Decorative paper or film containing highly refined pulp from fibers obtained from used beverage cartons
Patent Information
- Application Number
- JP2024524764
- Authority / Receiving Office
- JP · JP
- Patent Type
- Applications
- Current Assignee / Owner
- Priority Date
- 2021-10-29
- Filing Date
- 2022-10-25
- Publication Date
- 2025-10-03
AI Technical Summary
The multi-layered structure and unique composition of used beverage cartons (UBCs) make them difficult to efficiently recycle, leading to high contamination levels and microbial activity, which limits their use in food or beverage packaging applications.
The method involves refining UBC fibers into highly purified cellulose compositions or microfibrillated cellulose (MFC) to produce decorative papers or films that can be used in packaging laminates, incorporating additives like precipitated calcium carbonate (PCC) and polymeric gas barrier coatings to enhance properties, and applying metallized layers for improved barrier performance.
This approach allows UBC fibers to be reused in food or beverage packaging without contaminating the contents, maintaining mechanical properties and reducing microbial activity, thus expanding their applicability in high-value packaging applications.
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Abstract
Description
[Technical field]
[0001] The present disclosure relates to a method for recycling fiber fractions from used beverage cartons (UBC). [Background technology]
[0002] Beverage cartons' multi-layer construction offers a resource-efficient, lightweight and recyclable packaging solution that can be made from renewable resources. Sustainably sourced virgin cellulose fibres provide strength and rigidity, while the other layers provide barriers against liquids, water vapour, oil / grease, oxygen and light to protect the packaged contents. The right combination of materials ensures food safety during transport and storage, and prevents food spoilage and waste by protecting the contents from deterioration. These barrier layers consist of a variety of polymers, or combinations of polymers and aluminium foil or coatings, depending on the type of product being packaged and whether the product is kept refrigerated or distributed and stored at room temperature.
[0003] In its simplest form, a beverage carton comprises at least one paperboard layer and at least one liquid barrier layer, usually a polyolefin layer. The beverage carton may further comprise additional barrier layers, typically aluminum foil or coating layers, or high barrier polymer layers such as polyamide or EVOH. Such beverage cartons are often referred to as aseptic beverage cartons, as they are often used for aseptic packaging.
[0004] The general construction of an aseptic carton includes an outer layer of polyolefin, usually LDPE (low density polyethylene), which provides a moisture and liquid barrier, protects the printing ink layers applied to the substrate, and allows the package to be heat sealed. The type of paperboard used depends on the product being packaged, the market it is sold to, and the manufacturing conditions, but is usually a two- or three-ply, or up to five-ply material with an outer layer that is bleached or coated with clay, often containing CTMP (chemi-thermomechanical pulp), TMP (thermomechanical pulp), brown pulp, or high-yield pulp; the paperboard gives the package the necessary mechanical rigidity and usually accounts for about 65-75% of the total package weight. The inside of the paperboard is coated with LDPE, which bonds with an aluminum foil layer that provides an odor, light, and gas barrier. Adhesion of the aluminum foil to the innermost plastic layer is achieved, for example, by the use of a bonding layer of EMAA (poly(ethylene-co-methacrylic acid)). Finally, an inner layer of LDPE is applied to allow the carton to be heat sealed.
[0005] The term used beverage carton (UBC) is used herein to denote post-consumer beverage cartons, in particular post-consumer sterile beverage cartons, which are obtained from containers and packaging materials that have been collected after use.
[0006] The composition of UBC is different compared to many other recycled materials. UBC is typically characterized by the following: Large quantities of bleached or unbleached synthetic, semi-synthetic or mechanical fibres High plastic content High aluminum content from foils and coatings Food or liquid residues High bacterial (microorganism) content High amount of organic material including various oils and fats High content of monovalent and polyvalent ions or salts Possible presence of heavy metals · Non-intentionally added substances (NIAS) Mixed waste containing packaging and packaging items, including disposable parts (long strings such as caps, straws and packaging wires)
[0007] The collected UBC may contain printing inks and varnishes. Although the majority of the fibers are not usually directly exposed to printing inks, dissolved ink or ink debris may be redeposited on the fibers during the degradation process.
[0008] Recycling can be categorized as primary, secondary, tertiary, and quaternary. Primary recycling refers to the reprocessing of materials back into their original use or into a comparable product of equal or better quality, which is not currently an option since used cartons cannot be returned directly to their original use. Secondary recycling is the most widespread recycling option for UBC, where the material is processed and used in applications that do not require the virgin material properties. The paper fibers are separated from the polymer and aluminum residues (also referred to herein as poly-Al residues) and the fibers are incorporated into paper products. Another secondary recycling process involves converting shredded UBC into construction materials. Tertiary recycling involves breaking down the product into its chemical components and then recycling those chemicals into various products. Quaternary recycling of UBC involves incineration with energy recovery, although this process is not considered recycling in many countries.
[0009] Due to its multi-layered structure and unique composition, UBC is difficult to recycle and reuse efficiently. As a result, today, UBC is often collected and disposed of in landfills, incinerated, or processed into various low-value fractions, such as polymer-rich, fiber-rich, and wastewater or sludge fractions. The fiber-rich fraction is typically used in composites, non-food packaging applications, and other grades where higher impurity content is acceptable, such as tissue, towels, liners, and writing paper.
[0010] Paperboard typically constitutes 65-75% of the total weight of a carton, so recovery of this fraction is the main focus of carton recycling approaches. Recycling can be achieved by recovering the paper fibers using a conventional Hydrapulper or drum pulper at the paper mill. A Hydrapulper is a large cylindrical vessel with an impeller at the bottom that breaks down the paper fibers, producing a relatively dilute slurry of fibers that can be further processed in a mill. Contact between water and the paper layers occurs in the Hydrapulper, and the layers are separated by hydraulic forces inside the pulper. No chemicals are required, but solvents and acid or alkaline solutions may be used to improve separation efficiency. The concentration of pulp in the Hydrapulper is typically less than 15% by weight. Hydrapulpers are generally equipped with a lager that removes long string-like material such as PolyAl residue, caps, straws, and baling wire from the slurry. After removal from the pulper, the PolyAl residue is washed in a rotating perforated cylinder to recover entrained fibers. Drum pulpers are essentially rotating, tilting drums equipped with baffles to separate debris from the fibers with minimal fiber loss in the pulping and screening sections.
[0011] Although many paper mills have Hydrapulpers capable of recycling UBC, the fact that the theoretical maximum yield is only 75%, compared to 85% or more for other paper packaging, is a disincentive, as is the challenge of economically processing the PolyAl residues. Furthermore, recovered UBC fibers contain high amounts of impurities, especially from food residues and non-intentionally added substances (NIAS), which may make them unsuitable for blending into virgin or less contaminated pulp streams. Currently, there are strict regulations and limitations on the use of recycled materials in the boardmaking process. Fibers obtained from UBC may contain components that should not be returned to the boardmaking process. Examples include plastic particles, metals, metal compounds, optical brighteners (OBAs) or fluorescent whitening agents (FWAs), ink residues or mineral oils, especially microorganisms, toxic components, and food residues. These impurities may interfere with the wet-end chemistry (process performance), but may also affect the properties of the final product (mechanical or product performance, barrier properties, impurities, microbial growth, etc.).
[0012] Fibers derived from UBC can often exhibit high microbial activity or high microbial load, and microbial inactivation or sterilization of the fiber or pulp is typically required prior to reuse.
[0013] Another challenge with recycled UBC is that fibers derived from UBC are considered to be downgraded when they are recycled and reused. This downgrading is in part due to a reduction in mechanical properties caused by excessive mechanical and chemical processing. Recycled fibers may be mechanically damaged or processed in ways that affect their strength, mechanical performance, etc.
[0014] Generally, only virgin paper fibres are used in the manufacture of paperboard for food or beverage packaging applications. There is a need to increase the amount of recycled fibres in paperboard for food packaging applications. It is generally believed that due to the high levels of contamination, microbial load and degradation of recycled materials, UBC fibres cannot be efficiently reused in food and beverage packaging laminates and products.
[0015] There is therefore a need to find a way to enable pulp from UBC to be used in food or beverage packaging substrates and laminates, especially at high contents, without affecting the mechanical properties of the substrates and laminates or posing a risk of contamination of the packaged contents. Summary of the Invention
[0016] It is an object of the present disclosure to provide a method by which pulp from post-consumer beverage cartons (UBC) can be reused in applications and products where typically only virgin paper fiber is used, such as food or beverage packaging substrates and laminates.
[0017] The object of the present disclosure is to provide a method by which pulp from used beverage cartons (UBC) can be reused in food or beverage packaging substrates and laminates without adversely affecting the mechanical properties of the substrates and laminates or posing the risk of contaminating the packaged contents.
[0018] It is an object of the present disclosure to provide a method that allows pulp from used beverage cartons (UBC) to be recycled into food or beverage packaging substrates and laminates without contamination of the non-UBC pulp and process water streams with the UBC pulp.
[0019] The above objectives, as well as other objectives which will be realized by those skilled in the art in light of the present disclosure, are accomplished by various aspects of the present disclosure.
