SE542944C2 - A method for improving adhesion during production of film - Google Patents

A method for improving adhesion during production of film

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Publication number
SE542944C2
SE542944C2 SE1851113A SE1851113A SE542944C2 SE 542944 C2 SE542944 C2 SE 542944C2 SE 1851113 A SE1851113 A SE 1851113A SE 1851113 A SE1851113 A SE 1851113A SE 542944 C2 SE542944 C2 SE 542944C2
Authority
SE
Sweden
Prior art keywords
film
layer
suspension
cellulose
mixture
Prior art date
Application number
SE1851113A
Other languages
Swedish (sv)
Other versions
SE1851113A1 (en
Inventor
Hensdal Cecilia Land
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 SE1851113A priority Critical patent/SE542944C2/en
Priority to EP19861890.2A priority patent/EP3853264A4/en
Priority to PCT/IB2019/057603 priority patent/WO2020058803A1/en
Publication of SE1851113A1 publication Critical patent/SE1851113A1/en
Publication of SE542944C2 publication Critical patent/SE542944C2/en

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    • 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

Abstract

The present invention relates to a a method for manufacturing at least one layer of a film characterized by that the method comprises the steps of:providing a first suspension comprising microfibrillated cellulose, providing a second suspension comprising microfibrillated dialdehyde cellulose,mixing the first suspension with the second suspension to form a mixture, in which mixture less than 5% of the anhydroglucose units (AGU) of the total cellulose present therein comprise a dialdehyde,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 present invention further relates to a film comprising said at least one layer of film.

Description

“iÜ 29 3G A METHOÛ FOR iiviF-”RÛViNG AÜHESÉÛN DURENG FWQODUCTÉON OFFiLhii Teohnioai tieid "the present invention reiates to a tiirn having improved adhesionproperties during torrning. it/iore partiouiariy, the present invention reiates to amethod ot ntanutaoturing sueh a tiirn and a tiim produced.
Background Üuring oasting ot tiims ooniprising native miorotioriiiated oeiiuiose, itmay happen that the tiim detaohes trom the suostrate oetore it is devvatered.The tiim then runs the risk ot oeoomiitg non-tiat or tvrinitied, virhioh ruins theduaiity ot the tiim. To overoonte this prooierrt, a piastioizor sueh as sortaitoi isusuaiiy used as an additive, even up to 38% addition. i-tovirever, sorhitoi is amoisture sensitive ohernioai which deteriorates tite oxygen harrier properties oi the tiirn, espeoiaiiy at high reiative hurnidity in the air, tienoe, there is a need to find a soiution ot producing tiirns vvith goodadhesion properties during torming ot tiirn, white avoiding the use ot moisturesensitive additives.
Summaryit is an oioieot oi the present invention, to provide an improved method tor ntanutaeturing a tiirn oomprising native rniorotioriiiated oeiiuiose,having improved adhesion properties vvhiie rnaintaining barrier properties otthe tiirn. 'the ooieot oi the present int/ention is at ieast partiaiiy achieved hymeans ot a method tor manufacturing a ieast one iayer oi a tiim vvherein themethod oornprises the steps of: providing a tirst suspension oornprising rnioroiioriiiated oeiiuiose, 1G EÜ 2 oroviding a second suspension oornprising rniorotihriiiated diaidehydeoeiioiose, rnixing the iirst suspension with the seoond sosoension to iorni antixtore, in which ntixtore iess than 5% ot the anhydrogiuoose units (AGU) otthe totai oeiiuiose oornprise a diaidehyde, aooiying said rnixtore to a soiostrate to torm a iioroos weh and dryiitg said web to torrn at ieast one iayer ot said iiirn.
According to one aspect ot the inventiont in said rnixttire, heiow oreterahiy ioettiveen di - 3%, rnore oreterahiy ioetween di - 2% ot theanhydrogiooose tinits (Aíåti) oi the totai oeiioiose in the ntixttire ooinorise adiaidehyde.
