EP3822409B1 - Mfc réticulé - Google Patents

Mfc réticulé

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Publication number
EP3822409B1
EP3822409B1 EP19208620.5A EP19208620A EP3822409B1 EP 3822409 B1 EP3822409 B1 EP 3822409B1 EP 19208620 A EP19208620 A EP 19208620A EP 3822409 B1 EP3822409 B1 EP 3822409B1
Authority
EP
European Patent Office
Prior art keywords
film
mfc
chemically modified
aqueous composition
crosslinking agent
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
EP19208620.5A
Other languages
German (de)
English (en)
Other versions
EP3822409C0 (fr
EP3822409A1 (fr
Inventor
Ali Naderi
Johan Larsson
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.)
Billerud AB
Original Assignee
Billerud 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 Billerud AB filed Critical Billerud AB
Priority to EP19208620.5A priority Critical patent/EP3822409B1/fr
Priority to CN202080077855.8A priority patent/CN114641597A/zh
Priority to PCT/EP2020/081884 priority patent/WO2021094440A1/fr
Priority to JP2022553220A priority patent/JP2023501001A/ja
Priority to EP20803189.8A priority patent/EP4058632A1/fr
Publication of EP3822409A1 publication Critical patent/EP3822409A1/fr
Application granted granted Critical
Publication of EP3822409C0 publication Critical patent/EP3822409C0/fr
Publication of EP3822409B1 publication Critical patent/EP3822409B1/fr
Active legal-status Critical Current
Anticipated expiration legal-status Critical

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Classifications

    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H11/00—Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only
    • D21H11/16—Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only modified by a particular after-treatment
    • D21H11/18—Highly hydrated, swollen or fibrillatable fibres
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H11/00—Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only
    • D21H11/16—Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only modified by a particular after-treatment
    • D21H11/20—Chemically or biochemically modified fibres
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/03—Non-macromolecular organic compounds
    • D21H17/05—Non-macromolecular organic compounds containing elements other than carbon and hydrogen only
    • D21H17/06—Alcohols; Phenols; Ethers; Aldehydes; Ketones; Acetals; Ketals
    • 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
    • D21H17/03—Non-macromolecular organic compounds
    • D21H17/05—Non-macromolecular organic compounds containing elements other than carbon and hydrogen only
    • D21H17/14—Carboxylic acids; Derivatives thereof
    • 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
    • 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
    • D21H19/10—Coatings without pigments
    • D21H19/12—Coatings without pigments applied as a solution using water as the only solvent, e.g. in the presence of acid or alkaline 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
    • 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
    • D21H19/64—Inorganic 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
    • D21H23/00—Processes or apparatus for adding material to the pulp or to the paper
    • D21H23/02—Processes or apparatus for adding material to the pulp or to the paper characterised by the manner in which substances are added
    • D21H23/22—Addition to the formed paper
    • D21H23/24—Addition to the formed paper during paper manufacture
    • 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
    • D21H23/00—Processes or apparatus for adding material to the pulp or to the paper
    • D21H23/02—Processes or apparatus for adding material to the pulp or to the paper characterised by the manner in which substances are added
    • D21H23/22—Addition to the formed paper
    • D21H23/24—Addition to the formed paper during paper manufacture
    • D21H23/26—Addition to the formed paper during paper manufacture by selecting point of addition or moisture content of the paper

