EP2625337B1 - Surface treatment composition and paper or paperboard comprising a surface treatment composition - Google Patents

Surface treatment composition and paper or paperboard comprising a surface treatment composition Download PDF

Info

Publication number
EP2625337B1
EP2625337B1 EP11831005.1A EP11831005A EP2625337B1 EP 2625337 B1 EP2625337 B1 EP 2625337B1 EP 11831005 A EP11831005 A EP 11831005A EP 2625337 B1 EP2625337 B1 EP 2625337B1
Authority
EP
European Patent Office
Prior art keywords
starch
composition
salt
paper
paperboard
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
EP11831005.1A
Other languages
German (de)
French (fr)
Other versions
EP2625337A1 (en
EP2625337A4 (en
Inventor
Philip Hakansson
Kaj Backfolk
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Stora Enso AB
Original Assignee
Stora Enso AB
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Stora Enso AB filed Critical Stora Enso AB
Publication of EP2625337A1 publication Critical patent/EP2625337A1/en
Publication of EP2625337A4 publication Critical patent/EP2625337A4/en
Application granted granted Critical
Publication of EP2625337B1 publication Critical patent/EP2625337B1/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/21—Macromolecular organic compounds of natural origin; Derivatives thereof
    • D21H17/24—Polysaccharides
    • D21H17/28—Starch
    • 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
    • D21H17/66—Salts, e.g. alums
    • 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
    • D21H19/44—Coatings with pigments characterised by the other ingredients, e.g. the binder or dispersing agent
    • D21H19/54—Starch
    • 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
    • D21H21/16—Sizing or water-repelling 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
    • 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
    • D21H21/52—Additives of definite length or shape
    • D21H21/54—Additives of definite length or shape being spherical, e.g. microcapsules, beads
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/0011—Pre-treatment or treatment during printing of the recording material, e.g. heating, irradiating
    • B41M5/0017—Application of ink-fixing material, e.g. mordant, precipitating agent, on the substrate prior to printing, e.g. by ink-jet printing, coating or spraying
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
    • B41M5/52—Macromolecular coatings
    • B41M5/5218—Macromolecular coatings characterised by inorganic additives, e.g. pigments, clays
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
    • B41M5/52—Macromolecular coatings
    • B41M5/5236—Macromolecular coatings characterised by the use of natural gums, of proteins, e.g. gelatins, or of macromolecular carbohydrates, e.g. cellulose

