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EP1778916B1 - Füllstoff für papierherstellung - Google Patents

Füllstoff für papierherstellung Download PDF

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Publication number
EP1778916B1
EP1778916B1 EP05752686.5A EP05752686A EP1778916B1 EP 1778916 B1 EP1778916 B1 EP 1778916B1 EP 05752686 A EP05752686 A EP 05752686A EP 1778916 B1 EP1778916 B1 EP 1778916B1
Authority
EP
European Patent Office
Prior art keywords
filler
clay
cellulose derivative
paper
weight
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Not-in-force
Application number
EP05752686.5A
Other languages
English (en)
French (fr)
Other versions
EP1778916A1 (de
Inventor
Erik Sanne
Kjell Andersson
Johan Nyander
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Akzo Nobel NV
Nouryon Pulp and Performance Chemicals AB
Original Assignee
Akzo Nobel NV
Akzo Nobel Pulp and Performance Chemicals AB
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Akzo Nobel NV, Akzo Nobel Pulp and Performance Chemicals AB filed Critical Akzo Nobel NV
Priority to EP13188113.8A priority Critical patent/EP2835468B1/de
Priority to SI200532077A priority patent/SI1778916T1/sl
Priority to EP05752686.5A priority patent/EP1778916B1/de
Publication of EP1778916A1 publication Critical patent/EP1778916A1/de
Application granted granted Critical
Publication of EP1778916B1 publication Critical patent/EP1778916B1/de
Not-in-force legal-status Critical Current
Anticipated expiration legal-status Critical

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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
    • D21H17/63—Inorganic compounds
    • D21H17/67—Water-insoluble compounds, e.g. fillers, pigments
    • D21H17/68—Water-insoluble compounds, e.g. fillers, pigments siliceous, e.g. clays
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/21—Macromolecular organic compounds of natural origin; Derivatives thereof
    • D21H17/24—Polysaccharides
    • D21H17/25—Cellulose
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H23/00—Processes or apparatus for adding material to the pulp or to the paper
    • D21H23/02—Processes or apparatus for adding material to the pulp or to the paper characterised by the manner in which substances are added
    • D21H23/04—Addition to the pulp; After-treatment of added substances in the pulp