[0020] The present invention is based on the recognition that many of the problems associated with recycling UBC-derived fibers into paperboard can be reduced or solved by preparing recycled UBC fibers in the form of highly refined cellulose or microfibrillated cellulose (MFC) compositions to produce highly refined cellulose or MFC papers or films, such as machine glazed (MG) paper, glassine paper, greaseproof paper, MFC films, etc. Depending on the type of paper or film being produced, the highly refined cellulose composition can be used alone or in combination with other less refined fibers. Highly refined cellulose or MFC papers or films can be advantageously used as carriers for additives, coatings or layers that improve the appearance, printability, texture or feel of the paper or film, and can be used as decorative papers or films in packaging laminates.
[0021] By incorporating UBC derived fibers into another decorative film or substrate of a packaging laminate, the method of the present invention allows for greater amounts of UBC fibers to be incorporated into paperboard, such as paperboard for packaging laminates, than would be possible if the UBC fibers were mixed with non-UBC fibers. The UBC containing decorative paper or film of the present invention can be produced separately from the non-UBC containing paper or paperboard layers used in the packaging laminate, thereby preventing or at least minimizing contamination of the non-UBC pulp and process water streams with the UBC pulp.
[0022] According to a first aspect shown herein, there is provided a decorative paper or film for a food or liquid packaging laminate, the decorative paper or film comprising: The present invention includes a substrate layer comprising a highly refined cellulosic composition including fibers obtained from used beverage cartons (UBC) and 1-30% by weight precipitated calcium carbonate (PCC).
[0023] The substrate layer comprises a highly refined cellulose composition to improve the appearance, printability, texture and / or feel of the paper or film, and 1-30 wt. % PCC as a filler and / or pigment.
[0024] Precipitated calcium carbonate PCC, also known as refined calcium carbonate, purified calcium carbonate, or synthetic calcium carbonate, has the same chemical formula (CaCO3) as other types of calcium carbonate such as limestone, marble, and chalk. The calcium, carbon, and oxygen atoms can be arranged in three different ways to form three different calcium carbonate minerals. The most common arrangement of precipitated and ground calcium carbonate is the hexagonal shape known as calcite. PCC is used as a filler and / or pigment in paper pulp production. PCC enhances the whiteness and opacity of pulp and paper. Calcium carbonate with PCC is considered to be non-toxic.
[0025] The PCC is preferably a PCC formed directly in the pulp suspension, which can be obtained, for example, by adding to the pulp suspension calcium hydroxide and a reactant capable of reacting with calcium hydroxide to form a PCC, for example carbon dioxide gas or a salt.
[0026] The PCC is preferably a PCC formed directly in the pulp suspension by carbonation, a chemical reaction in which calcium hydroxide reacts with carbon dioxide to form insoluble calcium carbonate. Carbonation typically involves adding calcium hydroxide (preferably in the form of milk of lime) and carbon dioxide gas (CO2) to an aqueous solution to form the PCC.
[0027] In addition to the formation of PCC, the carbonation process has also been found to cause impurities to flocculate and precipitate, resulting in further purification of the pulp suspension and highly refined cellulose composition containing fibers obtained from used beverage cartons (UBC).
[0028] The highly refined cellulose composition is preferably refined to a Shopper-Riegler (SR) value, as determined by standard ISO 5267-1, in the range of 50 to 100. In some embodiments, the highly refined cellulose composition has a Shopper-Riegler (SR) number, as determined by standard ISO 5267-1, in the range of 70 to 100, preferably in the range of 85 to 98, more preferably in the range of 90 to 98. Refining or beating of cellulose pulp refers to the mechanical treatment and modification of cellulose fibers to impart desired properties to them.
[0029] Fibers obtained from UBC are preferably present in the highly refined cellulose composition in an amount of 20-100% by weight, based on the total dry fiber weight of the highly refined cellulose composition. In some embodiments, fibers obtained from UBC are the predominant fiber type in the highly refined cellulose composition. In some embodiments, fibers obtained from UBC are present in the highly refined cellulose composition in an amount of 50-100% by weight, 60-100% by weight, or 70-100% by weight, based on the total dry fiber weight of the highly refined cellulose composition. Fibers obtained from UBC may be mixed with non-UBC cellulose fibers. The remainder of the dry fiber weight of the fiber fraction may typically be composed of non-UBC cellulose fibers. Non-UBC cellulose fibers may be obtained, for example, from chemical pulp, chemi-mechanical pulp (CMP), chemi-thermomechanical pulp (CTMP), high temperature chemi-thermomechanical pulp (HT-CTMP), thermo-mechanical pulp (TMP), or brochure. The fibers may be softwood, hardwood, or non-wood fibers and may be bleached or unbleached. The non-UBC cellulosic fibers are preferably virgin or pre-consumer recycled fibers. In some embodiments, the highly refined cellulosic composition is composed entirely or almost entirely of fibers derived from UBC.
[0030] Depending on the purpose of the decorative paper or film, the highly refined cellulose composition can be used alone in the substrate layer or in combination with another less refined cellulose composition. The substrate layer preferably comprises at least 10% by weight of the highly refined cellulose composition. In some embodiments, the substrate layer comprises at least 20, 30, 40, 50, 60, 70, 80 or 90% by weight of the highly refined cellulose composition. In some embodiments, the remaining fibers in the substrate layer are less refined cellulose compositions. The less refined cellulose composition may comprise fibers obtained from, for example, chemical pulp, CMP, CTMP, HT-CTMP, TMP, or broked. The fibers may be softwood, hardwood, or non-wood fibers and may be bleached or unbleached. In some embodiments, the highly refined cellulose composition is composed entirely or almost entirely of fibers obtained from UBC. A less refined cellulose composition may have, for example, a Shopper-Riegler (SR) value in the range of 20 to 40, as measured by standard ISO 5267-1.
[0031] The substrate layer formed from the highly refined cellulose composition and PCC can exhibit good decorative properties by itself, but also provides a smooth, dense substrate suitable for coating with additional coating layers.
[0032] In some embodiments, the decorative paper or film for food or liquid packaging laminate further comprises a polymeric gas barrier coating disposed on one or both sides of the substrate layer. In addition to providing barrier properties to the packaging laminate in which the decorative paper or film is included, the polymeric gas barrier coating can also prevent odors or contaminants present in the substrate layer from migrating to an adjacent laminate layer.
[0033] In some embodiments, the decorative paper or film includes a polymeric gas barrier coating disposed on both sides of a substrate layer.
[0034] In some embodiments, the polymeric gas barrier coating comprises one or more water-soluble or water-dispersible film-forming polymers selected from the group consisting of polysaccharides, polyvinyl alcohol, polyvinyl alcohol acetate, polyvinyl acetate, polyvinylpyrrolidone, acrylic polymers, acrylic copolymers, polyurethanes, and latex emulsions such as styrene / acrylic latex. In some embodiments, the polysaccharides are selected from starch, modified starch, and cellulose derivatives, preferably carboxymethyl cellulose. In some embodiments, the polyvinyl alcohol is hydrolyzed to at least 88%, preferably greater than 92%.
[0035] The coat weight of the polymeric gas barrier coating is preferably in the range of 0.1 to 12 gsm, preferably in the range of 0.3 to 12 gsm, more preferably in the range of 1 to 8 gsm. The polymeric gas barrier coating can be applied as a single layer or as multiple layers. The polymeric gas barrier coating can be applied by, for example, rod coating, blade coating, spray coating, curtain coating, gravure coating, flexographic printing, or surface sizing or film pressing techniques.
[0036] In some embodiments, a calendering process is applied to the substrate layer before and / or after the polymeric gas barrier coating is applied. Calendering can include machine calendering, soft calendering and / or super calendering. One preferred method is to mechanically or soft calender the substrate layer before coating, and soft calender or super calender the coated substrate layer after coating.
[0037] In some embodiments, the decorative paper or film further comprises a metallized layer formed on the polymeric gas barrier coating.
[0038] Metallization refers to a set of processes used to deposit layers of metals or metal oxides onto a solid surface, either atom by atom or molecule by molecule. Multiple layers of the same or different materials can be combined. Processes can be further specified based on the vapor source: physical vapor deposition (PVD) uses liquid or solid sources, while chemical vapor deposition (CVD) uses chemical vapors.
[0039] In some embodiments, the metallization layer is formed by vapor deposition of a metal or metal oxide onto the polymeric gas barrier coating, preferably by physical vapor deposition (PVD) or chemical vapor deposition (CVD).
[0040] In some embodiments, the metallization layer comprises a metal or metal oxide selected from the group consisting of aluminum, magnesium, silicon, copper, aluminum oxide, magnesium oxide, silicon oxide, and combinations thereof, preferably aluminum oxide. Aluminum oxide vacuum coatings, also known as AlOx coatings, can provide similar barrier properties as aluminum metal coatings, but with the added advantage that thin AlOx coatings are transparent to visible light.
