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WO2012007363A1 - Composition de fibre cellulosique - Google Patents

Composition de fibre cellulosique Download PDF

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Publication number
WO2012007363A1
WO2012007363A1 PCT/EP2011/061571 EP2011061571W WO2012007363A1 WO 2012007363 A1 WO2012007363 A1 WO 2012007363A1 EP 2011061571 W EP2011061571 W EP 2011061571W WO 2012007363 A1 WO2012007363 A1 WO 2012007363A1
Authority
WO
WIPO (PCT)
Prior art keywords
cellulosic
composition
cellulosic fibres
fibres
board
Prior art date
Application number
PCT/EP2011/061571
Other languages
English (en)
Inventor
Jeroen Jansen
Johan Nyander
Anette Monica HEIJNESSON-HULTÉN
Marcel Cornelis Paulus Van Eijk
Boen Ho O
Gerard Henk Beijers
Ronald Christopher Lai
Peter Marten Van Der Horst
Jerker Nilsson
Original Assignee
Akzo Nobel Chemicals International B.V.
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 Chemicals International B.V. filed Critical Akzo Nobel Chemicals International B.V.
Priority to BR112013000141A priority Critical patent/BR112013000141A2/pt
Priority to AU2011278462A priority patent/AU2011278462A1/en
Priority to EP11730021.0A priority patent/EP2593603A1/fr
Priority to KR1020137001576A priority patent/KR20130132381A/ko
Priority to JP2013519038A priority patent/JP2013531749A/ja
Priority to CA2803650A priority patent/CA2803650A1/fr
Priority to CN201180033282XA priority patent/CN102971462A/zh
Publication of WO2012007363A1 publication Critical patent/WO2012007363A1/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
    • D21H11/00—Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only
    • D21H11/16—Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only modified by a particular after-treatment
    • D21H11/20—Chemically or biochemically modified fibres
    • 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
    • D21H5/00—Special paper or cardboard not otherwise provided for
    • D21H5/12—Special paper or cardboard not otherwise provided for characterised by the use of special fibrous materials
    • D21H5/1263—Special paper or cardboard not otherwise provided for characterised by the use of special fibrous materials of fibres which have been swollen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
    • B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
    • B29C48/40—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
    • B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
    • B29C48/40—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders
    • B29C48/435—Sub-screws
    • B29C48/44—Planetary screws
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
    • B29C48/50—Details of extruders
    • B29C48/505—Screws
    • B29C48/535—Screws with thread pitch varying along the longitudinal axis
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
    • B29C48/50—Details of extruders
    • B29C48/505—Screws
    • B29C48/54—Screws with additional forward-feeding elements
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
    • B29C48/50—Details of extruders
    • B29C48/505—Screws
    • B29C48/56—Screws having grooves or cavities other than the thread or the channel
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
    • B29C48/50—Details of extruders
    • B29C48/505—Screws
    • B29C48/57—Screws provided with kneading disc-like elements, e.g. with oval-shaped elements
    • 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
    • D21H5/00—Special paper or cardboard not otherwise provided for
    • D21H5/008—Special paper or cardboard not otherwise provided for characterised by the use of special fibrous materials as well as special compounds
    • 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
    • D21H5/00—Special paper or cardboard not otherwise provided for
    • D21H5/12—Special paper or cardboard not otherwise provided for characterised by the use of special fibrous materials
    • D21H5/1236—Special paper or cardboard not otherwise provided for characterised by the use of special fibrous materials of fibres which have been treated to render them suitable for sheet formation, e.g. fibrillatable fibres
    • 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
    • D21H5/00—Special paper or cardboard not otherwise provided for
    • D21H5/12—Special paper or cardboard not otherwise provided for characterised by the use of special fibrous materials
    • D21H5/1245—Special paper or cardboard not otherwise provided for characterised by the use of special fibrous materials of long or continuous filaments
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
    • B27N—MANUFACTURE BY DRY PROCESSES OF ARTICLES, WITH OR WITHOUT ORGANIC BINDING AGENTS, MADE FROM PARTICLES OR FIBRES CONSISTING OF WOOD OR OTHER LIGNOCELLULOSIC OR LIKE ORGANIC MATERIAL
    • B27N3/00—Manufacture of substantially flat articles, e.g. boards, from particles or fibres
    • 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
    • D21H11/00—Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only
    • D21H11/16—Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only modified by a particular after-treatment
    • D21H11/18—Highly hydrated, swollen or fibrillatable fibres
    • 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
    • D21H15/00—Pulp or paper, comprising fibres or web-forming material characterised by features other than their chemical constitution
    • D21H15/02—Pulp or paper, comprising fibres or web-forming material characterised by features other than their chemical constitution characterised by configuration
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H27/00—Special paper not otherwise provided for, e.g. made by multi-step processes
    • D21H27/10—Packing paper

Definitions

  • the present invention relates to a cellulosic fibre composition, a method of making a cellulosic fibre composition, the use of a cellulosic fibre composition in the production of paper and board, a process for making a cellulosic pulp mixture in which a cellulosic fibre composition is used, the use of a pulp mixture for making paper and board, a process for producing paper and board in which a cellulosic fibre composition or pulp mixture is used, paper and board comprising a cellulosic fibre composition or pulp mixture and various uses of paper and board comprising a cellulosic fibre composition or pulp mixture.
  • Strength is important to cellulosic products like paper and board, and increasing the strength of such products provides several benefits. For instance, increasing the strength of paper makes it possible to increase filler loadings and reduce virgin fibre usage, thereby reducing raw material costs in paper making processes. Similarly, increasing the strength of board makes it possible to reduce the grammage while maintaining the strength properties of cellulosic products made from the board, which also leads to savings in virgin fibre usage and reduced transportation costs, thus environmental and economic benefits.
  • microfibrillar cellulose which is obtained from cellulosic fibres that have been delaminated to small fragments with a large proportion of the microfibrils of the fibre walls uncovered.
  • WO 00/47628, WO 2004/055268, WO 2007/001229 and WO 2008/076056 disclose microfibrillar cellulose, methods for preparing same and use of same as an additive in the production of a paper product.
  • WO 00/47628 discloses microfibrillar cellulose comprising anionic charge wh ich may be used in a papermaking machine to increase the rate of drainage and/or dewatering during paper manufacture and to improve strength of a sheet of paper.
  • modified cellulosic fibres like microfibrillar cellulose may absorb and retain a substantial amount of water. These characteristics may lead to higher water content of the cellulosic web entering the press and drying sections of the machine, thereby requiring more energy to remove the remaining water and dry the cellulosic web and/or reducing the paper machine speed and productivity.
  • Modified cellulosic fibres like microfibrillar cellulose may also contain a substantial amount of fines, i.e. very small cellulosic fibres and fibre fragments.
  • Cellulosic fines are generally difficult to retain in paper and board making processes, which may lead to accumulation of the fines in the white water that is re-circulated in the processes.
  • These problems may be alleviated or solved by reducing the drainage rate, increasing the dosage of retention aids and/or co-using or increasing the dosage of cationic coagulants, e.g. low molecular weight, highly cationic, organic polymers and aluminium compounds.
  • Modified cellulosic fibres like microfibrillar cellulose may also be difficult to produce, and the methods for producing them may be complicated and provide modified cellulosic fibres in low yields or at low dry solids contents. Accordingly, there is still a need of cellulosic fibre compositions which impart high strength to paper and board and provide improvements in the manufacture of paper and board, in particular in terms drainage and retention performance, drying of paper and board, and productivity. There is also a need of improved methods for producing cellulosic fibre compositions which impart high strength to paper and board.
  • a cellulosic fibre composition and a cellulosic pulp mixture preferably high concentration products, which do not absorb or retain a substantial amount of water.
  • the present invention relates to a composition
  • a composition comprising cellulosic fibres having an average degree of substitution of anionic groups of from 0.001 to 0.25, a length weighted mean fibre length up to 1 , 100 ⁇ and a length weighted mean fibre width over 10 ⁇ .
  • the present invention relates to a composition comprising cellulosic fibres having an average degree of substitution of anionic groups of from 0.001 to 0.25, a length weighted mean fibre length up to 1 , 100 ⁇ , and wherein at least 50 % by weight of the cellulosic material is insoluble in water.