Definitions

  • the present disclosure relates to the production of films comprising microfibrillated cellulose (MFC).
  • MFC microfibrillated cellulose
  • MFC microfibrillated cellulose
  • TEMPO-oxidized cellulose nanofibres are used to form a film that is crosslinked with ions to withstand oxygen at increased relative humidity (RH).
  • RH relative humidity
  • the crosslinking is performed by immersion in a solution of ions for hours and the film is thereafter washed for hours and dried for days.
  • JP2016089307 discloses a method of coating a paper made of cellulose with an acid-type cellulose nanofiber dispersion that is crosslinked with a polyvalent metal compound.
  • the crosslinking is taught to be conducted by immersion and washing for more than 35 minutes.
  • the paper is thereafter laminated with a heat-seal layer and evaluated as suitable for paper container that can be used under hot water treatment.
  • EP2371892 discloses a lab method of spraying cross-linking solution over a nanocellulose film to crosslink it, wherein the film is very thin (below 1 ⁇ m) and the concentration of crosslinker is relatively high.
  • An objective of the present disclosure is to provide a method of producing an MFC-based film having improved oxygen-barrier properties, which method allows for high productivity in full-scale production of the film on a paper machine.
  • the reason for applying the crosslinking agent to a "dry" MFC film is that such a film comprises regions of dense/crystallized MFC structures separated by regions of less dense/amorphous MFC, which is more accessible for the crosslinking agent.
  • the crosslinking agent crosslinks the regions of less dense/amorphous MFC and thereby reduces their mobility. Further, the inventors believe that the relatively short time period of step b) may focus the crosslinking action to the regions where it is most needed.
  • the present disclosure provides a method for producing a crosslinked film comprising microfibrillated cellulose (MFC), wherein the method comprises the steps of:
  • step b) is instead drying the film from step a) such that the moisture content of the film is less than 30%, such as less than 25% within five minutes of the performance of step a), such as within three minutes of the performance of step a).
  • the method is suitably carried out in a full-scale paper machine, i.e. a paper machine running at a speed of at least 300 m/min and having a trim width of at least 1500 mm, such as at least 3000 mm. Consequently, only a very limited period of time is available for the completion of each step of the process.
  • Steps a) and b) are preferably carried out in or after a drying section of the paper machine.
  • a drying section of the paper machine there is typically arranged a press section.
  • a forming section such as a wire section.
  • Step a) may be carried out by means of a size press or a film press.
  • step a) comprises the spraying the aqueous composition onto the film.
  • aqueous composition is added by means of a size press or film press, is typically has a viscosity of 10-1000 mPas, preferably 10-300 mPas, when measured as dynamic viscosity with a Brookfield rotational viscometer using spindle no.4 at 100 rpm and 25 °C according to the Brookfield instruction sheet.
  • a curtain coater or a direct rod coater is used for the application of the aqueous composition.
  • the viscosity of the aqueous composition is typically 100-800 mPas when measured as dynamic viscosity with a Brookfield rotational viscometer using spindle no.4 at 100 rpm and 25 °C according to the Brookfield instruction sheet.
  • a blade coater is used for the application of the aqueous composition.
  • the viscosity of the aqueous composition is typically 400-1500 mPas when measured as dynamic viscosity with a Brookfield rotational viscometer using spindle no.4 at 100 rpm and 25 °C according to the Brookfield instruction sheet.
  • the aqueous composition may comprise a polymer, such as starch, carboxymethyl cellulose (CMC), polyvinyl alcohol (PVOH) or MFC.
  • a polymer such as starch, carboxymethyl cellulose (CMC), polyvinyl alcohol (PVOH) or MFC.
  • the composition may comprise a rheology modifier.
