EP1819876B1 - Papierleimungsmittel - Google Patents

Papierleimungsmittel Download PDF

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Publication number
EP1819876B1
EP1819876B1 EP05816209A EP05816209A EP1819876B1 EP 1819876 B1 EP1819876 B1 EP 1819876B1 EP 05816209 A EP05816209 A EP 05816209A EP 05816209 A EP05816209 A EP 05816209A EP 1819876 B1 EP1819876 B1 EP 1819876B1
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Prior art keywords
paper
polymer
weight
paper size
acid
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German (de)
English (en)
French (fr)
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EP1819876A2 (de
Inventor
Markus Schmid
Roland Ettl
Klaus Lorenz
Rainer Dyllick-Brenzinger
Andreas Brockmeyer
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BASF SE
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BASF SE
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Classifications

    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
    • D21H21/16—Sizing or water-repelling agents
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/03—Non-macromolecular organic compounds
    • D21H17/05—Non-macromolecular organic compounds containing elements other than carbon and hydrogen only
    • D21H17/07—Nitrogen-containing compounds
    • D21H17/08—Isocyanates
    • 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
    • D21H17/14—Carboxylic acids; Derivatives thereof
    • D21H17/15—Polycarboxylic acids, e.g. maleic acid
    • D21H17/16—Addition products thereof with hydrocarbons
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/03—Non-macromolecular organic compounds
    • D21H17/05—Non-macromolecular organic compounds containing elements other than carbon and hydrogen only
    • D21H17/17—Ketenes, e.g. ketene dimers
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/33—Synthetic macromolecular compounds
    • D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H17/35—Polyalkenes, e.g. polystyrene

Definitions

  • the invention relates to a paper sizing agent comprising a stable aqueous dispersion of a reactive sizing agent, a process for its preparation and its use for sizing paper, board and cardboard.
  • Reactive sizing agents such as alkyl ketene dimers are widely used for sizing paper, board and board.
  • Reactive sizing agents are usually sold as ready-to-use dispersions. They usually contain cationic polymers such as cationic starch or synthetic cationic polymers which impart substantivity to cellulose to the reactive sizing agents and / or act as protective colloids.
  • the sizing dispersions In order for the sizing dispersions to be suitable for use, they must be sufficiently stable to viscosity so that they remain pumpable and dilutable until they are added to the paper machine. In practice, the dispersions often have to remain thin for several weeks at temperatures up to 40 ° C. These requirements are difficult to meet due to the inherent instability of colloidal systems. In many cases, the viscosity of the dispersions increases sharply until they can no longer be pumped or the dispersions coagulate. The higher the content of the reactive size dispersions, the more pronounced are the problems.
  • alkyl diketene (AKD) dispersions with cationic starch as a protective colloid and an anionic dispersant as a stabilizer are known.
  • AKD dispersions which contain a protective colloid in the form of a copolymer of N-vinylpyrrolidone and N-vinylimidazole or a condensation product based on polyethyleneimines.
  • AKD dispersions which contain as protective colloid reaction products of polymers containing amino groups from the group of polymers containing vinylamine units, polyamidoamines and polymaidoamines grafted with polyethyleneimine with diketenes in a weight ratio of polymer to diketene of 10,000: 1 to 1: 3.
  • the object of the invention is to provide paper sizing agents based on aqueous dispersions of reactive sizing agents which have a good sizing effect and sufficient viscosity stability.
  • the paper size additives of the invention contain from 1 to 50% by weight of reactive sizing agent, based on the total weight of the paper sizing agent.
  • stable dispersion is intended to mean that the dispersion remains liquid when stored for 4 weeks at 40 ° C and does not coagulate.
  • linear polymer is meant a polymer that is substantially free of branching and crosslinking.
  • Polyalkyleneimines such as in particular polyethylenimines, are not considered to be “linear polymers” due to their branched via tertiary amino groups structure.
  • basic nitrogen atoms are those nitrogen atoms which can be protonated in aqueous solution by a Bronsted acid.
  • Basic nitrogen atoms are in particular primary, secondary and tertiary amino groups, of which primary amino groups are preferred.
  • the basic nitrogen atoms in the nitrogen-containing polymer are preferably at least 90 mol%, in particular substantially quantitatively protonated.