  • the present invention relates to a composition comprising cellulosic fibres having an average degree of substitution of anionic groups of from 0.001 to 0.25 and a length weighted mean fibre length / width ratio up to 30.
  • the present invention relates to a composition comprising cellulosic fibres having an average degree of substitution of anionic groups of from 0.001 to 0.25 and a length weighted mean fibre width over 35 ⁇ .
  • the present invention relates to a composition
  • a composition comprising cellulosic fibres having a specific surface area of at least 1 .5 m 2 /g, a length weighted mean fibre length / width ratio up to 30 and a dry solids content of at least 5 % by weight, based on the weight of the composition.
  • the present invention relates to a composition
  • a composition comprising cellulosic fibres having a specific surface area of at least 1 .5 m 2 /g, a length weighted mean fibre length / width ratio up to 30, and up to 30 % by weight, based on the total weight of the cellulosic fibres, of cellulosic fibres with a length weighted mean fibre length up to 100 ⁇ .
  • the present invention relates to a method of producing a composition comprising cellulosic fibres which comprises subjecting cellulosic fibres to chemical treatment and mechanical treatment, wherein the chemical treatment comprises treating cellulosic fibres with (i) at least one agent containing a carboxyl group, optionally substituted, (ii) at least one oxidant and at least one transition metal, or (iii) at least one nitroxyl radical, and the mechanical treatment comprises subjecting cellulosic fibres to extrusion with a twin-screw extruder or a planetary extruder.
  • the present invention relates to a method of producing a composition comprising cellulosic fibres which comprises subjecting cellulosic fibres having an average degree of substitution of anionic groups of from 0.001 to 0.25 to extrusion.
  • the invention relates to the composition comprising cellulosic fibres obtainable by the methods of the invention.
  • the present invention relates to the use of the composition comprising cellulosic fibres in the production of paper and board, usually as an additive and, in particular, as a strength additive.
  • the present invention relates to a process for producing a cellulosic pulp mixture which comprises mixing the composition comprising cellulosic fibres with cellulosic pulp.
  • the present invention relates to the cellulosic pulp mixture obtainable by the process, and to the use of the cellulosic pulp mixture in the production of paper and board.
  • the present invention relates to a process for producing paper and board which comprises forming an aqueous suspension comprising the cellulosic pulp mixture and dewatering the obtained suspension.
  • the present invention relates to a process for producing paper and board which comprises adding the composition comprising cellulosic fibres to an aqueous cellulosic pulp suspension and dewatering the obtained suspension.
  • the present invention relates to a process for producing paper and board which comprises mixing a composition comprising cellulosic fibres subjected to extrusion with cellulosic pulp.
  • the present invention relates to paper and board containing the composition comprising cellulosic fibres or cellulosic pulp mixture, and to paper and board obtainable by the processes of the invention.
  • the present invention relates to various board grades, and to the production thereof.
  • the present invention relates to various uses of the paper and board, e.g. for packaging of beverages and liquid food.
  • Fig. 1 is a side view of the configuration of an extruder screw.
  • composition comprising cellulosic fibres of the invention, herein also referred to as “the cellulosic fibre composition” or “the composition”, contains cellulosic fibres which can be derived from a wide variety of sources including wood fibres, non-wood fibres and mixtures thereof.
  • Wood fibres may be derived from hardwood and softwood, e.g. from chemical pulps, mechanical pulps, thermo-mechanical pulps, chemical thermo-mechanical pulps, recycled fibres and newsprint.
  • suitable wood fibres include birch, beech, aspen, e.g. European aspen, alder, eucalyptus, maple, acacia, mixed tropical hardwood, pine, e.g. loblolly pine, fir, hemlock, larch, spruce, e.g. Black spruce or Norway spruce, and mixtures thereof.
  • Non-wood fibres may be derived from seed fibres, e.g. cotton linters, seed hull fibres, e.g. soybean hulls, pea hulls and corn hulls, bast fibres, e.g. flax, hemp, jute, ramie and kenaf, leaf fibres, e.g. manila hemp and sisal hemp, stalk and straw fibres, e.g. bagasse, corn and wheat, grass fibres, e.g. bamboo and reed canary grass, cellulosic fibres from algae, e.g. velonia, bacteria and fungi, and parenchymal cells, e.g. vegetables such as sugar beets, and fruits, e.g. citrus fruits such as lemons, limes, oranges and grapefruits.
  • seed fibres e.g. cotton linters
  • seed hull fibres e.g. soybean hulls, pea hulls and corn hulls
  • the cellulosic fibres of the composition may or may not contain ionic groups.
  • the cellulosic fibres of the composition are free or essentially free from anionic groups, e.g. the cellulosic fibres of the composition have an average degree of substitution of anionic groups of below 0.001 .
  • the cellulosic fibres of the composition have an average degree of substitution of anionic groups of from 0.001 , usually from about 0.01 , or from about 0.02, up to 0.25, or up to about 0.20, usually up to about 0.15, or up to 0.10, or up to about 0.05.
  • the cellulosic fibres are preferably dispersible in water, but not water-soluble.
  • DS average degree of substitution
  • anionic groups or su bstituent groups, per anhydroglucose unit of cellulose.
  • the degree of substitution of anionic groups can be determined by the methods of ASTM D1439-03 and conductometric titration as described by S. Katz, R.P. Beatson and A.M. Scallan in Svensk Papperstidning No. 6/1984, pp. 48- 53.
  • Suitable anionic groups include carboxyl groups and substituted carboxyl groups, e.g. carboxyalkyl groups such as carboxymethyl groups.
  • the counter-ion of the anionic group is usually an alkali metal or alkaline earth metal, e.g. sodium or potassium, suitably sodium.
  • the carboxyl group can be illustrated by the formula -COO " Na + , and the carboxymethyl group by the formula -CH 2 COO " Na + .
  • the cellulosic fibre composition of the invention may contain both water-soluble cellulosic material and water-insoluble cellulosic material.
  • at least 50, or at least 70, preferably at least 80 or at least 85 % by weight of the cellulosic material present in the composition is insoluble in water, measured on an aqueous cellulosic composition containing 1 % by weight of cellulosic material at 20 °C.
  • the water-insoluble material is usually swellable and dispersible in water.
  • the cellulosic fibres of the composition of the invention may have a specific surface area of at least 1 .5, or at least about 2, usually at least about 3 m 2 /g, and the specific surface area may be up to about 150, usually up to about 50, up to about 15, or up to about 10 m 2 /g.
  • the specific surface area is determined by adsorption of N 2 at 177 K according to the BET method using a Micromeritics TriStar 3000 instrument, which operates according to ISO 9277:1995.
  • the cellulosic fibres of the composition of the invention may have a length weighted mean fibre length of from about 150, or from about 200, usually from about 300 ⁇ , and the length weighted mean fibre length may be up to about 2,000, usually up to about 1 ,500, or up to about 1 ,100, usually up to about 1 ,000, or up to about 800 ⁇ ; and they may have a length weighted mean fibre width of from about 10, usually from about 15 ⁇ , and the length weighted mean fibre width may be up to about 60, usually up to about 50, or up to about 45, usually up to about 30 ⁇ .
  • the cellulosic fibres of the composition of the invention have length weighted mean fibre width over 35 ⁇ , or from about 40, up to about 60, or up to about 50.
  • the cellulosic fibres of the composition of the invention may have a length weighted mean fibre length / width ratio up to about 40, or up to about 35, usually up to about 30, or up to about 25, and the length weighted mean fibre length / width ratio may be at least about 5, or at least about 10, usually at least about 12.
  • the length weighted mean fibre length and length weighted mean fibre width are measured by means a Fiber Tester of Lorenzen & Wettre, Sweden, which operates according to ISO 16065-2:2007, and the length weighted mean length / width ratio is calculated from such data.
  • the cellulosic fibre composition of the invention may contain fines in an amount of from about 1 , or from about 2, usually from about 5 % by weight, based on the total weight of the cellulosic fibres, and the composition may contain fines in an amount of up to about 40, or up to about 35, usually up to about 30 % by weight, based on the total weight of the cellulosic fibres.
