EP1470292B1 - Process for manufacturing paper - Google Patents

Process for manufacturing paper Download PDF

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Publication number
EP1470292B1
EP1470292B1 EP03734931.3A EP03734931A EP1470292B1 EP 1470292 B1 EP1470292 B1 EP 1470292B1 EP 03734931 A EP03734931 A EP 03734931A EP 1470292 B1 EP1470292 B1 EP 1470292B1
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EP
European Patent Office
Prior art keywords
anionic
cationic
polymer
aromatic
vinyl addition
Prior art date
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EP03734931.3A
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German (de)
English (en)
French (fr)
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EP1470292A1 (en
Inventor
Sten FRÖLICH
Fredrik Solhage
Erik Lindgren
Hans E. Johansson-Vestin
Kjell Andersson
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Akzo Nobel NV
Nouryon Pulp and Performance Chemicals AB
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Akzo Nobel NV
Akzo Nobel Pulp and Performance Chemicals AB
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Priority to EP03734931.3A priority Critical patent/EP1470292B1/en
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Classifications

    • DTEXTILES; PAPER
    • D21PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21HPULP 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
    • D21H23/00Processes or apparatus for adding material to the pulp or to the paper
    • D21H23/02Processes or apparatus for adding material to the pulp or to the paper characterised by the manner in which substances are added
    • D21H23/04Addition to the pulp; After-treatment of added substances in the pulp
    • D21H23/06Controlling the addition
    • D21H23/14Controlling the addition by selecting point of addition or time of contact between components
    • DTEXTILES; PAPER
    • D21PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21HPULP 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
    • D21H17/00Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20Macromolecular organic compounds
    • D21H17/33Synthetic macromolecular compounds
    • D21H17/34Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H17/41Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups
    • D21H17/42Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups anionic
    • DTEXTILES; PAPER
    • D21PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21HPULP 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
    • D21H17/00Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20Macromolecular organic compounds
    • D21H17/33Synthetic macromolecular compounds
    • D21H17/34Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H17/41Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups
    • D21H17/44Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups cationic
    • DTEXTILES; PAPER
    • D21PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21HPULP 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
    • D21H3/00Paper or cardboard prepared by adding substances to the pulp or to the formed web on the paper-making machine and by applying substances to finished paper or cardboard (on the paper-making machine), also when the intention is to impregnate at least a part of the paper body
    • DTEXTILES; PAPER
    • D21PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21HPULP 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
    • D21H17/00Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/03Non-macromolecular organic compounds
    • D21H17/05Non-macromolecular organic compounds containing elements other than carbon and hydrogen only
    • D21H17/17Ketenes, e.g. ketene dimers
    • DTEXTILES; PAPER
    • D21PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21HPULP 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
    • D21H17/00Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20Macromolecular organic compounds
    • D21H17/21Macromolecular organic compounds of natural origin; Derivatives thereof
    • D21H17/24Polysaccharides
    • D21H17/28Starch
    • D21H17/29Starch cationic
    • DTEXTILES; PAPER
    • D21PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21HPULP 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
    • D21H17/00Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20Macromolecular organic compounds
    • D21H17/33Synthetic macromolecular compounds
    • D21H17/34Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H17/37Polymers of unsaturated acids or derivatives thereof, e.g. polyacrylates
    • D21H17/375Poly(meth)acrylamide
    • DTEXTILES; PAPER
    • D21PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21HPULP 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
    • D21H17/00Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20Macromolecular organic compounds
    • D21H17/33Synthetic macromolecular compounds
    • D21H17/34Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H17/41Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups
    • D21H17/44Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups cationic
    • D21H17/45Nitrogen-containing groups
    • DTEXTILES; PAPER
    • D21PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21HPULP 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
    • D21H17/00Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20Macromolecular organic compounds
    • D21H17/33Synthetic macromolecular compounds
    • D21H17/34Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H17/41Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups
    • D21H17/44Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups cationic
    • D21H17/45Nitrogen-containing groups
    • D21H17/455Nitrogen-containing groups comprising tertiary amine or being at least partially quaternised
    • DTEXTILES; PAPER
    • D21PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21HPULP 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
    • D21H21/00Non-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
    • D21H21/14Non-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
    • D21H21/16Sizing or water-repelling agents

