Methods for bio-based derivatization of cellulosic and synthetic materials and articles obtained therefrom

Abstract

The present disclosure generally relates to methods for treating cellulosic or synthetic materials by using bio-based coatings and / or compositions containing blends of glycerides and / or fatty acid salts to provide new and / or improved properties, such as water and oil / grease resistance (also referred to as oleophobic and hydrophobic barrier properties), separately or in combination, and to products obtained by these methods.

Description

[Technical Field]

[0001] The present disclosure generally relates to methods for treating cellulosic or synthetic materials by using bio-based coatings and / or compositions containing blends of glycerides and / or fatty acid salts to provide new and / or improved properties, such as water and oil / grease resistance (also referred to as oleophobic and hydrophobic barrier properties), either separately or in combination, and to the products obtained thereby. [Background technology]

[0002] Cellulose-based materials have a wide range of industrial applications as bulking agents, absorbents, and printing ingredients. These uses are preferred over other material sources due to their high thermal stability, good oxygen barrier properties, and chemical / mechanical resilience (see, e.g., Aulin et al., Cellulose (2010) 17:559-574, incorporated herein by reference in its entirety). Also of great importance is the fact that these materials are completely biodegradable and completely non-toxic once dispersed in the environment. Cellulose and its derivatives are the materials of choice for environmentally friendly solutions in applications such as food and disposable packaging.

[0003] On the other hand, many of the advantages of cellulose are countered by the hydrophilic / oleophilic nature of the material, which exhibits a high affinity for water / fat and is easily hydrated (see, e.g., Aulin et al., Langmuir (2009) 25(13):7675-7685, incorporated herein by reference in its entirety). While this is beneficial for applications such as absorbents and tissues, it presents a problem when safe packaging of moisture / lipid-containing materials (e.g., food) is required. Long-term storage of food, particularly cooked foods containing significant amounts of water and / or fat, is problematic for cellulose trays, for example, because they can first become soggy and then eventually fail. Furthermore, due to the high relative porosity of the material, multiple coatings may be required to offset the inefficiency of maintaining sufficient coating on the cellulosic surface, which can increase costs.

[0004] Such problems are typically addressed industrially by coating cellulose fibers with some kind of hydrophobic organic material / fluorocarbon or silicone to physically shield the underlying hydrophilic cellulose from the water / lipids in the contents, and include wicking between the fibers, i.e., preventing grease from flowing into the folds, 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) to the surface to be treated.

[0005] Industrially, compounds based on fluorocarbon chemistry have long been used to produce articles with improved resistance to penetration by oil and grease due to fluorocarbons' ability to reduce the surface energy of articles. One emerging issue with the use of perfluorinated hydrocarbons is that they are highly persistent in the environment. The EPA and FDA have recently begun reviewing the sources, environmental fate, and toxicity of these compounds. A recent study reported a very high occurrence (over 90%) of perfluorooctanesulfonate in blood samples taken from schoolchildren. The cost and potential environmental liability of these compounds have led manufacturers to seek alternative means of producing articles that are resistant to penetration by oil and grease.

[0006] Although lowering surface energy improves an article's penetration resistance, lowering surface energy also has several drawbacks. For example, textile fabrics treated with fluorocarbons exhibit good stain resistance, but once soiled, the ability of cleaning compositions to penetrate and release the stain from the fabric can be affected, potentially resulting in reduced service life and permanently soiled fabrics. Another example is grease-resistant paper that is subsequently printed and / or coated with an adhesive. In this case, the necessary grease resistance is achieved by treating with fluorocarbons, but the low surface energy of the paper can cause problems related to the acceptance of printing inks or adhesives, including blocking, backtrap mottling, poor adhesion, and registration. If the grease-resistant paper is to be used as a pressure-sensitive label with adhesive coated on one side, low surface energy can reduce adhesive strength. To improve their printability, coatability, or adhesion, low surface energy articles can be treated with post-formation processes such as corona discharge, chemical treatment, and flame treatment. However, these processes increase the manufacturing cost of the article and have other drawbacks.

[0007] It would be desirable to design a "green" bio-based coating that is hydrophobic, oleophobic, and compostable, including base paper / film, that could allow for maintaining the coating on the surface of the paper and preventing wicking into the interstices of the fibers, or reducing the adhesion of materials to cellulosic surfaces, at a reduced cost, without sacrificing biodegradability and / or recyclability.

[0008] Another problem is that synthetic films such as plastic bags, plastic wrap, plastic containers, etc. are often permeable and require one or more coating layers to achieve oil and grease resistance and / or water resistance and / or to reduce gas permeability. Again, fluorocarbon- and / or petroleum-based coatings are typically used to provide the synthetic films with the desired barrier properties.

[0009] Another problem is that conventional coatings for imparting hydrophobic and / or oleophobic barrier properties, including the fluorocarbon and petrochemical coatings referred to herein, tend to perform poorly in the folds, creases, and the like of the articles to which they are coated. Specifically, these articles typically have poor water and / or grease resistance in these areas. This "grease creasing effect" can be defined as the sorption of grease in a paper structure caused by folding, pressing, or crushing the paper structure. A conventional solution to the grease creasing effect is to add latex, butadiene, or similar resins to the coating to achieve improved coating coverage in these areas. However, with such conventional solutions, the water and / or oil and grease resistance in these areas may still be poorer than in flat areas of the article, the addition of resin components increases costs, and the latex and butadiene are not completely biobased because they are synthetic and / or not easily recyclable. Thus, there is room for improving the barrier properties of three-dimensional objects having complex or simple shapes with folds, creases, and the like.

[0010] U.S. Patent Application Publication No. 2018 / 0066073 (hereinafter also referred to as the "'073 Publication"), which is incorporated herein by reference in its entirety, discloses a tunable method for treating substrates, particularly cellulosic materials, with compositions that provide increased hydrophobicity and / or oleophobicity without sacrificing their biodegradability. In particular, the '073 application discloses methods for attaching sugar fatty acid esters (or "SFAEs") onto cellulosic materials to provide treated materials that exhibit increased hydrophobicity, oleophobicity, barrier function, and mechanical properties. Summary of the Invention

[0011] Various embodiments of the present disclosure provide methods for imparting oil and grease and / or water resistance to cellulosic and synthetic materials using blends of glycerides and / or fatty acid salts, and also provide articles (or products) obtained by such methods, which have improved properties including, but not limited to, oil and grease and / or water resistance.

[0012] In one embodiment, the present disclosure provides a method for imparting hydrophobic and / or oleophobic barrier properties to a substrate, the method comprising: preparing a formulation for imparting hydrophobic and / or oleophobic barrier properties to the substrate, the formulation comprising a blend of one or more glycerides and / or one or more fatty acid salts; and contacting a surface of the substrate with the formulation to impart hydrophobic and / or oleophobic barrier properties to the substrate. Formulations of the present disclosure may also be referred to herein as "compositions," "compositions of the disclosed methods," "treatment compositions," etc. Blends of one or more glycerides and / or one or more fatty acid salts may also be referred to as "glyceride / FAS blends," etc., and should be inferred to require both glycerides and fatty acid salts.

[0013] It was unexpected that a formulation comprising one or more fatty acid salts (generally non-polar and hydrophobic based on their fatty acid chains) and one or more glycerides (generally non-polar and hydrophobic based on their fatty acid chains; particularly triglycerides since all of the hydroxyl groups on the glycerol residues are esterified) could be used to impart both water resistance and oil and / or grease resistance to a substrate.

[0014] In one embodiment, the method of the present disclosure includes a step of predetermining the content of the glyceride / FAS blend to be included in the formulation. In some aspects, the predetermining step can be performed before preparing the formulation or before contacting the surface of the substrate with the formulation. In some aspects, the predetermining step is performed to achieve a desired effect. In some aspects, the predetermining step is performed to achieve a desired level of water resistance and / or a desired level of oil and grease resistance.

[0015] In one embodiment, the substrate contacted with the formulation is a cellulosic material, a synthetic polymeric material, or a natural or synthetic woven material. In one embodiment, the cellulosic material can be cellulose fibers, microfibrillated cellulose (MFC), nanofibrillated cellulose, or cellulose nanocrystals.

[0016] In one embodiment, the step of contacting the substrate with the formulation includes forming a solution of the formulation and cellulose fibers. This can be referred to as a wet-end process because the components of the formulation (i.e., glycerides and / or fatty acid salts) that impart barrier properties are mixed with the cellulose fibers in solution (as opposed to, for example, coating the surface of a solid material with the formulation). In one embodiment, the solution of the formulation and cellulose fibers is an emulsion. The emulsion may be formed after the formulation and cellulose fibers are mixed, or one or both of the formulation or the cellulose fibers may be in emulsion form prior to mixing.

[0017] In one embodiment, the glyceride / FAS blend is present in the solution at a concentration of at least 0.025% (wt / wt) of the total cellulose fiber present in the solution. In a related aspect, the glyceride / FAS blend is present at a concentration of from about 0.05% (wt / wt) to about 0.1% (wt / wt), from about 0.1% (wt / wt) to about 0.5% (wt / wt), from about 0.5% (wt / wt) to about 1.0% (wt / wt), or from about 1.0% (wt / wt) to about 2.0% (wt / wt) of the total fiber present. , 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).

[0018] In one embodiment, glycerides, fatty acid salts, and / or sugar fatty acid esters can be added to the solution as emulsifiers or emulsifying agents, such as to facilitate solubilization of the cellulose fibers.

[0019] In one embodiment, articles formed using such solutions have hydrophobic and / or oleophobic barrier properties. Articles formed from the solutions include paper, paperboard, bacon board, insulation materials, food storage cartons, compost bags, food storage bags, release papers such as for adhesives such as pressure sensitive adhesives, shipping bags, weed blocking / barrier fabrics or films, mulching films, flower pots, packing beads, bubble wrap, laminates, envelopes, gift cards, credit cards, gloves, raincoats, OGR paper, shopping bags, diapers, membranes, tableware, tea bags, coffee or tea containers, containers for holding hot or cold beverages, cups, plates, bottles for storing carbonated liquids, bottles for storing non-carbonated liquids, lids, food packaging films, garbage disposal containers, food handling equipment, fabrics, water storage and transport equipment, storage and transport equipment for alcoholic or non-alcoholic beverages, outer casings or screens for electronic products, interior or exterior parts of furniture, curtains, upholstery, fabrics, films, boxes, sheets, trays, pipes, water conduits, clothing, medical devices, pharmaceutical packaging, contraceptives, camping equipment, molded cellulosic materials, and combinations thereof.

[0020] In one embodiment, the step of contacting the substrate with the formulation comprises coating the surface of the substrate with the formulation. In one embodiment, the glyceride / FAS blend is present on the surface of the substrate in a concentration of at least about 0.05 g / m 2 In a related embodiment, the glyceride / FAS blend is present on the surface of the cellulose-based material at a coating weight of about 0.05 g / m 2 ~Approx. 1.0g / m 2 , about 1.0g / m 2 ~about 2.0g / m 2 , about 2g / m 2 ~about 3g / m 2 In a related aspect, this can be present at a coating weight of about 3 g / m 2 ~approx. 4g / m 2 , approximately 4 g / m 2 ~about 5g / m 2 , about 5g / m 2 ~about 10g / m 2, or approximately 10 g / m 2 ~about 20g / m 2 It can exist in.

[0021] In one embodiment, the substrate contacted with the formulation is paper, paperboard, bacon board, insulating material, paper pulp, food storage cartons, compost bags, food storage bags, release paper such as for pressure sensitive adhesives, shipping bags, weed blocking / barrier fabric or film, mulching film, flower pots, packing beads, bubble wrap, oil absorbing material, laminates, envelopes, gift cards, credit cards, gloves, raincoats, OGR paper, shopping bags, diapers, membranes, tableware, tea bags, coffee or tea containers, containers for holding hot or cold beverages, cups, dishes. , bottles for storing carbonated liquids, bottles for storing non-carbonated liquids, lids, food packaging films, garbage disposal containers, food handling equipment, fabric fibers, water storage and transport equipment, storage and transport equipment for alcoholic or non-alcoholic beverages, outer casings or screens for electronic products, interior or exterior furniture parts, curtains, upholstery, fabrics, films, boxes, sheets, trays, pipes, water conduits, clothing, medical devices, pharmaceutical packaging, contraceptives, camping equipment, molded cellulosic materials, and combinations thereof.

[0022] In one embodiment, the blend of one or more glycerides and / or one or more fatty acid salts is derived from oilseeds, while in other embodiments, the glycerides and / or fatty acid salts are derived from other sources of naturally occurring edible fats and oils.

[0023] In one embodiment, the one or more glycerides may comprise a blend of one or more monoglycerides, one or more diglycerides, and one or more triglycerides. The mono-, di-, and triglycerides may be blended in any weight ratio. That is, any one of the mono-, di-, or triglycerides may be the predominant glyceride component of the blend by weight. In other embodiments, it is contemplated that the blend may contain no monoglycerides, no diglycerides, or no triglycerides.

