WO2005035872A1 - Procede de fabrication de papier, de carton et de carton epais - Google Patents

Procede de fabrication de papier, de carton et de carton epais Download PDF

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Publication number
WO2005035872A1
WO2005035872A1 PCT/EP2004/011023 EP2004011023W WO2005035872A1 WO 2005035872 A1 WO2005035872 A1 WO 2005035872A1 EP 2004011023 W EP2004011023 W EP 2004011023W WO 2005035872 A1 WO2005035872 A1 WO 2005035872A1
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Prior art keywords
monomer
water
insoluble
weight
uncrosslinked
Prior art date
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PCT/EP2004/011023
Other languages
German (de)
English (en)
Inventor
Oliver Birkert
Rainer Blum
Volker Braig
Simon Champ
Dieter Distler
Reinhold J. Leyrer
Volker Schädler
Oliver Koch
Original Assignee
Basf Aktiengesellschaft
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 Aktiengesellschaft filed Critical Basf Aktiengesellschaft
Priority to CA002540117A priority Critical patent/CA2540117A1/fr
Priority to US10/574,344 priority patent/US20070119560A1/en
Priority to EP04765774A priority patent/EP1673506A1/fr
Priority to BRPI0414844-4A priority patent/BRPI0414844A/pt
Publication of WO2005035872A1 publication Critical patent/WO2005035872A1/fr

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Classifications

    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/06—Paper forming aids
    • D21H21/10—Retention agents or drainage improvers
    • 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
    • D21H11/00—Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only
    • D21H11/08—Mechanical or thermomechanical pulp
    • 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
    • D21H17/21—Macromolecular organic compounds of natural origin; Derivatives thereof
    • D21H17/24—Polysaccharides
    • D21H17/28—Starch
    • D21H17/29—Starch 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
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/33—Synthetic macromolecular compounds
    • D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H17/37—Polymers of unsaturated acids or derivatives thereof, e.g. polyacrylates
    • D21H17/375—Poly(meth)acrylamide
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/63—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
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/71—Mixtures of material ; Pulp or paper comprising several different materials not incorporated by special processes
    • 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
    • D21H21/16—Sizing or water-repelling agents
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
    • D21H21/18—Reinforcing agents
    • 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
    • D21H21/50—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 form
    • D21H21/52—Additives of definite length or shape
    • 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
    • D21H23/04—Addition to the pulp; After-treatment of added substances in the pulp

