WO2020075056A1 - Couche de barrière à l'oxygène comprenant de la cellulose de dialdéhyde microfibrillée - Google Patents

Couche de barrière à l'oxygène comprenant de la cellulose de dialdéhyde microfibrillée Download PDF

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Publication number
WO2020075056A1
WO2020075056A1 PCT/IB2019/058546 IB2019058546W WO2020075056A1 WO 2020075056 A1 WO2020075056 A1 WO 2020075056A1 IB 2019058546 W IB2019058546 W IB 2019058546W WO 2020075056 A1 WO2020075056 A1 WO 2020075056A1
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Prior art keywords
barrier layer
cellulose
mixture
fibrous
film
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PCT/IB2019/058546
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English (en)
Inventor
Isabel KNÖÖS
Original Assignee
Stora Enso Oyj
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Priority to EP19872212.6A priority Critical patent/EP3864075A4/fr
Publication of WO2020075056A1 publication Critical patent/WO2020075056A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D101/00—Coating compositions based on cellulose, modified cellulose, or cellulose derivatives
    • C09D101/02—Cellulose; Modified cellulose
    • C09D101/04—Oxycellulose; Hydrocellulose
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/10—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of paper or cardboard
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
    • B65D65/38—Packaging materials of special type or form
    • B65D65/40—Applications of laminates for particular packaging purposes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
    • C08L1/02—Cellulose; Modified cellulose
    • C08L1/04—Oxycellulose; Hydrocellulose, e.g. microcrystalline cellulose
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
    • C08L1/08—Cellulose derivatives
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • 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
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/63—Inorganic compounds
    • D21H17/67—Water-insoluble compounds, e.g. fillers, pigments
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H19/00—Coated paper; Coating material
    • D21H19/10—Coatings without pigments
    • D21H19/14—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12
    • D21H19/34—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12 comprising cellulose or 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
    • D21H19/00—Coated paper; Coating material
    • D21H19/36—Coatings with pigments
    • D21H19/38—Coatings with pigments characterised by the pigments
    • D21H19/40—Coatings with pigments characterised by the pigments siliceous, e.g. clays
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • 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
    • D21H19/52—Cellulose; 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
    • 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
    • D21H19/56—Macromolecular organic compounds or oligomers thereof obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H19/60—Polyalkenylalcohols; Polyalkenylethers; Polyalkenylesters
    • 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
    • D21H19/80—Paper comprising more than one coating
    • D21H19/82—Paper comprising more than one coating superposed
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
    • B29D7/00—Producing flat articles, e.g. films or sheets
    • B29D7/01—Films or sheets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2001/00—Use of cellulose, modified cellulose or cellulose derivatives, e.g. viscose, as moulding material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2029/00—Use of polyvinylalcohols, polyvinylethers, polyvinylaldehydes, polyvinylketones or polyvinylketals or derivatives thereof as moulding material
    • B29K2029/04—PVOH, i.e. polyvinyl alcohol
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
    • B29K2105/0005—Condition, form or state of moulded material or of the material to be shaped containing compounding ingredients
    • B29K2105/0032—Pigments, colouring agents or opacifiyng agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/724—Permeability to gases, adsorption
    • B32B2307/7242—Non-permeable
    • B32B2307/7244—Oxygen barrier
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B29/00—Layered products comprising a layer of paper or cardboard

Definitions

  • the present invention relates to a method for manufacturing at least one fibrous barrier layer comprising dialdehyde polysaccharide.
  • the present invention also relates to a fibrous barrier layer, such as a barrier film, having low oxygen transmission rate at high relative humidity.
  • Microfibrillated cellulose is widely used to manufacture barrier films for instance in multilayer paper laminates.
  • MFC gas barrier properties
  • the gas barrier properties of MFC based films are dependent on the moisture or the relative humidity in the surrounding environment. Therefore, it is quite common that MFC films are coated with a polymer film to prevent moisture or water vapor to swell and disrupt the MFC film.
