EP1727937B1 - Dispersion aqueuse d'agents d'encollage reactifs, procede de preparation correspondant et utilisation - Google Patents

Dispersion aqueuse d'agents d'encollage reactifs, procede de preparation correspondant et utilisation Download PDF

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Publication number
EP1727937B1
EP1727937B1 EP05707645.7A EP05707645A EP1727937B1 EP 1727937 B1 EP1727937 B1 EP 1727937B1 EP 05707645 A EP05707645 A EP 05707645A EP 1727937 B1 EP1727937 B1 EP 1727937B1
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Prior art keywords
aqueous dispersion
dispersion according
weight
aqueous
acid
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EP1727937A1 (fr
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Johann Bonn
Roland Ettl
Klaus Lorenz
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BASF SE
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BASF SE
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    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • 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
    • 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
    • D21H3/00—Paper or cardboard prepared by adding substances to the pulp or to the formed web on the paper-making machine and by applying substances to finished paper or cardboard (on the paper-making machine), also when the intention is to impregnate at least a part of the paper body

Definitions

  • the invention relates to aqueous dispersions of reactive sizing agents which comprise polymers containing protective vinylamine units as a protective colloid, the protective colloid containing less than 0.0001% by weight, based on the protective colloid, of diketene. Furthermore, the invention relates to a process for preparing the aqueous dispersions, their use for sizing of paper, cardboard and cardboard, and a method for sizing paper, cardboard and cardboard.
  • Aqueous alkyldiketene dispersions stabilized with cationic starch or with anionic emulsifiers are commercially available engine sizing agents for paper.
  • the full sizing effect of papers sized with alkyldiketene dispersions develops only when the sized papers are stored.
  • Such papers can not be further processed immediately following papermaking, e.g. finished with coating colors, or printed. Instead, they must be stored for at least 24 hours until sufficient sizing effect is achieved.
  • cationic polymers increase the speed of sizing.
  • DE-A-3 316 179 describes AKD dispersions containing ethyleneimine units-containing polymers and a water-soluble dicyandiamide-formaldehyde condensation product. Although the latter increases the rate of sizing formation (so-called promoter effect), it does not contribute to the stabilization of the dispersion.
  • AKD dispersions which contain as protective colloids either copolymers of N-vinylpyrrolidone and N-vinylimidazole or condensation products based on polyethyleneimines.
  • the preparation of these AKD dispersions is very complicated by the copolymerization or condensation of the protective colloids.
  • the older German patent application with the file number 10 237 912.2 discloses a method for sizing paper in which a reactive sizing agent, a retention agent and a cationic polymer selected from polymers containing vinylamine units, polymers containing vinylguanadine units, polyethyleneimines, ethyleneimine grafted polyamidoamines and polydiallyldimethylammonium chlorides are added to the aqueous slurry of cellulosic fibers.
  • the cationic polymers are added separately from the reactive sizes, or the components are metered together, but without a dispersion of the components is prepared beforehand.
  • 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 preparation of the protective colloid is very expensive.
  • aqueous dispersions of reactive sizes which contain cationic vinylamine units as protective colloid polymers, wherein the protective colloid contains less than 0.0001 wt .-%, based on the protective colloid, of diketenes.
  • Diketenes in this sense are understood to mean the C 12 -C 22 -alkyl ketene dimers described in more detail below.
  • aqueous dispersions whose protective colloids are essentially free of diketenes, and those whose protective colloids are completely free of diketenes are particularly preferred.
  • aqueous dispersions which generally contain less than 0.0001% by weight of reactive sizing agent.
  • Reactive sizing agents in addition to the C 12 - to C 22 -Alkketendimere also described in more detail below C 5 - to C 22 alkyl or C 5 - to C 22 -Alkenylbernsteinklahydride, C 12 to C 36 alkyl isocyanates, organic isocyanates and / or their mixtures understood.
  • aqueous dispersions whose protective colloids are substantially free of reactive sizes, and those whose protective colloids are completely free of reactive sizes are particularly preferred.
  • aqueous dispersions which contain less than 1% by weight, based on the aqueous dispersion, of cationic starch.
  • aqueous dispersions which are substantially free of cationic starch, and particularly preferred are those which are entirely free of cationic starch.
  • At least one polymer comprising vinylamine units is used as protective colloid for the reactive sizing agent in the aqueous dispersions according to the invention.
