EP2888404B1 - Procédé de fabrication de papier, de carton-pâte et de carton - Google Patents

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

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Publication number
EP2888404B1
EP2888404B1 EP13745049.0A EP13745049A EP2888404B1 EP 2888404 B1 EP2888404 B1 EP 2888404B1 EP 13745049 A EP13745049 A EP 13745049A EP 2888404 B1 EP2888404 B1 EP 2888404B1
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EP
European Patent Office
Prior art keywords
polymer
paper
acrylamide
water
methacrylamide
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EP13745049.0A
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German (de)
English (en)
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EP2888404A1 (fr
Inventor
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
    • D21H17/38—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 paperboard comprising dewatering a filler-containing paper stock containing at least one water-soluble polymer which is obtainable by the Hofmann degradation of an acrylamide and / or methacrylamide-containing polymer, with sheet formation in the wire section and subsequent 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.
  • 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.
  • the older registration WO 2012/175392 teaches the use of acrylamide-based amphoteric copolymers obtainable by copolymerizing 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.
  • 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. 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, 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.
  • 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 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.
  • 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.
  • 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 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. Very particularly preferably, the addition takes place after the addition of the dry strength agent, 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 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 a 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 ⁇ 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, synthetic cationic or anionic retention aids 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 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 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, 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 optionally a 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 proportions of 20 to 90 mol%, more preferably in proportions of 30 to 80 mol% in copolymerized Form included.
  • 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 N, N-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 phosphonic acids and
  • 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-tetramethylbutyl (meth) acrylamide, ethylhexyl (meth) acrylamide, N, N-dimethylacrylamide, N, N-dimethylmethacrylamide, N-vinylformamide, N-vinylacetamide, N-methyl-N-vinylacetamide and mixtures thereof.
  • 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).
  • 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 ie at least one sulfonic acid group, phosphonic acid group or carboxylic acid group.
  • 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 hydrogencarbonate, potassium hydrogencarbonate, 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 N, N-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 in the polymer is stable under the reaction conditions of Hofmann degradation, (monomers b) copolymerized, based on the total moles of 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 DADMAC is not included (monomers c).
  • Such 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 achieved, for example, with methylenebisacrylamide, triallylamine, tetraallylammonium chloride or N, N'-divinylpropyleneurea.
  • the monomer mixture used to prepare the prepolymer has the following composition: 30 to 95 mol% Acrylamide and / or methacrylamide (monomers a) and 5 to 70 mol% one or more monoethylenically unsaturated monomers whose corresponding structural unit in the polymer is stable under the reaction conditions of Hofmann degradation and / or diallyldimethylammonium chloride (monomers b) and up to 1.0 wt .-% based on the total weight of the monomers a and b of one or more compounds having two or more ethylenically unsaturated radicals whose corresponding structural units in the polymer are stable under the reaction conditions of Hofmann degradation.
  • the monomer mixture used to prepare the prepolymer has the following composition: 50 to 90 mol% Acrylamide and / or methacrylamide and 10 to 50 mol% one or more monoethylenically unsaturated monomers whose corresponding structural unit in the polymer is stable under the reaction conditions of Hofmann degradation and / or diallyldimethylammonium chloride (monomers b) and up to 1.0 wt .-% based on the total weight of the monomers a and one or more compounds having two or more ethylenically unsaturated radicals whose corresponding structural units in the polymer are stable under the reaction conditions of Hofmann degradation.
  • a monomer mixture of the following composition is preferred for the production of the prepolymer: 60 to 80 mol% Acrylamide and / or methacrylamide (monomer a) 20 to 40 mol% 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.
  • 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 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.