The skiiied person onderstands that the ÛA~MFC added in the seoondsuspension oan have diitereitt degrees oi oxidation, detined as the oortion otAGUs that have a diaidehyde. The arnoont ot DAMFC needed to he addeddeoends on the degree ot oxidation in the oorresoonding suspension. Arriixtore oi iÉiANiFC and native MFC naturaiiy has an average degree oioxidation that is tower than that of the iIšA-MFC part of the rriixtore. in thatsense, said rnixture containing both hfiFC and Ditt-MFC oouid theoretioaiiy oeinterpreted as a IDA-MFC with iow degree of oxidation. it has sorprisingiy been toond that ose oi Dia-MFC as an additive ieadsto irnorot/ed adhesion orooerties ooon tiirit ritaiting, i.e. a haianoed adherenoebetween the casted tiirn suspension and the onderiyirig stiostrate. By“haianced adherenoe” rneans in this context that the casted iiint suspensionadheres weii enough to the sohstrate during drying to not detaoh thereirorn(witere detaching oi the tiirn tiirooid iead to wrinides and ooooies in therestiiting tiirn surface), and at the sarne tinfie does not stick too hard to thesortaoe. Too strong attaohinerit ot the iiirrt onto the stiostrate during rnaitingoouid iead to orohierits with detaohing the dried tiirn onoe it is ready. 1G EÜ 3 The dry oontent ot the inixtore apoiied to the soostrate is oreterahiyioetween t-t 0% hy weight. Deoending on the suostrate onto vifhich thernixtore is apoiied, the dry oontent ot the ntixtore ntay very.
According to another aspect ot the iriventicn, the rnierotihriiiateddiaideityde oeiioiose ot said second suspension hes an everege degree otoxidation between 'iti-tštštfs, preterahiy between ßfkffiitit/s.
Aooording to another asoeot ot the invention, the seoond suspensionoontprises eiso native MFC in addition to rniorotioriiieted diaidehyde oeiioiose.
According to another aspect ot the inventiort, drying oi the weo to iorrnat ieest one iayer ot said tiiin is oertorrned under heat treatrnent ot said tyeo.Such heat treetrnent may he achieved hy ineans ot heating the suhstrete ontowhich the rnixture is oast. in one exernoie, said stiostrate is a ooiyrner, oiexigiass cr rrietai sohstrate, and heat treatment is aceontoiished hy nteans otheating said ooiyiner, oiexi giass or rnetei sohstrate so that it has reached atentoerature oettyeen 45 - tät) QC, preteraoiy hetirveen 5G - 8G °C, when thernixture is aooiied. The siriiied oerson understands that other oonventionaiheat treetinent rnethods are aiso oonoeivahie sooh es iilšdrying. Drying theiiini under heat treatment ieads to the advantage ot irnorotred orossiinitingoettireen the rniorotihriiiated tiioers in the tiirn.
The rnixture inay turther ooinorise additives, oreteraoiy any one ot astarch, oarhoxyrnethyi ceiioiose, e tiiier, oiay, taioorn, ooiyvinyi aicohoi(PVOH), retention ohernioais, tiocouiation edditiyes, detiocouiating additiyes,dry strength edditives, sotteners, or rnixttires thereot. it inay he oossiiznie toadd additives that irviii improve different properties ct the rnixture and/'or theproduced tiiiri suoh es iatex end/or ooiyvinyi aioohoi tor enhancing the duotiiityot the tiirn. it ntay he oossihie to add the additive to the tirst suspension, the second suspension and/for' to the ritixttire.
The oresent invention further reiates to a tiirn oornorising a rnixture otrniorotioriiieted oeiioiose and rniorotioriiieted diaidehyde ceiiuiose, yyitereirt thetiirn is ntanotaotored trorn a mixtore in which iess than 5% ot the anhydrogiocose units (AGU) ot the totai oeiioiose present in the rnixture 1G EÜ 4 eernprise a diaideityde. The iiini preierahiy has a grarnrnage ei iess than 50g/"ntå preteraeiy between 'ie-EQ g/rriz.
Aeeoreiing te ene aspect, said iiirn is a rntiitiiayer' tiirn eornprising rneitethan one iayer. For instance, a iayer ei poiyethyiene (PE) en at ieast one sideei the iiirn eernprising rnieretieriiiated dieidehyde eeiiuiese eise irnprevesstrainahiiity ei the iiini and provides heatseaiirig properties.
