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
  • D21H11/00—Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only
  • D21H11/16—Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only modified by a particular after-treatment
  • D21H11/18—Highly hydrated, swollen or fibrillatable fibres
• • D—TEXTILES; PAPER
  • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
  • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
  • D21H11/00—Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only
  • D21H11/02—Chemical or chemomechanical or chemothermomechanical pulp
  • D21H11/04—Kraft or sulfate pulp
• • D—TEXTILES; PAPER
  • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
  • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
  • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
  • D21H17/03—Non-macromolecular organic compounds
  • D21H17/05—Non-macromolecular organic compounds containing elements other than carbon and hydrogen only
  • D21H17/14—Carboxylic acids; Derivatives thereof
• • D—TEXTILES; PAPER
  • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
  • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
  • D21H19/00—Coated paper; Coating material
  • D21H19/10—Coatings without pigments
  • D21H19/12—Coatings without pigments applied as a solution using water as the only solvent, e.g. in the presence of acid or alkaline compounds
• • D—TEXTILES; PAPER
  • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
  • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
  • D21H19/00—Coated paper; Coating material
  • D21H19/10—Coatings without pigments
  • D21H19/14—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12
  • D21H19/18—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12 comprising waxes
• • D—TEXTILES; PAPER
  • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
  • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
  • D21H19/00—Coated paper; Coating material
  • D21H19/36—Coatings with pigments
• • D—TEXTILES; PAPER
  • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
  • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
  • D21H19/00—Coated paper; Coating material
  • D21H19/36—Coatings with pigments
  • D21H19/44—Coatings with pigments characterised by the other ingredients, e.g. the binder or dispersing agent
  • D21H19/46—Non-macromolecular organic compounds
• • D—TEXTILES; PAPER
  • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
  • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
  • D21H19/00—Coated paper; Coating material
  • D21H19/36—Coatings with pigments
  • D21H19/44—Coatings with pigments characterised by the other ingredients, e.g. the binder or dispersing agent
  • D21H19/52—Cellulose; Derivatives thereof
• • 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
  • D21H23/00—Processes or apparatus for adding material to the pulp or to the paper
  • D21H23/02—Processes or apparatus for adding material to the pulp or to the paper characterised by the manner in which substances are added
  • D21H23/22—Addition to the formed paper
  • D21H23/50—Spraying or projecting
• • D—TEXTILES; PAPER
  • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
  • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
  • D21H27/00—Special paper not otherwise provided for, e.g. made by multi-step processes
  • D21H27/10—Packing paper
• • D—TEXTILES; PAPER
  • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
  • D21J—FIBREBOARD; MANUFACTURE OF ARTICLES FROM CELLULOSIC FIBROUS SUSPENSIONS OR FROM PAPIER-MACHE
  • D21J1/00—Fibreboard
  • D21J1/08—Impregnated or coated fibreboard
• • D—TEXTILES; PAPER
  • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
  • D21J—FIBREBOARD; MANUFACTURE OF ARTICLES FROM CELLULOSIC FIBROUS SUSPENSIONS OR FROM PAPIER-MACHE
  • D21J5/00—Manufacture of hollow articles by transferring sheets, produced from fibres suspensions or papier-mâché by suction on wire-net moulds, to couch-moulds

Definitions

• the present disclosure relates to an enhanced cellulose nanofibrils (CNF) (or enhanced CNF binder), methods of making the enhanced CNF binder, methods of making wet-laid, dry-laid, or molded articles with the enhanced CNF binder by incorporating the enhanced CNF with the furnish in the wet-end of a paper-making process, methods of coating cellulose-based materials, intermediate formed fiber articles, and/or molded articles with the enhanced CNF binder, and cellulose-based articles obtained by all of these methods, wherein the enhanced CNF includes a saccharide fatty acid ester-, glyceride-, fatty acid salt-, natural wax- and/or cellulose crosslinker- (SGF) blend bound to the CNF.
• CNF cellulose nanofibrils
• Cellulosic materials have a wide range of applications in industry as bulking agents, absorbents, and printing components. Their employment is preferred to that of other sources of material for their high thermal stability, good oxygen barrier function, and chemical/mechanical resilience (see, e.g., Aulin et al., Cellulose (2010) 17:559-574; incorporated herein by reference in its entirety). Of great relevance is also the fact that these materials are fully biodegradable once dispersed in the environment, and that they are totally nontoxic. Cellulose and derivatives thereof are the material of choice for environmentally friendly solutions in applications such as packaging for foodstuff and disposable goods.
• cellulose The many advantages of cellulose are nonetheless countered by the hydrophilicity/lipophilicity of the cellulose material, which shows a high affinity for water/fats and are easily hydrated (see, e.g., Aulin et al., Langmuir (2009) 25(13):7675-7685; incorporated herein by reference in its entirety). While this is a benefit for applications such as absorbents and tissues, it becomes an issue when the safe packaging of watery/lipid containing materials (e.g., foodstuffs) is required. Long term storage of food, especially ready-made meals which contain a significant amount of water and/or fat, is made problematic in cellulose trays, for example, as they would first become soggy and then ultimately fail. Further, multiple coatings may be required to offset low efficiency of maintaining sufficient coating on the cellulosic surface due to the high relative porosity of the material, resulting in increased costs.
• watery/lipid containing materials e.g., foodstuffs
• hydrophobic organic material/fluorocarbons e.g., per- and polyfluoroalkyl substances (PFAS)
• PFAS per- and polyfluoroalkyl substances
• wax e.g., wax
• synthetic polymers e.g., polyethylene
• silicones which would physically shield the underlying hydrophilic cellulose from the water/lipids in the contents, including the prevention of wicking in the fiber interstices, grease flowing into creases, or allowing the release of attached materials.
• materials such as PVC/PEI/PE are routinely used for this purpose and are physically attached (i.e., spray coated or extruded) on the surfaces to be treated.
• lowering the surface energy improves the penetration resistance of the articles
• lowering the surface energy also has some disadvantages.
• a textile fabric treated with a fluorocarbon will exhibit good stain resistance; however, once soiled, the ability of cleaning compositions to penetrate and hence release the soil from the fabric may be affected, which can result in permanently soiled fabrics of reduced useful life.
• Another example is a greaseproof paper which is to be subsequently printed and/or coated with an adhesive. In this case the requisite grease resistance is attained by treatment with the fluorocarbon, but the low surface energy of the paper may cause problems related to printing ink or adhesive receptivity, including scuffing, back trap mottle, poor adhesion, and register.
• the low surface energy may reduce the strength of the adhesion.
• the low surface energy articles can be treated by post forming processes such as corona discharge, chemical treatment, flame treatment, or the like. However, these processes increase the cost of producing the articles and may have other disadvantages.
