WO2001042564A1 - Compositions possedant une influence sur la resistance du papier - Google Patents

Compositions possedant une influence sur la resistance du papier Download PDF

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Publication number
WO2001042564A1
WO2001042564A1 PCT/FI2000/001041 FI0001041W WO0142564A1 WO 2001042564 A1 WO2001042564 A1 WO 2001042564A1 FI 0001041 W FI0001041 W FI 0001041W WO 0142564 A1 WO0142564 A1 WO 0142564A1
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WO
WIPO (PCT)
Prior art keywords
weight
active agent
surface active
composition according
fibers
Prior art date
Application number
PCT/FI2000/001041
Other languages
English (en)
Inventor
Susanna Koskinen
Taru SYRJÄNEN
Salme Koskimies
Original Assignee
Neste Chemicals Oy
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 Neste Chemicals Oy filed Critical Neste Chemicals Oy
Priority to AU21746/01A priority Critical patent/AU2174601A/en
Publication of WO2001042564A1 publication Critical patent/WO2001042564A1/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
    • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/50—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by form
    • D21H21/56—Foam
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
    • D21H21/18—Reinforcing agents
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/33—Synthetic macromolecular compounds
    • D21H17/46—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H17/47—Condensation polymers of aldehydes or ketones
    • D21H17/49—Condensation polymers of aldehydes or ketones with compounds containing hydrogen bound to nitrogen
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/33—Synthetic macromolecular compounds
    • D21H17/46—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H17/47—Condensation polymers of aldehydes or ketones
    • D21H17/49—Condensation polymers of aldehydes or ketones with compounds containing hydrogen bound to nitrogen
    • D21H17/51—Triazines, e.g. melamine
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
    • D21H21/22—Agents rendering paper porous, absorbent or bulky
    • D21H21/24—Surfactants

