WO2006122934A2 - Method for producing paper, paperboard and cardboard in the presence of water-swellable polymers - Google Patents

Method for producing paper, paperboard and cardboard in the presence of water-swellable polymers Download PDF

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Publication number
WO2006122934A2
WO2006122934A2 PCT/EP2006/062346 EP2006062346W WO2006122934A2 WO 2006122934 A2 WO2006122934 A2 WO 2006122934A2 EP 2006062346 W EP2006062346 W EP 2006062346W WO 2006122934 A2 WO2006122934 A2 WO 2006122934A2
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WO
WIPO (PCT)
Prior art keywords
water
paper
swellable
polymer
polymers
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PCT/EP2006/062346
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German (de)
French (fr)
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WO2006122934A3 (en
Inventor
Simon Champ
Roland Ettl
Samantha Champ
Original Assignee
Basf Aktiengesellschaft
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Basf Aktiengesellschaft filed Critical Basf Aktiengesellschaft
Priority to US11/913,823 priority Critical patent/US20080190576A1/en
Priority to EP06755211A priority patent/EP1883733A2/en
Priority to CA002608428A priority patent/CA2608428A1/en
Priority to JP2008511692A priority patent/JP2008540866A/en
Publication of WO2006122934A2 publication Critical patent/WO2006122934A2/en
Publication of WO2006122934A3 publication Critical patent/WO2006122934A3/en

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Classifications

    • DTEXTILES; PAPER
    • D21PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21HPULP 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
    • D21H23/00Processes or apparatus for adding material to the pulp or to the paper
    • D21H23/02Processes or apparatus for adding material to the pulp or to the paper characterised by the manner in which substances are added
    • D21H23/04Addition to the pulp; After-treatment of added substances in the pulp
    • D21H23/06Controlling the addition
    • D21H23/14Controlling the addition by selecting point of addition or time of contact between components
    • D21H23/16Addition before or during pulp beating or refining
    • DTEXTILES; PAPER
    • D21PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21HPULP 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
    • D21H21/00Non-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
    • D21H21/14Non-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
    • D21H21/22Agents rendering paper porous, absorbent or bulky
    • DTEXTILES; PAPER
    • D21PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21HPULP 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
    • D21H27/00Special paper not otherwise provided for, e.g. made by multi-step processes
    • D21H27/002Tissue paper; Absorbent paper
    • DTEXTILES; PAPER
    • D21PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21HPULP 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
    • D21H27/00Special paper not otherwise provided for, e.g. made by multi-step processes
    • D21H27/10Packing paper
    • DTEXTILES; PAPER
    • D21PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21HPULP 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
    • D21H27/00Special paper not otherwise provided for, e.g. made by multi-step processes
    • D21H27/30Multi-ply