• bio-based coating which is hydrophobic, lipophobic and compostable, including a base paper/film that would allow for keeping coatings on the surface of said paper and preventing wicking into the fiber interstices, or reducing sticking of materials to the cellulosic surface, at reduced costs, without sacrificing biodegradability and/or recyclability.
• U.S. Patent Application Publication No. 2018/0066073 discloses tunable methods of treating cellulosic materials with a composition that provides increased barrier properties, such as water resistance and/or oil and grease resistance (OGR), without sacrificing the biodegradability thereof.
• the '073 application discloses methods of binding of saccharide fatty acid esters (“SFAE”) on cellulosic materials to provide treated materials that display higher water resistance, lipid resistance, barrier function, and other mechanical properties.
• SFAE saccharide fatty acid esters
• the '097 application discloses tunable methods of treating cellulosic materials with a composition that provides increased barrier properties, such as water resistance and/or OGR resistance, without sacrificing the biodegradability thereof.
• the '097 application discloses methods of binding blends of glycerides and/or fatty acid salts.
• the '097 application discloses that the barrier formulation including the blends of glycerides and/or fatty acid salts can additionally include SFAE for imparting the water and/or OGR resistance and/or for providing the function of an emulsifier.
• PCT/US2020/014923 discloses methods of treating fibrous cellulosic materials with sucrose fatty acid ester containing particles (carrier systems) that allow for modifications of surfaces, including making such surfaces water resistance and/or oil/grease resistance.
• the methods as disclosed provide combining at least one SFAE with a polymer (e.g., latexes) to form micellular particles and applying such particles to substrates including fibrous cellulose-based materials (e.g., pulp) to form, inter alia, molded products.
• a polymer e.g., latexes
• fibrous cellulose-based materials e.g., pulp
• U.S. Ser. No. 16/568,953 discloses tunable methods of treating cellulosic materials with a barrier coating comprising a prolamin and at least one polyol fatty acid ester that provides increased oil and/or grease resistance to such materials without sacrificing the biodegradability thereof.
• the methods as disclosed provide for adhering of the barrier coating on articles including articles comprising cellulosic materials and articles made by such methods.
• the materials thus treated display higher lipophobicity and may be used in any application where such features are desired.
• U.S Ser. No. 16/456,499 discloses tunable methods of treating cellulosic materials with a barrier coating comprising at least two polyol and/or saccharide fatty acid ester that provides increased water, oil and grease resistance to such materials without sacrificing the biodegradability thereof.
• the methods as disclosed provide for adhering of the barrier coating on articles including articles comprising cellulosic materials and articles made by such methods.
• the materials thus treated display higher hydrophobicity and lipophobicity and may be used in any application where such features are desired.
• CNF has been used as a binder in the papermaking process.
• the inventors determined that the use of CNF as an additive on the wet-end and in coating applications can provide improved OGR.
• the use of CNF presents certain problems.
• One problem is that, when the CNF is used as a wet-end addition to the papermaking furnish, the CNF tends to slow the drainage rate (or dewatering) of the fiber mat from the slurry. This is detrimental, for example, because the water removal rate dictates the production speed of the cellulose-based product.
• Another problem is that the CNF tends to agglomerate when used as an additive as a slurry or spray, which can negatively affect its efficiency and/or its functional properties.
• the disclosure is directed to an enhanced cellulose nanofibril binder, which includes: cellulose nanofibrils (CNF); and an SGF blend bound to the CNF, wherein the SGF blend comprises one or more selected from the group consisting saccharide fatty acid esters (SFAE), glycerides, fatty acid salts (“FAS”), natural waxes, and cellulose crosslinkers.
• CNF cellulose nanofibrils
• SGF blend comprises one or more selected from the group consisting saccharide fatty acid esters (SFAE), glycerides, fatty acid salts (“FAS”), natural waxes, and cellulose crosslinkers.
• the term “SGF blend” means one or more saccharide fatty acid esters (SFAE), and/or one or more glycerides), and/or one or more fatty acid salts (FAS), and/or one or more natural waxes, and/or one or more cellulose crosslinkers.
• the SGF blend used in the present disclosure does not include a SFAE; in some embodiments the SGF blend does not include a glyceride; in some embodiments the SGF blend does not include a FAS; in some embodiments the SGF blend does not include the natural waxes; and in some embodiments the SGF blend does not include the cellulose crosslinkers.
• the SGF blend consists essentially of the SFAE, glycerides, and/or FAS. In some embodiments, the SGF blend consists of the SFAE, glycerides, and/or FAS.
• the enhanced cellulose nanofibril binder (or enhanced CNF) according to the present disclosure can provide certain benefits.
• the enhanced CNF when used in the furnish on the wet-end of the papermaking process, the enhanced CNF maintains or increases the drainage rate of the fiber mat from the slurry. Also, the enhanced CNF does not suffer the same problem of agglomeration as conventional CNF.
• the enhanced cellulose nanofibril binder consists essentially of the CNF and the SGF blend.
• the enhanced cellulose nanofibril binder is obtained by a method that includes: obtaining an aqueous mixture of cellulose nanofibrils (CNF); obtaining an aqueous SGF blend; and mixing the aqueous mixture of CNF with the aqueous SGF blend to obtain a CNF/SGF mixture.
• the mixing of the CNF with the SGF blend (and thereby contacting the CNF with the SGF blend) can be sufficient to bind the SGF blend to the CNF.
• the SGF blend can be bound to the CNF by exposing the CNF/SGF mixture to heat, radiation, a catalyst, or a combination thereof for a sufficient time.
• the method may further include a step of reducing the water content of the CNF/SGF mixture, such as by draining the water.
• the enhanced cellulose nanofibril binder according to the present disclosure is obtained by a method that includes: obtaining an aqueous mixture of cellulose pulp (e.g., woodpulp); obtaining an aqueous SGF blend; mixing the aqueous mixture of cellulose pulp with the aqueous SGF blend to obtain a cellulose/SGF mixture; and subjecting the cellulose/SGF mixture to mechanical shear forces to obtain the enhanced cellulose nanofibril binder.
• a method that includes: obtaining an aqueous mixture of cellulose pulp (e.g., woodpulp); obtaining an aqueous SGF blend; mixing the aqueous mixture of cellulose pulp with the aqueous SGF blend to obtain a cellulose/SGF mixture; and subjecting the cellulose/SGF mixture to mechanical shear forces to obtain the enhanced cellulose nanofibril binder.
• the present disclosure provides a method of making a cellulose-based article, the method including: adding the enhanced cellulose nanofibril binder according to the present disclosure to an aqueous papermaking furnish; and draining the water from the furnish to obtain a fibrous web.
• a method for imparting a barrier property to a cellulose-based material including contacting the cellulose-based material with an aqueous barrier formulation for imparting the barrier property, the barrier formulation including the enhanced cellulose nanofibril binder according to the present disclosure; and binding the barrier formulation to a surface of the cellulose-based material to obtain a bound cellulose-based material having die barrier property, wherein the barrier property is one or more selected from the group consisting of water resistance, lipid resistance, and gas resistance.