Definitions

  • the present invention refers to a process for manufacturing paper and board comprising the addition of two different polymers to an aqueous cellulose-containing suspension one being an aromatic-containing cationic vinyl addition polymer and the other an anionic polymer having a weight average molecular weight in the range of from about 6,000 up to about 100,000 selected from the group consisting of vinyl addition polymers.
  • Internal sizing agents are usually added to the wet end of the paper making process whereby the adsorption capability of the paper of liquids is decreased.
  • Commonly used internal sizing agents are sizing agents based on rosin derivatives and cellulose-reactive sizing agents, notably ketene dimers and acid anhydrides.
  • Multipurpose office paper need to be rather heavily sized in order to function properly in today's high speed reproducing machines.
  • One way of attaining paper which is fully sized, i.e. having a cobb 60 number below 30 or measuring the contact angle of a water droplet on the paper where angles larger the 80 degrees after 10 seconds indicate good sizing, is to add more sizing agent to the suspension.
  • the likelihood of ending up with runability problems in the paper mill increases as well as the production costs.
  • dewatering and retention agents are also added to the suspension.
  • the latter agents enhance both dewatering and retention of the pulp suspension.
  • sizing efficiency is improved by the addition of at least two different types of polymers to the pulp suspension which polymers simultaneously function as dewatering and retention agents.
  • US 5595629 relates to a papermaking process comprising forming an aqueous cellulosic papermaking slurry and adding a cationic polymer and an anionic polymer to the slurry to increase retention and/or drainage.
  • US 5584966 discloses a process to improve formation of paper during the papermaking process utilizing a combination of polysilicate microgels (PSM) in combination with cationic and anionic polymers.
  • PSM polysilicate microgels
  • specifically improved sizing can be obtained by a process for manufacturing paper and board comprising providing a suspension comprising cellulose and at least a sizing agent, dewatering said suspension thereby forming a paper-web, whereby an aromatic-containing cationic vinyl addition polymer, and an anionic polymer having a weight average molecular weight in the range of from about 6,000 up to about 100,000 selected from the group consisting of vinyl addition polymers and condensation polymers vinyl addition polymer are added to the suspension.
  • the present invention is not restricted to specific types of cellulose suspensions, but can be applied on cellulose suspensions containing virgin or recycled pulp and different fillers such as calcium carbonate.
  • the pH of the suspension may also vary from being acidic, which is the case if sizing agents derived from rosins are used, to being neutral or alkaline. If cellulose-reactive sizing agents are used the pH of the cellulose suspension is neutral to alkaline, i.e. in the range from about 5 up to about 10, which also makes it possible to include inorganic filler materials in the suspension, e.g. precipitated calcium carbonate and clays.
  • the two different polymers are suitable added to a fairly diluted lignocellulose-containing suspension commonly referred to as the thin stock having a concentration of from 0.1 up to 3.0 % by weight based on dry fibres.
  • the cellulose suspension contains at least a sizing agent selected from the group consisting of ketene dimers and acid anhydrides normally present in an amount of from 0.01 to 5 % by weight based on dry fibres, and has a pH value where the cellulose-reactive sizing agent still functions properly, i.e. a pH in the range from 5 up to 10.
  • a sizing agent selected from the group consisting of ketene dimers and acid anhydrides normally present in an amount of from 0.01 to 5 % by weight based on dry fibres, and has a pH value where the cellulose-reactive sizing agent still functions properly, i.e. a pH in the range from 5 up to 10.
  • Cellulose-reactive sizing agents are ketene dimers, acid anhydrides, and mixtures thereof.
  • an aromatic-containing cationic vinyl addition polymer and an anionic vinyl addition polymer having a weight average molecular weight in the range of from about 6,000 up to about 100,000 is added to the cellulose suspension.
  • the cationic polymer is added to the suspension prior to the addition of the anionic polymer.