Aeeertding te ene aspect et the invention, at ieast ene iayer ei the iiirnis a water vaper barrier iiirn centprising any ene ot peiyetityiene (PE),peiypropyiene (PP), peiyarnide, peiyethyiene terephtitaiate (PET) er ethyienevinyi aieehei (EVOi/i). The water veper earrier tiirn hes ereierahiy egranfirnage eetwfeen t i) - 60 gfrnz, preieraeiy 3G ~ 5G g/rriz. in ene aspect, said tiirn is a rneitiieyer iiirn wherein at ieast ene iayer eithe tiint is a nietaiiized harrier iayer. Ešy “rnetaiiized harrier iayer” means a thiniayer et rnetei previding iïierrier preperties redecing perrneahiiity te eg.exygen, water, water vapoiir and tight. According to ene aspect ei theinverttien, said rnetaiiized earrier iayer is a physieai vapeer depesited rnetai errnetai exide iayer, er a chernicai vapetir depesited rnetai er rnetai exide iayer,wherein said rnetai er rnetai oxide is seieeted irern the group eensisting eiaiiirniniurn, aiernirtiunt exides, magnesium exides, siiiciurn oxides, eepeer,magnesium and siiicen. Preieraeiy, the rnetaiiized iearrier iayer has a weightbetween 5G - 250 rng/rnå preieraeiy eetiiveert T/T» - 150 rng/rnzfiiie presentinvention ierther reiates te a paokaging rnateriai eentprising a ease materiaiiantinated with et ieast ene iayer ei the iiirn previeesiy described eernprising ainixtore ei a ntieroiihriiiated ceiieiese and a niicrotieriiiated diaidehydeeeiiuiese. Said base rnateriai is preteraeiy paper er paperheard. Aecerding teone aspect ei the inventien, the paper er paperpoard ot said packagingrnateriai has a grarrrniage between 2G - 5% gfrnff, for inetanee between 80 -«490 g/'rnå The paei-raging rnateriai rnay centprise e rneitiiayer iiirn trrhieh inadditien to the tiirn confiprising a rrrixtere ei a rniereiihriiiated eeiiuiese and arnierotieriiiated diaidehyde ceiiuiese eise eernprises ene er rnere ot a vvater vaper harrier iayer and/er a rnetaiiized harrier iayer previeusiy deserihed 1G EÜ Aaaarding ta anathar asaaat, tha inyantian aisa raiatas ta tha usa atiliA-it/EFC as an additiva tar infiaraving adhasian araaartias in inanuiaataring aiiiirn, iivhara said tiint aarnarisas rniaraiihriiiatad aaiitiiasa.
Dasariatian ai Ernhadirnants Tha ntathad aaaarding ta tha arasant invantian raiatas ta araviding atirst stisaansian aarnarising rniaratihriiiatad aaiiuiasa and inixing said tirstsasaansian yvith a saaand sasaansiart ttvhiah in its turn aarnarisasrriiaraiihriiiatad diaidahyda aaiitiiasa (DA-iviiïíšii, ta iarrn a rnixtura. Aaaardingta tha invantiart, in said rnixtara iass than 5% at tha anhydragiaaasa artits(AGU) at tha tatai aaiitiiasa arasant tharain aarnarisa a diaidahyda.
Tha rnixttira is than aaaiiad anta a stihstrata ta tarrn a tihraas wah andsaid tfvah is tharaaitar driad ta tarnt at iaast ana iayar at tha tiini. it hassurarisingiy haan tatind that hy tarrrting a rnixtura aarnprisirtg rniaratihriiiatadaaiiuiasa and ntiaraiihriiiatad aaiiaiasa tram diaiaaityda aaiitiiasa (Dash/EPC)tha adhasian hatvvaan tha rnixtara and tha sahstrata is irnaravad ta stiah anaxtant that išiiviriiïí) rnay raaiaaa rnaistiirasaitsitiya additivas saah assaraitai.