• a barrier formulation including the enhanced cellulose nanofibril binder according to the present disclosure a second SGF blend, the second SGF blend including one or more saccharide fatty acid esters (SFAE), one or more glycerides, and/or one or more fatty acid salts; and water.
• SFAE saccharide fatty acid esters
• a method for imparting a barrier property to a cellulose-based material including: contacting the cellulose-based material with a barrier formulation for imparting the barrier property, the barrier formulation including (a) cellulose nanofibrils (CNF), and (b) the SGF blend; and binding the barrier formulation to a surface of the cellulose-based material to obtain a bound cellulose-based material having the barrier property, wherein the barrier property is one or more selected from the group consisting of water resistance, lipid resistance, and gas resistance.
• the barrier formulation including (a) cellulose nanofibrils (CNF), and (b) the SGF blend
• the method for imparting a barrier property according to the present disclosure can provide the same benefits noted above, which includes maintaining or increasing the drainage rate when the method is applied to a wet-end process, and preventing agglomeration of the CNF.
• the cellulose-based material used in the method for imparting a barrier property according to the present disclosure includes cellulose fiber, and the step of contacting includes forming an aqueous mixture of the barrier formulation and cellulose fiber.
• the aqueous mixture is in the form of a slurry having a solid content of about 0.1 to 10.0 wt. %, 0.1 to 6.0 wt. %, or about 0.1 to 2.0 wt. %, or about 0.2 to 1.5 wt. %.
• the method further includes reducing the water content of the aqueous mixture, such as by draining the water.
• the step of contacting in the method for imparting a barrier property according to the present disclosure includes coating the surface of a cellulose-based substrate with the formulation by a process of immersion, spraying, painting, printing, or any combination of any of these processes.
• the SGF blend is present at a weight of at least about 0.05 g/m 2 on the surface of the substrate.
• the cellulose-based substrate is not particularly limited.
• examples of the cellulose-based substrate include a surface of an article selected from paper, paperboard, bacon board, insulating material, paper pulp, a carton for food storage, a compost bag, a bag for food storage, release paper, a shipping bag, weed-block/barrier fabric or film, mulching film, plant pots, packing beads, bubble wrap, oil absorbent material, laminates, envelops, gift cards, credit cards, gloves, raincoats, OGR paper, a shopping bag, diapers, membranes, eating utensil, a tea bag, a container for coffee or tea, a container for holding hot or cold beverages, a cup, a plate, a bottle for carbonated liquid storage, a bottle for non-carbonated liquid storage, a lid, film for wrapping food, a garbage disposal container, a food handling implement, a fabric fibre, a water storage and conveying implement, a storage and conveying implement for alcoholic or non-alcoholic beverages, an outer casing or screen
• the method for imparting a barrier property according to the present disclosure provides a bound cellulose-based material that exhibits a water contact angle of equal to or greater than 90°.
• the method for imparting a barrier property according to the present disclosure provides a bound cellulose-based material that exhibits a TAPPI T 559 KIT test value of from 3 to 12.
• the method for imparting a barrier property provides a bound cellulose-based material that exhibits a water contact angle of equal to or greater than 90° and/or a TAPPI T 559 KIT test value of from 3 to 12 in the absence of any secondary hydrophobes.
• the method of making the enhanced CNF further includes reducing the water content of the CNF/SGF mixture.
• a method of making an enhanced cellulose nanofibril binder including: obtaining an aqueous mixture of cellulose pulp; obtaining an aqueous SGF blend; mixing the aqueous mixture of cellulose pulp with the aqueous SGF blend to obtain a cellulose/SGF mixture; and subjecting the cellulose/SGF mixture to mechanical shear forces to obtain the enhanced cellulose nanofibril binder.
• the method includes subjecting the cellulose pulp to a pre-treatment prior to obtaining the cellulose/SGF mixture and/or prior to subjecting the cellulose/SGF mixture to the mechanical shear force.
• a method of making a molded article including: providing a forming tool having a three-dimensional shape having a forming portion, bringing said forming portion into contact with a cellulose composition so that said forming portion is covered with a wet layer of pulp; and dewatering the layer of pulp on the forming tool to achieve the molded article, wherein the cellulose composition includes cellulose pulp and an enhanced cellulose nanonbril binder according to the present disclosure.
• another method of making a molded article including: providing a forming tool having a three-dimensional shape having a finning portion, bringing the forming portion into contact with a cellulose composition so that said forming portion is covered with a wet layer of pulp; and dewatering the layer of pulp on the forming tool to achieve the molded article, wherein the cellulose composition includes allulose pulp and a barrier formulation according to the present disclosure.
• another method of making a molded article including: providing a forming tool having a three-dimensional shape having a forming portion, bringing the forming portion into contact with a cellulose composition so that said forming portion is covered with a wet layer of pulp; dewatering the layer of pulp on the forming tool to obtain an intermediate molded article; and coating a surface of the intermediate molded article with a barrier formulation according to the present disclosure by a process of immersion, spraying, painting, printing, or any combination of any of these processes to achieve the molded article.
• the method of making the molded article includes conducting the dewatering at temperatures >100° C. to achieve a dry content of at least about 70 wt. %, preferably at least about 80 wt. %.
• the layer of pulp present on the forming tool is dewatered by means of press-drying performed at temperatures >100° C., preferably at temperatures between about 120 to 250° C. or more preferably between about 150 to 220° C.
• the forming tool is porous or perforated so that water can be removed during forming during a dewatering/drying step.
• the barrier formulation consists essentially of CNF and the SGF blend.
• the barrier formulation when a total weictht of the barrier formulation is considered to be 100% by weight, the barrier formulation includes about 4% by weight to about 96% by weight of CNF, and about 4% by weight to about 96% by weight of the SGF blend.
• the amount of the CNF can be about 10% by weight to about 70% by weight.
• the amount of the SGF blend can be about 30% by weight to about 90% by weight.
• the one or more prolamins are selected from wheat (gliadin), barley (hordein), rye (secalin), corn (zein), sorghum (kafirin), and/or oats (avenin).
• the molded article exhibits a water contact angle of equal to or greater than 90°, equal to or greater than 100°, equal to or greater than 110°, or equal to or greater than 120°.
• the molded article exhibits a water contact angle of equal to or greater than 90° and/or a TAPPI T 559 KIT test value of from 3 to 12 in the absence of any secondary hydrophobes.
• the charged polymer consists of one or more cationic polymer.
• the one or more cationic polymer may include a polyacrylamide.
• the polyacrylamide may include polyDADMAC (poly diallyldimethylammonium chloride) or alum (aluminum sulfate).
• one or more prolamins can be added in the wet-end to aid in the retention of the SGF blend, CNF, and/or enhanced CNF on the cellulose-based material.
