FIELD OF THE DISCLOSURE

[0001] 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.

BACKGROUND OF THE DISCLOSURE

[0002] 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. [0003] 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.

[0004] This problem is usually addressed in the industry by coating the cellulose fiber with some kind of hydrophobic organic material/fluorocarbons (e.g., per- and polyfluoroalkyl substances (PFAS)), 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. For example, 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.

[0005] Industry has utilized compounds based on fluorocarbon chemistry for many years to produce articles having improved resistance to penetration by oil and grease, due to the ability of fluorocarbons to lower the surface energy of the articles. One emerging issue with the use of perfluorinated hydrocarbons is that they are remarkably persistent in the environment. The EPA and FDA have recently begun a review of the source, environmental fate, and toxicity of these compounds. A recent study reported a very high (>90%) rate of occurrence of perfluorooctane sulfonate in blood samples taken from school children. The expense and potential environmental liability of these compounds has driven manufacturers to seek alternative means of producing articles having resistance to penetration by oil and grease.

[0006] While lowering the surface energy improves the penetration resistance of the articles, lowering the surface energy also has some disadvantages. For example, 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. If a greaseproof paper is to be used as a pressure sensitive label having an adhesive applied on one side, the low surface energy may reduce the strength of the adhesion. To improve their printability, coat-ability or 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.

[0007] It would be desirable to design a “green,” 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.

[0008] Another problem is that conventional coatings for imparting hydrophobic and/or lipophobic barrier properties, including the fluorocarbon and petrochemical coatings noted herein, is that they tend to perform poorly at the folds, creases, and the like of the article coated with the material. Specifically, the article typically has inferior water resistance and/or grease resistance at these locations. Such a "grease creasing effect" may be defined as the sorption of grease in a paper structure that is created by folding, pressing or crushing said paper structure. A conventional solution to the grease creasing effect is to add a latex, a polyvinyl alcohol, or similar resin to the coating to achieve improved coating coverage at these locations. However, with this conventional solution, the water resistance and/or oil and grease resistance of these locations may still be inferior to the flat portions of the article; this conventional solution increases cost by the addition of the resin component; and this conventional solution is not entirely bio-based, since the latex and polyvinyl alcohol may either be synthetic and/or not easily recyclable.

[0009] U.S. Patent Application Publication No. 2018/0066073 (hereinafter “the ‘073 publication”), which is incorporated herein by reference in its entirety, 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. In particular, 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.

[0010] U.S. Provisional Patent Application Publication No. 63/022,097, filed May 8, 2020, (hereinafter “the ‘097 application”), which is incorporated herein by reference in its entirety, 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. In particular, 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.

[0011] PCT/US2020/014923 (hereinafter “the ‘923 application”), which is incorporated herein by reference in its entirety, 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. Compositions comprising combinations of SFAE, a latex and optionally a mineral or other additives are also disclosed.

[0012] US 16/568,953 (hereinafter “the ‘953 application”), which is incorporated herein by reference in its entirety, 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.

[0013] US 16/456,499 (hereinafter “the ‘499 application”), which is incorporated herein by reference in its entirety, 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.

[0014] US 16/456,433 (hereinafter “the ‘433 application”), which is incorporated herein by reference in its entirety, discloses methods of treating cellulosic materials with compositions that allow greater retention of inorganic particles on cellulosic substrates. The methods as disclosed provide combining SFAE with such inorganic particles and applying such combinations on cellulosic materials to eliminate or reduce the use of retention aids or binders for fdler in the paper making process. Compositions comprising such combinations of SFAE and inorganic particles are also disclosed.

[0015] The use of a binder obtained from a natural source has also become of increasing importance for providing a “green,” biobased product.

[0016] Nanocellulose is a term referring to nano-structured cellulose, which may be cellulose nanocrystals (CNC or NCC), cellulose nanofibrils (CNF) (which are also referred to in the art as cellulose nanofibers and nanofibrilated cellulose), or bacterial nanocellulose.

[0017] CNF is a material composed of nanosized cellulose fibrils typically having a high aspect ratio (length to width ratio). CNF is typically obtained from woodpulp or another natural source of cellulose fibers, typically by a process that includes subjecting the pulp/fibers to mechanical shear forces.

[0018] CNF has been used as a binder in the papermaking process. In this regard, the inventors determined that the use of CNF as an additive on the wet-end and in coating applications can provide improved OGR. However, 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. [0019] Based on the summary above, there is still a need for “green,” bio-based coatings for cellulose-based materials that provide improved water and/or OGR resistance, and “green” cellulose-based molded articles having improved water and/or OGR resistance.

SUMMARY OF THE DISCLOSURE

[0020] The present disclosure provides methods that address one or more of the limitations and/or concerns in the conventional art discussed above and/or provide one or more improvements thereon. However, the present disclosure is not required to address any of the limitations and/or concerns.

[0021] In one embodiment, 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.

[0022] As used herein, 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. In some embodiments, 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. In some embodiments, the SGF blend consists essentially of the SFAE, glycerides, and/or F AS. In some embodiments, the SGF blend consists of the SF AE, glycerides, and/or FAS.

[0023] The enhanced cellulose nanofibril binder (or enhanced CNF) according to the present disclosure can provide certain benefits. For example, 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.

[0024] In one aspect of the present disclosure, the enhanced cellulose nanofibril binder consists essentially of the CNF and the SGF blend.

[0025] In another aspect of the enhanced cellulose nanofibril binder, a weight ratio of the CNF to the SGF blend is about 1:99 to about 99: 1, or about 5:95 to about 95:5, or about

10:90 to about 90: 10, or about 15:85 to about 85:15, or about 20:80 to about 80:20, or about

25:75 to about 75:25, or about 30:70 to about 70:30, or about 35:65 to about 65:35, or about

40:60 to about 60:40, or about 45:55 to about 55:45, or about 50:50.

