Hemicellulose-containing coating

Abstract

The present invention describes a method for treating cellulosic materials with a composition comprising hemicellulose and / or lignin and a sucrose fatty acid ester to modify the barrier function of such materials. The disclosed method uses hemicellulose or lignin in combination with a sugar fatty acid ester to form a film on the cellulosic material, and the disclosure includes providing products made by such methods. Materials so treated exhibit more effective barrier function and mechanical properties and can be used in any application where such characteristics are desirable.

Description

Technical Field

[0001] [Background of the Invention] The present invention mainly relates to treating hemicellulose, and more specifically, to a method for producing a hemicellulose-based coating that overcomes resistance to high relative humidity using a bio-based ester that binds to hemicellulose, such esters and methods being useful for modifying hemicellulose for the development of coatings for paper, paperboard, and packaging products.

Background Art

[0002] In many food packaging applications, protecting food from oxygen is important because oxidation of aromatic, fatty, and vitamin compounds by the ingress of oxygen degrades the quality and / or flavor of the product. This can be done by using a barrier material with low permeability to oxygen. This material is also preferably flexible, mechanically resistant, transparent, and low cost. Other barrier properties, such as aroma and grease barriers, can also be of great importance.

[0003] Hemicellulose is a polysaccharide biosynthesized in most plants and acts as a matrix material between the microfibrils of cellulose and as a bond between lignin and cellulose. Hemicellulose is commercially used as a sweetener, thickener, and emulsifier in foods. So far, the non-food use of hemicellulose is very limited.

[0004] Hemicellulose interacts with the permeability of liquids / moisture and oxygen, and aroma and grease increase at high relative humidity. The water solubility of the material is an advantage in coating methods but can be a disadvantage in many packaging applications.

[0005] Such problems are typically addressed in the industry by coating hemicellulose with certain hydrophobic organic materials / fluorocarbons, silicones, which physically block the underlying hemicellulose from water / lipids of the inclusions and include prevention of uptake in fiber gaps, inflow into grease wrinkles, or detachment of the bonded materials. For example, materials such as PVC / PEI / PE are customarily used for such purposes and physically bonded to the surface to be treated (i.e., spray-coated or extruded).

[0006] It is desirable to design a "green" bio-based coating that can be used with hemicellulose without sacrificing the biodegradability and / or recyclability of the products made therefrom, is hydrophobic / oleophobic, and is compostable. SUMMARY OF THE INVENTION

[0007] The present disclosure relates to a method of treating cellulosic materials with a hemicellulose-containing coating, including treating the cellulosic material with a composition that provides an increase in hydrophobicity and / or oleophobicity while maintaining the biodegradability / recyclability of the cellulosic components. The disclosed method provides for combining sugar fatty acid esters (SFAE) with hemicellulose and does not require the use of an organic carrier, base, or individual catalyst for binding the coating to the cellulosic material. The binding reaction can be applied to cellulose or pre-formed materials.

[0008] In one embodiment, a composition comprising a SFAE-hemicellulose-bonded cellulosic material is disclosed, wherein the SFAE and hemicellulose are present in concentrations sufficient for the bonded cellulosic material to exhibit low permeability to oxygen. In a related aspect, the sugar fatty acid ester contains at least one saccharide and at least one aliphatic group containing 8 to 30 carbons, and the coating is present in a concentration sufficient to render the bonded cellulosic material hydrophobic as compared to a similar material except that it is not coated. In another aspect, the SFAE-hemicellulose coating is removably or non-removably bonded to the cellulosic material.

[0009] In a further aspect, the SFAE is present in a concentration sufficient for the bonded hemicellulosic material to exhibit a water contact angle of 90° or greater, and the water contact angle is optionally brought about in the absence of a second hydrophobic substance. In a related aspect, the coating contains a hemicellulose content of 1 to 99% by dry weight.

[0010] In one embodiment, a composition comprising a SFAE-lignin-bonded cellulosic material is disclosed, wherein the SFAE and lignin are present in concentrations sufficient for the bonded cellulosic material to exhibit water resistance.

[0011] In a related aspect, examples of the composition containing the cellulosic material include paper, paper sheets, cardboard, pulp for papermaking, cartons for food storage, parchment paper, cakeboard, meat wrapping paper, release paper / liner, food storage bags, shopping bags, transport bags, bacon board, insulating materials, tea bags, containers for coffee or tea, compost bags, tableware, containers for hot or cold beverages, cups, lids, plates, bottles for storing carbonated liquids, gift cards, bottles for storing non-carbonated liquids, food wrap films, containers for raw garbage disposal, food handling utensils, fabric fibers (e.g., cotton or cotton blends), water storage and transportation utensils, containers for alcoholic or non-alcoholic beverages, external casings or screens for electronic products, internal or external components of furniture, curtains, and interior decoration items.

[0012] In one embodiment, a method of producing a molded cup lid, comprising the steps of applying a composition containing SFAE and hemicellulose to a foldable paper sheet, drying the foldable sheet for a time sufficient for the composition to adhere to the sheet, placing the sheet in a mold of a cup lid, completely drying the sheet, and optionally heating the lid for an additional time sufficient to fully mold the lid, is disclosed.

[0013] In one aspect, the foldable paper is micro-embossed. In another aspect, the sugar fatty acid ester contains at least one saccharide and at least one aliphatic group containing 8 to 30 carbons, and the composition is present in a concentration sufficient to make the bound cellulose-based material hydrophobic compared to similar materials except for not containing the composition.

[0014] In a related aspect, SFAE and hemicellulose are present in a concentration sufficient for the bound cellulose-based material to exhibit low permeability to oxygen. In a further related aspect, a manufactured product comprising a molded cup lid produced by such a method is disclosed.

[0015] In one embodiment, a method of producing a molded cup lid, comprising the steps of applying a composition containing SFAE and lignin to a foldable paper sheet, drying the foldable sheet for a time sufficient for the composition to adhere to the sheet, placing the sheet in a mold of a cup lid, completely drying the sheet, and optionally heating the lid for an additional time sufficient to fully mold the lid, is disclosed. In one aspect, the foldable paper is micro-embossed.

[0016] In a related aspect, a manufactured product comprising a molded cup lid produced by the above method is disclosed. In a further related aspect, the SFAE is saturated or unsaturated.

Brief Description of the Drawings

[0017]

Figure 1

Figure 2

Figure 3

Figure 4

Figure 5

Mode for Carrying Out the Invention

[0018] Before describing the present compositions, methods, and methodologies, it should be understood that the present invention is not limited to such compositions, methods, and conditions because the specific compositions, methods, and experimental conditions described may vary. The scope of the present invention is limited only by the appended claims, and it should also be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting.

[0019] In this specification and the appended claims, the singular forms "a," "an," and "the" include plural referents unless the context clearly dictates otherwise. For example, reference to "sugar fatty acid ester" includes one or more sugar fatty acid esters and / or compositions of the type described herein that will be apparent to those skilled in the art upon reading the present disclosure.

[0020] Unless otherwise defined, all scientific and technical terms used in this specification have the same meaning as commonly understood by one of ordinary skill in the art to which this disclosure pertains. It is understood that any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention, as modifications and variations are within the spirit and scope of the present disclosure.

[0021] As used herein, the terms "about," "approximately," "substantially," and "significantly" are understood by those of ordinary skill in the art and vary to some extent depending on the context in which they are used. When there is any use of a term that is not clear to those of ordinary skill in the art considering the context in which it is used, "about" and "approximately" mean plus or minus <10% of the particular term, and "substantially" and "significantly" mean plus or minus >10% of the particular term. "Comprising" and "consisting essentially of" have their conventional meanings in the art.

[0022] In one embodiment, the present disclosure shows that by treating cellulose with a combination of sugar fatty acid ester - hemicellulose, the resulting material is, among other things, resistant to high relative humidity. Such sugar fatty acid esters, for example, can be easily digested as such once removed by bacterial enzymes. The derivatized surface exhibits very high heat resistance and can withstand temperatures as high as 250°C and can be more gas - impermeable than the underlying base substrate. Thus, the material is an ideal solution to the problem of derivatizing cellulose in any embodiment where cellulose - containing materials can be utilized.

[0023] Advantages of the products and methods described herein include that the coating composition is made from renewable agricultural resources - sugars and vegetable oils; is biodegradable; has a low toxicity profile and is suitable for food contact; can be adjusted to reduce the coefficient of friction of the paper / board surface even at high water resistance levels (i.e., not making the paper too slippery for downstream processing or end use); can be used with or without special emulsification equipment or emulsifiers; and is compatible with traditional paper recycling programs, i.e., does not adversely affect the recycling operation as, for example, polyethylene, polylactic acid, or wax-coated paper would.

[0024] As used herein, "bio-based" means a material intentionally made from substances derived from living (or once-living) organisms. In a related aspect, a material containing at least about 50% of such substances is considered bio-based.

[0025] As used herein, "bind" means to adhere or cause to adhere as an essentially single mass, including its grammatical variations.

[0026] As used herein, "cellulosic" means a natural, synthetic, or semi-synthetic material that can be molded or extruded into an object (e.g., a bag, a sheet) or a film or filament and can be used to make such an object or film or filament, and is structurally and functionally similar to cellulose, such as coatings and adhesives (e.g., carboxymethyl cellulose). In another example, cellulose, which is a complex carbohydrate (C 6 H 10 O 5 ) n composed of glucose units and which is the main component of the cell walls in most plants, is cellulosic.

[0027] As used herein, "coating weight" is the weight of the material (wet or dry) applied to a substrate. It is expressed in pounds per specified linear yard or grams per square meter.

[0028] As used herein, "compostable" means that the solid product is biodegradable in soil.

[0029] As used herein, "edge wicking" in a paper structure means the absorption of water at the outer limit points of the structure by one or more mechanisms including, but not limited to, capillary penetration of pores between fibers, diffusion through fibers and bonds, and surface diffusion of fibers. In a related aspect, edge wicking in the treated product is prevented by the coating containing the sugar fatty acid ester described herein. In one aspect, there is a similar problem where grease / oil enters the folds that may be present in the paper or paper product. The "grease creasing effect" created by folding, pressing, or compressing the paper structure can be defined as the absorption of grease in the paper structure.

[0030] As used herein, "effect" means imparting specific properties to a particular material, including its grammatical variations.