  • the addition of the cationic polymer is followed by a shear stage or stages, whereas the anionic polymer is added after any stage providing significant shear but before the formation of the paper web.
  • the aromatic-containing cationic vinyl addition polymer may be linear or branched and contain monomers having anionic or potentially anionic groups as long as the overall charge of the polymer is cationic.
  • the cationic polymer is preferably obtained by polymerising a reaction mixture essentially free from monomers having anionic groups or groups which can be rendered anionic in aqueous compositions.
  • the cationic polymer can be a homo polymer or a copolymer containing cationic aromatic monomers, cationic non-aromatic monomers and non-ionic monomers, the latter also being non-aromatic.
  • the cationic vinyl addition polymer contains cationic aromatic monomers selected from the group consisting of acrylamide, (meth)acrylamide, acrylate and (meth)acrylate, whereby said cationic monomers preferably have at least one aromatic group covalently linked to a nitrogen atom either direct or via hydrocarbon groups which can have heteroatoms.
  • the aromatic-containing cationic vinyl addition polymer contains aromatic (meth)acrylamide and/or (meth)acrylate monomers which are present in the polymer in an amount from about 2 molar % up to about 97 molar %.
  • the aromatic-containing cationic vinyl addition polymer is suitably obtained by polymerising a cationic monomer or a reaction mixture containing a monomer mixture comprising a cationic monomer represented by the general formula (I): wherein R 1 is H or CH 3 ; R 2 and R 3 are independently from another a hydrogen or an alkyl group having from 1 to 3 carbon atoms, usually 1 to 2 carbon atoms; A 1 is O or NH; B 1 is an alkylene group having from 2 to 8 carbon atoms, suitably from 2 to 4 carbon atoms, a hydroxy propylene group or a hydroxy ethylene group; Q is a substituent containing an aromatic group, suitably a phenyl or substituted phenyl group, which can be attached to the nitrogen by means of an alkylene group usually having from 1 to 3 carbon atoms, suitably 1 to 2 carbon atoms, and preferably Q is a benzyl group (- CH 2 - C 6 H 5 ); and X is an anionic
  • Suitable monomers represented by the general formula (I) include quaternary monomers obtained by treating dialkylaminoalkyl (meth)acrylates, e.g. dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate and dimethylaminohydroxypropyl (meth)acrylate, and dialkylaminoalkyl (meth)acrylamides, e.g. dimethylaminoethyl (meth)acrylamide, diethylaminoethyl (meth)acrylamide, dimethylaminopropyl (meth)acrylamide, and diethylaminopropyl (meth)acrylamide, with benzyl chloride.
  • dialkylaminoalkyl (meth)acrylates e.g. dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate and dimethylaminohydroxypropyl (meth)acryl
  • Preferred cationic monomers of the general formula (I) include dimethyl-aminoethylacrylate benzyl chloride quaternary salt, dimethylaminoethylmethacrylate benzyl chloride quaternary salt and dimethylaminopropyl(meth)acrylamide benzyl chloride quaternary salt.
  • the cationic vinyl addition polymer can be a homopolymer prepared from a cationic monomer having an aromatic group or a copolymer prepared from a monomer mixture comprising a cationic monomer having an aromatic group and one or more copolymerizable monomers.
  • suitable copolymerizable monomers of this type include (meth)acrylamide; acrylamide-based monomers like N-alkyl (meth)acrylamides and N,N-dialkyl (meth)acrylamides, e.g. N-n-propylacrylamide, N-isopropyl (meth)acrylamide, N-n-butyl (meth)acrylamide, N-isobutyl (meth)acrylamide and N-t-butyl (meth)acrylamide; and dialkylaminoalkyl (meth)acrylamides, e.g.
  • Preferred copolymerizable non-ionic monomers include acrylamide and methacrylamide, i.e. (meth)acrylamide, and the main polymer is preferably an acrylamide-based polymer.
  • Suitable copolymerizable cationic monomers include the monomers represented by the general formula (III): wherein R 7 is H or CH 3 ; R 8 and R 9 are preferably a hydrocarbon group, suitably an alkyl group having from 1 to 3 carbon atoms; R 10 can be a hydrogen or preferably a hydrocarbon group, suitably an alkyl group having from 1 to 8 carbon atoms, usually 1 to 2 carbon atoms; A 3 is O or NH; B 3 is an alkylene group of from 2 to 4 carbon atoms, suitably from 2 to 4 carbon atoms, or a hydroxy propylene group, and X - is an anionic counterion, usually methylsulphate or a halide like chloride.
  • R 7 is H or CH 3
  • R 8 and R 9 are preferably a hydrocarbon group, suitably an alkyl group having from 1 to 3 carbon atoms
  • R 10 can be a hydrogen or preferably a hydrocarbon group, suitably an alkyl group having from