[0041] The metallization layer may have a thickness in the range of 1 to 500 nm. In some embodiments, the metallization layer has a layer thickness in the range of 1 to 100 nm, preferably in the range of 10 to 100 nm, and more preferably in the range of 20 to 50 nm. In some embodiments, the metallization layer has a layer thickness in the range of 50 to 250 mg / m 2 in the range of 75 to 150 mg / m 2 The composition has a basis weight in the range of 1000 to 2000 g.
[0042] One preferred type of metallized coating, often used for its barrier properties, especially water vapor barrier properties, is an aluminum metal physical vapor deposition (PVD) coating. Such coatings consist essentially of aluminum metal and may typically have a thickness of 10-50 nm. The thickness of the metallized layer represents less than 1% of the aluminum metal material typically present in aluminum foil of conventional thickness for packaging, i.e., 6.3 μm.
[0043] In some embodiments, the oxygen transfer rate (OTR) of the decorative paper or film is greater than or equal to 100 cc / m when measured at 50% relative humidity and 23° C. according to standard ASTM F-1927. 2 / 24h / atm or less, preferably 50cc / m 2 / 24h / atm or less, preferably 20cc / m 2 / 24h / atm or less, preferably 10cc / m 2 / 24h / atm.
[0044] In some embodiments, the decorative paper or film further comprises a polymeric seal layer disposed on at least one side of the substrate layer.
[0045] In some embodiments, the decorative paper or film includes a polymeric seal layer disposed on both sides of a substrate layer.
[0046] In some embodiments, the polymeric sealing layer is applied by adhesive lamination, which can be performed using polymer dispersions including, for example, polyolefins, styrene-acrylate (SA) latex, or polyvinyl alcohol (PVOH).
[0047] In some embodiments, the polymeric sealing layer is applied in the form of a thermal laminate of a thermoplastic polymer film, by extrusion coating laminate of a thermoplastic polymer, or by application of a solution or dispersion of a thermoplastic polymer.
[0048] The polymer sealing layer may comprise any of the polymers commonly used in paper or paperboard based packaging materials in general, or thermoplastic polymers used in liquid packaging boards in particular. Examples include polyethylene (PE), polyethylene terephthalate (PET), polypropylene (PP), polyhydroxyalkanoate (PHA), polylactic acid (PLA), polyglycolic acid (PGA), thermoplastic starch, thermoplastic cellulose. Polyethylene, particularly low density polyethylene (LDPE) and high density polyethylene (HDPE), is the most common and versatile polymer used in liquid packaging boards. In some embodiments, the polymer sealing layer comprises a polyolefin layer, preferably a polyethylene layer.
[0049] The basis weight of each polymeric sealing layer is preferably 50 g / m 2 To achieve a continuous and substantially defect-free film, the thickness should be at least 8 g / m 2 , preferably at least 12 g / m 2 A polymer layer basis weight of between 8 and 50 g / m is typically required. In some embodiments, the polymer sealing layer has a basis weight of between 8 and 50 g / m 2 in the range of 12 to 50 g / m 2 The range is.
[0050] In some embodiments, the basis weight of the substrate layer is in the range of 15 to 120 gsm, preferably in the range of 20 to 70 gsm.
[0051] In some embodiments, the density of the substrate layer is between 800 and 1800 kg / m 3 in the range of 850 to 1350 kg / m 3 The range is.
[0052] In some embodiments, the highly refined cellulosic composition has a Shopper-Riegler (SR) number, as determined by standard ISO 5267-1, in the range of 50 to 100, preferably in the range of 85 to 98, and more preferably in the range of 90 to 98.
[0053] In some embodiments, the highly refined cellulose composition has a fiber content of at least 10 million fibers per gram with a length >0.2 mm, preferably at least 15 million fibers per gram on a dry weight basis.
[0054] In some embodiments, the highly refined cellulose composition has an average fibril area of at least 14%, preferably at least 20%, and more preferably at least 22% of the fibers having a length value >0.2 mm.
[0055] In some embodiments, the highly refined cellulose composition is a microfibrillated cellulose (MFC) composition.
[0056] In some embodiments, the highly refined cellulose composition comprises: i) providing a fiber fraction comprising 20-100% by weight of fiber obtained from used beverage cartons (UBC), based on the total dry fiber weight of the fiber fraction; ii) optionally subjecting the fiber fraction to a mechanical, chemical or enzymatic pretreatment, or a combination thereof; iii) optionally subjecting the pretreated fiber fraction to refining at a concentration ranging from 0.5 to 30% by weight to a Shopper-Riegler (SR) value ranging from 50 to 100 as determined by standard ISO 5267-1 in order to obtain a highly refined cellulose composition; 14. A food or liquid packaging laminate according to any one of claims 1 to 13, obtained by
[0057] The fiber derived from UBC is preferably present in the fiber fraction in an amount of 20-100% by weight, based on the total dry fiber weight of the fiber fraction. In some embodiments, the fiber derived from UBC is the predominant fiber type of the fiber fraction. In some embodiments, the fiber derived from UBC is preferably present in the fiber fraction in an amount of 50-100% by weight, 60-100% by weight, or 70-100% by weight, based on the total dry fiber weight of the fiber fraction. In some embodiments, the fiber fraction is composed entirely or almost entirely of fiber derived from UBC.
[0058] For practical reasons, the fibers obtained from UBC may be mixed with non-UBC cellulosic fibers. In some embodiments, the fibers of the fiber fraction provided in step (i) consist of 20-80% by weight of fibers obtained from chemical pulp, CMP, CTMP, HT-CTMP, TMP or broked, and 20-80% by weight of fibers obtained from UBC. The fibers may be softwood, hardwood or non-wood fibers, and may be bleached or unbleached. In some embodiments, the highly refined cellulose composition consists entirely or almost entirely of fibers obtained from UBC. The remainder of the dry fiber weight of the fiber fraction may typically be composed of non-UBC cellulosic fibers. The non-UBC cellulosic fibers may be obtained, for example, from chemical pulp, CMP, CTMP, HT-CTMP, TMP or broked. The fibers may be softwood, hardwood or non-wood fibers, and may be bleached or unbleached. The non-UBC cellulosic fibers are preferably virgin or pre-consumer regenerated fibers.
[0059] In addition to fiber, the fiber fraction may further comprise ingredients or additives normally present in the preparation of highly refined cellulosic compositions.
[0060] It is generally believed that fibers from UBC cannot be reused for food or beverage packaging laminates because fibers obtained from UBC usually contain a large amount of contaminants. In order to reduce the amount of contaminants in the highly refined cellulose composition, the fiber fraction used in the method of the present invention is preferably subjected to purification before being subjected to pretreatment and purification. The purification preferably includes a fine screening method to remove cellulose fines and small particle contaminants. The fine screening method can be optionally combined with an electro-osmosis method to remove further contaminants.
[0061] In some embodiments, the fibers obtained from UBC have been subjected to purification using a fine screening process. The inventors have found that it is advantageous to subject the raw UBC fiber fraction obtained after removing the PolyAl residue to a fine screening process to remove fines and small particulate matter. Fine screening has been found to significantly accelerate the subsequent washing, bleaching and inactivation of the UBC fiber fraction. The relatively small amount of fines in the recycled UBC fiber fraction is responsible for the high level of impurities, high water retention and / or high drain resistance of the fiber fraction. Fine screening to remove fines and fines removes a significant portion of the particulate contaminants and reduces the drain resistance, allowing repeated washing steps to be carried out in less time, resulting in a fiber fraction of higher purity.
[0062] In some embodiments, the fiber obtained from UBC is a purified UBC fiber fraction produced according to a method comprising the steps of: a) subjecting the UBC starting material to a polymer and aluminum membrane separation process to obtain a UBC polymer and aluminum fraction and a raw UBC fiber fraction; b) optionally subjecting the raw UBC fiber fraction to a coarse screening process to remove coarse particles; c) subjecting the raw UBC fiber fraction to a fine screening process to remove cellulose fines and fine contaminants, the fine screening process comprising at least one fine screening step and at least one dilution step; d) optionally subjecting the fine screened UBC fiber fraction to a washing process to further remove contaminants; e) optionally subjecting the fine screened UBC fiber fraction to a bleaching process; f) subjecting the fine screened, optionally bleached UBC fiber fraction to a dewatering process to a consistency of at least 20% by weight; g) subjecting the dewatered UBC fiber fraction to an inactivation method to obtain a refined UBC fiber fraction.
[0063] In some embodiments, the fibers obtained from UBC are subjected to purification using electro-osmosis. The inventors have found that subjecting the UBC fiber fraction, especially the fine-screened UBC fiber fraction, to electro-osmosis to remove further contaminants not only effectively removes metal and non-metal ions and salts, but also reduces the content of mineral oil saturated hydrocarbons (MOSH), mineral oil aromatic hydrocarbons (MOAH), OBA and other organic contaminants in the fiber fraction. This realization allows a large portion of the collected UBC to be recycled and reused. Alternatively, the residual contaminant content of the finished recycled fiber portion can be reduced, allowing more recycled UBC material to be used in new paperboard products. Furthermore, electro-osmosis has also been found to reduce the microbial activity of the UBC fiber fraction.