Definitions

  • the present invention relates to a surface treatment composition comprising starch particles, intended for the coating or surface sizing of paper, paperboard or other fibrous webs.
  • the invention also relates a paper or paperboard comprising said composition.
  • the predominant part of all paper and paperboard that is to be used in copying machines, laser printers, inkjet printers and other different printing methods such as offset printing and flexoprinting, is surface treated with some sort of composition in order to improve printability as well as other properties of the paper or paperboard.
  • the composition is often either a surface sizing composition or a coating color.
  • the surface treatment composition is called a surface sizing. If the composition contains some sort of pigment in the form of solid particles, the composition is called a pigmentation composition or a coating color.
  • Surface sizing compositions mainly consists of modified starches or other hydrocolloids or surface sizing agents. Furthermore, surface sizing improves the surface strength and printability of the paper or paperboard surface.
  • compositions containing pigments are most often used to improve the printability of the paper.
  • smoothness of the surface of the paper or board is improvement and the control of printing ink absorption can be improved.
  • the colorant of the ink should mainly be absorbed on the surface of the paper and the solvent of the ink should be penetrated into the paper. To these advantages may be added that the paper exhibits an improved "feeling".
  • a conventional coating color usually contains an inorganic pigment that most often consists of calcium carbonate and/or clay.
  • Other pigments exist too, such as e.g. silicon dioxide and in rare occasions, organic pigments such as plastic pigments.
  • the paste also contains a binding agent that can consist of dissolved starch and/or a synthetic binding agent. Examples of common synthetic binding agents are styrene butadiene latex and acrylate latex.
  • Multivalent cations e.g. calcium
  • sizing or coating compositions in the form of lubricants, e.g. calcium stearate.
  • concentration of calcium, in e.g. calcium stearate is not high enough to give rise to the desired effects on the print quality. Therefore, the calcium amounts needs to be higher than traditionally used in such products.
  • multivalent salts to coating and/or sizing compositions
  • the high concentration of salt needed in order to achieve the desired effects oftentimes causes rheology problems and undesired precipitations.
  • This is especially a problem when high amounts, such as 1-5 parts of salt, is added to anionically charged sizing, pigmentation or coating compositions.
  • Multivalent cations interact strongly with typical anionic-charged polymers or minerals, or additives which are used in papermaking. Improvement in calcium stability of anionically charged particles can e.g. be improved by providing steric or electrosteric stability. However, high amounts of electrolytes may cause colloidal flocculation and precipitation.
  • Ink-jet printing can be done with different types of inks, either dye-based inks, pigment based inks or inks based on the combination of pigment and dye.
  • Starch especially cross-linked starch, improves the printing properties of a paper or paperboard when printed with dye-based inks.
  • Cross-linked starch used as a surface treating composition is described in for example WO03021039 .
  • the printing properties for pigment based inks improves by the presence of metal salts.
  • additives such as salts of multivalent metals
  • the present invention relates to a surface treatment composition for paper, paperboard or other fibrous webs wherein the composition comprises starch particles that comprise at least one salt.
  • the at least one salt is incorporated in the starch particle. In this way it is possible to increase the amount of salt added to a surface treatment composition and also to the surface of a paper or paperboard.
  • the at least one salt is a salt of a multivalent metal, such as a divalent or trivalent metal.
  • the salt is preferably a calcium, magnesium or aluminum salt, preferably calcium chloride or polyaluminum chloride.
  • the starch is preferably cross-linked starch.
  • cross-linked starch in a surface treatment composition it is possible to subject the composition and/or the starch to elevated temperature without dissolving the entire amount of starch particles. In this way the starch particles tend to stay on the surface of a treated paper or paperboard and thus not being absorbed into the paper or paperboard. This improves the printing properties of the paper or paperboard.
  • Another advantage with the cross-linked starch is that the absorption of the printed ink is improved. It is important that the colorant of the ink is absorbed and mainly kept on the surface of the paper and that the solvent, i.e. water or ink solvent, is quickly released by the composition and absorbed by the paper.
  • the composition Due to the improved absorption of the composition it is also possible increase the amount of ink added to the paper or paperboard.
  • the paper or paperboard is thus not as sensitive to large amount of ink, which makes it possible to improve the printing quality of prints demanding high amounts of ink, such as pictures. Also, some solvent of inks demands cross-linked polymers in order to work properly.
  • the starch is preferably cross-linked by one or more compounds chosen from the group that consists of methylamine compounds, polyvalent acids, polyvalent acid esters, polyvalent acid halides, polyvalent acid anhydrides, polyaldehydes, polyepoxides, polyisocyanates, divinyl compounds, phosphoryl chloride, polyamine polyepoxide resin, 1,4-butane diolglycidyl ether, epichlorohydrin, trimetaphosphates, mixtures of anhydrides of acetic acid and two and three protonic acids, sodium hypochlorite, or mixtures thereof.
  • the composition comprises starch particles in an amount of more than 65% by weight, and at least 10% by weight of the starch in the composition consists of starch particles in the entire temperature range of 20-50°C. Both bulk and stiffness of the treated paper or paperboard is improved when starch in the form of particles is present in the composition.
  • the ratio between the salt and starch of the composition is between 1:50 to 1:5. There is an optimal amount of both starch and salt in the composition. More or less starch respectively salt will deteriorate ink-jet printing properties of the paper or paperboard.
  • the composition preferably comprises dissolved starch.
  • the dissolved starch will work as a binder of the composition.
  • composition may also comprise an additive, preferably an anionic or amphoteric additive which will modify the starch particles. In this way it is possible to alter the charge of the particles making them more stable or more compatible to other additives or to the fibers.
  • an additive preferably an anionic or amphoteric additive which will modify the starch particles. In this way it is possible to alter the charge of the particles making them more stable or more compatible to other additives or to the fibers.
  • the invention also relates to a paper or paperboard product comprising a surface layer of a surface treatment composition as described herein.
  • the surface-treatment composition of the present invention comprises starch particles encapsulating at least one salt.
  • the salt can be said to be trapped in the starch particle.
  • the use of such particles in a surface treatment composition increases the printing properties of both dye based and pigment based inks. Also, such composition decreases rheology and viscosity problems that are connected with prior art compositions comprising as high concentrations of salt as the inventive composition. Consequently, higher concentrations of the salts in a surface treatment composition may be used without causing rheology or viscosity problems.
  • the surface treatment composition according to the invention By addition of the surface treatment composition according to the invention to a surface of a paper or paperboard, it is possible to increase the amount of salt on the surface of the paper or paperboard at the same time as the amount of salt, seeing to the entire paper or paperboard, is decreased compared to prior art solutions. This is due to that the surface treatment composition and thus also the salt of the composition is, to a larger extent, retained on the surface of the paper or paperboard. The added salt is thus not absorbed into the paper or paperboard making it possible to decrease the amount of salt added in order to achieve the desired amount of salt on the surface and thus also good printing properties.