[0026] In one embodiment, 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.

Alternatively, the SGF blend can be bound to die 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.

[0027] In one embodiment, 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. [0028] In one aspect, the method of obtaining the enhanced CNF may farther include a step of reducing the water content of cellulose/SGF mixture, such as by draining the water. [0029] In one aspect, the method of obtaining the enhanced CNF may further include 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.

[0030] In one aspect, the pre-treatment may include lower the pH of the aqueous mixture of cellulose pulp by adding an acid.

[0031] In one embodiment, the present disclosure provides a barrier formulation that includes the enhanced CNF according to the present disclosure. The composition of the barrier formulation can be chosen to tuneably derivative a cellulose-based material by a method known in the art, such as in the ‘073 publication or ‘097 application.

[0032] In one embodiment, 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.

[0033] In one aspect, the method further includes molding the fibrous web into a molded article having a three-dimensional shape.

[0034] In one embodiment, a method for imparting a barrier property to a cellulose- based material is provided, the method 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 the barrier property, wherein the barrier property is one or more selected from the group consisting of water resistance, lipid resistance, and gas resistance. [0035] In one embodiment, a barrier formulation is provided, the 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.

[0036] In one aspect, the second SGF blend of the barrier formulation can be chosen to tuneably derivative a cellulose-based material by a method known in the art, such as in the ‘073 publication or ‘097 application.

[0037] In one aspect, the barrier formulation of the present disclosure can include a pigment conventionally used in the papermaking industry.

[0038] In one embodiment, a method for imparting a barrier property to a cellulose- based material, the method 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.

[0039] 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.

[0040] In one aspect, when a total weight of the barrier formulation used in the method for imparting a barrier property according to the present disclosure is considered to be 100% by weight, the barrier formulation includes about 4% by weight to about 96% by weight of the CNF, and about 4% by weight to about 96% by weight of the SGF blend. [0041] In one aspect, 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.

[0042] In one aspect, the SGF blend can be present in the aqueous mixture or dispersion at a total concentration of at least 0.025% (wt/wt) of the total cellulose fiber present in the aqueous mixture.

[0043] In one aspect, the aqueous mixture includes one or more pigments conventionally used in the papermaking industry.

[0044] In one aspect, 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.%.

[0045] In one aspect, the method further includes reducing the water content of the aqueous mixture, such as by draining the water.

[0046] In another aspect, 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.

[0047] In one aspect, the SGF blend is present at a weight of at least about 0.05 g/m ² on the surface of the substrate.

[0048] The cellulose-based substrate is not particularly limited. In one aspect, 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 noncarbonated 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 for electronic goods, an internal or external piece of furniture, a curtain, upholstery, fabric, film, a box, a sheet, a tray, a pipe, a water conduit, clothing, a medical device, pharmaceutical packaging, a contraceptive, camping equipment, cellulosic material that is molded, and combinations thereof.

[0049] In one aspect, 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°.

[0050] In one aspect, 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.

[0051] In one aspect, 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° and/or a TAPPI T 559 KIT test value of from 3 to 12 in the absence of any secondary hydrophobes.

[0052] In one embodiment, a method of making an enhanced cellulose nanofibril binder is provided, the method including: 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 and allowing the SGF blend bind to the CNF. [0053] In one aspect, the method of making the enhanced CNF further includes reducing the water content of the CNF/SGF mixture.

[0054] In one embodiment, a method of making an enhanced cellulose nanofibril binder is provided, the method 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.

[0055] In one aspect, 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.

[0056] In one embodiment, a method of making a molded article is disclosed, the method 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 nanofibril binder according to the present disclosure.

[0057] In one embodiment, another method of making a molded article is disclosed, the method 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; and dewatering the layer of pulp on the forming tool to achieve the molded article, wherein the cellulose composition includes cellulose pulp and a barrier formulation according to the present disclosure.

[0058] In one embodiment, another method of making a molded article is disclosed, the method 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.

[0059] In one aspect, 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.%.

[0060] In one aspect, the layer of pulp present on the forming tool is de watered 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.

[0061] In one aspect, the cellulose composition for the method of making the molded articles comprises a fiber mixture consisting essentially of chemithermomechanical pulp (CTMP), thermomechanical pulp (TMP), chemical pulp or semichemical pulp, or a combination thereof. The pulps can be either bleached or unbleached.

[0062] In one aspect, the forming tool is porous or perforated so that water can be removed during forming during a dewatering/drying step.

[0063] In one aspect, the method of making the molded article further includes coating a surface of the molded article with a barrier formulation comprising the SGF blend by a process of immersion, spraying, painting, printing, or any combination of any of these processes.

[0064] In one aspect, the coating of the surface of the molded article with the barrier formulation takes place while the molded article is an intermediate molded article having a relatively high aqueous content and a fiber content of about 20 to 50 wt.%, preferably about

30 to 40 wt.%.

[0065] In one embodiment, the disclosure provides a cellulose-based product obtained according to any of the methods disclosed herein, which is a three dimensional molded product, such as a molded food packaging product, made from cellulose fibers.

[0066] In one aspect, the three dimensional shape obtained by the methods of making the molded article is not particularly limited.

[0067] In one aspect, examples of the three dimensional shape are a bowl, a cup, a plate, a fork, a spoon, or a knife.

[0068] In some embodiments, the barrier formulation consists essentially of CNF and the SGF blend.

[0069] In some embodiments, a weight ratio in the barrier formulation of CNF to SGF blend is from about 20: 1 to about 1:5. In some embodiments, the weight ratio may be about 5: 1 to about 1:5.

[0070] In some embodiments, when a total weight 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. In some embodiments, the amount of the CNF can be about 10% by weight to about 70% by weight. In some embodiments, the amount of the SGF blend can be about 30 % by weight to about 90% by weight.