Definitions

  • the present invention relates to a filler comprising clay and cellulose derivative.
  • the invention further relates to a method of making the filler, the use of the filler in papermaking, a process for papermaking in which the filler is used as an additive as well as paper comprising the filler.
  • an aqueous suspension containing cellulosic fibres, fillers and additives referred to as the stock
  • a headbox which ejects the stock onto a forming wire
  • Water is drained from the stock through the forming wire so that a wet web of paper is formed on the wire, and the web is further dewatered and dried in the drying section of the paper machine.
  • Highly filled paper is an established trend in the paper industry, not only due to the savings in the decreased use of fibre, but also due to improved product quality, such as higher opacity and better printability.
  • SC paper super calanderred paper
  • kaolin clay is the most commonly used filler.
  • the day particles have a flake or plate shape, and at calandering the flakes are uniformly oriented, giving a high gloss and smoothness to the paper.
  • the amount of filler can be as high as 30% or more.
  • a high degree of filler causes a decrease in paper strength as well as linting and dusting.
  • a rule of thumb at filler usage in paper is that a 10% increase in filler content decreases the strength by 20%.
  • Problems with linting and dusting occur, as small fibre fragments and fillers are not properly bound into the paper. This can give a specific problem at rotogravure printing of SC paper, called missing dots, when ink is missing in dots in the print.
  • Addition of a binding agent can increase the strength of the paper as well as decrease the linting and dusting.
  • starch has been used as a binding agent.
  • SC paper making the calandering of the paper is done at a load of 100-350 kN/m. Starch makes the paper brittle and it can break at such heavy loads. Starch also makes the paper denser already prior to calandering. Therefore, no starch or small additions (1-2 kg/tonne dry paper) is used in SC paper making.
  • EP 758695 A2 discloses a water-dispersible sheet and a cigarette using the sheet.
  • the sheet comprises a water-resolvable base paper made from fibrous raw materials and a water-dispersilble coating layer containing water-soluble polymer and an alkaline compound.
  • the water-resolvable base paper is made from a mixture of water-dispersible fibres and fibrous carboxymethyl cellulose acid or fibrous carboxyethyl cellulose acid.
  • US 5,759,346 describes a method of improving strength and reducing lint and dust in the production of tissue paper.
  • the filler is a kaolin clay which has been pre-treated with a cationic starch.
  • WO 01/86067 describes a method for pre-treating a filler with a hydrophobic polymer, which is a synthetic polymer comprising acrylate and styrene monomers.
  • a hydrophobic polymer which is a synthetic polymer comprising acrylate and styrene monomers.
  • the use of the pre-treated filler improves wet strength and reduces the linting of the paper.
  • WO 95/13324 refers to calcium carbonate treated with a cellulose derivative such as sodium carboxymethyl cellulose ("CMC") having a degree of substitution of 0.70. Said treated calcium carbonate is used as filler in alkaline papermaking suspensions whereby the brightness of the paper is increased.
  • CMC sodium carboxymethyl cellulose
  • the present invention generally relates to a filler comprising clay and cellulose derivative.
  • the present invention further generally relates to a filler comprising clay and carboxymethyl cellulose derivate.
  • the present invention also generally relates to a method of making the filler by mixing clay with a cellulose derivative, the use of the filler as an additive in papermaking as well as paper comprising the filler.
  • the invention further generally relates to papermaking process in which the filler is introduced into an aqueous cellulosic suspension.
  • the invention relates to a filler comprising day and a cellulose derivative having a degree of substitution of net anionic groups from 0.05 up to 0.65 and containing cationic groups.
  • the invention also relates to a filler comprising clay and a cellulose derivative having a degree of substitution of carboxyalkyl groups from 0.05 up to 0.65 and containing cationic groups.
  • the invention further relates to a method of producing a filler which comprises mixing clay with a cellulose derivative having a degree of substitution of net ionic groups from 0.05 up to 0.65 and containing cationic groups.
  • the invention also relates to a method of producing a filler which comprises mixing clay with a cellulose derivative having a degree of substitution of carboxyalkyl groups from 0.05 up to 0.65 and containing cationic groups.
  • the invention further relates to a filler obtainable by these methods.
  • the invention further relates to a papermaking process which comprises providing an aqueous suspension containing cellulosic fibres, introducing into the suspension a filler comprising clay and cellulose derivative having a degree of substitution of net ionic groups from 0.05 up to 0.65 and containing cationic groups, and dewatering the suspension to form a web or sheet of paper.
  • the invention also relates to a papermaking process which comprises providing an aqueous suspension containing cellulosic fibres, introducing into the suspension a filler comprising clay and cellulose derivative having a degree of substitution of carboxyalkyl groups from 0.05 up to 0.65 and containing cationic groups and dewatering the suspension to form a web or sheet of paper.
