EP2486189B1 - Verfahren zur herstellung eines auf der oberfläche eines anderen substrats geformten substrats aus siliciumpigmenten - Google Patents

Verfahren zur herstellung eines auf der oberfläche eines anderen substrats geformten substrats aus siliciumpigmenten Download PDF

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Publication number
EP2486189B1
EP2486189B1 EP10822323.1A EP10822323A EP2486189B1 EP 2486189 B1 EP2486189 B1 EP 2486189B1 EP 10822323 A EP10822323 A EP 10822323A EP 2486189 B1 EP2486189 B1 EP 2486189B1
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EP
European Patent Office
Prior art keywords
substrate
silica
water soluble
soluble silicate
solution
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EP10822323.1A
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English (en)
French (fr)
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EP2486189A1 (de
EP2486189A4 (de
Inventor
Philip HÅKANSSON
Kaj Backfolk
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Stora Enso Oyj
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Stora Enso Oyj
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Publication of EP2486189A4 publication Critical patent/EP2486189A4/de
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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
    • D21H19/00—Coated paper; Coating material
    • D21H19/36—Coatings with pigments
    • D21H19/38—Coatings with pigments characterised by the pigments
    • D21H19/40—Coatings with pigments characterised by the pigments siliceous, e.g. clays
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/63—Inorganic compounds
    • D21H17/67—Water-insoluble compounds, e.g. fillers, pigments
    • D21H17/68—Water-insoluble compounds, e.g. fillers, pigments siliceous, e.g. clays
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/63—Inorganic compounds
    • D21H17/70—Inorganic compounds forming new compounds in situ, e.g. within the pulp or paper, by chemical reaction with other substances added separately
    • 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
    • D21H19/00—Coated paper; Coating material
    • D21H19/10—Coatings without pigments
    • D21H19/14—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12
    • D21H19/24—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12 comprising macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H19/32—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12 comprising macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds obtained by reactions forming a linkage containing silicon in the main chain of the macromolecule

