SE545264C2 - Mfc film with peg - Google Patents

Mfc film with peg

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Publication number
SE545264C2
SE545264C2 SE2151408A SE2151408A SE545264C2 SE 545264 C2 SE545264 C2 SE 545264C2 SE 2151408 A SE2151408 A SE 2151408A SE 2151408 A SE2151408 A SE 2151408A SE 545264 C2 SE545264 C2 SE 545264C2
Authority
SE
Sweden
Prior art keywords
mfc
range
film
peg
mfc film
Prior art date
Application number
SE2151408A
Other languages
Swedish (sv)
Other versions
SE2151408A1 (en
Inventor
Isabel Knöös
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
Priority to SE2151408A priority Critical patent/SE545264C2/en
Priority to PCT/IB2022/060918 priority patent/WO2023089466A1/en
Publication of SE2151408A1 publication Critical patent/SE2151408A1/en
Publication of SE545264C2 publication Critical patent/SE545264C2/en

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    • DTEXTILES; PAPER
    • D21PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21HPULP 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
    • D21H11/00Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only
    • D21H11/16Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only modified by a particular after-treatment
    • D21H11/18Highly hydrated, swollen or fibrillatable fibres
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L1/00Compositions of cellulose, modified cellulose or cellulose derivatives
    • C08L1/02Cellulose; Modified cellulose
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B29/00Layered products comprising a layer of paper or cardboard
    • B32B29/02Layered products comprising a layer of paper or cardboard next to a fibrous or filamentary layer
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00Layered 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
    • B32B5/02Layered 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
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18Manufacture of films or sheets
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING 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
    • C09D101/00Coating compositions based on cellulose, modified cellulose, or cellulose derivatives
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING 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
    • C09D101/00Coating compositions based on cellulose, modified cellulose, or cellulose derivatives
    • C09D101/02Cellulose; Modified cellulose
    • DTEXTILES; PAPER
    • D21PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21HPULP 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
    • D21H19/00Coated paper; Coating material
    • D21H19/10Coatings without pigments
    • D21H19/14Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12
    • D21H19/34Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12 comprising cellulose or derivatives thereof
    • DTEXTILES; PAPER
    • D21PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21HPULP 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
    • D21H19/00Coated paper; Coating material
    • D21H19/36Coatings with pigments
    • D21H19/44Coatings with pigments characterised by the other ingredients, e.g. the binder or dispersing agent
    • D21H19/52Cellulose; Derivatives thereof
    • DTEXTILES; PAPER
    • D21PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21HPULP 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
    • D21H19/00Coated paper; Coating material
    • D21H19/80Paper comprising more than one coating
    • D21H19/82Paper comprising more than one coating superposed
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2255/00Coating on the layer surface
    • B32B2255/02Coating on the layer surface on fibrous or filamentary layer
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2255/00Coating on the layer surface
    • B32B2255/20Inorganic coating
    • B32B2255/205Metallic coating
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2260/00Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
    • B32B2260/02Composition of the impregnated, bonded or embedded layer
    • B32B2260/021Fibrous or filamentary layer
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2260/00Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
    • B32B2260/04Impregnation, embedding, or binder material
    • B32B2260/046Synthetic resin
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00Properties of the layers or laminate
    • B32B2307/40Properties of the layers or laminate having particular optical properties
    • B32B2307/414Translucent
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00Properties of the layers or laminate
    • B32B2307/70Other properties
    • B32B2307/718Weight, e.g. weight per square meter
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00Properties of the layers or laminate
    • B32B2307/70Other properties
    • B32B2307/724Permeability to gases, adsorption
    • B32B2307/7242Non-permeable
    • B32B2307/7244Oxygen barrier
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/06Layered 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
    • B32B27/10Layered 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
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2301/00Characterised by the use of cellulose, modified cellulose or cellulose derivatives
    • C08J2301/02Cellulose; Modified cellulose
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2471/00Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
    • C08J2471/02Polyalkylene oxides
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00Applications
    • C08L2203/16Applications used for films
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/02Polyalkylene oxides
    • DTEXTILES; PAPER
    • D21PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21CPRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
    • D21C9/00After-treatment of cellulose pulp, e.g. of wood pulp, or cotton linters ; Treatment of dilute or dewatered pulp or process improvement taking place after obtaining the raw cellulosic material and not provided for elsewhere
    • D21C9/001Modification of pulp properties
    • D21C9/007Modification of pulp properties by mechanical or physical means

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Wood Science & Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Medicinal Preparation (AREA)
  • Materials For Medical Uses (AREA)
  • Laminated Bodies (AREA)

Abstract

The present invention relates to microfibrillated cellulose (MFC) composition for preparation of oxygen barrier films or coatings, said composition comprising:MFC at a concentration in the range of 50-98 wt%, and a low molecular weight polyethylene glycol (LMW-PEG) having a molecular weight in the range of 300-500 g/mol at a concentration in the range of 2-8 wt%, based on the total dry weight of the MFC composition. The invention further relates to an MFC film and a multilayer material comprising the MFC composition.