• references to “a saccharide fatty acid ester” includes one or more saccharide fatty acid esters and/or compositions of the type described herein which will become apparent to those persons skilled in the art upon reading this disclosure and so forth.
• the present disclosure provides an enhanced cellulose nanofibril binder.
• Cellulose nanofibrils also referred to herein as CNF
• CNF Cellulose nanofibrils
• the CNF for use in the embodiments of the present disclosure is not particularly limited.
• the CNF can be commercially obtained, or the CNF can be made by known methods, which typically include subjecting a source of cellulose fibers (e.g., woodpulp) to a mechanical shearing force.
• a source of cellulose fibers e.g., woodpulp
• the properties of the CNF are not particularly limited.
• the CNF may have typical fibril widths of about 5 to 20 nanometers, and may have lengths of several micrometers.
• the enhanced CNF can be obtained by contacting conventionally made CNF with an SGF blend and allowing the SGF blend to bind to the CNF.
• the enhanced CNF can be made obtained by subjecting a source of cellulose fibers (e.g., woodpulp) to a mechanical shearing stress while the CNF is in mixture with an SGF blend.
• the enhanced CNF provides benefits compared to conventionally used CNF, such as maintaining or increasing the drainage rate of the fiber mat from the slurry and reduced agglomeration of the CNF.
• the present disclosure provides methods for imparting a barrier property to a cellulose-based material.
• the methods include contacting the cellulose-based material with a barrier formulation for imparting the barrier property, and binding the barrier formulation to a surface of the cellulose-based material to obtain a bound cellulose-based material having the barrier property, wherein the barrier property is one or more selected from the group consisting of water resistance, gas resistance, and lipid resistance.
• the barrier formulation may include the enhanced CNF, or the barrier formulation may include the enhanced CNF and the SGF blend.
• the methods of the present disclosure can provide a solvent-free, bio-based, high temperature-tolerant barrier (or barrier coating) for oil and grease (OGR), water, and/or gases (e.g., oxygen, nitrogen, and carbon dioxide) and/or formed fiber (e.g., molded) products having these properties.
• OGR oil and grease
• gases e.g., oxygen, nitrogen, and carbon dioxide
• formed fiber e.g., molded
• barrier coatings can be configured to provide improved water resistance and lipid (oil/grease) resistance without the use of PFAS.
• These barrier properties can be provided by the SGF blend (see, e.g., the '073 publication, the '953 publication, the '923 application, the '499 application, the '433 application, and the '097 application, all of which have been incorporated herein by reference).
• the enhanced CNF can be used on the wet end of the papermaking process by adding the enhanced CNF directly into the papermaking furnish.
• a combination of CNF and the SGF blend can be added directly into the papermaking furnish to obtain similar benefits.
• One or more charged polymers such as polyDADMAC or polyacrylamide, could also be added to the furnish as a retention aid for promoting the absorption of the SGF blend and/or the CNF onto the cellulosic surfaces.
• the charged polymer can be used to control the electrostatic charge of the formulation containing the SGF blend.
• prolamins can be used as a binder. This is explained, for example, in U.S. provisional application No. 63/044,820 filed Jun. 26, 2020 (hereinafter “the '820 application), which is incorporated herein by reference in its entirety.
• the barrier formulations can be coated onto a cellulose-based material or substrate (e.g., an already formed paper product) by immersion, spraying, painting, printing, extrusion coating, metering or any combination of any of these processes.
• the barrier formulation may contain the enhanced CNF in a sufficient amount to impart a desired water resistance and/or OGR to the cellulose-based material.
• the barrier formulation may contain CNF and the SGF blend in suitable amounts to impart a desired water resistance and/or OGR to the cellulose-based material.
• the barrier formulation may contain the enhanced CNF and the SGF blend in suitable amounts to impart a desired water resistance and/or OGR to the cellulose-based material.
• the interaction between the SGF blend and the CNF may be by ionic, hydrophobic, van der Waals interaction, covalent bonding, or a combination thereof.
• “bind”, including grammatical variations thereof, means to cohere or cause to cohere essentially as a single mass, and may refer to ionic, hydrophobic, van der Waals interaction, or covalent bonding, or a combination thereof.
• the interaction between the SGF blend and the cellulose-based material may be by ionic, hydrophobic, van der Waals interaction, covalent bonding, or a combination thereof.
• the interaction between the enhanced CNF and the cellulose-based material may be by ionic, hydrophobic, van der Waals interaction, covalent bonding, or a combination thereof.
• the barrier formulation may also contain one or more conventional binders used in papermaking, such as latex, PvOH, and starch.
• cellulosic means natural, synthetic, or semisynthetic materials that can be molded or extruded into objects (e.g., bags, sheets) or films or filaments, which may be used for making such objects or films or filaments, that is structurally and functionally similar to cellulose, e.g., coatings and adhesives (e.g., carboxymethylcellulose).
• objects e.g., bags, sheets
• films or filaments which may be used for making such objects or films or filaments, that is structurally and functionally similar to cellulose, e.g., coatings and adhesives (e.g., carboxymethylcellulose).
• cellulose a complex carbohydrate (C 6 H 10 O 5 ) n that is composed of glucose units, which forms the main constituent of the cell wall in most plants, is cellulosic.
• hydrophobe means a substance that does not attract water.
• waxes, rosins, resins, saccharide fatty acid esters, fatty acid salts, glycerides having long fatty acid chains; di- and triglycerides, diketenes, shellacs, vinyl acetates, PLA, PEI, oils, fats, lipids, other water repellant chemicals or combinations thereof are hydrophobes.
• hydroophobicity means the property of being water-repellent, tending to repel and not absorb water.
• cellulose-containing material or “cellulose-based material” means a composition which consists essentially of cellulose.
• such material may include, but is not limited to, paper, paper sheets, paperboard, paper pulp, a carton for food storage, parchment paper, cake board, butcher paper, release paper/liner for a pressure sensitive adhesive, a bag for food storage, a shopping bag, a shipping bag, bacon board, insulating material, tea bags, containers for coffee or tea, a compost bag, eating utensil, container for holding hot or cold beverages, cup, a lid, plate, a bottle for carbonated liquid storage, gift cards, a bottle for non-carbonated liquid storage, film for wrapping food, a garbage disposal container, a food handling implement, a fabric fibre (e.g., cotton or cotton blends), a water storage and conveying implement, alcoholic or non-alcoholic drinks, an outer casing or screen for electronic goods, an internal or external piece of furniture, a curtain and upholstery.
• a fabric fibre e.g., cotton or cotton blends
• fibers in solution or “pulp” means a lignocellulosic fibrous material prepared by chemically or mechanically separating cellulose fibers from wood, fiber crops or waste paper.
