WO2021005446A1 - Papier ou carton rendu hydrophobe comprenant un ou plusieurs plis - Google Patents

Papier ou carton rendu hydrophobe comprenant un ou plusieurs plis Download PDF

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Publication number
WO2021005446A1
WO2021005446A1 PCT/IB2020/056061 IB2020056061W WO2021005446A1 WO 2021005446 A1 WO2021005446 A1 WO 2021005446A1 IB 2020056061 W IB2020056061 W IB 2020056061W WO 2021005446 A1 WO2021005446 A1 WO 2021005446A1
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Prior art keywords
paper
paperboard
cellulose
fatty acid
grafting
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PCT/IB2020/056061
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English (en)
Inventor
Susanne HANSSON
Raija BÅDENLID
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Stora Enso Oyj
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Stora Enso Oyj
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Publication of WO2021005446A1 publication Critical patent/WO2021005446A1/fr
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B3/00—Preparation of cellulose esters of organic acids
    • C08B3/08—Preparation of cellulose esters of organic acids of monobasic organic acids with three or more carbon atoms, e.g. propionate or butyrate
    • C08B3/10—Preparation of cellulose esters of organic acids of monobasic organic acids with three or more carbon atoms, e.g. propionate or butyrate with five or more carbon-atoms, e.g. valerate
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/10—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of paper or cardboard
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/306—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl acetate or vinyl alcohol (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • 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
    • B32B29/00—Layered products comprising a layer of paper or cardboard
    • B32B29/002—Layered products comprising a layer of paper or cardboard as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B29/005—Layered products comprising a layer of paper or cardboard as the main or only constituent of a layer, which is next to another layer of the same or of a different material next to another layer of paper or cardboard layer
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
    • C08L1/08—Cellulose derivatives
    • C08L1/10—Esters of organic acids, i.e. acylates
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H11/00—Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only
    • D21H11/16—Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only modified by a particular after-treatment
    • D21H11/18—Highly hydrated, swollen or fibrillatable fibres
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/03—Non-macromolecular organic compounds
    • D21H17/05—Non-macromolecular organic compounds containing elements other than carbon and hydrogen only
    • D21H17/18—Non-macromolecular organic compounds containing elements other than carbon and hydrogen only forming new compounds in situ, e.g. within the pulp or paper, by chemical reaction with itself, or other added substances, e.g. by grafting on the fibres
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H19/00—Coated paper; Coating material
    • D21H19/10—Coatings without pigments
    • D21H19/14—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12
    • D21H19/20—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12 comprising macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • 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
    • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
    • D21H21/16—Sizing or water-repelling agents
    • 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
    • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
    • D21H21/18—Reinforcing agents
    • 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
    • D21H27/00—Special paper not otherwise provided for, e.g. made by multi-step processes
    • D21H27/10—Packing paper
    • 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
    • D21H27/00—Special paper not otherwise provided for, e.g. made by multi-step processes
    • D21H27/30—Multi-ply
    • 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
    • B32B2255/00—Coating on the layer surface
    • B32B2255/12—Coating on the layer surface on paper layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2255/00—Coating on the layer surface
    • B32B2255/24—Organic non-macromolecular coating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/718—Weight, e.g. weight per square meter
    • 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
    • B32B2307/726—Permeability to liquids, absorption
    • B32B2307/7265—Non-permeable
    • 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
    • B32B2307/73—Hydrophobic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B3/00—Preparation of cellulose esters of organic acids
    • C08B3/08—Preparation of cellulose esters of organic acids of monobasic organic acids with three or more carbon atoms, e.g. propionate or butyrate
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/03—Non-macromolecular organic compounds
    • D21H17/05—Non-macromolecular organic compounds containing elements other than carbon and hydrogen only
    • D21H17/11—Halides
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/03—Non-macromolecular organic compounds
    • D21H17/05—Non-macromolecular organic compounds containing elements other than carbon and hydrogen only
    • D21H17/14—Carboxylic acids; Derivatives thereof