Definitions

  • the invention relates to a process for the production of paper, cardboard and cardboard by adding uncrosslinked organic microparticles and at least one retention agent for the paper stock and dewatering the paper stock on a sieve.
  • Inorganic microparticles such as bentonite or colloidal silicon dioxide brine are used in the manufacture of paper together with cationic polymers to improve the retention and drainage of the paper stock, cf. EP-A-0 235 893, EP-A-0 335 575, EP-A-0 310 959, US-A-4388 150 and WO-A-94/05595.
  • a cationic polymer is metered in in an amount of more than 0.03% by weight, based on dry paper stock, the mixture is then subjected to the action of a shear field, the flakes initially formed being broken down into microfibres, then bentonite is added or silica and dewatered the pulp thus obtained without further action by shear forces.
  • a microparticle system consisting of a cationic polymer and a finely divided inorganic component is metered into the paper stock after the last shear stage before the headbox and then the paper stock is dewatered.
  • the multi-component systems comprising cationic polymers and inorganic microparticles give papers with an improved formation.
  • organic microparticles which can be uncrosslinked or crosslinked and which each contain at least 1% by weight, but mostly at least 5% by weight, of an ionic comonomer in copolymerized form.
  • the particle size of the uncrosslinked, water-insoluble microparticles is below 60 nm, while for the crosslinked microparticles it is less than 750 nm.
  • the organic microparticles are used in paper manufacture together with a high molecular weight ionic polymer as a retention agent.
  • bentonite or finely divided silica can also be used in paper production. Both synthetic organic polymers and polysaccharides can be considered as high molecular weight polymers.
  • binders based on aqueous styrene-acrylate polymer dispersions with an average film-forming temperature below 10 ° C. are known.
  • the polymers can optionally contain up to 1% by weight of a monomer containing acid groups in copolymerized form.
  • the particle size of the dispersed polymer particles is preferably in the range from 100 to 300 nm.
  • the binders are used, for example, for the production of coating compositions such as plastic dispersion plasters, tile adhesives, paints and, in particular, low-emission emulsion paints.
  • aqueous mixtures which contain anionic, crosslinked, polymeric particles with a particle size in the non-swollen state of less than 750 nm, in particular from 25 to 300 nm, and colloidal anionic silica particles.
  • the blends are used in the manufacture of paper together with a cationic polymer as a drainage and retention aid. However, they can also be used as flocculants and for the treatment of wastewater and sludge.
  • microparticle systems which are used in papermaking as an additive to the paper stock are known from EP-A-0 497 030 and EP-A-0 0635 602. From US-A-6 083 997 the production of an anionic nanocomposite is known which is used as a retention and drainage agent in papermaking.
  • water glass is mixed with an anionic polyelectrolyte based on polysulfonates, polyacrylates or polyphosphates and either mixed with silica or the silica is produced in situ.
  • the object of the present invention is to provide a further method for producing paper, cardboard and cardboard using a microparticle system.
  • the object is achieved according to the invention with a process for the production of paper, cardboard and cardboard by adding ionic, water-insoluble, uncrosslinked, organic microparticles and at least one retention agent to a paper material and dewatering the paper material on a sieve if the organic microparticles are water-insoluble , uncrosslinked, organic polymers with an average particle size of less than 500 nm and a copolymerized ionic monomer content of less than 1% by weight or water-insoluble, uncrosslinked, organic microparticles with an average particle size of less than 500 nm and a copolymerized content ionic monomers of at most 10 wt .-%, which can be obtained by polymerizing the monomers in the presence of silica, water glass, bentonite and or mixtures thereof.
  • the specified particle sizes are always the weight-average particle sizes d50. It was determined by dynamic light scattering on a 0.01% by weight dispersion at 23 ° C. using an Autosizer lic from Malvern Instuments, England.
  • the average particle size of the water-insoluble, uncrosslinked, organic polymers is preferably 10 to 100 nm and the content of copolymerized ionic monomers is 0.1 to 0.95% by weight.
  • Microparticles with average particle sizes of the water-insoluble, uncrosslinked, organic polymers of 10 to 80 nm and a content of polymerized ionized see monomers from 0.2 to 0.7 wt .-%.