[0024] In one embodiment, the one or more glycerides differ in their fatty acid alkyl groups. For example, the one or more glycerides can contain fatty acid groups with different carbon numbers, different degrees of unsaturation, and / or different olefin configurations and positions. In one embodiment, the plurality of glycerides includes tripalmitin and / or tristearin.

[0025] In one embodiment, the one or more fatty acid salts include one or more calcium, potassium, or sodium salts. The calcium, potassium, or sodium salts of fatty acids are obtained from naturally occurring sources such as oilseeds. The one or more fatty acid salts may include one or more selected from sodium oleate, sodium stearate, sodium palmitate, calcium oleate, calcium stearate, or calcium palmitate.

[0026] In one embodiment, hydrophobic barrier properties are imparted to the substrate by a blend of one or more glycerides and / or one or more fatty acid salts in the absence of a secondary hydrophobic material.

[0027] In one embodiment, the formulation used in the disclosed method also includes one or more emulsifiers or emulsifying antes. The one or more emulsifiers can be present in the formulation at a concentration sufficient to form an emulsion of the glyceride and / or fatty acid salt with water. In one embodiment, the weight ratio of the glyceride / FAS blend to the one or more emulsifiers is about 0.1:99.9 to about 99.0:0.1, about 10:90 to about 90:10, about 20:80 to 80:20, about 35:65 to 65:35, about 40:60 to about 60:40, or about 50:50. In one embodiment, the emulsifier may be selected from water, buffers, sugar fatty acid esters, polyvinyl alcohol (PvOH), carboxymethylcellulose (CMC), milk proteins, wheat gluten, gelatin, prolamins, soy protein isolates, starches, acetylated polysaccharides, alginates, carrageenans, chitosan, inulin, long chain fatty acids, waxes, agar, alginates, glycerol, gums, lecithin, poloxamers, monoglycerol, diglycerol, monosodium phosphate, monostearate, propylene glycol, detergents, cetyl alcohol, glycerol esters, (saturated) ((poly)unsaturated) fatty acid methyl esters, and combinations thereof.

[0028] In one embodiment, the formulation used in the methods of the present disclosure also includes one or more sugar fatty acid esters.

[0029] In one embodiment, one or more sugar fatty acid esters (SFAEs) are added to the formulation to provide emulsifier functionality. To this end, the weight ratio of the glyceride / FAS blend to the one or more SFAEs is about 0.1:99.9 to about 99.0:0.1, about 10:90 to about 90:10, about 20:80 to 80:20, about 35:65 to 65:35, about 40:60 to about 60:40, or about 50:50.

[0030] In one embodiment, the method of the present disclosure includes a step of predetermining the content of SFAE to be included in the formulation. In some aspects, the predetermining step can be performed before preparing the formulation or before contacting the surface of the substrate with the formulation. In some aspects, the predetermining step is performed to achieve a desired effect. In some aspects, the predetermining step is performed to achieve a desired level of water resistance and / or a desired level of oil and grease resistance. In one embodiment, the predetermining step can be performed to achieve an emulsion of the glyceride / FAS blend.

[0031] In one embodiment, the SFAE can be present in the formulation at a concentration of 10% (wt / wt) to 25% (wt / wt) of the total cellulose fiber present in the solution, and can provide additional properties as described below.

[0032] In one embodiment, the formulation used in the method of the present disclosure also includes one or more pigments commonly used in the papermaking industry. The one or more pigments can be present in the formulation at a concentration of about 0.1% to about 90% by weight, based on the total weight of the formulation. In other aspects, the pigment concentration can be about 1% to 10%, about 11% to 20%, about 21% to 30%, about 31% to 40%, about 41% to 50%, 51% to 60%, 61% to 70%, 71% to 80%, 81% to 90%, or any other range between 0.1% and 90% by weight. The use of pigments is well known in the papermaking industry, and the pigment concentration can be selected to vary the properties of the final product. In one embodiment, the one or more pigments are selected from clay, calcium carbonate, titanium dioxide, kaolin, talc, or plastic pigments.

[0033] In one embodiment, one or more pigments are pretreated before being included in the formulation. Pretreatment may include contacting the pigment with a glyceride / FAS blend and / or one or more SFAEs by the methods of the present disclosure for a period of time sufficient to bond the glyceride / FAS / SFAE to the pigment. The pretreated pigment may be included in the wet end (e.g., added directly to the papermaking furnish) or may be added to the formulation of the present disclosure.

[0034] In one embodiment, the formulation used in the method of the present disclosure is completely bio-based. In one embodiment, the formulation used in the method is free of fluorocarbons. In one embodiment, the formulation used in the method is free of petroleum-derived compounds. In one embodiment, the article produced by the method is completely bio-based.

[0035] In one embodiment, the formulation used in the disclosed method includes one or more charged polymers to aid in the retention of glycerides and / or fatty acid salts on the substrate. The one or more charged polymers may include one or more cationic polymers, anionic polymers, nonionic polymers, and / or zwitterionic polymers. In one embodiment, the charged polymer includes a combination of a relatively low molecular weight cationic polymer and a relatively high molecular weight anionic polymer.

[0036] In one embodiment, the charged polymer comprises one or more cationic polymers. The one or more cationic polymers may include polyacrylamide. The polyacrylamide may include polyDADMAC (polydiallyldimethylammonium chloride).

[0037] In one embodiment, the cationic polymer has 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, blends of charged polymers are used to achieve a "bimodal" type weight-average MW using combinations of charged polymers having any MW within the aforementioned ranges (e.g., a first charged polymer having a weight-average MW of less than 1,000,000 in combination with a second charged polymer having a weight-average MW of greater than 2,000,000; the weight ratio of the first charged polymer to the second charged polymer is 10:90 to 90:10). In one embodiment, the concentration of the cationic polymer in the formulation is about 0.01% to about 5%, about 0.01% to about 3%, 0.05% to about 0.1%, or about 0.1% to about 1%, or about 1% to about 3% by weight, based on the total weight of the formulation as 100%. In some embodiments, the weight ratio of cationic polymer to glyceride / FAS blend in the formulation 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.

[0038] Without being bound by any theory, it is believed that long chain polymers (especially long chain cationic polymers) may tend to encapsulate the ester(s) of the glyceride, thereby inhibiting the fatty acid chains of the glyceride. One mechanism for achieving a combination of both oil and grease barrier properties and water barrier properties is hypothesized to be an increased dispersion of the substituted chains in a planar orientation (i.e., the chains lie in different planes).

[0039] In one embodiment, the formulation for use in the methods of the present disclosure also includes one or more binders selected from starch, protein, prolamine, polymer, polymer emulsion, PvOH, or combinations thereof. In one embodiment, the formulation does not contain a binder.

[0040] In one embodiment, the substrate to which hydrophobic and / or oleophobic barrier properties have been imparted exhibits a 3M Grease Kit test value of about 3 to about 12. In one embodiment, the surface of the substrate to which hydrophobic and / or oleophobic barrier properties have been imparted exhibits a water contact angle of at least 90°. In one embodiment, the surface of the substrate to which hydrophobic and / or oleophobic barrier properties have been imparted exhibits an HST value of at least 65 seconds.

[0041] In one embodiment, an article obtained by the method of the present disclosure is provided.

[0042] In one embodiment, an emulsion is provided. The emulsion can be used as a formulation in the methods of the present disclosure. The emulsion may comprise from about 0.01% to about 80% by weight of one or more emulsifiers, from about 0.01% to about 95% by weight of a blend of one or more glycerides and / or one or more fatty acid salts, with the remainder being water or other suitable solvent. In one embodiment, the emulsion also comprises 0.01 to about 3% of a charged polymer as a retention aid. The emulsion may also comprise materials to stabilize the emulsion for a period of time (e.g., weeks, months, etc.), such as nano- or microfibrillated cellulose, gums, or thickeners. In one embodiment, the one or more emulsifiers comprise a sugar fatty acid ester (SFAE). In some embodiments, the SFAE content is less than the glyceride / FAS blend content (e.g., a weight ratio of SFAE:glyceride / FAS of 1:99 to 40:60), and in other embodiments, the SFAE content is greater than the glyceride / FAS blend content (e.g., a weight ratio of SFAE:glyceride / FAS of 60:50 to 95:5).

[0043] In one embodiment, a moldable composition is provided. The moldable composition may include about 75% to about 97% by weight of cellulosic fibers and about 2% to about 25% by weight of one or more glycerides, one or more fatty acid salts, and / or one or more sugar fatty acid esters (SFAEs). In some aspects, the moldable composition contains about 2% to about 25% of one or more glycerides. In some aspects, the moldable composition contains about 2% to about 25% of one or more fatty acid salts. In some aspects, the moldable composition contains about 2% to about 25% of one or more SFAEs. When the molding composition includes a combination of one or more glycerides and one or more SFAEs, the weight ratio of glyceride:SFAE can be about 1:99 to about 99:1, about 10:90 to about 90:10, about 20:80 to about 80:20, about 30:70 to about 70:30, about 40:60 to about 60:40, or about 50:50. When the molding composition includes one or more glycerides, one or more fatty acid salts, and one or more SFAEs, the weight ratio of glyceride / FAS blend:SFAE can be about 1:99 to about 99:1, about 10:90 to about 90:10, about 20:80 to about 80:20, about 30:70 to about 70:30, about 40:60 to about 60:40, or about 50:50.

[0044] The molding composition may further contain a pigment at a concentration of about 0.1% to about 80% by weight, assuming the total weight of the formulation to be 100% by weight. In other aspects, the pigment weight may be about 1-10%, about 11-20%, about 21-30%, about 41-50%, about 51-60%, about 61-70%, or about 71-80% by weight. The content and type of pigment can be selected to change the properties of a molded article obtained from the molding composition. For example, clay can be added to increase the rigidity of the molded article. In one embodiment, the pigment is pretreated using the techniques described herein.

[0045] In one embodiment, the molding composition can further include one or more emulsifiers, and the weight ratio of the total weight of the glyceride, fatty acid salt, and sugar fatty acid ester to the one or more emulsifiers is about 0.1:99.9 to about 99.0:0.1, about 10:90 to about 90:10, about 20:80 to 80:20, about 35:65 to 65:35, about 40:60 to about 60:40, or about 50:50. In one embodiment, the emulsifier can be selected from water, buffers, sugar fatty acid esters, polyvinyl alcohol (PvOH), carboxymethylcellulose (CMC), milk proteins, wheat gluten, gelatin, prolamins, soy protein isolates, starches, acetylated polysaccharides, alginates, carrageenans, chitosan, inulin, long chain fatty acids, waxes, agar, alginates, glycerol, gums, lecithin, poloxamers, monoglycerol, diglycerol, monosodium phosphate, monostearate, propylene glycol, detergents, cetyl alcohol, glycerol esters, (saturated) ((poly)unsaturated) fatty acid methyl esters, and combinations thereof.

[0046] In one embodiment, the moldable composition can further include one or more charged polymers as retention aids. In some aspects, the charged polymers are those described above for use in the formulations of the present disclosure. In some aspects, the weight ratio of cationic polymer to the total weight of glyceride, fatty acid salt, and sugar fatty acid ester in the moldable composition is about 0.1:99.9 to about 20:80, 0.5:99.5 to about 15:85, about 1:99 to about 10:90, or about 2.5:97.5 to about 7.5:92.5. In some aspects, the content of the charged polymer is 0.01 to 5 wt % based on the total dry weight of the cellulose fibers.

[0047] In one embodiment, the molding composition can be formed without the addition of water. 60.0℃( 140°F ) That's all, 65.5℃( 150°F ) That's all, 79.4℃( 175°F ) That's all, 93.3℃( 200°F )That's all, 107℃( 225°F ) Greater than or equal to, or 121℃( 250°F ) When heated to a temperature above this range, the composition is flexible, moldable, and shapable. The target temperature for achieving flexibility for molding and shaping the composition can be varied, for example, by varying the sugar fatty acid ester (SFAE). For example, the sugar fatty acid ester (SFAE) content can be varied within the ranges described above, the sugar selection can be varied (e.g., monosaccharides, disaccharides, and trisaccharides, as well as higher polysaccharides), the sugar substitution can be varied (mono-, di-, tri-, tetra-, penta-, hexa-, hepta-, and octaesters), the fatty acid chain length and saturation can be varied, and the like. In some aspects, the SFAE is a sucrose fatty acid ester. In some aspects, the SFAE is a xylose fatty acid ester. In some aspects, the SFAE is a glucose fatty acid ester. In one embodiment, the SFAE is a combination of one or more sucrose fatty acid esters, xylose fatty acid esters, and / or glucose fatty acid esters.

[0048] The molding compositions of the present disclosure unexpectedly possess hydrophobic and / or oleophobic barrier properties after being heated, molded, and then cooled to ambient temperature. The molding compositions further maintain their three-dimensional shape (and barrier properties) after being cooled to room temperature. This provides several advantages. For example, the molding compositions can be prepared in bulk and later used to mold multiple solid, three-dimensional articles (including the exemplary articles listed above), which will possess hydrophobic and / or oleophobic barrier properties.