  • the protonation can be carried out by reaction with a mineral acid, such as hydrochloric acid, sulfuric acid or phosphoric acid, but is preferably carried out by reaction with a carboxylic acid.
  • Suitable carboxylic acids are, above all, formic acid, acetic acid, propionic acid, oxalic acid, tartaric acid, citric acid and the like.
  • Substantially quantitative protonation is obtained when the nitrogen-containing polymer is adjusted to a pH of less than 5 with the chosen acid.
  • the nitrogen-containing polymer used in the invention contains at least 3 mmol / g, preferably at least 5 mmol / g basic nitrogen atoms, especially 7.5 to 23 mmol / g, and most preferably 12 to 18 mmol / g.
  • molar fraction refers to the monomer composition of the polymer.
  • the average molecular weight Mw of the nitrogen-containing polymer is e.g. 500 to 10 million, preferably 750 to 5 million and particularly preferably 1 000 to 2 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% strength aqueous sodium chloride solution at 25 ° C., a pH of 7 and a polymer concentration of 0.5% by weight. ).
  • Suitable nitrogen-containing polymers include hydrolysis products of homopolymers and copolymers of N-vinylcarboxamides and / or N-vinylcarboximides.
  • the acyl group (s) is cleaved off by the action of acids, bases or enzymes to form vinylamine units.
  • Suitable N-vinylcarboxamides are generally open-chain and cyclic N-vinylcarboxamides.
  • Preferred N-vinylcarboxamides are open-chain N-vinylcarboxamides, in particular those open-chain N-vinylcarboxamides whose hydrolysis yields a primary amine.
  • Examples of particularly suitable N-vinylcarboxamides are N-vinylformamide, N-vinyl-N-methylformamide, N-vinylacetamide, N-vinyl-N-methylacetamide, N-vinyl-N-ethylacetamide and N-vinylpropionamide, in particular N-vinylformamide.
  • suitable N-vinylimides are N-vinylsuccinimide and N-vinylphthalimide. The monomers mentioned can be polymerized either alone or in mixture with one another or together with other monomers.
  • Vinylamine containing polymers are z. B. from the 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 known.
  • Suitable monoethylenically unsaturated monomers which are copolymerized with the N-vinylcarboxamides are all compounds which can be copolymerized therewith.
  • vinyl esters of saturated carboxylic acids of 1 to 6 carbon atoms such as vinyl formate, vinyl acetate, vinyl propionate and vinyl butyrate and vinyl ethers such as C 1 - to C 6 -alkyl vinyl ethers, for example methyl or ethyl vinyl ether.
  • Suitable comonomers are esters, amides and nitriles of ethylenically unsaturated C 3 - to C 6 -carboxylic acids, for example methyl acrylate, methyl methacrylate, ethyl acrylate and ethyl methacrylate, acrylamide and methacrylamide and also acrylonitrile and methacrylonitrile.
  • carboxylic acid esters are derived from glycols or polyalkylene glycols, wherein in each case only one OH group is esterified, e.g. Hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, hydroxypropyl methacrylate, hydroxybutyl methacrylate and acrylic acid monoesters of polyalkylene glycols having a molecular weight of 500 to 10,000.
  • Suitable comonomers are amides of ethylenically unsaturated carboxylic acids such as acrylamide, methacrylamide and N-alkyl mono- and diamides of monoethylenically unsaturated carboxylic acids having alkyl radicals of 1 to 6 carbon atoms, e.g. N-methylacrylamide, N, N-dimethylacrylamide, N-methylmethacrylamide, N-ethylacrylamide, N-propylacrylamide and tert-butylacrylamide.
  • amides of ethylenically unsaturated carboxylic acids such as acrylamide, methacrylamide and N-alkyl mono- and diamides of monoethylenically unsaturated carboxylic acids having alkyl radicals of 1 to 6 carbon atoms, e.g. N-methylacrylamide, N, N-dimethylacrylamide, N-methylmethacrylamide, N-ethylacrylamide, N-propylacrylamide and ter
  • N-vinylpyrrolidone N-vinylcaprolactam
  • acrylonitrile methacrylonitrile
  • N-vinylimidazole substituted N-vinylimidazoles
  • N-vinyl-2-methylimidazole N-vinyl-4-methylimidazole
  • N-vinyl-5-methylimidazole N-vinyl-2-ethylimidazole
  • N-vinylimidazolines such as N-vinylimidazoline, N-vinyl-2-methylimidazoline and N- vinyl-2-ethylimidazoline.
