EP3332063B1 - Verfahren zur herstellung von papier - Google Patents

Verfahren zur herstellung von papier Download PDF

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Publication number
EP3332063B1
EP3332063B1 EP16750742.5A EP16750742A EP3332063B1 EP 3332063 B1 EP3332063 B1 EP 3332063B1 EP 16750742 A EP16750742 A EP 16750742A EP 3332063 B1 EP3332063 B1 EP 3332063B1
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weight
units
mol
acid
paper
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EP16750742.5A
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German (de)
English (en)
French (fr)
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EP3332063A1 (de
Inventor
Anton Esser
Hans-Joachim Haehnle
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Solenis Technologies Cayman LP
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Solenis Technologies Cayman LP
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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
    • D21H17/37—Polymers of unsaturated acids or derivatives thereof, e.g. polyacrylates
    • 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
    • D21H17/38—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing crosslinkable groups
    • D21H17/40—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing crosslinkable groups unsaturated
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/33—Synthetic macromolecular compounds
    • D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H17/41—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/63—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
    • D21H17/63—Inorganic compounds
    • D21H17/67—Water-insoluble compounds, e.g. fillers, pigments
    • D21H17/675—Oxides, hydroxides or carbonates
    • 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
    • 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
    • D21H21/06—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
    • 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
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21J—FIBREBOARD; MANUFACTURE OF ARTICLES FROM CELLULOSIC FIBROUS SUSPENSIONS OR FROM PAPIER-MACHE
    • D21J1/00—Fibreboard

Definitions

  • the invention relates to a process for the production of paper and board, comprising adding this aqueous suspension to a paper stock, dewatering the paper stock obtained and then pressing the paper sheet and drying it.
  • Paper production is a process in which a solid phase consisting of cellulose or wood fibers and various inorganic additives is separated from an aqueous phase.
  • the initial concentration of the solid phase in the paper stock suspension (thin stock) is typically in a range between 15 g/l and 1.5 g/l.
  • the separation of the solid phase and the aqueous phase takes place in several stages and can be modulated within these stages through the choice of mechanical parameters or the targeted addition of chemical additives.
  • the paper stock is dewatered by spraying it onto a screen or by injecting it between two screens, which are referred to as the bottom screen or top screen, depending on their position relative to the injected paper stock.
  • the water is separated from the paper stock solely by gravity or by a combination of gravity and centrifugal forces and runs off through the openings of the wires.
  • retention and drainage aids also plays an important role in wire drainage.
  • chemical additives include, in particular, high-molecular, slightly cationic polyacrylamides, cationic starch, but also polymers based on vinylformamide and ethyleneimine. That's how she describes it US6273998 the use of vinylamine copolymers in combination with microparticles such as bentonite as a retention aid that is added to the paper stock in the wet-end process.
  • EP-A-950138 the two-stage treatment of paper stock with a cationic polymer and microparticles and after shearing in the second stage with a cross-linked anionic polymer.
  • WO-A-04/087818 WO-A-05/012637 and WO-A-2006/066769 describe aqueous slurries of finely divided fillers which have been treated with water-soluble amphoteric copolymers based on polyvinylamine. These slurries make it possible to increase the filler content in paper while retaining the paper properties, in particular dry strength.
  • the dryness achieved in the wire section depends not only on the mechanical requirements of the wire section and the choice of chemical additives, but also very much on the paper stock system and the basis weight of the paper web. Even if the primary goal is efficient dewatering of the paper stock, good end properties of the paper should continue to be achieved will. Dewatering too quickly can lead to premature immobilization of the paper fibers and thus lead to poor strength properties or poor optical properties.
  • Initial wet structural strength is the strength of a wet paper that has never been dried. This is the strength of a wet paper as it is in papermaking after it has passed through the wire and press sections of the paper machine. It typically contains about 50% water.
  • An increase in the initial wet structure strength allows the application of higher pull-off forces and thus faster operation of the paper machine (cf. EP-A-0 780 513 ) or the use of larger amounts of filler.
  • the WO 2009/156274 teaches the use of amphoteric copolymers, which can be obtained by copolymerization of N-vinylcarboxamide with anionic comonomers and subsequent hydrolysis of the vinylcarboxamide, as a paper stock additive to increase the initial wet structural strength of paper.
  • the treatment takes place, for example, in the thick stock or in the thin stock in the paper manufacturing process.
  • the DE 60115692 T2 describes a process for making paper from paperboard, comprising forming a cellulosic suspension, flocculating the suspension, draining the suspension on a screen to form a sheet and then drying the sheet, characterized in that the suspension is flocculated using a flocculation system comprising a siliceous material and organic microparticles having an unswollen particle diameter of less than 750 nanometers.
