EP2504487A1 - Method for manufacturing nanofibrillated cellulose pulp and use of the pulp in paper manufacturing or in nanofibrillated cellulose composites - Google Patents

Method for manufacturing nanofibrillated cellulose pulp and use of the pulp in paper manufacturing or in nanofibrillated cellulose composites

Info

Publication number
EP2504487A1
EP2504487A1 EP10832694A EP10832694A EP2504487A1 EP 2504487 A1 EP2504487 A1 EP 2504487A1 EP 10832694 A EP10832694 A EP 10832694A EP 10832694 A EP10832694 A EP 10832694A EP 2504487 A1 EP2504487 A1 EP 2504487A1
Authority
EP
European Patent Office
Prior art keywords
pulp
cellulose
optical brightening
brightening agent
refining
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.)
Granted
Application number
EP10832694A
Other languages
German (de)
French (fr)
Other versions
EP2504487A4 (en
EP2504487B1 (en
Inventor
Markus Nuopponen
Taru PÄIVÄLÄINEN
Antti Laukkanen
Jouni Paltakari
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.)
UPM Kymmene Oy
Original Assignee
UPM Kymmene 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
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=41395280&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=EP2504487(A1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by UPM Kymmene Oy filed Critical UPM Kymmene Oy
Publication of EP2504487A1 publication Critical patent/EP2504487A1/en
Publication of EP2504487A4 publication Critical patent/EP2504487A4/en
Application granted granted Critical
Publication of EP2504487B1 publication Critical patent/EP2504487B1/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
    • D21C9/00—After-treatment of cellulose pulp, e.g. of wood pulp, or cotton linters ; Treatment of dilute or dewatered pulp or process improvement taking place after obtaining the raw cellulosic material and not provided for elsewhere
    • D21C9/001—Modification of pulp properties
    • D21C9/002—Modification of pulp properties by chemical means; preparation of dewatered pulp, e.g. in sheet or bulk form, containing special additives
    • D21C9/005—Modification of pulp properties by chemical means; preparation of dewatered pulp, e.g. in sheet or bulk form, containing special additives organic compounds
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H11/00—Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only
    • D21H11/16—Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only modified by a particular after-treatment
    • D21H11/18—Highly hydrated, swollen or fibrillatable fibres
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21D—TREATMENT OF THE MATERIALS BEFORE PASSING TO THE PAPER-MAKING MACHINE
    • D21D1/00—Methods of beating or refining; Beaters of the Hollander type
    • D21D1/20—Methods of refining
    • 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
    • D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H17/41—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups
    • D21H17/42—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups anionic
    • 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
    • D21H21/30—Luminescent or fluorescent substances, e.g. for optical bleaching
    • 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
    • D21H21/32—Bleaching agents