  • Such copolymers preferably contain at least 50 mol% of at least one N-vinylcarboxamide in copolymerized form.
  • the comonomers are preferably free of acid groups.
  • N-vinylformamide homopolymers or N-vinylformamide copolymers for example vinyl formate, vinyl acetate, vinyl propionate, acrylonitrile, N-vinylcaprolactam, N-vinylurea, N-vinylpyrrolidone or C 1 -C 6 Alkyl vinyl ethers whose N-vinylformamide units are then hydrolyzed to N-vinylamine units to a degree of hydrolysis of preferably 25 to 100 mol%, more preferably 50 to 100 mol% and most preferably 70 to 100 mol%.
  • the hydrolysis of the above-described polymers is carried out by known methods by the action of acids, bases or enzymes.
  • acids are used as hydrolyzing agents
  • the vinylamine units of the polymers are present as the ammonium salt, while hydrolysis with bases gives rise to the free amino groups.
  • the vinylamine polymers are preferably used in salt-free form.
  • Salt-free aqueous solutions can be prepared, for example, from the salt-containing polymer solutions described above by means of ultrafiltration on suitable membranes at separation limits of, for example, 1,000 to 500,000 daltons, preferably 10,000 to 300,000 daltons.
  • Preferred vinylamine polymers are vinylamine homopolymers having a degree of hydrolysis of from 25 to 100 mol%, and from 25 to 100 mol% hydrolyzed copolymers of vinylformamide and vinyl acetate, vinyl alcohol, vinylpyrrolidone or acrylamide, in each case having K values of from 30 to 150, in particular 60 until 90.
  • nitrogen-containing polymer one may use polymers containing polymerized units of monomers having side groups comprising basic nitrogen atoms, or their copolymers with monomers having no (basic) nitrogen atoms in an appropriate ratio.
  • Suitable monomers having side groups comprising basic nitrogen atoms are e.g. Allylamine, basic acrylates, e.g. Dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl acrylate, diethylaminoethyl methacrylate, dimethylaminopropyl acrylate, dimethylaminopropyl methacrylate, diethylaminopropyl acrylate, dimethylaminobutyl acrylate and diethylaminobutyl acrylate; basic (meth) acrylamides, e.g.
  • Suitable monomers without (basic) nitrogen atoms are those mentioned above.
  • cationic starch and "cationically modified starch” are used interchangeably herein. Suitable cationic starches are commercially available.
  • the starting starch can be any type of starch, such as. Potato starch, corn starch, wheat starch, waxy maize starch and tapioca starch. Starches having an amylopectin content of more than 50% by weight, preferably 80 to 100% by weight, are preferred, with those having an amylopectin content of at least 90% by weight being particularly preferred.
  • cationizing agents are dialkylaminoalkyl epoxides and dialkylaminoalkyl halides. Instead of the alkyl groups, the cationizing agents may also contain aryl groups.
  • Preferred cationizing agents are, for example, N, N-dimethylaminoethyl chloride, N, N-diethylaminoethyl chloride, N, N-dimethylaminopropyl chloride, 3-dibutylamino-1,2-epoxypropane, 2-bromo-5-diethylaminopentane hydrobromide, N- (2,3-epoxypropyl ) -piperidine, 2,3-epoxypropyltrimethylammonium chloride and N, N- (2,3-epoxypropyl) -methylaniline.
  • hydrochloric acid or other salts can also be used.
  • the reaction between the starting starch and the cationizing reagent is preferably carried out in an alkaline medium.
  • the proportion of reagent to be used depends on the desired degree of substitution.
  • the degree of substitution is the ratio of cationic group to carbohydrate unit (i.e., glucose unit). He can assume a maximum value of 3.