  • the invention was based on the object of increasing the initial wet structure strength of the still moist paper web before the transition to the drying section during the production of paper, in order to achieve higher machine speeds in the paper production process compared to known methods.
  • the designation for the molded body made of fibrous material changes.
  • paper should be understood to mean a mass per unit area of 7 g/m 2 to 225 g/m 2 and cardboard should be understood to mean a mass per unit area of from 225 g/m 2 .
  • Paper stock also referred to as pulp
  • pulp is understood below to mean a mixture of substances consisting of one or more types of fibrous substances, fillers and various auxiliary substances suspended in water before sheet formation.
  • Total paper stock is the paper stock after the addition of all filler slurries and auxiliaries. If it is a reference to the total dry paper stock, also referred to as total paper stock (solid), this is to be understood as the mass that results from the dryness determination according to DIN EN ISO 638 DE.
  • Fillers are provided as so-called aqueous slurry and mixed with the rest of the paper stock.
  • the term filler includes calcium carbonate, which can be used in the form of ground (GCC) lime, chalk, marble or precipitated calcium carbonate (PCC).
  • filler is to be understood as meaning particles with an average particle size (volume average) of ⁇ 10 ⁇ m, preferably from 0.3 to 5 ⁇ m, in particular from up to 0.5 to 2 ⁇ m.
  • the mean particle size (volume mean) of the fillers is generally determined in the context of this document using the method of quasi-elastic light scattering (DIN-ISO 13320-1), for example using a Mastersizer 2000 from Malvern Instruments Ltd. Fillers usually have a BET specific surface area of ⁇ 20 m 2 /g.
  • Aqueous slurry is understood to mean a composition containing filler, which generally has a filler content of ⁇ 5% by weight, based on the aqueous slurry.
  • the suspension preferably contains 10 to 70% by weight, in particular 20 to 60% by weight, of filler.
  • the aqueous suspension of the filler can also contain additional organic or inorganic auxiliaries.
  • an aqueous slurry which comprises at least one inorganic filler, a water-soluble amphoteric polymer and microparticles.
  • the water-soluble amphoteric polymer can be obtained by copolymerizing the monomer mixture comprising the monomers a) and b) and subsequent complete or partial hydrolysis of the —CO—R 1 groups of the polymer.
  • the choice of the monomer composition and the degree of hydrolysis ensures that the difference in the proportions of the cationic and the anionic monomer units in moles, based in each case on the total number of moles of all monomer units, is an absolute maximum of 10 mol%.
  • the ratio of amidine units to amine units is, for example, 100:1 to 1:30, preferably 40:1 to 1:15, particularly preferably 8:1 to 1:8.
  • cationic units are the sum of amine and amidine units
  • anionic units include the acid units which are formed during the copolymerization from the monomers of group (b) and which are present in the form of the free acid groups and/or in present in salt form.
  • group (a) monomers are open-chain N-vinylamide compounds of the formula (I), such as N-vinylformamide, N-vinyl-N-methylformamide, N-vinylacetamide, N-vinyl-N-methylacetamide, N-vinyl-N- ethylacetamide, N-vinylpropionamide and N-vinyl-N-methylpropionamide and N-vinylbutyramide.
  • the monomers of group (a) can be used alone or as a mixture in the copolymerization with the monomers of the other groups. From this group, preference is given to using N-vinylformamide in the copolymerization.
  • copolymers to be used according to the invention contain at least one monomer from group (b) that is a monoethylenically unsaturated monomer having at least one free acid group or at least one acid group in salt form.
  • the acid group can be present as a free acid group or in a salt form.
  • Preferred salts are the water-soluble salts such as alkali metal, alkaline earth metal or ammonium salts.
  • Suitable bases for the partial or complete neutralization of the acid groups of the monomers (b) 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.
  • alkali metal or alkaline earth metal bases ammonia, amines and/or alkanolamines.
  • Suitable monomers of this group (b) are, for example, monoethylenically unsaturated sulfonic acids, phosphonic acids, monocarboxylic acids and dicarboxylic acids and their salts. Also suitable are monoethylenically unsaturated monoesters of phosphonic acids, monoamides of phosphonic acids, and dicarboxylic acid anhydrides. Suitable monomers (b) are also esters of phosphoric acid with alcohols having a polymerizable, ⁇ , ⁇ -ethylenically unsaturated double bond. One or the two remaining protons of the phosphoric acid group can be neutralized by suitable bases. In addition, another acid function can be esterified with alcohols that do not have any polymerizable double bonds.