  • the average particle size of the microparticles is usually in the range from 15 to 50 nm.
  • microparticles of water-insoluble, uncrosslinked, organic polymers contain either at least one anionic monomer or one cationic monomer in copolymerized form.
  • Aqueous dispersions which contain anionic microparticles are known from EP-A-0 810 274 cited in the prior art, page 3, line 3 to page 15, line 59.
  • Suitable water-insoluble, uncrosslinked, organic polymers which carry an ionic charge can be obtained, for example, by free-radical aqueous emulsion polymerization of a monomer mixture
  • the monomers with ionic groups can either give the polymer an anionic charge if, for example, monoethylenically unsaturated monomers with acid groups are used in the polymerization, or a cationic charge if the polymerization is carried out in the presence of monoethylenically unsaturated, basic monomers.
  • the glass transition temperature T g means the limit value of the glass transition temperature which, according to G. Kanig (cf. colloid journal & magazine for polymers, volume 190, page, equation 1), strives with increasing molecular weight. It is determined using the DSC method (Differential Scanning Calorimetry, 20K min, midpoint).
  • the T g values for the homopolymers of most monomers are known, cf. for example Ulimann 's Encyclopedia of Industrial Chemistry, Verlag Chemie Weinheim, 1992, Volume 5, Vol. A21, page 169.
  • the monomer (a) is selected, for example, from at least one C to C 0 alkyl acrylate, C 5 to C 10 alkyl methacrylate, C 5 to C 10 cycloalkyl (meth) acrylate, d to do dialkyl maleate and / or C. to C 10 dialkyl fumarate.
  • Typical monomers (b) are selected, for example, from at least one vinylaromatic monomer and / or an ⁇ , ⁇ -unsaturated carboxylic acid nitrile or dinitrile.
  • D to C n alkyl groups are to be understood as meaning linear or branched alkyl radicals having 1 to n carbon atoms, for example methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, n-hexyl, 2 -Ethylhexyl, n-octyl, isooctyl and n-decyl.
  • C 5 - to C 10 - cycloalkyl groups represent, for example, cyclopentyl, cyclohexyl or cyclooctyl, which can optionally be substituted in each case by 1, 2 or 3 alkyl groups having 1 to 4 carbon atoms.
  • the water-insoluble, uncrosslinked, organic polymer is preferably composed of
  • the sum of the monomer units (a) and (b) is always 100.
  • the monomer (c) is selected, for example, from ⁇ , ⁇ -unsaturated C 3 to C 6 carboxylic acids, ⁇ , ⁇ -unsaturated C 4 to C 8 dicarboxylic acids, their anhydrides, monoethylenically unsaturated alkylsulfonic acids, monoethylenically unsaturated phosphonic acids and / or monoethylenically unsaturated arylsulfonic acids.
  • the monomer (c) can optionally be used in the polymerization in a form partially or completely neutralized with alkali metal, alkaline earth metal and / or ammonium bases.
  • Suitable bases are, for example, sodium hydroxide solution, potassium hydroxide solution, sodium carbonate, potash, sodium hydrogen carbonate, ammonia and amines such as Trimethylamine, propylamine or butylamine, pyridine, piperidine, morpholine and alkanolamines such as monoethanolamine, diethanolamine and triethanolamine, calcium oxide, calcium hydroxide, magnesium oxide and magnesium hydroxide.
  • Preferred monomers of group (c) are acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, maleic anhydride, itaconic acid, itaconic anhydride, vinylsulfonic acid, methallylsulfonic acid, vinylbenzenesulfonic acid, acrylamidoethanesulfonic acid, acrylamido-2-methylpropanesulfonic acid (2-sulfatethyl) (2-sulfatethyl) meth) acrylate.
  • Particularly preferred monomers in this group are acrylic acid, methacrylic acid and acrylamido-2-methylpropanesulfonic acid, mixtures of these monomers and their alkali metal and ammonium salts, in particular their sodium salts.
  • the monomer (c) stands for cationic monomers, this includes, for example, the following monomers: diallyldimethylammonium chloride, di-d-to C 2 -alkylamino-C 2 - to C 4 -alkyl (meth) acrylates and di-d-bis C 2 alkylamino C 2 to C alkyl (meth) acrylamides.
  • the dialkylaminoalkyl (meth) acrylates and dialkylaminoalkyl (meth) acrylamides mentioned are preferably used in the form of salts with mineral acids, organic acids or in quaternized form.
  • the quaternizing agent used is, for example, methyl chloride, ethyl chloride or dimethyl sulfate.
  • Examples of preferred cationic monomers are diallyldimethylammonium chloride and the following salts of sulfuric acid or hydrochloric acid or compounds quaternized with methyl chloride: dimethylaminoethyl methacrylate, dimethylami- noethyl acrylate, dimethylaminopropyl methacrylate, dimethylaminoethyl methacrylamide and dimethylaminopropyl (meth) acrylamide.
  • the polymers can also contain vinylamine units in the form of salts with mineral acids or in quaternized form as cationic groups.