  • Suitable reactive sizing agents for the paper sizing agents according to the invention are, for example, C 12 - to C 22 -alkyl ketene dimers, C 5 - to C 22 -alkyl or C 5 - to C 22 -alkenylsuccinic anhydrides, C 12 - to C 36 -alkyl isocyanates and / or organic isocyanates, such as Dodecyl isocyanate, octadecyl isocyanate, tetradecyl isocyanate, hexadecyl isocyanate, eicosyl isocyanate and decyl isocyanate.
  • Preferably used engine sizing agents are alkyl ketene dimers and long-chain alkyl or alkenylsuccinic anhydrides.
  • alkylketene dimers examples include tetradecyldiketene, stearydikethene, lauryldiketen, palmityldiketen, oleyldiketen, Behenyldiketen or mixtures thereof. Also suitable are alkyldiketenes having different alkyl groups, such as stearyl palmitate diketene, behenylstearyl diketene, behenylenyldiketene or palmitylbehenyldiketene. Stearyldiketen, Palmityldiketen, Behenyldiketen or mixtures of Behenyldiketen and Stearyldiketen are preferably used.
  • Suitable reactive sizing agents substituted succinic anhydrides are, for example, decenylsuccinic anhydride, n-Octadecenylbemsteinklareanhydrid, dodecenylsuccinic anhydride and n-Hexadecenylbernsteinklahydrid.
  • the aqueous dispersions according to the invention usually have a content of reactive sizes of from 1 to 50% by weight, based on the total weight of the dispersion.
  • the dispersions have a content of 1 to 50 wt .-%, preferably 5 to 35 wt.%, Based on the total weight of the dispersion, of C 12 to C 22 alkyldiketenes.
  • C 5 - to C 22 -alkyl or C 5 - to C 22 -alkenyl-succinic anhydrides their content is, for example, 1 to 25 wt .-%, preferably 2 to 10 wt .-%, based on the total weight of the dispersion.
  • the sizing agents of the present invention typically contain an anionic dispersant.
  • the content of anionic dispersants in the aqueous dispersion is for example 0.01 to 5 wt .-%, preferably 0.01 to 2.5 wt .-% and most preferably 0.1 to 1 wt .-%, based on the reactive.
  • the anionic dispersants may be in the form of the free acids, the alkali metal, alkaline earth metal and / or ammonium salts.
  • the ammonium salts can be derived from both ammonia and from primary, secondary and tertiary amines, for example, the ammonium salts of dimethylamine, trimethylamine, hexylamine, cyclohexylamine, dicyclohexylamine, ethanolamine, diethanolamine and triethanolamine are.
  • the condensation products described above are known and commercially available. They are prepared by condensing said components, it being possible to use the corresponding alkali metal, alkaline earth metal or ammonium salts instead of the free acids.
  • Suitable catalysts in the condensation are, for example, acids such as sulfuric acid, p-toluenesulfonic acid and phosphoric acid.
  • Naphthalenesulfonic acid or its alkali metal salts are condensed with formaldehyde preferably in a molar ratio of 1: 0.1 to 1: 2 and usually in a molar ratio of 1: 0.5 to 1: 1.
  • the molar ratio for the production of condensates of 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, it is also possible to use the alkali metal and ammonium salts of phenolsulfonic acid.
  • the condensation of the abovementioned starting materials may optionally be carried out additionally 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 from 4,000 to 25,000.
  • anionic dispersants are salts which are obtained, for example, by neutralizing the condensation products with lithium hydroxide, sodium hydroxide, Potassium hydroxide or ammonia receives.
  • the pH of the salts is, for example, in the range of 7 to 10.
  • anionic dispersants are lignosulfonic acid and its alkali metal, alkaline earth metal or ammonium salts.
  • amphiphilic copolymers contain as hydrophilic monomers (b), for example, C 3 - to C 10 - monoethylenically unsaturated carboxylic acids or their anhydrides, 2-acrylamido-2-methylpropanesulfonic acid, vinylsulfonic acid, styrenesulfonic acid, vinylphosphonic acid, salts of said monomers or mixtures thereof as hydrophilic monomers polymerized in an anionic group.
  • hydrophilic monomers (b) for example, C 3 - to C 10 - monoethylenically unsaturated carboxylic acids or their anhydrides, 2-acrylamido-2-methylpropanesulfonic acid, vinylsulfonic acid, styrenesulfonic acid, vinylphosphonic acid, salts of said monomers or mixtures thereof as hydrophilic monomers polymerized in an anionic group.