  • the amount of cationic polymers is for example 10 to 100 wt .-%, preferably 15 to 75 wt .-%, particularly preferably 20 to 50 wt .-%, based on the reactive size.
  • Vinylamine containing polymers 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 obtainable, for example, by polymerizing N-vinylformamide, N-vinyl-N-methylformamide, N-vinylacetamide, N-vinyl-N-methylacetamide, N-vinyl-N-ethylacetamide and N-vinylpropionamide.
  • the monomers mentioned can be polymerized either alone or together with other monomers.
  • 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, in each case only one OH group being esterified, for example 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.
  • 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.
  • amino alcohols such as Dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl acrylate, diethylaminoethyl methacrylate, dimethylaminopropyl acrylate, dimethylaminopropyl methacrylate, diethylaminopropyl acrylate, dimethylaminobutyl 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 sulfonic acids or in quaternized form.
  • Suitable quaternizing agents are, for example, dimethyl 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 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 and basic (meth) acrylamides, e.g.
  • 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-butylacryl
  • 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.
  • N-vinylimidazoles and N-vinylimidazolines are also used, except in the form of the free bases, in neutralized or quaternized form with mineral acids or organic acids, the quaternization preferably being carried out with dimethyl sulfate, diethyl sulfate, methyl chloride or benzyl chloride. Also suitable are diallyldialkylammonium halides, e.g. Diallyl dimethyl ammonium chloride.
  • the degree of hydrolysis of the homo- and copolymers used is 90 to 95 mol%.
  • the degree of hydrolysis of the homopolymers is synonymous with the content of the polymers of vinylamine units.
  • hydrolysis of the ester groups to form vinyl alcohol units may occur. This is especially the case when carrying out the hydrolysis of the copolymers in the presence of sodium hydroxide solution.
  • Polymerized acrylonitrile is also chemically altered upon hydrolysis. This produces, for example, amide groups or carboxyl groups.
  • the vinylamine units containing homo- and copolymers may optionally contain up to 20 mol% of amidine units, for example, by reaction of formic acid with two adjacent amino groups or by intramolecular reaction of an amino group with an adjacent amide group, for example, of copolymerized N-vinylformamide.
  • the average molecular weights M w of the polymers containing vinylamine units are, for example, 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. ).
  • Particular preference is given to using cationic polymers which have K values of from 85 to 90.
  • the polymers containing vinylamine units are preferably used in salt-free form.
  • Salt-free aqueous solutions of polymers containing vinylamine units can be prepared, for example, from the above-described salt-containing polymer solutions 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.
  • Derivatives of polymers containing vinylamine units can also be used as cationic polymers. It is thus possible, for example, to prepare a large number of suitable derivatives from the vinylamine units by amidation, alkylation, sulfonamide formation, urea formation, thiourea formation, carbamate formation, acylation, carboxymethylation, phosphonomethylation or Michael addition 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 are obtainable by free-radically polymerizing, for example, N-vinylformamide in aqueous medium in the presence of at least one of the stated grafting bases together with copolymerizable other monomers and then hydrolyzing the grafted vinylformamide units in a known manner to give vinylamine units.
  • Preferred polymers containing vinylamine units are vinylamine homopolymers having a degree of hydrolysis of from 1 to 100 mol%, preferably from 25 to 100 mol%, and from 1 to 100 mol%, preferably from 25 to 100 mol%, of hydrolyzed copolymers of vinylformamide and vinyl acetate, vinyl alcohol, vinyl pyrrolidone or acrylamide each having K values of 30 to 150, especially 60 to 90.
  • the polymers containing vinylamine units are used in the aqueous dispersions according to the invention as protective colloids for reactive sizes, in order to obtain aqueous sizing dispersions which have both an increased rate of sizing formation and a sufficient storage stability.
  • Suitable reactive sizes for the dispersions according to the invention are, for example, C 12 -C 22 -alkyl ketene dimers, C 5 -C 22 -alkyl or C 5 -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.
  • substituted succinic anhydrides suitable as reactive sizes are decenylsuccinic anhydride, n-octadecenylsuccinic anhydride, dodecenylsuccinic anhydride and n-hexadecenylsuccinic anhydride.
  • 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 whose content is, for example, 1 to 25 wt .-%, preferably 2 to 10 wt .-%, based on the total weight of the dispersion.
  • 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 primary, secondary and tertiary amines, e.g.
  • the ammonium salts of dimethylamine, trimethylamine, hexylamine, cyclohexylamine, dicyclohexylamine, ethanolamine, diethanolamine and triethanolamine are suitable.