Definitions

  • the present invention describes a process for the production of paper, paperboard and cardboard in the presence of water-swellable polymers. Furthermore, the invention relates to the use of water-swellable polymers in the production of paper, board and cardboard and paper products with water-swellable polymers.
  • Water-swellable polymers according to the invention are polymers which can absorb at least 1% of their own weight of water. Preferably, they absorb at least 10% of their own weight, more preferably at least 25% of their own weight, and most preferably at least 50% of their own weight in water. Water-swellable polymers in the context of the present invention are in particular so-called superabsorbent polymers which can absorb at least 100% of their own weight in water.
  • hydrogels are commonly used as a gel-like suspension of absorbent products for making diapers, tampons, sanitary napkins and other personal care products, but also as water-retaining agents in agricultural horticulture.
  • water-swellable polymers may also be of interest in other areas.
  • polyurethane foams and so-called airlaid cellulose matts have been used to increase the water absorption capacity of tissue papers while maintaining wet strength. These are also used in the production of packaging material, the packaging material should also retain the strength while absorbing liquids. These are, for example, packaging material for frozen foods. In papermaking, an increase in bulk (so-called bulk) is desired without sacrificing the strength of the paper. These could also be potential applications for water-swellable polymers.
  • EP 0 437 816 A1 describes a superabsorbent wet laid nonwoven material which is obtained by a process comprising the following steps: mixing the superabsorbent polymer particles with a liquid to form a slurry, mixing the resulting slurry with fibers, filtering the superabsorbent polymer Fiber mixture and then drying to obtain a highly absorbent wet-laid nonwoven material.
  • the materials thus obtained are used, inter alia, in diapers, incontinence articles, packaging papers for foodstuffs and dressing materials such as patches.
  • EP 1 068 392 B1 discloses an improved wet process for producing an absorbent structure. Accordingly, in a device for web formation by the wet process, a fiber suspension is processed, which additionally contains water-swellable, water-insoluble superabsorbent particles. A wetted superabsorbent particle-containing wet web is formed, deprived of water and then transported to the dryer section. It is crucial that the contact between superabsorbent and suspension to fleece inlet into the dryer section is at most 45 seconds, which does not give the superabsorbent sufficient time to swell.
  • US 5,997,690 and US 6,290,813 B1 disclose a process for making superabsorbent wet-laid nonwoven material wherein a slurry of water-swellable, water-insoluble superabsorbent particles with fibers is first prepared, the superabsorbent particles having a particle size of less than 250 microns prior to addition. This slurry is then added to a saline solution. Thereafter, a wet web is formed, which is washed with water and then dried. The wet laid nonwoven materials thus obtained have a residual salt content of less than 40% in the dry state.
  • US 2002/0060013 A1 relates to a method for producing wet-laid
  • Nonwoven materials containing at least 1% by weight of an absorbent polymer having a thermo-reversible liquid holding capacity.
  • US 2003/0014038 A1 discloses superabsorbent articles which contain a core with swellable branched superabsorbent particles which is in a liquid-permeable shell.
  • the articles disclosed in this document can be added with effective amounts of an antibiotic or antibacterial agent so that the end products can be used in the medical field.
  • the object of the present invention was therefore to find a process for the production of paper, paperboard and cardboard in the presence of a water-swellable polymer, which solves the aforementioned problems, namely the size of the swollen polymer in the Compared to the paper thickness and on the other hand, the high water content of the swollen polymer, which is usually up to 99.9 wt .-%, eliminated.
  • the object was achieved by a process for the production of paper, paperboard and cardboard in the presence of a water-swellable polymer by adding the water-swellable polymer to a fiber suspension, wherein the water-swellable polymers contained fiber suspension is ground.
  • a water-swellable polymer is understood as meaning water-absorbing polymers which can absorb at least 1% of their own weight of water. Preferably, they take up at least 10% of their own weight, more preferably at least 25% of their own weight, and most preferably at least 50% of their own weight in water.
  • Water-swellable polymers for the purposes of the present invention are in particular so-called superabsorbent polymers which can absorb at least 100% of their own weight of water.
  • polymers of (co) polymerized hydrophilic monomers graft (co) polymers of one or more hydrophilic monomers on a suitable graft base, crosslinked cellulose or starch ethers, crosslinked carboxymethylcellulose, partially crosslinked polyalkylene oxide or in aqueous liquids swellable natural products, such as guar derivatives.
  • Such hydrogels are commonly used as aqueous solutions of absorbent products for the manufacture of diapers, tampons, sanitary napkins, and other personal care products.
  • the water-swellable polymers contained fiber suspension is ground.
  • This grinding is usually carried out to a degree of beating by Schopper-Riegler of 10, preferably 25, more preferably 35, most preferably 50 and more preferably 70.
  • the milling can be carried out, for example, in a conventional pulper.
  • the fiber-containing polymer suspension is subjected to the usual papermaking process.
  • paper process chemicals are added.
  • paper pulps may also be added to the fiber suspension prior to addition of the water-swellable polymer.
  • the mixture containing water-swellable polymers can pass through one or more shear stages, both prior to the addition of the paper processing chemicals and thereafter. Subsequently, the mixture is dewatered with foliar formation on a sieve and drying of the leaves.
  • the additives customarily used in papermaking are added in the customary amounts, for example fixing agents, retention aids, including microparticle systems, dry and wet strength agents, massagers, biocides and / or dyes.
  • 0.1 to 20% by weight of a water-swellable polymer is added to the fiber suspension.
  • the amount of water-swellable polymers in the fiber suspension is preferably between 0.5 and 10% by weight, more preferably between 0.8 and 5% by weight and very particularly preferably between 1 and 2.5% by weight, based in each case on the dry content of the suspension.
  • the fiber suspension to which the water-swellable polymer is added usually contains from 0.5 to 4% by weight of fibers, preferably from 0.5 to 2.5% by weight of fibers and most preferably from 0.8 to 1.5 % By weight of fibers, in each case based on the dry content of the suspension.
  • the suspension preferably has a fraction of about 1% by weight of fibers, based on the solids content of the suspension.
  • the water-swellable polymers may have any particle size before swelling in aqueous solution, preferably the particle size is in the range of 10 nm to 10 mm, more preferably in the range of 50 nm to 5 mm and particularly preferably in the range of 100 nm to 1 mm.
  • the water-swellable polymers usually have particle sizes in the range of 100 nm to 100 mm, preferably in the range of 0.5 mm to 25 mm and particularly preferably in the range of 0.1 mm to 10 mm.
  • the form of addition of the water-swellable polymer to the fiber suspension is irrelevant.
  • a solid mixture of the fiber with a solid mixture of the water-swellable polymer in the above-mentioned quantitative ranges of the individual components are mixed together.
  • the mixture is mixed with sufficient water to form a water-swellable polymer-containing fiber suspension.
  • the water-swellable polymer is given in this way the possibility to swell in the presence of the fibers.
  • water-swellable polymers can also be used in the process according to the invention. These can be added to the fiber suspension both as a mixture at the same time as well as separately from one another. Preferably, however, a water-swellable polymer is used.
  • the superabsorbent polymer particles which can be used in the process according to the invention can be obtained by polymerization of a monomer solution comprising
  • Monomers i), ii) and optionally iii) can be grafted at least partially,
  • Suitable monomers i) are, for example, ethylenically unsaturated carboxylic acids, such as acrylic acid, methacrylic acid, maleic acid, fumaric acid and itaconic acid, or derivatives thereof, such as acrylamide, methacrylamide, acrylic esters and methacrylic acid esters. Particularly preferred monomers are acrylic acid and methacrylic acid. Very particular preference is given to acrylic acid.
  • Preferred hydroquinone half ethers are hydroquinone monomethyl ether (MEHQ) and / or tocopherols.
  • Tocopherol is understood as meaning compounds of the following formula
  • R 1 is hydrogen or methyl
  • R 2 is hydrogen or methyl
  • R 3 is hydrogen or methyl
  • R 4 is hydrogen or an acid radical having 1 to 20 carbon atoms.
  • Preferred radicals for R 4 are acetyl, ascorbyl, succinyl, nicotinyl and other physiologically acceptable carboxylic acids.
  • the carboxylic acids can be mono-, di- or tricarboxylic acids.
  • R 4 is particularly preferably hydrogen or acetyl. Especially preferred is RRR-alpha-tocopherol.
  • the monomer solution preferably contains at most 130 ppm by weight, more preferably at most 70 ppm by weight, preferably at least 10 ppm by weight, particularly preferably at least 30 ppm by weight, particularly preferably by 50 ppm by weight, hydroquinone halide, in each case based on acrylic acid, wherein acrylic acid salts are taken into account arithmetically as acrylic acid.
  • acrylic acid salts are taken into account arithmetically as acrylic acid.
  • an acrylic acid having a corresponding content of hydroquinone half-ether can be used.
  • the superabsorbent polymers are crosslinked, ie the polymerization is carried out in the presence of compounds having at least two polymerisable groups which can be radically copolymerized into the polymer network.
  • Suitable crosslinkers ii) are, for example, ethylene glycol dimethacrylate, diethylene glycol diacrylate, allyl methacrylate, trimethylolpropane triacrylate, triallylamine, tetraallyloxyethane, as described in EP-A-0 530 438, di- and triacrylates, as in EP-A 547 847, EP-A 559 476, EP-A 632 068, WO 93/21237, WO 03/104299, WO 03/104300, WO 03/104301 and described in the German patent application with the file number DE 103 31 450.4, mixed acrylates containing in addition to acrylate groups further ethylenically unsaturated groups, such as in German patent applications DE 103 31 456.3 and DE 103
  • Useful crosslinkers ii) include in particular N 1 N '- methylenebisacrylamide and N 1 N' - diacrylate methylenebismethacrylamide, esters of unsaturated mono- or polycarboxylic acids of polyols, such as diacrylate or triacrylate, for example butanediol or ethylene glycol or - methacrylate and trimethylolpropane triacrylate and allyl compounds, such as allyl (meth) acrylate, triallyl cyanurate, maleic acid diallyl esters, polyallyl esters, tetraallyloxyethane, triallylamine, tetraallylethylenediamine, allyl esters of phosphoric acid and vinylphosphonic acid derivatives, as described, for example, in EP-A-0 343 427.
  • crosslinkers ii) are pentaerythritol di-, pentaerythritol tri- and pentaerythritol tetraallyl ethers, polyethylene glycol diallyl ether, ethylene glycol diallyl ether, glycerol and glycerol triallyl ethers, polyallyl ethers based on sorbitol, and ethoxylated variants thereof.
  • Useful in the process according to the invention are di (meth) acrylates of polyethylene glycols, wherein the polyethylene glycol used has a molecular weight between 300 and 1000.
  • crosslinkers ii) are di- and triacrylates of 3 to 20 times ethoxylated glycerol, 3 to 20 times ethoxylated trimethylolpropane, 3 to 20 times ethoxylated trimethylolethane, in particular di- and triacrylates of 2 to 6-fold ethoxylated glycerol or trimethylolpropane, the 3-fold propoxylated glycerol or trimethylolpropane, and the 3-times mixed ethoxylated or propoxylated glycerol or trimethylolpropane, the 15-times ethoxylated glycerol or trimethylolpropane, and at least 40-times ethoxylated glycerol, Trimethylolethane or trimethylolpropane.
  • Very particularly preferred crosslinkers ii) are the polyethoxylated and / or propoxylated glycerols esterified with acrylic acid or methacrylic acid to form di- or triacrylates, as described, for example, in German Patent Application DE 103 19 462.2.
  • Particularly advantageous are di- and / or triacrylates of 3- to 10-fold ethoxylated glycerol.
  • diacrylates or triacrylates of 1 to 5 times ethoxylated and / or propoxylated glycerol.
  • Most preferred are the triacrylates of 3 to 5 times ethoxylated and / or propoxylated glycerin.
  • acrylamide, methacrylamide, crotonic acid amide, dimethylaminoethyl methacrylate, dimethylaminoethyl acrylate, dimethylaminopropyl acrylate, diethylaminopropyl acrylate, dimethylaminobutyl acrylate, dimethylaminoethyl methacrylate, diethylamine are copolymerizable with the monomers i).
  • water-soluble polymers iv) it is possible to use polyvinyl alcohol, polyvinylpyrrolidone, starch, starch derivatives, polyglycols or polyacrylic acids, preferably polyvinyl alcohol and starch.
  • the reaction is preferably carried out in a kneader, as described, for example, in WO 01/38402, or on a belt reactor, as described, for example, in EP-A 955 086.
  • the hydrogel after leaving the polymerization reactor at a higher temperature is advantageous, particularly preferably at least 70 0 C, most preferably at least 80 0 C, and preferably less than 100 0 C 1 mounted, for example, in insulated containers.
  • the monomer conversion is further increased.
  • the acid groups of the hydrogels obtained are usually partially neutralized, preferably from 25 to 95 mol%, preferably from 27 to 80 mol%, particularly preferably from 27 to 30 mol% or from 40 to 75 mol%, using the customary neutralizing agents may be, preferably alkali metal hydroxides, alkali metal oxides, alkali metal carbonates or Alkalimetallhydrogencarbonate and mixtures thereof. Instead of alkali metal salts and ammonium salts can be used. Sodium and potassium are particularly preferred as alkali metals, but most preferred are sodium hydroxide, sodium carbonate or sodium bicarbonate and mixtures thereof.
  • the neutralization is achieved by mixing the neutralizing agent as an aqueous solution, as a melt, or preferably as a solid.
  • sodium hydroxide with a water content well below 50 wt .-% may be present as a waxy mass with a melting point above 23 ° C. In this case, a dosage as general cargo or melt at elevated temperature is possible.
  • the neutralization can be carried out after the polymerization at the hydrogel stage. However, it is also possible to neutralize up to 40 mol%, preferably 10 to 30 mol%, particularly preferably 15 to 25 mol%, of the acid groups prior to the polymerization by adding a part of the neutralizing agent to the monomer solution and the desired final degree of neutralization after the polymerization is adjusted at the level of the hydrogel.
  • the monomer solution can be neutralized by mixing in the neutralizing agent.
  • the hydrogel can be mechanically comminuted, for example by means of a meat grinder, wherein the neutralizing agent can be sprayed, sprinkled or poured on and then carefully mixed in. For this purpose, the gel mass obtained can be further gewolfft for homogenization. Neutralization of the monomer solution directly to the final degree of neutralization is preferred.
  • the neutralized hydrogel is then dried with a belt or roller dryer until the residual moisture content is preferably less than 15% by weight, in particular less than 10% by weight, the water content being in accordance with that recommended by EDANA (European Disposables and Nonwovens Association) Test Method No. 430.2-02 "Moisture content" is determined.
  • EDANA European Disposables and Nonwovens Association
  • a fluidized bed dryer or a heated ploughshare mixer can be used for drying.
  • the dried hydrogel is thereafter ground and classified, wherein for grinding usually one- or multi-stage roller mills, preferably two- or three-stage roller mills, pin mills, hammer mills or vibratory mills can be used.
  • superabsorbent polymer particles are generally postcrosslinked. This postcrosslinking can be carried out in aqueous gel phase.
  • ground and sieved polymer particles base polymer
  • crosslinking agents suitable for this purpose are compounds which contain at least two groups which can form covalent bonds with the carboxylate groups of the hydrophilic polymer or which can crosslink at least two carboxyl groups or other functional groups of at least two different polymer chains of the base polymer.
  • Suitable postcrosslinkers v) are compounds which contain at least two groups which can form covalent bonds with the carboxylate groups of the polymers.
  • Suitable compounds are, for example, alkoxysilyl compounds, polyaziridines, polyamines, polyamidoamines, di- or polyglycidyl compounds, as described in EP-A 083 022, EP-A 543 303 and EP-A 937 736, polyhydric alcohols, as described in DE-C 33 14 019, DE-C 35 23 617 and EP-A 450 922, or IJ-hydroxyalkylamides, as described in DE-A 102 04 938 and US Pat. No. 6,239,230.
  • mixed functionality such as glycidol, 3-ethyl-3-oxetanemethanol (trimethylolpropane oxetane), as described in EP-A 1 199 327, noethanol, diethanolamine, triethanolamine or compounds which form a further functionality after the first reaction, such as ethylene oxide, propylene oxide, isobutylene oxide, aziridine, azetidine or oxetane.
  • DE-A 40 20 780 cyclic carbonates, in DE-A 198 07 502 2-oxazolidone and its derivatives, such as N- (2-hydroxyethyl) -2-oxazolidone, in DE-A 198 07 992 Bis- and Poly-2-oxazolidinone, in DE-A 198 54 573 2-oxotetrahydro-1, 3-oxazine and its derivatives, in DE-A 198 54 574 N-acyl-2-oxazolidone, in DE-A 102 04 937 cyclic ureas , German Patent Application DE 103 34 584.1 describes bicyclic amide acetals, EP-A1 199 327 oxetanes and cyclic ureas, and WO 03/031482 describes morpholine-2,3-dione and its derivatives as suitable post-crosslinking agents v).
  • the postcrosslinking is usually carried out so that a solution of the postcrosslinker is sprayed onto the hydrogel or the dry base polymer particles. Subsequent to the spraying, it is thermally dried, whereby the postcrosslinking reaction can take place both before and during the drying.
  • the spraying of a solution of the crosslinker is preferably carried out in mixers with moving mixing tools, such as screw mixers, paddle mixers, disk mixers, plowshare mixers and paddle mixers.
  • moving mixing tools such as screw mixers, paddle mixers, disk mixers, plowshare mixers and paddle mixers.
  • Vertical mixers are particularly preferred, plowshare mixers and paddle mixers are very particularly preferred.
  • Suitable mixers are, for example, Lödige ® mixers, Bepex ® mixers, Nauta ® mixer, Processall mixers and Schugi ® ® mixer.
  • the thermal drying is preferably carried out in contact dryers, more preferably paddle dryers, very particularly preferably disk dryers.
  • Suitable dryers include for example Bepex ® dryers and Nara ® dryers.
  • fluidized bed dryers can also be used.
  • the drying can take place in the mixer itself, by heating the jacket or blowing hot air. Also suitable is a downstream dryer, such as a hopper dryer, a rotary kiln or a heatable screw. However, it is also possible, for example, to use an azeotropic distillation as the drying process.
  • Preferred drying temperatures are in the range 50 to 25O 0 C, preferably at 50 to 200 0 C, and particularly preferably at 50 to 15O 0 C.
  • the preferred residence time at this temperature in the reaction mixer or dryer is below 30 minutes and more preferably below 10 minutes.
  • the papers, boards and cardboards produced by the process according to the invention have an increased water absorption capacity compared to conventional paper qualities without loss of strength.
  • the papers can absorb water and also hold under heat, such as when used in laser printers.
  • all paper qualities can be produced, e.g. Cardboard, single / multi-layer carton, single / multi-layer liner, corrugated medium, papers for newspaper printing, so-called medium-fine writing and printing papers, natural gravure papers and lightweight base papers.
  • wood pulp, thermomechanical pulp (TMP), chemo-thermo-mechanical pulp (CTMP), pressure pulp (PGW), wood pulp and sulphite and sulphate pulp can be used to produce such papers.
  • the pulps can be short fiber as well as long fiber.
  • tissue papers such as toilet paper, paper handkerchiefs and facial tissues as well as kitchen paper, furthermore hygiene or sanitary papers, packaging papers, for example for foodstuffs or multilayer papers which can be used in hygiene articles or packaging materials, are preferably produced.
  • the last-mentioned multilayer papers consist of several different paper layers, the paper layer produced by the process according to the invention being incorporated either above a conventional paper layer or between two conventional paper layers.
  • the present invention furthermore relates to the use of water-swellable polymers in the production of paper, paperboard and cardboard in the process according to the invention.
  • Another object of the present invention are also paper, cardboard and
  • the invention relates to so-called tissue papers, such as toilet paper, paper handkerchiefs and facial tissues and kitchen paper, further hygiene or sanitary papers, packaging papers, for example, for food, or even multi-layer paper, which can be used in hygiene articles or packaging materials.
  • tissue papers such as toilet paper, paper handkerchiefs and facial tissues and kitchen paper
  • packaging papers for example, for food, or even multi-layer paper, which can be used in hygiene articles or packaging materials.
  • the dry breaking length of the dried paper sheets was determined according to the test method according to DIN EN ISO 1924-2.
  • a mixture of bleached birch sulphate and bleached pine sulphite in the ratio of 70/30 at a solids concentration of 1% was admixed with 1% by weight, based on the solids content of the paper stock suspension, of the previously swollen water-swellable polymer 1. This mixture was added to the laboratory pulper without specking until a Schopper-Riegler freeness of 35 was reached.
  • Example 1 was repeated except that 2.5% by weight, based on the solids content of the pulp suspension, of the previously swollen water-swellable polymer 1 was added to the bleached birch sulphate bleach bleached pine sulphite blend.
  • a mixture of bleached birch sulphate and bleached pine sulphite in a ratio of 70/30 at a solids concentration of 1% was admixed with 1% by weight, based on the solids content of the paper stock suspension, of the previously swollen water-swellable polymer 1.
  • This mixture was added to the laboratory pulper without specking until a Schopper-Riegler freeness of 35 was reached.
  • a cationic polyacrylamide retention aid (poly min ® KE 2020, BASF Aktiengesellschaft) in this mixture.
  • the metered amount of the retention agent was 0.03% polymer, based on the solids content of the paper stock suspension.
  • Example 3 was repeated except that 2.5% by weight, based on the solids content of the pulp suspension, of the previously swollen water-swellable polymer 1 was added to the bleached birch sulphate bleached pine sulphite blend.
  • a mixture of bleached birch sulphate and bleached pine sulphite in a ratio of 70/30 at a solids concentration of 1% was admixed with 1% by weight, based on the solids content of the pulp suspension, of the previously swollen water-swellable polymer 1. This mixture was tapped in the laboratory pulper until it reached a grinding degree of 35 according to Schopper-Riegler. Immediately thereafter, the metered addition, a cationic polyacrylamide retention aid (poly min ® KE 2020, BASF Aktiengesellschaft) and a filler (Hydrocarb ® OG from Omya) in this mixture. The metered amount of the retention agent and the filler was 0.03% polymer or 20% filler, based on the solids content of the paper stock suspension.
  • Example 5 was repeated except that 2.5% by weight, based on the solids content of the paper stock suspension, of the previously swollen water-swellable polymer 1 was added to the mixture of bleached birch sulphate and bleached pine sulphite. Comparative Example 1
  • a mixture of bleached birch sulphate and bleached pine sulphite in a ratio of 70/30 at a solids concentration of 1% was beaten without specks in the laboratory pulper until a Schopper-Riegler freeness of 35 was reached.
  • a cationic starch Solvitose BKN ®
  • a cationic polyacrylamide retention aid Polymin ® KE 2020, BASF Aktiengesellschaft
  • a filler Hydrocarb ® OG from Omya
  • the paper sheets were each made on a Rapid-Köthen sheet former according to ISO 5269/2 with a sheet weight of 80 g / m 2 and then dried for 5 minutes at 100 0 C. Subsequently, the dry break length of the paper sheets was checked. The results are summarized in Table 1.
  • the paper sheets were each cut to a size of 200 mm x 15 mm. These cut paper strips were each hung in a beaker filled with water, with the upper end of the paper strip being clamped to the edge of the beaker. At the beginning of the test, the paper strips dipped about 10 to 20 mm into the water, marking the place of immersion (lower limit). After 10 minutes, the paper strips were pulled out of the water. The upper limit to which the water had run was also marked. Then the distance between the lower and upper limit, ie the distance that the water traveled, was measured. The results are summarized in Table 2.

