EP3853264A1 - Procédé pour améliorer l'adhérence pendant la production d'un film - Google Patents

Procédé pour améliorer l'adhérence pendant la production d'un film

Info

Publication number
EP3853264A1
EP3853264A1 EP19861890.2A EP19861890A EP3853264A1 EP 3853264 A1 EP3853264 A1 EP 3853264A1 EP 19861890 A EP19861890 A EP 19861890A EP 3853264 A1 EP3853264 A1 EP 3853264A1
Authority
EP
European Patent Office
Prior art keywords
film
cellulose
mixture
layer
suspension
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Withdrawn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
EP19861890.2A
Other languages
German (de)
English (en)
Other versions
EP3853264A4 (fr
Inventor
Cecilia LAND HENSDAL
Isabel KNÖÖS
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 EP3853264A1 publication Critical patent/EP3853264A1/fr
Publication of EP3853264A4 publication Critical patent/EP3853264A4/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B15/00—Preparation of other cellulose derivatives or modified cellulose, e.g. complexes
    • C08B15/02—Oxycellulose; Hydrocellulose; Cellulosehydrate, e.g. microcrystalline cellulose
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B15/00—Preparation of other cellulose derivatives or modified cellulose, e.g. complexes
    • C08B15/10—Crosslinking of cellulose
    • 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
    • C08J7/042—Coating with two or more layers, where at least one layer of a composition contains a polymer binder
    • C08J7/0423—Coating with two or more layers, where at least one layer of a composition contains a polymer binder with at least one layer of inorganic material and at least one layer of a composition containing a polymer binder
    • 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
    • C08J7/0427—Coating with only one layer of a composition containing a polymer binder
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L29/00—Compositions 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; Compositions of hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers
    • C08L29/02—Homopolymers or copolymers of unsaturated alcohols
    • C08L29/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
    • 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
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/724—Permeability to gases, adsorption
    • B32B2307/7242—Non-permeable
    • B32B2307/7244—Oxygen barrier
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • 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
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/04—Homopolymers or copolymers of ethene
    • C08J2323/06—Polyethene
    • 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
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/04—Homopolymers or copolymers of ethene
    • C08J2323/08—Copolymers of ethene
    • 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
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/10—Homopolymers or copolymers of propene
    • C08J2323/12—Polypropene
    • 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
    • C08J2333/00—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 only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
    • C08J2333/04—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 only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
    • C08J2333/06—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 only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C08J2333/10—Homopolymers or copolymers of methacrylic acid esters
    • C08J2333/12—Homopolymers or copolymers of methyl methacrylate
    • 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
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • 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
    • C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
    • 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
    • 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 film having improved adhesion properties during forming. More particularly, the present invention relates to a method of manufacturing such a film and a film produced.
  • a plasticizer such as sorbitol is usually used as an additive, even up to 30% addition.
  • sorbitol is a moisture sensitive chemical which deteriorates the oxygen barrier properties of the film, especially at high relative humidity in the air.
  • the object of the present invention is at least partially achieved by means of a method for manufacturing a least one layer of a film wherein the method comprises the steps of:
  • the anhydroglucose units (AGU) of the total cellulose in the mixture comprise a dialdehyde.
  • the DA-MFC added in the second suspension can have different degrees of oxidation, defined as the portion of AGUs that have a dialdehyde.
  • the amount of DA-MFC needed to be added depends on the degree of oxidation in the corresponding suspension.
  • 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, said mixture containing both MFC and DA-MFC could theoretically be interpreted as a DA-MFC with low degree of oxidation.
  • DA-MFC as an additive leads to improved adhesion properties upon film making, i.e. a balanced adherence between the casted film suspension and the underlying substrate.
  • balanced adherence means in this context that the casted film suspension adheres well enough to the substrate during drying to not detach therefrom (where detaching of the film would lead to wrinkles and bubbles in the resulting film surface), and at the same time does not stick too hard to the surface. Too strong attachment of the film onto the substrate during making could lead to problems with detaching the dried film once it is ready.
  • the dry content of the mixture applied to the substrate is preferably between 1 -10% by weight. Depending on the substrate onto which the mixture is applied, the dry content of the mixture may vary.
  • the m icrof ibri I lated dialdehyde cellulose of said second suspension has an average degree of oxidation between 10-50%, preferably between 30-40%.
  • the second suspension comprises also native MFC in addition to microfibrillated dialdehyde cellulose.
  • drying of the web to form at least one layer of said film is performed under heat treatment of said web.
  • heat treatment may be achieved by means of heating the substrate onto which the mixture is cast.
  • said substrate is a polymer, plexi glass or metal substrate, and heat treatment is accomplished by means of heating said polymer, plexi glass or metal substrate so that it has reached a temperature between 45 - 120°C, preferably between 50 - 80°C, when the mixture is applied.
  • IR-drying Drying the film under heat treatment leads to the advantage of improved crosslinking between the microfibrillated fibers in the film.
  • the mixture may further comprise additives, preferably any one of a starch, carboxymethyl cellulose, a filler, clay, talcum, polyvinyl alcohol (PVOH), retention chemicals, flocculation additives, deflocculating additives, dry strength additives, softeners, or mixtures thereof. It may be possible to add additives that will improve different properties of the mixture and/or the produced film such as latex and/or polyvinyl alcohol for enhancing the ductility of the film. It may be possible to add the additive to the first suspension, the second suspension and/or to the mixture.
  • additives preferably any one of a starch, carboxymethyl cellulose, a filler, clay, talcum, polyvinyl alcohol (PVOH), retention chemicals, flocculation additives, deflocculating additives, dry strength additives, softeners, or mixtures thereof. It may be possible to add additives that will improve different properties of the mixture and/or the produced film such as latex and/or polyvinyl alcohol for
  • the present invention further relates to a film comprising a mixture of microfibrillated cellulose and microfibrillated dialdehyde cellulose, wherein the film is manufactured from a mixture in which less than 5% of the
  • anhydroglucose units (AGU) of the total cellulose present in the mixture comprise a dialdehyde.
  • the film preferably has a grammage of less than 50 g/m 2 , preferably between 10-50 g/m 2
  • said film is a multilayer film comprising more than one layer.
  • a layer of polyethylene (PE) on at least one side of the film comprising microfibrillated dialdehyde cellulose also improves strainability of the film and provides heat-sealing properties.
  • 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) or ethylene vinyl alcohol (EVOH).
  • the water vapor barrier film has preferably a
  • said film is a multilayer film wherein at least one layer of the film is a metallized barrier layer.
  • metallized barrier layer means a thin layer of metal providing barrier properties reducing permeability to e.g.
  • said metallized barrier layer is a physical vapour deposited metal or metal oxide layer, or a chemical vapour deposited metal or metal oxide layer, wherein said metal or metal oxide is selected from the group consisting of aluminium, aluminium oxides, magnesium oxides, silicium oxides, copper, magnesium and silicon.
  • the metallized barrier layer has a weight between 50 - 250 mg/m 2 , preferably between 75 - 150 mg/m 2 .
  • the present invention further relates to a packaging material comprising a base material laminated with at least one layer of the film previously described comprising a mixture of a microfibrillated cellulose and a microfibrillated dialdehyde cellulose.
  • Said base material is preferably paper or paperboard.
  • the paper or paperboard of said packaging material has a grammage between 20 - 500 g/m 2 , for instance between 80 - 400 g/m 2 .
  • the packaging material may comprise a multilayer film which in addition to the film comprising a mixture of a microfibrillated cellulose and a microfibrillated dialdehyde cellulose also comprises one or more of a water vapor barrier layer and/or a metallized barrier layer previously described
  • the invention also relates to the use of DA-MFC as an additive for improving adhesion properties in manufacturing of film, where said film comprises microfibrillated cellulose.
  • the method according to the present invention relates to providing a first suspension comprising microfibrillated cellulose and mixing said first suspension with a second suspension which in its turn comprises
  • D-MFC microfibrillated dialdehyde cellulose
  • AGU anhydroglucose units
  • the mixture is then applied onto a substrate to form a fibrous web and said web is thereafter dried to form at least one layer of the film.
  • DA-MFC dialdehyde cellulose
  • the at least one layer of the film 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 said film.
  • the drying of said web may be done in any conventional way, however preferably under heat treatment.
  • the dry content of the at least one layer of the film after drying is preferably above 95% by weight.
  • the substrate may be a polymer, plexi glass or metal substrate onto which the mixture is casted.
  • the cast coated fibrous web is dried in any conventional manner and thereafter optionally peeled off from the substrate. It may be possible to cast or coat more than one layer onto the substrate forming a multilayer film. 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 microfibrillated cellulose of the first suspension, i.e. not microfibrillated dialdehyde cellulose (DA-MFC). It may also be possible that one or more layers of the film is a water vapor barrier film comprising any one of polyethylene (PE), polypropylene (PP), polyamide, polyethylene terephthalate (PET) or ethylene vinyl alcohol
  • one or more layers of the film is a metallized barrier layer, comprising any one of aluminium, aluminium oxides, magnesium oxides, silicium oxides, copper, magnesium and silicon.
  • the film may comprise two, three, four, five, six, seven, eight, nine, ten or more layers.
  • a packaging material including a layer of the mixture according to the invention may comprise further barrier layers for preventing migration of air, water and flavors through the base material.
  • a packaging material may include at least one water vapor barrier layer comprising any one of polyethylene (PE), polypropylene (PP), polyamide, polyethylene terephthalate (PET) or ethylene vinyl alcohol (EVOH).
  • the packaging material may also include one or more metallized barrier layer(s) comprising any one of aluminium, aluminium oxide, magnesium oxide or silicium oxide.
  • 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.
  • native MFC refers to MFC that is made from conventional chemical, chemimechanical 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
  • 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"), or quaternary ammonium (cationic cellulose).
  • TEMPO N-oxyl mediated oxidation
  • quaternary ammonium cationic cellulose
  • 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-OFI moieties to aldehyde moieties.
  • crosslinkable functional groups aldehyde groups
  • the microfibrillated dialdehyde cellulose in the second 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 such that fibrillation occurs to produce microfibrillated dialdehyde cellulose.
  • the microfibrillated dialdehyde cellulose in the second suspension preferably has an oxidation degree between 10-50%, preferably between 30- 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 mixture may further comprise additives, preferably any one of a starch, carboxymethyl cellulose, a filler, retention chemicals, clay, talcum, polyvinyl alcohol, flocculation additives, deflocculating additives, dry strength additives, softeners, or mixtures thereof. It may be possible to add additives that will improve different properties of the mixture and/or the produced film. It may be possible to add the additive to the first suspension, the second suspension and/or to the mixture.
  • additives preferably any one of a starch, carboxymethyl cellulose, a filler, retention chemicals, clay, talcum, polyvinyl alcohol, flocculation additives, deflocculating additives, dry strength additives, softeners, or mixtures thereof. It may be possible to add additives that will improve different properties of the mixture and/or the produced film. It may be possible to add the additive to the first suspension, the second suspension and/or to the mixture.
  • Figure 1 shows a photo of a film with undulated surface due to poor adhesion during film making.
  • Example I DA-MFC as an adhesion enhancer
  • a first suspension of native microfibrillated cellulose (MFC) was diluted to a solids content of 3 wt%. 10 wt% of polyvinyl alcohol was added and also 5 wt% of clay or talcum, according to Table 1. (Added relative to 100% MFC)
  • a second suspension with a solids content of 3 wt% was also prepared by mixing 60% microfibrillated dialdehyde cellulose (DA-MFC) with a degree of oxidation of 40%, with 40% MFC. The total degree of oxidation in the second suspension was thus 24%.
  • D-MFC microfibrillated dialdehyde cellulose
  • Test 1 A first mixture with no added DA-MFC, i.e. corresponding to said first suspension only, is referred to as Test 1 , whereas Tests 2, 3 and 4 were prepared by mixing the first suspension with increased added amounts of the second suspension, ending up with mixtures No. 2, 3 and 4 having 1wt%, 5wt% and 7wt% respectively of said second suspension.
  • Tests 2,3 and 4 the portion of AGUs in the mixture containing a dialdehyde was thus 0.24%
  • the mixtures were used for casting of films on a heated Plexiglas or on a plasma treated polypropylene (PP) substrate, where the degree of plasma treatment was 100%.
  • Test 1 the film was cast and dried on a heated Plexiglas substrate, described in the following.
  • a metal plate was preheated in an oven at 70°C for over 2h.
  • Coating was performed in room temperature of 23°C, by placing a frame with dimension of approximately an A4 sheet on the Plexiglas, applying the mixture inside the frame and using a rod like tool to fill out said frame and create the fibrous web.
  • the frame was removed from the Plexiglas, and next said Plexiglas with the web was placed on top of the preheated metal plate consequently heating also said Plexiglas to a temperature between 45 - 55°C, whereupon the web was allowed to dry to form a film.
  • Tests 2, 3 and 4 were cast on a plasma treated polypropylene substrate in room temperature.
  • the adhesion to the substrate of the respective films was evaluated by visual inspection of the film surface after drying, and by evaluating film behaviour opon detaching the film from the substrate after drying.
  • the casted film should firstly present an essentially planar/flat surface on the substrate with no undulations and/or detached areas or bubbles appearing across the film surface.
  • the film should also detach from the substrate after that the film is ready, i.e. it should be possible to peel off the film from the substrate after completion of the film making without rupturing said film. If the film adhesion to the substrate is too strong, the film will rupture when trying to detach it. In other words, a“good adhesion” represents a sophisticated balance between too weak adhesion leading to bubbles and undulations in the film, and too strong adhesion leading to ruptures upon removing the dried film from the substrate.
  • Figure 1 shows a photo of a film made from a mixture of MFC, PVOFI, talcum and 0.24wt% DA-MFC, where the adhesion was too low leading to undulations spreading across the film during the drying phase of film making process.
  • Table 1 Adhesion test result with varying amounts of added DA-MFC with D.O. of 24% The results from Example 1 show that microfibrillated dialdehyde cellulose may serve as an additive for the purpose of enhancing adhesion during casting of barrier films comprising microfibrillated cellulose.

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  • Inorganic Chemistry (AREA)
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Abstract

La présente invention concerne un procédé de fabrication d'au moins une couche d'un film, caractérisé en ce que le procédé comprend les étapes consistant à : fournir une première suspension comprenant de la cellulose microfibrillée ; fournir une seconde suspension comprenant de la cellulose de dialdéhyde microfibrillée ; mélanger la première suspension avec la seconde suspension pour former un mélange, dans ledit mélange moins de 5% des unités d'anhydroglucose (AGU) de la cellulose totale présente à l'intérieur comprenant un dialdéhyde ; appliquer ledit mélange sur un substrat pour former une bande fibreuse et sécher ladite bande pour former au moins une couche dudit film. La présente invention concerne en outre un film comprenant ladite au moins une couche de film.
EP19861890.2A 2018-09-19 2019-09-10 Procédé pour améliorer l'adhérence pendant la production d'un film Withdrawn EP3853264A4 (fr)

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SE1851113A SE542944C2 (en) 2018-09-19 2018-09-19 A method for improving adhesion during film production
PCT/IB2019/057603 WO2020058803A1 (fr) 2018-09-19 2019-09-10 Procédé pour améliorer l'adhérence pendant la production d'un film

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SE543028C2 (en) * 2018-10-08 2020-09-29 Stora Enso Oyj An oxygen barrier layer comprising microfibrillated dialdehyde cellulose
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SE542944C2 (en) 2020-09-22
SE1851113A1 (en) 2020-03-20

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