  • the filler can be introduced into the cellulosic suspension by adding the clay and cellulose derivative separately or together as a single composition.
  • the present invention provides a new filler that is suitably for use in papermaking. It has surprisingly been found that the filler according to the invention makes it possible to reduce some of the problems associated with fillers commonly used in papermaking and incorporated in paper. More specifically, by employing the filler of this invention in papermaking processes it is possible to reduce the linting and dusting of paper and provide paper with excellent printing and mechanical properties. Additional advantages shown by the present invention include good and/or improved dewatering and fines retention, which leads to benefits in terms of paper machine runnability.
  • the present invention makes it possible to reduce the linting and dusting of the paper without adversely affecting the mechanical properties of the paper produced and without decreasing the dewatering and retention of fines and filler in the papermaking process.
  • the cellulose derivative can be mixed with and more effectively be adsorbed on or attached to the clay surface during simple processing.
  • the filler of the invention can be regarded as a modified filler, or cellulose derivative-treated filler.
  • the filler according to the invention comprises a clay and a cellulose derivative.
  • suitable clays include those having a flake or plate like shape.
  • suitable clays include talc, hydrotalcit, kaolin, calcinated clay, bentonite or mixtures thereof, preferably kaolin, calcinated clay or talc, most preferably kaolin and calcinated day.
  • suitable clays include those having a specific surface area in the range from 2 m 2 /g to 800 m 2 /g, suitably from 2 m 2 /g to 600 m 2 /g, most preferably from 5 m 2 /g to 20 m 2 /g.
  • the particle size is usually from 0.1 ⁇ m to 50 ⁇ m, preferably from 0.1 ⁇ m to 5 ⁇ m and most preferably from 0.8 ⁇ m to 3 ⁇ m.
  • Natural kaolin clay has the chemical formula Al 2 O 3 * 2SiO 2 * 2H 2 O.
  • Kaolin clays include so called dioctahedral 1:1 aluminium silicates.
  • the kaolin clay usually have a particle size of from 1 ⁇ m to 5 ⁇ m, preferably from 1 ⁇ m to 3 ⁇ m.
  • the kaolin clay usually has a surface area of from 3 m 2 /g to 10 m 2 /g, suitably from 5 m 2 /g to 8 m 2 /g.
  • Calcinated clay has the formula Al 2 O 3 * SiO 2 .
  • the calcinated clay usually has a specific surface area of from 10 m 2 /g to 20 m 2 /g, suitably from 15 m 2 /g to 17 m 2 /g.
  • the calcinated clay usually has a particle size in the range of from 0.8 ⁇ m to 4 ⁇ m, preferably from 0.8 ⁇ m to 2 ⁇ m.
  • the filler according to the invention further comprises a cellulose derivative. It is preferred that the cellulose derivative is water-soluble or at least partly water-soluble or water-dispersible, preferably water-soluble or at least partly water-soluble.
  • the cellulose derivative is ionic.
  • the cellulose derivative can be cationic or amphoteric, preferably amphoteric. Examples of suitable cellulose derivatives include cellulose ethers, e.g. amphoteric cellulose ethers.
  • the cellulose derivative has ionic or charged groups, or substituents. Examples of suitable ionic groups include anionic and cationic groups. Examples of suitable anionic groups include carboxylate, e.g. carboxyalkyl, sulphonate, e.g.
  • the alkyl group can be methyl, ethyl propyl and mixtures thereof, suitably methyl; suitably the cellulose derivative contains an anionic group comprising a carboxylate group, e.g. a carboxyalkyl group.
  • the counter-ion of the anionic group is usually an alkali metal or alkaline earth metal, suitably sodium.
  • Suitable cationic groups of cellulose derivatives according to the invention include salts of amines, suitably salts of tertiary amines, and quaternary ammonium groups, preferably quaternary ammonium groups.
  • the substituents attached to the nitrogen atom of amines and quaternary ammonium groups can be same or different and can be selected from alkyl, cycloalkyl, and alkoxyalkyl, groups, and one, two or more of the substituents together with the nitrogen atom can form a heterocyclic ring.
  • the substituents independently of each other usually comprise from 1 to 24 carbon atoms, preferably from 1 to 8 carbon atoms.
  • the nitrogen of the cationic group can be attached to the cellulose or derivative thereof by means of a chain of atoms which suitably comprises carbon and hydrogen atoms, and optionally O and/or N atoms.
  • the chain of atoms is an alkylene group with from 2 to 18 and suitably 2 to 8 carbon atoms, optionally interrupted or substituted by one or more heteroatoms, e.g. 0 or N such as alkyleneoxy group or hydroxy propylene group.
  • Preferred cellulose derivatives containing cationic groups include those obtained by reacting cellulose or derivative thereof with a quaternization agent selected from 2, 3-epoxypropyl trimethyl ammonium chloride. 3-chloro-2-hydroxypropyl trimethyl ammonium chloride and mixtures thereof.
  • the cellulose derivatives of this invention can contain non-ionic groups such as alkyl or hydroxy alkyl groups, e.g. hydroxymeyhyl, hydroxyethyl, hydroxypropyl, hydroxylbutyl and mixtures thereof, e.g. hydroxyethyl methyl, hydroxypropyl methyl, hydroxybutyl methyl, hydroxyethyl ethyl, hydroxypropoyl and the like.
  • the cellulose derivative contains both ionic groups and non-ionic groups.
  • Suitable cellulose derivatives according to the invention include carboxyalkyl celluloses, e.g. carboxymethyl cellulose carboxyethyl cellulose, carboxypropyl cellulose, sulphoethyl carboxymethyl cellulose, carboxymethyl hydroxyethyl cellulose ("CM-HEC”), carboxymethyl cellulose wherein the cellulose is substituted with one or more non-ionic substituents, preferably carboxymethyl cellulose ("CMC").
  • suitable cellulose derivatives and methods for their preparation include those disclosed In U.S. Pat. No. 4,940,785 , which is hereby incorporated herein by reference.
  • degree of substitution or "DS", as used herein, mean the number of substituted ring sites of the beta-anhydroglucose rings of the cellulose derivative. Since there are three hydroxyl groups on each anhydroglucose ring of the cellulose that are available for substitution, the maximum value of DS is 3.0.
  • the cellulose derivative has a degree of substitution of net ionic groups ("DS NI ”) from 0.05 up to 0.65, I.e. the cellulose derivative has an average degree of net ionic substitution per glucose unit from 0.05 up to 0.65.
  • the net ionic substitution can be net anionic, or net cationic.
  • the cellulose derivative has a degree of substitution of carboxyalkyl groups ("DS CA ”) from 0.05 up to 0.65.
  • DS NI , DS NA , DS NC and DS CA independently of each other are usually up to 0.60, suitably up to 0.50. preferably up to 0.45 and more preferably up to 0.40, whereas DS NI , DS NA , DS NC and DS CA independently of each other are at least 0.05, preferably at least 0.10 and more preferably at least 0.15.
  • the ranges of DS NI , DS NA , DS NC and DS CA independently of each other are usually from 0.05 to 0.60, suitably from 0.05 to 0.50, preferably from 0.10 to 0.45 and more preferably from 0.15 to 0.40.
  • Cellulose derivatives that are amphoteric usually have a degree of anionic substitution ("DS A ”) in the range of from 0.01 to 1.0 as long as DS NI and DS NA are as defined herein from 0.05, preferably from 0.10, and more preferably from 0.15 and suitably up to 0.75, preferably up to 0.5, and more preferably up to 0.4.
  • Cellulose derivatives that are cationic or amphoteric can have a degree of cationic substitution ("DS C ") in the range of from 0.01 to 1.0 as long as DS NI and DS NC are as defined herein; suitably from 0.02, preferably from 0.03, and more preferably from 0.05 and suitably up to 0.75, preferably up to 0.5. and more preferably up to 0.4.
  • DS A or DS C can of course be higher than 0.65 as long as DS NA and DS NC , respectively, are as defined herein. For example, if DS A is 0.75 and DS C is 0.15, then DS NA is 0.60.
  • Suitable cellulose derivatives having degrees of substitution as defined above include the water-soluble low DS carboxyalkyl cellulose derivatives.
  • the water-soluble cellulose derivatives suitably has a solubility of at least 85 % by weight based on total weight of dry cellulose derivative, in an aqueous solution, preferably at least 90 % by weight, more preferably at least 95 % by weight, and most preferably at least 98 % by weight
  • the cellulose derivative usually has an average molecular weight which is at least 20,000 Dalton, preferably at least 50,000 Dalton, and the average molecular weight is usually up to 1,000,000 Dalton, preferably up to 500,000 Dalton.
  • the cellulose derivative is at least in part adsorbed on or attached to the clay.
  • at least 10 % by weight, preferably at least 30 % by weight, more preferably at least 45 % by weight and most preferably at least 60 % by weight of the cellulose derivate is adsorbed on or attached to the clay.
  • the filler according to the invention usually has a clay content of at least 0.0001 % by weight; the day content can be from 0.0001 to 99.5 % by weight, suitably from 0.1 to 90 % by weight, and preferably from 60 to 80 % by weight, based on the weight of the solids of the filler, i.e. based on the dry weight of the filler.
  • the filler usually has a cellulose derivative content of at least 0.01 % by weight; the cellulose derivative content can be from 0.01 to 30 % by weight, suitably from 0.1 to 20 % by weight, and preferably from 0.3 to 10 % by weight, based on the weight of the solids of the filler.
  • the filler according to the invention can be supplied as a solid material that can be essentially free of water. It can also be supplied as an aqueous composition.
  • the content of aqueous phase, or water, can vary within wide limits, depending on the method of production and intended use.
  • the present invention also relates to a method of making a filler which comprises mixing a cellulose derivative, e.g. any one of the cellulose derivatives defined herein, with clay.
  • a cellulose derivative e.g. any one of the cellulose derivatives defined herein
  • the cellulose derivative and clay are suitably used in amounts so as to provide a filler according to the invention having contents of cellulose derivative and clay as defined herein.
  • the cellulose derivative and clay used can be present as solids or in aqueous compositions, and mixtures thereof.
  • the clay is suitably present as a finely divided material.
  • the mixing can be achieved by adding the cellulose derivative to the filler, or vice versa, in a batch, semi-batch or continuous process.
  • the cellulose derivative is added as a solid to an aqueous composition of the clay and the composition obtained is then suitably subjected to effective dispersing to dissolve the cellulose derivative.
  • the mixing is carried out by first forming a neutral to alkaline aqueous phase, suitably an aqueous solution, of cellulose derivative which is then mixed with an aqueous composition of clay.
  • the aqueous phase of cellulose derivative Prior to mixing with the clay, the aqueous phase of cellulose derivative can be subjected to pre-treatment, e.g. homogenisation, centrifugation and/or filtration, for example for separating undissolved cellulose derivative, if any, from the aqueous phase.
  • pre-treatment e.g. homogenisation, centrifugation and/or filtration, for example for separating undissolved cellulose derivative, if any, from the aqueous phase.
  • the cellulose derivative is mixed with the clay to allow at least part of the cellulose derivative to adsorb on or attach to the clay, preferably so that it is hardly removed from the material by dilution with water.
  • This can be accomplished by carrying out mixing under a period of time that is sufficient long to allow the adsorption on attachment.
  • the mixing time is at least 1 min, preferably at least 5 mln, more preferably at least 10 min and most preferably at least 20 min. Mixing periods of even several hours (1 - 10 h) are possible if it is desired to reach a high degree of attachment.
  • At least 10 % by weight, preferably at least 30 % by weight, more preferably at least 45 % by weight and most preferably at least 60 % by weight of the cellulose derivate is transferred from the aqueous phase and adsorbed on or attached to the clay or other components present in the clay.
  • the pH of the aqueous phase of cellulose derivative is usually adjusted for sorption of the specific cellulose derivative used at a value from 4 to 13, preferably from 6 to 10, more preferably from 7 to 8.5.
  • a suitable base or acid can be used for adjusting the pH.
  • suitable bases include bicarbonates and carbonates of alkali metals and alkali metal hydroxides, suitably sodium bicarbonate, sodium carbonate and sodium hydroxide.
  • suitable acids include mineral acids, organic acids and acid salts, suitably sulphuric acid and its acid salts, such as alum. In general, at a lower pH. i.e. a pH from 4.0 to neutral, adsorption of the cellulose derivative is higher but solubility is decreased, whereas at higher pH the adsorption is reduced but solubility is increased.
  • the temperature is not critical in operations in non-pressurized conditions the temperature is typically from 10 to 100 °C, preferably from 20 to 80 °C. However, higher temperatures are more favourable, suitably the temperature of the aqueous composition during mixing is from 30 up to 70 °C. more preferably from 40 up to 60 °C.
  • the filler obtained by the method of the invention can be used as such, for example in papermaking. If present as an aqueous composition, it can be used directly or it can be dried, if desired, for example to simplify shipping.
  • the present invention also relates to a process for the production of paper which comprises providing an aqueous suspension containing cellulosic fibres ("cellulosic suspension”), introducing into the cellulosic suspension a filler, e.g. any one of the fillers defined herein, and dewatering the cellulosic suspension to form a web or sheet of paper.
  • the filler is introduced into the cellulosic suspension by adding it as a single composition.
  • the clay and cellulose derivative e.g. any one of the cellulose derivatives defined herein
  • the filler is formed in situ in the cellulosic suspension.
  • the filler according to the invention can be added to the cellulosic suspension in amounts which can vary within wide limits depending on, inter alia, type of cellulosic suspension, type of paper produced, point of addition, etc.
  • the filler is usually added in an amount within the range of from 1 to 50 % by weight, suitably from 5 to 40 % by weight, and usually from 10 to 30 % by weight, based on the weight of dry fibres.
  • the paper according to the invention usually has a content of filler of this invention within the range of from 1 to 50 % by weight, suitably from 5 to 40 % by weight, and usually from 10 to 30 % by weight, based on the weight of dry fibres.
  • other components may of course be introduced into the cellulosic suspension.
  • components include conventional fillers, optical brightening agents, sizing agents, coagulant flocculants, drainage and retention aids, dry strength agents, wet strength agents, etc.
  • suitable conventional fillers include Kaolin, china clay titanium dioxide, gypsum, talc, natural and synthetic calcium carbonates, e.g. chalk, ground marble and precipitated calcium carbonate, hydrogenated aluminum oxides (aluminum trihydroxides), calcium sulphate, barium sulphate, calcium oxalate, etc.
  • the filler according to the invention can be present in an amount of at least 1 % by weight, suitably at least 5 % by weight, preferably at least 10 % by weight, more preferable at least 20 % by weight, and suitably up to 99 % by weight, based on the dry weight of all fillers.
  • suitable sizing agents include non-cellulose-reactive sizing agents, e.g. rosin-based sizing agents like rosin-based soaps, rosin-based emulsions/dispersions, and cellulose-reactive sizing agents, e.g.
  • emulsions/dispersions of acid anhydrides like alkenyl succinic anhydrides (ASA), alkenyl and alkyl kelene dimers (AKD) and multimers.
  • suitable drainage and retention aids include organic polymeric products, e.g. cationic, anionic and non-ionic polymers including cationic polyethylene imines, cationic, anionic and non-ionic polyacrylamides, cationic polyamines, cationic starch, and cationic guar; inorganic materials, e.g. aluminium compounds, anionic microparticulate materials like colloidal silica-based particles, clays of smectite type, e.g.
  • cationic polymers and anionic microparticulate materials e.g. cationic starch and anionic colloidal silica-based particles, cationic polyacrylamide and anionic colloidal silica-based particles as well as cationic polyacrylamide and bentonite or montmorllonite.
  • suitable wet strength agents include polyamines and polyaminoamides. Paper containing filler according to the invention and cationic starch shows very good strength properties.
  • paper include not only paper and the production thereof, but also other cellulosic fibre-containing sheet or web-like products, such as for example board and paperboard, and the production thereof.
  • the process can be used in the production of paper from different types of aqueous suspensions of cellulosic (cellulose-containing) fibres and the suspensions should suitably contain at least 25% by weight and preferably at least 50% by weight of such fibres, based on a dry substance.
  • the cellulosic fibres can be based on virgin fibres and/or recycled fibres, including fibres of wood or annual or perennial plants.
  • the cellulosic suspension can be wood-containing or wood-free, and it can be based on fibres from chemical pulp such as sulphate, sulphite and organosolve pulps, mechanical pulp such as thermo-mechanical pulp, chemo-thermo-mechanical pulp, refiner pulp and ground wood pulp, from both hardwood and softwood, and can also be based on recycled fibres, optionally from de-inked pulps, and mixtures thereof.
  • the cellulosic suspension suitably has a pH in the acid to neutral to alkaline range, e.g. from 4 to 10, preferably from 5 to 8.
  • Fillers according to the invention have been prepared by treating clay with cellulose derivatives.
  • Cellulose derivatives used were carboxymethyl cellulose (“CMC”) (according to prior art) and quaternary ammonium carboxymethyl cellulose (“QN-CMC”) (according to invention).
  • the mole weight of the CMC was ⁇ 200,000 Dalton.
  • the clay used in the examples was kaolin clay.
  • CMC 0.35 DS CA 0.35 (prior art)
  • Akzo Nobel DS CA 0.5 (prior art)
  • CMC was first dissolved into water to a consistency of 0.5 % by weight. Thereafter, the CMC composition was added to the clay filler slurry and mixed during 35 to 40 minutes at a temperature of 50 °C.
  • SC paper (super caelered) was prepared using kaolin clay treated with carboxymethyl cellulose (CMC).
  • CMC carboxymethyl cellulose
  • the CMC used was QN-CMC (invention) and CMC 0.5 (prior art) as described in Example 1.
  • the preparation of the CMC-modified clay has been done as described in Example 1.
  • the SC paper was then tested for ash content, total retention and linting.
  • the paper sheets were produced from a SC pulp furnish consisting of 80% mechanical pulp and 20% chemical pulp.
  • the furnish suspension contained 50% day filler, had a consistency of 0.5% by weight, pH of 7.7 and a conductivity of 0.3 mS/cm.
  • To the pulp suspension or to the clay slurry an amount of 2% CMC/tonne dry clay was added.
  • the addition sequence was the following: Addition of separate CMC when used: 0 sec. Addition of filler: 15 sec. Addition of retention polymer: 30 sec. Addition of retention silica: 45 sec. Sheet making: 105 sec.
  • the paper sheets prepared in the following examples were made according to standard using a Dynamical Sheet Former ("Formette", CTP Grenoble).
  • newsprint paper was prepared using a clay treated with CMC.
  • the CMC used was CMC 0.35 (prior art) and CMC 0,5 (prior art as defined in example 1.
  • the clay used was a kaolin clay.
  • the preparation of the CMC-modified day ha been done as described in Example 1.
  • Tensile strength index was measured on the paper and the results are displayed in table 3.
  • Paper sheets were produced from a newsprint pulp furnish consisting of 75% mechanical pulp and 25% de-inked newsprint pulp.
  • the furnish suspension contained 10% calcinated clay filler, had a consistency of 0.3%, pH of 7.2 and conductivity of 1.0 mS/cm.
  • To the pulp suspension or to the clay slurry an amount of 2% CMC/tonne dry clay was added.
  • the addition sequence was the following: Addition of separate CMC when used: 0 sec. Addition of filler: 15 sec. Sheet making: 105 sec.
  • the paper sheets prepared in the following examples were made according to standard using a Dynamical Sheet Former ("Formette”. CTP Grenoble).
  • a SC paper furnish was prepared using a clay treated with CMC.
  • Three different kinds of CMC were used to prepare the filler, CMC 0.35 (prior art), CMC 0.5 (prior art) and QNC-CMC (invention).
  • the types of CMC are as defined in example 1.
  • the preparation of the CMC-modified clay have been done as described in Example 1, but the CMC and clay filler slurry has been mixed for 15 minutes or 4 hours respectively.
  • the SC paper furnish that was used consisted of 80% mechanical pulp and 20% chemical pulp.
  • the furnish suspension contained 50% clay filler, had a consistency of 0.25%, pH of 7.8 and conductivity of 0.3 mS/cm.
  • To the clay slurry an amount of 2% CMC/tonne dry clay was added and to the pulp suspension a retention system containing cationic polymer (Eka retention polymer PL 1510) and silica particles (Eka retention silica NP 780) was added. Both the polymer and silica particles were added in an amount of 1 kg/tonne dry fibres.
  • the addition sequence was the following: Addition of CMC treated filler: 0 sec. Addition of retention polymer: 15 sec. Addition of retention silica: 30 sec. Dewatering: 45 sec.
  • dewatering values are presented in table 4, Table 4 5 Test No. Type of CMC Pre-treatment of filler for 4 hours Dewatering time (s) Pre-treatment of filler for 15 minutes Dewatering time (s) 1 CMC 0.35 (prior art) 45.0 48.8 2 QN-CMC (invention) 40.4 33.0 3 CMC 0.5 (prior art) 64.7 58.7