  • fines means cellulosic fibres having a length weighted mean fibre length up to 100 ⁇ .
  • the cellulosic fibre composition of the invention may have a dry solids content of at least about 0.1 , or at least about 0.5, usually at least about 5, or at least about 10, or at least about 15 % by weight, and the dry solids content may be up to about 90, or up to about 70, usually up to about 50, or up to about 45 % by weight, based on the total weight of the composition.
  • the dry solids of the composition usually consist or essentially consist of cellulosic fibres
  • the composition may have a cellulosic fibre content which is the same as the dry solids content stated above.
  • the remainder of the cellulosic fibre composition may be water.
  • the method of producing the cellulosic fibre composition of the invention comprises subjecting cellulosic fibres to chemical treatment and mechanical treatment.
  • the chem ical treatment may be carried out prior to or simultaneously with the mechanical treatment, usually prior to the mechanical treatment.
  • Cellulosic fibres for use in the method can be derived from a wide variety of sources including wood fibres, non-wood-fibres and mixtures thereof, as further defined above in respect of the cellulosic fibre composition of the invention.
  • the method of producing the cellulosic fibre composition of the invention comprises subjecting cellulosic fibres having anionic groups to mechanical treatment, wherein the cellulosic fibres may have anionic groups and an average degree of substitution of anionic groups as defined above in respect of the cellulosic fibre composition of the invention.
  • the cellulosic fibres for use in the process can be derived from a wide variety of sources including wood fibres, non-wood-fibres and mixtures thereof, as further defined above in respect of the cellulosic fibre composition of the invention, and cellulosic fibres suitable for use in the process can be provided by any method for introducing anionic groups in cellulose that is known in the art.
  • the chemical treatment of the invention comprises treating cellulosic fibres with at least one agent containing a carboxyl group, optionally substituted, which chemical treatment is suitably carried out with an amount of the agent containing a carboxyl group, optionally substituted, and any compounds that are co-used as defined below so as to achieve the desired degree of substitution, which can be determined by the method defined above in respect of the cellulosic fibre composition of the invention.
  • the chemical treatment of the invention comprises treating the cellulosic fibres with at least one oxidant and at least one transition metal.
  • the chemical treatment of the invention comprises treating the cellulosic fibres with at least one nitroxyl radical.
  • suitable agent containing a carboxyl group examples include carboxylating agents and carboxyalkylating agents.
  • suitable carboxyalkylating agents include chloroacetic acid, e.g. monochloroacetic acid, and salts thereof, suitably the sodium salt.
  • the treatment may be conducted under alkaline conditions by contacting the cellulosic fibres with strong alkali, e.g. sodium hydroxide, and the agent containing a carboxyl group. These reagents may be applied to the cellulosic fibres separately or together.
  • the reaction is conveniently performed in an aqueous system which comprises a water-miscible organic solvent, e.g.
  • Suitable oxidants include radical generating oxidants, e.g. inorganic or organic peroxy compounds, ozone, ozonides, e.g. dimethyloxiran, halogen (e.g. chlorine or bromine) containing oxidants, and oxygen, preferably inorganic peroxy compounds such as those selected from hydrogen peroxide and hydrogen peroxide generating compou n d s l i ke a l ka l i m eta l sa lts of perca rbon ate , perborate , peroxysu lfate , peroxyphosphate or peroxysilicate, or corresponding weak acids, preferably hydrogen peroxide.
  • radical generating oxidants e.g. inorganic or organic peroxy compounds, ozone, ozonides, e.g. dimethyloxiran, halogen (e.g. chlorine or bromine) containing oxidants, and oxygen, preferably inorganic peroxy compounds such as those
  • Suitable organic peroxy compounds include peroxy carboxylic acids, e.g. peracetic acid and perbenzoic acid, and hydroperoxides, e.g. isopropyl cumyl hydroperoxide, 1 ,1 ,3,3-tetramethyl butyl hydroperoxide, cumyl hydroperoxide, t-butyl hydroperoxide and t-amyl hydroperoxide.
  • suitable halogen containing oxidants include alkali metal chlorite, alkali metal hypochlorite, chlorine dioxide and chloro sodium salt of cyanuric acid. It is also possible to use ultrasonic sound or photo or electro Fenton reactions, i.e. in situ generation of hydroxyl radicals by radiation or electric currents.
  • the oxidant may be used in the treatment an amount of from about 0.05 to about 5, usually from about 0.1 to about 3 % by weight, based on the weight of the cellulosic fibres.
  • transition metals include iron, copper, manganese, tungsten, molybdenum, tin, chromium and combinations thereof, preferably iron.
  • the transition metal is suitably used in ionic form, e.g. Fe 2+ , and it may be used in the form of a salt, e.g. FeS0 4 , or complex with common complexing agents, e.g. EDTA, DTPA, phosphates or complexing agents based on phosphoric acid, oxalic acid, ascorbic acid, nitrite acetate, garlic acid, fulvic acid or polyoxomethalates.
  • the amount of transition metal used depends on the amount of oxidant used and in most cases it is from about 0.000001 to about 20, or from about 0.00001 to about 10, usually from about 0.0001 to about 1 % by weight, based on the weight of the oxidant.
  • the transition metal suitable in ionic form, can be added to the cellulosic fibres before, after or simultaneously with adding the oxidant, for example in the form of an aqueous solution.
  • nitroxyl radicals examples include the 2,2,6,6-tetramethyl piperidine-1 -oxyl (TEMPO) radical and derivatives thereof, e.g. 4-hydroxy-TEMPO.
  • TEMPO 2,2,6,6-tetramethyl piperidine-1 -oxyl
  • one or more compounds are preferably co-used.
  • sodium hypochlorite NaCIO
  • NaCIO sodium hypochlorite
  • the nitroxyl radical may be used in the treatment in an amount of from about 0.05 to about 5, usually from about 0.1 to about 3 % by weight, based on the weight of the cellulosic fibres.
  • Each of the compounds that are preferably co-used with the nitroxyl radical in the treatment can be used in an amount of from about 1 to about 20 % by weight, based on the weight of the cellulosic fibres, suitably sodium hypochlorite is used in an amount of from about 3 to about 20 % by weight and sodium bromide is used in an amount of from about 2 to about 10 % by weight.
  • the cellulosic fibres may be dispersed in water, alcohol or any other suitable liquid, usually in an aqueous suspension.
  • the dry solids content of the aqueous suspension of cellulosic fibres in the chemical treatment may be from about 1 , or from about 5, usually from about 10, up to about 60, or up to about 50, usually up to about 40 % by weight, based on the total weight of the suspension.
  • Further additives that may be used in the chemical treatment include mineral acids, e.g. hydrochloric acid and sulphuric acid, or sodium hydroxide, and the chemical treatment may be carried out at a pH from about 1 to about 10.
  • the chemical treatment may be carried out at acidic or neutral pH from about 1 to about 8, or from about 2 to about 6, usually from about 3 to about 5.
  • the chemical treatment may be carried out at alkaline pH from about 8 to about 10.
  • the chemical treatment may be carried out for about 10 to about 120, or from about 20 to about 80, usually from about 40 to about 60 minutes, and the temperature may be from about 5, usually from about 20, or from about 60, up to about 100, usually to about 80, or up to about 30 °C.
  • the temperature may be from about 20 to about 100, usually from about 60 to about 80 °C.
  • the temperature may be from about 5, usually around about 20, up to about 30 °C.
  • the cellulosic fibres are subjected to a chemical treatment at a dry solids content of from about 1 to about 50 % by weight with from about 0.1 to about 3 % by weight of H 2 0 2 as the oxidant, based on the weight of dry cellulosic fibres, and an aqueous solution of about 0.00001 to about 10 % by weight of FeS0 4 as the transition metal, based on the weight of the oxidant, during from about 20 to about 80 minutes at from about 70 to about 95 °C at a pH from about 3 to about 5.
  • the cellulosic fibres are subjected to a chemical treatment at a dry solids content of from about 1 to about 50 % by weight with from about 0.1 to about 3 % by weight of TEMPO, from about 3 to about 20 % by weight of NaCIO, and from about 2 to 10 % by weight of sodium bromide, during from about 20 to about 80 minutes at from about 5 to about 30 °C at a pH from about 9 to about 10, where the amounts of chemicals are based on the weight of dry cellulosic fibres.
  • the cellulosic fibre composition obtained by the chemical treatment may be washed one or more times with water and/or solvents to remove any chemicals, diluted with water and/or dried or concentrated to a dry solids content suitable for the subsequent mechanical treatment.
  • the mechanical treatment of the invention comprises subjecting cellulosic fibres to extrusion by using one or more extruders, and the extrusion may be continuous or batch- wise.
  • the cellulosic fibres may have a dry solids content of from about 5, or from about 8, usually from about 10, or from about 15, up to about 70, usually up to about 55, or up to about 50, often up to about 45, or up to about 40 % by weight.
  • the remainder of the cellulosic fibre composition may be water.
  • suitable extruders for use in the process include twin-screw extruders, or double shaft extruders.
  • the screws may be co-rotating or counter rotating, preferably co- rotating.
  • the screws may have one or more screw elements, including conveying, mixing and kneading elements, along the length of the extruder.
  • suitable extruders include planetary roller extruders, also referred to as planetary mixers.
  • the planetary roller extruder usually has a central main spindle and from 4 to 20 rolling planetary spindles.
  • the length of the screw of twin-screw extruders, or the main spindle / barrel of planetary roller extruders may be at least about 3, or at least about 5, usually at least about 10, or at least about 15 times the diameter of the screw or main spindle / barrel, and the length may be up to about 70, or up to about 60, usually up to about 50 times the diameter of the screw or main spindle / barrel.
  • the diameter of the screw or main spindle is usually at least about 15 mm and may be up to about 150 mm or even higher.
  • the extruder comprises one or more kneading elements.
  • the extruder may have a flexible screw configuration with intermeshing screw elements that can be assembled into several conveying, mixing and kneading sections.
  • the cellulosic fibres may be fed into the extruder, passed through alternating sets of transport, mixing and kneading sections until the kneaded cellulosic fibres are ejected.
  • the cellulosic fibres may be passed through the extruder one or more times. In the process, the cellulosic fibres are preferably subjected to shearing and kneading forces.
  • the extrusion may be carried out at a temperature of from about 20 to about 100, usually from about 40 to about 80 °C.
  • Twin-screw extruders and planetary roller extruders are commercially available from several manufacturers such as BQhler, Berstorff, e.g. Berstorff ZE 25 and Berstorff ZE 40, Bottenfeld Extrusionstechnik, and Entex, e.g. Extex PLWE100.
  • the cellulosic fibres and the composition thereof obtained by these chemical and/or mechanical treatment steps of the invention may have a specific surface area, length weighted mean fibre length, length weighted mean fibre width, length weighted mean fibre length / width ratio, fines content, dry solids content, degree of substitution of anionic groups and cellulosic fibre content as defined above in respect of the cellulosic fibre composition of the invention.
  • cellulosic fibre composition it is also possible to further dry or concentrate the cellulosic fibre composition by suitable drying techniques, e.g. freeze drying, etc., to higher dry solids contents, e.g. up to about 90 % by weight.
  • suitable drying techniques e.g. freeze drying, etc.
  • transportation of the obtained cellulosic fibre composition may be simplified.
  • water to or dilute the cellulosic fibre composition to a dry solids content lower than about 10 % by weight, e.g. from about 0.1 to about 10, usually from about 0.5 to about 5 % by weight.
  • the use of the obtained cellulosic fibre composition may be simplified, e.g. for mixing with an aqueous cellulosic pulp suspension for use in paper and board making.
  • the invention also relates to the use of the cellulosic fibre composition of the invention or obtained by the method of the invention in the production of paper and board.
  • the invention also relates to the use of a composition comprising cellulosic fibres subjected to extrusion , as described above, as an additive in the production of paper and board , wherein the composition subjected to extrusion may have or may not have been subjected to chemical treatment, as described above.
  • Paper and board can be produced from an aqueous suspension comprising the cellulosic fibre composition.
  • the cellulosic fibre composition is used as an additive to an aqueous cellulosic pulp suspension to impart strength to paper and board produced from the resulting aqueous cellulosic pulp suspension.
  • the cellulosic fibre composition may be mixed with or added to the cellulosic pulp suspension in an amount of from about 0.1 to about 25, suitably from about 0.5 to about 15, or from about 1 to 10, usually from about 2 to about 8 % by weight, calculated as dry cellulosic fibres of the composition on dry cellulosic pulp.
  • the invention further relates to a process for producing a cellulosic pulp mixture which comprises mixing the cellulosic fibre composition of the invention or obtained by the method of the invention with cellulosic pulp.
  • the cellulosic pulp can be derived from a wide variety of sources including wood fibres, non-wood fibres and mixtures thereof. Examples of suitable wood and non-wood fibres include those defined above in respect of the cellulosic fibre composition of the invention.
  • the cellulosic pulp is derived from wood fibres such as hardwood, softwood and mixtures thereof, and preferably comprising softwood fibres.
  • the cellulosic pulp may be derived from chemical pulp, e.g. sulfate and sulfite pulp, organosolv pulp, recycled fibers, and/or mechanical pulp including e.g.
  • RMP refiner mechanical pulp
  • PRMP pressurized refiner mechanical pulp
  • P-RC APMP pretreatment refiner chemical alkaline peroxide mechanical pulp
  • thermo-mechanical pulp TMP
  • TMCP thermo- mechanical chemical pulp
  • HT-TMP high-temperature TMP
  • APP alkaline peroxide mechanical pulp
  • API P alkaline peroxide mechanical pulp
  • ATMP alkaline peroxide thermomechanical pulp
  • thermopulp groundwood pulp (GW), stone groundwood pulp (SGW), pressure groundwood pulp (PGW), super pressure groundwood pulp (PGW- S), thermo groundwood pulp (TGW), thermo stone groundwood pulp (TSGW), chemi- mechanical pulp (CMP), chemirefinermechanical pulp (CRMP), chemithermo-mechanical pulp (CTMP), high-temperature CTMP (HT-CTMP), sulfite-modified thermo-mechanical pulp (SMTMP), reject CTMP (CTMP R ), groundwood CTMP (G-CTMP), semichemical pulp (SC), neutral
  • the cellulosic fibre composition may be mixed with or added to the cellulosic pulp in an amount of from about 0.1 to about 25, suitably from about 0.5 to about 15, or from about 1 to 10, usually from about 2 to about 8 % by weight, calculated as dry cellulosic fibres of the composition on dry cellulosic pulp.
  • the mixing is made in a substantially dry state.
  • the mixing of the cellulosic fibre composition with the cellulosic pulp may be made to form a cellulosic pulp mixture, which may have a dry solids content of at least about 10, usually at least about 15, usually from about 20, up to about 90, or up to about 50 % by weight, based on the total weight of the cellulosic pulp mixture.
  • the remainder of the cellulosic pulp mixture may be water.
  • the cellulosic pulp mixture may be added to or mixed with water to form an aqueous suspension comprising the cellulosic pulp mixture and then dewatering the obtained suspension.
  • the aqueous suspension may have a dry solids content of up to about 10 % by weight, e.g. from about 0.1 , or from about 0.2, usually from about 0.3, up to about 10, or up to about 8, up to about 6, usually up to about 5 % by weight, based on the total weight of the cellulosic pulp mixture.
  • the mixing is made in a substantially wet state.
  • the mixing of the cellulosic fibre composition with the cellulosic pulp may be made to form a cellulosic pulp mixtu re in the form of an aq ueous suspension and then dewatering the obtained suspension.
  • the process may comprise adding the cellulosic fibre composition to an aqueous cellulosic pulp suspension and dewatering the obtained suspension .
  • the aqueous suspension may have a dry solids content of up to about 10 % by weight, e.g. from about 0.1 , or from about 0.2, usually from about 0.3, up to about 10, or up to about 8, up to about 6, usually up to about 5 % by weight, based on the total weight of the cellulosic pulp mixture.
