WO2005061793A1 - Charge pour procede de fabrication de papier - Google Patents

Charge pour procede de fabrication de papier Download PDF

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Publication number
WO2005061793A1
WO2005061793A1 PCT/SE2004/001970 SE2004001970W WO2005061793A1 WO 2005061793 A1 WO2005061793 A1 WO 2005061793A1 SE 2004001970 W SE2004001970 W SE 2004001970W WO 2005061793 A1 WO2005061793 A1 WO 2005061793A1
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WO
WIPO (PCT)
Prior art keywords
filler
cellulose derivative
cellulose
calcium salt
paper
Prior art date
Application number
PCT/SE2004/001970
Other languages
English (en)
Inventor
Peter Marten Van Der Horst
Erik Sanne
Kjell Rune Andersson
Cherryleen Garcia-Lindgren
Marie-Louise Wallberg
Sune WÄNNSTRÖM
Original Assignee
Eka Chemicals Ab
M-Real Corporation
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
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=34707294&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=WO2005061793(A1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by Eka Chemicals Ab, M-Real Corporation filed Critical Eka Chemicals Ab
Priority to EP04809143.3A priority Critical patent/EP1704282B2/fr
Priority to AU2004303745A priority patent/AU2004303745B2/en
Priority to ES04809143.3T priority patent/ES2675222T3/es
Priority to CN2004800385136A priority patent/CN1898439B/zh
Priority to NZ547789A priority patent/NZ547789A/en
Priority to JP2006546916A priority patent/JP4799424B2/ja
Priority to PL04809143T priority patent/PL1704282T3/pl
Priority to CA2550261A priority patent/CA2550261C/fr
Priority to BRPI0418030A priority patent/BRPI0418030B1/pt
Publication of WO2005061793A1 publication Critical patent/WO2005061793A1/fr

