EP3697964B1 - Procédé de fabrication de papier monocouche ou multicouche - Google Patents

Procédé de fabrication de papier monocouche ou multicouche Download PDF

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Publication number
EP3697964B1
EP3697964B1 EP18782462.8A EP18782462A EP3697964B1 EP 3697964 B1 EP3697964 B1 EP 3697964B1 EP 18782462 A EP18782462 A EP 18782462A EP 3697964 B1 EP3697964 B1 EP 3697964B1
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Prior art keywords
mol
paper
monomers
polymer
suspension
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EP18782462.8A
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German (de)
English (en)
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EP3697964A1 (fr
Inventor
Christoph Hamers
Anton Esser
Frans De Bruyn
Christopher Alan GRAY
Ralph ISERMANN
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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
    • D21H17/46—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
    • 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
    • D21F—PAPER-MAKING MACHINES; METHODS OF PRODUCING PAPER THEREON
    • D21F11/00—Processes for making continuous lengths of paper, or of cardboard, or of wet web for fibre board production, on paper-making machines
    • D21F11/02—Processes for making continuous lengths of paper, or of cardboard, or of wet web for fibre board production, on paper-making machines of the Fourdrinier type
    • D21F11/04—Processes for making continuous lengths of paper, or of cardboard, or of wet web for fibre board production, on paper-making machines of the Fourdrinier type paper or board consisting on two or more layers
    • 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
    • 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
    • D21H17/41—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups
    • D21H17/42—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups anionic
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/33—Synthetic macromolecular compounds
    • D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H17/41—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups
    • D21H17/44—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups cationic
    • D21H17/45—Nitrogen-containing groups
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • 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
    • 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
    • D21H23/50—Spraying or projecting
    • 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
    • D21H25/00—After-treatment of paper not provided for in groups D21H17/00 - D21H23/00
    • D21H25/04—Physical treatment, e.g. heating, irradiating
    • D21H25/06—Physical treatment, e.g. heating, irradiating of impregnated or coated paper
    • 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
    • D21H27/00—Special paper not otherwise provided for, e.g. made by multi-step processes
    • D21H27/30—Multi-ply

Definitions

  • the invention relates to a method for producing single-ply or multi-ply paper.
  • the method comprises dewatering an aqueous fibrous suspension to obtain a fibrous web, dewatering the fibrous web under pressure to form a partially dewatered fibrous web, spraying the partially dewatered fibrous web on at least one surface side with an aqueous spray solution or spray suspension to form a sprayed partially dewatered fibrous web and dewatering the sprayed partially dewatered fibrous web using heat to form a single-ply paper, wherein the aqueous spray solution or spray suspension contains a water-soluble polymer P.
  • the method comprises dewatering two aqueous fiber suspensions to obtain two fiber webs, joining the two fiber webs to form a layer composite, dewatering the layer composite under pressure to form a partially dewatered layer composite, spraying the partially dewatered layer composite on at least one surface side with an aqueous spray solution or spray suspension to form a sprayed layer composite, and dewatering the sprayed layer composite using heat to form a multi-layer paper, wherein the aqueous spray solution or spray suspension contains a water-soluble polymer P.
  • the aqueous spray solution or spray suspension contains a water-soluble polymer P.
  • Multi-layer papers are made from paper stock mixtures or fiber mixtures with the same or different material composition by pressing together individual, still wet paper webs or paper layers.
  • An important quality feature of multi-layer packaging papers or cardboard is their strength. This is largely determined by the internal cohesion of the materials used. The layer adhesion in the sense of the cohesion in the border area between the individual paper layers can represent a weak point. The trend towards using increased amounts of recycled raw material leads to ever shorter paper fiber lengths and therefore fundamentally poorer paper strengths. There is also a trend in folding box cardboard to use ever more voluminous fiber mixtures to increase flexural rigidity. Both trends increase the need to increase layer adhesion.
  • adhesive starch or starch derivatives are often used.
  • a native or modified starch based on wheat, corn, potato or tapioca is sprayed onto a paper web in the form of an aqueous suspension.
  • gelatinization occurs and in this way a Solidification is caused.
  • native starch often has the disadvantage that only a low solids content can be used due to its high viscosity in aqueous solution. Subsequent exposure to heat can also cause the starch composite to become partially or completely irreversibly brittle.
  • EP0953679A discloses polymers to improve the strength of single- and multi-ply papers that are obtainable by polymerizing at least 5% by weight (meth)acrylic acid and are applied to a paper layer by spraying, among other things.
  • Some of the examples describe the spraying of a first fibrous web, which is made from a fibrous slurry from old corrugated cardboard and has a moisture content of 86%, with various terpolymers obtained by polymerizing acrylic acid, acrylamide and acrylonitrile.
  • a second fibrous web which is also made from a fibrous slurry from old corrugated cardboard and has a moisture content of 96%, is bonded to the sprayed first fibrous web by pressing.
  • polymers obtained by polymerizing N-vinylformamide and subsequent, at least partial hydrolysis of the formamide groups are used in combination with starch.
  • the examples disclose spraying a first fibrous web, which is made from a fibrous slurry from old corrugated cardboard and has a moisture content of 82%, with various suspensions or solutions containing a starch and/or a polymer solution.
  • a second fibrous web which is also made from a fibrous slurry from old corrugated cardboard and has a moisture content of 92%, is then bonded to the sprayed first fibrous web by pressing.
  • polymers in the examples are a polyallylamine and polymers obtained by polymerization of N-vinylformamide and subsequent, at least partial, hydrolysis of the formamide groups.
  • the DE 198 29 757 A1 describes aqueous adhesive dispersions containing A) 0.1-10 wt. % adhesive polymer in the form of a dispersion, based on the total weight of the dispersion, B) 0.1-100 parts by weight of component A), of an anionic or cationic polyelectrolyte and C) 0-50 parts by weight, based on 100 parts by weight of components A), of at least one polyalkylene glycol with a molecular weight of 200-100,000 g/mol.
  • the EP1378603A2 describes a method for converting a paper machine in which a state-of-the-art size pressing station is replaced by a contactless application station for liquid or pasty agents.
  • the EN 42 41 117 A1 describes the use of copolymers which are formed by polymerizing a) 5 to 99 mol% of N-vinylcarboxamides, b) 95 to 1 mol% of monoethylenically unsaturated carboxylic acids and/or alkali metal, alkaline earth metal, ammonium or amine salts thereof and optionally c) up to 30 mol% of other monoethylenically unsaturated compounds and optionally d) up to 2 mol% of crosslinking agent and subsequent partial or complete cleavage of the formyl groups from the N-vinylcarboxamide units in the copolymer to form amine or ammonium groups.
  • the invention is based on the object of providing a process for producing single-ply or multi-ply paper or cardboard, with which single-ply or multi-ply paper or cardboard with improved strength is obtained. This process should also be simple to carry out. Furthermore, the strength should be increased when exposed to larger
  • Shear forces must be present. It should also be difficult for the paper to split, particularly along the original fiber webs in the case of multi-ply paper.
  • Other desirable properties include maintaining strength under the influence of heat or increased humidity when storing the single-ply or multi-ply paper or cardboard produced or during further processing.
  • Preferred is a process for producing dried multi-ply paper comprising the steps (A) dewatering a first aqueous pulp suspension having a dry matter content of between 0.1% and 6% on a first screen to form a first pulp web having a dry matter content of between 14% and 25%, (B) dewatering a second aqueous pulp suspension having a dry matter content of between 0.1% and 6% by weight on a second screen to form a second pulp web having a dry matter content of between 14% and 25% by weight, (C) joining the first fibrous web to the second fibrous web in such a way that the two fibrous webs touch each other on one entire surface side, thereby forming a layer composite, (D-2) Dewatering the layer composite by pressing, resulting in a partially dewatered layer composite, (E-2) Spraying the partially dewatered composite layer on at least one surface side with a spray solution or spray suspension, thereby forming a sprayed composite layer, (F-2) Dewatering the sprayed layer composite by
  • Dry content is understood here as the ratio of the mass of a sample after drying to the mass of the sample before drying, expressed as a percentage by weight (wt.%).
  • the dry content is preferably determined by drying at 105°C until the mass is constant. Drying is carried out at 105°C ( ⁇ 2°C) in a drying oven until the mass is constant. Mass is constant here when the rounded first decimal place of the percentage no longer changes for dry contents of 1 to 100 wt.% and the rounded second decimal place of the percentage no longer changes for dry contents of 0 to less than 1 wt.%. Drying is carried out at ambient pressure, possibly 101.32 KPa, without correction for deviations caused by weather and altitude. In the examples section, under dry content determination, you will find further information on how to carry out the procedure in practice.
  • the first aqueous pulp suspension is understood to mean a composition containing (a-a) water and (a-b) first pulp containing cellulose fibers.
  • An alternative term for pulp suspension is paper pulp.
  • first aqueous fiber suspension For example, grinding an aqueous fiber suspension is a mechanical process for shortening fibers and, in the case of cellulose fibers, also for defibrillating the fibers.
  • the dewatering ability of the first aqueous fiber suspension is determined by the degree of grinding achieved.
  • One method for measuring the degree of grinding of a fiber suspension is to determine the dewatering kinetics according to Schopper Riegler in units of degrees Schopper Riegler (°SR).
  • Fibers can be used as fibers. All fibers from wood or annual plants that are commonly used in the paper industry can be used. Suitable annual plants for the production of fibers are, for example, rice, wheat, sugar cane and kenaf.
  • Wood pulp e.g. from softwood or hardwood, includes, for example, groundwood, thermomechanical pulp (TMP), chemo-thermomechanical pulp (CTMP), pressure groundwood, semi-chemical pulp, high-yield pulp and refiner mechanical pulp (RMP).
  • Coarse groundwood pulp typically has a freeness of 40-60 °SR compared to normal groundwood pulp with 60-75 °SR and fine groundwood pulp with 70-80 °SR. Pulps, e.g.
  • Recovered fibers can come from waste paper, for example.
  • the waste paper can optionally be subjected to a deinking process beforehand.
  • Mixed waste paper can typically have around 40 °SR compared to waste paper from a deinking process with around 60 °SR.
  • Recovered fibers from waste paper can be used alone or in a mixture with other, particularly native fibers.
  • An aqueous pulp suspension can be obtained, for example, by recycling existing paper or cardboard, for example by mechanically treating waste paper in a pulper together with water until the aqueous pulp suspension has the desired consistency.
  • Another example of the combination of two fiber sources is the mixing of a primary pulp suspension with recycled broke from a coated paper that is produced using the primary pulp suspension.
  • the first aqueous pulp suspension may contain other components that may be deliberately added to it or may be present through the use of waste paper or existing paper.
  • a dry matter content of 2% to 4% by weight based on the aqueous fiber suspension (corresponds roughly to a fiber concentration of 20 to 40 g/L if almost exclusively fiber is present) is usually referred to as thick stock.
  • This is usually distinguished from a dry matter content of 0.1% to less than 2% by weight based on the aqueous fiber suspension (corresponds roughly to a fiber concentration of 1 to less than 20 g/L if almost exclusively fiber is present), in particular 0.5% to 1.5% by weight (5 to 15 g/L).
  • the dry matter content or dry weight of an aqueous fiber suspension includes all components that are non-volatile or, preferably, non-volatile when the dry matter content is determined by drying at 105°C to constant mass.
  • a possible further component of the first aqueous fiber suspension is (a-c) an organic polymer that is different from a fiber.
  • the organic polymer (a-c) can be neutral, cationic or anionic.
  • a neutral organic polymer (ac) can be uncharged-neutral because it does not contain any polymer units with a functional group that carries a charge at least at a pH of 7.
  • a functional group that carries a charge at least at a pH of 7 is understood here to mean an atom or a linked group of atoms that is covalently bonded to the rest of the polymer unit.
  • the functional group permanently carries a charge or acts on its own, ie independently of other components of the polymer unit or other polymer units, in its uncharged form in pure Water as an acid or as a base. The acid effect leads to the creation of a negative charge on the corresponding functional group of the polymer unit when deprotonation is carried out with a base.
  • An example of a functional group with a permanent positive charge is -(CH 2 -) 4 N + (a tetraalkylated nitrogen) such as that in diallyldimethylammonium or in 2-(N,N,N-trimethylammonium)ethyl acrylate.
  • Examples of a functional group that leads to the creation of negative charges in the polymer unit are -COOH (a carboxylic acid), -SO 2 OH (a sulfonic acid), -PO(OH) 2 (a phosphonic acid), -O-SO 2 OH (a monoesterified sulfuric acid) or -O-PO(OH) 2 (a monoesterified phosphoric acid).
  • Examples of a neutral organic polymer (a-c) which does not contain any polymer units having a functional group carrying a charge at least at a pH of 7 are polyacrylamide, poly(acrylamide-co-acrylonitrile), poly(vinyl alcohol) or poly(vinyl alcohol-co-vinyl acetate).
  • a neutral organic polymer (ac) can also be amphoteric-neutral because it contains polymer units with a functional group that carries a negative charge at least at a pH of 7, as well as polymer units with a functional group that carries a positive charge at least at a pH of 7, and furthermore the number of all negative charges and the number of all positive charges of the functional groups balance each other out.
  • An organic polymer in which the number of positive charges differs from the number of negative charges by less than 7 mol% units is also considered to be amphoteric-neutral herein, where 100 mol% units are the number of all polymerized monomers to produce the organic polymer.
  • an organic polymer that has been produced by polymerizing 30 mol% acrylic acid and 70 mol% N-vinylformamide and in which half of the polymerized N-vinylformamide units are hydrolyzed is considered amphoteric-neutral with a difference of 5 mol% units between the functional groups - COOH and -CH 2 -CH(NH 2 )-.
  • a cationic organic polymer (a-c) can be purely cationic, i.e. it contains polymer units with a functional group that carries a positive charge at least at a pH of 7, but it does not contain polymer units with a functional group that carries a negative charge at least at a pH of 7.
  • Examples of a purely cationic organic polymer (a-c) are poly(allylamine), poly(diallylamine), poly(diallyldimethylammonium chloride), poly(acrylamide-co-diallyldimethylammonium chloride) or poly(acrylamide-co-2-(N,N,N-trimethylammonium)ethyl acrylate chloride).
  • a cationic organic polymer (ac) can also be amphoteric-cationic, ie it contains polymer units with a functional group that carries a positive charge at least at a pH of 7, as well as polymer units with a functional group that carries a negative charge at least at a pH of 7, and the number of all positive charges is higher than the number of all negative charges of the functional groups.
  • An organic polymer is considered to be amphoteric-cationic herein if the number of positive charges differs from that number of negative charges by equal to or more than 7 mol% units, where 100 mol% units are the number of all polymerized monomers to produce the organic polymer.
  • an organic polymer obtained by polymerization of 30 mol% acrylic acid and 70 mol% N-vinylformamide, in which 57% of the polymerized N-vinylformamide units are hydrolyzed is considered to be amphoteric-cationic with a difference of 10 mol% units between the functional groups -COOH and -CH 2 -CH(NH 2 )-.
  • An anionic organic polymer (a-c) can be purely anionic, i.e. it contains polymer units with a functional group that carries a negative charge at least at a pH of 7, but it does not contain polymer units with a functional group that carries a positive charge at least at a pH of 7.
  • Examples of a purely anionic organic polymer (a-c) are poly(acrylic acid), poly(styrene-co-n-butyl acrylate-co-acrylic acid) or poly(acrylamide-co-acrylonitrile-co-acrylic acid).