  • Polymers with such groups can be obtained, for example, if the polymerization is carried out in the presence of vinylformamide as a comonomer and then the vinylformamide units present in the copolymer are hydrolyzed to vinylamine units with sulfuric acid.
  • the monomers of group (c) are present in less than 1 part by weight, based on 100 parts by weight of the sum of monomers (a) and (b), in the monomer mixture which is subjected to the polymerization.
  • the monomer mixture preferably contains 0.01 to 0.95, in particular 0.2 to 0.7 parts by weight of at least one monomer (c), based on 100 parts by weight of the monomers (a) and (b).
  • paper is also used to produce such microparticles from water-insoluble, uncrosslinked, organic polymers with an average particle size of less than 500 nm and a content of copolymerized ionic Monomers of up to 10% by weight, which can be obtained by polymerizing the monomers on which these polymers are based in the presence of silica, water glass, bentonite and / or mixtures thereof.
  • the content of monomers of group (c) is, for example, 0.1 to 10, preferably 1.5 to 7 and in particular 2 to 5% by weight.
  • Examples of monomers (a) are vinyl ethers of C - to C 10 -alkanols, branched and unbranched C 3 - to C 10 -olefins, d- to Cio-alkyl acrylates, C 5 - to C 10 -alkyl methacrylates, C 5 - to C ⁇ o-Cycloa! kyl (meth) acrylates, d- to Cio-Dialkylmaleinate and / or d- to do-Dialkylfumarate.
  • Particularly preferred monomers in this group are, for example, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, n-hexyl acrylate, 2-ethylhexalacrylate, n-hexyl methacrylate, 2-ethylhexyl methacrylate, di-n-butyl maleinate and / or di n-butyl fumarate.
  • Suitable monomers (b) are vinyl aromatic monomers such as styrene or ⁇ -methylstyrene and styrene or ⁇ -methylstyrene substituted with 1, 2 or 3 d to C 4 alkyl groups, chlorine and / or methoxy groups.
  • Preferred monomers of group (b) have a glass transition temperature above 80 ° C. Examples include styrene, ⁇ -methylstyrene, o- or p-vinyltoluene, acrylonitrile, methacrylonitrile, maleic acid dinitile, fumaric acid dinitrile or mixtures thereof.
  • the copolymers can optionally include other monoethylenically unsaturated monomers such as acrylamide, methacrylamide, N-vinylpyrrolidone and N-vinylcaprolactam. contain polymerized. The amounts are, for example, 0 to 10 parts by weight, based on 100 parts by weight of the monomers (a) and (b).
  • the monomers are polymerized by the known methods of emulsion polymerization in the presence of initiators which form free radicals under the polymerization conditions, such as peroxides, hydroperoxides, azo compounds or redox initiators, and in the presence of emulsifiers. More detailed explanations can be found in EP-A-0 810 274, pages 4 and 5 already mentioned. However, the polymerization of the monomers in question can also be carried out in the presence of silica, water glass, bentonite and / or mixtures thereof. Aqueous dispersions of ionic, water-insoluble, uncrosslinked, organic polymers with an average particle size below 500 nm are obtained.
  • the polymerization can also be carried out by mixing water, the monomers, a hydrocarbon which is liquid at room temperature, such as hexane, Pentane, isooctane, toluene and / or xylene, and at least one surface-active agent produces an emulsion and the monomers are polymerized in the presence of free radical initiators.
  • a hydrocarbon which is liquid at room temperature, such as hexane, Pentane, isooctane, toluene and / or xylene
  • at least one surface-active agent produces an emulsion and the monomers are polymerized in the presence of free radical initiators.
  • Copolymers which contain copolymerized n-butyl acrylate and styrene in a weight ratio of 1: 1 and 0.2 to 0.7% by weight of methacrylic acid or acrylic acid are particularly preferred.
  • the average molecular weight M w of the polymers is, for example, 500,000 to 5 million, preferably 1 million to 3 million.
  • the ionic, water-insoluble, uncrosslinked, organic microparticles described above are added to the paper stock together with at least one retention agent in the production of paper.
  • the organic microparticles support the action of the retention aid.
  • the organic microparticles are used, for example, in amounts of 0.1 to 1% by weight, preferably in amounts of 0.2 to 0.6% by weight, based on dry paper stock.
  • the amounts of retention aid are, for example, 0.01 to 0.09, preferably 0.02 to 0.04% by weight, based on dry paper stock.