  • 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 for 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 mol 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 diisobutene. Most preferred is diisobutene.
  • the molar ratio between maleic anhydride and olefin is, for example, in the range from 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 solutions or dispersions, where 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-based 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.
  • amphiphilic copolymers are e.g. in amounts of 0.05 to 20, preferably 0.5 to 10 wt .-%, based on the reactive sizing agent, used as an anionic dispersant for the preparation of sizing dispersions.
  • the amphiphilic copolymers are used in amounts of 0.1 to 2, in particular 0.6 to 1 wt .-%, based on the sizing agent to be dispersed.
  • 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 0.01 to 1 wt .-%.
  • 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, for example, in US Pat EP-A-437 764 and EP-A-658,228 are described.
  • Suitable non-cellulosic-reactive substances are, for example, fatty acids, amides and esters as well as waxes.
  • Examples thereof, but not exhaustive, are stearyl behenyl ester, myristate stearylate, isododecyl stearate, dioleyl carbonate, oleic acid stearylate, oleyl N, N-distearyl urethane, paraffin, di-oleic acid glycerol ester, glycerol tris-oleic acid ester and glyceryl tris-stearate.
  • 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.
  • the monomers of group (c) are used to modify the properties of the copolymers.
  • 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 sizing agent is preferably added in the form of a melt and dispersed with vigorous stirring or shearing.
  • first the sizing agent with the anionic dispersant is converted into an emulsion. Then, an aqueous solution of a polymer containing vinylamine units is added, and the emulsifying step is repeated.
  • aqueous sizing agent dispersions which contain 0.1 to 65% by weight, preferably 1 to 50% by weight and more preferably 5 to 35% by weight, of an alkyldiketene or 0.1 to 65% by weight.
  • -% preferably 1 to 50 wt .-%, more preferably 1 to 25 wt .-% and in particular 2 to 10 wt .-% of an alkenylsuccinic anhydride as sizing agent dispersed.
  • Such highly concentrated sizing dispersions have a relatively low viscosity, eg in the range of 20 to 1,000 mPas (measured with a Brookfield viscometer and a temperature of 20 ° C).
  • the pH is, for example, from 2 to 8, and is preferably in the range of from 3 to 4.
  • aqueous sizing agent dispersions having a mean particle size of the sizing agents in the range from 100 to 3,000 nm are obtained
  • the average particle sizes may also be less than 100 nm, for example between 50 and 100 nm, or greater than 3000 nm, for example up to 4 ⁇ m .
  • 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 all fibers obtained from annual plants.
  • 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, polyvinyltetrahydropyrins, 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 dichloro
  • 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 from 0.01 to 0.3% by weight, 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 inventive aqueous dispersions described above as engine size 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% by weight.
  • the molecular weights Mw of the polymers were measured by light scattering.
  • the mean 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.
  • Cationic polymer obtained by hydrolysis of poly-N-vinylformamide having a K value of 90 with a degree of hydrolysis of 95 mol% (polymer containing 95 mol% of vinylamine units and 5 mol% of vinylformamide units).
  • Cationic polymer obtained by hydrolysis of poly-N-vinylformamide having a K value of 75 with a degree of hydrolysis of 65 mol% (polymer containing 65 mol% of vinylamine units and 35 mol% of vinylformamide units).
  • Cationic polymer obtained by hydrolysis of poly-N-vinylformamide having a K value of 110 with a degree of hydrolysis of 95 mol% (polymer containing 95 mol% of vinylamine units and 5 mol% of vinylformamide units).
  • the resulting emulsion was homogenized by means of a high-pressure homogenizer at 170 bar and 75 ° C and then rapidly cooled with ice.
  • the dispersion had a viscosity of 120 mPas at 22 ° C. and an average particle size of 1.6 ⁇ m .
  • dispersion 1 20 g of dispersion 1 were mixed by means of an intensive stirrer with 12 g of a 30 wt .-% polymer dispersion prepared from the monomers styrene, butyl acrylate and a cationic acrylamide (Basoplast ® 270D), having an average particle size of 45 nm.
  • the resulting dispersion had a viscosity of 700 mPas at 22 ° C. and a mean particle size of 1.7 ⁇ m .
  • Test Nos. 1 and 2 are comparative examples, and Tests 3 to 6 are examples according to the invention.
  • the blends were then processed on a Rapid-Kothen sheet former into a sheet having a basis weight of 150 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%.
  • the leaves were coated from both sides with an adhesive tape streak-free. From the leaves strips were cut with the dimensions 25 x 75 mm.
  • the test strips were immersed in a 30% hydrogen peroxide bath at 70 ° C or in a 3% lactic acid bath at 25 ° C. The edge penetration was determined by differential weighing. The results obtained are shown in Table 3.