Definitions

  • compositions having influence on the strength of paper having influence on the strength of paper
  • the present invention relates to compositions for the treatment of fibrous material such as paper web during paper manufacturing, particularly to foamable compositions containing additives influencing the paper strength.
  • the invention is also directed to the use of foamable compounds to improve the strenght of fibrous material.
  • problems are caused by the natural flocculation of the fibers, that is, the tendency to form flakes or aggregates that are difficult to break. They may thus be incorporated into the web being formed, influencing the smoothness of the web and its final properties. This problem is particularly severe when handling of slurries containing long or synthetic fibers, or having a high fiber content. This is the case when a heavy web is produced or when fibers causing a slow dewatering by nature are used or the speed of the paper machine is high, or when it is important to lower the treatment costs of the drained liquid.
  • the problem due to the flocculation of the fibers may be reduced by dispersing the fibers to very high volumes of water.
  • the fiber concentration is from 10 to 100 mg/1 rather than from 1 to 10 g/1, which is the concentration generally used. It is, however, commercially uneconomic to handle such high water volumes.
  • a method has been suggested wherein the fibers are dispersed in a liquid polymeric medium having a high viscosity, such as aqueous sugar or natural gum mixtures. Because of the high viscosity of the medium, the drainage thereof through the web being formed and the wire supporting it is slow and troublesome, and accordingly, this method is not particularly suitable for continuous large scale production of fiber products.
  • the patent publication US 3937273 suggests a method wherein the headbox slice of the paper machine is modified to be very low and adjusted with sharp bends in series. As the fiber suspension passes through the slice, the bends cause in the suspension very intense small scale turbulences that break the flakes or aggregates formed. Then the suspension flows to a second low slice and passes on the wire forming the paper web in a normal manner for a paper machine.
  • Patent GB 1209409 discloses a method wherein a uniform fiber suspension is produced in a foam provided by dispersing air in water in the presence of a foaming additive. Such foams may be drained off relatively easily, and thus, they do not restrict the performance of the paper machine inacceptably.
  • the favourable rheology of the foams is believed to result from the pseudoplastic behaviour of the densely packed resistant bubbles, limiting the migration of the fibers, and thus preventing the formation of flakes and aggregates.
  • the high quality of the suspension is preserved, and the drainage is quick.
  • Patent GB 1129757 presents a method and an apparatus for forming a fiber web from a foaming medium.
  • the chemical nature of the surface active agent is not critical provided that the foaming capacity thereof is sufficient to provide a thick viscose foam of small air bubbles.
  • the surface active agent may be an anionic, cationic or non-ionic agent.
  • the fiber product may be produced by dispersing the fibers in a foamed liquid medium. This medium is produced by dispersing air as ex- tremely fine bubbles in an aqueous solution containing a surface active agent. The dispersion is carried out using high shear force to attain the desired properties.
  • the publication underlines that the air content of the foamed liquid medium must be at least 65 % by volume.
  • Patent GB 1329409 discloses improvements to increase the smoothness of the web.
  • the method shows the influence of the air content of the foam on the behaviour of the fibers in a foamed medium.
  • Fiber material may be produced by using foamed liquid medium having an air content higher than 65 %.
  • the size distribution of the bubbles in the foamed liquid medium is very critical. According to this publication, not all foamed liquid media produced by dispersing gas as bubbles in a liquid containing a surface active agent are suitable for the dispersion of fibers, but instead, some of them may be used to aggregate fibers (and particles) rather than to disperse them.
  • the fibers are dispersed very evenly and uniformly throughout the foamed liquid medium containing gas from 55 to 75 % by volume. If the gas content is below 55 % by volume, the number of the gas bubbles incorporated into the foam is relatively small, and the size distribution thereof is relatively wide. They then divide the medium into liquid pockets, in which the fibers accumulate. Since the viscosity of the liquid is relatively low, the fibers may migrate freely and thus aggregate in the liquid pockets.
  • the packing density of the bubbles is so high that the spherical bubbles will deform and adopt a polyhedric form.
  • the medium containing such bubbles there are surface tension forces in the planes of the lamellas between the bubbles attracting the fibers to junction lines of the lamellas being formed between the bubbles. This causes aggregation of the fibers to bundles that follow these lines.
  • the dispersion of fibers in such a foam is on an average better than in a medium comprising only water.
  • the number of the gas bubbles, and the shape and size thereof in the medium are factors that determine the tendency of a particular foamed liquid medium to favour the dispersion, or the aggregation of fibers.
