WO2018171914A1 - Procédé de fabrication d'un matériau fibreux cellulosique formé en mousse, feuille en vrac et matériau d'emballage stratifié comprenant le matériau fibreux cellulosique - Google Patents

Procédé de fabrication d'un matériau fibreux cellulosique formé en mousse, feuille en vrac et matériau d'emballage stratifié comprenant le matériau fibreux cellulosique Download PDF

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Publication number
WO2018171914A1
WO2018171914A1 PCT/EP2017/076146 EP2017076146W WO2018171914A1 WO 2018171914 A1 WO2018171914 A1 WO 2018171914A1 EP 2017076146 W EP2017076146 W EP 2017076146W WO 2018171914 A1 WO2018171914 A1 WO 2018171914A1
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WO
WIPO (PCT)
Prior art keywords
foam
layer
cellulosic fibre
formed cellulosic
packaging
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PCT/EP2017/076146
Other languages
English (en)
Inventor
Erikki SAHARINEN
Jaakko ASIKAINEN
Original Assignee
Tetra Laval Holdings & Finance S.A.
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Publication date
Application filed by Tetra Laval Holdings & Finance S.A. filed Critical Tetra Laval Holdings & Finance S.A.
Publication of WO2018171914A1 publication Critical patent/WO2018171914A1/fr

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Classifications

    • 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
    • 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
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/18—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by features of a layer of foamed material
    • 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
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/18—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by features of a layer of foamed material
    • B32B5/20—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by features of a layer of foamed material foamed in situ
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21F—PAPER-MAKING MACHINES; METHODS OF PRODUCING PAPER THEREON
    • D21F11/00—Processes for making continuous lengths of paper, or of cardboard, or of wet web for fibre board production, on paper-making machines
    • D21F11/002—Processes for making continuous lengths of paper, or of cardboard, or of wet web for fibre board production, on paper-making machines by using a foamed suspension
    • 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
    • D21H17/20—Macromolecular organic compounds
    • D21H17/33—Synthetic macromolecular compounds
    • D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H17/37—Polymers of unsaturated acids or derivatives thereof, e.g. polyacrylates
    • D21H17/375—Poly(meth)acrylamide
    • 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
    • D21H17/20—Macromolecular organic compounds
    • D21H17/33—Synthetic macromolecular compounds
    • D21H17/46—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H17/53—Polyethers; Polyesters
    • 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
    • D21H21/06—Paper forming aids
    • D21H21/10—Retention agents or drainage improvers
    • 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
    • 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
    • D21H21/50—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 form
    • D21H21/56—Foam