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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
    • D21H3/00—Paper 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
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/63—Inorganic compounds
    • D21H17/67—Water-insoluble compounds, e.g. fillers, pigments
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H23/00—Processes or apparatus for adding material to the pulp or to 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
    • 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
    • D21H17/26—Ethers thereof
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/63—Inorganic compounds
    • D21H17/67—Water-insoluble compounds, e.g. fillers, pigments
    • D21H17/675—Oxides, hydroxides or carbonates
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/71—Mixtures of material ; Pulp or paper comprising several different materials not incorporated by special processes
    • D21H17/74—Mixtures of material ; Pulp or paper comprising several different materials not incorporated by special processes of organic and inorganic material
    • 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 calcium salt 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.
  • 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.
  • Calcium carbonate-based fillers are commonly used, because of their superior light scattering properties.
  • a major drawback in the production of highly filled paper, particularly with fillers having high surface area, is the high consumption of sizing agent.
  • sizing agent is required in order to obtain corresponding sizing results.
  • cellulosic suspensions are more difficult to size when the amount of filler increases.
  • Sizing is primarily performed in order to achieve water repellence in paper or board and reduce edge wicking. It will also affect mechanical properties of paper and board, such as dimensional stability, friction coefficient, pliability and folding endurance. Additionally, sizing may improve printability specifically by controlling ink spreading and adhesion.
  • the sizing process involves the deposition of hydrophobic substances, commonly referred to as sizing agents, on the fibre surface.
  • sizing agents are non-cellulose-reactive sizing agents, e.g. rosin-based sizing agents, and cellulose- reactive sizing agents, e.g. alkyl ketene dimers (“AKD”) and acid anhydrides such as alkenyl succinic anhydride (“ASA”).
  • ASA alkenyl succinic anhydride
  • Voutilainen has shown that fillers with high surface area adsorb AKD even better than fibres (Voutilainen, P., "Competitive Adsorption of Alkyl Ketene Dimer on Pulp Fibers and CaCO3 Fillers", Proceedings from International Paper and Coating Chemistry Symposium, 1996).
  • the presence of Al- and Si-oxides on the filler surface may additionally adsorb cationic starch contained in the AKD particles.
  • the surface of the pigment can be modified with an anionic starch-soap complex.
  • Cooked starch from corn or potato is complexed with fatty acid salts and precipitated onto pigment surfaces when mixed with precipitated calcium slurry or papermaking furnish containing high levels of calcium ions.
  • U.S. Patent No. 5,972,100 suggests a system consisting of a cellulose-reactive size (such as AKD), a cationic dispersing agent (such as cationic starch or polyamides) and a filler. Aside from improved sizing, the invention allows independent control of both filler loading and sizing separately.
  • a cellulose-reactive size such as AKD
  • a cationic dispersing agent such as cationic starch or polyamides
  • WO 95/13324 refers to calcium carbonate treated with a cellulose derivative such as sodium carboxymethyl cellulose ("CMC") having a degree of substitution of 0.7. Said treated calcium carbonate is used as filler in alkaline papermaking suspensions whereby the brightness of the paper is increased.
  • CMC sodium carboxymethyl cellulose
  • U.S. Patent No. 3,730,830 discloses a process for making paper, specifically photographic paper, comprising the use of synthetic polymer fibres. Prior to the addition of the synthetic fibres to the fibre suspension, inorganic pigment or carbon is added to a slurry containing carboxymethyl cellulose and the synthetic fibres thereby achieving uniform dispersion of the polymer fibres among the cellulose fibres in the paper stock.
  • the present invention generally relates to a filler comprising calcium salt and cellulose derivative.
  • the present invention further generally relates to a filler comprising calcium salt and carboxyalkyl cellulose derivative.
  • the invention also generally relates to a method of making the filler by mixing a calcium salt-containing material 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 a papermaking process in which the filler is introduced into an aqueous cellulosic suspension.
  • the invention relates to a filler comprising calcium salt and cellulose derivative having a degree of substitution of net ionic groups up to about 0.65.
  • the invention also relates to a filler comprising calcium salt and a cellulose derivative having a degree of substitution of carboxyalkyl groups up to about 0.65.
  • the invention further relates to a method of producing a filler which comprises mixing a calcium salt-containing material with a cellulose derivative having a degree of substitution of net ionic groups up to about 0.65.
  • the invention also relates to a method of producing a filler which comprises mixing a calcium salt-containing material with a cellulose derivative having a degree of substitution of carboxyalkyl groups up to about 0.65.
  • 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 calcium salt and cellulose derivative having a degree of substitution of net ionic groups up to about 0.65, 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 calcium salt and cellulose derivative having a degree of substitution of carboxyalkyl groups up to about 0.65, and dewatering the suspension to form a web or sheet of paper.
  • the filler can be introduced into the cellulosic suspension by adding the calcium salt and cellulose derivative together as a single composition.
  • the present invention provides a new filler that is suitable 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 provide paper with excellent printing properties, e.g. high smoothness, high opacity and whiteness, improved mechanical properties, e.g. dry strength, tensile strength, Scott bond and bending stiffness, and improved sizing effect. Additional advantages shown by the present invention include good and/or improved dewatering and fines retention, which lead to benefits in terms of paper machine runnability.
