SE1950871A1 - Paper or paperboard material comprising one or more plies - Google Patents

Paper or paperboard material comprising one or more plies

Info

Publication number
SE1950871A1
SE1950871A1 SE1950871A SE1950871A SE1950871A1 SE 1950871 A1 SE1950871 A1 SE 1950871A1 SE 1950871 A SE1950871 A SE 1950871A SE 1950871 A SE1950871 A SE 1950871A SE 1950871 A1 SE1950871 A1 SE 1950871A1
Authority
SE
Sweden
Prior art keywords
paper
paperboard
cellulose
grafting
mfc
Prior art date
Application number
SE1950871A
Other languages
Swedish (sv)
Inventor
Raija Bådenlid
Susanne Hansson
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 SE1950871A priority Critical patent/SE1950871A1/en
Priority to PCT/IB2020/056061 priority patent/WO2021005446A1/en
Publication of SE1950871A1 publication Critical patent/SE1950871A1/en

Links

Classifications

    • 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

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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

The 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. The invention also relates to a method for manufacturing paper or paperboard.

Description

PAPER OR PAPERBOARD MATERIAL COMPRISING ONE OR MORE PLIES Technical field The present invention relates to a paper or paperboard comprised of one ormore plies wherein at least one p|y comprises a mixture of cellulose fibers and astrength enhancement agent selected from the group consisting of microfibrillated cellulose (MFC) and highly refined cellulose.
Backgroundlt is known to use microfibrillated and nanofibrillated cellulose as additives to improve mechanical properties, such as strength, for paper and paperboardmaterials. However, due to its highly hydrophilic properties, addition of MFC to apaper making furnish may not be suitable when it is desired to produce hydrophobiccellulose-based materials.
Paper- and paperboard are usually treated with sizing agents to increase theresistance to penetration of water and other liquids into the paper or paperboard. Acommon sizing agent is AKD which is added to the pulp at the wet end of a papermaking machine. Use of AKD is however associated with certain drawbacks such asmigration and clogging that can result both in machine stops and/or possibly issueswith the final product.
There is a need for a cellulose-based fiber material, such as paper orpaperboard, with good strength properties and at the same time providing water- repellence, wet-strength function and edge-wick resistance.
Summary of the invention lt is an object of the present invention to solve or at least alleviate theproblems presented above, and provide a cellulose-based material, such as paper orpaperboard, with hydrophobic properties and edge-wick resistance, and at the sametime providing an improved wet-strength.
The objects of the invention are at least partially obtained by means of a paperor paperboard according to claim 1. Said paper or paperboard comprises one or more plies wherein at least one ply comprises a mixture of cellulose fibers and astrength enhancement agent selected from the group consisting of microfibrillatedcellulose (MFC) and highly refined cellulose, wherein said paper or paperboard hasbeen subjected to grafting with a fatty acid halide such that ester bonds are formedbetween carbonyl groups of the fatty acid halide and hydroxyl groups of the cellulosefibers and the strength enhancement agent.
The inventors have surprisingly found that application of grafting technologyonto a paper or paperboard material comprising a strength enhancement agent in theform of microfibrillated cellulose or highly refined cellulose leads to a material with thedesired properties of being hydrophobic, having edge wick resistance, and at thesame time providing for improved wet strength properties. Untreated paper orpaperboard 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 moistand/or wet environment. AKD in itself may not give enough wet-strength since it ismainly physically interacting with the fibers. By grafting of fatty acid halides, however,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.
Grafting technology utilizes fatty acid halides (C16 or C18, preferably C16) inliquid, spray or gas phase to graft the available hydroxyl groups on cellulose-basedsubstrates, i.e. the fatty acids will be covalently attached to the fibers to a certaindegree. There will also be free, unbound fatty acids, present in the final productbecause of the hydrolysis of the reagent. The technology is applied on pre-made anddried paper and boards to limit the hydrolysis to occur. The moist content of thesubstrate should be below 20 %, preferably below 15 %, even more preferably below10 %.