• the cellulose fibers themselves contain bound SFAE, glyceride, and/or FAS as isolated entities, and where the bound cellulose fibers have separate and distinct properties from free fibers (e.g., pulp- or cellulose fiber- or nanocellulose or microfibrillated cellulose-SFAE blend bound material would not form hydrogen bonds between fibers as readily as unbound fibers).
• “repulpable” means to make a paper or paperboard product suitable for crushing into a soft, shapeless mass for reuse in the production of paper or paperboard.
• TAPPI T 530 Hercules size test (i.e., size test for paper by ink resistance) may be used to determine water resistance. Ink resistance by the Hercules method is best classified as a direct measurement test for the degree of penetration. Others classify it as a rate of penetration test. There is no one best test for “measuring sizing.” Test selection depends on end use and mill control needs. This method is especially suitable for use as a mill control sizing test to accurately detect changes in sizing level. It offers the sensitivity of the ink float test while providing reproducible results, shorter test times, and automatic end point determination.
• Sizing as measured by resistance to permeation through or absorption into paper of aqueous liquids, is an important characteristic of many papers. Typical of these are bag, containerboard, butcher's wrap, writing, and some printing grades.
• oxygen permeability means the degree to which a polymer allows the passage of a gas or fluid.
• Oxygen permeability (Dk) of a material is a function of the diffusivity (D) (i.e., the speed at which oxygen molecules traverse the material) and the solubility (k) (or the amount of oxygen molecules absorbed, per volume, in the material). Values of oxygen permeability (Dk) typically fall within the range 10-150 ⁇ 10 ⁇ 11 (cm 2 ml O 2 )/(s ml mmHg). A semi-logarithmic relationship has been demonstrated between hydrogel water content and oxygen permeability (Unit: Barrer unit).
• the Barrer unit can be converted to hPa unit by multiplying it by the constant 0.75.
• biodegradable including grammatical variations thereof, means capable of being broken down especially into innocuous products by the action of living things (e.g., by microorganisms).
• “Gurley second” or “Gurley number” is a unit describing the number of seconds required for 100 cubic centimeters (deciliter) of air to pass through 1.0 square inch of a given material at a pressure differential of 4.88 inches of water (0.176 psi) (ISO 5636-5:2003)(Porosity).
• “Gurley number” is a unit for a piece of vertically held material measuring the force required to deflect said material a given amount (1 milligram of force). Such values may be measured on a Gurley Precision Instruments device (Troy, New York).
• HLB The hydrophilic-lipophilic balance of a surfactant is a measure of the degree to which it is hydrophilic or lipophilic, determined by calculating values for the different regions of the molecule.
• the HLB value can be used to predict the surfactant properties of a molecule:
• “soyate” means a mixture of salts of fatty acids from soybean oil.
• the SFAE for use in the methods and barriers formulas of the present disclosure may include or be derived from “soyate.”
• oilseed fatty acids means fatty acids from plants, including but not limited to soybeans, peanuts, rapeseeds, barley, canola, sesame seeds, cottonseeds, palm kernels, grape seeds, olives, safflowers, sunflowers, copra, corn, coconuts, linseed, hazelnuts, wheat, rice, potatoes, cassavas, legumes, camelina seeds, mustard seeds, and combinations thereof.
• the fatty acid chains of the SFAE/glyceride/FAS blend can be oilseed fatty acids.
• wet strength means the measure of how well a web of fibers holding paper together (or other three-dimensional, solid, cellulose-based product) can resist a force of rupture when the paper is wet.
• the wet strength may be measured using a Finch Wet Strength Device from Thwing-Albert Instrument Company (West Berlin, N.J.). Where the wet strength is typically effected by wet strength additives such as kymene, cationic glyoxylated resins, polyamidoamine-epichlorohydrin resins, polyamine-epichlorohydrin resins, including epoxide resins.
• wet strength additives such as kymene, cationic glyoxylated resins, polyamidoamine-epichlorohydrin resins, polyamine-epichlorohydrin resins, including epoxide resins.
• the barrier formulation coated cellulose-based material as disclosed herein effects such wet strength in the absence of such additives.
• wet means covered or saturated with water or another liquid.
• the methods disclosed herein may include an additional step of exposing the contacted cellulose-based material to heat, radiation, a catalyst or a combination thereof for a sufficient time to bind the SGF blend, CNF, and/or enhanced CNF to the cellulose-based material.
• radiation may include, but is not limited to UV, IR, visible light, or a combination thereof.
• the reaction may be carried out at room temperature (i.e., 25° C.) to about 150° C., about 50° C. to about 100° C., or about 60° C. to about 80° C.
• natural waxes refers to relatively high molecular weight/high melting point materials.
• specific examples of “natural waxes” include, for example, biowaxes obtained from renewable resources, such as vegetable oils, fatty acids, and fatty esters, etc., (see, e.g., https://www.researchgate.net/publication/318385619_High_Quality_Biowaxes_from_Fatty_Acids_and_Fatty_Esters_Catalyst_and_Reaction_Mechanism_for_Accompanying_Reactions; and https://www.researchgate.net/figure/a-Preparation-of-canola-PFFA-18-biowax-b-Preparation-of-nanocellulose-from-canola_fig1_306527797).
• glycolglycerol as used herein has its common meaning and refers to acylglycerols, which are esters formed from glycerol and fatty acids. Glycerol has three hydroxyl functional groups, which can be esterified with one, two, or three fatty acids to form mono-, di-, and triglycerides. These structures can vary in their aliphatic chain as they can contain different carbon numbers, different degrees of unsaturation, and different configurations and positions of olefins.
• the fatty acids of the glycerides can be independently selected from one or more saturated fatty acids, one or more monounsaturated fatty acids, and/or one or more polyunsaturated fatty acids.
• a triglyceride may comprise three different fatty acid groups attached to the glycerol residue.
• Exemplary saturated fatty acids for use in the formulations/compositions of the disclosure can be selected from butyric acid (butanoic acid), caproic acid (hexanoic acid), caprylic acid (octanoic acid), capric acid (decanoic acid), lauric acid, (dodecanoic acid), myristic acid (tetradecanoic acid), palmitic acid (hexadecanoic acid), stearic acid (octadecanoic acid), arachidic acid (icosanoic acid), behenic acid (docosanoic acid), or lignoceric acid (tetracosanoic acid).
• Exemplary monounsaturated fatty acids for use in the formulations/compositions of the disclosure can be selected from caproleic acid, (dec-9-enoic acid), lauroleic acid ((Z)-dodec-9-enoic acid), myristoleic acid ((Z)-tetradec-9-enoic acid), palmitoleic acid ((Z)-hexadec-9-enoic acid), oleic acid ((Z)-octadec-9-enoic acid), elaidic acid ((E)-octadec-9-enoic acid), vaccenic acid ((E)-octadec-11-enoic acid), gadoleic acid ((Z)-icos-9-enoic acid), erucic acid ((Z)-docos-13-enoic acid), brassidic acid ((E)-docos-13-enoic acid), or nervonic acid ((Z)-tetracos
• the one or more glycerides may vary in their fatty acid alkyl groups.