  • excellent printing properties e.g. high smoothness, high opacity and whiteness
  • improved mechanical properties e.g. dry strength, tensile strength, Scott bond and bending stiffness
  • Additional advantages shown by the present invention include good and/or improved dewatering and fines retention, which lead to benefits in terms of paper machine runnability.
  • the present invention makes it possible to reduce the sizing demand and, thus, generally improving sizing efficiency.
  • the improved sizing efficiency is exhibited for different types of sizing agents, including non-cellulose and cellulose-reactive sizing agents, specifically cellulose-reactive sizing agents such as ketene dimers and acid anhydrides.
  • the invention provides improved sizing efficiency and sizing stability of filled paper, especially with high filler loading and/or when fillers with high surface areas are used.
  • the cellulose derivative can be mixed with and more effectively be adsorbed on or attached to the calcium salt-containing material during simple processing.
  • the filler of the invention can be regarded as a modified filler, or cellulose derivative-treated filler.
  • the present invention it has been found that very good results can be obtained by adding the calcium salt-containing material and cellulose derivative to a cellulosic suspension together in a pre-mixed or pre-treated form.
  • the pre-treatment of the calcium salt-containing material with the cellulose derivative provides a convenient way of separately processing only one component of the cellulosic suspension to produce a modified filler, which can be used instead of or partly replacing conventional filler.
  • a modified filler which can be used instead of or partly replacing conventional filler.
  • the cellulose derivative is adsorbed to the calcium salt-containing material when mixing the components.
  • the filler according to the invention comprises a calcium salt and a cellulose derivative.
  • Suitable calcium salts include calcium carbonate, calcium sulphate and calcium oxalate, preferably calcium carbonate, and mixtures thereof.
  • Calcium carbonate is the main constituent in limestone, marble, chalk and dolomite. Calcium carbonate can be obtained directly from the above mentioned naturally occurring species of stone and is then referred to as ground calcium carbonate ("GCC"). Calcium carbonate can also be synthetically produced, commonly referred to as precipitated calcium carbonate (“PCC").
  • the calcium carbonate is preferably obtained from calcium hydroxide and a material which produces carbonate ions in the aqueous phase, such as an alkali metal carbonate or carbon dioxide.
  • GCC and PCC can be used in the present invention, preferably PCC, including any of the various crystalline forms or morphologies that exist, e.g. calcite of rhombohedral, prismatic, tabular, cuboid and scalenohedral forms and aragonite of acicular form.
  • the PCC usually has a specific area of from about 2 to about 20 m 2 /g, suitably from about 7 to about 12 m 2 /g.
  • the calcium salt can be present as essentially pure calcium salt, including mixtures of one or more calcium salts. It can also be present in the form of a mixture together with one or more other components.
  • calcium salt-containing materials comprising fibres or fibrils of cellulose, lignocellulose or similar vegetable materials
  • at least part of the calcium salt can be deposited on the fibres or fibrils.
  • the average thickness of the fibrils can be from about 0.01 up to about 10 ⁇ m, suitably up to about 5 ⁇ m and preferably up to about 1 ⁇ m.
  • the average length of the fibrils can be from about 10 ⁇ m up to about 1500 ⁇ m.
  • suitable calcium salt- containing materials include the composite materials disclosed in U.S. Patent Nos. 5,731 ,080; 5,824,364; 6,251,222; 6,375,794; and 6,599,391, the disclosures of which are hereby incorporated herein by reference.
  • Commercially available composite materials of this type include SuperFill ® of M-Real Oy.
  • the filler according to the invention further comprises a cellulose derivative.
  • 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 anionic, cationic or amphoteric, preferably anionic or amphoteric.
  • suitable cellulose derivatives include cellulose ethers, e.g. anionic and amphoteric cellulose ethers, preferably anionic cellulose ethers.
  • the cellulose derivative preferably has ionic or charged groups, or substituents. Examples of suitable ionic groups include anionic and cationic groups.
  • anionic groups include carboxylate, e.g. carboxyalkyl, sulphonate, e.g. sulphoalkyl, phosphate and phosphonate groups in which 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 about 24 carbon atoms, preferably from 1 to about 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. O 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. hydroxymethyl, 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.
  • the filler comprises a calcium salt containing fibres or fibrils of cellulose or lignocellulose and a cellulosic derivative containing cationic groups.
  • the cationic groups can be any one of those listed in this application.
  • the filler comprises a calcium salt which is substantially free from fibres or fibrils of cellulose or lignocellulose and a cellulosic derivative which can be either anionic, cationic or amphoteric.
  • 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 ("DSNI") up to about 0.65, i.e. the cellulose derivative has an average degree of net ionic substitution per glucose unit up to about 0.65.
  • the net ionic substitution can be net anionic, net cationic or net neutral.
  • net anionic groups the average number of anionic groups minus the average number of cationic groups, if any, per glucose unit
  • DS N ⁇ the degree of substitution of net anionic groups
  • the cellulose derivative has a degree of substitution of carboxyalkyl groups ("DS C A") up to about 0.65, i.e.
  • the cellulose derivative has an average degree of carboxyalkyl substitution per glucose unit up to about 0.65.
  • the carboxyalkyl groups are suitably carboxymethyl groups and then DS C A referred to herein is the same as the degree of substitution of carboxymethyl groups ("DS C M").