[0031] As used herein, "hemicellulose" means heteropolymers such as arabinoxylans (i.e., matrix polysaccharides) that are present with cellulose in almost all terrestrial plant cell walls, including its grammatical variations. Cellulose is crystalline, strong, and resistant to hydrolysis, while hemicellulose has a random and amorphous structure. In one embodiment, the coating described herein has a hemicellulose content of 1 - 99% by dry weight, preferably 30 - 90%, most preferably 60 - 90%, and may have a crosslinking agent or hydrophobizing agent in a content of 0 - 30% by dry weight, preferably 0 - 20%, more preferably 0 - 15%, particularly 0 - 10%, most preferably 0 - 5%.

[0032] As used herein, "hydrophobic substance" means a substance that does not attract water. For example, wax, rosin, resin, sugar fatty acid ester, diketene, shellac, vinyl acetate, PLA, PEI, oil, fat, lipid, other water-repellent chemicals, or combinations thereof are hydrophobic substances.

[0033] As used herein, "hydrophobicity" is water-repellency and means a property of repelling and not absorbing water.

[0034] As used herein, "lipid resistance" or "oleophobicity" is lipophobicity and means a property of repelling and not absorbing lipids, greases, fats, etc. In related aspects, grease resistance can be measured by the "3M kit" test or the TAPPI T559 kit test.

[0035] As used herein, "cellulose-containing material" or "cellulose-based material" means a composition consisting essentially of cellulose. For example, such materials include, but are not limited to, paper, paper sheets, cardboard, papermaking pulp, food storage cartons, parchment paper, cakeboard, meat wrapping paper, release paper / liner, food storage bags, shopping bags, transport bags, bacon board, insulation 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 wrap film, garbage disposal containers, food handling utensils, fabric fibers (e.g., cotton or cotton blend), water storage and transportation utensils, alcoholic or non-alcoholic beverages, external casings or screens for electronic products, internal or external components of furniture, curtains, and interior decoration items.

[0036] As used herein, "release paper" means a paper sheet used to prevent an adhesive surface from adhering prematurely to an adhesive or mastic. In one aspect, the coatings described herein can be used to produce materials with low surface energy, instead of or reducing the use of silicon or other coatings. Determination of surface energy can be readily accomplished by measurement of the contact angle (e.g., Optical Tensiometer and / or High Pressure Chamber; Dyne Testing, Staffordshire, United Kingdom) or the use of Surface Energy Test Pens or Inks (see, e.g., Dyne Testing, Staffordshire, United Kingdom).

[0037] As used herein, "removable" in relation to SFAE means that once the SFAE coating is applied, it can be removed from the cellulose-based material (e.g., removable by manipulating physical properties). As used herein, "non-removable" in relation to SFAE means that once the SFAE coating is applied, it binds substantially irreversibly to the cellulose-based material (e.g., removable by chemical means).

[0038] As used herein, "fibers in solution state" or "pulp" means a lignocellulosic fiber material prepared by chemically or mechanically separating cellulose fibers from wood, fiber crops, or paper scraps. In related aspects where cellulose fibers are treated by the methods described herein, the cellulose fibers themselves contain the bound sugar fatty acid esters as discrete entities, and the bound cellulose fibers have different properties from the free fibers (e.g., if it is a pulp or cellulose fiber or nanocellulose or microfibrillated cellulose - sugar fatty acid ester binding material, it does not form hydrogen bonds between fibers as readily as non-bound fibers).

[0039] As used herein, "foldable paper" means a sheet of cellulose that has been processed in such a way that it has plasticity (e.g., can be deformed without losing its original integrity). Such paper may include micro-embossing (i.e., small wrinkles that allow for a shape with raised relief), or may originally be moldable (e.g., FIBREFORM® available from BillerudKorsnas, SWEDEN).

[0040] As used herein, "repulpable" means making a paper or paperboard product suitable for being crushed into a shapeless soft mass for reuse in the manufacture of paper or paperboard.

[0041] As used herein, "adjustable" means, including its grammatical variations, adjusting or adapting a method to achieve a particular result.

[0042] As used herein, "water contact angle" means the angle measured through a liquid where the liquid / vapor interface meets a solid surface. It quantifies the wettability of the solid surface by the liquid. The contact angle reflects the strength of the interaction between the molecules of the liquid and the solid, compared to the strength with which each interacts with its own kind. On many highly hydrophilic surfaces, water droplets exhibit a contact angle of 0° to 30°. Generally, when the water contact angle is greater than 90°, the solid surface is considered hydrophobic. The water contact angle can be easily obtained using an optical tensiometer (see, e.g., Dyne Testing, Staffordshire, United Kingdom).

[0043] As used herein, "water vapour permeability" means breathability or the ability of a textile to move moisture. There are at least two different measurement methods. One of them, the MVTR (moisture vapour transmission rate) test conducted in accordance with ISO 15496, indicates the water vapour permeability (WVP) of the fabric and thus the degree of sweat transport to the outside air. By measurement, the number of grams of moisture (water vapour) passing through one square metre of fabric in 24 hours is determined (the higher the level, the higher the breathability).

[0044] In one aspect, the TAPPI T 530 Hercules sizing test (i.e., the sizing test of paper by ink resistance) may be used to determine water resistance. The ink resistance by the Hercules method is best classified as a direct measurement test of the degree of penetration. Otherwise, it is classified as the rate of the penetration test. There is no best test for "measuring sizing". The test selection depends on the end use and the needs of mill control. This method is particularly suitable for use as a mill control sizing test that accurately detects changes in sizing levels. It provides the sensitivity of an ink float test while producing reproducible results, shortening the test time, and automatically determining the end point.

[0045] Sizing, measured by resistance to the permeation of an aqueous liquid through paper or absorption of an aqueous liquid into paper, is an important feature of many papers. These are typical ones such as bags, container board, meat wrapping, writing, and some printing grades.

[0046] This method may be used to monitor the production of paper or board for specific end uses, provided that an acceptable correlation has been established between the test values and the end use performance of the paper. Due to the nature of the tests and the penetrants, it does not always show a sufficient correlation to be applicable to all end use requirements. This method measures sizing by degree of penetration. Other methods measure sizing by surface contact, surface penetration, or absorption. A sizing test is selected based on the ability to simulate the means of water contact or absorption in the end use. This method can also be used to optimize the cost of sizing chemicals.

[0047] As used herein, "oxygen permeability" means the degree to which a polymer allows the passage of gases or fluids. The oxygen permeability (Dk) of a material is a function of the diffusion rate (D) (i.e., the speed at which oxygen molecules cross the material) and the solubility (k) (or the amount of oxygen molecules absorbed per unit volume of the material). The value of oxygen permeability (Dk) typically falls within the range of 10 - 150×10 -11 (cm 2 ml O 2 ) / (s ml mmHg). A semi-logarithmic relationship has been shown between the hydrogel water content and the oxygen permeability (in Barrers). The International Organization for Standardization (ISO) specifies permeability using the SI unit of pressure, hectopascal (hPa). Thus, Dk = 10 -11 (cm 2 ml O 2 ) / (s ml hPa). The Barrer unit can be converted to the hPa unit by multiplying it by the constant 0.75.

[0048] As used herein, "biodegradability" means, including its grammatical variations, the ability to be decomposed by the action of living organisms (e.g., by microorganisms) into particularly harmless products.

[0049] As used herein, "recyclable" means a material that can be processed or (for used and / or waste products) fabricated to produce the said material suitable for reuse, including its grammatical variations.

[0050] As used herein, "Gurley second" or "Gurley number" is a unit that indicates the number of seconds required for 100 cubic centimeters (deciliters) of air to pass through a given material of 1.0 square inch under a water pressure difference of 4.88 inches (0.176 psi) (ISO 5636-5:2003) (porosity). Also regarding rigidity, the "Gurley number" is a unit of a portion of the said material that measures the force required to bend a vertically held material by a given amount (a force of 1 milligram). Such values can be measured with an apparatus from Gurley Precision Instruments (Troy, New York).

[0051] The hydrophilic-lipophilic balance (HLB) of a surfactant is a measure of the degree to which it is hydrophilic or lipophilic, determined by calculating values for different regions of its molecules.

[0052] The Griffin method for nonionic surfactants, described in 1954, is: [Chem.] [wherein M h is the molecular mass of the hydrophilic portion of the molecule, and M is the molecular mass of the entire molecule.], and the result is shown on a scale of 0 to 20. An HLB value of 0 corresponds to a completely lipophilic / hydrophobic molecule, and an HLB value of 20 corresponds to a completely hydrophilic / lipophobic molecule.

[0053] The HLB value can be used to predict the surfactant properties of a molecule. <10: Lipophilic (water-insoluble) >10: Water-soluble (lipid-insoluble) 1.5 - 3: Defoaming agent 3 - 6: W / O (water-in-oil type) emulsifier 7 - 9: Wetting and spreading agent 13 - 15: Detergent 12 - 16: O / W (oil-in-water type) emulsifier 15 - 18: Solubilizer or hydrotrope

[0054] In some embodiments, the HLB value of the sugar fatty acid ester (or the composition containing said ester) described herein can be in a lower range. In other embodiments, the HLB value of the sugar fatty acid ester (or the composition containing said ester) described herein can be in a medium to higher range.

[0055] As used herein, "SEFOSE (registered trademark)" is the name of a sucrose fatty acid ester (soybean oil fatty acid ester) containing one or more unsaturated fatty acids made from soybean oil, and is commercially available under the trade name SEFOSE 1618U from Procter & Gamble Chemicals (Cincinnati, OH) (see the following polysoybean oil fatty acid sucrose). As used herein, "OLEAN (registered trademark)" is the name of a sucrose fatty acid ester having the formula C n+12 H 2n+22 O 13 and in which all fatty acids are saturated fatty acids, and is available from Procter & Gamble Chemicals.

[0056] As used herein, "soybean oil fatty acid ester" means a mixture of salts of fatty acids derived from soybean oil.

[0057] As used herein, "oilseed fatty acids" means fatty acids derived 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, linseed, hazelnut, wheat, rice, potato, cassava, legume fruits, camelina seed, mustard seed, and combinations thereof.