Definitions

  • the present invention relates to a process for the production of a substrate comprising silica pigments which is formed on the surface of the substrate.
  • Silica is often used as a pigment during manufacturing of printing paper, especially paper for ink-jet printers or presses.
  • the silica pigments can also be used generally in digital printing techniques, such as electrophotography, liquid toner or thermal inks, but also in impact printing techniques such as offset of flexography. Besides the increased printing properties, silica also improves the optical properties of a paper or paperboard.
  • Silica pigments can be produced in a number of different ways.
  • One way is to treat sodium silicate (waterglass) with a pH reducing medium which will result in the formation of silica pigments.
  • Other methods can for example be dialysis, electrodialysis, peptization, acid neutralization and ion-exchange.
  • Silica pigments used in paper applications, often have high surface area either because of small particle size or high porosity.
  • One effect of high surface area of such pigments is that they are able to bind a lot of water.
  • conventional pigments such as calcium carbonate, kaolin or talcum
  • high surface area silica pigment dispersions therefore requires special attention in order to achieve high solid content coating or surface treatment dispersions.
  • Increasing the dry content of a dispersion comprising silica pigments through the addition of stabilizers and/or thickening agents will partly provide steric or electrosteric stability to the dispersion, but the final dry content is still significantly lower than what is obtained for standard pigment coating formulations.
  • binders secures that the pigments binds to each other and to the fibers, which hence improves surface strength and e.g. decrease problems with dusting.
  • problems with rheology can occur during the transfer process of the mixture of stabilizer, binder and silica pigments to a surface of the paper.
  • the dry content of the composition need to be decreased and the dry content of compositions comprising silica pigments is thus quite low which reduces the production rate and increases the water content applied to the paper. As a consequent, the paper must be exposed to immense heat treatment in order for the paper to dry.
  • cationic polymers prevent, for example so called bleeding of the print if it is exposed to water or feathering or wicking which might occur along the fibers.
  • anionic silica pigments problems with high viscosity and precipitations often occur.
  • silica pigments of today are its current cost structure. It is normally very expensive to buy produced silica pigments since the manufacturing process and drying of the pigments in order to make them usable in the paper mills are very energy demanding. Also, it is quite complicated to store and handle the produced silica pigments at the paper mills. Since silica pigments are porous their volume is often quite big and they thus take up a lot of room. As an alternative, the silica pigments can be transported as a solution to the mills but this is also expensive since the dry content of a silica solution, need to be quite low in order for the solution to be stable, i.e. a lot of water also needs to be transported.
  • US 25 688 50 discloses a fire resistive vapour barrier paper which comprises a flexible paper sheet coated on at least one surface thereof with coating having a base which consists of bitumen and water-soluble alkali metal silicate.
  • US 30 85 861 discloses a method of preparing finely divided precipitated siliceous pigment from a water-soluble alkali mebal salt.
  • Another object of the invention is to produce a substrate comprising silica pigments in a cost effective way.
  • the present invention describes a process for the production of a substrate wherein the process comprises; providing a substrate comprising cellulosic fibers, applying a solution comprising water soluble silicate to the surface of the substrate and treating the substrate so that the water soluble silicate is polymerized forming silica pigments on the surface of the substrate and finally drying the substrate with the formed silica pigments on the surface.
  • the water soluble silicate is preferable an alkali metal silicate or a silicic acid.
  • the polymerization and/or precipitation of the water soluble silicate may occur by addition of a pH altering medium or by the aid of ion-exchange.
  • Other known methods for the polymerization and formation of silica pigments to occur such as dialysis or electrodialys, may also be used. It is important that the polymerization and formation of silica pigment occur on the surface of the substrate. Therefore, the treatment of the water soluble silicate much be done so that that the silica pigments are polymerized and formed on the surface.
  • the substrate may be treated by addition of a pH altering medium to the surface of the substrate in order for the silica pigments to polymerize and form on the surface of the substrate.
  • the pH altering medium may be a pH reducing or pH increasing medium.
  • the reaction in which silica pigments are formed is a well know reaction of water soluble silicate, preferable alkali metal silicate or silicic acid, at a reduced or increased pH. It is preferred that the solution comprises alkali metal silicate and that a pH reducing medium is added to the surface of the substrate so that silica pigments are formed on the surface of the substrate. It is also possible that the reaction in which silica pigments are formed is a reaction of silicic acid at an increased or reduced pH.
  • silica pigments By separately adding a solution comprising water soluble silicate and a pH altering medium to a surface of a substrate, it is possible to produce silica pigments directly on the surface of the substrate and thus to avoid the disadvantages mentioned above with the production, such as compatibility and runnability, transportation and storage of the silica pigments.
  • a reaction in which silica pigments are formed will occur.
  • the reaction will either occur during the addition of the pH altering medium and the solution comprising water soluble silicate to the surface or after the addition of the pH altering medium and the solution comprising water soluble silicate to the surface of the substrate.
  • the pH reducing medium may be an inorganic or organic acid such as sulfuric acid, hydrochloride acid or acetic acid, acid salts, pigments or gases.
  • Other examples of pH reducing mediums are sodium orthoborate (borax), sodium bisulfite, sodium bicarbonate, sodium dihydrogen phosphate, carbon dioxide or a combination of two or more of these substances.
  • Acid salts of weak bases and strong acids such as ammonium sulfate, aluminum sulfate, polyaluminum chloride (PAC), polyaluminum nitrate (PAN) and the like may also be used alone or in combination with any of the substances mentioned above.
  • the pH increasing medium may be an alkaline solution such as sodium hydroxide or calcium hydroxide.
  • silica pigments such as silica gel, precipitated silica and colloidal silica
  • the type of silica pigment formed depends on the pH during the reaction.
  • the specific type of silica formed on the surface of the substrate may be controlled by the amount and concentration of the pH altering medium added.
  • the pH during the reaction in which silica is formed may be basic, neutral or even acid. If a pH reducing medium is added, the reaction will occur when the pH is reduced but it is not always necessary to neutralize the pH of the solution comprising water soluble silicate or to make it acid, even though it sometimes is preferred.
  • different type of silica pigments are formed. If for example polyaluminum chloride is used, an aluminum silicate is produced.
  • alkali metal silicates such as sodium silicate (waterglass), or silicic acid being preferred.
  • the solution comprising water soluble silicate may first be added to the surface of the substrate followed by the pH altering medium. It is also possible to first add the pH altering medium to the surface of the substrate followed by the solution comprising water soluble silicate. The reaction in which silica is formed will thus occur after the addition of the solutions to the surface of the substrate.
  • the pH altering medium and the solution comprising water soluble silicate are mixed directly before addition to the surface of the substrate.
  • the reaction in which silica is formed will thus occur during the addition, directly before addition or after the addition of the solutions to the surface of the substrate. It is possible that the reaction in which silica pigments is formed are delayed, so even if the solutions are mixed before addition, the reaction can occur on the surface of the substrate.
  • the major part of the silica pigments is formed on the surface of the substrate in order to achieve the advantages mentioned here, especially in order to achieve the increased bonding of the pigments to the fibers.