  • DSNI, DSNA. DSNC and DS C A independently of each other are usually up to about 0.60, suitably up to about 0.50, preferably up to about 0.45 and more preferably up to 0.40, whereas DSNI, DSNA, DS N c and DS C A independently of each other are usually at least 0.01 , suitably at least about 0.05, preferably at least about 0.10 and more preferably at least about 0.15.
  • the ranges of DSNI, DSNA, DS N c and DS CA independently of each other are usually from about 0.01 to about 0.60, suitably from about 0.05 to about 0.50, preferably from about 0.10 to about 0.45 and more preferably from about 0.15 to about 0.40.
  • Cellulose derivatives that are anionic or amphoteric usually have a degree of anionic substitution ("DS A ") in the range of from 0.01 to about 1.0 as long as DS N ⁇ and DSNA are as defined herein; suitably from about 0.05, preferably from about 0.10, and more preferably from about 0.15 and suitably up to about 0.75, preferably up to about 0.5, and more preferably up to about 0.4.
  • DS A degree of anionic substitution
  • Cellulose derivatives that are cationic or amphoteric can have a degree of cationic substitution ("DS C ") in the range of from 0.01 to about 1.0 as long as DS N ⁇ and DS N c are as defined herein; suitably from about 0.02, preferably from about 0.03, and more preferably from about 0.05 and suitably up to about 0.75, preferably up to about 0.5, and more preferably up to about 0.4.
  • the cationic groups are suitably quaternary ammonium groups and then DS C referred to herein is the same as the degree of substitution of quaternary ammonium groups ("DS QN ").
  • DS A or DS can of course be higher than 0.65 as long as DSN A and DS N c, 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 disclosed in co- pending patent applications filed in the name of Akzo Nobel N.V. of even date.
  • 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 calcium salt or other components present in the calcium salt-containing material.
  • the filler according to the invention usually has a calcium salt content of at least 0.0001 % by weight; the calcium salt content can be from about 0.0001 to about 99.5 % by weight, suitably from about 0.1 to about 90 % by weight, and preferably from about 60 to about 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 about 0.01 to about 30 % by weight, suitably from about 0.1 to about 20 % by weight, and preferably from about 0.3 to about 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 a calcium salt-containing material, e.g. any one of the calcium salt-containing materials defined herein, which comprises calcium salt, and optionally one or more other components.
  • a cellulose derivative e.g. any one of the cellulose derivatives defined herein
  • a calcium salt-containing material e.g. any one of the calcium salt-containing materials defined herein, which comprises calcium salt, and optionally one or more other components.
  • the cellulose derivative and calcium salt-containing material are suitably used in amounts so as to provide a filler according to the invention having contents of cellulose derivative and calcium salt as defined herein.
  • the cellulose derivative and calcium salt-containing material used can be present as solids or in aqueous compositions, and mixtures thereof.
  • the calcium salt-containing material 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 calcium salt-containing material 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 calcium salt-containing material.
  • the aqueous phase of cellulose derivative Prior to mixing with the calcium salt-containing material, 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 calcium salt-containing material to allow at least part of the cellulose derivative to adsorb on or attach to the calcium salt- containing material, 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 about 1 min, preferably at least about 5 min, more preferably at least about 10 min and most preferably at least about 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 about 10 % by weight, preferably at least about 30 % by weight, more preferably at least about 45 % by weight and most preferably at least about 60 % by weight of the cellulose derivate is transferred from the aqueous phase and adsorbed on or attached to the calcium salt or other components present in the calcium salt-containing material.
  • the pH of the aqueous phase of cellulose derivative is usually adjusted for sorption of the specific cellulose derivative used at a value from about 4 to about 13, preferably from about 6 to about 10, more preferably from about 7 to about 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 about 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 about 10 to about 100 °C, preferably from about 20 to about 80 °C. However, higher temperatures are more favourable, suitably the temperature of the aqueous composition during mixing is from about 30 up to about 70 ⁇ C, more preferably from about 40 up to about 60 °C.
  • the mixing and attaching of cellulose derivative can be done simultaneously with precipitation of the calcium salt on the fibrils or fibres or after the precipitation. It is also possible to add the cellulose derivative before the precipitation.
  • the cellulose derivative is added either during beating or in a separate sorption after beating.
  • the cellulose derivative can be adsorbed on or attached to the calcium salt-containing material or fibre or fibril surfaces and/or sorbed into the fibres or fibrils.
  • Methods of adsorbing similar cellulose derivatives to similar filler materials are disclosed in U.S. Patent Nos. 5,731,080; 5,824,364; 6,251 ,222; 6,375,794; and 6,599,391 , the disclosures of which are incorporated herein by reference
  • 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 calcium salt, or calcium salt-containing material e.g. any one of the calcium salt-containing materials defined herein
  • cellulose derivative e.g. any one of the cellulose derivatives defined herein
  • other components may of course be introduced into the cellulosic suspension.
  • components include conventional fillers, optical brightening agents, sizing agents, 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 about 20 % by weight, and suitably up to about 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 ketene 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.
  • suitable combinations of drainage and retention aids include 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 bentoinite or montmorillonite.
  • suitable wet strength agents include polyamines and polyaminoamides. Paper containing filler according to the invention and cationic starch shows very good strength properties.