Definitions

  • the present invention relates to a method of manufacturing a new foam-formed cellulosic fibre-material.
  • the invention also relates to a new foam-formed cellulosic fibre-material as well as to a bulk sheet and a laminated packaging material comprising the form-foamed cellulosic fibre-material.
  • Packaging containers of the single use disposable type for liquid foods are often produced from a packaging laminate based on paperboard or carton.
  • One such commonly occurring packaging container is marketed under the trademark Tetra Brik Aseptic® and is principally employed for aseptic packaging of liquid foods such as milk, fruit juices etc., which are sold for long term ambient storage.
  • the packaging material in this known packaging container is typically a laminate comprising a bulk layer of paper or paperboard and outer, liquid-tight layers of thermoplastics.
  • the laminate in these packaging containers normally comprises at least one additional layer, most commonly an aluminium foil.
  • innermost layer On the inside of the laminate, i.e. the side intended to face the food contents of a container produced from the laminate, there is an innermost layer, applied onto the aluminium foil, which innermost, inside layer may be composed of one or several part layers, comprising heat sealable thermoplastic polymers, such as adhesive polymers and/or polyolefins. Also on the outside of the bulk layer, there is an outermost heat sealable polymer layer.
  • the packaging containers are generally produced by means of modern, high- speed packaging machines of the type that form, fill and seal packages from a web or from prefabricated blanks of packaging material.
  • Packaging containers may thus be produced by reforming a web of the laminated packaging material into a tube by both of the longitudinal edges of the web being united to each other in an overlap joint by welding together the inner- and outermost heat sealable thermoplastic polymer layers.
  • the tube is filled with the intended liquid food product and is thereafter divided into individual packages by repeated transversal seals of the tube at a predetermined distance from each other below the level of the contents in the tube.
  • the packages are separated from the tube by incisions along the transversal seals and are given the desired geometric configuration, normally parallelepipedic or cuboid, by fold formation along prepared crease lines in the packaging material.
  • the main advantage of this continuous tube-forming, filling and sealing packaging method concept is that the web may be sterilised continuously just before tube-forming, thus providing for the possibility of an aseptic packaging method, i.e. a method wherein the liquid content to be filled as well as the packaging material itself are reduced from bacteria and the filled packaging container is produced under clean conditions such that the filled package may be stored for a long time even at ambient temperature, without the risk of growth of microorganisms in the filled product.
  • an aseptic packaging method i.e. a method wherein the liquid content to be filled as well as the packaging material itself are reduced from bacteria and the filled packaging container is produced under clean conditions such that the filled package may be stored for a long time even at ambient temperature, without the risk of growth of microorganisms in the filled product.
  • Tetra Brik®-type packaging method is, as stated above, the possibility of continuous high-speed packaging, which has considerable impact on cost efficiency.
  • Packaging containers for sensitive liquid food can also be produced from sheet-like blanks or prefabricated blanks of a laminated packaging material.
  • packages are produced by first of all building the blank up to form an open tubular container capsule, of which one open end is closed off by means of folding and heat- sealing of integral end panels.
  • the thus closed container capsule is filled with the food product in question, e.g. juice, through its open end, which is thereafter closed off by means of further folding and heat-sealing of corresponding integral end panels.
  • An example of a packaging container produced from sheet-like and tubular blanks is the conventional so-called gable-top package.
  • packages of this type which have a moulded top and/or screw cap made of plastic.
  • the layer of an aluminium foil in the packaging laminate provides gas barrier properties quite superior to most polymeric gas barrier materials.
  • the conventional aluminium-foil based packaging laminate for liquid food aseptic packaging is still the most cost-efficient packaging material, at its level of performance, available on the market today. Decreasing the costs of today ' s packaging material further, can be made by down-gauging the thickness of the polymer layers or by seeking to replace the aluminium foil barrier by one or more different barrier layers.
  • the paperboard is a major component of liquid carton packaging material, however also representing a major part of the total packaging material costs.
  • One way of producing such a cellulose-based bulk layer, or part of a bulk material is by foam-forming, wherein cellulosic fibres are mixed with a foam and the foam-fibre mixture is distributed on a forming wire where the foam is sucked through the wire so that a fibre web is formed. The fibre web and the foam are thereby separated and then the fibre web is dried using pressing and drying at elevated temperature.
  • the foam is achieved by using a surfactant.
  • the type of surfactant used in foam forming has significant effects on the mechanical properties and quality of the resulting product.
  • Anionic surfactants e.g. SDS, are often cost efficient (low amount of the surfactant is needed to produce high quality foam at a low cost).
  • anionic surfactants have been shown to be inferior to e.g. non-ionic surfactants, e.g. filler retention of foam-formed samples has been shown to be significantly higher when using a non-ionic surfactant instead of an anionic surfactant and the effect of the strength additive (cationic starch) in increasing the strength of foam-formed samples has been shown to be less in the presence of anionic surfactants than with non-ionic surfactants. It is an object of the invention to at least partly overcome one or more of the above-identified limitations of the prior art.
  • the above and other objects of the invention are achieved, in full or in part, by a method as defined by claim 1 .
  • the above object is achieved by a method for manufacturing a foam-formed cellulosic fibre-material comprising the steps of providing an aqueous foam comprising a gas dispersed as bubbles in an aqueous phase, wherein said aqueous phase comprises an anionic surfactant; adding cellulose fibres to the aqueous foam composition, thus forming a fibrous foam composition; adding a retention system to the fibrous foam composition obtained in the step of adding cellulose fibres to the aqueous foam composition, wherein the retention system comprises a combination of cationic polyacrylamide (CPAM) and microparticles; or polyethylene oxide (PEO) and tannic acid (TA); distributing the fibrous foam composition onto a substrate or into a mould; and reducing the amount of water in the distributed fibrous foam composition to obtain the foam-formed cellulosic fibre-material
  • CPAM cationic polyacrylamide
  • any other natural fibre material could be used.
  • the method is not raw-material specific.
  • foam-formed cellulosic fibre-material in its final shape is referred to as board or bulk material.
  • the resulting foam-formed cellulosic fibre-material has a low density, typically below 450 kg/m 3 . Further, the resulting foam-formed cellulosic fibre-material has a relatively high delamination strength, typically at least 100 J/m 2 , preferably at least 140 J/m 2 and even more preferred at least 170 J/m 2 .
  • the first step in producing a foam-formed cellulosic fibre-material involves providing foam comprising cellulose fibres.
  • foam may be produced by mixing cellulose fibres and a foaming fluid comprising a liquid and a surfactant.
  • the liquid may be water.
  • the amount of the surfactant may be from 0.01 to 1000 ppm (weight to weight), such as from 0.01 to 100 ppm, such as from 0.01 to 10 ppm, such as from 0.05 to 10 ppm, such as from 0.1 to 8 ppm.
  • a rotor mixer or a general foam-generator may be used to generate foam comprising cellulosic fibres.
  • the foam may generally be formed by bringing a gas into the mixture. Air is one example of an appropriate gas. Other suitable gases are oxygen and nitrogen. The gas may be brought into the mixture in the form of pressurized gas and by the vortex caused by stirring.
  • the retention system is added with a time interval between each component of the retention system, such that the second component is added after predetermined time interval after the first component is added.
  • the time interval may be between 0 and 40 s, preferably between 0 and 20 s, even more preferred between 0 and 10 s, and most preferably 5 s.
  • CPAM may be added before the microparticles.
  • microparticles may be added before CPAM.
  • PEO may be added before TA.
  • TA may be added before PEO.
  • the surfactant is SDS and TA is added before PEO.
  • the foam is mixed before dewatering from 1 s to 40 s, such as from 1 to 20 s, such as from 5 s to 10 s, such as about 5 s
  • the fibrous foam composition may be distributed into a mould or on to a substrate and subsequently dewatered and dried to obtain a final three-dimensional shape.
  • the fibrous foam composition may be distributed into a mould or on to a substrate and subsequently dewatered and dried to obtain a final three-dimensional shape.
  • the improved internal bond strength i.e. delamination strength
  • the step of reducing the amount of water in the distributed fibrous composition may include dewatering and/or drying.
  • the substrate onto which the fibrous foam composition is distributed may be a wire form or a forming wire. Distribution onto wire form or a forming wire represents one way of dewatering the fibrous foam. After initial dewatering on a forming wire, the foam-formed cellulosic fibre-material (the fibrous web) may be compressed mechanically, in one or several consecutive wet press nips.
  • the resulting dewatered foam-formed cellulosic fibre-material may be dried, using any conventional drying method, such as cylinder drying, impingement drying or Condebelt drying, alternatively equipped with IR (infra red) dryers, to a final moisture content between 0 to 15 % (weight/weight).
  • any conventional drying method such as cylinder drying, impingement drying or Condebelt drying, alternatively equipped with IR (infra red) dryers, to a final moisture content between 0 to 15 % (weight/weight).
  • the cellulose fibres are provided as a liquid dispersion comprising cellulose fibres (a fibre dispersion).
  • concentration of the cellulose fibres in the liquid dispersion comprising cellulose fibres may be 0.1 % to 10 % (weight/weight).
  • the liquid dispersion comprising cellulose fibres may be an aqueous dispersion comprising cellulose fibres.
  • the cellulose fibres may be chemical, chemimechanical or mechanical pulp as soft wood kraft, CTMP or TMP.
  • the cellulose fibres may in an embodiment be or comprise non-wood fibres with vegetable or plant origin, such as for example cotton, bamboo, hemp, bagasse, etc.
  • the fibre dispersion may be added to the foaming fluid after foam has been generated from the fluid (including the surfactant).
  • liquid dispersion comprising cellulosic fibres may be combined with the foaming fluid prior to foaming.
  • the total amount of fibres in the fibrous foam composition may be from 0.1 to 10 wt% (weight/weight), such as from 0.1 to 7 wt%, such as from 0.1 to 5, such as from 0.5 to 5, such as from 0.5 to 4, such as from 0.5 to 3 wt %, based on the total wet foam composition.
  • the foam-formed cellulosic fibre-material of the invention may further comprise additive amounts (such as below 30 wt%) of other materials, such as microfibrillar cellulose, heavily refined hardwood pulp, and/or strength chemicals or agents, such as starch and derivatives thereof, or carboxymethyl cellulose and derivatives thereof .
  • additives may be added to influence the properties of the resulting foam-formed cellulosic fibre-material, e. g. refined hardwood pulp may be added in order to increase the sheet strength.
  • cationic starch may be added in order to increase the sheet strength.
  • Cationic starch may be added at less than 6 wt% of the cellulose composition, preferably at from 0.5 to 5.5 wt%, such as from 1 to 5 wt%, such as from 1 .5 to 4 wt%, such as from 2 to 5 wt%.
  • the anionic surfactant may be sodium dodecyl sulphate (SDS) and/or sodium lauryl ether sulfate (SLES). SDS is also called sodium lauryl sulphate (SLS). Both SDS and SLES are efficient and cost effective surfactants.
  • the surfactant is sodium dodecyl sulphate (SDS).
  • SDS is an anionic surfactant, i.e. it has a negative charge in an aqueous environment. Furthermore, SDS is an efficient and inexpensive surfactant and is widely used in numerous health-safe applications like shampoos and toothpaste, which require a non-toxic surfactant. In addition, SDS is a very efficient foaming agent and thus the required SDS concentration in pulp suspension to form an acceptable foam is low. The required concentration of nonionic surfactants is typically 10 times higher than the required concentration of SDS. Cationic surfactants adsorb to the anionic sites on fibres and thus their concentration in the web is increased, resulting in a product having a higher surfactant content and a decreased strength.
  • PVA polyvinyl alcohol
  • SDS is negatively charged which effects cationic process chemicals, e.g. CPAM (cationic polyacrylamide) (retention chemical), cationic starch (dry strength agent) and AKD (alkyl ketene dimer) (sizing agent) (dispersion stabilized typically with cationic polymers).
  • CPAM cationic polyacrylamide
  • cationic starch dry strength agent
  • AKD alkyl ketene dimer
  • the anionic SDS molecule is aligned so that the anionic end (i.e. the hydrophilic end) is towards the water phase and hydrophobic end is towards the air phase.
  • the air bubbles in the foam have a large surface area with a high negative surface charge.
  • the anionic bubble surface might "compete" with fibres for the adsorption of cationic strengthening aids and cationic retention polymers.
  • anionic air bubbles could probably detach cationic polymers that are already adsorbed on the fibre surfaces, particularly if high shear forces exist in the process. Therefore, detrimental effects depend on the delay times in foam, i.e. how long time the cationic strengthening aids and cationic retention polymers are present in the foam, i.e.
  • cationic starch may be added into thick stock (i.e. the fibre dispersion or the cellulose fibre mixture) before mixing foam with thick stock. Then SDS does not disturb adsorption of cationic starch onto fibres. The delay time in foam should be short because some extent of desorption occurs in foam. High foam density (600 kg/m 3 - 750 kg/m 3 ) promotes cationic starch retention, when compared to lower foam densities. Alternatively, cationic starch may be added into foam at foam density 600 kg/m 3 - 750 kg/m 3 .
  • the delay time of cationic starch in the foam, before dewatering may be 1 s to 40 s, such as 5 s to 20 s, such as 15 s. Under laboratory conditions, longer delay times, such as 1 hour, were used in order to clarify the effects.
  • the amount of the surfactant may be from 0.05 to 10 g/l of liquid, such as from 0.1 to 8 g/l of liquid.
  • the surfactant is SDS and the amount of SDS is from 0.05 to 10 g/l of liquid, such as from 0.1 to 8 g/l of liquid.
  • Retention system and dosing manner may be as described below.
  • Adding a retention system has the effect that less fibres and particles leave the material during the step of reducing the amount of water in the material as they are retained in the material. This increases the quality of the resulting material: as the non- retained material is mostly small by dimensions and well-bonding, its contribution to bonding is significant. In addition, dewatering and the retention of other chemicals are also improved, resulting in savings in raw material and production costs.
  • the additions are preferably made into pipe-line in two separate insertion points with a clear time delay between the points.
  • the time delay between the points may be between 0 and 15 s, preferably between 0 and 10 s, most preferably 5 s.
  • Starch retention may be increased by good solids retention with increased dosage of retentions chemicals.
  • the retention system may be a combination of cationic polyacrylamide (CPAM) and microparticles, the latter may have a negative electrostatic charge and a very high surface area. Addition of CPAM and microparticles has the advantage that it improves the solids retention.
  • CPAM cationic polyacrylamide
  • CPAM may be added in an amount smaller than 1000 g/t of dry solids content. Typically, CPAM may be added in an amount of 300 g/t.
  • microparticles may be polymeric or inorganic or a combination thereof.
  • polymeric microparticle is microparticles of poly(vinylamine).
  • inorganic microparticles are microparticles of bentonite and/or silica.
  • the microparticles may be bentonite. Such micropaticles have the advantage that they are frequently used in conventional paper making and thus cost efficient and readily available.
  • the microparticles may be added in an amount smaller than 2000 g/t of dry solids content. Typically, the microparticles may be added in an amount of 200 g/t to 2000 g/t, such as e.g. 1000 g/t.
  • CPAM When using SDS as the foaming agent and CPAM and microparticles as the retention system, cationic charge of CPAM interacts with foamed SDS and thus the effectivity of the retention system decreases.
  • an increased amount of CPAM (400 g/t -1000 g/t) may be fed into the head-box feed line before microparticle addition when the foam density is 600 kg/m 3 to 750 kg/m 3 .
  • CPAM may be fed into the thick stock (i.e. the fibre dispersion or the cellulose fibre mixture) before mixing foam with thick stock and feeding micro-particles close to head-box into head-box feeding line.
  • the retention system may comprise polyethylene oxide (PEO) and tannic acid (TA).
  • PEO polyethylene oxide
  • TA tannic acid
  • the PEO has a molecular weigth (MW) of 6 ⁇ 10 6 to 8x 10 6 .
  • Polyethylene oxide (PEO) and tannic acid (TA) may be added in amounts smaller than 450 g/t each, of dry solids.
  • PEO may be added in an amount of 450 g/t of dry solids.
  • TA may be added in an amount of 450 g/t of dry solids.
  • PEO may be added in an amount of 300 g/t.
  • TA may be added in an amount of 300 g/t.
  • any compound containing phenolic groups e.g. kraft lignin or formaldehyde resin may be used.
  • Sizing agent(s) such as alkyl succinic anhydride (ASA), alkyl ketene dimer (AKD) and rosin, may be added to the fibrous foam composition to improve the board's (i.e. the foam-formed cellulosic fibre-material) hydrophobicity and thereby its water repelling properties.
  • ASA alkyl succinic anhydride
  • ALD alkyl ketene dimer
  • rosin may be added to the fibrous foam composition to improve the board's (i.e. the foam-formed cellulosic fibre-material) hydrophobicity and thereby its water repelling properties.
  • the sizing agent(s) may be added to the fibrous foam composition in amounts up to 4 kg/tonne of dry solids content.
  • the internal sizing is usually done by adding AKD (alkylketene dimer).
  • the method may further comprise the step of performing hydrophobic sizing by adding alkylketene dimer (AKD), alkyl succinic anhydride (ASA) and/or rosin sizing directly before the step of distributing the fibrous foam composition onto a substrate or into a mould.
  • alkylketene dimer alkylketene dimer
  • ASA alkyl succinic anhydride
  • rosin sizing directly before the step of distributing the fibrous foam composition onto a substrate or into a mould.
  • One advantage of adding the sizing agent at this stage is that the sizing agent has good performance. If added earlier, the surfactant may wash away the sizing agent, resulting in lower hydrophobicity and thus increasing the tendency of the resulting material to absorb liquid when dry.
  • the sizing agent(s) is/are added in a total amount of no more than 4 kg/t of dry solid
  • alkylketene dimer (AKD), alkyl succinic anhydride (ASA) and/or rosin sizing is added less than 20 seconds, preferably less than 10 seconds, such as 7 seconds, before the step of distributing the fibrous foam composition onto a substrate or into a mould.
  • alkylketene dimer (AKD)
  • ASA alkyl succinic anhydride
  • rosin sizing is added less than 20 seconds, preferably less than 10 seconds, such as 7 seconds, before the step of distributing the fibrous foam composition onto a substrate or into a mould.
  • the dose may be 4 kg/t or less of dry solids content.
  • AKD such as Fennosize KD364M
  • dosed at 4 kg/tonne of dry solids content (active substance) or less may be added to the foam as closely as possible before the step of distributing the fibrous foam composition onto a substrate or into a mould.
  • AKD is added less 20 seconds, preferably less than 10 seconds, such as 7 seconds, before the step of distributing the fibrous foam composition onto a substrate or into a mould.
  • This sizing agent works efficiently in SDS foam-forming.
  • the sizing agent is fed into the foam just before the head box.
  • the method may further comprise the step of performing hydrophobic sizing by applying sizing agent by spray on the distributed fibrous foam composition obtained in the step of distributing the fibrous foam composition onto a substrate or into a mould, wherein the sizing agent comprises alkylketene dimer (AKD), alkyl succinic anhydride (ASA) and/or rosin.
  • sizing agent comprises alkylketene dimer (AKD), alkyl succinic anhydride (ASA) and/or rosin.
  • ASA alkyl succinic anhydride
  • the sizing agent(s) is/are added in a total amount of no more than
  • the density of the fibrous foam composition to be reduced from an amount of water may be approximately 600 to 750 kg/m 3 . Further, the average bubble size may be 100 ⁇ or below. Thus, before the amount of water has been reduced in step (e), the density of the fibrous foam composition is approximately 600-750 kg/m 3 . This has the advantage that at this density the anionic surfactant content does not interact too much with the cationic chemicals, ensuring target level strength properties for board. At the same time the foam quality is good enough to produce acceptable formation.