  • An anionic organic polymer (ac) can also be amphoteric-anionic, ie it contains polymer units with a functional group that carries a negative charge at least at a pH of 7, as well as polymer units with a functional group that carries a positive charge at least at a pH of 7, and the number of all negative charges is higher than the number of all positive charges of the functional groups.
  • An organic polymer is considered to be amphoteric-anionic here if the number of negative charges differs from the number of positive charges by equal to or more than 7 mol% units, where 100 mol% units are the number of all polymerized monomers to produce the organic polymer.
  • an organic polymer that has been produced by polymerizing 30 mol% acrylic acid and 70 mol% N-vinylformamide and in which 29% of the polymerized N-vinylforamide units are hydrolyzed, with 10 mol% units difference between the functional groups -COOH and -CH 2 -CH(NH 2 )- is considered to be amphoteric-anionic.
  • the organic polymer (a-c) can also be differentiated according to whether it is linear, branched or crosslinked.
  • Crosslinking can be achieved, for example, by adding a crosslinker during the polymerization of the starting monomers or by adding a crosslinker after polymerization, in particular just before the organic polymer (a-c) is added to the aqueous fiber suspension.
  • polyacrylamide can be crosslinked during polymerization by adding the crosslinker methylenebisacrylamide to acrylamide or by adding a crosslinker such as glyoxal after polymerization. If necessary, both types of crosslinking can be combined.
  • a crosslinked organic polymer that has a high degree of crosslinking, typically during monomer polymerization, is particularly worthy of mention here. This is present in the first aqueous fiber suspension as particles, in particular as so-called organic microparticles.
  • the organic polymer (a-c) can also be differentiated into natural, modified-natural or synthetic.
  • a natural organic polymer is usually obtained from nature, with appropriate isolation steps being used where appropriate but no targeted chemical-synthetic modification.
  • An example of a natural organic polymer (a-c) is unmodified starch. Cellulose is not an example of a natural organic polymer (a-c) - this is a fiber material (a-b).
  • a modified-natural organic polymer is modified by a chemical-synthetic process step.
  • An example of a modified-natural organic polymer (a-c) is cationic starch.
  • a synthetic organic polymer (a-c) is obtained chemically-synthetically from individual monomers.
  • An example of a synthetic organic polymer (a-c) is polyacrylamide.
  • An organic polymer (a-c) here also includes two or more different organic polymers. Accordingly, an organic polymer (a-c) as a possible further component of the first aqueous fiber suspension is then divided into a first organic polymer (a-c-1), a second organic polymer (a-c-2), ... etc.
  • a possible further component of the first aqueous fiber suspension is (ad) a filler.
  • a filler (ad) is an inorganic particle, in particular an inorganic pigment.
  • Inorganic pigments include all pigments based on metal oxides, silicates and/or carbonates that are usually used in the paper industry, in particular pigments from the group consisting of calcium carbonate, which can be used in the form of ground lime, chalk, marble (GCC) or precipitated calcium carbonate (PCC), talc, kaolin, bentonite, satin white, calcium sulfate, barium sulfate and titanium dioxide.
  • An inorganic particle is also a colloidal solution of polysilicic acids, in which the silica particles typically have a particle size between 5 and 150 nm.
  • a filler (a-d) can also be two or more different fillers. Accordingly, a filler (a-d) as a possible further component of the first aqueous fiber suspension is then divided into a first filler (a-d-1), a second filler (a-d-2), ... etc.
  • inorganic pigments with an average particle size (volume average) ⁇ 10 ⁇ m, preferably from 0.3 to 5 ⁇ m, in particular from 0.5 to 2 ⁇ m, are used.
  • the average particle size (volume average) of the inorganic pigments and the particles of the powder composition is generally determined in this document using the quasi-elastic light scattering method (DIN-ISO 13320-1), for example using a Mastersizer 2000 from Malvern Instruments Ltd.
  • a possible further component of the first aqueous fiber suspension is (ae) another paper auxiliary.
  • Another paper auxiliary (ae) is different from the aforementioned components (ab), (ac) and (ad).
  • Another paper auxiliary (ae) is, for example, a machine sizing agent, a water-soluble salt of a trivalent metal cation, a defoamer, a non-polymeric wet strength agent, a biocide, an optical brightener or a paper dye.
  • a machine sizing agent are alkyl ketene dimers (AKD), alkenyl succinic anhydrides (ASA) and resin size.
  • Examples of a water-soluble salt of a trivalent metal cation are aluminum(III) salts, in particular AlCl 3 such as AlCl 3 ⁇ 6 H 2 O, Al 2 (SO 4 ) 3 such as Al 2 (SO 4 ) 3 ⁇ 18 H 2 O, or KAI(SO 4 ) 2 ⁇ 12 H 2 O.
  • Another paper auxiliary (a-e) here also includes two or more different other paper auxiliary agents. Accordingly, another paper auxiliary (a-e) as a possible further component of the first aqueous fiber suspension is then divided into a first other paper auxiliary (a-e-1), a second other paper auxiliary (a-e-2), ... etc.
  • organic polymer (a-c) and more than one filler (a-d) are often added to the first aqueous pulp suspension.
  • this serves, for example, to influence technical properties of the paper production process itself or technical properties of the paper produced.
  • retention agents, dewatering agents, wet strength agents or dry strength agents are used.
  • Examples of a retention agent are cationic, amphoteric or anionic organic polymers (ac).
  • Examples are an anionic polyacrylamide, a cationic polyacrylamide, a cationic starch, a cationic polyethyleneimine or a cationic polyvinylamine.
  • a retention agent is, for example, a filler (ad), which is an anionic microparticle, in particular colloidal silica or bentonite. Combinations of the above examples are also possible.
  • One combination is in particular a dual system consisting of a cationic polymer with an anionic microparticle or an anionic Polymer with a cationic microparticle.
  • a synthetic organic polymer (ac) or a dual system is preferred as a retention agent.
  • a cationic first organic polymer (ac-1) is already present in combination with a first filler (ad-1), for example a suitable bentonite, and optionally a second filler (ad-2) is then calcium carbonate.
  • the first fiber suspension preferably contains an organic polymer (a-c) which is a synthetic organic polymer.
  • an organic polymer (a-c) which is a polyacrylamide.
  • an organic polymer (a-c) which is a cationic polyacrylamide.
  • an organic polymer (a-c) which is a cationic polyacrylamide and acts as a retention agent.
  • the weight amount of organic polymer (a-c) is 0.001 wt.% to 0.2 wt.% based on the weight amount of first fiber (a-b) in the first fiber suspension.
  • the weight amount of first fiber (a-b) refers to the dry content of first fiber (a-b) and the weight amount of organic polymer (a-c) refers to the solid content of organic polymer (a-c).
  • the solid content of the organic polymer (a-c) is determined from a material sample of the organic polymer (a-c) by drying this sample in a circulating air drying cabinet at 140°C for 120 minutes. For example, in the case of an aqueous polymer solution, suspension or emulsion, the sample is placed in a metal lid for drying.
  • the amount by weight of organic polymer (a-c) is 0.005 wt.% to 0.1 wt.% based on the amount by weight of first fiber (a-b) in the first fiber suspension, particularly preferably 0.01 wt.% to 0.08 wt.%, very particularly preferably 0.02 wt.% to 0.06 wt.% and especially preferably 0.3 wt.% to 0.05 wt.%.
  • the amount by weight of organic polymer (a-c) which is a cationic polyacrylamide is 0.001 wt.% to 0.2 wt.% based on the amount by weight of first fiber (a-b) in the first fiber suspension.
  • no anionic organic polymer is added to the first fiber suspension.
  • a dry strength agent examples include a synthetic organic polymer (a-c) such as polyvinylamine, polyethyleneimine, polyacrylamide or glyoxylated polyacrylamide or a natural organic polymer (a-c) such as unmodified starch.
  • the dry matter content of the first aqueous fiber suspension is preferably between 0.11 wt.% and 5 wt.%, very preferably between 0.12 wt.% and 4 wt.%, particularly preferably between 0.13 wt.% and 3 wt.%, 2 wt.%, 1 wt.%, 0.6 wt.% or 0.35 % by weight as an upper limit and most preferably between 0.14 % by weight and 0.30 % by weight.
  • the first sieve which has a first sieve top and a first sieve bottom, has sieve meshes as openings.
  • the first aqueous fiber suspension is applied to the sieve via the headbox.
  • the headbox ensures that the fiber suspension is applied evenly and across the entire width of the sieve.
  • the sieve top is an essentially flat surface at the moment of the headbox, i.e. apart from the sieve meshes or other material-related unevenness and a certain radius bend in the case of a ring sieve. This allows the production of a uniformly thin, as homogeneous as possible fiber web.
  • a fiber web produced in this way is flat, i.e. it has a very small height in relation to its length and width.
  • the fiber of the fiber suspension and possible other components that are to be present in the ultimately produced paper, for example a filler, are ideally retained entirely or at least substantially in the forming fiber web. Possible other components of the fiber suspension that are added to support the retention of the other components, to support the dewatering of the fiber suspension or to support uniform sheet formation, for example an organic polymer, have their effect during this process.
  • the dry portion of the fiber web which determines the dry content of the fiber web, contains the retained components of fiber, possible other components that are to be present in the ultimately produced paper, and the possible other components. Depending on their retention behavior, these components are, for example, the aforementioned fiber, organic polymers, fillers and other paper auxiliaries.
  • the fiber web is strong enough to be removed from the screen.
  • the screen contains, for example, a metal or plastic mesh.
  • the screen is preferably an endless screen. After the resulting fiber web is separated from an endless screen, the endless screen runs back to the material application, where new fiber suspension is applied to the running endless screen.
  • the screen is very preferably an endless screen that runs around several rollers.
  • Well-known screen types for endless screens are the fourdrinier screen, the double-wire former with an endless lower screen and an additional endless upper screen, the round screen and the round screen former. A fourdrinier screen is preferred.
  • the dewatering of the fiber suspension on the top of the screen can be supported by applying a negative pressure on the bottom of the screen.
  • the negative pressure is understood to be a lower pressure than the pressure on the top of the screen, which corresponds, for example, to the ambient pressure.
  • the dry content of the first fibrous web is preferably 15 wt.% to 24 wt.%, very preferably 16 wt.% to 23 wt.%, particularly preferably 17 wt.% to 22 wt.%, very particularly preferably 17.5 wt.% to 22 wt.% and especially preferably 18 wt.% to 21 wt.%.
  • the square meter weight of a fibrous web is defined here as the mass of components per square meter of fibrous web that remain after drying, preferably as a constant mass in the aforementioned dry content determination at a drying temperature of 105°C.
  • the square meter weight of a fibrous web is preferably 20 to 120 g/m 2 .
  • the square meter weight of the first fibrous web or the sum of all square meter weights of the fibrous webs is not necessarily exactly the square meter weight of the dried single-ply or multi-ply paper.
  • the sum of all the square meter weights of the fibrous webs is not the grammage of the dried multi-layer paper ultimately produced from it, because at least one of the layers is sprayed as a fibrous web with a slight increase in grammage, the layer composite could lose some of the aforementioned components after drying during dewatering by pressing and, more formally, during dewatering via heated cylinders, with a slight reduction in grammage, or the dried multi-layer paper or its wetter precursors could stretch or compress during said dewatering or other steps. In the latter case, one square meter of the fibrous web would no longer correspond to one square meter of the dried multi-layer paper.
  • the square meter weight of the flat first fibrous web can approximately correspond to the dried single-layer paper or to the proportion of the layer that results from this fibrous web in the further process for a multi-layer paper in the total grammage of the dried multi-layer paper.
  • the weight per square meter of the first fibrous web is, for example, 30 to 100 g/m 2 , 30 to 60 g/m 2 , 65 to 105 g/m 2 , 35 to 50 g/m 2 or 70 to 90 g/m 2 .
  • the second aqueous fiber suspension is understood to mean a composition containing (b-a) water and (b-b) second fiber containing cellulose fibers.
  • the statements and preferences for step (A) also apply mutatis mutandis to step (B), whereby an organic polymer (b-c) or a first organic polymer (b-c-1) and a second organic polymer (b-c-2) etc., a filler (b-d) or a first filler (b-d-1) and a second filler (b-d-2) etc., another paper auxiliary (b-e) or a first other paper auxiliary (b-e-1) and a second other paper auxiliary (b-e-2), a second screen having a second screen top side and a second screen bottom side, a second fiber web and a square meter weight of the second fiber web are meant.
  • the second fiber material (bb) is the same as the first fiber material (ab).
  • the organic polymer (bc) is the same as the organic polymer (ac) or the first organic polymer (bc-1) is equal to the first organic polymer (ac-1), very preferably the first organic polymer (bc-1) is equal to the first organic polymer (ac-1) and the second organic polymer (bc-2) is equal to the second organic polymer (ac-2).
  • the second organic polymer (bc) is contained in the same amount by weight per second fiber (bb) as the first organic polymer (ac) per first fiber (ab).
  • the amount by weight of organic polymer (ac), which is a cationic polyacrylamide is 0.001 wt. % to 0.2 wt. % based on the amount by weight of first fiber (ab) in the first fiber suspension and the amount by weight of organic polymer (bc), which is a cationic polyacrylamide, is 0.001 wt. % to 0.2 wt. % based on the amount by weight of second fiber (bb) in the second fiber suspension.
  • the filler (bd) is the same as the filler (ad) or the first filler (bd-1) is the same as the first filler (ad-1), very preferably the first filler (bd-1) is the same as the first filler (ad-1) and the second filler (bd-2) is the same as the second filler (ad-2).
  • the other paper auxiliary (be) is the same as the other paper auxiliary (ae) or the first other paper auxiliary (be-1) is the same as the first other paper auxiliary (ae-1), very preferably the first other paper auxiliary (be-1) is the same as the first other paper auxiliary (ae-1) and the second other paper auxiliary (be-2) is the same as the second other paper auxiliary (ae-2).
  • the composition of the second fiber suspension is the same as the composition of the first fiber suspension.
  • the weight per square meter of the first fibrous web is higher than the weight per square meter of the second fibrous web, very preferably the weight per square meter of the first fibrous web is 65 to 105 g/m 2 and the weight per square meter of the second fibrous web is 30 to 60 g/m 2 .
  • an organic polymer (a-c) is added as a retention agent to the first aqueous fiber suspension containing (a-a) water and (a-b) first fiber before dewatering in step (A).
  • the amount of polymer (a-c) added is 0.001% by weight to 0.2% by weight based on the first fiber (a-b).
  • the amount of polymer (a-c) added is 0.020% by weight to 0.15% by weight.
  • the polymer (a-c) is very particularly preferably a cationic polymer and especially preferably a cationic polyacrylamide.
  • an organic polymer (ac) is added as a retention agent to the first aqueous fiber suspension containing (aa) water and (ab) first fiber before dewatering in step (A), and an organic polymer (bc) is added as a retention agent to the second aqueous fiber suspension containing (ba) water and (bb) second fiber before dewatering in step (B).
  • the amount of polymer (ac) added is 0.001% by weight to 0.2% by weight based on the first fiber (ab)
  • the amount of organic polymer (bc) added is 0.001% by weight to 0.2% by weight based on the second fiber (bb).
  • the amount of polymer (ac) added is 0.020% by weight to 0.15% by weight, and the amount of polymer (bc) added is 0.0020% by weight to 0.15% by weight.
  • the polymer (ac) and the polymer (bc) are a cationic polymer and especially preferably a cationic polyacrylamide.
