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
  • D21H17/63—Inorganic compounds
  • D21H17/67—Water-insoluble compounds, e.g. fillers, pigments
  • D21H17/68—Water-insoluble compounds, e.g. fillers, pigments siliceous, e.g. clays
• • D—TEXTILES; PAPER
  • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
  • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
  • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
  • D21H17/20—Macromolecular organic compounds
  • D21H17/33—Synthetic macromolecular compounds
  • D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • D21H17/37—Polymers of unsaturated acids or derivatives thereof, e.g. polyacrylates
  • D21H17/375—Poly(meth)acrylamide
• • D—TEXTILES; PAPER
  • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
  • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
  • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
  • D21H17/20—Macromolecular organic compounds
  • D21H17/33—Synthetic macromolecular compounds
  • D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • D21H17/41—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
  • D21H17/455—Nitrogen-containing groups comprising tertiary amine or being at least partially quaternised
• • D—TEXTILES; PAPER
  • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
  • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
  • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
  • D21H17/20—Macromolecular organic compounds
  • D21H17/33—Synthetic macromolecular compounds
  • D21H17/46—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
  • D21H17/54—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen
  • D21H17/55—Polyamides; Polyaminoamides; Polyester-amides
• • D—TEXTILES; PAPER
  • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
  • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
  • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
  • D21H17/20—Macromolecular organic compounds
  • D21H17/33—Synthetic macromolecular compounds
  • D21H17/46—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
  • D21H17/54—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen
  • D21H17/56—Polyamines; Polyimines; Polyester-imides
• • D—TEXTILES; PAPER
  • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
  • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
  • D21H23/00—Processes or apparatus for adding material to the pulp or to the paper
  • D21H23/76—Processes or apparatus for adding material to the pulp or to the paper characterised by choice of auxiliary compounds which are added separately from at least one other compound, e.g. to improve the incorporation of the latter or to obtain an enhanced combined effect
  • D21H23/765—Addition of all compounds to the pulp

Definitions

• the present invention has for its object to provide a process for the production of paper and cardboard, according to which one can produce papers with good formation and surface quality and which are well printable.
• All paper grades can be produced using these processes, e.g. Papers for newspaper printing (high-pressure / offset printing), so-called medium-fine writing and printing papers, gravure printing papers and also lightweight coating base papers. Wood pulp, thermomechanical material (TMP), chemo-thermomechanical material (CTMP), pressure sanding (PGW), and sulphite and sulphate pulp, which can be short or long fibers, are used as the main raw material components for the production of such papers.
• TMP thermomechanical material
• CTMP chemo-thermomechanical material
• PGW pressure sanding
• sulphite and sulphate pulp which can be short or long fibers
• filler-free and filler-containing papers can be produced by the process according to the invention.
• the filler content in the paper can be up to a maximum of 30% by weight and is preferably in the range from 5 to 25% by weight of filler.
• Suitable fillers are, for example, clay, kaolin, chalk, talc, titanium dioxide, calcium sulfate, barium sulfate, aluminum oxide, satin white or mixtures of the fillers mentioned.
• an aqueous slurry of fiber and filler is first prepared.
• the concentration of the aqueous pulp is initially 2.5 to 5% by weight and includes both the content of fibrous materials, fine materials and fillers.
• a pulp whose substance concentration is in the range from 2.5 to 5% by weight is added in process section a) from 0.1 to 2% by weight, preferably from 0.5 to 1.5% by weight. an activated bentonite. Then the paper stock concentration is adjusted to a value of 0.3 to 2% by weight by dilution with water.
• Bentonite is generally understood to mean layered silicates which are swellable in water. These are primarily the clay mineral montmorillonite and similar clay minerals, e.g. Nontronite, hectorite, saponite, Volkonskoit, sauconite, beidellite, allevardite, illite, halloysite, attapulgite and sepiolite.
• the layered silicate must be swellable in water and, in extreme cases, be able to disintegrate into its elementary layers through this swelling. If this property is not inherent, the layered silicate must be activated before use, i.e. converted to its water-swellable sodium, potassium, ammonium or hydroxonium form. Such activation of the bentonites is achieved by treating the layered silicates with the appropriate bases or soda or potash.