  • Step b) may be carried out by means of heated cylinders, such as steam-heated cylinders, and/or contactless drying, preferably using hot air and/or infrared radiation.
  • the method may further comprise the steps of:
  • steps i) and ii) are carried out in a paper machine, such as the same paper machine as the one used for steps a) and b). Thereby, the overall efficiency of the method may be improved.
  • steps a) and b) are carried out offline, which means that they are not carried out in the paper machine used for steps i) and ii). Steps a) and b) may even be carried out at a different location than steps i) and ii).
  • Step ii) is preferably carried out in the forming section of a paper machine.
  • the width of the wire of the forming section may be at least 1500 mm, such as at least 3000 mm.
  • the method further comprises a step of fibrillating cellulosic fibres to provide the MFC of step i).
  • This step may comprise mechanical, enzymatic and/or chemical sub-steps known to the skilled person.
  • a chemical sub-step may introduce a chargeable moiety that facilitates the crosslinking.
  • MFC means nano-scale cellulose particle fibres or fibrils with at least one dimension less than 100 nm.
  • MFC comprises partly or totally fibrillated cellulose or lignocellulose fibres.
  • the liberated fibrils have a diameter less than 100 nm, whereas the actual fibril diameter or particle size distribution and/or aspect ratio (length/width) depends on the source and the manufacturing methods.
  • the smallest fibril is called elementary fibril and has a diameter of approximately 2-4 nm, while it is common that the aggregated form of the elementary fibrils, also defined as microfibril is the main product that is obtained when making MFC e.g. by using an extended refining process or a pressure-drop disintegration process.
  • the length of the fibrils can vary from around 1 to more than 10 micrometers.
  • a coarse MFC grade might contain a substantial fraction of fibrillated fibres, i.e. protruding fibrils from the tracheid (cellulose fibre), and with a certain amount of fibrils liberated from the tracheid.
  • MFC cellulose microfibrils, fibrillated cellulose, nanofibrillated cellulose (NFC), fibril aggregates, nanoscale cellulose fibrils, cellulose nanofibres, cellulose nanofibrils (CNF), cellulose microfibres (CMF), cellulose fibrils, microfibrillar cellulose, microfibril aggregrates and cellulose microfibril aggregates.
  • MFC can also be characterized by various physical or physical-chemical properties such as large surface area or its ability to form a gel-like material at low solids content (1-5 wt.%) when dispersed in water.
  • the cellulose fibre is preferably fibrillated to such an extent that the final specific surface area of the formed MFC is from about 1 to about 200 m 2 /g, or more preferably 50-200 m 2 /g when determined for a freeze-dried material with the BET method ( Brunauer, Stephen, Paul Hugh Emmett, and Edward Teller. "Adsorption of gases in multimolecular layers.” Journal of the American chemical society 60.2 (1938): 309-319 .). Nitrogen (N2) gas adsorption isotherms are recorded using an ASAP 2020 (Micromeritics, USA) instrument. Measurements are performed at liquid nitrogen temperatures (i.e., 77 K), and the specific surface areas of the samples were obtained from the isotherms using the BET method.
  • MFC multi-pass refining
  • pre-hydrolysis followed by refining or high shear disintegration or liberation of fibrils.
  • One or several pre-treatment step(s) is/are usually required in order to make MFC manufacturing both energy efficient and sustainable.
  • the cellulose fibres of the pulp to be supplied may thus be pre-treated enzymatically or chemically, for example to hydrolyse or swell fibre or reduce the quantity of hemicellulose or lignin.
  • the cellulose fibres may be chemically modified before fibrillation. After such chemical modification, it is typically easier to disintegrate the fibres into MFC or nanofibrillar size or NFC.
  • the nanofibrillar cellulose may contain some hemicelluloses; the amount is dependent on factors such as plant source and pulping process.