  • Preferred anionic dispersants are copolymers of maleic anhydride with C 4 - to C 12 -olefins, more preferably C 8 -olefins, such as octene-1 and düsobutene. Very particular preference is Düsobuten.
  • 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 aqueous solution or dispersions, wherein the anhydride group is present 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 free acid-free copolymers are used in the form of water-soluble salts, e.g. the corresponding alkali metal, alkaline earth metal and ammonium salts are used.
  • the molecular weight Mw of the amphiphilic copolymers is, for example, 800 to 250,000, usually 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.
  • aqueous dispersions according to the invention may contain further components, such as, for example, non-cellulose-reactive hydrophobic substances which contribute to improving the stability and are described, for example, in EP-A-437 764 and EP-A-658 228.
  • Suitable non-cellulose-reactive substances are, for example, fatty acids, amides and esters as well as waxes.
  • Examples thereof, but not exhaustive, are stearyl behenyl ester, myristate stearyl, stearic isododecyl ester, dioleyl carbonate, oleic acid stearyl ester, oleyl N, N-distearyl urethane, parrafin, di-oleic acid glycerol ester, tris-oleic acid glycerol ester and tris-stearic acid glycerol ester.
  • Suitable monomers of group (a) are styrene, acrylonitrile, methacrylonitrile or mixtures of styrene and acrylonitrile or of styrene and methacrylonitrile.
  • monomers of group (b) are used acrylic acid and / or methacrylic acid esters of C 1 - to C 18 -alcohols and / or vinyl esters of saturated C 2 - to C 4 -carboxylic acids.
  • monomer of group (b) butyl acrylate and butyl methacrylate, for example, acrylic acid isobutyl acrylate, acrylic acid n-butyl acrylate and methacrylic acid isobutyl acrylate.
  • Examples of monomers of group (c) are butadiene, isoprene, C 3 to C 5 monoethylenically unsaturated carboxylic acids, acrylamidomethylpropanesulfonic acid, sodium vinylsulfonate, vinylimidazole, N-vinylformamide, acrylamide, methacrylamide, N-vinylimidazoline and cationic polymers such as dimethylaminopropylmethacrylamide or dimethylaminoethylacrylate-methochloride. From 1 to 32 parts by weight of a monomer mixture of components (a) to (c) are used per 1 part by weight of the copolymer.
  • the monomers of components (a) and (b) can be copolymerized in any ratio, for example in a molar ratio of 0.1: 1 to 1: 0.1. If necessary, the monomers of group (c) are used to modify the properties of the copolymers. Details on the preparation of these additional polymer dispersions can be found in the WO-A-96/31650 and the literature quoted there.
  • polymer dispersions are used in the aqueous dispersions of reactive sizes according to the invention, preference is given to those which contain cationic polymers such as dimethylaminopropylmethacrylamide and / or dimethylaminoethyl acrylate in combination with styrene, acrylonitrile, butadiene and / or acrylic acid esters.
  • cationic polymers such as dimethylaminopropylmethacrylamide and / or dimethylaminoethyl acrylate in combination with styrene, acrylonitrile, butadiene and / or acrylic acid esters.
  • polymer dispersions When such polymer dispersions are used, their content is generally 25 to 300% by weight, preferably 50 to 250% by weight and more preferably 75 to 200% by weight, based on the reactive sizing agent.
  • the invention further provides a process for the preparation of the aqueous dispersions of reactive sizes according to the invention.
  • the reactive sizing agents are usually heated to a temperature above their melting point and emulsified in molten form in water under the action of shear forces.
  • the liquid alkenyl succinic anhydride can be emulsified already at room temperature.
  • lipophilic substances such as fatty acids, waxes, resin acids and resins, fatty acid amides or esters, the melting point of the reactive sizing agent may optionally be lowered, thereby improving the stability of the resulting dispersion.
  • the dispersing step is preferably carried out 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. It has not been proven to provide the nitrogen-containing polymer and to provide it with an anionic dispersant.
  • apparatuses known to those skilled in the art are used, for example high-pressure homogenizers, colloid mills and ultrasonic dispersants. The resulting dispersion is cooled in each case.