  • the concentration of the foaming additive should be relatively high in the fiber suspension to enable the foam to carry the dispersed fibers from the dispersing apparatus to the wire. It is believed that surface ac- tive agents interfere with forces forming bonds between the fibers, and thus the presence thereof decreases the density and the strenght of a paper product obtained with a web forming method using foam. It has been possible to reduce this problem to some extent by using fiber with a higher degree of milling, or by adding reinforcing agents thereto. However, the reduction of the amount of the surface active agent needed would be a better solution.
  • An object of the present invention is to provide a foamable composition improving the strength of fibrous material, particularly wood fiber material.
  • This composition may be used in the production of paper wherein the fibers are dispersed in a foaming liquid medium resulting in a uniform fiber web with a good specific volume.
  • Another object of the invention is the use of a compound that may be foamed easily and sufficiently in said composition, the foam forming ability thereof, the stability of the foam obtained therewith, the influence thereof on the strength of the fiber bonds, and other properties being in particular suitable for the production of paper.
  • the composition of the invention comprises a surface active agent, a resin that may be cured thermally or with an acid, such as a urea- formaldehyde or a melamin-formaldehyde resin, or a mixture thereof, and water.
  • the composition may also contain a cationic acryl amide copolymer.
  • the constituents are mixed together in the form of sufficiently dilute aqueous solutions in the following order: resin, copolymer, surface active agent, water, and acid.
  • the resin preferably an aqueous solution of urea- formaldehyde, is added in an amount varying from 0.5 to 5 %, by weight, preferably from 0.5 to 3 %, by weight relative to the dry weight of the fibers, calculated as dry resin.
  • the dry matter content of the urea-formaldehyde resin is from 30 to 60 %, by weight, preferably from 35 to 50 %, by weight, the molar ratio of formaldehyde to urea being from 1.8 to 3.8 : 1.
  • the resin is preferably diluted to form an aqueous solution having a concentration from 1 to 5 %, by weight.
  • the cationic acryl amide copolymer is added in an amount of 0 - 3 %, preferably 0.5 - 1 %, calculated as dry copolymer, relative to the dry weight of the fibers.
  • the cati- onic acryl amide copolymer is typically used as an aqueous 10 - 50 % solution having a cationicity of 20 - 100 %, preferably 25 - 80 %, the molecular weight of the copolymer being between 10,000 and 300,000, preferably between 50,000 and 300,000.
  • the cationic acryl amide copolymer may be produced from monomers comprising acryl amide, or from monomers in copolymeric cationic form, such as quater- nary acryl amide alkyl-N-alkylamine, secondary or tertiary acryl amine alkyl-N- alkylamine, or primary acryl amine, esters of acrylic acid, the alcohol moiety thereof being a quaternary n-alkylamine alkoxide, or from a secondary or tertiary n- alkylamine alkoxide, or a primary amine alkoxide.
  • an anionic or neutral surface active agent such as an eth- oxylated alkyl sulphate (AES) having from 12 to 14 carbon atoms in its alkyl chain, or a salt thereof, an alkyl glycoside or a salt thereof, or a synthesis product of alkenyl succinic anhydride and alkyl glycoside, or a salt thereof.
  • AES eth- oxylated alkyl sulphate
  • alkenyl succinic anhydride ASA
  • alkyl glycoside A
  • alkenyl succinic anhydride having from 10 to 24 carbon atoms, preferably from 10 to 20 carbon atoms in its alkenyl chain, and from alkyl glycoside having from 1 to 20 carbon atoms, preferably from 8 to 10 carbon atoms in its alkyl chain.
  • the molar ratio of ASA to AG is 0.1 - 10 : 1, preferably 0.75 — 1.25 : 1. It is carried out at a temperature of 60 - 100 °C, in an inert atmosphere, preferably in a nitrogen atmosphere.
  • the synthesis product obtained may be converted to a corresponding salt by adding a base such as sodium hydoxide to adjust the pH of the mixture to a value from 5 to 10, preferably 7.
  • R ⁇ C ⁇ -C ⁇ o -alkyl
  • R 2 C ⁇ 4 -C 2 o -alkenyl
  • the surface active agent is preferably an ethoxylated alkyl sulphate, or a sodium salt thereof, or alkyl glycoside or a sodium salt thereof being added in an amount of 0.1 - 7 %, by weight, preferably 2 - 3 %, by weight, relative to the dry weight of the fibers, or a sodium salt of the synthesis product of alkenyl succinic anhydride and alkyl glycoside, being added in an amount of 1 - 30 %, by weight, preferably 15 - 25 %, by weight, relative to the dry weight of the fibers, or a mixture of the above substances.
  • an acid such as hydrochloric acid or acetic acid may be added to the mix- ture to adjust the pH thereof below 6.
  • Water may be added to disperse the fibers at a consistency suitable for the production of paper.
  • constituents of the composition according to the invention may be added individually to the fiber suspension without mixing them first together.
  • the composition of the invention or the constituents thereof are added to the fiber suspension at one or several suitable points of the process.
  • the foaming of the mixture is preferably carried out by means of high shear in a suitable manner by using known foaming apparatuses wherein gas inert to the compounds present, such as nitrogen or air is fed into the mixture.
