EP2888404A1 - Procédé de fabrication de papier, de carton-pâte et de carton - Google Patents

Procédé de fabrication de papier, de carton-pâte et de carton

Info

Publication number
EP2888404A1
EP2888404A1 EP13745049.0A EP13745049A EP2888404A1 EP 2888404 A1 EP2888404 A1 EP 2888404A1 EP 13745049 A EP13745049 A EP 13745049A EP 2888404 A1 EP2888404 A1 EP 2888404A1
Authority
EP
European Patent Office
Prior art keywords
paper
polymer
pulp
water
acrylamide
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP13745049.0A
Other languages
German (de)
English (en)
Other versions
EP2888404B1 (fr
Inventor
Anton Esser
Hans-Joachim HÄHNLE
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Priority to PL13745049T priority Critical patent/PL2888404T3/pl
Priority to EP13745049.0A priority patent/EP2888404B1/fr
Publication of EP2888404A1 publication Critical patent/EP2888404A1/fr
Application granted granted Critical
Publication of EP2888404B1 publication Critical patent/EP2888404B1/fr
Active legal-status Critical Current
Anticipated expiration legal-status Critical

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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
    • D21H17/38—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing crosslinkable groups
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/33—Synthetic macromolecular compounds
    • D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H17/41—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups
    • D21H17/44—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups cationic
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/33—Synthetic macromolecular compounds
    • D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H17/41—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups
    • D21H17/44—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups cationic
    • D21H17/45—Nitrogen-containing groups
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/63—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
    • 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 which contains at least one water-soluble polymer which is obtained by the Hofmann degradation of an acrylamide- and / or methacrylamide-containing polymer is available, with sheet formation in the wire section and then pressing 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.
  • 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 is e.g. in thick stock or thin paper in the papermaking process.
  • the prior application WO 2012/175392 teaches the use of amphoteric copolymers based on acrylamide, which are obtainable by copolymerization of acrylamide with anionic comonomers as a stock additive to increase the initial wet strength of paper.
  • the treatment takes place in the thick matter in the papermaking process.
  • the press section of the paper machine must be set so that the dry content of the wet paper web after leaving the press section exceeds a minimum value dependent on the composition of the material.
  • 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.
  • a process for the production of paper, paperboard and paperboard comprising dewatering a filler-containing paper stock containing at least one water-soluble polymer, with formation of sheets in the wire section and subsequent pressing of the paper in the press section, resulting in a paper stock with a Fibrous concentration in the range of 20 to 40 g / l which doses at least one water-soluble polymer, then the paper stock to a pulp concentration in the range of 5 to 15 g / l diluted, drained the diluted paper stock to form a sheet and the sheet in the press section to a Solid content G (x) wt .-% or greater presses and G (x) calculates after
  • G (x) 48 + (x - 15) x 0.4
  • x is the number value of the filler content of the dry paper, paperboard or cardboard (in% by weight)
  • G (x) is the number of minimum solids (in% by weight) on which the sheet is pressed, wherein the water-soluble polymer is obtainable by the Hofmann degradation of an acrylamide- and / or methacrylamide-containing polymer and optionally a subsequent post-crosslinking.
  • the present invention further relates to a process for the production of paper,
  • Paperboard and paperboard comprising dewatering a solid-containing paper stock containing at least one water-soluble polymer to form a sheet in the wire section and then pressing the paper in the press section to yield a stock at a pulp concentration in the range of 20 to 40 g / l dosing a water-soluble polymer, then diluting the pulp to a pulp concentration in the range of 5 to 15 g / l, dewatering the diluted pulp to form a sheet and keeping the sheet in the press section at a solids content of> 48% by weight, preferably 49% - 53 wt .-% pressed, wherein the water-soluble polymer is obtainable by the Hofmann degradation of an acrylamide and / or methacrylamide-containing polymer and optionally a subsequent post-crosslinking.
  • pulp a mixture of water and pulp is understood below, which additionally contains, depending on the stage in the manufacturing process of the paper, paperboard or cardboard, the water-soluble polymer, filler and optionally paper auxiliaries.