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Abstract

The invention relates to a method for producing paper, paperboard and cardboard in the presence of a water-swellable polymer by adding the latter to a fibre suspension. According to said method, the fibre suspension containing water-swellable polymers is milled.

Description

Verfahren zur Herstellung von Papier, Pappe und Karton in Gegenwart von wasser- quellbaren Polymeren Process for the production of paper, paperboard and cardboard in the presence of water-swellable polymers
Beschreibungdescription
Die vorliegende Erfindung beschreibt ein Verfahren zur Herstellung von Papier, Pappe und Karton in Gegenwart von wasserquellbaren Polymeren. Weiterhin betrifft die Erfindung die Verwendung von wasserquellbaren Polymeren bei der Herstellung von Papier, Pappe und Karton sowie Papierprodukte mit wasserquellbaren Polymeren.The present invention describes a process for the production of paper, paperboard and cardboard in the presence of water-swellable polymers. Furthermore, the invention relates to the use of water-swellable polymers in the production of paper, board and cardboard and paper products with water-swellable polymers.
Wasserquellbare Polymere im Sinne der Erfindung sind Polymere, die mindestens 1 % ihres eigenen Gewichts an Wasser aufnehmen können. Bevorzugt nehmen sie mindestens 10 % ihres eigenen Gewichts, besonders bevorzugt mindestens 25 % ihres eigenen Gewichts und insbesondere bevorzugt mindestens 50 % ihres eigenen Ge- wichts an Wasser auf. Wasserquellbare Polymere im Sinne der vorliegenden Erfindung sind insbesondere sogenannte superabsorbierende Polymere, die mindestens 100 % ihres eigenen Gewichts an Wasser aufnehmen können. Bei diesen handelt es sich beispielsweise um Polymere aus (co)polymerisierten hydrophilen Monomeren, Propf(co)polymere von einem oder mehreren hydrophilen Monomeren auf einer geeig- neten Propfgrundlage, vernetzte Cellulose- oder Stärkeether, vernetzte Carboxy- methylcellulose, teilweise vernetztes Polyalkylenoxid oder in wässrigen Flüssigkeiten quellbare Naturprodukte, wie beispielsweise Guarderivate. Solche Hydrogele werden üblicherweise als gelartige Suspension absorbierender Produkte zur Herstellung von Windeln, Tampons, Damenbinden und anderen Hygieneartikeln, aber auch als was- serzurückhaltende Mittel im landwirtschaftlichen Gartenbau verwendet.Water-swellable polymers according to the invention are polymers which can absorb at least 1% of their own weight of water. Preferably, they absorb at least 10% of their own weight, more preferably at least 25% of their own weight, and most preferably at least 50% of their own weight in water. Water-swellable polymers in the context of the present invention are in particular so-called superabsorbent polymers which can absorb at least 100% of their own weight in water. These are, for example, polymers of (co) polymerized hydrophilic monomers, graft (co) polymers of one or more hydrophilic monomers on a suitable graft base, crosslinked cellulose or starch ethers, crosslinked carboxymethylcellulose, partially crosslinked polyalkylene oxide or aqueous products swellable natural products such as guar derivatives. Such hydrogels are commonly used as a gel-like suspension of absorbent products for making diapers, tampons, sanitary napkins and other personal care products, but also as water-retaining agents in agricultural horticulture.
Die Verwendung von wasserquellbaren Polymeren kann aber auch in anderen Bereichen von Interesse sein. Bisher werden zur Erhöhung der Wasseraufnahmefähigkeit von Tissuepapieren unter gleichzeitigem Erhalt der Nassfestigkeit Polyurethanschäu- me und sogenannte airlaid cellulose matts eingesetzt. Diese werden ebenfalls bei der Herstellung von Verpackungsmaterial verwendet, wobei das Verpackungsmaterial bei gleichzeitiger Aufnahme von Flüssigkeiten ebenfalls die Festigkeit behalten soll. Dabei handelt es sich beispielsweise um Verpackungsmaterial für tiefgefrorene Lebensmittel. In der Papierherstellung ist eine Erhöhung des Volumens (sog. bulk) erwünscht, ohne dass dabei die Festigkeit des Papiers leidet. Dies könnten ebenfalls potenzielle Anwendungsgebiete für wasserquellbare Polymeren sein.However, the use of water-swellable polymers may also be of interest in other areas. Up to now, polyurethane foams and so-called airlaid cellulose matts have been used to increase the water absorption capacity of tissue papers while maintaining wet strength. These are also used in the production of packaging material, the packaging material should also retain the strength while absorbing liquids. These are, for example, packaging material for frozen foods. In papermaking, an increase in bulk (so-called bulk) is desired without sacrificing the strength of the paper. These could also be potential applications for water-swellable polymers.
EP 0 437 816 A1 beschreibt ein hochabsorbierendes Nasslege-Vliesmaterial, welches durch ein Verfahren umfassend folgende Schritte erhalten wird: Mischen der Superab- sorber Polymer Partikel mit einer Flüssigkeit zur Bildung einer Aufschlämmung, Mischen der so erhaltenen Aufschlämmung mit Fasern, Filtrieren des Superabsorber Polymer-Faser-Gemisches und anschließend Trocknen unter Erhalt eines hochabsor- bierenden Nasslege-Vliesmaterials. Die so erhaltenen Materialen werden u.a. in Windeln, Inkontinenzartikeln, Verpackungspapieren für Lebensmittel und Verbandsmate- rialen wie Pflastern eingesetzt.EP 0 437 816 A1 describes a superabsorbent wet laid nonwoven material which is obtained by a process comprising the following steps: mixing the superabsorbent polymer particles with a liquid to form a slurry, mixing the resulting slurry with fibers, filtering the superabsorbent polymer Fiber mixture and then drying to obtain a highly absorbent wet-laid nonwoven material. The materials thus obtained are used, inter alia, in diapers, incontinence articles, packaging papers for foodstuffs and dressing materials such as patches.
Aus der EP 1 068 392 B1 ist ein verbessertes Nassverfahren zur Herstellung einer absorbierenden Struktur bekannt. Demnach wird in einer Vorrichtung zur Vliesbildung nach dem Nassverfahren eine Fasersuspension verarbeitet, welche zusätzlich was- serquellbare, wasserunlösliche Superabsorber-Teilchen enthält. Es wird ein benetztes Superabsorber-Teilchen enthaltendes Nassvlies gebildet, dem Wasser entzogen wird und anschließend in die Trockenpartie befördert wird. Dabei ist entscheidend, dass der Kontakt zwischen Superabsorber und Suspension bis zum Vlieseinlauf in die Trockenpartie höchstens 45 Sekunden beträgt, wodurch der Superabsorber nicht ausreichend Zeit zum Quellen erhält.EP 1 068 392 B1 discloses an improved wet process for producing an absorbent structure. Accordingly, in a device for web formation by the wet process, a fiber suspension is processed, which additionally contains water-swellable, water-insoluble superabsorbent particles. A wetted superabsorbent particle-containing wet web is formed, deprived of water and then transported to the dryer section. It is crucial that the contact between superabsorbent and suspension to fleece inlet into the dryer section is at most 45 seconds, which does not give the superabsorbent sufficient time to swell.
US 5,997,690 und US 6,290,813 B1 offenbaren ein Verfahren zur Herstellung von hochabsorbierendem Nasslege-Vliesmaterial, wobei zunächst eine Anschlämmung von wasserquellbaren, wasserunlöslichen Superabsorber-Teilchen mit Fasern hergesellt wird, wobei die Superabsorber-Teilchen vor Zugabe eine Teilchengröße von weniger als 250 Mikrometer haben. Dieser Anschlämmung wird anschließend eine salz- haltige Lösung zugesetzt. Danach wird eine nasse Bahn gebildet, die mit Wasser gewaschen und anschließend getrocknet wird. Die so erhaltenen Nasslege- Vliesmateriale haben im trockenen Zustand einen Restsalzgehalt von weniger als 40 %.US 5,997,690 and US 6,290,813 B1 disclose a process for making superabsorbent wet-laid nonwoven material wherein a slurry of water-swellable, water-insoluble superabsorbent particles with fibers is first prepared, the superabsorbent particles having a particle size of less than 250 microns prior to addition. This slurry is then added to a saline solution. Thereafter, a wet web is formed, which is washed with water and then dried. The wet laid nonwoven materials thus obtained have a residual salt content of less than 40% in the dry state.
US 2002/0060013 A1 betrifft ein Verfahren zur Herstellung von Nasslege-US 2002/0060013 A1 relates to a method for producing wet-laid
Vliesmaterialen, die mindestens 1 Gew.-% eines absorbierenden Polymeren mit einer thermo-reversiblen Flüssigkeitsaufnahmekapazität enthalten.Nonwoven materials containing at least 1% by weight of an absorbent polymer having a thermo-reversible liquid holding capacity.
Aus der US 2003/0014038 A1 sind superabsorbierende Artikel bekannt, die einen Kern mit quellbaren verzweigten superabsorbierenden Partikel, welcher in einer flüssigkeitsdurchlässigen Hülle ist, enthalten. Die in dieser Schrift offenbarten Artikel können mit wirksamen Mengen eines Antiobiotikums oder eines antibakteriellen Mittels versetzt werden, so dass die Endprodukte im medizinischen Bereich eingesetzt werden können.US 2003/0014038 A1 discloses superabsorbent articles which contain a core with swellable branched superabsorbent particles which is in a liquid-permeable shell. The articles disclosed in this document can be added with effective amounts of an antibiotic or antibacterial agent so that the end products can be used in the medical field.
Nachteilig an den Verfahren aus dem Stand der Technik ist, dass die zuvor genannten Probleme nicht ausreichend gelöst bzw. beseitigt werden.A disadvantage of the methods of the prior art is that the aforementioned problems are not sufficiently solved or eliminated.
Aufgabe der vorliegenden Erfindung war es daher, ein Verfahren zur Herstellung von Papier, Pappe und Karton in Gegenwart eines wasserquellbaren Polymeren zu finden, das die zuvor genannten Probleme, nämlich die Größe des gequollenen Polymers im Vergleich zur Papierdicke und zum anderen der hohe Wassergehalt des gequollenen Polymeren, der üblicherweise bei bis zu 99,9 Gew.-% liegt, beseitigt.The object of the present invention was therefore to find a process for the production of paper, paperboard and cardboard in the presence of a water-swellable polymer, which solves the aforementioned problems, namely the size of the swollen polymer in the Compared to the paper thickness and on the other hand, the high water content of the swollen polymer, which is usually up to 99.9 wt .-%, eliminated.
Die Aufgabe wurde gelöst durch ein Verfahren zur Herstellung von Papier, Pappe und Karton in Gegenwart eines wasserquellbaren Polymeren durch Zugabe des wasser- quellbaren Polymeren zu einer Fasersuspension, wobei die wasserquellbare Polymere enthaltene Fasersuspension gemahlen wird.The object was achieved by a process for the production of paper, paperboard and cardboard in the presence of a water-swellable polymer by adding the water-swellable polymer to a fiber suspension, wherein the water-swellable polymers contained fiber suspension is ground.
Unter einem wasserquellbaren Polymeren im Sinne der vorliegenden Erfindung wer- den wasserabsorbierende Polymere verstanden, die mindestens 1 % ihres eigenen Gewichts an Wasser aufnehmen können. Bevorzugt nehmen sie mindestens 10 % ihres eigenen Gewichts, besonders bevorzugt mindestens 25 % ihres eigenen Gewichts und insbesondere bevorzugt mindestens 50 % ihres eigenen Gewichts an Wasser auf. Wasserquellbare Polymere im Sinne der vorliegenden Erfindung sind insbe- sondere sogenannte superabsorbierende Polymere, die mindestens 100 % ihres eigenen Gewichts an Wasser aufnehmen können. Bei diesen handelt es sich beispielsweise um Polymere aus (co)polymerisierten hydrophilen Monomeren, Propf(co)polymere von einem oder mehreren hydrophilen Monomeren auf einer geeigneten Propfgrundla- ge, vernetzte Cellulose- oder Stärkeether, vernetzte Carboxymethylcellulose, teilweise vernetztes Polyalkylenoxid oder in wässrigen Flüssigkeiten quellbare Naturprodukte, wie beispielsweise Guarderivate. Solche Hydrogele werden üblicherweise als wässrige Lösungen absorbierender Produkte zur Herstellung von Windeln, Tampons, Damenbinden und anderen Hygieneartikeln verwendet.For the purposes of the present invention, a water-swellable polymer is understood as meaning water-absorbing polymers which can absorb at least 1% of their own weight of water. Preferably, they take up at least 10% of their own weight, more preferably at least 25% of their own weight, and most preferably at least 50% of their own weight in water. Water-swellable polymers for the purposes of the present invention are in particular so-called superabsorbent polymers which can absorb at least 100% of their own weight of water. These are, for example, polymers of (co) polymerized hydrophilic monomers, graft (co) polymers of one or more hydrophilic monomers on a suitable graft base, crosslinked cellulose or starch ethers, crosslinked carboxymethylcellulose, partially crosslinked polyalkylene oxide or in aqueous liquids swellable natural products, such as guar derivatives. Such hydrogels are commonly used as aqueous solutions of absorbent products for the manufacture of diapers, tampons, sanitary napkins, and other personal care products.
Nach dem erfindungsgemäßen Verfahren wird die wasserquellbare Polymere enthaltene Fasersuspension gemahlen. Diese Mahlung erfolgt üblicherweise bis zu einem Mahlgrad nach Schopper-Riegler von 10, bevorzugt von 25, besonders bevorzugt von 35, ganz besonders bevorzugt von 50 und insbesondere bevorzugt von 70. Die Mahlung kann beispielsweise in einem konventionellen Pulper erfolgen.According to the method of the invention, the water-swellable polymers contained fiber suspension is ground. This grinding is usually carried out to a degree of beating by Schopper-Riegler of 10, preferably 25, more preferably 35, most preferably 50 and more preferably 70. The milling can be carried out, for example, in a conventional pulper.
Anschließend wird die wasserquellbare Polymere enthaltene Fasersuspension dem üblichen Papierherstellungsprozess unterzogen. Bevorzugt werden nach der Mahlung Papierprozesschemikalien zugesetzt. Selbstverständlich können der Fasersuspension aber auch vor Zugabe des wasserquellbaren Polymeren bereits Papierprozesschemi- kalien zugesetzt werden.Subsequently, the fiber-containing polymer suspension is subjected to the usual papermaking process. Preferably, after the milling, paper process chemicals are added. Of course, paper pulps may also be added to the fiber suspension prior to addition of the water-swellable polymer.
Die wasserquellbare Polymere enthaltene Mischung kann sowohl vor der Zugabe der Papierprozesschemikalien als auch danach jeweils eine oder mehrere Scherstufen durchlaufen. Anschließend wird die Mischung unter Blattbildung auf einem Sieb und Trocknen der Blätter entwässert. Als Papierprozesschemikalien werden die üblicherweise bei der Papierherstellung verwendeten Additive in den üblichen Mengen zugesetzt, z.B. Fixiermittel, Retenti- onsmittel inklusive Mikropartikelsysteme, Trocken- und Naßfestmittel, Masselei- mungsmittel, Biozide und/oder Farbstoffe.The mixture containing water-swellable polymers can pass through one or more shear stages, both prior to the addition of the paper processing chemicals and thereafter. Subsequently, the mixture is dewatered with foliar formation on a sieve and drying of the leaves. As paper process chemicals, the additives customarily used in papermaking are added in the customary amounts, for example fixing agents, retention aids, including microparticle systems, dry and wet strength agents, massagers, biocides and / or dyes.
In dem erfindungsgemäßen Verfahren werden der Fasersuspension 0,1 bis 20 Gew.- % eines wasserquellbaren Polymeren zugesetzt. Bevorzugt beträgt die Menge an wasserquellbaren Polymeren in der Fasersuspension zwischen 0,5 und 10 Gew.%, besonders bevorzugt zwischen 0,8 und 5 Gew.-% und ganz besonders bevorzugt zwi- sehen 1 und 2,5 Gew-%, jeweils bezogen auf den Trockengehalt der Suspension.In the process according to the invention, 0.1 to 20% by weight of a water-swellable polymer is added to the fiber suspension. The amount of water-swellable polymers in the fiber suspension is preferably between 0.5 and 10% by weight, more preferably between 0.8 and 5% by weight and very particularly preferably between 1 and 2.5% by weight, based in each case on the dry content of the suspension.
Die Fasersuspension, zu der das wasserquellbare Polymere gegeben wird, enthält in der Regel 0,5 bis 4 Gew.-% Fasern, bevorzugt 0,5 bis 2,5 Gew.-% Fasern und ganz besonders bevorzugt 0,8 bis 1,5 Gew.-% Fasern, jeweils bezogen auf den Trockenge- halt der Suspension. Insbesondere bevorzugt hat die Suspension einen Anteil von ca. 1 Gew.-% Fasern, bezogen auf den Trockengehalt der Suspension.The fiber suspension to which the water-swellable polymer is added usually contains from 0.5 to 4% by weight of fibers, preferably from 0.5 to 2.5% by weight of fibers and most preferably from 0.8 to 1.5 % By weight of fibers, in each case based on the dry content of the suspension. In particular, the suspension preferably has a fraction of about 1% by weight of fibers, based on the solids content of the suspension.
Die wasserquellbaren Polymere können vor dem Aufquellen in wässriger Lösung jede Partikelgröße haben, bevorzugt liegt die Partikelgröße im Bereich von 10 nm bis 10 mm, besonders bevorzugt im Bereich von 50 nm bis 5 mm und besonders bevorzugt im Bereich von 100 nm bis 1 mm. Nach dem Aufquellen haben die wasserquellbaren Polymere üblicherweise Partikelgrößen im Bereich von 100 nm bis 100 mm, bevorzugt im Bereich von 0,5 mm bis 25 mm und besonders bevorzugt im Bereich von 0,1 mm bis 10 mm.The water-swellable polymers may have any particle size before swelling in aqueous solution, preferably the particle size is in the range of 10 nm to 10 mm, more preferably in the range of 50 nm to 5 mm and particularly preferably in the range of 100 nm to 1 mm. After swelling, the water-swellable polymers usually have particle sizes in the range of 100 nm to 100 mm, preferably in the range of 0.5 mm to 25 mm and particularly preferably in the range of 0.1 mm to 10 mm.
Die Zugabeform des wasserquellbaren Polymeren zu der Fasersuspension ist unerheblich. So kann beispielsweise eine feste Mischung der Faser mit einer festen Mischung des wasserquellbaren Polymeren in den zuvor genannten Mengenbereichen der einzelnen Komponenten miteinander vermengt werden. Anschließend wird die Mischung mit ausreichend Wasser versetzt, so dass eine wasserquellbare Polymere enthaltene Fasersuspension entsteht. Dem wasserquellbaren Polymeren wird auf diesem Wege die Möglichkeit gegeben, in Gegenwart der Fasern aufzuquellen.The form of addition of the water-swellable polymer to the fiber suspension is irrelevant. Thus, for example, a solid mixture of the fiber with a solid mixture of the water-swellable polymer in the above-mentioned quantitative ranges of the individual components are mixed together. Subsequently, the mixture is mixed with sufficient water to form a water-swellable polymer-containing fiber suspension. The water-swellable polymer is given in this way the possibility to swell in the presence of the fibers.
Ebenso ist es möglich, eine gelartige Suspension eines wasserqellbaren Polymeren in Wasser vorzubereiten, in der das wasserquellbare Polymere aufquillt, wobei diese gelartige Suspension anschließend der Fasersuspension zugesetzt wird. In dieser Ausführungsform des erfindungsgemäßen Verfahrens ist es möglich, wenn die gelartige Suspension mit gequollenem wasserquellbaren Polymeren einer Scherstufe ausgesetzt wird. Dabei hängt die Dauer und Scherrate von dem eingesetzten wasserquellba- ren Polymeren ab. Die optimale Dauer und Scherrate wird der Fachmann im Rahmen seiner üblichen Versuche ermitteln. In einer anderen Ausführungsform des erfindungsgemäßen Verfahrens wird das was- serquellbare Polymere durch Sprühen in die Fasersuspension eingebracht.It is likewise possible to prepare a gel-like suspension of a water-swellable polymer in water in which the water-swellable polymer swells, this gel-like suspension then being added to the fiber suspension. In this embodiment of the process according to the invention, it is possible for the gelatinous suspension to be exposed to a shear stage with swollen water-swellable polymer. The duration and shear rate depend on the water-swellable polymer used. The optimum duration and shear rate will be determined by one skilled in the art within the scope of his usual experiments. In another embodiment of the method according to the invention, the water-swellable polymer is introduced by spraying into the fiber suspension.
Selbstverständlich können in dem erfindungsgemäßen Verfahren auch mehrere was- serquellbare Polymere eingesetzt werden. Diese können sowohl als Mischung gleichzeitig als auch getrennt voneinander der Fasersuspension zugesetzt werden. Bevorzugt wird jedoch ein wasserquellbares Polymer verwendet.Of course, several water-swellable polymers can also be used in the process according to the invention. These can be added to the fiber suspension both as a mixture at the same time as well as separately from one another. Preferably, however, a water-swellable polymer is used.
Herstellverfahren für superabsorbierende Polymere werden in „ Modern Superabsor- bent Polymer Technology" , F. L. Buchholz and A. T. Graham, Wiley-VCH, 1998, Seiten 69 bis 118 beschrieben. Dabei wird eine Monomerlösung zu einem Grundpolymer polymerisiert, beispielsweise in einem Kneter oder einem Bandreaktor.Production processes for superabsorbent polymers are described in "Modern Superabsorbed Polymer Technology", F.L. Buchholz and A.T. Graham, Wiley-VCH, 1998, pages 69 to 118. A monomer solution is polymerized into a base polymer, for example in a kneader or a belt reactor.
Die im erfindungsgemäßen Verfahren einsetzbaren superabsorbierenden Polymerpartikel können durch Polymerisation einer Monomerlösung, enthaltendThe superabsorbent polymer particles which can be used in the process according to the invention can be obtained by polymerization of a monomer solution comprising
i) mindestens ein ethylenisch ungesättigtes, säuregruppentragendes Monomer, ii) mindestens einen Vernetzer, iii) gegebenenfalls ein oder mehrere mit i) copolymerisierbare ethylenisch und/oder allylisch ungesättigte Monomere und iv) gegebenenfalls ein oder mehrere wasserlösliche Polymere, auf die diei) at least one ethylenically unsaturated, acid group-carrying monomer, ii) at least one crosslinker, iii) optionally one or more ethylenically and / or allylically unsaturated monomers copolymerizable with i) and iv) optionally one or more water-soluble polymers to which the
Monomere i), ii) und ggf. iii) zumindest teilweise aufgepfropft werden können,Monomers i), ii) and optionally iii) can be grafted at least partially,
wobei das dabei erhaltene Grundpolymer getrocknet, klassiert,wherein the base polymer thereby obtained dried, classified,
v) gegebenenfalls mit mindestens einem Nachvemetzer nachbehandelt, getrocknet und thermisch nachvernetztv) optionally post-treated with at least one Nachvemetzer, dried and thermally postcrosslinked
wird, hergestellt werden.will be produced.
Geeignete Monomere i) sind beispielsweise ethylenisch ungesättigte Carbonsäuren, wie Acrylsäure, Methacrylsäure, Maleinsäure, Fumarsäure und Itaconsäure, oder deren Derivate, wie Acrylamid, Methacrylamid, Acrylsäureester und Methacrylsäureester. Besonders bevorzugte Monomere sind Acrylsäure und Methacrylsäure. Ganz besonders bevorzugt ist Acrylsäure.Suitable monomers i) are, for example, ethylenically unsaturated carboxylic acids, such as acrylic acid, methacrylic acid, maleic acid, fumaric acid and itaconic acid, or derivatives thereof, such as acrylamide, methacrylamide, acrylic esters and methacrylic acid esters. Particularly preferred monomers are acrylic acid and methacrylic acid. Very particular preference is given to acrylic acid.
Die Monomere i), insbesondere Acrylsäure, enthalten vorzugsweise bis zu 0,025 Gew.-% eines Hydrochinonhalbethers. Bevorzugte Hydrochinonhalbether sind Hydrochinonmonomethylether (MEHQ) und/oder Tocopherole.The monomers i), in particular acrylic acid, preferably contain up to 0.025 wt .-% of a Hydrochinonhalbethers. Preferred hydroquinone half ethers are hydroquinone monomethyl ether (MEHQ) and / or tocopherols.
Unter Tocopherol werden Verbindungen der folgenden Formel verstanden
Figure imgf000007_0001
Tocopherol is understood as meaning compounds of the following formula
Figure imgf000007_0001
wobei R1 Wasserstoff oder Methyl, R2 Wasserstoff oder Methyl, R3 Wasserstoff oder Methyl und R4 Wasserstoff oder ein Säurerest mit 1 bis 20 Kohlenstoffatomen bedeutet.wherein R 1 is hydrogen or methyl, R 2 is hydrogen or methyl, R 3 is hydrogen or methyl and R 4 is hydrogen or an acid radical having 1 to 20 carbon atoms.
Bevorzugte Reste für R4 sind Acetyl, Ascorbyl, Succinyl, Nicotinyl und andere physiologisch verträgliche Carbonsäuren. Die Carbonsäuren können Mono-, Di- oder Tricar- bonsäuren sein.Preferred radicals for R 4 are acetyl, ascorbyl, succinyl, nicotinyl and other physiologically acceptable carboxylic acids. The carboxylic acids can be mono-, di- or tricarboxylic acids.
Bevorzugt ist alpha- Tocopherol mit R1 = R2 = R3 = Methyl, insbesondere racemisches alpha- Tocopherol. R4 ist besonders bevorzugt Wasserstoff oder Acetyl. Insbesondere bevorzugt ist RRR-alpha-Tocopherol.Preferred is alpha-tocopherol with R 1 = R 2 = R 3 = methyl, in particular racemic alpha-tocopherol. R 4 is particularly preferably hydrogen or acetyl. Especially preferred is RRR-alpha-tocopherol.
Die Monomerlösung enthält bevorzugt höchstens 130 Gew.-ppm, besonders bevorzugt höchstens 70 Gew.-ppm, bevorzugt mindestens 10 Gew.-ppm, besonders bevorzugt mindestens 30 Gew.-ppm, insbesondere bevorzugt um 50 Gew.-ppm, Hydrochinon- halbether, jeweils bezogen auf Acrylsäure, wobei Acrylsäuresalze rechnerisch als Ac- rylsäure mit berücksichtigt werden. Beispielsweise kann zur Herstellung der Monomerlösung eine Acrylsäure mit einem entsprechenden Gehalt an Hydrochinonhalbether verwendet werden.The monomer solution preferably contains at most 130 ppm by weight, more preferably at most 70 ppm by weight, preferably at least 10 ppm by weight, particularly preferably at least 30 ppm by weight, particularly preferably by 50 ppm by weight, hydroquinone halide, in each case based on acrylic acid, wherein acrylic acid salts are taken into account arithmetically as acrylic acid. For example, to prepare the monomer solution, an acrylic acid having a corresponding content of hydroquinone half-ether can be used.
Die superabsorbierenden Polymere sind vernetzt, d.h. die Polymerisation wird in Ge- genwart von Verbindungen mit mindestens zwei polymerisierbaren Gruppen, die in das Polymernetzwerk radikalisch einpolymerisiert werden können, durchgeführt. Geeignete Vernetzer ii) sind beispielsweise Ethylenglykoldimethacrylat, Diethylenglykoldiacrylat, Allylmethacrylat, Trimethylolpropantriacrylat, Triallylamin, Tetraallyloxyethan, wie in EP-A-O 530 438 beschrieben, Di- und Triacrylate, wie in EP-A 547 847, EP-A 559 476, EP-A 632 068, WO 93/21237, WO 03/104299, WO 03/104300, WO 03/104301 und in der deutschen Patentanmeldung mit dem Aktenzeichen DE 103 31 450.4 beschrieben, gemischte Acrylate, die neben Acrylatgruppen weitere ethylenisch ungesättigte Gruppen enthalten, wie in den deutschen Patentanmeldungen mit den Aktenzeichen DE 103 31 456.3 und DE 103 55 401.7 beschrieben, oder Vernetzermischungen, wie beispielsweise in DE-A-195 43 368, DE-A-196 46 484, WO-A-90/15830 und WO-A- 02/32962 beschrieben. Geeignete Vernetzer ii) sind insbesondere N1N' - Methylenbisacrylamid und N1N' - Methylenbismethacrylamid, Ester ungesättigter Mono- oder Polycarbonsäuren von Polyolen, wie Diacrylat oder Triacrylat, beispielsweise Butandiol- oder Ethylenglykol- diacrylat bzw. - methacrylat sowie Trimethylolpropantriacrylat und Allylverbindungen, wie Allyl(meth)acrylat, Triallylcyanurat, Maleinsäurediallylester, Polyallylester, Tetraal- lyloxyethan, Triallylamin, Tetraallylethylendiamin, Allylester der Phosphorsäure sowie Vinylphosphonsäurederivate, wie sie beispielsweise in EP- A- 0 343 427 beschrieben sind. Weiterhin geeignete Vernetzer ii) sind Pentaerythritoldi-, Pentaerythritoltri- und Pentaerythritoltetraallylether, Polyethylenglykoldiallylether, Ethylenglykoldiallylether, Glyzerindi- und Glyzerintriallylether, Polyallylether auf Basis Sorbitol, sowie ethoxy- lierte Varianten davon. Im erfindungsgemäßen Verfahren einsetzbar sind Di(meth)acrylate von Polyethylenglykolen, wobei das eingesetzte Polyethylenglykol ein Molekulargewicht zwischen 300 und 1000 aufweist.The superabsorbent polymers are crosslinked, ie the polymerization is carried out in the presence of compounds having at least two polymerisable groups which can be radically copolymerized into the polymer network. Suitable crosslinkers ii) are, for example, ethylene glycol dimethacrylate, diethylene glycol diacrylate, allyl methacrylate, trimethylolpropane triacrylate, triallylamine, tetraallyloxyethane, as described in EP-A-0 530 438, di- and triacrylates, as in EP-A 547 847, EP-A 559 476, EP-A 632 068, WO 93/21237, WO 03/104299, WO 03/104300, WO 03/104301 and described in the German patent application with the file number DE 103 31 450.4, mixed acrylates containing in addition to acrylate groups further ethylenically unsaturated groups, such as in German patent applications DE 103 31 456.3 and DE 103 55 401.7, or crosslinker mixtures, as described, for example, in DE-A-195 43 368, DE-A-196 46 484, WO-A-90/15830 and WO-A- 02/32962. Useful crosslinkers ii) include in particular N 1 N '- methylenebisacrylamide and N 1 N' - diacrylate methylenebismethacrylamide, esters of unsaturated mono- or polycarboxylic acids of polyols, such as diacrylate or triacrylate, for example butanediol or ethylene glycol or - methacrylate and trimethylolpropane triacrylate and allyl compounds, such as allyl (meth) acrylate, triallyl cyanurate, maleic acid diallyl esters, polyallyl esters, tetraallyloxyethane, triallylamine, tetraallylethylenediamine, allyl esters of phosphoric acid and vinylphosphonic acid derivatives, as described, for example, in EP-A-0 343 427. Further suitable crosslinkers ii) are pentaerythritol di-, pentaerythritol tri- and pentaerythritol tetraallyl ethers, polyethylene glycol diallyl ether, ethylene glycol diallyl ether, glycerol and glycerol triallyl ethers, polyallyl ethers based on sorbitol, and ethoxylated variants thereof. Useful in the process according to the invention are di (meth) acrylates of polyethylene glycols, wherein the polyethylene glycol used has a molecular weight between 300 and 1000.
Besonders vorteilhafte Vernetzer ii) sind jedoch Di- und Triacrylate des 3- bis 20-fach ethoxylierten Glyzerins, des 3- bis 20-fach ethoxylierten Trimethylolpropans, des 3- bis 20-fach ethoxylierten Trimethylolethans, insbesondere Di- und Triacrylate des 2- bis 6- fach ethoxylierten Glyzerins oder Trimethylolpropans, des 3-fach propoxylierten Glyzerins oder Trimethylolpropans, sowie des 3-fach gemischt ethoxylierten oder propoxy- lierten Glyzerins oder Trimethylolpropans, des 15-fach ethoxylierten Glyzerins oder Trimethylolpropans, sowie des mindestens 40-fach ethoxylierten Glyzerins, Trimethylolethans oder Trimethylolpropans.However, particularly advantageous crosslinkers ii) are di- and triacrylates of 3 to 20 times ethoxylated glycerol, 3 to 20 times ethoxylated trimethylolpropane, 3 to 20 times ethoxylated trimethylolethane, in particular di- and triacrylates of 2 to 6-fold ethoxylated glycerol or trimethylolpropane, the 3-fold propoxylated glycerol or trimethylolpropane, and the 3-times mixed ethoxylated or propoxylated glycerol or trimethylolpropane, the 15-times ethoxylated glycerol or trimethylolpropane, and at least 40-times ethoxylated glycerol, Trimethylolethane or trimethylolpropane.
Ganz besonders bevorzugte Vernetzer ii) sind die mit Acrylsäure oder Methacrylsäure zu Di- oder Triacrylaten veresterten mehrfach ethoxylierten und/oder propoxylierten Glyzerine wie sie beispielsweise in der älteren deutschen Anmeldung mit Aktenzeichen DE 103 19 462.2 beschrieben sind. Besonders vorteilhaft sind Di- und/oder Triacrylate des 3- bis 10-fach ethoxylierten Glyzerins. Ganz besonders bevorzugt sind Di- oder Triacrylate des 1- bis 5- fach ethoxylierten und/oder propoxylierten Glyzerins. Am meisten bevorzugt sind die Triacrylate des 3- bis 5-fach ethoxylierten und/oder propoxylierten Glyzerins. Diese zeichnen sich durch besonders niedrige Restgehalte (typischerweise unter 10 Gew.-ppm) im superabsorbierenden Polymer aus und die wässri- gen Extrakte der damit hergestellten superabsorbierenden Polymere weisen eine fast unveränderte Oberflächenspannung (typischerweise mindestens 0,068 N/m) im Ver- gleich zu Wasser gleicher Temperatur auf.Very particularly preferred crosslinkers ii) are the polyethoxylated and / or propoxylated glycerols esterified with acrylic acid or methacrylic acid to form di- or triacrylates, as described, for example, in German Patent Application DE 103 19 462.2. Particularly advantageous are di- and / or triacrylates of 3- to 10-fold ethoxylated glycerol. Very particular preference is given to diacrylates or triacrylates of 1 to 5 times ethoxylated and / or propoxylated glycerol. Most preferred are the triacrylates of 3 to 5 times ethoxylated and / or propoxylated glycerin. These are characterized by particularly low residual contents (typically below 10 ppm by weight) in the superabsorbent polymer and the aqueous extracts of the superabsorbent polymers produced therewith have an almost unchanged surface tension (typically at least 0.068 N / m) compared to water same temperature.
Mit den Monomeren i) copolymerisierbare ethyienisch ungesättigte Monomere iii) sind beispielsweise Acrylamid, Methacrylamid, Crotonsäureamid, Dimethylaminoethyl- methacrylat, Dimethylaminoethylacrylat, Dimethylaminopropylacrylat, Diethylami- nopropylacrylat, Dimethylaminobutylacrylat, Dimethylaminoethylmethacrylat, Diethyla- minoethylmethacrylat, Dimethylaminoneopentylacrylat und Dimethylaminoneopentyl- methacrylat.For example, acrylamide, methacrylamide, crotonic acid amide, dimethylaminoethyl methacrylate, dimethylaminoethyl acrylate, dimethylaminopropyl acrylate, diethylaminopropyl acrylate, dimethylaminobutyl acrylate, dimethylaminoethyl methacrylate, diethylamine are copolymerizable with the monomers i). minoethyl methacrylate, dimethylaminoneopentyl acrylate and dimethylaminoneopentyl methacrylate.
Als wasserlösliche Polymere iv) können Polyvinylalkohol, Polyvinylpyrrolidon, Stärke, Stärkederivate, Polyglykole oder Polyacrylsäuren, vorzugsweise Polyvinylalkohol und Stärke, eingesetzt werden.As water-soluble polymers iv) it is possible to use polyvinyl alcohol, polyvinylpyrrolidone, starch, starch derivatives, polyglycols or polyacrylic acids, preferably polyvinyl alcohol and starch.
Die Herstellung eines geeigneten Grundpolymers sowie weitere geeignete hydrophile ethylenisch ungesättigte Monomere i) werden in DE-A 199 41 423, EP-A 686 650, WO 01/45758 und WO 03/104300 beschrieben.The preparation of a suitable base polymer and further suitable hydrophilic ethylenically unsaturated monomers i) are described in DE-A 199 41 423, EP-A 686 650, WO 01/45758 and WO 03/104300.
Die Umsetzung wird vorzugsweise in einem Kneter, wie beispielsweise in WO 01/38402 beschrieben, oder auf einem Bandreaktor, wie beispielsweise in EP-A 955 086 beschrieben, durchgeführt.The reaction is preferably carried out in a kneader, as described, for example, in WO 01/38402, or on a belt reactor, as described, for example, in EP-A 955 086.
Vorteilhaft wird das Hydrogel nach dem Verlassen des Polymerisationsreaktors noch bei höherer Temperatur, vorzugsweise mindestens 5O0C, besonders bevorzugt mindestes 700C, ganz besonders bevorzugt mindestens 800C, sowie vorzugsweise weniger als 1000C1 gelagert, beispielsweise in isolierten Behältern. Durch die Lagerung, üblicherweise 2 bis 12 Stunden, wird der Monomerumsatz weiter erhöht.The hydrogel after leaving the polymerization reactor at a higher temperature, preferably at least 5O 0 C is advantageous, particularly preferably at least 70 0 C, most preferably at least 80 0 C, and preferably less than 100 0 C 1 mounted, for example, in insulated containers. By storage, usually 2 to 12 hours, the monomer conversion is further increased.
Die Säuregruppen der erhaltenen Hydrogele sind üblicherweise teilweise neutralisiert, vorzugsweise zu 25 bis 95 mol-%, bevorzugt zu 27 bis 80 mol-%, besonders bevorzugt zu 27 bis 30 mol-% oder 40 bis 75 mol-%, wobei die üblichen Neutralisationsmittel verwendet werden können, vorzugsweise Alkalimetallhydroxide, Alkalimetalloxide, Al- kalimetallcarbonate oder Alkalimetallhydrogencarbonate sowie deren Mischungen. Statt Alkalimetallsalzen können auch Ammoniumsalze verwendet werden. Natrium und Kalium sind als Alkalimetalle besonders bevorzugt, ganz besonders bevorzugt sind jedoch Natriumhydroxid, Natriumcarbonat oder Natriumhydrogencarbonat sowie deren Mischungen. Üblicherweise wird die Neutralisation durch Einmischung des Neutralisationsmittels als wässrige Lösung, als Schmelze, oder bevorzugt auch als Feststoff erreicht. Beispielsweise kann Natriumhydroxid mit einem Wasseranteil deutlich unter 50 Gew.-% als wachsartige Masse mit einem Schmelzpunkt oberhalb 23°C vorliegen. In diesem Fall ist eine Dosierung als Stückgut oder Schmelze bei erhöhter Temperatur möglich.The acid groups of the hydrogels obtained are usually partially neutralized, preferably from 25 to 95 mol%, preferably from 27 to 80 mol%, particularly preferably from 27 to 30 mol% or from 40 to 75 mol%, using the customary neutralizing agents may be, preferably alkali metal hydroxides, alkali metal oxides, alkali metal carbonates or Alkalimetallhydrogencarbonate and mixtures thereof. Instead of alkali metal salts and ammonium salts can be used. Sodium and potassium are particularly preferred as alkali metals, but most preferred are sodium hydroxide, sodium carbonate or sodium bicarbonate and mixtures thereof. Usually, the neutralization is achieved by mixing the neutralizing agent as an aqueous solution, as a melt, or preferably as a solid. For example, sodium hydroxide with a water content well below 50 wt .-% may be present as a waxy mass with a melting point above 23 ° C. In this case, a dosage as general cargo or melt at elevated temperature is possible.