Tha at iaast ana iayar ai tha tiirn is aradaaad iay aaaiying said rriixtarata a stihsrtrata ta tarrn a tiaratis waa and drying said tivah ta tarrn at iaast anaiayar ai said tiirri. Tha drying ai said waa rnay ha dana in any aanvantianaiway, hawavar aratarahiy andar haat traatrnant. Tha dry aantant ai tha at iaastana iayar at tha iiint aitar drying is araiarahiy ahava 95% ay ttraight.
Tha stiastrata may ha a aaiyrnar, aiaxi giass ar inatai suhstrata antawhiah tha rnixtara is aastad. Tha aast aaatad iihraus waia is driad in anyaanvantianai inannar and tharaattar aatianaiiy aaaiad att train tha siihstrata. itmay ha aassihia ta aast ar aaat rnara than ana iayai' anta tha suiastrataianning a rnaitiiayar' tiirn. it is aassiaia ta aradtiaa a tiirn aarnarising rnara thanana iayar yvharain at iaast ana at tha iayars aanftarisas tha niixtura aaaardingta tha invantiart. it rnay aisa ha aassiaia that ntara than ana iayar at tha tiirn 1G EÜ 6 eemerises the mixtere aeeereing te the inventien. it may aise be eessibie thatene er ntere tayers et the tiim eniy eernerises rnieretibriiiatee eeiiuiese et thetirst stiseensien, te. net rnieretibriiiatee eiaieehyee eeiteiese (DA-MFC). itmay aise be eessihie that ene er :nere iayers et the fitnt is a water vaber'barrier tiirrt eemerising any ene et eeiyethyiene (PE), eeiyereeyiene (PF),eeiyamicte, eetyethyiene tereehtitaiate (PET) er ethyiene vinyi aieehei(tšVQt-t). it may aise be eessieie that ene er mere iayers et the tiim is ametaiiizee barrier iayer, eerrterising any ene et aiumirtiem, aieminiem exieies,magnesium exiees, siiieitirn exiees, eeeeer, ntagnesient anet siiieen. The tiim may eemerise twe, three, tetir, tive, six, seven, eight, nine, ten er mere iayers.
A eaekagšng ntateriat ineieeing a iayer et the mixtere aeeereing te theinventien rhay eemprise turther iearrier iayers ter ereventing migration et air,water ane ttavers threugh the base rnateriai. Aeeerctšng te ene aseeet aeaeitaging rhateriai rhay ineiecte at ieast ene tyater vaeer barrier iayereemensing any ene et eeiyethyiene (PE), eeiyereeyiene (FP), eeiyarniee,eeiyethyiene tereehthaiate (PET) er ethyiene vinyi aieehei (Ett/Ott). Theeaekaging materia! may aise ineitiee ene er mere rhetaiiizee iearrier iayeits)eemerising any ene et aiumirtiem, aieminient exiee, magnesium exiee er siiieitirn exiee. iyiieretibriiiatee eeituiese (MFC) er se eaiiee eeiiutese rhieretibriis (Git/EF) shaii in the eentext et the eresent aeeiieatien mean a naneeeaie eeiiuieseeartieie tieer er tibrii with at ieast ene dimension iess than tet) rim. MFCeemerises eartiy er tetaiiy tibriiiatee eeiitiiese er iigneeeiieiese tihers. Theeeiietese tiber is erfeterahiy tibriiiatee te such an extent that the tinai seeeitiesurface area et the termeet tt/iFC is trem abetit t te abeirt SSG int/g, stieh asirem t te EGO m2/g er mere breteraeiy 50-209 ntÉ/'g when eetermineei ter atreeze-eriee materiat with the SET rhethee., The term “native MFC” reters teMFC that is maeie trem eenventienai ehemieai, ettemimeehanieai and/ermeehanieai euie witheet further ehemieai treatment, e.g. saie native MFC isiaeiring sbeeiai tenetienai greues. 1G EÜ »t Various methods exist to make MFC, such as singie or inuitioie oassretining, pre-hydroiysis toiioyyed hy retining or high shear disintegration oriioeration ot tihriis. One or severai pre-treatment steps are usuaiiy required inorder to make MFC manufacturing ooth energy-efficient and sustainaoie. Theceiiuiose tibers ot the ouio to he suooiied may thus he pre-treatedenzymaticaiiy or cherriicaiiy, tor exarnoie to reduce the otiantity othemiceiiuiose or iignin. The ceiiuiose tioers rnay he chemicaiiy rnoditiedoetore tioriiiation, wherein the ceiiuiose rnoiecuies contain tunctionai grouosother (or more) than tound in the originai ceiiuiose. Such groups inciude,among others, oarooxymethyi, aideityde and/or carooxyi groups (oeiiuioseootained oy i\i~oxyi mediated oxidation, tor examoie "Tiššivtiïitïïy or ouaternaryaminoniuin (cationic oeiiuiose). Atter being rrtoditied or oxidized in one ot theaooveoescrioed methods, it is easier to disintegrate the tiioers into hfiFC orNFC.