  • the dry content of the paper is understood as meaning the solids content of paper, board, cardboard and fibrous material 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.
  • filler is understood to mean inorganic pigment.
  • 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, paperboard and cardboard can be 5 to 40% by weight, based on the paper, paperboard or 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. According to a further preferred embodiment, 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.
  • a process for producing paper whose filler content is from 25 to 40% by weight for example SC papers.
  • the aqueous paper pulp containing at least one water-soluble polymer, pulp and filler is dewatered in the wire section to form a sheet and the sheet is pressed in the press section, that is, 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.
  • a solids content of at least 48% by weight is pressed in order to obtain paper with good initial wet structural strength.
  • paperboard and paperboard having a filler content of 17 to 32% by weight in the press section at least a solids content in the range of 49 to 55% by weight is pressed.
  • the fibers are treated according to the invention by metering the water-soluble polymer into the pulp at a pulp concentration in the range from 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. Pulp, bleached and unbleached pulp and pulp from all annual plants. Wood pulp includes, for example, groundwood, thermo-mechanical pulp (TMP), chemo-thermo-mechanical pulp (CTMP), pressure groundwood, semi-pulp, high yield pulp and refiner mechanical pulp (RMP). As pulp, for example, sulphate, sulphite and soda pulps come into consideration. Preferably, unbleached pulp, also referred to as unbleached kraft pulp, is used.
  • 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 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 polymer to an aqueous paper stock having a pulp concentration of 20 to 40 g / l. Particularly preferred is a process variant in which a water-soluble polymer is added to the aqueous paper stock at a time which is prior to the addition of the filler. With very particular preference, the addition takes place after the addition of the dry strength promoter, for example the starch.
  • the water-soluble polymers are preferably added in an amount of 0.05 to 5.00 wt .-%, based on pulp (solid).
  • Typical application rates are, for example, 0.5 to 50 kg, preferably 0.6 to 10 kg of at least one water-soluble polymer, per ton of dry pulp. Particularly preferably, the amounts of water-soluble polymer used is 0.6 to 3 kg of polymer (solid), based per ton of dry pulp.
  • the exposure time of the water-soluble polymer to a pure pulp or pulp after metering to sheet formation is, for example, 0.5 seconds to 2 hours, preferably 1.0 seconds to 15 minutes, particularly preferably 2 to 20 seconds.
  • inorganic pigment is added as filler to the pulp.
  • Suitable inorganic pigments are all pigments customarily usable 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 which is 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 (volume average) 10 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 (volume 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 preferably metered after the addition of the water-soluble polymer.
  • 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 may optionally be admixed 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 shear polymers and dual systems, dewatering 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 are 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 polyethylenimine or cationic polyvinylamine.
  • anionic microparticles colloidal silicic acid, bentonite
  • anionic polyacrylamides cationic polyacrylamides
  • cationic starch cationic polyethylenimine 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 synthetic dry strength agents such as polyvinylamine, polyethyleneimine, glyoxylated polyacrylamide (PAM), amphoteric polyacrylamides or natural dry strength agents such as starch.
  • synthetic dry strength agents such as polyvinylamine, polyethyleneimine, glyoxylated polyacrylamide (PAM), amphoteric polyacrylamides or natural dry strength agents such as starch.
  • these dry contents are set when passing through the press section.
  • the wet nonwoven fabric is abraded onto the press felt by a suction cup (suction roll or static vacuum element).
  • suction cup suction roll or static vacuum element.
  • the task of the press felt is the transport of the fibrous web through
  • the dry content of the web is, depending on the design of the press section and the composition of the pulp, 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 polymer used according to the invention is obtainable by the Hofmann degradation of an acrylamide- and / or methacrylamide-containing polymer and, if appropriate, subsequent postcrosslinking.
  • acrylamide- and / or methacrylamide-containing polymers are obtainable by free-radical copolymerization of a monomer mixture comprising acrylamide and / or methacrylamide.
