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 of (i) polymers containing vinylamine units and (ii) ethyleneimine units containing polymers and (c) at least one water-soluble amphoteric polymer to form a paper stock, dewatering the paper stock with sheet formation and drying the paper product obtained, wherein the (i) vinylamine-containing polymer and (c) at least one water-soluble amphoteric polymer as in claims 1 and 2 are defined.
• JP 54-030913 a process for producing paper with high dry strength is known in which an aluminum sulfate solution is first added to the paper stock. A water-soluble amphoteric polymer is then metered in. The paper stock is then dewatered on the paper machine to form sheets, and the paper products are dried.
• suitable amphoteric polymers are copolymers of acrylamide, acrylic acid and dimethylaminoethyl (meth) acrylate.
• a process for producing paper with high dry strength in which first a water-soluble cationic polymer is added to the paper stock and then a water-soluble anionic polymer is added.
• Suitable anionic polymers are, for example, homopolymers or copolymers of ethylenically unsaturated C 3 -C 5 carboxylic acids.
• the copolymers contain at least 35% by weight of an ethylenically unsaturated C 3 -C 5 carboxylic acid (for example acrylic acid) in copolymerized form.
• the cationic polymers described in the examples are polyethyleneimine, polyvinylamine, polydiallyldimethylammonium chloride and condensation products of adipic acid and diethylenetriamine reacted with epichlorohydrin.
• 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 cardboard, in which alum, a polyallylamine and an anionic or amphoteric polymer are added to a fiber suspension.
• the combination results in papers with a high strength.
• JP 05-272092 describes a process for the production of paper with high dry strength, in which an aluminum sulfate solution is first added to the paper stock, and then a water-soluble amphoteric polymer with high molecular weight is metered in, then the paper stock is dewatered on the paper machine with sheet formation and the paper products are dried.
• amphoteric polymers which are mentioned are copolymers of acrylamide, acrylic acid, dimethylaminoethyl (meth) acrylate, (meth) acrylamide and sodium (meth) allyl sulfonate. These amphoteric polymers are characterized by very high molecular weights and low solution viscosities.
• JP 08-269891 A variant of the in JP 05-272092 procedure is described in JP 08-269891 disclosed.
• an aluminum sulfate solution is also first added to the paper stock, and then a water-soluble amphoteric polymer with a high molecular weight is added, then the paper stock is dewatered on the paper machine to form sheets and the paper products are dried.
• the amphoteric polymers used are, for example, copolymers of acrylamide, acrylic acid, dimethylaminoethyl methacrylate, (meth) acrylamide, sodium (meth) allyl sulfonate and a crosslinker such as methylenebisacrylamide or triallylamine. 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 the preparation of polymers with 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), the ratio (b) / (a)) 0 , 00004, and their use as a solidifying agent.
• WO 98/06898 A1 describes a process for paper manufacture in which a cationic starch or a cationic wet strength agent and a water-soluble amphoteric polymer are added to the paper stock.
• This amphoteric polymer is made up of the nonionic monomers acrylamide and methacrylamide, an anionic monomer, a cationic monomer and a crosslinker, the amount of anionic and cationic monomer not being more than 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 cardboard, whereby to improve the strength properties of a paper product to the paper stock 0.05 to 0.5% by weight, based on dry paper stock, of a polyvinylamine obtained by hydrolysis of polyvinylformamide with a degree of hydrolysis of 25 to 100 % is accessible, is added in combination with an anionic polyacrylamide, the paper stock is then dewatered with sheet formation and the paper dries.
• the EP 0 919 578 A1 relates to amphoteric polymers (type B), which are produced by means of a two-stage polymerization.
• a polymer (type A) is produced by the copolymerization of methallylsulfonic acid with other vinyl monomers, then, in the presence of the type A polymer, a further polymerization of vinyl monomers to form the type B polymer takes place, the type A polymers having a molecular weight of 1,000 to 5,000,000 and the type B polymers have a molecular weight of 100,000 to 10,000,000.