• a sodium bentonite is preferably used for the application according to the invention.
• the activated bentonite is added to the aqueous pulp, based on dry paper stock, in an amount of 0.1 to 2, preferably 0.5 to 1.5% by weight.
• the bentonite can be added either in solid form or, preferably, in the form of an aqueous slurry.
• the cationic polyelectrolytes of component b) have a high charge density.
• These compounds are, for example, the following polymers: polyethyleneimines, polyamines with a molecular weight of more than 50,000, polyamidoamines modified by grafting ethyleneimine, polyamidoamines, polyetheramines, polyvinylamines, modified polyvinylamines, polyalkylamines, polyvinylimidazoles, polyvinylpyridines, polyvinylimidazolines, Polyvinyltetrahydropyridines, polydialkylaminoalkyl vinyl ethers, polydialkylaminoalkyl (meth) acrylates, polydialkylaminoalkyl (meth) acrylamides in protonated or quaternized form.
• Other suitable compounds of this type are polydiallyldialkylammonium halides, in particular polydiallyldimethylammonium chloride.
• the polyelectrolytes are
• Polyethyleneimines are prepared, for example, by polymerizing ethyleneimine in aqueous solution under the action of acidic catalysts by known processes. Modified polyethyleneimines are obtained by crosslinking polyethyleneimines to such an extent that the resulting polymers are still water-soluble. Suitable crosslinkers are, for example, epichlorohydrin, dichloroethane or xylylene dichloride.
• Water-soluble condensation products containing condensed ethyleneimine are prepared, for example, by firstly condensing 1 mol of a dicarboxylic acid having 4 to 10 carbon atoms with 1 to 2 mols of a polyalkylene polyamine which has 3 to 10 basic nitrogen atoms in the molecule into polyamidoamines, then ethyleneimine onto the condensation products grafted and the ethyleneimine-modified polyamidoamines reacted with a crosslinking agent, so that water-soluble condensation products are obtained.
• Suitable crosslinkers are, for example, epichlorohydrin, cf.
• component b) are also suitable as component b) are the condensation products known from DE-AS 17 71 814, which are crosslinking products of polyamidoamines with bifunctional crosslinking agents.
• Cationic polyelectrolytes with a high charge density are also obtained by condensation of di- and polyamines, such as ethylenediamine, diethylenetriamine, triethylenetetramine and the higher homologues with crosslinking agents, such as dichloroethane, epichlorohydrin, and the reaction products of polyethylene glycols and epichlorohydrin in a molar ratio of 1: at least 2 or by Reaction of primary and secondary amines, such as methylamine or dimethylamine with epichlorohydrin, dichloroethane, dichloropropane or dichlorobutane.
• di- and polyamines such as ethylenediamine, diethylenetriamine, triethylenetetramine and the higher homologues with crosslinking agents, such as dichloroethane, epichlorohydrin
• crosslinking agents such as dichloroethane, epichlorohydrin
• crosslinking agents such as dichloroethane, epichlorohydrin
• Polyvinylamines are prepared by polymerizing N-vinylformamide and hydrolyzing the resulting polymers by the action of acids or bases, the formyl groups being split off from the polymer. Those polymers which contain copolymerized N-vinylformamide and vinylamine units are also very effective. Such polymers are produced by partial hydrolysis of polyvinylformamides.
• the polymers of vinyl heterocycles are obtained by subjecting the monomers on which these polymers are based to the polymerization, for example polymerizing N-vinylimidazole or its derivatives, for example 2-methyl-1-vinylimidazole or 2-benzyl-1-vinylimidazole, N-vinylpyridine or the like Derivatives and N-vinylimidazolines, for example 2-methyl-1-vinyl-imidazoline, 2-phenyl-1-vinyl-imidazoline or 2-benzyi-l-vinyi-imidazoiin.
• the heterocyclic cationic monomers are preferably used in the polymerization in neutralized or quaternized form.
• cationic polyelectrolytes are b) di-G to C 3 -alkylamino-Cz to C6-alkyl (meth) acrylates, di-G to C 3 -alkylamino-C 2 to C 6 -alkyl (meth) acrylamides and dialkylaminoalkyl vinyl ethers.