  • All customary polymers known for this purpose can be used as retention agents, for example polyacrylamides, cationic polyacrylamides such as copolymers of acrylamide and dimethylaminoethyl acrylate which is quaternized with methyl chloride, polyvinylamines, polydiallyldimethylammonium chlorides, anionic polyacrylamides such as copolymers of acrylamide and acrylic acid or copolymers from acrylamide and methacrylic acid, also polydialkylaminoalkyl (meth) acrylamides such as polydimethylaminoethyl acrylamide and polydimethylaminoethyl methacrylamide, which are used in protonated or quaternized form, and polyethylene oxides, which can optionally be cationically and / or anionically modified.
  • polyacrylamides cationic polyacrylamides such as copolymers of acrylamide and dimethylaminoethyl acrylate which is quaternized with methyl
  • Polyamidoamines grafted with ethyleneimine and crosslinked with dichlorohydrin ethers of polyethylene glycols are considered as retention agents.
  • Other common retention aids are cationic starches. Such starches are produced, for example, by reacting starch with cationizing agents such as 3-chloro-2-hydroxypropyltrimethylammonium chloride. The degree of substitution of the kattonic starch is, for example, 0.01 to 1, preferably 0.02 to 0.5.
  • the retention aids have a high molecular weight and thus differ essentially from fixatives which are based on the same monomer base.
  • Retention agent is, for example, at least 500,000, preferably> 1 million and mostly> 2 million and in particular> 5 million.
  • All paper qualities can be produced by the process according to the invention, e.g. Cardboard, single / multi-layer cardboard box, single / multi-layer liner, corrugated material, papers for newspaper printing, so-called medium-fine writing and
  • thermomechanical material TMP
  • CTMP chemo-thermomechanical material
  • PGW pressure cut
  • wood pulp as well as sulphite and sulphate pulp.
  • the pulps can be both short-fiber and long-fiber.
  • the process according to the invention is preferably used to produce wood-free grades which give bright white paper products.
  • the papers can optionally contain up to 40% by weight, mostly 5 to 35% by weight, of fillers.
  • Suitable fillers are e.g. Titanium dioxide, natural and precipitated chalk, talc, kaolin, satin white, calcium sulfate, barium sulfate, clay and / or aluminum oxide.
  • Papermaking can also take place in the presence of customary process chemicals.
  • at least one fixing agent, strengthening agent for paper and / or a mass sizing agent can also be added to the paper stock.
  • Suitable fixing agents are, for example, polymers containing vinylamine units, polydi allyldimethylammonium chloride, polyethyleneimines, polyalkylene polyamines and / or dicyandiamide polymers.
  • the molecular weight M w of the fixing agent is, for example, up to 300,000 and is usually in the range from 50,000 to 1 million.
  • water-insoluble, uncrosslinked, organic polymers with an average particle size of less than 500 nm and a copolymerized ionic monomer content of less than 1% by weight together with at least one cationic, anionic, amphoteric or neutral synthetic organic polymer and or cationic starch dosed as a retention aid to the paper stock before the last shear stage before the headbox.
  • water-insoluble, uncrosslinked, organic polymers having an average particle size of less than 500 nm and a copolymerized ionic monomer content of less than 1% by weight are metered into the paper stock together with at least one retention agent and a finely divided inorganic component after the last shear step before the headbox.
  • the procedure can also be such that the retention agent before the last shear stage before the headbox and water-insoluble, uncrosslinked, organic polymers with an average particle size of less than 500 nm and a copolymerized ionic monomer content of less than 1% by weight alone or dosed together with the finely divided inorganic component after the last shear step before the headbox.
  • combinations of a polymeric organic retention agent and such water-insoluble, uncrosslinked, organic microparticles with an average particle size of less than 500 nm and a content of copolymerized ionic monomers of at most 10% by weight can be used in the production of paper can be obtained by polymerizing the monomers in the presence of silica, water glass, bentonite and / or mixtures thereof.
  • water-insoluble, uncrosslinked, organic polymers with an average particle size of less than 500 nm and a copolymerized ionic monomer content of less than 1% by weight are used together with polymers of monoethylenically unsaturated carboxylic acids, for example homopolymers of acrylic acid or methacrylic acid, copolymers of acrylic acid and methacrylic acid, copolymers of acrylic acid and maleic acid and / or copolymers of methacrylic acid and maleic acid. These polymers may optionally contain other monomers such as acrylamide and / or methacrylamide in copolymerized form.
  • the molecular weight M w of this group of polymers is, for example, 2,000 to 200,000 and is preferably in the range from 5,000 to 110,000. These polymers bring about an increase in the charge of the microparticles or a pre-aggregation of the microparticles and thus an improved retention in papermaking.