[0064] In some embodiments, the fiber obtained from UBC is a purified UBC fiber fraction produced according to a method comprising the steps of: a) subjecting the UBC starting material to a polymer and aluminum membrane separation process to obtain a UBC polymer and aluminum fraction and a raw UBC fiber fraction; b) optionally subjecting the raw UBC fiber fraction to a coarse screening process to remove coarse particles; c) subjecting the raw UBC fiber fraction to a fine screening process to remove cellulose fines and fine contaminants, the fine screening process comprising at least one fine screening step and at least one dilution step; d) optionally subjecting the fine screened UBC fiber fraction to a bleaching process; e) subjecting the fine screened and optionally bleached UBC fiber fraction to electroosmosis to remove further contaminants; f) optionally subjecting the fine screened, optionally bleached UBC fiber fraction to a dewatering process to a consistency of at least 20% by weight; g) subjecting the optionally dewatered UBC fiber fraction to an inactivation method to obtain a purified UBC fiber fraction; and a purified fiber fraction produced according to a method comprising the steps of:
[0065] To obtain a raw fiber fraction suitable for further washing and inactivation, the plastic and / or aluminum content is first removed. This is done by a) subjecting the UBC starting material to a polymer and aluminum film separation process to obtain a UBC polymer and aluminum fraction and a raw UBC fiber fraction. If the UBC starting material does not contain aluminum, the UBC polymer and aluminum fraction may contain only polymer and no aluminum. The resulting raw UBC fiber fraction is composed mainly of cellulosic material and contains significantly less plastic and aluminum than the UBC starting material. The polymer and aluminum film separation process may include chopping the UBC starting material and mixing the chopped UBC starting material with water or an aqueous solution. When the mixture is agitated, the fibers absorb the water and the plastic and aluminum layers of the laminate break apart. The various fractions are separated by mechanical filtration and / or flotation to obtain the UBC polymer and aluminum fraction and the raw UBC fiber fraction.
[0066] The raw UBC fiber fraction obtained in step (a) preferably comprises at least 80% by weight of cellulose fibers on a dry weight basis. In some embodiments, the raw UBC fiber fraction obtained in step (a) preferably comprises at least 90% by weight of cellulose fibers, preferably at least 95% by weight of cellulose fibers on a dry weight basis.
[0067] In some embodiments, the raw UBC fiber fraction obtained in step (a) has a Shopper-Riegler (SR) value, determined by standard ISO 5267-1, in the range of 15 to 35, preferably in the range of 18 to 30.
[0068] In some embodiments, the raw UBC fiber fraction obtained in step (a) has a water retention value (WRV) determined by standard ISO 23714 in the range of 110-200%, preferably in the range of 120-180%, more preferably in the range of 125-175%.
[0069] In some embodiments, the raw UBC fiber fraction obtained in step (a) has a "Fines A" content of greater than 22%, preferably greater than 25%, as measured using an FS5 fiber optic analyzer (Valmet).
[0070] In some embodiments, the raw UBC fiber fraction obtained in step (a) comprises more than 1 wt. % plastics, preferably more than 1.2 wt. % plastics, based on dry weight.
[0071] In some embodiments, the raw UBC fiber fraction obtained in step (a) contains more than 0.2 wt. % aluminum, preferably more than 0.5 wt. % aluminum, based on dry weight.
[0072] In some embodiments, the raw UBC fiber fraction obtained in step (a) comprises more than 20 mg / kg mineral oil saturated hydrocarbons (MOSH), preferably more than 50 mg / kg MOSH, on a dry weight basis.
[0073] In some embodiments, the raw UBC fiber fraction obtained in step (a) contains more than 20 mg / kg mineral oil aromatic hydrocarbons (MOAH), preferably more than 50 mg / kg MOAH, on a dry weight basis.
[0074] In some embodiments, the raw UBC fiber fraction obtained in step (a) comprises more than 5000 mg / kg extractables, preferably more than 10000 mg / kg extractables, on a dry weight basis.
[0075] In some embodiments, the raw UBC fiber fraction obtained in step (a) comprises more than 1000 mg / kg unsaturated fatty acids, preferably more than 2000 mg / kg unsaturated fatty acids on a dry weight basis.
[0076] In some embodiments, the raw UBC fiber fraction obtained in step (a) comprises more than 400 mg / kg resin acids, preferably more than 500 mg / kg resin acids on a dry weight basis.
[0077] The amount of extractant, unsaturated fatty acids, and resin acids were measured using the SCAN-CM49 method, in which the pulp was acidified to a pH < 3 using acetic acid. Extraction was performed by ASE (accelerated solvent extraction) using acetone at a temperature of 100°C and a pressure of 2000 psi for two cycles. Extracts were analyzed by GC-FID and calculated against an internal standard.
[0078] In some embodiments, the raw UBC fiber fraction obtained in step (a) has an ash content of more than 4% at 525° C. and / or more than 4% at 925° C. Raw UBC fiber fractions obtained from some types of sources, including mineral or pigment coated paper cartons, may also have significantly higher ash contents.
[0079] The term coarse particle as used herein generally refers to particles having a diameter or width greater than 1 mm.
[0080] The term cellulose fines as used herein generally refers to cellulose particles that are significantly smaller in size than cellulose fibers.
[0081] In some embodiments, the term cellulose fines as used herein refers to cellulosic fines, which are capable of passing through a 200 mesh screen (76 μm equivalent hole diameter) of a conventional laboratory fractionation device (SCAN-CM66:05). There are two main fiber fines, namely, primary fines and secondary fines. Primary fines are generated during pulping and bleaching and are removed from the cell wall matrix by chemical and mechanical treatments. As a result of their origin (i.e., complex intermediate lamellae, striated cells, parenchymal cells), primary fines exhibit a flake-like structure with only a small proportion of fibrous material. In contrast, secondary fines are generated during the refining of the pulp. Both primary and secondary fines increase the drain resistance of the pulp and reduce the dewatering rate in the forming section of the paper machine. The high specific surface area of fines compared to pulp fibers affects the retention of process chemicals, significantly affecting the process stability and end product performance.
[0082] In some embodiments, the term fine particle contaminants as used herein refers to fine particles that are not derived from cellulosic materials and are capable of passing through a 200 mesh screen (equivalent pore diameter of 76 μm) of a conventional laboratory sorting device (SCAN-CM66:05).
[0083] The fine screening method used to remove cellulose fines and small particle contaminants from the raw UBC fiber fraction includes at least one fine screening step. The fine screening step can include screening using one or more pressure screens, one or more hydrocyclones, one or more belt filters, or a combination thereof. Other screening methods known to those skilled in the art for removing fines from fiber mixtures can also be used.
[0084] The fine screening method used to remove cellulose fines and small particle contaminants from the raw UBC fiber fraction comprises at least one dilution step. The dilution step preferably comprises adding a diluent, preferably water or an aqueous solution, to reduce the concentration of the UBC fiber fraction. The dilution step may be performed before and / or after the fine screening step. Preferably, the dilution is performed at least before the fine screening step to reduce the concentration of the UBC fiber fraction before the fine screening step. The concentration of the UBC fiber fraction after dilution may vary depending on the screening or fractionation method used. In some embodiments, the dilution factor (DF) is >2, preferably >2.5, >3.0, >3.5, >4, >4.5 or >5. Preferably, the dilution step comprises diluting the UBC fiber fraction to a concentration in the range of 0.1-7 wt.%, preferably in the range of 0.3-5 wt.%, more preferably in the range of 0.5-2 wt.%. It is also possible to perform screening with greater consistency, especially at the end of a fine screening method comprising multiple screening steps.
[0085] In some embodiments, the fine screening process reduces the content of fines and small particle contaminants in the UBC fiber fraction by at least 20%, preferably at least 30%, more preferably at least 40%. More specifically, in some embodiments, the fine screening process reduces the fines content in the UBC fiber fraction by at least 20%, preferably at least 30%, more preferably at least 40%, where the fines content, "Fines A", was measured using an FS5 fiber optic analyzer (Valmet).
[0086] In some embodiments, the fine screening method in step (c) reduces "Fine A" to less than 20%, preferably less than 17%, more preferably less than 15%, as measured using an FS5 fiber optic analyzer (Valmet).
[0087] In some embodiments, the fine screening process removes between 0.1 and 10%, or between 0.1 and 7.5%, or between 0.1 and 5% by weight of the solids of the raw UBC fiber fraction.
[0088] The finely sorted UBC fiber fraction is optionally subjected to further washing methods to remove further contaminants, particularly dissolved, dispersed, soluble or extractable contaminants. Any suitable pulp washing method for removing contaminants from the pulp mixture can be used. Washing methods used to remove further contaminants from the raw UBC fiber fraction can include washing using one or more rotary vacuum washers, rotary pressure washers, pressurized and atmospheric diffusion washers, horizontal belt washers and dilution / extraction devices, or combinations thereof. Other washing methods known to those skilled in the art for removing fines from fiber mixtures can also be used. The washing method preferably includes two or more washing steps.
[0089] In electroosmosis, the UBC fiber section is exposed to an electric field to induce water movement around the charged particles. Electroosmosis can include electrophoresis, whereby charged particles in an electric field are attracted and move toward an electrode with an opposite charge. The electric field can be generated, for example, by supplying electricity to the anode and cathode electrodes of an electroosmosis device.