Definitions

  • the present invention relates to a paper or paperboard comprised of one or more plies wherein at least one ply comprises a mixture of cellulose fibers and a strength enhancement agent selected from the group consisting of microfibrillated cellulose (MFC) and highly refined cellulose.
  • MFC microfibrillated cellulose
  • microfibrillated and nanofibrillated cellulose as wet end additives to improve mechanical properties, such as strength, for paper and paperboard materials.
  • mechanical properties such as strength
  • addition of MFC to a papermaking furnish may not be suitable when it is desired to produce hydrophobic cellulose-based materials.
  • Paper- and paperboard are usually treated with sizing agents to increase the resistance to penetration of water and other liquids into the paper or paperboard.
  • a common sizing agent is AKD which is added to the pulp or furnish at the wet end of papermaking.
  • Use of AKD is however associated with certain drawbacks such as migration and clogging that can result both in machine stops and/or possibly issues with the final product. This is due to that AKD does not covalently bind to the cellulose fiber to any higher extent.
  • AKD can also have a negative effect on the mechanical properties due to a debondning effect where the AKD molecules interact and reduce the fiber-fiber connections that give the high mechanical properties to a cellulose-based substrate.
  • the internal sizing agent can be combined with a wet-strength agent.
  • a wet-strength agent improves the tensile properties of the paper or paperboard in the wet state by for example covalently binding to the cellulose fibers and also by forming a crosslinked network between the fibers that does not break upon wetting.
  • Common wet-strength agents include urea- formaldehyde (UF), melamine-formaldehyde (MF) and polyamide-epichlorohydrin (PAE).
  • UF formaldehyde
  • MF melamine-formaldehyde
  • PAE polyamide-epichlorohydrin
  • Other wet strength agents can give wet-strength by other mechanisms, and some of these wet-strength agents can also have a temporary wet-strength function.
  • the inventors have surprisingly found that application of grafting technology onto a paper or paperboard material comprising a strength enhancement agent in the form of microfibrillated cellulose or highly refined cellulose leads to a material with the desired properties of being hydrophobic, having edge wick resistance, and at the same time providing for improved wet strength properties.
  • Untreated paper or paperboard material i.e. products without sizing, grafting and/or other additives, disintegrates and/or breaks when subjected to a certain stress or load in a moist and/or wet environment.
  • AKD itself may not give enough wet-strength since it is mainly physically interacting with the fibers.
  • grafting of fatty acid halides covalent bonds can be formed with fibers in the substrate, giving an improved wet- strength of the grafted material and at the same time hydrophobizing the material.
  • -multiply products for non-food applications such as flora and fauna products, pharma products, beauty and personal care products and multi-pack products;
  • Grafting technology utilizes fatty acid halides (C16 or C18, preferably C16) in liquid, spray or gas phase to graft the available hydroxyl groups on cellulose-based substrates, i.e. the fatty acids will be covalently attached to the fibers to a certain degree.
  • hydrohalic acid e.g. hydrochloric acid
  • the grafting may preferably be followed by removal of the formed hydrohalic acid, and optionally by full or partial removal of the non-grafted residues.
  • the grafting process may optionally be repeated, in order to increase the amount of grafted fatty acid.
  • the substrate may be grafted both at the top- and bottom-side.
  • the technology is applied on pre-made and dried paper and boards to limit the hydrolysis to occur.
  • the moist content of the substrate should be below 20 %, preferably below 15 %, even more preferably below 10 %.
  • WO2012066015A1 describes a machine that treats a moving substrate containing hydroxyl groups with a grafting reagent.
  • a gas-phase process to graft fatty acid halides has also been described in W02017002005A1 , were vacuum is applied to withdraw the gas through the board to render the whole cellulose-based substrate treated.
  • sizing chemicals can be completely avoided, while still providing a desirable hydrophobicity and strength to the end material.
  • said paper or paperboard comprises two or more plies, wherein at least one ply comprises a mixture of cellulose fibers and a strength enhancement agent selected from the group consisting of
  • said cellulose fibers comprise fibers or a mix or fibers from softwood, hardwood, Kraft pulp (bleached or unbleached), sulphite pulp, dissolving pulp, chemical pulp, chemi-mechanical pulp (CMP), thermomechanical pulp (TMP), chemi- thermomechanical pulp (CTMP), high- temperature (FIT)-CTMP or recycled fibers.
  • said paper or paperboard is comprising at least a three plies, i.e. a three-ply structure, wherein at least a middle ply is arranged as a structural core layer with high bulk (bulk referring to the inverse of density), sandwiched between top and back plies according to an I-beam arrangement.
  • the structural core layer preferably mainly comprises mechanical pulp fibers, such as CTMP, TMP or pressure groundwood (PGW), preferably at least 60 wt%, but may also include other fibers, preferably Kraft pulp can be included to a certain extent, preferably at most 40 wt% calculated on the total fiber weight of the ply.
  • Said structural core layer (corresponding to a bulky middle ply) is arranged to provide bending stiffness to the overall structure.