The nanotioriiiar ceiiuiose may contain some itemiceiiuioses; theamount is deoendent on the oiant source. iviechanicai disintegration of theoretreated tioers, eg. hydroiysed, oresrweiied, or oxidized ceiitiiose rawmateriai is carried out with suitaoie equipment such as a retiner, grinder,homogenizer, coiioider, triction gränder, uitrasound sonicator, singie - or twin~sorevr extruder, tiuidizer such as nticrotiuidizer, macrotiuidizer or tiuidizentyoehorriogenizer. iïieoending on the MFC inanutacttirino method, the product:night aiso contain tines, or nanocrystaiiine ceiiuiose or eg. other cherrticaispresent in wood iihers or in oaoerntaking process. The product might aisocontain various arnounts ot micron size fiber oartioies that have not been etticientiy tioriiiated. tt/iFC can oe produced trom wood ceiiuiose iiherst ooth from hardwoodor sottyvood tihers. it can aiso he ntacie trorn microoiai sources, agricuituraitihers such as yvheat straw ouio, oamooo, oagasse, or other non~wood tihersources. it is oreterahiy made trom ouip inoiuding ouio trom Virgin tiher, eo \. , 1G EÜ 8 nteatianiaai, chentiaai artdfar rtherrnornechaniaai nuins. it can aiso be rnadetrain broite or recycied naner.
The above described definition oi iviFC inoindes, but is not iirnited to,the nronosed TAPPi standard Wt Snât on oeiiniase nano or rniorotibrii (SMF)deiining a oeiiniose nanotiner rnateriai containing niuitinie eiernentary iibriiewith bath orystaiiine and arrtornhous regions, itaving a high asnect ratio with tvidth at 5~30 nrn and asnect ratio usuaiiy greater than 50. iïtiaidehyde oeiiniase (ÜNMFC) is tynioaiiy obtained by reaating oeiiniase with an oxidieing agent such ae eadium neriodate. During tneneriodate oxidation, seiective oieavage ot the C263 bond oi theanhydrogincose unit (AGU) at ceiiuioee takes niace, witn oancnrrent oxidationot the G2- and C33~Oi~i rnaieties to aidehyde rnoieties. in this rrianner,orossiinitabie tunctionai granne (aidehyde granne) are intraduced to theoeiiuiase. The rniorotibriiiated diaidehyde oeiiuiose in the second snsnensionshouid in this context rnean a diaidetiyde ceiiuiose treated in suoh vvay that itis rnicroiibriiiated. The nroduotion ot the rnioroiioriiiated diaidehyde oeiiniase isdone by treating diaidehyde oeiiniase tor exarnnie by a narnogenizer or in anyotner way snch that tiiariiiatian occnre to nroduoe rnioroiibriiiated diaidehydeoeiiniaee. The rniorotibriiiated diaidehyde aeiiuiose in the second suspensionnreierabiy has an oxidation degree between iO-EtLW/e, nreterabiy between 3G-ßi-(ifi/ít. The degree oi oxidation was deterrnined according to the toiiowingdescription: atter the diaidehyde eeiitiiose reaction, the aniount oi (EQ-CShonds in the oeiiniose that are converted to diaidehydes is rneasured. Thedegree at oxidation is the amount oi C263 bonde that are convertedcornnared to aii (3283 bands. This ie rneaenred with a rriethod by ii, Zhaaand Ni). iieindei, “Deterrnination at iltegree ot Snbstitntiort oi Forrnyi Grannein Poiyaidehyde tliexran by the iiydroxyiarnine iiydrooitioride ivtetitod",Pharrnaoentioai Pieeearoh, voi. 8, nn. 4ÛO-4GQ, 1991, trvhere the avaiiabieaidehyde granne reacte titrith hydroxyiarnine itydrochiaride. This iornis oxiniegroups and reieases nydroahioria acid. The hydroahiaria acid is titrated irrith 1G EÜ 9 soditirn iiydroxide trntii pti »fi is reached, end the degree oi oxidation isthereeiter oeiouieted ironi according to the torniuie heiow. The receivedeidehyde content is divided hy ttvo to get the veiiie oi the degree ot oxidation, since en oxidized enhydrdgioodse unit hes two eidehyde groups.
