are esters, amides and nitriles of ethylenically unsaturated C 3 - to Cς carboxylic acids, for example methyl acrylate, methyl methacrylate, ethyl acrylate and ethyl methacrylate, acrylamide and methacrylamide, and acrylonitrile and methacrylonitrile.
Weitere geeignete Carbonsäureester leiten sich von Glykolen oder bzw. Polyalkylenglykolen ab, wobei jeweils nur eine OH-Gruppe verestert ist, z.B. Hydroxyethylacrylat, Hydroxyethylmethacrylat, Hydroxypropylacrylat, Hydroxybutylacrylat , Hydroxypropylmeth- acrylat, Hydroxybutyl ethacrylat sowie Acrylsäuremonoester von Polyalkylenglykolen einer Molmasse von 500 bis 10000. Weitere ge- eignete Comonomere sind Ester von ethylenisch ungesättigtenOther suitable carboxylic acid esters are derived from glycols or polyalkylene glycols, only one OH group being esterified in each case, e.g. Hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, hydroxypropyl methacrylate, hydroxybutyl ethacrylate and acrylic acid monoesters of polyalkylene glycols with a molecular weight of 500 to 10,000. Other suitable comonomers are esters of ethylenically unsaturated
Carbonsäuren mit Aminoalkoholen wie beispielsweise Dimethylamino- ethylacrylat, Dimethylaminoethylmethacrylat, Diethylaminoethyl- acrylat, Diethylaminoethylmethacrylat, Dimethylaminopropyl- acrylat, Dimethylaminopropylmethacrylat, Diethylaminopropyl- acrylat, Dimethylaminobutylacrylat und Diethylaminobutylacrylat . Die basischen Acrylate können in Form der freien Basen, der Salze mit Mineralsäuren wie Salzsäure, Schwefelsäure oder Salpetersäure, der Salze mit organischen Säuren wie Ameisensäure, Essigsäure, Propionsäure oder der Sulfonsäuren oder in quaternierter Form eingesetzt werden. Geeignete Quaternierungsmittel sind beispielsweise Di ethylsulfat, Diethylsulfat, Methylchlorid, Ethylchlorid oder Benzylchlorid.Carboxylic acids with amino alcohols such as dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl acrylate, diethylaminoethyl methacrylate, dimethylaminopropyl acrylate, dimethylaminopropyl methacrylate, diethylaminopropyl acrylate, dimethylaminobutyl acrylate and diethylaminobutyl acrylate. The basic acrylates can be used in the form of the free bases, the salts with mineral acids such as hydrochloric acid, sulfuric acid or nitric acid, the salts with organic acids such as formic acid, acetic acid, propionic acid or the sulfonic acids or in quaternized form. Suitable quaternizing agents are, for example, diethyl sulfate, diethyl sulfate, methyl chloride, ethyl chloride or benzyl chloride.
Weitere geeignete Comonomere sind Amide ethylenisch ungesättigter Carbonsäuren wie Acrylamid, Methacrylamid sowie N-Alkylmono- und Diamide von monoethylenisch ungesättigten Carbonsäuren mit Alkyl- resten von 1 bis 6 C-Atomen, z.B. N-Methylacrylamid, N,N-Dimethy- lacrylamid, N-Methylmethacrylamid, N-Ethylacrylamid, N-Propyla- crylamid und tert . Butylacrylamid sowie basische (Meth)acryl- amide, wie z.B. Dimethylaminoethylacrylamid, Dimethylaminoethyl- methacrylamid, Diethylaminoethylacrylamid, Diethylaminoethylmeth- acrylamid, Dimethylaminopropylacrylamid, Diethylaminopropylacryl- amid, Dimethylaminopropylmethacrylamid und Diethylaminopropyl- methacrylamid.Other suitable comonomers are amides of ethylenically unsaturated carboxylic acids such as acrylamide, methacrylamide and N-alkyl mono- and diamides of monoethylenically unsaturated carboxylic acids with alkyl residues of 1 to 6 carbon atoms, e.g. N-methyl acrylamide, N, N-dimethyl acrylamide, N-methyl methacrylamide, N-ethyl acrylamide, N-propylacrylamide and tert. Butylacrylamide and basic (meth) acrylic amides, e.g. Dimethylaminoethyl acrylamide, dimethylaminoethyl methacrylamide, diethylaminoethyl acrylamide, diethylaminoethyl methacrylamide, dimethylaminopropylacrylamide, diethylaminopropylacrylamide, dimethylaminopropyl methacrylamide and diethylaminopropyl methacrylamide.