[0058] As used herein, "wet strength" means a measure of how well the fiber web that holds the paper together can resist the force of breakage when the paper is in a wet state. Wet strength can be measured using the Finch Wet Strength Device from Thwing-Albert Instrument Company (West Berlin, NJ). In that case, wet strength is typically provided by wet strength additives such as aldehydes, cationic glyoxylated resins, polyamideamine-epichlorohydrin resins, polyamine-epichlorohydrin resins, including epoxy resins. In one embodiment, the cellulose-based material coated with the SFAE described herein provides such wet strength in the absence of such additives.

[0059] As used herein, "wet" means filled or saturated with water or another liquid.

[0060] In one embodiment, the method described herein includes contacting a cellulose-based surface with a sugar fatty acid ester or an emulsion containing the sugar fatty acid ester as a carrier for a coating agent capable of binding to the cellulose surface, the method comprising contacting the cellulose-based material with either the sugar fatty acid ester, the emulsion, or both, and exposing the contacted cellulose-based material to heat, radiation, a catalyst, or a combination thereof for a time sufficient to bind the sugar fatty acid ester or the coating agent to the cellulose-based material. In a related aspect, such radiation includes, 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.

[0061] Furthermore, the binding reaction between the SFAE and the cellulosic material may be carried out using substantially pure sugar fatty acid esters, or the sugar fatty acid esters may be part of an emulsion. In one embodiment, the sugar fatty acid ester emulsion can contain a mixture of mono-, di-, tri-, tetra-, penta-, hexa-, hepta-, or octa-esters. 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., zein), soy protein isolate, starch, modified starch, acetylated polysaccharides, alginates, carrageenans, chitosan, inulin, long-chain fatty acids, waxes, and combinations thereof.

[0062] In one embodiment, the sugar fatty acid ester or emulsion may be mixed with an epoxy derivative of the ester (see, e.g., U.S. Patent No. 9,096,773, which is hereby incorporated by reference in its entirety), and such epoxy derivatives can function, for example, as adhesives.

[0063] In one embodiment, the cellulosic material can be made oleophobic by the addition of polyvinyl alcohol (PvOH) and / or prolamin. In one aspect, prolamins include zein, gliadin, hordein, secalin, katirin, and avenin. In a related aspect, the prolamin is zein.

[0064] In one embodiment, catalysts and organic carriers (e.g., volatile organic compounds) are not required to carry out the binding reaction, including embodiments where enhancement of the material is not contemplated using the disclosed method. In a related aspect, the reaction time is substantially immediate (i.e., less than 1 second). Also, the resulting material exhibits low barrier properties.

[0065] As described herein, fatty acid esters of all sugars, including monosaccharides, disaccharides, and trisaccharides, are adaptable for use in connection with this aspect of the invention. In related aspects, the sugar fatty acid esters can be mono-, di-, tri-, tetra-, penta-, hexa-, hepta-, or octa-esters, and combinations thereof, including where the fatty acid moiety can be saturated, unsaturated, or a combination of these.

[0066] Without being bound by any theory, the interaction between the sugar fatty acid ester and the cellulose-based material can be by ionic, hydrophobic, van der Waals interactions, or covalent bonds, or a combination of these. In related aspects, the sugar fatty acid ester bound to the cellulose-based material is substantially irreversible (e.g., using SFAE including a combination of saturated and unsaturated fatty acids).

[0067] Also, the binding of the sugar fatty acid ester at a sufficient concentration is sufficient to make the cellulose-based material hydrophobic. That is, the hydrophobicity is achieved without adding wax, rosin, resin, diketene, shellac, vinyl acetate, PLA, PEI, oil, other water-repellent chemicals, or combinations thereof (i.e., a second hydrophobic substance), including where other properties such as strengthening, stiffening, and bulking of the cellulose-based material are achieved solely by the sugar fatty acid ester binding.

[0068] An advantage of the disclosed invention is that multiple fatty acid chains react with cellulose and two sugar molecules in the structure, such that, for example, the disclosed sucrose fatty acid ester produces a strong crosslinked network, improving the strength of fiber webs such as paper, paperboard, airlaid and wet nonwovens, and textiles. This is not typically seen with the chemical nature of other sizing or hydrophobic treatments. The sugar fatty acid esters described herein also generate / increase wet strength, a property not present when using many other water-resistant chemicals.

[0069] Another advantage is that the disclosed sugar fatty acid esters soften the fibers, increasing the space between them, thereby increasing the bulk without substantially increasing the weight. Also, it may be possible to repulp the fibers and cellulose-based materials modified as described herein. Also, for example, water may not be able to easily "push" through a low surface energy barrier and enter the sheet.

[0070] Saturated SFAEs are typically solids at nominal processing temperatures, and unsaturated SFAEs are typically liquids. This allows for the formation of a uniform and stable dispersion of saturated SFAEs in aqueous coatings, typically without significant interaction or incompatibility with other coating components that are typically hydrophilic. Furthermore, such dispersions allow for the preparation of high concentrations of saturated SFAEs without adversely affecting the rheology of the coating, uniform coating application, or coating performance characteristics. When the particles of saturated SFAE melt and spread during heating, drying, and compounding of the coating layer, the coating surface becomes hydrophobic. In one embodiment, a method is disclosed for producing a bulky fiber structure that retains strength even when exposed to water. Generally, a dried fiber slurry forms a dense structure that easily breaks down when exposed to water. Examples of formed fiber products made using the disclosed method include lightweight, strong, and water- and other liquid-resistant paper plates, drink holders (e.g., cups), lids, food trays, and packaging.

[0071] In one embodiment, a sugar fatty acid ester is mixed with polyvinyl alcohol (PvOH) to produce a sizing agent for a water-resistant coating. As described herein, a synergistic relationship between the sugar fatty acid ester and PvOH has been revealed. PvOH is itself a good film-forming agent and is known in the art to form strong hydrogen bonds with cellulose, but has little resistance to water, especially hot water. In an aspect, the use of PvOH helps to emulsify the sugar fatty acid ester into an aqueous coating. In one aspect, PvOH provides the sugar fatty acid ester with a rich source of OH groups for cross-linking along the fibers, increasing the strength of the paper, such as especially the wet strength, and the water resistance beyond what is possible with PvOH alone. For saturated sugar fatty acid esters having free hydroxyls on the sugar, cross-linking agents such as dialdehydes (e.g., glyoxal, glutaraldehyde, etc.) can also be used.

[0072] In one embodiment, the sugar fatty acid ester comprises or consists essentially of sucrose esters of fatty acids. Many methods are known and available for making or otherwise providing the sugar fatty acid esters according to the present invention, and all such methods are considered to be available for use within the broad scope of the present invention. For example, in some embodiments, the fatty acid ester is preferably synthesized by esterifying a sugar with one or more fatty acid moieties obtained from fatty seeds including but not limited to soybean oil, sunflower oil, olive oil, canola oil, peanut oil, and mixtures thereof.

[0073] In one embodiment, the sugar fatty acid ester comprises a sugar moiety including but not limited to a sucrose moiety in which one or more of the hydroxyl hydrogens are replaced by ester moieties. In a related aspect, the disaccharide ester has the formula I:

Chemical formula

Chemical formula

[0074] Suitable "R" groups include any form of aliphatic moiety, including those containing one or more substituents, and those substituents may occur on any carbon in the moiety. Also included are aliphatic moieties containing functional groups within the aliphatic moiety, such as ether, ester, thio, amino, phospho, etc. Oligomeric and polymeric aliphatic moieties, such as sorbitan, polysorbitan, and polyalcohol moieties, are also included. Examples of functional groups that can be added to the aliphatic (or aromatic) moiety containing the "R" group include, but are not limited to, halogen, alkoxy, hydroxy, amino, ether, and ester functional groups. In one embodiment, the moiety may have a crosslinkable functional group. In another embodiment, SFAE (e.g., activated clay / pigment particles) may be crosslinked to the surface. In another embodiment, double bonds present on the SFAE may be used to facilitate reaction with other surfaces.

[0075] Suitable disaccharides include raffinose, maltodextrose, galactose, combinations of sucrose, glucose, combinations of fructose, maltose, lactose, combinations of mannose, combinations of erythrose, isomaltose, isomaltulose, trehalose, trehalulose, cellobiose, laminaribiose, chitobiose, and combinations thereof.

[0076] In one embodiment, examples of the substrate for adding a fatty acid include starch, hemicellulose, lignin, or a combination thereof.

[0077] In one embodiment, the composition contains a starch fatty acid ester, and the starch may be derived from any suitable source such as dent corn starch, waxy corn starch, potato starch, wheat starch, rice starch, sago starch, tapioca starch, sorghum starch, sweet potato starch, and mixtures thereof.

[0078] More specifically, the starch can be unprocessed starch or starch processed by chemical, physical, or enzymatic processing.

[0079] Chemical processing includes any treatment of starch with chemicals that results in modified starch (e.g., plastarch material). Within the scope of chemical processing are included, but not limited to, starch depolymerization, starch oxidation, starch reduction, starch etherification, starch esterification, starch nitration, starch defatting, starch hydrophobization, etc. Chemically modified starch can also be prepared by using any combination of chemical treatments. Examples of chemically modified starch include reactions of alkenyl succinic anhydrides, particularly octenyl succinic anhydride, with starch to produce hydrophobically esterified starch; reactions of 2,3-epoxypropyltrimethylammonium chloride with starch to produce cationic starch; reactions of ethylene oxide with starch to produce hydroxyethyl starch; reactions of hypochlorite with starch to produce oxidized starch; reactions of acids with starch to produce acid-depolymerized starch; reactions of starch with solvents such as methanol, ethanol, propanol, methylene chloride, chloroform, carbon tetrachloride, etc. to defat the starch and produce defatted starch.

[0080] Physical modified starch is starch that has been physically treated in a form that provides physical modified starch. The scope of physical modification includes, but is not limited to, heat treatment of starch in the presence of water, heat treatment of starch in the absence of water, fragmentation of starch granules by any mechanical means, pressure treatment of starch to melt starch granules, etc. Physical modified starch can also be prepared by using any combination of physical treatments. Examples of physical modified starch include, for example, heat treatment of starch in an aqueous environment to swell starch granules without granule breakage; heat treatment of anhydrous starch granules to cause polymer rearrangement; fragmentation of starch granules by mechanical degradation; and pressure treatment of starch granules by an extruder to cause melting of starch granules.