[0049] Another unexpected advantage is that the hydrophobic and / or oleophobic barrier properties can be maintained uniformly throughout the article formed from the molding composition, including in folds, creases, etc. In other words, by adding a formulation to impart barrier properties to the wet end, a solid, three-dimensional product is obtained that has excellent barrier properties both flat and in folds, creases, etc. This is in contrast to the conventional approaches discussed above.

[0050] Another unexpected advantage is that the use of pigments can be incorporated into the molding composition without losing barrier properties. This result was highly unexpected because many inorganic pigments are hydrophilic, i.e., not water-resistant. In other words, with conventional methods, increasing the inorganic pigment content can result in a loss of barrier properties. In contrast, the method of the present disclosure beneficially provides articles / products that can be made with relatively high pigment content, having a combination of improved oil and grease resistance and water-resistant barrier properties.

[0051] In one embodiment, a method for thermally forming a molded article having hydrophobic and / or oleophobic barrier properties is provided, the method comprising the steps of preparing a molding composition comprising cellulose fibers and one or more glycerides, one or more fatty acid salts, and / or one or more sugar fatty acid esters; and dissolving the molding composition in at least one of a mixture of cellulose fibers and one or more glycerides, one or more fatty acid salts, and one or more sugar fatty acid esters. 60.0℃( 140°F ) to a temperature of 0.1 to 1.0 to increase the flexibility of the composition; and molding the heated composition into a molded article having a three-dimensional shape, wherein the molded article obtained by this method has hydrophobic and / or oleophobic barrier properties.

[0052] In one embodiment, the target temperature for the heating step of the thermoforming process is about 60.0℃( 140°F ) That's all, 65.5℃( 150°F ) That's all, 79.4℃( 175°F ) That's all, 93.3℃( 200°F) That's all, 107℃( 225°F ) Greater than or equal to, or 121℃( 250°F ) or more. The target temperature for achieving flexibility for molding the composition can be varied, for example, by varying the sugar fatty acid ester. For example, the sugar fatty acid content can be varied within the ranges mentioned above, the sugar selection can be varied (e.g., monosaccharides, disaccharides, trisaccharides, and higher polysaccharides), the sugar substitution can be varied (mono-, di-, tri-, tetra-, penta-, hexa-, hepta-, octa-esters), the fatty acid chain length and saturation can be varied, etc. In some aspects, the SFAE is a sucrose fatty acid ester. In some aspects, the SFAE is a xylose fatty acid ester. In some aspects, the SFAE is a glucose fatty acid ester. In one embodiment, the SFAE is a combination of one or more sucrose fatty acid esters, xylose fatty acid esters, and / or glucose fatty acid esters.

[0053] In one embodiment, the molding composition used in the thermoforming process is the molding composition of the present disclosure disclosed above.

[0054] In one embodiment, the molded article resulting from the thermoforming process is heated to ambient temperature (e.g., Approximately 20.0 to 22.2 degrees Celsius ( Approximately 68 degrees Fahrenheit ~ approximately 72 degrees Fahrenheit ) The thermoforming process retains its three-dimensional shape after cooling to room temperature (e.g., room temperature). In one embodiment, the formed article resulting from the thermoforming process can maintain its three-dimensional shape until reheated to the temperature range described above. Without being bound by any theory, it is believed that these unexpected properties are achieved by the use of one or more glycerides, one or more fatty acid salts, and / or one or more sugar fatty acid esters (SFAEs) at the disclosed levels. For example, it is believed that heating "melts" the glycerides / FAS / SFAEs bound to the cellulose fibers, thereby providing flexibility and, further, that the barrier properties imparted by the glycerides / FAS / SFAEs are retained after cooling.

[0055] In one embodiment, the formed article obtained by the thermoforming process is selected from paper, paperboard, bacon board, insulation material, food storage cartons, compost bags, food storage bags, release paper for pressure sensitive adhesives, shipping bags, weed blocking / barrier fabric or film, mulching film, flower pots, packing beads, bubble wrap, laminates, envelopes, gift cards, credit cards, gloves, raincoats, OGR paper, shopping bags, diapers, membranes, tableware, tea bags, coffee or tea containers, containers for holding hot or cold beverages, cups, plates, bottles for storing carbonated liquids, bottles for storing non-carbonated liquids, lids, food packaging films, garbage disposal containers, food handling equipment, fabric fibers, water storage and transport equipment, storage and transport equipment for alcoholic or non-alcoholic beverages, outer casings or screens for electronic products, interior or exterior parts of furniture, curtains, upholstery, fabrics, films, boxes, sheets, trays, pipes, water conduits, clothing, medical devices, pharmaceutical packaging, contraceptives, camping equipment, molded cellulosic materials, or combinations thereof.

[0056] In one embodiment, the surface of the molded article obtained from the thermoforming process exhibits a 3M Grease Kit test value of about 3 to about 12. In one embodiment, the surface of the molded article obtained from the thermoforming process exhibits a water contact angle of at least 90°. In one embodiment, the surface of the molded article obtained from the thermoforming process exhibits an HST value of at least 65 seconds.

[0057] Further features and advantages of the present disclosure are further described below. This Summary section is merely intended to describe certain features of the present disclosure and is not intended to limit the scope of the present disclosure. The inclusion of one or more features in this Summary section, even if specific features or embodiments of the present disclosure are not discussed, should not be construed as limiting the scope of the claims. DETAILED DESCRIPTION OF THE INVENTION

[0058] Before describing the compositions, methods, and methodologies of the present invention in more detail, it is to be understood that the disclosure is not limited to the particular compositions, methods, and experimental conditions described herein, as these may vary. It is also to be understood that the scope of the present invention will be limited only by the appended claims, and that the terminology used herein is for the purpose of describing particular embodiments only, and is not intended to be limiting.

[0059] 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. For example, reference to "glycerides" includes one or more glycerides and / or compositions of the type described herein that will be apparent to one of ordinary skill in the art, such as by reading this disclosure.

[0060] Unless otherwise defined, 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 can be used in the practice or testing of this disclosure, since modifications and variations are understood to be within the spirit and scope of the disclosure.

[0061] Unless otherwise stated, each range disclosed herein is to be understood to encompass and disclose each and every discrete point and all possible subranges within that range.

[0062] As used herein, the terms "about," "approximately," "substantially," and "significantly" will be understood by those of ordinary skill in the art and will vary to some extent depending on the context in which they are used. If there is any use of a term that is not clear to a person of ordinary skill in the art, "about" and "approximately" will mean plus or minus less than 10% of the particular term, and "substantially" and "significantly" will mean plus or minus more than 10% of the particular term, given the context in which the term is used. "Comprising" and "consisting essentially of" have their accustomed meanings in the art.

[0063] In one embodiment, the present disclosure demonstrates that treating the surface of a substrate, such as, for example, cellulose fibers, with a blend of one or more glycerides and / or one or more fatty acid salts (or a glyceride / FAS blend) renders the resulting surface particularly strongly hydrophobic. For example, in the case of cellulose fibers, the hydroxyl groups of cellulose can be masked by bulky organic chains. Furthermore, the glyceride / FAS blend (as well as other components disclosed herein to facilitate the use of glycerides and fatty acids, such as sugar fatty acid esters) is readily digestible as such once removed, for example, by bacterial enzymes. The derivatized surface of the substrate has been shown to exhibit considerable heat resistance, able to withstand temperatures as high as 250°C, and can be more impermeable to gases than the underlying base substrate. Therefore, such materials are ideal solutions for the problem of derivatizing hydrophilic surfaces, for example, of cellulose, in any embodiment in which cellulose materials may be used.

[0064] Advantages of the products and methods disclosed herein include that the coating compositions are made from renewable agricultural resources, such as vegetable oils; are biodegradable; have a low toxicity profile and are suitable for food contact; can be tailored to reduce the coefficient of friction of the substrate even at high levels of water resistance (e.g., for paper / paperboard surfaces, these treatments do not make the paper slippery for downstream processing or end use); can be used with or without special emulsifying equipment or emulsifiers (e.g., sugar fatty acid esters); and are compatible with conventional paper recycling programs, i.e., do not have the adverse effects on recycling operations that occur with polyethylene, polylactic acid, or wax coated paper.

[0065] As used herein, "bio-based" refers to a material intentionally made from substances derived from living (or formerly living) organisms. In a related aspect, a material containing at least about 50% of such materials is considered bio-based. However, as noted above, in one embodiment, the articles disclosed herein can contain up to 100% of such materials.

[0066] As used herein, "binding," including grammatical variations thereof, means to aggregate or cause to aggregate essentially as a single mass and may refer to ionic, hydrophobic, van der Waals interactions or covalent bonds, or a combination thereof.

[0067] As used herein, "cellulosic" refers to a natural, synthetic, or semi-synthetic material that can be molded or extruded into objects (e.g., bags, sheets) or films or filaments that can be used to make such objects or films or filaments that are structurally and functionally similar to cellulose, e.g., coatings and adhesives (e.g., carboxymethyl cellulose). In another example, the term "cellulosic" refers to a complex carbohydrate (CH) composed of glucose units that forms the major component of the cell walls of most plants. 10 O5) nThe cellulose is cellulosic.

[0068] As used herein, "coating weight" is the weight of material (wet or dry) to be applied to a substrate. This is the weight per specified ream. kilogram( lb ) or expressed in grams per square meter.

[0069] As used herein, "compostable" means that these solid products are biodegradable in soil.

[0070] As used herein, "edge wicking" refers to the sorption of water in a paper structure at its outer boundaries by one or more mechanisms, including, but not limited to, capillary penetration into pores between fibers, diffusion through fibers and bonds, and surface diffusion on fibers. In a related aspect, the glyceride and / or fatty acid salt-containing formulations described herein prevent edge wicking in treated products. In one aspect, a similar problem exists with respect to grease / oily creases that may be present in paper or paper products. Such a "grease crease effect" can be defined as the sorption of grease in a paper structure caused by folding, pressing, or crushing the paper structure.

[0071] As used herein, "effect," including grammatical variations thereof, means imparting a particular property to a particular material.

[0072] As used herein, "hydrophobic material" refers to a material that does not attract water. For example, waxes, rosins, resins, sugar fatty acid esters, fatty acid salts, glycerides, diglycerides and triglycerides with long fatty acid chains, diketene, shellac, vinyl acetate, PLA, PEI, oils, fats, lipids, other water-repellent chemicals, or combinations thereof are hydrophobic materials.

[0073] As used herein, "hydrophobic" refers to the property of being water repellent and tending to repel and not absorb water.

[0074] As used herein, "lipid resistance" or "lipophobicity" refers to the property of being lipid repellent and tending to repel and not absorb lipids, grease, fats, etc. In a related aspect, grease resistance can be measured by the "3M KIT" test, the TAPPI T559 Kit test, or the Cobb oil test.

[0075] As used herein, "cellulose-containing material" or "cellulose-based material" refers to a composition consisting essentially of cellulose. Examples of such materials include, but are not limited to, paper, paper sheets, paperboard, paper pulp, food storage cartons, parchment paper, cake board, butcher paper, release paper / liners for pressure-sensitive adhesives, food storage bags, shopping bags, shipping bags, bacon boards, insulating materials, tea bags, coffee or tea containers, compost bags, tableware, containers for holding hot or cold beverages, cups, lids, plates, bottles for storing carbonated liquids, gift cards, bottles for storing non-carbonated liquids, food packaging films, garbage disposal containers, food handling equipment, fabric fibers (e.g., cotton or cotton blends), water storage and transport equipment, alcoholic or non-alcoholic drinks, outer casings or screens for electronic products, interior or exterior furniture components, curtains, and upholstery.

[0076] As used herein, "release paper" refers to a paper sheet used to prevent adhesive surfaces from prematurely adhering to adhesives or mastics, for example, in the case of pressure-sensitive adhesives. In one embodiment, the coatings disclosed herein can be used to replace or reduce the use of silicon or other coatings to produce materials with low surface energy. Determining surface energy can be easily achieved by measuring contact angles (e.g., optical tensiometers and / or high-pressure chambers, Dyne Testing, Staffordshire, United Kingdom) or by using surface energy test pens or inks (see, for example, Dyne Testing, Staffordshire, United Kingdom).

[0077] "Removable," as used herein with respect to coatings and / or glyceride / FAS blends, means that the glyceride and fatty acid salt coating, once applied, can be removed from the substrate (e.g., cellulose-based material), such as by manipulating physical properties. "Non-removable," as used herein with respect to coatings and / or glyceride / FAS blends, means that the coating, once applied, is substantially irreversibly bonded to the substrate (e.g., cellulose-based material), such as by chemical means.

[0078] As used herein, "fibers in solution" or "pulp" refers to lignocellulosic fibrous material prepared by chemically or mechanically separating cellulose fibers from wood, fiber crops, or waste paper. In a related aspect, when cellulose fibers are treated by the methods of the present disclosure, the cellulose fibers themselves contain the bound glyceride / FAS blend as a separate entity, and the bound cellulose fibers have distinct and different properties from free fibers (e.g., pulp fibers or cellulose fibers or nanocellulose or microfibrillated cellulose-glyceride / fatty acid salt bound materials will not form hydrogen bonds between fibers as readily as unbound fibers).