Vrvaorr X Cris-OH oo t" =i /oà smsümpze >< Iiffw, ><-><1 109få. vitsen = the ernoiint of sodiont hydroxide needed to reeoh pii 4 (i)Csiaori = Ûji moi/inisamprs = dry tiiieigitt ot the eneiysed DAG sernpie (g) iii/iii; 'itšü g/'rrioL which is the rnoieouier weight di the dieidehyde ceiitiiose unit The ntixttire rney iiirthei' odrnprise edditives, preierehiy any ene oi esteroh, oerhoxyrriethyi oeiioiose, e tiiier, reterrtion ohernioeis, oiey, teioorn,poiyvinyi eioohoi, tioootiietien edditives, detideoriieting edditives, dry strengthedditives, sotterrers, or rriixttires thereot. it rney he possihie to edd edditivesthet viriii improve ditterent properties oi the ntixttire end/or the produced tiirn. itmay ide possihie to add the edditive to the iirst suspension, the second suspension end/or to the niixttire.
Brief description ot the tioure Figure i shows e photo di e iiirri vvith undtiieted stirieee due to poor edhesiort during iiirri making.
Exernpie Exentoie i: EDA-MFC es en edhesiorr enheneer A iirst suspension ot netive rriicroiihriiieted oeiiuiose (MFC) wes diioted to e soiids content ot 3 vvtft/íi. to vvtfl/í» oi poiyvirryi eioohoi Wes added end eiso5 wtñe oi oiey or teioorit, eooording to "iehie t. (Added reietive to “iüíitfß MFC) 1G EÜ A second suspension witn a soiids content oi 3 wtWa was aiso oreoaredny rnixirtg 60% rnioroiihriiiated diaidehyde ceiioiose (DA-MFC) »with a degreeoi oxidation oi 4t)%, tiirith 46% MFC. Tne totai degree oi oxidation in the second suspension was titos 249%.
A iirst rnixtore witn no added DAJViFC, i.e. oorresoondirig to said iirstsuspension oniy, is reierred to as Test i, irrhereas Tests 2, 3 and 4 irvereoreoared hy rnixing the iirst suspension iivitn inoreased added arnoonts oi tnesecond suspension, ending oo with inixtores i\io. 2, 3 and 4 having ivvtfrïféi,Swtfl/a and ?'wt% resoectiveiy oi said seoond sosoension. For "iests 2,3 and 4the portion oi AGUs in the rnixttire containing a diaidenyde was thus (itä/ritai .Qi/s and ißäiïs resoectiveiy.
The nfiixtures were used for casting oi iiirns on a neated Fiiexigias or ona oiasrna treated ooiyorooyiene (PP) soostrate, where the degree oi oiasrnatreatment was "iGCPI/s. For Test i, the iiirn was oast and oiried on a heateoiPiexigias soostrate, desorioed in the ioiiowing. A rnetai oiate was oreneated inan oven at 7G°C ior over än. Coating was oeriorrned in rooin tentoerattiire oi23 BC.. hy piaoing a irarne wfitn dimension oi aooroxinfiateiy an A4 sneet on thePiexigias, aooiying the rnixtore inside the irarne and using a rod iike tooi to tiiioot said irarne and create the iiorous ttfeio. The irarne was removed front tnePiexigias, and next said Piexigias with the weh was oiaoed on too ot theoreneated rnetai oiate oonseouentiy heating aiso said Piexigias to ateinoeratore between 45 ~ 55 °C, wheretioon the weh was aiiowed to dry to iorni a iiini.