[0081] Enzymatically modified starch is any starch that has been treated with an enzyme in any form that provides enzymatically modified starch. The scope of enzymatic modification includes, but is not limited to, the reaction of α - amylase with starch, the reaction of protease with starch, the reaction of lipase with starch, the reaction of phosphorylase with starch, the reaction of oxidase with starch, etc. Enzymatically modified starch can be prepared by using any combination of enzyme treatments. Examples of the enzymatic modification of starch include, for example, the reaction of an alpha - amylase enzyme with starch to produce depolymerized starch; the reaction of an alpha - amylase debranching enzyme with starch to produce debranched starch; the reaction of a protease enzyme with starch to produce starch with a reduced protein content; the reaction of a lipase enzyme with starch to produce starch with a reduced lipid content; the reaction of a phosphorylase enzyme with starch to produce enzymatically modified phosphorylated esterified starch; and the reaction of an oxidase enzyme with starch to produce enzymatically oxidized starch.

[0082] The disaccharide fatty acid ester can be a sucrose fatty acid ester represented by formula I [wherein the "R" group is aliphatic, linear or branched, saturated or unsaturated, and has about 8 to about 40 carbon atoms].

[0083] As used herein, the terms "sugar fatty acid ester" and "sucrose fatty acid ester" include compositions having different purities and mixtures of compounds at any purity level. For example, a sugar fatty acid ester compound can be a substantially pure material, i.e., it can include a compound having a predetermined number of "A" groups substituted by only one type of the structural I moiety (i.e., all "R" groups are the same and all of the sucrose moieties are substituted to an equal extent). It also includes compositions containing a blend of two or more sugar fatty acid ester compounds having different degrees of substitution but all of the substituents having the same "R" group structure. It also includes compositions that are mixtures of compounds in which the degree of substitution of the "A" group is different and the substituent moieties of the "R" group are independently selected from two or more of the "R" groups of structural I. In related aspects, the "R" groups can be the same or different, including the case where the sugar fatty acid esters in the composition are the same or different (i.e., a mixture of different sugar fatty acid esters).

[0084] In the composition according to the present invention, the composition can consist of a sugar fatty acid ester compound having a high degree of substitution. In one embodiment, the sugar fatty acid ester is sucrose polysoybean oil fatty acid.

[0085]

Chemical formula

[0086] Sucrose fatty acid esters can be prepared by esterification with substantially pure fatty acids by known esterification methods. They can also be prepared by transesterification using a sugar and a fatty acid ester in the form of a fatty acid glyceride derived from, for example, a natural source, such as an oil extracted from fatty seeds, such as soybean oil. The transesterification reaction for providing sucrose fatty acid esters using fatty acid glycerides is described, for example, in U.S. Patent Nos. 3,963,699; 4,517,360; 4,518,772; 4,611,055; 5,767,257; 6,504,003; 6,121,440; 6,995,232, and International Publication No. 1992 / 004361 (A1), each of which is hereby incorporated by reference in its entirety as part of this specification.

[0087] In addition to producing hydrophobic sucrose esters via transesterification, similar hydrophobicity can be achieved in cellulosic fiber articles by reacting an acid chloride directly with a polyol containing a ring structure similar to sucrose.

[0088] As described above, sucrose fatty acid esters can be prepared by transesterification of sucrose from a methyl ester feedstock prepared from glycerides derived from natural sources (see, for example, U.S. Patent No. 6,995,232, which is hereby incorporated by reference in its entirety as part of this specification). As a result of the fatty acid source, the feedstock used to prepare sucrose fatty acid esters contains various saturated and unsaturated fatty acid methyl esters having fatty acid moieties containing 12 to 40 carbon atoms. This is reflected in the sucrose fatty acid esters, which are products made from such sources, because the sucrose moiety containing the product contains a mixture of ester moiety substituents, and referring to Structure I above, the "R" groups are a mixture having 12 to 26 carbon atoms in a ratio reflecting the feedstock used to prepare the sucrose ester. To further illustrate this point, sucrose esters derived from soybean oil have soybean oil that is 26 wt% oleic acid (H 3C-CH 2 7 -CH=CH-[CH 2 7 -C(O)OH) triglyceride, 49 wt% linoleic acid (H 3 C-[CH 2 3 -[-CH 2 -CH=CH] 2 -[-CH 2 -] 7 -C(O)OH) triglyceride, 11 wt% linolenic acid (H 3 C-[-CH 2 -CH=CH-] 3 -[-CH 2 -] 7 -C(O)OH) triglyceride, and 14 wt% of various saturated fatty acid triglycerides described in the Seventh Ed. of the Merck Index, incorporated herein by reference, a mixture of species having an "R" group structure reflecting this. All of these fatty acid moieties are representative in the "R" group of the substituents of the sucrose fatty acid ester that is the product. Thus, when referring herein to sucrose fatty acid esters as the product of a reaction employing a fatty acid feedstock derived from a natural source, e.g., soybean oil fatty acids sucrose, the term is intended to include all of the various components typically found as a result of the source from which the sucrose fatty acid ester is prepared. In a related aspect, the disclosed sugar fatty acid esters may exhibit low viscosities (e.g., about 10 to 2000 centipoise at room temperature or standard atmospheric pressure). In another aspect, the unsaturated fatty acids may have one, two, three or more double bonds.

[0089] In one embodiment of the invention, the sugar fatty acid esters, in an aspect the disaccharide esters, are formed from fatty acids having on average more than about 6 carbon atoms, about 8 to 16 carbon atoms, about 8 to about 18 carbon atoms, about 14 to about 18 carbon atoms, about 16 to about 18 carbon atoms, about 16 to about 20 carbon atoms, about 20 to about 40 carbon atoms.

[0090] ​​​In one embodiment, the sugar fatty acid ester can be present in various concentrations to achieve hydrophobicity depending on the form of the cellulose-based material. In one aspect, when the sugar fatty acid ester (SFAE) is bound to the cellulose-based material as a coating, the SFAE is present on the surface of the cellulose-based material at least about 0.1 g / m 2 ~ about 1.0 g / m 2 、 about 1.0 g / m 2 ~ about 2.0 g / m 2 、 about 2 g / m 2 ~ about 3 g / m 2 of coating weight. In a related aspect, it is about 3 g / m 2 ~ about 4 g / m 2 、 about 4 g / m 2 ~ about 5 g / m 2 、 about 5 g / m 2 ~ about 10 g / m 2 、 about 10 g / m 2 ~ about 20 g / m 2 and can be present at. In another aspect, 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 all the fibers present. In a related aspect, it is about 0.05% (wt / wt) to about 0.1% (wt / wt), about 0.1% (wt / wt) to about 0.5% (wt / wt), about 0.5% (wt / wt) to about 1.0% (wt / wt), about 1.0% (wt / wt) to about 2.0% (wt / wt), about 2.0% (wt / wt) to about 3.0% (wt / wt), about 3.0% (wt / wt) to about 4.0% (wt / wt), about 4.0% (wt / wt) to about 5.0% (wt / wt), about 5.0% (wt / wt) to about 10% (wt / wt), about 10% (wt / wt) to about 50% (wt / wt) of all the fibers present. In another related aspect, the amount of SFAE may be equal to the amount of fibers present. In some embodiments, the SFAE can coat the entire outer surface of the cellulose-based material (e.g., coat an entire piece of paper or a cellulose-containing article).

[0091] In other embodiments, the coating can contain about 0.9% to about 1.0% (wt / wt), about 1.0% to about 5.0% (wt / wt), about 5.0 to about 10% (wt / wt), about 10% to about 20% (wt / wt), about 20% to about 30% (wt / wt), about 40% to about 50% (wt / wt) of sugar fatty acid esters based on the weight of the coating. In related aspects, the coating can contain about 25% to about 35% (wt / wt) of sugar fatty acid esters based on the weight of the coating.

[0092] In one embodiment, examples of the cellulosic material include, but are not limited to, paper, paperboard, paper sheets, pulp for papermaking, cups, boxes, trays, lids, release paper / liners, compost bags, shopping bags, transport bags, paperboard for bacon, tea bags, insulating materials, containers for coffee or tea, pipes and aqueducts, food-grade disposable cutlery, dishes and bottles, screens for TVs and portable devices, clothing (e.g., cotton or cotton blends), bandages, pressure-sensitive labels, pressure-sensitive tapes, feminine products, and containers for medical devices, drug delivery devices, pharmaceutical materials (e.g., pills, tablets, suppositories, gels, etc.) used on or inside the body such as contraceptives. Also, the disclosed coating technology can be used for furniture and interior decoration items, outdoor camping equipment, etc.

[0093] In one aspect, the coating described herein is resistant to a pH in the range of about 3 to about 9. In related aspects, the pH can be about 3 to about 4, about 4 to about 5, about 5 to about 7, about 7 to about 9.

[0094] In one embodiment, an alkanoic acid derivative is mixed with a sugar fatty acid ester to form an emulsion, and the emulsion is used to treat the cellulose-based material.

[0095] In one embodiment, the cellulose-containing material produced by the method described herein exhibits high hydrophobicity or high water resistance compared to the cellulose-containing material without treatment. In a related aspect, the treated cellulose-containing material exhibits high oleophobicity or grease resistance compared to the cellulose-containing material without treatment. In another related aspect, the treated cellulose-containing material may be biodegradable, compostable, and / or recyclable. In one aspect, the treated cellulose-containing material is hydrophobic (water resistant) and oleophobic (grease resistant).

[0096] In one embodiment, the treated cellulose-containing material may have improved mechanical properties compared to its untreated counterpart. For example, a paper bag treated by the method described herein exhibits increased burst strength, Gurley number, tensile strength, and / or maximum load energy. In one aspect, the burst strength is increased by about 0.5 to 1.0 times, about 1.0 to 1.1 times, about 1.1 to 1.3 times, about 1.3 to 1.5 times. In another aspect, the Gurley number is increased by about 3 to 4 times, about 4 to 5 times, about 5 to 6 times, and about 6 to 7 times. In yet another aspect, the tensile strain is increased by about 0.5 to 1.0 times, about 1.0 to 1.1 times, about 1.1 to 1.2 times, and about 1.2 to 1.3 times. In still another aspect, 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.