[0071] In some embodiments, the barrier formulation further includes one or more prolamins.

[0072] In some embodiments, the one or more prolamins are selected from wheat (gliadin), barley (hordein), rye (secalin), com (zein), sorghum (kafirin), and/or oats (avenin). [0073] In some embodiments, the cellulose-based material includes cellulose fiber suitable for making paper, and the aqueous mixture or dispersion is a papermaking furnish or stock.

[0074] In some embodiments, 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°.

[0075] In some embodiments, the molded article exhibits TAPPI T 559 KIT test value of from 3 to 12.

[0076] In some embodiments, the molded article exhibits reduced permeability to gases (referred to as “gas resistance”) (e.g., resistance to oxygen, nitrogen, and carbon dioxide). In some aspects, the gas resistance is a reduced permeability to oxygen.

[0077] In some embodiments, 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.

[0078] In some embodiments, the barrier formulation is tn the form of an emulsion .

[0079] In some embodiments, the barrier formulation is a stable aqueous composition.

[0080] In another embodiment, a method of making a cellulose-based product having a barrier property is provided, the method including: obtaining a furnish that includes an aqueous mixture of cellulose fiber; adding the SGF blend to the furnish; adding CNF to the furnish; and adding a retention aid to the furnish for aiding in the retention of the SGF blend on the cellulose fiber

[0081] In some embodiments, one or more charged polymers can be added in the wetend to aid in the retention of the SFAE on the cellulose-based material. The one or more charged polymers may include one or more cationic polymers, anionic polymers, nonionic polymers, and/or zwitterionic polymers. In some embodiments, the charged polymer includes a combination of a relatively low molecular weight cationic polymer and a relative high molecular weight anionic polymer.

[0082] In some embodiments, 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).

[0083] In some embodiments, 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.

DETAILED DESCRIPTION OF THE EMBODIMENTS

[0084] Before the present compositions, methods, and methodologies are described in more detail, it is to be understood that the disclosure is not limited to particular compositions, methods, and experimental conditions described, as such compositions, methods, and conditions may vary. It is also to be understood that the terminology used herein is for purposes of describing particular embodiments only, and is not intended to be limiting, since the scope of the present invention will be limited only in the appended claims.

[0085] As used in this specification and the appended claims, the singular forms "a," "an," and "the" include plural references unless the context clearly dictates otherwise. Thus, for example, 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.

[0086] Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this disclosure belongs. Any methods and materials similar or equivalent to those described herein may be used in the practice or testing of the disclosure, as it will be understood that modifications and variations are encompassed within the spirit and scope of the instant disclosure.

[0087] The present disclosure provides an enhanced cellulose nanofibril binder.

[0088] Cellulose nanofibrils (also referred to herein as CNF) and their method of production are well known in the art.

[0089] 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.

[0090] 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.

[0091] In some embodiments, 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. In other embodiments, 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.

[0092] As noted above, 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.

[0093] 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.

[0094] 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.

[0095] Another aspect of the present disclosure is that the 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).

[0096] In some embodiments, the enhanced CNF can be used on the wet end of the papermaking process by adding the enhanced CNF directly into the papermaking furnish. Alternatively, in other embodiments, a combination of CNF and the SGF blend can be added directly into the papermaking furnish to obtain similar benefits.

[0097] 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. In some aspects, the charged polymer can be used to control the electrostatic charge of the formulation containing the SGF blend.

[0098] In other embodiments, prolamins can be used as a binder. This is explained, for example, in U.S. provisional application No. 63/044,820 filed June 26, 2020 (hereinafter “the ‘820 application), which is incorporated herein by reference in its entirety. [0099] Prolamins may be used as a binder not only for the SGF blend and/or the CNF, but also for conventional pigments added to a papermaking furnish. Pigments are typically relatively small and charged on their surfaces, including their edges. Thus, the pigments can easily be caught up in (and selectively retained by) the prolamin matrix.

[0100] In addition to being added directly into the papermaking furnish, 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.

[0101] Alternatively, 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.

[0102] Alternatively, 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.

[0103] In the present disclosure, the interaction between the SGF blend and the CNF may be by ionic, hydrophobic, van der Waals interaction, covalent bonding, or a combination thereof. As used herein, "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.

[0104] In the present disclosure, 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. [0105] In the present disclosure, 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.

[0106] In some embodiments, the barrier formulation may also contain one or more conventional binders used in papermaking, such as latex, PvOH, and starch.

[0107] As used herein, "cellulosic" means natural, synthetic, or semisynthetic materials that can be molded or extruded into objects (e.g., bags, sheets) or fdms 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). In another example, cellulose, a complex carbohydrate (G,H ioOs) _n that is composed of glucose units, which forms the main constituent of the cell wall in most plants, is cellulosic.

[0108] Examples of the cellulosic material (or cellulose-based material) for use herein can be cellulose fibers conventionally used in the paper industry, microfibrillated cellulose (MFC), nanofibrilated cellulose (or CNF), or cellulose nanocrystals.

[0109] As used herein, "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 [0110] As used herein, "effect", including grammatical variations thereof, means to impart a particular property to a specific material.

[0111] As used herein, "hydrophobe" means a substance that does not attract water. For example, 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.

[0112] As used herein, "hydrophobicity" means the property of being water-repellent, tending to repel and not absorb water. [0113] As used herein, "lipid resistance" or "lipophobicity" means the property of being lipid-repellent, tending to repel and not absorb lipids, grease, fats and the like. In a related aspect, the grease resistance may be measured by a "3M KIT" test, a TAPPI T559 Kit test, or a Cobb oil test.

[0114] As used herein, "cellulose-containing material" or "cellulose-based material" means a composition which consists essentially of cellulose. For example, 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.