  • the foam-formed cellulosic fibre-material After the amount of water has been reduced (step (e)), the foam-formed cellulosic fibre-material has obtained its final shape and contains no or negligible amount of foam.
  • the density of the foam-formed cellulosic fibre-material preferably is 450 kg/m 3 or less, preferably 250-350 kg/m 3 , such as 300 kg/m 3 .
  • the average bubble size of the fibrous foam composition may be 100 ⁇ or below, such 80 ⁇ or below, such as 60 ⁇ or below. This has the advantage that bubbles keep individual fibres separated and thereby fibre floes are not generated, leading to good formation of the material typically having a specific formation, i.e.
  • the bubble radius may be determined as Sauter mean diameter D [3, 2], using optical measurement and averaging the diameter of measured bubbles.
  • the density of the fibrous foam composition, from which an amount of water is to be reduced may be approximately from 600 to 750 kg/m 3 and the average bubble size may be 100 ⁇ or below.
  • the foam comprising cellulosic fibres generated as described above may be run through a nozzle arrangement ("headbox") where pressure and forming tools generate a web of foam-formed cellulosic fibre-material.
  • Headbox nozzle distributes the fibre foam evenly in cross-direction on a forming wire and subsequent dewatering elements increase the solids content, typically to 15 to 20 % (weight/weight) after the forming section.
  • the web may be mechanically compressed to reach solids content level of 30 to 55%.
  • the web may be dried by using drying units such as hot cylinders, infra-red dryers or Condebelt dryer.
  • base board may be rolled onto a reel, wound to customer-width reels and stored, before future use to prepare for example a packaging material.
  • the foam-formed cellulosic fibre-material is used in-line, i.e. directly applying an additional layer in order to produce a more mechanically stable material, and eventually transform the foam-formed cellulose web to a laminated packaging material for liquid or semi-liquid food packaging.
  • a retention system comprising a combination of cationic polyacrylamide (CPAM) and microparticles is also provided.
  • CPAM cationic polyacrylamide
  • a retention system comprising a combination of polyethylene oxide (PEO) and tannic acid (TA) is also provided.
  • PEO polyethylene oxide
  • TA tannic acid
  • a retention system according to the present invention in a method for manufacturing a foam- formed cellulosic fibre-material is also provided, wherein in the method an aqueous foam comprising a gas dispersed as bubbles in an aqueous phase is provided, wherein said aqueous phase comprises an anionic surfactant.
  • a foam-formed cellulosic fibre-material obtainable by the method according to the present invention is also provided.
  • the foam-formed cellulosic fibre-material comprises cellulosic fibres chosen from the group comprising or consisting of chemi thermomechanical pulps, mechanical pulps like TMP (thermomechanical pulp) and PGW (pressurized ground wood pulp) and chemical pulps like soft wood kraft or any other lignocellulosic fibre material. These cellulosic fibres could be less or heavily refined fibre materials.
  • the foam-formed material may have a density of 200 to 450 kg/m 3 , preferably
  • the foam-formed cellulosic fibre-material may have a density of at most 450 kg/m 3 .
  • the density is 250-350 kg/m 3 , such as 300 kg/m 3 , such as 200 kg/m 3 . Since such a material comprises less cellulosic fibres than conventional material while still having the desired properties needed, the material costs are lower compared to when a conventional material is used for the same application.
  • the foam-formed cellulosic fibre-material according to the present invention has further improved internal bond strength, i.e. delamination strength, as compared to the corresponding foam-formed cellulose not comprising a heavily refined fibre pulp in its composition. In addition, it has also improved resistance to compression in thickness direction.
  • the foam-formed material may have a delamination strength of at least 100 J/m 2 , preferably at least 140 J/m 2 and even more preferred at least 170 J/m 2 .
  • the delamination strength may be 60-300 J/m 2 , such as 60-250 J/m 2 , such as 80-220 J/m 2 , such as 140-220 J/m 2 , such as 170-220 J/m 2 . These values are comparable to the values for conventional materials used in e.g. packaging materials.
  • the foam-formed material may have a density of at most 450 kg/m 3 and a tensile index (MD) of at least 20 Nm/g (kNm/kg).
  • MD tensile index
  • the tensile index is the tensile strength normalized by grammage (g/m 2 ).
  • the foam-formed material may have a compression strength ratio MD/CD between 1 .3 and 4.0, preferably between 2.0 and 3.5, and even more preferred between 2.5 and 3.0.
  • the foam-formed cellulosic fibre-material may have a grammage of at least 20 g/m 2 . In some embodiments the grammage is between 20 and 440 g/m 2 .
  • the foam-formed cellulosic fibre-material according to the present invention may be defined as having a density of at most 450 kg/m 3 , a grammage of at least 20 g/m 2 , an edge wicking index of lower than 1 kg/m 2 , such as 0,5 kg/m 2 or lower, a delamination strength of at least 100 J/m 2 , a compression strength ratio MD/CD between 1 .3 and 4.0, preferably between 2.0 and 3.5, even more preferred between 2.5 and 3.0, a z-strength of at least 150 kPa, and a residual strain of 3 to 8 % with a single loading of 2 MPa.
  • the foam-formed cellulosic fibre-material according to the present invention is thermally stable above 300 °C and has a low heat transfer, as opposed to foamed polymer layers in general. It has been observed that at relatively low densities of from 200 to 450 kg/m 3 , a foam-formed cellulosic fibre-material sheet does not lose too much of its original thickness in extrusion lamination operations, and also sufficiently maintains its initial delamination strength, as well as its tensile strength in z-direction, i.e. z-strength.
  • the foam-formed cellulosic fibre-material according to the present invention may be manufactured according to the method according to the present invention.
  • a cellulose bulk sheet for a packaging material comprises the foam- formed cellulosic fibre-material according to the invention, laminated or arranged in layer contact with a further sheet of a different cellulose material.
  • a bulk sheet has the advantage acting as a core in a sandwich material construction and its higher thickness provides the sandwich composite with high bending stiffness with overall low density, i.e. a high stiffness-to-weight ratio.
  • the bulk layer is structurally strong enough to keep the flanges/skins in their relative positions under loading.
  • the further sheet of a different cellulose material may be a paper. Since the further sheet is thinner and stiffer, it can act as a flange/skin in a sandwich composite that carries in-plane compression and tension loads.
  • the bulk layer or the foam-formed cellulosic fibre-material may have a surface weight grammage of at least 20 g/m 2 . In some embodiments the grammage is between 20 and 440 g/m 2 .
  • a laminated packaging material comprising a foam-formed cellulosic fibre-material according to the invention is also provided, wherein the foam-formed cellulosic fibre-material is laminated to at least one layer of polymer, such as a thermoplastic polymer, such as a polyolefin.
  • Laminated packaging materials may be obtained by various methods for laminating layers together, such as extrusion lamination, wet or dry adhesive lamination, heat-pressure lamination, and may also be including various coating methods.
  • Extrusion lamination is one example which may suitably be used to produce laminated packaging materials, in particular carton-based packages used for food such as liquid and semi-liquid food.
  • the laminated packaging material may further comprise an oxygen barrier. This has the advantage that a package made from the packaging material can be used to package goods that are sensitive to oxygen.
  • the oxygen barrier layer may be an aluminium foil.
  • the thickness of the aluminum foil is 3-15 ⁇ , such as 5-10 ⁇ , such as 5-8 ⁇ .
  • the barrier layer is a barrier film or coating.
  • the delamination strength of the packaging material may be 60-300 J/m 2 , such as 60-250 J/m 2 , such as 80-220 J/m 2 , such as 140-220 J/m 2 , such as 170-220 J/m 2 .
  • a laminated packaging material comprises a bulk layer, comprising a material from a foam-formed cellulosic fibre- material, also called foamed cellulose.
  • the bulk material layer can be arranged to provide for the most efficient contribution to the flexural rigidity of a laminate.
  • the bulk layer may thus be appropriately selected in order to obtain the desired stiffness suitable for the type of packaging container and the intended food product.
  • a bulk layer comprising foam-formed cellulosic fibre-material according to the present invention provides necessary delamination strength in combination with compression strength in the thickness direction, which provides sufficient distance between a barrier layer and an outermost thermoplastic layer of the packaging material.
  • a suitable bulk may thus comprise mainly or only the foam-formed cellulosic fibre-material, and accordingly has approximately, or exactly the same physical properties as the foam-formed cellulosic fibre-material according to the invention.
  • the bulk layer may further comprise an additional, integrated, flange or facing layer of a cellulose-based material, such as a thin paper, having higher tensile stiffness and a higher density, in order to provide sandwich constructional features within the bulk layer itself.
  • a cellulose-based material such as a thin paper, having higher tensile stiffness and a higher density
  • the layer of foam-formed cellulosic fibre-material may be laminated or arranged to be in contiguous layer contact with at least one facing paper layer, within the bulk layer.
  • the final laminated packaging material may comprise a bulk layer of the foam- formed cellulosic fibre-material and at least one additional, different cellulose material layer, such as a thin paper or a downgauged paperboard facing layer, the layers being laminated by subsequent lamination operations in the manufacturing of the laminated packaging material.
  • a multilayered bulk layer may be a laminate of individual layers produced independently and subsequently attached to each other.
  • a multilayered bulk may be formed already in the paper manufacturing machine.
  • a layer of foam-formed cellulosic fibre-material can be formed by one headbox (a nozzle arrangement), while another paper layer, or layer from different cellulose fibres, may be formed by another headbox in the same machine.
  • the use of multiple headboxes in the same paper machine is well known in the field of paper making. It is also possible to use a stratified head box to form the layers of a multilayered product.
  • the bulk layer or the foam-formed cellulosic fibre-material according to the invention may have a surface weight grammage of at least 20 g/m 2 .
  • the grammage is from 20 to 440 g/m 2 , such as from 25 to 350 g/m 2 , such as from 45 to 250 g/m 2 , such as from 60 to 220 g/m 2 , such as from 60 to 200 g/m 2 .
  • the optimal density of foam-formed cellulosic fibre- material to be used in laminated packaging materials is from 200 to 450 kg/m 3 , in particular from 200 to 400 kg/m 3 , such as from 300 to 400 kg/m 3 .
  • the bulk layer may have a thickness from 80 to 1 100 ⁇ , such as from 90 to 800 ⁇ , such as from 150 to 600 ⁇ , such as from 200 to 550 ⁇ , such as from 250 to 350 ⁇ .
  • the bulk layer may comprise the foam-formed cellulosic fibre-material as bulk material.
  • the bulk layer may be characterized by a density less than 700 kg/m 3 , such as from 100 to 600 kg/m 3 , such as from 100 to 500 kg/m 3 , such as from 200 to
  • 500 kg/m 3 such as from 300 to 500 kg/m 3 , such as from 300 to 400 kg/m 3 , such as from 200 to 400 kg/m 3 , such as from 200 to 300 kg/m 3 .
  • the foam-formed cellulosic fibre-material may provide at least 20 %, such as at least 25 % such as at least 30 %, such as at least 40% of the thickness of the bulk layer.
  • the percentages may be determined by examining the cross-section of the packaging material in a microscope.
  • the bulk layer may be comprised of foam-formed cellulosic fibre-material, thus not really constituting in itself a bulk layer, but rather a spacer layer for a final laminate or sandwich configuration, and the bulk spacer layer may have a density less than 450 kg/m 3 , preferably 200-300 kg/m 3 .
  • the bulk layer which includes a foam-formed cellulosic fibre-material layer and optionally an additional cellulose layer, may be provided with coatings such as for example clay coating, or may be surface modified. Such coatings or surface modifications may also be suitable for application to an additional layer, which is for example intended for printing, and arranged between the bulk layer (optionally including an additional cellulose layer) and the outermost heat sealable polymer layer.
  • the bulk layer optionally including an additional layer, such as a thin paper facing layer, can be surface modified or there may be an adhesive or binding layer in order to facilitate the compatibility and bonding between the bulk layer and additional layers.
  • the bulk layer may be surface-treated or surface-coated in order to improve adhesion and compatibility between surrounding layers of the packaging laminate, and/or to obtain additional desired properties such as improved stiffness.
  • Such surface treatment may be provided by means of exposure of the material surface to corona, ozone or flame treatments, or the like.
  • a laminated packaging material according to the invention may comprise a bulk layer comprising the foam-formed cellulosic fibre-material according to the invention, and at least one thermoplastic material layer laminated thereto.
  • the thermoplastic layer may be covering and protecting the cellulose-based bulk layer and may constitute an outer heat-sealable side of the laminated packaging material.
  • the side of the bulk layer which is to become the outer side of the closed and sealed packaging container may be printed with a decorative ink pattern, and subsequently coated by a thermoplastic, outer, liquid-tight and heat sealable layer.
  • the bulk layer may thus provide an opportunity to incorporate a foam-formed cellulosic fibre-material into a laminated packaging material suitable for preparing packaging containers for food products, especially for liquid and semi-liquid food products.
  • Lamination of the bulk layer and the bulk material of foam-formed cellulosic fibre-material to polymer layers may be carried out by melt extrusion operations, like extrusion coating and extrusion lamination of the plastic layers.
  • the extrusion may generally be performed at high temperatures such as, in the case of low density polyethylenes, up to about 330°C. Such temperatures have been shown not to become a major problem for a bulk layer comprising the foam-formed cellulosic fibre-material according to the present invention. This is in contrast to the case of bulk layers of foamed polymer layers, for which it has been shown that the polymer core collapses during extrusion coating, see WO2015/181281 .
  • the bulk layer may provide a distance between a barrier layer and an outermost thermoplastic heat sealable polymer layer, and thereby enables tailor-made laminated packaging material structures.
  • the laminated packaging material may comprise an additional layer between the outermost thermoplastic layer and the bulk layer.
  • the additional layer can for example be a paper or paperboard layer or a polymer film.
  • the additional layer may contain a print on the side which is to become the outside of the packaging container.
  • a grammage of at least 20 g/m 2 and in some embodiments between 20 and 100 g/m 2 are suitable.
  • the paper layer may be coated with a white coating or clay coating layer to improve the whiteness of the surface.
  • the additional layer is a polymer film its thickness preferably is 10-50 ⁇ . Examples of suitable films are oriented pre-manufactured films such as BOPP (biaxially oriented polypropylene), BoPET (biaxially oriented
  • polyethylene terephthalate polyamide
  • polyamide polyamide
  • oriented high density polyethylene films polyethylene terephthalate films
  • the additional layer may be selected from a paper layer having a grammage of between 20 and 100 g/m 2 and a polymer film having a thickness of 10-50 ⁇ .
  • the thickness of the outer layer of the packaging material, directed towards the outside of a package made from the material may for example be 5 ⁇ ⁇ , such as 7 ⁇ 30 ⁇ , such as 7 ⁇ ⁇ -20 ⁇ , such as 8 ⁇ ⁇ -15 ⁇ ⁇ .
  • thermoplastic layer When the outermost thermoplastic layer is covering the decorative print pattern, it has to be transparent so that the printed decor is well visible to the outside of the package without being deteriorated by the plastic layer quality.
  • a barrier layer may be arranged, for example by means of an intermediate laminate layer which may be a polyolefin-based layer of for example HDPE, LDPE, polypropylene, or another suitable thermoplastic polymer layer such as ethylene-acrylic acid copolymer (EAA), which further facilitates adhesion between the bulk layer and the oxygen barrier.
  • an intermediate laminate layer which may be a polyolefin-based layer of for example HDPE, LDPE, polypropylene, or another suitable thermoplastic polymer layer such as ethylene-acrylic acid copolymer (EAA), which further facilitates adhesion between the bulk layer and the oxygen barrier.
  • EAA ethylene-acrylic acid copolymer
  • the bulk layer and/or the barrier layer is treated or modified in order to achieve adhesion between the layers, in which case the laminate layer may not be needed.
  • a coating which modifies the surface of one or more of the substrates may be used.
  • the laminate layer may be applied by an extrusion process using commercially available extrusion equipment.
  • Materials suitable as laminate layer are known and conventionally comprise a polyolefin.
  • the laminating material may comprise a polyethylene or blends thereof.
  • the properties of laminating layers can be varied and tailored in order to achieve various final properties in a packaging material. Variations of the laminate layer for the desired type of packaging material for liquid and semi- liquid foods are thus found largely within the group of polyethylene polymers.
  • the thickness of the laminate layer of the packaging material may be 5 ⁇ -50 ⁇ , such as 10 ⁇ -30 ⁇ , such as 15 ⁇ -30 ⁇ , such as 17 ⁇ -25 ⁇ .
  • the barrier layer such as oxygen barrier layer (e.g. aluminium foil or a polymer film such as a vapour deposition coated thermoplastic film) may be arranged by means of the laminate layer on the side opposite the bulk layer.
  • oxygen barrier layer e.g. aluminium foil or a polymer film such as a vapour deposition coated thermoplastic film
  • the barrier layer may have an adhesive on the side opposite the optional laminate layer.
  • the adhesive is within the capacity of those skilled in the art to select depending on desired properties and compatibility with the layer with which it is in contact.
  • an example of adhesive is ethylene copolymers with comonomers having carboxylic acid functionality such as ethylene acrylic acid copolymer, for example marketed under the tradename Primacor® by Dow or Nucrel® by Dupont.
  • the adhesive layer of the packaging material according to the invention may have a thickness of 3 ⁇ >12 ⁇ , such as 4 ⁇ >10 ⁇ such as 5 ⁇ -9 ⁇ .
  • the adhesive layer may be characterized by different methods including for example infrared spectroscopy (IR).
  • the packaging material may further contain an innermost heat-sealable layer.
  • a heat-sealable layer is a heat-sealable polyolefin polymer which is applied as a layer to be directed towards the inside of the container, i.e. in direct food contact.
  • the heat-sealable layer for the innermost layer may be a polyethylene polymer of the low density type, selected from the group consisting of LDPE, LLDPE, VLDPE, ULDPE or mLLDPE and blends of two or more thereof.
  • the arrangement of the heat- sealable layer is similar to the laminate layer and what was disclosed above in connection with the laminate layer applies also to the heat-sealable innermost layer.
  • polypropylene or propylene co- or ter-polymers are conceivable within the scope of the invention as long as they are compatible with and achieve the desired effect in combination with other components of the packaging material and in particular the adhesive as described herein.
  • Suitable examples to be used as innermost layers are blends between LDPE and mLLDPE (e.g. 50/50, 40/60, 60/40, 30/70, 70/30, 20/80, 80/20 weight% blend ratios), such as LDPE of extrusion grade.
  • the thickness of the innermost layer of the packaging material is for example 5 ⁇ -50 ⁇ , such as 10 ⁇ -30 ⁇ , such as 15 ⁇ -30 ⁇ , such as 17 ⁇ -25 ⁇ .
  • the different layers present in the packaging material are possible to detect, for example by microscopy. It may not be possible to separate one or more of the layers, for example the adhesive from the heat-sealable layer, and thus in certain embodiments the layer forming the inside of the packaging container may be a combination of the adhesive and the heat-sealable layer where the heat-sealable layer is facing the liquid or semi-liquid food product.
  • the above mentioned layers of the packaging material are conventionally applied to the respective side of the bulk material by extrusion coating and extrusion lamination techniques.
  • the packaging material may comprise an additional layer between the bulk layer and the outermost heat-sealable decor-covering layer.
  • This additional layer may have a surface weight grammage of at least 20 g/m 2 .
  • the additional layer may be a paper layer or a polymer layer or polymer film.
  • the additional layer may be surface coated or surface modified in order to increase adhesion to the adjacent layers.
  • a binding layer may be present.
  • the binding layer may be selected from materials listed under the description of the laminate layer.
  • the packaging material may be transformed into a packaging container.
  • the packaging container may be an aseptic packaging container.
  • the packaging container may be a packaging container for liquid or semi-liquid food.
  • a packaging container formed from the packaging material according to the invention may be of any known shape.
  • the container may be a substantially brick- or wedge-shaped container that is durable when exposed to handling and distribution and resistant to moisture and oxygen gas during long term storage, due to the high quality packaging material, which in turn also provides for sufficient seal quality and gas barrier properties.
  • paperboard-based packages for liquid packaging where the invention may be useful is a brick shaped packaging container, a gable top packaging container, a wedged-shape packaging container, a square-, rectangular- or octagonal- based packaging container. More specific examples are the so called, Tetra Brik®, Tetra Brik® Aseptic, Tetra Brik® Edge, Tetra Gemina® Aseptic, Tetra Prisma®
  • Tetra Rex ® Aseptic, Tetra Rex ®, and Tetra Top® and Tetra Evero® packages or other kinds of bottle-like packages comprising a sleeve of the paperboard-based packaging material.
  • the package may relate to a Tetra Brik® package of a known size such as 200 ml, 250 ml, 500 ml, and 1000 ml which optionally may have a squared base, or a slanted top such as for example Tetra Brik® Edge.
  • the present invention relates to a packaging container comprising the laminated packaging material according to the invention.
  • the invention relates to a packaging container intended for liquid or semi-liquid food packaging, comprising the laminated packaging material.
  • Figure 1 shows an equipment for evaluating retention systems efficiency in foam forming with DDJ (Dynamic Drainage Jar).
  • DDJ Dynamic Drainage Jar
  • Figure 2 shows the turbidity of DDJ filtrates of pulp suspensions wherein different retention systems were used at different concentrations of SDS. Filled diamonds represent pulp suspensions to which no retention system was added; filled squares represent pulp suspensions to which CPAM was added before the
  • microparticles were added; filled triangles represent pulp suspensions to which PEO was added before TA was added; and ⁇ denote pulp suspensions to which TA was added before PEO was added.
  • the dose of each retention aid component, i.e. CPAM, microparticles, PEO and TA was 0.3 kg/t of dry pulp.
  • Figure 3 shows the turbidity of DDJ filtrates of pulp suspensions with different retention systems at high shear forces.
  • Figure 4 shows the grammage of sheets having been prepared using different retention systems and different types of cationic starch (CS).
  • the variables were cationic starch quality (charge density), mixing time and retention system.
  • Figures 5a and 5b show the effect of different retention systems and different cationic starches on tensile index, i.e. tensile strength normalized by grammage (g/m 2 ) (Fig. 5a) and on delamination resistance (Fig. 5b).
  • Figures 6a to 6d show the effect of different retention systems and different cationic starches on stretch (Fig. 6a), tensile stiffness index, (Fig. 6b), modulus of elasticity (Fig. 6c) and on compressive strength (Fig. 6d).
  • Figures 7a and 7b are cross-sectional views of laminated packaging materials according to the present invention.
  • a “foam-formed cellulosic fibre-material”, “foamed cellulose material”, “foamed cellulose” or a “foam-formed material of cellulose fibres” is a material that provides volume or thickness to an article from the material, without necessarily adding a lot of weight, i.e. by having a higher bulk property than conventional fibrous papers or paperboards.
  • foam property is the inverse of the material ' s density.
  • foamed cellulose is a fibrous material, with tunable density, that can be manufactured by a foam forming process.
  • Delamination is when a material separates into different layers. Delamination is a mode of failure for fibrous materials like paperboard where fibre layers and fibres separate leading to significant loss of mechanical properties.
  • the “delamination strength” can be characterised by the internal bond strength of the material and can be determined by for example the Huygen Internal Bonding Energy testing device which follows TAPPI T569 and provides a value of J/m 2 . Paper materials are subjected to out-of-plane loading in many converting operations, such as in printing, creasing, lamination, splicing and folding, which may result in delamination.
  • the "internal bond strength" measured by a Scott Bond type test, may correlate with the "delamination resistance" of the paper material in such converting operations.
  • Internal bond strength (J/m 2 ) is defined as the energy per unit in-plane area required to delaminate a paper material in the through-thickness direction, i.e. z- direction, in a Scott Bond type test.
  • compression strength of board is the maximum compressive force per unit width that a test piece can withstand until the onset of failure. It is expressed in kilonewtons per metre (kN/m). Measurement standard ISO 9895:2008.
  • compression strength ratio MD/CD is determined as the ratio of machine directional (MD) compression strength to cross directional (CD) compression strength, which are both measured according to standard ISO 9895:2008
  • Z-strength is thickness directional tensile strength, measurement standard ISO
  • EWI Erdge wicking index
  • the "ply grammage" of a layer in a laminated packaging material is the weight per unit area in g/m 2 of that layer.
  • Thickness is the distance between two flat surfaces, which are placed on each side of a paper material and subjected to a pressure of 100 kPa. It is expressed in micrometers ( ⁇ ).
  • a “bulk layer” or a “core layer” is a layer that contributes largely to the mechanical rigidity and strength properties and dimensional stability properties, of a laminated material. This is normally the thickest layer of a laminated (sandwich) material, without necessarily being the strongest or densest material. In a stiff sandwich material, there is often a "bulky” distancing or spacer layer in the center, between two flange layers, i.e. facing layers, which contribute to the total stiffness of the construction by their Young ' s modulus and/or higher tensile stiffness properties. The grammage of the bulk layer is assessed in accordance with ISO 536.
  • the bulk layer thickness can be assessed by microscopy or by a ply grammage method, as discussed herein below.
  • the grammage of a bulk layer in a laminated packaging material is calculated as the difference between the total grammage and the ply grammages of the polymer and aluminium foil layers.
  • low density in connection with a cellulose material or bulk material for a laminated packaging material for liquid packaging, means a density which is lower than that of normal paperboard or carton for that purpose, i.e. ultimately lower than 900 kg/m 3 , such as lower than 700 kg/m 3 , such as from 100 to 600 kg/m 3 , such as from 100 to 500 kg/m 3 , such as from 200 to 500 kg/m 3 , such as lower than 450 kg/m 3 .
  • a "thickness" referring to the packaging material, a packaging container, or layers thereof, is, unless otherwise defined, determined by microscopy, for example by a suitable microscope such as those marketed under the name Olympus, for example BX51 .
  • Liquid or semi-liquid food generally refers to food products having a flowing content that optionally may contain pieces of food.
  • Dairy and milk, soy, rice, grains and seed drinks, juice, nectar, still drinks, energy drinks, sport drinks, coffee drinks, tea drinks, coconut water, wine, soups, jalapenos, tomatoes, sauce (such as pasta sauce), beans and olive oil are some non-limiting example of food products contemplated.
  • Aseptic in connection with a packaging material and packaging container refers to conditions where microorganisms are eliminated, in-activated or killed or where the level of microorganisms is significantly reduced.
  • microorganisms are bacteria, spores and yeasts.
  • an aseptic process is used when a product is aseptically packed in a packaging container.
  • heat-sealing refers to the process of welding one surface of a thermoplastic material to another thermoplastic surface.
  • a heat-sealable material should, under the appropriate conditions such as when sufficient heating and pressure are applied, be able to generate a seal when pressed against and in contact with another suitable thermoplastic material.
  • Suitable heating can be achieved by induction heating or ultrasonic heating or other conventional contact or convection heating means, e.g. hot air.
  • a stirrer 1 is placed in a jar 2 having a 100 mesh wire 3 and a valve 4, and wherein a tube 5 connects the jar 2 via the valve 4 with a suction flask 6 which can be evacuated.
  • DJJ Dynamic Drainage Jar
  • a tube 5 connects the jar 2 via the valve 4 with a suction flask 6 which can be evacuated.
  • 500 mL of a pulp suspension is added at consistency of 0.5% into jar 2.
  • the stirrer blade of the stirrer 1 is placed at the "height" of 250 ml.
  • 0.4 mL of a defoamer such as a silicone defoamer, is transferred to suction flask 6.
  • a foam is created by stirring the suspension in the jar 2 at high shear 1400 rpm with foaming agent until the density of 500g/l is reached, whereafter the stirring speed is lowered tol OOOrpm.
  • the retention system to be tested is added with an interval of 5 s between each component of the retention system.
  • the stirrer 1 is turned off and the suction flask is evacuated 5 s after the last addition of component of the retention system. All the foam is suck into suction flask 6 where foam is killed by defoamer. Air is removed from filtrate with vacuum. A filtrate sample is removed and analysed with a turbidity meter. The turbidity is expressed as NTU (Nephelometric Turbidity Units).
  • Grammage (in (g/m 2 ) was determined using a version of ISO 536 having less samples and smaller samples size. Circular test pieces with an in-plane area of 100 ⁇ 1 cm2 were produced using a cutting device (disc cutter or punch). Five circular test pieces were each weighed on a balance reading to an accuracy of ⁇ 0.5%. The grammage of each test piece was calculated by dividing the mass of the test piece by the in-plane area.
  • Thickness (the distance (in ⁇ ) between the two flat surfaces, which are placed on each side of the paper material and subjected to a pressure of 100 kPa) is determined using a version of ISO 534 wherein fewer samples were analysed, but several spots per sample were measured. Circular test pieces with an in-plane area of 100 ⁇ 1 cm 2 were produced using a cutting device (disc cutter or punch). Five test pieces were produced for each sample. For each test piece, the thickness was measured as dead-weight micrometer in accordance with ISO 534 in three different spots and the test piece thickness was evaluated as the average value of these three measurements.
  • Tensile properties were determined using a version of ISO 1924:3. Test piece of a given dimension, 15 mm wide and long enough (>150 mm) were strained to break at a constant rate of elongation (100 mm/min) using a testing machine that
  • test pieces were used for each sample in accordance with ISO 1924:3.
  • Modulus of elasticity was determined according to ISO 1924-2:2008.
  • Compression strength (short-span compression test (SCT)) was determined using a version of ISO 9895 wherein 10 samples in each directions were tested. A test piece, 15 mm wide and > 70 mm long was clamped between two clamps, spaced 0.70 mm apart, which were forced towards each other until a compressive failure occurred. The maximum force was measured and the compression strength was calculated. The paper or board was tested on 10 test pieces in MD and 10 test pieces in CD direction separately.
  • Edge wicking in lactic acid 23°C, 1 h is determined as follows. Water resistant tape (e.g. Scotch El-tape no. 5 from 3M) was applied on both sides of the sample (wrinkles were avoided). A cutting device was used to cut out 1 set of 5 test pieces, 75 mm (CD) x 25 mm (MD), and the pieces were marked accordingly. The 5 pieces were weighed together, and the result was rounded down/up to the nearest mg. 1 % (volume/volume) lactic acid solution was prepared and poured into a vessel (247x395 mm) to a level of 10 ⁇ 1 mm. The vessel was of plastic or stainless steel. The temperature in the vessel was held at 23 °C ⁇ 1 °C.
  • Water resistant tape e.g. Scotch El-tape no. 5 from 3M
  • test pieces were removed after 1 h ⁇ 2 min and placed between two blotting papers.
  • a brass-roller (face width 200 mm and weight 10 ⁇ 0.5 kg) was moved once back and forth over the test pieces between the blotting papers without applying any extra pressure.
  • the test pieces were weighed together, and the result was rounded down/up to the nearest mg.
  • the edge wicking index was calculated as
  • Delamination resistance is determined as follows. A test piece was cut out and mounted between a steel anvil and an L-shaped aluminium bracket using double- sided adhesive tape. A specific pressure was subjected to the metal plates to ensure repeatable bonding and a pendulum was released from an initial horizontal position and allowed to hit the L-shaped bracket when reaching its vertical position, causing the test piece to delaminate. The consumed energy by the delamination process was evaluated by recording the peak excess swing of the pendulum. The internal bond strength was calculated as the recorded energy divided by the in-plane area of the test piece.
  • Residual z strain (the residual strain in z-direction (thickness direction)) after a specified load on the sample was determined with a Lloyd LR10K loading device.
  • the sample area exposed to loading was 15.2 cm 2 , with a circular radius of 22 mm.
  • the board sample was placed onto the loading table and a maximum pressure of 2 MPa (force 3041 N) was applied on the sample for a period of 1 s.
  • the relative change was calculated with the initial thickness of the sheet (measured with a separate standard device) and the reading of displacement sensor showing the absolute thickness change in the compression.
  • the residual strain was determined as the point where there was no additional clear drop in the loading force. At least five parallel measurements were carried out in separate points.
  • the residual strain measurement can also be made with sequential loadings, reporting the magnitude of thickness change after each loading.
  • Fig. 1 shows an equipment (Dynamic Drainage Jar, DJJ), used for the analysis of a retention system's efficiency in foam forming, wherein a stirrer 1 is placed in a jar 2 having a 100 mesh wire 3 and a valve 4, and wherein a tube 5 connects the jar 2 via the valve 4 with a suction flask 6 which can be evacuated.
  • DJJ Dynamic Drainage Jar
  • Fig. 2 shows the effect of SDS amount on turbidity (value is relative to the amount of solids that went through the 100 mesh wire) for different retention systems.
  • the pulp contained 80% chemithermomechanical pulp (CTMP) and 20% heavily refined hardwood pulp (hrHW).
  • CTMP chemithermomechanical pulp
  • hrHW heavily refined hardwood pulp
  • the turbidity was measured using nephelometer and result is expressed as nephelometric turbidity units (NTU). High turbidity means low retention.
  • the amount of surfactant (SDS) had no effect on turbidity in these test points.
  • CS cationic starch
  • Cationic starch is added to the fibre suspension (the furnish) in order to increase the sheet strength.
  • Cationic starch may be added at less than 6 wt%
  • Table 1 The effect of different retention systems and different cationic starch charge density on sheet properties with short and long reaction time.
  • the grammage was 90 g/m 2 .
  • Furnish was a mixture of CTMP 600 (90%) and hrHW (10%).
  • Fig. 4 clearly demonstrates that the grammage of sheets is lower than the set target (90 g/m 2 ) with long mixing time. This is seen for all tested retention systems for all tested types of CS and for both retention systems. This effect may be as a result of lower retention.
  • the structure of foam may be different after long mixing time compared to after short mixing time, although the foam density is the same if average bubble size is not equal.
  • Fig. 6a shows that the CPAM + MP system gave the best results for stretch for both Raisamyl 70021 and Raisamyl 80021 at short mixing time in foam.
  • the CPAM + MP system gave better tensile stiffness index than the PEO + TA system with Raisamyl 70021 , whereas there was no difference in tensile stiffness indices for the two retention systems when used with Raisamyl 80021 .
  • the tensile stiffness index is tensile stiffness normalised by grammage.
  • Fig. 6c shows that for Raisamyl 80021 , both retention systems increased the modulus of elasticity after a short mixing time.
  • Fig. 6d shows that for Raisamyl 70021 , 80021 and 90621 , a shorter delay time in foamincreased the compressive strength. It also shows that the compression strength is further improved by the TA + PEO retention system.
  • Fig. 7a schematically shows a cross-section of an example of a laminated packaging material.
  • the outer, decor-covering layer (21 ) is a polyolefin such as a suitable PE or PP or blends or copolymers thereof.
  • the outer layer may be used to provide cover of a printed pattern, a hole and/or weakening (not shown in the figure) which is provided in the bulk layer (22), which layer is arranged on one side of the outer layer (21 ).
  • an additional layer (27) of paper or cellulose is arranged between the outer layer (21 ) and the bulk layer (22) between the outer layer (21 ) and the bulk layer (22) between the outer layer (21 ) and the bulk layer (22) an additional layer (27) of paper or cellulose is arranged.
  • the bulk layer (22), on the side opposite the outer layer, has a laminate layer (23) selected from suitable polyolefins such as PE or PP or blends or copolymers thereof.
  • the laminate layer provides adhesion to the oxygen barrier (24), which is arranged on the opposite side of the laminate layer (23).
  • the barrier layer (24) provides the desired barrier such as oxygen, light, water and vapour barrier depending on the specific need determined by the product to be packed.
  • the barrier layer can for example be an aluminium foil or a vapour deposited film, such as a metallized or vapour deposition coated film, such as a PECVD (plasma enhanced chemical vapour deposition) coated film.
  • an adhesive polymer (25) is arranged on the barrier layer.
  • the adhesive (25) may for example be applied by extrusion coating.
  • the adhesive could be a suitable ethylene (meth)acrylic acid copolymer (E(M)AA) adhesive marketed under the tradename Primacor ® or Nucrel®.
  • E(M)AA ethylene (meth)acrylic acid copolymer
  • the adhesive is provided with a heat-sealable layer (26) such as a suitable polyolefin such as PE or PP or blends or copolymers thereof.
  • the heat-sealable layer is the layer facing the product in the finished packed packaging container.
  • Fig. 7b schematically shows a cross-section of a second example of a laminated packaging material.
  • the outer layer (21 ) (to be directed towards the outside of a package made from the material) is a polyolefin such as a suitable PE or PP or blends or copolymers thereof.
  • the outer layer may be used to provide cover for a printed pattern, a hole and/or weakening (not shown in the figure) which is provided in one or more of the other layers of the laminate.
  • a thin paper (27) of a surface weight of about 100 g/m2 or lower is arranged.
  • the thin paper layer (27) is laminated to a bulk layer (22), opposite the outer layer, by an intermediate thermoplastic outer binding layer (28).
  • the binding layer (28) may be selected from suitable polyolefins such as PE or PP or blends or copolymers thereof.
  • the binding layer (28) binds the bulk cellulose layer (22) and the thin paper layer (28) together.
  • the bulk layer (22), is further laminated to a laminate layer (23) of
  • the laminate layer (23) provides adhesion to an oxygen barrier layer (24), which is arranged on the opposite side of the laminate layer (23).
  • the barrier layer (24) provides the desired barrier such as oxygen, light, water and vapour barrier depending on the specific need determined by the product to be packed.
  • the barrier layer can for example be an aluminium foil or a vapour deposited film, such as a metallized or vapour deposition coated film, such as a PECVD coated film.
  • an adhesive polymer (25) is arranged on the barrier layer.
  • the adhesive (25) may for example be applied by extrusion coating.
  • the adhesive could be a suitable ethylene (meth)acrylic acid copolymer (E(M)AA) adhesive marketed under the tradename Primacor® or Nucrel®.
  • E(M)AA ethylene (meth)acrylic acid copolymer
  • the adhesive is provided with a heat-sealable layer (26) such as a suitable polyolefin such as PE or PP or blends or copolymers thereof.
  • the heat-sealable layer is the layer facing the product in the finished packed packaging container.
  • a packaging material according to the present invention may be a laminate packaging material which comprises an outermost thermoplastic, heat sealable decor- covering layer which on one side of the layer has a bulk layer comprising the foam- formed cellulosic fibre-material of the invention, which bulk layer on the side opposite the decor-covering layer has a laminate layer, said laminate layer, on the side opposite the bulk layer has an oxygen barrier, and said oxygen barrier, on the side opposite the laminate layer has a heat-sealable layer.
  • a laminated packaging material may comprise a bulk layer having a density of less than 700 kg/m 3 and comprising foam-formed cellulosic fibre-material according to the present invention.
  • the packaging material further comprises an additional layer arranged by means of a binding layer, such as for example a thermoplastic polymer binding layer, such as a polyolefin-based polymer or copolymer binding layer, wherein the binding layer is arranged between the bulk layer and the additional layer.
  • the additional layer has a decorative printed pattern arranged on the side opposite the binding layer.
  • the bulk layer is provided with a barrier layer on the side opposite the binding layer.
  • a barrier layer may be provided with a heat-sealable layer on the side opposite from the bulk layer.
  • the outermost layer covering the printed decorative pattern is a polyolefin layer, such as an outermost heat-sealable polyolefin layer to be in contact with the surroundings of a packaging container, for example low density polyethylene (LDPE) or polypropylene.
  • LDPE low density polyethylene
  • the outermost thermoplastic layer provides additional protection, e.g. moisture resistance and scratch/wear resistance, and stability to the packaging container.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Paper (AREA)
  • Laminated Bodies (AREA)

Abstract

L'invention concerne un procédé de fabrication d'un matériau fibreux cellulosique formé en mousse. Elle concerne en outre des systèmes de retenue et leur utilisation. Elle concerne en outre un matériau fibreux cellulosique formé en mousse, une feuille cellulosique en vrac pour matériau d'emballage, et un matériau d'emballage stratifié comprenant le matériau fibreux cellulosique formé en mousse.
PCT/EP2017/076146 2017-03-24 2017-10-13 Procédé de fabrication d'un matériau fibreux cellulosique formé en mousse, feuille en vrac et matériau d'emballage stratifié comprenant le matériau fibreux cellulosique WO2018171914A1 (fr)

Applications Claiming Priority (2)

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EP17162841 2017-03-24
EP17162841.5 2017-03-24

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WO2018171914A1 true WO2018171914A1 (fr) 2018-09-27

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Cited By (7)

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SE1951497A1 (en) * 2019-12-18 2021-06-19 Stora Enso Oyj Coated paper or paperboard
SE2050753A1 (en) * 2020-06-24 2021-12-25 Stora Enso Oyj Water-resistant paper or paperboard
US11255051B2 (en) 2017-11-29 2022-02-22 Kimberly-Clark Worldwide, Inc. Fibrous sheet with improved properties
US11313061B2 (en) 2018-07-25 2022-04-26 Kimberly-Clark Worldwide, Inc. Process for making three-dimensional foam-laid nonwovens
US11591755B2 (en) 2015-11-03 2023-02-28 Kimberly-Clark Worldwide, Inc. Paper tissue with high bulk and low lint
CN115748307A (zh) * 2022-11-24 2023-03-07 中国海诚工程科技股份有限公司 一种叠式泡沫薄板成型绿色包装材料及其制备方法
SE2151606A1 (en) * 2021-12-22 2023-06-23 Stora Enso Oyj Free-standing wet low-density cellulose fibre foam

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EP1185736A1 (fr) * 1999-03-31 2002-03-13 Pulp and Paper Research Institute of Canada Agent de retention comprenant du peo
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EP2949597A1 (fr) * 2014-05-28 2015-12-02 Tetra Laval Holdings & Finance S.A. Matériau d'emballage et contenant d'emballage
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EP0963485A2 (fr) * 1997-02-05 1999-12-15 Akzo Nobel N.V. Collage pour la production de papier
US6033524A (en) * 1997-11-24 2000-03-07 Nalco Chemical Company Selective retention of filling components and improved control of sheet properties by enhancing additive pretreatment
EP1185736A1 (fr) * 1999-03-31 2002-03-13 Pulp and Paper Research Institute of Canada Agent de retention comprenant du peo
JP2006028654A (ja) * 2004-07-13 2006-02-02 Meisei Kagaku Kogyo Kk 熱発泡性シート及びその製造方法、並びに当該熱発泡性シートを用いた低密度発泡シートの製造方法
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EP2781652A1 (fr) * 2013-03-20 2014-09-24 Ahlstrom Corporation Non-tissé obtenu par voie humide comprenant de la cellulose nanofibrillaire et son procédé de fabrication
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Publication number Priority date Publication date Assignee Title
US11591755B2 (en) 2015-11-03 2023-02-28 Kimberly-Clark Worldwide, Inc. Paper tissue with high bulk and low lint
US11255051B2 (en) 2017-11-29 2022-02-22 Kimberly-Clark Worldwide, Inc. Fibrous sheet with improved properties
US11313061B2 (en) 2018-07-25 2022-04-26 Kimberly-Clark Worldwide, Inc. Process for making three-dimensional foam-laid nonwovens
US11788221B2 (en) 2018-07-25 2023-10-17 Kimberly-Clark Worldwide, Inc. Process for making three-dimensional foam-laid nonwovens
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SE1951497A1 (en) * 2019-12-18 2021-06-19 Stora Enso Oyj Coated paper or paperboard
SE544302C2 (en) * 2019-12-18 2022-03-29 Stora Enso Oyj Coated paper or paperboard and a method for manufacturing a coated paper or paperboard
WO2021260606A1 (fr) * 2020-06-24 2021-12-30 Stora Enso Oyj Matériau fibreux résistant à l'eau et son procédé de fabrication
SE544175C2 (en) * 2020-06-24 2022-02-22 Stora Enso Oyj Water-resistant paper or paperboard
SE2050753A1 (en) * 2020-06-24 2021-12-25 Stora Enso Oyj Water-resistant paper or paperboard
SE2151606A1 (en) * 2021-12-22 2023-06-23 Stora Enso Oyj Free-standing wet low-density cellulose fibre foam
WO2023119213A1 (fr) * 2021-12-22 2023-06-29 Stora Enso Oyj Mousse de fibres de cellulose à faible densité humide autonome
CN115748307A (zh) * 2022-11-24 2023-03-07 中国海诚工程科技股份有限公司 一种叠式泡沫薄板成型绿色包装材料及其制备方法

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