• the JP 2001-279595 relates to a process for the production of paper with high strength, wherein a mixture of a cationic, anionic or amphoteric polyacrylamide with a water-soluble aluminum compound is added to the fibers. A further polyacrylamide is then metered in. This not only increases strength, but also improves drainage at the same time.
• a paper product with improved strength properties which can be obtained by applying a polyvinylamine and a polymeric anionic compound which can form a polyelectrolyte complex with polyvinylamine, or a polymeric compound with aldehyde functions such as polysaccharides containing aldehyde groups, to the surface of a paper product. Not only is an improvement in the dry and wet strength of the paper obtained, but a sizing effect of the treatment agents is also observed.
• JP 2005-023434 describes a process for the production of paper with high strength, which is obtained by metering two polymers.
• the first polymer is a branched amphoteric polyacrylamide.
• As the second polymer a copolymer of a cationic vinyl monomer can be considered as the main monomer.
• WO 2006/120235 A1 describes a process for producing papers with a filler content of at least 15% by weight, in which the filler and fibers are treated together with cationic and anionic polymers. The treatment takes place alternately with cationic and anionic polymers and comprises at least three steps.
• EP 1 849 803 A1 is also known a paper additive for strengthening that 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 present invention was therefore based on the object of providing a further process for the production of paper, paperboard and cardboard with high dry strength, in which the dry strength properties of the paper products are further improved compared to those of known products, and in which at the same time faster drainage of the Paper stock is made possible.
• the stated components of the consolidation system can be added to the paper stock in any order or as a mixture of two or more components.
• trivalent metal or semimetal cations are suitable as trivalent cations in the process according to the invention.
• Preferred metal cations are Al 3+ , Zr 3+ and Fe 3+ .
• Al 3+ is very particularly preferred.
• the metal and semi-metal cations are used in the form of their salts.
• Al 3+ this can be used, for example, in the form of aluminum sulfate, polyaluminium chloride or aluminum lactate.
• any mixtures of the trivalent metal cations mentioned can also be used, but only one trivalent metal cation is preferably used in the process according to the invention.
• different salts of this metal cation can be used in any mixtures.
• a trivalent metal cation is used in one of the salt forms described.
• the trivalent cations are usually added to the paper stock in amounts between 3 and 100 mol per ton of dry paper, preferably in the range from 10 to 30 mol per ton of dry paper.
• the water-soluble cationic polymer (b) is selected from the group of (i) polymers containing 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 from 4 to 10 meq / g.
• the water-soluble cationic polymers (b) usually have average molecular weights in the range from 10,000 to 10,000,000 Daltons, preferably in the range from 20,000 to 5,000,000 Daltons, particularly preferably in the range from 40,000 to 3,000,000 Daltons.
• Polymers (i) containing vinylamine units are known, cf. those mentioned in relation to the prior art DE 35 06 832 A1 and DE 10 2004 056 551 A1 .
• polymers containing (i) vinylamine units preference is given to using the reaction products which are obtainable by polymerizing N-vinylformamide and subsequent cleavage of formyl groups from the vinylformamide units polymerized into the polymer with the formation of amino groups.
• Examples of monomers of the formula (I) are N-vinylformamide, N-vinyl-N-methylformamide, N-vinyl acetamide, N-vinyl-N-methylacetamide, N-vinyl-N-ethylacetamide, N-vinyl propionamide and N-vinyl-N -methylpropionamide and N-vinylbutyramide.
• the monomers of group (a) can be used alone or as a mixture in the copolymerization with the monomers of the other groups.
• Preferred monomer of this group is N-vinylformamide.
• polymers can 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 polymerized vinylcarboxamide units is carried out to such an extent that the molar excess of amine units over 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 amino alcohols, 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-vinyl lactams, nitrogen-containing heterocycles with ⁇ , ⁇ -ethylenically unsaturated double bonds, vinyl aromatics, 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 ethacrylate, ethyl (meth) acrylate, ethyl ethacrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, tert.
• Suitable additional monomers of group (2.) are also the esters of ⁇ , ⁇ -ethylenically unsaturated mono- and dicarboxylic acids with amino alcohols, preferably C 2 -C 12 -amino alcohols. These can be C 1 -C 8 monoalkylated or dialkylated on the amine nitrogen.
• Acrylic acid, methacrylic acid, fumaric acid, maleic acid, itaconic acid, crotonic acid, maleic anhydride, monobutyl maleate and mixtures thereof are suitable as acid components of these esters.
• Acrylic acid, methacrylic acid and mixtures thereof are preferably used.
• 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.
• Also suitable as monomers of group (2.) are 2-hydroxyethyl (meth) acrylate, 2-hydroxyethyl ethacrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, and mixtures thereof.
• Suitable additional monomers of group (2.) are also acrylic acid amide, methacrylic acid amide, 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 to products which have amidine units during or after the hydrolysis, cf. e.g. EP 0 528 409 A1 or DE 43 28 975 A1 .
• amidine units are formed in a secondary reaction in that vinylamine units react with an adjacent vinylformamide unit or - if a nitrile group is present as an adjacent group in the polymer - with it.
• the specification of vinylamine units in the amphoteric copolymers or in unmodified homopolymers or copolymers always means the sum of vinylamine and amidine units.
• Suitable monomers of group (2.) are also N-vinyl lactams and their derivatives, which can 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.
• N-vinylimidazoles and alkylvinylimidazoles are suitable as monomers of group (2.), in particular methylvinylimidazoles such as, for example, 1-vinyl-2-methylimidazole, 3-vinylimidazole-N-oxide, 2- and 4-vinylpyridine-N-oxides, and 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 betaine derivatives and quaternization products these monomers as well as
• the aforementioned monomers can be used individually or in the form of any mixtures. They are typically used in amounts of 1 to 90 mol%, preferably 10 to 80 mol% and particularly preferably 10 to 60 mol%.
• other monoethylenically unsaturated monomers of group (2.) also include anionic monomers, which are referred to above as monomers (2.1). If appropriate, they can 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 amphoteric copolymer formed has an overall cationic charge.
• anionic monomers of group (2.1) 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.
• Suitable monomers of this group are also monomers containing sulfonic groups, such as vinylsulfonic acid, acrylamido-2-methylpropanesulfonic acid and styrene sulfonic acid, and monomers containing phosphonic groups, such as vinylphosphonic acid.
• the monomers of this group can be used alone or in a mixture with one another, in partially or completely neutralized form, in the copolymerization.
• alkali metal or alkaline earth metal bases, ammonia, amines and / or alkanolamines are used for neutralization.
• Examples are caustic soda, potassium hydroxide, soda, potash, sodium hydrogen carbonate, magnesium oxide, calcium hydroxide, calcium oxide, triethanolamine, ethanolamine, morpholine, diethylenetriamine or tetraethylene pentamine.
• a further modification of the copolymers is possible by using 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, sobitol or glucose. These are so-called crosslinkers. If at least one monomer from the above group is used in the polymerization, the amounts used are up to 2 mol%, e.g. 0.001 to 1 mole percent.
• controllers known from the literature can be used, e.g. Sulfur compounds such as mercaptoethanol, 2-ethylhexyl thioglycolate, thioglycolic acid and dodecyl mercaptan 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 can be obtained by free-radical polymerizing, for example, N-vinylformamide in an aqueous medium in the presence of at least one of the graft bases mentioned, optionally together with other copolymerizable 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 vinylcarboxamide copolymers is in the EP 0 438 744 A1 , Page 8, line 20 to page 10, line 3, described in detail. The statements made there apply accordingly to the preparation of the purely cationic and / or amphoteric polymers containing vinylamine units to be used according to the invention and having an overall cationic charge.
• the above-described homopolymers and copolymers (i) containing vinylamine units can be prepared by solution, precipitation, suspension or emulsion polymerization.
• Solution polymerization in aqueous media is preferred.
• Suitable aqueous media are water and mixtures of water and at least one water-miscible solvent, for example an alcohol such as methanol, ethanol, n-propanol or isopropanol.
• the polymers (ii) containing ethyleneimine units include all polymers obtainable by polymerizing ethyleneimine in the presence of acids, Lewis acids or haloalkanes, such as homopolymers of ethyleneimine or graft polymers of ethyleneimine, cf. U.S. 2,182,306 or U.S. 3,203,910 . These polymers can optionally be subsequently subjected to crosslinking.
• Suitable crosslinkers are, for example, all multifunctional compounds which contain groups reactive toward primary amino groups, for example multifunctional epoxides such as bisglycidyl ethers of oligo- or polyethylene oxides or other multifunctional alcohols such as glycerol or sugars, multifunctional carboxylic esters, multifunctional isocyanates, multifunctional acrylic or methacrylic esters - or methacrylic acid amides, epichlorohydrin, multifunctional acid halides, multifunctional nitriles, ⁇ , ⁇ -chlorohydrin ethers of oligo- or polyethylene oxides or of other multifunctional alcohols such as glycerol or sugars, divinyl sulfone, maleic anhydride or ⁇ -halo-acid chlorides, ⁇ -halogenoalkanes, in particular, multifunctional haloalkanes, ⁇ -dichlorocarboxylic acid chlorides, multifunctional haloalkanes.
• Further crosslinkers are
• Polymers containing ethyleneimine units are, for example, from EP 0 411 400 A1 , DE 24 34 816 A1 and U.S. 4,066,494 known.
• a method for producing such compounds is for example in DE 24 34 816 A1 described, where ⁇ , ⁇ -chlorohydrin ethers of oligo- or polyethylene oxides as crosslinkers application Find.
• Reaction products of polyethyleneimines with monocarboxylic acids to form amidated polyethyleneimines are from the WO 94/12560 A1 known.
• Michael addition products of polyethyleneimines with ethylenically unsaturated acids, salts, esters, amides or nitriles of monoethylenically unsaturated carboxylic acids are the subject of the WO 94/14873 A1 .
• Phosphonomethylated polyethyleneimines are extensively described in WO 97/25367 A1 described.
• Carboxylated polyethyleneimines can be obtained, for example, with the aid of a stretchers synthesis by reacting polyethyleneimines with formaldehyde and ammonia / hydrogen cyanide and hydrolyzing the reaction products.
• Alkoxylated polyethyleneimines can be prepared by reacting polyethyleneimines with alkylene oxides such as ethylene oxide and / or propylene oxide.
• the water-soluble cationic polymer (b) used can be the (i) polymers containing vinylamine units or (ii) polymers containing ethyleneimine units in each case alone. It is of course also possible to use any mixture of (i) polymer containing vinylamine units and (ii) polymer containing ethyleneimine units. In such a mixture 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 from 5: 1 to 1: 5, and particularly preferably in the range from 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% by weight, based in each case on dry paper stock, are 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) can also contain crosslinkers and / or regulators.
• crosslinkers and regulators are also those which are 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 -amino alcohols, amides of ⁇ , ⁇ -ethylenically unsaturated monocarboxylic acids and their N-alkyl and N, N-dialkyl derivatives, nitrogen-containing heterocycles with ⁇ , ⁇ -ethylenically unsaturated double bonds and mixtures thereof.
• Suitable monomers of this group are the esters of ⁇ , ⁇ -ethylenically unsaturated mono- and dicarboxylic acids with amino alcohols, preferably C 2 -C 12 -amino alcohols. These can be C 1 -C 8 monoalkylated or dialkylated on the amine nitrogen.
• Acrylic acid, methacrylic acid, fumaric acid, maleic acid, itaconic acid, crotonic acid, maleic anhydride, monobutyl maleate and mixtures thereof are suitable as acid components of these esters.
• Acrylic acid, methacrylic acid and mixtures thereof are preferably used.
• 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 are also suitable as monomers, in particular methylvinylimidazoles such as 1-vinyl-2-methylimidazole, 3-vinylimidazole-N-oxide, 2- and 4-vinylpyridine-N-oxides and betaine derivatives and quaternization products of these monomers and mixtures from that.
• the particular quaternary compounds of the aforementioned monomers are also suitable.
• the quaternary compounds of the monomers are obtained by reacting the monomers with known quaternizing agents, for example with methyl chloride, benzyl chloride, ethyl chloride, butyl bromide, dimethyl sulfate and diethyl sulfate or alkyl epoxides.
• the monomers of this group can be used alone or in a mixture with one another, in partially or completely neutralized form, in the copolymerization.
• Alkali metal or alkaline earth metal bases, ammonia, amines and / or alkanolamines, for example, are used for neutralization. Examples are caustic soda, potassium hydroxide, soda, potash, sodium hydrogen carbonate, magnesium oxide, calcium hydroxide, calcium oxide, triethanolamine, ethanolamine, morpholine, diethylenetriamine or tetraethylene pentamine.
• 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-vinyl lactams and mixtures thereof.
• Monomers of the formula (I) are, for example, N-vinylformamide, N-vinyl-N-methylformamide, N-vinyl acetamide, N-vinyl-N-methylacetamide, N-vinyl-N-ethylacetamide, N-vinyl propionamide and N-vinyl-N- methylpropionamide and N-vinylbutyramide.
• These monomers can be used alone or in a mixture in the copolymerization with the monomers of the other groups.
• Preferred monomer of this group is N-vinylformamide.
• Suitable representatives of this monomer group are e.g. Methyl (meth) acrylate, methyl ethacrylate, 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.
• Also suitable as monomers of this group are 2-hydroxyethyl (meth) acrylate, 2-hydroxyethyl ethacrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate , 6-hydroxyhexyl (meth) acrylate and mixtures thereof.
• Suitable additional monomers are also acrylic acid amide, methacrylic acid amide, 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 also N-vinyllactams and their derivatives, which can 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.
• the proportion of monomers whose polymers contain the structural units (C) is usually at least 50% by weight in the water-soluble amphoteric polymer, 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 particularly 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 to produce the water-soluble polymer (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 from 5: 1 to 1: 5, preferably 2: 1 to 1: 2 and is particularly preferably 1: 1.
• amphoteric polymers (c) are known in the literature, as is 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.
• JP 54-030913 The production is carried out in JP 54-030913 , the disclosure of which is expressly referred to at this point.
• the water-soluble amphoteric polymers (c) used are preferably those as in EP 0 659 780 A1 , EP 0 919 578 A1 , EP 1 849 803 A1 , JP 08-269891 , JP 2005-023434 and JP 2001-1279595 disclosed.
• 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 0.01 to 2.0% by weight, preferably 0.03 to 1.0% by weight 0.1 to 0.5% by weight, based in each case on dry paper stock, are used.
• the present invention also relates to the papers produced by the process described above, as well as cardboard and cardboard.
• Wood pulp includes, for example, ground wood, thermomechanical pulp (TMP), chemothermomechanical pulp (CTMP), pressure pulp, semi-pulp, high-yield pulp, and refiner mechanical pulp (RMP).
• TMP thermomechanical pulp
• CMP chemothermomechanical pulp
• RMP refiner mechanical pulp
• sulfate, sulfite and soda cellulose can be used as the pulp.
• unbleached pulp also known as unbleached kraft pulp
• Suitable annual plants for the production of paper stocks are, for example, rice, wheat, sugar cane and kenaf.
• the process according to the invention is particularly suitable for the production of dry-resistant papers from waste paper (including deinked waste paper) which is used either alone or in a mixture with other fibrous materials.
• waste paper including deinked waste paper
• the process according to the invention is of technical interest for the production of paper, paperboard and cardboard from waste paper and in special cases also from deinked waste paper, 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 pulp suspension is, for example, in the range from 4.5 to 8, mostly from 6 to 7.5.
• an acid such as sulfuric acid or aluminum sulfate can be used to adjust the pH.
• the order in which components (a), (b) and (c) are added is arbitrary, and the components can be added to the fiber suspension individually or in any mixture.
• the cationic components namely the (a) trivalent cations in the form of a salt and (b) water-soluble cationic polymers, are first metered into the paper stock.
• the cationic components (a) and (b) can be added separately or as a mixture to the thick stock (fiber concentration> 15 g / l, for example in the range from 25 to 40 g / l to 60 g / l) or preferably in the Thin material (fiber concentration ⁇ 15 g / l, e.g.
• the addition point is preferably in front of the sieves, but it can also be between a shear stage and a screen or after it.
• the addition of the cationic components (a) and (b) to the paper stock can, as described above, take place one after the other, simultaneously or also as a mixture of (a) and (b). If, in the case of water-soluble component (b), a mixture of (i) polymers containing vinylamine units and (ii) polymers containing ethyleneimine units is used, it is also possible to meter them in succession, simultaneously or as a mixture of (i) and (ii).
• the water-soluble amphoteric polymer (c) is usually only added to the paper stock after the addition of the cationic components (a) and (b), but can also be added to the paper stock at the same time and also in a mixture with (a) and (b).
• water-soluble amphoteric polymer (c) first and then the cationic components (a) and (b) or first to add one of the cationic components (a) or (b) to the paper stock, then the water-soluble amphoteric polymer (c) and then add the other cationic component (a) or (b).
• the (a) trivalent cation is preferably added first in the form of a salt, then the (b) water-soluble cationic polymer and then the (c) water-soluble amphoteric polymer.
• the (a) trivalent cation is added first in the form of a salt, then the (c) water-soluble amphoteric polymer and finally the (b) water-soluble cationic polymer.
• a mixture of (a) is added first trivalent cation in the form of a salt and the (c) water-soluble amphoteric polymer to the paper stock. Then the (b) water-soluble cationic polymer is metered in.
• the process chemicals usually used in papermaking can be used in the usual amounts, e.g. Retention aids, drainage aids, other dry strength agents such as starch, pigments, fillers, optical brighteners, defoamers, biocides and paper dyes.
• the process according to the invention gives papers with a dry-strength finish whose dry strength has an increased dry strength compared with papers produced by known processes.
• the drainage rate is improved in the method according to the invention compared to known methods.
• the K value of the polymers was determined according to Fikentscher, CelluloseChemie, Volume 13, 58-64 and 71-74 (1932 ) at a temperature of 25 ° C in 5 wt .-% aqueous saline solutions at a pH of 7 and a polymer concentration of 0.5%.
• K k * 1000.
• Alum (technical aluminum sulfate 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 approx. 600,000 Dalton, solids content 16% by weight (Luredur® PR 8284 from BASF SE)
• Polyallylamine molecular weight about 15,000 Dalton, solids content 93% by weight (PAA-HCI-3S from Nittobo)
• a paper made from 100% recovered paper (mixture of the types: 1.02, 1.04, 4.01) was whipped free of specks with drinking water at a consistency of 4% in a laboratory pulper and ground to a freeness of 40 ° SR in a laboratory refiner. This substance was then diluted with drinking water to a consistency of 0.7%.
• the trivalent cations and polymers indicated in the tables were added successively to the paper 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 of the examples and comparative examples.
• the table shows the amounts of the trivalent cations and polymers used in each case in percent by weight, based on the solids content of the paper stock. After the last addition of a water-soluble polymer to the paper stock, enough stock was removed (approx.

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