  • the EP2551104A1 teaches the use of MFC and polyvinyl alcohol (PVOH) and/or polyuronic acid with improved barrier properties at higher relative humidity (RH).
  • PVOH polyvinyl alcohol
  • RH relative humidity
  • Another solution is to coat the film with a film that has high water fastness and/or low water vapor transmission rate.
  • the JP2000303386A discloses e.g.
  • a dispersion comprising microfibrillated dialdehyde cellulose can spontaneously form crosslink to a certain degree, which leads to a material with an oxygen barrier which is not deteriorated at high relative humidity as native MFC films are.
  • the present invention relates to a method for manufacturing at least one fibrous barrier layer wherein the method comprises the steps of:
  • MFC microfibrillated cellulose
  • D-MFC microfibrillated dialdehyde cellulose
  • said inorganic pigment can be mixed firstly with MFC and then DA-MFC is added to form said mixture. It is equally possible to firstly mix the inorganic pigment with DA-MFC and then MFC is added to form said mixture.
  • polyvinyl alcohol is also added in addition to said at least one inorganic pigment.
  • “fibrous barrier layer” may refer to a film which in its turn can be laminated e.g. onto a base layer such as paper board and/or paper, and it may also refer to a layer in a multilayer structure which has been created by wet coating directly onto a substrate and subsequently dried thereon.
  • dialdehyde polysacharide is microfibrillated dialdehyde cellulose.
  • Particularly preferred inorganic pigments that promote efficient oxygen barrier function are pigments selected from the group consisting of clays and nanoclays, talcum, silicates, carbonates, alkaline earth metal carbonates and ammonium carbonate; and oxides such as transition metal oxides and other metal oxides.
  • the PVOH to be added preferably has a degree of hydrolysis between 80-99 mol%, more preferably between 88-99 mol%. Furthermore, the PVOFI preferably has a viscosity above 5 mPaxs in a 4 % aqueous solution at 20 °C DIN 53015 / JIS K 6726.
  • the cellulose derivative“dialdehyde cellulose” can be produced by chemically modifying cellulose with sodium periodate and thereby selectively cleaving the C2-C3 bond of the anhydroglucose unit (AGU) in the cellulose chain, forming two aldehyde groups at said location.
  • degree of oxidation (D.O.) is understood to refer to the portion of the total number of anhydroglucose units that undergo said reaction (forming the two aldehydes). The degree of oxidation is given in %.
  • the DA-MFC added in the first suspension can have different degrees of oxidation, defined as the portion of AGUs that have a dialdehyde, as explained above.
  • the DA-MFC used for manufacturing of the fibrous layer is
  • microfibrillated dialdehyde cellulose The mechanical treatment may be carried out by means of a refiner, grinder, homogenizer, colloider, friction grinder, ultrasound sonicator or fluidizer. All conventional homogenizers and fluidizers available may be used, such as Gaulin homogenizer, microfluidizer, macrofluidizer or fluidizer-type
  • microfibrillate refers to a mechanical treatment whereby microfibrillated (cellulose) fibers are obtained.
  • oxygen transmission rate means a measure of the amount of oxygen gas that passes through the film over a given time period, that is: cm 3 /m 2 /24h.
  • the dried fibrous barrier layer is a film, such as a free-standing film.
  • the substrate is a paper or paperboard substrate and the mixture is applied onto the substrate as a coating to form said wet fibrous web, wherein after drying said fibrous barrier layer and said substrate forms two layers of a multilayer structure.
  • the coating as such can be applied and dried in one or more layers.
  • At least one inorganic pigment is added to said suspension and intermixed to form a mixture.
  • the at least one inorganic pigment may be a nano size or a non-nano size particles or pigments.
  • “inorganic pigment in nano-scale” refers to nano size pigments such as nanoclays and nanoparticles of layered mineral silicates, for instance selected from the group comprising montmorillonite, bentonite, kaolinite, hectorite and hallyosite.