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Claims (12)

  1. Dispersions aqueuses d'agents de collage réactifs, qui contiennent en tant que colloïde protecteur des polymères contenant des motifs vinylamine cationiques, caractérisées en ce que le colloïde protecteur contient moins de 0,0001 % en poids, par rapport au colloïde protecteur, de dicétènes.
  2. Dispersion aqueuse selon la revendication 1, caractérisée en ce que le colloïde protecteur est pratiquement exempt de dicétènes.
  3. Dispersions aqueuses selon la revendication 1 ou 2, caractérisées en ce que les dispersions aqueuses contiennent moins de 1 % en poids, par rapport à la dispersion aqueuse, d'amidon cationique.
  4. Dispersions aqueuses selon la revendication 3, caractérisées en ce que les dispersions aqueuses sont pratiquement exemptes d'amidon cationique.
  5. Dispersions aqueuses selon l'une quelconque des revendications 1 à 4, caractérisées en ce que les polymères contenant des motifs vinylamine cationiques consistent en des homo- ou copolymérisats de N-vinylformamide hydrolysés à raison de 1 à 100 % en moles.
  6. Dispersions aqueuses selon l'une quelconque des revendications 1 à 5, caractérisées en ce que les polymères contenant des motifs vinylamine cationiques présentent une masse moléculaire moyenne Mw de 1 000 à 2 millions.
  7. Dispersions aqueuses selon l'une quelconque des revendications 1 à 6, caractérisées en ce que la teneur en colloïde protecteur vaut de 10 à 100 % en poids, par rapport à l'agent de collage réactif.
  8. Dispersions aqueuses selon l'une quelconque des revendications 1 à 7, caractérisées en ce qu'on utilise comme agent de collage réactif des dimères d'alkyl(C12-C22)cétènes, des anhydrides alkyl(C5-C22)- ou alcényl(C5-C22)succiniques et/ou des isocyanates d'alkyle (C12-C36).
  9. Dispersions aqueuses selon la revendication 8, caractérisées en ce que la teneur en agents de collage réactifs vaut de 1 à 50 % en poids, par rapport au poids total de la dispersion.
  10. Procédé pour la préparation de dispersions aqueuses selon l'une quelconque des revendications 1 à 9, caractérisé en ce que dans un mélange aqueux on homogénéise sous l'effet de forces de cisaillement les agents de collage réactifs et les polymères contenant des motifs vinylamine cationiques en présence d'un dispersant anionique, à des températures de 20 à 100 °C.
  11. Procédé pour le collage dans la masse du papier, du carton et du carton fort, par addition de dispersions aqueuses selon l'une quelconque des revendications 1 à 9, à une suspension aqueuse de fibres de cellulose et déshydratation de la pâte à papier.
  12. Utilisation des dispersions aqueuses selon l'une quelconque des revendications 1 à 9, en tant qu'agent de collage dans la masse dans la fabrication du papier, du carton, du carton fort et du carton pour emballage de liquides.
EP05707645.7A 2004-03-01 2005-02-26 Dispersion aqueuse d'agents d'encollage reactifs, procede de preparation correspondant et utilisation Not-in-force EP1727937B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102004010447A DE102004010447A1 (de) 2004-03-01 2004-03-01 Wässrige Dispersion von Reaktivleimungsmitteln, Verfahren zu ihrer Herstellung und ihre Verwendung
PCT/EP2005/002051 WO2005083174A1 (fr) 2004-03-01 2005-02-26 Dispersion aqueuse d'agents d'encollage reactifs, procede de preparation correspondant et utilisation