  • at least said structural core layer comprises a strength enhancement agent in the form of microfibrillated cellulose (MFC) or highly refined cellulose.
  • MFC microfibrillated cellulose
  • the structural core layer has also been subjected to grafting treatment, which means that also the flanging layers (top- and bottom) have been grafted.
  • “bulky” refers to a thicker ply with lower density compared to the flanging plies (i.e. top and back ply) in the structure.
  • said middle ply exhibits a density of below 400 kg/m3, preferably of below 350 kg/m3, even more preferably of below 300 kg/m3.
  • MFC may be added in an amount of between 0.1 - 10 wt%, preferably between 1 - 7 wt%, or between 1 - 5 wt% as calculated on the total solid content of the ply.
  • said paper or paperboard has been subjected to grafting with a fatty acid halide through the entire thickness of said paper or paperboard.
  • a surface of said paper or paperboard subjected to grafting with a fatty acid halide has a water contact angle above 90°, preferably above 100°.
  • the fatty acid halide grafting results in a paper or paperboard having a Cobb60 value below 30 g/m 2 (as determined according to standard ISO 535:2014 after 60 seconds), preferably below 20 g/m 2 , and more preferably below 15 g/m 2 .
  • the fatty acid halide grafting results in a paper or paperboard having an edge-wick index (Lactic acid 1 % solution, 1 h at 23 °C and 50 % relative humidity) below 1.5 kg/m 2 h, preferably below 1 kg/m 2 h, and even more preferably below 0.5 kg/m 2 h.
  • said paper or paperboard subjected to grafting with a fatty acid halide has a Z-strength of at least 150 kPa, preferably of at least 250 kPa, most preferably of at least 350 kPa as determined according to standard ISO 15754:2009.
  • said paper or paperboard subjected to grafting with a fatty acid halide has a wet tensile strength in machine direction (MD) in the range of 0.5-10 kN/m, as determined according to standard 3781 :201 1.
  • said paper or paperboard subjected to grafting with a fatty acid halide has a relative wet tear strength in machine direction (MD) in the range of 20-100 %, as determined according to TAPPI T 496 sp-13 (T 496 cm-85) and ISO 1974:2012.
  • MD machine direction
  • the grammage of said paper or paperboard prior to grafting is in the range of 40-700 g/m 2 .
  • the thickness of said paper or paperboard prior to grafting is in the range of 40-1000 pm.
  • the density of said paper or paperboard prior to grafting is in the range of 350-1300 kg/m 3 .
  • the density of said paper or paperboard subjected to grafting with a fatty acid halide is in the range of 350-1300 kg/m 3 .
  • said cellulose fibers comprise fibers or a mix or fibers from soft wood, hard wood, sulphate pulp, sulphite pulp, dissolving pulp, chemical pulp, thermomechanical pulp (TMP), chemi- thermomechanical pulp (CTMP) or high-temperature (HT)-CTMP.
  • said strength enhancement agent is MFC.
  • MFC cellulose microfibrils, fibrillated cellulose, nanofibrillated cellulose, fibril aggregates, nanoscale cellulose fibrils, cellulose nanofibers, cellulose nanofibrils, cellulose microfibers, cellulose fibrils, microfibrillar cellulose, microfibril aggregates and cellulose microfibril aggregates.
  • MFC can also be characterized by various physical or physical-chemical properties such as large surface area or its ability to form a gel-like material at low solids (1 -5 wt%) when dispersed in water.
  • the cellulose fiber is preferably fibrillated to such an extent that the final specific surface area of the formed MFC is from about 1 to about 300 m2/g, such as from 1 to 200 m2/g or more preferably 50-200 m2/g when determined for a freeze-dried material with the BET method.
  • said strength enhancement agent is highly refined cellulose.
  • said highly refined cellulose is cellulose refined to an SR value in the range of 70-94, preferably in the range of 70-90, and wherein the cellulose fibers have a length of ⁇ 1 mm.
  • the Schopper-Riegler value can be obtained through the standard method defined in EN ISO 5267-1. This SR value is determined for a pulp, with or without additional chemicals, thus the fibers have not consolidated into a film or started any hornification or such.
  • the dry solid content of this kind of web, before disintegrated and measuring SR, is less than 50 % (w/w).
  • a combination of MFC and highly refined pulp can also be utilized as strength enhancement agent.
  • the dry weight ratio between said cellulose fibers and said strength enhancement agent in the at least one ply is in the range of 80:20 to 99.9:0.1 , preferably in the range of 90:10 to 99:0.5.
  • the present invention also relates to a method for manufacturing paper or paperboard, said method comprising at least the steps of:
  • MFC microfibrillated cellulose
  • said paper or paperboard comprises two or more plies, wherein at least one ply comprises a mixture of cellulose fibers and a strength enhancement agent selected from the group consisting of microfibrillated cellulose (MFC), and highly refined cellulose.
  • MFC microfibrillated cellulose
  • said paper or paperboard is subjected to grafting with a fatty acid halide through the entire thickness of said paper or paperboard.
  • the applied amount of fatty acid halide is between 0.1 -4 g/m 2 of total dry weight of the substrate, preferably between 0.5-2 g/m 2 .
  • the method for analyzing the amount of free and grafted fatty acids in the treated substrate is based on the method for AKD analysis. Free fatty acids are extracted from the board sample with an organic solvent and analyzed with GC-FID after silylation. The same board sample is subsequently submitted to alkaline hydrolysis for breaking the ester bonds to cellulose and the released fatty acids are thereafter extracted and analyzed with GC-FID after silylation. The sum of the analyzed free and bound fatty acids constitutes the total amount of fatty acid halide.