  • step (A) the first fiber suspension is applied to the top of the first sieve and dewatering is assisted by applying a negative pressure to the first sieve bottom
  • step (B) the second fiber suspension is applied to the top of the second sieve and dewatering is assisted by applying a negative pressure to the second sieve bottom
  • step (A) the first fiber suspension is applied to the top of the first sieve and dewatering is assisted by applying a negative pressure to the first sieve bottom
  • step (B) the second fiber suspension is applied to the top of the second sieve and dewatering is assisted by applying a negative pressure to the second sieve bottom.
  • step (A) the first fiber suspension is applied to the top of the first sieve and dewatering is assisted by applying a negative pressure to the bottom of the first sieve
  • step (B) the second fiber suspension is applied to the top of the second sieve and dewatering is assisted by applying a negative pressure to the bottom of the second sieve.
  • step (C) the joining of the first fibrous web with the second fibrous web creates the layer composite.
  • One surface side of the first fibrous web comes into permanent contact with one surface side of the second fibrous web.
  • the surface sides touch each other at least to the extent that the fibrous webs then adhere weakly to each other.
  • the fibrous webs are arranged or brought together in such a way that the fibrous webs lie on top of each other across their entire width or the fibrous webs cover each other completely.
  • Joining corresponds to completely placing the first fibrous web and the second fibrous web on top of each other. For example, joining takes place spatially and temporally almost immediately before pressing in step (D-2).
  • step (D-1) the first fibrous web is pressed, which leads to further dewatering and a corresponding increase in the dry content in the resulting partially dewatered first fibrous web.
  • Step (D-1) begins when the first fibrous web from step (A) reaches the so-called couching line.
  • Couching involves dewatering by exerting mechanical pressure on the first fibrous web.
  • step (D-2) the layer composite is pressed, which leads to further dewatering and a corresponding increase in the dry content in the resulting partially dewatered layer composite.
  • Step (D-2) begins when the layer composite from step (C) reaches the so-called couching line. During couching, dewatering takes place by exerting mechanical pressure on the layer composite.
  • the removal of water by mechanical pressure is more energy-efficient than the removal of water by adding heat or by drying.
  • a water-absorbent belt e.g. a felt-like fabric
  • the drainage is supported by the absorption of the pressed water.
  • a roller is suitable for exerting pressure on the layer composite.
  • passing the layer composite through two rollers, possibly resting on the water-absorbent belt, is suitable.
  • the surface of the roller consists of steel, granite or hard rubber, for example.
  • the surface of a roller can be covered with a water-absorbent material.
  • the water-absorbent materials have a high degree of absorbency, porosity, strength and elasticity. After contact with the first fibrous web or the layer composite, the water-absorbent materials are ideally dewatered again on a side facing away from the first fibrous web or the layer composite, e.g. using a doctor blade.
  • a partially dewatered first fibrous web is created.
  • the partially dewatered first fibrous web is strong enough to be fed to the next step without mechanical support.
  • the partially dewatered first fibrous web has, for example, a dry content of between 35% by weight and 65% by weight.
  • the partially dewatered first fibrous web preferably has a dry content of between 37% by weight and 60% by weight, very preferably between 38% by weight and 55% by weight, particularly preferably between 39% by weight and 53% by weight, very particularly preferably between 40% by weight and 52% by weight.
  • a partially dewatered layer composite is created.
  • the partially dewatered layer composite is strong enough to be fed to the next step without mechanical support.
  • the partially dewatered layer composite has, for example, a dry content of between 35% and 65% by weight.
  • the partially dewatered layer composite preferably has a dry content of between 37% and 60% by weight, very preferably between 38% and 55% by weight, particularly preferably between 39% and 53% by weight, and most preferably between 40% and 52% by weight.
  • the spraying in step (E-1) or (E-2) with the spray solution or spray suspension preferably takes place from a spray device.
  • the spray device contains, for example, one or more nozzles.
  • the spray solution or spray suspension is sprayed from the nozzle(s) onto the surface side of the partially dewatered layer composite to be sprayed.
  • the spray solution or spray suspension is preferably under an overpressure compared to the ambient pressure, for example 0.5 to 15 bar, preferably 0.5 to 4.5 bar and very preferably 0.8 to 2.5 bar.
  • the overpressure is built up at the latest shortly before it exits the nozzle.
  • a container for storing the spray solution or spray suspension can be part of the spray device.
  • the partially dewatered first fibrous web or the partially dewatered layer composite each have two surface sides.
  • One surface side or both surface sides of the partially dewatered first fibrous web or the partially dewatered layer composite can be sprayed in step (E-1) or (E-2).
  • step (F-1) the sprayed, partially dewatered first fibrous web from step (E-1) is further dewatered by supplying heat, which produces the dried single-ply paper at the end of step (F-1).
  • the heat is supplied to the sprayed, partially dewatered first fibrous web, for example, by heated cylinders over which the sprayed, partially dewatered first fibrous web is guided, by IR radiators, by warm air that is guided over the sprayed, partially dewatered first fibrous web, or by a combination of two or all three measures.
  • step (F-2) the sprayed layer composite from step (E-2) is further dewatered by supplying heat, which produces the dried multi-layer paper at the end of step (F-2).
  • the heat is supplied to the sprayed, partially dewatered first fibrous web and the partially dewatered layer composite, for example, by heated cylinders over which the sprayed layer composite is guided, by IR radiators, by warm air that is guided over the sprayed layer composite, or by a combination of two or all three measures.
  • the heat is supplied at least by heated cylinders.
  • the cylinders can be heated by electricity or, in particular, steam. Typical temperatures of the cylinders are 120 to 160°C.
  • a cylinder can have a coating on its surface that improves the surface quality of the dried single-ply paper or multi-ply paper.
  • the dried single-ply paper has the highest strength in comparison with the strength of the first fibrous web, the partially dewatered first fibrous web or the sprayed partially dewatered first fibrous web.
  • the dried multi-ply paper has the highest strength in comparison with the first fibrous web or the combined strengths of all fibrous webs, with a layer composite, with a partially dewatered layer composite or with a sprayed layer composite.
  • a measure of the strength of the dried single-ply paper or the dried multi-ply paper is, for example, the internal strength.
  • the internal strength is a measure of the strength of the dried multi-ply paper.
  • a dried single-ply paper or a dried multi-ply paper is defined herein as a sheet material having a grammage, ie a basis weight of the dried paper, of up to 600 g/m 2 .
  • the term paper in the narrower sense is typically used for grammages up to 225 g/m 2
  • the term cardboard is used for grammages from 150 g/m 2 .
  • the grammage of the dried single-ply paper or the dried multi-ply paper is preferably 20 to 400 g/m 2 , very preferably 40 to 280 g/m 2 , particularly preferably 60 to 200 g/m 2 , very particularly preferably 80 to 160 g/m 2 , especially preferably 90 to 140 g/m 2 and very especially preferably 100 to 130 g/m 2 .
  • the dried multi-layer paper preferably has two, three or four layers, very preferably two or three layers and particularly preferably two layers. With two layers, there is exactly one first fibrous web and one second fibrous web in the process. With three layers, there is an additional fibrous web as the third fibrous web and with four layers, there is another additional fibrous web as the fourth fibrous web. A third and optionally a fourth fibrous web are connected to the layer composite of the first fibrous web and the second fibrous web. Steps (D-2), (E-2) and (F-2) then follow.
  • the first fibrous web and the second fibrous web each make a contribution to the grammage of the dried multi-ply paper. These contributions can be the same or different. The contributions are approximately calculated from the square meter weights of the respective fibrous web.
  • the contribution of the first fibrous web to the grammage of the dried multi-ply paper is preferably higher than the contribution of the second fibrous web, very preferably the ratio is 3 or more parts of first fibrous web to 2 or fewer parts of second fibrous web.
  • the ratio of 3 or more parts of first fibrous web to 2 or fewer parts of second fibrous web is particularly preferably 4 parts of first fibrous web to 1 part of second fibrous web.
  • the dry content of the dried single-ply paper or the dried multi-ply paper is, for example, at least 88% by weight.
  • the dry content of the dried single-ply paper or the dried multi-ply paper is preferably between 89% by weight and 100% by weight, very preferably between 90% by weight and 98% by weight, particularly preferably between 91% by weight and 96% by weight, very particularly preferably between 92% by weight and 95% by weight and especially preferably between 93% by weight and 94% by weight.
  • step (F-1) or step (F-2) can be followed by calendering the dried single-ply or multi-ply paper.
  • a method is preferred in which, after step (D-1) and before step (F-1), no application of a material by immersing the partially dewatered first fibrous web or the sprayed partially dewatered first fibrous web in an aqueous solution or by coating one surface of the partially dewatered first fibrous web or the sprayed partially dewatered first fibrous web with an aqueous solution is carried out.
  • a method is very preferred in which, after step (D-1) and before step (F-1), with the exception of step (E-1), no application of a material that contributes to increasing the grammage of the dried single-ply paper by at least 2 g/m 2 is carried out.
  • a method is particularly preferred in which, after step (D-1) and before step (F-1), with the exception of step (E-1), no application of a material that contributes to increasing the grammage of the dried single-ply paper by at least 1 g/m 2 is carried out.
  • Very particularly preferred is a process in which, after step (D-1) and before step (F-1), only step (E-1) is used to apply a material which contributes to increasing the grammage of the dried single-ply paper.
  • a method is preferred in which, after step (D-2) and before step (F-2), no application of a material by immersing the partially dewatered layer composite or the sprayed layer composite in an aqueous solution or by coating one surface side of the partially dewatered layer composite or the sprayed layer composite with an aqueous solution takes place.
  • a method is very preferred in which, after step (D-2) and before step (F-2), with the exception of step (E-2), no application of a material that contributes to increasing the grammage of the dried multi-layer paper by at least 2 g/m 2 takes place.
  • a method is particularly preferred in which, after step (D-2) and before step (F-2), with the exception of step (E-2), no application of a material that contributes to increasing the grammage of the dried multi-layer paper by at least 1 g/m 2 takes place.
  • Very particularly preferred is a process in which, after step (D-2) and before step (F-2), only step (E-2) is used to apply a material which contributes to increasing the grammage of the dried multi-ply paper.
  • a polymer P is water-soluble if its solubility in water under standard conditions (20 °C, 1013 mbar) and pH 7.0 is at least 5% by weight, preferably at least 10% by weight.
  • the weight percentages refer to the solid content of polymer P.
  • the solid content of polymer P is determined after its production as an aqueous polymer solution.
  • a sample of the polymer solution in a metal lid is dried in a circulating air drying cabinet at 140 °C for 120 minutes. Drying takes place at ambient pressure, optionally 101.32 KPa, without correction for deviations resulting from weather and sea level.
  • the spray solution or spray suspension preferably has a pH of 5.5 or greater.
  • the spray solution or spray suspension very preferably has a pH between 5.8 and 12, particularly preferably between 6.2 and 11, very particularly preferably between 6.4 and 10, especially preferably between 6.8 and 9 and particularly especially preferably between 7.2 and 8.8.
  • the density of the spray solution or spray suspension can be approximately assumed to be 1 g/cm 3 .
  • the spray solution or spray suspension preferably contains between at least 85% by weight and 99.99% by weight of water (ea) based on the total weight of the spray solution or Spray suspension, very preferably between at least 95 wt.% and 99.95 wt.% water, particularly preferably between 98 wt.% and 99.9 wt.% water and most preferably between 99 wt.% and 99.7 wt.% water.
  • water ea
  • the spray solution or spray suspension preferably contains between 0.01% by weight and less than 15% by weight of polymer P (e-b) based on the total weight of the spray solution or spray suspension, very preferably between 0.05% by weight and less than 5% by weight of polymer P, particularly preferably between 0.1% by weight and less than 2% by weight of polymer P, very particularly preferably between 0.15% by weight and less than 1% by weight of polymer P and especially preferably between 0.3% by weight and less than 0.8% by weight of polymer P.
  • the weight of polymer P in a spray solution or spray suspension refers to the solid content of polymer P.
  • the further layer connector (e-c), which is different from a polymer P, is, for example, an organic polymer.
  • a natural polysaccharide, a modified polysaccharide, a protein or a polyvinyl alcohol is preferred.
  • a mixture of several layer connectors is also included.
  • a natural polysaccharide is, for example, natural starch or guar gum.
  • a modified polysaccharide is, for example, a chemically modified starch or a cellulose ether.
  • a protein is, for example, glutin or casein.
  • a cellulose ether is, for example, carboxymethyl cellulose.
  • a natural starch is, for example, a starch from corn, wheat, oats, barley, rice, millet, potatoes, peas, cassava, sorghum or sago.
  • a degraded starch has a reduced weight-average molecular weight compared to the natural starting starch.
  • the degradation of the starch can occur enzymatically, by oxidation, acid action or base action. Enzymatic degradation and degradation by acid action or base action in the presence of water leads to increased levels of oligosaccharides or dextrins via hydrolysis. Some degraded starches are commercially available.
  • the degradation of starch is a chemical process.
  • the chemical modification here is a functionalization of a natural starch by covalently attaching a chemical group or breaking down covalent bonds in the starch.
  • a chemically modified starch is obtainable, for example, by esterification or etherification of a natural starch followed by starch degradation. The esterification can be supported by an inorganic or organic acid. For example, an anhydride of the acid or a chloride of the acid is used as a reagent.
  • a common procedure for etherifying a starch involves treating the starch with an organic reagent that contains a reactive halogen atom, an epoxy functionality or a sulfate group in an alkaline, aqueous reaction mixture.
  • Known types of etherification of starches are alkyl ethers, uncharged hydroxyalkyl ethers, carboxylic acid alkyl ethers or 3-trimethylammonium-2-hydroxypropyl ether.
  • a chemically modified starch is, for example, phosphated degraded starch and acetylated degraded starch.
  • a chemically modified starch can be neutral, anionic or cationic.
  • the other layer connector (e-c) can be neutral, anionic or cationic.
  • Neutral is divided into uncharged neutral and amphoteric neutral. The distinction is made according to the definitions given for the organic polymer (a-c).
  • Uncharged neutral means that at a pH of 7 there are no charge-bearing atoms or functional groups.
  • Amphoteric neutral means that at a pH of 7 there are atoms or functional groups with a positive charge as well as atoms or functional groups with a negative charge, but the total charges differ by less than 7 mol%, with all charges adding up to 100 mol%.
  • Cationic is divided accordingly into purely cationic and amphoteric cationic.
  • Anionic is divided accordingly into purely anionic and amphoteric anionic.
  • a further layer connector (e-c) which is uncharged-neutral, amphoteric-neutral, purely anionic, amphoteric-anionic or amphoteric cationic.
  • a further layer connector (e-c) which is neutral or anionic.
  • a further layer connector (e-c) which is uncharged-neutral or purely anionic.
  • a further layer connector (e-c) which is uncharged-neutral.
  • the spray solution or spray suspension preferably contains between 0% by weight and 15% by weight of a further layer connector (e-c) based on the total weight of the spray solution or spray suspension.
  • the amount of further layer connector (e-c) is between 0.05% by weight and less than 5% by weight of further layer connector (e-c), particularly preferably between 0.1% by weight and less than 2% by weight of further layer connector (e-c), very particularly preferably between 0.15% by weight and less than 1% by weight of further layer connector (e-c) and especially between 0.3% by weight and less than 0.8% by weight of further layer connector (e-c).