  • the monomers acrylamide and methacrylamide are based on the monomer composition of the prepolymer, individually or as a mixture in proportions of 10 mol% to 100 mol%, preferably in fractions of 20 to 90 mol%, particularly preferably in fractions of 30 to 80 mol% in copolymerized form.
  • the monomer mixture preferably has the following composition: a) acrylamide and / or methacrylamide (monomers a) b) optionally one or more monoethylenically unsaturated monomers whose corresponding structural unit in the polymer is stable under the reaction conditions of Hofmann degradation, and / or DADMAC ( Diallyldimethylammonium chloride) (monomers b), (c) optionally one or more compounds having two or more ethylenically unsaturated radicals, and their corresponding structural units in the polymer are stable under the reaction conditions of Hofmann degradation, wherein DADMAC is not included (monomers c).
  • Monoethylenically unsaturated monomers whose corresponding structural units in the polymer are stable under the reaction conditions of Hofmann degradation are, for example, nitriles of ⁇ , ⁇ -ethylenically unsaturated mono- and dicarboxylic acids, such as acrylonitrile and methacrylonitrile, amides of ⁇ , ⁇ -ethylenically unsaturated monocarboxylic acids and their N-alkyl and ⁇ , ⁇ -dialkyl derivatives, N-vinyl lactams, nitrogen-containing heterocycles, vinyl aromatics, C 2 -C 8 monoolefins, ⁇ , ⁇ -ethylenically unsaturated mono- and dicarboxylic acids and their salts, anhydrides of ⁇ , ⁇ -ethylenically unsaturated mono - and dicarboxylic acids, ethylenically unsaturated sulfonic acids and their salts, ethylenically unsaturated phospho
  • members of this group (b) are e.g. 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-
  • Suitable 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.
  • Suitable monomers (b) 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.
  • N-vinylimidazoles and alkylvinylimidazoles are also suitable as 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 betaine derivatives and quaternization products thereof monomers.
  • DMAC diallyldimethylammonium chloride
  • Additional monomers are ethylene, propylene, isobutylene, butadiene, styrene, ⁇ -methylstyrene, vinyl acetate, vinyl propionate, vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride and mixtures thereof.
  • monomers which carry at least one acid function i. at least one sulfonic acid group, phosphonic acid group or carboxylic acid group.
  • salts of the abovementioned compounds By way of example may be mentioned:
  • Vinylsulfonic acid, allylsulfonic acid, methallylsulfonic acid, styrenesulfonic acid, acrylamidomethylenephosphonic acid, 2-acrylamido-2-methylpropanesulfonic acid, vinylphosphonic acid, CH 2 CH-NH-CH 2 -PO 3, monomethyl vinylphosphonate, allylphosphonic acid, monomethyl allylphosphonate, acrylamidomethylpropylphosphonic acid.
  • monoethylenically unsaturated carboxylic acids having 3 to 8 carbon atoms and the water-soluble salts such as alkali metal, alkaline earth metal or ammonium salts of these carboxylic acids and the monoethylenically unsaturated carboxylic anhydrides into consideration.
  • This group of monomers includes, for example, acrylic acid, methacrylic acid, dimethacrylic acid, ethacrylic acid, ⁇ -chloroacrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, mesaconic acid, citraconic acid, glutaconic acid, aconitic acid, methylenemalonic acid, allylacetic acid, vinylacetic acid and crotonic acid.
  • the acid group-carrying monomers can be present in unneutralized, partially neutralized or completely neutralized form, wherein the phosphonic acids one or both protons can be neutralized by suitable bases.
  • Suitable bases for the partial or complete neutralization of the acid groups of the monomers are, for example, alkali metal or alkaline earth metal bases, ammonia, amines and / or alkanolamines.
  • alkali metal or alkaline earth metal bases ammonia, amines and / or alkanolamines.
  • Examples are sodium hydroxide, potassium hydroxide, Sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, magnesium hydroxide, magnesium oxide, calcium hydroxide, calcium oxide, triethanolamine, ethanolamine and morpholine.