  • Another advantage with the present surface treatment composition is that it improves the printing properties of a paper or boards since the colorant of the ink which is printed is absorbed on the surface and thus not absorbed by the treated paper or paperboard.
  • the cross-linked starch will absorb the ink and since the starch is added and retained on the surface of a paper or paperboard the ink is thus also retained on the surface and not absorbed further into the paper or paperboard.
  • the ink will also come in contact with the incorporated salt since the starch particle will absorb the ink and the ink will thus get in contact with the salt within the starch particle. This also improves the printability since the ink is absorbed on the surface of the paper or paperboard.
  • the surface treatment composition is suitable for both dye based and pigment based inks.
  • the composition preferably also comprises dissolved starch.
  • the dissolved starch will work as a binder.
  • the composition will also comprise dissolved salt that is released when the starch is dissolved.
  • the dissolved salt will improve the printing properties of a treated paper or paperboard in the same way as metal salts used in prior art, i.e. when salt is added as a separate component to a paper or paperboard surface.
  • the dissolved salt will also decrease the viscosity of the composition which makes it possible to increase the dry content of the composition.
  • the surface treatment composition can be seen as both a surface sizing composition and a coating color.
  • the surface treatment composition according to the invention preferably comprises both dissolved starch as well as starch particles. Consequently, the composition gives both sizing and coating properties to the treated paper or paperboard.
  • the salt is a salt of a multivalent metal, such as a divalent or trivalent metal salt, for example calcium, magnesium or aluminum salt, which is added. It is preferred to use calcium chloride or polyaluminium chloride.
  • Use of particles comprising multivalent metals salts according to the invention render it possible to dose a higher concentration of multivalent metals salt to a sizing or a coating composition without effecting the rheology of the composition negatively. In this way, the printability of the sized or coated paper or board can be improved.
  • use of the particles according to the invention also reduces the concentration of the free anion of the multivalent salt, e.g. a chloride ion, in the composition whereby the risk of corrosion is reduced.
  • the starch particle is preferably cross-linked.
  • the dry starch particles is preferably of a size of between 1-1000 ⁇ m, even more preferably between 1-100 pm. It is preferred that the starch particle is a cross-linked starch gel. At none or a very low degree of cross-linking, the starch dissolves if a starch slurry is heated. At an increased degree of cross-linking the amount of the starch that dissolves decreases.
  • the starch used in the invention may have very different degrees of cross-linking.
  • the composition may also contain other types of soluble starch or some synthetic polymer, in order to obtain an adequate amount of binder and further improved printability properties.
  • polymers are styrene-acrylate, styrene maleic acid anhydride, polyvinylalcohol, polyvinylpyrrolidon, polyvinylformamide.
  • the starch may also be cross-linked fragmented starch.
  • the starch is preferably based on potato, maize, wheat, waxy maize, rice or tapioca.
  • the starch may be non-ionic or ionic for example anionic, cationic or amphoteric.
  • the starch may be additionally modified.
  • the starch may be modified to act as cation active, anion active, amphoteric or hydrophobic.
  • Cationic cross-linked starch may react better with dye-based inks which is anionic.
  • the starch exhibits a degree of substitution of 0.01 - 0.30 and even more preferred 0.02 - 0.20. Uncharged starch too may however work according to the invention.
  • the surface treatment composition may also comprise a minor amount of other pigments in the form of solid particles.
  • pigments may e.g. be constituted by calcium carbonate, clay, silicon dioxide and/or aluminum oxide. It is however also conceivable, and in many cases preferable, that the solid content of the composition is essentially only constituted by the inventive starch particles.
  • the composition may also comprise surfactants.
  • the composition may also comprise an additive, preferably a charged additive which makes it possible to alter the charge of the starch particle in a desired way.
  • the additive may preferably be anionic or amphoteric. By the addition of the additive to the composition comprising starch particles the particles will be modified. It is thus possible to modify the starch particles in order to make them more stable, make them more compatible with the fibers or with other components normally used in papermaking.
  • the additive may preferably be carboxymethyl cellulose (CMC), polyvinyl alcohol, anionic galactoglucomannan, anionic starch, polyphosphoric acid, alginate polyacrylic acid, protein, anionic polyacryl amide, anionic silica, papermakers alum and polymethacrylic acid.
  • the composition according to the invention also improves brightness, opacity, bulk, surface smoothness and air resistance of a sized or coated paper or paperboard.
  • the starch particles of the surface treatment composition are amorphous and that they thereby have a much larger specific surface than conventional pigments.
  • the high specific surface of the composition is probably also the reason for the improved printing properties of the paper when inkjet printers are used as the absorption of ink into the paper is improved due to an increased number capillaries having a smaller radius. This large surface also advantageously absorbs printing ink in offset printing.
  • the starch particles even if being non gelatinised, exhibit an advantageously sticky surface.
  • the invention further relates to a paper or paperboard product comprising the surface treatment composition described above.
  • the paper or paperboard is especially suitable for printing with flexographic or digital printing techniques, such as inkjet, electrophotography, liquid toner or electrostatic printing.
  • An big advantage with the composition according to the invention is that it can be used for both dye-based and pigment based inks.
  • it is suitable for hybrid printed products, in which one of the printing methods is based on pigmented water based inkjet inks.
  • the invention is also applicable for hybrid inks, which here relates to inks containing both dye and pigment particles.
  • the addition of the surface treatment composition to a surface of a paper or paperboard may take place in any conventional way. It is for example possible to transfer the composition to the surface by rod coating, blade coating, fountain coating, spray coating or other known coating techniques.
  • the salt may be incorporated in the starch particle in several different ways.
  • the salt may be incorporated in the starch particles before or after the cross-linking of the starch. If cross-linked fragmented starch is used, the salt may be incorporated before or after the fragmentation of the starch.
  • cross-linked starch particles alternatively cross-linked fragmented starch may be added to a solution comprising dissolved salt.
  • the starch particle will swell in the solution and dissolved salt is thus absorbed and thus incorporated by the starch particles forming the particles according to the invention.
  • the salt can thus be added in liquid or solid state just before the extruder which is used for the production of cross-linked starch. If necessary, the pressure and/or temperature is raised during the extrusion.
  • a third way to incorporate the salt in the starch particles is to add the salt to a starch slurry and treated in a jet cooker.
  • a jet cooker the temperature and pressure is raised by adding direct steam into the cooker.
  • starch particles comprising salt is formed.
  • the invention may beneficially be used for papers of different types, such as paper for inkjet printers, envelope paper, copying paper, paper for laser printers or other types of paper or paperboard. It is also possible to add the composition to a non-fibrous material, such as a biopolymer film preferably located on the surface of a fibrous material.
  • a non-fibrous material such as a biopolymer film preferably located on the surface of a fibrous material.