[0079] "Repulpable" herein means producing a paper or paperboard product suitable for being broken down into a soft, shapeless mass for reuse in the manufacture of paper or paperboard.

[0080] As used herein, "adjustable," including grammatical variations thereof, means adjusting or adapting a method to achieve a particular result.

[0081] As used herein, "water contact angle" refers to the angle, measured through a liquid, at which a liquid / vapor interface meets a solid surface. It quantifies the wettability of a solid surface by a liquid. The contact angle reflects the strength with which liquid and solid molecules interact with each other compared to the strength with which each interacts with its own molecules. On many highly hydrophilic surfaces, a drop of water exhibits a contact angle between 0° and 30°. Generally, a solid surface is considered hydrophobic if the water contact angle is greater than 90°. Water contact angles can be readily obtained using an optical tensiometer (see, e.g., Dyne Testing, Staffordshire, United Kingdom).

[0082] "Water vapor permeability" as used herein refers to breathability, or the ability of a textile to transport moisture. There are at least two different measurement methods. One of them, the MVTR test (Water Vapor Transmission Rate) according to ISO 15496, indicates the water vapor transmission rate (WVP) of a fabric and therefore its ability to transport sweat to the outside air. The measurement determines the number of grams of moisture (water vapor) that pass through one square meter of fabric in 24 hours (the higher the level, the more breathable it is).

[0083] In one embodiment, waterfastness can be determined using the TAPPI T 530 Hercules sizing test (i.e., paper sizing test by ink fastness). Ink fastness by the Hercules method is best classified as a test that directly measures penetration. Alternatively, it is classified as a speed of penetration test. There is no single best test for "measuring sizing." The choice of test depends on the end use and mill control needs. This method is particularly suitable for use as a mill control sizing test to accurately detect changes in sizing levels. It offers the sensitivity of the ink float test while providing reproducible results, shorter test times, and automatic endpoint determination.

[0084] Sizing, measured by the resistance to penetration or absorption of aqueous liquids into the paper, is an important property of many papers, typical of which are bags, container board, meat wrap, document, and some printing grades.

[0085] This method can be used to monitor the production of paper or paperboard for a specific end use, provided an acceptable correlation is established between the test value and the paper's end-use performance. Due to the nature of the test and the penetrant, it may not correlate well enough to be applicable to all end-use requirements. This method measures sizing by penetration rate. Other methods measure sizing by surface contact, surface penetration, or absorption. Sizing tests are selected based on their ability to simulate the means of water contact or absorption in the end use. This method can also be used to optimize sizing chemical usage costs.

[0086] As used herein, "oxygen permeability" refers to the degree to which a polymer allows the passage of a gas or fluid. The oxygen permeability (Dk) of a material is a function of the diffusivity (D) (i.e., how quickly oxygen molecules move through the material) and the solubility (k) (or the amount of oxygen molecules absorbed per volume in the material). Oxygen permeability (Dk) values ​​are typically between 10 and 150 x 10 -11 (cm 2 The relationship between hydrogel water content and oxygen permeability (units: barrers) is semi-logarithmic. The International Organization for Standardization (ISO) specifies permeability using the SI unit of hectopascal (hPa) for pressure. Therefore, Dk = 10 -11 (cm 2 ml O2) / (s ml hPa). Barrer units can be converted to hPa by multiplying them by the constant 0.75.

[0087] As used herein, "biodegradable," including grammatical variations thereof, means capable of being broken down by the action of living organisms (eg, by microorganisms), especially into harmless products.

[0088] As used herein, "recyclable," including grammatical variations thereof, means that said material is capable of being treated or processed (post-consumer and / or scrap) to create a material suitable for reuse.

[0089] In this specification, "Gurley seconds" or "Gurley number" refers to the number of cubic centimeters (deciliters) of air that 12.39 cm (1.21 kPa) 4.88 inches (0.176 psi) ] With a water pressure difference of 6.45 square centimeters ( 1.0 square inch ) The "Gurley number" is a unit of measurement that expresses the number of seconds required for a given amount of pressure to pass through a given material (ISO 5636-5:2003) (porosity). Furthermore, for stiffness, the "Gurley number" is a unit of measurement for a piece of material that measures the force required to deflect a given amount (1 milligram force) of the material held vertically. Such values ​​can be measured with a Gurley Precision Instruments device (Troy, New York).

[0090] HLB - The hydrophilic-lipophilic balance of a surfactant is a measure of how hydrophilic or lipophilic it is and is determined by calculating values ​​for different regions of the molecule.

[0091] Griffin's method for nonionic surfactants, described in 1954, HLB=20 * M h / M [In the formula, M h is the molecular weight of the hydrophilic portion of the molecule, and M is the molecular weight of the entire molecule. and the results are given on a scale of 0 to 20, where an HLB value of 0 corresponds to a completely lipophilic / hydrophobic molecule and a value of 20 corresponds to a completely hydrophilic / lipophobic molecule.

[0092] The HLB value can be used to predict the surfactant properties of a molecule. Less than 10: Fat-soluble (water-insoluble) Over 10: Water soluble (lipid insoluble) 1.5~3: Defoamer 3-6: W / O (water-in-oil) emulsifier 7-9: Wetting agent 13-15: Cleaning agent 12-16: O / W (oil-in-water) emulsifier 15-18: Solubilizers or hydrotropes

[0093] In one embodiment, the HLB values ​​of the glyceride / FAS blends (or compositions comprising said esters) disclosed herein can be in the lower range. In one embodiment, the HLB values ​​of the glyceride / FAS blends (or compositions comprising said glyceride / FAS blends) disclosed herein can be in the medium to higher range. In one embodiment, the HLB values ​​of the sugar fatty acid esters (or compositions comprising said esters) disclosed herein can be in the lower range. In other embodiments, the HLB values ​​of the sugar fatty acid esters (or compositions comprising said esters) disclosed herein can be in the medium to higher range.

[0094] As used herein, "SEFOSE®" refers to a sucrose fatty acid ester (soyate) made from soybean oil containing one or more fatty acids that are unsaturated, which is commercially available from Procter & Gamble Chemicals (Cincinnati, Ohio) under the trade name SEFOSE 1618U (see sucrose polysoyate below). As used herein, "OLEAN®" refers to a sucrose fatty acid ester of formula C, available from Procter & Gamble Chemicals. n+12 H 2n+22 O 13 where all fatty acids are saturated. In the examples of the '073 application mentioned above, which are incorporated herein by reference in their entirety, SEFOSE is used as an SFAE to impart barrier properties to substrates containing cellulosic materials.

[0095] As used herein, "soyate" refers to a mixture of salts of fatty acids from soybean oil.

[0096] As used herein, "oilseed fatty acid" refers to fatty acids from plants including, but not limited to, soybean, peanut, rapeseed, barley, canola, sesame seed, cottonseed, palm kernel, grape seed, olive, safflower, sunflower, copra, corn, coconut, flaxseed, hazelnut, wheat, rice, potato, cassava, legumes, camelina seed, mustard seed, and combinations thereof. The fatty acid chains of the glycerides and fatty acid salts may be oilseed fatty acids.

[0097] As used herein, "wet strength" refers to a measure of how well the web of fibers holding paper (or other three-dimensional solid cellulose-based product) together resists breaking forces when the paper is wet. Wet strength can be measured using a Finch Wet Strength Device from Thwing-Albert Instrument Company (West Berlin, NJ). In this case, wet strength is typically provided by wet strength additives such as kymene, cationic glyoxylated resins, polyamidoamine-epichlorohydrin resins, polyamine-epichlorohydrin resins, including epoxide resins. In one embodiment, the glyceride / FAS blend-coated cellulose-based materials disclosed herein provide wet strength in the absence of such additives.

[0098] As used herein, "wet" means covered or saturated with water or another liquid.

[0099] In one embodiment, a method of the present disclosure can include contacting a cellulosic surface with an emulsion containing a glyceride / FAS blend as a carrier for bonding a glyceride / FAS blend to the cellulosic surface or as a carrier for a coating agent capable of bonding to the cellulosic surface. Such methods can include contacting a cellulosic-based material with the glyceride / FAS blend, the emulsion, or both. The methods can also include a further bonding step involving exposing the contacted cellulosic-based material to heat, radiation, a catalyst, or a combination thereof for a time sufficient to bond the glyceride / FAS blend or coating agent to the cellulosic-based material. In a related aspect, such radiation can include, but is not limited to, UV, IR, visible light, or a combination thereof. In another related aspect, the reaction can 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.

[0100] Furthermore, the coupling reaction between the glyceride / FAS blend and the cellulosic material can be carried out using a substantially pure glyceride / FAS blend or can be part of an emulsion. In one embodiment, the emulsion can contain a mixture of mono-, di-, tri-, tetra-, penta-, hexa-, hepta-, or octaesters. In another embodiment, the emulsion can contain proteins, polysaccharides, and lipids, including, but not limited to, milk proteins (e.g., casein, whey protein, etc.), wheat gluten, gelatin, prolamins (e.g., corn zein), soy protein isolate, starch, modified starch, acetylated polysaccharides, alginates, carrageenans, chitosan, inulin, long-chain fatty acids, waxes, and combinations thereof.

[0101] In one embodiment, the emulsion can be mixed with an epoxy derivative of the ester (see, e.g., U.S. Pat. No. 9,096,773, incorporated herein by reference in its entirety), and such an epoxy derivative can function, for example, as an adhesive.

[0102] In one embodiment, cellulosic materials can be rendered oleophobic by the addition of polyvinyl alcohol (PvOH) and / or prolamins. In one aspect, the prolamins include zein, gliadin, hordein, secalin, cathilin, and avenin. In a related aspect, the prolamin is zein.

[0103] In one embodiment, no catalyst or organic carrier (e.g., volatile organic compound) is required to carry out the bonding reaction, including the fact that no enhancement of materials using the methods of the present disclosure is contemplated. In a related aspect, the reaction time is substantially instantaneous (i.e., less than 1 second). Furthermore, the resulting materials exhibit low blocking properties.

[0104] In one embodiment, the substrate can be a synthetic film or synthetic woven fabric made from a polymer such as, but not limited to, polyethylene, polypropylene, PVC, polycarbonate, polyester, PVDC, polyamide, polylactic acid, polybutylene succinate, polyhydroxyalkanoate, or 1,4 butanediol. The formulation can be applied to the synthetic polymer film to impart the benefits described herein. The use of the formulation to impart the benefits avoids the traditional use of chlorofluorocarbons and petroleum-based compounds, providing one or more of improved oil and grease resistance, water resistance, and gas and vapor barrier properties.

[0105] The use of synthetic polymer films as substrates may require the use of an additional adhesive component or layer between the substrate and the coating described herein to adhere the coating to the substrate. Exemplary materials for such adhesive components or layers may include, for example, polyvinyl alcohol, latex, or blends thereof.

[0106] Glycerides and fatty acid salts suitable for use in the glyceride / FAS blends of the present disclosure are well known in the art and are not particularly limited, and it will be apparent to those skilled in the art from this disclosure as a whole and its examples that they may vary depending on the property(ies) desired in the final product.

[0107] The term "glyceride" as used herein has its general 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 chains, as they can contain different carbon numbers, different degrees of unsaturation, and different configurations and positions of olefins.

[0108] Glycerides can be obtained by esterification with substantially pure fatty acids by known esterification processes. Glycerides can also be extracted from vegetable oils and animal fats by known extraction methods.

[0109] The term "fatty acid" as used herein has its ordinary meaning and refers to a carboxylic acid having an aliphatic chain that may be saturated or unsaturated. As used herein, the term fatty acid may refer to a fatty acid group attached to the glycerol residue of a glyceride.

[0110] The fatty acid group of the glyceride can be any known fatty acid. In a preferred embodiment, the fatty acid is known to be present in food, is edible, and / or is FDA approved. In one embodiment, the fatty acid is obtained from oilseeds. In another embodiment, the fatty acid is obtained from other sources of natural edible fats and oils.

[0111] 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, meaning, for example, that a triglyceride can contain three different fatty acid groups attached to a glycerol residue.

[0112] Exemplary saturated fatty acids for use in the formulations / compositions of the present 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).

[0113] Exemplary monounsaturated fatty acids for use in the formulations / compositions of the present disclosure may be selected from caproleic acid (dec-9-enoic acid), lauroleic acid ((Z)-dodec-9-enoic acid), myristoleic acid ((Z)-tetradec-9-enoic acid), palmitoleic acid ((Z)-hexadec-9-enoic acid), oleic acid ((Z)-octadec-9-enoic acid), elaidic acid ((E)-octadec-9-enoic acid), vaccenic acid ((E)-octadec-11-enoic acid), gadoleic acid ((Z)-icosa-9-enoic acid), erucic acid ((Z)-docosa-13-enoic acid), brassidic acid ((E)-docosa-13-enoic acid), or nervonic acid ((Z)-tetracos-15-enoic acid).