  • saturated alcohols for esterifying phosphoric acid are C 1 -C 6 -alkanols, such as methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, tert-butanol, n-pentanol, n-hexanol and their isomers.
  • Possible group (b) monomers are, for example, monoethylenically unsaturated carboxylic acids having 3 to 8 carbon atoms and the water-soluble salts such as alkali metal, alkaline earth metal or ammonium salts of these carboxylic acids.
  • 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 dicarboxylic acid anhydrides of the abovementioned acids are also suitable.
  • the aforementioned monomers (b) can be used individually or in the form of any desired mixtures.
  • the copolymers can optionally contain at least one further monomer of group (c) in copolymerized form.
  • these monomers are nitriles of ⁇ , ⁇ -ethylenically unsaturated mono- and dicarboxylic acids such as acrylonitrile and methacrylonitrile.
  • acrylonitrile and methacrylonitrile When such copolymers are hydrolyzed, 5 ring amidines are then obtained.
  • Examples of representatives of this group (c) are, for example, methyl (meth)acrylate (the wording "...(meth)acrylate” means both “...methacrylate” and “...acrylate”), methyl ethacrylate, ethyl(meth )acrylate, ethyl ethacrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, tert-butyl ethacrylate, n-octyl (meth)acrylate, 1,1,3,3- tetramethylbutyl (meth)acrylate, ethylhexyl (meth)acrylate, and mixtures thereof.
  • Suitable additional monomers (c) are also the esters of ⁇ , ⁇ -ethylenically unsaturated mono- and dicarboxylic acids with amino alcohols, preferably C 2 -C 12 -amino alcohols. These can be C 1 -C 8 monoalkylated or dialkylated on the amine nitrogen.
  • suitable acid components of these esters are acrylic acid, methacrylic acid, fumaric acid, maleic acid, itaconic acid, crotonic acid, maleic anhydride, monobutyl maleate and mixtures thereof. Acrylic acid, methacrylic acid and mixtures thereof are preferably used.
  • N-methylaminomethyl (meth)acrylate N-methylaminoethyl (meth)acrylate, N,N-dimethylaminomethyl (meth)acrylate, N,N-dimethylaminoethyl (meth)acrylate, N,N-diethylaminoethyl (meth)- acrylate, N,N-dimethylaminopropyl (meth)acrylate, N,N-diethylaminopropyl (meth)acrylate and N,N-dimethylaminocyclohexyl (meth)acrylate.
  • Suitable additional monomers (c) are also acrylamide, methacrylamide, N-methyl(meth)acrylamide (the wording "...(meth)acrylamide” stands for “...acrylamide” and for “...methacrylamide”), 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 and mixtures thereof.
  • Also suitable as monomers (c) are 2-hydroxyethyl (meth)acrylate, 2-hydroxyethyl ethacrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate and mixtures thereof.
  • Suitable monomers (c) are also N-vinyllactams and their derivatives, which can have, for example, one or more C 1 -C 6 -alkyl substituents (as defined above). These include N-vinylpyrrolidone, N-vinylpiperidone, N-vinylcaprolactam, N-vinyl-5-methyl-2-pyrrolidone, N-vinyl-5-ethyl-2-pyrrolidone, N-vinyl-6-methyl-2-piperidone, N-vinyl-6-ethyl-2-piperidone, N-vinyl-7-methyl-2-caprolactam, N-vinyl-7-ethyl-2-caprolactam and mixtures thereof.
  • esters of vinyl alcohol and allyl alcohol with C 1 -C 30 monocarboxylic acids are also suitable.
  • N-vinylimidazoles and alkylvinylimidazoles are also suitable as monomers (c) are N-vinylimidazoles and alkylvinylimidazoles, in particular methylvinylimidazoles such as 1-vinyl-2-methylimidazole, 3-vinylimidazole N-oxide, 2- and 4-vinylpyridine N-oxides and betaine derivatives and quaternization products of these monomers .
  • Suitable additional monomers are also ethylene, propylene, isobutylene, butadiene, styrene, ⁇ -methyl styrene, vinyl acetate, vinyl propionate, vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride and mixtures thereof.
  • the aforementioned monomers (c) can be used individually or in the form of any desired mixtures.
  • a further modification of the copolymers is possible by using, in the copolymerization, monomers (d) which contain at least two double bonds in the molecule, e.g Polyalkylene glycols or polyols such as pentaerythritol, sobit or glucose. Also suitable are allyl and vinyl ethers of polyalkylene glycols or polyols such as pentaerythritol, sobit or glucose. If at least one monomer of group (d) is used in the copolymerization, the amounts used are up to 2 mol%, for example 0.001 to 1 mol%.