• Another class of compounds belonging to component b) are polymerized diallyldi-C 1 -C 3 -alkylammonium halides, in particular polydi-allyldimethylammonium chloride.
• the molecular weight of the cationic polyelectrolytes of component b) is in the range from 50,000 to 3,000,000, preferably 200,000 to 2,000,000. Polymers of this type are known and the majority are commercially available.
• the charge density of the cationic polyelectrolytes at pH 4.5 is preferably in the range from 5 to 20 meq / g polyelectrolyte.
• the pulp as component c) is metered in with a high molecular weight polymer based on acrylamide or methacrylamide.
• This polymer is also mixed with the paper stock, which is then dewatered in the usual way on a sieve. Based on dry paper stock, 0.003 to 0.03, preferably 0.005 to 0.015,% by weight of a high molecular weight polymer of component c) is used.
• This group of polymers includes the homopolymers of acrylamide and methacrylamide and the copolymers of the two monomers with anionic or cationic monomers.
• the homopolymers and copolymers have an average mass molecular weight (determined by the light scattering method) of 1 million to 20 million.
• Anionically modified polymers of acrylamide or methacrylamide are obtained by copolymerizing acrylamide or methacrylamide with monoethylenically unsaturated C 3 - to C s -carboxylic acids, which may or may not be partially or completely neutralized, or by partial hydrolysis of the amide groups of an acrylamide or methacrylamide homopolymer.
• the anionically modified polyacrylamides mainly the copolymers of acrylamide and acrylic acid are used.
• the copolymerized acrylic acid content in the copolymer can be 5 to 80% by weight.
• the G- to C 2 -alkylamino-C 2 to Cs-alkyl (meth) acrylates for example diethylaminoethyl acrylate, dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, dimethylaminopropylacrylate, dimethylaminobutyylate acrylate and methacrylate, these monomers being subjected to the copolymerization in the form of the salt with hydrochloric acid or sulfuric acid or in quaternized form, for example quaternized by reaction with methyl chloride, dimethyl sulfate or benzyl chloride.
• the G- to C 2 -alkylamino-C 2 to Cs-alkyl (meth) acrylates for example diethylaminoethyl acrylate, dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, dimethylaminopropylacrylate
• Suitable cationic monomers for modifying the (meth) acrylamide polymers are dialkylaminoalkyl (meth) acrylamides, dialkylaminoalkyl vinyl ethers, N-vinylimidazoles, N-vinylpyridine and diallyldimethylammonium chloride.
• polyacrylamide, copolymers of acrylamide and acrylic acid, copolymers of acrylamide and dimethylaminoethyl acrylate, copolymers of acrylamide and diethylaminoethyl acrylate, copolymers of acrylamide and N-vinylimidazoline, copolymers of acrylamide and 2-methyl-1-vinylimidazoiin are preferably used for the process according to the invention and copolymers of acrylamide and 2-phenyl-1-vinylimidazoline.
• the cationic monomers are used in neutralized or quaternized form.
• the two classes of compounds then differ in that the compounds c) have a molecular weight which is at least 1 million higher than the molecular weight of the compounds b).
• Another distinguishing feature of the two connection classes b) and c) lies in the charge density.
• the compounds c) - provided they are cationically modified - have a charge density of at most 3.5 mVaVg polyelectrolyte (measured at pH 4.5): For anionic modification of the polyacrylamides, vinylsulfonic acid, acrylamidopropanesulfonic acids and / or their alkali, ammonium or Amine salts are used.
• the starting point is an aqueous pulp, the concentration of which is 2.5 to 5% by weight.
• the activated bentonite is added in the amounts indicated above.
• the bentonite is preferably added in the form of a 3 to 6% aqueous dispersion.
• the pulp containing the bentonite is then diluted with water.
• the white water is preferably used for this in the production plant.
• metered in at least one compound according to b) in the amount specified above Due to the flow conditions in the line system, there is sufficient mixing of the cationic polymer with the paper stock.
• the high molecular weight polymer of component c) can be added.
• compounds c) are added before the headbox, advantageously at a point between the pressure sorter and the headbox.
• the polymers b) and c) are preferably metered in in the form of dilute aqueous solutions. Due to the auxiliary system used, paper production can take place in closed water cycles. Paper with good printability is obtained which also has good printability in the offset process.