• the one or more glycerides may contain fatty acid groups having different carbon numbers, different degrees of unsaturation, and/or different configurations and positions of olefins.
• the plurality of glycerides may include tripalmitin and/or tristearin.
• fatty acid salt (or “FAS”) as used herein has its common meaning and refers to a salt of any one or more of the fatty acids disclosed herein above.
• Exemplary cations for the fatty acid salts include but are not limited to calcium, potassium, and sodium salts.
• the fatty acid salts can be synthesized by known methods or extracted from plant oils or animal fats by known methods.
• One exemplary process comprises adding sodium hydroxide to fatty acids found in animal fats or plant oils (such as from oilseeds). For example, sodium palmitate can be obtained from palm oil.
• the SGF blend may contain only one or more glycerides, may contain only one or more fatty acid salts, or may contain both one or more glycerides and one or more fatty acid salts.
• the weight ratio of glycerides to fatty acid salts can be from about 0.1:99.9 to about 99:0.1, from about 10:90 to about 90:10, from about 20:80 to about 80:20, from about 35:65 to about 65:35, from about 40:60 to about 60:40, from about 45:55 to about 55:45, or about 50:50.
• the weight ratio of the SFAE in the SGF blend may be 0:100 to 100:0 or any weight ratio therebetween (e.g., 1:99; 5:95; 10:90; 20:80; 30:70; 40:60; 50:50; 60:50; 70:30; 80:20; 90:10; 95:5; 99:1).
• the weight ratio of the glycerides in the SGF blend may be 0:100 to 100:0 or any weight ratio therebetween (e.g., 1:99; 5:95; 10:90; 20:80; 30:70; 40:60; 50:50; 60:50; 70:30; 80:20; 90:10; 95:5; 99:1).
• the weight ratio of the fatty acid salts in the SGF blend may be 0:100 to 100:0 or any weight ratio therebetween (e.g., 1:99; 5:95; 10:90; 20:80; 30:70; 40:60; 50:50; 60:50; 70:30; 80:20; 90:10; 95:5; 99:1).
• the binding of the SGF blend alone is enough to make the contacted substrate hydrophobic: i.e., hydrophobicity is achieved in the absence of the addition of waxes, rosins, resins, diketenes, shellacs, vinyl acetates, PLA, PEI, oils, other water repellant chemicals or combinations thereof (i.e., secondary hydrophobes), including that other properties such as, inter alia, strengthening, stiffing, and bulking of the cellulose-based material is achieved by glyceride/fatty acid salt binding alone.
• the SFAE may comprise or consist essentially of sucrose esters of fatty acids.
• the SFAE may comprise a saccharide moiety, including but not limited to a sucrose moiety, which has been substituted by an ester moiety at one or more of its hydroxyl hydrogens.
• disaccharide esters for use in this disclosure can have the structure of Formula I of the '073 publication, which is incorporated herein by reference.
• a starch fatty acid ester can be used, where the starch may be derived from any suitable source such as dent corn starch, waxy corn starch, potato starch, wheat starch, rice starch, sago starch, tapioca starch, sorghum starch, sweet potato starch, and mixtures thereof.
• the SFAE compounds may have a high degree of substitution.
• the saccharide fatty acid ester is a sucrose polysoyate.
• saccharide fatty acid esters may be made by esterification with substantially pure fatty acids by known processes of esterification. They can be prepared also by trans-esterification using saccharide and fatty acid esters in the form of fatty acid glycerides derived, for example, from natural sources, for example, those found in oil extracted from oil seeds, for example soybean oil. Trans-esterification reactions providing sucrose fatty acid esters using fatty acid glycerides are described, for example, in U.S. Pat. Nos.
• the cellulose-based products generated by the methods disclosed herein can be configured to exhibit greater hydrophobicity (or water resistance) relative to the same cellulose-containing material without the treatment.
• the treated cellulose-containing material exhibits greater lipophobicity (or OGR) relative to the same cellulose-containing material without the treatment.
• the treated cellulose-containing material may be biodegradable, compostable, and/or recyclable.
• the treated cellulose-containing material is both hydrophobic (water resistant) and lipophobic (lipid resistant) (OGR).
• the cellulose-based products of the present disclosure may have improved mechanical properties compared to that same material untreated.
• paper bags treated by the process as disclosed herein show increased burst strength, Gurley Number, Tensile Strength and/or Energy of Maximum Load.
• the burst strength is increased by a factor of between about 0.5 to 1.0 fold, between about 1.0 and 1.1 fold, between about 1.1 and 1.3 fold, between about 1.3 to 1.5 fold.
• the Gurley Number increased by a factor of between about 3 to 4 fold, between about 4 to 5 fold, between about 5 to 6 fold and about 6 to 7 fold.
• the Tensile Strain increased by a factor of between about 0.5 to 1.0 fold, between about 1.0 to 1.1 fold, between about 1.1 to 1.2 fold and between about 1.2 to 1.3 fold.
• the Energy of Max Load increased by a factor of between about 1.0 to 1.1 fold, between about 1.1 to 1.2 fold, between about 1.2 to 1.3 fold, and between about 1.3 to 1.4 fold
• the cellulose-containing material can be a base paper comprising microfibrillated cellulose (MFC) or cellulose nanofiber (CNF) as described for example in U.S. Pub. No. 2015/0167243 (incorporated herein by reference in its entirety), where the MFC or CNF is added during the forming process and paper making process and/or added as a coating or a secondary layer to a prior forming layer to decrease the porosity of said base paper.
• the resulting contacted base paper is tuneably water and lipid resistant.
• the resulting base paper may exhibit a Gurley value of at least about 10-15 (i.e., Gurley Air Resistance (sec/100 cc, 20 oz.
• the barrier coating disclosed herein may be a laminate for one or more layers or may provide one or more layers as a laminate or may reduce the amount of coating of one or more layers to achieve the same performance effect (e.g., water resistance, grease resistance, and the like).
• the laminate may comprise a biodegradable and/or composable heat seal or adhesive.
• the SGF blend may be combined with one or more coating components for internal and surface sizing (alone or in combination), including but not limited to, pigments (e.g., clay, calcium carbonate, titanium dioxide, plastic pigment), binders (e.g., starch, soy protein, polymer emulsions, PvOH, casein), and additives (e.g., glyoxal, glyoxalated resins, zirconium salts, polyethylene emulsion, carboxymethyl cellulose, acrylic polymers, alginates, polyacrylate gums, polyacrylates, microbiocides, oil based defoamers, silicone based defoamers, stilbenes, direct dyes and acid dyes).