WO2012066015A1 describes a machine that treats a moving substratecontaining hydroxyl groups with a grafting reagent. A gas-phase process to graft fattyacid halides has also been described in WO2017002005A1, were vacuum is appliedto withdraw the gas through the board to render the whole cellulose-based substratetreated.
Grafting of the fatty acid halide to the MFC-containing paper or paperboard can beachieved by applying a fatty acid halide to the surface of the substrate and heatingthe substrate to form covalent bonds between the fatty acid residue and the availablehydroxyi groups. The reaction between the fatty acid halide, e.g. fatty acid chloride,and the hydroxyl groups results in ester bonds between the reagent and the fiberand/or fibrils. Upon the reaction with the hydroxyi groups on the substrate or withwater in the substrate or in the air, hydroha|ic acid, e.g. hydroch|oric acid, is formedas a reaction byproduct. The grafting may preferably be followed by removal of theformed hydroha|ic acid, and optionally by full or partial removal of the ungraftedresidues. The grafting process may optionally be repeated, in order to increase the amount of grafted fatty acid residues.
According to one aspect of the invention, said paper or paperboard comprisestwo or more plies, wherein at least one ply comprises a mixture of cellulose fibersand a strength enhancement agent selected from the group consisting ofmicrofibrillated cellulose (MFC) and highly refined cellulose.
According to yet another aspect of the invention, said paper or paperboardhas been subjected to grafting with a fatty acid halide through the entire thickness of said paper or paperboard.
According to yet another aspect of the invention, a surface of said paper orpaperboard subjected to grafting with a fatty acid halide has a water contact angleabove 90°, preferably above 100°.
According to yet another aspect of the invention, said paper or paperboardsubjected to grafting with a fatty acid halide has a wet tensile strength in machinedirection (MD) in the range of 0.5-5 kN/m, as determined according to standard3781 :201 1.
According to yet another aspect of the invention, the grammage of said paper or paperboard prior to grafting is in the range of 40-700 g/m2.
According to yet another aspect of the invention, the thickness of said paperor paperboard prior to grafting is in the range of 40-1000 um.
According to yet another aspect of the invention, the density of said paper orpaperboard prior to grafting is in the range of 350-1300 kg/m3.
According to yet another aspect of the invention, the density of said paper orpaperboard subjected to grafting with a fatty acid halide is in the range of 350-1300kg/m3.
According to yet another aspect of the invention, said cellulose fiberscomprise fibers or a mix or fibers from soft wood, hard wood, sulphate pulp, sulphitepulp, disso|ving pulp, chemical pulp, thermomechanical pulp (TMP), chemi-thermomechanical pulp (CTMP) or high-temperature (HT)-CTMP.
According to one aspect of the invention, said strength enhancement agent isMFC. ln an MFC material, the cellulose fiber is preferably fibri||ated to such an extentthat the final specific surface area of the formed MFC is from about 1 to about 500m2/g, such as from 10 to 400 m2/g or more preferably 50-300 m2/g when determinedfor a solvent exchanged and freeze-dried material with the BET method.
According to yet another aspect of the invention, said strength enhancementagent is highly refined cellulose. Preferably, said highly refined cellulose is celluloserefined to an SR value in the range of 70-94, preferably in the range of 70-90, andwherein the cellulose fibers have a length of <1mm. The Schopper-Riegler value canbe obtained through the standard method defined in EN ISO 5267-1. This SR valueis determined for a pulp, with or without additional chemicals, thus the fibers have notconsolidated into a film or started any hornification or such. The dry solid content ofthis kind of web, before disintegrated and measuring SR, is less than 50 % (w/w). Todetermine the Schopper Riegler value it is preferable to take a sample just after thewire section where the wet web consistency is relatively low. The skilled personunderstands that paper making chemicals, such as retention agents or dewateringagents, have an impact on the SR value. The SR value specified herein, is to be understood as an indication but not a Iimitation, to reflect the Characteristics of thematerial itself.
A combination of MFC and highly refined pulp can also be utilized.
According to yet another aspect of the invention, the dry weight ratio betweensaid cellulose fibers and said strength enhancement agent in the at least one ply is inthe range of 80:20 to 99.9:0.1, preferably in the range of 90:10 to 99:05.