Description

    TECHNICAL FIELD
  • The present invention relates to a surface treatment composition comprising starch particles, intended for the coating or surface sizing of paper, paperboard or other fibrous webs. The invention also relates a paper or paperboard comprising said composition.
    • BACKGROUND OF THE INVENTION
  • The predominant part of all paper and paperboard that is to be used in copying machines, laser printers, inkjet printers and other different printing methods such as offset printing and flexoprinting, is surface treated with some sort of composition in order to improve printability as well as other properties of the paper or paperboard. The composition is often either a surface sizing composition or a coating color.
  • If the composition mainly comprises starch in a dissolved form, the surface treatment composition is called a surface sizing. If the composition contains some sort of pigment in the form of solid particles, the composition is called a pigmentation composition or a coating color.
  • Surface sizing compositions mainly consists of modified starches or other hydrocolloids or surface sizing agents. Furthermore, surface sizing improves the surface strength and printability of the paper or paperboard surface.
  • Compositions containing pigments, i.e. pigmentation compositions or coating colors, are most often used to improve the printability of the paper. Moreover, the smoothness of the surface of the paper or board is improvement and the control of printing ink absorption can be improved. The colorant of the ink should mainly be absorbed on the surface of the paper and the solvent of the ink should be penetrated into the paper. To these advantages may be added that the paper exhibits an improved "feeling".
  • A conventional coating color usually contains an inorganic pigment that most often consists of calcium carbonate and/or clay. Other pigments exist too, such as e.g. silicon dioxide and in rare occasions, organic pigments such as plastic pigments. Besides plastic pigments, the paste also contains a binding agent that can consist of dissolved starch and/or a synthetic binding agent. Examples of common synthetic binding agents are styrene butadiene latex and acrylate latex.
  • Inkjet printing, puts high demands on a printing paper, since the ink must be quickly dried on the substrate and yet provide a high print quality with, e.g. a high optical print density, minimized feathering and bleeding and low strike-through. In recent years it has been found that when multivalent salts, such as calcium chloride, are added to the surface size, the applied ink will precipitate fast on the surface of the paper and give rise to a significant improvement in print quality. This is especially advantageous in inkjet printing. US6207258 discloses a composition useful for surface treating a sheet substrate for inkjet printing, the composition comprising a salt of a divalent metal.
  • Multivalent cations, e.g. calcium, are sometimes added to sizing or coating compositions in the form of lubricants, e.g. calcium stearate. However, the concentration of calcium, in e.g. calcium stearate is not high enough to give rise to the desired effects on the print quality. Therefore, the calcium amounts needs to be higher than traditionally used in such products.
  • One problem with the addition multivalent salts to coating and/or sizing compositions is that the high concentration of salt needed in order to achieve the desired effects oftentimes causes rheology problems and undesired precipitations. This is especially a problem when high amounts, such as 1-5 parts of salt, is added to anionically charged sizing, pigmentation or coating compositions. Multivalent cations interact strongly with typical anionic-charged polymers or minerals, or additives which are used in papermaking. Improvement in calcium stability of anionically charged particles can e.g. be improved by providing steric or electrosteric stability. However, high amounts of electrolytes may cause colloidal flocculation and precipitation.
  • Ink-jet printing can be done with different types of inks, either dye-based inks, pigment based inks or inks based on the combination of pigment and dye. Starch, especially cross-linked starch, improves the printing properties of a paper or paperboard when printed with dye-based inks. Cross-linked starch used as a surface treating composition is described in for example WO03021039 . The printing properties for pigment based inks improves by the presence of metal salts.
  • US2006254738 , US3368987 , JP20000127610 and US2007246179 describes compositions used for treatments of paper or paperboard.
  • It is an object of the present invention to find a solution to the problem of adding additives, such as salts of multivalent metals, to surface sizing and/or coating or pigmentation compositions without disturbing the rheological profile of the composition at the same time as it improves the printing properties of both dye-based and pigment based inks.
    • SUMMARY OF THE INVENTION
  • The above object, and other advantages, is achieved by the surface treatment composition of the present invention.
  • The present invention relates to a surface treatment composition for paper, paperboard or other fibrous webs wherein the composition comprises starch particles that comprise at least one salt.
  • The at least one salt is incorporated in the starch particle. In this way it is possible to increase the amount of salt added to a surface treatment composition and also to the surface of a paper or paperboard.
  • The at least one salt is a salt of a multivalent metal, such as a divalent or trivalent metal. The salt is preferably a calcium, magnesium or aluminum salt, preferably calcium chloride or polyaluminum chloride.
  • The starch is preferably cross-linked starch. By using cross-linked starch in a surface treatment composition it is possible to subject the composition and/or the starch to elevated temperature without dissolving the entire amount of starch particles. In this way the starch particles tend to stay on the surface of a treated paper or paperboard and thus not being absorbed into the paper or paperboard. This improves the printing properties of the paper or paperboard. Another advantage with the cross-linked starch is that the absorption of the printed ink is improved. It is important that the colorant of the ink is absorbed and mainly kept on the surface of the paper and that the solvent, i.e. water or ink solvent, is quickly released by the composition and absorbed by the paper. Due to the improved absorption of the composition it is also possible increase the amount of ink added to the paper or paperboard. The paper or paperboard is thus not as sensitive to large amount of ink, which makes it possible to improve the printing quality of prints demanding high amounts of ink, such as pictures. Also, some solvent of inks demands cross-linked polymers in order to work properly.