[0115] As used herein, "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. In a related aspect, where cellulose fibers are treated by the methods as disclosed herein, 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). [0116] As used herein, "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.

[0117] As used herein, "tunable", including grammatical variations thereof, means to adjust or adapt a process to achieve a particular result.

[0118] As used herein, "water contact angle" means the angle measured through a liquid, where a liquid/vapor interface meets a solid surface. It quantifies the wettability of the solid surface by the liquid. The contact angle is a reflection of how strongly the liquid and solid molecules interact with each other, relative to how strongly each interacts with its own kind. On many highly hydrophilic surfaces, water droplets will exhibit contact angles of 0° to 30°. Generally, if the water contact angle is larger than 90°, the solid surface is considered hydrophobic. Water contact angle may be readily obtained using an Optical Tensiometer (see, e.g., Dyne Testing, Staffordshire, United Kingdom).

[0119] As used herein, "water vapour permeability" means breathability or a textile's ability to transfer moisture. There are at least two different measurement methods. One, the MVTR Test (Moisture Vapour Transmission Rate) in accordance with ISO 15496, describes the water vapor permeability (WVP) of a fabric and therefore the degree of perspiration transport to the outside air. The measurements determine how many grams of moisture (water vapor) pass through a square meter of fabric in 24 hours (the higher the level, the higher the breathability).

[0120] In one aspect, 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.

[0121] 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.

[0122] This method may be used to monitor paper or board production for specific end uses provided acceptable correlation has been established between test values and the paper's end use performance. Due to the nature of the test and the penetrant, it will not necessarily correlate sufficiently to be applicable to all end use requirements. This method measures sizing by rate of penetration. Other methods measure sizing by surface contact, surface penetration, or absorption. Size tests are selected based on the ability to simulate the means of water contact or absorption in end use. This method can also be used to optimize size chemical usage costs.

[0123] As used herein, "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 x 10 ^{-1 1} (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 International Organization for Standardization (ISO) has specified permeability using the SI unit hectopascal (hPa) for pressure. Hence Dk = 10 " (cm ² ml O ₂ ) /(s ml hPa). The Barrer unit can be converted to hPa unit by multiplying it by the constant 0.75. [0124] As used herein "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).

[0125] As used herein, "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.

[0126] As used herein, "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). In addition, for stiffness, "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).

[0127] 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.

[0128] Griffin's method for non-ionic surfactants as described in 1954 works as follows:

HLB = 20 * M _h /M

[0129] where M _h is the molecular mass of the hydrophilic portion of the molecule, and M is the molecular mass of the whole molecule, giving a result on a scale of 0 to 20. An HLB value of 0 corresponds to a completely lipophilic/hydrophobic molecule, and a value of 20 corresponds to a completely hydrophilic/lipophobic molecule.

[0130] The HLB value can be used to predict the surfactant properties of a molecule: < 10 : Lipid-soluble (water-insoluble)

> 10 : Water-soluble (lipid-insoluble)

1.5 to 3 : anti-foaming agent

3 to 6 : W/O (water in oil) emulsifier

7 to 9 : wetting and spreading agent

13 to 15 : detergent

12 to 16 : O/W (oil in water) emulsifier

15 to 18 : solubiliser or hydrotrope.

[0131] In some embodiments, the HLB values for the SFAE/glyceride/FAS blend (or the entire formulation comprising said blend) as disclosed herein may be in the lower range. In some embodiments, the HLB values for the SFAE/glyceride/FAS blend (or the entire formulation comprising said blend) as disclosed herein may be in the middle to higher ranges. [0132] As used herein, "SEFOSE®" denotes a sucrose fatty acid ester made from soybean oil (soyate) which is commercially available from Procter & Gamble Chemicals (Cincinnati, OH) under the trade name SEFOSE 1618U (see sucrose polysoyate below), which contains one or more fatty acids that are unsaturated. SEFOSE® is an exemplary SFAE for use in the methods and barrier formulations of the present disclose.

[0133] As used herein, "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."

[0134] As used herein, "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, com, 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.

[0135] As used herein "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, NJ). 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. In embodiments, the barrier formulation coated cellulose- based material as disclosed herein effects such wet strength in the absence of such additives. [0136] As used herein "wet" means covered or saturated with water or another liquid. [0137] 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. In a related aspect, such radiation may include, but is not limited to UV, IR, visible light, or a combination thereof. In another related aspect, 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.

[0138] As used herein, the term “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_Qual ity_Biowaxes_from_Fatty_ Acids_and_Fatty_Esters_Catalyst_and_Reaction_Mechanism_for_A ccompanying_Reactions ; and https://www. researchgate .net/figure/a-Preparation-of-canola-PFFA- 18-biowax-b- Preparation-of-nanocellulose-from-canola_figl_306527797).

[0139] As used herein, the term “cellulose crosslinkers” means known cellulose crosslinkers such as glyoxal, and small reactive dialdehydes or anhydrides.

[0140] The term “glycerides” 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.

[0141] The glycerides may be obtained by esterification with substantially pure fatty acids by known processes of esterification. The glycerides can also be extracted from plant oils and animal fats by known methods of extraction.

[0142] The term “fatty acid” as used herein has its common meaning and refers to a carboxylic acid with an aliphatic chain, which may be saturated or unsaturated. The term fatty acid as used herein may refer to the fatty acid group bound to the glycerol residue of the glyceride.

[0143] The fatty acid groups of the glycerides can be any known fatty acid. In preferred embodiments, the fatty acid is known to be present in food, is edible, and/or is approved by the FDA. In some embodiments, the fatty acids are obtained from oilseeds. In other embodiments, the fatty acids are obtained from other sources of naturally edible fats and oil.

[0144] 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. By independently, this means, for example, that a triglyceride may comprise three different fatty acid groups attached to the glycerol residue.