  • One or several binders may be added to the pH altering medium and/or to the solution comprising water soluble silicate in order to provide surface or internal strength alternatively wet strength to the substrate. It is also possible to add the binder separately, i.e. without mixing it with the pH altering medium or the solution comprising water soluble silicate.
  • Possible binders are starch, sodium carboxymethyl cellulose, hydroxyethyl cellulose, resins, nanocellulose or microfibrillated cellulose, protein, polyvinylalcohol-polyvinyl acetate, acrylate based polymers, guar gum, polyvinyl alcohol (PVOH), polyvinyl acetate (PVA), styrene acrylate, styrene butadiene or mixtures of these substances.
  • Other binders or rheology modifying agents can also be used.
  • additives can also be added either to the pH altering medium and/or to the solution comprising water soluble silicate.
  • Example of such additives are optical brightening agents (OBA), calcium chloride, cationic polymers, organic or inorganic pigments, crosslinkers, humidfiers, fibers, primers, hydrophobic agents, biocides or lubricants.
  • the application of the solution comprising water soluble silicate and the pH altering medium to the surface of the substrate can be done in a number of different ways. Examples of possible methods are; by the aid of rolls in combination of one or several film presses, with the aid of spray nozzles positioned in one or several lines across the substrate, with spray nozzles adapted for dosage of at least two components, with the aid of curtain coaters or with a combination of any of these methods. If a curtain coater is used, it is possible that two or more curtains origin from the same coater if both a solution comprising water soluble silicate and a pH altering medium is added, so that the solution comprising water soluble silicate is added through one curtain and the pH altering medium through another.
  • the application of the solution comprising water soluble silicate and the pH altering medium can further be made by use of a sheet or web-fed printing or converting machine.
  • An offset, flexographic or an inkjet printing press can for instance first print the solution comprising water soluble silicate and then transfer the pH altering medium to the surface and thus create wet on wet application step before either applying a third layer without or with intermediate drying.
  • pH altering medium and the solution comprising water soluble silicate are mixed directly before the addition to the surface of the substrate it is preferred that the mixing is done in a spray nozzle or on a roll which then transfers the formed silica to the substrate.
  • the amount of silica pigments of the substrate depends on the end use of the final product produced. If the final product is a fine paper used for printing, the silica content may preferable be between 0,1-10 g/m2 per side. However, if it is a medium to high quality ink-jet printing paper the silica content is preferable higher.
  • the concentration of water soluble silicate in the solution which is added to the substrate is regulated in such a way that the amount of silica on the surface of the substrate is within the desired range, i.e.
  • the concentration of the water soluble silicate in the solution and the amount of solution added is regulated so that the amount of silica on the surface is within the desired range.
  • the concentration of the pH altering medium might also be regulated in order to adjust and improve certain functional properties of the paper such as static electricity, ink setting mechanisms or de-inkability.
  • An advantage with the present invention is that the dry content of the added solution can be increased compared to if silica pigments were directly added to the surface of the substrate as described in prior art. Since the solution comprising water soluble silicate and the pH altering medium is separately added to the surface of the substrate the problems as previously described with a solution comprising silica pigments are avoided and it is thus possible to increase the total dry content of the added solutions. Consequently, less water is added to the substrate and the drying demands are decreased.
  • the silica pigments will bond stronger to the fibers and the amount of binders can possible be reduced without decreasing the quality of the substrate. Since the solution comprising water soluble silicate is added directly to the surface of the substrate the solution will partly be absorbed by the fibers on the surface of the substrate and the formed silica pigment will thus partly be incorporated into the fiber structure of the surface of the substrate which increases the bond between the silica pigments and the substrate.
  • a substrate comprising more than one layer of silica pigments on the surface. This can for example be done by addition of a second solution comprising water soluble silicate and a second pH altering medium. It is also possible to produce more than two layers of silica, such as three, four, five or more in the same manner.
  • An additional advantage with the process according to the invention is that it is also possible to add a cationic polymer to the surface of the substrate without the disadvantages mentioned above. Since the formation of the anionic silica particles occur on the surface of the substrate there is no mixing of the anionic silica particles and the cationic polymers before addition of the components to the surface of the substrate. Consequently, the anionic silica particles and the cationic polymers will thus not be able to react and form the mentioned precipitations.
  • cationic polymers are cationic starches, cationic guars and cationic polyacrylamides, the application of which to papermaking have all been described in the prior art.
  • Other cationic polymers may also be used in combination with the silica pigments, either alone or in addition to the cationic starches, cationic guars and cationic polyacrylamides.
  • cationic polymers examples include polyethyleneimine, polydiallyldimethylammonium chloride, copolymers of acrylamide with 2-methylacryloxyethyltrimethyl ammonium chloride, amine-epichlorohydrin condensation products and cationic wet strength resins obtained by condensing polyamines with dicarboxylic acids and then further reacting the prepolymer with epichlorohydrin.
  • Cationic starches are particularly useful in that they have the advantages of low cost and of imparting dry strength to the paper.
  • the cationic starch used may be derived from any of the common starch producing materials such as corn starch, potato starch, wheat starch and tapioca starch although the potato starches usually yield the most desirable cationized products.
  • the disadvantages mention above can be avoided and the production cost for a substrate, especially an ink-jet printing paper, is strongly reduced.
  • the energy demand for the production of a substrate comprising silica pigments according to the invention is reduced since there is no need for drying or pretreatment of the silica pigments in order for them to be stable enough to transportation to the site of usage (often from the producer to the customer's mill).
  • the energy demand for the production of a substrate according to the invention is decreased since it is possible to increase the dry content of the solutions added to the surface.
  • the substrate is dried after the addition of the pH altering medium and/or the solution comprising water soluble silicate in order for a dried substrate to form.
  • All known processes for drying cellulosic substrates may be used. Since the temperature especially of the surface of the substrate is increased during drying, the reaction in which silica pigments is formed may be accelerated during the drying of the substrate. Thus, the silica pigments may be formed during the drying of the substrate.
  • the substrate according to the invention will show improved bond between the fibers and the formed silica pigments. Furthermore, the substrate comprises salts which are formed during the production of silica pigments. It is preferred that the substrate is a printing substrate of paper or paperboard which will be printed in a subsequent printing process.
  • substrate means to also include but not being limited to a paper or paperboard comprising cellulosic fibers.
  • Other materials suitable for printing are also included, such as plastics, polymer coated paper or paperboard, textiles etc. It may also be possible to provide substrates which will be used as flame retardants with silica pigments, i.e. flame retardant substrates.
  • the substrate comprises cellulosic fibers and by this, not only cellulosic fibers but all components which origins from cellulosic fibers are included. Examples of such components are microfibrillated cellulose (nanocellulose) or regenerated cellulose.
  • the cellulosic fibers may be softwood and/or hardwood fibers.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Paper (AREA)
  • Silicon Compounds (AREA)
  • Pigments, Carbon Blacks, Or Wood Stains (AREA)