  • the amount by weight of a further layer connector (e-c) is equal to or less than the amount by weight of polymer P (e-b), determined as the solid content of polymer P (e-b) and as the solid content of further layer connector (e-c), in a spray solution or spray suspension, very preferably equal to or less than half the amount by weight of polymer P (e-b), particularly preferably equal to or less than a third of the amount by weight of polymer P (e-b) and very particularly preferably equal to or less than a quarter of the amount by weight of polymer P (e-b).
  • the spray solution or spray suspension preferably contains no further layer connector (e-c) which is a cationic starch.
  • the spray solution or spray suspension particularly preferably contains no further layer connector (e-c) which is a starch.
  • the spray solution or spray suspension particularly preferably contains no further layer connector (e-c) which is purely cationic.
  • the spray solution or spray suspension very particularly preferably contains no further layer connector (e-c) which is cationic.
  • the spray solution or spray suspension especially preferably contains no further layer connector (e-c) which is an organic polymer and is different from polymer P.
  • the spraying aid (ed), which is different from a polymer P and the further layer connector, is, for example, a viscosity regulator, a pH regulator, a defoamer or a biocide.
  • the spray solution or spray suspension preferably contains between 0% by weight and less than 2% by weight of spray auxiliary agent (e-d) based on the total weight of the spray solution or spray suspension.
  • the amount of spray auxiliary agent (e-d) is between 0.001% by weight and less than 1% by weight of spray auxiliary agent (e-d), particularly preferably between 0.005% by weight and less than 0.8% by weight of spray auxiliary agent (e-d) and very particularly preferably between 0.01% by weight and less than 0.5% by weight of spray auxiliary agent (e-d).
  • the amount by weight of a spray auxiliary agent (e-d) is equal to or less than one tenth of the amount by weight of polymer P (e-b), determined as the solids content of polymer P (e-b), in a spray solution or spray suspension, very preferably equal to or less than one twentieth of the amount by weight of polymer P (e-b), particularly preferably equal to or less than one thirtieth of the amount by weight of polymer P (e-b) and very particularly preferably equal to or less than one fortieth of the amount by weight of polymer P (e-b).
  • the spray solution or spray suspension preferably does not contain any polydiallyldimethylammonium chloride or pentaethylenehexamine which is substituted with an alkyl having at least 5 C atoms or with an arylalkyl.
  • the spray solution or spray suspension very preferably does not contain any homo- or copolymer of protonated or quaternized dialkylaminoalkyl acrylate, homo- or copolymer of protonated or quaternized dialkylaminoalkyl methacrylate, homo- or copolymer of protonated or quaternized dialkylaminoalkylacrylamide, homo- or copolymer of protonated or quaternized dialkylaminoalkyl methacrylamide, homo- or copolymer of diallyldimethylammonium chloride or pentaethylenehexamine which is substituted with an alkyl having at least 5 C atoms or with an arylalkyl.
  • the spray solution or spray suspension preferably does not contain any filler according to the previous definition of filler (a-d).
  • the application amount of spray solution or spray suspension is preferably 0.05 to 5 g/m 2 based on the solids content of the spray solution or spray suspension and based on the sprayed area. Very preferred is 0.1 to 3 g/m 2 , particularly preferred is 0.3 to 1.5 g/m 2 , very particularly preferred is 0.4 to 1.0 g/m 2 and especially preferred is 0.5 to 0.8 g/m 2 .
  • Solution, precipitation, suspension or emulsion polymerization are available for polymerizing the monomers (i) and (ii) to form polymer P.
  • 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. Examples of an alcohol are methanol, ethanol or n-propanol.
  • the polymerization takes place radically, for example by using radical polymerization initiators, for example peroxides, hydroperoxides, so-called redox catalysts or azo compounds that decompose into radicals.
  • the polymerization is carried out, for example, in water or a water-containing mixture as a solvent in a temperature range of 30 to 140°C, and it can be carried out under ambient pressure, reduced pressure or increased pressure.
  • a water-soluble polymerization initiator is preferably selected, for example 2,2'-azobis(2-methylpropionamidine) dihydrochloride.
  • polymerization regulators When polymerizing the monomers (i) and (ii) to form polymer P, polymerization regulators can be added to the reaction. Typically, 0.001 to 5 mol% based on the total amount of all monomers (i) and (ii) are used.
  • Polymerization regulators are known from the literature and are, for example, sulfur compounds, sodium hypophosphite, formic acid or tribromochloromethane. Individual examples of sulfur compounds are mercaptoethanol, 2-ethylhexylthioglycolate, thioglycolic acid and dodecyl mercaptan.
  • the polymer P has a weight-average molecular weight Mw between 75,000 and 5,000,000 Daltons.
  • the polymer P has a weight-average molecular weight Mw between 100,000 and 4,500,000 Daltons, particularly preferably between 180,000 and 2,500,000 Daltons, and especially preferably between 210,000 and 1,500,000 Daltons.
  • the weight-average molecular weight can be determined using static light scattering, for example at a pH of 9.0 in a 1000 millimolar saline solution.
  • the polymer P has a cationic equivalent of less than 3 meq/g, very preferably less than 2.4 meq/g, particularly preferably less than 2.2 and more than 0.1 meq/g, and especially preferably from 2.0 meq/g to 0.5 meq/g.
  • the cationic equivalent is preferably determined by titration of an aqueous solution of the polymer P, adjusted to a pH of 3, with an aqueous potassium polyvinyl sulfate solution.
  • the determination of the cationic equivalent is carried out by i) providing a predetermined volume of an aqueous solution of the polymer P, adjusted to a pH of 3, in a particle charge detector, for example the particle charge detector PCD-02 manufactured by Mütek, ii) titrating the provided aqueous solution with an aqueous potassium polyvinyl sulfate solution, for example with a concentration of N/400, to the point where the streaming potential is zero, and iii) calculating the electrical charge.
  • a particle charge detector for example the particle charge detector PCD-02 manufactured by Mütek
  • the C 3 -C 6 -alkyls can be linear or branched.
  • C 1 -C 6 alkyl is methyl, ethyl, n-propyl, 1-methylethyl, n-butyl, 2-methylpropyl, 3-methylpropyl, 1,1-dimethylethyl, n-pentyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl or n-hexyl.
  • R 1 is preferably H or C 1 -C 4 alkyl, very preferably H or C 1 -C 2 alkyl, particularly preferably H or C 1 alkyl and very particularly preferably H, ie the monomer (i) is N-vinylformamide.
  • a monomer of the formula I in the singular also includes a mixture of different monomers of the formula I as monomer (i).
  • the total amount of all monomers (i) is preferably 45 to 85 mol% based on all monomers polymerized to obtain the polymer P, i.e. all monomers (i) and (ii) or, according to the following specifications of (ii), consequently (i), (ii-A), (ii-B), (ii-C) and (ii-D) or (i), (ii-1), (ii-2), (ii-3), (ii-4), (ii-5), (ii-6), (ii-7) and (ii-8), very preferably 50 to 83 mol%, particularly preferably 55 to 82 mol%, very particularly preferably 60 to 81 mol% and especially preferably 62 to 80 mol%.
  • An ethylenically unsaturated monomer is herein a monomer that contains at least one C 2 unit whose two carbon atoms are connected by a carbon-carbon double bond.
  • this is ethylene.
  • a vinyl derivative is present.
  • an E/Z isomer or an ethene-1,1-diyl derivative is present.
  • Monoethylenically unsaturated monomer here means that exactly one C 2 unit is present in the monomer.
  • the total amount of all monomers (ii) is preferably 15 to 55 mol% based on all monomers polymerized to obtain the polymer P, i.e. all monomers (i) and (ii) or, according to the following specifications of (ii), consequently (i), (ii-A), (ii-B), (ii-C) and (ii-D) or (i), (ii-1), (ii-2), (ii-3), (ii-4), (ii-5), (ii-6), (ii-7) and (ii-8), very preferably 17 to 50 mol%, particularly preferably 18 to 45 mol%, very particularly preferably 19 to 40 mol% and especially preferably 20 to 38 mol%.
  • the polymer P By polymerizing monomers of formula I, the polymer P initially contains amide groups resulting from these monomers.
  • this is the formamide group -NH-C( O)H.
  • the amide group can be hydrolyzed using acid or base, splitting off the carboxylic acid and forming a primary amino group in the polymer P.
  • Basic hydrolysis of the amide group is preferred. If not all amide groups are hydrolyzed, it is known that the formation of a cyclic, six-membered amidine is possible by condensation of the primary amino group with an adjacent amide group. In this respect, the hydrolysis of an amide group leads to the formation of a primary amino group or an amidine group on the polymer P in accordance with the following reaction scheme.
  • the polymer P contains additional cyano groups.
  • the primary amino group in the polymer P formed by hydrolysis can, as is known, react with one of these cyano groups to form a cyclic, 5-membered amidine.
  • the hydrolysis of an amide group leads to an amidine group on the polymer P according to the following reaction scheme.
  • the ethylene derivative substituted with cyano in the following reaction scheme is polymerized acrylonitrile.
  • the conditions for hydrolysis of the amide groups in the polymer P can also lead to the hydrolysis of other groups in the polymer P which are sensitive to hydrolysis under these conditions.
  • hydrolyze Acetate groups in polymer P which originate from vinyl acetate as monomer (ii). Accordingly, a secondary hydroxy group is formed in polymer P, as shown below.
  • Examples of the one or more ethylenically unsaturated monomers (ii) are (ii-A) an anionic monomer, (ii-B) an uncharged monomer, (ii-C) a cationic monomer and (ii-D) a zwitterionic monomer.
  • An anionic monomer (ii-A) is preferably acrylic acid, methacrylic acid or their alkali metal, alkaline earth metal or ammonium salts.
  • An uncharged monomer (ii-B) is preferably acrylonitrile, methacrylonitrile or vinyl acetate.
  • the one or more ethylenically unsaturated monomers (ii) are preferably selected from (ii-A) an anionic monomer, (ii-B) an uncharged monomer, (ii-C) a cationic monomer, (ii-D) 0 - 10 mol% a zwitterionic monomer, wherein the total amount of all monomers (i) and (ii-A) to (ii-D) is 100 mol% and mol% refers to the total amount of all monomers (i) and (ii-A) to (ii-D).
  • the one or more ethylenically unsaturated monomers (ii) are preferably selected from (ii-A) an anionic monomer, wherein at least 50% of all anionic monomers are acrylic acid, methacrylic acid or their alkali metal, alkaline earth metal or ammonium salts based on the total number of anionic monomers, (ii-B) an uncharged monomer, wherein at least 50% of all uncharged monomers are vinyl acetate, acrylonitrile or methacrylonitrile based on the total number of all uncharged monomers, where the total amount of all monomers (i), (ii-A) and (ii-B) is 100 mol% and mol% refers to the total amount of all monomers (i), (ii-A) and (ii-B).
  • the one or more ethylenically unsaturated monomers (ii) are preferably selected from (ii-1) Acrylic acid or methacrylic acid or their alkali metal, alkaline earth metal or ammonium salts, (ii-2) Acrylonitrile or methacrylonitrile, (ii-3) Vinyl acetate, (ii-4) a monoethylenically unsaturated sulfonic acid, a monoethylenically unsaturated phosphonic acid, a monoethylenically unsaturated mono- or diester of phosphoric acid or a monoethylenically unsaturated carboxylic acid having 4 to 8 carbon atoms other than methacrylic acid, or their alkali metal, alkaline earth metal or ammonium salts, (ii-5) a quaternized, monoethylenically unsaturated monomer, a monoethylenically unsaturated monomer which carries at least one secondary or tertiary amino group
  • Monomers (ii-1) and (ii-4) are examples of an anionic monomer (ii-A).
  • Monomers (ii-2), (ii-3) and (ii-6) are examples of an uncharged monomer (ii-B).
  • Monomers (ii-5) are examples of a cationic monomer (ii-C).
  • Monomers (ii-8) can be an example of a zwitterionic monomer (ii-D).
  • Alkali metal, alkaline earth metal or ammonium salts have, for example, sodium ions, potassium ions, magnesium ions, calcium ions or ammonium ions as cations. Accordingly, alkali metal or alkaline earth metal bases, ammonia, amines or alkanolamines have been used to neutralize the free acids. For example, sodium hydroxide, potassium hydroxide, soda, potash, sodium hydrogen carbonate, magnesium oxide, calcium hydroxide, calcium oxide, triethanolamine, ethanolamine, morpholine, diethylenetriamine or tetraethylenepentamine have been used. Alkali metal and ammonium salts are preferred, very preferably sodium, potassium or (NH 4 ) + salts.
  • the monomers (ii-4) do not include a monomer which simultaneously carries a group which is protonated at pH 7 or carries a quaternized nitrogen.
  • monoethylenically unsaturated sulfonic acids are, for example, vinylsulfonic acid, acrylamido-2-methylpropanesulfonic acid, allylsulfonic acid, methallysulfonic acid, sulfoethyl acrylate, sulfoethyl methacrylate, sulfopropyl acrylate, sulfopropyl methacrylate, 2-hydroxy-3-methacryloxypropylsulfonic acid or styrenesulfonic acid.
  • monoethylenically unsaturated phosphonic acids are, for example, vinylphosphonic acid, vinylphosphonic acid monomethyl ester, allylphosphonic acid, allylphosphonic acid monomethyl ester, acrylamidomethylpropylphosphonic acid or acrylamidomethylenephosphonic acid.
  • monoethylenically unsaturated mono- or diesters of phosphoric acid are, for example, monoallylphosphoric acid ester, methacrylethylene glycol phosphoric acid or methacrylethylene glycol phosphoric acid.
  • the monomers (ii-4) there are monoethylenically unsaturated carboxylic acids having 4 to 8 C atoms which are different from methacrylic acid, for example dimethacrylic acid, ethacrylic acid, maleic acid, fumaric acid, itaconic acid, mesaconic acid, citraconic acid, methylenemalonic acid, allylacetic acid, vinylacetic acid or crotonic acid.
  • methacrylic acid for example dimethacrylic acid, ethacrylic acid, maleic acid, fumaric acid, itaconic acid, mesaconic acid, citraconic acid, methylenemalonic acid, allylacetic acid, vinylacetic acid or crotonic acid.
  • the monomers (ii-5) do not include a monomer that simultaneously carries a group that is deprotonated at pH 7.
  • salt form means that a corresponding anion ensures charge neutrality in the case of a quaternized nitrogen or in the case of protonation.
  • Such anions are, for example, chloride, bromide, hydrogen sulfate, sulfate, Hydrogen phosphate, methyl sulfate, acetate or formate. Chloride and hydrogen sulfate are preferred, chloride is particularly preferred.
  • quaternized, monoethylenically unsaturated monomers are, for example, [2-(acryloyloxy)ethyl]trimethylammonium chloride, [2-(methacryloyloxy)ethyl]trimethylammonium chloride, [3-(acryloyloxy)propyl]trimethylammonium chloride, [3-(methacryloyloxy)propyl]trimethylammonium chloride, 3-(acrylamidopropyl)trimethylammonium chloride or 3-(methacrylamidopropyl)trimethylammonium chloride.
  • Preferred quaternizing agents used are dimethyl sulfate, diethyl sulfate, methyl chloride, ethyl chloride or benzyl chloride. Methyl chloride is particularly preferred.
  • monoethylenically unsaturated monomers which carry at least one secondary or tertiary amino group and whose at least one secondary or tertiary amino group is protonated at pH 7 are, for example, esters of ⁇ , ⁇ -ethylenically unsaturated monocarboxylic acids with amino alcohols, mono- and diesters of ⁇ , ⁇ -ethylenically unsaturated dicarboxylic acids with amino alcohols, amides of ⁇ , ⁇ -ethylenically unsaturated monocarboxylic acids with dialkylated diamines, vinylimidazole or alkylvinylimidazole.