  • a monomer mixture is used for the polymerization, with at least one monoethylenically unsaturated monomer selected as component (b). from the group consisting of monocarboxylic acids, dicarboxylic acids and dicarboxylic acid anhydrides, said monomer having at least one free acid group or at least one acid group in salt form.
  • a monomer mixture is used for the polymerization whose monoethylenically unsaturated monomer with at least one free acid group or at least one acid group in salt form (component (b) is selected from the group consisting of sulfonic acids, phosphonic acids, monoesters of phosphonic acids, monoamides of phosphonic acids and esters of phosphoric acid with alcohols having a polymerizable ⁇ , ⁇ -ethylenically unsaturated double bond.
  • component (b) is selected from the group consisting of sulfonic acids, phosphonic acids, monoesters of phosphonic acids, monoamides of phosphonic acids and esters of phosphoric acid with alcohols having a polymerizable ⁇ , ⁇ -ethylenically unsaturated double bond.
  • the hydrolysis of the polymers obtained by the process described above is carried out by known processes by the action of acids, bases or enzymes, for example hydrochloric acid, sodium hydroxide or potassium hydroxide.
  • the originally anionic copolymer receives cationic groups as a result of the hydrolysis and thus becomes amphoteric.
  • amidine units (II) and (III) are formed by reacting adjacent vinylamine units of the formula (VI) with vinylformamide units or those of the formula IV and V by reacting adjacent vinylamine units of the formula (VI) with acrylonitrile or methacrylonitrile groups (if present in the polymer).
  • the hydrolysis of the copolymers is, for example, in EP-B-0 672 212 on page 4, lines 38 - 58 and on page 5, lines 1 - 25 and in the examples of EP 528 409 revealed in detail.
  • amphoteric polymer is preferably used in which the hydrolysis was carried out in the presence of bases, preferably in the presence of sodium hydroxide solution.
  • Their degree of hydrolysis is equivalent to the molar percentage total content of the primary amino groups and amidine groups of the polymers, based on the N-vinylcarboxamide units originally present.
  • amphoteric copolymers which contain N-vinylformamide in copolymerized form as component (a) are of particular industrial importance.
  • the water-soluble amphoteric polymers are prepared by customary methods known to those skilled in the art. Suitable methods are for example in EP-A-0 251 182 , WO-A-94/13882 and EP-B-0 672 212 described, to which reference is made here. Furthermore, the production of the in WO-A-04/087818 and WO-A-05/012637 described water-soluble amphoteric polymers.
  • the water-soluble amphoteric polymers can be prepared by solution, precipitation, suspension or emulsion polymerization.
  • Solution polymerization in aqueous media is preferred.
  • Suitable aqueous media are water and mixtures of water and at least one water-miscible solvent, e.g. an alcohol such as methanol, ethanol, n-propanol, isopropanol, etc.
  • the polymerization temperatures are preferably in a range from about 30 to 200.degree. C., particularly preferably 40 to 110.degree.
  • the polymerization usually takes place under atmospheric pressure, but it can also take place under reduced or superatmospheric pressure.
  • a suitable pressure range is between 0.1 and 5 bar.
  • the monomers (b) containing acid groups are preferably used in the salt form.
  • the pH is preferably adjusted to a value in the range from 6 to 9 for the copolymerization.
  • the pH can be kept constant during the polymerization by using a conventional buffer or by measuring the pH and adding acid or base accordingly.
  • the monomers can be polymerized with the aid of free-radical initiators.
  • the peroxo and/or azo compounds customary for this purpose can be used as initiators for the radical polymerization, for example alkali metal 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 permaleate, cumene hydroperoxide, diisopropyl peroxydicarbamate, bis-(o-toluoyl)-peroxide, didecanoyl peroxide, dioctanoyl peroxide, dilauroyl peroxide, tert-butyl perisobutyrate, tert-butyl peracetate, di-tert.
  • 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 /Cul.
  • the polymerization can be carried out in the presence of at least one regulator.
  • regulators the usual compounds known to those skilled in the art, such as sulfur compounds, e.g. B. mercaptoethanol, 2-ethylhexyl thioglycolate, thioglycolic acid, sodium hypophosphite, formic acid or dodecyl mercaptan and tribromochloromethane or other compounds which regulate the molecular weight of the polymers obtained can be used.
  • the average molar mass M w of the water-soluble amphoteric polymer is, for example, at least 10,000, preferably at least 100,000 daltons and in particular at least 500,000 daltons.