  • the present invention also relates to the use of a fatty acid halide for hydrophobization of a paper or paperboard comprised of one or more plies, wherein at least one ply comprises a mixture of cellulose fibers and a strength enhancement agent selected from the group consisting of microfibrillated cellulose (MFC) and highly refined cellulose.
  • MFC microfibrillated cellulose
  • the present invention relates to a paper or
  • paperboard comprised of one or more plies, wherein at least one ply comprises a mixture of cellulose fibers and a strength enhancement agent selected from the group consisting of microfibrillated cellulose (MFC) and highly refined cellulose, and wherein said paper or paperboard has been subjected to grafting with a fatty acid halide such that ester bonds are formed between carbonyl groups of the fatty acid halide and hydroxyl groups of the cellulose fibers and the strength enhancement agent.
  • Paper and paperboard structures can be built up by one or more plies. A structure comprising more than one ply is referred to as multiply structures. Some boards structures are built up by a three-layer fiber construction, i.e. in three plies.
  • the top and the back ply can be based on bleached and/or unbleached sulphate pulp and the middle ply can consist of CTMP.
  • the middle ply can also consist of CTMP and bleached and/or unbleached sulphate pulp.
  • a reverse layer can also be utilized of unbleached sulphate pulp.
  • Multiply structures with more than three plies, such as five plies or more, are also within the scope of the present invention.
  • Another option is to have a three-layered structure with chemical pulp, optionally combined with CTMP in one or more plies as well as additional layers with surface sizing and/or single, double and/or triple mineral coating.
  • multilayer Kraft back board which is built up of three plies with bleached or unbleached chemical pulp in outer plies and unbleached chemical pulp and CTMP in mid ply, possibly combined with a double coating.
  • the strength enhancement agent can be added to one, several or all of the plies of a multiply structure, preferably it is placed in the middle ply(ies) for the substrates that have more than one ply. It is generally the mid ply that is the bulkiest ply, giving an increase in the bending stiffness. By adding MFC to this bulky mid layer, the Z-strength is improved.
  • the grafting technology used onto a paper or paperboard material comprising a strength enhancement agent leads to a material with the properties of being hydrophobic, having edge wick resistance, and at the same time providing for improved wet strength properties.
  • the grafting technology is based on the concept of applying a fatty acid halide onto a cellulose substrate such that the fatty acid penetrates the cellulose substrate and resulting in a hydrophobization thereof. Grafting can be accomplished in various ways.
  • grafting is performed by firstly drying a cellulose substrate to a dry content above 80%, and thereafter adding a vaporized fatty acid halide to the first side of the cellulose substrate, and, at the same time perform vacuum sucking at the second side of the cellulose substrate, such that the vaporized fatty acid penetrates the cellulose substrate in a predetermined direction through the substrate.
  • said substrate can comprise at least one outer polymer layer forming an outer surface of said substrate, wherein said polymer comprises any of the following; polyethylene (PE), polyethylene terephthalate (PET), polyvinyl alcohol (PVOFI), polyvinyl acetate (PVA), polypropylene (PP), polylactic acid (PLA) and/or polyamide (PA).
  • PE polyethylene
  • PET polyethylene terephthalate
  • PVFI polyvinyl alcohol
  • PVA polyvinyl acetate
  • PP polypropylene
  • PA polylactic acid
  • PA polyamide
  • Formette lab sheets were prepared of CTMP fibers with MFC and/or AKD, see Table 1. Drying of the sheets was performed with a pressure that was varied between 1 to 5 bar at a temperature of 100 Q C.
  • the tensile strength was measured according to standard ISO 1924-3:2005.
  • the wet strength was measured according to ISO 3781 :201 1 for the hydrophobized sheets with fatty acid grafting or AKD sizing.
  • the relative wet strength is the difference between the tensile strength and the wet strength in percentage.
  • edge wick penetration testing was performed with lactic acid (LA) (1 %) for 1 h at conditioned climate of 23 Q C and 50 % RH. The thickness of the sheets was determined and the surfaces were masked with a plastic film on both sides prior to cutting them into five pieces to reveal raw edges. These were thereafter immersed into the LA bath for 1 h, and the amount of absorbed liquid was subsequently weighed. Thereafter the edge penetration wick index can be calculated in kg/m 2 .
  • LA lactic acid
  • the Cobb6o value was determined according to standard ISO 535:2014 after 60 seconds for the hydrophobized sheets with fatty acid grafting or AKD sizing.
  • the LA wick tests also showed an improvement of applying the grafting technique compared to AKD sizing, and values as low as 0.19 and 0.20 kg/m 2 h were achieved for the grafted MFC sheets with fine and coarse MFC, respectively, see Table 2. These values are also in line with the grafted reference samples without MFC.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Biochemistry (AREA)
  • Materials Engineering (AREA)
  • Paper (AREA)