  • At least one sizing agent is introduced into the cellulosic suspension to produce sized paper containing filler.
  • the sizing agents are cellulose-reactive sizing agents of the types mentioned herein.
  • Suitable ketene dimers have the general formula (I) below, wherein R 1 and R 2 represent saturated or unsaturated hydrocarbon groups, usually saturated hydrocarbons, the hydrocarbon groups suitably having from 8 to 36 carbon atoms, usually being straight or branched chain alkyl groups having 12 to 20 carbon atoms, such as hexadecyl and octadecyl groups.
  • the ketene dimers may be liquid at ambient temperature, i.e.
  • acid anhydrides can be characterized by the general formula (II) below, wherein R 3 and R 4 can be identical or different and represent saturated or unsaturated hydrocarbon groups suitably containing from 8 to 30 carbon atoms, or R 3 and R 4 together with the -C-O-C- moiety can form a 5 to 6 membered ring, optionally being further substituted with hydrocarbon groups containing up to 30 carbon atoms.
  • acid anhydrides which are used commercially include alkyl and alkenyl succinic anhydrides and particularly isooctadecenyl succinic anhydride.
  • Suitable ketene dimers, acid anhydrides and organic isocyanates include the compounds disclosed in U.S. Pat. No. 4,522,686, which is hereby incorporated herein by reference.
  • 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 about 50 % by weight, suitably from about 5 to about 40 % by weight, and usually from about 10 to about 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 about 50 % by weight, suitably from about 5 to about 40 % by weight, and usually from about 10 to about 30 % by weight, based on the weight of dry fibres.
  • these components can be added to the cellulosic suspension in amounts which can vary within wide limits depending on, inter alia, type and number of components, type of cellulosic suspension, filler content, type of paper produced, point of addition, etc.
  • Sizing agents are usually introduced into the cellulosic suspension in an amount of at least about 0.01 % by weight, suitably at least about 0.1 % by weight, based on the weight of dry fibres, and the upper limit is usually about 2 % by weight, suitably about 0.5 % by weight.
  • drainage and retention aids are introduced into the cellulosic suspension in amounts that give better drainage and/or retention than what is obtained when not using these aids.
  • Drainage and retention aids, dry strength agents and wet strength agents, independently of each other, are usually introduced in an amount of at least about 0.001% by weight, often at least about 0.005% by weight, based on dry fibres, and the upper limit is usually about 5% and suitably about 1.5% by weight.
  • 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 neutral to alkaline range, e.g. from about 6 to about 10, preferably from about 6.5 to about 8.0.
  • the paper produced can be dried, coated and calendered.
  • the paper can be coated with, for example, calcium carbonate, gypsum, aluminium silicate, kaolin, aluminium hydroxide, magnesium silicate, talc, titanium dioxide, barium sulphate, zinc oxide, synthetic pigment, and mixtures thereof.
  • the grammage of the paper produced can vary within wide limits depending on the type of paper produced; usually the grammage is within the range from about 20 to about 500 g/m 2 , suitably from about 30 to about 450 g/m 2 , and preferably from 30 to about 110 g/m 2 .
  • the invention is used for the production of uncoated and coated offset paper, electrophotography paper, uncoated and coated fine paper, optionally containing mechanical pulp, as well as writing and printing papers.
  • An especially preferred product is coated offset paper in which high gloss and high opacity and bulk are combined.
  • Fillers according to the invention and for comparison were prepared by treating calcium salt-containing material with cellulose derivatives.
  • CMC carboxymethyl celluloses
  • the average molecular weights of the cellulose derivatives used were in the range of from 100,000 to 400,000.
  • Calcium salt- containing materials used were different precipitated calcium carbonates (“PCC”) having a surface area of 5.7 and 10.0 m 2 /g, respectively.
  • Another calcium salt-containing material used was SuperFill ® (P
  • the fillers were prepared by dissolving CMC into water to a consistency of 0.5 % by weight. Thereafter, the obtained CMC composition was added to PCC filler slurry and mixed during 25 to 45 minutes at a temperature of about 50 °C.
  • the fillers according to the invention (“Invention Product”) and for comparison (“Comparison Product”) were the following:
  • IP1 CMC (DS N ⁇ 0.3)-treated PCC (5.7 m 2 /g)
  • IP2 CMC (DS N ⁇ 0.3)-treated PCC (10 m 2 /g)
  • IP3 CMC (DS N ⁇ 0.32)-treated SuperFill ®
  • IP4 QN-CMC (DSNI 0.23)-treated SuperFill ®.
  • Paper according to the invention was produced using IP1 according to Example 1. Paper used for comparison was produced using CP1 according to Example 1 and using filler containing no cellulose derivative.
  • Paper sheets were produced from pulp consisting of chemical pulp and containing untreated PCC in varying amounts (% by weight, based on dry paper), as indicated in Table 1.
  • To the pulp suspension was added 2.0 kg/tonne dry fibres of filler according to Example 1 and filler containing no cellulose derivative; 3.0 kg/tonne dry fibres of AKD (aqueous dispersion Eka Keydime C223), and a retention system comprising cationic starch (Eka PL 1510) and silica particles (Eka NP 780). Both the cationic starch and silica particles were added in an amount of 0.15 kg/tonne dry fibres.
  • the addition sequence was as follows:
  • Paper sheets were produced from pulp of the same type used in Example 2 and containing 30 % by weight, based on dry paper, of untreated PCC (surface area of 10 m 2 /g) or CMC (DS N ⁇ 0.3)-treated PCC (10 tn 2 /g) (IP2 according to Example 1).
  • PCC surface area of 10 m 2 /g
  • CMC DS N ⁇ 0.3
  • PCC tn 2 /g
  • Paper sheets were manufactured from a fibre furnish containing 70% by weight of mixed hardwood pulp and 30%) by weight of softwood pulp refined at 22° and 25° SR, respectively, in a method similar to Example 3 except that no cationic starch was used and use was made of untreated SuperFill ® filler (CP2) or CMC-treated SuperFill ® filler (IP3 and IP4), which was added in an amount so as to give a paper sheet containing 30% by weight of SuperFill ® filler.
  • CP2 untreated SuperFill ® filler
  • IP3 and IP4 CMC-treated SuperFill ® filler