  • Suitable cationic copolymerizable monomers include acid addition salts and quaternary ammonium salts of the dialkylaminoalkyl (meth)acrylates and dialkylaminoalkyl (meth)acrylamides mentioned above, usually prepared using acids like HCl, H 2 SO 4 , etc., or quaternizing agents like methyl chloride, dimethyl sulphate, etc.; and diallyldimethylammonium chloride.
  • Preferred copolymerizable cationic monomers include dimethylaminoethyl (meth)acrylate methyl chloride quaternary salt, diallyldimethylammonium chloride and and dimethylaminopropyl(meth)acrylamide benzyl chloride quartenary salt.
  • Copolymerizable anionic monomers like acrylic acid, methacrylic acid, itaconic acid, various sulfonated vinyl addition monomers, etc. can also be employed and, preferably, in minor amounts.
  • the cationic vinyl addition polymer can be prepared from a monomer mixture generally comprising from 1 to 99 mole%, suitably from 2 to 50 mole% and preferably from 5 to 20 mole% of cationic monomer having an aromatic group, preferably represented by the general formula (I), and from 99 to 1 mole%, suitably from 98 to 50 mole%, and preferably from 95 to 65 mole% of other copolymerizable monomers which preferably comprises acrylamide or methacrylamide ((meth)acrylamide), the monomer mixture suitably comprising from 98 to 50 mole% and preferably from 95 to 80 mole% of (meth)acrylamide, the rest up to 100% preferably of compounds according to formula I and II.
  • a monomer mixture generally comprising from 1 to 99 mole%, suitably from 2 to 50 mole% and preferably from 5 to 20 mole% of cationic monomer having an aromatic group, preferably represented by the general formula (I), and from 99 to 1 mole%, suitably from 98 to 50 mole
  • the cationic polymer can be a polymer subjected to aromatic modification using an agent containing an aromatic group.
  • Suitable modifying agents of this type include benzyl chloride, benzyl bromide, N-(3-chloro-2-hydroxypropyl)-N-benzyl-N,N-dimethylammonium chloride, and N-(3-chloro-2-hydroxypropyl) pyridinium chloride.
  • Suitable polymers for such an aromatic modification include vinyl addition polymers. If the polymer, contains a tertiary nitrogen which can be quatemized by the modifying agent, the use of such agents usually results in that the polymer is rendered cationic.
  • the polymer to be subjected to aromatic modification can be cationic, for example a cationic vinyl addition polymer.
  • the charge density of the cationic polymer is within the range of from 0.1 to 6.0 meqv/g of dry polymer, suitably from 0.2 to 4.0 and preferably from 0.5 to 3.0.
  • the weight average molecular weight of the cationic polymer is usually at least about 500,000, suitably above about 1,000,000 and preferably above about 2,000,000.
  • the upper limit is not critical; it can be about 30,000,000, usually 20,000,000 and suitably 10,000,000.
  • the cationic vinyl addition polymer can be added into the suspension in amounts which can vary within wide limits depending on, inter alia, type of suspension, salt content, type of salts, filler content, type of filler, point of addition, etc. Generally the cationic vinyl addition polymer is added in an amount that give better sizing, dewatering and retention than is obtained when not adding it provided the anionic vinyl addition polymer is added.
  • the cationic polymer is usually added in an amount of at least 0.002%, often at least 0.005% by weight, based on dry pulp, whereas the upper limit is usually 1.0% and suitably 0.5% by weight.
  • an anionic vinyl addition polymer having a weight average molecular weight in the range of from about 6,000 up to about 100,000 is added to the cellulose suspension.
  • the anionic polymer can be linear, branched or cross-linked, yet suitably essentially linear, and usually water-soluble or water-dispersable.
  • the anionic polymer may furthermore be a homopolymer or a copolymer containing at least two different types of monomers.
  • the anionic polymer is a vinyl addition polymer having a weight average molecular weight in the range of from about 6,000 up to about 100,000.
  • Suitable anionic vinyl addition polymers are polymers obtained from a reaction mixture comprising vinylic unsaturated monomers, preferably vinylic unsaturated aromatic containing monomers, having one or more anionic groups or groups rendered anionic in aqueous solutions, suitably at least one sulphonate group.
  • anionic groups attached to vinylic unsaturated monomers are phosphate groups, phosphonate groups, sulphate groups, sulphonic acid groups, sulphonate groups, carboxylic acid groups, carboxylate groups such as acrylic acid, methacrylic acid, ethyl acrylic acid, crotonic acid, itaconic acid, maleic acid or salts thereof, alkoxide groups, maleic acid groups and phenolic groups, i.e.