Weiterhin sind als Comonomere geeignet N-Vinylpyrrolidon, N-Vi- nylcaprolactam, Acrylnitril, Methacrylnitril, N-Vinylimidazol sowie substituierte N-Vinylimidazole wie z.B. N-Vinyl-2-methyl- imidazol, N-Vinyl-4-methylimidazol, N-Vinyl-5-methylimidazol, N- Vinyl-2-ethylimidazol und N-Vinylimidazoline wie N-Vinylimidazo- lin, N-Vinyl-2-methylimidazolin und N-Vinyl-2-ethylimidazolin. N- Vinyli idazole und N-Vinylimidazoline werden außer in Form der freien Basen auch in mit Mineralsäuren oder organischen Säuren neutralisierter oder in quaternisierter Form eingesetzt, wobei die Quaternisierung vorzugsweise mit Dimethylsulfat, Diethyl- sulfat, Methylchlorid oder Benzylchlorid vorgenommen wird. In Frage kommen auch Diallyldialkylammoniumhalogenide wie z.B. Diallyldimethylammoniumchlorid.Also suitable as comonomers are N-vinylpyrrolidone, N-vinylcaprolactam, acrylonitrile, methacrylonitrile, N-vinylimidazole and substituted N-vinylimidazoles such as N-vinyl-2-methylimidazole, N-vinyl-4-methylimidazole, N-vinyl -5-methylimidazole, N-vinyl-2-ethylimidazole and N-vinylimidazolines such as N-vinylimidazoline, N-vinyl-2-methylimidazoline and N-vinyl-2-ethylimidazoline. N-Vinylidazole and N-Vinylimidazoline are except in the form of free bases are also used in neutralized or in quaternized form with mineral acids or organic acids, the quaternization preferably being carried out with dimethyl sulfate, diethyl sulfate, methyl chloride or benzyl chloride. Diallyldialkylammonium halides, such as diallyldimethylammonium chloride, are also suitable.
Die Copolymerisate enthalten beispielsweiseThe copolymers contain, for example
- 95 bis 5 mol-%, vorzugsweise 90 bis 10 mol-% mindestens eines N-Vinylcarbonsäureamids und- 95 to 5 mol%, preferably 90 to 10 mol% of at least one N-vinylcarboxamide and
5 bis 95 mol-%, vorzugsweise 10 bis 90 mol-% andere, damit copolymerisierbare monoethylenisch ungesättigte Monomere5 to 95 mol%, preferably 10 to 90 mol% of other monoethylenically unsaturated monomers copolymerizable therewith
in einpolymerisierter Form. Die Comonomeren sind vorzugsweise frei von Säuregruppen.in polymerized form. The comonomers are preferably free from acid groups.
Um Vinylamineinheiten enthaltende Polymerisate herzustellen, geht man vorzugsweise von Homopolymerisäten des N-Vinylformamids oder von Copolymerisaten aus, die durch Copolymerisieren vonTo prepare vinylamine unit-containing polymers, it is preferable to start from homopolymers of N-vinylformamide or from copolymers which are obtained by copolymerizing
- N-Vinylformamid mit- N-vinylformamide with
- Vinylformiat, Vinylacetat, Vinylpropionat, Acrylnitril, N-Vi- nylcaprolactam, N-Vinylharnstoff , N-Vinylpyrrolidon oder Cι~ bis C6-Alkylvinylethern- Vinyl formate, vinyl acetate, vinyl propionate, acrylonitrile, N-vinyl caprolactam, N-vinyl urea, N-vinyl pyrrolidone or Cι ~ to C 6 alkyl vinyl ethers
und anschließende Hydrolyse der Homo- oder der Copolymerisate unter Bildung von Vinylamineinheiten aus den einpolymerisierten N-Vinylformamideinheiten erhältlich sind, wobei der Hydrolysegrad z.B. 1 bis 100 mol-%, vorzugsweise 70 bis 100 mol-% beträgt. Der Hydrolysegrad beträgt insbesondere 80 bis 100 mol-%. Die Hydrolyse der oben beschriebenen Polymerisate erfolgt nach bekannten Verfahren durch Einwirkung von Säuren, Basen oder Enzymen. Bei Verwendung von Säuren als Hydrolysemittel liegen die Vinylamineinheiten der Polymerisate als Ammoniumsalz vor, während bei der Hydrolyse mit Basen die freie Aminogruppen entstehen. Die Vinylamineinheiten enthaltenden Polymere können in Form der freien Ba- sen, der Ammoniaksalze oder auch in uaternierter Form als Promotor eingesetzt werden.and subsequent hydrolysis of the homo- or the copolymers to form vinylamine units from the polymerized N-vinylformamide units, the degree of hydrolysis being e.g. Is 1 to 100 mol%, preferably 70 to 100 mol%. The degree of hydrolysis is in particular 80 to 100 mol%. The polymers described above are hydrolysed by known processes by the action of acids, bases or enzymes. When acids are used as hydrolysis agents, the vinylamine units of the polymers are in the form of the ammonium salt, while the free amino groups are formed in the hydrolysis with bases. The polymers containing vinylamine units can be used in the form of the free bases, the ammonia salts or also in uaternized form as a promoter.