[0114] Exemplary polyunsaturated fatty acids for use in the formulations / compositions of the present disclosure are 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), columbic 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-gamma ... -linolenic acid (DGLA) ((8Z,11Z,14Z)-icosa-8,11,14-trienoic acid), arachidonic acid ((5Z,8Z,11Z,14Z)-icosa-5,8,11,14-tetraenoic acid), eicosapentaenoic acid (EPA) ((5Z,8Z,11Z,14Z,17Z)-icosa-5,8,11,14,17-pentaenoic acid), docosapentaenoic acid (DPA) ((7Z,10Z,13Z,16Z,19Z)-docosa-7,10,13,16,19-pentaenoic acid), and docosahexaenoic acid (DHA) ((4Z,7Z,10Z,13Z,16Z,19Z)-docosa-4,7,10,13,16,19-hexaenoic acid).

[0115] In one embodiment, the one or more glycerides can comprise 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 can be the predominant glyceride component of the blend by weight (i.e., greater than 50% by weight when the total weight of glycerides is considered to be 100% by weight). In other embodiments, the blend is free of monoglycerides, free of diglycerides, or free of triglycerides.

[0116] In one embodiment, the glycerides may include a combination of one or more water-insoluble glycerides (e.g., as noted above, triglycerides are typically strongly non-polar and hydrophobic) and one or more water-soluble glycerides (optionally in a weight ratio of 0.1:99.9 to 99.9:0.1), or only water-insoluble glycerides. The solubility of a glyceride can be determined, for example, by its HLB value.

[0117] Those skilled in the art will appreciate that the HLB value of one or more glycerides can be selected by varying one or more of the aforementioned glyceride parameters. In this regard, when multiple glycerides are used, each glyceride can be selected to have similar or different HLB values ​​(e.g., a lower range is used in combination with a higher range).

[0118] As used herein, the term "fatty acid salt" has its general meaning and refers to any one or more salts of the fatty acids disclosed herein. Exemplary cations of fatty acid salts include, but are not limited to, calcium, potassium, and sodium salts. Fatty acid salts can be synthesized by known methods or extracted from vegetable oils or animal fats by known methods. One exemplary method involves adding sodium hydroxide to fatty acids found in animal fats or vegetable oils (such as those derived from oilseeds). For example, sodium palmitate can be obtained from palm oil.

[0119] In one embodiment, the glyceride / FAS blend may contain only one or more glycerides, only one or more fatty acid salts, or both one or more glycerides and one or more fatty acid salts. When the glyceride / FAS blend contains both one or more glycerides and one or more fatty acids, the weight ratio of glyceride to fatty acid salt may 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.

[0120] Without being bound by theory, the interaction between the glyceride / FAS blend and the cellulose-based material may be due to ionic, hydrophobic, van der Waals interactions, or covalent bonds, or a combination thereof. In a related aspect, the binding of the glyceride / FAS blend to the cellulose-based material is substantially irreversible (e.g., using glycerides or fatty acid salts containing a combination of saturated and unsaturated fatty acids).

[0121] In one embodiment, hydrophobic barrier properties are imparted to the substrate by the glyceride / FAS blend in the absence of a secondary hydrophobe.

[0122] Furthermore, at sufficient concentrations, the binding of the glyceride / FAS blend alone is sufficient to render the contacted substrate hydrophobic, i.e., hydrophobicity is achieved without the addition of waxes, rosins, resins, diketenes, shellacs, vinyl acetates, PLA, PEI, oils, other water-repellent chemicals, or combinations thereof (i.e., secondary hydrophobes), including, among other things, that other properties such as strengthening, stiffening, and bulking of cellulose-based materials are achieved by the glyceride / fatty acid salt binding alone.

[0123] An advantage of the present disclosure is that multiple fatty acid chains react with cellulose. This is believed to create a crosslinked network, resulting in improved strength in fibrous webs such as paper, paperboard, airlaid and wetlaid nonwovens, and textiles. This is not typically seen with other sizing or hydrophobic treatment chemicals. The glycerides and fatty acid salts disclosed herein also create / increase wet strength, a property not present when using many other water-resistant chemicals.

[0124] Saturated glycerides and fatty acid salts are typically solid at nominal processing temperatures, while unsaturated glycerides and fatty acid salts are typically liquid. This allows for the formation of a uniform and stable dispersion of saturated glycerides and fatty acid salts in the aqueous coating without significant interaction or incompatibility with other coating components, which are typically hydrophilic. Furthermore, this dispersion allows for the preparation of high concentrations of saturated glycerides and fatty acid salts without adversely affecting the rheology, uniform coating application, or performance properties of the coating. If the saturated glyceride and fatty acid salt particles are melted and spread after heating, drying, and solidifying the coating layer, the coating surface will become hydrophobic.

[0125] In one embodiment, the amount of glyceride / FAS blend used to impart hydrophobicity depends on the form of the substrate (e.g., the form of the cellulose-based material) and the method of contacting the surface of the substrate. In one aspect, when the glyceride / FAS blend is combined as a coating on the cellulose-based material, the glyceride / FAS blend is applied to the surface of the cellulose-based material in an amount of at least about 0.05 g / m 2 ~Approx. 1.0g / m 2 , about 1.0g / m 2 ~about 2.0g / m 2 , about 2g / m 2 ~about 3g / m 2 In a related aspect, this is present at a coating weight of about 3 g / m 2 ~approx. 4g / m 2 , approximately 4 g / m2 ~about 5g / m 2 , about 5g / m 2 ~about 10g / m 2 , about 10g / m 2 ~about 20g / m 2 In another embodiment, when the cellulose-based material is a solution containing cellulose fiber, the glyceride / FAS blend is present at a concentration of at least about 0.025% (wt / wt) of the total fiber present. In a related embodiment, this may be from about 0.05% (wt / wt) to about 0.1% (wt / wt), from about 0.1% (wt / wt) to about 0.5% (wt / wt), from about 0.5% (wt / wt) to about 1.0% (wt / wt), from about 1.0% (wt / wt) to about 2.0% (wt / wt), or about 2. The glyceride / FAS blend may be present in an amount of from 0% (wt / wt) to about 3.0% (wt / wt), from about 3.0% (wt / wt) to about 4.0% (wt / wt), from about 4.0% (wt / wt) to about 5.0% (wt / wt), from about 5.0% (wt / wt) to about 10% (wt / wt), or from about 10% (wt / wt) to about 50% (wt / wt). In a further related aspect, the amount of glyceride / FAS blend may be equal to the amount of fiber present. In one embodiment, the glyceride / FAS blend may coat the entire exterior surface of a cellulose-based material (e.g., coating the entire paper or cellulose-containing article).

[0126] In other embodiments, the coating may comprise, by weight of the coating (wt / wt), about 0.9% to about 1.0%, about 1.0% to about 5.0%, about 5.0% to about 10%, about 10% to about 20%, about 20% to about 30%, or about 40% to about 50% of the glyceride / FAS blend.

[0127] In one embodiment, a method for producing a bulky fibrous structure that retains its strength when exposed to water is disclosed. Generally, the dried fibrous slurry forms a dense structure that easily disintegrates when exposed to water. Molded fibrous products made using the disclosed method can include paper plates, drink holders (e.g., cups), lids, food trays, and packaging that are lightweight, strong, and can withstand exposure to water and other liquids.

[0128] In one embodiment, the glyceride / FAS blend can be mixed with polyvinyl alcohol (PvOH) to produce a sizing agent for a water-resistant coating. A synergistic relationship between glycerides and fatty acid salts and PvOH has been demonstrated. While PvOH itself is known in the art to be a good film former and to form strong hydrogen bonds with cellulose, it is not very resistant to water, especially hot water. In an aspect, the use of PvOH helps emulsify the glycerides and fatty acid salts into an aqueous coating. In one aspect, PvOH provides a rich source of OH groups for the glycerides to crosslink along the fiber, thereby increasing the strength of the paper, e.g., particularly wet strength, and water resistance, to a greater extent than is possible with PvOH alone. For monoglycerides and diglycerides with free hydroxyls on the glycerol residue, crosslinkers such as dialdehydes (e.g., glyoxal, glutaraldehyde, etc.) can also be used.

[0129] In other embodiments, the effectiveness of the glyceride / FAS blend can be enhanced by the addition of one or more sugar fatty acid esters (SFAEs). As disclosed herein, all sugar fatty acid esters, including monosaccharides, disaccharides, and trisaccharides, are suitable for use in connection with embodiments of the present disclosure, including their use as emulsifiers. In a related embodiment, the sugar fatty acid esters can be mono-, di-, tri-, tetra-, penta-, hexa-, hepta-, or octaesters, and combinations thereof, including that the fatty acid moieties can be saturated, unsaturated, or combinations thereof.

[0130] Without being bound by any theory, the interaction between the sugar fatty acid ester and the cellulose-based material may be due to ionic, hydrophobic, van der Waals interactions, or covalent bonds, or a combination thereof. In a related aspect, the binding of the sugar fatty acid ester to the cellulose-based material is substantially irreversible (e.g., using an SFAE containing a combination of saturated and unsaturated fatty acids).

[0131] An additional advantage of using sugar fatty acid esters is that they also contain multiple fatty acid chains that react with cellulose. Furthermore, the two sugar molecules in the structure, such as the disclosed sucrose fatty acid esters, create a rigid crosslinked network, thereby improving the strength of fibrous webs such as paper, paperboard, airlaid and wetlaid nonwovens, and textiles. This is typically not seen with other sizing or hydrophobic treatment chemicals. The sugar fatty acid esters disclosed herein, especially when used in combination with glyceride / FAS blends, can also create / increase wet strength, a property not found with many other water-resistant chemicals.

[0132] Another advantage of using additional sugar fatty acid esters is that they limit the hydrogen bonding between the cellulose fibers, thereby increasing the space between them and therefore increasing the bulk without substantially increasing the weight.

[0133] When used in one embodiment, the sugar fatty acid ester may comprise or consist essentially of a sucrose ester of a fatty acid. Many methods are known and available for making or otherwise providing the sugar fatty acid esters of the present invention, and all such methods are considered to be available for use within the broad scope of the present disclosure. For example, in one particular embodiment, it may be preferred that the fatty acid ester be synthesized by esterifying a sugar with one or more fatty acid moieties obtained from oilseeds, including, but not limited to, soybean oil, sunflower oil, olive oil, canola oil, peanut oil, and mixtures thereof.

[0134] In one embodiment, the sugar fatty acid ester comprises a sugar moiety, including but not limited to a sucrose moiety, substituted at one or more of its hydroxyl hydrogens with an ester moiety. In a related aspect, the disaccharide ester for use in the present disclosure may have the structure of Formula I of the '073 publication, which is incorporated herein by reference in its entirety.

[0135] Suitable disaccharides for the sugar fatty acid ester also include xylose, glucose, raffinose, maltodextrose, galactose, combinations of glucose, combinations of fructose, combinations of maltose, lactose, mannose, combinations of erythrose, isomaltose, isomaltulose, trehalose, trehalulose, cellobiose, laminaribiose, chitobiose, and combinations thereof.

[0136] In other embodiments, the starch fatty acid esters disclosed in the '073 publication can be used, where the starch can be derived from any suitable source, such as dent corn starch, waxy corn starch, potato starch, wheat starch, rice starch, sago starch, tapioca starch, sorghum starch, sweet potato starch, and mixtures thereof.

[0137] For use in the compositions of the present disclosure, the sugar fatty acid ester compound may have a high degree of substitution. In one embodiment, the sugar fatty acid ester is sucrose polysoyate.

[0138] [ka]

[0139] As used herein, sugar fatty acid esters can be prepared by the methods disclosed in the '073 application. For example, sugar fatty acid esters can be made by esterification with substantially pure fatty acids using known esterification processes. They can also be prepared by transesterification using sugars and fatty acid esters in the form of fatty acid glycerides derived from natural sources, such as those found in oils extracted from oilseeds, such as soybean oil. Transesterification reactions using fatty acid glycerides to provide sucrose fatty acid esters are described, for example, in U.S. Pat. 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 WO 1992 / 004361, all of which are incorporated herein by reference in their entirety.

[0140] In one embodiment, the sugar fatty acid esters can be present in different concentrations in combination with the glyceride / FAS blend to impart hydrophobicity depending on the form of the cellulose-based material. In one aspect, when the sugar fatty acid esters (SFAEs) are combined as a coating on the cellulose-based material, the SFAEs are applied to the surface of the cellulose-based material in an amount of at least about 0.05 g / m 2 ~Approx. 1.0g / m 2 , about 1.0g / m 2 ~about 2.0g / m 2 , about 2g / m 2 ~about 3g / m 2 In a related aspect, this is present at a coating weight of about 3 g / m 2 ~approx. 4g / m 2 , approximately 4 g / m 2 ~about 5g / m 2 , about 5g / m 2 ~about 10g / m 2 , about 10g / m 2 ~about 20g / m 2In another embodiment, when the cellulose-based material is a solution containing cellulose fibers, the SFAE is present at a concentration of at least about 0.025% (wt / wt) of the total fiber present. In a related embodiment, this may be from about 0.05% (wt / wt) to about 0.1% (wt / wt), from about 0.1% (wt / wt) to about 0.5% (wt / wt), from about 0.5% (wt / wt) to about 1.0% (wt / wt), from about 1.0% (wt / wt) to about 2.0% (wt / wt), or about 2. The SFAE may be present at 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). In a further related aspect, the amount of SFAE may be equal to the amount of fiber present. In one embodiment, the SFAE may coat the entire exterior surface of the cellulose-based material (e.g., coat the entire paper or cellulose-containing article).