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  • Inorganic Chemistry (AREA)
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Claims (19)

  1. Verfahren zur Papierherstellung, das das Bereitstellen einer wässrigen, Cellulosefasern enthaltenden Suspension, das Einbringen eines Füllstoffes, umfassend Ton und ein Cellulose-Derivat mit einem Substitutionsgrad ionischer Nettogruppen von 0,05 bis 0,65 in vorgemischter Form in die Suspension umfasst, wobei das Cellulose-Derivat kationische Gruppen enthält, und das Entwässern der Suspension, um eine Papierbahn oder einen Papierbogen herzustellen, umfasst.
  2. Füllstoff umfassend Ton und ein Cellulose-Derivat mit einem Substitutionsgrad ionischer Nettogruppen von 0,05 bis 0,65, wobei das Cellulose-Derivat kationische Gruppen enthält.
  3. Verfahren zur Herstellung eines Füllstoffes, das das Mischen von Ton mit einem Cellulose-Derivat mit einem Substitutionsgrad ionischer Nettogruppen von 0,05 bis 0,65 umfasst, wobei das Cellulose-Derivat kationische Gruppen enthält.
  4. Verfahren nach Anspruch 1, Füllstoff nach Anspruch 2 oder Verfahren nach Anspruch 3, dadurch gekennzeichnet, dass der Substitutionsgrad mindestens 0,10 beträgt.
  5. Verfahren nach Anspruch 1 oder 4, Füllstoff nach Anspruch 2 oder 4 oder Verfahren nach Anspruch 3 oder 4, dadurch gekennzeichnet, dass der Substitutionsgrad von 0,15 bis 0,40 beträgt.
  6. Verfahren nach einem der Ansprüche 1, 4 und 5, Füllstoff nach einem der Ansprüche 2, 4 und 5 oder Verfahren nach einem der Ansprüche 3 bis 5, dadurch gekennzeichnet, dass das Cellulose-Derivat ein Celluloseether ist.
  7. Verfahren nach einem der Ansprüche 1 und 4 bis 6, Füllstoff nach einem der Ansprüche 2 und 4 bis 6 oder Verfahren nach einem der Ansprüche 3 bis 6, dadurch gekennzeichnet, dass das Cellulose-Derivat Carboxymethylgruppen enthält.
  8. Verfahren nach einem der Ansprüche 1 und 4 bis 7, Füllstoff nach einem der Ansprüche 2 und 4 bis 7, oder Verfahren nach einem der Ansprüche 3 bis 7, dadurch gekennzeichnet, dass das Cellulose-Derivat quaternäre Ammoniumgruppen enthält.
  9. Verfahren nach einem der Ansprüche 1 und 4 bis 7, dadurch gekennzeichnet, dass das Cellulose-Derivat anonisch ist.
  10. Verfahren nach einem der Ansprüche 1 und 4 bis 8, Füllstoff nach einem der Ansprüche 2 und 4 bis 8 oder Verfahren nach einem der Ansprüche 3 bis 7 und 9, dadurch gekennzeichnet, dass das Cellulose-Derivat amphoter ist.
  11. Verfahren nach einem der Ansprüche 1 und 4 bis 10, Füllstoff nach einem der Ansprüche 2, 4 bis 8 und 10 oder Verfahren nach einem der Ansprüche 3 bis 8 und 10, dadurch gekennzeichnet, dass das Cellulose-Derivat mindestens teilweise wasserlöslich ist.
  12. Verfahren nach einem der Ansprüche 1 und 4 bis 11, Füllstoff nach einem der Ansprüche 2, 4 bis 8, 10 und 11 oder Verfahren nach einem der Ansprüche 3 bis 8, 10 und 11, dadurch gekennzeichnet, dass der Füllstoff einen Cellulose-Derivatgehalt von 0,3 bis 10 Gew.% hat, basierend auf dem Gewicht der Feststoffe des Füllstoffes.
  13. Verfahren nach einem der Ansprüche 1 und 4 bis 12, Füllstoff nach einem der Ansprüche 2, 4 bis 8 und 10 bis 12 oder Verfahren nach einem der Ansprüche 3 bis 8 und 10 bis 12, dadurch gekennzeichnet, dass der Füllstoff einen Tongehalt von 60 bis 80 Gew.% hat, basierend auf dem Gewicht der Feststoffe des Füllstoffes.
  14. Verfahren nach einem der Ansprüche 1 und 4 bis 13, Füllstoff nach einem der Ansprüche 2, 4 bis 8 und 10 bis 13 oder Verfahren nach einem der Ansprüche 3 bis 8 und 10 bis 13, dadurch gekennzeichnet, dass der Ton Kaolin ist.
  15. Verfahren nach einem der Ansprüche 1 und 4 bis 14, Füllstoff nach einem der Ansprüche 2, 4 bis 8 und 10 bis 14 oder Verfahren nach einem der Ansprüche 3 bis 8 und 10 bis 14, dadurch gekennzeichnet, dass der Ton kalzinierter Ton ist.
  16. Verfahren nach einem der Ansprüche 1 und 4 bis 15, Füllstoff nach einem der Ansprüche 2, 4 bis 8 und 10 bis 15 oder Verfahren nach einem der Ansprüche 3 bis 8 und 10 bis 15, dadurch gekennzeichnet, dass der Ton Talk ist.
  17. Papier umfassend einen Füllstoff nach einem der Ansprüche 2, 4 bis 8 und 10 bis 16.
  18. Papier nach Anspruch 16, dadurch gekennzeichnet, dass der Gesamtfüllstoffgehalt des Papiers von 5 bis 40 Gew.% beträgt, basierend auf dem trockenen Papier.
  19. Verfahren nach einem der Ansprüche 1 und 4 bis 16, dadurch gekennzeichnet, dass der Füllstoff in einer Menge von 5 bis 30 Gew.% hinzugefügt wird, basierend auf der trockenen Faser.
EP05752686.5A 2004-06-22 2005-06-08 Füllstoff für papierherstellung Not-in-force EP1778916B1 (de)