  • the cellulosic pulp mixture is used in the production of paper and board wherein the cellulosic pulp mixture may constitute at least part of the cellulosic pulp used in the process, usually the total amount of cellulosic pulp used in the process.
  • an aqueous suspension comprising the cellulosic pulp mixture is formed and then dewatered.
  • Various additives may be introduced in the aqueous suspension comprising the cellulosic pulp mixture prior to dewatering, including the additives and their addition levels as defined below in respect of the process for producing paper and board of the invention, in particular one or more drainage and retention aids.
  • the invention further relates to a process for producing paper and board which comprises providing an aqueous suspension comprising the cellulosic fibre composition according to the invention or produced according to the process of the invention and dewatering the obtained suspension.
  • the invention further relates to a process for producing paper and board which comprises adding the cellulosic fibre composition according to the invention or produced according to the process of the invention to an aqueous suspension comprising cellulosic pulp and dewatering the obtained suspension.
  • the invention further relates to a process for producing paper and board which comprises mixing a composition comprising cellulosic fibres subjected to extrusion, as described above, with cellulosic pulp, wherein the composition subjected to extrusion may have or may not have been subjected to chemical treatment, as described above.
  • a process for producing paper and board which comprises mixing a composition comprising cellulosic fibres subjected to extrusion, as described above, with cellulosic pulp, wherein the composition subjected to extrusion may have or may not have been subjected to chemical treatment, as described above.
  • aqueous suspension of the cellulosic fibre composition Preferably, in the process, use is made of an aqueous suspension of the cellulosic fibre composition.
  • the cellulosic pulp used in the process may be derived from the cellulosic pulp defined above. Examples of suitable wood and non-wood fibres include those defined above i n respect of th e cellulosic fibre
  • the cellulosic pulp is derived from wood fibres such as hardwood, softwood and mixtures thereof, and preferably comprising softwood fibres.
  • the cellulosic fibre composition can be added to the cellulosic pulp suspension in an amount of from about 0.1 to about 25, suitably from about 0.5 to about 15, or from about 1 to 10, usually from about 2 to about 8 % by weight, calculated as dry cellulosic fibres of the composition on dry cellulosic pulp.
  • Further additives may also be used in the process of the invention, and they may be added to the cellulosic fibre composition, to the aqueous suspension comprising the cellulosic fibre composition, to the aqueous suspension comprising cellulosic pulp and/or to the aqueous suspension comprising the cellulosic pulp mixture, usually to the aqueous suspension comprising cellulosic fibre composition and/or cellulosic pulp and/or cellulosic pulp mixture.
  • suitable further additives include one or more drainage and retention aids, cationic coagulants, dry strength agents, wet strength agents, e.g.
  • the further additives preferably comprise one or more drainage and retention aids.
  • the expression "drainage and retention aid”, as used herein, refers to one or more additives which, when added to an aqueous cellulosic suspension, give better drainage and/or retention than is obtained when not using said one or more additives.
  • the one or more drainage and retention aids may comprise anionic polymers, cationic polymers, siliceous materials and combinations thereof, preferably at least one cationic polymer.
  • suitable anionic polymers include anionic polyacrylamide and anionic naphthalene- formaldehyde condensation polymers, e.g. anionic naphthalene sulfonates.
  • suitable cationic polymers include cationic polysaccharides, e.g. cationic starches, and cationic synthetic polymers, e.g. cationic polyacrylamides, cationic poly(diallyldimethyl- ammonium chlorides), cationic polyethylene imines, cationic polyamines and cationic polyamidoamines.
  • the weight average molecular weight of the anionic and cationic polymers may be above about 5,000, or above about 10,000, usually above about 1 ,000,000 g/mole.
  • the upper limit is not critical; it can be about 50,000,000 g/mole, usually 30,000,000 g/mole.
  • suitable siliceous materials include anionic silica-based particles and anionic clays of the smectite type, e.g. bentonite.
  • the siliceous material has particles in the colloidal range of particle size.
  • Anionic silica-based particles, i.e. particles based on Si0 2 or silicic acid, are preferably used and such particles are usually supplied in the form of aqueous colloidal dispersions, so-called sols.
  • silica-based particles include colloid- al silica and different types of polysilicic acid, either homopolymerised or co-polymerised, for example polymeric silicic acid, polysilicic acid microgel, polysilicate and polysilicate microgel.
  • the silica-based sols can be modified and contain other elements, e.g. aluminum, boron, magnesium, nitrogen, zirconium, gallium, titanium and the like, which can be present in the aqueous phase and/or in the silica-based particles.
  • Examples of preferred drainage and retention aids for use in the process include cationic starches, cationic polyacrylamides, anionic polyacrylamides, anionic siliceous materials and combinations thereof.
  • suitable combinations of drainage and retention aids comprise (i) cationic starch and anionic siliceous material, preferably silica-based particles, (ii) cationic polyacrylamide and anionic siliceous material, preferably silica-based particles, (iii) cationic starch, cationic polyacrylamide and anionic siliceous material, preferably silica-based particles, (iv) cationic polyacrylamide, anionic polyacrylamide and anionic siliceous material, preferably silica-based particles, and (v) cationic starch, anionic polyacrylamide and anionic siliceous material, preferably silica-based particles.
  • the one or more drainage and retention aids can be added to the suspension in amounts which can vary within wide limits depending on, inter alia, type and number of additives, type of suspension, point of addition, etc.
  • the anionic polymers are usually added in an amount of at least 0.001 , often at least 0.005 % by weight, based on dry weight of the suspension, and the upper limit is usually 3 and suitably 1.5 % by weight.
  • the cationic polymers are usually added in an amount of at least about 0.001 , often at least about 0.005 % by weight, based on dry weight of the suspension, and the upper limit is usually about 3 and suitably about 1.5 % by weight.
  • the siliceous materials are usually added in an amount of at least about 0.001 , often at least about 0.005 % by weight, based on dry weight of the suspension, and the upper limit is usually about 1.0 and suitably about 0.6 % by weight.
  • the drainage and retention aids can be added in conventional manner and in any order.
  • a siliceous material it is common to add a cationic polymer before adding the siliceous material, even if the opposite order of addition may also be used. It is further common to add a cationic polymer before a shear stage, which can be selected from pumping, mixing, cleaning, etc., and to add the siliceous material after that shear stage.
  • suitable coagulants include organic and inorganic coagulants.
  • suitable organic coagulants include low molecular weight cationic polymers, e.g. homo and copolymers of diallyl dimethyl ammonium chloride (DADMAC), polyamines, polyamideamines, polyethylene imines, and dicyandiamide condensation polymers having a molecular weight in the range of from 1 ,000 to 700 ,000 , suitably from 1 0,000 to 500,000.
  • suitable inorganic coagulants include aluminium compounds, e.g. alum and polyaluminium compounds, e.g. polyaluminium chlorides, polyaluminium sulphates, polyaluminium silicate sulphates and mixtures thereof.
  • the coagulant is preferably added prior to adding the one or more drainage and retention aids.
  • the cationic coagulant can be added in an amount of at least about 0.001 , or from about 0.05, usually from about 0.1 , up to about 3.0, usually up to about 2.0 % by weight, calculated as dry coagulant on dry suspension,
  • each of the dry strength agent, wet strength agent and sizing agent as defined above can be added to the suspension in an amount of from about 0.01 to about 1 , usually from about 0.1 to about 0.5 % by weight, calculated as dry agent on dry suspension.
  • the process of the invention may comprise the use of mineral fillers of conventional types, e.g. kaolin, china clay, titanium dioxide, gypsum, talc and natural and synthetic calcium carbonates, e.g. chalk, ground marble and precipitated calcium carbonate.
  • mineral fillers of conventional types, e.g. kaolin, china clay, titanium dioxide, gypsum, talc and natural and synthetic calcium carbonates, e.g. chalk, ground marble and precipitated calcium carbonate.
  • the process may produce single ply paper or board in which the cellulosic fibre composition, as defined herein, is distributed throughout the paper or board, preferably substantially uniformly distributed throughout the paper and board.
  • Single ply paper and board contain just one ply or layer containing cellulosic fibres.