Definitions

  • the invention relates to a method of manufacturing nanofibrillated cellulose pulp.
  • the invention further relates to use of the pulp in paper manufacturing or in nanofibrillated cellulose composites.
  • the new additive would preferably have features to reduce the inter-fiber bonding and, thus, increase a refining efficiency due to decreased energy consumption of the refining stage.
  • the additive would preferably have features to reduce fiber-water and fiber-fiber bonding that occurs during drying and concentrating.
  • the additive would preferably be some of those additives that are often added for another purpose on later process stages. Summary of the Invention
  • the present invention solves at least some of the above mentioned problems by providing a method for pulp manufacturing wherein the produced pulp consist at least partly of nanofibrillated cellulose.
  • the method comprises a step in which at least one type of optical brightening agent (OBA) is dosed before and/or during at least one pre- refining and/or fibrillation stage.
  • OSA optical brightening agent
  • the invention further discloses a use of the produced pulp in nanofibrillated cellulose composites or in paper or paperboard manufacturing including base paper manufacturing and finishing stages like, for example, the use in paper or paperboard coatings.
  • optical brightening agents can increase the production efficiency of the nanofibrillated cellulose pulp if the additives are dosed before or during a pre-refining stage and/or a fibrillation stage.
  • Optical brightening agents have been found to be able to create bonding with cellulose in such a way that the optical brightening agents can act as substituents in inter-fiber bonding and, thus, inhibiting hydrogen bonding of fibrils in cellulose.
  • the increased production efficiency is mainly due to decreased energy consumption of the fibrillation stage because of the substituent effect.
  • Optical brightening agents are also able to create bonding with water and, thus, to increase the efficiency of drying and concentrating processes.
  • optical brightening agents are able to enable redispersing of nanofibrillated containing cellulose. Due to the dispersive effect, an optical brightening agent can be used as a dispersing agent in nanofibrillated concentrating and/or redispersing process and, therefore, help the process. In addition, due to the dispersive effect, the quality of the nanofibrillated cellulose pulp can be increased.
  • At least one kind of optical brightening agent is added before a pulp pre-refining stage. According to another embodiment, at least one kind of optical brightening agent is added before a pulp fibrillation stage. According to another embodiment, at least one kind of optical brightening agent is dosed into the pulp at the pre-refining stage. According to another embodiment, at least one kind of optical brightening agent is dosed into the pulp at the fibrillation stage.
  • the amount of the nanofibrillated cellulose in the produced pulp is more than 30 w-%, preferably more than 40 w-%, 50 w-%, 60 w-% or 70 w-%, and can be even up to 1 00 w-% measured from the dried pulp.
  • the nanofibrillated cellulose pulp that can be produced according to the invention and, thus, contains one or more optical brightening agents, may be used in various end product applications.
  • the cellulose pulp may be used, for example, in nanofibrillated cellulose composites, and/or in paper manufacturing, for example, in a base paper and/or in a finishing stage of produced paper.
  • the finishing stages of produced paper includes, for example, coating stages.
  • Fig. 5 shows some turbidity and centrifugation experimental test results of the fluidized samples.
  • cellulose raw material refers to any cellulose raw material source that can be used in a production of cellulose pulp, refined pulp, or microfibrillar cellulose.
  • the cellulose raw material can be based on any plant material that contains cellulose, for example wood material.
  • the wood material can be from softwood trees, such as spruce, pine, fir, larch, douglas-fir or hemlock, or from hardwood trees, such as birch, aspen, poplar, alder, eucalyptus or acacia, or from a mixture of softwoods and hardwoods.
  • Non-wood material can be from agricultural residues, grasses or other plant substances such as straw, leaves, bark, seeds, hulls, flowers, vegetables or fruits from cotton, corn, wheat, oat, rye, barley, rice, flax, hemp, manila hemp, sisal hemp, jute, ramie, kenaf, bagasse, bamboo or reed.
  • agricultural residues, grasses or other plant substances such as straw, leaves, bark, seeds, hulls, flowers, vegetables or fruits from cotton, corn, wheat, oat, rye, barley, rice, flax, hemp, manila hemp, sisal hemp, jute, ramie, kenaf, bagasse, bamboo or reed.
  • cellulose pulp refers in this application to cellulose fibers, which are isolated from any cellulose raw material using chemical, mechanical, thermomechanical, or chemithermo - mechanical pulping process(es). Typically the diameter of the fibers varies between 1 5-25 ⁇ and the length exceeds 500 ⁇ , but the present invention is not intended to be limited to these parameters.
  • paper manufacturing refers to manufacturing process of any paper-like material, for example, paperboards, papers and/or paper composites.
  • At least part of the lignin that has been included in cellulose raw material is advantageously removed from the cellulose raw material when it is processed into cellulose pulp to be used in the nanofibrillated cellulose production.
  • chemical pulp may be used more preferably for nanofibrillated cellulose production than mechanical pulp.
  • the yield of the process wherein cellulose raw material is processed into cellulose pulp to be used in the nanofibrillated pulp production has been at least 50 %, at least 60 %, at least 70 % or at least 80 %.
  • the cellulose pulp used in the nanofibrillated cellulose production may be preferably unbleached or bleached chemithermo or chemical pulp, more preferably unbleached or bleached chemical pulp, and the most preferably unbleached chemical pulp, because the method of the invention may be the most advantageous compared to other processes when the used cellulose pulp is chemically produced unbleached pulp.
  • the term "refined pulp” refers to refined cellulose pulp. The refining of cellulose pulp is carried out with suitable equipment such as a refiner, grinder, homogenizer, colloider, friction grinder, fluidizer such as microfluidizer, macrofluidizer or fluidizer-type homogenizer or ultrasound sonicator.
  • cellulose fibers typically have not been fully fibrillated; a large fraction of cellulose fibers with unchanged dimensions are still present in addition to refined cellulose material.
  • the large fibers in the refined pulp may have fibrillated surface.
  • the finest fraction of cellulose based material in the "refined pulp” consists of nanofibrillated cellulose, i.e. cellulose microfibrils and microfibril bundles with diameter less than 200 nm.
  • nanofibrillated cellulose refers to a collection of isolated cellulose microfibrils or microfibril bundles derived from cellulose raw material.
  • Microfibrils have typically high aspect ratio: the length might exceed one micrometer while the number-average diameter is typically below 200 nm.
  • the diameter of microfibril bundles can also be larger but generally less than 1 ⁇ .
  • the smallest microfibrils are similar to the so called elementary fibrils, which are typically 2-1 2 nm in diameter.
  • the dimensions of the fibrils or fibril bundles are dependent on the raw material and disintegration method.
  • the nanofibrillated cellulose may also contain some hemicelluloses; the amount may be dependent on the plant source.
  • Nanofibrillated cellulose can also be any chemically or physically modified derivate of cellulose microfibrils or microfibril bundles.
  • the chemical modification could be based for example on carboxymethylation, oxidation, esterification, or etherification reaction of cellulose molecules. Modification could also be realized by physical adsorption of anionic, cationic, or non-ionic substances or any combination of these on cellulose surface.
  • nanofibrillated cellulose can be carried out before, after, or during the production of nanofibrillated cellulose.
  • nanofibrillated cellulose There are several widely used synonyms for nanofibrillated cellulose.
  • MFC microfibrillated cellulose
  • Nanofibrillated cellulose described in this application is not the same material as the so called cellulose whiskers, which are also known as: cellulose nanowhiskers, cellulose nanocrystals, cellulose nanorods, rod-like cellulose microcrystals or cellulose nanowires.
  • Nanofibrillated cellulose and normal cellulose are usually produced using different kind of refiners, because the refiners that are used conventionally in the pulp refiner production may not, at least efficiently, be used in nanofibrillated cellulose production. However, the refiners used in the conventional pulp production may be used as pre-refiners in nanofibrillated cellulose production.
  • the term “fibrillation stage” means the stage that causes more fibrillar cellulose
  • the term “pre-refiner stage” means the stage that may advantageously be used for pre-refining before a fibrillation stage in nanofibrillated cellulose production.
  • Properties of nanofibrillated cellulose pulp differs hugely from conventional cellulose pulp due to many nano-sized particles of the nanofibrillated cellulose pulp and, thus, nanofibrillated cellulose cannot be though as a same material as conventional cellulose pulp.
  • Nanofibrillated cellulose is, for example, gel-like material even in low consistency, and its water removal rate is usually slow.
  • Paper sheets that contain a lot of nanofibrillated cellulose have special properties comparing to the sheets made from normal cellulose pulp, for example, they have usually high strength properties, their porosity is very low, and the sheets are usually (at least partly) transparent.
  • FIGS. 1 a-1 d The differences between cellulose pulp, refined cellulose pulp and nanofibrillated cellulose pulp are illustrated in figures 1 a-1 d in optical microscopy pictures. Magnification is the same in the figures 1 a - 1 c.
  • Figure 1 a shows an optical microscopy picture of typical cellulose pulp.
  • Figure 1 b shows an microscopy picture of typical refined cellulose pulp.
  • Figures 1 c and 1 d show microscopy pictures of typical nanofibrillated cellulose pulp.
  • Figure 1 d shows the same situation as figure 1 c but with higher magnification wherein individual microfibrils and microfibril bundles with diameter less than 1 00 nm can be detected.
  • the present invention provides a method for manufacturing nanofibrillated cellulose pulp by pre-refining and/or fibrillating the pulp with a presence of at least one kind of optical brightening agent.
  • the present invention provides the use of the produced pulp in paper manufacturing or in nanofibrillated cellulose composites.
  • optical brightening agents are dye-like compounds which absorb short-wave light in the ultraviolet and violet region of the electromagnetic spectrum not visible to the human eye and re-emit the light in the longer-wave blue region.
