EP0972110B1 - Procede pour produire du papier, du carton-pate et du carton a haute resistance a la traction a l'etat sec - Google Patents

Procede pour produire du papier, du carton-pate et du carton a haute resistance a la traction a l'etat sec Download PDF

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EP0972110B1
EP0972110B1 EP98921399A EP98921399A EP0972110B1 EP 0972110 B1 EP0972110 B1 EP 0972110B1 EP 98921399 A EP98921399 A EP 98921399A EP 98921399 A EP98921399 A EP 98921399A EP 0972110 B1 EP0972110 B1 EP 0972110B1
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Prior art keywords
starch
cationic
weight
units
paper
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EP0972110B2 (fr
EP0972110A1 (fr
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Rainer Dyllick-Brenzinger
Primoz Lorencak
Hubert Meixner
Peter Baumann
Ellen KRÜGER
Andreas Stange
Martin Rübenacker
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BASF SE
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BASF SE
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Classifications

    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/06—Paper forming aids
    • D21H21/10—Retention agents or drainage improvers
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
    • D21H21/18—Reinforcing agents
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/21—Macromolecular organic compounds of natural origin; Derivatives thereof
    • D21H17/24—Polysaccharides
    • D21H17/28—Starch
    • D21H17/29—Starch cationic
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/33—Synthetic macromolecular compounds
    • D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H17/41—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups
    • D21H17/44—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups cationic
    • D21H17/45—Nitrogen-containing groups
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/33—Synthetic macromolecular compounds
    • D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H17/41—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups
    • D21H17/44—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups cationic
    • D21H17/45—Nitrogen-containing groups
    • D21H17/455—Nitrogen-containing groups comprising tertiary amine or being at least partially quaternised
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/33—Synthetic macromolecular compounds
    • D21H17/46—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H17/54—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen
    • D21H17/55—Polyamides; Polyaminoamides; Polyester-amides
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/33—Synthetic macromolecular compounds
    • D21H17/46—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H17/54—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen
    • D21H17/56—Polyamines; Polyimines; Polyester-imides
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H23/00—Processes or apparatus for adding material to the pulp or to the paper
    • D21H23/76—Processes or apparatus for adding material to the pulp or to the paper characterised by choice of auxiliary compounds which are added separately from at least one other compound, e.g. to improve the incorporation of the latter or to obtain an enhanced combined effect
    • D21H23/765—Addition of all compounds to the pulp

Definitions

  • the invention relates to a method for producing paper, Cardboard and cardboard with high dry strength by adding cationic, anionic and / or amphoteric starch as a dry strength agent for paper stock and dewatering of the paper stock with leaf formation.
  • aqueous slurries of native starches by heating be converted into a water-soluble form as a mass additive use in the manufacture of paper.
  • the retention of in Starch is dissolved in water to the paper fibers in the paper stock however slight.
  • An improvement in the retention of natural products of cellulose fibers in the manufacture of paper for example known from US-A-3 734 820. It contains graft copolymers described by grafting dextran, one in the naturally occurring polymer with a molecular weight from 20,000 to 50 million, with cationic monomers, e.g.
  • Diallyldimethylammonium chloride, mixtures of diallyldimethylammonium chloride and acrylamide or mixtures of acrylamide and basic methacrylates, such as dimethylaminoethyl methacrylate become.
  • the graft polymerization is preferably carried out in In the presence of a redox catalyst.
  • From US-A-4 097 427 is a process for cationization of starch, where you can cook the starch in one alkaline medium in the presence of water-soluble quaternary Performs ammonium polymers and an oxidizing agent.
  • quaternary ammonium polymers include also quaternized Diallyldialkylaminopolymerisate or quaternized polyethyleneimines into consideration.
  • the oxidizing agent used is, for example Ammonium persulfate, hydrogen peroxide, sodium hypochlorite, Ozone or tert-butyl hydroperoxide.
  • modified cationic starches are used as dry strength agents in the manufacture of paper the paper stock added.
  • the wastewater is very high COD (chemical oxygen demand) burdened.
  • From US-A-3 467 608 is a method for producing a cationic starch known as a slurry of Starch in water together with a polyalkyleneimine or polyalkylene polyamine with a molecular weight of at least 50,000 to a temperature of about 70 to about 0.5 to 5 hours Heated to 110 ° C.