  • the paper sizing agent of the invention has a viscosity e.g. in the range of 20 to 1,000 mPas, preferably 100 to 500 mPas (measured with a Brookfield viscometer and a temperature of 22 ° C). Viscosity during 4 weeks of storage at 40 ° C preferably increases at most to less than twice the initial viscosity immediately after production.
  • the pH is preferably in the range of 3 to 4.
  • the dispersions according to the invention are used as engine size agents in the production of paper, board and cardboard.
  • the production of paper, paperboard and cardboard is usually done by dewatering a slurry of cellulosic fibers.
  • Suitable cellulosic fibers are all conventional types, for example cellulosic fibers from wood pulp and fibers obtained from annual plants in Be-tracht.
  • Wood pulp includes, for example, groundwood, thermomechanical pulp (TMP), chemothermomechanical pulp (CTMP), pressure groundwood, 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 include sulphate, sulphite and soda pulps.
  • unbleached pulps also referred to as unbleached kraft pulp, are used.
  • the fibers mentioned can be used alone or in a mixture.
  • the pH of the cellulose fiber slurry is, for example, 4 to 8, preferably 6 to 8.
  • the dewatering of the stock can be carried out batchwise or continuously on a paper machine.
  • the dewatering of the paper stock is preferably carried out additionally 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 achieves a significant improvement in the runnability of the paper machines.
  • cationic retention agents one can use all commercially available products. These are, for example, cationic polyacrylamides, polydiallyldimethylammonium chlorides, high molecular weight polyvinylamines, high molecular weight polyvinylamines having K values of more than 150, polyethyleneimines, polyamines having a molecular weight of more than 50,000, modified polyamines grafted with ethyleneimine and optionally crosslinked, polyetheramides , Polyvinylimidazoles, polyvinylpyrrolidines, polyvinylimidazolines, polyvinyltetrahydropyrines, poly (dialkylaminoalkylvinylethers), poly (dialkylaminoalkyl (meth) acrylates) in protonated or quaternized form and polyamidoamines of a dicarboxylic acid such as adipic acid and polyalkylenepolyamines such as diethylenetriamine grafted with ethyleneimine and with polyethylene glycol dichlor
  • the cationic polymers used as retention aids have, for example, Fikentscher K values of greater than 150 (determined in 5% aqueous common salt solution at a polymer concentration of 0.5% by weight, a temperature of 25 ° C. and a pH Value of 7). They are preferably used in amounts of 0.01 to 0.3 wt .-%, based on dry cellulose fibers.
  • adjuvants known to those skilled in the literature may be added to the stock prior to sheet formation. These are, for example, fixing agents, solidifiers and defoamers.
  • the present invention relates to the use of the paper sizing agent according to the invention as a sizing agent for the production of paper, cardboard and cardboard.
  • the percentages in the examples are percent by weight.
  • the K values were after H. Fikentscher, Cellulosic Chemistry, 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 average particle diameter of the dispersed particles of the polymer dispersions was determined both by Fraunhofer diffraction with a Coulter device of the type LS 230 with a small volume module and by electron microscopy. The viscosities were determined with a Brookfield viscometer at a temperature of 22 ° C.
  • the ink buoyancy time (measured in minutes) is the time required for a test ink according to DIN 53 126 to 50% penetration through a test sheet.
  • the water absorption is given in g / m 2 .
  • the paper sheet is coated on both sides with an adhesive tape streak-free. Then strips are cut with the dimensions 25 x 75 mm. These test strips are immersed in a 30% hydrogen peroxide bath at 70 ° C or in a 3% lactic acid bath at 25 ° C. The edge penetration is determined by differential weighing of the dry test strips and the dip in the bath test strip.
  • the mixture was homogenized by means of a high-pressure homogenizer at 100 bar and 75 ° C in two passes and cooled rapidly with ice.
  • the dispersion obtained had a viscosity of 80 mPas (22 ° C.) and an average particle size of 1.3 ⁇ m. After 4 weeks of storage at 40 ° C, the dispersion had a viscosity of 120 mPas.
