• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    The present invention relates to a method for manufacturing at least one fibrous barrier layer wherein the method comprises the steps of:providing a first suspension comprising microfibrillated dialdehyde cellulose,mixing the first suspension with polyvinlyalcohol (PVOH) 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. The present invention also relates to a fibrous barrier layer comprising a mixture of a microfibrillated dialdehyde cellulose and PVOH.
    公开号:SE1851213A1
    申请号:SE1851213
    申请日:2018-10-08
    公开日:2020-04-09
    发明作者:Susanne Hansson
    申请人:Stora Enso Oyj；
    IPC主号:
    专利说明:

    A FLEXIBLE BARRIER LAYER CONIPRISING IVIICROFIBRILLATEDDIALDEHYDE CELLULOSE Technical fieldThe present invention relates to a method for manufacturing at least one fibrous barrier layer comprising microfibrillated dialdehyde cellulose. Thepresent invention also relates to a fibrous barrier layer, such as a barrier film,having good flexibility and low oxygen transmission rate at high relativehumidity.
    Backgroundl/licrofibrillated cellulose (l/IFC) is widely used to manufacture barrier films for instance in multilayer paper laminates. However, the gas barrierproperties of l/IFC based films are dependent on the moisture or the relativehumidity in the surrounding environment. Therefore, it is quite common thatl/IFC films are coated with a polymer film to prevent moisture or water vaporto swell and disrupt the l/IFC film. The EP2551104A1 teaches the use of l/IFCand polyvinyl alcohol (PVOH) and/or polyuronic acid with improved barrierproperties at higher relative humidity (RH). Another solution is to coat the filmwith a film that has high water fastness and/or low water vapor transmissionrate. The JP2000303386A discloses e.g. latex coated on l/IFC film, whileUS2012094047A teaches the use of wood hydrolysates mixed withpolysaccharides such as l/IFC that can be coated with a polyolefin layer. lnaddition to this chemical modification, the possibility of cross-linking fibrils orfibrils and copolymers has been investigated. This improves water fastness ofthe films but also water vapor transmission rates. Another way to decreasethe moisture sensitivity of cellulose is to chemical modify the cellulose withsodium periodate to obtain dialdehyde cellulose (DAC). By fibrillating ofdialdehyde cellulose a barrier film with improved moisture resistant can beproduced. This is presented e.g. in WO2015034426. However, a dispersioncomprising microfibrillated dialdehyde cellulose (DA-l/IFC) is very unstable 2 since the DA-l/IFC sediments and is spontaneously crosslinking to certaindegree already in the dispersion leading to that the microfibrils are bound orentangled. The crossiinks further render the DA-l/IFC barrier film brittle, whichmay restrain the processing and handling. For instance, if the film is part of apaper 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 filmwhich presents good gas barrier properties even at high relative humidy andalso having a good strainability.
    Summary lt is an object of the present invention to provide an improved barrierfilm or barrier layer comprising microfibrillated dialdehyde cellulose, which hasgood barrier properties at high relative humidities as well as improved strainat break.
    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 leastone fibrous barrier layer wherein the method comprises the steps of: providing a first suspension comprising microfibrillated dialdehydecellulose (DA-l/IFC), mixing the first suspension with polyvinlyalcohol (PVOH)to form a mixture, applying said mixture to a substrate to form a wet fibrousweb and drying said wet web on said substrate to form a fibrous barrier layer. lt is understood that “fibrous barrier layer” may refer to a film which inits turn can be laminated e.g. onto a base layer such as paper board and/orpaper, and it may also refer to a layer in a multilayer structure which has beencreated by wet coating directly onto a substrate and subsequently driedthereon. 3 lt has been found that addition of polyvinyl alcohol (PVOH) to a mixturecomprising DA-l/IFC in making of film leads to films with improved strain atbreak compared to DA-MFC films without PVOH, and at the same time preserves the gas barrier function at high humidities.