  • The starch is preferably cross-linked by one or more compounds chosen from the group that consists of methylamine compounds, polyvalent acids, polyvalent acid esters, polyvalent acid halides, polyvalent acid anhydrides, polyaldehydes, polyepoxides, polyisocyanates, divinyl compounds, phosphoryl chloride, polyamine polyepoxide resin, 1,4-butane diolglycidyl ether, epichlorohydrin, trimetaphosphates, mixtures of anhydrides of acetic acid and two and three protonic acids, sodium hypochlorite, or mixtures thereof.
  • The composition comprises starch particles in an amount of more than 65% by weight, and at least 10% by weight of the starch in the composition consists of starch particles in the entire temperature range of 20-50°C. Both bulk and stiffness of the treated paper or paperboard is improved when starch in the form of particles is present in the composition.
  • The ratio between the salt and starch of the composition is between 1:50 to 1:5. There is an optimal amount of both starch and salt in the composition. More or less starch respectively salt will deteriorate ink-jet printing properties of the paper or paperboard.
  • The composition preferably comprises dissolved starch. The dissolved starch will work as a binder of the composition.
  • The composition may also comprise an additive, preferably an anionic or amphoteric additive which will modify the starch particles. In this way it is possible to alter the charge of the particles making them more stable or more compatible to other additives or to the fibers.
  • The invention also relates to a paper or paperboard product comprising a surface layer of a surface treatment composition as described herein.
    • DETAILED DESCRIPTION OF THE INVENTION
  • The surface-treatment composition of the present invention comprises starch particles encapsulating at least one salt. The salt can be said to be trapped in the starch particle. The use of such particles in a surface treatment composition increases the printing properties of both dye based and pigment based inks. Also, such composition decreases rheology and viscosity problems that are connected with prior art compositions comprising as high concentrations of salt as the inventive composition. Consequently, higher concentrations of the salts in a surface treatment composition may be used without causing rheology or viscosity problems.
  • By addition of the surface treatment composition according to the invention to a surface of a paper or paperboard, it is possible to increase the amount of salt on the surface of the paper or paperboard at the same time as the amount of salt, seeing to the entire paper or paperboard, is decreased compared to prior art solutions. This is due to that the surface treatment composition and thus also the salt of the composition is, to a larger extent, retained on the surface of the paper or paperboard. The added salt is thus not absorbed into the paper or paperboard making it possible to decrease the amount of salt added in order to achieve the desired amount of salt on the surface and thus also good printing properties.
  • Another advantage with the present surface treatment composition is that it improves the printing properties of a paper or boards since the colorant of the ink which is printed is absorbed on the surface and thus not absorbed by the treated paper or paperboard. The cross-linked starch will absorb the ink and since the starch is added and retained on the surface of a paper or paperboard the ink is thus also retained on the surface and not absorbed further into the paper or paperboard. Furthermore, the ink will also come in contact with the incorporated salt since the starch particle will absorb the ink and the ink will thus get in contact with the salt within the starch particle. This also improves the printability since the ink is absorbed on the surface of the paper or paperboard. In this way the surface treatment composition is suitable for both dye based and pigment based inks.
  • The composition preferably also comprises dissolved starch. The dissolved starch will work as a binder. As a consequence of the dissolved starch, the composition will also comprise dissolved salt that is released when the starch is dissolved. The dissolved salt will improve the printing properties of a treated paper or paperboard in the same way as metal salts used in prior art, i.e. when salt is added as a separate component to a paper or paperboard surface. Furthermore, the dissolved salt will also decrease the viscosity of the composition which makes it possible to increase the dry content of the composition.
  • The surface treatment composition can be seen as both a surface sizing composition and a coating color. The surface treatment composition according to the invention preferably comprises both dissolved starch as well as starch particles. Consequently, the composition gives both sizing and coating properties to the treated paper or paperboard.
  • The salt is a salt of a multivalent metal, such as a divalent or trivalent metal salt, for example calcium, magnesium or aluminum salt, which is added. It is preferred to use calcium chloride or polyaluminium chloride. Use of particles comprising multivalent metals salts according to the invention, render it possible to dose a higher concentration of multivalent metals salt to a sizing or a coating composition without effecting the rheology of the composition negatively. In this way, the printability of the sized or coated paper or board can be improved. Moreover, use of the particles according to the invention also reduces the concentration of the free anion of the multivalent salt, e.g. a chloride ion, in the composition whereby the risk of corrosion is reduced.