  • the process may also produce multi ply paper and board comprising two or more plies or layers containing cellulosic fibres wherein at least one of said two or more plies or layers comprises the cellulosic fibre composition, as defined herein.
  • the cellulosic fibre composition is distributed throughout at least one of said two or more plies, more preferably substantially uniformly distributed throughout at least one of said two or more plies.
  • Multi ply board according to the invention can be produced by forming at least one ply comprising the cellulosic fibres composition, as defined herein, and attaching said at least one ply to one or more plies containing cellulosic fibres to form the multi ply board.
  • multi ply board can be produced by forming the individual plies or layers separately in one or several web-forming units and then couching them together in the wet state.
  • suitable grades of multi ply board of the invention include those comprising from two to seven plies or layers comprising cellulosic fibres and wherein at least one of said plies or layers comprises the cellulosic fibre composition, as defined herein, preferably one or more of the middle (internal) plies or layers.
  • the board e.g. single or multi ply board
  • suitable process steps include coating, e.g. starch coating and pigment coating, creasing, printing and cutting.
  • suitable boards of the invention include coated board, e.g. starch and/or pigment coated, and printed board.
  • board refers to board comprising cellulosic fibres including solid board, e.g. solid bleached sulphate board (SBS) and solid unbleached sulphate board (SUS), paper board, carton board, e.g.
  • solid board e.g. solid bleached sulphate board (SBS) and solid unbleached sulphate board (SUS)
  • SBS solid bleached sulphate board
  • SUS solid unbleached sulphate board
  • folding boxboard FBB
  • folding carton board liquid packaging board
  • LPB liquid packaging board
  • the board may have a grammage of at least about 130, usually at least about 140 or at least about 150 g/m 2 , and it may be up to about 1 ,400, or up to about 1 ,300 g/m 2 .
  • the board may have a bulk density of at least about 120, usually at least about 150, or at least about 200 kg/m 3 , and it may be up to about 1 ,400, usually up to about 800, or up to about 600 kg/m 3 .
  • the invention further relates to a method for producing a packaging material which comprises providing board comprising one or more plies comprising the cellulosic fibres composition, as defined herein, and subjecting the board to one or more converting operations selected from printing, varnishing, coating, e.g. plastics coating, extrusion coating and barrier coating, laminating, e.g. plastic film laminating and metal foil laminating, e.g aluminium foil laminating, metallizing, die cutting, i.e.
  • the method includes one or more converting operations comprising scoring or creasing, more preferably two or more operations comprising scoring or creasing, for example cutting and scoring or creasing.
  • the invention also relates to a packaging material comprising board which comprises one or more plies comprising the cellulosic fibre composition, as defined herein, wherein it further comprises one or more creases.
  • the creases also referred to as scores, grooves or folding lines, make it easier to fold and erect the packaging material prior to filling.
  • the packaging materials of the invention can have one or more layers of plastic film, metal foil, e.g. aluminium, and/or barrier coating.
  • the invention further relates to a procedure of making a package which comprises providing a blank of packaging material comprising board comprising one or more plies comprising the cellulosic fibre composition, as defined herein, filling the blank with a solid or liquid content to obtain an unsealed package, and then sealing the obtained package.
  • the packaging material comprises one or more grooves, creases or scores.
  • blade as used herein, means an unfilled package or packaging material.
  • the blank is folded and erected prior to filling. Examples of suitable methods for sealing include gluing and heat sealing.
  • the invention further relates to a procedure of making a package which comprises providing a reel of packaging material comprising board comprising one or more plies comprising the cellulosic fibre composition, as defined herein, whereupon the reel of packaging material is introduced into a filling machine, filled with a solid or liquid content, sealed and cut into separate packages which may be folded to the desired shape.
  • suitable solid and liquid contents include solid and liquid foodstuffs, e.g. tomato products, soup, cream, chocolate and cereals, beverages, e.g. milk, fruit juice, wine and water, pharmaceuticals, cosmetics, cigarettes, tobacco and detergents.
  • the invention further comprises sterilizing the package and/or the solid or liquid content.
  • sterilizing means reducing the number of microorganisms.
  • suitable methods and means for sterilization include heat, e.g. rapid heating and cooling, chemicals, e.g. ozone and hydrogen peroxide, irradiation, e.g. IR and UV irradiation.
  • the filling can be made under high hygiene or sterile conditions.
  • the invention also relates to a packaging comprising board comprising one or more plies containing the cellulosic fibre composition, as defined herein, wherein it further comprises a solid or liquid content.
  • the invention further relates to uses of the packaging material comprising board, which comprises one or more plies containing the cellulosic fibre composition, as defined herein, for packaging of solid or liquid foodstuffs, beverages, pharmaceuticals, cosmetics, cigarettes, tobacco or detergents.
  • suitable packaging of the invention include foodstuff packaging, beverage packaging, sterile packaging and aseptic packaging.
  • Parts and % relate to parts by weight and % by weight, respectively, and all suspensions are aqueous, unless otherwise stated.
  • Chemical Treatment 1 Chemical treatment 1 (referred to as "CT1 ”) was carried out using cellulosic fibres at a dry solids content of 10 % by weight with 40 ppm Fe +2 (added as FeS0 4 ) and 1 % H 2 0 2 , based on the weight of dry cellulosic fibres, at pH 4 (adjusted with H 2 S0 4 ) an d a temperature of 70 °C for 30 min.
  • Chemical treatment 2 (referred to as "CT2") was carried out as in Chemical Treatment 1 except that the amount of H 2 0 2 used was 0.1 % by weight, based on the weight of dry cellulosic fibres, and the temperature was 90 °C
  • Chemical treatment 3 (referred to as "CT3") was carried out using cellulosic fibers at a dry s o l i d c o n t e n t of 2 % b y w e i g h t w i t h 1 , 6 % b y w e i g h t T E M P O (2,2,6,6- tetramethylpiperidine-1 -oxyl radical), based on the weight of dry cellulosic fibers, and 10 % by weight of NaBr and 3.7 % by weight of NaCIO, based on the weight of dry cellulosic fibers, at pH 10 (adjusted with NaOH) and temperature of 20 °C for 60 min.
  • Chemical Treatment 4 was carried out using cellulosic fibers at a dry s o l i d c o n t e n t of 2 % b w
  • Chemical treatment 4 (referred to as "CT4") was carried out by treating cellulosic fibers with monochloroacetic acid under alkaline conditions according to the general procedure for preparation of carboxymethyl cellulose disclosed by WO 00/47628. By using varying amounts of reactants, cellulosic compositions having different degrees of substitution of anionic / carboxymethyl groups were obtained.
  • Mechanical treatment 1 (referred to as “MT1 " in the tables below) was carried out using untreated or chemically treated cellulosic fibres.
  • the cellulosic fibres were washed with water and concentrated to a desired dry solids content and then passed through a co- rotating twin-screw extruder (Berstorff ZE 25A-UTS-UG) which had a screw diameter of 25 mm, core diameter of 17 mm, centre distance of 21 .5 mm and extrusion unit length of 48D (1200 mm) having 10 barrels with individual heating/cooling possibilities which were cooled with tap water.
  • MT1 co- rotating twin-screw extruder
  • the extruder screws were built up with conveying and kneading elements and had the screw configuration as shown in Figure 1 , where left and right screws were equal.
  • the drive power at maximum admissible screw speed (1200 rpm) was 22.6 kW (Siemens DC motor, type 1 GG5134-OGH46-6WV1 ).
  • the pulp was fed gravimetrically with a feeding device (K-Tron-Soder T20).
  • the extruder was run at a screw speed of 1000 rpm.
  • the cellulosic fibres were fed at a feed rate of 0.8 kg dry solids/h, unless otherwise stated.
  • Mechanical treatment 2 was carried out using untreated or chemically treated cellulosic fibres.
  • the cellulosic fibres were washed with water and concentrated to a desired dry solids content and then passed through a planetary roller extruder (Entex PLWE100 with a 5.25 l/d barrel).
  • the cooled central spindle had a diameter of 100 mm and the planetary roller extruder had 6 rolling planetary spindles.
  • Mechanical treatment 3 (referred to as "MT3" in the tables below) was used for comparison and carried out according to the procedure of Example 1 b of WO 2007/001229 in which a cellulosic fibre suspension at a desired dry solids content was passed through a pearl mill (Drais PMC 25TEX) once or twice, unless otherwise stated, using zirconium oxide pearls (2.0 mm in diameter, 65% filling grade), rotor speed of 1200 rpm and a flow rate of 100 l/h.
  • MT3 Mechanical treatment 3
  • Length weighted mean fibre length (referred to as “Fibre Lengh” in the tables below) and length weighted mean fibre width (referred to as “Fibre Width” in the tables below) of the cellulosic fibres were measured by means a Fiber Tester of Lorenzen & Wettre, Sweden, which operates according to ISO 16065-2:2007.
  • the length weighted mean fibre length / width ratio (referred to as “Length / Width Ratio" in the tables below) was calculated from such data.
  • the content of cellulosic fibres having a length weighted mean fibre length up to 100 ⁇ was determined using the same Lorenzen & Wettre Fiber Tester.
  • Specific surface areas were determined by adsorption of N 2 at 177 K according to the BET method using a Micromeritics TriStar 3000 instrument, which operates according to ISO 9277:1995.
  • the cellulosic fibres to be analysed were frozen in a freezing equipment at the consistency received after any chemical and/or mechanical treatments, freeze dried in a Heto FD3 freeze drier, degassed at 90 °C for 3 hours and thereafter analysed for specific surface area.
  • Water retention values (referred to as "WRV" in the tables below) were determined according to SCAN-C 62:00.
  • the samples to be analysed were aqueous pulp suspensions at a consistency of 0.5 % in which the dry pulp consisted of 95 % by weight of CTMP and 5 % by weight of cellulosic fibre composition according to the invention or cellulosic composition used for comparison, unless otherwise stated.
  • the water retention value is a measure of the capacity of the pulp to hold or retain water, and an indication of the energy needed to remove the water and dry the cellulosic sheet; a lower water retention value indicates less energy to remove water and dry the cellulosic sheet.
  • Average degree of substitution of anionic / carboxymethyl groups was determined by the method of conductometric titration as described by S. Katz, R.P. Beatson and A.M. Scallan in Svensk Papperstidning No. 6/1984, pp. 48- 53.
  • Cellulosic compositions were used as additives in a paper and board making process in which paper or board sheets with a grammage of approximately 150 g/m 2 were made according to ISO 5269-1 :1998 using a dynamic sheet former (Formette Dynamic, supplied by Fibertech AB, Sweden).
  • the pulp used consisted of 90 % high bulk CTMP (CSF 700 ml) and 1 0 % softwood (S R 28).
  • Pulp suspensions at a consistency of 0.5 % and conductivity 1 .0 mS/cm at pH 7 were formed in a mixing chest and the following additions were made: (i) chemically treated and/or mechanically treated cellulosic composition, if any, was added to the suspension in an amount of 5 % by weight, calculated as dry cellulosic composition on dry suspension, whereupon the obtained suspension was mixed for 15 seconds,
  • cationic potato starch (Pearlbond 970) was added to the suspension in an amount of 1 0 kg/t, based on dry suspension , whereupon the suspension was mixed for 30 seconds, and
  • a siliceous material in the form of silica-bases particles (Eka N P 442, Eka Chemicals) was added to the suspension in an amount of 0.3 kg/t, calculated as Si0 2 and based on dry suspension, whereupon the suspension was mixed for 15 seconds,
  • the obtained suspension was pumped from the mixing chest through a traversing nozzle on a wire positioned on a rotating drum of the dynamic sheet former where it was dewatered for 90 seconds for sheet formation.
  • the obtained paper or board sheets were pressed in a plane press at 5 bar for 5 minutes and thereafter dried restrained in a plane drier at 1 15 °C for 12 minutes.
  • the paper or board sheets were conditioned in a climate room according to I SO 1 87: 1 990 and thereafter analysed in terms of tensile strength index (Nm/g) according to ISO 1924- 3:2005 using an Alwetron TH1 of Lorenzen & Wettre, Sweden.
  • Cellulosic fibres of bleached kraft birch pulp were subjected to chemical treatment and/or mechanical treatment and the obtained compositions were analysed. The results are shown in Table 1 , in which the dry solids content (% by weight) of the cellulosic fibres in the mechanical treatment is given in parenthesis.
  • Test Nos. 1 and 2 refer to cellulosic fibre compositions subjected to extrusion (MT1 ). Table 1
  • Test No. 1 refers to the cellulosic fibres derived from the bleached birch kraft pulp used as a reference.
  • Test Nos. 2 and 3 refer to cellulosic fibre compositions which had been passed through the pearl mill (MT3) used for comparison once and twice, respectively.
  • Example 3 Cellulosic fibres of bleached kraft birch pulp were subjected to chemical treatment and/or mechanical treatment and the obtained compositions were used as add itives in the production of paper / board and analysed. The results are shown in Table 3, in which the dry solids content (% by weight) of the cellulosic fibres in the mechanical treatment is given in parenthesis.
  • Test No. 1 refers to the cellulosic fibres derived from bleached birch kraft pulp used as a reference.
  • Test Nos. 2 and 3 refer to cellulosic fibre compositions subjected to extrusion (MT1 ) at a feed rate of 0.8 and 1 .2 kg dry solids/h, respectively.
  • Example 4 Cellulosic fibres of birch were subjected to chemical treatment and/or mechanical treatment and the obtained compositions were used as additives in the production of paper / board and analysed. The results are shown in Table 4, in which the dry solids content (% by weight) of the cellulosic fibres in the mechanical treatment is given in parenthesis.
  • Test No. 1 refers to the reference pulp suspension when no cellulosic fibre composition was used as an additive.
  • Test No. 2 refers to the composition of cellulosic fibres derived from birch used for comparison, and Test Nos. 3 to 8 refer to different cellulosic fibre compositions used as additives.
  • Table 4 shows that the use of the compositions comprising cellulosic fibres according to the invention in Test Nos. 4-8 resulted in paper / board with improved tensile strength index over the compositions comprising cellulosic fibres used for comparison.
  • Test No. 1 refers to the composition of cellulosic fibres derived from birch.
  • Test Nos. 2 to 4 refer to cellulosic fibre compositions derived from birch which had been passed through the pearl mill (MT3) used for comparison.
  • MT3 pearl mill
  • Example 6 Cellulosic fibres of pine were su bjected to chemical treatment and/or mechanical treatment and the obtained compositions were used as additives in the production of paper / board an analysed. The results are shown in Table 6, in which the dry solids content (% by weight) of the cellulosic fibres in the mechanical treatment is given in parenthesis.
  • Test No. 1 refers to the pulp suspension when no cellulosic fibre composition was used as an additive.
  • Test No. 2 refers to the cellulosic fibres derived from pine used for comparison.
  • Test Nos. 3 to 8 refer to different cellulosic fibre compositions used as additives.
  • Table 6 shows that the use of the compositions comprising cellulosic fibres according to the invention in Test Nos. 4-8 resulted in paper / board with significantly improved tensile strength index over the compositions comprising cellulosic fibres used for comparison.
  • Test No. 1 refers to the composition of cellulosic fibres derived from pine used for comparison.
  • Test Nos. 2 to 5 refer to cellulosic fibre compositions which had been subjected to extrusion (MT1 ) according to the invention.
  • Test No. 1 refers to the composition of cellulosic fibres derived from pine.
  • Test Nos. 2 to 4 refer to cellulosic fibre compositions which had been passed through the pearl mill (MT3) once and twice, respectively, used for comparison.
  • Test No. 1 refers to the pulp suspension when no cellulosic fibre composition was used as an additive.
  • Test No. 2 refers to the cellulosic fibres derived from pine used for comparison.
  • Test Nos. 3 to 5 refer to different cellulosic fibre compositions used as additives.
  • Table 9 shows that the use of the compositions comprising cellulosic fibres according to the invention in Test Nos. 4-5 resulted in paper / board with significantly improved tensile strength index over the compositions comprising cellulosic fibres used for comparison.
  • Cellulosic fibres of pine were subjected to chemical treatment and/or mechanical treatment and used as additives in the production of paper / board and analysed. The results are shown in Table 10, in which the dry solids content (% by weight) of the cellulosic fibres in the mechanical treatment is given in parenthesis.
  • Test No. 1 refers to the pulp suspension when no cellulosic fibre composition was used an additive.
  • Test Nos. 2 to 3 refer to different cellulosic fibre compositions used additives according to the invention.
  • Example 1 1 Cellulosic fibres were subjected to chemical treatment and/or mechanical treatment and the obtained compositions were used as additives in the production of paper / board and analysed. The results are shown in Table 1 1 , in which the dry solids content (% by weight) of the cellulosic fibres in the mechanical treatment is given in parenthesis. Test No. 1 refers to the pulp suspension when no cellulosic fibre composition was used as an additive. Test Nos. 2 to 6 refer to different cellulosic compositions used as additives.
  • Table 1 1 shows that the use of the compositions comprising cellulosic fibres of pine in Test Nos. 3-5 and cotton linter in Test No. 6 according to the invention resulted in paper / board with a good balance between improved tensile strength index and low water retention values which indicate less energy to remove water and dry the cellulosic sheet over the composition according to Test No. 2 used for comparison.
  • Test No. 1 refers to the pulp suspension when no cellulosic fibre composition was used as an additive.
  • Test Nos. 2 to 4 refer to the cellulosic composition used for comparison and Test Nos. 5-7 refer to the cellulosic fibre composition according to the invention.
  • Table 12 shows that, at a tensile strength index improvement of paper / board of about 30 %, the composition of the invention according to Test No.7 resulted in a lower water retention value which indicate less energy to remove water and dry the cellulosic sheet over the composition used for comparison according to Test No. 3. Table 12 also shows that, at about the same water retention value, the composition of the invention resulted in increased tensile strength index over the composition used for comparison.
  • Example 13 Cellulosic fibres of various sources were subjected to chemical treatment and/or mechanical treatment and the obtained compositions were used as add itives in the production of paper / board and analysed. The results are shown in Table 13, in which the dry solids content (% by weight) of the cellulosic fibres in the mechanical treatment is given in parenthesis.
  • Test No. 1 refers to the pulp suspension when no cellulosic fibre composition was used as an additive.
  • Test Nos. 2 to 6 refer to different cellulosic compositions used as additives.
  • Table 13 shows that the use of the compositions comprising cellulosic fibres according to the invention in Test Nos. 2-6 resulted in paper / board with significantly improved tensile strength index and low retention values.
  • Example 14 Cellulosic fibres of various sources were subjected to chemical treatment and/or mechanical treatment and the obtained compositions were used as add itives in the production of paper / board and analysed. The results are shown in Table 14, in which the dry solids content (% by weight) of the cellulosic fibres in the mechanical treatment is given in parenthesis. Cotton means cotton linter.
  • Test No. 1 refers to the pulp suspension when no cellulosic fibre composition was used as an additive.
  • Test Nos. 2 to 7 refer to different cellulosic fibre compositions used as additives.
  • the mechanical treatment MT2 * was carried out by feeding the cellulosic fibre composition through the planetary roller extruder twice.
  • Table 14 shows that the use of the compositions comprising cellulosic fibres according to the invention resulted in paper / board with significantly improved tensile strength index.

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Abstract

La présente invention concerne une composition comprenant des fibres cellulosiques présentant un degré moyen de substitution de groupes anioniques allant de 0,001 à 0,25, et - une longueur moyenne pondérée des fibres allant jusqu'à 1 100 μm et une largeur moyenne pondérée des fibres supérieure à 10 μm, ou - une longueur moyenne pondérée des fibres allant jusqu'à 1 100 μm, au moins 50 % en poids du matériau cellulosique étant insolubles dans l'eau, ou - un rapport entre une longueur moyenne pondérée des fibres et une largeur moyenne pondérée des fibres allant jusqu'à 30, ou - une largeur moyenne pondérée des fibres supérieure à 35 μm. L'invention concerne également une composition comprenant des fibres cellulosiques présentant une surface spécifique d'au moins 1,5 m2/g, un rapport entre une longueur moyenne pondérée des fibres et une largeur moyenne pondérée des fibres allant jusqu'à 30, et une teneur en matière sèche d'au moins 5 % en poids, sur la base du poids de la composition, ou jusqu'à 30 % en poids, sur la base du poids total des fibres cellulosiques, de fibres cellulosiques dotées d'une longueur moyenne pondérée des fibres allant jusqu'à 100 μm. L'invention concerne également un procédé de production d'une composition comprenant des fibres cellulosiques consistant à soumettre des fibres cellulosiques à un traitement chimique et à un traitement mécanique, le traitement chimique consistant à traiter les fibres cellulosiques avec (i) au moins un agent contenant un groupe carboxyle, éventuellement substitué, (ii) au moins un oxydant et au moins un métal de transition, ou (iii) au moins un radical nitroxyle, et le traitement mécanique consistant à soumettre des fibres cellulosiques à une extrusion au moyen d'une extrudeuse à deux vis ou d'une extrudeuse à vis planétaires. L'invention concerne également un procédé de production d'une composition comprenant des fibres cellulosiques consistant à soumettre des fibres cellulosiques présentant un degré moyen de substitution de groupes anioniques allant de 0,001 à 0,25 à une extrusion. L'invention concerne également une composition comprenant des fibres cellulosiques pouvant être obtenues par les procédés, un processus de production d'un mélange de pâte cellulosique consistant à mixer la composition à une pâte cellulosique, un mélange de pâte cellulosique pouvant être obtenu par le processus, et l'utilisation de la composition et du mélange de pâte cellulosique comme additif dans la production de papier et de carton, des processus de production de papier et de carton au cours desquels la composition ou le mélange de pâte cellulosique sont utilisés, le papier et le carton pouvant être obtenus par les processus, et diverses utilisations du papier et du carton.
PCT/EP2011/061571 2010-07-12 2011-07-08 Composition de fibre cellulosique WO2012007363A1 (fr)

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BR112013000141A BR112013000141A2 (pt) 2010-07-12 2011-07-08 ''composição, método de produção de uma composição, utilizada da composição processo para a produção de uma mistura de polpa de celulose, mistura de polpa de celulose, utilização da mistura de polpa de celulose, processo para a produção de papel e papelão, utilização do papelão, e, embalagem que compreende papelão''
AU2011278462A AU2011278462A1 (en) 2010-07-12 2011-07-08 Cellulosic fibre composition
EP11730021.0A EP2593603A1 (fr) 2010-07-12 2011-07-08 Composition de fibre cellulosique
KR1020137001576A KR20130132381A (ko) 2010-07-12 2011-07-08 셀룰로스 섬유 조성물
JP2013519038A JP2013531749A (ja) 2010-07-12 2011-07-08 セルロース繊維組成物
CA2803650A CA2803650A1 (fr) 2010-07-12 2011-07-08 Composition de fibre cellulosique
CN201180033282XA CN102971462A (zh) 2010-07-12 2011-07-08 纤维素纤维组合物

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EP2207508A1 (fr) * 2007-11-09 2010-07-21 Honeywell International Inc. Dispositifs hémostatiques contenant un adsorbant
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EP2633119A4 (fr) * 2010-10-26 2015-08-12 Zeo Ip Pty Ltd Composition de fibres de cellulose
US9441052B2 (en) 2011-06-15 2016-09-13 Upm-Kymmene Corporation Method and a system for manufacturing cellulosic material
US9334610B2 (en) 2012-04-26 2016-05-10 Stora Enso Oyj Fibrous web of paper or board and method of making the same
WO2013160553A1 (fr) * 2012-04-26 2013-10-31 Stora Enso Oyj Bande continue fibreuse de papier ou de carton et son procédé de fabrication
US10364533B2 (en) 2012-04-26 2019-07-30 Stora Enso Oyj Hydrophobically sized fibrous web and a method for the preparation of a sized web layer
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KR20130132381A (ko) 2013-12-04
JP2013531749A (ja) 2013-08-08
TW201213421A (en) 2012-04-01
CN102971462A (zh) 2013-03-13
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