  • optical brightening agents make the material, for example paper, to look less yellow to the human eyes and, thus, human eyes interpret the blue light as a higher degree of whiteness.
  • the optical brightening agents are used to achieve better optical properties of the produced paper, for example, for a whitening effect of the produced paper.
  • Optical brightening agent types that are typically used in the pulp and paper industry are, for example, di-, tetra-, and hexasulphonated stilbene compounds.
  • the amount of sulphonated groups has an effect on the chemical properties of the optical brightening agent and, thus, the type of the used OBA may have an effect on the method according to an example embodiment of the invention.
  • the more the optical brightening agent has sulphonated groups the bigger may be the effect of the used optical brightening agent on the method accordant with the invention.
  • Some other most cornmercialiy available optical brightening agents in pulp and paper industries are based on coumarin and pyrazolone chemistries, Those mentioned optical brightening agent types are only some examples and also other types of optical brightening agents known in prior art can be used in this invention.
  • those chemical types mentioned in the application, Le stilbene, coumarin and pyrazoline are preferred to use in the practice of this invention. From those chemicals, the anionic stilbene compounds may be the most preferably used in the invention.
  • optical brightening agents are quite expensive additives, thus, solutions provided in this invention are intended to be the most efficient if optical brightening agents are used in nanofibrillated pulp production wherein the optical brightening agent is otherwise added in a later stage to the pulp or to the end product.
  • optical brightening agents are typically added at the wet end of the papermaking process, which include, for example, the fan pulp or the machine chest.
  • optical brightening agent in accordance with some example embodiments of the invention does not necessarily increase additive costs but, quite the contrary, the retention of the optical brightening agent to the nanofibrillated pulp may be improved if the optical brightening agent is added before or during pre-refining stage or before or during a fibrillation step and, therefore, the overall costs of the used optical brightening agent may be decreased.
  • the total amount of the needed optical brightening agent dosage according to an example embodiment of the invention can be smaller if the optical brightening agent is added accordant with some example embodiments of the invention due to several fiber - optical brightening agent bondings that may be formed during nanofibrillated cellulose pre-refining and/or fibrillation stages. Therefore, the efficiency of the nanofibrillated cellulose production can further be increased when the optical brightening agent is added to the produced pulp before or during the refining stage, not only because of the decreased energy consumption but also because of less additive costs.
  • the optical brightening agent dosage to the nanofibrillated cellulose production may increase an ability of the nanofibrillated cellulose to carry the optical brightening agent and, therefore, a need for other optical brightening agent carriers e.g. Polyvinyl Alcohol (PVOH) may decrease.
  • PVOH Polyvinyl Alcohol
  • the method comprises a step wherein at least one type of the optical brightening agent (OBA) is dosed as a refining additive to the pulp which contains cellulose.
  • OSA optical brightening agent
  • the dosage is preferably done before a pre-refining and/or fibrillation stage.
  • one type of the optical brightening agent can be added into the pulp at the pre-refining or the fibrillation stage.
  • the pulp is fibrillated in at least one fibrillation stage after the additive addition, no matter in which stage the additive is added to the process.
  • the anionic optical brightening agent is capable of inhibiting hydrogen bonding between the cellulose fibrils in cellulose and can therefore be used to create a dispersive effect, which dispersive effect can increase the quality of the produced nanofibrillated cellulose. Due to the dispersive effect, optical brightening agent can be used as a dispersing agent in the nanofibrillated concentrating/redispersing process and, therefore, may help the process.
  • Nanofibrillated cellulose that contains optical brightening agent may improve not only the refining efficiency and the quality of the produced pulp but also both the strength and the optical properties of the end product to be produced from the pulp manufactured according to an example embodiment of the invention.
  • the improvements in strength properties are mainly due to the features of nanofibrillated cellulose and the improvements in optical properties are mainly due to the features of the optical brightening agent.
  • the novel invention can provide at least some of the following advantages:
  • the amount of nanofibrillated cellulose in the pulp manufactured according to the invention may be 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95 or 1 00 w- %, including any and all ranges and subranges therein.
  • the pulp manufacturing process according to invention has at least one fibrillation stage, possibly at least 2, 3 or 4 fibrillation stages. According to the invention at least one type of the optical brightening agent is added
  • the pulp is fibrillated after at least one additive dosage in at least one fibrillation stage in order to form some nanofibrillated cellulose material.
  • the addition of the optical brightening agent before or during the refining decreases the cellulose-cellulose bonding through hydroxyl groups by forming hydrogen bonds with the cellulose fibrils.
  • the addition of the optical brightening agent creates a dispersive effect to the pulp suspension through the repulsive forces between the anionic groups.
  • a bleached birch pulp made with conventional chemical pulping process was used as raw cellulose pulp.
  • optical brightening agents Two different kinds of optical brightening agents were used as the refining additive: disulphonic type of the optical brightening agent and hexasulphonic type of the optical brightening agent. In addition, reference samples without addition of the optical brightening agent were performed.
  • the pre-refining stage was performed with Voith refiner. Addition of the used optical brightening agent was always 2 w-%. The whole amount was dosed to the pulp before the pre-refiner stage, after which the samples were refined at energy of 200 kWh/t. The pre-refinings were performed in the consistency of 4%.
  • the obtained pulps were diluted to 1 .6% for fluidizer and to 2% for Masuko.
  • the optical brightening agents were dosed to the pre-refining process in order to improve their bonding to fiber surface. ple preparation
  • the part of the samples was fluidized with the M-700 Microfluidics Processor. Those samples were dispersed with a mixer in 1 .6% consistency during 30 minutes. After dispersing, the samples were passed three times through fluidizer so that in the first pass there was only an APM chamber with diameter at 500 ⁇ . In the second pass, the fiber suspension was passed through two sequential chambers with diameters at 500 ⁇ and 200 ⁇ . The third pass was carried out so that the fiber suspension passed through sequential 500 ⁇ and 1 00 ⁇ diameter chambers. The condenser of the fluidizer was switched off during all these trials, as it was found to improve fibrillation in the first part of experiments.
  • the grinded samples were dispersed in 2% consistency with a mixer during 1 5 minutes before the treatment with Masuko.
  • the dispersed samples were passed four times through Masuko in such a way that in the first pass the gap between the grinding stones was looser than with the following three passes.
  • the grinder was washed after the first and third pass. racterization
  • the gel-like fiber suspensions obtained from Masuko and from fluidizer were characterized by measuring viscosity (Brookfield) and turbidity of the samples and by observing optical microscope and SEM images of the samples. In addition, with centrifugation measurements the dry matter content was measured from both the liquid and the solid phase in order to determine the amount of nano-sized material in the sample. paration of paper sheets
  • Refining result can be estimated by measuring the viscosity level of the nanofibrillated cellulose sample, because the viscosity level of the pulp material goes along with the portion of nanofibrillated cellulose in the pulp.
  • more refined, and thus, more fibrillated nanofibrillated cellulose is more gel-like material than less nanofibrillated cellulose. Therefore, more gellike material means more nanofibrillated cellulose in the sample and this bigger part of nanofibrillate cellulose can be seen in higher viscosity level in the sample.
  • Samples with optical brightening agent - dosage were clearly more viscous than the reference samples. The amount of unfibrillated fibers can be estimated from optical microscopy pictures.
  • FIGs 2a - 2c wherein viscosity results with some optical microscopy pictures of Masuko grinded samples are shown.
  • the figure 2a presents the viscosity results of the reference sample 21 , the sample with disulphonic optical brightening agent dosage 22, and the sample with hexasulphonic optical brightening agent dosage 23.
  • Figure 2b shows an optical microscopy picture of the reference sample 21
  • figure 2c shows an optical microscopy picture of the sample 23 with hexasulphonic optical brightening agent dosage.
  • Figures 3a and 3b show an optical microscopy images of fluidisator samples, wherein the reference sample (shown in figure 3a) and the sample 32 with hexasulphonic optical brightening agent (shown in figure 3b) are presented. The sample presented in figure 3b with the dosage of the optical brightening agent is clearly better fibrillated than the reference sample shown in figure 3a.
  • Figures 4a and 4b show the same situation with SEM pictures (magnification : 1 0 000 x) in which the reference sample (in figure 4a) and the sample with hexasulphonated optical brightening agent addition (in figure 4b) are presented. As can be seen, the samples with hexasulphonated optical brightening agent looks clearly better compared to the reference sample, as many smaller fibrils can be seen in the image.
  • Quality of the nanofibrillated cellulose can be analyzed using centrifugation of nano-sized material and measuring the turbidity of the samples. Centrifugation results are supposed to describe the degree of fibrillation so that the more the nano-sized material has more efficient fibrillation than less nano-sized material. When it comes to turbidity results, the smaller the value for turbidity is, the more there should be nano-sized material in the sample.
  • Figure 5 shows turbidity and centrifugation results of the fluidized samples. In this figure the reference sample 51 , the sample 52 with disulphonic type of the optical brightening agent dosage, and the sample 53 with addition of hexasulphonic type of the optical brightening agent are presented.