[0141] In other embodiments, the coating may comprise, by weight (wt / wt) of the coating, about 0.9% to about 1.0%, about 1.0% to about 5.0%, about 5.0% to about 10%, about 10% to about 20%, about 20% to about 30%, or about 40% to about 50% sugar fatty acid ester. In a related aspect, the SFAE is present in the formulation at a concentration of 5% (wt / wt) to 25% (wt / wt) of the total cellulosic fiber present in the solution, which can provide additional properties compared to thermoforming processes, as discussed below.

[0142] In one embodiment, cellulose-based materials include, but are not limited to, paper, paperboard, paper sheets, paper pulp, cups, boxes, trays, lids, release paper / liners, compost bags, shopping bags, shipping bags, bacon boards, tea bags, insulating materials, coffee or tea containers, pipes and water lines, food-grade disposable cutlery, plates and bottles, screens for televisions and mobile devices, clothing (e.g., cotton or cotton blends), bandages, pressure-sensitive labels, pressure-sensitive tapes, feminine products, and medical devices to be used on or within the body, such as contraceptives, drug delivery devices, containers for pharmaceutical materials (e.g., pills, tablets, suppositories, gels, etc.), etc. Such coating techniques can also be used on furniture and interior decor, outdoor camping equipment, etc.

[0143] In one aspect, the coatings described herein are tolerant to a pH ranging from about 3 to about 9. In a related aspect, the pH can be from about 3 to about 4, from about 4 to about 5, from about 5 to about 7, or from about 7 to about 9.

[0144] In one embodiment, there is provided a method for treating the surface of a cellulose-containing (or cellulosic) material, comprising: R-CO-X formula (II) X-CO-R-CO-X1 Formula (III) wherein R is a linear, branched, or cyclic aliphatic hydrocarbon radical having 6 to 50 carbon atoms; X and X1 are independently Cl, Br, R-CO-OR, or O(CO)OR; and when the alkanoic acid derivative comprises formula (III), X and X1 are the same or different. applying to a surface a composition containing an alkanoic acid derivative, The glyceride / FAS blend disclosed herein is the carrier and the process does not require organic bases, gaseous HCl, VOCs, or catalysts. A method is disclosed.

[0145] In one embodiment, the alkanoic acid derivative is mixed with a glyceride and / or a fatty acid salt to form an emulsion, and the emulsion is used to treat the cellulose-based material.

[0146] In one embodiment, sugar fatty acid esters (SFAEs) can be used as emulsifiers and can include a mixture of one or more mono-, di-, tri-, tetra-, penta-, hexa-, hepta-, or octaesters. In another aspect, the fatty acid moieties of the sugar fatty acid esters can contain saturated groups, unsaturated groups, or combinations thereof. In one aspect, the sugar fatty acid ester-containing emulsions can also contain proteins, polysaccharides, and / or lipids, including, but not limited to, milk proteins (e.g., casein, whey protein, etc.), wheat gluten, gelatin, prolamins (e.g., corn zein), soy protein isolates, starches, acetylated polysaccharides, alginates, carrageenans, chitosan, inulin, long-chain fatty acids, waxes, and combinations thereof.

[0147] In one embodiment, the sugar fatty acid ester (SFAE) emulsifiers disclosed herein can be used to carry coatings or other chemicals used in papermaking, including, but not limited to, glyceride / FAS blends, agarite, esters, diesters, ethers, ketones, amides, nitriles, aromatics (e.g., xylene, toluene), acid halides, anhydrides, talc, alkyl ketene dimer (AKD), alabaster, alganic acid, alum, albaline, adhesives, barium carbonate, barium sulfate, chlorine dioxide, clay, dolomite, diethylenetriamine pentaacetate, EDTA, enzymes, formamidine sulfate, guar gum, gypsum, lime, magnesium bisulfate, milk of lime, milk of magnesia, polyvinyl alcohol (PvOH), rosin, rosin soap, satin, soap / fatty acids, sodium bisulfate, soda ash, titania, surfactants, starch, modified starch, hydrocarbon resins, polymers, waxes, polysaccharides, proteins, and combinations thereof.

[0148] In one embodiment, the formulation used in the method of the present disclosure includes one or more charged polymers to aid in the retention of one or more glycerides and / or one or more fatty acid salts on the substrate. As described above, the charged polymer is believed to help impart benefits (e.g., barrier properties including oil and grease resistance and water resistance) by aligning the fatty acid groups of the glyceride / FAS blend. When the formulation further includes one or more sugar fatty acid esters (SFAEs), the retention aid is also believed to facilitate the alignment of the fatty acid groups of the SFAEs to aid in imparting benefits.

[0149] The one or more charged polymers can include one or more cationic polymers, anionic polymers, nonionic polymers, and / or zwitterionic polymers. In one embodiment, the concentration of the cationic polymer in the formulation is about 0.01% to about 5%, about 0.01% to about 3%, 0.05% to about 0.1%, or about 0.1% to about 1%, or about 1% to about 3% by weight, based on the total weight of the formulation. In some aspects, the weight ratio of cationic polymer to glyceride / FAS blend in the formulation is about 0.1:99.9 to about 20:80, 0.5:99.5 to about 15:85, about 1:99 to about 10:90, or about 2.5:97.5 to about 7.5:92.5.

[0150] In other embodiments, the weight ratio of cationic polymer to the sum of the glyceride / FAS blend and sugar fatty acid ester (SFAE) in the formulation (blend:(blend+SFAE)) is from about 0.1:99.9 to about 20:80, 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.

[0151] In one embodiment, the charged polymer has a weight average molecular weight of 500,000 to 10,000,000. In one embodiment, 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, etc. In one embodiment, the charged polymer is a combination of two polymers with different weight average MW to achieve a bimodal type blend.

[0152] Exemplary cationic polymers for use as retention aids include, but are not limited to, polyacrylamide (e.g., polyDADMAC (polydiallyldimethylammonium chloride)), poly(ethyleneimine) (PEI), poly-1-(lysine) (PLL), poly[2-(N,N-dimethylamino)ethyl methacrylate] (PDMAEMA), and chitosan.

[0153] In one embodiment, the coated material (e.g., cellulose-containing material) produced by the method of the present disclosure exhibits greater hydrophobicity or water resistance compared to the untreated cellulose-containing material. In a related aspect, the treated cellulose-containing material exhibits greater oleophobicity or grease resistance compared to the untreated cellulose-containing material. 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 oleophobic (grease-resistant).

[0154] In one embodiment, the treated substrate may have improved mechanical properties compared to the same untreated material. For example, paper bags treated by the method of the present disclosure exhibit increases in burst strength, Gurley number, tensile strength, and / or maximum load energy. In one aspect, the burst strength increases by about 0.5 to 1.0 times, about 1.0 to 1.1 times, about 1.1 to 1.3 times, or about 1.3 to 1.5 times. In another aspect, the Gurley number increases by about 3 to 4 times, about 4 to 5 times, about 5 to 6 times, or about 6 to 7 times. In yet another aspect, the tensile strain increases by about 0.5 to 1.0 times, about 1.0 to 1.1 times, about 1.1 to 1.2 times, or about 1.2 to 1.3 times. In other embodiments, the maximum load energy is increased by about 1.0 to 1.1 times, about 1.1 to 1.2 times, about 1.2 to 1.3 times, and about 1.3 to 1.4 times.

[0155] In one embodiment, the cellulose-containing material is a base paper containing microfibrillated cellulose (MFC) or cellulose nanofibers (CNF), as described, for example, in U.S. Patent Application Publication No. 2015 / 0167243 (incorporated herein by reference in its entirety), where the MFC or CNF is added during the forming and papermaking process and / or added to a previous forming layer as a coating or secondary layer to reduce the porosity of the base paper. In a related aspect, the base paper is contacted with a glyceride / FAS blend formulation as described above. In a further related aspect, the contacted base paper is further contacted with polyvinyl alcohol (PvOH). In one embodiment, the resulting contacted base paper is controllably water- and oil-resistant. In a related aspect, the resulting base paper may exhibit a Gurley value of at least about 10 to 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 glyceride / FAS blend coating 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 for one or more layers to achieve similar performance benefits (e.g., water resistance, grease resistance, etc.). In a related aspect, the laminate may include a biodegradable and / or composable heat seal or adhesive.

[0156] In one embodiment, the glyceride / FAS blend can be formulated as an emulsion, with the choice of emulsifier and the amount used being determined by the nature of the composition and the agent's ability to facilitate dispersion of the sugar fatty acid ester. In one aspect, emulsions are used in the methods of the present disclosure. In one aspect, emulsifiers may include, but are not limited to, water, buffers, sugar fatty acid esters, polyvinyl alcohol (PvOH), carboxymethylcellulose (CMC), milk proteins, wheat gluten, gelatin, prolamins, soy protein isolates, starches, acetylated polysaccharides, alginates, carrageenans, chitosan, inulin, long chain fatty acids, waxes, agar, alginates, glycerol, gums, lecithin, poloxamers, monoglycerol, diglycerol, monosodium phosphate, monostearate, propylene glycol, detergents, cetyl alcohol, glycerol esters, (saturated) ((poly)unsaturated) fatty acid methyl esters (e.g., methyl stearate, methyl palmitate, methyl palmitoleate (cis-9)), and combinations thereof. In another embodiment, the weight ratio of the glyceride / FAS blend to the one or more emulsifiers is about 0.1:99.9 to about 99.0:0.1, about 10:90 to about 90:10, about 20:80 to 80:20, about 35:65 to 65:35, about 40:60 to about 60:40, or about 50:50. It will be apparent to one skilled in the art that the ratio can vary depending on the property(ies) desired in the final product.

[0157] In one embodiment, the glyceride / FAS blend may be combined with one or more coating ingredients for internal and surface sizing (single or in combination), including, but not limited to, pigments (e.g., clay, calcium carbonate, titanium dioxide, plastic pigments), binders (e.g., starch, soy protein, polymer emulsions, PvOH, casein), and additives (e.g., glyoxal, glyoxalated resins, zirconium salts, polyethylene emulsions, carboxymethyl cellulose, acrylic polymers, alginates, polyacrylate gums, polyacrylates, biocides, oil-based defoamers, silicone-based defoamers, stilbenes, direct dyes, and acid dyes). In a related aspect, such components can provide one or more properties, including, but not limited to, building a fine porous structure, forming a light-scattering surface, improving ink receptivity, improving gloss, binding pigment particles, binding the coating to the paper, reinforcing the base sheet, filling the pores of the 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 retention, dispersing pigments, maintaining coating dispersion, preventing coating / coating color deterioration, controlling foaming, reducing entrapped air and coating craters, increasing whiteness and brightness, and controlling color and hue. It will be apparent to one skilled in the art that combinations can vary depending on the property(ies) desired in the final product.

[0158] In one embodiment, methods using formulations including glyceride / FAS blends can be used to provide a material layer that exhibits desired properties (e.g., water resistance, low surface energy, etc.), thereby reducing the amount of primary / secondary layer needed to achieve similar properties and lowering the cost of applying primary / secondary coatings (e.g., silicone-based layers, starch-based layers, clay-based layers, PLA layers, PEI layers, etc.). In one aspect, the material can be coated over a layer of glyceride and / or fatty acid salt (e.g., a heat-sealable agent). In one embodiment, the composition is fluorocarbon- and silicone-free.

[0159] In other embodiments, methods using formulations including glyceride / FAS blends can be used to reduce the cost of the coating compositions disclosed by the '073 publication. For example, the use of glyceride / FAS blends can reduce the amount of SFAE while providing materials that exhibit desired properties (e.g., water resistance, oil and grease resistance, low surface energy, etc.).

[0160] In one embodiment, the composition increases both the mechanical and thermal stability of the treated product. In one aspect, the surface treatment is thermally stable at temperatures from about -100°C to about 300°C. In a further related aspect, the surface of the treated substrate (e.g., cellulose-based material) exhibits a water contact angle of about 60° to about 120°. In another related aspect, the surface treatment is chemically stable at temperatures from about 200°C to about 300°C.

[0161] Substrates, which can be dried (e.g., at about 80-150°C) before application, can be treated with a modifying formulation containing a glyceride / FAE blend, for example, by immersion and exposing the surface to the composition for less than 1 second. The substrate can be heated to dry the surface, after which the modified material is ready for use. In one aspect, according to the methods of the present disclosure, the substrate can be treated with any suitable coating / sizing process typically performed in a paper mill (see, for example, Smook, G., Surface Treatments in Handbook for Pulp & Paper Technologists, (2016), 4th Ed., Cpt. 18, pp. 293-309, TAPPI Press, Peachtree Corners, GA USA, which is incorporated herein by reference in its entirety).