  • the acid component is preferably acrylic acid or methacrylic acid.
  • the amino alcohols preferably C 2 -C 12 amino alcohols, can be C 1 -C 8 -mono- or C 1 -C 8 -dialkylated on the amine nitrogen. Examples are dialkylaminoethyl acrylates, dialkylaminoethyl methacrylates, dialkylaminopropyl acrylates or dialkylaminopropyl methacrylates.
  • the acid component is preferably fumaric acid, maleic acid, monobutyl maleate, itaconic acid or crotonic acid.
  • the amino alcohols preferably C 2 -C 12 amino alcohols, can be C 1 -C 8 -mono- or C 1 -C 8 -dialkylated on the amine nitrogen.
  • Amides of ⁇ , ⁇ -ethylenically unsaturated monocarboxylic acids with dialkylated diamines are, for example, dialkylaminoethylacrylamides, dialkylaminoethylmethacrylamides, dialkylaminopropylacrylamides or dialkylaminopropylacrylamides.
  • diallyl-substituted amines that have exactly two ethylenic double bonds and are quaternized or protonated at pH 7, for example diallylamine or diallyldimethylammonium chloride.
  • Examples of the monomers (ii-6) are monoesters of ⁇ , ⁇ -ethylenically unsaturated monocarboxylic acids with C 1 -C 30 -alkanols, monoesters of ⁇ , ⁇ -ethylenically unsaturated monocarboxylic acids with C 2 -C 30 -alkanediols, diesters of ⁇ , ⁇ -ethylenically unsaturated dicarboxylic acids with C 1 -C 30 -alkanols or C 2 -C 30 -alkanediols, primary amides of ⁇ , ⁇ -ethylenically unsaturated monocarboxylic acids, N-alkylamides of ⁇ , ⁇ -ethylenically unsaturated monocarboxylic acids, N,N-dialkylamides of ⁇ , ⁇ -ethylenically unsaturated monocarboxylic acids, nitriles of ⁇ , ⁇ -ethylenically unsaturated
  • Monoesters of ⁇ , ⁇ -ethylenically unsaturated monocarboxylic acids with C 2 -C 30 alkanediols are, for example, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxyethyl ethacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 3-hydroxybutyl acrylate, 3-hydroxybutyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, 6-hydroxyhexyl acrylate or 6-hydroxyhexyl methacrylate.
  • Primary amides of ⁇ , ⁇ -ethylenically unsaturated monocarboxylic acids are, for example, acrylamide or methacrylamide.
  • N-alkyl amides of ⁇ , ⁇ -ethylenically unsaturated monocarboxylic acids are, for example, N-methylacrylamide, N-methylmethacrylamide, N-isopropylacrylamide, N-isopropylmethacrylamide, N-ethylacrylamide, N-ethylmethacrylamide, N-(n-propyl)acrylamide, N-(n-propyl)methacrylamide, N-(n-butylacrylamide, N-(n-butyl)methacrylamide, N-(tert.-butyl)acrylamide, N-(tert.-butyl)methacrylamide, N-(n-octyl)acrylamide, N-(n-octyl)methacrylamide, N-(1,1,3,3-tetramethylbutyl)acrylamide, N-(1,1,3,3-tetramethylbutyl)methacrylamide, N-(2-ethylhexyl)
  • N,N-dialkylamides of ⁇ , ⁇ -ethylenically unsaturated monocarboxylic acids are, for example, N,N-dimethylacrylamide or N,N-dimethylmethacrylamide.
  • Esters of vinyl alcohol with C 1 or C 3 -C 30 monocarboxylic acids are, for example, vinyl formate or vinyl propionate.
  • N-vinyllactams are 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 or N-vinyl-7-ethyl-2-caprolactam.
  • vinyl aromatics examples include styrene and methylstyrene.
  • vinyl halides are vinyl chloride and vinyl fluoride.
  • vinylidene halides are vinylidene chloride and vinylidene fluoride.
  • C 2 -C 8 monoolefins examples are ethylene, propylene, isobutylene, 1-butene, 1-hexene or 1-octene.
  • C 4 -C 10 olefins with exactly two double bonds that are conjugated are butadiene and isoprene.
  • the monomers (ii-7) act as crosslinkers.
  • Examples of the monomers (ii-7) are triallylamine, methylenebisacrylamide, glycol diacrylate, glycol dimethacrylate, glycerol triacrylate, pentaerythritol triallyl ether, N,N-divinylethyleneurea, tetraallylammonium chloride, polyalkylene glycols or polyols such as pentaerythritol, sorbitol and glucose that are at least twice esterified with acrylic acid and/or methacrylic acid.
  • Examples of monomers (ii-8) are the sulfobetaine 3-(dimethyl(methacryloylethyl)ammonium)propanesulfonate, the sulfobetaine 3-(2-methyl-5-vinylpyridinium)propanesulfonate, the carboxybetaine N-3-methacrylamidopropyl-N,N-dimethyl-beta-ammonium-propionate, the carboxybetaine N-2-acrylamidoethyl-N,N-dimethyl-beta-ammonium-propionate, 3-vinylimidazole-N-oxide, 2-vinylpyridine-N-oxide or 4-vinylpyridine-N-oxide.
  • the content of the monomers (ii-2) in mol% refers to the total number of all monomers (i) and (ii), i.e. all monomers used in the polymerization.
  • the total number of all monomers is 100 mol%.
  • cyano or nitrile groups of the polymerized monomers (ii-2) can also be partially hydrolyzed to carboxamide or carboxylic acid groups.
  • a cyano or nitrile group can also react with a polymerized monomer (i) to form a cyclic, 5-membered amidine.
  • Very preferred is 0 to 34 mol% of the monomers (ii-2), particularly preferred is 0.1 to 34 mol% and very particularly preferred is 1 to 27 mol%.
  • the content of the monomers (ii-3) in mol% refers to the total number of all monomers (i) and (ii), i.e. all monomers used in the polymerization.
  • the total number of all monomers is 100 mol%.
  • the acetate groups of the polymerized monomers (ii-3) can partially or completely hydrolyze to secondary hydroxy groups.
  • Very preferred is 0 to 34 mol% of the monomers (ii-3), particularly preferred is 0.1 to 34 mol% and very particularly preferred is 1 to 27 mol%.
  • a polymer P which is obtainable by polymerizing (iii) 50 to 85 mol% a monomer of formula I, (iii) 15 to 50 mol% one or more ethylenically unsaturated monomers other than a monomer of formula I, where among the monomers (ii) (ii-4) 0 to 10 mol% a monoethylenically unsaturated sulfonic acid, a monoethylenically unsaturated phosphonic acid, a monoethylenically unsaturated mono- or diester of phosphoric acid or a monoethylenically unsaturated carboxylic acid having 4 to 8 carbon atoms other than methacrylic acid, or whose alkali metal, alkaline earth metal or ammonium salts are contained, and optionally by subsequent partial or complete hydrolysis of the units of the monomers (i) polymerized into the polymer P.
  • the content of the monomers (ii-4) in mol% refers to the total number of all monomers (i) and (ii), ie all monomers used in the polymerization.
  • the total number of all monomers is 100 mol%.
  • Very preferred is 0 to 5 mol% of the monomers (ii-4), particularly preferred is 0.1 to 5 mol% and very particularly preferred is 1 to 3 mol%.
  • a polymer P which is obtainable by polymerizing (iii) 50 to 85 mol% a monomer of formula I, (iii) 15 to 50 mol% one or more ethylenically unsaturated monomers other than a monomer of formula I, where among the monomers (ii) (ii-5) 0 to 20 mol% a quaternized, monoethylenically unsaturated monomer, a monoethylenically unsaturated monomer which carries at least one secondary or tertiary amino group and whose at least one secondary or tertiary amino group is protonated at pH 7, or a diallyl-substituted amine which has exactly two ethylenic double bonds and is quaternized or protonated at pH 7, or their salt form, and optionally by subsequent partial or complete hydrolysis of the units of the monomers (i) polymerized into the polymer P.
  • the content of the monomers (ii-5) in mol% refers to the total number of all monomers (i) and (ii), i.e. all monomers used in the polymerization.
  • the total number of all monomers is 100 mol%.
  • Very preferred is 0 to 34 mol% of the monomers (ii-5), particularly preferred is 0.1 to 34 mol% and very particularly preferred is 1 to 27 mol%.
  • a polymer P which is obtainable by polymerizing (iii) 50 to 85 mol% a monomer of formula I, (iii) 15 to 50 mol% one or more ethylenically unsaturated monomers other than a monomer of formula I, where among the monomers (ii) (ii-6) 0 to 35 mol% a monoethylenically unsaturated monomer which carries no charge at pH 7 and is different from acrylonitrile, methacrylonitrile and vinyl acetate, or an ethylenically unsaturated monomer whose exactly two double bonds are conjugated, which carries no charge at pH 7 and is different from acrylonitrile, methacrylonitrile and vinyl acetate, and optionally by subsequent partial or complete hydrolysis of the units of the monomers (i) polymerized into the polymer P.
  • the content of the monomers (ii-6) in mol% refers to the total number of all monomers (i) and (ii), ie all monomers used in the polymerization.
  • the total number of all monomers is 100 mol%.
  • Very preferred is 0 to 34 mol% of the monomers (ii-6), particularly preferred is 0.1 to 34 mol% and very particularly preferred is 1 to 27 mol%.
  • a polymer P which is obtainable by polymerizing (iii) 50 to 85 mol% a monomer of formula I, (iii) 15 to 50 mol% one or more ethylenically unsaturated monomers other than a monomer of formula I, where among the monomers (ii) (ii-7) 0 to 1 mol% a monomer which has at least two ethylenically unsaturated double bonds which are not conjugated and which is different from a diallyl-substituted amine which has exactly two ethylenic double bonds, and optionally by subsequent partial or complete hydrolysis of the units of the monomers (i) polymerized into the polymer P.
  • the content of the monomers (ii-7) in mol% refers to the total number of all monomers (i) and (ii), i.e. all monomers used in the polymerization.
  • the total number of all monomers is 100 mol%.
  • Very preferred is 0 to 0.5 mol% of the monomers (ii-7), particularly preferred is 0.001 to 0.5 mol% and very particularly preferred is 0.01 to 0.1 mol%.
  • the content of the monomers (ii-7) in mol% refers to the total number of all monomers (i) and (ii), i.e. all monomers used in the polymerization.
  • the total number of all monomers is 100 mol%.
  • Very preferred is 0 to 3 mol% of the monomers (ii-8), particularly preferred is 0.1 to 3 mol% and very particularly preferred is 1 to 2 mol%.
  • a polymer P which is obtainable by polymerizing (iii) 50 to 85 mol% a monomer of formula I (ii-1) 15 to 50 mol% Acrylic acid or methacrylic acid or their alkali metal, alkaline earth metal or ammonium salts, (ii-2) 0 to 35 mol% Acrylonitrile or methacrylonitrile, (ii-3) 0 to 35 mol% vinyl acetate, (ii-4) 0 to 35 mol% a monoethylenically unsaturated sulfonic acid, a monoethylenically unsaturated phosphonic acid, a monoethylenically unsaturated mono- or diester of phosphoric acid or a monoethylenically unsaturated carboxylic acid having 4 to 8 carbon atoms other than methacrylic acid, or their alkali metal, alkaline earth metal or ammonium salts, (ii-5) 0 to 35 mol% a quaternized,
  • Very preferred is a content of (i) of 50 to 83 mol% and of (ii-1) of 17 to 50 mol%. Particularly preferred is a content of (i) of 55 to 82 mol% and of (ii-1) of 18 to 45 mol%. Very particular preference is given to a content of (i) of 60 to 81 mol% and of (ii-1) of 19 to 40 mol%. Particularly preferred is a content of (i) of 62 to 80 mol% and of (ii-1) of 20 to 38 mol%.
  • a polymer P which is obtainable by polymerizing (iii) 50 to 85 mol% a monomer of formula I (ii-1) 15 to 50 mol% Acrylic acid or methacrylic acid or their alkali metal, alkaline earth metal or ammonium salts, (ii-2) 0 to 35 mol% Acrylonitrile or methacrylonitrile, (ii-3) 0 to 35 mol% Vinyl acetate, and optionally by subsequent partial or complete hydrolysis of the units of the monomers of the formula (I) polymerized into the polymer P to form primary amino groups or amidine groups, the ester group of polymerized vinyl acetate being partially or completely hydrolyzed, the total amount of all monomers (i), (ii-1), (ii-2) and (ii-3) being 100 mol% and mol% referring to the total amount of all monomers (i), (ii-1), (ii-2) and (ii-3).
  • Very preferred is a content of (i) of 50 to 83 mol% and of (ii-1) of 17 to 50 mol%. Particularly preferred is a content of (i) of 55 to 82 mol% and of (ii-1) of 18 to 45 mol%. Very particular preference is given to a content of (i) of 60 to 81 mol% and of (ii-1) of 19 to 40 mol%. Particularly preferred is a content of (i) of 62 to 80 mol% and of (ii-1) of 20 to 38 mol%.
  • a polymer P which is obtainable by polymerizing (iii) 50 to 85 mol% a monomer of formula I (ii-1) 15 to 50 mol% Acrylic acid or methacrylic acid or their alkali metal, alkaline earth metal or ammonium salts, (ii-2) 0 to 35 mol% Acrylonitrile or methacrylonitrile, and optionally by subsequent partial or complete hydrolysis of the units of the monomers of the formula (I) polymerized into the polymer P to form primary amino groups or amidine groups, where the total amount of all monomers (i), (ii-1) and (ii-2) is 100 mol% and mol% refers to the total amount of all monomers (i), (ii-1) and (ii-2).
  • Very preferred is a content of (i) of 50 to 83 mol% and of (ii-1) of 17 to 50 mol%. Particularly preferred is a content of (i) of 55 to 82 mol% and of (ii-1) of 18 to 45 mol%. Very particularly preferred is a content of (i) of 60 to 81 mol% and of (ii-1) of 19 to 40 mol%. Particularly preferred is a content of (i) of 62 to 80 mol% and of (ii-1) of 20 to 38 mol%.
  • the process is preferably carried out in a paper machine.
  • the paper machine for a single-ply paper preferably has equipment which comprises a first wire section with the first wire, which has a first wire top and a first wire bottom, a press section, a spray device containing the spray solution or spray suspension and a drying section with heated cylinders, and in the paper machine these are arranged in the order first wire section, followed by the press section, followed by the spray device and then the drying section.
  • the spray device is preferably located at the end of the press section.
  • step (A) takes place in the first Wire section
  • step (D-1) takes place in the press section
  • step (F-1) takes place in the dryer section.
  • the paper machine for a multi-ply paper preferably has equipment that includes a first wire section with the first wire, which has a first wire top and a first wire bottom, a second wire section with the second wire, which has a second wire top and a second wire bottom, a press section, a spray device containing the spray solution or spray suspension and a drying section with heated cylinders, and in the paper machine these are arranged in the order first wire section and second wire section, followed by the press section, followed by the spray device and then the drying section.
  • the spray device is preferably located at the end of the press section.
  • step (A) takes place in the first wire section
  • step (B) takes place in the second wire section
  • step (C) takes place before the press section, preferably at the end of the first wire section and the second wire section
  • step (D-2) takes place in the press section
  • step (E-2) at the end of the press section or between the press section and the dryer section
  • step (F-2) takes place in the dryer section.