  • the water-insoluble, uncrosslinked, organic polymers with a copolymerized ionic monomer content of less than 1% by weight are used together with inorganic microparticles from the group bentonite, colloidal silica, phyllosilicates and / or f one-part calcium carbonate.
  • the particle size of the inorganic substances mentioned is, for example, 1 nm to 100,000 nm, preferably 5 to 500 nm.
  • This particle size information relates in each case to the inorganic substances dispersed in water.
  • 0.01 to 10, preferably 0.05 to 2 and in particular 0.1 to 1.2 parts by weight of at least one type of inorganic microparticle are used per part by weight of the organic microparticles.
  • organic microparticles with a group (c) monomer content of up to at most 10% by weight are produced by polymerizing the monomers in the presence of silica, water glass and / or bentonite, - based on the weight of the resulting microparticles - Appropriate amounts of inorganic microparticles used in the polymerization.
  • Bentonite, colloidal silica, silicates and / or calcium carbonate are examples of inorganic components of the microparticle system.
  • Colloidal silica is to be understood as meaning products based on silicates, for example silica microgel, silica sol, polysilicates, aluminum silicates, borosilicates, polyborosilicates, clay or zeolites.
  • Calcium carbonate can be used, for example, in the form of chalk, ground calcium carbonate or precipitated calcium carbonate as the inorganic component of the microparticle system.
  • Bentonite is generally understood to mean layered silicates that are swellable in water.
  • clay mineral montmorrillonite and similar clay minerals such as nontronite, hectorite, saponite, sauconite, beidellite, allevardite, illite, halloysite, attapulgite and sepiolite.
  • layered silicates are preferably activated before their use, ie converted into a form which is more swellable in water, by treating the layered silicates with an aqueous base, such as aqueous solutions of sodium hydroxide solution, potassium hydroxide solution, soda ash or potash. Bentonite in the form treated with sodium hydroxide solution is preferably used as the inorganic component of the microparticle system.
  • the platelet diameter of the bentonite dispersed in water in the form treated with sodium hydroxide solution is, for example, 1 to 2 ⁇ , the thickness of the platelets is approximately 1 nm.
  • the bentonite has a specific surface area of 60 to 800 m 2 / g.
  • Typical bentonites are described, for example, in EP-B-0235893.
  • bentonite is typically added to the cellulose suspension in the form of an aqueous bentonite slurry. This bentonite slurry can contain up to 10% by weight of bentonite.
  • the slurries normally contain approx. 3 - 5% by weight bentonite.
  • Products from the group of silicon-based particles, silica microgels, silica sols, aluminum silicates, borosilicates, polyborosilicates or zeolites can be used as colloidal silica. These have a specific surface area of 50-1000 m 2 / g and an average particle size distribution of 1-250 nm, normally in the range 40-100 nm. The production of such components is described, for example, in EP-A-0041056, EP-A- 0185068 and US-A-5176891.
  • Clay or kaolin is a water-containing aluminum silicate with a platelet structure.
  • the crystals have a layer structure and an aspect ratio (diameter to thickness ratio) of up to 30: 1.
  • the particle size is at least 50% less than 2 mm.
  • Natural calcium carbonate ground calcium carbonate, GCC
  • precipitated calcium carbonate precipitated calcium carbonate, PCC
  • GCC is manufactured by grinding and classifying processes using grinding aids. It has a particle size of 40 - 95% less than 2 mm, the specific surface is in the range of 6 - 13 m 2 / g.
  • PCC is made by introducing carbon dioxide into calcium hydroxide solution. The average particle size is in the range of 0.03 - 0.6 mm, the specific surface can be strongly influenced by the choice of the precipitation conditions. It is in the range of 6 - 13 m 2 / g.
  • the process according to the invention gives papers with particularly good strength.
  • the retention of fillers is improved compared to known processes.
  • FPAR First Pass Ash Retention
  • a dynamic drainage jar was set to 900 rpm and then filled with 500 ml of fabric suspension (8g / l). After 10 seconds of stirring, x% of a polyacrylamide solution was added, the mixture was stirred at 900 rpm for 20 seconds and then reduced to 400 rpm. Then x%, based on the substance, of the anionic flocculation component was added as a dilute dispersion and the mixture was stirred at 400 rpm for a further 15 seconds.