In den meisten Fällen beträgt der Hydrolysegrad der verwendeten Homo- und Copolymerisate 90 bis 95 mol-%. Der Hydrolysegrad der Homopolymerisate ist gleichbedeutend mit dem Gehalt der Polymerisate an Vinylamineinheiten. Bei Copolymerisaten, die Vinylester einpolymerisiert enthalten, kann neben der Hydrolyse der N-Vinyl- formamideinheiten eine Hydrolyse der Estergruppen unter Bildung von Vinylalkoholeinheiten eintreten. Dies ist insbesondere dann der Fall, wenn man die Hydrolyse der Copolymerisate in Gegenwart von Natronlauge durchführt. Einpolymerisiertes Acrylnitril wird 5 ebenfalls bei der Hydrolyse chemisch verändert. Hierbei entstehen beispielsweise Amidgruppen oder Carboxylgruppen. Die Vinylamineinheiten enthaltenden Homo- und Copolymeren können gegebenenfalls bis zu 20 ιtιol-% an Amidineinheiten enthalten, die z.B. durch Reaktion von Ameisensäure mit zwei benachbarten Aminogrup-In most cases, the degree of hydrolysis of the homopolymers and copolymers used is 90 to 95 mol%. The degree of hydrolysis of the homopolymers is synonymous with the vinylamine units in the polymers. In the case of copolymers which contain vinyl esters in copolymerized form, in addition to the hydrolysis, the N-vinyl formamide units undergo hydrolysis of the ester groups to form vinyl alcohol units. This is particularly the case if the copolymers are hydrolysed in the presence of sodium hydroxide solution. Polymerized acrylonitrile 5 is also chemically modified during hydrolysis. This creates, for example, amide groups or carboxyl groups. The homo- and copolymers containing vinylamine units can optionally contain up to 20% by weight of amidine units, which can be obtained, for example, by reacting formic acid with two adjacent amino groups.
10 pen oder durch intramolekulare Reaktion einer Aminogruppe mit einer benachbarten Amidgruppe z.B. von einpolymerisiertem N-Vinylformamid entsteht. Die Molmassen Mw der Vinylamineinheiten enthaltenden Polymerisate betragen z.B. 500 bis 10 Millionen, vorzugsweise 1000 bis 5 Millionen (bestimmt durch Lichtstreuung) .10 pen or by intramolecular reaction of an amino group with an adjacent amide group, for example of polymerized N-vinylformamide. The molar masses M w of the polymers containing vinylamine units are, for example, 500 to 10 million, preferably 1000 to 5 million (determined by light scattering).
15 Dieser Molmassenbereich entspricht beispielsweise K-Werten von 30 bis 150, vorzugsweise 60 bis 90 (bestimmt nach H. Fikentscher in 5 %iger wässriger Kochsalzlösung bei 25°C, einen pH-Wert von 7 und einer Polymerkonzentration von 0,5 Gew.-%). Besonders bevorzugt werden kationische Polymere eingesetzt, die K-Werte von 85 bis15 This molar mass range corresponds, for example, to K values of 30 to 150, preferably 60 to 90 (determined according to H. Fikentscher in 5% aqueous saline solution at 25 ° C., a pH of 7 and a polymer concentration of 0.5% by weight). %). Cationic polymers with a K value of 85 to are particularly preferred
20 90 haben.Have 20 90.
Die mittleren Molmassen Mw der Vinylamineinheiten enthaltenden Polymeren betragen z.B. 8000 bis 2 Millionen, vorzugsweise 70000 bis 240000.The average molecular weights M w of the polymers containing vinylamine units are, for example, 8000 to 2 million, preferably 70,000 to 240,000.
2525
Die Vinylamineinheiten enthaltenden Polymeren werden vorzugsweise in salzfreier Form eingesetzt. Salzfreie wässrige Lösungen von Vinylamineinheiten enthaltenden Polymerisaten können beispielsweise aus den oben beschriebenen salzhaltigen Polymerlösungen mitThe polymers containing vinylamine units are preferably used in salt-free form. Salt-free aqueous solutions of polymers containing vinylamine units can, for example, from the salt-containing polymer solutions described above
30 Hilfe einer Ultrafiltration an geeigneten Membranen bei Trenngrenzen von beispielsweise 1000 bis 500 000 Dalton, vorzugsweise 10 000 bis 300 000 Dalton hergestellt werden.30 With the aid of ultrafiltration on suitable membranes at separation limits of, for example, 1000 to 500,000 daltons, preferably 10,000 to 300,000 daltons.