[0145] 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).

[0146] 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-en-ic 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-15-enoic acid).

[0147] Exemplary polyunsaturated fatty acids for use in the formulations/compositions of the disclosure can be selected from linoleic acid (LA) ((9Z,12Z)-octadeca-9,12-dienoic acid), alpha-Linolenic acid (ALA) ((9Z,12Z,15Z)-octadeca- 9, 12, 15 -trienoic acid), gamma-Linolenic acid (GLA) ((6Z,9Z,12Z)-octadeca-6,9,12-trienoic acid), columbinic acid ((5E,9E,12E)-octadeca-5,9,12-trienoic acid), stearidonic acid ((6Z,9Z,12Z,15Z)-octadeca-6,9,12,15-tetraenoic acid), mead acid ((5Z,8Z, 11Z)-icosa-5,8,11- trienoic acid), dihomo-Υ-linolenic acid (DGLA) ((8Z,1 lZ,14Z)-icosa-8,l 1,14-trienoic acid), arachidonic acid ((5Z,8Z,l lZ,14Z)-icosa-5,8,11,14-tetraenoic acid), eicosapentaenoic acid

(EPA) ((5Z,8Z,l lZ,14Z,17Z)-icosa-5,8,1 1,14,17-pentaenoic acid), docosapentaenoic acid (DPA) ((7Z,10Z,13Z,16Z,19Z)-docosa-7,10,13,16,19-pentaenoic acid), docosahexaenoic acid (DHA) ((4Z,7Z, 10Z, 13Z, 16Z, 19Z)-docosa-4,7, 10,13,16,19-hexaenoic acid) .

[0148] In some embodiments, the one or more glycerides may include a blend of one or more monoglycerides, one or more diglycerides, and/or one or more triglycerides. In this regard, the mono-, di-, and triglycerides can be blended in any weight ratio. That is, any one of the mono-, di-, or triglycerides could be the major glyceride component of the formulation by weight (that is, greater than 50% by weight when a total weight of glycerides is considered to be 100% by weight). In other embodiments, the formulation does not include a monoglyceride; does not include a diglyceride; or does not include a triglyceride.

[0149] The one or more glycerides may vary in their fatty acid alkyl groups. For example, 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.

[0150] In some embodiments, the glycerides may include a combination of one or more water insoluble glycerides (e.g., as noted above, triglycerides are typically strongly nonpolar and hydrophobic) and one or more water soluble glycerides (in any weight ratio from 0.1:99.9 to 99.9:0.1); or only insoluble glycerides; or only insoluble glycerides. The solubility of the glyceride can be determined, for example, by its HLB value.

[0151] A person of ordinary skill in the art will appreciate that the HLB value of the one or more glycerides can be selected by varying one or more of the parameters of the glycerides noted above. In this regard, when a plurality of glycerides are used, each glyceride may have be chosen to have similar or different HLB values (e.g., lower range used in combination with higher range).

[0152] The term “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.

[0153] The one or more fatty acid salts may include one or more calcium, potassium or sodium salts. The calcium, potassium or sodium salts of fatty acids can be obtained from a naturally occurring source, such as oil seeds. The one or more fatty acid salts can include one or more selected from sodium oleate, sodium stearate, sodium palmitate, calcium oleate, calcium stearate, or calcium palmitate.

[0154] In some embodiments, 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. When the SGF blend contains 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.

[0155] 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).

[0156] 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). [0157] 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).

[0158] The weight ratio of the natural waxes 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).

[0159] The weight ratio of the cellulose crosslinkers 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).

[0160] At a sufficient concentration, and based on the selection of the blend, 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.

[0161] The use of CNF alone as a binder has also been shown to increase the hydrophobicity of the contacted substrate.

[0162] Saturated SFAE, glycerides, and fatty acid salts are typically solids at nominal processing temperatures, whereas unsaturated SFAE, glycerides, and fatty acid salts are typically liquids. This permits the formation of uniform, stable dispersions of saturated glycerides and fatty acid salts in aqueous coatings without significant interactions or incompatibilities with other coating components, which are typically hydrophilic. In addition, this dispersion allows for high concentrations of saturated glycerides and fatty acid salts to be prepared without adversely affecting coating rheology, uniform coating application, or coating performance characteristics. The coating surface will become hydrophobic when the particles of saturated glycerides and fatty acid salts melt and spread upon heating, drying and consolidation of the coating layer. The natural waxes of the present disclosures are also solids at nominal processing temperatures.

[0163] Saccharide fatty acid esters of all saccharides, including mono-, di-saccharides and tri-saccharides, are adaptable for use in connection with aspects of the present disclosure. The saccharide fatty acid ester may be a mono-, di-, tri-, tetra-, penta-, hexa-, hepta-, or octaester, and combinations thereof, including that the fatty acid moieties may be saturated, unsaturated or a combination thereof.

[0164] The SFAE may comprise or consist essentially of sucrose esters of fatty acids. [0165] Many methods are known and available for making or otherwise providing the SFAE of the present disclosure, and all such methods are believed to be available for use within the broad scope of the present disclosure. For example, in certain embodiments it may be preferred that the fatty acid esters are synthesized by esterifying a saccharide with one or more fatty acid moieties obtained from oil seeds including but not limited to, soybean oil, sunflower oil, olive oil, canola oil, peanut oil, and mixtures thereof.

[0166] 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. In a related aspect, disaccharide esters for use in this disclosure can have the structure of Formula I of the ‘073 publication, which is incorporated herein by reference.