    According to one aspect of the invention, the PVOH to be added to thefirst suspension preferably has a degree of hydrolysis between 80 - 99 mol°/>,more preferably between 88 - 99 mol°/>. Furthermore, the PVOH preferablyhas 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 producedby chemically modifying the cellulose with sodium periodate therebyselectively cleaving the C2-C3 bond of the anhydroglucose unit (AGU) in thecellulose chain, forming two aldehyde groups at said location. The term“degree of oxidation” (D.O.) is understood to refer to the portion of the totalnumber of anhydroglucose units that undergo said reaction (forming the twoaldehydes). The degree of oxidation is given in °/>. The skilled personunderstands that the DA-l/IFC added in the first suspension can havedifferent degrees of oxidation, defined as the portion of AGUs that have adialdehyde, as explained above. The amount of DA-l/IFC needed to be addedin order to achieve a specific D.O. in the final mixture depends on the degreeof oxidation in the corresponding suspension. For instance, a mixture of DA-l/IFC and native l/IFC naturally has an average degree of oxidation that islower than that of the DA-l/IFC part of the mixture. ln that sense, such amixture containing both l/IFC and DA-l/IFC could theoretically be interpretedas a DA-MFC with low degree of oxidation.
    The DA-l/IFC used for manufacturing of the fibrous layer ismechanically treated to obtain microfibrillated dialdehyde cellulose. Themechanical treatment may be carried out by means of a refiner, grinder, homogenizer, colloider, friction grinder, ultrasound sonicator or fluidizer. All 4 conventional homogenizers and fluidizers available may be used, such asGaulin homogenizer, microfluidizer, macrofluidizer or fluidizer-typehomogenizer. lt is also understood that the term “microfibrillate” refers to amechanical treatment whereby microfibrillated (cellulose) fibers are obtained.
    By “oxygen transmission rate” (OTR) means a measure of the amountof 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 layeris a film.
    According to another aspect of the invention, the substrate is a paperor paperboard substrate and the mixture is applied onto the substrate as acoating to form said wet fibrous web, wherein after drying said fibrous barrierlayer and said substrate forms two layers of a multilayer structure. Thecoating as such can be applied and dried in one or more layers.
    According to yet another aspect of the invention, the mixture comprises5-30wt°/> PVOH and 70-95wt% microfibrillated dialdehyde cellulose based onthe total dry weight of the mixture.
    According to yet another aspect of the invention, the mixture comprises15-25wt°/> PVOH and 75-85 wt% microfibrillated dialdehyde cellulose.
    According to yet another aspect of the invention, a second suspensioncomprising microfibrillated cellulose is provided, wherein said first suspensionis mixed with said second suspension. The mixed first and secondsuspension containing DA-l/IFC and l/IFC is further mixed with PVOH. ln oneembodiment, the mixture comprises between 20-45 wt% of microfibrillatedcellulose, 50-75wt°/> microfibrillated dilaldehyde cellulose and 5-30wt°/> PVOHbased on the total fiber weight of the mixture. ln another embodiment, themixture comprises 30-40wt% microfibrillated cellulose, 50-60 wt%microfibrillated dialdehyde cellulose and 10-20wt°/> PVOH based on the totalfiber weight of the mixture.
    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 layerhas an oxygen transmission rate in the range of from 0.1 to 100 cc/m2/24haccording to ASTM F-1927, at a relative humidity of 50 °/> at 23°C and/or at arelative humidity of 80% at 23°C at a barrier layer thickness 10-70 um.
    According to another aspect of the invention, the fibrous barrier layerhas a strain at break of at least 2%, preferably at least 3%.
    According to another aspect of the invention, the substrate is a polymeror metal substrate.
    According to another aspect of the invention, said method furthercomprises the step of pressing the film upon and/or after drying. Thetemperature may be increased to 70-150°C during such pressing of the film. lt is within the scope of the invention to add further additives to themixture, including one or more of a starch, carboxymethyl cellulose, a filler,clay, retention chemicals, flocculation additives, deflocculating additives, drystrength additives, softeners, cellulose nanocrystals or mixtures thereof.
    According to another aspect of the invention, the microfibrillateddialdehyde cellulose in the first suspension has an oxidation degree between20-50%.
    Furthermore, the present invention relates to a fibrous barrier layerhaving an oxygen transmission rate in the range of from 0.1 to 100 cc/m2/24haccording to ASTM F-1927, at a relative humidity of 50 °/> at 23°C and/or at arelative humidity of 80% at 23°C, and at a barrier layer thickness 10-70 um,and wherein at least one fibrous barrier layer comprises a mixture of amicrofibrillated dialdehyde cellulose and PVOH.