Abstract

L'invention concerne une charge qui contient du sel de calcium ainsi qu'un dérivé cellulosique dans lequel le degré de substitution des groupes ioniques totaux peut atteindre environ 0,65, la charge étant sensiblement exempte de fibres ou de fibrilles de cellulose ou de lignocellulose. L'invention concerne ainsi une charge qui contient du sel de calcium ainsi qu'un dérivé cellulosique dans lequel le degré de substitution des groupes ioniques totaux peut atteindre environ 0,65, le dérivé cellulosique contenant des groupes cationiques. Par ailleurs, l'invention concerne un procédé de production d'une charge qui consiste à mélanger un matériau contenant du sel de calcium à un dérivé cellulosique dans lequel le degré de substitution des groupes ioniques totaux peut atteindre environ 0,65, en l'absence substantielle de fibres ou de fibrilles de cellulose ou de lignocellulose. L'invention concerne également un procédé de production d'une charge qui consiste à mélanger un matériau contenant du sel de calcium à un dérivé cellulosique dans lequel le degré de substitution des groupes ioniques totaux peut atteindre environ 0,65, le dérivé cellulosique contenant des groupes cationiques. L'invention concerne en outre une charge pouvant être obtenue au moyen de ces procédés. De plus, l'invention concerne un procédé de fabrication de papier qui consiste à: fournir d'abord une suspension aqueuse contenant des fibres cellulosiques; introduire ensuite dans la suspension une charge contenant du sel de calcium et un dérivé cellulosique dans lequel le degré de substitution des groupes ioniques totaux peut atteindre environ 0,65, la charge étant sensiblement exempte de fibres ou de fibrilles de cellulose ou de lignocellulose; et enfin, essorer la suspension pour obtenir une bande ou une feuille de papier. L'invention concerne un procédé de fabrication de papier qui consiste à: fournir une suspension aqueuse contenant des fibres cellulosiques; introduire dans la suspension une charge contenant du sel de calcium et un dérivé cellulosique dans lequel le degré de substitution des groupes ioniques totaux peut atteindre environ 0,65, le dérivé cellulosique contenant des groupes cationiques; et enfin, essorer la suspension pour obtenir une bande ou une feuille de papier.
PCT/SE2004/001970 2003-12-22 2004-12-20 Charge pour procede de fabrication de papier WO2005061793A1 (fr)

Priority Applications (9)