[0167] Suitable disaccharides for the SFAE may also include xylose, glucose, raffinose, maltodextrose, galactose, combinations of glucose, combinations of fructose, maltose, lactose, combinations of mannose, combinations of erythrose, isomaltose, isomaltulose, trehalose, trehalulose, cellobiose, laminaribiose, chitobiose and combinations thereof. [0168] In other embodiments, a starch fatty acid ester can be used, where the starch may be derived from any suitable source such as dent com starch, waxy com starch, potato starch, wheat starch, rice starch, sago starch, tapioca starch, sorghum starch, sweet potato starch, and mixtures thereof.

[0169] For use in the compositions of the present disclosure, the SFAE compounds may have a high degree of substitution. In some embodiments, the saccharide fatty acid ester is a sucrose polysoyate.

A Sucrose Polysoyate (SEFOSE® 1618U)

[0170] The SFAE can be produced in the manner disclosed in the ‘073 application

For example, 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 transesterification 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. Patent Nos. 3,963,699; 4,517,360; 4,518,772; 4,611,055; 5,767,257; 6,504,003; 6,121,440; and 6,995,232, and International Publication WO 1992004361, herein incorporated by reference in their entireties.

[0171] 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. In a related aspect, the treated cellulose- containing material exhibits greater lipophobicity (or OGR) relative to the same cellulose- containing material without the treatment. In a further related aspect, the treated cellulose- containing material may be biodegradable, compostable, and/or recyclable. In one aspect, the treated cellulose-containing material is both hydrophobic (water resistant) and lipophobic (lipid resistant) (OGR).

[0172] The cellulose-based products of the present disclosure may have improved mechanical properties compared to that same material untreated. For example, paper bags treated by the process as disclosed herein show increased burst strength, Gurley Number, Tensile Strength and/or Energy of Maximum Load. In one aspect, 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. In another aspect, 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. In still another aspect, 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. And in another aspect, 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 [0173] 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. In embodiments, the resulting contacted base paper is tuneably water and lipid resistant. In a related aspect, 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. cyl.)), or at least about 100, at least about 200 to about 350. In one aspect, 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). In a related aspect, the laminate may comprise a biodegradable and/or composable heat seal or adhesive.

[0174] In embodiments, 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). In a related aspect, 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

[0175] In a wet end application, 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. In related aspects, 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) of the total fiber present.

[0176] In a wet end application, 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. In related aspects, 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) to about 30% (wt/wt), about 30% (wt/wt) to about 40% (wt/wt), about 40% (wt/wt) to about 50% (wt/wt), about 60% (wt/wt) to about 70% (wt/wt), about 70% (wt/wt) to about 80% (wt/wt), or about 80% (wt/wt) to about 90% (wt/wt) of the total fiber present. [0177] In a wet end application, 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. In related aspects, 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), about 20% (wt/wt) to about 30% (wt/wt), about 30% (wt/wt) to about 40% (wt/wt), about 40% (wt/wt) to about 50% (wt/wt), about 60% (wt/wt) to about 70% (wt/wt), about 70% (wt/wt) to about 80% (wt/wt), or about 80% (wt/wt) to about 90% (wt/wt) of the total fiber present.

[0178] As used herein, "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 [0179] In a coating application, 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. In related aspects, the SGF blend may be present at a coating weight of about 0.05 g/m ² to about 1.0g/m ² , about 1.0g/m ² to about 2.0g/m ² , about 2g/m ² to about 3g/m ² 3g/m ² to about 4g/m ² , about 4g/m ² to about 5g/m ² , about 5g/m ² to about 10g/m ² , or about 10g/m ² to about 20g/m ² on a surface of the cellulose- based material.

[0180] In a coating application, 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. In related aspects, the SGF blend may be present at a coating weight of about 0.05 g/m ² to about 1.0g/m ² , about 1.0g/m ² to about 2.0g/m ² , about 2g/m ² to about 3g/m ² 3g/m ² to about 4g/m ² , about 4g/m ² to about 5g/m ² , about 5g/m ² to about 10g/m ² , or about 10g/m ² to about 20g/m ² on a surface of the cellulose- based material. [0181] In a coating application, 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). In related aspects, the CNF can be present at a coating weight of about 0.05 g/m ² to about 1.0g/m ² , about 1.0g/m ² to about 2.0g/m ² , about 2g/m ² to about 3g/m ² , 3g/m ² to about 4g/m ² , about 4g/m ² to about 5g/m ² , about 5g/m ² to about 10g/m ² , about 10g/m ² to about 20g/m ² , or about 20g/m ² to about 30g/m ² on a surface of the cellulose-based material.

[0182] The hydrophobic barrier property might be imparted to the substrate by the SGF blend and/or the enhanced CNF in the absence of any secondary hydrophobes.

[0183] 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.

[0184] 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. In some aspects, 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. In some aspects, the step of predetermining can be performed to increase dewatering rate of the fumish or fiber slurry. Increasing the dewatering rate improves the rate, for example, of producing a cellulose-based article. As noted above, 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.

[0185] The methods disclosed herein may include a step of predetermining a content of the SGF blend and/or predetermining the components of the SGF blend to be included in the barrier formulations. In some aspects, this step of predetermining can be performed prior to the preparing the barrier formulation, or can be performed prior to the contacting the cellulose-based material with the formulation. 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.

[0186] As noted above, 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. In other aspects, 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. [0187] As noted above, 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.

[0188] The charged polymer may consist of one or more cationic polymer. The one or more cationic polymer may include a polyacrylamide. The polyacrylamide may include polyDADMAC (poly diallyldimethylammonium chloride).

[0189] The cationic polymer may have a weight average molecular weight of 500,000 to 10,000,000. In some aspects, the weight average MW is 500,000 to 1,000,000, 1,000,001 to 2,000,000, 2,000,001 to 3,000,000, 3,000,001 to 4,000,000, 4,000,001 to 5,000,000, 5,000,001 to 6,000,000, 6,000,001 to 7,000,000, 7,000,001 to 8,000,000, 8,000,001 to 9,000,000, or 9,000,001 to 10,0000. In some aspects, 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). In some embodiments, 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%. In some aspects, 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. In some aspects, 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.