Claims (9)

  1. Verfahren zur Herstellung eines Substrats, wobei das Verfahren die folgenden Schritte umfasst:
    - bereitstellen eines Substrats umfassend Zellulosefasern,
    - aufbringen einer wasserlösliches Substrat umfassenden Lösung auf die Oberfläche des Substrats,
    - behandlung des Substrats auf solche Weise, dass das wasserlösliche Silikat polymerisiert wird, wobei sich auf der Oberfläche des Substrats Silikapigmente bilden,
    - trocknen des Substrats.
  2. Verfahren nach Anspruch 1, wobei es sich bei dem wasserlöslichen Silikat um Alkalimetallsilikat oder Kieselsäure handelt.
  3. Verfahren nach einem der vorhergehenden Ansprüche, wobei das Substrat durch Zugabe eines pH-Wert-verändernden Mediums auf die Oberfläche des Substrats behandelt wird.
  4. Verfahren nach Anspruch 3, wobei das pH-Wert-verändernde Medium ein pH-Wert-reduzierendes Medium ist.
  5. Verfahren nach Anspruch 4, wobei das pH-Wert-reduzierende Medium eine anorganische oder organische Säure, ein saures Metallsalz oder ein Gas oder eine Kombination von zwei oder mehreren dieser Substanzen ist.
  6. Verfahren nach einem der Ansprüche 3-5, wobei die wasserlösliches Silikat umfassende Lösung auf die Oberfläche des Substrats aufgebracht wird, gefolgt von der Zugabe des pH-Wert-verändernden Mediums.
  7. Verfahren nach einem der vorherigen Ansprüche, wobei ein kationisches Polymer zusätzlich auf die Oberfläche des Substrats aufgebracht wird.
  8. Substrat, das in einem Verfahren nach einem der Ansprüche 1-7 hergestellt wurde.
  9. Substrat nach Anspruch 8, wobei das Substrat ein Drucksubstrat ist.
EP10822323.1A 2009-10-09 2010-10-05 Verfahren zur herstellung eines auf der oberfläche eines anderen substrats geformten substrats aus siliciumpigmenten Active EP2486189B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
SE0950745A SE534210C2 (sv) 2009-10-09 2009-10-09 Process för tillverkning av ett substrat innehållande kiseldioxidpigment som bildas på ytan av substratet
PCT/SE2010/051074 WO2011043725A1 (en) 2009-10-09 2010-10-05 A process for the production of a substrate comprising silica pigments which is formed on the surface of the substrate