Die Neutralisation kann nach der Polymerisation auf der Stufe des Hydrogels durchgeführt werden. Es ist aber auch möglich bis zu 40 mol-%, vorzugsweise 10 bis 30 mol- %, besonders bevorzugt 15 bis 25 mol-%, der Säuregruppen vor der Polymerisation zu neutralisieren indem ein Teil des Neutralisationsmittels bereits der Monomerlösung zugesetzt und der gewünschte Endneutralisationsgrad erst nach der Polymerisation auf der Stufe des Hydrogels eingestellt wird. Die Monomerlösung kann durch Einmischen des Neutralisationsmittels neutralisiert werden. Das Hydrogel kann mechanisch zerkleinert werden, beispielsweise mittels eines Fleischwolfes, wobei das Neutralisationsmittel aufgesprüht, übergestreut oder aufgegossen und dann sorgfältig unterge- mischt werden kann. Dazu kann die erhaltene Gelmasse noch mehrmals zur Homogenisierung gewolft werden. Die Neutralisation der Monomerlösung direkt auf den End- neutralisationsgrad ist bevorzugt.The neutralization can be carried out after the polymerization at the hydrogel stage. However, it is also possible to neutralize up to 40 mol%, preferably 10 to 30 mol%, particularly preferably 15 to 25 mol%, of the acid groups prior to the polymerization by adding a part of the neutralizing agent to the monomer solution and the desired final degree of neutralization after the polymerization is adjusted at the level of the hydrogel. The monomer solution can be neutralized by mixing in the neutralizing agent. The hydrogel can be mechanically comminuted, for example by means of a meat grinder, wherein the neutralizing agent can be sprayed, sprinkled or poured on and then carefully mixed in. For this purpose, the gel mass obtained can be further gewolfft for homogenization. Neutralization of the monomer solution directly to the final degree of neutralization is preferred.
Das neutralisierte Hydrogel wird dann mit einem Band- oder Walzentrockner getrock- net bis der Restfeuchtegehalt vorzugsweise unter 15 Gew.- %, insbesondere unter 10 Gew.- % liegt, wobei der Wassergehalt gemäß der von der EDANA (European Disposables and Nonwovens Association) empfohlenen Testmethode Nr. 430.2-02 "Moisture content" bestimmt wird. Wahlweise kann zur Trocknung aber auch ein Wirbelbetttrockner oder ein beheizter Pflugscharmischer verwendet werden.The neutralized hydrogel is then dried with a belt or roller dryer until the residual moisture content is preferably less than 15% by weight, in particular less than 10% by weight, the water content being in accordance with that recommended by EDANA (European Disposables and Nonwovens Association) Test Method No. 430.2-02 "Moisture content" is determined. Alternatively, a fluidized bed dryer or a heated ploughshare mixer can be used for drying.
Das getrocknete Hydrogel wird hiernach gemahlen und klassiert, wobei zur Mahlung üblicherweise ein- oder mehrstufige Walzenstühle, bevorzugt zwei- oder dreistufige Walzenstühle, Stiftmühlen, Hammermühlen oder Schwingmühlen eingesetzt werden können.The dried hydrogel is thereafter ground and classified, wherein for grinding usually one- or multi-stage roller mills, preferably two- or three-stage roller mills, pin mills, hammer mills or vibratory mills can be used.
Zur Verbesserung der Anwendungseigenschaften, wie beispielsweise Flüssigkeitsleitfähigkeit (SFC) in der Windel und Absorption unter Druck (AUL), werden superabsorbierende Polymerpartikel im allgemeinen nachvernetzt. Diese Nachvernetzung kann in wässriger Gelphase durchgeführt werden. Vorzugsweise werden aber gemahlene und abgesiebte Polymerpartikel (Grundpolymer) an der Oberfläche mit einem Nachvernet- zer beschichtet, getrocknet und thermisch nachvernetzt. Dazu geeignete Vernetzer sind Verbindungen, die mindestens zwei Gruppen enthalten, die mit den Carboxy- latgruppen des hydrophilen Polymeren kovalente Bindungen bilden können oder die mindestens zwei Carboxylgruppen oder andere funktionelle Gruppen mindestens zweier verschiedener Polymerketten des Grundpolymers miteinander vernetzen können.To improve application properties, such as diaper fluid conductivity (SFC) and absorption under pressure (AUL), superabsorbent polymer particles are generally postcrosslinked. This postcrosslinking can be carried out in aqueous gel phase. Preferably, however, ground and sieved polymer particles (base polymer) are coated on the surface with a post-crosslinker, dried and postcrosslinked thermally. Crosslinking agents suitable for this purpose are compounds which contain at least two groups which can form covalent bonds with the carboxylate groups of the hydrophilic polymer or which can crosslink at least two carboxyl groups or other functional groups of at least two different polymer chains of the base polymer.
Hierzu geeignete Nachvernetzer v) sind Verbindungen, die mindestens zwei Gruppen enthalten, die mit den Carboxylatgruppen der Polymere kovalente Bindungen bilden können. Geeignete Verbindungen sind beispielsweise Alkoxysilylverbindungen, Polya- ziridine, Polyamine, Polyamidoamine, Di- oder Polyglycidylverbindungen, wie in EP-A 083 022, EP-A 543 303 und EP-A 937 736 beschrieben, mehrwertige Alkohole, wie in DE-C 33 14 019, DE-C 35 23 617 und EP-A 450 922 beschrieben, oder IJ- Hydroxyalkylamide, wie in DE-A 102 04 938 und US 6,239,230 beschrieben. Geeignet sind ferner Verbindungen mit gemischter Funktionalität, wie Glycidol, 3-Ethyl-3- oxetanmethanol (Trimethylolpropanoxetan), wie in EP-A 1 199 327 beschrieben, Ami- noethanol, Diethanolamin, Triethanolamin oder Verbindungen, die nach der ersten Reaktion eine weitere Funktionalität ausbilden, wie Ethylenoxid, Propylenoxid, Isobuty- lenoxid, Aziridin, Azetidin oder Oxetan.Suitable postcrosslinkers v) are compounds which contain at least two groups which can form covalent bonds with the carboxylate groups of the polymers. Suitable compounds are, for example, alkoxysilyl compounds, polyaziridines, polyamines, polyamidoamines, di- or polyglycidyl compounds, as described in EP-A 083 022, EP-A 543 303 and EP-A 937 736, polyhydric alcohols, as described in DE-C 33 14 019, DE-C 35 23 617 and EP-A 450 922, or IJ-hydroxyalkylamides, as described in DE-A 102 04 938 and US Pat. No. 6,239,230. Also suitable are compounds having mixed functionality, such as glycidol, 3-ethyl-3-oxetanemethanol (trimethylolpropane oxetane), as described in EP-A 1 199 327, noethanol, diethanolamine, triethanolamine or compounds which form a further functionality after the first reaction, such as ethylene oxide, propylene oxide, isobutylene oxide, aziridine, azetidine or oxetane.
Des weiteren sind in DE-A 40 20 780 zyklische Karbonate, in DE-A 198 07 502 2-Oxazolidon und dessen Derivate, wie N-(2-Hydroxyethyl)-2-oxazolidon, in DE-A 198 07 992 Bis- und Poly-2-oxazolidinone, in DE-A 198 54 573 2-Oxotetrahydro- 1 ,3-oxazin und dessen Derivate, in DE-A 198 54 574 N-Acyl-2-oxazolidone, in DE-A 102 04 937 zyklische Harnstoffe, in der deutschen Patentanmeldung mit dem Aktenzeichen DE 103 34 584.1 bizyklische Amidacetale, in EP-A1 199 327 Oxetane und zyklische Harnstoffe und in WO 03/031482 Morpholin-2,3-dion und dessen Derivate als geeignete Nachvemetzer v) beschrieben.Furthermore, in DE-A 40 20 780 cyclic carbonates, in DE-A 198 07 502 2-oxazolidone and its derivatives, such as N- (2-hydroxyethyl) -2-oxazolidone, in DE-A 198 07 992 Bis- and Poly-2-oxazolidinone, in DE-A 198 54 573 2-oxotetrahydro-1, 3-oxazine and its derivatives, in DE-A 198 54 574 N-acyl-2-oxazolidone, in DE-A 102 04 937 cyclic ureas , German Patent Application DE 103 34 584.1 describes bicyclic amide acetals, EP-A1 199 327 oxetanes and cyclic ureas, and WO 03/031482 describes morpholine-2,3-dione and its derivatives as suitable post-crosslinking agents v).
Die Nachvernetzung wird üblicherweise so durchgeführt, dass eine Lösung des Nach- vernetzers auf das Hydrogel oder die trockenen Grundpolymerpartikel aufgesprüht wird. Im Anschluss an das Aufsprühen wird thermisch getrocknet, wobei die Nachvernetzungsreaktion sowohl vor als auch während der Trocknung stattfinden kann.The postcrosslinking is usually carried out so that a solution of the postcrosslinker is sprayed onto the hydrogel or the dry base polymer particles. Subsequent to the spraying, it is thermally dried, whereby the postcrosslinking reaction can take place both before and during the drying.
Das Aufsprühen einer Lösung des Vernetzers wird vorzugsweise in Mischern mit be- wegten Mischwerkzeugen, wie Schneckenmischer, Paddelmischer, Scheibenmischer, Pflugscharmischer und Schaufelmischer, durchgeführt werden. Besonders bevorzugt sind Vertikalmischer, ganz besonders bevorzugt sind Pflugscharmischer und Schaufelmischer. Geeignete Mischer sind beispielsweise Lödige®-Mischer, Bepex®-Mischer, Nauta®-Mischer, Processall®-Mischer und Schugi®-Mischer.The spraying of a solution of the crosslinker is preferably carried out in mixers with moving mixing tools, such as screw mixers, paddle mixers, disk mixers, plowshare mixers and paddle mixers. Vertical mixers are particularly preferred, plowshare mixers and paddle mixers are very particularly preferred. Suitable mixers are, for example, Lödige ® mixers, Bepex ® mixers, Nauta ® mixer, Processall mixers and Schugi ® ® mixer.
Die thermische Trocknung wird vorzugsweise in Kontakttrocknern, besonders bevorzugt Schaufeltrocknern, ganz besonders bevorzugt Scheibentrocknern, durchgeführt. Geeignete Trockner sind beispielsweise Bepex®-Trockner und Nara®-Trockner. Überdies können auch Wirbelschichttrockner eingesetzt werden.The thermal drying is preferably carried out in contact dryers, more preferably paddle dryers, very particularly preferably disk dryers. Suitable dryers include for example Bepex ® dryers and Nara ® dryers. Moreover, fluidized bed dryers can also be used.
Die Trocknung kann im Mischer selbst erfolgen, durch Beheizung des Mantels oder Einblasen von Warmluft. Ebenso geeignet ist ein nachgeschalteter Trockner, wie beispielsweise ein Hordentrockner, ein Drehrohrofen oder eine beheizbare Schnecke. Es kann aber auch beispielsweise eine azeotrope Destillation als Trocknungsverfahren benutzt werden.The drying can take place in the mixer itself, by heating the jacket or blowing hot air. Also suitable is a downstream dryer, such as a hopper dryer, a rotary kiln or a heatable screw. However, it is also possible, for example, to use an azeotropic distillation as the drying process.
Bevorzugte Trocknungstemperaturen liegen im Bereich 50 bis 25O0C, bevorzugt bei 50 bis 2000C, und besonders bevorzugt bei 50 bis 15O0C. Die bevorzugte Verweilzeit bei dieser Temperatur im Reaktionsmischer oder Trockner beträgt unter 30 Minuten, be- sonders bevorzugt unter 10 Minuten. Die nach dem erfindungsgemäßen Verfahren hergestellten Papiere, Pappen und Kartons haben eine erhöhte Wasseraufnahmekapazität im Vergleich zu herkömmlichen Papierqualitäten ohne dabei Verluste bei der Festigkeit in Kauf zu nehmen. Die Papiere können Wasser aufnehmen und auch unter Hitzeinwirkung, wie beispielsweise bei Verwendung in Laserdruckern, halten.Preferred drying temperatures are in the range 50 to 25O 0 C, preferably at 50 to 200 0 C, and particularly preferably at 50 to 15O 0 C. The preferred residence time at this temperature in the reaction mixer or dryer is below 30 minutes and more preferably below 10 minutes. The papers, boards and cardboards produced by the process according to the invention have an increased water absorption capacity compared to conventional paper qualities without loss of strength. The papers can absorb water and also hold under heat, such as when used in laser printers.
Nach dem erfindungsgemäßen Verfahren können sämtliche Papierqualitäten hergestellt werden, z.B. Karton, ein- /mehrlagiger Faltschachtel karton, ein- /mehrlagiger Liner, Wellenstoff, Papiere für den Zeitungsdruck, sogenannte mittelfeine Schreib- und Druckpapiere, Naturtiefdruckpapiere und leichtgewichtige Streichrohpapiere. Um solche Papiere herzustellen, kann man beispielsweise von Holzschliff, thermomechani- schem Stoff (TMP), chemo-thermomechanischem Stoff (CTMP), Druckschliff (PGW), Holzstoff sowie Sulfit- und Sulfatzellstoff ausgehen. Die Zellstoffe können sowohl kurzfaserig als auch langfaserig sein.By the method according to the invention, all paper qualities can be produced, e.g. Cardboard, single / multi-layer carton, single / multi-layer liner, corrugated medium, papers for newspaper printing, so-called medium-fine writing and printing papers, natural gravure papers and lightweight base papers. For example, wood pulp, thermomechanical pulp (TMP), chemo-thermo-mechanical pulp (CTMP), pressure pulp (PGW), wood pulp and sulphite and sulphate pulp can be used to produce such papers. The pulps can be short fiber as well as long fiber.