[0190] In some aspects, as noted above, prolamins can be used as the retention aid of a barrier formulation including the enhanced CNF and/or the SGF blend instead of a charged polymer.

[0191] 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. In some aspects, the formulation may not contain any binder other than the enhanced CNF. [0192] The barrier formulation can be provided in the form of an emulsion. The emulsion can be used as the barrier formulation of the methods of the present disclosure. In some aspects, the emulsion may not contain any emulsifier other than an SGF blend.

Alternatively, the emulsion can include about 0.01% to about 80% by weight of one or more emulsifiers. The emulsion may also include material for stabilizing the emulsion over a period of time (e.g., weeks, months, etc.), such as a nano or microfibrilized cellulose, a gum, or a thickening agent. A list of exemplary emulsifiers is described above.

[0193] The cellulose-based material or substrate, which may be dried prior to application (e.g., at about 80-150°C), may be treated with the modifying formulations by dipping, for example, and allowing the surface to be exposed to the composition for less than 1 second. The substrate may be heated to dry the surface, after which the modified material is ready for use. In one aspect, according to the method as disclosed herein, the substrate may be treated by any suitable coating/sizing process typically carried out in a paper mill (see, e.g., Smook, G., Surface Treatments n Handbook for Pulp & Paper Technologists, (2016), 4 ^th Ed., Cpt. 18, pp. 293-309, TAPPI Press, Peachtree Comers, GA USA, herein incorporated by reference in its entirety).

[0194] No special preparation of the cellulose-based material is necessary in practicing this disclosure, although for some applications, the material may be dried before treatment. In embodiments, the methods as disclosed may be used on any cellulose-based surface, including but not limited to, a fdm, a rigid container, fibers, pulp, a fabric or the like. In one aspect, the barrier formulations may be applied by conventional size press (vertical, inclined, horizontal), gate roll size press, metering size press, calender size application, tube sizing, on-machine, off-machine, single-sided coater, double-sided coater, short dwell, simultaneous two-side coater, blade or rod coater, gravure coater, gravure printing, flexographic printing, ink-jet printing, laser printing, water box on a calender, and combinations thereof.

[0195] Depending on the source, the cellulose treated in the methods herein may be paper, paperboard, pulp, softwood fiber, hardwood fiber, or combinations thereof, nanocellulose, cellulose nanofibres, whiskers or microfibril, microfibrillated, cotton or cotton blends, cellulose nanocrystals, or nanofibrilated cellulose.

[0196] In addition, fibers and cellulose-based material modified as disclosed herein, may be repulped. Further, for example, water cannot be easily "pushed" past the low surface energy barrier into the sheet.

[0197] In embodiments, the amount of the barrier formulation applied is sufficient to completely cover at least one surface of a substrate, such as at least one surface of a cellulose- containing material. For example, in embodiments, the barrier formulation may be applied to the complete outer surface of a container, the complete inner surface of a container, or a combination thereof, or one or both sides of a base paper. In other embodiments, the complete upper surface of a film may be covered by the barrier formulation, or the complete under surface of a film may be covered by the barrier formulation, or a combination thereof.

In some embodiments, the lumen of a device/instrument may be covered by the barrier formulation or the outer surface of the device/instrument may be covered by the barrier formulation or a combination thereof.

[0198] In embodiments, 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. In one aspect, one surface may be coated with a barrier formulation and the opposing surface may be coated with an agent including, but not limited to, proteins, wheat glutens, gelatins, prolamins, soy protein isolates, starches, modified starches, acetylated polysaccharides, alginates, carrageenans, chitosans, inulins, long chain fatty acids, waxes, and combinations thereof. In a related aspect, the barrier formulation can be added to a furnish, and the resulting material on the web may be provided with an additional coating of the barrier formulation (having the same or different composition as the formulation added on the wet end).

[0199] Any suitable coating process may be used to deliver any of the various barrier formulations in the course of practicing the methods. In embodiments, 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.

[0200] The permeability of a surface to various gases such as water vapour and gases (e g., oxygen, nitrogen, and carbon dioxide) may also be altered by the barrier formulations as the barrier function of the material is enhanced. The standard unit measuring permeability is the Barrer and protocols to measure these parameters are also available in the public domain (ASTM std F2476-05 for water vapour and ASTM std F2622-8 for oxygen, for gas testing in general - https://www.ametekmocon.com/products/searchbybrand/mocon.

M0C0N Permeation Testing Analyzers are recognized as the industry-leading solution for over 50 years and are the basis for many global permeability testing standards such as ASTM D3985 and ASTM F1249. The extensive line of M0C0N analyzers represent decades of technical leadership and continuous innovation in partnership with our customers, distributors and institutions. Our M0C0N Permeation Analyzers offer a wide range of testing capabilities across the most diverse range of products and materials”..). In some aspects, permeability to vapours and gases can be further reduced by adding one or more prolamins to the barrier formulation.

[0201] In embodiments, materials treated according to the disclosed methods display a complete biodegradability as measured by the degradation in the environment under microorganismal attack.

[0202] Various methods are available to define and test biodegradability including the shake-flask method (ASTM E1279 - 89(2008)) and the Zahn-Wellens test (OECD TG 302 B).

[0203] Various methods are available to define and test compostability including, but not limited to, ASTM D6400.

[0204] 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. [0205] The barrier coated product of the present disclosure may have an HST value of at least about 65 seconds, at least about 120 seconds, at least about 240 seconds, at least about 480 seconds, etc.

[0206] 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.

[0207] In some embodiments, 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.

[0208] In some embodiments, 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.