Publications (3)

Publication Number Publication Date
EP2486189A1 EP2486189A1 (de) 2012-08-15
EP2486189A4 EP2486189A4 (de) 2014-01-22
EP2486189B1 true EP2486189B1 (de) 2014-12-10

Family

ID=43857005

Family Applications (1)

Application Number Title Priority Date Filing Date
EP10822323.1A Active EP2486189B1 (de) 2009-10-09 2010-10-05 Verfahren zur herstellung eines auf der oberfläche eines anderen substrats geformten substrats aus siliciumpigmenten

Country Status (6)

Country Link
EP (1) EP2486189B1 (de)
CN (1) CN102686801B (de)
BR (1) BR112012008197A2 (de)
PT (1) PT2486189E (de)
SE (1) SE534210C2 (de)
WO (1) WO2011043725A1 (de)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
SE537737C2 (sv) * 2013-03-01 2015-10-06 Stora Enso Oyj In-Line-framställning av kiseldioxid för retentionsändamål ien pappers- eller kartongtillverkningsprocess
SE543549C2 (en) * 2018-03-02 2021-03-23 Stora Enso Oyj Method for manufacturing a composition comprising microfibrillated cellulose
DE102018124255A1 (de) * 2018-10-01 2020-04-02 Technische Universität Darmstadt Faservliese mit asymmetrischer Silica-Imprägnierung und Verfahren zur Herstellung der Vliese sowie deren Verwendungen

Family Cites Families (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2383653A (en) * 1941-06-04 1945-08-28 Du Pont Silicic acid sols
US2568850A (en) * 1951-04-11 1951-09-25 Carey Philip Mfg Co Vapor barrier paper and the manufacture thereof
US3085861A (en) * 1955-04-08 1963-04-16 Pittsburgh Plate Glass Co Preparation of siliceous pigment
NL128891C (de) * 1959-05-05
ES361856A1 (es) * 1968-04-06 1970-11-16 Roehm & Haas Gmbh Procedimiento para el revestimiento de papel y configura- ciones superficiales textiles.
US3928540A (en) * 1971-07-26 1975-12-23 Ppg Industries Inc Process for preparing silica pigment
US4554181A (en) * 1984-05-07 1985-11-19 The Mead Corporation Ink jet recording sheet having a bicomponent cationic recording surface
JPS61287447A (ja) * 1985-06-11 1986-12-17 Nippon Shokubai Kagaku Kogyo Co Ltd 耐熱性触媒担体組成物の製造法
JPS61287477A (ja) * 1985-06-13 1986-12-17 Inax Corp 無機質塗膜の形成方法
US4816074A (en) * 1985-07-12 1989-03-28 E.C.C. America Inc. Kaolinite aggregation using sodium silicate
AU603115B2 (en) * 1986-06-17 1990-11-08 J.M. Huber Corporation Synthetic alkali metal alumino-silicates, methods and uses, compositions and their methods of preparation
AU700330B2 (en) * 1995-03-31 1998-12-24 Nippon Paper Industries Co. Ltd. Recording paper
GB0410749D0 (en) * 2004-05-14 2004-06-16 Dow Corning Ireland Ltd Coating apparatus
FR2872180A1 (fr) * 2004-06-24 2005-12-30 Arjowiggins Papiers Couches So Papier revetu d'une composition pigmentee comportant de la silice imprimable par offset

Also Published As

Publication number Publication date
CN102686801A (zh) 2012-09-19
SE0950745A1 (sv) 2011-04-10
CN102686801B (zh) 2015-07-01
SE534210C2 (sv) 2011-05-31
BR112012008197A2 (pt) 2016-04-12
PT2486189E (pt) 2015-03-09
EP2486189A1 (de) 2012-08-15
EP2486189A4 (de) 2014-01-22
WO2011043725A1 (en) 2011-04-14

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