  • the molar masses of the polymers are then, for example, from 10,000 to 10 million, preferably from 100,000 to 5 million (determined, for example, by light scattering on their non-hydrolyzed precursor).
  • This molar mass range corresponds, for example, to K values of 5 to 300, preferably 10 to 250 (determined according to H. Fikentscher in 5% strength aqueous common salt solution at 25° C. and a polymer concentration of 0.1% by weight).
  • aqueous slurry Other components of the aqueous slurry are microparticles.
  • the microparticle can have either an organic or an inorganic character.
  • Suitable polymeric microparticles include anionic microparticles. These organic polymers have limited solubility in water and may be crosslinked. Unswollen organic microparticles have a particle size of less than 750 nm.
  • Anionic organic microparticles such as those in U.S. 6,524,439 are obtainable by hydrolysis of an acrylamide polymer microparticle or by polymerization of anionic monomers such as (meth)acrylic acid and its salts, 2-acrylamido-2-methylpropanesulfonates, sulfoethyl (meth)acrylates, vinylsulfonic acid, styrenesulfonic acid, maleic acid or other dibasic acids or their salts and mixtures thereof.
  • anionic monomers such as (meth)acrylic acid and its salts, 2-acrylamido-2-methylpropanesulfonates, sulfoethyl (meth)acrylates, vinylsulfonic acid, styrenesulfonic acid, maleic acid or other dibasic acids or their salts and mixtures thereof.
  • anionic monomers can also be copolymerized with nonionic monomers such as (meth)acrylamide, N-alkylacrylamides, N,N-dialkylacrylamides, methyl (meth)acrylate, acrylonitrile, N-vinylmethylacetamide, N-vinylmethylformamide, vinyl acetate, N- vinylpyrrolidone and mixtures thereof.
  • nonionic monomers such as (meth)acrylamide, N-alkylacrylamides, N,N-dialkylacrylamides, methyl (meth)acrylate, acrylonitrile, N-vinylmethylacetamide, N-vinylmethylformamide, vinyl acetate, N- vinylpyrrolidone and mixtures thereof.
  • the polymerization of the monomers into microparticles is typically carried out in the presence of a multifunctional crosslinking agent.
  • a multifunctional crosslinking agent such as crosslinkers are for example in U.S. 6,524,439 described, and have at least two double bonds or one double bond and one reactive group or two reactive groups.
  • crosslinkers for example, its N,N-methylene-bis-(meth)acrylamide, Polyethyleneglycoldi(meth)acrylate, N-vinylacrylamide, divinylbenzene, triallylammonium salts, N-methylallylacrylamideglycidyl(meth)acrylate, acrolein, methylolacrylamide, dialdehydes such as glyoxal, diepoxy compounds and epichlorohydrin.
  • the multifunctional crosslinking agent is used in an amount that gives a sufficiently crosslinked polymer.
  • at least 4 ppm of multifunctional crosslinking agent can be used per mole of monomer.
  • a quantity of from 4 to 6000 ppm, particularly preferably from 20 to 4000 ppm, and in particular from 40 to 2000 ppm, of multifunctional crosslinking agent is preferably used per mole of monomers.
  • the polymerization can be carried out in the presence of at least one regulator.
  • Such polymerizations for the production of polymer particles are, for example, in U.S. 5,961,840 , U.S. 5,919,882 , 5,171,808 and U.S. 5,167,766 described.
  • the usual compounds known to those skilled in the art such as sulfur compounds, e.g. B. mercaptoethanol, 2-ethylhexyl thioglycolate, thioglycolic acid, sodium hypophosphite, formic acid or dodecyl mercaptan and tribromochloromethane or other compounds which regulate the molecular weight of the polymers obtained can be used.
  • sulfur compounds e.g. B. mercaptoethanol, 2-ethylhexyl thioglycolate, thioglycolic acid, sodium hypophosphite, formic acid or dodecyl mercaptan and tribromochloromethane or other compounds which regulate the molecular weight of the polymers obtained
  • sulfur compounds e.g. B. mercaptoethanol, 2-ethylhexyl thioglycolate, thioglycolic acid, sodium hypophosphite, formic acid or dodecyl
  • the polymerisation to form a microparticle usually takes place by means of inverse emulsion polymerisation or inverse microemulsion polymerisation and is generally known to the person skilled in the art.
  • Such polymerizations are for example in the US2003/0192664 (Page 6) whose teaching is expressly referred to.
  • Anionic organic microparticles are preferred, in particular copolymers of acrylamide and one or more anionic monomers.