  • the dead volume of 25 ml was removed and discarded. 100 ml were collected in a volumetric flask and aspirated through a weighed white band filter. The filters were dried in a drying cabinet at 120 ° C, weighed and ashed at 550 ° C. The filler content was calculated from the residue depending on the filler composition according to the following relationship (1 - (filler in the filtrate, filler in the sample)) x100
  • Dry tear length, wet tear length Device: BXC-FR2.5TN.D09-002 from Zwick / Roell
  • colloidal silica with an average particle size of 5 to 10 nm and a solids content of 10% by weight.
  • Bentonite Commercially available swellable clay of the type montmorrillonite with a solids content of 90% and 10% water (see US-A-4 306 781), available under the trademark Microfloc® XFB from BASF Aktiengesellschaft Fixing agent A
  • Copolymer of acrylic acid and maleic acid with a molecular weight M w of 70,000 and a solids content of 45% available under the name Sokalan® CP45 from BASF Aktiengesellschaft
  • Solvitose® BPN Cold soluble starch with a solids content of 95%, available from Avebe.
  • the solids content of the dispersion was about 33%.
  • the copolymer contained 0.6% methacrylic acid in a polymerized form.
  • the light transmission of a 0.01% solution was 99%.
  • the weight-average particle size d50 was 61 nm.
  • the pH of the dispersion was 4.0 and the glass transition temperature Tg of the polymer was 23 ° C.
  • the monomer emulsion (feed 1) and the initiator solution (feed 2) were added to the polymerization vessel at the same time, starting at 180 min, and maintaining the temperature.
  • the temperature of 85 ° C. was maintained for a further 30 minutes, the reaction mixture was then cooled to room temperature and filtered through a filter with a mesh size of 45 ⁇ m. The pH was then adjusted to 4.0 by adding 3% aqueous sodium hydroxide solution.
  • the solids content of the dispersion was approximately 16%.
  • the copolymer contained 0.95% of polymerized methacrylic acid.
  • the weight-average particle size d50 was 76 nm.
  • the pH of the dispersion was 4.0 and the glass transition temperature Tg of the polymer was 31 ° C.
  • the monomer mixture (feed 1) and the initiator solution (feed 2) were added to the polymerization vessel at the same time, starting at 180 min and maintaining the temperature, within 210 min.
  • the 85 ° C. was maintained for a further 30 min, the resulting dispersion was then cooled to room temperature and filtered through a filter with a mesh size of 400 ⁇ m. The pH was then adjusted to 6.7 by adding 3% aqueous sodium hydroxide solution.
  • Feed 2 40 g sodium persulfate solution (7% ⁇ g, aqueous)
  • the solids content of the dispersion was about 25%.
  • the copolymer contained 3% copolymerized methacrylic acid.
  • the weight-average particle size d50 was 68 nm.
  • the pH of the dispersion was 6.7.
  • the glass transition temperature Tg of the polymer was 21 ° C.
  • the dispersion was divided. A portion of the dispersion was then added with a 3% strength aqueous sodium hydroxide solution until the pH was 10.5. An aqueous dispersion with a solids content of approximately 23.5% was obtained.
  • the effectiveness of the polymers described above as a retention agent was first assessed on a fabric model consisting of a 70/30 mixture of pine sulfate / birch sulfate with 70% Schopper Riegler 33 and 30% Schopper Riegler 70, 30% Hydrocarb OG (based on pulp) and 0.6% solvitose ® BPN (based on pulp) tested according to the test instructions given above.
  • the pulp had a consistency of 8 g / l, the pH of the pulp was 6.7.
  • the type and amount of the starting materials and the results are given in Tables 1 to 4.
  • a wood-free paper stock with a stock concentration of 8 g / l and a pH of 6.7 was used as the fabric model. 0.1% (commercial goods) of fixative A, based on dry paper stock, were mixed in, the pulp was then added, the amounts of cationic polymer A and microparticles given in Table 5 were added, the components were thoroughly mixed and the pulp was dewatered as above described. The results are shown in Table 5.
  • Example 7 was repeated with the exception that the use of fixing agent A was dispensed with. The results are shown in Table 5.
  • a wood-free paper stock with a stock concentration of 8 g / l and a pH of 6.7 was used as the fabric model.
  • Example 9 was repeated with the exception that the use of anionic polymer A was omitted. The results are shown in Table 6.
  • Example 1 was repeated with the exceptions that 0.4 kg of commercial goods of cationic polymer A were used per t of paper and 2 kg of polymer 1 per t of paper. Ash retention (FPAR) was 89%.
  • Example 1 was repeated with the exception that 0.4 kg of commercial goods of the cationic polymer A per t of paper and 2 kg of an anionically emulsified styrene latex with a particle size of 30 nm and a solids content of 33% were used. Ash retention (FPAR) was 81%.