Application Number Priority Date Filing Date Title
EP04809143.3A EP1704282B2 (fr) 2003-12-22 2004-12-20 Charge utilisee dans la fabrication du papier
AU2004303745A AU2004303745B2 (en) 2003-12-22 2004-12-20 Filler for papermaking process
ES04809143.3T ES2675222T3 (es) 2003-12-22 2004-12-20 Material de carga para un procedimiento de fabricación de papel
CN2004800385136A CN1898439B (zh) 2003-12-22 2004-12-20 用于造纸方法的填料
NZ547789A NZ547789A (en) 2003-12-22 2004-12-20 Filler for papermaking process comprising a calcium salt and a cellulose derivative
JP2006546916A JP4799424B2 (ja) 2003-12-22 2004-12-20 抄紙方法のためのてん料
PL04809143T PL1704282T3 (pl) 2003-12-22 2004-12-20 Wypełniacz do sposobu wytwarzania papieru
CA2550261A CA2550261C (fr) 2003-12-22 2004-12-20 Charge pour procede de fabrication de papier
BRPI0418030A BRPI0418030B1 (pt) 2003-12-22 2004-12-20 enchimento, papel, e processo para a produção de papel

Applications Claiming Priority (2)

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EP03445149.2 2003-12-22
EP03445149 2003-12-22

Related Child Applications (1)

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EP10186029.4A Previously-Filed-Application EP2325388B1 (fr) 2003-12-22 2004-12-20 Filtre pour procédé de fabrication du papier

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WO2005061793A1 true WO2005061793A1 (fr) 2005-07-07

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JP (1) JP4799424B2 (fr)
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AU (1) AU2004303745B2 (fr)
BR (1) BRPI0418030B1 (fr)
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NZ (1) NZ547789A (fr)
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US10301774B2 (en) 2009-03-30 2019-05-28 Fiberlean Technologies Limited Process for the production of nano-fibrillar cellulose suspensions
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US10577469B2 (en) 2015-10-14 2020-03-03 Fiberlean Technologies Limited 3D-formable sheet material
US10633796B2 (en) 2010-04-27 2020-04-28 Fiberlean Technologies Limited Process for the manufacture of structured materials using nano-fibrillar cellulose gels
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RU2473725C1 (ru) * 2011-08-16 2013-01-27 Общество с ограниченной ответственностью "Оптимальные химические технологии+консалтинг" Способ получения картона с белым покровным слоем
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EP3090024B1 (fr) * 2013-12-30 2018-03-28 Kemira OYJ Composition d'agrégat de charge et sa production
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RU2345189C2 (ru) 2009-01-27
CN101871181A (zh) 2010-10-27
ES2675222T3 (es) 2018-07-09
TWI356862B (en) 2012-01-21
BRPI0418030B1 (pt) 2018-09-25
EP2037041A1 (fr) 2009-03-18
PL1704282T3 (pl) 2018-09-28
SI2037041T1 (sl) 2017-01-31
NZ547789A (en) 2010-03-26
CA2550261A1 (fr) 2005-07-07
RU2006126678A (ru) 2008-01-27
AU2004303745B2 (en) 2008-11-06
EP1704282B1 (fr) 2018-04-25
EP1704282A1 (fr) 2006-09-27
PL2325388T3 (pl) 2016-09-30
EP2325388A1 (fr) 2011-05-25
PT2037041T (pt) 2017-01-02
JP2007515572A (ja) 2007-06-14
PT2325388T (pt) 2016-07-12
KR20060108725A (ko) 2006-10-18
TW200536993A (en) 2005-11-16
DK2325388T3 (en) 2016-07-04
CN1898439A (zh) 2007-01-17
TR201809764T4 (tr) 2018-07-23
PT1704282T (pt) 2018-07-04
ES2578731T3 (es) 2016-07-29
BRPI0418030A (pt) 2007-04-17
LT2037041T (lt) 2016-12-27
KR100810389B1 (ko) 2008-03-04
CA2550261C (fr) 2012-02-14
JP4799424B2 (ja) 2011-10-26
EP2037041B1 (fr) 2016-09-28
PL2037041T3 (pl) 2017-07-31
EP1704282B2 (fr) 2023-08-30
EP2325388B1 (fr) 2016-04-06
SI2325388T1 (sl) 2016-08-31
AU2004303745A1 (en) 2005-07-07
CN1898439B (zh) 2012-04-25
DK2037041T3 (en) 2017-01-16
AR050757A1 (es) 2006-11-22
ES2630379T3 (es) 2017-08-21

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