Bevorzugt werden nach dem erfindungsgemäßen Verfahren sogenannte Tissuepapie- re, wie Toilettenpapier, Papiertaschentücher und Kosmetiktücher sowie Küchenpapier, weiterhin Hygiene- bzw. Sanitärpapiere, Verpackungspapiere, beispielsweise für Lebensmittel, oder auch Multischichtpapiere, die in Hygieneartikeln oder Verpackungs- materialen eingesetzt werden können, hergestellt. Die zuletzt genannten Multischichtpapiere bestehen aus mehreren unterschiedlichen Papierschichten, wobei die Papierschicht, die nach dem erfindungsgemäßen Verfahren hergestellt wurde, entweder o- berhalb einer herkömmlichen Papierschicht oder zwischen zwei herkömmlichen Papierschichten eingearbeitet wird.According to the method of the invention, so-called tissue papers such as toilet paper, paper handkerchiefs and facial tissues as well as kitchen paper, furthermore hygiene or sanitary papers, packaging papers, for example for foodstuffs or multilayer papers which can be used in hygiene articles or packaging materials, are preferably produced. The last-mentioned multilayer papers consist of several different paper layers, the paper layer produced by the process according to the invention being incorporated either above a conventional paper layer or between two conventional paper layers.
Gegenstand der vorliegenden Erfindung ist weiterhin die Verwendung von wasser- quellbaren Polymeren bei der Herstellung von Papier, Pappe und Karton in dem erfindungsgemäßen Verfahren.The present invention furthermore relates to the use of water-swellable polymers in the production of paper, paperboard and cardboard in the process according to the invention.
Ein weiterer Gegenstand der vorliegenden Erfindung sind auch Papier, Pappe undAnother object of the present invention are also paper, cardboard and
Karton, die nach dem erfindungsgemäßen Verfahren hergestellt werden. Insbesondere betrifft die Erfindung sogenannte Tissuepapiere, wie Toilettenpapier, Papiertaschentücher und Kosmetiktücher sowie Küchenpapier, weiterhin Hygiene- bzw. Sanitärpapiere, Verpackungspapiere, beispielsweise für Lebensmittel, oder auch Multischichtpapie- re, die in Hygieneartikeln oder Verpackungsmaterialen eingesetzt werden können.Cardboard produced by the process according to the invention. In particular, the invention relates to so-called tissue papers, such as toilet paper, paper handkerchiefs and facial tissues and kitchen paper, further hygiene or sanitary papers, packaging papers, for example, for food, or even multi-layer paper, which can be used in hygiene articles or packaging materials.
Die Erfindung wird anhand der folgenden, nicht einschränkenden Beispiele näher erläutert.The invention will be further illustrated by the following non-limiting examples.
Beispiele Die Prozentangaben in den Beispielen bedeuten Gewichtsprozent, sofern aus dem Zusammenhang nichts anderes hervorgeht.Examples The percentages in the examples are by weight unless otherwise indicated in the context.
Die Trockenreißlänge der getrockneten Papierblättern wurde gemäß der Prüfmethode nach DIN EN ISO 1924-2 bestimmt.The dry breaking length of the dried paper sheets was determined according to the test method according to DIN EN ISO 1924-2.
Wasserquellbares Polymer 1Water swellable polymer 1
Bei Raumtemperatur wurde als wasserquellbares Polymer Luquasorb® 1280 der BASF Aktiengesellschaft in einem geringen Überschuss Wasser für eine Stunde gequollen.At room temperature, 1280 of BASF Aktiengesellschaft in a slight excess of water was swollen for one hour as a water-swellable polymer Luquasorb ®.
Beispiel 1example 1
Eine Mischung aus gebleichtem Birkensulfat und gebleichtem Kiefernsulfit im Verhält- nis von 70/30 bei einer Feststoffkonzentration von 1 % wurde mit 1 Gew.-%, bezogen auf den Trockengehalt der Papierstoffsuspension, des zuvor gequollenen wasserquell- baren Polymeren 1 versetzt. Diese Mischung wurde im Laborpulper stippenfrei aufgeschlagen, bis ein Mahlgrad nach Schopper-Riegler von 35 erreicht wurde.A mixture of bleached birch sulphate and bleached pine sulphite in the ratio of 70/30 at a solids concentration of 1% was admixed with 1% by weight, based on the solids content of the paper stock suspension, of the previously swollen water-swellable polymer 1. This mixture was added to the laboratory pulper without specking until a Schopper-Riegler freeness of 35 was reached.
Beispiel 2Example 2
Beispiel 1 wurde wiederholt, jedoch wurden 2,5 Gew.-%, bezogen auf den Trockengehalt der Papierstoffsuspension, des zuvor gequollenen wasserquellbaren Polymeren 1 zu der Mischung aus gebleichtem Birkensulfat und gebleichtem Kiefernsulfit gegeben. Example 1 was repeated except that 2.5% by weight, based on the solids content of the pulp suspension, of the previously swollen water-swellable polymer 1 was added to the bleached birch sulphate bleach bleached pine sulphite blend.
Beispiel 3Example 3
Eine Mischung aus gebleichtem Birkensulfat und gebleichtem Kiefernsulfit im Verhältnis von 70/30 bei einer Feststoffkonzentration von 1 % wurde mit 1 Gew.-%, bezogen auf den Trockengehalt der Papierstoffsuspension, des zuvor gequollenen wasserquell- baren Polymeren 1 versetzt. Diese Mischung wurde im Laborpulper stippenfrei aufgeschlagen, bis ein Mahlgrad nach Schopper-Riegler von 35 erreicht wurde. Unmittelbar danach dosierte man ein kationisches Polyacrylamid als Retentionsmittel (PoIy- min® KE 2020 der BASF Aktiengesellschaft) in diese Mischung. Die Dosiermenge des Retentionsmittels betrug 0,03 % Polymer, bezogen auf den Trockengehalt der Papierstoffsuspension.A mixture of bleached birch sulphate and bleached pine sulphite in a ratio of 70/30 at a solids concentration of 1% was admixed with 1% by weight, based on the solids content of the paper stock suspension, of the previously swollen water-swellable polymer 1. This mixture was added to the laboratory pulper without specking until a Schopper-Riegler freeness of 35 was reached. Immediately thereafter, the metered addition, a cationic polyacrylamide retention aid (poly min ® KE 2020, BASF Aktiengesellschaft) in this mixture. The metered amount of the retention agent was 0.03% polymer, based on the solids content of the paper stock suspension.
Beispiel 4Example 4
Beispiel 3 wurde wiederholt, jedoch wurden 2,5 Gew.-%, bezogen auf den Trockengehalt der Papierstoffsuspension, des zuvor gequollenen wasserquellbaren Polymeren 1 zu der Mischung aus gebleichtem Birkensulfat und gebleichtem Kiefernsulfit gegeben.Example 3 was repeated except that 2.5% by weight, based on the solids content of the pulp suspension, of the previously swollen water-swellable polymer 1 was added to the bleached birch sulphate bleached pine sulphite blend.
Beispiel 5Example 5
Eine Mischung aus gebleichtem Birkensulfat und gebleichtem Kiefernsulfit im Verhältnis von 70/30 bei einer Feststoffkonzentration von 1 % wurde mit 1 Gew.-%, bezogen auf den Trockengehalt der Papierstoffsuspension, des zuvor gequollenen wasserquellbaren Polymeren 1 versetzt. Diese Mischung wurde im Laborpulper stippenfrei aufge- schlagen, bis ein Mahlgrad nach Schopper-Riegler von 35 erreicht wurde. Unmittelbar danach dosierte man ein kationisches Polyacrylamid als Retentionsmittel (PoIy- min® KE 2020 der BASF Aktiengesellschaft) und einen Füllstoff (Hydrocarb® OG der Firma Omya) in diese Mischung. Die Dosiermenge des Retentionsmittels und des Füllstoffs betrug 0,03 % Polymer bzw. 20 % Füllstoff, bezogen auf den Trockengehalt der Papierstoffsuspension.A mixture of bleached birch sulphate and bleached pine sulphite in a ratio of 70/30 at a solids concentration of 1% was admixed with 1% by weight, based on the solids content of the pulp suspension, of the previously swollen water-swellable polymer 1. This mixture was tapped in the laboratory pulper until it reached a grinding degree of 35 according to Schopper-Riegler. Immediately thereafter, the metered addition, a cationic polyacrylamide retention aid (poly min ® KE 2020, BASF Aktiengesellschaft) and a filler (Hydrocarb ® OG from Omya) in this mixture. The metered amount of the retention agent and the filler was 0.03% polymer or 20% filler, based on the solids content of the paper stock suspension.
Beispiel 6Example 6
Beispiel 5 wurde wiederholt, jedoch wurden 2,5 Gew.-%, bezogen auf den Trockenge- halt der Papierstoffsuspension, des zuvor gequollenen wasserquellbaren Polymeren 1 zu der Mischung aus gebleichtem Birkensulfat und gebleichtem Kiefernsulfit gegeben. Vergleichsbeispiel 1Example 5 was repeated except that 2.5% by weight, based on the solids content of the paper stock suspension, of the previously swollen water-swellable polymer 1 was added to the mixture of bleached birch sulphate and bleached pine sulphite. Comparative Example 1
Eine Mischung aus gebleichtem Birkensulfat und gebleichtem Kiefernsulfit im Verhältnis von 70/30 bei einer Feststoffkonzentration von 1 % wurde im Laborpulper stippen- frei aufgeschlagen, bis ein Mahlgrad nach Schopper-Riegler von 35 erreicht wurde. Anschließend wurde eine kationische Stärke (Solvitose® BKN) in einer Menge von 0,06 Gew.-%, bezogen auf den Trockengehalt der Papierstoffsuspension, zugegeben.A mixture of bleached birch sulphate and bleached pine sulphite in a ratio of 70/30 at a solids concentration of 1% was added without specks in the laboratory pulper until a Schopper-Riegler freeness of 35 was reached. Subsequently, a cationic starch (Solvitose BKN ®) in an amount of 0.06 wt .-%, based on the dry content of the paper stock suspension.
Vergleichsbeispiel 2Comparative Example 2
Eine Mischung aus gebleichtem Birkensulfat und gebleichtem Kiefernsulfit im Verhältnis von 70/30 bei einer Feststoffkonzentration von 1 % wurde im Laborpulper stippenfrei aufgeschlagen, bis ein Mahlgrad nach Schopper-Riegler von 35 erreicht wurde. Anschließend wurde eine kationische Stärke (Solvitose® BKN) in einer Menge von 0,06 Gew.-%, bezogen auf den Trockengehalt der Papierstoffsuspension, zugegeben. Unmittelbar danach dosierte man ein kationisches Polyacrylamid als Retentionsmittel (Polymin® KE 2020 der BASF Aktiengesellschaft) und einen Füllstoff (Hydrocarb® OG der Firma Omya) in diese Mischung. Die Dosiermenge des Retentionsmittels und des Füllstoffs betrug 0,03 % Polymer bzw. 20 % Füllstoff, bezogen auf den Trockengehalt der Papierstoffsuspension.A mixture of bleached birch sulphate and bleached pine sulphite in a ratio of 70/30 at a solids concentration of 1% was beaten without specks in the laboratory pulper until a Schopper-Riegler freeness of 35 was reached. Subsequently, a cationic starch (Solvitose BKN ®) in an amount of 0.06 wt .-%, based on the dry content of the paper stock suspension. Immediately thereafter, the metered addition, a cationic polyacrylamide retention aid (Polymin ® KE 2020, BASF Aktiengesellschaft) and a filler (Hydrocarb ® OG from Omya) in this mixture. The metered amount of the retention agent and the filler was 0.03% polymer or 20% filler, based on the solids content of the paper stock suspension.
Herstellung der PapierblätterProduction of paper sheets
Die Papierblätter wurden jeweils auf einem Rapid-Köthen-Blattbildner nach ISO 5269/2 mit einem Blattgewicht von 80 g/m2 gefertigt und anschließend 5 Minuten bei 1000C getrocknet. Anschließend wurde die Trockenreißlänge der Papierblätter geprüft. Die Ergebnisse sind in Tabelle 1 zusammengefasst.The paper sheets were each made on a Rapid-Köthen sheet former according to ISO 5269/2 with a sheet weight of 80 g / m 2 and then dried for 5 minutes at 100 0 C. Subsequently, the dry break length of the paper sheets was checked. The results are summarized in Table 1.
Tabelle 1Table 1
Figure imgf000015_0001
Prüfung der Wasseraufnahme nach dem wicking-Test
Figure imgf000015_0001
Testing the water absorption after the wicking test
Die Papierblätter wurden jeweils auf eine Größe von 200 mm x 15 mm geschnitten. Diese geschnittenen Papierstreifen wurden je in ein Becherglas, das mit Wasser gefüllt war, gehängt, wobei das obere Ende des Papierstreifens mit einer Klammer an dem Rand des Becherglases befestigt wurde. Die Papierstreifen tauchten zu Beginn des Tests ca. 10 bis 20 mm in das Wasser ein, wobei die Stelle des Eintauchens (untere Grenze) markiert wurde. Nach 10 Minuten wurden die Papierstreifen aus dem Wasser gezogen. Die obere Grenze, bis zu der das Wasser gelaufen war, wurde ebenfalls markiert. Anschließend wurde die Distanz zwischen unterer und oberer Grenze, also die Strecke, die das Wasser zurückgelegt hat, gemessen. Die Ergebnisse sind in Tabelle 2 zusammengefasst.The paper sheets were each cut to a size of 200 mm x 15 mm. These cut paper strips were each hung in a beaker filled with water, with the upper end of the paper strip being clamped to the edge of the beaker. At the beginning of the test, the paper strips dipped about 10 to 20 mm into the water, marking the place of immersion (lower limit). After 10 minutes, the paper strips were pulled out of the water. The upper limit to which the water had run was also marked. Then the distance between the lower and upper limit, ie the distance that the water traveled, was measured. The results are summarized in Table 2.
Tabelle 2Table 2
Figure imgf000016_0001
Figure imgf000016_0001

