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.

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