Abstract

The invention relates to a method for manufacturing pulp. The manufactured pulp contains at least 30 w-% nanofibrillated cellulose material measured from the dried pulp. The method comprises the following stages: introducing raw material to a system which raw material includes cellulose, dosing at least one type of an optical brightening agent as a refining additive to the system, and refining the raw material in the presence of the dosed optical brightening agent in at least one pre-refining stage or fibrillation stage in order to form fibrillar cellulose material. The invention further relates to a use of the produced pulp in nanofibrillated cellulose composites or in paper or paperboard manufacturing including base paper production and finishing stages, including, for example, paper and paperboard coatings.

Description

METHOD FOR MANUFACTU RING NANOFIBRILLATED CELLULOSE PULP AND USE OF THE PULP IN PAPER MAN UFACTU RING OR IN NANOFI BRILLATED CELLULOSE COMPOSITES Field of the Invention
The invention relates to a method of manufacturing nanofibrillated cellulose pulp. The invention further relates to use of the pulp in paper manufacturing or in nanofibrillated cellulose composites.
Background of the Invention
Many stages of pulp production, especially refining stages, consume lots of energy. Specially a production of nanofibrillated cellulose consumes a great deal of energy due to several fibrillarion passages that are needed to achieve nano-sized material. Because the energy consumption of the manufactured pulp increases hugely when the produced pulp includes nanofibrillated cellulose, there may be an efficiency problem when the produced pulp consist at least partly of nanofibrillated cellulose. Sometimes another problem in the nanofibrillated cellulose pulp production is poor water removal due to several strong bonds between cellulose fibers and the water to be removed. Due to the above mentioned problems, it is beneficial to add at least one compound capable of substantially inhibiting hydrogen bonding of fibrils in cellulose, especially in a process preparing nanofibrillated cellulose. For this purpose some polyhydroxy compounds, such as sucrose, are used in prior art. However, those known compounds have some problems. For example, known additives have generally been used only for refining stages, which will cause extra additive costs. Thus, it would be more beneficial to use those kind of additives which were anyway added to the process for another purpose on later process stages instead of those known additives used only for the above mentioned purpose. There is, therefore, a need for a new solution for increasing the efficiency of the nanofibrillated cellulose pulp production. There is, thus, a need for an additive that could cause a smaller energy consumption of pre-refining and/or fibrillation stages and a better water removability in the pulp production. The new additive would preferably have features to reduce the inter-fiber bonding and, thus, increase a refining efficiency due to decreased energy consumption of the refining stage. In addition, the additive would preferably have features to reduce fiber-water and fiber-fiber bonding that occurs during drying and concentrating. Moreover, the additive would preferably be some of those additives that are often added for another purpose on later process stages. Summary of the Invention
The present invention solves at least some of the above mentioned problems by providing a method for pulp manufacturing wherein the produced pulp consist at least partly of nanofibrillated cellulose. The method comprises a step in which at least one type of optical brightening agent (OBA) is dosed before and/or during at least one pre- refining and/or fibrillation stage. The invention further discloses a use of the produced pulp in nanofibrillated cellulose composites or in paper or paperboard manufacturing including base paper manufacturing and finishing stages like, for example, the use in paper or paperboard coatings.
Aspects of the invention are characterized by what is stated in the independent claims 1 , 1 0 and 1 1 . Various embodiments of the invention are disclosed in the dependent claims.
The inventors of the present invention have surprisingly found that optical brightening agents can increase the production efficiency of the nanofibrillated cellulose pulp if the additives are dosed before or during a pre-refining stage and/or a fibrillation stage. Optical brightening agents have been found to be able to create bonding with cellulose in such a way that the optical brightening agents can act as substituents in inter-fiber bonding and, thus, inhibiting hydrogen bonding of fibrils in cellulose. The increased production efficiency is mainly due to decreased energy consumption of the fibrillation stage because of the substituent effect. Optical brightening agents are also able to create bonding with water and, thus, to increase the efficiency of drying and concentrating processes. Due to the above mentioned things, optical brightening agents are able to enable redispersing of nanofibrillated containing cellulose. Due to the dispersive effect, an optical brightening agent can be used as a dispersing agent in nanofibrillated concentrating and/or redispersing process and, therefore, help the process. In addition, due to the dispersive effect, the quality of the nanofibrillated cellulose pulp can be increased.
According to an embodiment of the present invention, at least one kind of optical brightening agent is added before a pulp pre-refining stage. According to another embodiment, at least one kind of optical brightening agent is added before a pulp fibrillation stage. According to another embodiment, at least one kind of optical brightening agent is dosed into the pulp at the pre-refining stage. According to another embodiment, at least one kind of optical brightening agent is dosed into the pulp at the fibrillation stage.
According to an embodiment, the amount of the nanofibrillated cellulose in the produced pulp is more than 30 w-%, preferably more than 40 w-%, 50 w-%, 60 w-% or 70 w-%, and can be even up to 1 00 w-% measured from the dried pulp.
The nanofibrillated cellulose pulp that can be produced according to the invention and, thus, contains one or more optical brightening agents, may be used in various end product applications. The cellulose pulp may be used, for example, in nanofibrillated cellulose composites, and/or in paper manufacturing, for example, in a base paper and/or in a finishing stage of produced paper. The finishing stages of produced paper includes, for example, coating stages. Description of the Drawings
In the following, the invention will be illustrated by drawings in which show microscopy pictures of cellulose pulp, refined cellulose pulp and nanofibrillated cellulosepulps; show some viscosity results of experimental test together with some optical microscopy pictures taken during experimental test from Masuko grinded samples; show optical microscopy images of some fluidisator samples taken during experimental test; show SEM (scanning electron microscope) pictures of the samples shown also in figures 3a-3b; and
Fig. 5 shows some turbidity and centrifugation experimental test results of the fluidized samples.
Detailed Description of the Invention
In this application, the term "cellulose raw material" refers to any cellulose raw material source that can be used in a production of cellulose pulp, refined pulp, or microfibrillar cellulose. The cellulose raw material can be based on any plant material that contains cellulose, for example wood material. The wood material can be from softwood trees, such as spruce, pine, fir, larch, douglas-fir or hemlock, or from hardwood trees, such as birch, aspen, poplar, alder, eucalyptus or acacia, or from a mixture of softwoods and hardwoods. Non-wood material can be from agricultural residues, grasses or other plant substances such as straw, leaves, bark, seeds, hulls, flowers, vegetables or fruits from cotton, corn, wheat, oat, rye, barley, rice, flax, hemp, manila hemp, sisal hemp, jute, ramie, kenaf, bagasse, bamboo or reed.
The term "cellulose pulp" refers in this application to cellulose fibers, which are isolated from any cellulose raw material using chemical, mechanical, thermomechanical, or chemithermo - mechanical pulping process(es). Typically the diameter of the fibers varies between 1 5-25 μιη and the length exceeds 500 μιη, but the present invention is not intended to be limited to these parameters.
In this application, the term "paper manufacturing" refers to manufacturing process of any paper-like material, for example, paperboards, papers and/or paper composites.
According to an example embodiment of the invention, at least part of the lignin that has been included in cellulose raw material is advantageously removed from the cellulose raw material when it is processed into cellulose pulp to be used in the nanofibrillated cellulose production. Thus, chemical pulp may be used more preferably for nanofibrillated cellulose production than mechanical pulp. According to an example embodiment of the invention, the yield of the process wherein cellulose raw material is processed into cellulose pulp to be used in the nanofibrillated pulp production has been at least 50 %, at least 60 %, at least 70 % or at least 80 %.
According to an example embodiment, the cellulose pulp used in the nanofibrillated cellulose production may be preferably unbleached or bleached chemithermo or chemical pulp, more preferably unbleached or bleached chemical pulp, and the most preferably unbleached chemical pulp, because the method of the invention may be the most advantageous compared to other processes when the used cellulose pulp is chemically produced unbleached pulp. The term "refined pulp" refers to refined cellulose pulp. The refining of cellulose pulp is carried out with suitable equipment such as a refiner, grinder, homogenizer, colloider, friction grinder, fluidizer such as microfluidizer, macrofluidizer or fluidizer-type homogenizer or ultrasound sonicator. Typically, all cellulose fibers have not been fully fibrillated; a large fraction of cellulose fibers with unchanged dimensions are still present in addition to refined cellulose material. The large fibers in the refined pulp may have fibrillated surface. The finest fraction of cellulose based material in the "refined pulp" consists of nanofibrillated cellulose, i.e. cellulose microfibrils and microfibril bundles with diameter less than 200 nm.
The term "nanofibrillated cellulose, (NFC)" refers to a collection of isolated cellulose microfibrils or microfibril bundles derived from cellulose raw material. Microfibrils have typically high aspect ratio: the length might exceed one micrometer while the number-average diameter is typically below 200 nm. The diameter of microfibril bundles can also be larger but generally less than 1 μιη. The smallest microfibrils are similar to the so called elementary fibrils, which are typically 2-1 2 nm in diameter. The dimensions of the fibrils or fibril bundles are dependent on the raw material and disintegration method. The nanofibrillated cellulose may also contain some hemicelluloses; the amount may be dependent on the plant source.
Mechanical disintegration of nanofibrillated cellulose from cellulose raw material, cellulose pulp, or refined pulp is carried out with suitable equipment such as a refiner, grinder, homogenizer, colloider, friction grinder, ultrasound sonicator, fluidizer such as microfluidizer, macrofluidizer or fluidizer-type homogenizer. Nanofibrillated cellulose can also be any chemically or physically modified derivate of cellulose microfibrils or microfibril bundles. The chemical modification could be based for example on carboxymethylation, oxidation, esterification, or etherification reaction of cellulose molecules. Modification could also be realized by physical adsorption of anionic, cationic, or non-ionic substances or any combination of these on cellulose surface. The described modification can be carried out before, after, or during the production of nanofibrillated cellulose. There are several widely used synonyms for nanofibrillated cellulose. For example: nanocellulose, microfibrillar cellulose, nanofibrillar cellulose, cellulose nanofiber, nano-scale fibrillated cellulose, microfibrillated cellulose (MFC), or cellulose microfibrils. Nanofibrillated cellulose described in this application is not the same material as the so called cellulose whiskers, which are also known as: cellulose nanowhiskers, cellulose nanocrystals, cellulose nanorods, rod-like cellulose microcrystals or cellulose nanowires. In some cases, similar terminology is used for both materials, for example by Kuthcarlapati et al. (Metals Materials and Processes 20(3):307-31 4, 2008) where the studied material was called "cellulose nanofiber" although they clearly referred to cellulose nanowhiskers. Typically these materials do not have amorphous segments along the fibrillar structure as microfibrillar cellulose, which leads to more rigid structure. Cellulose whiskers are also shorter than microfibrillar cellulose; typically the length is less than one micrometer.
In conventional pulp production, it is usually an aim to get long, quite undamaged, fibrillated fibers, while in the nanofibrillated cellulose production an aim is to crush fibers into small pieces. Nanofibrillated cellulose and normal cellulose are usually produced using different kind of refiners, because the refiners that are used conventionally in the pulp refiner production may not, at least efficiently, be used in nanofibrillated cellulose production. However, the refiners used in the conventional pulp production may be used as pre-refiners in nanofibrillated cellulose production. In this application, the term "fibrillation stage" means the stage that causes more fibrillar cellulose, and the term "pre-refiner stage" means the stage that may advantageously be used for pre-refining before a fibrillation stage in nanofibrillated cellulose production. Properties of nanofibrillated cellulose pulp differs hugely from conventional cellulose pulp due to many nano-sized particles of the nanofibrillated cellulose pulp and, thus, nanofibrillated cellulose cannot be though as a same material as conventional cellulose pulp. Nanofibrillated cellulose is, for example, gel-like material even in low consistency, and its water removal rate is usually slow. Paper sheets that contain a lot of nanofibrillated cellulose have special properties comparing to the sheets made from normal cellulose pulp, for example, they have usually high strength properties, their porosity is very low, and the sheets are usually (at least partly) transparent.
The differences between cellulose pulp, refined cellulose pulp and nanofibrillated cellulose pulp are illustrated in figures 1 a-1 d in optical microscopy pictures. Magnification is the same in the figures 1 a - 1 c. Figure 1 a shows an optical microscopy picture of typical cellulose pulp. Figure 1 b shows an microscopy picture of typical refined cellulose pulp. Figures 1 c and 1 d show microscopy pictures of typical nanofibrillated cellulose pulp. As can be seen in figure 1 c, the large cellulose fibers shown in figures 1 a and 1 b are not anymore clearly visible. Figure 1 d shows the same situation as figure 1 c but with higher magnification wherein individual microfibrils and microfibril bundles with diameter less than 1 00 nm can be detected.
According to an example embodiment the present invention provides a method for manufacturing nanofibrillated cellulose pulp by pre-refining and/or fibrillating the pulp with a presence of at least one kind of optical brightening agent. In addition, according to another example embodiment, the present invention provides the use of the produced pulp in paper manufacturing or in nanofibrillated cellulose composites.
The optical brightening agents (OBAs) are dye-like compounds which absorb short-wave light in the ultraviolet and violet region of the electromagnetic spectrum not visible to the human eye and re-emit the light in the longer-wave blue region. In other words, optical brightening agents make the material, for example paper, to look less yellow to the human eyes and, thus, human eyes interpret the blue light as a higher degree of whiteness. In prior art the optical brightening agents are used to achieve better optical properties of the produced paper, for example, for a whitening effect of the produced paper. Optical brightening agent types that are typically used in the pulp and paper industry are, for example, di-, tetra-, and hexasulphonated stilbene compounds. The amount of sulphonated groups has an effect on the chemical properties of the optical brightening agent and, thus, the type of the used OBA may have an effect on the method according to an example embodiment of the invention. Generally, the more the optical brightening agent has sulphonated groups the bigger may be the effect of the used optical brightening agent on the method accordant with the invention. Some other most cornmercialiy available optical brightening agents in pulp and paper industries are based on coumarin and pyrazolone chemistries, Those mentioned optical brightening agent types are only some examples and also other types of optical brightening agents known in prior art can be used in this invention. However, according to an embodiment of the invention, those chemical types mentioned in the application, Le stilbene, coumarin and pyrazoline, are preferred to use in the practice of this invention. From those chemicals, the anionic stilbene compounds may be the most preferably used in the invention.
Optical brightening agents are quite expensive additives, thus, solutions provided in this invention are intended to be the most efficient if optical brightening agents are used in nanofibrillated pulp production wherein the optical brightening agent is otherwise added in a later stage to the pulp or to the end product. In papermaking, optical brightening agents are typically added at the wet end of the papermaking process, which include, for example, the fan pulp or the machine chest. The use of the optical brightening agent in accordance with some example embodiments of the invention does not necessarily increase additive costs but, quite the contrary, the retention of the optical brightening agent to the nanofibrillated pulp may be improved if the optical brightening agent is added before or during pre-refining stage or before or during a fibrillation step and, therefore, the overall costs of the used optical brightening agent may be decreased. In the other words, it is possible that the total amount of the needed optical brightening agent dosage according to an example embodiment of the invention can be smaller if the optical brightening agent is added accordant with some example embodiments of the invention due to several fiber - optical brightening agent bondings that may be formed during nanofibrillated cellulose pre-refining and/or fibrillation stages. Therefore, the efficiency of the nanofibrillated cellulose production can further be increased when the optical brightening agent is added to the produced pulp before or during the refining stage, not only because of the decreased energy consumption but also because of less additive costs. Moreover, the optical brightening agent dosage to the nanofibrillated cellulose production according to some example embodiments of this invention may increase an ability of the nanofibrillated cellulose to carry the optical brightening agent and, therefore, a need for other optical brightening agent carriers e.g. Polyvinyl Alcohol (PVOH) may decrease. Thus, the production efficiency can also be increased this way due to the invention.
According to an embodiment of the invention, the method comprises a step wherein at least one type of the optical brightening agent (OBA) is dosed as a refining additive to the pulp which contains cellulose. In the method the dosage is preferably done before a pre-refining and/or fibrillation stage. In addition or alternatively, one type of the optical brightening agent can be added into the pulp at the pre-refining or the fibrillation stage. Thus, it is possible to add the optical brightening agent to a pre-refining stage, and/or the optical brightening agent can be added to some or all of the following fibrillation stages. According to an advantageous embodiment of the invention, the pulp is fibrillated in at least one fibrillation stage after the additive addition, no matter in which stage the additive is added to the process.
The anionic optical brightening agent is capable of inhibiting hydrogen bonding between the cellulose fibrils in cellulose and can therefore be used to create a dispersive effect, which dispersive effect can increase the quality of the produced nanofibrillated cellulose. Due to the dispersive effect, optical brightening agent can be used as a dispersing agent in the nanofibrillated concentrating/redispersing process and, therefore, may help the process.
Nanofibrillated cellulose that contains optical brightening agent may improve not only the refining efficiency and the quality of the produced pulp but also both the strength and the optical properties of the end product to be produced from the pulp manufactured according to an example embodiment of the invention. The improvements in strength properties are mainly due to the features of nanofibrillated cellulose and the improvements in optical properties are mainly due to the features of the optical brightening agent.
The method according to an example embodiment of the invention comprises at least the following:
- introducing raw material to a system which raw material includes cellulose,
- dosing at least one type of an optical brightening agent as a refining additive to the system, and
refining the raw material in the presence of the dosed optical brightening agent in at least one pre-refining or fibrillation stage in order to form fibrillar cellulose material.
When compared to the pulp produced according to the invention with pulp produced according to prior art, the novel invention can provide at least some of the following advantages:
- lower energy consumption to reach the targeted pulp fibrillation degree,
- better quality of the produced nanofibrillated cellulose pulp,
- better processing properties, including, for example, better water removability and better dispersing properties,
- better strength properties compared to the same total energy consumption of refining, and - better optical properties compared to the same amount of the optical brightening agent (due to better retention of the optical brightening agent). The amount of nanofibrillated cellulose in the pulp manufactured according to the invention may be 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95 or 1 00 w- %, including any and all ranges and subranges therein.
The pulp manufacturing process according to invention has at least one fibrillation stage, possibly at least 2, 3 or 4 fibrillation stages. According to the invention at least one type of the optical brightening agent is added
- before at least one of the mentioned fibrillation stages or before the pre-refining stage, possibly before at least 2, 3, 4 or 5 of the mentioned fibrillation stages or before the pre- fibrillation stage,
and/or
- to at least one of the mentioned fibrillation stages or to the pre-refining stage, possibly to at least 2, 3, 4 or 5 of the mentioned fibrillation stages or to the pre-refining stage.
In addition, according to the invention, the pulp is fibrillated after at least one additive dosage in at least one fibrillation stage in order to form some nanofibrillated cellulose material.
As it presented above, the addition of the optical brightening agent before or during the refining decreases the cellulose-cellulose bonding through hydroxyl groups by forming hydrogen bonds with the cellulose fibrils. At the same time, the addition of the optical brightening agent creates a dispersive effect to the pulp suspension through the repulsive forces between the anionic groups. Experimental tests
Experimental tests were carried out in processes wherein some amounts of optical brightening agents were dosed as refining additives. In addition, paper sheets were made from the produced pulps and tested afterwards.
1 . Used pulp
A bleached birch pulp made with conventional chemical pulping process was used as raw cellulose pulp.
2. Used optical brightening agents
Two different kinds of optical brightening agents were used as the refining additive: disulphonic type of the optical brightening agent and hexasulphonic type of the optical brightening agent. In addition, reference samples without addition of the optical brightening agent were performed.
3. Pre-refining
The pre-refining stage was performed with Voith refiner. Addition of the used optical brightening agent was always 2 w-%. The whole amount was dosed to the pulp before the pre-refiner stage, after which the samples were refined at energy of 200 kWh/t. The pre-refinings were performed in the consistency of 4%.
The obtained pulps were diluted to 1 .6% for fluidizer and to 2% for Masuko. The optical brightening agents were dosed to the pre-refining process in order to improve their bonding to fiber surface. ple preparation
4a: Fluidizer
The part of the samples was fluidized with the M-700 Microfluidics Processor. Those samples were dispersed with a mixer in 1 .6% consistency during 30 minutes. After dispersing, the samples were passed three times through fluidizer so that in the first pass there was only an APM chamber with diameter at 500 μιη. In the second pass, the fiber suspension was passed through two sequential chambers with diameters at 500 μιη and 200 μιη. The third pass was carried out so that the fiber suspension passed through sequential 500 μιη and 1 00 μιη diameter chambers. The condenser of the fluidizer was switched off during all these trials, as it was found to improve fibrillation in the first part of experiments.
4b: Masuko ultra-fine friction grinder.
The grinded samples were dispersed in 2% consistency with a mixer during 1 5 minutes before the treatment with Masuko. The dispersed samples were passed four times through Masuko in such a way that in the first pass the gap between the grinding stones was looser than with the following three passes. The grinder was washed after the first and third pass. racterization
The gel-like fiber suspensions obtained from Masuko and from fluidizer were characterized by measuring viscosity (Brookfield) and turbidity of the samples and by observing optical microscope and SEM images of the samples. In addition, with centrifugation measurements the dry matter content was measured from both the liquid and the solid phase in order to determine the amount of nano-sized material in the sample. paration of paper sheets
Paper sheets were made in a laboratory from the produced pulps. t results
Refining result can be estimated by measuring the viscosity level of the nanofibrillated cellulose sample, because the viscosity level of the pulp material goes along with the portion of nanofibrillated cellulose in the pulp. In general, more refined, and thus, more fibrillated nanofibrillated cellulose is more gel-like material than less nanofibrillated cellulose. Therefore, more gellike material means more nanofibrillated cellulose in the sample and this bigger part of nanofibrillate cellulose can be seen in higher viscosity level in the sample. Samples with optical brightening agent - dosage were clearly more viscous than the reference samples. The amount of unfibrillated fibers can be estimated from optical microscopy pictures.
Based on both the viscosity results and the optical microscope images, the optical brightening agent dosage had a clear effect on fibrillation. Some of these results can be seen in Figures 2a - 2c wherein viscosity results with some optical microscopy pictures of Masuko grinded samples are shown. The figure 2a presents the viscosity results of the reference sample 21 , the sample with disulphonic optical brightening agent dosage 22, and the sample with hexasulphonic optical brightening agent dosage 23. Figure 2b shows an optical microscopy picture of the reference sample 21 and figure 2c shows an optical microscopy picture of the sample 23 with hexasulphonic optical brightening agent dosage.
Also, preliminary redispersion tests on the fluidized samples were performed when the samples were oven dried. Differences in the disintegration of the dried films in water was detected. Reference samples did not broken into smaller pieces almost at all, but the optical brightening agent modified samples disintegrated clearly. Figures 3a and 3b show an optical microscopy images of fluidisator samples, wherein the reference sample (shown in figure 3a) and the sample 32 with hexasulphonic optical brightening agent (shown in figure 3b) are presented. The sample presented in figure 3b with the dosage of the optical brightening agent is clearly better fibrillated than the reference sample shown in figure 3a. Figures 4a and 4b show the same situation with SEM pictures (magnification : 1 0 000 x) in which the reference sample (in figure 4a) and the sample with hexasulphonated optical brightening agent addition (in figure 4b) are presented. As can be seen, the samples with hexasulphonated optical brightening agent looks clearly better compared to the reference sample, as many smaller fibrils can be seen in the image.
Quality of the nanofibrillated cellulose can be analyzed using centrifugation of nano-sized material and measuring the turbidity of the samples. Centrifugation results are supposed to describe the degree of fibrillation so that the more the nano-sized material has more efficient fibrillation than less nano-sized material. When it comes to turbidity results, the smaller the value for turbidity is, the more there should be nano-sized material in the sample. Figure 5 shows turbidity and centrifugation results of the fluidized samples. In this figure the reference sample 51 , the sample 52 with disulphonic type of the optical brightening agent dosage, and the sample 53 with addition of hexasulphonic type of the optical brightening agent are presented. As can be seen, according to the turbidity results, the samples with OBA dosages were the most nano-sized. Also centrifugation results indicated that amount of nano-sized material increases along with OBA addition. The paper sheets tested afterwards showed that internal strengths of the sheets produced according to the invention were clearly higher than the internal strength properties of the reference sheets produced without optical brightening agent addition.
One skilled in the art understands readily that the different embodiments of the invention may have applications in environments where optimization of a nanofibrillated cellulose pulp fibrillation is desired. Therefore, it is obvious that the present invention is not limited solely to the above-presented embodiments, but it can be modified within the scope of the appended claims.

Claims

Claims:
1 . A method for manufacturing pulp, wherein the manufactured pulp contains at least 30 w-% nanofibrillated cellulose material measured from the dried pulp, the method comprising:
- introducing raw material to a system which raw material includes cellulose,
- dosing at least one type of an optical brightening agent as a refining additive to the system, and
refining the raw material in the presence of the dosed optical brightening agent in at least one pre-refining stage or fibrillation stage in order to form fibrillar cellulose material.
2. The method according to claim 1 , characterized in that the refining is made in the presence of the dosed optical brightening agent in at least one fibrillation stage in order to form fibrillar cellulose material.
3. The method according to claim 1 or 2, characterized in that manufactured pulp contains at least 40 w-%, at least 50 w-%, at least 60 w-%, or at least 70 w-% nanofibrillated cellulose material measured from the dried pulp.
4. The method according to any preceding claim 1 to 3, characterized in that at least part of the raw material is selected from the following group:
- unbleached chemical pulp,
- bleached chemical pulp,
- unbleached chemithermo pulp, and
- bleached chemithermo pulp.
5. The method according to any preceding claim 1 to 4, characterized in that at least one type of the optical brightening agent is dosed before the pre-refining stage.
6. The method according to any preceding claim 1 to 5, characterized in that at least one type of the optical brightening agent is added to the pre-refining stage.
7. The method according to any preceding claim 1 to 6, characterized in that at least one type of the optical brightening agent is dosed before the fibrillation stage.
8. The method according to any preceding claim 1 to 7, characterized in that at least one type of the optical brightening agent is dosed to the fibrillation stage.
9. The method according to any preceding claim 1 to 8, characterized in that at least one dosed optical brightening agent type is selected from the group of stilbene, coumarin and pyrazo!ine compounds.
10. A use of a pulp in nanofibrillated cellulose composites, wherein at least part of the pulp is manufactured according to the method of any preceding claim.
1 1 . A use of a pulp in manufacturing of paper or paperboard including
- base paper production, and
- finishing stages of paper or paperboard,
wherein at least part of the pulp is manufactured according to the method of any preceding claim 1 to 9.
12. The use according to claim 1 1 , wherein said finishing stages comprise coatings for the paper or paperboard.
EP10832694.3A 2009-11-24 2010-11-05 Method for manufacturing nanofibrillated cellulose pulp and use of the pulp in paper manufacturing or in nanofibrillated cellulose composites Active EP2504487B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FI20096233A FI123289B (en) 2009-11-24 2009-11-24 Process for the preparation of nanofibrillated cellulosic pulp and its use in papermaking or nanofibrillated cellulose composites
PCT/FI2010/050897 WO2011064441A1 (en) 2009-11-24 2010-11-05 Method for manufacturing nanofibrillated cellulose pulp and use of the pulp in paper manufacturing or in nanofibrillated cellulose composites

Publications (3)

Publication Number Publication Date
EP2504487A1 true EP2504487A1 (en) 2012-10-03
EP2504487A4 EP2504487A4 (en) 2014-01-22
EP2504487B1 EP2504487B1 (en) 2016-07-20

Family

ID=41395280

Family Applications (1)

Application Number Title Priority Date Filing Date
EP10832694.3A Active EP2504487B1 (en) 2009-11-24 2010-11-05 Method for manufacturing nanofibrillated cellulose pulp and use of the pulp in paper manufacturing or in nanofibrillated cellulose composites

Country Status (5)

Country Link
US (1) US20130000855A1 (en)
EP (1) EP2504487B1 (en)
CN (1) CN102686799A (en)
FI (1) FI123289B (en)
WO (1) WO2011064441A1 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10731298B2 (en) 2012-06-15 2020-08-04 University Of Maine System Board Of Trustees Release paper and method of manufacture

Families Citing this family (57)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA2710273A1 (en) 2007-12-20 2009-07-09 University Of Tennessee Research Foundation Wood adhesives containing reinforced additives for structural engineering products
FI124724B (en) * 2009-02-13 2014-12-31 Upm Kymmene Oyj A process for preparing modified cellulose
SI2808440T1 (en) 2009-03-30 2019-11-29 Fiberlean Tech Ltd Process for the production of nano-fibrillar cellulose suspensions
PT2236545E (en) 2009-03-30 2014-11-06 Omya Int Ag Process for the production of nano-fibrillar cellulose gels
GB0908401D0 (en) 2009-05-15 2009-06-24 Imerys Minerals Ltd Paper filler composition
ES2464733T3 (en) 2010-04-27 2014-06-03 Omya International Ag Process for the production of gel-based composite materials
SI2386682T1 (en) 2010-04-27 2014-07-31 Omya International Ag Process for the manufacture of structured materials using nano-fibrillar cellulose gels
GB201019288D0 (en) 2010-11-15 2010-12-29 Imerys Minerals Ltd Compositions
AU2012208922B2 (en) 2011-01-21 2016-10-13 Fpinnovations High aspect ratio cellulose nanofilaments and method for their production
WO2012115590A1 (en) 2011-02-24 2012-08-30 Innventia Ab Single-step method for production of nano pulp by acceleration and disintegration of raw material
US8835141B2 (en) * 2011-06-09 2014-09-16 The United States Of America As Represented By The Secretary Of Agriculture Methods for integrated conversion of lignocellulosic material to sugars or biofuels and nano-cellulose
FI20115882A0 (en) * 2011-09-08 2011-09-08 Teknologian Tutkimuskeskus Vtt Oy A process for making a fiber yarn
FI126041B (en) 2011-09-12 2016-06-15 Stora Enso Oyj Method for controlling retention and intermediate used in the process
FI126457B (en) 2011-11-14 2016-12-15 Upm Kymmene Corp Method for producing fibril pulp
FI126118B (en) * 2012-02-10 2016-06-30 Upm Kymmene Corp Cellulose pulp pretreatment method
FI126013B (en) * 2012-02-13 2016-05-31 Upm Kymmene Corp Process and system for the treatment of fibril cellulose, as well as fibril cellulose material
GB2502955B (en) * 2012-05-29 2016-07-27 De La Rue Int Ltd A substrate for security documents
FI127817B (en) * 2012-08-21 2019-03-15 Upm Kymmene Corp Method for making paper product and paper product
FI127526B (en) * 2012-11-03 2018-08-15 Upm Kymmene Corp Method for producing nanofibrillar cellulose
SE537517C2 (en) 2012-12-14 2015-05-26 Stora Enso Oyj Wet-laid sheet material comprising microfibrillated cellulosic process for making them
FR3003581B1 (en) * 2013-03-20 2015-03-20 Ahlstroem Oy FIBROUS MEDIUM BASED ON FIBERS AND NANOFIBRILS OF POLYSACCHARIDE
EP2799618B1 (en) 2013-04-29 2016-04-27 Blankophor GmbH & Co. KG Use of micronized cellulose and fluorescent whitening agent for surface treatment of cellulosic materials
US9656914B2 (en) 2013-05-01 2017-05-23 Ecolab Usa Inc. Rheology modifying agents for slurries
FI127014B (en) * 2013-05-15 2017-09-29 Upm Kymmene Corp A process for preparing nanofibril cellulose and a paper product
FI125942B (en) * 2013-07-26 2016-04-15 Upm Kymmene Corp Modification procedure of nanofibrillar cellulose composition
US10695947B2 (en) 2013-07-31 2020-06-30 University Of Maine System Board Of Trustees Composite building products bound with cellulose nanofibers
US9410288B2 (en) 2013-08-08 2016-08-09 Ecolab Usa Inc. Use of nanocrystaline cellulose and polymer grafted nanocrystaline cellulose for increasing retention in papermaking process
US9303360B2 (en) * 2013-08-08 2016-04-05 Ecolab Usa Inc. Use of nanocrystaline cellulose and polymer grafted nanocrystaline cellulose for increasing retention in papermaking process
AU2013399666B2 (en) * 2013-09-04 2017-05-25 Halliburton Energy Services, Inc. Nano-carbohydrate composites as a lost circulation materials - LCM origami and other drilling fluid applications
FI126042B (en) * 2014-03-31 2016-06-15 Upm Kymmene Corp Process for the manufacture of nanofibrillar cellulose and nanofibrillar cellulose product
GB201409047D0 (en) * 2014-05-21 2014-07-02 Cellucomp Ltd Cellulose microfibrils
FI126688B (en) 2014-06-30 2017-03-31 Upm Kymmene Corp Method and apparatus for controlling the quality of nanofibrillar cellulose
US9970159B2 (en) * 2014-12-31 2018-05-15 Innovatech Engineering, LLC Manufacture of hydrated nanocellulose sheets for use as a dermatological treatment
KR20170141237A (en) 2015-05-01 2017-12-22 에프피이노베이션스 A dry mixed re-dispersible cellulose filament/carrier product and the method of making the same
JP6821664B2 (en) * 2015-06-04 2021-01-27 ブルース クロスリー Manufacturing method of cellulose nanofibril
WO2017064559A1 (en) 2015-10-14 2017-04-20 Fiberlean Technologies Limited 3d-formable sheet material
WO2017066540A1 (en) 2015-10-15 2017-04-20 Ecolab Usa Inc. Nanocrystalline cellulose and polymer-grafted nanocrystalline cellulose as rheology modifying agents for magnesium oxide and lime slurries
FI130254B (en) * 2016-02-03 2023-05-11 Kemira Oyj A process for producing microfibrillated cellulose and a product thereof
SE539833C2 (en) * 2016-04-01 2017-12-12 Stora Enso Oyj Process for production of film comprising microfibrillated cellulose
EP3440030A1 (en) * 2016-04-04 2019-02-13 FiberLean Technologies Limited Compositions and methods for providing increased strength in ceiling, flooring, and building products
US11846072B2 (en) 2016-04-05 2023-12-19 Fiberlean Technologies Limited Process of making paper and paperboard products
DK3440259T3 (en) 2016-04-05 2021-03-29 Fiberlean Tech Ltd PAPER AND PAPER PRODUCTS
ES2919328T3 (en) 2016-04-22 2022-07-26 Fiberlean Tech Ltd Fibers comprising microfibrillated cellulose and methods of manufacturing fibers and nonwovens thereof
SE539950C2 (en) * 2016-05-20 2018-02-06 Stora Enso Oyj An uv blocking film comprising microfibrillated cellulose, amethod for producing said film and use of a composition hav ing uv blocking properties
US10724173B2 (en) 2016-07-01 2020-07-28 Mercer International, Inc. Multi-density tissue towel products comprising high-aspect-ratio cellulose filaments
US10570261B2 (en) 2016-07-01 2020-02-25 Mercer International Inc. Process for making tissue or towel products comprising nanofilaments
US10463205B2 (en) 2016-07-01 2019-11-05 Mercer International Inc. Process for making tissue or towel products comprising nanofilaments
JP2020500222A (en) * 2016-09-01 2020-01-09 エイチエス・マニュファクチャリング・グループ・リミテッド・ライアビリティ・カンパニー Method for bio-based derivatization of cellulosic surfaces
WO2018053475A1 (en) 2016-09-19 2018-03-22 Mercer International Inc. Absorbent paper products having unique physical strength properties
SE541755C2 (en) * 2017-03-01 2019-12-10 Stora Enso Oyj Process for production of film comprising microfibrillated cellulose
US10822442B2 (en) 2017-07-17 2020-11-03 Ecolab Usa Inc. Rheology-modifying agents for slurries
US10865317B2 (en) 2017-08-31 2020-12-15 Kimberly-Clark Worldwide, Inc. Low-fluorine compositions with cellulose for generating superhydrophobic surfaces
CN111684130A (en) * 2017-12-04 2020-09-18 芬欧汇川集团 Method for producing pulp precursor material for composite applications from chemical pulp and product thereof
WO2019161272A1 (en) 2018-02-15 2019-08-22 North Carolina State University Synthesis of micron and nanoscale carbon spheres and structures using hydrothemal carbonization
JP7273058B2 (en) 2018-04-12 2023-05-12 マーサー インターナショナル インコーポレイテッド Methods for improving high aspect ratio cellulose filament blends
CN112673053B (en) * 2018-07-19 2023-05-02 凯米拉公司 Cellulose composition
FI129352B (en) * 2019-05-03 2021-12-31 Valmet Technologies Inc Monitoring and controlling of refining of fibrous pulp