[0090] In some embodiments, the electroosmotic process comprises the following steps. providing a slurry comprising a UBC fiber fraction and a liquid; exposing the slurry to an electric field to induce liquid flow in the slurry; separating the liquid from the UBC fiber fraction, thereby obtaining a liquid-reduced slurry; adding a wash liquid, preferably water, to the drained slurry; exposing the drained slurry to an electric field to induce a flow of the slurry wash; and Separating the wash liquor from the UBC fiber fraction, thereby obtaining a refined UBC fiber fraction.
[0091] Examples of electroosmotic techniques that can be applied to the present invention include, but are not limited to, those described in US Pat. No. 9,447,541 B2 and US Pat. No. 10,913,759 B2.
[0092] Electroosmosis removes metallic and non-metallic ions and salts from the UBC fiber fraction, but also reduces the OBA content of the UBC fiber fraction. Electroosmosis has also been shown to reduce microbial activity in the UBC fiber fraction.
[0093] Electroosmosis is usually also accompanied by dewatering of the UBC fiber fraction. The degree of dewatering is related to the amount of contaminants removed by the electroosmosis process, but can also be influenced by the drain resistance of the UBC fiber fraction, the additional pressure or vacuum applied, the permeability of the press fabric, the speed, the thickness of the filter cake, the consistency, etc. Dewatering is preferably performed in a continuous mode, such as a belt, wire, or press fabric.
[0094] In some embodiments, the fine screened UBC fiber fraction is subjected to a bleaching process. The bleaching process may be performed before or after the electroosmosis process. The bleaching process may be selected from the group consisting of, for example, hydrogen peroxide bleaching, ozone bleaching, oxygen bleaching, chloride bleaching, hypochlorous acid bleaching, and extractive bleaching. In a preferred embodiment, the bleaching process is combined with heating the fine screened UBC fiber fraction to a temperature of 50° C. or higher, for example 80° C. or higher, preferably 90° C. or higher, more preferably 100° C. or higher. The bleaching process may, for example, comprise a combination of heating and hydrogen peroxide bleaching, or heating and hypochlorous acid bleaching. Such a bleaching process may also preferably lead to at least partial inactivation of the UBC fiber fraction.
[0095] In some embodiments, the fibers obtained from the UBC are subjected to drying at elevated temperature to a consistency of at least 70% by weight, preferably at least 80% by weight, and more preferably at least 90% by weight.
[0096] The high temperature is preferably 80°C or higher, preferably 90°C or higher, more preferably 100°C or higher, for example in the range of 110 to 180°C.
[0097] In some embodiments, the heat treatment is carried out in a heated disperser (also known as a thermal disperser). A heated disperser is a device that uses a combination of heat and mechanical treatment of fibers at high concentrations to liquefy, decompose and disperse sticky visible contaminants. The temperature in the heated disperser is preferably 80°C or higher, preferably 90°C or higher, more preferably 100°C or higher, for example in the range of 110-180°C. The heat treatment in the heated disperser can usually be carried out for 5 seconds to 120 minutes, preferably 5 seconds to 30 minutes. The heat treatment in the heated disperser can improve the dissolution of starch and residual barrier polymers and additives, etc. The heat treatment in the heated disperser can also preferably result in at least partial inactivation of the UBC fiber fraction.
[0098] The UBC fiber fraction is subjected to an inactivation process to obtain a refined UBC fiber fraction. As used herein, the term "inactivation" refers to a process or treatment that inactivates microorganisms, i.e., reduces the microbial activity or microbial load of the UBC fiber fraction. The inactivation process kills or inactivates microorganisms and other potential pathogens present in the UBC fiber fraction. The inactivation process may result in complete sterilization or partial inactivation, i.e., disinfection or sanitization, of the fiber fraction.
[0099] Preferably, the inactivation reduces the microbial activity of the UBC fiber fraction by at least 30%, preferably at least 40%, at least 50%, or at least 60%, for example in the range of 60-100%. Preferably, the inactivation method reduces the activity of microorganisms and other potential pathogens present in the UBC fiber fraction to a level that is normally acceptable for fibers used in food or beverage packaging substrates and laminates. The inactivated refined UBC fiber fraction has suitable chemical purity, suitable biological purity, and suitable mechanical properties for reuse in food or beverage packaging substrates and laminates.
[0100] In some embodiments, the inactivation method includes heat inactivation, chemical inactivation, and / or radiation inactivation. Heat inactivation can be selected from the group consisting of, for example, steam inactivation and dry heat inactivation. Chemical inactivation can be selected from the group consisting of, for example, ethylene oxide, nitrogen dioxide, ozone, glutaraldehyde and formaldehyde, hydrogen peroxide, and peracetic acid inactivation. Radiation inactivation can be selected from the group consisting of, for example, non-ionizing radiation inactivation and ionizing radiation inactivation. Inactivation methods may include a combination of two or more inactivation techniques.
[0101] In some embodiments, the inactivation method is carried out using chemicals that are traditionally used for bleaching fibers used in paper and paperboard. The inactivation can be carried out, for example, using hydrogen peroxide or ozone. Such inactivation using chemicals that are traditionally used for bleaching fibers can be advantageous because it can also lead to at least partial bleaching of the UBC fiber portion.
[0102] In some embodiments, the heat treatment and inactivation method can be combined when the inactivation method involves high temperature. For example, inactivation by autoclave at 121°C also constitutes heat treatment of the UBC fiber portion. As another example, heat treatment in a disperser at a temperature that results in inactivation of the fiber fraction can also constitute an inactivation method.
[0103] The refined UBC fiber fraction is preferably suitable for demanding end uses, such as direct or indirect contact with food. The refined UBC fiber fraction is preferably suitable for reuse in food or beverage packaging substrates and laminates.
[0104] The refined UBC fibre fraction may preferably be used as the fibre fraction in step (i) of the process of the present invention.
[0105] In some embodiments, the refined UBC fiber fraction comprises at least 96% by weight cellulosic fiber, preferably at least 98% by weight cellulosic fiber, on a dry weight basis.
[0106] In some embodiments, the refined UBC fiber fraction has a Shopper-Riegler (SR) value in the range of 15 to 35, preferably in the range of 18 to 30, as determined by standard ISO 5267-1.
[0107] In some embodiments, the refined UBC fiber fraction has a water retention value (WRV) determined by standard ISO 23714 in the range of 110-200%, preferably in the range of 120-180%, more preferably in the range of 125-175%.
[0108] In some embodiments, the refined UBC fiber fraction has a "Fines A" content of less than 20%, preferably less than 17%, and more preferably less than 15%, as measured using an FS5 fiber optic analyzer (Valmet).
[0109] In some embodiments, the refined UBC fiber fraction has a kappa number, measured according to standard ISO 302:2015, of greater than 5, preferably greater than 10, more preferably greater than 20. Refined UBC fiber fractions obtained from some types of sources, for example sources containing mechanical pulp, may have significantly higher kappa numbers, such as 30 or higher or 40 or higher, measured according to standard ISO 302:2015.
[0110] In some embodiments, the refined UBC fiber fraction contains less than 0.5% plastics by weight, preferably less than 0.1% plastics by weight, on a dry weight basis.
[0111] In some embodiments, the refined UBC fiber fraction contains less than 0.5% aluminum by weight, preferably less than 0.1% aluminum by weight, on a dry weight basis.
[0112] In some embodiments, the refined UBC fiber fraction contains less than 0.1 wt. % OBA, preferably less than 0.05 wt. % OBA, on a dry weight basis.
[0113] In some embodiments, the purified UBC fiber fraction contains less than 50 mg / kg mineral oil saturated hydrocarbons (MOSH), preferably less than 20 mg / kg MOSH, on a dry weight basis.
[0114] In some embodiments, the purified UBC fiber fraction contains less than 50 mg / kg mineral oil aromatic hydrocarbons (MOAH), preferably less than 20 mg / kg MOAH, on a dry weight basis.
[0115] In some embodiments, the refined UBC fiber fraction contains less than 5000 mg / kg extractables, preferably less than 4000 mg / kg extractables, on a dry weight basis.
[0116] In some embodiments, the refined UBC fiber fraction contains less than 800 mg / kg unsaturated fatty acids, preferably less than 600 mg / kg unsaturated fatty acids on a dry weight basis.
[0117] In some embodiments, the refined UBC fiber fraction contains less than 200 mg / kg resin acids, preferably less than 100 mg / kg resin acids on a dry weight basis.
[0118] The amount of extractant, unsaturated fatty acids, and resin acids were measured using the SCAN-CM49 method, in which the pulp was acidified to a pH < 3 using acetic acid. Extraction was performed by ASE (accelerated solvent extraction) using acetone at a temperature of 100°C and a pressure of 2000 psi for two cycles. Extracts were analyzed by GC-FID and calculated against an internal standard.
[0119] In some embodiments, the refined UBC fiber fraction has less than 2% ash at 525° C. and / or less than 1% ash at 925° C. Refined UBC fiber fractions obtained from some types of sources, including mineral or pigment coated paper cartons, may also have significantly higher ash contents.