  • 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, for example, ascorbic acid / iron (II) sulfate / sodium peroxodisulfate, tert-butyl hydroperoxide / sodium disulfite, tert-butyl hydroperoxide / sodium hydroxymethanesulfinate, H 2 O 2 / 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. 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 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 10 million, preferably 100,000 to 5 million (as determined by light scattering).
  • 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 for example made EP-A-0 377 313 and WO-A-2006/075115 known.
  • the preparation of polymers containing vinylamine groups is described, for example, in WO-A-2006/075115 , 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.
  • the Hofmann degradation is preferably carried out in aqueous solution.
  • 0.1 to 2.0, preferably 0.8 to 1.1, particularly preferably 1.0 molar equivalents of hypohalite are used per mole 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 of -15 to 90 ° C, preferably -5 to 40 ° C optionally in the presence of quaternary ammonium salts as a stabilizer to prevent side reaction of the resulting amino groups with the amide groups of the starting polymer.
  • the aqueous reaction solution is passed into a reactor in which an acid is introduced for the decarboxylation of the reaction product.
  • the pH of the reaction product containing vinylamine units is 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.
  • the Hofmann degraded polymer can be post-reacted with crosslinkers.
  • Crosslinkers are compounds which carry at least two reactive groups which can react with the primary amino groups of the Hofmann product.
  • Suitable crosslinkers are, for example, multifunctional epoxides, such as bisglycidyl ethers of oligo- or polyethyleneoxides or other multifunctional alcohols, such as glycerol or sugars, multifunctional carboxylic acid esters, polyfunctional isocyanates, polyfunctional acrylic or methacrylic acid esters, polyfunctional 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.
  • Other crosslinkers are in WO 97/25367 , Pages 8 to 16 described.
  • 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.
  • a 2 l glass apparatus with anchor stirrer, reflux condenser, internal thermometer and nitrogen inlet tube was charged with 295.5 g of distilled water, 189.6 g of a 65% strength by weight aqueous solution of DADMAC and 1.0 g of 75% strength by weight phosphoric acid.
  • the pH was adjusted to 3.
  • the template was deoxygenated while being heated to the polymerization temperature of 75 ° C.
  • 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 100g of a 0.6% wt .-% aqueous bisulfite solution
  • Feed 3 100g of a 0.88% 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 placed in a beaker and cooled to 5 ° C. using an ice bath. While stirring continuously, 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. Finally, the pH of the resulting solution was adjusted to pH 3.5 with 10.0 g of 25% strength by weight sodium hydroxide solution.
  • Feed 1 0.5 g of triallylamine was dissolved in 160.0 g of distilled water with the addition of 0.75 g of 75 wt .-% phosphoric acid. Subsequently, 253.0 g of a 50 wt .-% strength acrylamide solution was added and the pH was adjusted to 4.0 by means of 0.4 g of 25 wt .-% sodium hydroxide solution.
  • Feed 2 120 g of a 0.6 wt .-% aqueous bisulfite solution
  • Feed 3 120.6 g of a 0.88% 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 wt .-% aqueous NaOCl solution and 20.5 g of distilled water were placed in a beaker, and cooled by means of an ice bath to 5 ° C. 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 2 120 g of a 0.6 wt .-% aqueous bisulfite solution
  • Feed 3 120.6 g of a 0.88% by weight aqueous sodium persulfate solution
  • Polymer VII (85 mol% acrylamide and 15 mol% acrylic acid)
  • Polymer VIII (not according to the invention) (comparative example corresponds to polymer I from EP application no. 11170740.2)
  • Feed 1 In a beaker, the following components were mixed: 250 g of 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-amide inopropane) di hydrochloride
  • Feed 3 16.5 g of a 1 wt .-% aqueous solution of 2,2'-azobis (2-amide inopropane) -di hydrochloride
  • 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.
  • Feed 1 In a beaker, the following components were mixed: 250 g of 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.
  • Polymer X (not according to the invention) (corresponds to polymer III from EP application no. 11170740.2)
  • Feed 1 In a beaker, the following components were mixed: 250 g of 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-amide inopropane) -di hydrochloride
  • Feed 3 16.0 g of a 1 wt .-% aqueous solution of 2,2'-azobis (2-amide inopropane) -di hydrochloride
  • 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.
  • 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 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)
  • 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 reference time of the papers within the press arrangement, in each case up to a solids content of 50% by weight of the wet leaves was pressed.
  • 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 initial wet texture strength at 50% dry content was determined using an adjustment method described in the above reference.
  • 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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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Paper (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Claims (8)