  • the spray device preferably comprises at least one nozzle, very preferably one or more nozzles, which enables the spray solution or spray suspension to be sprayed under an overpressure of 0.5 to 4.5 bar compared to the ambient pressure.
  • the first fiber suspension for a single-ply paper passes through the paper machine under dewatering on a screen, dewatering by pressing, spraying of at least one surface side and dewatering by heat supply to a single-ply paper in the direction from the screen section to the drying section.
  • the first fiber suspension and the second fiber suspension for a multi-ply paper pass through the paper machine under dewatering on a screen, joining, dewatering by pressing, spraying of at least one surface side and dewatering by heat supply to a multi-ply paper in the direction from the screen sections to the drying section.
  • the dried single-ply paper is preferably obtainable from a process in which the spray solution or spray suspension has a pH of 5.5 or greater.
  • the dry matter content is determined by drying at 105°C to constant mass.
  • the dried single-ply paper preferably has a dry matter content of at least 88% by weight.
  • the dried single-ply paper preferably has an internal strength of 180 to 500 J/ m2 , very preferably of 200 to 430 J/ m2 , particularly preferably of 210 to 400 J/ m2 and most particularly preferably of 230 to 380 J/ m2 , the internal strength corresponding to that of Tappi specification T833 pm-94.
  • the dried multi-ply paper is preferably obtainable from a process in which the spray solution or spray suspension has a pH of 5.5 or greater.
  • the dry matter content is determined by drying at 105°C to constant mass.
  • the dried multi-ply paper preferably has a dry matter content of at least 88% by weight.
  • the dried multi-ply paper is preferably made of two plies, very preferably of one ply with a grammage of 20 to 60 g/ m2 and one ply with 60 to 100 g/ m2 .
  • the dried multi-ply paper preferably has an internal strength of 180 to 500 J/ m2 , very preferably of 200 to 430 J/ m2 , particularly preferably of 210 to 400 J/ m2 and most particularly preferably of 230 to 380 J/ m2 , the internal strength corresponding to that of Tappi specification T833 pm-94.
  • the spray solution or spray suspension in the spray device preferably has a pH of 5.5 or greater.
  • the dry matter content is determined by drying at 105°C to constant mass.
  • a paper machine is preferred which has a device for generating a negative pressure on the first screen bottom or the second screen bottom.
  • a paper machine is very preferred which has a device for generating a negative pressure on the first screen bottom and a device for generating a negative pressure on the second screen bottom.
  • Another invention is a process for producing dried single-ply or multi-ply paper, in which, compared to the previous process, the polymer P there is replaced by a polymer PA.
  • the objects of this other invention are, in addition to the said process, the corresponding paper obtainable by this process and a paper machine suitable for this process, which contains a spray device containing the aqueous spray solution or spray suspension with polymer PA.
  • the polymer PA which is different from a polymer P, is a Michael system-modified polymer containing primary amine groups, an alkylated polyvinylamine containing primary amine groups, or a graft polymerization polymer containing primary amine groups.
  • a Michael system-modified polymer containing primary amine groups is obtainable by reacting Michael systems with a starting polymer containing primary amine groups. This reaction to the polymer type of formula II shown is in the WO 2007/136756 described.
  • Michael systems are understood to be compounds with an unsaturated double bond that is conjugated to an electron-withdrawing group. Suitable Michael systems are described by formula III. where R 2 and R 3 independently represent H, alkyl, alkenyl, carbonyl, carboxyl or carboxamide and X 1 represents an electron-withdrawing group or an electron-withdrawing amine.
  • Michael systems are acrylamide, N-alkylacrylamide, methacrylamide, N,N-dimethylacrylamide, N-alkylmethacrylamide, N-(2-methylpropanesulfonic acid acrylamide, N-(glycolic acid)acrylamide, N-[3-(propyl)trimethylammonium chloride]acrylamide, acrylonitrile, methacrylonitrile, acrolein, methyl acrylate, alkyl acrylate, methyl methacrylate, alkyl methacrylate, aryl acrylate, aryl methacrylates, [2-(methacryloyloxy)ethyl]-trimethylammonium chloride, N-[3-(dimethyl-amino)propyl]methacrylamide, N-ethylacrylamide, 2-hydroxyethyl acrylate, 3-sulfopropyl acrylate, 2-hydroxyethyl methacrylate, glycidyl methacrylate, pen
  • Acrylamide is the preferred Michael system.
  • the Michael systems are used in an amount of 1 to 75 mol% based on the primary amino groups and/or amidine groups.
  • the reaction conditions for the conversion are given in the WO 2007/136756 described, the disclosure of which is expressly incorporated by reference.
  • Reaction products containing units of formula IV are obtainable by polymer-analogous reaction of the primary amino groups of polyvinylamines with alkylating agents.
  • the alkylation can also be carried out with alkyl glycidyl ethers, glycidol (2,3-epoxy-1-propanol) or chloropropanediol.
  • Preferred alkyl glycidyl ethers are butyl glycidyl ether, 2-ethylhexyl glycidyl ether, hexadecyl glycidyl ether and C 12 /C 14 glycidyl ether.
  • the reaction with alkyl glycidyl ethers is generally carried out in water, but can also be carried out in aqueous/organic solvent mixtures.
  • Reaction products containing units of the formula V and VII are obtainable by polymer-analogous reaction of the primary amino groups of the polyvinylamines with alkylating agents or acylating agents.
  • alkylating agents are selected from chloroacetic acid, salts of chloroacetic acid, bromoacetic acid, salts of bromoacetic acid, halogen-substituted alkanoic acid acrylamides and halogen-substituted alkenoic acid acrylamides, 3-chloro-2-hydroxypropyltrimethylammonium chloride, 2-(diethylamino)ethyl chloride hydrochloride, (dialkylamino)alkyl chlorides such as 2-(dimethylamino)ethyl chloride, 3-Chloro-2-hydroxypropylalkyl-dimethylammonium chlorides such as 3-chloro-2-hydroxypropyllauryldimethylammonium chloride, 3-chloro-2-hydroxypropyl-cocoalkyl-dimethylammonium chloride, 3-chloro-2-hydroxypropylstearyldimethylammonium chloride, (haloalkyl)trimethylammonium chlorides such
  • Such acylating agents are selected from succinic anhydride, substituted succinic anhydrides substituted with linear or crosslinked C 1 -C 18 alkyl or linear or crosslinked C 1 -C 18 alkenyl, maleic anhydride, glutaric anhydride, 3-methylglutaric anhydride, 2,2-dimethylsuccinic anhydride, cyclic alkylcarboxylic anhydrides, cyclic alkenylcarboxylic anhydrides and alkenylsuccinic anhydrides (ASA).
  • succinic anhydride substituted succinic anhydrides substituted with linear or crosslinked C 1 -C 18 alkyl or linear or crosslinked C 1 -C 18 alkenyl
  • maleic anhydride glutaric anhydride
  • 3-methylglutaric anhydride 2,2-dimethylsuccinic anhydride
  • 2,2-dimethylsuccinic anhydride 2,2-dimethylsuccinic anhydride
  • a graft polymerization polymer containing primary amine groups is, for example, hydrolyzed graft polymers of, for example, N-vinylformamide on polyalkylene glycols, polyvinyl acetate, polyvinyl alcohol, polyvinylformamides, polysaccharides such as starch, oligosaccharides or monosaccharides.
  • the graft polymers are obtainable by, for example, radically polymerizing N-vinylformamide in an aqueous medium in the presence of at least one of the grafting bases mentioned, optionally together with other copolymerizable monomers, and then hydrolyzing the grafted vinylformamide units in a known manner to form polymerized vinylamine units.
  • Such graft polymers are used, for example, in the DE-A-19515943 , DE-A-4127733 and DE-A-10041211 described.
  • the solids content is determined by distributing 0.5 to 1.5 g of the polymer solution in a 4 cm diameter metal lid and then drying it in a circulating air drying cabinet at 140°C for 120 minutes. The ratio of the mass of the sample after drying under the above conditions to the weighed sample mass multiplied by 100 gives the solids content of the polymer solution in wt.%. Drying is carried out at ambient pressure, if necessary 101.32 KPa, without correction for deviations caused by weather and altitude.
  • the degree of hydrolysis is the proportion in % of the hydrolyzed N-CHO groups of the N-vinylformamide monomers used in the polymerization in the total amount of the polymerization used N-vinylformamide.
  • the degree of hydrolysis of the homopolymers or copolymers in which N-vinylformamide is used in the polymerization and which are subjected to hydrolysis is determined by enzymatic analysis of the formic acid or formates released during hydrolysis (test set from Boehringer Mannheim).
  • the polymer content indicates the content of polymer without counterions in the aqueous solution in wt.%, i.e. counterions are not taken into account.
  • the polymer content is the sum of the weight fractions of all structural units of the polymer in g that are present in 100 g of the aqueous solution. It is determined mathematically. For this purpose, potentially charge-bearing structural units in the charged form are included, i.e. e.g. amino groups in the protonated form and acid groups in the deprotonated form. Counterions of the charged structural units such as a sodium cation, chloride, phosphate, formate, acetate, etc. are not taken into account.
  • the calculation can be carried out in such a way that, for a batch, starting from the amounts of monomers used, possibly a degree of hydrolysis of certain monomers and possibly a proportion of reactants that is converted in a polymer-analogous manner by reacting with the polymer to form a covalent bond, the molar amounts of the structural units of the polymer present at the end of the reaction are determined and these are converted into weight fractions using the molar masses of the structural units. For this purpose, a complete, i.e. 100% conversion of all monomers or reactants used is assumed. The sum of the weight fractions gives the total amount of polymer in this batch. The polymer content results from the ratio of the total amount of polymer to the total mass of the batch.
  • the total mass of the batch therefore contains reaction medium, possibly cations or anions and everything added to the reaction batch that is not assumed to be incorporated into the polymer. Substances removed from the reaction batch (e.g. any distilled water, etc.) are deducted.
  • the total content of primary amino groups and/or amidine groups can be determined in a similar way to the procedure described above for the polymer content.
  • the molar composition of the structural units of the polymer present at the end of the reaction is determined based on the amounts of monomers used, the analytically determined degree of hydrolysis, the ratio of amidine groups to primary amino groups determined using 13 C NMR spectroscopy and, if applicable, the proportion that was converted in a polymer-analogous manner by reaction with the polymer to form a covalent bond.
  • the molar proportion of primary amino groups and/or amidine units in meq that is present in 1 g of polymer can be calculated.
  • the K values are determined according to H. Fikentscher, Cellulose Chemistry, Volume 13, 48-64 and 71-74 measured under the conditions specified.
  • the figures in brackets indicate the concentration of the polymer solution based on the polymer content and the solvent. The measurements were carried out at 25°C and a pH of 7.5.
  • the weight-average molecular weight Mw is determined using static light scattering.
  • the sample is dissolved in a 1000 millimolar sodium chloride solution at a pH of 9.0.
  • the Mw is given in Daltons.
  • the water used in the examples of polymerizations under A-2) and hydrolyses under A-3) is completely demineralized.
  • reaction mixture is post-polymerized for a further three hours at 73°C. During the entire polymerization and post-polymerization, approx. 190 g of water are distilled off. The mixture is then cooled to room temperature under normal pressure.
  • a slightly yellow, viscous solution with a solids content of 19.7 wt.% and a polymer content of 19.5 wt.% is obtained.
  • the K value of the polymer is 90 (0.5 wt.% in water).
  • the Mw is 0.34 million Daltons.
  • the pH value is expected to be between 6 and 7 due to the buffer used.
  • Feed 3 is then added over 5 minutes and post-polymerized for a further two hours at 73°C. During the entire polymerization and post-polymerization, approximately 190 g of water are distilled off. The mixture is then cooled to room temperature under normal pressure. A slightly yellow, viscous solution with a solids content of 15.9 wt.% and a polymer content of 15.6 wt.% is obtained. The K value of the copolymer is 122 (0.1 wt.% in 5 wt.% aqueous NaCl solution). The Mw is 2.2 million Daltons.
  • a slightly yellow, viscous solution with a solids content of 16.0 wt.% and a polymer content of 15.7 wt.% is obtained.
  • the K value of the copolymer is 85 (0.5 wt.% in 5 wt.% aqueous NaCl).
  • the Mw is 0.8 million Daltons.
  • the pH value is expected to be between 6 and 7 due to the buffer used.
  • the mixture is kept at 63°C for 3 hours while water is constantly distilled off.
  • the temperature is then increased to 75°C and the pressure is set to approx. 390 mbar to ensure continuous distillation.
  • feed 2 is added over 15 minutes.
  • the temperature is then held at 75°C for a further 1.25 hours.
  • Feed 3 is then added over 20 minutes, the vacuum is broken and the mixture is cooled to room temperature. During the polymerization and post-polymerization, approx. 270 g of water are distilled off.
  • a slightly yellow, viscous solution with a solids content of 10.2 wt.% and a polymer content of 9.9 wt.% is obtained.
  • the K value of the copolymer is 152 (0.1 wt.% in 5 wt.% aqueous NaCl).
  • the Mw is 4.1 million Daltons.
  • reaction mixture is post-polymerized for a further 2.5 hours at 80°C. During the entire polymerization and post-polymerization, approx. 200 g of water are distilled off. The mixture is then cooled to room temperature under normal pressure. A slightly yellow, viscous solution with a solids content of 25.0 wt.% and a polymer content of 24.5 wt.% is obtained.
  • the K value of the copolymer is 90 (0.5 wt.% in 5 wt.% aqueous NaCl solution).
  • the Mw is 0.9 million Daltons.
  • a slightly yellow, viscous solution with a solids content of 21.5 wt.% and a polymer content of 21.3 wt.% is obtained.
  • the K value of the copolymer is 86 (0.5 wt.% in 5 wt.% aqueous NaCl solution).
  • the Mw is 0.7 million Daltons.
  • Example H-H1P1 H1P1 (polymer VFA[32] from P1)
  • Example P-P1 603.3 g of the polymer solution obtained according to Example P-P1 are mixed with 8.6 g of a 40% by weight aqueous sodium bisulfite solution in a 1 L four-necked flask with a blade stirrer, internal thermometer, dropping funnel and reflux condenser at a stirrer speed of 80 rpm and then heated to 80°C. Then 94.9 g of a 25% aqueous sodium hydroxide solution are added. The mixture is kept at 80°C for 3.5 h. The product obtained is cooled to room temperature and adjusted to pH 3.0 with 31.7 g of 37% by weight hydrochloric acid.
  • a slightly yellow, viscous solution with a polymer content of 14.0 wt.% is obtained.
  • the degree of hydrolysis of the polymerized vinylformamide units is 32 mol%.
  • Example H-H2P1 H2P1 (polymer VFA[100] from P1)
  • a slightly yellow, viscous solution with a polymer content of 7.2 wt.% is obtained.
  • the degree of hydrolysis of the vinylformamide units is 100 mol%.
  • Example P-P2 1224.3 g of the polymer solution obtained according to Example P-P2 are mixed in a 2 L four-necked flask equipped with a blade stirrer, internal thermometer, dropping funnel and reflux condenser at a stirrer speed of 80 rpm with 704.4 g of water and 8.9 g of a 40 wt. % aqueous sodium bisulfite solution and then heated to 80°C. Then 140.4 g of a 25% by weight sodium hydroxide solution are added. The mixture is kept at 80°C for 5 hours. It is then cooled to room temperature and adjusted to pH 8.5 with 37% hydrochloric acid.
  • a slightly yellow, slightly cloudy and viscous solution with a polymer content of 7.1 wt.% is obtained.
  • the degree of hydrolysis of the vinylformamide units is 50 mol%.
  • 600.0 g of the polymer solution obtained according to Example P-P3 are mixed with 4.5 g of a 40 wt.% aqueous sodium bisulfite solution in a 2 L four-neck flask with a blade stirrer, internal thermometer, dropping funnel and reflux condenser at a stirrer speed of 80 rpm and then heated to 80°C. Then 150.0 g of a 25% aqueous sodium hydroxide solution are added. The mixture is kept at 80°C for 7 hours. The product obtained is cooled to room temperature and adjusted to pH 8.5 with 37% hydrochloric acid.
  • a slightly yellow, viscous solution with a polymer content of 7.7 wt.% is obtained.
  • the degree of hydrolysis of the vinylformamide units is 100 mol%.
  • Example P-P3 600.0 g of the polymer solution obtained according to Example P-P3 are mixed with 4.5 g of a 40 wt.% aqueous sodium bisulfite solution in a 2 L four-neck flask with a blade stirrer, internal thermometer, dropping funnel and reflux condenser at a stirrer speed of 80 rpm and then heated to 80°C. Then 72.0 g of a 25% aqueous sodium hydroxide solution are added. The mixture is kept at 80°C for 3.5 h. The product obtained is cooled to room temperature and adjusted to pH 8.5 with 37% hydrochloric acid.
  • a slightly yellow, slightly cloudy and viscous solution with a polymer content of 10.4 wt.% is obtained.
  • the degree of hydrolysis of the vinylformamide units is 51 mol%.
  • Example P-P3 600.0 g of the polymer solution obtained according to Example P-P3 are mixed with 4.5 g of a 40% by weight aqueous sodium bisulfite solution in a 2 L four-neck flask with a blade stirrer, internal thermometer, dropping funnel and reflux condenser at a stirrer speed of 80 rpm and then heated to 80°C. Then 45.5 g of a 25% aqueous sodium hydroxide solution are added. The mixture is kept at 80°C for 7 hours. The product obtained is cooled to room temperature and adjusted to pH 8.5 with 37% hydrochloric acid.
  • a slightly yellow, slightly cloudy and viscous solution with a polymer content of 11.7 wt.% is obtained.
  • the degree of hydrolysis of the vinylformamide units is 30 mol%.
  • 159.8 g of the polymer solution obtained according to Example P-P4 are mixed with 0.7 g of a 40 wt. % aqueous sodium bisulfite solution in a 500 mL four-neck flask with a blade stirrer, internal thermometer, dropping funnel and reflux condenser at a stirrer speed of 80 rpm and then heated to 80°C. Then 11.8 g of a 25% aqueous sodium hydroxide solution are added. The mixture is kept at 80°C for 4.5 h. The product obtained is mixed with 71.4 g of water diluted and cooled to room temperature. A pH of 8.5 is then adjusted with 4.7 g of 37% hydrochloric acid.
  • a slightly yellow, slightly cloudy and viscous solution with a polymer content of 5.0 wt.% is obtained.
  • the degree of hydrolysis of the vinylformamide units is 51 mol%.
  • Example P-P5 1102.9 g of the polymer solution obtained according to Example P-P5 were mixed with 10.5 g of a 40 wt.% aqueous sodium bisulfite solution in a four-necked flask with a blade stirrer, internal thermometer, dropping funnel and reflux condenser at a stirrer speed of 80 rpm and then heated to 80°C. Then 355.6 g of a 25 wt.% sodium hydroxide solution are added. The mixture is kept at 80°C for 7 h and then cooled to room temperature and adjusted to pH 8.5 with 37% hydrochloric acid.
  • a slightly cloudy, viscous solution with a polymer content of 11.5 wt.% is obtained.
  • the degree of hydrolysis of the vinylformamide units is 100 mol%.
  • Example P-P6 600.0 g of the polymer solution obtained according to Example P-P6 are mixed with 4.5 g of a 40% by weight aqueous sodium bisulfite solution in a 2 L four-neck flask with a blade stirrer, internal thermometer, dropping funnel and reflux condenser at a stirrer speed of 80 rpm and then heated to 80°C. Then 83.3 g of a 25% by weight sodium hydroxide solution are added. The mixture is kept at 80°C for 3.5 h. The product obtained is cooled to room temperature and adjusted to pH 8.5 with 37% hydrochloric acid.
  • a slightly yellow, slightly cloudy and viscous solution with a polymer content of 15.3 wt.% is obtained.
  • the degree of hydrolysis of the vinylformamide units is 35 mol%.
  • the corresponding aqueous solutions from the examples containing the polymer mentioned and optionally the starch mentioned as a solid are added with stirring to a glass vessel with a 4-liter mark in which there are already 2 liters of drinking water.
  • this aqueous solution is added to add 20 g of polymer based on the polymer content or, in the case of the combination with starch, 10 g of polymer based on the polymer content.
  • 10 g of starch based on the solid content of the starch are added. After the addition, the mixture is slurried or dissolved.
  • a starch suspension of the commercial starch Cargill*size 35802 (cationic starch, available from Cargill, powder insoluble/partially soluble in water) is prepared by slurrying 20 g of the solid powder of this starch in 2 L of drinking water at room temperature and further diluting with drinking water to a total volume of 4 L.
  • the starch concentration in the aqueous suspension is 5 g/L based on solids content.
  • the pH of the aqueous suspension is 7.3.
  • Table TabB1 Spray solution L additives contained Concentration polymer [g / L] c) L0(-) a) - 0 L1(P1) a) P1 5 L2(H1P1) a) H1P1 5 L3(H2P1 ) H2P1 5 L4(H3P2) b) H3P2 5 L5(H4P3) b) H4P3 5 L6(H5P3) b) H5P3 5 L7(H6P3) b) H6P3 5 L8(P3) b) P3 5 L9(H7P4) b) H7P4 5 L10(H8P5) b) H8P5 5 L11(H9P6) b) H9P6 5 Footnotes: a) comparative b) according to the invention c) Concentration based on polymer content of the aqueous solution of the example Spray suspension S additives contained Concentration starch [ g / L] Concentration polymer [g / L
  • the mass of the wet sample (MF) is determined from a damp paper sample on a calibrated top-loading rapid balance that can weigh to 0.01 g.
  • the damp paper sample preferably has an area of at least 10 cm x 10 cm.
  • the damp paper sample is then placed in a calibrated drying cabinet that can maintain a set temperature to within ⁇ 2°C and dried at a set temperature of 105°C until the mass is constant. This is typically the case after 90 minutes.
  • the dried paper sample, while still warm, is then transferred to a desiccator that contains a suitable drying agent such as silica gel. After cooling to room temperature, the mass of the dried paper sample (MT) is determined on the aforementioned balance.
  • the percentage is often given with one decimal place. If this percentage value no longer changes with the rounded first decimal place, this is an indication that constant mass has been achieved for dry contents of 1 to 100 wt.%. For dry contents of 0 to less than 1 wt.%, the rounded second decimal place of the percentage value is the corresponding indication. Drying takes place at ambient pressure, possibly 101.32 kPa, without correction being made for deviations resulting from the weather and altitude. During drying, the normal ambient air pressure is maintained, possibly 101.32 kPa. No correction is made for slightly different air pressures caused by the weather and altitude. In the case of a moist sample which does not yet have the consistency of a sheet, e.g. a fiber suspension or paper pulp, the moist sample is dried in an appropriate dish with a large surface area.
  • a dried sheet of paper is examined after storage in a climate chamber at a constant 23 °C and 50% humidity for 12 hours.
  • the internal strength is determined using a procedure that corresponds to Tappi specification T833 pm-94.
  • Ten paper strips with a width of 2.5 cm and a length of 12.7 cm are cut from two sheets of paper in DIN A4 format, which were previously obtained from the dried paper web of the test machine.
  • Each individual paper sample is attached to a separate base plate and a metal angle using double-sided adhesive tape. The metal angle is knocked out with a pendulum, splitting the paper sample to be examined in a plane parallel to the paper surface. The energy required for this process is measured.
  • the device used for the measurement is an Internal Bond Test Station from TMI (Testing Machines Inc.
  • the double-sided adhesive tape is a product from 3M (width 25.4 mm, type Scotch No. 140).
  • the measuring device provides the energy required for splitting, based on a standardized area in J / m 2 .
  • the average value is calculated from 10 individual measurements.
  • the raw material for paper production is a paper pulp that is produced by beating paper webs in a pulper.
  • the paper pulp is obtained by dissolving it in drinking water and mechanically processing the paper webs in the pulper at a dry content of approx. 3.5 - 4% by weight.
  • the paper pulp then typically has a fineness of around 50° Schopper Riegler.
  • the paper webs are packaging base papers of the "Testliner 2" specification with a basis weight of 120 g / m 2 , which come from Thurpapier in Weinfelden (Switzerland).
  • the papers produced consist of two layers: a top layer with a grammage of 40 g / m 2 and a base layer with a grammage of 80 g / m 2 .
  • This paper is produced on a test paper machine of the Paper Technology Foundation (PTS) in Heidenau. To make the two-ply possible, the test machine is equipped with a headbox for the lower wire and an additional headbox for the upper wire in addition to a headbox for the lower wire.
  • the paper pulp is diluted with drinking water to a dry content of 0.35 wt.%.
  • the paper pulp is then pumped into the two headboxes and from there applied to the upper wire in the form of a fourdrinier wire and the lower wire in the form of a fourdrinier wire.
  • the wire for the top layer and the wire for the base layer run towards each other at an angle of 60° and form a narrow gap at the end.
  • the top layer and the base layer come into contact and form enough adhesion to detach from the wires deflected after the gap.
  • the layers that are weakly adhering to one another then run into the press section and are couched together on the side facing away from the sieves in the press section of the machine, i.e. pressed together while dewatering.
  • the resulting paper web is then sent through the heated cylinders of the drying section, where temperatures of up to 100°C can be reached, and the dried paper is rolled up at the end of the drying section.
  • the dry content of the dried paper obtained is typically 93-94% by weight for the previously described material type, the specified grammage and a machine speed of 0.85 m 2 per minute.
  • the contact pressures in the press section can be varied, resulting in different dry contents after the press section. These are between 40% by weight and 52% by weight, depending on the contact pressure in the test paper machine.
  • the dry content before the press can be varied by using a chemical dewatering agent and/or by applying a vacuum to the undersides of the upper and lower sieves. This allows the dry matter contents before the press in the test paper machine to be varied in a range between 15 wt.% and 22 wt.%.
  • a two-substance nozzle from Schlick is used for this.
  • the position of the spray nozzle is approx. 20 cm in front of the contact line of the paper web with the first cylinder of the drying section.
  • the pressure for opening the nozzle valve and atomizing the spray solution or spray suspension is 1 bar.
  • the spray width with even coverage is 35 cm. However, when preparing the dried paper sheets for later analysis, 5 cm at the edge are not taken into account.
  • the spray solution or spray suspension is sprayed with two different application quantities.
  • the first amount is in a range of around 0.1 L/ m2 . At an approximate concentration of 5 g/L, this corresponds to an application amount of 0.5 g/ m2 .
  • the second amount is in a range of around 0.2 L/ m2 . At an approximate concentration of 5 g/L, this corresponds to an application amount of 1.0 g/ m2 . Due to the high dilution, the density of the spray solution or spray suspension can be approximately assumed to be 1 g/ cm3 .
  • Dried papers are produced on the paper machine as described in C-3) taking into account the respective information in the tables TabC1 - Tab C4 regarding the concentration of the spray solution or spray dispersion and the machine settings.
  • the tables TabC1 to TabC4 also give the measured internal strengths of dried paper test sheets as described in C-1). ⁇ u>Table TabC1 ⁇ /u> "aP" - 0.1 L / m 2 Internal strength [J / m 2 ] Example No.
  • Table TabC1 it can be seen that, compared to the comparative examples, the papers produced with spray solutions according to the invention have a significantly improved internal strength. Furthermore, increasing the dry content after the wire section by means of negative pressure or increased retention polymer quantity leads to a further improvement in the internal strength in the papers produced with spray solutions according to the invention, while these measures have little and inconsistent effect in the comparative examples.
  • Table TabC2 "aP" - 0.2 L / m 2 Internal strength [J / m 2 ] Example No.
  • Table TabC2 shows that even with double the application quantity, the papers produced with spray solutions according to the invention have significantly improved internal strength compared to the comparative examples. Increasing the dry content after the wire section by means of negative pressure or increased retention polymer quantity leads to a further improvement in the internal strengths of the papers produced with spray solutions according to the invention, while these measures have little and inconsistent effect on the comparative examples.
  • Table TabC3 "aP" - 0.1 L / m 2 Internal strength [J / m 2 ] Example No.
  • Table TabC3 shows, as in Table TabC1 and Table TabC2, that the papers produced with spray dispersions according to the invention have a significantly improved internal strength compared to the comparative examples. Increasing the dry content after the wire section by means of negative pressure or increased retention polymer quantity leads to a further improvement in the papers produced with spray dispersions according to the invention. the internal strength, while these measures have little and inconsistent effect in the comparative examples. In comparison with Table TabC1, Table TabC3 shows that replacing half of the amount of polymers used with cationic starch no longer leads to an equivalent improvement in the internal strength of the papers.
  • Table TabC4 "aP" - 0.2 L / m 2 Internal strength [J / m 2 ] Example No.
  • Table TabC4 shows that even when the application quantity is doubled, the papers produced with spray suspensions according to the invention have significantly improved internal strength compared to the comparative examples. Increasing the dry content after the wire section by means of negative pressure or increased retention polymer quantity leads to a further improvement in the internal strength of the papers produced with spray suspensions according to the invention, while these measures have little or no effect on the comparative examples. In comparison with Table TabC2, Table TabC4 shows that replacing half of the amount of polymer used with cationic starch no longer leads to an equivalent improvement in the internal strength of the papers.

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Claims (13)

  1. Procédé de fabrication de papier séché à une ou plusieurs couches, comprenant pour un papier à une couche les étapes de
    (A) déshydratation d'une première suspension aqueuse de matière fibreuse, qui présente une teneur en matière sèche comprise entre 0,1 % en poids et 6 % en poids, sur un premier tamis, ce qui permet d'obtenir une première bande de matière fibreuse, qui présente une teneur en matière sèche comprise entre 14 % en poids et 25 % en poids,
    (D-I) déshydratation de la première bande fibreuse par pressage, ce qui permet d'obtenir une première bande fibreuse partiellement déshydratée,
    (E-I) pulvérisation de la première bande fibreuse partiellement déshydratée sur au moins une face avec une solution de pulvérisation ou une suspension de pulvérisation, ce qui permet d'obtenir une première bande fibreuse partiellement déshydratée pulvérisée,
    (F-I) égouttage la première bande fibreuse partiellement égouttée pulvérisée par apport de chaleur, ce qui permet d'obtenir le papier monocouche séché,
    ou contenant pour un papier à plusieurs couches les étapes
    (A) déshydratation d'une première suspension aqueuse de matière fibreuse, qui présente une teneur en matière sèche comprise entre 0,1 % en poids et 6 % en poids, sur un premier tamis, ce qui permet d'obtenir une première bande de matière fibreuse, qui présente une teneur en matière sèche comprise entre 14 % en poids et 25 % en poids,
    (B) déshydratation d'une seconde suspension aqueuse de matière fibreuse, qui présente une teneur en matière sèche comprise entre 0,1 % en poids et 6 % en poids, sur un second tamis, ce qui permet d'obtenir une seconde bande de matière fibreuse, qui présente une teneur en matière sèche comprise entre 14 % en poids et 25 % en poids,
    (C) l'assemblage de la première bande de matière fibreuse avec la deuxième bande de matière fibreuse de telle sorte que les deux bandes de matière fibreuse se touchent chacune sur un côté entier de la surface, ce qui permet d'obtenir un assemblage de couches,
    (D-2) déshydratation du composite de couches par pressage, ce qui permet d'obtenir un composite de couches partiellement déshydraté,
    (E-2) pulvérisation du composite de couches partiellement déshydraté sur au moins un côté de la surface avec une solution de pulvérisation ou une suspension de pulvérisation, ce qui permet d'obtenir un composite de couches pulvérisé,
    (F-2) déshydratation de l'ensemble des couches pulvérisées par apport de chaleur, ce qui permet d'obtenir le papier multicouche séché,
    dans lequel la solution de pulvérisation ou la suspension de pulvérisation contient
    (e-a) de l'eau
    (e-b) au moins un polymère P soluble dans l'eau, qui peut être obtenu par polymérisation de
    (i) 40 à 85 % en moles d'un monomère de la formule I
    Figure imgb0017
     dans lequel R1 = H ou alkyle en Ci-Ce,
    (ii) 15 à 60 % en moles d'un ou plusieurs composés éthyléniquement insaturés des monomères autres qu'un monomère de la formule I, dans lequel la quantité totale de tous les monomères (i) et (ii) est de 100 % en moles, et éventuellement par une hydrolyse partielle ou totale consécutive des unités de monomères de la formule (I) polymérisées dans le polymère P pour former des groupes amino primaires ou amidine,
    dans lequel la proportion d'eau est d'au moins 75 % en poids par rapport à la solution de pulvérisation ou à la suspension de pulvérisation.
  2. Procédé selon la revendication 1 de fabrication de papier multicouche séché, comprenant les étapes de
    (A) déshydratation d'une première suspension aqueuse de matière fibreuse, qui présente une teneur en matière sèche comprise entre 0,1 % en poids et 6 % en poids, sur un premier tamis, ce qui permet d'obtenir une première bande de matière fibreuse, qui présente une teneur en matière sèche comprise entre 14 % en poids et 25 % en poids,
    (B) déshydratation d'une seconde suspension aqueuse de matière fibreuse, qui présente une teneur en matière sèche comprise entre 0,1 % en poids et 6 % en poids, sur un second tamis, ce qui permet d'obtenir une seconde bande de matière fibreuse, qui présente une teneur en matière sèche comprise entre 14 % en poids et 25 % en poids,
    (C) l'assemblage de la première bande de matière fibreuse avec la deuxième bande de matière fibreuse de telle sorte que les deux bandes de matière fibreuse se touchent chacune sur un côté entier de la surface, ce qui permet d'obtenir un assemblage de couches,
    (D-2) déshydratation de l'assemblage de couches par pressage, ce qui permet d'obtenir un assemblage de couches partiellement déshydraté,
    (E-2) vaporisation du composite de couches partiellement déshydraté sur au moins une face avec une solution de vaporisation ou une suspension de vaporisation, ce qui permet d'obtenir un composite de couches vaporisé,
    (F-2) déshydratation de l'ensemble des couches partiellement déshydratées par apport de chaleur, ce qui permet d'obtenir le papier multicouche séché.
  3. Procédé selon la revendication 1 ou 2, dans lequel la solution de pulvérisation ou la suspension de pulvérisation a un pH de 5,5 ou plus.
  4. Procédé selon l'une quelconque des revendications 1 à 3, dans lequel, pour le papier à une seule couche dans l'étape (D-1), la première bande fibreuse partiellement déshydratée présente une teneur en matière sèche comprise entre 35 % en poids et 65 % en poids, et pour le papier à plusieurs couches dans l'étape (D-2), le composite de couches partiellement déshydraté présente une teneur en matière sèche comprise entre 35 % en poids et 65 % en poids, et/ou
    dans lequel, pour le papier monocouche de l'étape (F-1), le papier monocouche séché a une teneur en matière sèche d'au moins 88 % en poids, et pour le papier multicouche de l'étape (F-2), le papier multicouche séché a une teneur en matière sèche d'au moins 88 % en poids.
  5. Procédé selon l'une quelconque des revendications 1 à 4, dans lequel le polymère P peut être obtenu par polymérisation de
    (i) 40 à 85 % en moles, de préférence 50 à 85 % en moles, d'un monomère de la formule I,
    (ii) 15 à 60 % en moles, de préférence 15 à 50 % en moles, d'un ou plusieurs monomères à insaturation éthylénique autres qu'un monomère de la formule I,
    dans lequel les un ou plusieurs monomères éthyléniquement insaturés sont choisis parmi
    (ii-1) acide acrylique ou acide méthacrylique ou leurs sels de métaux alcalins, de métaux alcalino-terreux ou d'ammonium,
    (ii-2) acrylonitrile ou méthacrylonitrile,
    (ii-3) acétate de vinyle,
    (ii-4) un acide sulfonique à insaturation monoéthylénique, un acide sulfonique à insaturation néthylénique de l'acide phosphonique à insaturation monoéthylénique, un mono- ou diester à insaturation monoéthylénique de l'acide phosphorique ou un acide carboxylique à insaturation monoéthylénique ayant de 4 à 8 atomes de carbone, qui est différent de l'acide méthacrylique, ou leurs sels de métaux alcalins, de métaux alcalino-terreux ou d'ammonium,
    (ii-5) un monomère monoéthyléniquement insaturé quaternisé, un monomère monoéthyléniquement insaturé qui porte au moins un groupe amino secondaire ou tertiaire et dont au moins un groupe amino secondaire ou tertiaire est protoné à pH 7, ou une amine diallylsubstituée qui présente exactement deux doubles liaisons éthyléniques et qui est quaternisée ou protonée à pH 7, ou sa forme de sel,
    (ii-6) un monomère à insaturation monoéthylénique qui, à pH 7 et qui est différent de l'acrylonitrile, du méthacrylonitrile et de l'acétate de vinyle, ou un monomère à insaturation éthylénique dont exactement deux doubles liaisons éthyléniques sont conjuguées et qui ne porte pas de charge à pH 7,
    (ii-7) de 0 à 2 % en moles d'un monomère contenant au moins deux groupes de liaison à insaturation éthylénique présente des doubles liaisons qui ne sont pas conjuguées, et qui est différent d'une amine diallylsubstituée qui présente exactement deux doubles liaisons éthyléniques,
    (ii-8) 0 à 10 % en moles d'un monomère à insaturation éthylénique différent des monomères (ii-1) à (ii-7),
    dans lequel la quantité totale de tous les monomères (i) et (ii-1) à (ii-8) étant de 100 % en moles et % en moles se rapporte à la quantité totale de tous les monomères (i) et (ii-1) à (ii-8), et éventuellement par une hydrolyse partielle ou totale consécutive des unités des monomères de la formule (I) polymérisées dans le polymère P pour former des groupes amino primaires ou des groupes amidine, dans lequel en cas de présence d'unités polymérisées d'acétate de vinyle, celles-ci peuvent également être partiellement ou totalement hydrolysées.
  6. Procédé selon l'une quelconque des revendications 1 à 5, dans lequel les un ou plusieurs monomères éthyléniquement insaturés contiennent
    (ii-1) 15 à 50 % en moles d'acide acrylique ou d'acide méthacrylique ou de leur métal alcalin, des sels de métaux alcalino-terreux ou d'ammonium, et/ou
    (ii-2) 0 à 35 % en moles d'acrylonitrile ou de méthacrylonitrile, et/ou
    (ii-3) 0 à 35 % en moles d'acétate de vinyle, et/ou
    (ii-4) de 0 à 10 % en moles d'un acide sulfonique à insaturation monoéthylénique, de l'acide phosphonique à insaturation monoéthylénique, un mono- ou un diester à insaturation monoéthylénique de l'acide phosphorique ou d'un acide carboxylique à insaturation monoéthylénique ayant de 4 à 8 atomes de carbone, qui est différent de l'acide méthacrylique, ou de leurs sels de métaux alcalins, de métaux alcalino-terreux ou d'ammonium, et/ou
    (ii-5) de 0 à 20 % en moles d'un monomère quaternisé à insaturation monoéthylénique, un monomère monoéthyléniquement insaturé, qui porte au moins un groupe amino secondaire ou tertiaire et dont au moins un groupe amino secondaire ou tertiaire est protoné à pH 7, ou d'une amine diallylsubstituée, qui présente exactement deux doubles liaisons éthyléniques et est quaternisée ou protonée à pH 7, ou sa forme de sel, et/ou
    (ii-6) de 0 à 35 % en moles d'un monomère à insaturation monoéthylénique qui, à pH 7, ne porte pas de charge et est différent de l'acrylonitrile, le méthacrylonitrile et l'acétate de vinyle, ou un monomère à insaturation éthylénique dont exactement deux doubles liaisons sont conjuguées, qui ne porte pas de charge à pH 7 et qui est différent de l'acrylonitrile, le méthacrylonitrile et l'acétate de vinyle, et/ou
    (ii-7) de 0 à 1 % en moles d'un monomère contenant au moins deux groupes de liaison à insaturation éthylénique
    qui ne sont pas conjuguées et qui est différent d'une amine diallyl substituée qui présente exactement deux doubles liaisons éthyléniques, et/ou
    (ii-8) 0 à 5 % en moles d'un monomère à insaturation éthylénique dérivé des monomères (i) et (ii-1) à (ii-7),
    dans lequel % en moles se rapporte au nombre total de tous les monomères utilisés dans la polymérisation et le nombre total de tous les monomères est de 100 % en moles.
  7. Procédé selon l'une quelconque des revendications 1 à 6, dans lequel le polymère P peut être obtenu par
    polymérisation de
    (i) 50 à 85 % en moles d'un monomère de la formule I
    (ii-1) 15 à 50 % en moles d'acide acrylique ou d'acide méthacrylique ou de leurs sels de métaux alcalins, sels de métaux alcalino-terreux ou d'ammonium,
    (ii-2) 0 à 35 % en moles d'acrylonitrile ou de méthacrylonitrile
    dans lequel la quantité totale de tous les monomères (i) et (ii-1) à (ii-2) étant de 100 % en moles et % en moles se rapporte à la quantité totale de tous les monomères (i) et (ii-1) à (ii-2), et éventuellement par une hydrolyse partielle ou totale consécutive des unités des monomères de la formule (I) polymérisées dans le polymère P pour former des groupes amino primaires ou des groupes amidine.
  8. Procédé selon l'une quelconque des revendications 1 à 7, dans lequel, pour le papier monocouche, on déshydrate à l'étape (A) jusqu'à une teneur en matière sèche de 17 % en poids à 22 % en poids, et pour le papier multicouche, on déshydrate à chacune des étapes (A) et (B) jusqu'à une teneur en matière sèche de % en poids à 22 % en poids.
  9. Procédé selon l'une quelconque des revendications 1 à 8, dans lequel, pour le papier monocouche, on ajoute à la première suspension aqueuse de matières fibreuses, contenant (a-a) de l'eau et (a-b) une première matière fibreuse, avant l'égouttage dans l'étape (A), un polymère organique (a-c) en tant qu'agent de rétention, et pour le papier multicouche, on ajoute à la première suspension aqueuse de matières fibreuses, contenant (a- a) de l'eau et (a-b) une première matière fibreuse, avant l'égouttage dans l'étape (B), un polymère organique (a-c) en tant qu'agent de rétention. Un polymère organique (a-c) est ajouté comme agent de rétention à l'étape (A) d'égouttage, et un polymère organique (b-c) est ajouté comme agent de rétention à la deuxième suspension aqueuse de matière fibreuse, contenant (b-a) de l'eau et (b-b) la deuxième matière fibreuse, avant l'égouttage à l'étape (B), de préférence pour le papier à une seule couche, la quantité de polymère organique (a-c) ajouté étant de 0,001 % en poids par rapport au papier à deux couches% à 0,2 % en poids par rapport à la première pâte (a-b), et de préférence pour le papier multicouche, la quantité de polymère organique ajouté (a-c) est de 0,001 % à 0,2 % en poids par rapport à la première pâte (a-b), et de préférence la quantité de polymère organique ajouté (b-c) est de 0,001 % à 0,2 % en poids par rapport à la deuxième pâte (b-b).
  10. Procédé selon l'une quelconque des revendications 1 à 9, dans lequel, pour le papier monocouche, à l'étape (A), la première suspension de matière fibreuse est appliquée sur la première toile avec une première face supérieure de toile et une première face inférieure de toile sur la première face supérieure de toile, et l'égouttage est assisté par l'application d'une dépression sur la première face inférieure de toile, et pour le papier multicouche, à l'étape (A), la première suspension de matière fibreuse est appliquée sur la première toile avec une première face supérieure de toile et une première face inférieure de toile sur la première face supérieure de toile, à l'étape (B), la seconde suspension de matière fibreuse est appliquée sur le second tamis ayant une seconde face supérieure de tamis et une seconde face inférieure de tamis sur la seconde face supérieure de tamis et l'essorage est assisté par l'application d'une dépression sur la seconde face inférieure de tamis, ou, dans l'étape (A), la première suspension de matière fibreuse et, dans l'étape (B), la seconde suspension de matière fibreuse sont appliquées respectivement sur la première face supérieure du tamis et la seconde face supérieure du tamis correspondantes et l'essorage respectif est assisté par l'application d'une dépression sur la première face inférieure du tamis et la seconde face inférieure du tamis correspondantes.
  11. Procédé selon l'une quelconque des revendications 1 à 10, dans lequel, pour le papier à une seule couche, le procédé est mis en oeuvre dans une machine à papier dont l'équipement comprend une première section de toile avec la première toile ayant une première face supérieure de toile et une première face inférieure de toile, une section de presse, un dispositif de pulvérisation comprenant
    une section de séchage avec des cylindres chauffés, et dans la machine à papier, ceux-ci sont disposés dans l'ordre suivant : première section de toile, suivie de la section de presse, suivie du dispositif de pulvérisation et ensuite de la section de séchage, et pour le papier multicouche, le procédé est effectué dans une machine à papier dont l'équipement comprend une première section de toile avec la première toile ayant une première face supérieure de toile et une première face inférieure de toile, une deuxième section de toile avec la deuxième toile ayant une deuxième face supérieure de toile et une deuxième face inférieure de toile, une section de presse, un dispositif de pulvérisation contenant la solution ou la suspension de pulvérisation et une section de séchage avec des cylindres chauffés, et dans la machine à papier, ceux-ci sont disposés dans l'ordre de la première section de toile et de la deuxième section de toile, suivie de la section de presse, suivie du dispositif de pulvérisation et ensuite de la section de séchage.
  12. Procédé selon l'une quelconque des revendications 1 à 11, dans lequel, pour le papier monocouche, à l'étape (E-1), la solution de pulvérisation ou la suspension de pulvérisation pour la pulvérisation est mise sous une surpression de 0,5 à 4,5 bars par rapport à la pression ambiante, et pour le papier multicouche, à l'étape (E-2), la solution de pulvérisation ou la suspension de pulvérisation pour la pulvérisation est mise sous une surpression de 0,5 à 4,5 bars par rapport à la pression ambiante.
  13. Procédé selon l'une quelconque des revendications 1 à 12, dans lequel la teneur en matière sèche est déterminée par séchage à 105 °C jusqu'à masse constante.
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