  • the anionic vinyl addition polymer may also in some extent contain cationic groups such as monomers having cationic groups, though, preferable the only ionic groups present in the vinyl addition polymer are anionic.
  • the anionic groups are linked to aromatic vinylic (ethylenically) unsaturated monomers such as styrene, i.e. styrene sulphonate.
  • anionic vinyl addition polymer is a copolymer
  • said polymer can be obtained from a reaction mixture comprising non-ionic vinylic unsaturated monomers, e.g. acrylamide, (meth)acrylamide.
  • the anionic vinyl addition polymer may comprise from about 20 mole % up to about 100 mole % of anionic monomers containing at least one anionic charge.
  • the weight average molecular weight of the anionic vinyl addition polymer is in the range of from about 6,000 up to about 100,000.
  • the lower limit is suitably from about 7,000, preferably from about 8,000, preferably from about 15,000, preferably from about 25,000, whereas he upper limit is suitably up to about 80,000, preferably up to about 75,000, preferably up to 45,000, preferably up to about 40,000. Any combination of lower and higher limit can be a preferred range.
  • the anionic polymer is a vinyl addition polymer
  • the preferred ranges of the weight average molecular weight is from about 10,000 up to about 100,000, more preferably from about 15,000 up to about 75,000, most preferably from about 25,000 up to about 45,000.
  • the anionic vinyl addition polymer can have a degree of anionic substitution (DS A ) varying over a wide range dependent on, inter alia, the type of polymer used; DS A is usually from 0.01 to 2.0, suitably from 0.02 to 1.8 and preferably from 0.025 to 1.5; and the degree of aromatic substitution (DS Q ) can be from 0.001 to 1.0, usually from 0.01 to 1.0, suitably from 0.02 to 0.7 and preferably from 0.025 to 0.5.
  • the degree of cationic substitution (DS c ) can be, for example, from 0 to 0.2, suitably from 0 to 0.1 and preferably from 0 to 0.05, the anionic polymer having an overall anionic charge.
  • the anionic charge density of the anionic polymer is within the range of from 0.1 to 6.0 meqv/g of dry polymer, suitably from 0.5 to 5.0 and preferably from 1.0 to 5.0.
  • the anionic vinyl addition polymer can be added to the suspension in amounts which can vary within wide limits depending on, inter alia, type of stock, salt content, type of salts, filler content, type of filler, point of addition, etc. Generally the anionic polymer is added in an amount that give better sizing, dewatering and retention than is obtained when not adding the anionic polymer provided the cationic vinyl addition polymer is added.
  • the anionic polymer is usually added in an amount of at least 0.001%, often at least 0.005% by weight, based on dry pulp, whereas the upper limit is usually 3.0% and suitably 1.0% by weight.
  • the aromatic-containing cationic vinyl addition polymer can be provided as an aqueous composition, suitably aqueous solution, preferably comprising further cationic polymers, for example synthetic cationic polymers and naturally occurring polymers.
  • Suitable synthetic cationic polymers cationic are vinyl addition polymers such as acrylamide based polymers or acrylate based polymers.
  • Other synthetic cationic polymers include cationic condensation polymers like epihalohydrin polymers, e.g. polymers formed by reacting aliphatic amines and epichlorohydrine, polyamideamine polymers, polyethyleneimine polymers.
  • Preferred naturally occurring cationic polymers as cationic polysaccharides, particularly cationic starch and aromatic substituted cationic starch.
  • the aqueous solution preferably contains the aromatic-containing cationic vinyl addition polymer in a predominant amount, i.e. at least 50 % by weight, even though effects are present at considerably lesser amounts, down to amount at least 10 % by weight.
  • the further cationic polymers referred to in this paragraph may also be added separately.
  • inorganic anionic microparticulate materials like anionic silica-based particles, polysilicic acid and clays of the smectite type are added to the suspension.
  • the inorganic anionic microparticulate material can be added separately to the suspension or is preferably comprised in an aqueous composition also comprising the anionic polymer.
  • the process can also be useful in the manufacture of paper and board from cellulosic suspensions having high conductivity.