  • Mechanical disintegration of the pre-treated fibres, e.g. hydrolysed, pre-swelled, or oxidized cellulose rawmaterial is carried out with suitable equipment such as a refiner, grinder, homogenizer, collider, friction grinder, ultrasound sonicator, fluidizer such as microfluidizer, macrofluidizer or fluidizer-type homogenizer.
  • suitable equipment such as a refiner, grinder, homogenizer, collider, friction grinder, ultrasound sonicator, fluidizer such as microfluidizer, macrofluidizer or fluidizer-type homogenizer.
  • the product might also contain fines or e.g. other chemicals present in wood fibres or in papermaking process.
  • the product might also contain various amounts of micron size fibre particles that have not been efficiently fibrillated.
  • MFC is produced from wood cellulose fibres, both from hardwood or softwood fibres. It can also be made from, agricultural fibres such as wheat straw pulp, bamboo, bagasse, or other non-wood fibre sources. It is preferably made from pulp of virgin fibre, e.g. mechanical, chemical and/or thermomechanical pulps, preferably never-dried fibres.
  • MFC includes, but is not limited to, the proposed TAPPI standard W13021 on cellulose nanofibril (CNF) defining a cellulose nanofibre material containing multiple elementary fibrils with both crystalline and amorphous regions, having a high aspect ratio with width of 5-30nm and aspect ratio usually greater than 50.
  • CNF cellulose nanofibril
  • the amount of MFC in the film is preferably at least 50% by dry weight, such as at least 70% by dry weight, such as at least 80% by dry weight.
  • the film has a grammage according to ISO 536:2012 of 5-100 g/m 2 , such as 5-70 g/m 2 , such as 10-70 g/m 2 , such as 10-60 g/m 2 , such as 20-60 g/m 2 , such as 30-60 g/m 2 , preferably 45-60 g/m 2 , more preferably 50-60 g/m 2 .
  • step a) at least 75% of the water absorbed by the film following the application of step a) is removed within five minutes of the performance of step a).
  • step a) 50% of the water absorbed by the film following the application of step a) is removed within three minutes of the performance of step a), such as within two minutes of the performance of step a). Thereby, the efficiency of the method is increased.
  • step b) may be carried out such that the moisture content of the film is less than 30%, such as less than 25% within five minutes of the performance of step a), such as within three minutes of the performance of step a).
  • the MFC of step a) comprises a chargeable moiety selected from carboxy, carboxymethyl, carboxyalkyl, sulfonyl, sulfoethyl and phosphoryl groups.
  • the crosslinking agent may in such case be a divalent cation, and if the crosslinking agent is a metal ion, it is a divalent ion that has a concentration in the aqueous composition of 50 mM or lower.
  • the divalent cation is preferably selected from the group consisting of Zn 2+ , Ca 2+ , Cu 2+ and Mg 2+ . Zn 2+ and Ca 2+ are particularly preferred.
  • Ca 2+ may be considered to be the most preferred divalent cation since it is relatively small and better penetrates the amorphous regions than larger ions.
  • the concentration of the crosslinking agent may be 0.1-50 mM, such as 0.1-40 mM, preferably 0.1-30 mM. A relatively low concentration is advantageous since a too high concentration may cause the fibrils to crosslink too tight to each other yielding an impaired barrier.
  • the chemical modification introducing the chargeable moiety is preferably selected from the group consisting of TEMPO oxidation, alkoxylation, phosphorylation, sulfonation, sulfoethylation and chlorite oxidation preceded by introduction of aldehydes, for example through periodate oxidation.
  • the alkoxylation is preferably carboxymethylation.
  • the MFC of step a) comprises quaternary amines.
  • the crosslinking agent may in such case be a multivalent anion, such as a phosphate ion or a polycarboxylate ion.
  • the introduction of quaternary amines is preferably conducted via a compound that both contains a group reacting with hydroxyl groups to form covalent bonds as well as a quaternary ammonium group.
  • the introduction may also be conducted via a compound that both contains a group reacting with hydroxyl groups to form covalent bonds and a group that can further react to attach an amine.