  • Preferred anionic organic microparticles when unswollen, have an average particle diameter of ⁇ 750 nm, preferably ⁇ 500 nm, particularly in the range from 25 to 300 nm.
  • the anionic organic microparticles preferably contain 0 - 99 parts by weight a nonionic monomer 1 - 100 parts by weight an anionic monomer each based on the total weight of all monomers.
  • the anionic organic microparticles particularly preferably contain 10 - 90 parts by weight a nonionic monomer 10 - 90 parts by weight an anionic monomer each based on the total weight of all monomers.
  • the anionic organic microparticles particularly preferably contain 20 - 80 parts by weight a nonionic monomer 20 - 80 parts by weight an anionic monomer each based on the total weight of all monomers.
  • the anionic organic microparticles have a charge density of at least 2 meq/g.
  • inorganic microparticles In contrast to inorganic fillers, which have a BET specific surface area of ⁇ 20 m 2 /g, inorganic microparticles have a BET specific surface area of ⁇ 100 m 2 /g (BET measurement (DIN ISO 9277:2003-05) .
  • the inorganic microparticles are selected from bentonite, colloidal silica and silicates.
  • Bentonite is generally understood to mean phyllosilicates which are swellable in water. These are primarily the clay mineral montmorillonite and similar clay minerals such as nontronite, hectorite, saponite, sauconite, beidellite, allevardite, illite, halloysite, attapulgite and sepiolite.
  • These layered silicates are preferably activated prior to their use, i.e. converted into a water-swellable form, by treating the layered silicates with an aqueous base such as aqueous solutions of sodium hydroxide, potassium hydroxide, soda or potash.
  • the inorganic microparticles used are preferably bentonite in the form treated with sodium hydroxide solution.
  • the flake diameter of the bentonite dispersed in water in the form treated with caustic soda is 1 to 2 ⁇ m, for example, and the flake thickness is about 1 nm.
  • the bentonite has a specific surface area of 150 to 800 m 2 /g.
  • Typical bentonites are, for example, in the EP-B-0235893 described.
  • 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. Normally, the slurries contain approx. 3 - 5% by weight of bentonite.
  • Products from the group consisting of silicon-based particles, silica microgels, silica sols, aluminum silicates, borosilicates, polyborosilicates or zeolites can be used as colloidal silicic acid. These have a specific surface area of 200-1000 m 2 /g and an average particle size distribution of 1-250 nm, normally in the range 40-100 nm EP-A-0041056 , EP-A-0185068 and US-A-5176891 described.
  • Clay or kaolin is a hydrous aluminum silicate with a plate-like structure.
  • the crystals have a layered structure and an aspect ratio (ratio of diameter to thickness) of up to 30:1.
  • the particle size is at least 50% smaller than 2 ⁇ m.
  • a weight ratio of fillers to inorganic microparticles of at least 30:1 is preferably selected.
  • the aqueous slurry generally has a solids content of ⁇ 3% by weight, preferably ⁇ 8% by weight, in particular ⁇ 12% by weight, based on the aqueous slurry.
  • the proportion of the water-soluble, amphoteric polymer is generally 0.01-1% by weight, preferably 0.05-0.6% by weight, based on the filler (solid).
  • aqueous suspensions containing, preferably consisting of water, 5-70% by weight of filler, based on the aqueous suspension, and 0.001-1% by weight of water-soluble amphoteric polymer and 0.01-1% by weight of microparticles, each based on Filler (solid).
  • the aqueous slurry is metered into a paper stock.
  • All fibers from softwood and deciduous wood commonly used in the paper industry can be used as paper stock.
  • Mechanical pulp includes, for example, groundwood, thermomechanical pulp (TMP), chemothermomechanical pulp (CTMP), pressure groundwood, semi-chemical pulp, high-yield pulp, and refiner mechanical pulp (RMP).
  • Sulphate, sulfite and soda pulp for example, can be used as pulp.
  • Preference is given to using unbleached pulp which is also referred to as unbleached kraft pulp.
  • Suitable annual plants for the production of paper pulp are, for example, rice, wheat, sugar cane and kenaf.
  • Waste paper can also be used to produce the pulps, either on its own or in a mixture with other fibrous materials.
  • the waste paper can come from a deinking process, for example. However, it is not necessary for the waste paper to be used to be subjected to such a process. Furthermore, fiber mixtures made from a primary material and recycled coated broke can also be used.
  • the aqueous slurry is added to an aqueous suspension of fibers.
  • this is done in the absence of other process chemicals commonly used in papermaking.