  • the conductivity of the suspension that is dewatered on the wire is usually at least 1.0 mS/cm, suitably at least 2.0 mS/cm, and preferably at least 3.5 mS/cm.
  • Conductivity can be measured by standard equipment such as, for example, a WTW LF 539 instrument supplied by Christian Berner.
  • the values referred to above are suitably determined by measuring the conductivity of the cellulosic suspension that is fed into or present in the head box of the paper machine or, alternatively, by measuring the conductivity of white water obtained by dewatering the suspension.
  • High conductivity levels mean high contents of salts (electrolytes) which can be derived from the materials used to form the stock, from various additives introduced into the stock, from the fresh water supplied to the process, etc. Further, the content of salts is usually higher in processes where white water is extensively recirculated, which may lead to considerable accumulation of salts in the water circulating in the process.
  • salts electrophilic compounds
  • Parts and % relate to parts by weight and % by weight based on dry fibres, respectively, unless otherwise stated. All compound added to the furnish are calculated as dry material, if not otherwise indicated. In the examples, a good retention is shown by a low turbidity value in the white water, i.e. more fines and filler are retained in the formed sheet. A turbidity value under 120 is acceptable and a value under 90 is in this set of experiment excellent. The dewatering figure should also be low.
  • the sizing of the paper was measured by the contact angle of a water droplet on the paper. Contact angles larger the 80 degrees after 10 seconds are indicating a good sizing.
  • the pulp (at 3%) used was a 80/20 mixture of hardwood/softwood kraft.
  • Ground calcium carbonate filler (GCC) was added to the pulp, to a filler concentration of 40% on dry solids.
  • the resulting furnish was diluted to 0.3% before additional chemicals were added. The chemical additions are expressed as % on dry solids in the furnish.
  • the retention was evaluated by measuring the turbidity of the white water with a Nephelometer 156 from Novasine. A lower turbidity value signifies higher retention of solids in the DDA-unit.
  • the sizing of the formed, dried and cured paper was evaluated by measuring the contact angle of water after 10 seconds utilising a Dynamic Absoption and contact angle tester from Fibro Systems (DAT). A higher value of the contact angle means better sizing efficiency.
  • the furnish used was the same as used in example 1, however, in this example the furnish was adjusted to a conductivity of 400 ⁇ S/cm
  • the sizing dispersion as used in example 1 was added to the furnish followed by the addition of cationic starch.
  • the dosage for the size was 0.03% (calculated as active ketene dimer on dry furnish) and for the cationic starch 1.0%.
  • 0.1 % of an aromatic cationic polyacrylamide having benzyldimethylammonium groups was added prior to the addition of 0.07% of an anionic polystyrene sulphonate having different weight average molecular weights as indicated in table III and an anionic naphthalene sulphonate, respectively.
  • the added amounts of compounds are indicated in table III.
  • the retention and dewatering properties of the formed furnishes were evaluated by measuring the dewatering time using a DDA-unit.
  • the retention was evaluated by measuring the turbidity of the white water with a Nephelometer 156 from Novasine.
  • the sizing of the formed, dried and cured paper was evaluated by measuring the contact angle of water after 10 seconds utilising a DAT equipment.
  • Tests 3 to 5 are according to the present invention, i.e. the anionic vinyl addition polymer naving a weight average molecular weight in the range of from about 6,000 up to about 100,000.
  • the sizing efficiency is significantly increased while at the same time the turbidity and dewatering performance are high with regard to tests 3 to 5 compared to the blank.
  • the sizing efficiency is much higher, while simultaneously the turbidity value still indicates good retention. What is more, a contacting angle of 69.2 as obtained in test 6 is not an acceptable sizing degree.
  • the overall performance of tests 3 to 5 in respect of retention, dewatering and not least sizing clearly outperform test 1,2 and, 6.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Paper (AREA)
EP03734931.3A 2002-01-31 2003-01-22 Process for manufacturing paper Expired - Lifetime EP1470292B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP03734931.3A EP1470292B1 (en) 2002-01-31 2003-01-22 Process for manufacturing paper