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EP1727937A1 EP1727937A1 (fr) 2006-12-06
EP1727937B1 true EP1727937B1 (fr) 2014-04-09

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US (1) US8633274B2 (fr)
EP (1) EP1727937B1 (fr)
JP (1) JP4589379B2 (fr)
KR (1) KR101186382B1 (fr)
CN (1) CN1926283A (fr)
CA (1) CA2558148C (fr)
DE (1) DE102004010447A1 (fr)
ES (1) ES2462340T3 (fr)
PT (1) PT1727937E (fr)
WO (1) WO2005083174A1 (fr)

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WO2008074690A1 (fr) * 2006-12-20 2008-06-26 Basf Se Mélanges de produits d'encollage de papier
JP4957636B2 (ja) * 2008-04-17 2012-06-20 株式会社豊田中央研究所 表面修飾バイオファイバー、その製造方法、および表面修飾バイオファイバーを含有する樹脂複合材料
AT506695B1 (de) * 2008-11-14 2009-11-15 Kemira Chemie Ges Mbh Zusammensetzung zur papierleimung
KR101316336B1 (ko) * 2009-01-30 2013-10-08 허큘레스 인코포레이티드 제지에 있어서 첨가제로서의 4차 비닐아민-함유 중합체
PL2513373T3 (pl) * 2009-12-18 2014-03-31 Solenis Technologies Cayman Lp Kompozycja do zaklejania papieru
AT512143B1 (de) * 2011-11-08 2013-12-15 Chemiefaser Lenzing Ag Cellulosefasern mit hydrophoben Eigenschaften und hoher Weichheit und der dazugehörige Herstellungsprozess
WO2014132175A1 (fr) * 2013-03-01 2014-09-04 Basf Se Emulsion aqueuse d'un agent de collage
CN103410051A (zh) * 2013-07-09 2013-11-27 上海东升新材料有限公司 表面施胶剂乳液及其制备方法
CN103790071B (zh) * 2013-12-23 2016-04-13 齐鲁工业大学 一种锂皂石与聚乙烯吡咯烷酮协同稳定的asa施胶剂乳液
IT202200007787A1 (it) * 2022-04-20 2023-10-20 Fira S R L Composto per la produzione di carta ad elevata resistenza

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DE102004010447A1 (de) 2005-09-22
US20070167558A1 (en) 2007-07-19
JP4589379B2 (ja) 2010-12-01
KR20060134139A (ko) 2006-12-27
ES2462340T3 (es) 2014-05-22
EP1727937A1 (fr) 2006-12-06
JP2007525607A (ja) 2007-09-06
CA2558148A1 (fr) 2005-09-09
US8633274B2 (en) 2014-01-21
PT1727937E (pt) 2014-05-12
WO2005083174A1 (fr) 2005-09-09
KR101186382B1 (ko) 2012-09-26
CN1926283A (zh) 2007-03-07
CA2558148C (fr) 2015-12-08

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