[0162] In some applications, the material may be dried before processing, but no special preparation of the material is required to practice the present disclosure. In one embodiment, the method of the present disclosure can be used on any cellulose-based surface, including, but not limited to, films, rigid containers, fibers, pulp, fabrics, etc. In one aspect, the glyceride / FAE blend or coating thereof can be applied by conventional size presses (vertical, inclined, horizontal), gate roll size presses, metering size presses, calendar size application, tube sizing, on-machine, off-machine, single-sided coaters, double-sided coaters, short dwell, simultaneous two-sided coaters, blade or rod coaters, gravure coaters, gravure printing, flexographic printing, inkjet printing, laser printing, supercalendering, and combinations thereof.

[0163] Depending on the source, the cellulose treated in the methods herein can be paper, paperboard, pulp, softwood fiber, hardwood fiber, or combinations thereof, nanocellulose, cellulose nanofibers, whiskers or microfibrils, microfibrillated cotton or cotton blends, cellulose nanocrystals, or nanofibrillated cellulose.

[0164] Additionally, the modified fibers and cellulose-based materials disclosed herein can be repulped, and further, for example, water cannot be easily "pushed" across a low surface energy barrier into the sheet.

[0165] In one embodiment, the amount of the applied formulation containing the glyceride / FAE blend is sufficient to completely cover at least one surface of the substrate, e.g., at least one surface of the cellulose-containing material. For example, in one embodiment, the glyceride / FAE blend coating may be applied to the entire exterior surface of a container, the entire interior surface of a container, or a combination thereof, or to one or both sides of a base paper. In other embodiments, the entire upper surface of a film may be covered with the glyceride / FAE blend coating, the entire lower surface of a film may be covered with the glyceride / FAE blend coating, or a combination thereof. In one embodiment, the inner lumen of a device / instrument may be covered with the coating, the outer surface of a device / instrument may be covered with the glyceride / FAE blend coating, or a combination thereof.

[0166] In one embodiment, the amount of glyceride / FAE blend coating applied is sufficient to partially cover at least one surface of the cellulose-containing material. For example, only the surface exposed to the ambient atmosphere may be covered with the glyceride / FAE blend coating, or only the surface not exposed to the ambient atmosphere may be covered with the glyceride / FAE blend coating (e.g., masked). As will be apparent to those skilled in the art, the amount of glyceride / FAE blend coating applied may depend on the use of the material to be covered. In one aspect, one surface may be coated with the glyceride / FAE blend, and the opposite surface may be coated with an agent, including, but not limited to, proteins, wheat gluten, gelatin, prolamin, soy protein isolate, starch, modified starch, acetylated polysaccharides, alginate, carrageenan, chitosan, inulin, long-chain fatty acids, waxes, and combinations thereof. In a related aspect, the glyceride / FAE blend may be added to the furnish, and the resulting material on the web may be further coated with a glyceride / fatty acid salt coating.

[0167] Any suitable coating process may be used to deliver any of the various glyceride / FAE blend coatings and / or emulsions applied in the course of practicing this aspect of the method, hi one embodiment, the glyceride / FAE blend coating process includes dipping, spraying, painting, printing, and any combination of any of these processes, alone or in conjunction with other coating processes adapted for practicing the methods of the present disclosure.

[0168] For example, by increasing the concentration of the glyceride / FAE blend, the composition of the present disclosure can react more extensively with the treated substrate (e.g., cellulose), with the end result again demonstrating improved water / lipid repellency properties. However, higher coating weights do not necessarily increase water resistance. In one aspect, various catalysts can allow for more rapid "setting" to precisely adjust the amount of glyceride / FAE blend to suit a particular application.

[0169] It will be apparent to one skilled in the art that outside of any particular range or composition detailed herein, the choice of cellulose to be treated, the glyceride / FAE blend, reaction temperature, and exposure time are process parameters that can be optimized by routine experimentation to suit any particular application of the final product.

[0170] The derivatized materials have altered physical properties that can be defined and measured using appropriate tests known in the art. For hydrophobicity, analytical protocols may include, but are not limited to, contact angle measurements and moisture pickup. Other properties include stiffness, WVTR, porosity, tensile strength, lack of substrate degradation, burst and tear properties. Specific standardized protocols to follow are defined by the American Society for Testing and Materials (Protocol ASTM D7334-08).

[0171] The permeability of the surface to various gases, such as water vapor and oxygen, can also be modified by the glyceride / FAS blend coating process, as the barrier function of the material is increased. The standard unit for measuring permeability is the barrer, and protocols for measuring these parameters are also available in the public domain (ASTM std F2476-05 for water vapor and ASTM std F2622-8 for oxygen).

[0172] In one embodiment, materials treated according to the methods of the present disclosure exhibit complete biodegradability as measured by degradation in an environment under microbial challenge.

[0173] Various methods are available for defining and testing biodegradability, including the shake flask method (ASTM E1279-89(2008)) and the Zahn-Wellens test (OECD TG 302B).

[0174] A variety of methods are available for defining and testing compostability, including but not limited to ASTM D6400.

[0175] Cellulosic materials suitable for treatment by the methods of the present disclosure include, but are not limited to, plant fibers such as cotton and flax, wood fibers, regenerated cellulose (rayon and cellophane), partially alkylated cellulose (cellulose ethers), partially esterified cellulose (acetate rayon), and other modified cellulose materials, all of which have a significant percentage of their surface available for reaction / bonding. As noted above, the term "cellulose" includes these materials as well as others with similar polysaccharide structures and similar properties. Of these, microfibrillated cellulose (cellulose nanofibers), a relatively new material (see, e.g., U.S. Pat. No. 4,374,702; U.S. Patent Application Publication Nos. 2015 / 0167243; and 2009 / 0221812, the entire contents of which are incorporated herein by reference), is particularly suitable. In other embodiments, the cellulose may include, but is not limited to, cellulose triacetate, cellulose propionate, cellulose acetate propionate, cellulose acetate butyrate, nitrocellulose (cellulose nitrate), cellulose sulfate, celluloid, methylcellulose, ethylcellulose, ethylmethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, cellulose nanocrystals, hydroxyethylmethylcellulose, hydroxypropylmethylcellulose, ethylhydroxyethylcellulose, carboxymethylcellulose, and combinations thereof.

[0176] In addition to increasing its hydrophobicity, the modifications of cellulose disclosed herein may also increase its tensile strength, flexibility, and stiffness, thereby further broadening its range of uses. All biodegradable and partially biodegradable products made from or by using the modified cellulose disclosed in this application are within the scope of this disclosure, including recyclable and compostable products.

[0177] Among the possible applications of the coating technology disclosed herein are items including, but not limited to, paper, paperboard, paper pulp, cups, lids, boxes, trays, release paper / liners, compost bags, shopping bags, pipes and water pipes, food-grade disposable cutlery, plates and bottles, screens for televisions and mobile devices, clothing (e.g., cotton or cotton blends), bandages, pressure-sensitive labels, pressure-sensitive tape, feminine products, and containers for any purpose, such as medical devices to be used on or within the body, e.g., contraceptives, drug delivery devices, etc. The disclosed coating technology can also be used on furniture and upholstery, outdoor camping equipment, etc. [Example]

[0178] Hereinafter, embodiments of the present disclosure will be described in more detail with reference to examples, but the present disclosure is not limited to these.

[0179] [Example 1] <Glyceride / FAS blend> Formulations having the compositions listed in Table 1 below were prepared and coated onto bleached lightweight (40#) paper obtained from the University of Maine Process Development Center, Orono, Maine USA at the coating weights listed in Table 2 below.

[0180] The coated papers were tested for oil resistance using an adapted 30-second Cobb test from Tappi Standard Test Method T441 om-20 "Water Absorptiveness of Paper" and a 3M KIT test (Tappi Standard Test Method T559 "Grease Resistance"). Water resistance was tested using an adapted 120-second Cobb test from Tappi Standard Test Method T441 om-20 "Water Absorptiveness of Paper". The test results are shown in Table 2 below.

[0181] In the 30-second Cobb test, a small amount (2 cc) of vegetable oil is placed on a coated piece of paper pressed into a 1 / 4-inch diameter 2.54 cm (1 inch ) The oil was rapidly poured onto the ring. The milligrams of oil pick-up after 30 seconds of contact was measured. Results are reported in gsm.

[0182] The 120-second Cobb test for determining water resistance involves applying a small amount (2 cc) of water to a coated paper sheet pressed into a diameter 2.54 cm ( 1 inch ) The water was rapidly poured onto a ring of 120 ml of water and the milligrams of water pickup was measured after 120 seconds of contact. Results are reported in gsm.

[0183] [Table 1]

[0184] [Table 2]

[0185] The results shown in Table 2 demonstrate that the use of a formulation consisting essentially of glycerides and a formulation consisting essentially of fatty acid salts in the methods of the present disclosure can impart both oil and water resistance to a substrate (here, cellulose fibers).

[0186] Also, Test 1-7 demonstrated a combination of both excellent oil resistance and excellent water resistance using coating weights substantially similar to Tests 1-2 through 1-5. It was unexpected that a formulation consisting essentially of water-insoluble (non-polar, hydrophobic) glycerides would provide both of these properties.

[0187] It was observed that the majority of the glycerides were fairly insoluble in hot water. Increasing the degree of heating or prolonging the use of agitation did not improve solubility, but rather only increased the likelihood that the glycerides would solidify and float. It is hypothesized that sugar fatty acid esters can be beneficially used as emulsifiers in the formulations of the present disclosure to emulsify the glycerides. Of course, the use of sugar fatty acid esters also imparts benefits to the treated fibers, as previously shown by the use of sucrose esters in Tests 1-5 and as described in the '073 publication.

[0188] [Example 2] <Thermoforming method using molding composition> For Sample 2-1, 3 gram handsheets were made using BCTMP (bleached chemithermomechanical pulp) obtained from Stora Enso. The resulting handsheets were subjected to a 120 second oil Cobb test and a 120 second water Cobb test in the same manner as in Example 1. The results are shown in Table 3 below.

[0189] For Sample 2-2, 3-gram handsheets were prepared in the same manner as for Sample 2-1, except that the same SE-15 formulation obtained from HANGZHOU UNION BIOTECHNOLOGY CO., LTD. as used in Example 1 was also added directly to the furnish in the handsheet mold, along with poly-DADMAC (Paraform™ 289 obtained from Paradigm Chemical and Consulting, Ackworth, GA, USA) as a retention aid. The SE-15 formulation was added in an amount such that the furnish contained approximately 5 wt.% SE-15 based on the dry fiber weight of the BCTMP. The poly-DADMAC content in the furnish was approximately 0.3 wt.% based on the dry fiber weight of the BCTMP. The handsheets were subjected to a 120-second oil Cobb test and a 120-second water Cobb test in the same manner as in Example 1. The results are shown in Table 3 below.

[0190] For Sample 2-3, 3-gram handsheets were prepared in the same manner as Sample 2-2, except that the amount of SE-15 blend added to the furnish was increased to about 13 wt. % based on the dry fiber weight of the BCTMP, and the amount of polyDADMAC was increased to about 1.3 wt. % based on the dry fiber weight of the BCTMP. The handsheets were subjected to a 120-second oil Cobb test and a 120-second water Cobb test in the same manner as Example 1. The results are shown in Table 3 below.

[0191] The handsheet obtained from sample 2-3 was approximately 121°C( 250°F ) The composition was heated to about 100°C, at which point the formed fibrous handsheet became flexible, moldable, and shapable. The heated composition was then manually formed into small boats. 20.0°C( 68°F ) ~ 22.2°C( 72°F ) After cooling to ambient temperature, the handsheets retained and maintained their boat shape. The 120-second oil Cobb test and the 120-second water Cobb test were measured on the cooled molded handsheets in the same manner as in Example 1. The results are shown in Table 3 below.

[0192] [Table 3]

[0193] The results of Example 2 indicate that the use of relatively high levels of the SE-15 formulation (approximately 10-15% (wt / wt) of the total cellulose fiber present in the solution), containing sugar fatty acid esters, glycerides, and fatty acid salts, not only improved both oil and water resistance performance, but also imparted flexibility to the formed fiber pulp to be "melted and molded" into a dry article upon application of sufficient heat. Further testing revealed that the solid formed article was formed at approximately 65.5°C( 150°F ) Very, especially 121°C( 250°F )It was found that by heating to temperatures above 100°C, the solid formed article became flexible and could be shaped without the addition of water. Furthermore, upon cooling again, the water- and grease-resistant properties were retained, as shown in Table 3.

