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EP2443284B1 - Procédé de fabrication pour augmenter la résistance à sec de papier et de carton présentant - Google Patents

Procédé de fabrication pour augmenter la résistance à sec de papier et de carton présentant Download PDF

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Publication number
EP2443284B1
EP2443284B1 EP10724788.4A EP10724788A EP2443284B1 EP 2443284 B1 EP2443284 B1 EP 2443284B1 EP 10724788 A EP10724788 A EP 10724788A EP 2443284 B1 EP2443284 B1 EP 2443284B1
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units
polymer
polymers
process according
water
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German (de)
English (en)
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EP2443284B2 (fr
EP2443284A1 (fr
Inventor
Christian Jehn-Rendu
Ellen KRÜGER
Hans-Joachim HÄHNLE
Martin Rübenacker
Norbert Schall
Thomas MÜHLENBERND
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BASF SE
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BASF SE
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Classifications

    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
    • D21H21/18—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
    • D21H17/33—Synthetic macromolecular compounds
    • D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H17/37—Polymers of unsaturated acids or derivatives thereof, e.g. polyacrylates
    • 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
    • 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
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/63—Inorganic compounds
    • D21H17/66—Salts, e.g. alums
    • 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
    • D21H17/71—Mixtures of material ; Pulp or paper comprising several different materials not incorporated by special processes
    • D21H17/74—Mixtures of material ; Pulp or paper comprising several different materials not incorporated by special processes of organic and inorganic material

Definitions

  • the invention relates to a process for the production of paper, paperboard and cardboard with high dry strength by adding (a) at least one trivalent cation, (b) at least one water-soluble cationic polymer selected from the group consisting of (i) vinylamine units polymers and (ii) Ethyleniminiseren and (c) at least one water-soluble amphoteric polymer to a pulp, dewatering the stock to form sheets, and drying the resulting paper product.
  • JP 54-030913 a method for the production of paper with high dry strength is known in which the paper stock is first added an aluminum sulfate solution. Thereafter, a water-soluble amphoteric polymer is added. Subsequently, the paper stock is dewatered on the paper machine to form sheets, and the paper products are dried.
  • Suitable amphoteric polymers are, for example, copolymers of acrylamide, acrylic acid and dimethylaminoethyl (meth) acrylate.
  • Suitable anionic polymers are, for example, homopolymers or copolymers of ethylenically unsaturated C 3 -C 5 -carboxylic acids.
  • the copolymers contain at least 35 wt .-% of an ethylenically unsaturated C 3 - C 5 carboxylic acid (eg acrylic acid) in copolymerized form.
  • the cationic polymers described in the examples are polyethyleneimine, polyvinylamine, polydiallyldimethylammonium chloride and epichlorohydrin-reacted condensation products of adipic acid and diethylenetriamine.
  • the use of partially hydrolyzed homo- and copolymers of N-vinylformamide has also been considered.
  • the JP 02-112498 relates to a process for the production of corrugated board, wherein dosing alum, a polyallylamine and an anionic or amphoteric polymer to a fiber suspension.
  • the combination produces papers with a high strength.
  • JP 05-272092 discloses a process for producing high dry strength paper by first adding an aluminum sulphate solution to the stock followed by a high molecular weight, water soluble, amphoteric polymer dosed, then drained the paper stock on the paper machine with sheet formation and the paper products dried.
  • amphoteric polymers include copolymers of acrylamide, acrylic acid, dimethylaminoethyl (meth) acrylate, (meth) acrylamide and sodium (meth) allylsulfonate. These amphoteric polymers are characterized by very high molecular weights and low solution viscosities.
  • JP 08-269891 A variant of in JP 05-272092 described method is in JP 08-269891 disclosed.
  • an aluminum sulfate solution is also added to the paper stock first, followed by metering in a high molecular weight water-soluble amphoteric polymer, followed by dewatering of the paper stock on the paper machine and drying of the paper products.
  • Copolymers of acrylamide, acrylic acid, dimethylaminoethyl methacrylates, (meth) acrylamide, sodium (meth) allylsulfonate and a crosslinker such as methylenebisacrylamide or triallylamine are used as amphoteric polymers, for example.
  • These amphoteric polymers have a very high molecular weight and one opposite JP 05-272092 further reduced solution viscosity.
  • the EP 0 659 780 A1 describes a process for preparing polymers having a weight average molecular weight of 1,500,000 to 10,000,000 (a) and a weight average root mean square radius of 30 to 150 nm (b), wherein the ratio (b) / (a) ⁇ 0 , 00004, and their use as solidifying agents.
  • WO 98/06898 A1 describes a process for papermaking in which a cationic starch or a cationic wet strength agent and a water-soluble amphoteric polymer is added to the stock.
  • This amphoteric polymer is composed of the nonionic monomers acrylamide and methacrylamide, an anionic monomer, a cationic monomer and a crosslinker, the amount of anionic and cationic monomer not exceeding 9% by weight of the total monomers used in the amphoteric polymer.
  • the JP-A-1999-140787 relates to a process for the production of corrugated board, wherein to improve the strength properties of a paper product to the pulp 0.05 to 0.5 wt .-%, based on dry pulp, of a polyvinylamine obtained by hydrolysis of polyvinylformamide having a degree of hydrolysis of 25 to 100 %, is added in combination with an anionic polyacrylamide, the stock is then dewatered to form sheets and the paper is dried.
  • the EP 0 919 578 A1 relates to amphoteric polymers (type B) prepared by a two-stage polymerization.
  • a polymer (type A) is prepared by the copolymerization of methallylsulfonic acid with others Vinyl monomers, then in the presence of the type A polyamor there is a further polymerization of vinyl monomers to the B-type polymer wherein the type A polymers have a molecular weight of from 1,000 to 5,000,000 and the type B polymers have a molecular weight of from 100,000 to 10,000,000 exhibit.
  • this document comprises the use of the polymers of type B as solidifying agents for papermaking and the papers produced therewith, whereby the possibility of a combination with alum and anionic polyacrylamides is also described. Finally, the possibility of modifying the type B polymers by Hofmann degradation is also mentioned.
  • a paper product having improved strength properties which is obtained by dosing a mixture of an amphoteric, cationic or anionic polymer and a water-soluble aluminum solution to the pulp.
  • the JP 2001-279595 relates to a process for producing high-strength paper wherein a mixture of a cationic, anionic or amphoteric polyacrylamide with a water-soluble aluminum compound is added to the fibers. This is followed by a metered addition of another polyacrylamide. This not only increases the strength, but also improves drainage at the same time.
  • WO 03/052206 A1 discloses a paper product having improved strength properties obtainable by applying to the surface of a paper product a polyvinylamine and a polymeric anionic compound which can form a polyelectrolyte complex with polyvinylamine, or a polymeric compound having aldehyde functions such as aldehyde group-containing polysaccharides. Not only does the paper improve its dry and wet strength, it also observes a sizing effect of the treating agents.
  • JP 2005-023434 there is described a process for producing high strength paper obtained by metering two polymers.
  • the first polymer is a branched amphoteric polyacrylamide.
  • As the second polymer a copolymer of a cationic vinyl monomer as a main monomer is considered.
  • WO 2006/120235 A1 discloses a process for producing papers having a filler content of at least 15% by weight, in which filler and fibers are treated together with cationic and anionic polymers. The treatment is carried out alternately with cationic and anionic polymers and comprises at least three steps.
  • EP 1 849 803 A1 there is known a paper additive for strengthening which is obtained as a water-soluble polymer by polymerizing (meth) acrylamide, an ⁇ , ⁇ -unsaturated mono- or dicarboxylic acid or salts thereof, a cationic monomer and a crosslinking monomer. In a second stage, the remaining residual monomer is polymerized with further persulfate catalyst.
  • the said components of the solidification system may be added to the stock in any order or else as a mixture of two or more components.
  • trivalent metal or semimetallic cations are suitable as trivalent cations in the process according to the invention.
  • Preferred metal cations are Al 3+ , Zr 3+ and Fe 3+ . Most preferred is Al 3+ .
  • the metal and semimetal cations are used in the form of their salts.
  • Al 3+ this can be used, for example, in the form of aluminum sulfate, polyaluminum chloride or aluminum lactate.
  • any mixtures of said trivalent metal cations can be used, but preferably only a trivalent metal cation is used in the process according to the invention.
  • different salts of this metal cation can be used in any mixtures.
  • a trivalent metal cation in one of the described salt forms is used.
  • the trivalent cations are usually added to the stock in amounts of between 3 and 100 moles per ton of dry paper, preferably in the range of 10 to 30 moles per ton of dry paper.
  • the water-soluble cationic polymer (b) is selected from the group of polymers containing (i) vinylamine units and (ii) polymers containing ethyleneimine units.
  • the cationic polymers (b) are water-soluble.
  • the solubility in water under normal conditions (20 ° C., 1013 mbar) and pH 7.0 is for example at least 5% by weight, preferably at least 10% by weight.
  • the charge density of the cationic polymers (without counterion) is for example at least 1.0 meq / g and is preferably in the range of 4 to 10 meq / g.
  • the water-soluble cationic polymers (b) usually have average molecular weights in the range of 10,000 to 10,000,000 daltons, preferably in the range of 20,000 to 5,000,000 daltons, more preferably in the range of 40,000 to 3,000,000 daltons.
  • Examples of monomers of the formula (I) are N-vinylformamide, N-vinyl-N-methylformamide, N-vinylacetamide, N-vinyl-N-methylacetamide, N-vinyl-N-ethylacetamide, N-vinylpropionamide and N-vinyl-N methylpropionamide and N-vinylbutyramide.
  • the monomers of group (a) may be used alone or in admixture in the copolymerization with the monomers of the other groups.
  • Preferably used monomer of this group is N-vinylformamide.
  • polymers may optionally be modified by copolymerizing the N-vinylcarboxamides (1.) together with (2.) at least one other monoethylenically unsaturated monomer and then hydrolyzing the copolymers to form amino groups. If anionic monomers are used in the copolymerization, the hydrolysis of the copolymerized vinylcarboxamide units is carried out so far that the molar excess of amine units compared to the anionic units in the polymer is at least 5 mol%.
  • Examples of monomers of group (2) are esters of ⁇ , ⁇ -ethylenically unsaturated mono- and dicarboxylic acids with C 1 -C 30 -alkanols, C 2 -C 30 -alkanediols and C 2 -C 30 -aminoalcohols, amides of ⁇ , ⁇ -ethylenically unsaturated monocarboxylic acids and their N-alkyl and N, N-dialkyl derivatives, nitriles of ⁇ , ⁇ -ethylenically unsaturated mono- and dicarboxylic acids, esters of vinyl alcohol and allyl alcohol with C 1 -C 30 -monocarboxylic acids, N-vinyllactams, nitrogen-containing heterocycles having ⁇ , ⁇ -ethylenically unsaturated double bonds, vinylaromatics, vinyl halides, vinylidene halides, C 2 -C 8 monoolefins and mixtures thereof
  • Suitable representatives are e.g. Methyl (meth) acrylate (in which (meth) acrylate in the context of the present invention means both acrylate and methacrylate), methyl methacrylate, ethyl (meth) acrylate, ethyl ethacrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, tert. Butyl (meth) acrylate, tert-butyl ethacrylate, n-octyl (meth) acrylate, 1,1,3,3-tetramethylbutyl (meth) acrylate, ethylhexyl (meth) acrylate and mixtures thereof.
  • Suitable additional monomers of the group (2) are furthermore the esters of ⁇ , ⁇ -ethylenically unsaturated mono- and dicarboxylic acids with aminoalcohols, preferably C 2 -C 12 -aminoalcohols. These may be C 1 -C 8 monoalkylated or dialkylated on the amine nitrogen.
  • Suitable acid components of these esters are, for example, acrylic acid, methacrylic acid, fumaric acid, maleic acid, itaconic acid, crotonic acid, maleic anhydride, monobutyl maleate and mixtures thereof. Preference is given to using acrylic acid, methacrylic acid and mixtures thereof.
  • N-methylaminomethyl (meth) acrylate N-methylaminoethyl (meth) acrylate, N, N-dimethylaminomethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N , N-dimethylaminopropyl (meth) acrylate, N, N-diethylaminopropyl (meth) acrylate and N, N-dimethylaminocyclohexyl (meth) acrylate.
  • Such monomers of group (2) are 2-hydroxyethyl (meth) acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate and mixtures thereof.
  • Suitable monomers of group (2) are acrylamide, methacrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, n-propyl (meth) acrylamide, N- (n-butyl) (meth) acrylamide , tert-butyl (meth) acrylamide, n-octyl (meth) acrylamide, 1,1,3,3-tetramethylbutyl (meth) acrylamide, ethylhexyl (meth) acrylamide and mixtures thereof.
  • monomers of group (2) are nitriles of ⁇ , ⁇ -ethylenically unsaturated mono- and dicarboxylic acids such as, for example, acrylonitrile and methacrylonitrile.
  • the presence of units of these monomers in the copolymer leads during or after the hydrolysis to products which have amidine units, cf. eg EP 0 528 409 A1 or DE 43 28 975 A1 ,
  • amidine units are formed in a secondary reaction by reacting vinylamine units with an adjacent vinylformamide unit or, if a nitrile group is present as an adjacent group in the polymer.
  • the indication of vinylamine units in the amphoteric copolymers or in unmodified homo- or copolymers always means the sum of vinylamine and amidine units.
  • Suitable monomers of group (2) are furthermore N-vinyllactams and derivatives thereof which may have, for example, one or more C 1 -C 6 -alkyl substituents (as defined above). These include N-vinylpyrrolidone, N-vinylpiperidone, N-vinylcaprolactam, N-vinyl-5-methyl-2-pyrrolidone, N-vinyl-5-ethyl-2-pyrrolidone, N-vinyl-6-methyl-2-piperidone, N-vinyl-6-ethyl-2-piperidone, N-vinyl-7-methyl-2-caprolactam, N-vinyl-7-ethyl-2-caprolactam and mixtures thereof.
  • Suitable monomers of group (2) are N-vinylimidazoles and alkylvinylimidazoles, in particular methylvinylimidazoles such as, for example, 1-vinyl-2-methylimidazole, 3-vinylimidazole N-oxide, 2- and 4-vinylpyridine N-oxides and also betaine derivatives and quaternization products these monomers as well as ethylene, propylene, isobutylene, butadiene, styrene, ⁇ -methylstyrene, vinyl acetate, vinyl propionate, vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride and mixtures thereof.
  • methylvinylimidazoles such as, for example, 1-vinyl-2-methylimidazole, 3-vinylimidazole N-oxide, 2- and 4-vinylpyridine N-oxides and also betaine derivatives and quaternization products these monomers as well as ethylene, propylene
  • the aforementioned monomers can be used individually or in the form of any mixtures. Typically, they are used in amounts of 1 to 90 mol%, preferably 10 to 80 mol% and particularly preferably 10 to 60 mol%.
  • amphoteric Copoylmerisaten come as other monoethylenically unsaturated monomers of group (2.) and anionic monomers into consideration, which are referred to above as monomers (2.1). They may optionally be copolymerized with the neutral and / or cationic monomers (2.2) described above. However, the amount of anionic monomers (2.1) is at most 45 mol%, so that the resulting amphoteric copolymer has a total cationic charge.
  • anionic monomers of group (2.1) are ethylenically unsaturated C 3 -C 8 -carboxylic acids such as, for example, acrylic acid, methacrylic acid, dimethacrylic acid, ethacrylic acid, maleic acid, fumaric acid, itaconic acid, mesaconic acid, citraconic acid, methylenemalonic acid, allylacetic acid, vinylacetic acid and crotonic acid.
  • monomers containing sulfonic groups such as vinylsulfonic acid, acrylamido-2-methylpropanesulfonic acid and styrenesulfonic acid, and monomers containing phosphonic groups, such as vinylphosphonic acid.
  • the monomers of this group can be used alone or in admixture with each other, in partially or completely neutralized form in the copolymerization.
  • neutralization for example, alkali metal or alkaline earth metal bases, ammonia, amines and / or alkanolamines are used. Examples of these are sodium hydroxide solution, potassium hydroxide solution, soda, potash, sodium bicarbonate, magnesium oxide, calcium hydroxide, calcium oxide, triethanolamine, ethanolamine, morpholine, diethylenetriamine or tetraethylenepentamine.
  • a further modification of the copolymers is possible by using in the copolymerization monomers of group (3.) which contain at least two double bonds in the molecule, e.g. Triallylamine, methylenebisacrylamide, glycol diacrylate, glycol dimethacrylate, glycerol triacrylate, pentaerythritol triallyl ether, polyalkylene glycols esterified at least twice with acrylic acid and / or methacrylic acid, or polyols such as pentaerythritol, sobait or glucose. These are so-called crosslinkers. If at least one monomer of the above group is used in the polymerization, the amounts used are up to 2 mol%, e.g. 0.001 to 1 mole%.
  • regulators typically, from 0.001 to 5 mole percent is used. All regulators known from the literature can be used, for example sulfur compounds such as mercaptoethanol, 2-ethylhexyl thioglycolate, thioglycolic acid and dodecylmercaptan and sodium hypophosphite, formic acid or tribromochloromethane and terpinolene.
  • the polymers (i) containing vinylamine units also include hydrolyzed graft polymers of, for example, N-vinylformamide on polyalkylene glycols, polyvinyl acetate, polyvinyl alcohol, polyvinylformamides, polysaccharides such as starch, oligosaccharides or monosaccharides.
  • the graft polymers are obtainable by free-radically polymerizing, for example, N-vinylformamide in aqueous medium in the presence of at least one of the stated grafting bases together with copolymerizable other monomers and then hydrolyzing the grafted vinylformamide units in a known manner to give vinylamine units.
  • the hydrolysis of the copolymers described above can be carried out in the presence of acids or bases or else enzymatically.
  • the vinylamine groups formed from the vinylcarboxamide units are present in salt form.
  • the hydrolysis of vinylcarboxylic acid amide copolymers is described in U.S. Pat EP 0 438 744 A1 , Page 8, line 20 to page 10, line 3, described in detail.
  • the explanations made there apply correspondingly to the preparation of the cationic and / or amphoteric polymers containing vinylamine units to be used according to the invention and having a total cationic charge.
  • the homo- and copolymers (i) containing the vinylamine units described above can be prepared by solution, precipitation, suspension or emulsion polymerization. Preference is given to solution polymerization in aqueous media.
  • aqueous media are water and mixtures of water and at least one water-miscible solvent, e.g. an alcohol such as methanol, ethanol, n-propanol or isopropanol.
  • vinylamine units also include the reaction products obtained by Hofmann degradation of homo- or copolymers of acrylamide or methacrylamide in an aqueous medium in the presence of sodium hydroxide and sodium hypochlorite and subsequent decarboxylation of the carbamate groups of the reaction products in the presence of a Acid are available.
  • Such polymers are for example made EP 0 377 313 and WO 2006/075115 A1 known.
  • the preparation of polymers containing vinylamine groups is described, for example, in WO 2006/075115 A1 , Page 4, line 25 to page 10, line 22 and in the examples on pages 13 and 14 are treated in detail.
  • acrylamide and / or methacrylamide units are homopolymers or copolymers of acrylamide and methacrylamide.
  • Suitable comonomers are, for example, dialkylaminoalkyl (meth) acrylamides, diallylamine, methyldiallylamine and also the salts of the amines and the quaternized amines.
  • Dimethyldiallylammonium salts acrylamidopropyltrimethylammonium chloride and / or Methacrylamidopropyltrimethylammoniumchlorid
  • N-vinylformamide N-vinylacetamide
  • N-vinylpyrrolidone vinyl acetate
  • acrylic and methacrylic acid esters Dimethyldiallylammonium salts, acrylamidopropyltrimethylammonium chloride and / or Methacrylamidopropyltrimethylammoniumchlorid, N-vinylformamide, N-vinylacetamide, N-vinylpyrrolidone, vinyl acetate and acrylic and methacrylic acid esters.
  • anionic monomers such as acrylic acid, methacrylic acid, maleic anhydride, maleic acid, itaconic acid, acrylamidomethylpropanesulfonic acid, methallylsulfonic acid and vinylsulfonic acid and also the alkali metal, alkaline earth metal and ammonium salts of said acidic monomers, not more than 5 mol% of these monomers being included the polymerization can be used.
  • the amount of water-insoluble monomers is chosen in the polymerization so that the resulting polymers are soluble in water.
  • comonomers may also be used crosslinkers, e.g. ethylenically unsaturated monomers containing at least two double bonds in the molecule, such as triallylamine, methylenebisacrylamide, ethylene glycol diacrylate, ethylene glycol dimethacrylate, polyethylene glycol dimethacrylate and trimethylol trimethacrylate.
  • crosslinker e.g. ethylenically unsaturated monomers containing at least two double bonds in the molecule, such as triallylamine, methylenebisacrylamide, ethylene glycol diacrylate, ethylene glycol dimethacrylate, polyethylene glycol dimethacrylate and trimethylol trimethacrylate.
  • the amounts used are, for example, 5 to 5000 ppm.
  • the polymerization of the monomers can be carried out by any known method, e.g. by free-radical initiated solution, precipitation or suspension polymerization. If appropriate, it is possible to work in the presence of customary polymer
  • Hofmann degradation is for example from 20 to 40 wt .-% aqueous solutions of at least one acrylamide and / or methacrylamide units containing polymers.
  • the ratio of alkali metal hypochlorite to (meth) acrylamide units in the polymer is decisive for the resulting content of amine groups in the polymer.
  • the molar ratio of alkali metal hydroxide to alkali metal hypochlorite is for example 2 to 6, preferably 2 to 5.
  • For a certain amine group content in the degraded polymer is calculated for the degradation of the polymer required amount of alkali metal hydroxide.
  • the Hofmann degradation of the polymer is carried out, for example, in the temperature range from 0 to 45 ° C, preferably 10 to 20 ° C in the presence of quaternary ammonium salts as a stabilizer to prevent a side reaction of the resulting amino groups with the amide groups of the starting polymer.
  • the aqueous reaction solution is passed into a reactor in which an acid is introduced for the decarboxylation of the reaction product.
  • the pH of the reaction product containing vinylamine units is set to a value of 2 to 7.
  • the concentration of the decomposition products containing vinylamine units is, for example, more than 3.5% by weight, in most cases above 4.5% by weight.
  • the aqueous polymer solutions can be concentrated for example by means of ultrafiltration.
  • the polymers (ii) containing ethyleneimine units include all polymers obtainable by polymerization of ethyleneimine in the presence of acids, Lewis acids or haloalkanes, such as homopolymers of ethyleneimine or graft polymers of ethyleneimine, cf. US 2,182,306 or US 3,203,910 , If desired, these polymers can subsequently be subjected to crosslinking.
  • Suitable crosslinkers are, for example, all multifunctional compounds which contain reactive groups relative to primary amino groups, for example multifunctional epoxides such as bisglycidyl ethers of oligo- or polyethyleneoxides or other multifunctional alcohols such as glycerol or sugars, multifunctional carboxylic esters, mulifunctional isocyanates, polyfunctional acrylic or methacrylic acid esters, multifunctional acrylic acid - or methacrylic acid amides, epichlorohydrin, multifunctional acid halides, multifunctional nitriles, ⁇ , ⁇ -chlorohydrin ethers of oligo- or polyethylene oxides or other multifunctional alcohols such as glycerol or sugars, divinylsulfone, maleic anhydride or ⁇ -Halogencarbonklachloride, multifunctional haloalkanes in particular ⁇ , ⁇ -dichloroalkanes.
  • Other crosslinkers are in WO 97/25367 A1 , Pages 8
  • polymers containing ethyleneimine units are made EP 0 411 400 A1 .
  • a method for producing such compounds is described, for example, in DE 24 34 816 A1 wherein ⁇ , ⁇ -chlorohydrin ethers of oligo- or polyethylene oxides are used as crosslinkers application.
  • Reaction products of polyethylenimines with monobasic carboxylic acids to amidated polyethylenimines are known from the WO 94/12560 A1 known.
  • Michael addition products of polyethyleneimines to ethylenically unsaturated acids, salts, esters, amides or nitriles of monoethylenically unsaturated carboxylic acids are the subject of WO 94/14873 A1 , Phosphonomethylated polyethylenimines are described in detail in U.S. Pat WO 97/25367 A1 described.
  • Carboxylated polyethyleneimines are obtainable, for example, by means of a stretching synthesis by reacting polyethyleneimines with formaldehyde and ammonia / hydrogen cyanide and hydrolysing the reaction products.
  • Alkoxylated polyethyleneimines can be prepared by reacting Polyethyleiminen with alkylene oxides such as ethylene oxide and / or propylene oxide.
  • the water-soluble cationic polymer (b) used may be, in each case, the polymers containing (i) vinylamine units or polymers containing (ii) ethyleneimine units.
  • the polymers containing (i) vinylamine units or polymers containing (ii) ethyleneimine units may be, in each case, the polymers containing (i) vinylamine units or polymers containing (ii) ethyleneimine units.
  • the weight ratio of (i) polymers containing vinylamine units to (ii) polymers containing ethyleneimine units is, for example, 10: 1 to 1:10, preferably in the range of 5: 1 to 1: 5, and more preferably in the range of 2: 1 to 1: 2.
  • the at least one water-soluble cationic polymer (b) is particularly preferred in the process according to the invention for producing paper, for example in an amount of 0.01 to 2.0% by weight, preferably 0.03 to 1.0% by weight 0.1 to 0.5 wt .-%, each based on dry pulp, used.
  • amphoteric polymers (c) are water-soluble.
  • the solubility in water under normal conditions (20 ° C., 1013 mbar) and pH 7.0 is, for example, at least 5% by weight, preferably at least 10% by weight.
  • water-soluble amphoteric polymers (c) may also contain crosslinkers and / or regulators.
  • crosslinkers and regulators are also those already used in the water-soluble cationic polymers (b).
  • Examples of monomers whose polymers contain structural units (A) are esters of ⁇ , ⁇ -ethylenically unsaturated mono- and dicarboxylic acids with C 2 -C 30 -aminoalcohols, amides of ⁇ , ⁇ -ethylenically unsaturated monocarboxylic acids and their N-alkyl and N, N-dialkyl derivatives, nitrogen-containing heterocycles having ⁇ , ⁇ -ethylenically unsaturated double bonds and mixtures thereof.
  • Suitable monomers of this group are the esters of ⁇ , ⁇ -ethylenically unsaturated mono- and dicarboxylic acids with aminoalcohols, preferably C 2 -C 12 -aminoalcohols. These may be C 1 -C 8 monoalkylated or dialkylated on the amine nitrogen.
  • Suitable acid components of these esters are, for example, acrylic acid, methacrylic acid, fumaric acid, maleic acid, itaconic acid, crotonic acid, maleic anhydride, monobutyl maleate and mixtures thereof. Preference is given to using acrylic acid, methacrylic acid and mixtures thereof.
  • N-methylaminomethyl (meth) acrylate N-methylaminoethyl (meth) acrylate, N, N-dimethylaminomethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N , N-dimethylaminopropyl (meth) acrylate, N, N-diethylaminopropyl (meth) acrylate and N, N-dimethylaminocyclohexyl (meth) acrylate.
  • N-vinylimidazoles and alkylvinylimidazoles in particular methylvinylimidazoles such as, for example, 1-vinyl-2-methylimidazole, 3-vinylimidazole N-oxide, 2- and 4-vinylpyridine N-oxides and also betaine derivatives and quaternization products of these monomers and mixtures from that.
  • the respective quaternary compounds are also suitable.
  • the quaternary compounds of the monomers are obtained by reacting the monomers with known quaternizing agents, e.g. with methyl chloride, benzyl chloride, ethyl chloride, butyl bromide, dimethyl sulfate and diethyl sulfate or Alkylepoxiden.
  • Examples of monomers whose polymers contain structural units (B) are those which carry an acid function. These are selected from monoethylenically unsaturated sulfonic acids, monoethylenically unsaturated phosphonic acids and monoethylenically unsaturated carboxylic acids having 3 to 8 C atoms in the molecule and / or their alkali metal, alkaline earth metal or ammonium salts.
  • Examples of such monomers of this group are ethylenically unsaturated C 3 - to C 8 -carboxylic acids such as acrylic acid, methacrylic acid, dimethacrylic acid, ethacrylic acid, maleic acid, fumaric acid, itaconic acid, mesaconic acid, citraconic acid, methylenemalonic acid, allylacetic acid, vinylacetic acid and crotonic acid.
  • ethylenically unsaturated C 3 - to C 8 -carboxylic acids such as acrylic acid, methacrylic acid, dimethacrylic acid, ethacrylic acid, maleic acid, fumaric acid, itaconic acid, mesaconic acid, citraconic acid, methylenemalonic acid, allylacetic acid, vinylacetic acid and crotonic acid.
  • monomers containing sulfonic groups such as vinylsulfonic acid, acrylamido-2-methylpropanesulfonic acid and styrenes
  • the monomers of this group can be used alone or in admixture with each other, in partially or completely neutralized form in the copolymerization.
  • neutralization for example, alkali metal or alkaline earth metal bases, ammonia, amines and / or alkanolamines are used. Examples of this are caustic soda, Potassium hydroxide, soda, potash, sodium bicarbonate, magnesium oxide, calcium hydroxide, calcium oxide, triethanolamine, ethanolamine, morpholine, diethylenetriamine or tetraethylenepentamine.
  • Monomers whose polymers contain structural units (C) are monomers of the formula (I), esters of ⁇ , ⁇ -ethylenically unsaturated mono- and dicarboxylic acids with C 1 -C 30 -alkanols and C 2 -C 30 -alkanediols, (meth) acrylamides, nitriles of ⁇ , ⁇ -ethylenically unsaturated mono- and dicarboxylic acids, esters of vinyl alcohol and allyl alcohol with C 1 -C 30 -monocarboxylic acids, N-vinyllactams and mixtures thereof.
  • Monomers of the formula (I) are, for example, N-vinylformamide, N-vinyl-N-methylformamide, N-vinylacetamide, N-vinyl-N-methylacetamide, N-vinyl-N-ethylacetamide, N-vinylpropionamide and N-vinyl-N- methylpropionamide and N-vinylbutyramide.
  • These monomers may be used alone or in admixture in the copolymerization with the monomers of the other groups.
  • Preferably used monomer of this group is N-vinylformamide.
  • Suitable representatives of this monomer group are e.g. Methyl (meth) acrylate, methylethacrylate, ethyl (meth) acrylate, ethylethacrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, tert-butylethacrylate, n-octyl (meth) acrylate, 1,1,3,3-tetramethylbutyl (meth) acrylate, ethylhexyl (meth) acrylate and mixtures thereof.
  • Suitable monomers of this group are 2-hydroxyethyl (meth) acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate , 6-hydroxyhexyl (meth) acrylate and mixtures thereof.
  • Suitable monomers are acrylamide, methacrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, n-propyl (meth) acrylamide, N- (n-butyl) (meth) acrylamide, tert-butyl ( meth) acrylamide, n-octyl (meth) acrylamide, 1,1,3,3-tetramethylbutyl (meth) acrylamide, ethylhexyl (meth) acrylamide, and mixtures thereof.
  • nitriles of ⁇ , ⁇ -ethylenically unsaturated mono- and dicarboxylic acids such as acrylonitrile and methacrylonitrile are suitable.
  • Suitable monomers of this group are furthermore N-vinyllactams and derivatives thereof which may have, for example, one or more C 1 -C 6 -alkyl substituents (as defined above).
  • N-vinylpyrrolidone N-vinylpiperidone, N-vinylcaprolactam, N-vinyl-5-methyl-2-pyrrolidone, N-vinyl-5-ethyl-2-pyrrolidone, N-vinyl-6-methyl-2-piperidone, N-vinyl-6-ethyl-2-piperidone, N-vinyl-7-methyl-2-caprolactam, N-vinyl-7-ethyl-2-caprolactam and mixtures thereof.
  • the proportion of monomers whose polymers contain the structural units (C) in the water-soluble amphoteric polymer is at least 50% by weight, based on the total weight of the monomers used to prepare the water-soluble polymer (c).
  • the proportion of monomers whose polymers contain the structural units (C) is preferably at least 60% by weight, particularly preferably at least 75% by weight and especially preferably at least 85% by weight, but not more than 98% by weight. , in each case based on the total weight of the monomers, which are used for the preparation of the water-soluble Polymweren (c).
  • the molar ratio of the monomers whose polymers contain the structural units (A) to those whose polymers contain the structural units (B) is usually in the range of 5: 1 to 1: 5, preferably 2: 1 to 1: 2 and more preferably 1: 1.
  • amphoteric polymers (c) are known in the literature, as well as their preparation.
  • the amphoteric polymers can be prepared by radical polymerization of the aforementioned monomers in solution, as gel polymerization, precipitation polymerization, water-in-water polymerization, water-in-oil polymerization or by spray polymerization.
  • water-soluble amphoteric polymers such as in EP 0 659 780 A1 .
  • the at least one water-soluble amphoteric polymer (c) is particularly preferred in the process according to the invention for producing paper, for example in an amount of from 0.01 to 2.0% by weight, preferably from 0.03 to 1.0% by weight 0.1 to 0.5 wt .-%, each based on dry pulp, used.
  • the present invention also provides the papers produced by the process described above, as well as cardboard and paperboard.
  • suitable fibrous materials for the production of the pulps are all qualities customary for this purpose, eg wood pulp, bleached and unbleached pulp and pulps from all annual plants.
  • Wood pulp includes, for example, groundwood, thermomechanical pulp (TMP), chemothermomechanical pulp (CTMP), pressure groundwood, semi-pulp, high yield pulp, and refiner mechanical pulp (RMP).
  • pulp for example, sulphate, sulphite and soda pulps.
  • unbleached pulp also referred to as unbleached kraft pulp
  • Suitable annual plants for the production of pulps are, for example, rice, wheat, sugar cane and kenaf.
  • the inventive method is particularly suitable for the production of dry-proof papers from waste paper (including deinked waste paper), which is used either alone or in admixture with other fibers. It is also possible to start with fiber blends of primary and recycled coated broke, e.g. bleached pine sulfate in admixture with reclaimed coated broke.
  • the inventive method is for the production of paper, cardboard and cardboard from waste paper and in special cases from deinked waste paper of technical interest, because it significantly increases the strength properties of the recycled fibers. It is of particular importance for improving the strength properties of graphic papers and packaging papers.
  • the pH of the stock suspension is, for example, in the range of 4.5 to 8, usually 6 to 7.5.
  • an acid such as sulfuric acid or aluminum sulphate.
  • the order of addition of the components (a), (b) and (c) is arbitrary, wherein the components can be added to the fiber suspension individually or in each mixture.
  • the cationic components namely the (a) trivalent cations in the form of a salt and (b) water-soluble cationic polymers, are metered into the pulp.
  • the addition of the cationic components (a) and (b) may be carried out separately or in admixture with the thick material (fiber concentration> 15 g / l, for example in the range of 25 to 40 g / l up to 60 g / l) or preferably in the Thin material (fiber concentration ⁇ 15 g / l, for example in the range of 5 to 12 g / l) take place.
  • the point of addition is preferably in front of the screens, but it can also be between a shearing stage and a screen or afterwards.
  • the metering of the cationic components (a) and (b) to the paper stock can be carried out successively, simultaneously or as a mixture of (a) and (b) as described above.
  • the water-soluble amphoteric polymer (c) is usually added only after the addition of the cationic components (a) and (b) to the pulp, but can also be added to the pulp simultaneously and also in admixture with (a) and (b).
  • the addition of a mixture of the (a) trivalent cation in the form of a salt and the (c) water-soluble amphoteric polymer to the paper stock is first carried out. Subsequently, the (b) water-soluble cationic polymer is added.
  • the process chemicals commonly used in papermaking can be used in the usual amounts, e.g. Retention aids, dehydrating agents, other dry strength agents such as starch, pigments, fillers, optical brighteners, defoamers, biocides and paper dyes.
  • the process according to the invention gives dry-proof papers whose dry strength relative to papers produced by known processes has an increased dry strength.
  • the dewatering rate is improved compared to known methods.
  • Alum (aluminum sulfate technical powder [Al 2 (SO 4 ) 3 .14H 2 O])
  • Amphoteric polyacrylamide, solids content 19.2% by weight (Harmide® RB 217 from Harima)
  • Amphoteric polyacrylamide solids content 20% by weight (Polystron® PS-GE 200 R from Arakawa)
  • Amphoteric polyacrylamide solids content 20% by weight (Polystron® PS-GE 300 S from Arakawa)
  • Anionic polyacrylamide molecular weight about 600,000 daltons, solids content 16% by weight (Luredur® PR 8284 from BASF SE)
  • Polyallylamine molecular weight about 15 000 daltons, solids content 93% by weight (PAA-HCl-3S from Nittobo)
  • a paper made of 100% waste paper (mixture of the grades: 1.02, 1.04, 4.01) was pitched with drinking water at a consistency of 4% in a laboratory pulper speckok and ground in a laboratory refiner to a freeness of 40 ° SR. This substance was then diluted with drinking water to a consistency of 0.7%.
  • the trivalent cations and polymers shown in the Tables were added successively to the stock described above with stirring.
  • the polymer concentration of the aqueous solutions of the cationic and anionic polymers was 1% each, and that of the trivalent cation in aqueous solution was 10% each.
  • 0.27% of a commercially available defoamer (Afranil® SLO from BASF SE) was used in all examples and comparative examples.
  • the amounts of the trivalent cations and polymers used in each case are given in percent by weight, based on the solids content of the paper stock.
  • Examples 1 to 10 according to the invention show in particular the surprisingly good effect of the system consisting of three components on the dry strength and at the same time on the dewatering.
  • Table 1 example Trivalent cation Dosage [%] Cationic polymer Dosage [%] Amphoteric polymer Dosage [%] Comparative polymer Dosage [%] Burst pressure increase [%] SCT increase [%] CMT increase [%] Wet rice length increase Comparison 0 - - - Polymer V1 0.04 - - - - Comparison 1 - Polymer K1 0.15 - Polymer V2 0.15 18 16 18 145 Comparison 2 Cation 1 0.7 Polymer K1 0.15 - Polymer V2 0.15 15 13 16 155 Comparison 3 Cation 1 0.7 - Polymer A1 0.3 - 24 22 13 34 example 1 Cation 1 0.7 Polymer K1 0.15 Polymer A1 0.15 - 24 26 23 92

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  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)

Claims (22)

  1. Procédé de fabrication de papier, de bristol et de carton ayant une résistance à sec élevée par ajout
    (a) d'au moins un cation trivalent sous la forme d'un sel,
    (b) d'au moins un polymère cationique soluble dans l'eau et
    (c) d'au moins un polymère amphotère soluble dans l'eau à la pâte à papier, déshydratation de la pâte à papier avec formation de feuilles, puis séchage des produits de papier, caractérisé en ce que le polymère cationique soluble dans l'eau (b) est choisi dans le groupe constitué par (i) les polymères contenant des unités vinylamine et (ii) les polymères contenant des unités éthylène-imine.
  2. Procédé selon la revendication 1, caractérisé en ce que le (a) au moins un cation trivalent est choisi parmi Al3+, Zr3+ et Fe3+.
  3. Procédé selon la revendication 2, caractérisé en ce que le (a) au moins un cation trivalent sous la forme d'un sel est le sulfate d'aluminium, le polychlorure d'aluminium ou le lactate d'aluminium.
  4. Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce que le (a) au moins un cation trivalent sous la forme d'un sel est ajouté à la pâte à papier en quantités comprises entre 3 et 100 moles par t de papier sec.
  5. Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce qu'en tant que polymères contenant des unités vinylamine (i), des produits de réaction sont utilisés, qui peuvent être obtenus
    - par polymérisation d'au moins un monomère de formule
    Figure imgb0014
     dans laquelle R1, R2 = H ou alkyle en C1 à C6,
    puis clivage partiel ou total des groupes -CO-R1 des unités des monomères (I) polymérisées dans le polymère avec formation de groupes amino,
    et/ou
    - par décomposition de Hofmann de polymères qui comprennent des unités acrylamide et/ou méthacrylamide.
  6. Procédé selon la revendication 5, caractérisé en ce qu'en tant que polymères contenant des unités vinylamine (i), des produits de réaction sont utilisés, qui peuvent être obtenus par polymérisation de
    (1.) au moins un monomère de formule
    Figure imgb0015
     dans laquelle R1, R2 = H ou alkyle en C1 à C6,
    (2.) éventuellement au moins un autre monomère monoéthyléniquement insaturé et
    (3.) éventuellement au moins un monomère à effet réticulant contenant au moins deux doubles liaisons par molécule,
    puis clivage partiel ou total des groupes -CO-R1 des unités des monomères (I) polymérisées dans le polymère avec formation de groupes amino.
  7. Procédé selon la revendication 6, caractérisé en ce qu'en tant que polymères contenant des unités vinylamine (i), des produits de réaction sont utilisés, qui peuvent être obtenus par polymérisation de N-vinylformamide, puis clivage de groupes formyle des unités vinylformamide polymérisées dans le polymère avec formation de groupes amino.
  8. Procédé selon la revendication 6, caractérisé en ce qu'en tant que polymères contenant des unités vinylamine (i), des produits de réaction sont utilisés, qui peuvent être obtenus par copolymérisation de
    (1.) N-vinylformamide et
    (2.) acrylonitrile,
    puis clivage de groupes formyle des unités vinylformamide polymérisées dans le copolymère avec formation de groupes amino.
  9. Procédé selon la revendication 5, caractérisé en ce qu'en tant que polymères contenant des unités vinylamine (i), des produits de réaction sont utilisés, qui peuvent être obtenus par polymérisation de
    (1.) au moins un monomère de formule
    Figure imgb0016
     dans laquelle R1, R2 = H ou alkyle en C1 à C6,
    (2.1) au moins à chaque fois un monomère portant une fonction acide choisi parmi les acides sulfoniques monoéthyléniquement insaturés, les acides phosphoniques monoéthyléniquement insaturés et les acides carboxyliques monoéthyléniquement insaturés contenant 3 à 8 atomes C par molécule et/ou leurs sels de métaux alcalins, de métaux alcalino-terreux ou d'ammonium,
    (2.2) éventuellement au moins un autre monomère neutre et/ou cationique, et
    (3.) éventuellement au moins un monomère à effet réticulant contenant au moins deux doubles liaisons par molécule,
    puis clivage partiel ou total des groupes -CO-R1 des unités des monomères (I) polymérisées dans le polymère avec formation de groupes amino, la teneur en groupes amino dans le copolymère étant d'au moins 5 % en moles de plus que la teneur en groupes acides polymérisés des monomères (2.1).
  10. Procédé selon la revendication 9, caractérisé en ce qu'en tant que polymères contenant des unités vinylamine (i), des produits de réaction sont utilisés, qui peuvent être obtenus par polymérisation
    (1.) de N-vinylformamide,
    (2.1) d'acide acrylique, d'acide méthacrylique et/ou leurs sels de métaux alcalins, de métaux alcalino-terreux ou d'ammonium, et
    (2.2) éventuellement d'acrylonitrile et/ou de méthacrylonitrile,
    puis clivage partiel ou total de groupes formyle du N-vinylformamide polymérisé dans le polymère avec formation de groupes amino, la teneur en groupes amino dans le copolymère étant d'au moins 5 % en moles de plus que la teneur en groupes acides polymérisés des monomères (2.1).
  11. Procédé selon la revendication 5, caractérisé en ce qu'en tant que polymères contenant des unités vinylamine (i), des produits de réaction sont utilisés, qui peuvent être obtenus par décomposition de Hofmann d'homo- ou de copolymères d'acrylamide ou de méthacrylamide dans un milieu aqueux en présence de soude caustique et d'hypochlorite de sodium, puis décarboxylation des groupes carbamate des produits de réaction en présence d'un acide.
  12. Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce qu'en tant que polymère contenant des unités éthylène-imine (ii), au moins un polymère cationique soluble dans l'eau du groupe constitué par :
    - les homopolymères d'éthylène-imine,
    - les polyéthylène-imines mises en réaction avec des agents de réticulation au moins bifonctionnels,
    - les polyamidoamines greffées avec de l'éthylène-imine, qui sont mises en réaction avec des agents de réticulation au moins bifonctionnels,
    - les produits de réaction de polyéthylène-imines avec des acides carboxyliques monobasiques pour former des polyéthylène-imines amidées,
    - les produits d'addition de Michael de polyéthylène-imines sur des acides éthyléniquement insaturés, des sels, des esters, des amides ou des nitriles d'acides carboxyliques monoéthyléniquement insaturés,
    - les polyéthylène-imines phosphonométhylées,
    - les polyéthylène-imines carboxylées, et
    - les polyéthylène-imines alcoxylées,
    est utilisé.
  13. Procédé selon la revendication 12, caractérisé en ce qu'en tant que polymère contenant des unités éthylène-imine (ii), des homopolymères d'éthylène-imine et/ou des polyamidoamines greffées avec de l'éthylène-imine, puis mises en réaction avec des agents de réticulation au moins bifonctionnels sont utilisés.
  14. Procédé selon l'une quelconque des revendications 5 à 13, caractérisé en ce que le (b) au moins un polymère cationique soluble dans l'eau est utilisé en une quantité de 0,01 à 2,0 % en poids, par rapport à la pâte à papier sèche.
  15. Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce qu'en tant que (c), des polymères amphotères solubles dans l'eau qui sont formés par au moins trois unités structurales :
    (A) les unités structurales qui portent un groupe cationique permanent ou protonable dans un milieu aqueux,
    (B) les unités structurales qui portent un groupe déprotonable dans un milieu aqueux, et
    (C) les unités structurales non ioniques,
    sont utilisés.
  16. Procédé selon la revendication 15, caractérisé en ce que la proportion de monomères dont les polymères contiennent les unités structurales (C) dans le polymère amphotère soluble dans l'eau est d'au moins 50 % en poids, par rapport au poids total des monomères qui sont utilisés pour la fabrication du polymère amphotère soluble dans l'eau (c).
  17. Procédé selon la revendication 15, caractérisé en ce que des monomères de formule (II) et leurs sels sont utilisés en tant que monomères dont les polymères contiennent des unités structurales (B)
    Figure imgb0017
     dans laquelle
    R1 = H ou un groupe alkyle en C1-C4, et
    n est un nombre entier dans la plage allant de 1 à 8.
  18. Procédé selon la revendication 15 ou 16, caractérisé en ce que le (c) au moins un polymère amphotère soluble dans l'eau est utilisé en une quantité de 0,01 à 2,0 % en poids, par rapport à la pâte à papier sèche.
  19. Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce que le (a) cation trivalent sous la forme d'un sel est tout d'abord ajouté à la pâte à papier, puis le (b) polymère cationique soluble dans l'eau et enfin le (c) polymère amphotère soluble dans l'eau.
  20. Procédé selon l'une quelconque des revendications 1 à 18, caractérisé en ce que le (a) cation trivalent sous la forme d'un sel est tout d'abord ajouté à la pâte à papier, puis le (c) polymère amphotère soluble dans l'eau et enfin le (b) polymère cationique soluble dans l'eau.
  21. Procédé selon l'une quelconque des revendications 1 à 18, caractérisé en ce que le mélange du (a) cation trivalent sous la forme d'un sel et du (c) polymère amphotère soluble dans l'eau est tout d'abord ajouté à la pâte à papier, puis le (b) polymère cationique soluble dans l'eau.
  22. Papiers, qui peuvent être obtenus par un procédé selon les revendications 1 à 21.
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CN104532674A (zh) 2015-04-22
US8926797B2 (en) 2015-01-06
CA2763508A1 (fr) 2010-12-23
JP2012530196A (ja) 2012-11-29
EP2443284B2 (fr) 2020-11-18
JP5832426B2 (ja) 2015-12-16
ES2663702T3 (es) 2018-04-16
PL2443284T5 (pl) 2021-04-19
PL2443284T3 (pl) 2018-07-31
WO2010145956A1 (fr) 2010-12-23
CA2763508C (fr) 2018-07-17
EP2443284A1 (fr) 2012-04-25
CN102459760A (zh) 2012-05-16
ES2663702T5 (es) 2021-12-16

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