  • the water-soluble, amphoteric polymers can be added in the papermaking process, for example, in an amount of 0.01 to 1.00% by weight, based on dry fiber.
  • Typical application rates are, for example, 0.1 to 10 kg, preferably 0.3 to 4 kg, of the water-soluble, amphoteric polymer per tonne of dry fibrous material. In most cases, the amounts of amphoteric polymer used are 0.5 to 2.5 kg of polymer (solid), based on ton of dry fiber.
  • the process chemicals customarily used in papermaking can be used in the usual amounts in the process according to the invention, e.g. These substances are preferably added to the paper stock only after the fibrous stock has been treated according to the invention.
  • a paper machine consists of the following units: headbox, wire section, press section and dryer section.
  • the dewatering effect within the wire section is achieved by mechanical forces (gravity, centrifugal force).
  • hydrodynamic measures are also used. These usually lead to a negative pressure being created on the screens. These measures are particularly useful when dewatering has reached a level where the first capillary effects in the wet paper structure play a role.
  • sheet formation takes place in the wire section up to a dry content of the paper sheet of at least 18% by weight, preferably 19% by weight, in particular 20% by weight.
  • Sheet formation in the wire section preferably takes place up to a dry content of the paper sheet of at most 25% by weight.
  • sheet formation takes place in the wire section up to a dry content of the paper sheet in the range from 19 to 22% by weight.
  • the moist nonwoven is couched onto the press felt by a take-off suction device (suction roll or static vacuum element).
  • the task of the press felt is to transport the fibrous web through press nips of various modifications.
  • the dry content of the web is up to a maximum of 55% by weight.
  • the dry content increases with the pressure exerted on the paper web running through the press. The pressure and thus the dry content of the paper web can be varied over a relatively wide range in many paper machines.
  • the method according to the invention enables tear-free operation of the paper machine.
  • the paper web or paper sheet produced in the process shows a significantly increased initial wet structural strength.
  • the degree of hydrolysis of the water-soluble amphoteric polymers was determined by enzymatic analysis of the formic acid/formates released during the hydrolysis (test set from Boehringer Mannheim).
  • the structural composition of the polymers was calculated from the monomer mixture used, the degree of hydrolysis and the vinylamine/amidine ratio determined by means of 13 C-NMR spectroscopy.
  • the composition ratio is in mol% unless otherwise specified.
  • the dry content is determined in accordance with DIN EN ISO 638 DE using the heating cabinet method.
  • the dry content of the sheet of paper is the ratio of the mass of a sample that has been dried to a constant mass at a temperature of (105 ⁇ 2) °C under defined conditions to the mass of the sample before drying.
  • the dry content is given as a percentage by mass.
  • the K values were H. Fikentscher, Cellulose Chemistry, Volume 13, 48-64 and 71-74 measured under the specified conditions.
  • the information in brackets indicates the concentration of the polymer solution and the solvent.
  • the solids content of the polymers was determined by distributing 0.5 to 1.5 g of the polymer solution in a metal lid with a diameter of 4 cm and then drying it in a circulating air drying cabinet at 140° C. for two hours. The ratio of the mass of the sample after drying under the above conditions to the mass when the sample was taken gives the solids content of the polymer.
  • the average molecular weight M w is understood here, above and below, as the mass-average molecular weight M w , as can be determined by light scattering. The molecular weight was determined on the unhydrolyzed precursor.
  • amphoteric polymers were used to produce slurries.
  • Table 1 Water-soluble amphoteric polymers used polymer Composition vinyl formamide units/acrylic acid units/vinylamine + amidine units Mean Molecular Weight [daltons] P1 40/30/30 500000 p2 5/45/50 400000 P3 65/20/15 650000 P4 30/40/30 400000 P5 30/30/40 400000 P6 40/30/30 500000
  • the amount of berntonite suspension added was calculated in such a way that the proportion of bentonite (solid) corresponds to 0.3% by weight, based on PCC (solid). After a further 30 seconds, the number of revolutions of the Heiltof stirrer was reduced to 200 rpm.
  • the bentonite suspension was prepared according to the recommendations in the technical data sheet (Hydrocoll) for use as microparticles to support flocculation processes. This applies in particular to the sufficient swelling of the bentonite before use. The pH of the mixture is then adjusted to 8.5.
  • suspension A1 The procedure for preparing suspension A1 was followed, using the polymers P2 to P6 and microparticles listed in Table 1, the amounts or However, concentrations were maintained. Slurry 6 was made with ground calcium carbonate instead of precipitated calcium carbonate. Table 2 shows the compositions of the slurries produced.