  1. Procédé pour la fabrication de papier, carton et carton épais, comprenant l'égouttage d'une pâte à papier contenant une charge, qui contient au moins un polymère hydrosoluble, avec formation de la feuille sur la table de formation et pressage subséquent du papier dans la section des presses, dans lequel on ajoute par addition dosée ledit au moins un polymère hydrosoluble à une pâte à papier ayant une teneur en matière fibreuse dans la plage de 20 à 40 g/l, ensuite on dilue la pâte à papier jusqu'à une teneur en matière fibreuse dans la plage de 5 à 15 g/l, on égoutte la pâte à papier diluée, avec formation d'une feuille, et dans la section des presses on presse la feuille jusqu'à une teneur en matière solide de G(x) % en poids ou plus et G(x) se calcule selon G x = 48 + x − 15 ⋅ 0,4
    Figure imgb0008
    x représentant la valeur numérique de la teneur en charge du papier, carton ou carton épais, sec (en % en poids) et
    G(x) représente la valeur numérique de la teneur minimale en matière solide (en % en poids) jusqu'à laquelle la feuille est pressée,
    le polymère hydrosoluble pouvant être obtenu par la dégradation d'Hofmann d'un polymère contenant de l'acrylamide et/ou du méthacrylamide et éventuellement une post-réticulation subséquente,
    étant entendu que dans le cas d'une teneur en charge de 15 % en poids ou moins on effectue le pressage dans la section des presses jusqu'à au moins une teneur en matière solide de 48 % en poids,
    le polymère hydrosoluble étant ajouté à la pâte à papier ayant une teneur en matière fibreuse dans la plage de 20 à 40 g/l et avant l'addition d'une charge.
  2. Procédé selon la revendication 1, caractérisé en ce que la pâte à papier contient comme matière fibreuse exclusivement une matière fibreuse qui présente un degré de raffinage de ≤ 30° SR.
  3. Procédé selon l'une quelconque des revendications 1 et 2, caractérisé en ce qu'on ajoute le polymère hydrosoluble 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 polymère contenant de l'acrylamide et/ou du méthacrylamide peut être obtenu par polymérisation radicalaire d'un mélange de monomères comprenant
    a) de l'acrylamide et/ou du méthacrylamide
    b) éventuellement un ou plusieurs monomères à insaturation monoéthylénique, dont le motif structural correspondant dans le polymère est stable dans les conditions réactionnelles de la dégradation d'Hofmann, et/ou du chlorure de diallyldiméthylammonium,
    c) éventuellement un ou plusieurs composés comportant deux ou plus de deux radicaux à insaturation éthylénique, et dont les motif structuraux correspondants dans le polymère sont stables dans les conditions réactionnelles de la dégradation d'Hofmann.
  5. Procédé selon l'une quelconque des revendications 1 à 4, caractérisé en ce que le polymère contenant de l'acrylamide et/ou du méthacrylamide peut être obtenu par polymérisation radicalaire d'un mélange de monomères constitué de 50 à 90 % en moles d'acrylamide et/ou de méthacrylamide et 10 à 50 % en moles d'un ou de plusieurs monomères à insaturation monoéthylénique, dont le motif structural correspondant dans le polymère est stable dans les conditions réactionnelles de la dégradation d'Hofmann, et/ou de chlorure de diallyldiméthylammonium,
    ainsi que de jusqu'à 1,0 % en poids, par rapport au poids total des monomères a et b, d'un ou de plusieurs composés comportant deux ou plus de deux radicaux à insaturation éthylénique, dont les motifs structuraux correspondants dans le polymère sont stables dans les conditions réactionnelles de la dégradation d'Hofmann.
  6. Procédé selon l'une quelconque des revendications 1 à 5, caractérisé en ce que le polymère contenant de l'acrylamide et/ou du méthacrylamide peut être obtenu par polymérisation radicalaire d'un mélange de monomères constitué de : 60 à 80 % en moles d'acrylamide et/ou de méthacrylamide (monomère a) 20 à 40 % en moles de chlorure de diallyldiméthylammonium (monomère b)
    ainsi qu'éventuellement de 0,001 à 0,1 % en poids, par rapport à la quantité totale de monomère a et monomère b, d'un ou de plusieurs composés choisis parmi les méthylènebisacrylamides, la triallylamine, le chlorure de tétraallylammonium, la N,N'-divinyl-propylène-urée.
  7. Procédé selon l'une quelconque des revendications 1 à 6, caractérisé en ce que le polymère hydrosoluble peut être obtenu par la dégradation d'Hofmann d'un polymère contenant de l'acrylamide et/ou du méthacrylamide et post-réticulation subséquente avec un agent de réticulation choisi parmi des époxydes multifonctionnels, des esters d'acides carboxyliques multifonctionnels, des isocyanates multifonctionnels, des esters d'acide acrylique ou d'acide méthacrylique multifonctionnels, des amides d'acide acrylique ou d'acide méthacrylique multifonctionnels, l'épichlorhydrine, des halogénures d'acides multifonctionnels, des nitriles multifonctionnels, des α,ω-chlorhydrinéthers d'oligo-oxyéthylènes ou de polyoxyéthylènes ou d'autres alcools multifonctionnels, la divinylsulfone, l'anhydride maléique ou des chlorures d'acides ω-halogénocarboxyliques, des carbonates et halogéno-alcanes multifonctionnels.
  8. Procédé selon l'une quelconque des revendications 1 à 7 pour la fabrication de papier, carton et carton épais, ayant une teneur en charge de 17 à 32, caractérisé en ce qu'on effectue le pressage dans la section des presses jusqu'à au moins une teneur en matière solide dans la plage de 49 à 55.
EP13745049.0A 2012-08-22 2013-07-31 Procédé de fabrication de papier, de carton-pâte et de carton Active EP2888404B1 (fr)

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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
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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
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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
EP2888404A1 (fr) 2015-07-01
PL2888404T3 (pl) 2018-12-31

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