The present invention also relates to a method for manufacturing paper orpaperboard, said method comprising at least the steps of: a) providing a paper or paperboard substrate comprised of one or more plies,wherein at least one ply comprises a mixture of cellulose fibers and a strengthenhancement agent selected from the group consisting of microfibrillated cellulose(MFC) and highly refined cellulose, and b) subjecting said paper or paperboard to grafting with a fatty acid halidesuch that ester bonds are formed between carbonyl groups of the fatty acid halideand hydroxyl groups of the cellulose fibers and the strength enhancement agent.
According to one aspect of the method of the invention, said paper orpaperboard comprises two or more plies, wherein at least one ply comprises amixture of cellulose fibers and a strength enhancement agent selected from the group consisting of microfibrillated cellulose (MFC), and highly refined cellulose.
According to yet another aspect of the invention, said paper or paperboard issubjected to grafting with a fatty acid halide through the entire thickness of said paper or paperboard.
The present invention also relates to the use of a fatty acid halide forhydrophobization of a paper or paperboard comprised of one or more plies, whereinat least one ply comprises a mixture of cellulose fibers and a strength enhancementagent selected from the group consisting of microfibrillated cellulose (MFC), andhighly refined cellulose.
Detailed description of the invention The material according to the invention will now be further described in thefollowing. However, the embodiments referred to in this description are not to beseen as Iimiting the scope of the invention in any way, but are merely provided for a better understanding of the invention.
As previously described, the present invention relates to a paper orpaperboard comprised of one or more plies, wherein at least one ply comprises amixture of cellulose fibers and a strength enhancement agent selected from thegroup consisting of microfibrillated cellulose (MFC) and highly refined cellulose, andwherein said paper or paperboard has been subjected to grafting with a fatty acidhalide such that ester bonds are formed between carbonyl groups of the fatty acidhalide and hydroxyl groups of the cellulose fibers and the strength enhancementagent. Paper and paperboard structures can be built up by one or more plies, i.e. inmultiply structures. Some boards structures are build up by a three-layer fiberconstruction, i.e. in three plies. The top and the back ply can be based on bleachedand/or unbleached sulphate pulp and the middle ply can consist of CTMP. Themiddle 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 structureswith 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 withsurface sizing and/or single, double and/or triple coating. Yet another option ismultilayer Kraft back board which is built up of three plies with bleached orunbleached 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 placed in one, several or all of theplies of a multiply structure, preferably it is placed in the middle ply(ies) for thesubstrates that have more than one ply.
According to the invention, the grafting technology used onto a paper orpaperboard material comprising a strength enhancement agent (MFC or highlyrefined cellulose) leads to a material with the properties of being hydrophobic, havingedge wick resistance, and at the same time providing for improved wet strengthproperties. The grafting technology is based on the concept of applying a fatty acidhalide onto a cellulose substrate such that the fatty acid penetrates the cellulosesubstrate and resulting in a hydrophobing thereof. Grafting can be accomplished invarious ways. According to one example, grafting is performed by firstly drying acellulose substrate to a dry content above 80%, and thereafter adding a vaporizedfatty acid halide to the first side of the cellulose substrate, and, at the same timeperform vacuum sucking at the second side of the cellulose substrate, such that thevaporized fatty acid penetrates the cellulose substrate in a predetermined directionthrough the substrate.
The material according to the invention is suitable for use in a vast number of applications. A non-limiting list of examples include: - structures utilized for (but not limited to) liquid packaging boards (LPB) for use in thepackaging of liquids or liquid-containing products, as well as paper or paperboard fordry, fat, fresh and/or frozen food, and laminates thereof; -cup,material and laminates thereof for hot and cold food stuff; -general packaging, luxury packaging, and graphical board for their designatedapplications; -products for non-food applications, such as flora and fauna products, , pharmaproducts, beauty and personal care products and multi-pack products; -well and wrapping paper (food and non-food based); - pouches; -paper or paperboard for single-use items; -labels, grease-proof paper, high-density paper, sack paper and well structures. ln one aspect of the invention, said substrate can comprise at least one outerpolymer layer forming an outer surface of said substrate, wherein said polymercomprises any of the following; polyethylene (PE), polyethylene terephthalate (PET),polyvinyl alcohol (PVOH), polyvinyl acetate (PVA), polypropylene (PP) and/orpolyamide (PA).