• the parts given in the examples are parts by weight. The percentages relate to the weight of the fabrics.
• the charge density and molecular weights (light scattering) were determined according to D. Horn, Polyethylenimine / Physicochemical Properties and Application (IUPAC) Polymeric Amines and Ammonium Salts, Pergamon Press Oxford and New York, 1980, pages 333 to 355.
• Determining the dewatering time 1 l of the pulp slurry to be tested is dewatered in a Schopper-Riegler test device. The time that is determined for different outlet volumes is evaluated as a criterion for the drainage rate of the substance suspension examined in each case. The drainage times were determined in all cases specified here after the passage of 150, 200 and 250 ml of water.
• the retention was checked by determining the solids content in 250 ml of a filtrate obtained by dewatering the fiber slurry to be tested in a Schopper-Riegler device.
• High molecular polymer 1 (component c):. A homopolymer of acrylamide with a molecular weight of 3.5 million is used.
• thermomechanical substance TMP
• concentration of 3.2% is produced in a 20 liter container.
• the pH of the stock suspension is 5.7.
• the paper fiber suspension thus produced is stirred and mixed with a 5% aqueous slurry of a commercially available sodium bentonite, so that the amount of bentonite, based on paper stock, is 0.5%.
• the substance is diluted to a concentration of 0.85% by adding water.
• Filler-free newsprint in offset quality with a basis weight of 52 g / m 2 is made from 100% bleached TMP (thermomechanical fabric). It is initially assumed that the substance concentration is 2.95% and 0.7% sodium bentonite in the form of a 5% aqueous slurry is added in continuous operation. Then the paper stock is diluted in the mixing pump with white water to a concentration of 0.75% and metered into the line at the outlet of the mixing pump, based on dry paper stock, 0.05% of the above-mentioned polyelectrolyte 1 and after mixing between the pressure sorter and the headbox , 0.01% of the high molecular weight polymer 1. After adjusting the system balance, the values for headbox, white water are determined and the values for the first pass retention (FPR) are calculated. The machine speed and the paper production per unit of time are determined as a further parameter.
• TMP thermomechanical fabric
• the headbox concentration is 6.84 g / l
• the white water contains 2.32 g / l solids.
• the First Pass Retention (FPR) is 66.1%.
• the production speed is 577 m / min. You get 6.8 t of paper per hour.
• Example 1 is repeated with the exception that the polyelectrolyte 1 is omitted.
• the paper flocculates so strongly that perfect sheet formation is not guaranteed.
• the formation and surface quality of the sheet is insufficient for the printing requirements.
• Example 2 is repeated with the exception that the high molecular weight polymer 1 is omitted. In this case you get a good formation, but the drainage of the paper stock is bad, so that the machine can only run at a lower speed.

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• Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Dispersion Chemistry (AREA)
• Inorganic Chemistry (AREA)
• Paper (AREA)
• Making Paper Articles (AREA)
• Diaphragms For Electromechanical Transducers (AREA)
• Ultra Sonic Daignosis Equipment (AREA)

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• 1985
  • 1985-11-21 DE DE19853541163 patent/DE3541163A1/de not_active Withdrawn
• 1986
  • 1986-10-15 NZ NZ217951A patent/NZ217951A/xx unknown
  • 1986-10-16 CA CA000520637A patent/CA1278403C/en not_active Expired - Lifetime
  • 1986-10-16 AU AU63977/86A patent/AU578404B2/en not_active Ceased
  • 1986-10-20 US US06/920,604 patent/US4749444A/en not_active Expired - Fee Related
  • 1986-10-23 FI FI864294A patent/FI85397C/fi not_active IP Right Cessation
  • 1986-11-17 AT AT86115915T patent/ATE50814T1/de not_active IP Right Cessation
  • 1986-11-17 EP EP86115915A patent/EP0223223B1/de not_active Expired - Lifetime
  • 1986-11-17 DE DE8686115915T patent/DE3669336D1/de not_active Expired - Lifetime
  • 1986-11-18 JP JP61273079A patent/JPS62125098A/ja active Granted
  • 1986-11-20 NO NO864644A patent/NO168593C/no unknown

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