[0120] Preferably, at least 99% by weight of the refined UBC fiber fraction is identifiable by chemical analysis, more preferably at least 99.5% by weight, and most preferably at least 99.9% by weight.
[0121] In some embodiments, the purified UBC fiber fraction is mixed with fiber derived from chemical pulp, CMP, CTMP, HT-CTMP, TMP, or broch. The fiber may be softwood, hardwood, or non-wood fiber, and may be bleached or unbleached. In some embodiments, the highly refined cellulose composition is composed entirely or almost entirely of fiber derived from UBC.
[0122] In some embodiments, the refined UBC fiber fraction is co-refined with fiber derived from chemical pulp, CMP, CTMP, HT-CTMP, TMP, or shredder. The fiber may be softwood, hardwood, or non-wood fiber, and may be bleached or unbleached. In some embodiments, the highly refined cellulosic composition is composed entirely or almost entirely of fiber derived from UBC.
[0123] The refined UBC fibre fraction may preferably be used as the fibre fraction in step (i) of the process of the present invention.
[0124] In some embodiments, the fiber fraction provided in step (i) has a hemicellulose content in the range of 10 to 30% by weight, based on the total dry weight of the fiber fraction.
[0125] In some embodiments, the fibers obtained from the UBC are not dried prior to pretreatment and purification.
[0126] In some embodiments, the pretreatment is selected from oxidation, enzymatic treatment, and the use of swelling chemicals such as co-solvents or alkali, or a combination thereof. In some embodiments, the pretreatment is selected from enzymatic treatment and swelling with NaOH, or a combination thereof. The enzyme used in the enzymatic treatment may be, for example, laccase, cellulase, hemicellulase, or a mixture or combination thereof.
[0127] In some embodiments, the fiber fraction is purified to a concentration ranging from 1-10% by weight.
[0128] In some embodiments, the fiber fraction is refined with a total refinery energy in the range of 20-1500 kWh / t, preferably in the range of 50-500 kWh / t.
[0129] In some embodiments, the fiber fraction is purified until the Shopper-Riegler (SR) number, as determined by standard ISO 5267-1, is in the range of 50-100, preferably in the range of 70-100, preferably in the range of 85-98, more preferably in the range of 90-98.
[0130] In some embodiments, the highly refined cellulose composition has a fiber content of at least 10 million fibers per gram with a length >0.2 mm, preferably at least 15 million fibers per gram on a dry weight basis. The fiber content greater than 0.2 mm in length can be measured using a Fiber Tester Plus instrument.
[0131] In some embodiments, the highly refined cellulosic fiber composition has an average fibril area of at least 14%, preferably at least 20%, and more preferably at least 22% of the fibers having a length value >0.2 mm. The average fibril area is measured using a Fiber Tester Plus instrument.
[0132] The average fiber length for fibers with a length >0.2 mm and the fibril area for fibers with a length >0.2 mm were measured using an L&W Fiber Tester Plus (L&W / ABB) instrument (also referred to herein as "Fiber Tester Plus" or "FT+").) The definition of a fiber according to standard ISO 16065-2 is a fibrous particle greater than 0.2 mm.
[0133] A known sample weight of 0.100 g was used for each sample and the content of fibers >0.2 mm in length (million fibers per gram) was calculated using the following formula: Million fibers per gram = (number of fibers in sample) / (sample weight) / 1000000 = (Property ID 3141) / Property ID 3136) / 1000000
[0134] In some embodiments, the highly refined cellulose composition is a microfibrillated cellulose (MFC) composition.
[0135] Microfibrillated cellulose (MFC) is intended in the context of this patent application to mean cellulose particles, fibres or fibrils having a width or diameter between 20 nm and 1000 nm.
[0136] There are various methods to produce MFCs, such as single-pass or multi-pass purification, prehydrolysis followed by purification, or high-shear degradation or liberation of fibrils. To make the production of MFCs both energy-efficient and sustainable, one or more pretreatment steps are usually required. Thus, the cellulose fibers of the pulp used in producing MFCs may be natural or may have been enzymatically or chemically pretreated, for example to reduce the amount of hemicellulose or lignin. The cellulose fibers may be chemically modified before fibrillation, so that the cellulose molecules contain different (or more) functional groups than those found in the original cellulose. Such groups include, among others, carboxymethyl (CM), aldehyde and / or carboxyl groups (cellulose obtained by N-oxyl-mediated oxidation, e.g. "TEMPO"), or quaternary ammonium (cationic cellulose). After modification or oxidation by any of the above methods, the fibers are easier to decompose into MFCs.
[0137] According to a second aspect presented herein, there is provided a method for producing a decorative paper or film for a food or liquid packaging laminate, the method comprising: a) providing a pulp suspension comprising a highly refined cellulosic composition comprising fibres obtained from used beverage cartons (UBC) having a Shopper-Riegler (SR) number in the range of 50 to 100, as determined by standard ISO 5267-1, and optionally a less refined cellulosic composition having a Shopper-Riegler (SR) number in the range of 20 to 40; b) forming 1-30% by weight of precipitated calcium carbonate (PCC) in a pulp suspension; c) forming a paper or film substrate layer from the pulp suspension; Includes.
[0138] The pulp suspension comprises a highly refined cellulosic composition, and optionally a lesser refined cellulosic composition, suspended in an aqueous medium.
[0139] The highly refined cellulosic composition may be further defined as described above with reference to the first aspect.
[0140] The lesser refined cellulosic composition may be further defined as described above with reference to the first embodiment.
[0141] The PCC is formed directly in the pulp suspension, which can be obtained, for example, by adding to the pulp suspension calcium hydroxide and a reactant capable of reacting with calcium hydroxide to form the PCC, for example carbon dioxide gas or a salt.
[0142] PCC is preferably formed directly in the pulp suspension by carbonation, a chemical reaction in which calcium hydroxide reacts with carbon dioxide to form insoluble calcium carbonate. Carbonation typically involves adding calcium hydroxide (preferably in the form of milk of lime) and carbon dioxide gas (CO2) to an aqueous solution to form PCC.
[0143] In addition to the formation of PCC, the carbonation process has also been found to cause impurities to flocculate and precipitate, resulting in further purification of the pulp suspension and highly refined cellulose composition containing fibers obtained from used beverage cartons (UBC).
[0144] Formation of a paper or film substrate layer from the pulp suspension can be carried out using methods well known in the art, such as formation and dewatering on a Fourdrinier wire. The concentration of the pulp suspension may be in the range of, for example, 0.1 to 1.5% by weight.
[0145] In some embodiments, the method further comprises coating one or both sides of the paper or film substrate layer with a polymeric gas barrier coating to obtain a decorative paper or film for food or liquid packaging laminate.
[0146] In some embodiments, the polymeric gas barrier coating comprises one or more water-soluble film-forming polymers. In some embodiments, the polymeric gas barrier coating comprises one or more water-soluble or water-dispersible film-forming polymers selected from the group consisting of polysaccharides, proteins, hemicelluloses, polyvinyl alcohol, polyvinyl alcohol acetate, polyvinyl acetate, polyvinylpyrrolidone, acrylic polymers, acrylic copolymers, polyurethanes, and latex emulsions such as styrene / acrylic latex. In some embodiments, the polysaccharides are selected from starch, modified starch, alginates, alginic acid, and cellulose derivatives, preferably carboxymethylcellulose. In some embodiments, the polyvinyl alcohol is hydrolyzed to at least 88%, preferably more than 92%.
[0147] The coat weight of the polymeric gas barrier coating is preferably in the range of 0.1 to 12 gsm, preferably in the range of 0.3 to 12 gsm, more preferably in the range of 1 to 8 gsm. The polymeric gas barrier coating can be applied as a single layer or as multiple layers.
[0148] The polymer gas barrier coating may be applied, for example, by applying a coating solution or suspension by rod coating, blade coating, spray coating, curtain coating, gravure coating, flexographic printing, or surface sizing or film pressing techniques.
[0149] The decorative paper or film may further be provided with a polymeric sealing layer on one or both sides. The polymeric sealing layer may provide the decorative paper or film with liquid and moisture resistance and may also allow the decorative paper or film to be heat laminated to other layers of a packaging laminate or to be heat sealed to a finished packaging laminate. The polymeric sealing layer may be applied, for example, by extrusion coating, film lamination or dispersion coating.
[0150] Thermoplastic polymers are useful because they can be conveniently processed by extrusion coating techniques to form very thin, uniform films with good liquid barrier properties. In some embodiments, the polymer sealing layer comprises polypropylene or polyethylene. In a preferred embodiment, the polymer sealing layer comprises polyethylene, more preferably LDPE or HDPE.
[0151] In some embodiments, the polymeric sealing layer is applied by adhesive lamination, which can be performed using polymer dispersions including, for example, polyolefins, styrene-acrylate (SA) latex, or polyvinyl alcohol (PVOH).
[0152] In some embodiments, the polymeric sealing layer is applied in the form of a thermal laminate of a thermoplastic polymer film, by extrusion coating laminate of a thermoplastic polymer, or by application of a solution or dispersion of a thermoplastic polymer.