  • inorganic pigment not defined as nano scale refers to non-nano size particles such as talcum, silicates, carbonates, alkaline earth metal carbonates and ammonium carbonate, and oxides, such as transition metal oxides and other metal oxides.
  • the mixture comprises 20-90wt% of microfibrillated cellulose, 10-80wt% microfibrillated dialdehyde cellulose, 50-300 kg/ton PVOH and less than 250 kg/ton, preferably 50-150 kg/ton inorganic pigment in non-nano size, based on the total fiber weight of the mixture.
  • the mixture comprises 20-90wt% of microfibri Hated cellulose, 10-80wt% microfibrillated dialdehyde cellulose, 50-300kg/ton PVOH and less than 100 kg/ton, preferably 5-50 kg/ton inorganic pigment in nano size, based on the total fiber weight of the mixture.
  • the inorganic pigment in nano size is selected from the group comprising montmorillonite, bentonite, kaolinite, hectorite and hallyosite.
  • the inorganic pigment is selected from the group consisting of talcum, silicates, carbonates, alkaline earth metal carbonates and ammonium carbonate, and oxides, such as transition metal oxides and other metal oxides.
  • the dry content of the mixture applied to the substrate is between 1 -15 wt%.
  • the fibrous barrier layer has an oxygen transmission rate in the range of from 0.1 to 100 cc/m 2 /24h according to ASTM F-1927, at a relative humidity of 50 % at 23°C and/or at a relative humidity of 80% at 23°C at a barrier layer thickness 10-70 pm.
  • the substrate is a polymer or metal substrate.
  • said method further comprises the step of pressing the film upon and/or after drying.
  • the temperature may be increased to 70-150°C during such pressing of the film.
  • additives including one or more of a starch, carboxymethyl cellulose, a filler, retention chemicals, flocculation additives, deflocculating additives, dry strength additives, softeners, cellulose nanocrystals or mixtures thereof.
  • the microfibrillated dialdehyde cellulose in the suspension has an oxidation degree between 15- 50%.
  • the present invention relates to a fibrous barrier layer having an oxygen transmission rate in the range of from 0.1 to 100 cc/m 2 /24h according to ASTM F-1927, at a relative humidity of 50 % at 23°C and/or at a relative humidity of 80% at 23°C, and at a barrier layer thickness 10-70 pm, and wherein at least one fibrous barrier layer comprises a mixture of a dialdehyde polysaccharide and at least one inorganic pigment.
  • said fibrous barrier layer comprises a mixture of microfibrillated dialdehyde cellulose, polyvinyl alcohol and at least one inorganic pigment.
  • the fibrous barrier layer comprises a mixture of microfibrillated cellulose, microfibrillated dialdehyde cellulose, PVOH and at least one inorganic pigment.
  • the fibrous barrier layer has a basis weight of less than 55 g/m 2 , preferably between 10-50 g/m 2
  • said fibrous barrier layer is a film, preferably comprising more than one layer.
  • the fibrous barrier layer is a multilayer film wherein at least one layer of the film is a water vapor barrier film comprising any one of polyethylene (PE), polypropylene (PP), polyamide, polyethylene terephthalate (PET), polylactic acid (PLA) or ethylene vinyl alcohol (EVOH).
  • PE polyethylene
  • PP polypropylene
  • PET polyamide
  • PET polyethylene terephthalate
  • PVA polylactic acid
  • EVOH ethylene vinyl alcohol
  • a film comprising more than one layer wherein at least one of the layers comprises the mixture according to the invention. It may also be possible that more than one layer of the film comprises the mixture according to the invention. It may also be possible that one or more layers of the film only comprises native microfibrillated cellulose, i.e. which does not comprise microfibrillated dialdehyde cellulose (DA-MFC). The film may comprise two, three, four, five or more layers.