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EP02445012 2002-01-31
EP02445012 2002-01-31
EP03734931.3A EP1470292B1 (en) 2002-01-31 2003-01-22 Process for manufacturing paper
PCT/SE2003/000112 WO2003064767A1 (en) 2002-01-31 2003-01-22 Process for manufacturing paper

Publications (2)

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EP1470292A1 EP1470292A1 (en) 2004-10-27
EP1470292B1 true EP1470292B1 (en) 2014-06-25

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EP (1) EP1470292B1 (zh)
JP (1) JP2005516135A (zh)
KR (1) KR20040075104A (zh)
CN (1) CN1625631A (zh)
AR (1) AR038336A1 (zh)
AU (1) AU2003238688B2 (zh)
BR (1) BR0307252B1 (zh)
CA (1) CA2473638A1 (zh)
ES (1) ES2501166T3 (zh)
MX (1) MXPA04006655A (zh)
NO (1) NO336351B1 (zh)
PL (1) PL214002B1 (zh)
PT (1) PT1470292E (zh)
RU (1) RU2281994C2 (zh)
TW (1) TW593840B (zh)
WO (1) WO2003064767A1 (zh)
ZA (1) ZA200405126B (zh)

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DE60305848T2 (de) * 2002-11-28 2006-11-30 Canon K.K. Leimungsmittel und damit geleimtes Aufzeichnungsblatt
US7955473B2 (en) 2004-12-22 2011-06-07 Akzo Nobel N.V. Process for the production of paper
US20060254464A1 (en) 2005-05-16 2006-11-16 Akzo Nobel N.V. Process for the production of paper
US8273216B2 (en) 2005-12-30 2012-09-25 Akzo Nobel N.V. Process for the production of paper
JP5140000B2 (ja) 2005-12-30 2013-02-06 アクゾ ノーベル ナムローゼ フェンノートシャップ 紙の製造方法
WO2008066489A1 (en) 2006-12-01 2008-06-05 Akzo Nobel N.V. Packaging laminate
US8088250B2 (en) * 2008-11-26 2012-01-03 Nalco Company Method of increasing filler content in papermaking
JP5288538B2 (ja) * 2008-05-20 2013-09-11 ハイモ株式会社 抄紙方法
CN101613977B (zh) * 2009-07-15 2011-05-11 金东纸业(江苏)股份有限公司 造纸用增强纤维及其制备方法和应用
US8852400B2 (en) * 2010-11-02 2014-10-07 Ecolab Usa Inc. Emulsification of alkenyl succinic anhydride with an amine-containing homopolymer or copolymer
EP2882899A2 (en) 2011-11-14 2015-06-17 Kemira Oyj Akd composition and manufacture of paper and paperboard
FR2982887B1 (fr) * 2011-11-18 2014-01-31 Coatex Sas Polymeres faiblement anioniques pour sauces de couchage destinees a des papiers pour impression de type jet d'encre
JP6307439B2 (ja) * 2011-12-15 2018-04-04 インヴェンティア・アクチボラゲットInnventia Ab 紙および板紙の改善システムおよび方法
CN104822870B (zh) 2013-01-31 2017-10-27 格拉特菲尔特盖恩斯巴赫股份有限公司 用于纸或非织造网的交联/功能化系统
US9556558B2 (en) * 2014-01-07 2017-01-31 Api Intellectual Property Holdings, Llc Processes for producing high-yield pulp and paper products

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US5584966A (en) 1994-04-18 1996-12-17 E. I. Du Pont De Nemours And Company Paper formation
US5595629A (en) 1995-09-22 1997-01-21 Nalco Chemical Company Papermaking process
FR2740482B1 (fr) * 1995-10-30 1997-11-21 Snf Sa Procede pour ameliorer la retention dans un procede de fabrication du papier, carton et analogue
US5969011A (en) * 1997-02-05 1999-10-19 Akzo Nobel Nv Sizing of paper
US6033524A (en) * 1997-11-24 2000-03-07 Nalco Chemical Company Selective retention of filling components and improved control of sheet properties by enhancing additive pretreatment
EP0953680A1 (en) * 1998-04-27 1999-11-03 Akzo Nobel N.V. A process for the production of paper

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RU2004126318A (ru) 2005-03-10
CN1625631A (zh) 2005-06-08
CA2473638A1 (en) 2003-08-07
ES2501166T3 (es) 2014-10-01
AR038336A1 (es) 2005-01-12
PL371243A1 (en) 2005-06-13
AU2003238688B2 (en) 2006-04-06
TW593840B (en) 2004-06-21
PL214002B1 (pl) 2013-06-28
KR20040075104A (ko) 2004-08-26
NO336351B1 (no) 2015-08-03
MXPA04006655A (es) 2004-10-04
EP1470292A1 (en) 2004-10-27
BR0307252A (pt) 2004-12-14
JP2005516135A (ja) 2005-06-02
ZA200405126B (en) 2005-08-31
NO20043623L (no) 2004-11-01
RU2281994C2 (ru) 2006-08-20
TW200400305A (en) 2004-01-01
WO2003064767A1 (en) 2003-08-07
BR0307252B1 (pt) 2014-02-04
PT1470292E (pt) 2014-09-03

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