[0209] In some embodiments, the barrier coated product obtained by the methods of the present disclosure is folded into a three-dimensional shape and is contained within a sealed package. In these embodiments, the barrier layer may be an exposed layer (or outer layer) within the inside of the package. The material of the package can be any conventional material for storing, shipping, selling, etc. a food or beverage product. In these embodiments, the sealed package may also contain therein a food or beverage product. In these embodiments, the food or beverage product may contact the barrier paper layer. The seal of the sealed package may be a hermetic seal. [0210] In some embodiments, 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.

[0211] In some embodiments, the barrier coated product obtained by the methods of the present disclosure is bio-based. As used herein, “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. In some aspects, 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.

[0212] In some embodiments, the barrier coated product obtained by the methods of the present disclosure is recyclable. As used herein, "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.

[0213] In some embodiments, the barrier coated product of the present disclosure is biodegradable. As used herein "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).

EXAMPLES

[0214] In the following, although embodiments of the present disclosure are described in further detail by means of Examples, the present disclosure is not limited thereto.

[0215] Example 1

[0216] Example 1 is a lab study regarding the use of CNF in molded pulp products with barrier properties. [0217] The equipment used in Example 1 are as follows:

• Buchner funnel - large (which is believed to be about 8" diameter)

• Vacuum flask

• Lab vacuum pump

• Spray bottle

• Stop watch

[0218] The materials that may be used in Example 1 are as follows:

• Bleached kraft pulp (50% SWK, 50% HWK) slurried at 1% solids

• CNF slurry - 0.5% solids

• CNF slurry with 10% SE-15* added, 0.5% solids

• SE-9**/SE 30*** emulsion, 1% solids

• C-PAM (Cationic polyacrylamide), 0.1% solids

• Cationic Coagulant, 0.1% solids

• Pigment, 1% solids Capim DG Clay slurry from IMERYS.

[0219] * 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.

[0220] ** 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.

[0221] * * * 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.

[0222] The test procedure for Example 1 was as follows:

[0223] Blank or Control

[0224] (1) Add a sufficient quantity of bleached kraft slurry to the Buchner funnel to produce a fiber pad with a grammage of 150 gsm. Note the volume of furnish used for future runs.

[0225] (2) Start vacuum pump once slurry has been added to Buchner funnel.

[0226] (3) Note the time to drain furnish to the “wet line,” which is the point during the drainage process where the surface of the fiber slurry goes from shiny or “wet” look to a dull, textured surface.

[0227] (4) Continue to apply vacuum to the wet sample for 10 seconds.

[0228] (5) Remove the wet mat from the Buchner funnel, and place the wet mat between two blotters. Roll standard hand sheet roller across blotters twice to press test sample.

[0229] (6) Removed pressed sample and place in a 100°C oven until dry.

[0230] Internally treated (wet end application)

[0231] (1) Add one or more additives to an aliquot of furnish (volume determined during the production of the control sample) slurry and mix. See Table 1 below.

[0232] (2) Add a sufficient quantity of blended slurry to the Buchner funnel to produce a fiber pad with a grammage of 150 gsm.

[0233] (3) Start vacuum pump once slurry has been added to Buchner funnel.

[0234] (4) Note time to drain furnish to the "wet line."

[0235] (5) Continue to apply vacuum to the wet sample for 10 seconds. [0236] (6) Remove the wet mat from the Buchner funnel, and place the wet mat between two blotters. Roll standard hand sheet roller across blotters twice to press test sample.

[0237] (7) Remove pressed sample and place in a 100°C oven until dry.

[0238] Spray Treated (coating formed article)

[0239] (1) Add a sufficient quantity of bleached kraft slurry to the Buchner funnel to produce a fiber pad with a grammage of 150 gsm.

[0240] (2) Start vacuum pump once slurry has been added to Buchner funnel.

[0241] (3) Note time to drain furnish to the "wet line."

[0242] (4) Spray a known amount of a dilute suspension of the additive onto the surface of the wet mat. See Table 2 below.

[0243] (5) Continue to apply vacuum to the wet sample for 10 seconds.

[0244] (6) Remove the wet mat from the Buchner funnel, and place the wet mat between two blotters. Roll standard hand sheet roller across blotters twice to press test sample.

[0245] (7) Remove pressed sample and place in a 100 C oven until dry.

[0246] Table 1 — Internal Treatment

[0247] In Table 1, the additives are listed by their weight % on a dry basis.

[0248] Table 2 — Spray Treatment

[0249] In Table 2, the additives are listed by their weight % on a dry basis.

[0250] Based on experimental testing of the example embodiments, the data in

Table 3 shows the improvement obtained in water resistance and/or oil and grease resistance

Water resistance has been tested using a water Cobb test adapted from Tappi Standard Test Method T 441 om-20 “Water Absorptiveness of Paper.” Oil and grease resistance has been tested using a 3M KIT Test (Tappi Standard Test Method T 559 “Grease resistance”) and an oil Cobb test using vegetable oil adapted from Tappi Standard Test Method T 441 om-20.

[0251] Table 3

[0252] While there have been shown and described fundamental novel features of the disclosure as applied to the preferred and exemplary embodiments thereof, it will be understood that omissions and substitutions and changes in the form and details of the disclosure may be made by those skilled in the art without departing from the spirit of the disclosure. Moreover, as is readily apparent, numerous modifications and changes may readily occur to those skilled in the art. For example, any feature(s) in one or more embodiments may be applicable and combined with one or more other embodiments. Hence, it is not desired to limit the present disclosure to the exact construction and operation shown and described and, accordingly, all suitable modification equivalents may be resorted to falling within the scope of the present disclosure as claimed. In other words, although the embodiments of the disclosure have been described with reference to the above examples, it will be understood that modifications and variations are encompassed within the spirit and scope of the disclosure. Accordingly, the invention is limited only by the following claims. [0253] All references disclosed herein are hereby incorporated by reference in their entireties.