    According to one aspect of the invention, the fibrous barrier layercomprises a mixture of microfibrillated cellulose, microfibrillated dialdehydecellulose and PVOH.
    According to one aspect of the invention, the fibrous barrier layer has abasis 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 afilm, preferably comprising more than one layer. 6 According to one aspect of the invention, the fibrous barrier layer is amultilayer film wherein at least one layer of the film is a water vapor barrierfilm comprising any one of polyethylene (PE), polypropylene (PP), polyamide,polyethylene terephthalate (PET) or ethylene vinyl alcohol (EVOH). lt is possible to produce a film comprising more than one layer whereinat least one of the layers comprises the mixture according to the invention. ltmay also be possible that more than one layer of the film comprises themixture according to the invention. lt may also be possible that one or morelayers of the film only comprises native microfibrillated cellulose, i.e. whichdoes not comprise microfibrillated dialdehyde cellulose (DA-l/IFC). The filmmay 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 fibrousbarrier layer as described above. The base material may include, but is notlimited to, paper, cardboard, paperboard, fabric, plastic, polymer film, metal,composites and the like.
    The present invention further relates to the use of a fibrous barrierlayer comprising a mixture of a microfibrillated dialdehyde cellulose andPVOH as an oxygen barrier film.
    Description of Embodiments The method according to the present invention relates to a method formanufacturing at least one layer of a barrier film having at least oxygenbarrier properties, said method comprising providing a first suspensioncomprising microfibrillated dialdehyde cellulose, mixing the first suspensionwith polyvinlyalcohol (PVOH) to form a mixture, applying said mixture to asubstrate to form a wet fibrous web and drying said wet web on said substrateto form a fibrous barrier layer. lt has been found that by providing asuspension of dialdehyde cellulose which comprises at least a portion ofpolyvinyl alcohol, a film can be formed which has improved ductility whilemaintaining a good oxygen barrier property. 7 The fibrous barrier layer is produced by applying said mixture to asubstrate to form a fibrous web and drying said web to form at least one layerof film or coating. The drying of said web may be done in any conventionalway, preferably in combination with heat treatment and increased pressure.The dry content of the at least one layer of the film after drying is preferablyabove 90% by weight. l/licrofibrillated cellulose (l/IFC) or so called cellulose microfibrils (Cl/IF)shall in the context of the present application mean a nano-scale celluloseparticle fiber or fibril with at least one dimension less than 100 nm. l/IFCcomprises partly or totally fibrillated cellulose or lignocellulose fibers. Thecellulose fiber is preferably fibrillated to such an extent that the final specificsurface area of the formed l/IFC is from about 1 to about 300 m2/g, such asfrom 1 to 200 m2/g or more preferably 50-200 m2/g when determined for afreeze-dried material with the BET method. The term “native lVlFC” refers tol/IFC that is made from conventional chemical, chemimechanical and/ormechanical pulp without further chemical treatment, e.g. said native l/IFC islacking special functional groups.
    Various methods exist to make MFC, such as single or multiple passrefining, pre-hydrolysis followed by refining or high shear disintegration orliberation of fibrils. One or several pre-treatment steps are usually required inorder to make l/IFC manufacturing both energy-efficient and sustainable. Thecellulose fibers of the pulp to be supplied may thus be pre-treatedenzymatically or chemically. For example, the cellulose fibers may bechemically modified before fibrillation, wherein the cellulose moleculescontain functional groups other (or more) than found in the original cellulose.Such groups include, among others, carboxymethyl, aldehyde and/or carboxylgroups (cellulose obtained by N-oxyl mediated oxidation, for example"TEl/lPO"), or quaternary ammonium (cationic cellulose). After being modifiedor oxidized in one of the above-described methods, it is easier to disintegratethe fibers into l/IFC or NFC. 8 The nanofibrillar cellulose may contain some hemicelluloses; theamount is dependent on the plant source. Mechanical disintegration of thepre-treated fibers, e.g. hydrolysed, pre-swelled, or oxidized cellulose rawmaterial 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-typehomogenizer. Depending on the l/IFC manufacturing method, the productmight also contain fines, or nanocrystalline cellulose or e.g. other chemicalspresent in wood fibers or in papermaking process. The product might alsocontain various amounts of micron size fiber particles that have not been efficiently fibrillated. l/IFC can be produced from wood cellulose fibers, both from hardwood or softwood fibers. lt can also be made from microbial sources, agriculturalfibers such as wheat straw pulp, bamboo, bagasse, or other non-wood fibersources. lt is preferably made from pulp including pulp from virgin fiber, e.g.mechanical, chemical and/or thermomechanical pulps. lt can also be madefrom broke or recycled paper.