[0097] In one embodiment, the cellulose-containing material is a base paper containing microfibrillated cellulose (MFC) or cellulose nanofiber (CNF), as described, for example, in US Patent Application Publication No. 2015 / 0167243 (which is hereby incorporated by reference in its entirety), and the MFC or CNF is added during the forming process and the papermaking process and / or added to the prior forming layer as a coating or a secondary layer to reduce the porosity of the base paper. In a related aspect, the base paper is contacted with the above sugar fatty acid ester. In another related aspect, the contacted base paper is further contacted with polyvinyl alcohol (PvOH). In one embodiment, the obtained contacted base paper is adjustably water-resistant and lipid-resistant. In a related aspect, the obtained base paper may exhibit a Gurley air permeability resistance of at least about 10 to 15 (i.e., seconds / 100 cc, 20 ounce cylinder), or at least about 100, at least about 200 to about 350 Gurley values. In one aspect, the sugar fatty acid ester coating can be a single layer or a multi-layer laminate, or a single layer or multiple layers can be formed as a laminate, or the amount of the single layer or multiple layer coating can be reduced to achieve similar performance effects (e.g., water resistance, grease resistance, etc.). In a related aspect, the laminate may include biodegradability and / or a heat-sealable or adhesive that can be formed.

[0098] In one embodiment, the sugar fatty acid ester may be formulated as an emulsion, and the selection of the emulsifier and the amount used is dictated by the nature of the composition and the ability of the emulsifier to promote the dispersion of the sugar fatty acid ester. In one aspect, examples of the emulsifier include, but are not limited to, water, buffer, polyvinyl alcohol (PvOH), carboxymethyl cellulose (CMC), milk protein, wheat gluten, gelatin, prolamin, soy protein isolate, starch, acetylated polysaccharide, alginate, carrageenan, chitosan, inulin, long-chain fatty acid, wax, agar, alginate, glycerol, gum, lecithin, poloxamer, monoglycerol, diglycerol, monosodium phosphate, monostearate, propylene glycol, detergent, cetyl alcohol, and combinations thereof. In another aspect, the ratio of sugar ester:emulsifier can be about 0.1:99.9, about 1:99, about 10:90, about 20:80, about 35:65, about 40:60, and about 50:50. It will be apparent to those skilled in the art that the ratio may be varied according to the desired properties of the final product.

[0099] In one embodiment, the sugar fatty acid ester is not limited to, but includes, pigments (e.g., clay, calcium carbonate, titanium dioxide, plastic pigments), binders (e.g., starch, soybean protein, polymer emulsion, PvOH), and additives (e.g., glyoxal, glyoxalated resin, zirconium salt, calcium stearate, lecithin oleate, polyethylene emulsion, carboxymethyl cellulose, acrylic polymer, alginate, polyacrylate gum, polyacrylate, microbicide, oil-based defoamer, silicone-based defoamer, stilbene, direct dye, and acid dye), and can be combined with one or more coating components (alone or in combination) for internal and surface sizing. In related aspects, such components can build a microporous structure, provide a light-scattering surface, improve ink receptivity, improve gloss, bind pigment particles, bind the coating to paper or a base sheet reinforcement, fill pores in the pigment structure, reduce water sensitivity, resist wet pick in offset printing, prevent blade scratching, improve gloss in supercalendering, reduce dust generation, adjust coating viscosity, achieve water retention, disperse pigments, maintain coating dispersion, prevent degradation of the coating / coating colorant, control foaming, reduce entrained air and coating craters, increase whiteness and brightness, and control color and color shade, among other properties. It will be apparent to those skilled in the art that the combination can be varied according to the desired properties of the final product.

[0100] In one embodiment, the method of employing sugar fatty acid esters may be used to reduce the cost of applying a primary / secondary coating (e.g., a silicone-based layer, a starch-based layer, a clay-based layer, a PLA layer, a PEI layer, etc.), providing a layer of material that exhibits the required properties (e.g., water resistance, low surface energy, etc.), thereby reducing the amount of primary / secondary layers necessary to achieve similar properties. In one aspect, a material (e.g., a heat-sealable agent) can be coated on top of the SFAE layer. In one embodiment, the composition is fluorocarbon and silicone-free.

[0101] In one embodiment, the composition enhances both the mechanical and thermal stability of the treated product. In one aspect, the surface treatment is thermally stable at a temperature of about -100°C to about 300°C. In another related aspect, the surface of the 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 a temperature of about 200°C to about 300°C.

[0102] The substrate may be dried (e.g., at about 80 - 150°C) prior to coating, but can be treated using the modified composition, for example by dipping and exposing the surface to the composition for less than 1 second. The substrate can be heated to dry the surface, and then the modified material is immediately ready for use. In one aspect, in accordance with the methods described herein, the substrate may be treated by any suitable coating / sizing method typically carried out in a paper mill (see, e.g., Smook, G., Surface Treatments, Handbook for Pulp & Paper Technologists, (2016), 4 th Ed., Cpt. 18, pp. 293 - 309, TAPPI Press, Peachtree Corners, GA USA, which is hereby incorporated by reference in its entirety).

[0103] In some applications, the material may be dried before processing, but no special preparation of the material is required when practicing the present invention. In one embodiment, the disclosed method can be used on any cellulose-based surface, including but not limited to films, rigid containers, fibers, pulp, fabrics, etc. In one aspect, the sugar fatty acid ester or coating agent can be applied by conventional size presses (vertical, inclined, horizontal), gate roll size presses, metering size presses, calendar size coating, tube sizing, on-machine, off-machine, single-sided coater, double-sided coater, short-dwell, simultaneous double-sided coater, blade or rod coater, gravure coater, gravure printing, flexographic printing, inkjet printing, laser printing, supercalendering, and combinations thereof.

[0104] Depending on the source, the cellulose can be paper, paperboard, pulp, softwood fibers, hardwood fibers, or combinations thereof, nanocellulose, cellulose nanofibers, whiskers or microfibrils, microfibrillated cotton or cotton blends, cellulose nanocrystals, or nanofibrillated cellulose.

[0105] In one embodiment, the application amount of the sugar fatty acid ester coating is an amount sufficient to completely cover at least one surface of the cellulose-containing material. For example, in one embodiment, the sugar fatty acid ester coating may be applied to the entire outer surface of the container, the entire inner surface of the container, or a combination thereof, or one or both sides of the base paper. In other embodiments, the entire upper surface of the film may be coated with the sugar fatty acid ester coating, or the entire lower surface of the film may be coated with the sugar fatty acid ester coating, or a combination thereof. In some embodiments, the holes of the device / instrument may be coated with the coating, or the outer surface of the device / instrument may be coated with the sugar fatty acid ester coating, or a combination thereof. In one embodiment, the application amount of the sugar fatty acid ester coating is an amount sufficient to partially cover at least one surface of the cellulose-containing material. For example, only the surface exposed to the ambient atmosphere is coated with the sugar fatty acid ester coating, or only the surface not exposed to the ambient atmosphere is coated with the sugar fatty acid ester coating (e.g., masking). As will be apparent to those skilled in the art, the application amount of the sugar fatty acid ester coating may depend on the use of the material to be coated. In one aspect, one surface may be coated with the sugar fatty acid ester, 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 polysaccharide, alginate, carrageenan, chitosan, inulin, long-chain fatty acids, waxes, and combinations thereof. In a related aspect, SFAE can be added to the finished paper stock, and the resulting material on the web may be provided with an additional coating of SFAE.

[0106] Any suitable coating method may be used to deliver any of the various sugar fatty acid ester coatings and / or emulsions applied in the process of implementing this aspect of the method. In one embodiment, the coating method of the sugar fatty acid ester includes dipping, spraying, painting, printing, and any combination of any of these methods alone or in combination with other coating methods adapted to implement the disclosed method.

[0107] For example, by increasing the concentration of the sugar fatty acid ester, the compositions described herein can react more extensively with the cellulose being treated, and in the final result, improved water / oil repellent properties are still shown. However, it is not necessarily the case that the higher the coat weight, the greater the water resistance. In one aspect, various catalysts enable faster "curing" and precisely adjust the quality of the sugar fatty acid ester to meet specific applications.

[0108] It will be apparent to those skilled in the art that the selection of the cellulose to be treated, the sugar fatty acid ester, the reaction temperature, and the exposure time are parameters of the method that may be optimized by routine experimental methods to suit any specific application of the final product.

[0109] The derivatized material has modified physical properties that can be defined and measured using appropriate tests known in the art. For hydrophobicity, analysis protocols include, but are not limited to, contact angle measurement and moisture absorption. Other properties include rigidity, WVTR, porosity, tensile strength, lack of substrate decomposition, rupture, and tear properties. The specific standardized protocol to follow is defined by the American Society for Testing and Materials (Protocol ASTM D7334-08).

[0110] The permeability to various gases such as water vapor and oxygen on the surface may also be changed by the coating method of sugar fatty acid ester so that the barrier function of the material is enhanced. The standard unit for measuring permeability is the burer, and the protocols for measuring these parameters are also available in the public domain (ASTM standard F2476-05 for water vapor and ASTM standard F2622-8 for oxygen).

[0111] In one embodiment, a material processed according to the procedures of the present disclosure exhibits complete biodegradability as measured by degradation in an environment under microbial attack.

[0112] Various methods, including the flask shaking method (ASTM E1279-89(2008)) and the Zahn-Wellens test (OECD TG 302 B), are available for defining and testing biodegradability.

[0113] Various methods, including but not limited to ASTM D6400, are available for defining and testing compostability.

[0114] Suitable materials for processing by the method according to the present invention include various forms of cellulose such as cotton fibers, plant fibers such as linen, wood fibers, regenerated cellulose (rayon and cellophane), partially alkylated cellulose (cellulose ether), partially esterified cellulose (acetate rayon), and other modified cellulose materials, which have a significant proportion of surfaces available for reaction / bonding. As described above, the term "cellulose" includes all of these materials, as well as others having a similar polysaccharide structure and similar properties. Among these, microfibrillated cellulose (cellulose nanofiber) of relatively new materials (for example, see U.S. Patent No. 4,374,702, U.S. Patent Application Publication No. 2015 / 0167243, and U.S. Patent Application Publication No. 2009 / 0221812, which are hereby incorporated by reference in their entirety) is particularly suitable for this application. In other embodiments, cellulose includes, 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.