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Abstract

L'invention concerne un procédé de fabrication de papier, de carton et de carton épais par addition (i) d'au moins un agent de rétention et (ii) de microparticules organiques, ioniques, non-réticulées, insolubles dans l'eau, présentant une granulométrie moyenne inférieure à 500 nm et une teneur en monomères ioniques, introduits par polymérisation, inférieure à 1 % en poids, ou de microparticules organiques, non-réticulées, insolubles dans l'eau, présentant une granulométrie moyenne inférieure à 500 nm et une teneur maximale en monomères ioniques, introduits par polymérisation, de 10 % en poids, pouvant être obtenues par polymérisation des monomères en présence de silice, de verre soluble, de bentonite et/ou de mélanges de celles-ci, à de la pâte à papier, et déshydratation de la pâte à papier sur un tamis.
PCT/EP2004/011023 2003-10-06 2004-10-02 Procede de fabrication de papier, de carton et de carton epais WO2005035872A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
CA002540117A CA2540117A1 (fr) 2003-10-06 2004-10-02 Procede de fabrication de papier, de carton et de carton epais
US10/574,344 US20070119560A1 (en) 2003-10-06 2004-10-02 Method for producing paper, paperboard and cardboard
EP04765774A EP1673506A1 (fr) 2003-10-06 2004-10-02 Procede de fabrication de papier, de carton et de carton epais
BRPI0414844-4A BRPI0414844A (pt) 2003-10-06 2004-10-02 processo para produção de papel, papelão e cartolina

Applications Claiming Priority (2)

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DE10346750.5 2003-10-06
DE10346750A DE10346750A1 (de) 2003-10-06 2003-10-06 Verfahren zur Herstellung von Papier, Pappe und Karton

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CN (1) CN1863967A (fr)
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CA (1) CA2540117A1 (fr)
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US8039550B2 (en) 2005-05-20 2011-10-18 Akzo Nobel N.V. Process for preparing a polymer dispersion and a polymer dispersion
CN112726275A (zh) * 2020-12-25 2021-04-30 玖龙纸业（东莞）有限公司 一种造纸用助留剂及其应用

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FR2869626A3 (fr) * 2004-04-29 2005-11-04 Snf Sas Soc Par Actions Simpli Procede de fabrication de papier et carton, nouveaux agents de retention et d'egouttage correspondants, et papiers et cartons ainsi obtenus
DE102004038132B3 (de) * 2004-08-05 2006-04-13 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Papiererzeugnis mit erhöhter relativer Nassreißfestigkeit und Weichheit, Verfahren zu dessen Herstellung sowie dessen Verwendung
US20100000693A1 (en) * 2006-10-31 2010-01-07 Basf Se Method for producing a multi layer fiber web from cellulose fibers
US7854110B2 (en) * 2006-11-16 2010-12-21 Siemens Energy, Inc. Integrated fuel gas characterization system
CN101589197B (zh) * 2006-11-23 2011-09-21 荷兰应用科学研究会(Tno) 生物聚合物用作湿强度添加剂
BRPI0909931B1 (pt) 2008-06-20 2020-04-07 Int Paper Co composição para uso em fabricação de papel, método para fabricar uma folha de gravação, método para formar uma imagem e folha de gravação
CA2814988A1 (fr) * 2010-10-29 2012-05-03 Buckman Laboratories International, Inc. Fabrication de papier et produits fabriques ainsi avec microparticules polymeres reticulees ioniques
BR112014014398A2 (pt) * 2011-12-15 2017-06-13 Innventia Ab sistema e processo para melhorar papel e papelão
US20150041090A1 (en) * 2013-08-09 2015-02-12 Solenis Technologies, L.P. Polyethylene oxide treatment for drainage agents and dry strength agents
CN109594413A (zh) * 2018-11-26 2019-04-09 苏州恒康新材料有限公司 一种用于提高纸张抗张强度的造纸助剂

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EP0484617A1 (fr) * 1990-06-11 1992-05-13 Cytec Technology Corp. Microperles de polymères anioniques et amphotères réticulés
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US8039550B2 (en) 2005-05-20 2011-10-18 Akzo Nobel N.V. Process for preparing a polymer dispersion and a polymer dispersion
US8741999B2 (en) 2005-05-20 2014-06-03 Akzo Nobel Coatings International N.V. Process for preparing a polymer dispersion and a polymer dispersion
CN112726275A (zh) * 2020-12-25 2021-04-30 玖龙纸业（东莞）有限公司 一种造纸用助留剂及其应用

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US20070119560A1 (en) 2007-05-31
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BRPI0414844A (pt) 2006-11-21
EP1673506A1 (fr) 2006-06-28

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