  • The starch particle is preferably cross-linked. The dry starch particles is preferably of a size of between 1-1000 µm, even more preferably between 1-100 pm. It is preferred that the starch particle is a cross-linked starch gel. At none or a very low degree of cross-linking, the starch dissolves if a starch slurry is heated. At an increased degree of cross-linking the amount of the starch that dissolves decreases. The starch used in the invention may have very different degrees of cross-linking. From a relatively low degree of cross-linking, in which about 10 % by weight (by total weight of the composition) of the starch exist as solid particles at a temperature of about 20 to 50 °C, and the rest of the starch constitutes a binder in dissolved form, to a high degree of cross-linking, where about 100 % of the starch exist as solid particles in the temperature interval given above. It is preferred that at least 15 %, preferably at least 20 % by weight (by total weight of the composition) of the starch content of the composition at about 20 to 50 °C is constituted by starch particles according to the invention. It should be noted that what has just been stated is not contradictory to the limitation that more than 65 % by weight (by total weight of the composition) of the solids content should be starch particles, given that the solid pigments of the composition are essentially only composed of these starch particles or only at very small amounts comprise other types of pigments. Independent of the cross-linking degree, the composition may also contain other types of soluble starch or some synthetic polymer, in order to obtain an adequate amount of binder and further improved printability properties. Examples of such polymers are styrene-acrylate, styrene maleic acid anhydride, polyvinylalcohol, polyvinylpyrrolidon, polyvinylformamide.
  • The starch may also be cross-linked fragmented starch.
  • The starch is preferably based on potato, maize, wheat, waxy maize, rice or tapioca. The starch may be non-ionic or ionic for example anionic, cationic or amphoteric.
  • In order to further improve the paper properties that have been mentioned above, e.g. printability, the starch may be additionally modified. The starch may be modified to act as cation active, anion active, amphoteric or hydrophobic. Cationic cross-linked starch may react better with dye-based inks which is anionic.
  • Preferably, the starch exhibits a degree of substitution of 0.01 - 0.30 and even more preferred 0.02 - 0.20. Uncharged starch too may however work according to the invention.
  • According to one aspect of the invention, the surface treatment composition may also comprise a minor amount of other pigments in the form of solid particles. Such pigments may e.g. be constituted by calcium carbonate, clay, silicon dioxide and/or aluminum oxide. It is however also conceivable, and in many cases preferable, that the solid content of the composition is essentially only constituted by the inventive starch particles. The composition may also comprise surfactants.
  • The composition may also comprise an additive, preferably a charged additive which makes it possible to alter the charge of the starch particle in a desired way. The additive may preferably be anionic or amphoteric. By the addition of the additive to the composition comprising starch particles the particles will be modified. It is thus possible to modify the starch particles in order to make them more stable, make them more compatible with the fibers or with other components normally used in papermaking. The additive may preferably be carboxymethyl cellulose (CMC), polyvinyl alcohol, anionic galactoglucomannan, anionic starch, polyphosphoric acid, alginate polyacrylic acid, protein, anionic polyacryl amide, anionic silica, papermakers alum and polymethacrylic acid.
  • Furthermore, the composition according to the invention also improves brightness, opacity, bulk, surface smoothness and air resistance of a sized or coated paper or paperboard. One reason to this is that the starch particles of the surface treatment composition are amorphous and that they thereby have a much larger specific surface than conventional pigments. The high specific surface of the composition is probably also the reason for the improved printing properties of the paper when inkjet printers are used as the absorption of ink into the paper is improved due to an increased number capillaries having a smaller radius. This large surface also advantageously absorbs printing ink in offset printing. Furthermore, it has been observed that the starch particles, even if being non gelatinised, exhibit an advantageously sticky surface.
  • The invention further relates to a paper or paperboard product comprising the surface treatment composition described above. The paper or paperboard is especially suitable for printing with flexographic or digital printing techniques, such as inkjet, electrophotography, liquid toner or electrostatic printing. An big advantage with the composition according to the invention is that it can be used for both dye-based and pigment based inks. For example, it is suitable for hybrid printed products, in which one of the printing methods is based on pigmented water based inkjet inks. Moreover, the invention is also applicable for hybrid inks, which here relates to inks containing both dye and pigment particles.
  • The addition of the surface treatment composition to a surface of a paper or paperboard may take place in any conventional way. It is for example possible to transfer the composition to the surface by rod coating, blade coating, fountain coating, spray coating or other known coating techniques.
  • The salt may be incorporated in the starch particle in several different ways. The salt may be incorporated in the starch particles before or after the cross-linking of the starch. If cross-linked fragmented starch is used, the salt may be incorporated before or after the fragmentation of the starch.
  • It is possible that cross-linked starch particles alternatively cross-linked fragmented starch may be added to a solution comprising dissolved salt. The starch particle will swell in the solution and dissolved salt is thus absorbed and thus incorporated by the starch particles forming the particles according to the invention.
  • Another possibility for production of starch particles is during the production of cross-linked starch, the salt can thus be added in liquid or solid state just before the extruder which is used for the production of cross-linked starch. If necessary, the pressure and/or temperature is raised during the extrusion.
  • A third way to incorporate the salt in the starch particles, is to add the salt to a starch slurry and treated in a jet cooker. In a jet cooker, the temperature and pressure is raised by adding direct steam into the cooker. In this way starch particles comprising salt is formed.
  • The invention may beneficially be used for papers of different types, such as paper for inkjet printers, envelope paper, copying paper, paper for laser printers or other types of paper or paperboard. It is also possible to add the composition to a non-fibrous material, such as a biopolymer film preferably located on the surface of a fibrous material.
  • The invention is not limited to the described embodiments, but may be varied within the scope of the claims.