  • the mixture contains 0.5 to 40 wt .-% polyalkyleneimine or polyalkylene polyamine and 99.5 to 60% by weight starch.
  • the modified potato starch can be in one Mixture of methanol and diethyl ether can be precipitated.
  • Polyethyleneimine or polyalkylene polyamines are used as flocculants used.
  • a process is known from US-A-4 880 497 and US-A-4 978 427 for the production of paper with high dry and wet strength known, either on the surface of the paper or a hydrolyzed to the paper stock before sheet formation
  • copolymer as a solidifying agent by copolymerization of N-vinylformamide and ethylenically unsaturated Monomers such as vinyl acetate, vinyl propionate or Alkyl vinyl ether and hydrolyzing from 30 to 100 mol% of the Formyl groups of the copolymer with formation of amino groups is available.
  • the hydrolyzed copolymers are in quantities from 0.1 to 5% by weight, based on dry fibers.
  • DE-A-4 127 733 describes hydrolyzed graft polymers of Natural products containing N-vinylformamide and saccharide structures known to apply as a dry and wet strength agent Find. Hydrolysis of the graft polymers under acidic conditions However, the polysaccharides have a strong molecular weight reduction result.
  • WO-A-96/13525 describes a method for cationic modification of starch by reacting starch with polymers that Amino and / or ammonium groups contain in an aqueous medium Temperatures 115 to 180 ° C known under increased pressure, wherein a maximum of 10% by weight of the starch used can be broken down.
  • the invention is therefore based on the object of a method for Manufacture of paper, cardboard and cardboard with high dry strength to provide, with increased retention of starch in paper and therefore lower COD values in paper machine waste water reached and also compared to the stand the technology an acceleration of the drainage speed is achieved.
  • wood pulp includes thermomechanical substance (TMP), chemothermomechanical substance (CTMP), pressure cut, semi-pulp, high-yield pulp and Refiner Mechanical Pulp (RMP).
  • TMP thermomechanical substance
  • CMP chemothermomechanical substance
  • RMP Refiner Mechanical Pulp
  • pulp come for example Sulphate, sulphite and sodium pulp into consideration.
  • suitable Annual plants for the production of paper materials are, for example Rice, wheat, sugar cane and kenaf.
  • Waste paper also includes so-called deleted committee, due to the content of binder for coating and printing inks gives rise to the white pitch.
  • the so-called stickies give rise to stickies and envelopes derived from glue and adhesives from the back sizing of books and so-called hotmelts.
  • the fiber materials mentioned can be used alone or as a mixture with one another be used.
  • the pulps of the above Art contain varying amounts of water-soluble and water-insoluble Impurities.
  • the contaminants can, for example with the help of the COD value or also with the help of the so-called cationic needs are recorded quantitatively.
  • Under cationic The quantity of a cationic is required Polymers understood that is necessary to a defined amount to bring the white water to the isoelectric point.
  • Cationic, anionic and amphoteric starches are known and available in the stores.
  • cationic strengths by implementing native strengths with quaternizing agents such as 2,3- (epoxypropyl) trimethylammonium chloride.
  • Strength and starch derivatives are described in detail, for example in the book by Günther Tegge, starch and starch derivatives, Behr's Verlag, Hamburg 1984.
  • Starches are particularly preferred as dry strength agents used by the implementation of native, cationic, anionic and / or amphoteric starch with synthetic cationic Polymers are available.
  • Rye flour and others come as a starch Flour into consideration.
  • Proteins containing proteins are also suitable Starches from rye, wheat and legumes.
  • native Starches that have an amylopectin content of at least 95% by weight.
  • Amylopectin of at least 99% by weight.
  • Such strengths can for example by starch fractionation of common native starches or obtained from plants through breeding measures, which produce practically pure amylopectin starch.
  • Strengthen with an amylopectin content of at least 95, preferably at least 99% by weight is available on the market. you will be for example as waxy corn starch, wax potato starch or Waxy wheat starch offered.
  • the native strengths can either modified alone or in a mixture with cationic polymers become.
  • Modifying native strengths as well as cationic, anionic and / amphoteric starch with synthetic cationic Polymers are made according to known methods by heating Starches in an aqueous medium in the presence of cationic polymers to temperatures above the gelatinization temperature of the Strengthen. Methods of this type are, for example, from the References cited in the prior art EP-B-0 282 761 and WO-A-96/13525.