Claims

Patentansprüche claims
1. Verfahren zur Herstellung von Papier, Pappe und Karton in Gegenwart von was- serquellbaren Polymeren durch Zugabe des wasserquellbaren Polymeren zu ei- ner Fasersuspension, dadurch gekennzeichnet, dass die wasserquellbare Polymere enthaltene Fasersuspension gemahlen wird.1. A process for the production of paper, paperboard and cardboard in the presence of water-swellable polymers by adding the water-swellable polymer to a fiber suspension, characterized in that the water-swellable polymers contained fiber suspension is ground.
2. Verfahren nach Anspruch 1 , dadurch gekennzeichnet, dass das wasserquellbare Polymere mindestens 1 % seines eigenen Gewichts an Wasser aufnehmen kann.2. The method according to claim 1, characterized in that the water-swellable polymer can absorb at least 1% of its own weight of water.
3. Verfahren nach Anspruch 1 oder 2, dadurch gekennzeichnet, dass es sich bei den wasserquellbaren Polymeren um superabsorbierende Polymere handelt.3. The method according to claim 1 or 2, characterized in that it is superabsorbent polymers in the water-swellable polymers.
4. Verfahren nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, dass nach der Mahlung der wasserquellbare Polymere enthaltenen Fasersuspension Papierprozesschemikalien zugesetzt werden.4. The method according to any one of claims 1 to 3, characterized in that after the grinding of the water-swellable polymers contained fiber suspension paper process chemicals are added.
5. Verfahren nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, dass das wasserquellbare Polymere als gelartige Suspension der Fasersuspension zugesetzt wird.5. The method according to any one of claims 1 to 4, characterized in that the water-swellable polymer is added as a gel-like suspension of the fiber suspension.
6. Verfahren nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, dass das wasserquellbare Polymer durch Sprühen in die Fasersuspension eingebracht wird.6. The method according to any one of claims 1 to 4, characterized in that the water-swellable polymer is introduced by spraying into the fiber suspension.
7. Verfahren nach einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, dass der Fasersuspension 0,1 bis 20 Gew.-% eines wasserquellbaren Polymeren zugesetzt wird.7. The method according to any one of claims 1 to 6, characterized in that the fiber suspension is added to 0.1 to 20 wt .-% of a water-swellable polymer.
8. Verwendung von wasserquellbaren Polymeren bei der Herstellung von Papier, Pappe und Karton nach einem Verfahren gemäß Ansprüche 1 bis 7.8. Use of water-swellable polymers in the production of paper, paperboard and cardboard by a process according to claims 1 to 7.
9. Papier, Pappe und Karton hergestellt nach einem Verfahren nach Anspruch 1 bis 7.9. paper, board and board produced by a method according to claim 1 to 7.
10. Papier nach Anspruch 9, dadurch gekennzeichnet, dass es sich um Tissuepapie- re, Hygiene- bzw. Sanitärpapiere, Verpackungspapiere oder Multischichtpapiere handelt. 10. Paper according to claim 9, characterized in that it is tissue paper, hygiene or sanitary papers, packaging papers or multilayer papers.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009056436A2 (en) * 2007-10-30 2009-05-07 Basf Se Composite material consisting of a superabsorber and a supporting material and method for the production thereof by polymerization of the supporting material in the presence of a superabsorber

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101506256A (en) * 2006-08-17 2009-08-12 巴斯夫欧洲公司 Aqueous dispersions of cross-linked, tertiary ester groups containing emulsion polymerisates and water-absorbent materials on a carrier material made thereof
US20140261988A1 (en) * 2013-03-15 2014-09-18 Adalis Corporation Reinforcement to prevent tearing and provide structural support and moisture elimination in corrugated paper board
SE539751C2 (en) 2015-11-09 2017-11-14 Stora Enso Oyj Active moisture control material for packaging and a method for production thereof
NL2016217B1 (en) * 2016-02-03 2017-08-11 Claessens Marco Layered product comprising superabsorbent polymer
PT3899136T (en) 2018-12-17 2023-02-06 Kemira Oyj A process for producing paper or board and a product thereof
US11549216B2 (en) 2020-11-11 2023-01-10 Sappi North America, Inc. Oil/grease resistant paper products

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2729561A (en) * 1952-08-26 1956-01-03 John C Marrone Blowing dry starch into a papermaking furnish
GB2269602A (en) * 1992-08-13 1994-02-16 Courtaulds Plc Absorbent nonwoven fabric
JP2003048997A (en) * 2001-08-08 2003-02-21 Japan Atom Energy Res Inst Superabsorbent starch gel

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5997690A (en) * 1998-02-18 1999-12-07 Basf Corporation Smooth textured wet-laid absorbent structure
SE513918C2 (en) * 1999-03-19 2000-11-27 Sca Hygiene Prod Ab Absorbent paper and method of preparation thereof
US20030014038A1 (en) * 2001-05-07 2003-01-16 Bruce Fine Article and method of use for absorbing bodily fluids

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2729561A (en) * 1952-08-26 1956-01-03 John C Marrone Blowing dry starch into a papermaking furnish
GB2269602A (en) * 1992-08-13 1994-02-16 Courtaulds Plc Absorbent nonwoven fabric
JP2003048997A (en) * 2001-08-08 2003-02-21 Japan Atom Energy Res Inst Superabsorbent starch gel

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009056436A2 (en) * 2007-10-30 2009-05-07 Basf Se Composite material consisting of a superabsorber and a supporting material and method for the production thereof by polymerization of the supporting material in the presence of a superabsorber
WO2009056436A3 (en) * 2007-10-30 2010-03-11 Basf Se Composite material consisting of a superabsorber and a supporting material and method for the production thereof by polymerization of the supporting material in the presence of a superabsorber

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