  • gas inert to the compounds present such as nitrogen or air is fed into the mixture.
  • composition of the invention includes superior foam forming ability and stability of the foam. It clearly improves the paper strength even at low levels of the surface active agent, making the method economical also for so-called ordinary paper grades. That is, the use of the composition is not limited only to soft tissues.
  • the invention is now illustrated in more detail by means of some preferable embodiments described in the following examples, without intending to limit the invention thereto.
  • the semiester (SI) between an alkyl glycoside and an alkenyl succinic acid is produced from alkenyl succinic acid and alkyl glycoside, the molar ratio of the starting compounds being 1:1 in the synthesis.
  • alkyl glycoside aqueous solution 60 %, by weight 66.66 g, or 0.13 moles
  • alkenyl succinic acid (30.10 g, or 0.13 moles) is quickly added at the temperature of 80 °C while mixing at 200 rpm.
  • the reaction mixture is allowed to react under nitrogen atmosphere, at the temperature of 80 - 85 °C for four hours, while mixing at the speed of 200 rpm.
  • the mixture is allowed to cool to room temperature.
  • the synthesis product SI weighs 92.44 g, the water content thereof is 24.4 %, by weight, Ri being a C 8 -C ⁇ o -mixture, R being a C 16 -C 18 -mixture.
  • the synthesis product SI is converted to its sodium salt.
  • aqueous 75.8 %, by weight, solution, 5.0 g, or 9.92 mmoles an equimolar amount of sodium hydroxide (1.0 M solution, 9.29 ml, or 9.28 mmoles) is added while agitating the mixture gently with a glass rod.
  • the weight of the resulting sodium salt of the synthesis product SI is 14.3 g, the water content thereof being 63.4 %, by weight. Examples 2 - 8
  • Aqueous solutions having a different composition were prepared from urea- formaldehyde resin, sodium salt of an ethoxylated alkyl sulphate (AES), or the syn- thesis product SI, and polyacryl amide copolymer (PAM).
  • the foaming and strengthening performances of these compositions were determined. Table 1 shows the results obtained. Foaming was carried out with a rod mixer in a 3000 ml beaker filled with a measured amount (250 ml) of the aqueous solution. Foaming performance means the volume of the foam immediately after foaming, the mixing time being 1 minute. Air content means the relative volume of air in the foam compared to the volume of the foamed solution. Strengthening performance and adhesion were tested with the glass plate method.
  • a glass plate is wetted with the particular solution, a moist cellulose sheet is placed thereon and pressed into intimate contact with the glass plate.
  • the plate is freely dried in an oven for about 20 hours at 80 °C. Hydrogen bonds forming between the moist sheet and the glass plate are influenced by chemicals either strenghtening or weakening them. The influence was tested with fingers by pulling the sheet carefully off the glass plate after drying.
  • the concentrations are percentages by weight relative to the total weight of the solution. No fibers are included, but the concentration thereof is supposed to be 1 % by weight. Based on this, the metering of the chemicals was calculated relative to 1 kg of water.
  • the surface active agent is the sodium salt of an ethoxylated alkyl sulphate.
  • the surface active agent is the sodium salt of the synthesis product S 1.
  • Aqueous solutions having a different composition were prepared from urea- formaldehyde resin, sodium salt of an ethoxylated alkyl sulphate, or the synthesis product SI, and polyacryl amide copolymer (PAM).
  • the strengthening performance of these compositions were determined. Table 2 shows the results obtained. The strengthening performance was tested with a method wherein sheets having the grammage of 60 g/m 2 were made by adapting the standard SCAN-C 26:2. On these sheets, about 5 g of the solution to be tested was sprayed, and then, two sheets were placed against each other, pressed, dried and aerated according to the standard.
  • the bonding of the sheet pair was measured by adapting the standard TAPPI T 833 pm-94, and using the Scott Bond Tester -apparatus.
  • a clip fixed to the sheet with a double-sided adhesive tape is knocked off with a pendulum, thus cracking the sheet.
  • the energy needed to split the paper in the plane direction may be read from the apparatus. In this way, the influence of the chemicals on the bonding between the fibers may to some extent be determined quantitatively.
  • the surface active agent was a sodium salt of an ethoxylated alkyl sulphate
  • Example 17 the surface active agent was the sodium salt of the synthesis product S 1. * Concentrations are in % by weight relative to the dry weight of the fibers. Examples 19 - 23
  • Example 19 no chemicals are used for producing the sheets In Examples 20 - 22, the surface active agent was a sodium salt of an ethoxylated alkyl sulphate
  • Example 23 the surface active agent was the sodium salt of the synthesis product SI.
  • Sheets were made from 1 %, by weight, suspension. The suspension was first foamed in a foaming apparatus, at 3000 rpm for four minutes. Thereafter, sheets with the grammage of 60 g/m were made from the foam with a hand mould according to the standard SCAN-C 26:2. Scott Bond and tensile strengths were determined with the sheets. The results are shown in Table 4.
  • the surface active agent was the sodium salt of an ethoxylated alkyl sulphate.
  • Example 27 the surface active agent was the sodium salt of the synthesis product