  • cationic modification of the Above mentioned strengths come in all synthetic polymers Consider that contain amino and / or ammonium groups. This Compounds are referred to below as cationic polymers designated.
  • Suitable cationic polymers are, for example, homo- and copolymers containing vinylamine units.
  • Polymers of this type are obtained by known processes by polymerizing N-vinylcarboxamides of the formula in which R and R 1 are the same or different and are H or C 1 - to C 6 -alkyl, alone or in the presence of other monomers copolymerizable therewith and hydrolysis of the resulting polymers with acids or bases with elimination of the grouping and to form units of the formula in which R has the meaning given in formula (I).
  • comonomers 2 are unsaturated amides such as for example acrylamide, methacrylamide and N-alkyl mono- and diamides with alkyl radicals of 1 to 6 carbon atoms such as N-methyl acrylamide, N, N-dimethylacrylamide, N-methyl methacrylamide, N-ethyl acrylamide, N-propylacrylamide and tert-butyl acrylamide as well basic (meth) acrylamides, e.g.
  • dimethylaminoethyl Dimethylaminoethyl methacrylamide, diethylaminoethyl acrylamide, Diethylaminoethyl methacrylamide, dimethylaminopropylacrylamide, Diethylaminopropylacrylamide, dimethylaminopropylmethacrylamide and Diethylaminopropylmethacrylamide.
  • N-vinylpyrrolidone N-vinylcaprolactam
  • acrylonitrile methacrylonitrile
  • N-vinylimidazole as well as substituted N-vinylimidazoles such as e.g. N-vinyl-2-methylimidazole, N-vinyl-4-methylimidazole, N-vinyl-5-methylimidazole, N-vinyl-2-ethylimidazole, and N-vinylimidazolines such as e.g. vinylimidazoline, N-vinyl-2-methylimidazoline, and N-vinyl-2-ethylimidazoline.
  • N-vinylimidazoles and N-vinylimidazolines are excluded in the form of the free bases also with mineral acids or organic Acids neutralized or used in quaternized form, the quaternization preferably using dimethyl sulfate, Diethyl sulfate, methyl chloride or benzyl chloride is made.
  • the comonomers 2) contain sulfo groups Monomers such as vinylsulfonic acid, allylsulfonic acid, Methallylsulfonic acid, styrene sulfonic acid or 3-sulfopropyl acrylate in question.
  • the copolymers include terpolymers and those polymers that additionally contain at least one further monomer in copolymerized form.
  • copolymers which contain vinyl esters in copolymerized form
  • Polymerized acrylonitrile is also used the hydrolysis is chemically altered, e.g. Amide, cyclic Amidine and / or carboxyl groups are formed.
  • the hydrolyzed Poly-N-vinylformamides can optionally contain up to 20 mol% Contain amidine structures by reaction of formic acid with two adjacent amino groups in polyvinylamine or through Reaction of a formamide group with an adjacent amino group arise.
  • Ethyleneimine units also come as cationic polymers polymerized-containing compounds into consideration.
  • these are polyethyleneimines, which by polymerize ethyleneimine in the presence of acidic catalysts such as ammonium bisulfate, hydrochloric acid or chlorinated Hydrocarbons such as methyl chloride, ethylene chloride, carbon tetrachloride or chloroform.
  • acidic catalysts such as ammonium bisulfate, hydrochloric acid or chlorinated Hydrocarbons such as methyl chloride, ethylene chloride, carbon tetrachloride or chloroform.
  • Such polyethyleneimines have, for example, in 50 wt .-% aqueous Solution a viscosity of 500 to 33,000, preferably 1,000 up to 31,000 mPa ⁇ s (measured according to Brookfield at 20 ° C and 20 RPM).
  • the polymers in this group also include those grafted with ethyleneimine Polyamidoamines, which may still be by reaction can be crosslinked with an at least bifunctional crosslinker.
  • Products of this type are, for example, condensed a dicarboxylic acid such as adipic acid with a polyalkylene polyamine such as diethylenetriamine or triethylenetetramine, if appropriate Grafting with ethyleneimine and reacting with at least one bifunctional crosslinker, e.g. Bischlorohydrin ether of polyalkylene glycols manufactured, cf. US-A-4 144 123 and US-A-3 642 572.
  • bifunctional crosslinker e.g. Bischlorohydrin ether of polyalkylene glycols manufactured, cf. US-A-4 144 123 and US-A-3 642 572.
  • Starch modification also includes poly-diallyldimethylammonium chlorides into consideration.
  • Polymers of this type are known.
  • polymers of diallyldimethylammonium chloride should primarily homopolymers and copolymers with Acrylamide and / or methacrylamide can be understood.
  • the copolymerization can be made in any monomer ratio become.
  • the K value of the homo- and copolymers of Diallyldimethylammonium chloride is at least 30, preferably 95 to 180.
  • the substituent X- in the formulas (IV) and (V) can in principle be any acid residue of an inorganic and an organic acid.
  • the monomers of formula (IV) are obtained by neutralizing the free bases, ie 1-vinyl-2-imidazolines, with the equivalent amount of an acid.
  • the vinylimidazolines can also be neutralized, for example, with trichloroacetic acid, benzenesulfonic acid or toluenesulfonic acid.
  • quaternized 1-vinyl-2-imidazolines can also be used.
  • quaternizing agents are C 1 -C 18 -alkyl chlorides or bromides, benzyl chloride or bromide, epichlorohydrin, dimethyl sulfate and diethyl sulfate. Epichlorohydrin, benzyl chloride, dimethyl sulfate and methyl chloride are preferably used.
  • the Compounds of the formulas (IV) or (V) preferably in aqueous Medium polymerizes.
  • Copolymers also come as cationic polymers from 1 to 99 mol%, preferably 30 to 70 mol% of acrylamide and / or methacrylamide and 99 to 1 mol%, preferably 70 to 30 mol% of dialkylaminoalkyl acrylates and / or methacrylates in Question, e.g. Copolymers of acrylamide and N, N-dimethylaminoethyl acrylate or N, N-diethylaminoethyl acrylate.
  • Basic acrylates are preferably in neutralized with acids or in quaternized Form before. Quaternization can, for example with methyl chloride or with dimethyl sulfate.
  • the cationic Polymers have K values of 30 to 300, preferably 100 to 180 (determined according to H. Fikentscher in 5% aqueous Saline at 25 ° C and a polymer concentration of 0.5% by weight). At pH 4.5 they have a charge density of at least 4 meq / g polyelectrolyte.
  • Copolymers of 1 to 99 mol% are also suitable, preferably 30 to 70 mol% of acrylamide and / or methacrylamide and 99 to 1 mol%, preferably 70 to 30 mol% of dialkylaminoalkylacrylamide and / or methacrylamide.
  • the basic acrylamides and methacrylamides are also preferably in neutralized with acids or in quaternized form.
  • N-trimethylammonium ethyl acrylamide chloride N-trimethylammonium ethyl methacrylamide chloride, Trimethylammoniumethylacrylamidmethosulfat, Trimethylammonium ethyl methacrylamide methosulfate, N-ethyldimethylammonium ethyl acrylamide ethosulfate, N-Ethyldimethylammoniumethylmethacrylamidethosulfat, Trimethylammoniumpropylacrylamidchlorid, Trimethylammonium propyl methacrylamide chloride, trimethylammonium propyl acrylamide methosulfate, Trimethylammoniumpropylmethacrylamidmethosulfat and N-ethyldimethylammonium propylacrylamide ethosulfate. Trimethylammonium propyl methacrylamide chloride is preferred.
  • Polyallylamines are also suitable as cationic polymers. Polymers of this type are obtained by homopolymerization of allylamine, preferably in acid neutralized or in quaternized form or by copolymerizing allylamine with other monoethylenically unsaturated monomers, accordingly of the copolymers described above with N-vinylcarboxamides.
  • aqueous starch slurries contain per 100 parts by weight of water 0.1 to 10, preferably 2 to 6 parts by weight of starch. For example, 100 parts by weight of starch is used.
  • cationic polymer 0.5 up to 10 parts by weight of at least one cationic polymer.
  • cationic polymers partially hydrolyzed homo- or copolymers of N-vinylformamide, Polyethyleneimines, grafted with ethyleneimine and crosslinked polyamidoamines and / or polydiallyldimethylammonium chlorides into consideration.
  • the starch When heating the aqueous starch suspensions in the presence of The starch is first digested by cationic polymers.
  • Starch is the transfer of the fixed Starch grains in a water-soluble form, with superstructures (Helix formation, intramolecular hydrogen bonds, etc.) canceled be without the degradation of those who build strength Amylose and / or amylopectin units to oligosaccharides or Glucose is coming.
  • the aqueous starch suspensions, which are cationic Contain polymer dissolved, are in the implementation Temperatures above the gelatinization temperature of the starches heated.
  • the one used At least 90, preferably> 95% by weight of starch digested and modified with the cationic polymer. The strength is clearly resolved.
  • the reaction is preferably carried out at elevated pressure. in this connection it is usually the pressure that the reaction medium in the temperature range above the boiling point of water, e.g. developed at 115 to 180 ° C. For example, it lies at 1 to 10, preferably 1.2 to 7.9 bar.
  • the reaction mixture is subjected to shear. If one If the reaction is carried out in a stirred autoclave, this is stirred Reaction mixture, for example with 100 to 2,000, preferably 200 to 1,000 revolutions / minute.
  • the reaction can be practical be carried out in all equipment in which starch in open to technology, e.g. in a jet cooker.
  • the Residence times of the reaction mixture at the above temperatures from 115 to 180 ° C, for example, 0.1 seconds to 1 hour and is preferably in the range of 0.5 seconds up to 30 minutes.
  • At least 90% of the used Strength open-minded and modified Preferably be less than 5% by weight of the starch is broken down.
  • the native starch types can also be pretreated e.g. degraded oxidatively, hydrolytically or enzymatically or be chemically modified.
  • Wax starches such as waxy potato starch and waxy corn starch from of special interest.
  • the reaction products obtainable in this way have, for example a viscosity at a solids concentration of 3.5% by weight from 50 to 10,000, preferably 80 to 4,000 mPa ⁇ s, measured in a Brookfield viscometer at 20 rpm and one Temperature of 20 ° C.
  • the pH of the reaction mixtures is for example in the range of 2.0 to 9.0, preferably 2.5 to 8.
  • the so available modified with cationic polymers Starches are used as dry strength agents in paper pulp Amounts of, for example, 0.5 to 10, preferably 0.5 to 3.5 and particularly preferably 1.2 to 2.5% by weight, based on dry Paper stock, added.
  • a cationic polymer as a retention agent for the strengths described above, such as cationic Starch, preferably those starches modified with a polymer were, anionic and / or amphoteric starches.
  • Dosage of dry strength agents and retention aids to the paper can be produced, for example, by this be that the retention agent of the digested starch after cooling to 50 ° C or below.
  • the retention aid can also before adding the modified starch Paper stock can be added. From this order of addition is done, for example, when processing paper stock Use that have a high content of contaminants.
  • Condensates of dimethylamine and epichlorohydrin are also suitable, Condensates of dimethylamine and dichloroalkanes such as Dichloroethane or dichloropropane and condensation products Dichloroethane and ammonia.
  • the process uses a cationic starch in combination with cationic polymers containing vinylamine units and the K values of at least 30 (determined according to H. Fikentscher in aqueous solution at a polymer concentration of 0.5% by weight, a temperature of 25 ° C and a pH of 7).
  • a cationic is preferably used as the dry strength agent Strength that is available through implementation of 100 parts by weight of a native, cationic, anionic and / or amphoteric starch with 0.5 to 10 parts by weight of a vinylamine unit containing polymers with a K value of 60 to 150 at temperatures above the gelatinization temperature of the Strength.
  • Polymers containing vinylamine units are e.g. hydrolyzed homo- and copolymers of N-vinylformamide with a degree of hydrolysis of at least 60% is preferably used. These homopolymers and copolymers are not only used for cationization of starch but also the paper stock as a retention agent added for the cationically modified starches.
  • Those considered as retention agents for starch hydrolyzed homo- and copolymers of N-vinylformamide can generally have a degree of hydrolysis of 1 to 100%.
  • Starches to be used in dry strength agents are given in Amounts of 0.5 to 10, preferably 1 to 5 wt .-%, based on dry paper stock used.
  • the drainage of the paper stock according to the invention always takes place at least in the presence a retention aid for starch, the retention aid in Quantities of 0.01 to 0.3 wt .-%, based on dry paper stock be used. This gives you compared to the known Process significantly improved retention of starch and an increase in the rate of drainage of the paper stock on the paper machine.
  • microparticle systems can also be used as retention agents for starch use, with the paper stock a high molecular weight cationic synthetic polymer adds to the formed Macro flakes cut up by shearing the paper stock and then adds bentonite.
  • This method is for example known from EP-A-0 335 575.
  • a microparticle system can be used, for example, as cationic polymers Mixture of a polymer containing vinylamine units, e.g. Polyvinylamine and a cationic polyacrylamide, e.g. a copolymer of acrylamide and dimethylaminoethyl acrylate methochloride insert and add bentonite after the shear step.
  • cationic polymers as Retention agents for starches are mixtures of vinylamine units containing polymers and grafted with ethyleneimine cross-linked polyamidoamines and mixtures of vinylamine units containing polymers with polydiallyldimethylammonium chlorides.
  • the percentages mean weight percent in the examples.
  • the K values were calculated according to H. Fikentscher, Cellulose-Chemie, Volume 13, 58 to 64 and 71 to 74 (1932) at a temperature of 25 ° C in aqueous solution at a Polymer concentration of 0.5 wt .-% determined.
  • a paper stock with a stock density of 7.6 g / l was prepared from an open, ready-made commercially available shaft raw material based on waste paper.
  • the pH of the paper stock was 8.0.
  • samples were taken of this Paper pulp each have the amounts of hardener given in Table 1 1 and the polymers 1-4 added in succession. After this Mixing the paper stock with the additives was suction filtered and the starch content from the extinction measurement of the starch-iodine complex certainly. The results obtained are in Table 1 given. Another part of the pulp was after dosing of solidifier 1 and those in Table 1 specified polymers using a Schopper-Riegler device dewatered. The drainage time was determined according to DIN ISO 5267 for 700 ml filtrate. The results are shown in Table 1.
  • Example 1 was repeated with the exception that only pulping agent 1 was added to the paper stock in an amount of 2%, based on dry paper stock.
  • the starch content of the filtrate and the drainage time are given in Table 1.
  • Addition to paper stock, based on dry paper stock Starch content in the filtrate [Mg / l] drainage time [sec / 700 ml] 1 2% hardener 1 + 0.08% polymer 1 38 92 2 2% hardener 1 + 0.08% polymer 2 34 49 3 2% hardener 1 + 0.08% polymer 3 30 55 4 2% hardener 1 + 0.08% polymer 4 30 67
  • Waste paper base with a consistency of 0.76% was initially with 2% hardener 1 and then with 0.08% polymer 3 as Retention agent for cationic starch added. After offer The pulp of the strengthener and polymer was mixed together. Part of this paper stock was sucked off. From the The COD value and the starch retention by enzymatic became filtrate Degradation to glucose determined by HPLC. From the other Part of the paper stock was determined using a Schopper-Riegler device the drainage time for 500 ml of filtrate. The Results are shown in Table 2.
  • Example 5 was repeated with the changes shown in Table 2. The results are shown in Table 2.
  • example Addition to paper stock, based on dry paper stock COD [mgO 2 / l] strength retention (enzymatic method) drainage time [sec / 500 ml] 5 2% hardener 2 + 0.08% polymer 3 134 93 20 Comparative example 2 2% hardener 1 313 43 72 3 2% commercial cationic starch DS 0.035 162 92 78 4 - 135 68
  • a whipped finished commercial wave raw material based on waste paper with a substance concentration of 0.76% was successively mixed with 2% hardener 2 and 0.08% polymer 3.
  • paper sheets with a basis weight of 120 g per m 2 are produced on a Rapid-Köthen sheet former.
  • the sheets were tested for their dry strength, namely the dry tear length according to DIN ISO 1924, dry burst pressure according to DIN ISO 2758 and flat crush resistance CMT according to DIN EN 23035 equal to ISO 3035. The results are shown in Table 3.
  • Example 6 was repeated with the changes shown in Table 3, working in the absence of Polymer 3 (Comparative Example 5).
  • commercially available cationic starch was used (comparative example 6) and the zero value was determined (comparative example 7).
  • the results are shown in Table 3.
  • modified PEI with a charge density of 14.7 at pH 4.5 and 10.8 at pH 7 and an average molecular weight of approximately 700,000 D.
  • a paper dye based on waste paper with a COD value of 8000 mg oxygen / l and a substance concentration of 1% was successively mixed with 2% hardener 1, with 0.245% polymer 6 and 0.02% polymer 7.
  • paper sheets with a basis weight of approx. 110 g / m 2 are produced on the Rapid-Köthen sheet former.
  • the leaves were tested for their dry strength, namely the strip crush resistance (SCT) value according to DIN 54518 (ISO 9895), dry burst pressure according to DIN ISO 2758 and flat crush resistance CMT according to DIN EN 23035 (ISO 3035). The results are shown in Table 4.
  • SCT strip crush resistance
  • a waste paper-based paper stock with a COD value of 8000 mg oxygen / l and a substance concentration of 1% was mixed in succession with 2% hardener 1, 0.12% polymer 2 and 0.02% polymer 7. After mixing, paper sheets with a basis weight of approx. 110 g / m 2 are produced on the Rapid-Köthen sheet former. The leaves were tested for their dry strength using the methods given in Example 7. The results are shown in Table 4.
  • a paper material based on waste paper with a COD value of 8000 mg oxygen / l and a substance concentration of 1% was mixed with 2% hardener 1, 0.13% polymer 4 and 0.02% polymer 7 in succession. After mixing, paper sheets with a basis weight of approx. 110 g / m 2 are produced on the Rapid-Köthen sheet former. The leaves were tested for their dry strength using the methods given in Example 7. The results are shown in Table 4.
  • a paper material based on waste paper with a COD value of 8000 mg oxygen / l and a substance concentration of 1% was successively mixed with 2% hardener 1 and 0.02% polymer 7. After mixing, paper sheets with a basis weight of approx. 110 g / m 2 are produced on the Rapid-Köthen sheet former. The leaves were tested for their dry strength using the methods given in Example 7. The results are shown in Table 4.

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Claims (12)

  1. Procédé de préparation de papier, de carton-pâte et de carton présentant une haute stabilité à sec par addition d'amidon cationique, anionique et/ou amphotère, comme agent de stabilité à sec, à la pâte de papier et par déshydratation de la pâte de papier en présence d'un agent de rétention, avec formation de feuille, caractérisé en ce que, comme agent de rétention pour de l'amidon, on met en oeuvre au moins un polymère cationique du groupe
    des polymères contenant des unités vinylamine,
    des polyéthylèneimines,
    des polyamidoamines réticulées,
    des polyamidoamines greffées avec de l'éthylèneimine et réticulées,
    des chlorures de polydiallyldiméthylammonium,
    des polymères contenant des unités N-vinylimidazoline,
    des polymères contenant de l'acrylate de dialkylaminoalkyle ou du méthacrylate de dialkylaminoalkyle,
    des polymères contenant des unités dialkylaminoalkylacrylamide ou des unités dialkylaminoalkylméthacrylamide, et
    des polyallylamines.
  2. Procédé suivant la revendication 1, caractérisé en ce qu'on met en oeuvre un amidon cationique en combinaison avec des polymères cationiques qui contiennent des unités vinylamine et qui ont des valeurs K d'au moins 30 (déterminées d'après H. Fikentscher en solution aqueuse à une concentration en polymère de 0,5% en poids, à une température de 25°C et à une valeur de pH de 7).
  3. Procédé suivant l'une des revendications 1 et 2, caractérisé en ce qu'on met en oeuvre un amidon cationique qui peut être obtenu par réaction de 100 parties en poids d'un amidon cationique, anionique et/ou amphotère, naturel, avec 0,5 à 10 parties en poids d'un polymère contenant des unités vinylamine et ayant une valeur K de 60 à 150, à des températures au-dessus de la température de gélification de l'amidon.
  4. Procédé suivant la revendication 3, caractérisé en ce que, comme polymères contenant des unités vinylamine, on met en oeuvre des homopolymères ou copolymères de N-vinylformamide ayant un degré d'hydrolyse d'au moins 60%.
  5. Procédé suivant l'une des revendications 1 à 4, caractérisé en ce que, comme agent de rétention pour l'amidon, on met en oeuvre des homopolymères ou copolymères hydrolysés de N-vinylformamide ayant un degré d'hydrolyse de 1 à 100%.
  6. Procédé suivant l'une des revendications 1 à 5, caractérisé en ce qu'on met en oeuvre un amidon cationique présentant un degré de substitution D.S. de jusqu'à 0,15.
  7. Procédé suivant l'une des revendications 1 à 6, caractérisé en ce qu'on met en oeuvre l'agent de stabilité à sec en des quantités de 0,5 à 10% en poids, par rapport à la pâte de papier sèche.
  8. Procédé suivant l'une des revendications 1 à 7, caractérisé en ce qu'on met en oeuvre l'agent de stabilité à sec en des quantités de 1 à 5% en poids, par rapport à la pâte de papier sèche.
  9. Procédé suivant l'une des revendications 1 à 8, caractérisé en ce qu'on met en oeuvre l'agent de rétention pour amidon en des quantités de 0,01 à 0,3% en poids, par rapport à la pâte de papier sèche.
  10. Procédé suivant l'une des revendications 1 et 2, caractérisé en ce qu'on met en oeuvre un amidon cationique qui peut être obtenu par réaction de 100 parties en poids d'un amidon cationique, anionique et/ou amphotère, naturel, avec 0,5 à 10 parties en poids
    de chlorure de polydiallyldiméthylammonium,
    de polyamidoamines solubles dans l'eau, réticulées avec de l'épichlorhydrine,
    de polyamidoamines solubles dans l'eau, greffées avec de l'éthylèneimine et réticulées avec des éthers de bis-chlorhydrine de polyalkylèneglycols,
    et/ou
    de polyéthylèneimines solubles dans l'eau et de polyéthylèneimines réticulées solubles dans l'eau,
       à des températures supérieures à la température de gélification de l'amidon jusqu'à 180°C.
  11. Utilisation d'agent de rétention polymère cationique du groupe
    des polymères contenant des unités vinylamine,
    des polyéthylèneimines,
    des polyamidoamines réticulées,
    des polyamidoamines greffées avec de l'éthylèneimine et réticulées,
    des chlorures de polydiallyldiméthylammonium,
    des polymères contenant des unités N-vinylimidazoline,
    des polymères contenant de l'acrylate de dialkylaminoalkyle ou du méthacrylate de dialkylaminoalkyle,
    des polymères contenant des unités dialkylaminoalkylacrylamide ou des unités dialkylaminoalkylméthacrylamide, et
    des polyallylamines,
       pour augmenter la rétention des agents de stabilité à sec à partir d'amidon cationique, anionique et/ou amphotère lors de la fabrication de papier, de carton-pâte et de carton.
  12. Utilisation suivant la revendication 11, caractérisée en ce que, comme agent de rétention, on met en oeuvre des homopolymères ou copolymères hydrolysés de N-vinylformamide ayant un degré d'hydrolyse de 1 à 100% et une valeur K d'au moins 30 (déterminée d'après H. Fikentscher en solution aqueuse à une concentration en polymère de 0,5% en poids, à une température de 25°C et à une valeur de pH de 7) en des quantités de 0,01 à 0,3% en poids.
EP98921399A 1997-04-04 1998-03-26 Procede pour produire du papier, du carton-pate et du carton a haute resistance a la traction a l'etat sec Expired - Lifetime EP0972110B2 (fr)

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DE19713755 1997-04-04
DE19713755A DE19713755A1 (de) 1997-04-04 1997-04-04 Verfahren zur Herstellung von Papier, Pappe und Karton mit hoher Trockenfestigkeit
PCT/EP1998/001786 WO1998045536A1 (fr) 1997-04-04 1998-03-26 Procede pour produire du papier, du carton-pate et du carton a haute resistance a la traction a l'etat sec

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EP0972110B1 true EP0972110B1 (fr) 2004-06-02
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JP (1) JP2001518988A (fr)
KR (1) KR20010006002A (fr)
AT (1) ATE268410T1 (fr)
AU (1) AU730063B2 (fr)
CA (1) CA2284931C (fr)
DE (2) DE19713755A1 (fr)
ES (1) ES2222591T3 (fr)
NZ (1) NZ338029A (fr)
PT (1) PT972110E (fr)
WO (1) WO1998045536A1 (fr)
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AU7427598A (en) 1998-10-30
US6616807B1 (en) 2003-09-09
WO1998045536A1 (fr) 1998-10-15
PT972110E (pt) 2004-10-29
EP0972110B2 (fr) 2009-03-11
DE59811513D1 (de) 2004-07-08
ATE268410T1 (de) 2004-06-15
KR20010006002A (ko) 2001-01-15
NZ338029A (en) 2000-04-28
CA2284931C (fr) 2010-02-16
DE19713755A1 (de) 1998-10-08
ES2222591T3 (es) 2005-02-01
ZA982842B (en) 1999-01-20
AU730063B2 (en) 2001-02-22
EP0972110A1 (fr) 2000-01-19
JP2001518988A (ja) 2001-10-16

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