[0115] The modification of cellulose described herein, in addition to increasing its hydrophobicity, also enhances its tensile strength, flexibility, and rigidity, thereby possibly further expanding its range of use. Biodegradable and partially biodegradable products made from or using the modified cellulose described herein, including recyclable and compostable products, are all within the scope of this disclosure.

[0116] Among the available applications of the coating technology, such items include containers for all purposes, such as paper, cardboard, papermaking pulp, cups, lids, boxes, trays, release paper / liners, compost bags, shopping bags, pipes and aqueducts, disposable cutlery for food, plates and bottles, screens for TVs and portable devices, clothing (e.g., cotton or cotton blend), bandages, pressure-sensitive labels, pressure-sensitive tapes, feminine products, and medical devices used on or inside the body such as contraceptives, drug delivery devices, etc., but are not limited thereto. Also, the disclosed coating technology can be used for furniture and interior decoration items, outdoor camping equipment, etc.

[0117] The following examples are for illustrative purposes of the present invention and are not limiting.

Example

[0118] [Example 1] <Sugar fatty acid ester formulation> SEFOSE (registered trademark) is liquid at room temperature, and all coatings / emulsions containing this material were applied at room temperature using a bench-top type drawdown device. The type and size of the rod were changed to produce various coat weights.

[0119] (Formulation 1) 50 ml of SEFOSE® was added to a solution containing 195 ml of water and 5 grams of carboxymethyl cellulose (FINNFIX® 10; CP Kelco, Atlanta, GA). The formulation was mixed for 1 minute using a Silverson homogenizer set at 5000 rpm. This emulsion was coated onto a 50-gram base sheet made of bleached hardwood pulp and an 80-gram sheet composed of unbleached softwood. Both papers were placed in an oven (105 °C) for 15 minutes and dried. After removing from the oven, the sheets were placed on the bench and 10 drops of water (room temperature) were added to each sheet with a pipette. The base sheet selected for this test immediately absorbed the water droplets, but it was observed that for the sheets coated with various amounts of SEFOSE®, the level of water resistance increased as the coat weight increased (see Table 1).

[0120]

Table 1

[0121] It was observed that water resistance was lacking in the heavier sheets and that water resistance was not achieved if the sheets were not dry.

[0122] (Formulation 2) Addition of SEFOSE® to the cup stock: (Note that this is a single-layer stock without MFC treatment. Paperboard 110 grams made of eucalyptus pulp). 50 grams of SEFOSE® was added to 200 grams of 5% heat-ethylated starch (Ethylex 2025) and stirred for 30 seconds using a bench-top Kadimill. The paper samples were coated and placed in an oven at 105 °C for 15 minutes. 10 - 15 test droplets were placed on the coated side of the paperboard and the water hold-out time was measured and recorded in the table below. The water penetration of the untreated paperboard control was instantaneous (see Table 2).

[0123]

Table 2

[0124] (Complex 3) Pure SEFOSE® was warmed to 45 °C and placed in a spray bottle. A uniform spray was applied to the paper stock listed in the previous example, as well as to a single piece of fiberboard and a quantity of cotton cloth. When water droplets were placed on the samples, penetration into the substrate occurred within 30 seconds, but after drying in an oven at 105 °C for 15 minutes, the water droplets evaporated before being absorbed into the substrate.

[0125] Ongoing investigations were related to whether SEFOSE® could be compatible with compounds used in oil-resistant and grease-resistant coatings. SEFOSE® is useful for improving water resistance and rigidity. To conduct the rigidity test, 240 g of paperboard stock was used. The results are shown in Table 3. These data were obtained at a single coat weight of 5 grams per square meter, and the average of five samples is reported. The results are in Taber rigidity units recorded using the inventors' V-5 Taber rigidity tester model 150-E.

[0126] [Table 3]

[0127] [Example 2] [Binding of Sugar Esters to Cellulosic Substrates] To determine whether SEFOSE® binds reversibly to cellulosic materials, pure SEFOSE® was mixed with pure cellulose in a 50:50 ratio. SEFOSE® was reacted at 300 °F for 15 minutes, and the mixture was extracted with methylene chloride (a nonpolar solvent) or distilled water. The samples were refluxed for 6 hours, and a gravimetric analysis of the samples was performed.

[0128] [Table 4]

[0129] [Example 3] <Investigation of Cellulose-based Surfaces> Scanning electron microscope images of the base paper with and without MFC indicate that a base with fewer pores has the potential to require much less waterproofing agent reacting on the surface. Figures 1 and 2 show untreated Whatman filter paper with void fraction. Figures 1 and 2 indicate that the exposed surface area where the derivatizing agent can react is relatively large. However, it is also shown that there are sufficient places for water to escape in the highly porous sheet. Figures 3 and 4 show a comparison of paper made from recycled pulp before and after coating with MFC (they are two magnifications of the same sample, and the left side of the image clearly does not contain MCF). Tests show that derivatization of sheets with far fewer pores shows higher promise for long-term water / vapor barrier performance. The last two images are a precise close-up of the average "pores" of a single filter paper and a precise close-up of CNF-coated paper at the same magnification for comparison.

[0130] From the above data, it became clear that at the critical point, with the addition of more materials, the performance correspondingly improved. Without being bound by any theory, it seems that the reaction is faster in unbleached paper, suggesting that the presence of lignin may promote the reaction.

[0131] In fact, it is suggested that products such as SEFOSE® are liquid and can be easily emulsified, and can be easily adapted to function in coating equipment commonly used in paper mills.

[0132] [Example 4] "Phluphi" Liquid SEFOSE® was mixed and reacted with bleached hardwood fibers to produce various forms that created a waterproof handcrafted sheet. When sucrose ester was mixed with pulp before sheet formation, it was found that most of it was retained with the fibers. With sufficient heating and drying, a brittle and fluffy but highly hydrophobic handcrafted sheet was formed. In this example, 0.25 grams of SEFOSE® was mixed with 4.0 grams of bleached hardwood fibers in 6 liters of water. The mixture was stirred manually and the water was poured into a standard handcrafted sheet mold. The resulting fiber mat was removed and dried at 325°F for 15 minutes. The generated sheet exhibited significant hydrophobicity and greatly reduced hydrogen bonding between the fibers themselves. (A water contact angle greater than 100 degrees was observed). An emulsifier can be added. SEFOSE® and the fibers can be in a ratio of about 1:100 to 2:1.

[0133] Subsequent tests showed that talc was the only spectator in this and was removed from further tests.

[0134] [Example 5] <Environmental Effects on SEFOSE® Coating Properties> As an attempt to better understand the reaction mechanism between sucrose ester and fibers, a low-viscosity coating was applied to a bleached kraft sheet that had a wet strength resin added but no water resistance (no sizing). All coatings were measured using a Brookfield viscometer at 100 rpm and were less than 250 cps.

[0135] SEFOSE® was emulsified with Ethylex 2025 (starch) and applied to paper via a gravure roll. For comparison, SEFOSE® was also emulsified with Westcote 9050 PvOH. As shown in Figure 5, the oxidation of the double bonds in SEFOSE® is enhanced by heat and the presence of additional chemical environments that enhance its oxidative chemical properties. (See also Table 5.)

[0136]

Table 5

[0137] [Example 6] [Effect of unsaturated fatty acid chain on saturated fatty acid chain] SEFOSE (registered trademark) was reacted with bleached softwood pulp, dried, and formed into a sheet. Then, CH 2 Cl 2 , toluene, and water were used for extraction to determine the degree of reaction with the pulp. Extraction was carried out for at least 6 hours using a Soxhlet extraction glass apparatus. The extraction results are shown in Table 6.

[0138] [Table 6]

[0139] The data shows that essentially all of SEFOSE (registered trademark) remains in the sheet. To further verify this, the same procedure was carried out with pulp alone, and it was found that about 0.01 g was obtained per 10 g of pulp. Without being bound by any theory, this can be easily explained as residual pulping chemicals that were not completely removed or more likely as extracts.

[0140] The experiment was repeated using pure cellulose fibers (e.g., α - cellulose from Sigma Aldrich (St. Louis, MO)). As long as the loading level of SEFOSE (registered trademark) remained less than about 20% of the mass of the fibers, more than 95% of the mass of SEFOSE (registered trademark) was retained with the fibers and was not extracted by either polar or non - polar solvents. Without being bound by any theory, optimizing the baking time and temperature may further enhance the sucrose esters remaining with the fibers.

[0141] As shown by the data, it became clear that generally SEFOSE® cannot be extracted from the material after drying. On the other hand, when fatty acids containing all saturated fatty acid chains (for example, OLEAN® available from Procter & Gamble Chemicals (Cincinnati, OH)) are used instead of SEFOSE®, almost 100% of the OLEAN® in the material can be extracted using hot water (at 70 °C or higher). OLEAN® is identical to SEFOSE®, the only difference being that saturated fatty acids are bonded (in OLEAN®) instead of unsaturated fatty acids (in SEFOSE®).

[0142] Another notable aspect is that multiple fatty acid chains show reactivity with cellulose and two sugar molecules in the structure, resulting in SEFOSE® forming a strong crosslinked network, leading to improved strength of fiber webs such as paper, paperboard, airlaid and wet nonwovens, and textiles.

[0143] [Example 7] <Addition of SEFOSE® to achieve water resistance> Using both hardwood and softwood kraft pulp, 2-gram and 3-gram hand-made sheets were produced. When SEFOSE® was added to the 1% pulp slurry at a level of 0.1% or more and the water was drained to form the hand-made sheet, SEFOSE® was retained with the fibers, imparting water resistance. At 0.1% - 0.4% of SEFOSE®, the water beaded up on the surface in less than a few seconds. When the SEFOSE® loading exceeded 0.4%, the water resistance time increased rapidly to several minutes and then to several hours towards a loading rate level higher than 1.5%.

[0144] [Example 8] <Manufacture of bulky fiber materials> When SEFOSE (registered trademark) is added to pulp, it softens the fibers, increases the space between them, and acts to make them bulky. For example, when a 3% slurry of hardwood pulp containing 125 g (dry state) of pulp was drained and dried, it was found to occupy a volume of 18.2 cubic centimeters. 12.5 g of SEFOSE (registered trademark) was added to a similar 3% hardwood pulp slurry containing an equal amount of 125 g of dry fiber. After draining and drying, the resulting mat occupied 45.2 cubic centimeters.