Tests 2, 3 and 4 vvere east on a oiasrna treated ooiyorooyiene stiostrate in roorn ternoeratore.
Fiirns were soooessiuiiy oasted witn aii tne tested niixtores vvhenadding the DA-hfiFC rnixtore (Taoie i), with varying weight/s content oi DA- ti? EÜ it MFC as exeiainee aeeve. "the tttms ttvith eiay neeeieei a higher ameunt et BA-itfttïü than the titm with taieutrt in ereer te achieve en aeeeetahie aehesien.
The aeihesien te the seestrate et the respective titms was evatttatee eyviseai inseeetien et the tiirrt sertaee etter erytng, ane hy evaitteting titmieehavtettr eeen eetaeiting the titm trem the stthstrate after ctrytng. tn ercter temeet the reettirement ter e “geee ehesien", the eestee ttim sheeie ttrstiypresent an essentteiiy eiener/tiat sertaee en the seestrate with ne eneteiatiensana/er eetaehee areas et' ieehetes aeeearing eeress the titm surtaee.Seeencztiy, the titm sheeiei aise eetaeh trem the stiestrate atter that the titm isreaey, i.e. tt shettie tee eessiete te eeet ett the titm item the stthstrate aftereemetetten et the titm making withettt rttetertng said titm. it the tttrn eehesiente the seestrete ts tee streng, the titm wiit reetttre ttfheri trying te eetaeh it. tnether weres, a “geee acthesien” reeresents e seehtstieateczt hetartee hetweentee ttfeat: aehesien teaeirig te heheies and unettiatierts in the tiirn, ane teestreng eehesien teeeing te reetttres tteen remeying the ctrtee tiim trem the sttestrete. in Taieie t, e “geee aehesien” ttiitiittng the aeeve eetinee requirements et eresentittg a eienar surtaee eeen eemetetten et tiim erytng, and eeeneemetetten ieetng eetaettahie tyitheut reetering, is rnarkee as “OtCï “AintestGK” ts te he tnteteretect as a tew ehsetyee vtfrtttktes, te. iess than threewrinkies ter ene titm sheet et a aeerexirnatety A4 size. “Tee tew” is te ieeinterereteci as e eemearahiy iarge numieer et wrtrtittes, te. mere than threewrintries ter ene tiirn sheet et eeerexttnateiy A4 size.
Figure t shews e ehete et a titm maee ttem a mtxtere et MFC, PVÛt-t,tateum and tlâfßityrtïs Ditt-MFC, ttvhere the aehesien was tee tew teaczting teeneetatiens seteaeing aeress the tiirn euring the erytng ehase et titm making ereeess, 1G 12 Test 'i "test 2 Test 3 Test 4Aoitesion resoitAotoitive Substrate üt/w aooeo 1% aooieo šttè aooieo “ite aoioeoQin-MFC üÅ-»MFC üA-tiiiFC QAMFCNone Pâexigies Too iovv OK not testeti not testeoPVOH -i- PP Too iow Too iow Aimost OK OKoentonitePVOH + PP Too iovv Too iovif Aintost OK OKKeoünnePVQi-i PP Too iovir Too iotv OK not testeo+Taioorn Tabie t: Aonesšon test resnit with varying amoonts ot aooeo ÜA~MF$with Üß. of 24% The resnits trorn išxampie i show titet rnioroiioriiieteo oiaioenyoeoeiioiose rney serve as an aooitive for the purpose ot ennanoing aoiiiesionduring oasting oi oarrier fiirna oomorising ntioroiiorâiiateo oeiitziose. "ine oositive resnits irnpiies titat aooition ot sinaii arnonnts oi IDA-itIiFCto e inixtore intended for iiim making oooio repiaoe oonventionaâ inoistore sensitive aooitive in the tonn oi sorizaitoi. in view ot tne aoove oetešieo oesoriotion of the present invention, otherntoctiiioetiorts and Variations nfiii oeoorne apoarent to those skiiieci in the art.i-iowever, it sitonio oe aooarent ttiat soon other anooiiioations and Variationsrney oe eifeoteci without oeoartšng ironi the spirit and soooe oi tite ânventiort,

Claims (20)

1. A method for manufacturing at least one layer of a film characterized by thatthe method comprises the steps of: providing a first suspension comprising microfibrillated cellulose, providing a second suspension comprising microfibrillated dialdehydecellulose, mixing the first suspension with the second suspension to form a mixture, inwhich mixture less than 5% of the anhydroglucose units (AGU) of the total cellulosepresent therein comprise a dialdehyde, applying said mixture to a substrate to form a fibrous web, and drying said web to form at least one layer of said film.