According to the invention it is also conceivable to replace or minimize thegrammage of one or two polymer layers at the front- and/or backside of thesubstrate/Iaminate, especially with regards to the outer layer utilized for condensation.
Examples Two grades of MFC were employed, one finer grade that has been passedthrough a homogenizer for five passages and one coarser grade that only has beenhighly refined.
Formette lab sheets were prepared of CTMP fibers with MFC and/or AKD.The hot-pressing of the sheets was performed with a pressure that was varied between 1 to 5 bar at a temperature of 100 °C. See Table 1.
The sheets that did not contain any AKD were treated with palmitoyl chloride(PTC) by spraying the reagent onto one side of the substrate with a spray gun withmax 100 ml volume and an operating pressure of 1.5 bar, followed by infrared (IR)heat-treatment of the same surface. The corresponding grafted samples arepresented in Table 1.
Table 1. Recipes of Formette lab sheets. 4 Retention aid MFC fine MFC coarse AKD i Grammage Density g __________________________________________________ PTc-Fs-MFC fiOO 0.8 kg/:OO 50 kg/:OO NO NO 107 404 f _-PïC_f_ES_-_MEC_searsfimí __________ -0_-_S__l§g/ï9n ____________________________ -_1319 ________________ __________ filis/.tšln ____________________ .NQ ____________________ -197 __________ _________ -386 _________ __AKD-Fs-MFC fiOO 0.8 kg/:OO 50 kg/:OO NO 3 kg/:OO 104 402 -AKD.f_1_ ____________________________ .NQ _______________ _________ -âO_lig/_t<>_n ______________ -åka/ten _______________ .194 _________ _________ .314 __________ _.
The method for measurement of contact angle (CA) is based on the standardISO TC 6/SC 2/WG 41: Paper and board - Measurement of water contact angle byoptical methods. Contact angle was measured for 10 seconds and values for eachsecond and at 0.1 s were noted. The values are an average from 5 drops. The liquid used was Milli-Q water, drop size was 4 ul and drops were evaluated by the software calculation program Circle.
The wet strength was measured according to ISO 3781 :2011 for thehydrophobized sheets with fatty acid grafting or AKD sizing. The relative wet strengthis the difference between the tensile strength and the wet strength in percentage.
The edge wick penetration testing was performed with lactic acid (LA) (1 %)for 1 h at conditioned climate of 23 °C and 50 % RH. The thickness of the sheets wasdetermined and the surfaces were masked with a plastic film on both sides prior tocutting them into five pieces to reveal raw edges. These were thereafter immersedinto the LA bath for 1 h, and the amount of absorbed liquid was subsequentlyweighed. Thereafter the edge penetration wick index can be calculated in kg/m2.
The hydrophobicity of the fatty acid grafted sheets were greatly enhancedcompared to the unsized sheets, which could be validated by their high (water)contact angles; values between 120-130 °C were achieved. Also, the contact anglesfor the AKD sized sheets were in the same range. The Formette sheet without any hydrophobation agent absorbs the water droplet immediately.
Another important feature for many paper and board products is the wetstrength. Formette lab sheets without any additives have a very low wet strength andhave therefore not been measured. The addition of AKD to the sheets with MFC gavea wet strength of 0.75 and 0.72 kN/m for the fine and the coarse MFC, respectively,see Table 2. However, for the fatty acid grafted samples, the wet strength becamemore than twice as high: 1.81 and 1.63 kN/m for the fine and the coarse MFC, respectively, which is a very impressive value for weak Formette sheets.
The LA wick tests also showed a clear improvement of applying the graftingtechnique compared to AKD sizing, and values as low as 0.19 and 0.20 kg/m2h wereachieved for the grafted MFC sheets with fine and coarse MFC, respectively. SeeTable 2.
These results confirm that despite the hydrophilic nature of MFC, it is possibleto improve both the wet strength and the edge wick penetration by grafting of fattyacid halides. lt has also been shown how these characteristics can be furtherimproved compared to AKD utilization.
Table 2. Results for the MFC strenqth enhanced sheets.
Wet strength Relative Wet strength LA Wick (kN/m) (%) (kg/mm)PTc-Fs-MFC fine 1.81 25.7 0.19PTc-Fs-MFC come 1.63 26 0.20AKD-Ps-MFC fine 0.75 10.1 0.25 AKD-FS-MFC coarse 0.72 12.4 0.25