[0153] The polymer sealing layer may comprise any of the polymers commonly used in paper or paperboard based packaging materials in general, or thermoplastic polymers used in liquid packaging boards in particular. Examples include polyethylene (PE), polyethylene terephthalate (PET), polypropylene (PP), polyhydroxyalkanoate (PHA), polylactic acid (PLA), polyglycolic acid (PGA), thermoplastic starch, thermoplastic cellulose. Polyethylene, particularly low density polyethylene (LDPE) and high density polyethylene (HDPE), is the most common and versatile polymer used in liquid packaging boards. In some embodiments, the polymer sealing layer comprises a polyolefin layer, preferably a polyethylene layer.
[0154] The basis weight of each polymeric sealing layer is preferably 50 g / m 2 To achieve a continuous and substantially defect-free film, the thickness should be at least 8 g / m 2 , preferably at least 12 g / m 2 A polymer layer basis weight of between 8 and 50 g / m is typically required. In some embodiments, the polymer sealing layer has a basis weight of between 8 and 50 g / m 2 in the range of 12 to 50 g / m 2 The range is.
[0155] According to a third aspect presented herein there is provided a method of producing a laminate for packaging food or liquids, said method comprising laminating a decorative film according to the first aspect or produced according to the second aspect to a paper or paperboard substrate.
[0156] This lamination can be done, for example, using wet adhesive lamination or by thermal lamination using a thermoplastic polymer. The thermoplastic polymer used can be the same as that used for the polymeric sealing layer. The thermal lamination can be, for example, extrusion coating lamination or lamination using a thermoplastic polymer film as a bonding layer. In some embodiments, the polymeric gas barrier layer or polymeric sealing layer of the decorative film also serves as a bonding layer between the decorative film and the paper or paperboard substrate. Thus, the polymeric gas barrier layer or polymeric sealing can serve as a bonding layer between the paperboard layer and the barrier layer. In another embodiment, the decorative film is laminated to the paper or paperboard substrate by wet-on-wet lamination.
[0157] While the invention has been described with reference to various exemplary embodiments, those skilled in the art will recognize that various changes can be made and equivalents substituted for elements thereof without departing from the scope of the invention. In addition, many modifications can be made to adapt a particular situation or material to the teachings of the invention without departing from the essential scope thereof. Therefore, it is not to be understood that the invention is limited to the particular embodiment disclosed as the best mode contemplated for carrying out this invention, but the invention is intended to include all embodiments falling within the scope of the appended claims. [Brief description of the drawings]
[0158] [Figure 1] Figure 1 shows the Shopper-Riegler values plotted against the refining specific energy applied to unrefined and refined recycled UBC pulp. [Diagram 2] FIG. 1 shows the Schopper-Riegler values plotted against the water retention value, WRV, of unrefined and refined recycled UBC pulp. [Diagram 3] FIG. 1 is a plot of tensile index versus sheet density for unrefined and refined recycled UBC pulp. [Figure 4]FIG. 1 shows Tear Index plotted against sheet density for unrefined and refined recycled UBC pulp. EXAMPLES
[0159] Example 1 - Preparation of raw UBC pulp The collected spent UBC starting material was subjected to a polymer and aluminum film separation process to obtain a polymer and aluminum fraction and a fiber fraction. The UBC was treated with water at a consistency of about 18-20 wt. % in a drum pulper (drum speed 10.7 U / min) at about 50°C for 25 min. The polymer aluminum fraction was separated from the UBC and the remaining pulp is referred to here as raw UBC pulp (1). The screening drum was equipped with 8 mm holes. The polymer and aluminum fraction constituted about 30-35 wt. % of the dry weight of the UBC starting material. The fiber composition of the raw UBC pulp was as follows: Bleached softwood kraft: 12% by weight Unbleached softwood kraft: 25% by weight Unbleached hardwood kraft: 20% by weight Coniferous wood CTMP: 33% by weight Hardwood CTMP: 10% by weight
[0160] The results of the fiber and moisture analysis of the raw UBC pulp, designated sample (1), are shown in Tables 1, 2 and 3.
[0161] The amount of extractables in this pulp sample was 13,900 mg / kg (acetone extractable), while the amount of unsaturated fatty acids (free and bound) was 2,365 mg / kg. The amount of resin acids was 511 mg / kg, of which free sterols were 49 mg / kg and bound sterols were 37 mg / kg.
[0162] The pH of the filtrate was 6.74, the amount of suspended solids was 33 mg / L, the BOD after 5 days was 500 mg / L, the COD was 820 mg / L, the phosphorus and total nitrogen contents of the filtrate were 2.1 mg / L and 26 mg / L, respectively.
[0163] Example 2 - Crude Screening of Raw UBC The raw UBC pulp prepared in Example 1 was then diluted and coarsely sieved at a consistency of 1.6 wt%. The screener was equipped with a step rotor next to a contoured hole screen basket to efficiently remove large flat contaminants (rotor speed 730 m / min). The screen holes had a diameter of 1.6 mm. The accept stream (output, consistency 1.4 wt%) was then collected and analyzed. The rejects (reject rate 14 wt%) were subjected to another screening and peeling unit with 2.4 mm screening holes. The accepts were then collected and used as the output stream, while the rejects were subjected to a reject sorter with 2.4 mm holes in the screen (reject sorter, rotor speed 1600 m / min, consistency 2.2 wt%, dilution water 50 L / min). The temperature of the resulting accept stream (consistency 1.4 wt%) was about 37°C. The output stream, designated as sample (2), was analyzed and the results are shown in Tables 1 to 3.
[0164] Example 3 - Fine screening and washing The output stream from Example 2 was diluted with hot water (68°C) to a consistency of 1% by weight, and then subjected to high speed washing / dewatering and separation by feeding the pulp suspension around a smooth roll in a belt washer under wire tension. The consistency of the pulp after washing and draining was about 12% by weight, and the temperature of the pulp was about 60°C. The washing / dewatering in the belt washer reduced the ash content of the fiber fraction by 49%. The basis weight of the dewatered fiber substrate was about 31 gsm.
[0165] The treated UBC was further subjected to a dilution step, then to a fine screening using two forward screening cleaners (hydrocyclones) at a consistency of 1.4 wt.% (rejection 4.7 wt.%, dilution water 60 l / min), then to a second forward washing step at a consistency of 1.2 wt.% (rejection 5.7 wt.%, dilution water 65 l / min) and to two rotor cleaners (multi-foil rotors) based on the centrifugal screening principle operated in cascade mode at a consistency of 1.3 wt.%, then to a thickening step (inlet consistency 1.2 wt.%, accept consistency 6.1 wt.%). The ash content of the accept was 2.1 wt.%. The temperature of the pulp was about 60-70 °C. The slit size of the screens was 0.15 mm. The obtained refined UBC pulp, denoted as sample (3), was analyzed and the results are shown in Tables 1-3.
[0166] Example 4 - Thickening, heat dispersion, dehydration The fine screened, washed and thickened material obtained in Example 3 was further fed to a screw press and a heated screw and heater (inlet consistency 3.4 wt%, accept consistency 40 wt%, screw speed 50 U / min), followed by a heated disperser at about 115°C (rotor speed 1500 U / min, inlet consistency 35 wt%, gap 4.4 mm, accept consistency 10.5 wt%). The consistency of the pulp after the disperser was 10.5 wt%. Dilution and washing at low consistency (using a high-speed washing / dewatering unit) were carried out, followed by dewatering in a screw press to a consistency of about 30 wt%.
[0167] The washed and screened material, designated as sample (4), was analyzed with the results shown in Tables 1-3. The results showed that a significant amount of extractives could be removed compared to reference sample 1 (unprocessed UBC pulp). The amount of extractives in this pulp sample was 3200 mg / kg (acetone extractables), while the amount of unsaturated fatty acids (free and bound) was 591 mg / kg. The amount of resin acids was 62 mg / kg, of which the amounts of free and bound sterols were 15 and 8 mg / kg, respectively.
[0168] The pH of the filtrate was 8.4, the amount of suspended solids was 16 mg / l, and after 5 days the BOD was 13 mg / l and the COD was 44 mg / l. The phosphorus and total nitrogen contents of the filtrate were 0.7 mg / l and <1 mg / l, respectively.
[0169] Example 5 - Heat and high concentration inactivation The material obtained in Example 4 was further subjected to a screening press and a heating screen operated at T>80°C, and further subjected to a high consistency disperser, also operated at a high temperature, the purpose of which was to further dewater the pulp and inactivate the microbial activity at higher consistency. After the high consistency disperser, the pulp was inactivated at high consistency using 3.3% peroxide, NaOH and silicate at a temperature of about 85°C. The purpose of this treatment was to inactivate any remaining microbial activity.
[0170] The resulting inactivated UBC pulp, designated as sample (5), was analyzed and the results are shown in Tables 1-3. The results show that the amount of extractables, for example, can be further reduced, but also that microbial activity is greatly reduced. The amount of extractables in this pulp sample was 2500 mg / kg (acetone extractables), while the amount of unsaturated fatty acids (free and bound) was 495 mg / kg. The amount of resin acids was 49 mg / kg, and free and bound sterols were reduced to 11 mg / kg and 8 mg / kg, respectively.