  • the monomers of this group (b) can be used alone or in a mixture.
  • Preferred monoethylenically unsaturated monomers whose corresponding structural units are stable in the polymer reaction conditions of Hofmann degradation are, for example, nitriles of ⁇ , ⁇ -ethylenically unsaturated mono- and dicarboxylic acids, such as acrylonitrile and methacrylonitrile, amides of ⁇ , ⁇ -ethylenically unsaturated monocarboxylic acids and their N-alkyl and ⁇ , ⁇ -dialkyl derivatives, N-vinyl lactams and DADMAC.
  • the prepolymers preferably contain at least 5 mol%, preferably at least 10 mol% and preferably at most 90 mol%, preferably at most 70 mol% and in a particularly preferred form at most 50 mol% of one or more monoethylenically unsaturated monomers, the corresponding structural unit is stable in the polymer under the reaction conditions of the Hofmann degradation, (monomers b) polymerized in, based on the total number of moles of the monomers (a and b).
  • the prepolymers can be used in amounts of up to 5% by weight, preferably up to 3% by weight, in particular up to 1% by weight, very particularly preferably up to 1% by weight and at least 0.0001% by weight, in particular at least 0.001% by weight, based on the total weight of the monomers a and b used for the polymerization, of compounds having two or more ethylenically unsaturated radicals whose corresponding structural units in the polymer are stable under the reaction conditions of Hofmann degradation in copolymerized form , wherein DADMAC is not included (monomers c).
  • Such a modification of the prepolymers by copolymerizing compounds having two or more ethylenically unsaturated radicals whose corresponding structural units in the polymer are stable under the reaction conditions of Hofmann degradation is described, for example, with methylenebisacrylamide, triallylamine, tetraallylamonium chloride or ⁇ , ⁇ ' - Reached divinylpropyleneurea.
  • the monomer mixture used to prepare the prepolymer particularly preferably has the following composition:
  • the monomer mixture used to prepare the prepolymer has the following composition: 50 to 90 mol% acrylamide and / or methacrylamide and
  • diallyldimethylammonium chloride (monomer b) and optionally from 0.001 to 0.1% by weight, based on the total amount of monomer a and monomer b of one or more compounds selected from methylenebisacrylamide, triallylamine, tetraallylammonium chloride, N, N ' divinylpropyleneurea.
  • the prepolymers can be prepared by solution, precipitation, suspension, gel 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, for example an alcohol, such as methanol, ethanol, n-propanol, isopropanol etc.
  • the polymerization temperatures are preferably in a range from about 30 to 200.degree. C., more preferably 40 to 1 10 ° C.
  • the polymerization is usually carried out under atmospheric pressure, but it can also proceed under reduced or elevated pressure. A suitable pressure range is from 0.1 to 10 bar.
  • the acid group-containing monomers (b) are preferably used in the salt form. To prepare the polymers, 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 metal or ammonium peroxidisulfates, diacetyl peroxide, dibenzoyl peroxide, succinyl peroxide,
  • tert-butyl hydroperoxide e.g. Ascorbic acid / iron (II) sulfate / sodium peroxodisulfate, tert-butyl hydroperoxide / sodium disulfite, tert-butyl hydroperoxide / sodium hydroxymethanesulfinate, H2O2 / CUI.
  • initiator mixtures or redox initiator systems e.g. Ascorbic acid / iron (II) sulfate / sodium peroxodisulfate, tert-butyl hydroperoxide / sodium disulfite, tert-butyl hydroperoxide / sodium hydroxymethanesulfinate, H2O2 / CUI.
  • 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. Mercaptoethanol,
  • the molecular weight of the water-soluble prepolymer is, for example, at least 50,000, preferably at least 100,000 daltons and in particular at least 500,000 daltons.
  • the molecular weights of the prepolymer are then e.g. 50 000 to
  • This molar mass range corresponds, for example, to K values of 50 to 300, preferably 70 to 250 (determined according to H. Fikentscher in 5% strength aqueous sodium chloride solution at 25 ° C. and a polymer concentration of 0.1% by weight).