Priority Applications (3)

Application Number Priority Date Filing Date Title
EP13188113.8A EP2835468B1 (de) 2004-06-22 2005-06-08 Füller für Papierherstellungsverfahren
SI200532077A SI1778916T1 (sl) 2004-06-22 2005-06-08 Polnilo za postopek izdelave papirja
EP05752686.5A EP1778916B1 (de) 2004-06-22 2005-06-08 Füllstoff für papierherstellung

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP04445072 2004-06-22
PCT/SE2005/000862 WO2005124021A1 (en) 2004-06-22 2005-06-08 Filler for paper making process
EP05752686.5A EP1778916B1 (de) 2004-06-22 2005-06-08 Füllstoff für papierherstellung

Related Child Applications (2)

Application Number Title Priority Date Filing Date
EP13188113.8A Division EP2835468B1 (de) 2004-06-22 2005-06-08 Füller für Papierherstellungsverfahren
EP13188113.8A Division-Into EP2835468B1 (de) 2004-06-22 2005-06-08 Füller für Papierherstellungsverfahren

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EP1778916A1 EP1778916A1 (de) 2007-05-02
EP1778916B1 true EP1778916B1 (de) 2016-03-23

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EP05752686.5A Not-in-force EP1778916B1 (de) 2004-06-22 2005-06-08 Füllstoff für papierherstellung
EP13188113.8A Active EP2835468B1 (de) 2004-06-22 2005-06-08 Füller für Papierherstellungsverfahren

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EP (2) EP1778916B1 (de)
CN (2) CN1965128A (de)
CA (1) CA2571083C (de)
ES (1) ES2574007T3 (de)
PL (1) PL1778916T3 (de)
PT (1) PT1778916E (de)
SI (1) SI1778916T1 (de)
TW (1) TWI278556B (de)
WO (1) WO2005124021A1 (de)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20090025895A1 (en) * 2006-02-20 2009-01-29 John Stuart Cowman Process for the Manufacture of Paper and Board
PL2158359T3 (pl) * 2007-06-08 2014-04-30 Fpinnovations Zawiesiny wypełniacza poddanego obróbce lateksem do stosowania w produkcji papieru
CL2008002019A1 (es) * 2007-07-16 2009-01-16 Akzo Nobel Chemicals Int Bv Composicion de carga que comprende una carga, un compuesto inorganico cationico, un compuesto organico cationico y un polisacarido anionico; metodo para preparar dicha composicion; uso como aditivo para una suspension celulosica acuosa; procedimiento para producir papel; y papel.
AR086593A1 (es) * 2011-06-08 2014-01-08 Akzo Nobel Chemicals Int Bv Proceso para la produccion de papel y carton
CN102677543B (zh) * 2012-06-11 2014-03-12 岳阳林纸股份有限公司 一种造纸高加填料的方法

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Publication number Priority date Publication date Assignee Title
US3730830A (en) * 1971-11-24 1973-05-01 Eastman Kodak Co Process for making paper
WO1982001020A1 (en) * 1980-09-19 1982-04-01 O Sunden Paper making process utilizing an amphoteric mucous structure as binder
SE451470B (sv) * 1985-12-09 1987-10-12 Boliden Ab Anvendning av ett syraadditionssalt av en alkylamin for reglering av viskositeten hos pappersbestrykningssmetar
GB8621680D0 (en) * 1986-09-09 1986-10-15 Du Pont Filler compositions
DE3733507A1 (de) 1987-10-03 1989-04-13 Degussa Verfahren zur herstellung von tertiaeren oder quaternaeren stickstoffenthaltenden celluloseethern
SE501216C2 (sv) * 1992-08-31 1994-12-12 Eka Nobel Ab Vattenhaltig, stabil suspension av kolloidala partiklar samt framställning och användning av densamma
US5492560A (en) 1993-11-10 1996-02-20 Minerals Technologies, Inc. Treatment of inorganic pigments with carboxymethylcellulose compounds
DK0811017T3 (da) * 1995-02-21 1999-09-20 Cellcat Gmbh Cellulosepartikler, fremgangsmåde til deres fremstilling og deres anvendelse
JP2947735B2 (ja) * 1995-08-09 1999-09-13 三島製紙株式会社 水分散性シート並びにこれを用いたたばこ
US5759346A (en) 1996-09-27 1998-06-02 The Procter & Gamble Company Process for making smooth uncreped tissue paper containing fine particulate fillers
DE19842962A1 (de) * 1998-09-19 2000-03-23 Wolff Walsrode Ag Wäßrige Formulierung für die Oberflächenpräparation von Papier und Karton
FI117716B (fi) 2000-04-18 2007-01-31 Ciba Sc Holding Ag Menetelmä täyteaineen esikäsittelemiseksi, modifioitu täyteaine ja sen käyttö
US20030085012A1 (en) * 2001-09-07 2003-05-08 Jones J Philip E Hyperplaty clays and their use in paper coating and filling, methods for making same, and paper products having improved brightness

Also Published As

Publication number Publication date
EP1778916A1 (de) 2007-05-02
TWI278556B (en) 2007-04-11
CN103556526A (zh) 2014-02-05
CA2571083A1 (en) 2005-12-29
TW200613611A (en) 2006-05-01
WO2005124021A1 (en) 2005-12-29
EP2835468A1 (de) 2015-02-11
PT1778916E (pt) 2016-06-03
CA2571083C (en) 2010-12-21
PL1778916T3 (pl) 2016-10-31
SI1778916T1 (sl) 2016-07-29
ES2574007T3 (es) 2016-06-14
CN1965128A (zh) 2007-05-16
EP2835468B1 (de) 2020-03-11

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