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  • Paper (AREA)

Abstract

L'invention concerne des compositions destinées au traitement de matière fibreuse telle qu'une bande papier, lors de fabrication de papier, en particulier des compositions moussantes contenant des additifs possédant de l'influence sur la résistance du papier. L'invention concerne aussi l'utilisation de composés moussants afin d'améliorer la résistance d'une matière fibreuse. La composition moussante permettant d'influencer la résistance de matière fibreuse comprend une résine, ou un mélange de résines qui peuvent être durcies thermiquement ou au moyen d'un acide, un agent tensioactif, et éventuellement un copolymère acrylamide cationique.
PCT/FI2000/001041 1999-12-08 2000-11-29 Compositions possedant une influence sur la resistance du papier WO2001042564A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU21746/01A AU2174601A (en) 1999-12-08 2000-11-29 Compositions having influence on the strength of paper

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FI992633A FI107951B (fi) 1999-12-08 1999-12-08 Vaahtoavat kuitumateriaalin lujuuteen vaikuttavat koostumukset
FI19992633 1999-12-08

Publications (1)

Publication Number Publication Date
WO2001042564A1 true WO2001042564A1 (fr) 2001-06-14

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Application Number Title Priority Date Filing Date
PCT/FI2000/001041 WO2001042564A1 (fr) 1999-12-08 2000-11-29 Compositions possedant une influence sur la resistance du papier

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AU (1) AU2174601A (fr)
FI (1) FI107951B (fr)
WO (1) WO2001042564A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013160564A1 (fr) * 2012-04-26 2013-10-31 Stora Enso Oyj Nappe fibreuse collée de manière hydrophobe et procédé de préparation d'une couche de nappe collée
US9334610B2 (en) 2012-04-26 2016-05-10 Stora Enso Oyj Fibrous web of paper or board and method of making the same

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0150777A2 (fr) * 1984-01-26 1985-08-07 James River Corporation Of Virginia Procédé pour la fabrication d'un tissu non-tissé fibreux
US4959125A (en) * 1988-12-05 1990-09-25 The Procter & Gamble Company Soft tissue paper containing noncationic surfactant
WO1994001620A1 (fr) * 1992-07-03 1994-01-20 Kaysersberg Procede destine a diminuer l'interaction entre fibres dans un tissu et mise en ×uvre de ce procede, notamment pour fabriquer des tissus multi-strates
US5415798A (en) * 1994-01-14 1995-05-16 Betz Paperchem Inc. Concentrated high flash point surfactant compositions
WO1995021299A1 (fr) * 1994-02-01 1995-08-10 Kaysersberg Procede de fabrication d'une feuille de papier ou de nontisse en milieu mousse, utilisant un agent tensio-actif non-ionique
US5720851A (en) * 1994-07-13 1998-02-24 Sca Hygiene Paper Ab Method and arrangement for producing a foam-formed fibre or paper web

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0150777A2 (fr) * 1984-01-26 1985-08-07 James River Corporation Of Virginia Procédé pour la fabrication d'un tissu non-tissé fibreux
US4959125A (en) * 1988-12-05 1990-09-25 The Procter & Gamble Company Soft tissue paper containing noncationic surfactant
WO1994001620A1 (fr) * 1992-07-03 1994-01-20 Kaysersberg Procede destine a diminuer l'interaction entre fibres dans un tissu et mise en ×uvre de ce procede, notamment pour fabriquer des tissus multi-strates
US5415798A (en) * 1994-01-14 1995-05-16 Betz Paperchem Inc. Concentrated high flash point surfactant compositions
WO1995021299A1 (fr) * 1994-02-01 1995-08-10 Kaysersberg Procede de fabrication d'une feuille de papier ou de nontisse en milieu mousse, utilisant un agent tensio-actif non-ionique
US5720851A (en) * 1994-07-13 1998-02-24 Sca Hygiene Paper Ab Method and arrangement for producing a foam-formed fibre or paper web

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013160564A1 (fr) * 2012-04-26 2013-10-31 Stora Enso Oyj Nappe fibreuse collée de manière hydrophobe et procédé de préparation d'une couche de nappe collée
US9334610B2 (en) 2012-04-26 2016-05-10 Stora Enso Oyj Fibrous web of paper or board and method of making the same
US9663901B2 (en) 2012-04-26 2017-05-30 Stora Enso Oyj Hydrophobically sized fibrous web and a method for the preparation of a sized web layer
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

Also Published As

Publication number Publication date
AU2174601A (en) 2001-06-18
FI107951B (fi) 2001-10-31
FI19992633A (fi) 2001-06-09

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