2. A method according to claim 1, wherein in said mixture between 0.1 - 3%,more preferably between 0.1 - 2% of the anhydroglucose units (AGU) of the total cellulose in the mixture comprise a dialdehyde.
3. The method according to any of the preceding claims wherein the dry content of the mixture applied to the substrate is between 1-10% by weight.
4. The method according to any of the preceding claims, wherein themicrofibrillated dialdehyde cellulose of said second suspension has an average degree of oxidation between 10-50%, preferably between 30-40%.
5. The method according to any of the preceding claims wherein the substrate is a polymer, plexi glass or metal substrate.
6. The method according to any one of claims 1 - 5, wherein said drying of the film comprises heating the temperature of said substrate to between 45-120°C.
7. The method according to any one of the preceding claims, wherein saidmixture further comprises any one of a starch, carboxymethyl cellulose, a filler, clay,talcum, retention chemicals, flocculation additives, deflocculating additives, dry strength additives, softeners, polyvinyl alcohol or mixtures thereof.
8. A film obtainable according to the method of any one of the previous claims,wherein the film comprises intermixed microfibrillated cellulose and microfibrillateddialdehyde cellulose such that less than 5% of the anhvdroqlucose units (AGU) of thetotal cellulose present in the film comprise a dialdehyde, and wherein the film has a basis weight of less than 50 g/ m2, preferably between 10-50 g/m2.
9. The film as claimed in any one of the claims 8, wherein said film is a multilayer film comprising more than one layer.
10. The film as claimed in any one of the claims 8 - 9, wherein said film is amultilayer film and wherein at least one layer of the film is a water vapor barrier filmcomprising any one of polyethylene (PE), polypropylene (PP), polyamide,polyethylene terephthalate (PET) or ethylene vinyl alcohol (EVOH).
11. The film according to claim 10, wherein the water vapor barrier film has a grammage between 10 - 60 g/m2, preferably 30 - 50 g/m2.
12. The film according to any one of claims 8 - 11, wherein said film is a multilayer film and wherein at least one layer of the film is a metallized barrier layer.
13. The film according to claim 12, wherein said metallized barrier layer is aphysical vapour deposited metal or metal oxide layer, or a chemical vapour deposited metal or metal oxide layer.
14. The film according to claim 13, wherein said metal or metal oxide isselected from the group consisting of aluminium, aluminium oxides, magnesium oxides, silicium oxides, copper, magnesium and silicon.
15. The film according to any one of claims 12 - 14, wherein said metallized barrier layer has a weight between 50 - 250 mg/mz, preferably 75 - 150 mg/mz.
16. A packaging material comprising a base material and at least one layer of the film as claimed in any one of claims 8-15.
17. The packaging material according to claim 16, wherein the base material is paper or paperboard.
18. The packaging material according to claim 17, wherein the paper or paperboard has a grammage between 20 - 500 g/m2.
19. The packaging material according to claim 18, wherein the paper or paperboard has a grammage between 80 - 400 g/m2.
20. Use of microfibrillated dialdehyde cellulose as an additive in themanufacturing of a film according to any one of claims 8 - 15, for improving adhesion properties during film making.
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