Description

Technical field The present disclosure relates to microfibrillated cellulose (MFC) useful, for example, as oxygen barrier films or coatings in paper and paperboard. The present invention further relates to multilayer materials comprising such MFCjå and to methods for manufacturing such Background Films and coatings made from nanocellulosic materials such as microfibrillated cellulose (MFC), have emerged as an interesting alternative to conventional gas barrier films, such as aluminum and synthetic polymer films and various laminates thereof. Nanocellulosic films have been developed, in which cellulosic fibrils have been dispersed and/or suspended in aqueous media and thereafter re-organized and rebonded together to form a dense film with high barrier properties. ln addition to providing excellent gas barrier properties, the MFC films and coatings are also inherently transparent or translucent to visible light, making them especially useful in applications where transparency or translucency of the film in the visible light spectrum (typically in the range of 389 to 2740 awm) is required. An MFC coatings may for example be used as a varnish or overlay varnish.
MFC films can be made by applying an MFC suspension on a porous substrate, for example a membrane or wire, forming a web followed by dewatering of the web by draining water through the substrate to form the film. This can be accomplished e.g. by use of a paper- or paperboard machine type of process. US2012298319A teaches a method of manufacturing of an MFC film by applying a furnish comprising MFC directly on porous substrate thus allowing the MFC to be dewatered and filtered.
Alternatively, the film can be made by use of casting technologies, including applying an MFC dispersion onto a non-porous cast substrate, such as apolymeric or metal substrate, and drying said film by evaporation and/or wet pressing. Films made by casting technologies usually provide a more uniform thickness distribution and a smoother surface. The publication EP2771390 A4 describes preparation of MFC films, in which an aqueous cellulose nanofiber dispersion is coated on a paper or polymeric substrate, dried and finally peeled off as a nanofiber film sheet.
A problem with MFC films is that they may be brittle and provide low strain at break and tear resistance since the fiber network formed from short fibers will not have the ability to stretch in the same way as longer fibers. When forming MFC films of low grammage and thickness, the film may easily break during wet web forming, converting or handling. Also, the gas barrier properties of such MFC films tend to deteriorate at high temperatures and high humidity. Moreover, MFC is a relatively expensive material, making the cost of pure MFC films high.
Various additives have been considered in order to address the problems associated with improving the mechanical properties of MFC films. However, while the use of a given additive may solve one specific problem, it may not be able to solve or maintain other physical or mechanical requirements and may even cause new problems. As an example, the addition of longer cellulose fibers in the MFC films may improve the mechanical properties of the films but will at the same time impair the gas barrier properties and transparency or translucency of the film. Adding a plasticizer such as sorbitol is a good way to get better strain at break but this also reduces the gas barrier properties of the films when increasing the humidity. Other additives may adversely affect the re-use of the material such as in the form of broke or pre- or post-consumer reject.
Thus, there remains a need for improved MFC films combining good oxygen barrier properties with an acceptable high strain at break.
Description of the invention lt is an object of the present disclosure to provide an improved microfibrillated cellulose (MFC) composition for preparation of oxygen barrier films or coatings, which eliminates or alleviates at least some of the problems in the prior art. lt is a further object of the present disclosure to provide a microfibrillated cellulose (MFC) composition which enables the manufacturing of an MFC film combining good oxygen barrier properties with an acceptable strain at break. lt is a further object of the present disclosure to enable the manufacturing of an MFC film, which shows good oxygen barrier properties, is easy to handle, easy to produce at higher speeds, easy to convert, and/or makes use of more cost- efficient raw materials.
The above-mentioned objects, as well as other objects as will be realized by the skilled person in the light of the present disclosure, are achieved by the various aspects of the present disclosure.
The present disclosure is based on the inventive realization that including very small amounts of a low molecular weight polyethylene glycol (LMW-PEG) having a molecular weight in the range of 300-500 g/mol in a microfibrillated cellulose (MFC) composition allows for preparation of oxygen barrier films or coatings combining good oxygen barrier properties with an acceptable strain at break. The molecular weight of the PEG has been found to be important for achieving both good oxygen barrier properties and an acceptable strain at break. PEG having a molecular weight higher than 500 g/mol may give an even lower oxygen transmission rate (OTR), but at the cost of a lower strain at break. The amount of LMW-PEG should preferably be in the range of 2-8 wt% based on the total dry weight of the MFC composition. The optimal combination of oxygen barrier properties and strain at break seems to be achieved with about 5 wt% of LMW- PEG having a molecular weight in the range of 300-500 g/mol. lt is surprising that so small amounts of LMW-PEG can give these positive effects on strain at break and still not affect the OTR too much.
The LMW-PEG is also expected to facilitate redispersion and thereby re-use of the MFC material such as in the form of broke or pre- or post-consumer reject.According to a first aspect illustrated herein, there is provided a microfibrillated cellulose (MFC) comprising: MFC at a concentration in the range of 50-98 wt%, and a low molecular weight polyethylene glycol (LMW-PEG) having a molecular weight in the range of 300-500 g/mol at a concentration in the range of 2-8 wt%, based on the total dry weight of the MFC__ "jmmay be comprised solely of a mixture of MFC and phosphorylated cellulose fibers, or it can comprise the mixture of MFC and phosphorylated cellulose fibers combined with other ingredients or additives. The MFC composition preferably includes MFC as its main component based on the total dry weight of the MFC composition. Specifically, the MFC composition comprises MFC at a concentration in the range of 50-98 wt%. ln some embodiments, the MFC composition comprises in the range of 60-98 wt%, preferably in the range of 70-98 wt%, more preferably in therange of 80-98 wt% of MFC, based on the total dry weight of the MFC com position.
Microfibrillated cellulose (MFC) shall in the context of the patent application mean a cellulose particle, fiber or fibril having a width or diameter of from 20 nm tonm.
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 is usually required in order to make MFC manufacturing both energy efficient and sustainable. The cellulose fibers of the pulp used when producing MFC may thus be native or pre-treated enzymatically or chemically, for example to reduce the quantity of hemicellulose or lignin. 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, carboxymethyl (CM), 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.
MFC can be produced from wood cellulose fibers, both from hardwood or softwood fibers. lt can also be made from microbial sources, agricultural fibers such as wheat straw pulp, bamboo, bagasse, or other non-wood fiber sources. lt can be made from pulp, including pulp from virgin fiber, e.g. mechanical, chemical and/or thermomechanical pulps. lt can also be made from broke or recycled paper. ln some embodiments, the MFC comprises less than 50 wt%, preferably less than 30 wt%, and more preferably less than 20 wt%, of MFC fibers having a diameter above 1000 nm. ln some embodiments, the MFC comprises less than 10 wt%, preferably below 7.5 wt%, more preferably below 5 wt%, of fibers having a length of > 0.2 mm, as measured using an FS5 optical fiber analyzer (Valmet).
There are different synonyms for MFC such as cellulose microfibrils, fibrillated cellulose, nanocellulose, nanofibrillated cellulose, fibril aggregates, nanoscale cellulose fibrils, cellulose nanofibers, cellulose nanofibrils, cellulose microfibers, cellulose fibrils, microfibrillar cellulose, microfibril aggregates and cellulose microfibril aggregates.
The MFC of the MFC composition may be unmodified MFC or chemically modified MFC, or a mixture thereof. ln some embodiments, the MFC is an unmodified MFC.
Unmodified MFC refers to MFC made of unmodified or native cellulose fibers. The unmodified MFC may be a single type of MFC, or it can comprise a mixture of two or more types of MFC, differing e.g. in the choice of cellulose raw material or manufacturing method.
Chemically modified MFC refers to MFC made of cellulose fibers that have undergone chemical modification before, during or after fibrillation. ln some embodiments, the MFC is a chemically modified MFC. The chemically modified MFC may be a single type of chemically modified MFC, or it can comprise a mixture of two or more types of chemically modified MFC, differing e.g. in the type of chemical modification, the choice of cellulose raw material or the manufacturing method. ln some embodiments, the MFC of the MFC composition has a Schopper-Riegler (SR) number > 70, preferably > 80, and more preferably > 90, as measured according to the standard ISO 5267- The MFC film composition comprises the LMW-PEG at a concentration in the range of 2-8 wt%, based on the total dry weight of the MFC composition. ln some embodiments, the MFC composition comprises in the range of 2-7 wt%, preferably in the range of 3-6 wt%, more preferably in the range of 4-6 wt% of LMW-PEG, based on the total dry weight of the MFC composition.The LMW-PEG of the inventive composition has a molecular weight in the range of 300 - 500 g/mol. ln some embodiments, the LMW-PEG has a molecular weight in the range of 350 - 450 g/mol. One preferred LMW-PEG is PEG 400, which typically has a molecular weight in the range of 380 - 420 g/mol. Unless otherwise specified, the term "molecular weight" as used herein with reference to PEG refers to the number average molecular weight Mn.
The formulation of the MFC composition may vary depending on the intended use of the MFC composition and on the intended mode of application or formation of a film or coating of the MFC composition. The MFC composition may include a wide range of ingredients in varying quantities to improve the end performance of a film or coating of the MFC composition. ln some embodiments, the MFC composition further comprises a water-soluble polymer selected from the group consisting of a starch, a polyvinyl alcohol (PVOH), a cellulose derivative, a hemicellulose, a polyacrylamide, a polydiallyldimethylammonium chloride (PDADMAC), a polyvinylamine (PVAm), a polyethyleneimine (PEI), a protein or a mixture thereof, preferably a PVOH.
The PVOH may be a single type of PVOH, or it can comprise a mixture of two or more types of PVOH, differing e.g. in degree of hydrolysis or viscosity or different functional groups. The PVOH may for example have a degree of hydrolysis in the range of 80-99 mol%, preferably in the range of 88-99 mol%. Furthermore, the PVOH may preferably have a viscosity above 5 mPa> ln some embodiments, the MFC composition comprises in the range of 0.1-20 wt%, preferably in the range of 1-15 wt% of the water-soluble polymer, based on the total dry weight of the MFC composition. ln some embodiments, the MFC composition further comprises a pigment that promotes oxygen barrier function of a barrier film, preferably a pigment selected from the group consisting of clays and nanoclays, talcum, silicates, carbonates,alkaline earth metal carbonates, ammonium carbonate, metal oxides and transition metal oxides. ln some embodiments, the MFC composition comprises in the range of 0.1-20 wt%, preferably in the range of 1-10 wt% of the pigment, based on the total dry weight of the MFC composition.
The MFC composition may further comprise additives such as starch, fillers, retention aids, flocculation additives, deflocculating additives, dry strength additives, softeners, lubricants, wet strength agents, colorants or dyes, defoamers, fixatives, biocides, pH regulators, UV blocking agents, or mixtures thereof. The MFC composition may for example comprise additives that will improve different properties of the MFC composition and/or a film or coating formed thereof, such as latex and/or polyvinyl alcohol (PVOH) for enhancing the ductility of the coating.
The MFC composition above is useful in the preparation of MFC films, particularly oxygen barrier films.
The MFC film may be a free standing MFC film, an MFC coating on a substrate, or an MFC layer of a multilayer material. The film may for example be prepared by casting, coating or wet laid process.
MFC film has a grammage in the range of 10-gsm, preferably in the range of 12-50 gsm, more preferably in the range of 15-40 gsm. Correspondingly, in some embodiments, a coating can have a grammage in the range of 1-20 gsm, or more preferably in the range of 1-10 gsm.
The present disclosure is based on the inventive realization that including very small amounts of a low molecular weight polyethylene glycol (LMW-PEG) having a molecular weight in the range of 300-500 g/mol in a microfibrillated cellulose(MFC) composition allows for preparation of oxygen barrier films or coatings combining good oxygen barrier properties with an acceptable strain at break.
The addition of the LMW-PEG in the MFC film improves the mechanical strength, particularly the strain at break, of the film as compared to a corresponding MFC film without the LMW-PEG. ln some embodiments, the MFC film has a strain at break at least 10% higher, preferably at least 15% higher, more preferably at least 20% higher, than the tear index ofa corresponding film without the LMW-PEG, as measured according to the standard ISO-1924-3, modified with clamped length of 20 mm and a speed of 2 mm/min. ln some embodiments, the film has a strain at break of at least 2.5%, preferably at least 3%, as measured according to the standard ISO-1924-3, modified with clamped length of 20 mm and a speed of 2 mm/min.
Reference material for MFC-film with sorbitol has shown that a strain at break of 3% is preferred for handling of the film in converting. ln some embodiments, the film has an oxygen transfer rate (OTR) less than 20 cc/m2/24h/atm higher, preferably less than 10 cc/m2/24h/atm higher, than the OTR of a corresponding film without the LMW-PEG, as measured according to the standard ASTM F-1927-98 at 80% relative humidity and 23 °C. ln some embodiments, the film has an oxygen transfer rate (OTR) of less than 20 cc/m2/24h/atm, preferably less than 10 cc/m2/24h/atm, as measured according to the standard ASTM F-1927-98 at 80% relative humidity and 23 °C. ln some embodiments, the film has a transparency of at least 75%, preferably at least 80%, as measured according to the standard DIN ln some embodiments, the film further comprises a metallization layer disposed on at least one surface thereof. A metallization layer is formed by vapor deposition of a metal or metal oxide on the surface, preferably by physical vapor deposition (PVD) or chemical vapor deposition (CVD), more preferably by physical vapor deposition (PVD). The metallization layer may for example comprise aluminum or an aluminum oxide. Metallization layers are normally merely nanometer-thick, i.e. have a thickness in the order of magnitude of nanometers. The metallization layer may for example have a thickness in the range of from 1 to 500 nm. ln some embodiments, the metallization layer has a layer thickness in the range of 10-nm, preferably in the range of 20-50 nm.
The MFC films or coatings may preferably be used as an oxygen barrier layer in a multilayer material, such as a paper or paperboard comprised of two or more plies.
The MFC films or coatings may preferably be used as an oxygen barrier layer in a paper or paperboard based packaging material, particularly in a liquid packaging board (LPB), for use in the packaging of liquids or liquid containing products. The improved strain at break of the inventive MFC films, makes them suitable for conversion. Combined with good oxygen barrier properties, this makes the films interesting for use as a replacement for an aluminum foil layers commonly used in liquid packaging board. àš>;i:-~:f<;->=---aspect illustrated herein, there is provided a multilayer material comprising at least: a substrate layer and an MFC layer comprising an MFC described above with reference to the first aspect. ln the multilayer material, the MFC layer may be attached to the substrate layer directly, or via one or more intermediate layers. For example, the MFC layer may be coated or wet laid directly onto the substrate layer, or an MFC film may be laminated to the substrate layer using an intermediate adhesive layer. ln some embodiments, the substrate layer is paper or paperboard.ln some embodiments, the paper or paperboard has a basis weight in the range of 20-500 gsm (g/m2), preferably in the range of 80-400 gsm. ln some embodiments, the multilayer material is a paper or paperboard comprised of two or more plies, wherein at least one ply comprises an MFC as described above with reference to the first aspect. ln some embodiments, the multilayer material comprises one or more heat sealable layers, such as one or more polyethylene layers. ln some embodiments, the multilayer material is a liquid packaging board (LPB). ln some embodiments, the liquid packaging board comprises the layers: Extruded polyolefin/Paperboard/Extruded polyolefin/MFC film/Extruded polyolefin The laminate may further include tie layer/s comprising a tie resin applied between the extruded polyolefin layer/s and the MFC film. ln some embodiments, the extruded polyolefin is a polyethylene (PE), preferably low density polyethylene (LDPE).
According to a aspect illustrated herein, there is provided method of preparing an MFC film, said method comprising: a) preparing an aqueous dispersion comprising: MFC at a concentration in the range of 50-98 wt%, and a low molecular weight polyethylene glycol (LMW-PEG) having a molecular weight in the range of 300- 500 g/mol at a concentration in the range of 2-8 wt%, based on the total dry weight ofb) forming a wet film of the aqueous dispersion är: c) drying the wet film to obtain the MFC film.
Thanks to the high solubility of the LMW-PEG, the aqueous MFC composition may be prepared in a number of different ways. The aqueous MFC composition may for example be prepared by mixing dry MFC and dry LMW-PEG and dispersing the dry mixture in water, or by adding LMW-PEG, in dry or dissolved form, to an aqueous MFC dispersion. ln some embodiments of the method, the step a) comprises mixing MFC having a Schopper-Riegler (SR) number > 70, preferably > 80, and more preferably > 90, as measured according to the standard ISO 5267-1, with the LMW-PEG. ln some embodiments, the drying in step c) is performed at a temperature above 50 °C, preferably above 70 °C, more preferably above 90 °C. The drying temperature refers to the temperature in the film during the drying. The drying source may have a much higher temperature than the actual film. Drying at elevated temperature may further improve the mechanical properties of coatings or films formed of the MFC composition. Drying means that the solid content of the MFC film is at least 80 wt%, preferably at least 85 wt% and more preferably at least 90% after the drying.
According to a lššïtšfæ-aspect illustrated herein, there is provided the use of a low molecular weight polyethylene glycol (LMW-PEG) having a molecular weight in the range of 300-500 g/mol at a concentration in the range of 2-8 wt% as a strength enhancement agent in an MFC composition for preparation of oxygen barrier films or coatings.
The MFC composition comprises the LMW-PEG at a concentration in the range of 2-8 wt%, based on the total dry weight of the MFC composition. ln some embodiments, the MFC composition comprises in the range of 2-7 wt%, preferablyin the range of 3-6 wt%, more preferably in the range of 4-6 wt% of LMW-PEG, based on the total dry weight of the MFC composition.
The LMW-PEG of the inventive composition has a molecular weight in the range of 300 - 500 g/mol. ln some embodiments, the LMW-PEG has a molecular weight in the range of 350 - 450 g/mol. One preferred LMW-PEG is PEG 400, which typically has a molecular weight in the range of 380 - 420 g/mol. ln some embodiments, the MFC composition of the *<~**'=š*->.-«aspect is an MFC composition as described above :'1;..:°::::*:::::::,. får.. :::::;;,.
The term "wt%" as used herein (e.g. with reference to pulp compositions or pulp fractions) refers to weight percent based on the total dry weight of the composition.
The term "consistency" as used herein (e.g. with reference to pulp compositions or pulp fractions) refers to weight percentage of dry solid substances in the composition based on the total weight of the composition.
Unless otherwise specified, the term "molecular weight" as used herein with reference to PEG refers to the number average molecular weight Mn.
While the invention has been described with reference to various exemplary embodiments, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted for elements thereof without departing from the scope of the invention. ln addition, many modifications may be made to adapt a particular situation or material to the teachings of the invention without departing from the essential scope thereof. Therefore, it is intended that the invention not be limited to the particular embodiment disclosed as the best mode contemplated for carrying out this invention, but that the invention will include all embodiments falling within the scope of the appended claims.
Brief description of the drawinqs Fig. 1 is a diagram showing OTR at 23/80 for films consisting of 100% MFC, 10% PVOH, 5% Closite clay and different PEG quality and amount.EXAMPLES Materials The PVOH grade had 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 bentonite was Na-Cloisite.
The mixture for manufacturing the films were prepared as follows. Polyvinyl alcohol was jet cooked for 2 h at a solids content of 14%. The bentonite clay was mixed with high shear rate for 2 h at a solids content of 8% and the left at leasth for swelling with no mixing.
Unmodified MFC, seen as 100%, at a solids content of 3 wt% was mixed with 10 wt% PVOH, 5% of Bentonite clay and a changed amount of either PEG 400 or PEG 600. The suspension was mixed and deaerated in a vacuum assisted mixing using a magnetic stirrer. The film was produced by rod coating the dispersion on a heated metallic surface. The film was dry after 5 to 10 minutes. The estimated drying temperatures was 90 degrees at the start and around 60 degrees when dry.
The reference film was prepared in the same way as the samples but only using native MFC and adding 15% sorbitol instead of the PVOH, bentonite clay and PEG. Sorbitol was added as a 50% solution.
The films referred to as Reference and Sample 1 to 7 were after drying separated from the metallic substrate. The obtained films had a thickness of 35-45 um and a grammage of about 50 g/m Analysis The films were characterized with strain at break according to the standard ISO- 1924-3, modified with clamped length of 20 mm and a speed of 2 mm/min. The oxygene transmission rate was measured according to the standard ASTM F- 1927-98 at 80% relative humidity and 23 °C.
MFC PVOH Clay PEG PEG Sorbitol OTR Strain at 400 600 23/80 break Reference 100 15 38 3,0 Sample 1 100 10 5 2,4 2,3 Sample 2 100 10 5 2 7,0 2,8 Sample 3 100 10 5 5 8,4 3,1 Sample 4 100 10 5 10 20 2,4 Sample 5 100 10 5 2 4,4 2,0 Sample 6 100 10 5 5 4,4 2,2 Sample 7 100 10 5 3 2 4,0 3,0

Claims (22)

Claims
1. A microfibrillated cellulose (MFC) film having a grammage in the range of 10- 100 gsm, characterized in that it comprises: MFC at a concentration in the range of 50-98 wt%, and a low molecular weight poiyethylene glycol (LMW-PEG) having a molecular weight in the range of 300-500 g/mol at a concentration in the range of 2-8 wt%, based on the total dry weight of the MFC film.
2. The MFC film according to any one of the preceding claims, wherein the MFC film comprises in the range of 60-98 wt%, preferably in the range of 70-98 wt%, more preferably in the range of 80-98 wt% of MFC, based on the total dry weight of the MFC film.
3. The MFC film according to any one of the preceding claims, wherein the MFC is unmodified MFC.
4. The MFC film according to any one of the preceding claims, wherein the MFC has a Schopper-Riegler (SR) number > 70, preferably > 80, and more preferably > 90, as measured according to the standard ISO 5267-
5. The MFC film according to any one of the preceding claims, wherein the MFC film comprises in the range of 2-7 wt%, preferably in the range of 3-6 wt%, more preferably in the range of 4-6 wt% of LMW-PEG, based on the total dry weight of the MFC film.
6. The MFC film according to any one of the preceding claims, wherein the LMW-PEG has a molecular weight in the range of 350 - 450 g/mol.
7. The MFC film according to any one of the preceding claims, wherein the MFC film further comprises a water-soluble polymer selected from the group consistingof a starch, a polyvinyl alcohol (PVOH), a cellulose derivative, a hemicellulose, a polyacrylamide, a polydiallyldimethylammonium chloride (PDADMAC), a polyvinylamine (PVAm), a polyethyleneimine (PEI), a protein or a mixture thereof, preferably a PVOH.
8. The MFC film according to claim 7, wherein the MFC film comprises in the range of 0.1 -20 wt%, preferably in the range of 1-15 wt% of the water-solubie polymer, based on the total dry weight of the MFC film.
9. The MFC film according to any one of the preceding claims, wherein the MFC film further comprises a pigment that promotes oxygen barrier function of a barrier film, preferably a pigment selected from the group consisting of clays and nanoclays, talcum, silicates, carbonates, alkaline earth metal carbonates, ammonium carbonate, metal oxides and transition metal oxides.