  • D-MFC microfibrillated dialdehyde cellulose
  • the present invention further relates to a packaging material e.g. intended for food stuff comprising a base material and at least one fibrous barrier layer as described above.
  • the base material may include, but is not limited to, paper, cardboard, paperboard, fabric, plastic, polymer film, metal, composites and the like.
  • the present invention further relates to the use of a fibrous barrier layer comprising a mixture of a microfibrillated dialdehyde cellulose, microfibrillated cellulose, and at least one inorganic pigment as an oxygen barrier film.
  • the method according to the present invention relates to a method for manufacturing at least one layer of a barrier film having at least oxygen barrier properties, said method comprising:
  • MFC microfibrillated cellulose
  • D-MFC microfibrillated dialdehyde cellulose
  • PVOFI polyvinyl alcohol
  • microfibrillated dialdehyde cellulose and microfibrillated cellulose which also comprises at least one inorganic pigment, a film can be formed which has a good oxygen barrier property at high relative humidity, such as 80% at 23°C.
  • the fibrous barrier layer is produced by applying said mixture to a substrate to form a fibrous web and drying said web to form at least one layer of film or coating.
  • the drying of said web may be done in any conventional way, preferably in combination with heat treatment and increased pressure.
  • the dry content of the at least one layer of the film after drying is preferably above 90% by weight.
  • Microfibrillated cellulose or so called cellulose microfibrils (CMF) shall in the context of the present application mean a nano-scale cellulose particle fiber or fibril with at least one dimension less than 100 nm.
  • MFC comprises partly or totally fibrillated cellulose or lignocellulose fibers.
  • the cellulose fiber is preferably fibrillated to such an extent that the final specific surface area of the formed MFC is from about 1 to about 300 m 2 /g, such as from 1 to 200 m 2 /g or more preferably 50-200 m 2 /g when determined for a freeze-dried material with the BET method.
  • the term“native MFC” refers to MFC that is made from conventional chemical, chemo-mechanical and/or mechanical pulp without further chemical treatment, e.g. said native MFC is lacking special functional groups.
  • MFC multi-pass refining
  • pre-hydrolysis followed by refining or high shear disintegration or liberation of fibrils.
  • One or several pre-treatment steps are usually required in order to make MFC manufacturing both energy-efficient and sustainable.
  • the cellulose fibers of the pulp to be supplied may thus be pre-treated
  • the cellulose fibers may be chemically modified before fibrillation, wherein the cellulose molecules contain functional groups other (or more) than found in the original cellulose.
  • groups include, among others, carboxym ethyl, aldehyde and/or carboxyl groups (cellulose obtained by N-oxyl mediated oxidation, for example
  • TEMPO quaternary ammonium
  • the nanofibrillar cellulose may contain some hemicelluloses; the amount is dependent on the plant source.
  • Mechanical disintegration of the pre-treated fibers, e.g. hydrolysed, pre-swelled, or oxidized cellulose raw material is carried out with suitable equipment such as a refiner, grinder, homogenizer, colloider, friction grinder, ultrasound sonicator, single- or twin- screw extruder, fluidizer such as microfluidizer, macrofluidizer or fluidizer-type homogenizer.
  • suitable equipment such as a refiner, grinder, homogenizer, colloider, friction grinder, ultrasound sonicator, single- or twin- screw extruder, fluidizer such as microfluidizer, macrofluidizer or fluidizer-type homogenizer.
  • the product might also contain fines, or nanocrystalline cellulose or e.g. other chemicals present in wood fibers or in papermaking process.
  • the product might also contain various amounts of micron size fiber particles that have not been efficiently fibrillated.
  • MFC can be produced from wood cellulose fibers, both from hardwood or softwood fibers. It can also be made from microbial sources, agricultural fibers such as wheat straw pulp, bamboo, bagasse, or other non-wood fiber sources. It is preferably made from pulp including pulp from virgin fiber, e.g. mechanical, chemical and/or thermomechanical pulps. It can also be made from broke or recycled paper.
  • MFC includes, but is not limited to, the proposed TAPPI standard W13021 on cellulose nano or microfibril (CMF) defining a cellulose nanofiber material containing multiple elementary fibrils with both crystalline and amorphous regions, having a high aspect ratio with width of 5-30 nm and aspect ratio usually greater than 50.
  • CMF cellulose nano or microfibril
  • D-MFC Dialdehyde cellulose
  • anhydroglucose unit (AGU) of cellulose takes place, with concurrent oxidation of the C2- and C3-OFI moieties to aldehyde moieties.
  • crosslinkable functional groups aldehyde groups
  • the microfibrillated dialdehyde cellulose in the suspension should in this context mean a dialdehyde cellulose treated in such way that it is microfibrillated.
  • the production of the microfibrillated dialdehyde cellulose is done by treating dialdehyde cellulose for example by a homogenizer or in any other way so that fibrillation occurs to produce microfibrillated dialdehyde cellulose.
  • the microfibrillated dialdehyde cellulose in the suspension preferably has an oxidation degree between 15-50%, preferably between 20- 40%.
  • the degree of oxidation was determined according to the following description: after the dialdehyde cellulose reaction, the amount of C2-C3 bonds in the cellulose that are converted to dialdehydes is measured. The degree of oxidation is the amount of C2-C3 bonds that are converted compared to all C2-C3 bonds. This is measured with a method by H. Zhao and N.D. Heindel,“Determination of Degree of Substitution of Formyl Groups in Polyaldehyde Dexran by the Hydroxylamine Hydrochloride Method”, Pharmaceutical Research, vol. 8, pp.
  • M w 160 g/mol, which is the molecular weight of the dialdehyde cellulose unit
  • the PVOH to be added to the suspension preferably has a degree of hydrolysis between 80-99 mol%, more preferably between 88-99 mol%.
  • the PVOH preferably has a viscosity above 5 mPaxs in a 4 % aqueous solution at 20 °C DIN 53015 / J IS K 6726.
  • Particularly preferred inorganic pigments that promote efficient oxygen barrier function are pigments selected from the group consisting of clays and nanoclays, talcum, silicates, carbonates, alkaline earth metal carbonates and ammonium carbonate and oxides, such as transition metal oxides and other metal oxides.
  • the mixture may further comprise additives, preferably any one of a starch, carboxymethyl cellulose, a filler, retention chemicals, flocculation additives, deflocculating additives, dry strength additives, softeners, or mixtures thereof. It may be possible to add additives that will improve different properties of the mixture and/or the produced film. It may be possible to add the additive to the first suspension, the second suspension and/or to the mixture.
  • a reference sample was prepared, which corresponded to a film containing 75 wt% DA-MFC with a degree of oxidation of 40%, and 25 wt% MFC. To that, 250 kg PVOFI per ton dry fiber was added.
  • test sample (Sample 1 ) was also prepared which corresponded to a film containing 20 wt% MFC and 80wt% DA-MFC with a degree of oxidation of 30%. To that 100 kg PVOFI per ton dry fiber and 50 kg bentonite nanoclay per ton dry fiber were added.
  • the PVOFI grade has a viscosity of 12.5-17.5 mPa*s of a 4 % aqueous solution at 20 °C, DIN 53015 / JIS K 6726 and a hydrolysis degree of 99%.
  • the mixture for manufacturing the film according to Ref 1 was prepared as follows. Polyvinyl alcohol was jet cooked for 2 h at a solids content of 14%. Dialdehyde cellulose (DAC) with a degree of oxidation of 40% was mixed with MFC and PVOFI. The mixing time was 1 h. Afterwards, the mixture was run 3 passages in a Microfluidizer M-110EFI, resulting in a MFC-DA-MFC-PVOFI suspension. The solids content was 3 wt%. The suspension was deaerated in a vacuum desiccator under stirring. By adjusting the stirring speed up and down, the air bubbles were removed from the suspension. The film was then produced by rod coating the MFC-DA- MFC-PVOFI dispersion on a metal plate, which was then placed on another metal plate, pre-heated to 105°C. The estimated temperature during drying was 70 °C.
  • the mixture for manufacturing the film according to Sample 1 was prepared as follows. Polyvinyl alcohol was jet cooked for 2 h at a solids content of 14%. Dialdehyde cellulose (DAC) with a degree of oxidation of 30% was mixed with MFC. Afterwards, the mixture was run 3 passages in a Microfluidizer M-110EH, resulting in a MFC-DA-MFC-suspension. The solids content was 3 wt%. Said suspension, was mixed with PVOFI and Bentonite clay. The mixing time was 1 h. The solids content was 3.5 wt%. The suspension was deaerated in a vacuum desiccator under stirring. By adjusting the stirring speed up and down, the air bubbles were removed from the suspension.
  • DAC Dialdehyde cellulose
  • the film was then produced by rod coating the MFC-DA- MFC-PVOFI-bentonite dispersion on a metal plate, which was then placed on another metal plate, pre-heated to 105°C.
  • the estimated temperature during drying was 70 °C.
  • the two films referred to as Ref 1 and Sample 1 were separately coated on top of a base layer consisting of a MFC.
  • the obtained two-layered films had a thickness of 52-58 pm and a grammage of about 50 g/m 2
  • the DA-MFC film containing PVOH and inorganic pigment in the form of bentonite provides a better oxygen barrier at high relative humidities compared to the DA-MFC film containing only PVOFI as an additive.
  • high relative humidity corresponds to 80% or higher at ambient or increased temperature.
  • DAC with a degree of oxidation of 40% which had been stored in a refrigerator for 6 months, was fibrillated 3 passages in a Microfluidizer at a solids content of 1 wt%.
  • the resulting DA-MFC was mixed with native MFC (1 wt%) in the proportion: 60/40, respectively.
  • the same jet-cooked PVOFI from Example 1 was added in an amount of 100 kg dry/t dry fibrillar material, giving a reference mixture: Ref. 2.
  • bentonite nanoclay as in Example 1 , was added in an amount of 50 kg It dry fibrillar material, giving the sample mixture: Sample 2.
  • Both mixtures were deaerated in a vacuum desiccator according to procedure from Example 1.
  • Films were cast in polystyrene Petri dishes with an amount of mixture corresponding to 30 g dry/m 2 .
  • the films were dried in 23 °C, 50% RFI for 5 days.
  • the reference films without clay had white dots.
  • the oxygen transmission rate was measured according to ASTM F- 1927 at 23 °C, 80% RH and at 38 °C, 90% RH, with a Mocon Ox-Tran 2/21. Before measurement, the samples were stored in 23 °C, 80% RH for 24 h to shorten the time to a steady state value when in the instrument.
  • Example 2 The results of Example 2 are shown in Table 2.
  • the overrange value in the reference film is probably due to that too much crosslinking had occurred in advance within the DAC during the long storage, resulting in an uneven distribution of the components in the film, shown as visible white dots in the film.
  • the clay addition helped the material to get well dispersed despite the premature crosslinking and the film with clay had no white dots and good oxygen barrier properties at high relative humidity.

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Abstract

La présente invention concerne un procédé de fabrication d'au moins une couche de barrière fibreuse, le procédé comprenant les étapes consistant à : fournir une suspension comprenant de la cellulose microfibrillée mélangée (MFC) et de la cellulose de dialdéhyde microfibrillée (DA-MFC) ; ajouter au moins un pigment inorganique à ladite suspension et mélanger afin de former un mélange ; appliquer ledit mélange sur un substrat pour former une bande fibreuse humide ; et sécher ladite bande humide sur ledit substrat pour former une couche de barrière fibreuse. L'invention concerne également une couche de barrière fibreuse comprenant de la cellulose de dialdéhyde microfibrillée, de la cellulose microfibrillée et au moins un pigment inorganique.
PCT/IB2019/058546 2018-10-08 2019-10-08 Couche de barrière à l'oxygène comprenant de la cellulose de dialdéhyde microfibrillée WO2020075056A1 (fr)

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US11136721B2 (en) 2010-11-15 2021-10-05 Fiberlean Technologies Limited Compositions
US11162219B2 (en) 2009-05-15 2021-11-02 Fiberlean Technologies Limited Paper filler composition
US11512020B2 (en) 2016-04-04 2022-11-29 Fiberlean Technologies Limited Compositions and methods for providing increased strength in ceiling, flooring, and building products
CN115485433A (zh) * 2020-05-07 2022-12-16 斯道拉恩索公司 纳米涂覆的基材的制造方法

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WO2015034426A1 (fr) * 2013-09-06 2015-03-12 Kth Holding Pellicules barrières contre l'oxygène et la vapeur d'eau de faible sensibilité à l'humidité fabriquées à partir de cellulose fibrillée auto-réticulable
WO2017046755A1 (fr) * 2015-09-17 2017-03-23 Stora Enso Oyj Procédé de production de film ayant de bonnes propriétés de barrière
WO2017072124A1 (fr) * 2015-10-29 2017-05-04 Tetra Laval Holdings & Finance S.A. Film ou feuille de barrière et matériau d'emballage stratifié comprenant le film ou la feuille, et récipient d'emballage réalisé à partir de ce dernier
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WO2018189698A1 (fr) * 2017-04-12 2018-10-18 Stora Enso Oyj Film barrière comprenant de la cellulose microfibrillée et de la cellulose dialdéhyde microfibrillée et procédé de fabrication du film barrière

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WO2015034426A1 (fr) * 2013-09-06 2015-03-12 Kth Holding Pellicules barrières contre l'oxygène et la vapeur d'eau de faible sensibilité à l'humidité fabriquées à partir de cellulose fibrillée auto-réticulable
WO2017046755A1 (fr) * 2015-09-17 2017-03-23 Stora Enso Oyj Procédé de production de film ayant de bonnes propriétés de barrière
WO2017072124A1 (fr) * 2015-10-29 2017-05-04 Tetra Laval Holdings & Finance S.A. Film ou feuille de barrière et matériau d'emballage stratifié comprenant le film ou la feuille, et récipient d'emballage réalisé à partir de ce dernier
WO2017221137A1 (fr) * 2016-06-22 2017-12-28 Stora Enso Oyj Film microfibrillé
WO2018189698A1 (fr) * 2017-04-12 2018-10-18 Stora Enso Oyj Film barrière comprenant de la cellulose microfibrillée et de la cellulose dialdéhyde microfibrillée et procédé de fabrication du film barrière

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11162219B2 (en) 2009-05-15 2021-11-02 Fiberlean Technologies Limited Paper filler composition
US11377791B2 (en) 2009-05-15 2022-07-05 Fiberlean Technologies Limited Paper filler composition
US11732411B2 (en) 2009-05-15 2023-08-22 Fiberlean Technologies Limited Paper filler composition
US11136721B2 (en) 2010-11-15 2021-10-05 Fiberlean Technologies Limited Compositions
US11655594B2 (en) 2010-11-15 2023-05-23 Fiberlean Technologies Limited Compositions
US11512020B2 (en) 2016-04-04 2022-11-29 Fiberlean Technologies Limited Compositions and methods for providing increased strength in ceiling, flooring, and building products
CN115485433A (zh) * 2020-05-07 2022-12-16 斯道拉恩索公司 纳米涂覆的基材的制造方法

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SE1851216A1 (en) 2020-04-09

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