[0145] 30 g of standard bleached hardwood kraft pulp (manufactured by Old Town Fuel and Fiber, LLC, Old Town, ME) was sprayed with SEFOSE (registered trademark) warmed to 60 °C. This 4.3 cm 3 was placed in a disintegrator at 10,000 rpm and essentially repulped. The mixture was poured through a hand-laid sheet mold and dried at 105 °C. The resulting hydrophobic pulp occupied a volume of 8.1 cm 3 This material was cut into 2-inch squares, placed in a hydraulic press, and a pressure of 50 tons was applied for 30 seconds. The volume of the square was significantly reduced, but still occupied 50% more volume than a similar 2-inch square cut for a control without applied pressure.

[0146] It is also important that not only an increase in bulk and softness is observed, but that a fiber mat was obtained in which all of the hydrophobicity was retained by the forced repulped mat when drained. This quality is valuable in addition to the finding that water cannot easily "push through" the low surface energy barrier and enter the sheet. The binding of a single fatty acid chain of hydrophobicity does not exhibit this property.

[0147] Without being bound by any theory, this represents additional evidence that SEFOSE (registered trademark) has reacted with cellulose and the OH groups on the surface of the cellulose fibers are no longer available to participate in subsequent hydrogen bonding. Other hydrophobic materials interfere with the initial hydrogen bonding, but during repulping, this effect is reversed and the OH groups of cellulose are free to participate in hydrogen bonding during redrying.

[0148] [Example 9] <Bag paper test data> The following table (Table 7) shows the properties imparted by coating a 5 - 7 g / m 2 mixture of SEFOSE (registered trademark) and polyvinyl alcohol (PvOH) onto unbleached kraft bag stock (control). Also included for reference are commercially available bags.

[0149]

Table 7

[0150] As shown in the table, when the control base paper was coated with SEFOSE (registered trademark) and PvOH, tensile and burst increased.

[0151] [Example 10] <Wet / dry tensile strength> Three - gram handmade sheets were made from bleached pulp. Below, the wet and dry tensile strengths were compared at different addition levels of SEFOSE (registered trademark). Note that in these handmade sheets, SEFOSE (registered trademark) was not emulsified in any coating, but simply mixed into the pulp and drained without adding other chemical properties (see Table 8).

[0152]

Table 8

[0153] Also note that for wet strength, with a 5% addition, it does not fall much below the dry strength of the control.

[0154] [Example 11] <Use of esters containing less than eight saturated fatty acids> Several experiments were conducted using sucrose esters produced by binding less than eight fatty acids to the sucrose moiety. Samples of SP50, SP10, SP01, and F20W (Sisterna, The Netherlands) contain 50%, 10%, 1%, and essentially 0% monoesters, respectively. These commercial products are made by reacting sucrose with saturated fatty acids, which renders them less useful for further crosslinking or not useful for similar chemical properties, but useful when investigating emulsifying and water-repellent properties.

[0155] For example, 10 g of SP01 was mixed with 10 g of glyoxal in a 10% heated PvOH solution. The mixture was "heated" at 200°F for 5 minutes and applied by drawdown onto a porous base paper made from bleached hardwood kraft. The result was a crosslinked wax-based coating on the surface of the paper that exhibited good hydrophobicity. When a minimum of 3 g / m 2 was applied, the resulting contact angle was greater than 100°. Since glyoxal is a well-known crystallization agent used with compounds having OH groups, this method is a promising means of attaching fairly non-reactive sucrose esters to the surface by bonding the remaining alcohol groups of the sucrose ring to available alcohol groups in the substrate or other coating materials.

[0156] [Example 12] <HST Data and Moisture Absorption> To demonstrate that waterproof properties are observed with SEFOSE® alone, porous Twins River (Matawaska, ME) base paper was treated with various amounts of SEFOSE® (and PvOH or Ethylex 2025 which was emulsified and applied by drawdown) and assayed with the Hercules sizing test. The results are shown in Table 9.

[0157]

Table 9

[0158] As shown in Table 9, the water resistance increased with the increase of SEFOSE (registered trademark) applied to the surface of the paper (as indicated by the increase of HST (unit: second)).

[0159] This was also observed when using the coating of saturated sucrose ester products. As a specific example, the product F20W (available from Sisterna, The Netherlands) is described as having a very low monoester% in most molecules in the 4 - 8 substitution range. It should be noted that when preparing a stable emulsion using the F20W product and PvOH in equal parts by volume, the impregnation amount of the F20W product is only 50% of the total coating. Thus, when the impregnation amount is labeled as "0.5 g / m 2 ", there is also PvOH with a similar impregnation amount, and a total impregnation amount of 1.0 g / m 2 is obtained. The results are shown in Table 10.

[0160]

Table 10

[0161] As shown in Table 10, with the increase of F20W, the water resistance of the porous sheet increased. Therefore, the applied sucrose fatty acid ester itself makes the paper water - resistant.

[0162] Since the water resistance is not simply due to the presence of fatty acids that form ester bonds with cellulose, SEFOSE (registered trademark) was loaded onto a softwood hand - made sheet (bleached softwood kraft), and oleic acid that forms an ester bond with cellulose in the pulp was directly added to the pulp. The mass at time 0 represents the "absolutely dry" mass of the hand - made sheet taken out from an oven at 105 °C. The sample was placed in a humidity - controlled chamber maintained at RH50%. The change in mass was recorded over time (unit: minute). The results are shown in Table 11 and Table 12.

[0163]

Table 11

[0164]

Table 12

[0165] It should be noted that when oleic acid is directly added to the pulp to form an ester bond, the difference here is that it greatly slows down moisture absorption. In contrast, only 2% SEFOSE® slows down moisture absorption, and at higher concentrations, SEFOSE® does not slow it down. Without being bound by any theory, the structure of the SEFOSE® binder should not be explainable only by the structure formed by simple fatty acid esters and cellulose.

[0166] [Example 13] <Saturated SFAE> The class of saturated esters is a waxy solid at room temperature and, being saturated, is less reactive with the sample matrix or itself. When used at high temperatures (e.g., at least 40 °C, all tested, above 65 °C), these materials melt and can be applied as a liquid, then cooled and solidified to form a hydrophobic coating. Alternatively, these materials can be emulsified in solid form and applied as an aqueous coating to impart hydrophobic characteristics.

[0167] The data shown here represent the HST (Hercules size test) readings obtained from papers coated with various amounts of saturated SFAE.

[0168] The #45 bleached hardwood kraft sheet obtained from Turner Falls paper was used for the test coating. The Gurley porosity was measured for about 300 seconds, representing a fairly dense base sheet. S-370 obtained from Mitsubishi Foods (Japan) was emulsified with xanthan gum (up to 1% of the mass of the saturated SFAE formulation) before coating.

[0169] Coat weight of saturated SFAE formulation (pounds per ton) HST (average of 4 measurements per sample).

[0170]

Table 13

[0171] The obtained experimental data also confirmed that a limited amount of saturated SFAE may enhance the water resistance of coatings designed for other purposes / applications. For example, when saturated SFAE was blended with coatings based on Ethylex starch and polyvinyl alcohol, an increase in water resistance was observed in all cases.

[0172] The following examples were coated on #50 bleached recycled base with a Gurley porosity of 18 seconds.

[0173] 100 grams of Ethylex 2025 was heated at 10% solids (1 liter by volume), 10 grams of S-370 was added while hot, and mixed using a Silverson homogenizer. The resulting coating was applied using a common bench-top drawdown device, and the paper was dried under a heating lamp.

[0174] At a coat weight of 300# / ton, starch alone had an average HST of 480 seconds. For a mixture of starch and saturated SFAE with a similar coat weight, the HST increased to 710 seconds.

[0175] Sufficient polyvinyl alcohol (Selvol 205S) was dissolved in hot water to form a 10% solution. When this solution was coated on #50 paper as above, the average HST was 225 at a coat weight of 150 pounds / ton. Using the same solution and adding S-370, a mixture containing 90% PVOH / 10% S-370 on a dry weight basis (i.e., 90 ml of water, 9 grams of PvOH, 1 gram of S-370) was formed. The average HST increased to 380 seconds.

[0176] Saturated SFAE is compatible with prolamin (specifically, zein; see U.S. Patent No. 7,737,200, which is incorporated herein by reference in its entirety). Since one of the main barriers to the commercial production of the subject matter of the patent is that the formulation is water-soluble, the addition of saturated SFAE serves in this form.

[0177] [Example 14] <Other saturated SFAE> The size press evaluation of the saturated SFAE-based coating was carried out on a bleached lightweight sheet (about 35#) without sizing and with relatively poor formation. All evaluations were performed using Exceval HR 3010 PvOH emulsified with saturated SFAE. Sufficient saturated SFAE was added to account for 20% of the total solids. Samples of S-370 vs. C-1800 (available from Mitsubishi Foods (Japan)) were focused on for evaluation. Both of these esters performed better than the control. A portion of the important data is shown in Table 14.

[0178]

Table 14

[0179] The saturated compounds appear to result in an increase in the kit, and it should be noted that both S-370 and C-1800 have an increase in HST of approximately 100%.

[0180] [Example 15] <Wet strength additive> Laboratory tests have shown that the chemical properties of sucrose esters can be adjusted to achieve various characteristics, including their use as wet strength additives. When sucrose esters are prepared by attaching saturated groups to each alcohol functional group of sucrose (or other polyols), the result is a hydrophobic wax-like substance that is poorly miscible / soluble in water. Although adding these compounds to cellulosic materials can impart water resistance, either internally or as a coating, they do not chemically react with each other or with any part of the sample matrix and are thus easily removed by solvents, heat, and pressure.

[0181] When higher levels of water repellency and water resistance are desired, sucrose esters containing unsaturated functional groups are prepared and added to cellulosic materials with the aim of fixing the sucrose esters in the matrix and achieving oxidation and / or crosslinking that will help provide high resistance to removal by physical means. By adjusting the number and size of the unsaturated groups in the sucrose esters, a means is obtained to crosslink molecules that are not optimal for imparting water resistance but are used to impart strength.