Claims (7)

  1. A surface treatment composition for paper, paperboard or other fibrous webs, characterized in that the composition comprises starch particles in an amount of more than 65% by weight, and at least 10% by weight of the starch in the composition consists of starch particles in the entire temperature range of 20-50°C and wherein the starch particles comprise at least one salt of a multivalent metal and wherein the ratio between salt and starch of the composition is between 1:50 to 1:5 and the salt is incorporated in the starch particle.
  2. The composition according to claim 1, characterized in that the salt is a calcium, magnesium or aluminum salt, preferably calcium chloride or polyaluminum chloride.
  3. The composition according to any of the preceding claims characterized in that the starch is cross-linked starch.
  4. The composition according to claim 3, characterized in that the starch is cross-linked by one or more compounds chosen from the group that consists of methylamine compounds, polyvalent acids, polyvalent acid esters, polyvalent acid halides, polyvalent acid anhydrides, polyaldehydes, polyepoxides, polyisocyanates, divinyl compounds, phosphoryl chloride, polyamine polyepoxide resin, 1,4-butane diolglycidyl ether, epichlorohydrin, trimetaphosphates, mixtures of anhydrides of acetic acid and two and three protonic acids, sodium hypochlorite, or mixtures thereof.
  5. The composition according to any of the preceding claims characterized in that the composition comprises dissolved starch.
  6. The composition according to any of the preceding claims characterized in that the composition comprises an additive, preferably an anionic or amphoteric additive.
  7. Paper or paperboard, characterized in that it comprises a surface layer comprising the surface treatment composition according to any one of claims 1-6.
EP11831005.1A 2010-10-08 2011-10-04 Surface treatment composition and paper or paperboard comprising a surface treatment composition Active EP2625337B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
SE1051056A SE535500C2 (en) 2010-10-08 2010-10-08 Surface preparation composition and paper or paperboard containing a surface treatment composition
PCT/SE2011/051182 WO2012047162A1 (en) 2010-10-08 2011-10-04 Surface treatment composition and paper or paperboard comprising a surface treatment composition

Publications (3)

Publication Number Publication Date
EP2625337A1 EP2625337A1 (en) 2013-08-14
EP2625337A4 EP2625337A4 (en) 2017-03-08
EP2625337B1 true EP2625337B1 (en) 2019-07-17

Family

ID=45927967

Family Applications (1)

Application Number Title Priority Date Filing Date
EP11831005.1A Active EP2625337B1 (en) 2010-10-08 2011-10-04 Surface treatment composition and paper or paperboard comprising a surface treatment composition

Country Status (6)

Country Link
EP (1) EP2625337B1 (en)
CN (1) CN103154371B (en)
BR (1) BR112013008470B1 (en)
ES (1) ES2751096T3 (en)
SE (1) SE535500C2 (en)
WO (1) WO2012047162A1 (en)

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015136493A1 (en) * 2014-03-14 2015-09-17 Stora Enso Oyj A method for manufacturing a packaging material and a packaging material made by the method
WO2015140097A1 (en) 2014-03-17 2015-09-24 Tetra Laval Holdings & Finance S.A. Coating composition, printed packaging laminate, method for manufacturing of the packaging laminate and packaging container
US9365979B2 (en) * 2014-08-27 2016-06-14 Ecolab Usa Inc. Method of increasing paper surface strength by using polyaluminum chloride in a size press formulation containing starch
CN106560548B (en) * 2016-07-21 2018-01-12 肖智基 A kind of papermaking regenerated fiber reinforcing agent and its application method
SE541459C2 (en) * 2017-05-08 2019-10-08 Stora Enso Oyj Moisture control material
SE543520C2 (en) * 2018-11-14 2021-03-16 Stora Enso Oyj Surface treatment composition comprising nanocelluloose and particles comprising a salt of a multivalent metal
SE543902C2 (en) * 2019-05-14 2021-09-21 Stora Enso Oyj Method for applying starch to a paper or paperboard web

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3368987A (en) * 1964-02-17 1968-02-13 Monsanto Co Starch composition modified with half amide/half salt styrene maleic anhydride copolymers
US4020210A (en) * 1975-12-15 1977-04-26 Xerox Corporation Encapsulated water paper
MY125712A (en) * 1997-07-31 2006-08-30 Hercules Inc Composition and method for improved ink jet printing performance
JP2000127610A (en) * 1998-10-26 2000-05-09 Mitsubishi Paper Mills Ltd Ink-jet recording sheet
NZ508191A (en) * 1999-11-23 2002-03-28 Nat Starch Chem Invest A method of modulating surface sizing properties such as porosity reduction, resistance to liquid penetration and surface strength when used as surface size on paper
FI120318B (en) * 2004-06-23 2009-09-15 M Real Oyj Silicon containing starch composites, process for making them and use in making paper and paperboard
US20060254738A1 (en) * 2005-05-16 2006-11-16 Anderson Kevin R Cationic crosslinked starch containing compositions and use thereof
ATE518661T1 (en) * 2007-03-29 2011-08-15 Jujo Paper Co Ltd THERMAL RECORDING MATERIAL

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
None *

Also Published As

Publication number Publication date
SE535500C2 (en) 2012-08-28
ES2751096T3 (en) 2020-03-30
WO2012047162A1 (en) 2012-04-12
SE1051056A1 (en) 2012-04-09
EP2625337A1 (en) 2013-08-14
EP2625337A4 (en) 2017-03-08
CN103154371B (en) 2016-02-17
BR112013008470B1 (en) 2020-07-21
CN103154371A (en) 2013-06-12
BR112013008470A2 (en) 2016-08-09

Similar Documents

Publication Publication Date Title
EP2625337B1 (en) Surface treatment composition and paper or paperboard comprising a surface treatment composition
JP4995831B2 (en) Paper substrate with high printing density
EP2459663B1 (en) Coating compositions
CA2887097C (en) Silica-containing coating composition for printing substrate
JP5000698B2 (en) Aggregates for patterned paper, patterned paper using the same, and methods for producing the same
JP2011148194A (en) Ink jet recording paper
CN101370981B (en) Paper containing preaggregated filler and process for producing the same
JP2010100039A (en) Inkjet recording paper
FI123465B (en) Use of a composition for improving ink jet printing properties
EP2534302B1 (en) Surface treatment composition
CN106029393A (en) Lightweight coated paper for printing with industrial ink-jet printer
JP2010519380A (en) Pigment composition
US9616696B2 (en) Coating for paper adapted for inkjet printing
EP2486189B1 (en) A process for the production of a substrate comprising silica pigments which is formed on the surface of the substrate
JP2011246838A (en) Coated paper for printing
JPH05162437A (en) Aqueous ink jet recording paper
WO2003021039A1 (en) Surface treating composition, method in the manufacturing of paper or paperboard, paper or paperboard and use of a surface treating composition
JPH11277886A (en) Recording medium and ink jet recording method
JPH11277885A (en) Recording medium and ink jet recording method
JP2004122436A (en) Plain paper type inkjet recording sheet

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20130508

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

DAX Request for extension of the european patent (deleted)
RA4 Supplementary search report drawn up and despatched (corrected)

Effective date: 20170208

RIC1 Information provided on ipc code assigned before grant

Ipc: D21H 21/16 20060101ALI20170131BHEP

Ipc: B41M 5/52 20060101ALI20170131BHEP

Ipc: D21H 21/54 20060101ALI20170131BHEP

Ipc: B41M 5/00 20060101ALI20170131BHEP

Ipc: D21H 19/54 20060101AFI20170131BHEP

Ipc: D21H 17/28 20060101ALI20170131BHEP

Ipc: D21H 17/66 20060101ALI20170131BHEP

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: EXAMINATION IS IN PROGRESS

17Q First examination report despatched

Effective date: 20180523

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: GRANT OF PATENT IS INTENDED

INTG Intention to grant announced

Effective date: 20190329

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE PATENT HAS BEEN GRANTED

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 602011060557

Country of ref document: DE

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: AT

Ref legal event code: REF

Ref document number: 1155937

Country of ref document: AT

Kind code of ref document: T

Effective date: 20190815

REG Reference to a national code

Ref country code: NL

Ref legal event code: FP

REG Reference to a national code

Ref country code: LT

Ref legal event code: MG4D

REG Reference to a national code

Ref country code: AT

Ref legal event code: MK05

Ref document number: 1155937

Country of ref document: AT

Kind code of ref document: T

Effective date: 20190717

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20191017

Ref country code: AT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190717

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190717

Ref country code: HR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190717

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20191118

Ref country code: BG

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20191017

Ref country code: LT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190717

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: AL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190717

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20191018

Ref country code: LV

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190717

Ref country code: RS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190717

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20191117

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2751096

Country of ref document: ES

Kind code of ref document: T3

Effective date: 20200330

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: TR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190717

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: RO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190717

Ref country code: PL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190717

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190717

Ref country code: EE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190717

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MC

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190717

Ref country code: CZ

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190717

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200224

Ref country code: SM

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190717

Ref country code: SK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190717

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 602011060557

Country of ref document: DE

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

PG2D Information on lapse in contracting state deleted

Ref country code: IS

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20191031

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20191031

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20191004

26N No opposition filed

Effective date: 20200603

REG Reference to a national code

Ref country code: BE

Ref legal event code: MM

Effective date: 20191031

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190717

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20191031

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20191004

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190717

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190717

Ref country code: HU

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT; INVALID AB INITIO

Effective date: 20111004

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190717

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 20231019

Year of fee payment: 13

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20231020

Year of fee payment: 13

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: ES

Payment date: 20231227

Year of fee payment: 13

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: IT

Payment date: 20231026

Year of fee payment: 13

Ref country code: FR

Payment date: 20231025

Year of fee payment: 13

Ref country code: FI

Payment date: 20231020

Year of fee payment: 13

Ref country code: DE

Payment date: 20231020

Year of fee payment: 13