Auch Derivate von Vinylamineinheiten enthaltenden Polymeren kön- 35 nen als kationische Polymere eingesetzt werden. So ist es beispielsweise möglich, aus den Vinylamineinheiten enthaltenden Polymeren durch Amidierung, Alkylierung, Sulfonamidbildung, Harn- stoffbildung, Thioharnstoffbildung, Carbamatbildung, Acylierung, Carboximethylierung, Phosphonomethylierung oder Michaeladdition 40 der Aminogruppen des Polymeren eine Vielzahl von geeigneten Derivaten herzustellen. Von besonderem Interesse sind hierbei unver- netzte Polyvinylguanidine, die durch Reaktion von Vinylamineinheiten enthaltenden Polymeren, vorzugsweise Polyvinylaminen, mit Cyanamid (R^N-CN, wobei R1, R2 = H, Cι~ bis C4-Alkyl, C3- bis 45 C6-Cycloalkyl, Phenyl, Benzyl, alkylsubstituiertes Phenyl oder Naphthyl bedeuten) zugänglich sind, vgl. US-A-6, 087, 448, Spalte 3, Zeile 64 bis Spalte 5, Zeile 14.Derivatives of polymers containing vinylamine units can also be used as cationic polymers. For example, it is possible to produce a large number of suitable derivatives from the polymers containing vinylamine units by amidation, alkylation, sulfonamide formation, urea formation, thiourea formation, carbamate formation, acylation, carboxymethylation, phosphonomethylation or Michael addition 40 of the amino groups of the polymer. Of particular interest here are uncrosslinked polyvinylguanidines which are obtained by reacting polymers containing vinylamine units, preferably polyvinylamines, with cyanamide (R ^ N-CN, where R 1 , R 2 = H, C 1 -C 4 -alkyl, C 3 - to 45 C 6 -cycloalkyl, phenyl, benzyl, alkyl-substituted phenyl or Naphthyl mean) are accessible, cf. US-A-6, 087, 448, column 3, line 64 to column 5, line 14.
Zu den Vinylamineinheiten enthaltenden Polymeren gehören auch hydrolysierte Pfropfpolymerisate von beispielsweise N-Vinylforma- mid auf Polyalkylenglykolen, Polyvinylacetat, Polyvinylalkolhol , Polyvinylformamiden, Polysacchariden wie Stärke, Oligosacchariden oder Monosacchariden. Die Pfropfpolymerisate sind dadurch erhältlich, daß man beispielsweise N-Vinylformamid in wäßrigem Medium in Gegenwart mindestens einer der genannten Pfropfgrundlagen gegebenenfalls zusammen mit copolymerisierbaren anderen Monomeren radikalisch polymerisiert und die aufgepfropften Vinylformamid- einheiten anschließend in bekannten Weise zu Vinylamineinheiten hydrolysiert .The polymers containing vinylamine units also include hydrolyzed graft polymers of, for example, N-vinylformamide on polyalkylene glycols, polyvinyl acetate, polyvinyl alcohol, polyvinylformamides, polysaccharides such as starch, oligosaccharides or monosaccharides. The graft polymers can be obtained by free-radically polymerizing, for example, N-vinylformamide in an aqueous medium in the presence of at least one of the graft bases mentioned, together with copolymerizable other monomers, and then hydrolyzing the grafted vinylformamide units to vinylamine units in a known manner.
Bevorzugt in Betracht kommende Vinylamineinheiten enthaltende Polymere sind Vinylamin-Homopolymere, 10 bis 95 % hydrolysierte Polyvinylformamide, partiell oder vollständig, vorzugsweise zu 90 - 95 % hydrolysierte Copolymerisate aus Vinylformamid und Vinyl- acetat, Vinylalkohol , Vinylpyrrolidon oder Acrylamid jeweils mit K-Werten von 30 bis 150, insbesondere 60 bis 90.Polymers which preferably come into consideration as vinylamine units are vinylamine homopolymers, 10 to 95% hydrolyzed polyvinylformamides, partially or completely, preferably 90-95% hydrolyzed copolymers of vinylformamide and vinyl acetate, vinyl alcohol, vinylpyrrolidone or acrylamide, each with a K value of 30 up to 150, in particular 60 to 90.