[0171] Example 6 Comparative - UBC Processing in an OCC Plant In this case, the collected UBC pulp was subjected to drum pulper and separation based on the concept of a conventional OCC plant. The obtained UBC pulp (shown as sample (6)) was analyzed and the results are shown in Tables 1-2. The results show that the plastic content is relatively high, and the Al and Ca concentrations also remain at high levels.
[0172] Example 7 Comparative - UBC Processing in an OCC Plant As in Example 6, but the pulp was further treated in a heated disperser designed for the treatment of OCC. The resulting UBC pulp (designated as sample (7)) was analyzed and the results are shown in Tables 1-2. A slight improvement in fiber yield and a slight reduction in plastic content were observed. Compared to (6), metal salts are still at high levels, but a slight improvement was observed.
[0173] The solid concentration of this suspension was 7.6 wt%, the SR value was 33, and the WRV value was 163, indicating high drainage resistance. TIFF2024541236000002.tif242170TIFF2024541236000003.tif77170TIFF2024541236000004.tif156170
[0174] Example 8 - 3-ply liquid board manufacturing test The board making trials were carried out on a pilot machine based on Fourdrinier technology with three wires and three headboxes, followed by a press section, drying and surface sizing and calendering section and finally a winding station. Starch was added as ply binder in the amount of 1.8 gsm between the top and middle ply and between the middle and back ply.
[0175] The composition of the pulp mix and layers is given in Table 4 and the test results of the resulting three-ply boards are given in Table 5. The total basis weight of the three-ply boards is 250 g / m 2 The target moisture content was 7.5%.
[0176] Tests with virgin UBC pulp were not performed due to its high bacterial activity, unpleasant odor and high impurity content. Instead, as a reference, high kappa (brown) pulp was used in the middle layer together with blowk (internal furnish, i.e. recycled pulp).
[0177] Example 9 - Bulk pulp from mid-layer UBC The refined UBC pulp obtained in Example 4 was used in a paperboard making test of a three-ply liquid paperboard. The refined UBC pulp was prepared at a solid content of 35% by weight. No off-flavors were observed during the test, and the bacterial activity of this particular pulp was normal under papermaking conditions.
[0178] The total amount of UBC pulp in the board represented 30% of the total board basis weight (fiber), while the percentage in the interlayer was 53%.
[0179] There was a slight decrease in some of the strength properties of the board, but for example the Z strength was still above the benchmark. This example confirms that high yield or high kappa pulp can be substituted for UBC pulp.
[0180] Example 10 - Low amount of pulp from UBC in the middle layer In this case, the composition of the middle layer was changed to mix the UBC pulp with a lower amount and higher content of pulp than in the previous example. The total amount of pulp from UBC in the board was about 15%. This example confirms that high yield or high kappa pulp can replace UBC pulp.
[0181] Example 11 - Bulk pulp from highly refined UBC In this case, more highly refined pulp from UBC was added to the middle layer (53%) along with broken and high yield pulps. This amount corresponds to a 30% use of UBC Yura pulp in the entire board structure. Despite the high amount of UBC pulp, no effect was observed on the optical or mechanical properties (see Table II). In fact, a significant improvement in Z strength was obtained.
[0182] Example 12 - Small amount of pulp from highly refined UBC In this case, the composition of the middle layer was changed to mix a higher content of high yield pulp with less highly refined pulp from UBC than in the previous example. The total amount of pulp from UBC in the board was about 15%. This example confirms that UBC pulp can be used with a higher content of high yield pulp and does improve some strength properties such as Scott Bond and Z strength. TIFF2024541236000005.tif100170TIFF2024541236000006.tif235170
[0183] Example 13 - Effect of washing and refining on the strength properties of treated UBC pulp The UBC pulps from Examples 1, 4 and 5 were used as starting materials. Three samples of each pulp were prepared, one unrefined and two with two different levels of refinement in a Voith LR40 refiner (4% consistency, 3-1 filler, 0-60°C, specific edge load 2.5 J / m). 160 gsm sheets of each sample pulp were prepared according to standard procedures and the sheets were tested for strength and physical properties. The results are shown in Figures 1-4. In the figures, "RAW UBC" denotes the UBC pulp obtained in Example 1, "UBC+WT" denotes the UBC pulp obtained in Example 4 and "UBC WB" denotes the UBC pulp obtained in Example 5.
[0184] Although impurities and fines are removed during extensive refining and heat treatment of the UBC pulps obtained from Examples 4 and 5, the results surprisingly show that the strength properties of the regenerated and refined pulps can be maintained or improved.
[0185] Unless otherwise specified, the following parameters were measured according to the specified standard methods. Dry matter content: ISO 638 WRV100 mesh: ISO 23714 Fiber length Lc(l)FS5 ISO:ISO 16065 Drainage performance (SR): ISO 5267-1 pH: DIN 38404-C5:2009-7 Suspended solids: DIN EN 872:2005-04 BOD:DIN EN 1899-1:1998-05 COD:DIN 38409-H41 / SFS 5504:1988 Total phosphorus: DIN EN ISO 11885:2009-09 Total Nitrogen: DIN EN 25663:1993-11
Claims
1. A decorative paper or film for a food or liquid packaging laminate, said decorative paper or film comprising:
1. A decorative paper or film comprising a substrate layer, the substrate layer comprising a highly refined cellulose composition comprising fibers obtained from used beverage cartons (UBC), and 1 to 30% by weight of precipitated calcium carbonate (PCC).
2. 10. The decorative paper or film of claim 1, wherein the substrate layer comprises at least 50% by weight of the highly refined cellulose composition.
3. 10. The decorative paper or film of claim 1, wherein the substrate layer further comprises fibers obtained from chemical pulp, CMP, CTMP, HT-CTMP, TMP, or broke.
4. 10. The decorative paper or film of claim 1, comprising a polymeric gas barrier coating disposed on one or both sides of the substrate layer.
5. 5. The decorative paper or film of claim 4, wherein the polymeric gas barrier coating comprises one or more water-soluble or water-dispersible film-forming polymers selected from the group consisting of polysaccharides, polyvinyl alcohol, polyvinyl alcohol acetate, polyvinyl acetate, polyvinylpyrrolidone, acrylic polymers, acrylic copolymers, polyurethanes, and latex emulsions such as styrene / acrylic latex.
6. 10. The decorative paper or film of claim 1, further comprising a polymeric seal layer disposed on at least one side of the substrate layer.
7. 10. The decorative paper or film of claim 1 further comprising a polymeric seal layer disposed on both sides of the substrate layer.
8. 2. Decorative paper or film according to claim 1, wherein the polymeric sealing layer comprises a polyolefin layer, preferably a polyethylene layer.
9. 2. Decorative paper or film according to claim 1, wherein the basis weight of the substrate layer is in the range of 15 to 120 gsm, preferably in the range of 20 to 70 gsm.
10. 2. Decorative paper or film according to claim 1, wherein the highly refined cellulose composition has a Schopper-Riegler (SR) number, determined by standard ISO 5267-1, in the range of 50 to 100, preferably in the range of 70 to 100, preferably in the range of 85 to 98, more preferably in the range of 90 to 98.
11. 2. Decorative paper or film according to claim 1, wherein the highly refined cellulose composition has a content of at least 10 million fibres per gram, based on dry weight, having a length of >0.2 mm, preferably a content of at least 15 million fibres per gram, based on dry weight.
12. 2. Decorative paper or film according to claim 1, wherein the highly refined cellulose fiber composition has an average fibril area of at least 14%, preferably at least 20%, more preferably at least 22% of the fibers having a length value of >0.2 mm.
13. 2. The decorative paper or film of claim 1, wherein the highly refined cellulose composition is a microfibrillated cellulose (MFC) composition.
14. The highly refined cellulose composition comprises: i) providing a fiber fraction obtained from used beverage cartons (UBC) comprising 20-100% by weight of fiber based on the total dry fiber weight of the fiber fraction; ii) optionally subjecting the fiber fraction to a mechanical, chemical or enzymatic pretreatment, or a combination thereof; iii) subjecting the optionally pretreated fiber fraction to refining at a concentration ranging from 0.5 to 30% by weight to a Schopper-Riegler (SR) value ranging from 50 to 100, as determined by standard ISO 5267-1, in order to obtain a highly refined cellulose composition; 2. Decorative paper or film according to claim 1, obtained by
15. 1. A method for producing a decorative paper or film for a food or liquid packaging laminate, said method comprising: a) providing a pulp suspension comprising a highly refined cellulosic composition comprising fibers obtained from used beverage cartons (UBC) having a Schopper-Riegler (SR) number in the range of 50 to 100 as determined by standard ISO 5267-1, and optionally a less refined cellulosic composition having a Schopper-Riegler (SR) number in the range of 20 to 40; b) forming 1-30 wt. % precipitated calcium carbonate (PCC) in a pulp suspension; c) forming a paper or film substrate layer from the pulp suspension; A method comprising: