EP2723943B1 - Procédé de fabrication de papier, de papier-carton et de carton compact - Google Patents

Procédé de fabrication de papier, de papier-carton et de carton compact Download PDF

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Publication number
EP2723943B1
EP2723943B1 EP12728465.1A EP12728465A EP2723943B1 EP 2723943 B1 EP2723943 B1 EP 2723943B1 EP 12728465 A EP12728465 A EP 12728465A EP 2723943 B1 EP2723943 B1 EP 2723943B1
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Prior art keywords
mol
paper
polymerization
moles
monomers
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German (de)
English (en)
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EP2723943A1 (fr
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Anton Esser
Hans-Joachim HÄHNLE
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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
    • 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
    • D21H17/42—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups anionic
    • D21H17/43—Carboxyl groups or derivatives thereof
    • 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
    • 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
    • D21H17/375—Poly(meth)acrylamide
    • 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
    • D21H17/38—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing crosslinkable groups
    • D21H17/40—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing crosslinkable groups unsaturated
    • 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
    • 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
    • D21H17/42—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups anionic
    • 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
    • D21H17/63—Inorganic compounds
    • D21H17/67—Water-insoluble compounds, e.g. fillers, pigments
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/06—Paper forming aids
    • 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
    • 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
    • D21H21/20—Wet strength 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
    • D21H23/00—Processes or apparatus for adding material to the pulp or to the paper
    • D21H23/02—Processes or apparatus for adding material to the pulp or to the paper characterised by the manner in which substances are added
    • D21H23/22—Addition to the formed paper
    • D21H23/24—Addition to the formed paper during paper manufacture
    • D21H23/26—Addition to the formed paper during paper manufacture by selecting point of addition or moisture content of the paper
    • D21H23/28—Addition before the dryer section, e.g. at the wet end or press section

Definitions

  • the invention relates to a process for the production of paper, paperboard and cardboard comprising dewatering a filler-containing paper stock containing at least one water-soluble amphoteric copolymer, with formation of sheets in the wire section and subsequent pressing of the paper in the press section.
  • a limiting factor on the way to further increasing the speed of paper machines is the initial wet texture strength. It limits the maximum applicable force that can be exerted on a sheet just formed in the paper machine that has passed through the wire and press sections of the machine and is being transferred to the dryer section. In this case, the sheet must be removed from the press rollers. In order to be able to reliably ensure tear-free operation of a paper machine, the applied peel force at this point must be significantly smaller than the initial wet texture strength of the wet paper. An increase in the initial wet structure strength allows the use of higher take-off forces and thus a faster operation of the paper machine, cf. EP-B-0 780 513 ,
  • Initial wet web strength refers to the strength of a wet paper that has never been dried. This is the strength of a wet paper, as is the case in papermaking after passing through the wire and press section of the paper machine.
  • the wet nonwoven fabric is doffed onto the press felt by a suction cup (suction roll or static vacuum element).
  • the task of the press felt is the transport of the fibrous web by press nips of various modifications.
  • the dry content of the web is up to a maximum of 55%.
  • the dry content increases with the pressure exerted on the continuous paper web in the press. Printing and thus the dry content of the paper web can be varied over a relatively large range in many paper machines.
  • the initial wet structural strength can be increased by increasing the solids content of the paper at the point between the press and dryer sections in the manufacturing process.
  • the solids content improve this point of the process through additives to increase drainage. But there are limits to this possibility.
  • the WO 2009/156274 teaches the use of amphoteric copolymers obtainable by copolymerization of N-vinylcarboxamide with anionic comonomers and subsequent hydrolysis of the vinylcarboxamide as a stock additive to increase the initial wet strength of paper.
  • the treatment takes place, for example, in thick matter or in thin paper during the papermaking process.
  • Amphoteric copolymers based on acrylamide are widely known as retention agents.
  • the DE 1948994 describes amphoteric copolymers based on acrylamide with a K value according to Fikentscher of 200 to 250 as dehydrating agent. They thus have a molecular weight for retention agents usual in the range of 500 000 to 10 000 000 daltons and are usually added to the thin material.
  • amphoteric copolymers based on acrylamide for solidification is known. Their molecular weight is typically in the range of 50,000 to 500,000 daltons.
  • the invention has for its object to increase in the production of paper, the initial wet structural strength of the still wet paper web before the transition to the dryer section, in order to achieve higher machine speeds compared to known methods in the papermaking process.
  • paper stock is understood below as meaning a mixture of water and fibrous material which, depending on the stage in the production process of the paper, paperboard or paperboard, still contains the water-soluble amphoteric copolymer, filler and optionally paper auxiliaries.
  • the dry content of the paper is understood as meaning the solids content of paper, board and pulp with the heat-barrier method as determined in accordance with DIN EN ISO 638 DE.
  • pigment is used synonymously with the term filler, since in the production of paper the pigments are used as fillers. Under filler is, as usual in papermaking, inorganic pigment to understand.
  • the inventive method is used to produce paper, cardboard and cardboard comprising dewatering a filler-containing paper stock.
  • the filler content (x) of the paper, cardboard and paperboard can amount to 5 to 40% by weight, based on the paper, the cardboard or the cardboard.
  • a process for the production of paper is preferred whose filler content is 20 to 30 wt .-%.
  • Such papers are, for example, wood-free papers.
  • a process for the production of paper is preferred whose filler content is 10 to 20 wt .-%.
  • Such papers are used primarily as packaging papers.
  • a process for the production of paper is preferred whose filler content is 5 to 15 wt .-%. Such papers are used primarily for newspaper printing.
  • the at least one water-soluble amphoteric polymer, fibrous material and filler-containing aqueous paper material according to the invention is dewatered in the wire section to form a sheet and the sheet is pressed in the press section, ie further dehydrated.
  • the dewatering in the press section takes place up to a minimum solids content, but can also go beyond that.
  • This lower limit of the solids content up to which the product must be pressed is also referred to hereinafter as the limit dry content or else as the minimum solids content G (x) and is based on the pressed sheet which is a mixture of paper stock and water.
  • a solids content of at least 54% by weight is pressed in the press section in order to obtain paper with good initial wet structural strength.
  • the treatment of the fibers according to the invention is carried out by metering the amphoteric copolymer to the pulp at a pulp concentration in the range of 20 to 40 g / l.
  • a pulp concentration of 20 to 40 g / l corresponds to a pulp concentration of 2 to 4 wt .-% based on the aqueous pulp
  • the stock is diluted with water to a pulp concentration in the range of 5 to 15 g / L.
  • native and / or recovered fibers can be used as the fibrous material.
  • All fibers of coniferous and hardwoods commonly used in the paper industry can be used, for example.
  • 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 come into consideration.
  • unbleached pulp also referred to as unbleached kraft pulp
  • Suitable annual plants for the production of fibrous materials are for example rice, wheat, sugarcane and kenaf.
  • Waste paper may also be used to make the pulps, either alone or blended with other pulps.
  • the waste paper can come from a deinking process. But it is not necessary that the waste paper to be used is subjected to such a process. Furthermore, it is also possible to start from fiber blends of a primary material and recycled coated broke.
  • a pulp having a freeness of 20 to 30 SR can be used.
  • a pulp with a freeness of about 30 SR is used, which is ground during the production of the pulp.
  • pulp is used which has a freeness of ⁇ 30 SR.
  • the treatment of the pulp with the water-soluble amphoteric polymer is carried out in aqueous suspension, preferably in the absence of other process chemicals, commonly used in papermaking. It takes place in the papermaking process by adding at least one water-soluble amphoteric copolymer to an aqueous pulp having a pulp concentration of 20 to 40 g / l. Particularly preferred is a process variant in which an amphoteric copolymer is added to the aqueous paper stock at a time prior to the addition of the filler. Very particularly preferably, the addition takes place after the addition of the dry strength agent, for example the starch.
  • the water-soluble, amphoteric copolymers are preferably added in an amount of 0.05 to 5.00 wt .-%, based on pulp (solid).
  • Typical application rates are, for example, from 0.5 to 50 kg, preferably from 0.6 to 10 kg, of at least one water-soluble, amphoteric copolymer, per ton of dry pulp.
  • the amount of amphoteric copolymer used is particularly preferably 0.6 to 3 kg of polymer (solid), based on one ton of dry pulp.
  • the exposure time of the amphoteric copolymer to a pure pulp after metering to sheet formation is, for example, 0.5 second to 2 hours, preferably 1.0 second to 15 minutes, more preferably 2 to 20 seconds.
  • inorganic pigment is added as filler to the pulp.
  • Inorganic pigments are all pigments customarily used in the paper industry on the basis of metal oxides, silicates and / or carbonates, in particular of pigments from the group consisting of calcium carbonate, in the form of ground (GCC) lime, chalk, marble or precipitated calcium carbonate (PCC). talc, kaolin, bentonite, satin white, calcium sulfate, barium sulfate and titanium dioxide. It is also possible to use mixtures of two or more pigments.
  • inorganic pigments having an average particle size (Z-average) ⁇ 10 ⁇ m, preferably from 0.3 to 5 ⁇ m, in particular from 0.5 to 2 ⁇ m, are used.
  • the determination of the average particle size (Z-average) of the inorganic pigments and of the particles of the powder composition is carried out in the context of this document generally by the method of quasi-elastic light scattering (DIN-ISO 13320-1), for example, with a Mastersizer 2000 from Malvern Instruments Ltd. ,
  • the inorganic pigment is dosed after the addition of the water-soluble amphoteric copolymer.
  • the addition takes place in the stage in which the pulp is already present as a thin material, ie at a pulp concentration of 5 to 15 g / l.
  • the inorganic pigment is metered both in the thin and in the thick matter, wherein the ratio of the two addition amounts (adding thick matter / adding thin material) is preferably 5/1 to 1/5.
  • conventional paper auxiliaries can optionally be mixed with the paper stock, generally at a pulp concentration of 5 to 15 g / l.
  • Conventional paper auxiliaries are, for example, sizing agents, wet strength agents, cationic or anionic retention aids based on synthetic polymers, as well as dual systems, dehydrating agents, other dry strength agents, optical brighteners, defoamers, biocides and paper dyes. These conventional paper additives can be used in the usual amounts.
  • the sizing agents include alkylketene dimers (AKD), alkenylsuccinic anhydrides (A-SA) and rosin size.
  • Suitable retention agents are, for example, anionic microparticles (colloidal silicic acid, bentonite), anionic polyacrylamides, cationic polyacrylamides, cationic starch, cationic polyethyleneimine or cationic polyvinylamine.
  • anionic microparticles colloidal silicic acid, bentonite
  • anionic polyacrylamides cationic polyacrylamides
  • cationic starch cationic polyethyleneimine or cationic polyvinylamine
  • any combination thereof is conceivable, for example, dual systems consisting of a cationic polymer with an anionic microparticle or an anionic polymer with a cationic microparticle.
  • retention aids of this kind which can be added to the thick material, for example, but also to the thin material.
  • Dry strength agents are to be understood as meaning synthetic dry strength agents such as polyvinylamine, polyethyleneimine, glyoxylated polyacrylamide (PAM) or natural dry strength agents such as starch.
  • synthetic dry strength agents such as polyvinylamine, polyethyleneimine, glyoxylated polyacrylamide (PAM) or natural dry strength agents such as starch.
  • these dry contents are set when passing through the press section.
  • the wet nonwoven fabric is doffed onto the press felt by a suction cup (suction roll or static vacuum element).
  • the task of the press felt is the transport of the fibrous web by press nips of various modifications.
  • the dry content of the web is up to a maximum of 55%.
  • the dry content increases with the pressure exerted on the continuous paper web in the press. Printing and thus the dry content of the paper web can be varied over a relatively large range in many paper machines.
  • the water-soluble amphoteric copolymers used in the process according to the invention contain at least 20 mol%, preferably at least 25 mol% and in a particularly preferred form at least 30 mol% and at most 60 mol%, preferably at most 55 mol% and in a particularly preferred form at most 50 mol% acrylamide (monomers a) copolymerized, based on the total moles of monomers.
  • the water-soluble amphoteric copolymers used in the process according to the invention furthermore contain at least 20 mol%, preferably at least 25 mol% and at most 60 mol%, preferably at most 55 mol% and in a particularly preferred form at most 50 mol% of a cationic monomer (monomers b) copolymerized, based on the total moles of monomers.
  • the water-soluble amphoteric copolymers contain at least 20 mol%, preferably at least 25 mol% and preferably at most 60 mol%, preferably at most 55 mol% and more preferably at most 50 mol% of an anionic monomer (monomer c), which is selected from the group consisting of monoethylenically unsaturated C 3 - to C 5 monocarboxylic acids, monoethylenically unsaturated C 3 - to C 5 dicarboxylic acids, sulfonic acids, phosphonic acids and / or the salts of these acids copolymerized, based on the total moles of monomers.
  • an anionic monomer monomer (monomer c)
  • monoethylenically unsaturated C 3 - to C 5 monocarboxylic acids monoethylenically unsaturated C 3 - to C 5 dicarboxylic acids
  • sulfonic acids phosphonic acids and / or the salts of these acids copolymer
  • the water-soluble amphoteric copolymers can be up to 30 mol%, preferably up to 20 mol%, in particular up to 15 mol%, particularly preferably 0 to 10 mol% of one or more monoethylenically unsaturated monomers (monomer d), the of the monomers a), b) and c) are different, in copolymerized form, based on the total moles of monomers.
  • the water-soluble amphoteric copolymers can be up to 5 mol%, preferably up to 3 mol%, in particular up to 1 mol%, particularly preferably 0.5 mol% of one or more ethylenically unsaturated monomers (monomer e) containing at least have two ethylenically unsaturated double bonds in the molecule, in copolymerized form, based on the total number of moles of the monomers used for the polymerization.
  • the amount of cationic and anionic monomer is chosen such that the amount of the difference in the proportions of the cationic and anionic monomers in mol%, in each case based on the total moles of monomers used for the polymerization, is not more than 10 mol%.
  • amphoteric polymers are predominantly neutrally charged at pH 7 and 20 ° C.
  • alkyl includes straight-chain and branched alkyl groups. Suitable alkyl groups are, for. C 1 -C 6 alkyl and especially preferably C 1 -C 4 -alkyl groups. These include in particular methyl, ethyl, propyl, isopropyl, n-butyl, 2-butyl, sec-butyl, tert-butyl, n-pentyl, 2-pentyl, 2-methylbutyl, 3-methylbutyl, 1,2-dimethylpropyl , 1,1-dimethylpropyl, 2,2-dimethylpropyl, 1-ethylpropyl, n-hexyl, 2-hexyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2 , 3-dimethylbutyl, 1,1-dimethylbutyl, 2,2-dimethyl
  • Anionic monomers are to be understood below as meaning monomers with acid groups, that is to say radicals having a cleavable or split off proton.
  • Preferred cationic monomers are selected from esters of ⁇ , ⁇ -ethylenically unsaturated mono- and dicarboxylic acids with amino alcohols, preferably C 2 -C 12 -aminoalcohols, amides of ⁇ , ⁇ -ethylenically unsaturated mono- and dicarboxylic acids with diamines, and the N-C 1 -C 8 -monoalkylated or NC 1 -C 8 -dialkylated derivatives of the esters or amides.
  • esters e.g. Acrylic, methacrylic, fumaric, maleic, itaconic, crotonic, maleic, monobutyl, 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.
  • monomers (b) are N- [2- (dimethylamino) ethyl] acrylamide, N- [2- (dimethylamino) ethyl] methacrylamide, N- [3- (dimethylamino) propyl] acrylamide, N- [3- (Dimethylamino) propyl] methacrylamide, N- [4- (dimethylamino) butyl] acrylamide, N- [4- (dimethylamino) butyl] methacrylamide, N- [2- (diethylamino) ethyl] acrylamide, N- [2- (diethylamino ) ethyl] methacrylamide and mixtures thereof.
  • 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.
  • suitable monomers (b) 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 of these monomers ,
  • ethylenically unsaturated anionic monomers (c) which are used are monoethylenically unsaturated C 3 - to C 5 -carboxylic acids, such as acrylic acid, methacrylic acid, ethacrylic acid, crotonic acid, allylacetic acid and vinylacetic acid, monoethylenically unsaturated C 3 - to C 5 -dicarboxylic acids, such as maleic acid, itaconic acid, fumaric acid, Mesaconic acid, citraconic acid and methylenemalonic acid, sulfonic acids such as vinylsulfonic acid, styrenesulfonic acid, acrylamidomethylpropanesulfonic acid, allylsulfonic acid and methallylsulfonic acid, phosphonic acids such as vinylphosphonic acid and / or the salts of these acids in particular the alkali metal, alkaline earth metal and / or ammonium salts of these acids into consideration.
  • alkali metal or alkaline earth metal bases ammonia, amines and / or alkanolamines are used.
  • alkali metal or alkaline earth metal bases ammonia, amines and / or alkanolamines are used.
  • these are sodium hydroxide solution, potassium hydroxide solution, soda, potash, sodium bicarbonate, magnesium oxide, calcium hydroxide, calcium oxide, triethanolamine, ethanolamine, morpholine, diethylenetriamine or tetraethylenepentamine.
  • Preferred anionic monomers include acrylic acid, methacrylic acid, maleic acid, itaconic acid and acrylamido-2-methylpropanesulfonic acid. Particular preference is given to polymers based on acrylic acid.
  • the copolymers may optionally contain at least one further monomer of group (d) in copolymerized form which does not fall under any of monomers (a), (b) and (c) but is a monoethylenically unsaturated monomer other than these.
  • monomers (d) nitriles of ⁇ , ⁇ -ethylenically unsaturated mono- and dicarboxylic acids, such as acrylonitrile and methacrylonitrile called.
  • Examples of members of this group (d) are e.g. Methyl (meth) acrylate methyl methacrylate, ethyl (meth) acrylate, ethyl methacrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, tert-butyl ethacrylate, n-ocytl (meth) acrylate 1,1,3,3-Tetramethylbutyl (meth) acrylate, ethylhexyl (meth) acrylate, 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,
  • Suitable monomers (d) 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 additional monomers (d) are also ethylene, propylene, isobutylene, butadiene, styrene, ⁇ -methylstyrene, vinyl acetate, vinyl propionate, vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride and mixtures thereof.
  • the aforementioned monomers (d) can be used individually or in the form of any mixtures.
  • copolymerization monomers which contain at least two double bonds in the molecule, e.g. Triallylamine, tetraallylammonium chloride, 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, soudite or glucose.
  • the copolymerization monomers e.g.
  • allyl and vinyl ethers of polyalkylene glycols or polyols such as pentaerythritol, soudite or glucose. If at least one monomer of group (d) is used in the copolymerization, the amounts employed are up to 2 mole%, e.g. 0.001 to 1 mole%.
  • the preparation of the water-soluble amphoteric copolymers is carried out by customary methods known to the person skilled in the art.
  • the preparation of the water-soluble amphoteric copolymers can be carried out by solution, precipitation, suspension or emulsion polymerization. Preference is given to solution polymerization in aqueous media.
  • Suitable 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, isopropanol, etc.
  • the polymerization temperatures are preferably in a range of about 30 to 200 ° C, more preferably 40 to 110 ° C.
  • the polymerization can take place under atmospheric pressure but also under reduced or elevated pressure.
  • a suitable pressure range is between 0.1 and 5 bar.
  • the anionic monomers (c) are preferably used in the salt form.
  • the pH is preferably adjusted to a value in the range of 3 to 8 for copolymerization. By using a standard buffer or by measuring the pH and corresponding addition of acid or base, the pH can be kept constant during the polymerization.
  • the monomers can be polymerized by means of free-radical initiators.
  • the peroxo and / or azo compounds customary for this purpose can be used, for example alkali or ammonium peroxydisulfates, diacetyl peroxide, dibenzoyl peroxide, succinyl peroxide, di-tert-butyl peroxide, tert-butyl perbenzoate, tert-butyl perpivalate, tert-butyl peroxy-2-ethylhexanoate, tert-butyl permalate, cumene hydroperoxide, diisopropyl peroxydicarbamate, bis (o-toluoyl) peroxide, didecanoyl peroxide, dioctanoyl peroxide, dilauroyl peroxide, tert-butyl perisobutyrate, tert-butyl peracetate, di-tert-amyl peroxide tert-butyl hydroperoxide
  • initiator mixtures or redox initiator systems such as ascorbic acid / iron (II) sulfate / sodium peroxodisulfate, tert-butyl hydroperoxide / sodium disulfite, tert-butyl hydroperoxide / sodium hydroxymethanesulfinate, H 2 O 2 / CuI and sodium or ammonium peroxodisulfate / sodium disulfite.
  • initiator mixtures or redox initiator systems such as ascorbic acid / iron (II) sulfate / sodium peroxodisulfate, tert-butyl hydroperoxide / sodium disulfite, tert-butyl hydroperoxide / sodium hydroxymethanesulfinate, H 2 O 2 / CuI and sodium or ammonium peroxodisulfate / sodium disulfite.
  • the polymerization can be carried out in the presence of at least one regulator.
  • a regulator the usual compounds known in the art, such.
  • B. sulfur compounds for. As mercaptoethanol, 2-ethylhexyl thioglycolate, thioglycolic acid, sodium hypophosphite, formic acid or dodecyl mercaptan and Tribromchlormethan or other compounds which act regulating the molecular weight of the polymers obtained, are used.
  • the molecular weight of the water-soluble amphoteric copolymers is, for example, at least 10,000, preferably at least 100,000 daltons and in particular at least 250,000 daltons.
  • the molecular weights of the copolymers are then e.g. 10,000 to 10 million, preferably 100,000 to 5 million (as determined by light scattering).
  • This molar mass range corresponds, for example, to K values of 5 to 300, preferably 10 to 200 (determined according to H. Fikentscher in 5% strength aqueous sodium chloride solution at 25 ° C. and a polymer concentration of 0.1% by weight).
  • the water-soluble, amphoteric copolymers may carry an anionic or a cationic excess charge or be electrically neutral, if the same number of anionic and cationic groups are present in the copolymer.
  • the method according to the invention enables a tear-free operation of the paper machine.
  • the resulting in the process paper web or paper sheet shows a significantly increased wet structural strength.
  • Feed 1 In a beaker, the following components were mixed: 250 g deionized water 95.6 g 50% strength by weight aqueous acrylamide solution 121.9 g 80 wt .-%, aqueous solution of acryloyloxyethyltrimethylammonium chloride 148.1 g 32 wt .-%, aqueous sodium acrylate solution 0.2 g of 1% strength by weight aqueous solution of diethylenetriaminepentaacetic acid.
  • Feed 2 60.0 g of a 1 wt .-% aqueous solution of 2,2'-azobis (2-amidinopropane) dihydrochloride
  • Feed 3 16.5 g of a 1% strength by weight aqueous solution of 2,2'-azobis (2-amidinopropane) dihydrochloride
  • the original was heated to 63 ° C and the pressure was lowered by means of a water jet pump so far that the water just started to boil.
  • the feeds 1 and 2 were started simultaneously, the feed 1 in 2 hours and the feed 2 in 3 hours at a constant internal temperature to the template.
  • the reaction was held at 63 ° C. for a further hour, then the mixture was heated to 72 ° C. and the vacuum was reduced correspondingly.
  • the reaction mixture was kept at 72 ° C for a further 2 hours, then feed 3 was added all at once and postpolymerized at 72 ° C for a further 2 hours. Then the vacuum was released, the batch was diluted with 500 g of deionized water and cooled to room temperature. During the entire polymerization, 208 g of water were distilled off.
  • a clear, colorless, viscous solution of a polymer having the composition of 40 mol% acrylamide, 30 mol% acryloyloxyethyltrimethylammonium chloride and 30 mol% sodium acrylate was obtained.
  • Solids content 14.5% by weight
  • Feed 1 In a beaker, the following components were mixed: 250 g deionized water 119.5 g of 50% strength by weight aqueous acrylamide solution 113.8 g 80% strength by weight aqueous solution of acryloyloxyethyltrimethylammonium chloride 108.6 g 32 wt .-%, aqueous sodium acrylate solution 0.2 g of 1% strength by weight aqueous solution of diethylenetriaminepentaacetic acid.
  • the original was heated to 66 ° C and the pressure was lowered by means of a water jet pump so far that the water just started to boil.
  • the feeds 1 and 2 were started simultaneously, the feed 1 in 2 hours and the feed 2 in 3 hours at a constant internal temperature to the template.
  • the reaction was held for a further hour at 66 ° C, then was heated to 78 ° C and correspondingly reduced the vacuum.
  • the reaction mixture was kept for a further 2 hours at 78 ° C, then feed 3 was added all at once and postpolymerized at 78 ° C for a further 2 hours.
  • the vacuum was released, the batch was diluted with 500 g of deionized water and cooled to room temperature. During the entire polymerization, 200 g of water were distilled off.
  • Feed 1 In a beaker, the following components were mixed: 250 g deionized water 71.7 g 50% strength by weight aqueous acrylamide solution 130.1 g 80% strength by weight aqueous solution of acryloyloxyethyltrimethylammonium chloride 187.8 g 32 wt .-%, aqueous sodium acrylate solution 0.2 g of 1% strength by weight aqueous solution of diethylenetriaminepentaacetic acid.
  • the pH was adjusted to 4.1 by adding about 34 g of a 37% strength hydrochloric acid
  • Feed 2 60.3 g of a 1 wt .-% aqueous solution of 2,2'-azobis (2-amidinopropane) -di hydrochloride
  • Feed 3 16.0 g of a 1% strength by weight aqueous solution of 2,2'-azobis (2-amidinopropane) dihydrochloride
  • the original was heated to 63 ° C and the pressure was lowered by means of a water jet pump so far that the water just started to boil.
  • the feeds 1 and 2 were started simultaneously, the feed 1 in 2 hours and the feed 2 in 3 hours at a constant internal temperature to the template.
  • the reaction was held at 63 ° C. for a further hour, then the mixture was heated to 72 ° C. and the vacuum was reduced correspondingly.
  • the reaction mixture was kept at 72 ° C for a further 2 hours, then feed 3 was added all at once and postpolymerized at 72 ° C for a further 2 hours. Then the vacuum was released, the batch was diluted with 500 g of deionized water and cooled to room temperature. During the entire polymerization, 200 g of water were distilled off.
  • a clear, fabeless, viscous solution of a polymer having the composition of 30 mol% acrylamide, 32 mol% acryloyloxyethyltrimethylammonium chloride and 38 mol% sodium acrylate was obtained. Solids content: 14.8% by weight Viscosity: 12,000 mPas (Brookfield, spindle 7, 50 rpm, room temperature) K value 117 (0.1% solution of the polymer in a 5% by weight aqueous saline solution)
  • Feed 1 In a beaker, the following components were mixed: 287.7 g deionized water 214.3 g 50% strength by weight aqueous acrylamide solution 78.1 g of 80% strength by weight aqueous solution of acryloyloxyethyltrimethylammonium chloride 94.9 g of 32% strength by weight aqueous sodium acrylate solution 0.3 g of 1% strength aqueous solution of diethylenetriaminepentaacetic acid The pH was adjusted to 4.1 by the addition of about 20 g of a 37% strength hydrochloric acid.
  • Feed 2 67.1 g of a 1% strength by weight aqueous solution of 2,2'-azobis (2-amidinopropane) dihydrochloride
  • Feed 3 17.7 g of a 1% strength by weight aqueous solution of 2,2'-azobis (2-amidinopropane) dihydrochloride
  • the original was heated to 64 ° C and the pressure was lowered by means of a water jet pump so far, so the water just began to boil.
  • the feeds 1 and 2 were started simultaneously and he feed 1 in 2 hours and the feed 2 in 3 hours at a constant internal temperature to the template.
  • the feed vessel was rinsed with 50 ml of deionized water.
  • the reaction was maintained at 64 ° C. for a further 30 minutes, then 100 ml of deionized water were added and the mixture was heated to 72 ° C. and the vacuum was reduced correspondingly.
  • the reaction mixture was held at 72 ° C for an additional 1.5 hours.
  • feed 3 was added all at once and postpolymerized at 72 ° C. for a further 2 hours.
  • the vacuum was then released, the batch was diluted with 500 g of deionized water and cooled to room temperature. During the entire polymerization, 220 g of water were distilled off.
  • a clear, colorless, viscous solution of a polymer having the composition of 70 mol% acrylamide, 15 mol% acryloyloxyethyltrimethylammonium chloride and 15 mol% sodium acrylate was obtained.
  • Solids content 13.6% by weight
  • K value 129 (0.1% solution of the polymer in a 5% by weight aqueous saline solution)
  • Feed 1 In a 2 l 5-neck flask equipped with an anchor stirrer, a thermometer, a descending condenser and a nitrogen inlet 400 g of deionized water were submitted. Furthermore, the following feeds were provided: Feed 1: In a beaker, the following components were mixed: 290.2 g deionized water 183.7 g 50% strength by weight aqueous acrylamide solution 78.1 g of 80% strength by weight aqueous solution of acryloyloxyethyltrimethylammonium chloride 158.1 g of 32% strength by weight aqueous sodium acrylate solution 0.2 g of 1% strength aqueous solution of diethylenetriaminepentaacetic acid The pH was adjusted to 4.1 by the addition of about 20 g of 37% strength hydrochloric acid.
  • Feed 2 75.1 g of a 1% strength by weight aqueous solution of 2,2'-azobis (2-amidinopropane) dihydrochloride
  • Feed 3 18.0 g of a 1 wt .-% aqueous solution of 2,2'-azobis (2-amidinopropane) dihydrochloride
  • the original was heated to 66 ° C and the pressure was lowered by means of a water jet pump so far, so the water just began to boil.
  • the feeds 1 and 2 were started simultaneously and he feed 1 in 2 hours and the feed 2 in 3 hours at a constant internal temperature to the template.
  • the feed vessel was rinsed with 50 ml of deionized water.
  • the reaction was held at 66 ° C. for a further 30 minutes, then 100 ml of deionized water were added and the mixture was heated to 75 ° C. and the vacuum was reduced correspondingly.
  • the reaction mixture was held at 75 ° C for an additional 1.5 hours.
  • feed 3 was added all at once and postpolymerized at 75 ° C. for a further 2 hours.
  • the vacuum was then released, the batch was diluted with 500 g of deionized water and cooled to room temperature. During the entire polymerization, 220 g of water were distilled off.
  • a clear, colorless, viscous solution of a polymer having the composition of 60 mol% acrylamide, 15 mol% acryloyloxyethyltrimethylammonium chloride and 25 mol% sodium acrylate was obtained.
  • Solids content 12.1% by weight
  • the pulp concentration of the thin material in the examples must be set at 3.5 g / l.
  • Bleached birch sulphate was beaten open at a pulp concentration of 4% in the laboratory pulper until a freeness of 30 ° SR was reached.
  • An optical brightener (Blankophor® PSG) and a fully digested cationic starch (HiCat® 5163 A) were then added to the open material and allowed to act for 5 minutes.
  • the digestion of the cationic starch was previously carried out as a 10% starch slurry in a jet cooker at 130 ° C and 1 minute residence time.
  • the metered amount of the optical brightener was 0.5 wt .-% commercial goods, based on the solids content of the pulp suspension.
  • the dosage of the cationic starch was 0.8% starch (solid), based on the solids content of the pulp suspension.
  • the pulp content of the pulp suspension after addition of starch and optical brightener was 3.5% (35 g / l).
  • the pulp suspensions were processed two minutes after the pigment addition to a Rapid-Köthen sheet former according to ISO 5269/2 to sheets of a basis weight of 100 g / qm.
  • the wet leaves were then removed from the screen frame and placed between two Saugfilze.
  • the package consisting of absorbent felts and the wet paper was then pressed in a static press at a press pressure of 6 bar. It was pressed in each case up to a solids content of 50 wt .-% of the wet leaves.
  • the pulp suspensions in all 3 beakers were diluted by addition of water to a pulp concentration of 0.35% each. Thereafter, in each case a 20% strength by weight carbonate pigment slurry (PCC, Syncarb F474 from Omya) was added to the mixture. The added amount of the pigment suspension was adjusted in several preliminary experiments so that the pigment content in the laboratory sheets subsequently formed was about 20%.
  • the pulp suspensions were processed two minutes after the pigment addition to a Rapid-Köthen sheet former according to ISO 5269/2 to sheets of a basis weight of 100 g / qm. The wet leaves were then removed from the screen frame and placed between two Saugfilze.
  • the package consisting of absorbent felts and the wet paper was then pressed in a static press at a press pressure of 6 bar.
  • a static press at a press pressure of 6 bar.
  • Example 6 (not according to the invention - dosage in the thin material)
  • 50 g of the pretreated pulp suspension (thick stock) was diluted by the addition of 450 g of water to a pulp concentration of 0.35% (corresponding to 3.5 g / l).
  • 2 g of a 1% strength by weight aqueous solution of polymer I corresponding to 1% by weight of polymer (solid) based on pulp (solid) were added to 500 g of the diluted pulp suspension (thin material).
  • a 20% strength by weight carbonate pigment slurry PCC, Syncarb F474 from Omya
  • the pulp suspension was processed two minutes after the pigment addition to a Rapid-Köthen sheet former according to ISO 5269/2 to sheets of a basis weight of 100 g / qm.
  • the wet leaves were then removed from the screen frame and placed between two Saugfilze.
  • the package consisting of absorbent felts and the wet paper was then pressed in a static press at a press pressure of 6 bar. By adjusting the residence time of the papers within the press arrangement in each case up to a solids content of 50 wt .-% of the wet leaves was pressed.
  • the pulp suspensions were processed two minutes after the pigment addition to a Rapid-Köthen sheet former according to ISO 5269/2 to sheets of a basis weight of 100 g / qm.
  • the wet leaves were then removed from the screen frame and placed between two Saugfilze.
  • the package consisting of absorbent felts and the wet paper was then pressed in a static press at a press pressure of 6 bar. By adjusting the residence time within the press arrangement, in each case up to a solids content of the wet leaves was pressed, which is shown in Table 1.
  • Example 7 The procedure was as in Example 7 and untreated pigment (PCC, Syncarb F474 from Omya) used.
  • the press duration in the static press was adjusted so that the solids content of the wet leaves was below the limit dry content, taking into account the pigment content. In this case, below 50%, at 48.7%.
  • the wet strength and the initial wet strength of paper are to be distinguished from the initial wet texture strength because both properties are measured on papers which are moistened again to a defined water content after drying.
  • the initial wet strength is an important parameter in the assessment of non-permanent wet-strength papers. A dried and then re-wetted paper has a very different wet strength than a wet paper that is present just after passing through the wire and press section of a paper machine.
  • the Initial wet texture strength determined at 50% dry content.
  • the actual measurement of the initial wet structural strength was made on a vertical tensile testing machine with a special clamping device.
  • the force determined in the tractor was converted into the area-mass-independent so-called INF index.
  • INF index For a detailed description of the clamping device, the measuring procedure, the determination of the dry content in the paper and the data processing, the reference cited above can be used.

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Claims (8)

  1. Procédé de fabrication de papier, de papier-carton et de carton comprenant la déshydratation d'une pâte à papier contenant des charges, qui contient au moins un copolymère amphotère soluble dans l'eau, avec formation de feuilles dans la partie tamis, puis la compression du papier dans la partie presse, selon lequel ledit au moins un copolymère amphotère soluble dans l'eau est ajouté à une pâte à papier ayant une concentration en matière fibreuse dans la plage allant de 20 à 40 g/l, puis la pâte à papier est diluée à une concentration en matière fibreuse dans la plage allant de 5 à 15 g/l, la pâte à papier diluée est déshydratée avec formation d'une feuille, et la feuille est comprimée dans la partie presse à une teneur en solides de G(x) % en poids ou plus, G(x) étant calculé par : G x = 48 + x − 15 ⋅ 0,4
    Figure imgb0008
    x représentant la valeur numérique de la teneur en charges du papier, papier-carton ou carton séché (en % en poids) et
    G(x) représentant la valeur numérique de la teneur en solides minimale (en % en poids) à laquelle la feuille est comprimée,
    le copolymère amphotère soluble dans l'eau pouvant être obtenu par polymérisation d'un mélange de :
    a) 20 à 60 % en moles d'acrylamide, par rapport au nombre de moles total des monomères utilisés pour la polymérisation,
    b) 20 à 60 % en moles, par rapport au nombre de moles total des monomères utilisés pour la polymérisation, d'au moins un monomère cationique,
    c) 20 à 60 % en moles, par rapport au nombre de moles total des monomères utilisés pour la polymérisation, d'au moins un monomère anionique, qui est choisi parmi les acides carboxyliques en C3 à C5 monoéthyléniquement insaturés, les acides dicarboxyliques en C3 à C5 monoéthyléniquement insaturés, les acides sulfoniques, les acides phosphoniques et/ou les sels de ces acides,
    d) 0 à 30 % en moles, par rapport au nombre de moles total des monomères utilisés pour la polymérisation, d'un ou de plusieurs monomères monoéthyléniquement insaturés qui sont différents des monomères (a), (b) et (c), et
    e) 0 à 5 % en moles, par rapport au nombre de moles total des monomères utilisés pour la polymérisation, d'un ou de plusieurs composés qui comprennent au moins deux doubles liaisons éthyléniquement insaturées par molécule,
    le montant de la différence entre les proportions du monomère cationique et du monomère anionique en % en moles, à chaque fois par rapport au nombre de moles total des monomères utilisés pour la polymérisation, étant d'au plus 10 % en moles,
    le copolymère amphotère soluble dans l'eau étant ajouté à la pâte à papier ayant une concentration de matière fibreuse dans la plage allant de 20 à 40 g/l et avant l'ajout d'une charge,
    à une teneur en charges de 15 ou moins, une compression à une teneur en solides d'au moins 48 % en poids étant effectuée.