Die Herstellung von Papier, Pappe und Karton erfolgt üblicherweise durch Entwässern einer Aufschlämmung von Cellulosefasern. Besonders bevorzugt ist die Verwendung von Kraftzellstoff. Von besonderem Interesse ist weiterhin der Einsatz von TMP und CTMP. Der pH-Wert der Cellulosefaseraufschlämmung beträgt beispielsweise 4 bis 8, vorzugsweise 6 bis 8. Die Entwässerung des Papierstoffs kann diskontinuierlich oder kontinuierlich auf einer Pa- piermaschine vorgenommen werden. Die Reihenfolge der Zugabe von kationischem Polymer, Masseleimungsmittel und Retentionsmittel kann beliebig gewählt werden. Bevorzugt wird aber eine Verfahrensweise, bei der man zu der wäßrigen Cellulosefaserauf- schlämmung eine Mischung aus einer wäßrigen Alkyldiketendisper- sion und mindestens einer Vinylamineinheiten enthaltenden Verbindung oder zunächst das kationische Polymer, vorzugsweise Poly- vinylamin, und anschließend mindestens ein Alkylketendimer, oder eine Mischung von Alkylketendimeren zusetzt. Danach dosiert man vorzugsweise mindestens ein Retentionsmittel. Gemäß einer anderen Ausführungsform der Erfindung wird zunächst mindestens ein Alkyl- diketen, dann das Retentionsmittel und zuletzt das Vinylamineinheiten enthaltende Polymerisat dosiert. Alkylketendimere werden beispielsweise in Mengen von 0,01 bis 2 Gew.-%, vorzugsweise 0,01 bis 0,2 Gew.-%, jeweils bezogen auf trockenen Papierstoff, bei der Masseleimung von Papier verwendet. Falls die wässrigen Dispersion der Alkylketendimeren bereits mindestens ein als Promoter einzusetzendes Vinylamineinheiten enthaltendes Polymer ent- halten, so setzt man beispielsweise, bezogen auf Alkylketendimer, 0,0001 % bis 2 %, vorzugsweise 0,001 % bis 1 % Gew.-% des Promoters ein.Paper, cardboard and cardboard are usually produced by dewatering a slurry of cellulose fibers. The use of kraft pulp is particularly preferred. The use of TMP and CTMP is also of particular interest. The pH of the cellulose fiber slurry is, for example, 4 to 8, preferably 6 to 8. The paper stock can be dewatered discontinuously or continuously on a paper machine. The order of addition of cationic polymer, bulk sizing agent and retention agent can be chosen arbitrarily. However, a procedure is preferred in which a mixture of an aqueous alkyldiketene dispersion and at least one compound containing vinylamine units or first the cationic polymer, preferably polyvinylamine, and then at least one alkylketene dimer, or a mixture of Add alkylketene dimers. Then at least one retention aid is preferably metered in. According to another embodiment of the invention, at least one alkyl diketene is metered in first, then the retention agent and finally the polymer containing vinylamine units. Alkyl ketene dimers are used, for example, in amounts of 0.01 to 2% by weight, preferably 0.01 to 0.2% by weight, in each case based on dry paper stock, in the mass sizing of paper. If the aqueous dispersion of the alkyl ketene dimers already contains at least one polymer containing vinylamine units to be used as a promoter. hold, for example, based on alkyl ketene dimer, 0.0001% to 2%, preferably 0.001% to 1% by weight of the promoter is used.
Nach dem Entwässern des Papierstoffs und Trocknen des Papierprodukts erhält man in der Masse geleimte Papierprodukte wie Papier, Pappe oder Karton mit einem Flächengewicht von z.B. 20 bis 400 g/m2, vorzugsweise 40 bis 220 g/m2.After dewatering the paper stock and drying the paper product, mass-sized paper products such as paper, cardboard or cardboard are obtained with a basis weight of e.g. 20 to 400 g / m2, preferably 40 to 220 g / m2.
Das Entwässern des Papierstoffs erfolgt vorzugsweise zusätzlich in Gegenwart eines Retentionsmittels . Neben anionischen Retenti- onsmitteln oder nichtionischen Retentionsmitteln wie Polyacryl- amiden werden bevorzugt kationische Polymere als Retentions- und als Entwässerungshilfsmittel eingesetzt. Dadurch wird eine signi- fikante Verbesserung der Runnability der Papiermaschinen erreicht.The paper stock is preferably additionally dewatered in the presence of a retention agent. In addition to anionic retention aids or nonionic retention aids such as polyacrylamides, cationic polymers are preferably used as retention aids and as drainage aids. This leads to a significant improvement in the runnability of the paper machines.
Als kationische Retentionsmittel kann man sämtliche dafür im Handel erhältlichen Produkte verwenden. Hierbei handelt es sich beispielsweise um kationische Polyacrylamide, Polydiallyldimethy- lammoniumchloride, hochmolekulare Polyvinylamine, hochmolekulare Polyvinylamine mit K-Werten von mehr als 150, Polyethylenimine, Polyamine mit einer Molmasse von mehr als 50 000, modifizierte Polyamine, die mit Ethylenimin gepfropft und gegebenenfalls ver- netzt sind, Polyetheramide, Polyvinylimidazole, Polyvinylpyrroli- dine, Polyvinylimidazoline, Polyvinyltetrahydropyrine, Poly(dial- kylaminoalkylvinylether) , Poly (dialkylaminoalkyl (meth) acrylate) in protonierter oder in quaternierter Form sowie um Polyamido- amine aus einer Dicarbonsäure wie Adipinsäure und Polyalkylen- polyaminen wie Diethylentriaminamin, die mit Ethylenimin gepfropft und mit Polyethylenglykoldichlorhydrinethern gemäß der Lehre der DE-B-24 34 816 vernetzt sind oder um Polyamidoamine, die mit Epichlorhydrin zu wasserlöslichen Kondensationsprodukten umgesetzt sind sowie um Copolymerisate von Acrylamid oder Meth- acrylamid und Dialkylaminoethylacrylaten oder -methacrylaten, beispielsweise Copolymerisate aus Acrylamid und Dimethylamino- ethylacrylat in Form des Salzes mit Salzsäure oder in mit Methylchlorid quaternierter Form. Weitere geeignete Retentionsmittel sind sogenannte MicropartikelSysteme aus kationischen Polymeren wie kationischer Stärke und feinteiliger Kieselsäure oder aus kationischen Polymeren wie kationischem Polyacrylamid und Bentonit.All commercially available products for this purpose can be used as cationic retention agents. These are, for example, cationic polyacrylamides, polydiallyldimethylammonium chlorides, high molecular weight polyvinylamines, high molecular weight polyvinylamines with K values of more than 150, polyethyleneimines, polyamines with a molecular weight of more than 50,000, modified polyamines grafted with ethyleneimine and optionally grafted are networked, polyetheramides, polyvinylimidazoles, polyvinylpyrrolidines, polyvinylimidazolines, polyvinyltetrahydropyrins, poly (dialkylaminoalkyl vinyl ethers), poly (dialkylaminoalkyl (meth) acrylates) in protonated or in quaternized form, and also polyamidoamines from a dicarboxylic acid alkylene such as adipic acid and polyamine such as diethylenetriamine, which are grafted with ethyleneimine and crosslinked with polyethylene glycol dichlorohydrin ethers according to the teaching of DE-B-24 34 816 or to polyamidoamines which have been reacted with epichlorohydrin to form water-soluble condensation products, and to copolymers of acrylamide or methacrylamides d and dialkylaminoethyl acrylates or methacrylates, for example copolymers of acrylamide and dimethylaminoethyl acrylate in the form of the salt with hydrochloric acid or in the form quaternized with methyl chloride. Other suitable retention aids are so-called microparticle systems made from cationic polymers such as cationic starch and finely divided silica or from cationic polymers such as cationic polyacrylamide and bentonite.
Die kationischen Polymerisate, die als Retentionsmittel einge- setzt werden, haben beispielsweise K-Werte nach Fikentscher von mehr als 150 (bestimmt in 5 %iger wäßriger Kochsalzlösung bei einer Polymerkonzentration von 0,5 Gew.-%, einer Temperatur von 25°C und einem pH-Wert von 7) . Sie werden vorzugsweise in Mengen von 0,01 bis 0,3 Gew.-%, bezogen auf trockene Cellulosefasern, eingesetzt .The cationic polymers that are used as retention agents have, for example, K values according to Fikentscher of more than 150 (determined in 5% strength aqueous saline solution at a polymer concentration of 0.5% by weight and a temperature of 25 ° C and a pH of 7). They are preferably used in amounts of 0.01 to 0.3% by weight, based on dry cellulose fibers.
Falls sich aus dem Zusammenhang nichts anderes ergibt, bedeuten die Prozentangaben in den Beispielen Gewichtsprozent. Die K-Werte wurden nach H. Fikentscher, Cellulose-Chemie, Bd. 13, 58-64 und 71-74 (1932) in 5 %iger wäßriger Kochsalzlösung bei einer Temperatur von 25°C und einem pH-Wert von 7 bei einer Polymer- konzentration von 0,5 Gew.-% bestimmt. Die Molmassen Mw der Polymeren wurden durch Lichtstreuung gemessen.Unless the context indicates otherwise, the percentages in the examples mean percent by weight. The K values were determined according to H. Fikentscher, Cellulose-Chemie, Vol. 13, 58-64 and 71-74 (1932) in 5% aqueous saline solution at a temperature of 25 ° C. and a pH of 7 at a Polymer concentration of 0.5 wt .-% determined. The molecular weights Mw of the polymers were measured by light scattering.
BeispieleExamples
Cobb-WertCobb value
Bestimmung erfolgte nach DIN 53 132 durch Lagerung der Papierblätter für einen Zeitraum von 60 Sekunden in Wasser. Die Wasseraufnahme wird in g/m2 angegeben.Determination was carried out in accordance with DIN 53 132 by storing the paper sheets in water for a period of 60 seconds. The water absorption is given in g / m2.
Die HST-Werte wurden mit Hilfe des Hercules Size Testers gemäß TAPPI Test Methode T530 pm-89 bestimmt.The HST values were determined using the Hercules Size Tester in accordance with TAPPI test method T530 pm-89.
Dispersion 1Dispersion 1
Wäßrige Dispersion mit einem Feststoffgehalt von 12 % Stearyldiketen und 2% kationischer Stärke.Aqueous dispersion with a solids content of 12% stearyl diketene and 2% cationic starch.
Dispersion 2Dispersion 2
Wäßrige Dispersion mit einem Feststoffgehalt von 12 % Stearyldiketen und 2% kationischer Stärke sowie zusätzlich 0,12%, bezogen auf Stearyldiketen, eines Polyvinylamins mit einem K-Wert von 90.Aqueous dispersion with a solids content of 12% stearyldiketene and 2% cationic starch and an additional 0.12%, based on stearyldiketene, of a polyvinylamine with a K value of 90.
Dispersion 3Dispersion 3
Wäßrige Dispersion mit einem Feststoffgehalt von 12 % Stearyldiketen und 2% kationischer Stärke sowie zusätzlich 0,12%, bezogen auf Stearyldiketen, eines hydrolysierten Polyvinylformamids mit einem Hydrolysegrad von 81% und einem K-Wert von 90.Aqueous dispersion with a solids content of 12% stearyldiketene and 2% cationic starch and an additional 0.12%, based on stearyldiketene, of a hydrolyzed polyvinylformamide with a degree of hydrolysis of 81% and a K value of 90.
Dispersion 4Dispersion 4
Wäßrige Dispersion mit einem Feststoffgehalt von 12 % Stearyldi- keten und 2% kationischer Stärke sowie zusätzlich 0,12%, bezogen auf Stearyldiketen, eines modifizierten, hydrolysierten Polyvi- nylfomamids mit einem Hydrolysegrad von 95% und einem K-Wert von 90, wobei die Modifizierung durch Umsetzung des teilweise hydrolysierten Polyvinylformamids (67 mol.-% Vinylformamid- und 33 mol.-% Vinylamineinheiten) gemäß Beispiel 2 der WO-A-00/26468 durchgeführt wurde.Aqueous dispersion with a solids content of 12% stearyldiketene and 2% cationic starch as well as 0.12%, based on stearyldiketene, of a modified, hydrolyzed polyvinylformamide with a degree of hydrolysis of 95% and a K value of 90, the modification being carried out by reacting the partially hydrolyzed polyvinylformamide (67 mol% of vinylformamide and 33 mol% of vinylamine units) in accordance with Example 2 of WO-A-00/26468.
Beispiel 1example 1
Zu einem Papierstoff mit einer Stoffdichte von 8 g/1 aus einer vollständig gebleichten Mischung von 70 % Kiefern- und 30 % Bir- kensulfatzellstoff mit einem Mahlgrad von 35° (Schopper-Riegler) gab man, jeweils bezogen auf trockenes Cellulosefaserge isch, die in den Tabellen 1 und 2 angegebenen Mengen an Dispersionen 1 bis 4, 20% Calciumcarbonat, 0,6% einer kationischen Maisstärke und 0,04% eines kationischen Polyacrylamids (Polymin® KE2020) als Re- tentionsmittel . Der pH-Wert der Mischung wurde auf 7,0 eingestellt. Die Mischung wurde anschließend auf einem Rapid-Köthen- Blattbildner zu einem Blatt mit einem Flächengewicht von 100 g/m,2 verarbeitet. Das Blatt wurde dann auf einem mit Dampf beheizten Trockenzylinder bei einer Temperatur von 90 °C auf einen Wasserge- halt von 7% getrocknet. Unmittelbar nach dem Trocknen wurden der Cobb-Wert und der HST-Wert der Blätter bestimmt. Die Blätter wurden dann 24 Stunden bei 25°C und einer relativen Luftfeuchtigkeit von 50% gelagert. Die Messungen wurden anschließend wiederholt. Die dabei erhaltenen Ergebnisse sind in den Tabellen 1 und 2 an- gegeben.To a paper stock with a consistency of 8 g / 1 from a completely bleached mixture of 70% pine and 30% birch sulfate pulp with a freeness of 35 ° (Schopper-Riegler) was added, in each case based on dry cellulose fiber, the in the amounts of dispersions 1 to 4 given in Tables 1 and 2, 20% calcium carbonate, 0.6% of a cationic corn starch and 0.04% of a cationic polyacrylamide (Polymin® KE2020) as a retention agent. The pH of the mixture was adjusted to 7.0. The mixture was then processed on a Rapid-Koethen sheet former to form a sheet with a weight per unit area of 100 g / m 2. The sheet was then dried on a steam-heated drying cylinder at a temperature of 90 ° C to a water content of 7%. Immediately after drying, the Cobb value and the HST value of the leaves were determined. The leaves were then stored for 24 hours at 25 ° C and 50% relative humidity. The measurements were then repeated. The results obtained are given in Tables 1 and 2.
Tabelle 1Table 1
Test Nr. 1 und 2 sind Vergleichsbeispiele, die Tests 3 bis 7 sind Beispiele gemäß Erfindung. Tabelle 2Test Nos. 1 and 2 are comparative examples, and Tests 3 to 7 are examples according to the invention. Table 2
Test Nr. 8 und 9 sind Vergleichsbeispiele, die Tests 10 bis 14 sind Beispiele gemäß Erfindung. Test Nos. 8 and 9 are comparative examples, Tests 10 to 14 are examples according to the invention.

Claims

Patentansprüche claims
1. Verwendung von Vinylamineinheiten enthaltenden Polymeren mit einem K-Wert (bestimmt in 5%iger wäßriger Kochsalzlösung bei1. Use of polymers containing vinylamine units with a K value (determined in 5% strength aqueous sodium chloride solution)
25°C, einem pH-Wert von 7 und einer Polymerkonzentration von25 ° C, a pH of 7 and a polymer concentration of
0,5 Gew.-%) von 30 bis 150 als Promoter für die Masseleimung von Papier mit Alkyldiketenen.0.5% by weight) from 30 to 150 as a promoter for the mass sizing of paper with alkyl diketenes.
2. Verwendung nach Anspruch 2, dadurch gekennzeichnet, daß der K-Wert der Vinylamineinheiten enthaltenden Polymeren 60 bis 90 beträgt.2. Use according to claim 2, characterized in that the K value of the polymers containing vinylamine units is 60 to 90.
3. Verwendung nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß man als Vinylamineinheiten enthaltende Polymere hydrolysierte Poly-N-vinylformamide mit einem Hydrolysegrad von 1 bis 100% einsetzt.3. Use according to claim 1 or 2, characterized in that hydrolyzed poly-N-vinylformamides with a degree of hydrolysis of 1 to 100% are used as polymers containing vinylamine units.
4. Verwendung nach einem der Ansprüche 1 bis 3, dadurch gekenn- zeichnet, daß man als Vinyleinheiten enthaltende Polymere hydrolysierte Poly-N-vinylformamide mit einem Hydrolysegrad von 70 bis 100% einsetzt.4. Use according to one of claims 1 to 3, characterized in that hydrolyzed poly-N-vinylformamides with a degree of hydrolysis of 70 to 100% are used as polymers containing vinyl units.
5. Verwendung nach einem der Ansprüche 1 bis 4, dadurch gekenn- zeichnet, daß man Polyvinylamin als Promoter einsetzt.5. Use according to one of claims 1 to 4, characterized in that polyvinylamine is used as a promoter.
6. Verwendung nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, daß man die Vinylamineinheiten enthaltenden Polymeren in einer Menge von 0,0001 bis 2,0 Gew.-%, bezogen auf Al- kylketendimer, einsetzt. 6. Use according to one of claims 1 to 5, characterized in that the polymers containing vinylamine units are used in an amount of 0.0001 to 2.0% by weight, based on alkyl ketene dimer.
EP03793630A 2002-08-14 2003-07-24 Use of polymers containing vinylamine units as promoters for alkyldiketene glueing Withdrawn EP1530659A1 (en)

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DE10237911A DE10237911A1 (en) 2002-08-14 2002-08-14 Use of polymers comprising vinylamine units as promoters for bulk sizing of paper with alkyl diketenes
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