• pigments e.g., clay, calcium carbonate, titanium dioxide, plastic pigment
• binders e.g., starch, soy protein, polymer emulsions, PvOH, casein
• additives e.g., glyoxal,
• such components may provide one or more properties, including but not limited to, building a fine porous structure, providing light scattering surface, improving ink receptivity, improving gloss, binding pigment particles, binding coatings to paper, base sheet reinforcement, filling pores in pigment structure, reducing water sensitivity, resisting wet pick in offset printing, preventing blade scratching, improving gloss in supercalendering, reducing dusting, adjusting coating viscosity, providing water holding, dispersing pigments, maintaining coating dispersion, preventing spoilage of coating/coating color, controlling foaming, reducing entrained air and coating craters, increasing whiteness and brightness, and controlling color and shade. It will be apparent to one of skill in the art that combinations may be varied depending on the property(ies) desired for the final product
• the SGF blend may be present in the aqueous mixture or dispersion at a concentration of at least 0.025% (wt/wt) of the total cellulose fiber present in the dispersion.
• the SGF blend may be present at about 0.05% (wt/wt) to about 0.1% (wt/wt), about 0.1% (wt/wt) to about 0.5% (wt/wt), about 0.5% (wt/wt) to about 1.0% (wt/wt), about 1.0% (wt/wt) to about 2.0% (wt/wt), about 2.0% (wt/wt) to about 3.0% (wt/wt), about 3.0% (wt/wt) to about 4.0% (wt/wt), about 4.0% (wt/wt) to about 5.0% (wt/wt), about 5.0% (wt/wt) to about 10% (wt/wt), or about 10% (wt/wt) to about 50% (wt/wt/wt)
• CNF may be present in the aqueous mixture or dispersion at a concentration of at least 0.025% (wt/wt) of the total cellulose fiber present in the dispersion.
• the CNF may be present at about 0.05% (wt/wt) to about 0.1% (wt/wt), about 0.1% (wt/wt) to about 0.5% (wt/wt), about 0.5% (wt/wt) to about 1.0% (wt/wt), about 1.0% (wt/wt) to about 2.0% (wt/wt), about 2.0% (wt/wt) to about 3.0% (wt/wt), about 3.0% (wt/wt) to about 4.0% (wt/wt), about 4.0% (wt/wt) to about 5.0% (wt/wt), about 5.0%(wt/wt) to about 10% (wt/wt), about 10% (wt/wt) to about 20% (wt/wt), about 20% (wt/wt), about 20% (
• the enhanced CNF may be present in the aqueous mixture or dispersion at a concentration of at least 0.025% (wt/wt) of the total cellulose fiber present in the dispersion.
• the enhanced CNF may be present at about 0.05% (wt/wt) to about 0.1% (wt/wt), about 0.1% (wt/wt) to about 0.5% (wt/wt), about 0.5% (wt/wt) to about 1.0% (wt/wt), about 1.0% (wt/wt) to about 2.0% (wt/wt), about 2.0% (wt/wt) to about 3.0% (wt/wt), about 3.0% (wt/wt) to about 4.0% (wt/wt), about 4.0% (wt/wt) to about 5.0% (wt/wt), about 5.0%(wt/wt) to about 10% (wt/wt), about 10% (wt/wt) to about 20% (wt/wt),
• coating weight is the weight of a material (wet or dry) applied to a substrate. It is expressed in pounds per specified ream or grams per square meter
• the enhanced CNF may be present at a coating weight of at least about 0.05 g/m 2 on the surface of the substrate.
• the SGF blend may be present at a coating weight of about 0.05 g/m 2 to about 1.0 g/m 2 , about 1.0 g/m 2 to about 2.0 g/m 2 , about 2 g/m 2 to about 3 g/m 2 3 g/m 2 to about 4 g/m 2 , about 4 g/m 2 to about 5 g/m 2 , about 5 g/m 2 to about 10 g/m 2 , or about 10 g/m 2 to about 20 g/m 2 on a surface of the cellulose-based material.
• the SGF blend may be present at a coating weight of at least about 0.05 g/m 2 on the surface of the substrate.
• the SGF blend may be present at a coating weight of about 0.05 g/m 2 to about 1.0 g/m 2 , about 1.0 g/m 2 to about 2.0 g/m 2 , about 2 g/m 2 to about 3 g/m 2 3 g/m 2 to about 4 g/m 2 , about 4 g/m 2 to about 5 g/m 2 , about 5 g/m 2 to about 10 g/m 2 , or about 10 g/m 2 to about 20 g/m 2 on a surface of the cellulose-based material.
• the CNF may be present at a coating weight of at least about 0.05 g/m 2 (gsm) on the surface of the cellulose-based material (or substrate).
• the CNF can be present at a coating weight of about 0.05 g/m 2 to about 1.0 g/m 2 , about 1.0 g/m 2 to about 2.0 g/m 2 , about 2 g/m 2 to about 3 g/m 2 , 3 g/m 2 to about 4 g/m 2 , about 4 g/m 2 to about 5 g/m 2 , about 5 g/m 2 to about 10 g/m 2 , about 10 g/m 2 to about 20 g/m 2 , or about 20 g/m 2 to about 30 g/m 2 on a surface of the cellulose-based material.
• the barrier formulation may include one or more emulsifiers or emulsifying agents in a concentration sufficient to form an emulsion of the SGF blend and water and/or to form an emulsion of the enhanced CNF and water.
• Suitable emulsifiers or emulsifying agents include buffers, polyvinyl alcohol (PvOH), carboxymethyl cellulose (CMC), milk proteins, gelatins, starches, acetylated polysaccharides, alginates, carrageenans, chitosans, inulins, long chain fatty acids, waxes, agar, alginates, glycerol, gums, lecithins, poloxamers, mono-, di-glycerols, monosodium phosphates, monostearate, propylene glycols, detergents, cetyl alcohol, glycerol esters, (saturated) ((poly)unsaturated) fatty acid methyl esters, and combinations thereof.
• the methods disclosed herein may include a step of predetermining a content of the SGF blend and/or the components of the SGF blend to be included in the enhanced CNF.
• this step of predetermining can be performed prior to the preparing the enhanced CNF.
• the step of predetermining can be performed to achieve the desired effects.
• the step of predetermining can be performed to achieve a desired level of water resistance and/or a desired level of oil and grease resistance when the enhanced CNF is used in a barrier formulation and/or added to the papermaking furnish on the wet end.
• the step of predetermining can be performed to increase dewatering rate of the furnish or fiber slurry. Increasing the dewatering rate improves the rate, for example, of producing a cellulose-based article.
• dewatering a slurry containing CNF is one of the biggest problems directed to use of CNF.
• the increased dewatering rate applies, for example, to both the making of the enhanced CNF binder and the use of the enhanced CNF binder in a barrier formulation.
• Dewatering is well known in the papermaking industry, and is also explained in Smook, which is incorporated herein by reference in its entirety elsewhere in this disclosure.