  2. Procédé selon la revendication 1, caractérisé en ce que la pâte à papier contient en tant que matière fibreuse exclusivement une matière fibreuse qui présente un degré de broyage ≤ 30° SR.
  3. Procédé selon l'une quelconque des revendications 1 ou 2, caractérisé en ce que le copolymère amphotère soluble dans l'eau est ajouté en une quantité de 0,05 à 5,00 % en poids, par rapport à la matière fibreuse.
  4. Procédé selon l'une quelconque des revendications 1 à 3, caractérisé en ce que le copolymère amphotère soluble dans l'eau peut être obtenu par polymérisation d'un mélange contenant au moins un monomère cationique choisi parmi les esters d'acides mono- et dicarboxyliques α,β-éthyléniquement insaturés avec des amino-alcools, les amides d'acides mono- et dicarboxyliques α,β-éthyléniquement insaturés avec des diamines, ainsi que les dérivés N-monoalkylés en C1-C8 ou N-dialkylés en C1-C8 de ces esters ou de ces amides.
  5. Procédé selon l'une quelconque des revendications 1 à 4, caractérisé en ce que le copolymère amphotère soluble dans l'eau peut être obtenu par polymérisation d'un mélange contenant au moins un monomère anionique choisi parmi l'acide acrylique, l'acide méthacrylique, l'acide maléique, l'acide itaconique et l'acide acrylamido-2-méthylpropanesulfonique et les sels de ces acides.
  6. Procédé selon l'une quelconque des revendications 1 à 5, caractérisé en ce que le copolymère amphotère soluble dans l'eau peut être obtenu par polymérisation d'un mélange de :
    a) 20 à 50 % en moles d'acrylamide, par rapport au nombre de moles total des monomères utilisés pour la polymérisation,
    b) 20 à 40 % en moles, par rapport au nombre de moles total des monomères utilisés pour la polymérisation, d'au moins un monomère cationique,
    c) 25 à 40 % en moles, par rapport au nombre de moles total des monomères utilisés pour la polymérisation, d'au moins un monomère anionique, qui est choisi parmi les acides monocarboxyliques en C3 à C5 monoéthyléniquement insaturés, les acides dicarboxyliques en C3 à C5 monoéthyléniquement insaturés, les acides sulfoniques, les acides phosphoniques et/ou les sels de ces acides,
    d) 0 à 30 % en moles, par rapport au nombre de moles total des monomères utilisés pour la polymérisation, d'un ou de plusieurs monomères monoéthyléniquement insaturés, qui sont différents des monomères (a), (b) et (c), et
    e) 0 à 5 % en moles, par rapport au nombre de moles total des monomères utilisés pour la polymérisation, d'un ou de plusieurs composés qui comprennent au moins deux doubles liaisons éthyléniquement insaturées par molécule,
    le montant de la différence entre les proportions du monomère cationique et du monomère anionique en % en moles, à chaque fois par rapport au nombre de moles total des monomères utilisés pour la polymérisation, étant d'au plus 10 % en moles.
  7. Procédé selon l'une quelconque des revendications 1 à 6 pour la fabrication de papier, de papier-carton et de carton ayant une teneur en charges de 17 à 32, caractérisé en ce qu'une compression à au moins une teneur en solides dans la plage allant de 49 à 55 est effectuée dans la partie presse.
  8. Procédé selon l'une quelconque des revendications 1 à 7 pour la fabrication de papier, de papier-carton et de carton ayant une teneur en charges de 15 ou moins, caractérisé en ce qu'une compression à au moins une teneur en solides de 48 % en poids est effectuée dans la partie presse.
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EP2723943A1 (fr) 2014-04-30
WO2012175392A1 (fr) 2012-12-27
PL2723943T3 (pl) 2019-01-31
BR112013032550A8 (pt) 2020-10-27
ES2692543T3 (es) 2018-12-04
PT2723943T (pt) 2018-11-13
BR112013032550B1 (pt) 2021-05-18
CN103620115A (zh) 2014-03-05
BR112013032550A2 (pt) 2017-01-17
CN103620115B (zh) 2016-07-20

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