Family Cites Families (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3534912A (en) * 1967-01-11 1970-10-20 Beloit Corp Low speed refining of a papermaking pulp solution
US3591451A (en) * 1969-02-06 1971-07-06 Ethyl Corp Pretreatment of vegetable matter and delignification of the refined matter with chloring dioxide
AU723465B2 (en) * 1996-07-15 2000-08-24 Rhodia Chimie Supplementation of essentially amorphous cellulose nanofibrils with carboxycellulose which has a high degree of substitution
US7638016B2 (en) * 2005-02-19 2009-12-29 International Paper Company Method for treating kraft pulp with optical brighteners after chlorine bleaching to increase brightness
EP1848856A1 (en) * 2005-02-19 2007-10-31 International Paper Company Fixation of optical brightening agents onto papermaking fiber
US7914646B2 (en) * 2006-07-21 2011-03-29 Nalco Company Compositions and processes for paper production
WO2007091942A1 (en) * 2006-02-08 2007-08-16 Stfi-Packforsk Ab Method for the manufacturing of microfibrillated cellulose
WO2007096242A1 (en) * 2006-02-20 2007-08-30 Clariant International Ltd Improved process for the manufacture of paper and board
JP4831570B2 (en) 2006-03-27 2011-12-07 木村化工機株式会社 Functional cellulose material having high functional particle content and method for producing the same
JP4958097B2 (en) * 2006-07-19 2012-06-20 国立大学法人京都大学 Nanofiber sheet, method for producing the same, and fiber-reinforced composite material
RU2490388C2 (en) 2007-04-05 2013-08-20 Акцо Нобель Н.В. Method for improving optical properties of paper
JP5398180B2 (en) * 2007-06-11 2014-01-29 国立大学法人京都大学 Lignin-containing microfibrillated plant fiber and method for producing the same
AU2008330684B8 (en) * 2007-11-26 2014-01-23 The University Of Tokyo Cellulose nanofiber, production method of same and cellulose nanofiber dispersion
US8298373B2 (en) * 2008-02-07 2012-10-30 University Of New Brunswick Combined process of peroxide bleaching of wood pulps and addition of optical brightening agents
SE0800807L (en) 2008-04-10 2009-10-11 Stfi Packforsk Ab New procedure

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
No further relevant documents disclosed *
See also references of WO2011064441A1 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10731298B2 (en) 2012-06-15 2020-08-04 University Of Maine System Board Of Trustees Release paper and method of manufacture

Also Published As

Publication number Publication date
EP2504487A4 (en) 2014-01-22
FI20096233A0 (en) 2009-11-24
CN102686799A (en) 2012-09-19
US20130000855A1 (en) 2013-01-03
EP2504487B1 (en) 2016-07-20
FI20096233A (en) 2011-05-25
FI123289B (en) 2013-01-31
WO2011064441A1 (en) 2011-06-03

Similar Documents

Publication Publication Date Title
EP2504487B1 (en) Method for manufacturing nanofibrillated cellulose pulp and use of the pulp in paper manufacturing or in nanofibrillated cellulose composites
US9458571B2 (en) Method for producing furnish, furnish and paper
CA2824191C (en) High aspect ratio cellulose nanofilaments and method for their production
EP2236545B1 (en) Process for the production of nano-fibrillar cellulose gels
RU2535688C2 (en) Method of obtaining modified cellulose
Oliaei et al. Microfibrillated lignocellulose (MFLC) and nanopaper films from unbleached kraft softwood pulp
CA2641607A1 (en) Method for the manufacturing of microfibrillated cellulose
US11814794B2 (en) Cellulose fiber molded product and method for manufacturing the same
SE543552C2 (en) Refined cellulose fiber composition
Fathi et al. Prospects for the preparation of paper money from cotton fibers and bleached softwood kraft pulp fibers with nanofibrillated cellulose
Park et al. Utilization of cellulose micro/nanofibrils as paper additive for the manufacturing of security paper
AU2017327762A1 (en) Method for producing cellulose filaments with less refining energy
JP7346018B2 (en) Method for producing cellulose fiber slurry
WO2023209622A1 (en) Dried modified pulp with a certain content of microfibrils and pre-fibrillated fibers
EP3055454A1 (en) Method for manufacturing a paper, a paper and its use, a furnish and a wood based composition

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: 20120511

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)
A4 Supplementary search report drawn up and despatched

Effective date: 20140102

RIC1 Information provided on ipc code assigned before grant

Ipc: D21H 11/18 20060101AFI20131217BHEP

Ipc: D21H 21/30 20060101ALI20131217BHEP

Ipc: D21H 21/32 20060101ALI20131217BHEP

Ipc: D21D 1/20 20060101ALI20131217BHEP

Ipc: D21C 9/00 20060101ALI20131217BHEP

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

INTG Intention to grant announced

Effective date: 20160212

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

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: IE

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: AT

Ref legal event code: REF

Ref document number: 814210

Country of ref document: AT

Kind code of ref document: T

Effective date: 20160815

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 602010034947

Country of ref document: DE

REG Reference to a national code

Ref country code: SE

Ref legal event code: TRGR

REG Reference to a national code

Ref country code: LT

Ref legal event code: MG4D

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 7

REG Reference to a national code

Ref country code: NO

Ref legal event code: T2

Effective date: 20160720

REG Reference to a national code

Ref country code: NL

Ref legal event code: MP

Effective date: 20160720

REG Reference to a national code

Ref country code: AT

Ref legal event code: MK05

Ref document number: 814210

Country of ref document: AT

Kind code of ref document: T

Effective date: 20160720

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

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: 20160720

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: 20161120

Ref country code: NL

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: 20160720

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: 20160720

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: 20160720

Ref country code: IT

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: 20160720

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

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: 20160720

Ref country code: BE

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

Effective date: 20160720

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: 20160720

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: 20160720

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: 20161121

Ref country code: ES

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: 20160720

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: 20161021

REG Reference to a national code

Ref country code: DE

Ref legal event code: R026

Ref document number: 602010034947

Country of ref document: DE

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

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: 20160720

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: 20160720

PLBI Opposition filed

Free format text: ORIGINAL CODE: 0009260

PLAX Notice of opposition and request to file observation + time limit sent

Free format text: ORIGINAL CODE: EPIDOSNOBS2

26 Opposition filed

Opponent name: STORA ENSO OYJ

Effective date: 20170420

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

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: 20160720

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: 20161020

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: 20160720

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: 20160720

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: 20160720

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

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

Ref country code: CH

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

Effective date: 20161130

Ref country code: LI

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

Effective date: 20161130

REG Reference to a national code

Ref country code: IE

Ref legal event code: MM4A

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: 20160720

PLBB Reply of patent proprietor to notice(s) of opposition received

Free format text: ORIGINAL CODE: EPIDOSNOBS3

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

Ref country code: LU

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

Effective date: 20161130

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 8

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: 20161105

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

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: 20101105

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: 20160720

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: 20160720

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: 20160720

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: 20160720

PLCK Communication despatched that opposition was rejected

Free format text: ORIGINAL CODE: EPIDOSNREJ1

REG Reference to a national code

Ref country code: DE

Ref legal event code: R100

Ref document number: 602010034947

Country of ref document: DE

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 NON-PAYMENT OF DUE FEES

Effective date: 20161105

PLBN Opposition rejected

Free format text: ORIGINAL CODE: 0009273

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

Free format text: STATUS: OPPOSITION REJECTED

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: 20160720

27O Opposition rejected

Effective date: 20180721

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

Ref country code: GB

Payment date: 20231127

Year of fee payment: 14

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

Ref country code: SE

Payment date: 20231127

Year of fee payment: 14

Ref country code: NO

Payment date: 20231129

Year of fee payment: 14

Ref country code: FR

Payment date: 20231127

Year of fee payment: 14

Ref country code: FI

Payment date: 20231127

Year of fee payment: 14

Ref country code: DE

Payment date: 20231129

Year of fee payment: 14