  • Hofmann degradation also referred to as Hofmann rearrangement
  • Hofmann degradation is understood by one skilled in the art to be the degradation of primary acid amides to amines with the loss of one carbon atom (Rompp Online, version 3.12).
  • the amide groups of the prepolymer are reacted with hypohalites under alkaline conditions and then the carbamates formed are decarboxylated by acidification to give amino groups.
  • Such polymers are known, for example, from EP-A-0 377 313 and WO-A-2006/0751 15.
  • the preparation of polymers containing vinylamine groups is extensively treated, for example, in WO-A-2006/0751 15, page 4, line 25 to page 10, line 22 and in the examples on pages 13 and 14, the contents of which are expressly incorporated by reference becomes.
  • the Hofmann degradation is preferably carried out in aqueous solution.
  • 0.1 to 2.0, preferably 0.8 to 1, 1, more preferably 1, 0 molar equivalents of hypohalite are used per molar equivalent of amide group.
  • the strong base is used in amounts of 1.0 to 4.0 molar equivalents per molar equivalent of amide group, preferably 1.5 to 3.0 molar equivalents, more preferably 2.0 to 2.5 molar equivalents.
  • sodium hypochlorite (NaOCl) and sodium hypobromite (NaOBr) are used as hypohalites, with NaOCl being preferred.
  • Alkali hydroxides, alkaline earth hydroxides and alkaline earth oxides are used as the strong base.
  • Hofmann degradation of the polymer occurs e.g. in the temperature range from -15 to 90 ° C, preferably -5 to 40 ° C optionally in the presence of quaternary ammonium salts as a stabilizer to prevent a side reaction of the resulting amino groups with the amide groups of the starting polymer.
  • the aqueous reaction solution is passed into a reactor in which an acid for the decarboxylation of the reaction product is initially introduced.
  • the pH of the reaction product containing vinylamine units is adjusted to a value of 2 to 7.
  • the water-soluble polymer obtained by the Hofmann degradation of an acrylamide- and / or methacrylamide-containing polymer can be used in the process according to the invention.
  • the polymer obtained by the Hofmann degradation of an acrylamide- and / or methacrylamide-containing polymer is additionally postcrosslinked. postcrosslinking
  • the Hofmann degraded polymer can be post-reacted with crosslinkers.
  • Crosslinkers are to be understood as meaning compounds which carry at least two reactive groups which can react with the primary amino groups of the Hofmann product.
  • crosslinkers come e.g. multifunctional epoxides such as bisglycidyl ethers of oligo- or polyethylene oxides or other multifunctional alcohols such as glycerol or sugars, multifunctional carboxylic acid esters, multifunctional isocyanates, polyfunctional acrylic or methacrylic acid esters, multifunctional acrylic or methacrylic acid amides, epichlorohydrin, multifunctional acid halides, multifunctional nitriles, a, ⁇ - Chlorohydrin ethers of oligo- or polyethylene oxides or other multifunctional alcohols such as glycerol or sugars, divinylsulfone, maleic anhydride or ⁇ -halocarboxylic acid, multifunctional haloalkanes in particular ⁇ , ⁇ -dichloroalkanes and carbonates such as ethylene carbonate or propylene carbonate into consideration. Further crosslinkers are described in WO-A-97/25367, pages 8 to 16.
  • Preferred crosslinkers are multifunctional epoxides such as bisglycidyl ethers of oligo- or polyethylene oxides or other multifunctional alcohols such as glycerol or sugars.
  • the crosslinkers are optionally used in amounts of up to 5.0% by weight, preferably from 20 ppm to 2% by weight, based on the polymer obtained by the Hofmann degradation.
  • 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.
  • the preparation of the polymers takes place in the three successive steps: a) Preparation of the prepolymer b) Hofmann degradation of the prepolymer and optionally a postcrosslinking.