  • Example 1 was repeated except that the solution of the naphthalenesulfonic acid-formaldehyde condensate sodium salt and then the polyvinylamine 1 was added first to the initially introduced cationic starch solution. The mixture was mixed with the melt of the alkyl ketene dimer.
  • the dispersion obtained had a viscosity of 100 mPas (22 ° C.) and an average particle size of 1.5 ⁇ m. After 4 weeks of storage at 40 ° C, the dispersion had a viscosity of 180 mPas.
  • Example 1 was repeated except that the solution of the cationic starch initially introduced was first the solution of the polyvinylamine 1 and then the naphthalenesulfonic acid-formaldehyde condensate sodium salt. The mixture was mixed with the melt of the alkyl ketene dimer.
  • the dispersion obtained had a viscosity of 250 mPas (22 ° C.) and an average particle size of 2.5 ⁇ m. After 4 weeks storage at 40 ° C, the dispersion was coagulated and solid.
  • Example 1 was repeated except that 22 parts by weight of an 18% strength by weight solution of polyvinylamine 2 was used instead of polyvinylamine 1.
  • the dispersion obtained had a viscosity of 150 mPas (22 ° C.) and an average particle size of 1.4 ⁇ m. After 4 weeks of storage at 40 ° C, the dispersion had a viscosity of 300 mPas.
  • Example 4 was repeated, but adding the solution of polyvinylamine 2 after homogenization and cooling.
  • the dispersion obtained had a viscosity of 250 mPas (22 ° C.) and an average particle size of 2.8 ⁇ m. After 4 weeks of storage at 40 ° C, the dispersion was solid.
  • the mixture was homogenized by means of a high-pressure homogenizer at 100 bar and 75 ° C in two passes and cooled rapidly with ice.
  • the dispersion obtained had a viscosity of 50 mPas (22 ° C.) and an average particle size of 1.4 ⁇ m. After 4 weeks of storage at 40 ° C, the dispersion had a viscosity of 130 mPas.
  • the mixture was homogenized by means of a high-pressure homogenizer at 100 bar and 75 ° C in two passes and cooled rapidly with ice.
  • the dispersion obtained had a viscosity of 40 mPas (22 ° C.) and an average particle size of 0.9 ⁇ m. After 4 weeks storage at 40 ° C, the dispersion had a viscosity of 900 mPas.
  • Comparative Examples 3 and 5 show that no stable dispersion is obtained when the nitrogen-containing polymer is charged (Comparative Example 3) or added after the dispersing step (Comparative Example 5).
  • Comparative Examples 6 and 7 show the viscosity increase of dispersions which are not nitrogen-containing polymer (Comparative Example 6) or contain no cationic starch (Comparative Example 7) at 4 weeks storage at 40 ° C.

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  • Paper (AREA)
  • Diaphragms For Electromechanical Transducers (AREA)
  • Developing Agents For Electrophotography (AREA)
EP05816209A 2004-11-29 2005-11-29 Papierleimungsmittel Active EP1819876B1 (de)

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WO2005121201A1 (de) * 2004-06-08 2005-12-22 Basf Aktiengesellschaft Amphiphile polymerzusammensetzungen und ihre verwendung
ATE445734T1 (de) * 2006-06-09 2009-10-15 Basf Se Wässrige alkylketendimer-dispersionen
JP2010513734A (ja) * 2006-12-20 2010-04-30 ビーエーエスエフ ソシエタス・ヨーロピア 製紙用サイズ剤混合物
AT506695B1 (de) * 2008-11-14 2009-11-15 Kemira Chemie Ges Mbh Zusammensetzung zur papierleimung
DE102009036344A1 (de) * 2009-08-06 2011-02-10 Bk Giulini Gmbh Leimungsmittel für Papier
CN102656317B (zh) 2009-12-18 2016-03-30 索理思科技开曼公司 纸张施胶组合物