Abstract

L'invention concerne un papier ou un carton constitué d'un ou de plusieurs plis, au moins un pli comprenant un mélange de fibres de cellulose et un agent d'amélioration de la résistance choisi dans le groupe constitué par la cellulose microfibrillée (MFC) et la cellulose hautement raffinée, et ledit papier ou carton ayant été soumis à un greffage avec un halogénure d'acide gras de telle sorte que des liaisons ester sont formées entre des groupes carbonyle de l'halogénure d'acide gras et des groupes hydroxyle des fibres de cellulose et de l'agent d'amélioration de la résistance. L'invention concerne également un procédé de fabrication de papier ou de carton.
PCT/IB2020/056061 2019-07-08 2020-06-26 Papier ou carton rendu hydrophobe comprenant un ou plusieurs plis Ceased WO2021005446A1 (fr)

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SE1950871A SE1950871A1 (en) 2019-07-08 2019-07-08 Paper or paperboard material comprising one or more plies
SE1950871-2 2019-07-08

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WO2021005446A1 true WO2021005446A1 (fr) 2021-01-14

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Cited By (3)

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US20220242636A1 (en) * 2019-07-09 2022-08-04 Stora Enso Oyj Paperboard and laminate comprising a bio-barrier
WO2025033449A1 (fr) * 2023-08-09 2025-02-13 王子ホールディングス株式会社 Stratifié formant barrière contre les gaz et sac d'emballage
WO2025202957A1 (fr) * 2024-03-28 2025-10-02 Stora Enso Oyj Procédé de fabrication d'un carton multicouche et carton multicouche

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FR3160714A1 (fr) 2024-03-29 2025-10-03 Institut National de Recherche pour l’Agriculture, l’Alimentation et l’Environnement Procédé d’hydrophobation d’un substrat en matériau polysaccharidique

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US20150167243A1 (en) * 2012-06-13 2015-06-18 University Of Maine System Board Of Trustees Energy Efficient Process for Preparing Nanocellulose Fibers
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US20220242636A1 (en) * 2019-07-09 2022-08-04 Stora Enso Oyj Paperboard and laminate comprising a bio-barrier
WO2025033449A1 (fr) * 2023-08-09 2025-02-13 王子ホールディングス株式会社 Stratifié formant barrière contre les gaz et sac d'emballage
WO2025202957A1 (fr) * 2024-03-28 2025-10-02 Stora Enso Oyj Procédé de fabrication d'un carton multicouche et carton multicouche

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