  • Preparation of Polymer I a) Preparation of Prepolymer I (70 mol% acrylamide and 30 mol% DADMAC (dialyldimethylammonium chloride) unbranched)
  • Feed 1 Mixture of 253.0 g of a 50% strength by weight acrylamide solution, 60.0 g of distilled water and 0.9 g of sodium hydroxide
  • Feed 2 100 g of a 0.6% strength by weight aqueous bisulfite solution
  • Feed 3 100 g of a 0.88% strength by weight aqueous sodium persulfate solution
  • Feed 1 was metered in over a period of 2 hours while feeds 2 and 3 were metered in over a period of 5 hours. Subsequently, the temperature of the mixture was raised to 85 ° C. After the end of feeds 2 and 3, the batch was held at 85 ° C. for a further hour and then cooled.
  • the following feed was prepared: 234.5 g of a 14.1% strength by weight aqueous NaOCl solution and 20.5 g of distilled water were initially charged in a beaker and cooled to 5 ° C. using an ice bath. With constant stirring, 71.1 g of a 50% strength by weight sodium hydroxide solution were slowly added dropwise so that the temperature could be kept below 10 ° C. This feed was added dropwise from a cooled dropping funnel ( ⁇ 10 ° C) in 80 minutes to the cooled prepolymer sample so that the temperature during the addition was kept in the range 8-10 ° C. Subsequently, the reaction mixture was heated to 20 ° C within 10 minutes and kept at 20 ° C for 30 minutes. Subsequently, 558.1 g of this mixture were added dropwise with constant stirring to 135 g of 37% hydrochloric acid, with a strong evolution of gas was observed.
  • Feed 1 0.5 g of triallylamine was dissolved in 160.0 g of distilled water with addition of
  • Feed 2 120 g of a 0.6% strength by weight aqueous bisulfite solution
  • Feed 3 120.6 g of a 0.88% strength by weight aqueous sodium persulfate solution
  • Feed 1 was added in 3 hours while feeds 2 and 3 were fed in 6 hours. After the end of the addition of feed 2, the temperature was raised to 85 ° C and held for a further hour at this temperature and then cooled.
  • the following feed was prepared: For this purpose, 234.5 of a 14.1% strength by weight aqueous NaOCl solution and 20.5 g of distilled water were placed in a beaker and cooled to 5 ° C. by means of an ice bath. With constant stirring, 71.1 g of a 50% strength by weight sodium hydroxide solution were slowly added dropwise so that the temperature could be kept ⁇ 10 ° C.
  • Feed 1 0.25 g of triallylamine were dissolved in 160.0 g of distilled water with addition of
  • Feed 2 120 g of a 0.6% strength by weight aqueous bisulfite solution
  • Feed 3 120.6 g of a 0.88% strength by weight aqueous sodium persulfate solution
  • Feed 1 was added in 3 hours while feeds 2 and 3 were fed in 6 hours. After the end of feed 2, the temperature was raised to 85 ° C. After the end of feeds 2 and 3, the batch was held at 85 ° C. for a further hour and then cooled.
  • Polymer VIII (not according to the invention) (comparative example corresponds to polymer I from EP Application No. 1 1 170740.2)
  • a thermometer 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 3 16.5 g of a 1 wt .-% 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.
  • Viscosity 10,600 mPas (Brookfield, spindle 7, 50 rpm, room temperature)
  • K value 120 (0.1% solution of the polymer in a 5 wt .-% aqueous
  • Feed 1 The following components were mixed in a beaker:
  • Feed 2 63.5 g of a 1% aqueous solution of 2,2'-azobis (2-amidinopropane) dihydrochloride
  • Feed 3 17.0 g of a 1% 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 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.
  • Viscosity 42,000 mPas (Brookfield, spindle 7, 50 rpm, room temperature) K value 125 (0.1% solution of the polymer in a 5% aqueous saline solution)
  • Polymer X (not according to the invention) (corresponds to polymer III from EP application no. 1 1 170740.2) 400 g of deionized water were introduced into a 2 l 5-necked flask equipped with an anchor stirrer, a thermometer, a descending condenser and a nitrogen inlet. Furthermore, the following feeds were provided:
  • Feed 1 The following components were mixed in a beaker:
  • Feed 2 60.3 g of a 1 wt .-% aqueous solution of 2,2'-azobis (2-amidinopropane) dihydrochloride
  • Feed 3 16.0 g of a 1 wt .-% aqueous solution of 2,2'-azobis (2-amidinopropane) dihydrochloride
  • the initial charge was heated to 63 ° C and the pressure by means of a water jet pump lowered 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. After the end of feed 2, 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.
  • 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.
  • Viscosity 12,000 mPas (Brookfield, spindle 7, 50 rpm, room temperature)
  • K value 1 17 (0.1% solution of the polymer in a 5% strength by weight aqueous
  • Bleached birch sulphate was beaten nip-free at a pulp concentration of 4% in the laboratory pulp until a freeness of 30 ° SR was reached.
  • the opened substance is an optical brightener (Blankophor ® PSG) and a fully digested cationic starch (HICAT ® 5163 A) were then added 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 a residence time of 1 minute.
  • 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 on 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 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.
  • 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.
  • Example 14 15 and 16 (not according to the invention - dosage in the thin material)
  • a 20% strength by weight carbonate pigment slurry (PCC, Syncarb F474 from Omya) was then added to the mixture in each case The added amount of the pigment suspension was adjusted in several preliminary experiments in such a way that the pigment content in the laboratory sheets subsequently formed was about 20%.
  • the pulp suspension was processed two minutes after the pigment addition on a Rapid-Kothen sheet former according to ISO 5269/2 into sheets of a basis weight of 100 g / m 2.
  • the wet leaves were then removed from the screen frame and placed between two suction felts
  • 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 reference time of the paper e within the press arrangement was in each case pressed to a solids content of 50 wt .-% of the wet leaves.
  • 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 moistened paper has a very different wet strength than a damp paper directly after passing through the wire and press section of a paper machine is present.
  • the determination of the initial wet texture strength on the wet paper is carried out in each case according to the Voith process (see M.Schwarz and K. Bechtel "Initial structural strength in sheet formation", in Kliblatt fur Textilfabrikation 131, pages 950-957 (2003) no 16.
  • the wet sheets were pressed on a plastic backing after pressing in the static press and transferred to a cutting pad, and then the test strips were cut out of the sheet with a defined length and width and pressed under constant pressure.
  • four dry contents each were set in the range between 42% and 58% % Dry content determined e
  • Initial wet texture strength was measured on a vertical tensile testing machine with a special clamp. 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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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Paper (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

L'invention concerne un procédé de fabrication de papier, de carton-pâte et de carton. Il consiste à éliminer l'eau d'une pâte à papier contenant une charge, laquelle pâte à papier contient au moins un polymère hydrosoluble, à former une feuille dans la partie toile, puis à presser le papier dans la partie presse. Le ou les polymères hydrosolubles sont dosés pour obtenir une pâte à papier présentant une concentration de matière fibreuse comprise dans la plage allant de 20 à 40 g/l. Puis la pâte à papier est diluée jusqu'à ce que la concentration de matière fibreuse se situe dans la plage allant de 5 à 15 g/l. L'eau est éliminée de la pâte à papier amincie, ce qui permet de former une feuille, et cette feuille est pressée dans la partie presse jusqu'à obtenir une teneur en matières solides supérieure ou égale à G(x) pourcentage en poids et G(x) se calcule selon l'équation G(x) = 48 + (x -15) ∙ 0,4, x représentant la valeur numérique de la teneur en charge du papier, du carton-pâte ou du carton séché (en pourcentage en poids), et G(x) représentant la valeur numérique de la teneur minimale en matières solides (en pourcentage en poids), sur laquelle la feuille est pressée. Le polymère hydrosoluble peut être obtenu par la dégradation d'Hofmann d'un polymère contenant de l'acrylamide et/ou du méthacrylamide et éventuellement par une post-réticulation consécutive.
EP13745049.0A 2012-08-22 2013-07-31 Procédé de fabrication de papier, de carton-pâte et de carton Active EP2888404B1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
PL13745049T PL2888404T3 (pl) 2012-08-22 2013-07-31 Sposób wytwarzania papieru tektury i kartonu
EP13745049.0A EP2888404B1 (fr) 2012-08-22 2013-07-31 Procédé de fabrication de papier, de carton-pâte et de carton

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP12181322 2012-08-22
PCT/EP2013/066120 WO2014029593A1 (fr) 2012-08-22 2013-07-31 Procédé de fabrication de papier, de carton-pâte et de carton
EP13745049.0A EP2888404B1 (fr) 2012-08-22 2013-07-31 Procédé de fabrication de papier, de carton-pâte et de carton

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EP2888404B1 EP2888404B1 (fr) 2018-07-18

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JP (1) JP6238986B2 (fr)
CN (1) CN104583493B (fr)
BR (1) BR112015003272B1 (fr)
CA (1) CA2881868C (fr)
ES (1) ES2690592T3 (fr)
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US9051687B2 (en) 2012-08-22 2015-06-09 Basf Se Production of paper, card and board
FR3016363B1 (fr) * 2014-01-15 2017-05-26 Snf Sas Solution aqueuse de copolymeres cationiques derives d'acrylamide, procede de preparation et utilisation
JP6779976B2 (ja) * 2015-08-06 2020-11-04 ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ 紙の製造方法
JP2018044273A (ja) 2016-09-16 2018-03-22 栗田工業株式会社 紙の製造方法、製紙用添加剤の製造装置、及び紙の製造装置

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JPS6044439B2 (ja) * 1979-07-03 1985-10-03 星光化学工業株式会社 製紙用添加剤
US5239014A (en) * 1988-12-28 1993-08-24 Mitsui Toatsu Chemicals, Inc. Cationic acrylamide polymers and the applications of these polymers
US5039757A (en) * 1988-12-28 1991-08-13 Mitsui Toatsu Chemicals, Inc. Method of manufacturing cationic acrylamide polymers, cationic acrylamide polymers, and the applications of these polymers
JPH0457994A (ja) * 1990-06-26 1992-02-25 Mitsui Toatsu Chem Inc 製紙用添加剤
JP3273534B2 (ja) * 1995-09-14 2002-04-08 星光化学工業株式会社 製紙用添加剤及び製紙方法
US6197919B1 (en) * 1997-05-30 2001-03-06 Hercules Incorporated Resins of amphoteric aldehyde polymers and use of said resins as temporary wet-strength or dry-strength resins for paper
JPH11228641A (ja) * 1997-11-28 1999-08-24 Mitsui Chem Inc 新規な重合体およびその用途
JP2002212898A (ja) * 2000-11-13 2002-07-31 Hymo Corp 濾水性向上方法
JP2003301398A (ja) * 2002-04-08 2003-10-24 Mitsui Chemicals Inc 紙の抄造方法
JP4115869B2 (ja) * 2003-03-31 2008-07-09 ソマール株式会社 紙の製造方法
FR2880901B1 (fr) * 2005-01-17 2008-06-20 Snf Sas Soc Par Actions Simpli Procede de fabrication de papier et carton de grande resistance a sec et papiers et cartons ainsi obtenus
EP2288750B1 (fr) * 2008-05-15 2012-09-05 Basf Se Procédé de production de papier, de carton-pâte, et de carton présentant une résistance à sec élevée
WO2009156274A1 (fr) * 2008-06-24 2009-12-30 Basf Se Production de papier

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CA2881868C (fr) 2020-12-15
JP2015531032A (ja) 2015-10-29
EP2888404B1 (fr) 2018-07-18
BR112015003272B1 (pt) 2021-07-20
CA2881868A1 (fr) 2014-02-27
CN104583493B (zh) 2019-06-07
ES2690592T3 (es) 2018-11-21
CN104583493A (zh) 2015-04-29
BR112015003272A2 (pt) 2017-08-08
WO2014029593A1 (fr) 2014-02-27
JP6238986B2 (ja) 2017-11-29
PL2888404T3 (pl) 2018-12-31

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