[0182] The data presented here were obtained by adding SEFOSE® at various levels to bleached kraft sheets and obtaining wet tensile data. The percentages shown in the table represent the sucrose esters (%) of the treated 70# bleached paper (see Table 15).

[0183]

Table 15

[0184] The data show that adding unsaturated sucrose esters to paper tends to increase the wet strength as the loading level increases. Dry tensile is shown relative to the maximum strength of the sheet.

[0185] [Example 16] <Method for producing sucrose esters using acid chlorides> In addition to preparing hydrophobic sucrose esters via transesterification, similar hydrophobicity in fibrous articles could be achieved by reacting acid chlorides directly with polyols containing a ring structure similar to sucrose.

[0186] For example, 200 grams of palmitoyl chloride (CAS 112 - 67 - 4) was mixed with 50 grams of sucrose at room temperature. After mixing, the mixture was brought to 100°F and maintained at that temperature overnight (ambient pressure). The resulting material was washed with acetone and deionized water to remove any unreacted or hydrophilic materials. Analysis of the remaining material using C - 13 NMR revealed that a significant amount of hydrophobic sucrose ester had been produced.

[0187] It has been shown that adding fatty acid chlorides to cellulosic materials can impart hydrophobicity (BT3 and others), but the reaction itself causes several problems including the corrosive gaseous HCl by - product released, which is undesirable in the field as it is harmful to workers and the surrounding environment. One additional problem caused by the generation of hydrochloric acid is that as more is formed, i.e., as more polyol sites react, the fiber composition becomes weaker. Palmitoyl chloride was reacted with cellulose and cotton materials while increasing their amounts. As the hydrophobicity increased, the strength of the article decreased.

[0188] The above reaction was repeated several times using 200 grams of R - CO - chloride reacted with 50 grams each of other similar polyols including corn starch, xylan from oak, carboxymethyl cellulose, glucose, and extracted hemicellulose.

[0189] [Example 17] <Combination of SFAE - lignin and SFAE - hemicellulose> Hemicellulose was obtained from sugarcane bagasse. The bagasse was extracted at a ratio of bagasse:NaOH solvent of 1:5. After filtration, the supernatant was adjusted to pH 5.5 with HCl. Then the suspension was filtered, and then the supernatant was added to 4 volumes of ethanol to obtain pellets. Thereafter, the pellets were dried at 50 °C.

[0190] Hemicelluloses at various concentrations were prepared in dH 2 O. SFAE was added to the hemicellulose solution as an aqueous emulsion and mixed at 45 °C for 15 minutes using a magnetic stirrer. Then the hemicellulose and SFAE solutions were applied to the substrate and dried. Then the dried paper was in a state where it could be analyzed immediately (e.g., water contact angle, moisture permeability, O 2 permeability).

[0191] (Formed paper cup lid) A) Fibers coated with lignin Lignocellulose fibers can be obtained by the method described in U.S. Patent No. 20150233057 (which is hereby incorporated by reference in its entirety) and can be separated as a suspension.

[0192] The lignin fibers were mixed with an aqueous emulsion of SFAE to form a composite material. The suspension of cellulose fibers and SFAE was applied to a foldable sheet (micro-embossing or FIBREFORM (registered trademark)) and dried at ambient temperature (23 °C) for 120 minutes or more and placed in a mold for the cup lid.

[0193] For the obtained formed composite material, the oxygen permeability and moisture permeability were measured. The formed composite material was further held in a thermostatic bath maintained at the heating temperature for 30 minutes and cooled at ambient temperature (23 °C) for 2 hours or more to obtain a processed formed composite material.

[0194] B) Hemicellulose formed cup Cellulose fibers were obtained by the method described in U.S. Patent No. 20110262731 (which is hereby incorporated by reference in its entirety) and could be separated as a suspension.

[0195] Hemicellulose was separated and combined with the above SFAE.

[0196] Cellulose fibers were mixed with the hemicellulose - SFAE solution to form a composite material. A suspension of cellulose fibers and hemicellulose SFAE was applied to a foldable sheet (micro - embossed or FIBREFORM (registered trademark)), dried at ambient temperature (23°C) for 120 minutes or more, and placed in a mold for a cup lid.

[0197] For the obtained molded composite material, oxygen permeability and moisture permeability were measured. The molded composite material was further held in a thermostatic bath maintained at a heating temperature for 30 minutes and cooled at ambient temperature (23°C) for 2 hours or more to obtain a processed molded composite material.

[0198] [Example 18] [Other uses] It was found that when the cup base stock was densely treated with rosin, its water resistance increased. However, the Gurley for this paperboard was found to be 50 seconds, indicating a rather porous paperboard. This material is repulpable, and water vapor penetrates rapidly, softening the material. Pure SEFOSE (registered trademark) was applied to this paperboard and dried overnight in an oven at 100°C. The resulting material had a plastic - like feel and was completely waterproof. By mass, it was 50% (wt / wt) cellulose / 50% (wt / wt) SEFOSE (registered trademark). The Gurley was too high to be measured. Immersing the sample in water for 7 days did not significantly soften the material, but from greenhouse data, it is considered to biodegrade in approximately 150 days. General tapes and adhesives do not stick to this composite material.

[0199] Since zein has been shown to impart grease resistance to paper, experiments were carried out using saturated SFAE and zein. Stable aqueous dispersions of zein with 2 - 5% addition of saturated SFAE (up to 25% in water) were produced. Observation demonstrated that saturated SFAE "locks down" zein on paper by imparting water resistance (and further grease resistance) to the formulation.

[0200] While the invention has been described with reference to the above embodiments, it will be understood that modifications and variations are included within the spirit and scope of the invention. The invention is limited only by the following claims. References described herein are hereby incorporated by reference in their entirety as part of this specification.

Claims

1. A composition comprising a SFAE-hemicellulose-bound cellulose-based material, wherein the SFAE (sugar fatty acid ester) is present on the surface of the cellulose-based material at a coating weight of 0.1 g / m ２ to 20.0 g / m ２ and the bound cellulose-based material exhibits low permeability to oxygen due to the SFAE and hemicellulose.

2. The composition according to claim 1, wherein the sugar fatty acid ester contains at least one saccharide and at least one aliphatic group containing 8 to 30 carbon atoms, and the bound cellulosic material is hydrophobic as compared to a similar material except that it does not contain the composition.

3. The composition according to claim 1, wherein the SFAE-hemicellulose composition is bound to the cellulosic material either detachably or non-detachably.

4. The composition according to claim 1, wherein the bound hemicellulosic material exhibits a water contact angle of 90° or more by the SFAE, and the water contact angle is brought about in the absence of an optional second hydrophobic substance.

5. The composition according to claim 1, comprising a hemicellulose content of 1 to 99% by dry weight.

6. A composition comprising an SFAE-lignin-bonded cellulosic material, wherein the SFAE (sugar fatty acid ester) is present on the surface of the cellulosic material at a coating weight of 0.1 g / m ２ to 20.0 g / m ２ and the bonded cellulosic material exhibits water resistance due to the SFAE and lignin.

7. The composition according to claim 6, wherein the sugar fatty acid ester contains at least one saccharide and at least one aliphatic group containing 8 to 30 carbon atoms.

8. The composition according to claim 6, wherein the SFAE-lignin composition is bound to the cellulosic material either detachably or non-detachably.

9. The composition according to claim 6, wherein the bound lignin-based material exhibits a water contact angle of 90° or more by the SFAE, and the water contact angle is brought about in the absence of an optional second hydrophobic substance.

10. The composition according to claim 1 or 6, wherein the cellulosic material is selected from the group consisting of paper, paper sheet, cardboard, pulp for papermaking, carton for food storage, parchment paper, cakeboard, meat wrapping paper, release paper / liner, food storage bag, shopping bag, transport bag, bacon board, insulating material, tea bag, container for coffee or tea, compost bag, tableware, container for hot or cold beverage, cup, lid, plate, bottle for storing carbonated liquid, gift card, bottle for storing non-carbonated liquid, food wrap film, container for raw garbage treatment, food handling utensils, fabric fiber (e.g., cotton or cotton blend), water storage and transportation utensils, container for alcoholic or non-alcoholic beverage, external casing or screen for electronic products, internal or external components of furniture, curtain, and interior decoration supplies.

11. A method for producing a molded cup lid, comprising: a. applying a composition containing SFAE (sugar fatty acid ester) and hemicellulose to a foldable paper sheet; b. drying the foldable sheet for a time sufficient for the composition to adhere to the sheet; c. placing the sheet in a mold of a cup lid and completely drying the sheet; d. optionally, heating the lid for an additional time sufficient to fully form the lid; comprising a method wherein the SFAE and hemicellulose exhibit low oxygen permeability of the binding cellulosic material. **Claim 12** The method according to claim 11, wherein the foldable paper is micro-embossed. **Claim 13** The sugar fatty acid ester contains at least one saccharide and at least one aliphatic group containing 8 to 30 carbon atoms, and the binding cellulosic material is hydrophobic compared to a similar material except that it does not contain the composition. The method according to claim 11. **Claim 14** The SFAE is present at a coating weight of 0.1 g / m ２ to 20.0 g / m ２ The method according to claim 11, wherein the SFAE is present at a coating weight of 0.1 g / m to 20.0 g / m. **Claim 15** A manufactured article comprising a molded cup lid produced by the method according to claim 11. **Claim 16** A method of producing a molded cup lid, comprising: a. applying a composition containing SFAE (sugar fatty acid ester) and lignin to a foldable paper sheet; b. drying the foldable sheet for a time sufficient for the composition to adhere to the sheet; c. placing the sheet in a mold of a cup lid and completely drying the sheet; d. optionally, heating the lid for an additional time sufficient to fully form the lid; comprising a method wherein the SFAE and lignin render the binding cellulosic material water-resistant. **Claim 17** The method according to claim 16, wherein the foldable paper is micro-embossed. **Claim 18** The SFAE is present at a coating weight of 0.1 g / m ２ to 20.0 g / m ２ The method according to claim 16, wherein the SFAE is present at a coating weight of 0.1 g / m to 20.0 g / m. **Claim 19** A manufactured article comprising a molded cup lid produced by the method according to claim 16. **Claim 20** The manufactured article according to claim 19, wherein the SFAE is saturated or unsaturated.

Images