10. The MFC film according to claim 9, wherein the MFC film comprises in the range of 0.1-20 wt%, preferably in the range of 1-10 wt% of the pigment, based on the total dry weight of the MFC film.
11. The MFC film according to any one of the preceding claims, wherein the film has a grammage in the range of 10-100 gsm, preferably in the range of 12-gsm, more preferably in the range of 15-40 gsm.
12. The MFC film according to any one of the preceding claims, wherein the film has a strain at break at least 10% higher, preferably at least 15% higher, more preferably at least 20% higher, than the tear index of a corresponding film without the LMW-PEG, as measured according to the standard ISO-1924-3, modified with clamped length of 200 mm and a speed of 2 mm/min.
13. The MFC film according to any one of the preceding claims, wherein the film has a strain at break of at least 2.5%, preferably at least 3%, as measured according to the standard ISO-1924-3, modified with clamped length of 200 mm and a speed of 2 mm/min.
14. The MFC film according to any one of any one of the preceding claims, wherein the film has an oxygen transfer rate (OTR) less than 20 cc/m2/24h/atm higher, preferably less than 10 cc/m2/24h/atm higher, than the OTR of a corresponding film without the LMW-PEG, as measured according to the standard ASTM F-1927-98 at 80% relative humidity and 23 °C.
15. The MFC film according to any one of the preceding claims, wherein the film has an oxygen transfer rate (OTR) of less than 20 cc/m2/24h/atm, preferably less than 10 cc/m2/24h/atm, as measured according to the standard ASTM F-1927-98 at 80% relative humidity and 23 °C.
16. The MFC film according to any one of the preceding claims, wherein the film has a transparency of at least 75%, preferably at least 80%, as measured according to the standard DIN
17. The MFC film according to any one of the preceding claims, wherein the film further comprises a metallization layer disposed on at least one surface thereof.
18. A multilayer material comprising at least: a substrate layer and an MFC layer comprising an MFC film according to any one of the preceding claims.
19. The multilayer material according to claim 18, wherein the substrate layer is paper or paperboard.
20. The multilayer material according to claim 19, wherein the paper or paperboard has a basis weight in the range of 20-500 gsm, preferably in the range of 80-400 gsm.
21. A method of preparing an MFC film, said method being characterized by a) preparing an aqueous dispersion comprising: MFC at a concentration in the range of 50-98 wt%, and a low molecular weight polyethylene glycol (LMW-PEG) having a molecular weight in the range of 300- 500 g/mol at a concentration in the range of 2-8 wt%, based on the total dry weight of the aqueous dispersion; b) forming a wet film of the aqueous dispersion having a grammage in the range of 10-100 gsm; and c) drying the wet film to obtain the MFC film.
22. Use of a low molecular weight polyethylene glycol (LMW-PEG) having a molecular weight in the range of 300-500 g/mol at a concentration in the range of 2-8 wt% as a strength enhancement agent in an MFC film.
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WO2019073370A1 (en) * 2017-10-11 2019-04-18 Stora Enso Oyj Oxygen barrier film
WO2020261170A1 (en) * 2019-06-27 2020-12-30 Stora Enso Oyj Gas barrier film for packaging material
WO2021130668A1 (en) * 2019-12-23 2021-07-01 Stora Enso Oyj A method of making a cellulose film comprising microfibrillated cellulose

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Publication number Priority date Publication date Assignee Title
US20160002483A1 (en) * 2013-03-14 2016-01-07 Oregon State University Nano-cellulose edible coatings and uses thereof
WO2018138702A1 (en) * 2017-01-30 2018-08-02 Stora Enso Oyj Method of manufacturing a film comprising microfibrillated cellulose
WO2019073370A1 (en) * 2017-10-11 2019-04-18 Stora Enso Oyj Oxygen barrier film
WO2020261170A1 (en) * 2019-06-27 2020-12-30 Stora Enso Oyj Gas barrier film for packaging material
WO2021130668A1 (en) * 2019-12-23 2021-07-01 Stora Enso Oyj A method of making a cellulose film comprising microfibrillated cellulose

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