• the barrier formulations may include one or more pigments commonly used in the paper industry.
• the one or more pigments can be present in the formulation in a concentration of about 0.1% to about 90% by weight based on a total weight of the formulation.
• the concentration of the pigment can be from about 1% to 10% by weight, from about 11% to 20% by weight, from about 21% to 30% by weight, from about 31% to 40% by weight, from about 41% to 50% by weight, 51% to 60% by weight, 61% to 70% by weight, 71 to 80% by weight, 81% to 90% by weight, or any other range between 0.1% to 90% by weight.
• the use of pigments is well known in the paper industry, and the pigment concentration can be chosen to vary the properties of the final product.
• Example pigments include clay, calcium carbonate, titanium dioxide, kaolin, talc, plastic pigment, silica, silicates, metal oxides, alumina, aluminates, and diatomaceous earth.
• the barrier formulation may include one or more charged polymers to aid in the retention of the enhanced CNF and/or the SGF blend on the cellulose-based substrate.
• the one or more charged polymers may include one or more cationic polymers, anionic polymers, nonionic polymers, and/or zwitterionic polymers.
• the charged polymer may include a combination of a relatively low molecular weight cationic polymer and a relative high molecular weight anionic polymer.
• a blend of charged polymers are used to achieve a “bimodal”-type weight average MW using a combination of charged polymers having any MW in the ranges above (e.g., a first charged polymer having a weight average MW of less than 1,000,000 used in combination with a second charged polymer having a weight average MW greater than 2,000,000; wherein the weight ratio of the first charged polymer to the second charged polymer is 10:90 to 90:10).
• a concentration of the cationic polymer in the formulation is from about 0.01% to about 5% by weight, from about 0.01% to about 3% by weight, 0.05% to about 0.1% by weight, or from about 0.1% to about 1% by weight, or from about 1% to about 3% by weight when a total weight of the formulation is considered 100%.
• a weight ratio in the formulation of the cationic polymer to the enhanced CNF is from about 0.1:99.9 to about 20:80, from 0.5:99.5 to about 15:85, from about 1:99 to about 10:90, or from about 2.5:97.5 to about 7.5:92.5.
• a weight ratio in the formulation of the cationic polymer to the SGF blend is from about 0.1:99.9 to about 20:80, from 0.5:99.5 to about 15:85, from about 1:99 to about 10:90, or from about 2.5:97.5 to about 7.5:92.5.
• the barrier formulation may also include one or more conventional papermaking binders.
• Example binders include CNF, the enhanced CNF of the present disclosure, starch, polymers, polymer emulsions, PvOH, prolamins, or combinations thereof.
• the formulation may not contain any binder other than the enhanced CNF.
• the cellulose-based material may be dried before treatment.
• the methods as disclosed may be used on any cellulose-based surface, including but not limited to, a film, a rigid container, fibers, pulp, a fabric or the like.
• the amount of barrier formulation applied is sufficient to partially cover at least one surface of a cellulose-based material. For example, only those surfaces exposed to the ambient atmosphere are covered by the barrier formulation, or only those surfaces that are not exposed to the ambient atmosphere are covered by the barrier formulation (e.g., masking). As will be apparent to one of skill in the art, the amount of barrier formulation applied may be dependent on the use of the material to be covered.
• any suitable coating process may be used to deliver any of the various barrier formulations in the course of practicing the methods.
• the coating processes include immersion, spraying, painting, printing, and any combination of any of these processes, alone or with other coating processes adapted for practicing the methods as disclosed.
• materials treated according to the disclosed methods display a complete biodegradability as measured by the degradation in the environment under microorganismal attack.
• the barrier coated product of the present disclosure may have a TAPPI T 559 KIT test value of from about 3 to about 12, greater than 4, greater than 5, greater than 6, greater than 7, greater than 8, greater than 9, greater than 10, greater than 11, etc.
• a surface of the barrier coated product of the present disclosure may exhibit a water contact angle between about 60 to 120 degrees, of at least about 90 degrees, at least about 100 degrees, at least about 110 degrees, at least about 120 degrees, etc.
• the barrier formulation of the present disclosure forms a stable aqueous composition
• the term “stable aqueous composition” is defined as an aqueous composition which is substantially resistant to viscosity change, coagulation, and sedimentation over at least an 8-hour period when contained in a closed vessel and stored at a temperature in a range of from about 0 degrees C. to about 60 degrees C.
• Some embodiments of the barrier formulation are stable over at least a 24-hour period, and often over at least a 6-month period.
• the barrier coated product obtained by the methods of the present disclosure does not include a PFAS. In some embodiments, the barrier coated product of the present disclosure does not include a PFAS in the barrier coating.
• the barrier coated product obtained by the methods of the present disclosure is compatible with traditional paper recycling programs: i.e., poses no adverse impact on recycling operations, like polyethylene, polylactic acid, or wax coated papers do.
• the barrier coated product obtained by the methods of the present disclosure is bio-based.
• bio-based or “biobased” means a material intentionally made from substances derived from living (or once-living) organisms. In a related aspect, material containing at least about 50% of such substances is considered bio-based.
• the barrier coated product obtained by the methods of the present disclosure may be entirely bio-based. In some aspects, the barrier formulations of the present disclosure may be entirely bio-based.
• the barrier coated product obtained by the methods of the present disclosure is recyclable.
• “recyclable”, including grammatical variations thereof, means a material that is treatable or that can be processed (with used and/or waste items) so as to make said material suitable for reuse.
• the barrier coated product of the present disclosure is biodegradable.
• biodegradable including grammatical variations thereof, means capable of being broken down especially into innocuous products by the action of living things (e.g., by microorganisms).
• Example 1 is a lab study regarding the use of CNF in molded pulp products with barrier properties.
• Example 1 The equipment used in Example 1 are as follows:
• Example 1 The materials that may be used in Example 1 are as follows:
• SE-15 was obtained from HANGZHOU UNION BIOTECHNOLOGY CO., LTD. SE-15 is marketed as a sucrose fatty acid ester. SE-15 was analyzed and was found to contain about 15 to 30% by weight saccharide fatty acid ester, about 40 to 60% by weight glycerides, and a balance fatty acid salts plus trace components.
• **SE-9 was obtained from ZHEJIANG SYNOSE TECH.
• SE-9 is marketed as a sucrose fatty acid ester.
• SE-9 was analyzed and was found to be similar in composition to SE-15, except for having a higher glycerides content and about 10 to 20% less sucrose ester.
• SE-30 was obtained from EAST CHEMSOURCES LIMITED. SE-30 is marketed as a sucrose fatty acid ester. SE-30 was analyzed and was found to contain greater than 80% sucrose esters with a variety of substitutions. The remainder of the product was glycerides with relatively low (less than 5% by weight) salt.
• Example 1 The test procedure for Example 1 was as follows:

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