    The above described definition of l/IFC includes, but is not limited to,the proposed TAPPI standard W13021 on cellulose nano or microfibril (Cl/IF)defining a cellulose nanofiber material containing multiple elementary fibrilswith both crystalline and amorphous regions, having a high aspect ratio withwidth of 5-30 nm and aspect ratio usually greater than 50.
    Dialdehyde cellulose (DA-l/IFC) is typically obtained by reactingcellulose with an oxidising agent such as sodium periodate. During theperiodate oxidation, selective cleavage of the C2-C3 bond of theanhydroglucose unit (AGU) of cellulose takes place, with concurrent oxidationof the C2- and C3-OH moieties to aldehyde moieties. ln this manner,crosslinkable functional groups (aldehyde groups) are introduced to thecellulose. The microfibrillated dialdehyde cellulose in the second suspension 9 should in this context mean a dialdehyde cellulose treated in such way that itis microfibrillated. The production of the microfibrillated dialdehyde cellulose isdone by treating dialdehyde cellulose for example by a homogenizer or in anyother way so that fibrillation occurs to produce microfibrillated dialdehydecellulose. The microfibrillated dialdehyde cellulose in the second suspensionpreferably has an oxidation degree between 10-50°/>, preferably between 30-40°/>. The degree of oxidation was determined according to the followingdescription: after the dialdehyde cellulose reaction, the amount of C2-C3bonds in the cellulose that are converted to dialdehydes is measured. Thedegree of oxidation is the amount of C2-C3 bonds that are convertedcompared to all C2-C3 bonds. This is measured with a method by H. Zhaoand N.D. Heindel, “Determination of Degree of Substitution of Formyl Groupsin Polyaldehyde Dexran by the Hydroxylamine Hydrochloride Method",Pharmaceutical Research, vol. 8, pp. 400-402, 1991, where the availablealdehyde groups reacts with hydroxylamine hydrochloride. This forms oximegroups and releases hydrochloric acid. The hydrochloric acid is titrated withsodium hydroxide until pH 4 is reached, and the degree of oxidation isthereafter calculated from according to the formula below. The receivedaldehyde content is divided by two to get the value of the degree of oxidation, since an oxidized anhydroglucose unit has two aldehyde groups.
    X EX 100msample X MW 2 D.0 [%] =VNaoH = the amount of sodium hydroxide needed to reach pH 4 (I)CNaoH = 0,1 mol/Imsampie = dry weight of the analysed DAC sample (g) lVlw = 160 g/mol, which is the molecular weight of the dialdehyde cellulose unit The PVOH to be added to the first suspension preferably has a degreeof hydrolysis between 80 - 99 mol°/>, more preferably between 88 - 99 mol%.
    Furthermore, the PVOH preferably has a viscosity above 5 mPa>aqueous solution at 20 °C DIN 53015 / JlS K 6726.
    The mixture may further comprise additives, preferably any one of astarch, carboxymethyl cellulose, a filler, retention Chemicals, clay, talcum,polyvinyl alcohol, flocculation additives, deflocculating additives, dry strengthadditives, softeners, or mixtures thereof. lt may be possible to add additivesthat will improve different properties of the mixture and/or the produced film. ltmay be possible to add the additive to the first suspension, the second suspension and/or to the mixture.
    Example Example I: PVOH as additive to DA-l/IFC barrier film for improvinqstrain at break Two reference samples were prepared, whereof Ref 1 corresponded toa film containing only l/IFC and Ref 2 corresponded to a film containing60wt°/> DA-l/IFC and 40wt°/> MFC, where the degree of oxidation of the DA-l/IFC was 40%.
    A test sample (Sample 1) was also prepared which corresponded to afilm containing 75wt% DA-l/IFC with a degree of oxidation of 40%, and 25wt°/>PVOH.
    All three films referred to as Ref 1, Ref 2 and Sample 1 wereseparately coated on top of a base layer consisting of an l/IFC film. Theobtained two-layered films had a thickness of 52-58 um and a grammage ofabout 50 g/m2.
    The mixture for manufacturing the film according to Sample 1 wasprepared as follows. Polyvinyl alcohol was jet cooked for 2 h at a solids 11 content of 14%. Dialdehyde cellulose (DAC) with a degree of oxidation of40% was mixed with 25wt°/> PVOH. The mixing time was 1 h. Afterwards, themixture was run 3 passages in a l/licrofluidizer l/l-11OEH, resulting in a DA-l/IFC-PVOH suspension. The solids content was 3 wt-°/-.~. The suspension wasdeaerated in a vacuum desiccator under stirring. By adjusting the stirringspeed up and down, the air bubbles were removed from the suspension. Thefilm was then produced by rod coating the DA-l/IFC-PVOH dispersion on ametal plate, which was then placed on another metal plate, pre-heated to 105 °C. The estimated temperature during drying was 70 °C.
    All three films referred to as Ref 1, Ref 2 and Sample 1 were testedwith respect to the strain at break, E-modulus and the OTR at a relativehumidity of 50 % at 23°C and/or at a relative humidity of 80% at 23°Caccording to ASTM F-1927. The strain at break was measured by means of astandard tensile test (ISO 1924-2 with a span length of 20 mm), wherein thefilm to be tested was stretched with test speed of 2 mm/minute until a pointwhere it ruptured. The strain at break then corresponds to the percentelongation when rupturing, i.e. to what extent in °/-.~ the film deforms withoutbreaking upon being subjected to stretching. The results are shown in Table 1below. 12 Table 1: Mechanical properties and OTR of barrier films Sample Nanocellulose Additive Strain E-modulus OTR OTR0 in top layer 0 I 0 Ref 1 100% I/IFC - 2 6 2540 0 9 34 “““““““““““““““““““ 00éo00ë/;00t5Å0-00|00/0|0F0c0; ““““““““ “““““““““““““““““““““““““““““““““ ____________ 0§000e00s05020o 00000000000000000000000 Éoflš 0000000000000000 005000080 0000000000000000 0 40% MFC i Samp|e1 75 °/-.~ DA-l/IFC 25% PVOH 3.1 7950 0.8 3.4 The reference sample containing only l/IFC has a strain of 2.6 °/-.~. lf a film is made from l/IFC mixed with 60 °/-.~ DA-l/IFC, the barrier properties athigh moisture condition becomes significantly improved, but the strainbecomes much lower, below 2 °/>. lf the DA-l/IFC instead is mixed with 25 °/-.~of PVOH, the strain is improved above 3 °/> and the barrier properties are maintained.
    权利要求:
    Claims (26)
    [1] 1. A method for manufacturing at least one fibrous barrier layerwherein the method comprises the steps of: providing a first suspension comprising microfibrillated dialdehydecellulose, mixing the first suspension with po|yvin|ya|coho| (PVOH) to form amixture, 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] 2. The method according to claim 1, wherein the dried fibrous barrier layer is a film.
    [3] 3. The method according to claim 1, wherein the substrate is a paperor paperboard substrate and the mixture is applied onto the substrate as acoating to form said wet fibrous web, wherein after drying said fibrous barrierlayer and said substrate forms two layers of a multilayer structure.
    [4] 4. The method according to any one of claims 1 - 3, wherein themixture comprises 5-30wt°/> PVOH and 70-95wt% microfibrillated dialdehydecellulose based on the total dry weight of the mixture.
    [5] 5. The method according to any one of claims 1 - 3, wherein themixture comprises 15-25wt°/> PVOH and 75-85 wt°/> microfibrillateddialdehyde cellulose.
    [6] 6. The method according to any one of claims 1, 2 or 3, wherein asecond suspension comprising microfibrillated cellulose is provided, whereinsaid first suspension is mixed with said second suspension. 14
    [7] 7. The method according to claim 6, wherein the mixture comprisesbetween 20-45 wt% of microfibrillated cellulose, 50-75wt°/> microfibrillateddilaldehyde cellulose and 5-30wt°/> PVOH, preferably 30-40wt°/>microfibrillated cellulose, 50-60 wt% microfibrillated dialdehyde cellulose and10-20wt°/> PVOH based on the total fiber weight of the mixture.
    [8] 8. The method according to any one of the preceding c|aims, whereinthe PVOH to be added to the first suspension preferably has a degree ofhydrolysis between 80 - 99 mo|%, more preferably between 88 - 99 mo|%.