Claims (28)

1. Paper or paperboard comprised of one or more plies, wherein at least one ply comprises a mixture of cellulose fibers and a strengthenhancement agent selected from the group consisting of microfibrillated cellulose (MFC) and highly refined cellulose, wherein said paper or paperboard has been subjected to grafting with a fattyacid halide such that ester bonds are formed between carbonyl groups of the fattyacid halide and hydroxyl groups of the cellulose fibers and the strength enhancement agent.
2. Paper or paperboard according to claim 1, wherein said paper orpaperboard comprises two or more plies, wherein at least one ply comprises amixture of cellulose fibers and a strength enhancement agent selected from thegroup consisting of microfibrillated cellulose (MFC), and highly refined cellulose.
3. Paper or paperboard according to any one of the preceding claims,wherein said paper or paperboard has been subjected to grafting with a fatty acidhalide through the entire thickness of said paper or paperboard.
4. Paper or paperboard according to any one of the preceding claims,wherein a surface of said paper or paperboard subjected to grafting with a fatty acidhalide has a water contact angle above 90°, preferably above 100°.
5. Paper or paperboard according to any one of the preceding claims,wherein said paper or paperboard subjected to grafting with a fatty acid halide has awet tensile strength in the range of 0.5-5, or more preferably 0.8-4 kN/m, asdetermined according to standard ISO 3781 :201 1.
6. Paper or paperboard according to any one of the preceding claims,wherein the grammage of said paper or paperboard prior to grafting is in the range of50-700 g/m2, more preferably between 60-500 g/m2.
7. Paper or paperboard according to any one of the preceding claims,wherein the grammage of said paper or paperboard subjected to grafting with a fattyacid halide is in the range of 40-700 g/m2, more preferably between 60-500 g/m2.
8. Paper or paperboard according to any one of the preceding claims,wherein said cellulose fibers are from soft wood, hard wood, sulphate pulp, sulphitepulp, dissolving pulp, chemical pulp, thermomechanical pulp (TMP), chemi-thermomechanical pulp (CTMP) or high-temperature (HT)-CTMP, or a mixturethereof.
9. Paper or paperboard according to any one of the preceding claims,wherein said strength enhancement agent is MFC.
10. Paper or paperboard according to c|aim 9, wherein the final specificsurface area of the formed MFC is from about 1 to about 500 m2/g, such as from 10to 400 m2/g or more preferably 50-300 m2/g when determined for a so|ventexchanged and freeze-dried material with the BET method.
11. Paper or paperboard according to any one of claims 1-8, wherein saidstrength enhancement agent is highly refined cellulose.
12. Paper or paperboard according to c|aim 11, wherein said highly refinedcellulose is cellulose refined to an SR value in the range of 70-94, preferably in therange of 70-90, as determined according to standard method defined in EN ISO5267-1
13. Paper or paperboard according to any one of the preceding claims,wherein the dry weight ratio between said cellulose fibers and said strengthenhancement 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 99:05.
14. A method for manufacturing paper or paperboard, said method comprising: a) providing a paper or paperboard substrate comprised of one or moreplies, wherein at least one p|y comprises a mixture of cellulose fibers and a strengthenhancement agent selected from the group consisting of microfibrillated cellulose(MFC) and highly refined cellulose, and b) subjecting said paper or paperboard to grafting with a fatty acid ha|idesuch that ester bonds are formed between carbonyl groups of the fatty acid ha|ideand hydroxyl groups of the cellulose fibers and the strength enhancement agent.