[0194] While the basic novel features of the present disclosure have been shown and described as applied to its preferred exemplary embodiments, it should be understood that those skilled in the art may make omissions, substitutions, and changes in the form and details of the present disclosure without departing from the spirit of the disclosure. Moreover, as will be readily apparent, numerous variations and modifications 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. Therefore, it is not desired to limit the disclosure to the exact construction and operation shown and described, but all suitable modifications and equivalents may be resorted to as falling within the scope of the present disclosure as claimed. In other words, although embodiments of the present disclosure have been described with reference to the foregoing examples, it is understood that modifications and variations are encompassed within the spirit and scope of the present disclosure. The present invention is limited only by the claims.

[0195] All references cited herein are incorporated by reference in their entirety.

Claims

1. 1. A method of imparting hydrophobic and / or oleophobic barrier properties to a substrate, comprising: preparing a formulation for imparting said hydrophobic and / or oleophobic barrier properties to said substrate, said formulation comprising a blend of one or more glycerides and one or more fatty acid salts, said one or more fatty acid salts comprising calcium salts, potassium salts, sodium salts or combinations thereof; contacting a surface of the substrate with the formulation to impart the hydrophobic and / or oleophobic barrier properties to the substrate; A method comprising:

2. The method of claim 1 , wherein the substrate is a cellulosic or synthetic polymeric material.

3. The method of claim 1 , wherein the substrate is a natural or synthetic woven fabric.

4. The method of claim 1 , wherein the contacting step comprises forming a solution of the blend and cellulose fibers.

5. The method described in claim 4, wherein the blend of one or more glycerides and one or more fatty acid salts is present in the solution at a total concentration of at least 0.025% (wt / wt) of the total cellulose fiber present in the solution.

6. The method of claim 4 , further comprising forming a solid article using said solution, said solid article having said hydrophobic and / or oleophobic barrier properties.

7. The article formed is paper, paperboard, bacon board, insulating material, food storage cartons, compost bags, food storage bags, release paper, shipping bags, weed blocking / barrier fabric or film, mulching film, flower pots, packing beads, bubble wrap, laminate, envelopes, gift cards, credit cards, gloves, raincoats, OGR paper, shopping bags, diapers, membranes, tableware, tea bags, coffee or tea containers, containers for holding hot or cold beverages, cups, plates, bottles for storing carbonated liquids, bottles for storing non-carbonated liquids, lids, food packaging film, garbage disposal containers, food handling equipment, fabric fibers, water storage and transport equipment, storage and transport equipment for alcoholic or non-alcoholic beverages, outer casings or screens for electronic products, interior or exterior parts of furniture, curtains, upholstery, fabrics, films, boxes, sheets, trays, pipes, water conduits , clothing, medical devices, pharmaceutical packaging, contraceptives, camping equipment, molded cellulosic materials 7. The method of claim 6, wherein the hydroxybenzoate is selected from the group consisting of: hydroxybenzoates, ...

8. the contacting step comprising coating the surface of the substrate with the formulation. The method of claim 1 .

9. The blend of one or more glycerides and one or more fatty acid salts is applied to the surface of the substrate in an amount of at least 0.05 g / m ２ The method of claim 8, wherein the compound is present in an amount by weight of

10. The substrate may be paper, paperboard, bacon board, insulating material, paper pulp, food storage cartons, compost bags, food storage bags, release paper, shipping bags, weed blocking / barrier fabric or film, mulching film, flower pots, packing beads, bubble wrap, oil absorbing material, laminates, envelopes, gift cards, credit cards, gloves, raincoats, OGR paper, shopping bags, diapers, membranes, tableware, tea bags, coffee or tea containers, containers for holding hot or cold beverages, cups, plates, bottles for storing carbonated liquids, non-carbonated liquids 9. The method of claim 8, wherein the surface of an article is selected from the group consisting of storage bottles, lids, food packaging films, garbage disposal containers, food handling equipment, fabric fibers, water storage and transport equipment, alcoholic or non-alcoholic beverage storage and transport equipment, outer casings or screens for electronic products, interior or exterior furniture parts, curtains, upholstery, fabrics, films, boxes, sheets, trays, pipes, water conduits, clothing, medical devices, pharmaceutical packaging, contraceptives, camping equipment, molded cellulosic materials, and combinations thereof.

11. The method of claim 1, wherein the blend of one or more glycerides and one or more fatty acid salts is obtained from an oilseed.

12. 10. The method of claim 1, wherein the one or more glycerides comprise one or more monoglycerides, one or more diglycerides, and one or more triglycerides.

13. 2. The method of claim 1, wherein the one or more glycerides comprise tripalmitin and / or tristearin.

14. 10. The method of claim 1, wherein the one or more glycerides differ in their fatty acid alkyl groups.

15. 15. The method of claim 14, wherein the one or more glycerides contain fatty acid alkyl groups with different carbon numbers, different degrees of unsaturation, and / or different olefin configurations and positions.

16. 10. The method of claim 1, wherein the one or more fatty acid salts comprise one or more calcium, potassium, or sodium salts of fatty acids derived from edible fats and oils.

17. 10. The method of claim 1, wherein the one or more fatty acid salts comprise one or more calcium, potassium or sodium salts of fatty acids obtained from oil seeds.

18. 2. The method of claim 1, wherein the one or more fatty acid salts comprise one or more selected from the group consisting of sodium oleate, sodium stearate, sodium palmitate, calcium oleate, calcium stearate, and calcium palmitate.

19. 10. The method of claim 1, wherein the hydrophobic barrier properties are imparted to the substrate by blending the one or more glycerides with one or more fatty acid salts in the absence of a secondary hydrophobic material.

20. The method of claim 1 , wherein the formulation further comprises one or more emulsifiers.

21. 21. The method of claim 20, wherein the weight ratio of the blend of one or more glycerides and one or more fatty acid salts to the one or more emulsifiers is from 0.1:99.9 to 99.9:0.

01.

22. 10. The method of claim 1, wherein the formulation further comprises one or more sugar fatty acid esters.

23. 10. The method of claim 1, wherein the formulation further comprises one or more sugar fatty acid esters, the substrate comprises cellulosic fibers, and the concentration of the sugar fatty acid esters is from 10% (wt / wt) to 25% (wt / wt) of the total cellulosic fibers present in the formulation.

24. The method of claim 1 , wherein the formulation further comprises one or more pigments.

25. 25. The method of claim 24, wherein the one or more pigments are present in a concentration of 0.1% to 80% by weight based on the total weight of the formulation, where the total weight of the formulation is taken as 100% by weight.

26. 25. The method of claim 24, wherein the one or more pigments are selected from the group consisting of clay, calcium carbonate, titanium dioxide, and plastic pigments.

27. 25. The method of claim 24, wherein the one or more pigments have been pretreated by contacting the pigment with a glyceride, a fatty acid salt, and / or a sugar fatty acid ester for a period of time until the glyceride, fatty acid, and / or sugar becomes bound to the pigment.

28. 10. The method of claim 1, wherein the formulation consists of a blend of the one or more glycerides and one or more fatty acid salts, one or more emulsifiers, and water.

29. The method of claim 1 , wherein the formulation further comprises one or more charged polymers.

30. 30. The method of claim 29, wherein the one or more charged polymers comprise one or more cationic polymers.

31. 31. The method of claim 30, wherein the cationic polymer has a weight average molecular weight of 500,000 to 10,000,000.

32. 31. The method of claim 30, wherein the weight ratio of the cationic polymer to the glyceride / FAS blend in the formulation is from 0.1:99.9 to 20:

80.

33. 31. The method of claim 30, wherein the formulation consists of the blend of the one or more glycerides and one or more fatty acid salts, one or more emulsifiers, one or more cationic polymers, and water.

34. 10. The method of claim 1, wherein the formulation further comprises one or more binders selected from the group consisting of starch, protein, prolamine, polymer, polymer emulsion, PvOH, and combinations thereof.

35. 10. The method of claim 1, wherein the substrate to which the hydrophobic and / or oleophobic barrier properties have been imparted exhibits a 3M Grease KIT test value of 3-12.

36. 10. The method of claim 1, wherein the surface of the substrate to which the hydrophobic and / or oleophobic barrier properties have been imparted exhibits a water contact angle of at least 90 degrees.

37. 10. The method of claim 1, wherein the surface of the substrate imparted with hydrophobic and / or oleophobic barrier properties exhibits an HST value of at least 65 seconds.

38. An article obtainable by the method of claim 1.

39. An emulsion comprising 0.01% to 80% by weight of one or more emulsifiers, 0.01% to 95% by weight of a blend of one or more glycerides and one or more fatty acid salts, 0.01% to 95% by weight of one or more sugar fatty acid esters, and the remainder being water, wherein the one or more fatty acid salts comprise calcium salts, potassium salts, sodium salts, or combinations thereof.

40. The emulsion of claim 39, further comprising 0.01% to 5% by weight of a cationic polymer.

41. 1. A molding composition comprising 75% to 97% by weight of cellulose fibers and 2% to 25% by weight in total of one or more glycerides, one or more fatty acid salts, and one or more sugar fatty acid esters (SFAEs), wherein the one or more fatty acid salts comprise calcium salts, potassium salts, sodium salts, or combinations thereof.

42. 42. The molding composition of claim 41, further comprising one or more pigments.

43. 42. The molding composition of claim 41, which exhibits increased flexibility when heated to a temperature of 65.5°C (150°F) or greater compared to ambient temperature prior to said heating.

44. The molding composition of claim 41, which exhibits a 3M Grease Kit test value of 3 to 12 after being heated to a temperature of 65.5°C (150°F) or greater and subsequently cooled to ambient temperature.

45. The molding composition of claim 41, further comprising 0.01% to 5% by weight of a cationic polymer.

46. 1. A method of thermoforming a molded article having hydrophobic and / or oleophobic barrier properties, comprising: preparing a molding composition comprising cellulose fibers, a blend of one or more glycerides and one or more fatty acid salts, and optionally one or more sugar fatty acid esters, wherein the one or more fatty acid salts comprise calcium salts, potassium salts, sodium salts, or combinations thereof; heating the molding composition to a temperature of at least 65.5°C (150°F); forming the heated molding composition into a molded article having a three-dimensional shape; Including, The method wherein said molded article has said hydrophobic and / or oleophobic barrier properties.

47. 47. The method of claim 46, wherein the molded article retains its shape upon cooling to ambient temperature.

48. 47. The method of claim 46, wherein the molding composition comprises 75% to 97% by weight of cellulosic fibers and 2% to 25% by weight of one or more glycerides, one or more fatty acid salts, and / or one or more sugar fatty acid esters (SFAEs).

49. 49. The method of claim 48, wherein the molding composition further comprises 0.1% to 80% by weight of one or more pigments, based on 100% by weight of the total weight of the one or more pigments and the cellulose fibers.

50. 50. The method of claim 49, wherein the one or more pigments are selected from the group consisting of clay, calcium carbonate, titanium dioxide, and plastic pigments.

51. 50. The method of claim 49, wherein the one or more pigments have been pretreated by contacting the pigment with a glyceride, a fatty acid salt, and / or a sugar fatty acid ester for a period of time until the glyceride, fatty acid, and / or sugar becomes bound to the pigment.

52. 47. The method of claim 46, wherein the moldable composition further comprises one or more cationic polymers.

53. 53. The method of claim 52, wherein the cationic polymer has a weight average molecular weight of 500,000 to 10,000,000.

54. 53. The method of claim 52, wherein the content of the cationic polymer is 0.01 to 5% by weight based on the total dry weight of cellulose fibers in the molding composition.

55. 53. The method of claim 52, wherein the weight ratio of the cationic polymer to the total weight of glyceride, fatty acid salt, and sugar fatty acid ester in the formulation is 0.1:99.9 to 20:

80.

56. 47. The method of claim 46, wherein the molded article retains its three-dimensional shape upon cooling to ambient temperature.

57. 47. The method of claim 46, wherein the shaped article is selected from the group consisting of paper, paperboard, bacon board, insulating material, food storage cartons, compost bags, food storage bags, release paper, shipping bags, weed blocking / barrier fabric or film, mulching film, flower pots, packing beads, bubble wrap, laminate, envelopes, gift cards, credit cards, gloves, raincoats, OGR paper, shopping bags, diapers, membranes, tableware, tea bags, coffee or tea containers, containers for holding hot or cold beverages, cups, plates, bottles for storing carbonated liquids, bottles for storing non-carbonated liquids, lids, food packaging films, garbage disposal containers, food handling equipment, fabric fibers, water storage and transport equipment, alcoholic or non-alcoholic beverage storage and transport equipment, outer casings or screens for electronic products, interior or exterior parts of furniture, curtains, upholstery, fabrics, films, boxes, sheets, trays, pipes, water conduits, clothing, medical devices, pharmaceutical packaging, contraceptives, camping equipment, shaped cellulosic materials, and combinations thereof.

58. 47. The method of claim 46, wherein the surface of the molded article exhibits a 3M Grease KIT test value of 3 to 12.

59. 47. The method of claim 46, wherein the surface of the molded article exhibits a water contact angle of at least 90°.

60. 47. The method of claim 46, wherein the surface of the molded article exhibits an HST value of at least 65 seconds.

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