    [9] 9. The method according to any one of the preceding c|aims, whereinthe PVOH preferably has a viscosity above 5 mPa> aqueoussolution at 20 °C DIN 53015 / JIS K 6726.
    [10] 10. The method according to any one of the preceding c|aims whereinthe dry content of the mixture applied to the substrate is between 1-15°/> by weight.
    [11] 11. The method according to any one of the preceding c|aims whereinthe fibrous barrier layer has an oxygen transmission rate in the range of from0.1 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 layerthickness of 10-70 pm.
    [12] 12. The method according to any one of the preceding c|aims, whereinthe fibrous barrier layer has a strain at break of at least 2%, preferably at least3%.
    [13] 13. The method according to any one of c|aims 1-2, or 4-12, wherein the substrate is a polymer or metal substrate.
    [14] 14. The method according to any one of the preceding c|aims, whereinthe temperature is increased to 70-150°C during drying of the film.
    [15] 15. The method according to any one of the preceding c|aims, whereinsaid method further comprises the step of pressing the film upon and/or afterdrying.
    [16] 16. The method according to any of the preceding c|aims, wherein saidmixture further comprises any one of a starch, carboxymethyi cellulose, afi|er, clay, retention chemicals, f|occu|ation additives, def|occu|ating additives,dry strength additives, softeners, cellulose nanocrystals or mixtures thereof.
    [17] 17. The method according to any of the preceding c|aims wherein themicrofibri|ated dia|dehyde cellulose in the first suspension has an oxidationdegree between 20-50°/>.
    [18] 18. A fibrous barrier layer obtainable by means of a method accordingto any one of c|aims 1-17.
    [19] 19. A fibrous barrier layer having an oxygen transmission rate in therange of from 0.1 to 100 cc/m2/24h according to ASTM F-1927, at a relativehumidity of 50 °/> at 23°C and/or at a relative humidity of 80% at 23°C, andwith a barrier layer thickness of 10-70 um, and wherein at least one fibrousbarrier layer comprises a mixture of a microfibri|ated dia|dehyde cellulose andPVOH.
    [20] 20. The fibrous barrier layer as claimed in claim 19, comprising amixture of microfibri|ated cellulose, microfibri|ated dia|dehyde cellulose andPVOH. 16
    [21] 21. The fibrous barrier layer as claimed in any one of claims 19 or 20,wherein the fibrous barrier layer has a basis weight of less than 55 g/m2,preferably between 10-50 g/m2.
    [22] 22. The fibrous barrier layer as claimed in any one of the claims 19-21,wherein said fibrous barrier layer is a film, preferably comprising more thanonelayer
    [23] 23. The fibrous barrier layer as claimed in any one of the claims 19-22,wherein said fibrous barrier layer is a multilayer film and wherein at least onelayer of the film is a water vapor barrier film comprising any one ofpolyethylene (PE), polypropylene (PP), polyamide, polyethylene terephthalate(PET) or ethylene vinyl alcohol (EVOH).
    [24] 24. A packaging material comprising a base material and at least one fibrous barrier layer as claimed in any one of claims 19-23.
    [25] 25. A packaging material according to claim 24, wherein said basematerial is paper or paperboard.
    [26] 26. Use of a fibrous barrier layer according to any one of claims 18-23as an oxygen barrier film, wherein the film is obtainable by a methodaccording to any one of claims 1-17.
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    引用文献:
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    CN112321876A|2020-11-03|2021-02-05|海南赛诺实业有限公司|PVOHcoating film for protecting printing surface and preparation method thereof|JP5772814B2|2010-03-25|2015-09-02|凸版印刷株式会社|Gas barrier laminate and packaging material|
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    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    SE1851213A|SE543174C2|2018-10-08|2018-10-08|A flexible barrier layer comprising microfibrillated dialdehyde cellulose|SE1851213A| SE543174C2|2018-10-08|2018-10-08|A flexible barrier layer comprising microfibrillated dialdehyde cellulose|
    EP19871004.8A| EP3864074A1|2018-10-08|2019-10-08|A barrier layer comprising microfibrillated dialdehyde cellulose|
    PCT/IB2019/058547| WO2020075057A1|2018-10-08|2019-10-08|A barrier layer comprising microfibrillated dialdehyde cellulose|
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