15. The method according to c|aim 14, wherein said paper or paperboardcomprises two or more plies, wherein at least one p|y comprises a mixture ofcellulose fibers and a strength enhancement agent selected from the groupconsisting of microfibrillated cellulose (MFC), and highly refined cellulose.
16. The method according to any one of claims 14-15, wherein said paper orpaperboard is subjected to grafting with a fatty acid ha|ide through the entirethickness of said paper or paperboard.
17. The method according to any one of claims 14-16, wherein a surface ofsaid paper or paperboard subjected to grafting with a fatty acid ha|ide has a watercontact angle above 90°, preferably above 100°.
18. The method according to any one of claims 14-17, wherein said paper orpaperboard subjected to grafting with a fatty acid ha|ide has a wet tensile strength inthe range of 0.5-5, or more preferably 0.8-3 kN/m, as determined according tostandard ISO 3781 :201 1.
19. The method according to any one of claims 14-18, wherein grammage ofsaid paper or paperboard prior to grafting is in the range of 50-700 g/m2, morepreferably between 60-500 g/m2.
20. The method according to any one of claims 14-19, wherein thegrammage of said paper or paperboard subjected to grafting with a fatty acid halide is in the range of 40-700 g/m2, more preferably between 60-500 g/m2.
21. The method according to any one of claims 14-20, wherein saidcellulose fibers are 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, or a mixturethereof.
22. The method according to any one of claims 14-21, wherein said strengthenhancement agent is MFC.
23. The method according to claim 22, wherein the final specific surfacearea of the formed MFC is from about 1 to about 500 m2/g, such as from 10 to 400m2/g or more preferably 50-300 m2/g when determined for a so|vent exchanged andfreeze-dried material with the BET method.
24. The method according to any one of claims 14-21, wherein said strengthenhancement agent is highly refined cellulose.
25. The method according to claim 24, wherein said highly refined celluloseis cellulose refined to an SR value in the range of 70-94, preferably in the range of70-90, as determined according to standard method defined in EN ISO 5267-1.
26. The method according to any one of claims 14-25, wherein the dryweight ratio between said cellulose fibers and said strength enhancement agent inthe at least one ply is in the range of 80:20 to 99:1, preferably in the range of 90:10 to99:1.
27. Use of a fatty acid halide for hydrophobization of a paper or paperboardcomprised of one or more plies, wherein at least one ply comprises a mixture ofcellulose fibers and a strength enhancement agent selected from the groupconsisting of microfibrillated cellulose (MFC), and highly refined cellulose.
28. A product produced from the paper or paperboard substrate according toany of the claims 1-13, wherein the product is any one of the products from the groupcomprising:laminate structures for boards uti|ized for (but not limited to) liquid packaging boards(LPB) for use in the packaging of liquids or liquid-containing products, as well asboard for dry, fat, fresh and/or frozen food; -cup/beaker material for hot and cold food stuff, and general packaging, graphicalboard and luxury packaging; -products for non-food applications, such as flora and fauna products, graphicalproducts, pharma products, beauty and personal care products and multi-packproducts; -well and wrapping paper (food and non-food based); -paper or paperboard for single-use items; -labels and pouches; and -grease-proof paper, high-density paper, sack paper and well structures.
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