EP3864074A1 - A barrier layer comprising microfibrillated dialdehyde cellulose - Google Patents

A barrier layer comprising microfibrillated dialdehyde cellulose

Info

Publication number
EP3864074A1
EP3864074A1 EP19871004.8A EP19871004A EP3864074A1 EP 3864074 A1 EP3864074 A1 EP 3864074A1 EP 19871004 A EP19871004 A EP 19871004A EP 3864074 A1 EP3864074 A1 EP 3864074A1
Authority
EP
European Patent Office
Prior art keywords
barrier layer
cellulose
fibrous
mixture
film
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.)
Withdrawn
Application number
EP19871004.8A
Other languages
German (de)
French (fr)
Other versions
EP3864074A4 (en
Inventor
Susanne HANSSON
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Stora Enso Oyj
Original Assignee
Stora Enso Oyj
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Stora Enso Oyj filed Critical Stora Enso Oyj
Publication of EP3864074A1 publication Critical patent/EP3864074A1/en
Publication of EP3864074A4 publication Critical patent/EP3864074A4/en
Withdrawn legal-status Critical Current

Links

Classifications

    • 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
    • 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
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
    • 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
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/22—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
    • B32B5/24—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer
    • B32B5/26—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer another layer next to it also being fibrous or filamentary
    • 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
    • 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
    • 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
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/048—Forming gas barrier coatings
    • 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
    • C09D101/00—Coating compositions based on cellulose, modified cellulose, or cellulose derivatives
    • C09D101/02—Cellulose; Modified cellulose
    • C09D101/04—Oxycellulose; Hydrocellulose
    • 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
    • C09D129/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Coating compositions based on hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Coating compositions based on derivatives of such polymers
    • C09D129/02—Homopolymers or copolymers of unsaturated alcohols
    • C09D129/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
    • 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
    • D21H17/20—Macromolecular organic compounds
    • D21H17/33—Synthetic macromolecular compounds
    • D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H17/36—Polyalkenyalcohols; 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
    • D21H19/10—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
    • D21H19/56—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
    • D21H19/36—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
    • 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
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00—Layers arrangement
    • B32B2250/20—All layers being fibrous or filamentary
    • 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
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/02—Synthetic macromolecular fibres
    • B32B2262/0223—Vinyl resin fibres
    • 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
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/02—Synthetic macromolecular fibres
    • B32B2262/0253—Polyolefin fibres
    • 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
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/02—Synthetic macromolecular fibres
    • B32B2262/0261—Polyamide fibres
    • 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
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/02—Synthetic macromolecular fibres
    • B32B2262/0276—Polyester fibres
    • B32B2262/0284—Polyethylene terephthalate [PET] or polybutylene terephthalate [PBT]
    • 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
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/06—Vegetal fibres
    • B32B2262/062—Cellulose fibres, e.g. cotton
    • 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
    • B32B2307/718—Weight, e.g. weight per square meter
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    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/724—Permeability to gases, adsorption
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    • B32B2307/7244—Oxygen barrier
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    • B32B2307/724—Permeability to gases, adsorption
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    • B32B2307/7246—Water vapor barrier
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    • B32B2439/70—Food packaging
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    • B32B29/00—Layered products comprising a layer of paper or cardboard
    • 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
    • C08J2401/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
    • C08J2401/02—Cellulose; Modified cellulose
    • C08J2401/04—Oxycellulose; Hydrocellulose
    • 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
    • C08J2429/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
    • C08J2429/02—Homopolymers or copolymers of unsaturated alcohols
    • C08J2429/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids

Definitions

  • the present invention relates to a method for manufacturing at least one fibrous barrier layer comprising microfibrillated dialdehyde cellulose.
  • the present invention also relates to a fibrous barrier layer, such as a barrier film, having good mechanical properties and low oxygen transmission rate at high relative humidity.
  • Microfibrillated cellulose is widely used to manufacture barrier films for instance in multilayered 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.
  • DA- MFC dialdehyde microfibrillated cellulose
  • a barrier film with improved moisture resistant can be produced.
  • DA- MFC dialdehyde microfibrillated cellulose
  • a dispersion comprising DA- MFC is very unstable since the DA-MFC sediments and spontaneously crosslinks to a certain degree already in the dispersion, leading to that the microfibrils are bound or entangled.
  • the crosslinks further render the DA- MFC barrier film brittle, which restrain the processing and handling. For instance, if the film is part of a paper-based laminate structure, undesired cracks may appear in the film upon converting.
  • 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
  • PVOH polyvinyl alcohol
  • fibrous barrier layer may refer to a film (e.g. a free-standing 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.
  • PVOFI polyvinyl alcohol
  • the PVOFI 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 the cellulose with sodium periodate 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 suspension can have different degrees of oxidation, defined as the portion of AGUs that have a dialdehyde, as explained above.
  • the amount of DA-MFC needed to be added in order to achieve a specific D.O. in the final mixture depends on the degree of oxidation in the corresponding suspension. For instance, a mixture of DA- MFC and native MFC naturally has an average degree of oxidation that is lower than that of the DA-MFC part of the mixture. In that sense, such a mixture containing both MFC and DA-MFC could theoretically be interpreted as a DA-MFC with low degree of oxidation.
  • 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 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.
  • the mixture comprises between 20-90wt% of microfibrillated cellulose and 10-80wt% microfibrillated dialdehyde cellulose based on the total dry fiber weight of the mixture.
  • the added PVOFI is 50-300 kg/ton dry fiber.
  • the mixture comprises 50-70wt%
  • microfibri Hated cellulose and 30-50 wt% m i crof i brill ated dialdehyde cellulose.
  • the added PVOH is 100-200 kg/ton dry fiber content.
  • the dry content of the mixture applied to the substrate is between 1 -15% by weight.
  • 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 fibrous barrier layer has a strain at break of at least 1 %, preferably at least 3%.
  • 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, clay, retention chemicals, flocculation additives, deflocculating additives, dry strength additives, softeners, cellulose nanocrystals or mixtures thereof.
  • the m icrof ibri I lated 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 m i crof i bri I lated dialdehyde cellulose and PVOFI.
  • the fibrous barrier layer comprises a mixture of microfibrillated cellulose, microfibrillated dialdehyde cellulose and PVOH.
  • 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
  • PLA 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.
  • 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 PVOH 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 providing a suspension comprising intermixed microfibrillated cellulose (MFC) and microfibrillated dialdehyde cellulose (DA-MFC); adding polyvinyl alcohol (PVOFI) to said suspension and mix to form a mixture; applying said mixture to a substrate to form a wet fibrous web; and drying said wet web on said substrate to form a fibrous barrier layer.
  • MFC intermixed microfibrillated cellulose
  • D-MFC microfibrillated dialdehyde cellulose
  • PVOFI polyvinyl alcohol
  • microfibrillated dialdehyde cellulose and microfibrillated cellulose which also comprises at least a portion of polyvinyl alcohol, a film can be formed which has improved ductility while maintaining a good oxygen barrier property.
  • 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
  • Dialdehyde cellulose (DA-MFC) is typically obtained by reacting cellulose with an oxidising agent such as sodium periodate. During the periodate oxidation, selective cleavage of the C2-C3 bond of the
  • anhydroglucose unit (AGU) of cellulose takes place, with concurrent oxidation of the C2- and C3-OH 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 Flydroxylamine Hydrochloride Method”, Pharmaceutical Research, vol. 8, pp.
  • VNaO H the amount of sodium hydroxide needed to reach pH 4 (I)
  • 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%. Furthermore, the PVOH preferably has a viscosity above 5 mPaxs in a 4 % aqueous solution at 20 °C DIN 53015 / JIS K 6726.
  • the mixture may further comprise additives, preferably any one of a starch, carboxymethyl cellulose, a filler, retention chemicals, clay, talcum, 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 MFC, the DA-MFC, the mix of MFC and DA-MFC, or to the mixture of MFC, DA-MFC and PVOH.
  • additives preferably any one of a starch, carboxymethyl cellulose, a filler, retention chemicals, clay, talcum, 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 MFC, the DA-MFC, the mix of MFC and DA-
  • DA-MFC with D.O. 40% was mixed with native MFC in the proportion 60 wt-% / 40 wt-%.
  • the solids content of the mixture was 1 wt-%.
  • PVOFI Porill 15-99, Kuraray

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Abstract

The present invention relates to a method for manufacturing at least one fibrous barrier layer wherein the method comprises the steps of: providing a suspension comprising intermixed microfibrillated cellulose (MFC) and microfibrillated dialdehyde cellulose(DA-MFC); addingpolyvinyl alcohol (PVOH) to said suspension and mix to form a mixture; applying said mixture to a substrate to form a wet fibrous web;and drying said wet web on said substrate to form a fibrous barrier layer.

Description

A BARRIER LAYER COMPRISING MICROFIBRILLATED DIALDEHYDE
CELLULOSE
Technical field
The present invention relates to a method for manufacturing at least one fibrous barrier layer comprising microfibrillated dialdehyde cellulose. The present invention also relates to a fibrous barrier layer, such as a barrier film, having good mechanical properties and low oxygen transmission rate at high relative humidity.
Background
Microfibrillated cellulose (MFC) is widely used to manufacture barrier films for instance in multilayered paper laminates. However, 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). 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. latex coating on MFC film, while US2012094047A teaches the use of wood hydrolysates mixed with polysaccharides such as MFC that can be coated with a polyolefin layer. In addition to this, different chemical modification routes have been investigated to give the possibility to cross-link of fibrils with each other or fibrils with other compounds. This improves water fastness of the films but also water vapor transmission rates. Another way to decrease the moisture sensitivity of cellulose is to chemically modify the cellulose with sodium periodate to obtain dialdehyde cellulose (DAC). Thanks to being based on a renewable material, use of DAC allows for designing barrier structures with a high renewable content. By fibrillating DAC into dialdehyde microfibrillated cellulose (DA- MFC), a barrier film with improved moisture resistant can be produced. This is presented e.g. in WO2015034426. However, a dispersion comprising DA- MFC is very unstable since the DA-MFC sediments and spontaneously crosslinks to a certain degree already in the dispersion, leading to that the microfibrils are bound or entangled. The crosslinks further render the DA- MFC barrier film brittle, which restrain the processing and handling. For instance, if the film is part of a paper-based laminate structure, undesired cracks may appear in the film upon converting.
Hence, there is a need to find a way of manufacturing a barrier film which presents good gas barrier properties even at high relative humidity and also having a good mechanical properties.
Summary
It is an object of the present invention to provide an improved barrier film or barrier layer comprising microfibrillated dialdehyde cellulose, which has good barrier properties at high relative humidity as well as improved mechanical properties.
The invention is defined by the appended independent claims.
Embodiments are set forth in the appended dependent claims.
The present invention relates to a method for manufacturing at least one fibrous barrier layer wherein the method comprises the steps of:
providing a suspension comprising intermixed microfibrillated cellulose (MFC) and microfibrillated dialdehyde cellulose (DA-MFC);
adding polyvinyl alcohol (PVOH) to said suspension and mix to form a mixture;
applying said mixture to a substrate to form a wet fibrous web; and drying said wet web on said substrate to form a fibrous barrier layer. It is to be understood that said PVOH can be mixed firstly with MFC and thereafter DA-MFC is added to form said mixture. It is equally possible to firstly mix the PVOFI with DA-MFC and thereafter adding MFC to form said mixture. It is understood that“fibrous barrier layer” may refer to a film (e.g. a free-standing 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.
It has been found that addition of polyvinyl alcohol (PVOFI) to a mixture comprising MFC and DA-MFC in making of films leads to films with improved mechnical properties compared to corresponding films without PVOFI, and at the same time the gas barrier function at high humidities is preserved.
According to one aspect of the invention, the PVOFI 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” (DAC) can be produced by chemically modifying the cellulose with sodium periodate thereby selectively cleaving the C2-C3 bond of the anhydroglucose unit (AGU) in the cellulose chain, forming two aldehyde groups at said location. The term “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 skilled person understands that the DA-MFC added in the suspension can have different degrees of oxidation, defined as the portion of AGUs that have a dialdehyde, as explained above. The amount of DA-MFC needed to be added in order to achieve a specific D.O. in the final mixture depends on the degree of oxidation in the corresponding suspension. For instance, a mixture of DA- MFC and native MFC naturally has an average degree of oxidation that is lower than that of the DA-MFC part of the mixture. In that sense, such a mixture containing both MFC and DA-MFC could theoretically be interpreted as a DA-MFC with low degree of oxidation.
The DA-MFC used for manufacturing of the fibrous layer is
mechanically treated to obtain 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
homogenizer. It is also understood that the term“microfibrillate” refers to a mechanical treatment whereby microfibrillated (cellulose) fibers are obtained.
By“oxygen transmission rate” (OTR) means a measure of the amount of oxygen gas that passes through the film over a given time period, that is: cm3/m2/24h.
According to one aspect of the invention, the dried fibrous barrier layer is a free-standing film.
According to another aspect of the invention, 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.
In one embodiment, the mixture comprises between 20-90wt% of microfibrillated cellulose and 10-80wt% microfibrillated dialdehyde cellulose based on the total dry fiber weight of the mixture. To this fiber-based mixture, the added PVOFI is 50-300 kg/ton dry fiber. In another embodiment, the mixture comprises 50-70wt%
microfibri Hated cellulose and 30-50 wt% m i crof i brill ated dialdehyde cellulose. To this fiber-based mixture, the added PVOH is 100-200 kg/ton dry fiber content.
According to another aspect of the invention, the dry content of the mixture applied to the substrate is between 1 -15% by weight.
According to another aspect of the invention, the fibrous barrier layer has an oxygen transmission rate in the range of from 0.1 to 100 cc/m2/24h 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.
According to another aspect of the invention, the fibrous barrier layer has a strain at break of at least 1 %, preferably at least 3%.
According to another aspect of the invention, the substrate is a polymer or metal substrate.
According to another aspect of the invention, 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.
It is within the scope of the invention to add further additives to the mixture, including one or more of a starch, carboxymethyl cellulose, a filler, clay, retention chemicals, flocculation additives, deflocculating additives, dry strength additives, softeners, cellulose nanocrystals or mixtures thereof.
According to another aspect of the invention, the m icrof ibri I lated dialdehyde cellulose in the suspension has an oxidation degree between 15- 50%.
Furthermore, the present invention relates to a fibrous barrier layer having an oxygen transmission rate in the range of from 0.1 to 100 cc/m2/24h 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 m i crof i bri I lated dialdehyde cellulose and PVOFI. According to one aspect of the invention, the fibrous barrier layer comprises a mixture of microfibrillated cellulose, microfibrillated dialdehyde cellulose and PVOH.
According to one aspect of the invention, the fibrous barrier layer has a basis weight of less than 55 g/m2, preferably between 10-50 g/m2
According to one aspect of the invention, said fibrous barrier layer is a film, preferably comprising more than one layer.
According to one aspect of the invention, 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).
It is possible to produce 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.
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 PVOH as an oxygen barrier film.
Description of Embodiments
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 providing a suspension comprising intermixed microfibrillated cellulose (MFC) and microfibrillated dialdehyde cellulose (DA-MFC); adding polyvinyl alcohol (PVOFI) to said suspension and mix to form a mixture; applying said mixture to a substrate to form a wet fibrous web; and drying said wet web on said substrate to form a fibrous barrier layer.
It has been found that by providing a suspension of microfibrillated dialdehyde cellulose and microfibrillated cellulose which also comprises at least a portion of polyvinyl alcohol, a film can be formed which has improved ductility while maintaining a good oxygen barrier property.
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 (MFC) 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 m2/g, such as from 1 to 200 m2/g or more preferably 50-200 m2/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.
Various methods exist to make MFC, such as single or multiple 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
enzymatically or chemically. For example, 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. Such groups include, among others, carboxym ethyl, aldehyde and/or carboxyl groups (cellulose obtained by N-oxyl mediated oxidation, for example
"TEMPO"), or quaternary ammonium (cationic cellulose). After being modified or oxidized in one of the above-described methods, it is easier to disintegrate the fibers into MFC or NFC.
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. Depending on the MFC manufacturing method, 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.
The above described definition of 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.
Dialdehyde cellulose (DA-MFC) is typically obtained by reacting cellulose with an oxidising agent such as sodium periodate. During the periodate oxidation, selective cleavage of the C2-C3 bond of the
anhydroglucose unit (AGU) of cellulose takes place, with concurrent oxidation of the C2- and C3-OH moieties to aldehyde moieties. In this manner, crosslinkable functional groups (aldehyde groups) are introduced to the cellulose. 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 Flydroxylamine Hydrochloride Method”, Pharmaceutical Research, vol. 8, pp. 400-402, 1991 , where the available aldehyde groups reacts with hydroxylamine hydrochloride. This forms oxime groups and releases hydrochloric acid. The hydrochloric acid is titrated with sodium hydroxide until pH 4 is reached, and the degree of oxidation is thereafter calculated from according to the formula below. The received aldehyde content is divided by two to get the value of the degree of oxidation, since an oxidized anhydroglucose unit has two aldehyde groups.
VNaOH = the amount of sodium hydroxide needed to reach pH 4 (I)
CNaOH = 0,1 mol/l
rrisampie = dry weight of the analysed DAC sample (g)
Mw = 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%. Furthermore, the PVOH preferably has a viscosity above 5 mPaxs in a 4 % aqueous solution at 20 °C DIN 53015 / JIS K 6726.
The mixture may further comprise additives, preferably any one of a starch, carboxymethyl cellulose, a filler, retention chemicals, clay, talcum, 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 MFC, the DA-MFC, the mix of MFC and DA-MFC, or to the mixture of MFC, DA-MFC and PVOH.
Example - PVOH as additive to DA-MFC barrier film for improving mechanical properties
DA-MFC with D.O. 40% was mixed with native MFC in the proportion 60 wt-% / 40 wt-%. The solids content of the mixture was 1 wt-%. To this reference mixture of fibrillar material, PVOFI (Poval 15-99, Kuraray) was added in an amount of 100 kg dry/ton dry solids.
Both mixtures were stirred with a magnetic stirrer in a vacuum desiccator, to get rid of air bubbles, until no air bubbles could be seen. This took up to 2 h. Films were cast in polystyrene Petri dishes with an amount of mixture corresponding to 30 g dry/m2. The films were dried in 23 °C, 50% RFI for 5 days. The mechanical properties were measured with a material tester (Zwick Z010) at a testing speed of 2 mm/min and a span length of 20 mm. Strips with a width of 15 mm were used in this measurement.
The results are shown in Table 1 below. Table 1 : Mechanical properties of DA-MFC barrier films
As can be noted from the results displayed in Table 1 , adding PVOFI to a suspension comprising DA-MFC and MFC provides a way to make barrier films with improved strain at break, E-modulus and strength.

Claims

1. A method for manufacturing at least one fibrous barrier layer wherein the method comprises the steps of:
providing a suspension comprising intermixed microfibrillated cellulose (MFC) and microfibrillated dialdehyde cellulose (DA-MFC);
adding polyvinyl alcohol (PVOH) to said suspension and mix to form a mixture;
applying said mixture to a substrate to form a wet fibrous web; and drying said wet web on said substrate to form a fibrous barrier layer.
2. The method according to claim 1 , wherein the dried fibrous barrier layer is a free-standing film.
3. The method according to claim 1 , wherein 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.
4. The method according to any one of claims 1 - 3, wherein the mixture comprises between 20-90 wt% of microfibrillated cellulose and 10- 80wt% microfibrillated dialdehyde cellulose, preferably 50-70wt%
microfibrillated cellulose and 30-50wt% microfibrillated dialdehyde cellulose, based on the total fiber weight of the mixture.
5. The method according to any one of the previous claims, wherein the mixture comprises 50-300 kg/ton dry fiber of PVOH, preferably 100-200 kg/ton dry fiber
6. The method according to any one of the preceding claims, wherein the PVOH to be added to the suspension preferably has a degree of hydrolysis between 80-99 mol%, more preferably between 88-99 mol%.
7. The method according to any one of the preceding claims, wherein the PVOH preferably has a viscosity above 5 mPaxs in a 4 % aqueous solution at 20 °C DIN 53015 / JIS K 6726.
8. The method according to any one of the preceding claims wherein the dry content of the mixture applied to the substrate is between 1 -15% by weight.
9. The method according to any one of the preceding claims wherein the fibrous barrier layer has an oxygen transmission rate in the range of from 0.1 to 100 cc/m2/24h 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 with a barrier layer thickness of 10-70 pm.
10. The method according to any one of the preceding claims, wherein the fibrous barrier layer has a strain at break of at least 1 %, preferably at least 3%.
11. The method according to any one of claims 1 , or 4-10, wherein the substrate is a polymer or metal substrate.
12. The method according to any one of the preceding claims, wherein the temperature is increased to 70-150°C during drying of the film.
13. The method according to any one of the preceding claims, wherein said method further comprises the step of pressing the film upon and/or after drying.
14. The method according to any of the preceding claims, wherein said mixture further comprises any one of: a starch, carboxymethyl cellulose, a filler, clay, retention chemicals, flocculation additives, deflocculating additives, dry strength additives, softeners, cellulose nanocrystals or mixtures thereof.
15. The method according to any of the preceding claims wherein the m i crof i bri I lated dialdehyde cellulose in the first suspension has an oxidation degree between 15-50%, preferably 20-40 %.
16. A fibrous barrier layer obtainable by means of a method according to any one of claims 1 -15.
17. A fibrous barrier layer having an oxygen transmission rate in the range of from 0.1 to 100 cc/m2/24h 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 with a barrier layer thickness of 10-70 pm, and wherein at least one fibrous barrier layer comprises a mixture of a microfibrillated dialdehyde cellulose, microfibril lated cellulose and PVOH.
18. The fibrous barrier layer as claimed in any one of claims 16 or 17, wherein the fibrous barrier layer has a basis weight of less than 55 g/m2, preferably between 10-50 g/m2.
19. The fibrous barrier layer as claimed in any one of the claims 16-18, wherein said fibrous barrier layer is a film, preferably comprising more than one layer.
20. The fibrous barrier layer as claimed in any one of the claims 16-19, wherein said fibrous barrier layer is a multilayer film and 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).
21. A packaging material comprising a base material and at least one fibrous barrier layer as claimed in any one of claims 16-20.
22. A packaging material according to claim 21 , wherein said base material is paper or paperboard.
23. Use of a fibrous barrier layer according to any one of claims 17-22 as an oxygen barrier film, wherein the film is obtainable by a method according to any one of claims 1 -15.
EP19871004.8A 2018-10-08 2019-10-08 A barrier layer comprising microfibrillated dialdehyde cellulose Withdrawn EP3864074A4 (en)

Applications Claiming Priority (2)

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SE1851213A SE543174C2 (en) 2018-10-08 2018-10-08 A flexible barrier layer comprising microfibrillated dialdehyde cellulose
PCT/IB2019/058547 WO2020075057A1 (en) 2018-10-08 2019-10-08 A barrier layer comprising microfibrillated dialdehyde cellulose

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