  • the group reacting with hydroxyl groups is selected from any of epoxy, halohydrin capable of forming epoxy, active halogen, isocyanate, active vinyl or methylol.
  • examples of compounds bearing a group reacting with hydroxyl groups to form covalent bonds as well as a quaternary ammonium group are 2,3-epoxypropyl trimethylammonium chloride (EPTMAC), chlorocholine chloride (ClChCl), glycidyl trimethylammonium chloride and 3-chloro-2-hydroxypropyl trimethyl ammonium chloride. It may be advantageous to crosslink cationic amine-functional MFC since such functionalization chemistry is readily available on an industrial scale.
  • the fibres that are chemically modified have a charge density measured according to SCAN-CM 65:02 of 500-1800 ⁇ eq/g, such as 500-1000 ⁇ eq/g.
  • the film may further comprise nanofiller, e.g. in an amount of 1-20 wt.%.
  • Nanofillers are particles characterized by high surface areas and high aspect ratios. The high surface areas and aspect ratios may be beneficial in barrier applications, since the particles can make the diffusion of the gas molecules through the coating layer more difficult, thus improving the barrier properties.
  • Said nanofiller is preferably chosen from bentonite, kaolin or montmorillonite.
  • the crosslinker is not glutaraldehyde when the film comprises nanofiller. Instead, it may be Zn 2+ in a concentration of 0.1-5 mM or Ca 2+ in a concentration of 0.1-50 mM.
  • the crosslinking agent forms covalent bonds.
  • the crosslinking agent is preferably selected from the group consisting of borax, glutaraldehyde, citric acid or polycarboxylic acid.
  • Glutaraldehyde may be used together with a catalyst, such as zinc nitrate.
  • the crosslinked film produced by the method of the present disclosure is typically an oxygen barrier, preferably exhibiting an oxygen permeability (OP) of less than 500 ml ⁇ m m -2 d -1 bar -1 at 80% RH according to ASTM D3985 and F1927 standards.
  • OP oxygen permeability
  • the method for producing a crosslinked film comprising MFC comprises the steps of:
  • a suspension of low-charged MFC (0.1 wt%; total charge 40 ⁇ mol/g) was filtrated and thereafter dried (50 °C; 4 h) into a film.
  • the film was dipped for 5 seconds in a solution containing either borax or glutaraldehyde acting as crosslinker.
  • the latter chemical was employed in combination with zinc nitrate, which acts as catalyst for the reaction of glutaraldehyde with hydroxyl group.
  • the film was thereafter dried (50 °C; 4 h). Films of grammages of 30 g/m 2 and 60 g/m 2 were produced. No washing was performed between the dipping and the drying.
  • a suspension of carboxymethylated MFC (0.1 wt%; total charge 800 ⁇ mol/g) was filtrated and thereafter dried (50 °C; 4 h) into a film.
  • the film was dipped for 5 seconds in a solution containing either zinc nitrate hexahydrate, calcium chloride dihydrate, iron chloride hexahydrate or aluminum chloride hexahydrate acting as crosslinkers. Subsequently the film was dried (50 °C; 4 h). Films of grammages of 20 g/m 2 , 30 g/m 2 and 60 g/m 2 were produced. No washing was performed between the dipping and the drying.
  • the transmission rate (OTR) was measured on 5 cm 2 samples using a MOCON OX-TRAN 2/21 according to the ASTM D3985 and ASTM F1927 standards.
  • the OTR measurements were performed at 23° C and 50% RH or 80% RH, using the same relative humidity on both sides of the sample.
  • By multiplying OTR with film thickness (obtained by SEM) the oxygen permeability (OP) is obtained.
  • Table 1 Low/high charge MFC Crosslinker Ion conc. (mM) Nanofiller (10 wt%) O 2 Permeab. (50% RH) (ml ⁇ m m -2 d -1 bar -1 ) O 2 Permeab.
  • Table 1 shows reduction of oxygen permeability at 50% and 80% RH when divalent metal ions are applied at a concentration below 100 mM. In contrast, the trivalent metal ions and divalent metal ions in a higher concentration (i.e. 100 mM) failed to reduce oxygen permeability. For 80% RH, the best oxygen permeability values were obtained when Ca 2+ (1 or 10 mM) or Zn 2+ (1 mM) was added to a film comprising nanofiller. Table 1 also shows reduction of oxygen permeability at 80% RH when crosslinkers forming covalent bonds are applied.

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  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Biochemistry (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Laminated Bodies (AREA)
  • Paper (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)

Claims (15)

  1. Procédé de fabrication d'un film réticulé comprenant de la cellulose microfibrillée (MFC) modifiée chimiquement, dans lequel le procédé comprend les étapes suivantes :
    a) l'application d'une composition aqueuse comprenant un agent de réticulation sur un film comprenant de la MFC chimiquement modifiée, lequel film a une teneur en humidité inférieure à 15 %, telle qu'inférieure à 10 %, à condition que l'agent de réticulation soit un ion métallique, il s'agit d'un ion métallique divalent ayant une concentration dans la composition aqueuse inférieure à 50 mM, et la MFC chimiquement modifiée a une densité de charge mesurée selon la norme SCAN-CM 65:02 comprise entre 500 et 1 800 µeq/g ; et
    b) le séchage du film de l'étape a) de telle sorte qu'au moins 50 % de l'eau absorbée par le film après l'application de l'étape a) soit éliminée dans les cinq minutes suivant la réalisation de l'étape a),
    dans lequel
    la composition aqueuse de l'étape a) est ajoutée au film comprenant la MFC chimiquement modifiée au moyen d'une presse à encoller ou d'une presse à film,
    ou en pulvérisant la composition aqueuse sur le film,
    ou en utilisant un dispositif d'enduction à rideau ou un dispositif d'enduction à tige directe pour l'application de la composition aqueuse,
    ou en utilisant un dispositif d'enduction à lame pour l'application de la composition aqueuse.
  2. Procédé selon la revendication 1, dans lequel au moins 75 % de l'eau absorbée par le film après l'application de l'étape a) est éliminée dans les cinq minutes suivant l'exécution de l'étape a).
  3. Procédé selon la revendication 1 ou la revendication 2, dans lequel au moins 50 % de l'eau absorbée par le film après l'application de l'étape a) est éliminée dans les trois minutes suivant l'exécution de l'étape a), tel que dans les deux minutes suivant l'exécution de l'étape a).
  4. Procédé selon l'une quelconque des revendications précédentes, dans lequel le séchage de l'étape b) est effectué de telle sorte que la teneur en humidité du film soit inférieure à 30 %, telle qu'inférieure à 25 %, dans les cinq minutes suivant l'exécution de l'étape a).
  5. Procédé selon l'une quelconque des revendications précédentes, dans lequel la MFC chimiquement modifiée de l'étape a) comprend un groupement chargeable choisi parmi les groupes carboxy, carboxyméthyle, carboxyalkyle, sulfonyle, sulfoéthyle et phosphoryle.
  6. Procédé selon l'une quelconque des revendications précédentes, dans lequel l'agent de réticulation est un cation divalent, de préférence un ion métallique divalent, tel qu'un ion choisi dans le groupe constitué par Zn2+, Ca2+, Cu2+ et Mg2+.
  7. Procédé selon la revendication 6, dans lequel le film comprend en outre une nanocharge, par exemple en une quantité comprise entre 1 et 20 % en poids.
  8. Procédé selon l'une quelconque des revendications 6 à 7, dans lequel la concentration de l'ion divalent dans la solution de réticulation est comprise entre 0,1 et 50 mM, telle que comprise entre 0,1 et 40 mM, de préférence comprise entre 0,1 et 30 mM.
  9. Procédé selon l'une quelconque des revendications 1 à 5, dans lequel l'agent de réticulation forme des liaisons covalentes et est de préférence choisi dans le groupe constitué par le borax, le glutaraldéhyde, l'acide citrique et l'acide polycarboxylique.
  10. Procédé selon l'une quelconque des revendications 1 à 4, dans lequel la MFC chimiquement modifiée de l'étape a) comprend des amines quaternaires et l'agent de réticulation est un anion multivalent, tel qu'un ion phosphate ou un ion polycarboxylate.
  11. Procédé selon l'une quelconque des revendications précédentes, dans lequel l'application de l'étape a) est réalisée au moyen d'une presse à film ou d'une presse à encoller.
  12. Procédé selon l'une quelconque des revendications précédentes, dans lequel les étapes a) et b) sont réalisées dans une machine à papier, de préférence dans une section de séchage de la machine à papier ou après celle-ci.
  13. Procédé selon l'une quelconque des revendications précédentes, comprenant en outre les étapes suivantes :
    i) la fourniture d'une suspension aqueuse comprenant de la MFC chimiquement modifiée ;
    ii) la formation d'une nappe à partir de la suspension aqueuse et la déshydratation et le séchage de la nappe pour former le film sur lequel la composition aqueuse comprenant un agent de réticulation est appliquée à l'étape a).
  14. Procédé selon la revendication 13, comprenant en outre l'étape consistant à fibriller les fibres pour fournir la MFC chimiquement modifiée de l'étape i).
  15. Procédé selon la revendication 14, dans lequel les fibres sont chimiquement modifiées et ont une densité de charge mesurée selon la norme SCAN-CM 65:02 comprise entre 500 et 1 800 µeq/g, telle que comprise entre 500 et 1 000 µeq/g, et dans lequel la modification chimique peut être choisie parmi le groupe constitué par l'oxydation TEMPO, l'alcoxylation, la phosphorylation, la sulfonation, la sulfoéthylation et l'oxydation au chlorite précédée de l'introduction d'aldéhydes.
EP19208620.5A 2019-11-12 2019-11-12 Mfc réticulé Active EP3822409B1 (fr)

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EP19208620.5A EP3822409B1 (fr) 2019-11-12 2019-11-12 Mfc réticulé
CN202080077855.8A CN114641597A (zh) 2019-11-12 2020-11-12 交联的mfc
PCT/EP2020/081884 WO2021094440A1 (fr) 2019-11-12 2020-11-12 Cmf réticulée
JP2022553220A JP2023501001A (ja) 2019-11-12 2020-11-12 架橋型ｍｆｃ
EP20803189.8A EP4058632A1 (fr) 2019-11-12 2020-11-12 Cmf réticulée

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SE546304C2 (en) * 2022-02-10 2024-10-01 Stora Enso Oyj Surface-treated gas barrier film
CN115044993A (zh) * 2022-06-21 2022-09-13 天津大学 一种高电荷密度磷酸化纤维素纳米纤维及热浸泡制备方法

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WO2010074340A1 (fr) * 2008-12-26 2010-07-01 花王株式会社 Matériau barrière aux gaz, article moulé barrière aux gaz et procédé de fabrication de l'article moulé barrière aux gaz
WO2011065371A1 (fr) * 2009-11-24 2011-06-03 花王株式会社 Matériau en couche mince, procédé pour produire celui-ci, et dispersion aqueuse pour former un matériau en couche mince
CN105764810B (zh) * 2013-09-06 2021-04-09 比勒鲁迪克斯那斯公司 由自交联性原纤化纤维素制得的具有低湿度敏感性的氧和水蒸气阻隔膜
JP6428172B2 (ja) * 2014-11-07 2018-11-28 凸版印刷株式会社 耐水紙およびそれを用いた紙容器、並びに製造方法
JP6432288B2 (ja) * 2014-11-07 2018-12-05 凸版印刷株式会社 耐水紙および当該耐水紙の製造方法
JP6574601B2 (ja) * 2015-04-30 2019-09-11 国立大学法人 東京大学 セルロースフィルム、及びその製造方法
JP6569369B2 (ja) * 2015-08-05 2019-09-04 王子ホールディングス株式会社 シート、シートの製造方法、および積層体
CN107923126A (zh) * 2015-08-05 2018-04-17 王子控股株式会社 片材、片材的制造方法及叠层体
JP2018132655A (ja) * 2017-02-15 2018-08-23 旭化成株式会社 感光性複合材シート、樹脂繊維複合フィルム及び放熱・伝熱回路基板
KR20180115531A (ko) * 2017-04-13 2018-10-23 포항공과대학교 산학협력단 세포 배양용 셀룰로오스 나노섬유 3차원 구조체의 제조방법 및 그에 따라 제조된 세포 배양용 셀룰로오스 나노섬유 3차원 구조체
CN111247196B (zh) * 2017-10-17 2023-07-25 切卢特克股份公司 包含cnf和阴离子胶凝多糖的生物复合材料
JP2019162818A (ja) * 2018-03-20 2019-09-26 旭化成株式会社 薄膜セルロース微細繊維積層シート
CN110305351A (zh) * 2018-03-20 2019-10-08 中国石油化工股份有限公司 一种可全生物降解的智能控湿薄膜及其制备方法和应用
EP3581591A1 (fr) * 2018-06-13 2019-12-18 UPM-Kymmene Corporation Produit de cellulose nanofibrillaire et son procédé de fabrication
EP3581590A1 (fr) * 2018-06-13 2019-12-18 UPM-Kymmene Corporation Produit cellulose fibrillaire et son procédé de fabrication
SE543003C2 (en) * 2018-12-21 2020-09-22 Stora Enso Oyj Surface-treated fibrous materials and methods for their preparation

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EP3822409C0 (fr) 2026-01-07
EP4058632A1 (fr) 2022-09-21
CN114641597A (zh) 2022-06-17
EP3822409A1 (fr) 2021-05-19
JP2023501001A (ja) 2023-01-17
WO2021094440A1 (fr) 2021-05-20

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