  • Table 2 Preparation of the slurries siltation polymer filler microparticles A1 P1 PCC bentonite A2 p2 PCC bentonite A3 P3 PCC bentonite A4 P4 PCC bentonite A5 P5 PCC bentonite A6 P6 GCC bentonite A7 P6 PCC silica sol A8 p2 PCC silica sol PCC: precipitated calcium carbonate GCC: ground calcium carbonate
  • the amount of micropolymer solution added was calculated such that the solid fraction of micropolymer in the PCC slurry corresponds to 0.07% by weight of the solid PCC fraction. After a further 30 seconds, the number of revolutions of the Heiltof stirrer was reduced to 200 rpm and left at this until the slurry was used further. The pH of the mixture was then adjusted to 8.5.
  • the pH of the fibrous material was in the range between 7 and 8.
  • the ground material was then diluted to a solids concentration of 0.8% by weight by adding water.
  • An optical brightener (Blankophor PSG) and a cationic starch (HiCat 5163 A) were then added to the diluted pulp.
  • the cationic starch was digested beforehand as a 10% strength by weight starch slurry in a jet cooker at 130° C. and a residence time of 1 minute.
  • the dosage of the optical brightener was 0.3% by weight of commercial product, based on the total paper stock (solid).
  • the dosage of the cationic starch was 0.8% by weight of starch (solids), based on the total paper stock (solids).
  • sheets were produced which each contained about 25% by weight of an untreated PCC and 25% by weight of an untreated GCC.
  • the sheets of paper with a basis weight of 100g/sqm were produced on a dynamic sheet former from TechPap France.
  • the paper stock suspension was sprayed onto a screen that was clamped into a vertical, rapidly rotating drum is.
  • the dewatering and sheet formation in this system is determined not only by the sheet structure but above all by the centrifugal forces within the rotating drum.
  • the centrifugal force acting on the resulting sheet structure can also be varied.
  • the result is a variation in sheet drainage that leads to a variation in dryness in the wet paper structure. What is meant here is the dry content of the wet paper structure immediately after removal from a water-permeable base (wire) that is clamped in the drum of the dynamic sheet former.
  • the number of revolutions of the drum was varied in 5 steps between 600 and 1100 revolutions per minute, as a result of which dry contents in the range between 14% by weight and 21% by weight can be set.
  • the amount of filler added for sheet formation must be slightly adjusted upwards as the number of revolutions of the drum increases, since filler retention decreases with increasing dewatering. A small portion of the sheet structure, while still wet, is used to determine the dryness immediately after the wet paper sheet is removed from the wire of the dynamic sheet former.
  • the wet strength and the initial wet strength of paper are to be distinguished from the initial wet structural strength, because both properties are measured on papers which, after drying, are moistened again to a defined water content.
  • the initial wet strength is an important parameter when evaluating non-permanently wet-strength papers. A paper that has been dried and then moistened again has a completely different wet strength than a moist paper that is present immediately after it has passed through the wire and press sections of a paper machine.
  • the determination of the initial wet structure strength on the wet paper is carried out using the Voith method (cf. M. Schwarz and K. Bechtel "Initial structural strength during sheet formation", in Kliblatt für Textilfabrikation 131, pages 950 - 957 (2003) No. 16 . to do this, the wet sheets, after pressing in the static press, were knocked off onto a plastic base and transferred to a cutting base. The sample strips were then cut from the sheet with a defined length and width. These were pressed under constant pressure until the desired dry content was reached. Four solids contents in the range between 42% and 58% were set in each case for examining the paper sheets obtained according to the examples given above.
  • the initial wet structural strength at 50% dry content was determined using a fitting method described in the reference above.
  • the actual measurement of the initial wet structure strength was carried out on a vertical tensile testing machine with a special clamping device.
  • the force determined in the tractor was converted into the so-called INF index, which is independent of the area mass.
  • INF index is independent of the area mass.
  • Reference examples PCC 4 and PCC5 and reference example GCC9 and GCC10 show that setting the dry content above 18% by weight alone (in this case by setting the rotational speed of the dynamic sheet former), without additional treatment of the filler slurry with a 2-component system, leads to none significant increase in the INF(50%) index.
  • Examples 84, 85, 89, 90, 94 and 95 show that treatment of the filler with only the water-soluble amphoteric polymer or only the microparticles also has no effect when the dry content exceeds 18%.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Paper (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Making Paper Articles (AREA)
  • Diaphragms For Electromechanical Transducers (AREA)
  • Electronic Switches (AREA)
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US11795255B2 (en) 2018-09-14 2023-10-24 Solenis Technologies, L.P. Method for producing paper or cardboard
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