BR112012025330B1 (pt) * 2010-04-07 2020-12-08 Solenis Technologies Cayman, L.P. composições de polivinilaminas com amido catiônico e processo de fabricação de produtos de papel ou papelão
DE102010020249A1 (de) 2010-05-11 2011-11-17 Cs Compact System Gmbh Verfahren zur Emulgierung von Leimungsmitteln für die Papierherstellung, Verwendung von Polymeren sowie emulgierbereite Mischung
AT512143B1 (de) * 2011-11-08 2013-12-15 Chemiefaser Lenzing Ag Cellulosefasern mit hydrophoben Eigenschaften und hoher Weichheit und der dazugehörige Herstellungsprozess
EP2961886B1 (en) * 2013-03-01 2018-07-18 Basf Se Aqueous emulsion of a sizing agent
WO2014144025A1 (en) * 2013-03-15 2014-09-18 Dober Chemical Corp. Dewatering compositions and methods
CN104963240B (zh) * 2015-06-12 2017-03-22 金东纸业（江苏）股份有限公司 一种涂布纸的制造方法及涂布纸
CN105061774B (zh) * 2015-09-22 2017-10-17 东乡县鹤达实业有限公司 一种造纸增强剂及其制备方法
CN105297433B (zh) * 2015-10-30 2017-06-09 广西泰亿诺环保科技有限公司 一种石膏纤维柔性改性剂及其制备方法
CN110894698A (zh) * 2018-09-12 2020-03-20 上海昶法新材料有限公司 一种阳离子型施胶剂及其制备方法和应用

Family Cites Families (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3223544A (en) 1963-03-19 1965-12-14 American Cyanamid Co Manufacture of cationic paper sizing ketene dimer emulsions
US4606773A (en) * 1984-12-10 1986-08-19 Nalco Chemical Company Emulsification of alkenyl succinic anhydride sizing agents
CA1283748C (en) * 1986-06-25 1991-04-30 Takaharu Itagaki Vinylamine copolymer, flocculating agent and paper strength increasingagent using the same, as well as process for producing the same
US5688886A (en) * 1993-08-06 1997-11-18 Showa Highpolymer Co., Ltd. Acrylic rubber composition
DE19505751A1 (de) 1995-02-20 1996-08-22 Basf Ag Wäßrige Alkyldiketen-Dispersionen und ihre Verwendung als Leimungsmittel für Papier
DE19540998A1 (de) * 1995-11-03 1997-05-07 Basf Ag Wäßrige Alkyldiketen-Dispersionen und ihre Verwendung als Leimungsmittel für Papier
US6315824B1 (en) * 1996-02-02 2001-11-13 Rodrigue V. Lauzon Coacervate stabilizer system
DE19610995C2 (de) * 1996-03-21 2002-12-19 Betzdearborn Inc Papierleimungsmittel und -verfahren
DE19710616A1 (de) 1997-03-14 1998-09-17 Basf Ag Wäßrige Dispersionen von Reaktivleimungsmitteln, Verfahren zu ihrer Herstellung und ihre Verwendung
FI103735B (fi) * 1998-01-27 1999-08-31 Kemira Chemicals Oy Paperin tai vastaavan kuitutuotteen hydrofobointijärjestelmä
US6869471B2 (en) * 2001-11-19 2005-03-22 Akzo Nobel N.V. Process for sizing paper and sizing composition
DE10162052A1 (de) * 2001-12-17 2003-06-26 Basf Ag Verfahren zur Herstellung von Papier, Pappe und Karton
DE10237911A1 (de) 2002-08-14 2004-02-26 Basf Ag Verwendung von Vinylamineinheiten enthaltenden Polymeren als Promoter für die Alkyldiketenleimung
TW200504265A (en) * 2002-12-17 2005-02-01 Bayer Chemicals Corp Alkenylsuccinic anhydride surface-applied system and uses thereof
DE102004010447A1 (de) 2004-03-01 2005-09-22 Basf Ag Wässrige Dispersion von Reaktivleimungsmitteln, Verfahren zu ihrer Herstellung und ihre Verwendung

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ES2359072T3 (es) 2011-05-18
CN101068986B (zh) 2012-10-17
US20080041546A1 (en) 2008-02-21
DE502005010891D1 (de) 2011-03-03
PT1819876E (pt) 2011-03-07
EP1819876A2 (de) 2007-08-22
US8512520B2 (en) 2013-08-20
ATE496172T1 (de) 2011-02-15
WO2006058711A3 (de) 2006-09-28
WO2006058711A2 (de) 2006-06-08
CA2587527C (en) 2015-04-28
CN101068986A (zh) 2007-11-07

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