Polyol fatty acid ester carrier composition

Abstract

The present disclosure describes a method for treating cellulosic fiber materials with sucrose fatty acid ester-containing particles (carrier systems) that allow for surface modification, making such surfaces water-resistant and / or oil / grease-resistant. The disclosed method involves combining at least one sugar fatty acid ester (SFAE) with a polymer (e.g., latex) to form micellar particles, and applying such particles to a substrate containing a cellulosic fiber material (e.g., pulp) to form, among other things, a molded article. Also disclosed are compositions containing a combination of the SFAE, latex, and optionally minerals or other additives.

Description

[Technical Field]

[0001] Background of the Disclosure The present disclosure relates generally to treating fiber-containing substrates, and more particularly to treating such substrates with particles comprising sugar fatty acid esters (SFAEs) in combination with polymers such as latex and optionally minerals, such as compositions containing such combinations. Also particularly, the present disclosure relates to the use of such particles as carriers for coatings, and methods of applying carrier coatings to provide barrier properties to molded articles made from such substrates. [Background technology]

[0002] Traditionally, raw materials for producing cellulose fiber-based moldings can include wheat, wheat stalk, wood, sugarcane bagasse, reed, and edge paper. The materials can be pulped by hydrodynamic pulping to form a mixture that can then be hardened in a metal mold. This can then be surface-treated with a coating containing water-soluble acrylic, latex, resin, or EVA (ethyl vinyl acetate).

[0003] In the past decade, such methods have included the steps of: (a) screening non-toxic rice hull raw material, including straw, grains, waste residues, and starch-rich plants; (b) washing the rice hull raw material with water to remove dust, soil, and contaminants; (c) drying by centrifugation; (d) grinding the rice hull raw material into a powder; (e) thoroughly mixing the powder with an additional premix and water to form a mixture, the additional premix containing specific food gums, sulfates, hard acids, and treating agents, the specific food gums consisting of latex, pectin, and protein gel, and the treating agents consisting of specific food gums, calcium chloride, and alum; and (f) thermally forming the mixture into a product. (g) removing the product from the mold; and (h) drying (see, for example, Taiwan Patent Publication No. 500746, the entire contents of which are incorporated herein by reference).

[0004] A recent method includes the steps of: (a) separately preparing pulp using a first auxiliary containing an anionic material (e.g., aluminum silicate and natural wax emulsion) and a second auxiliary containing a nonionic and cationic material (e.g., fluorochemical resins, polymeric compounds, aliphatic polyamines, and alkyl acrylic copolymers); (b) uniformly mixing the pulp and the first auxiliary with water to form a pulp premix; (c) mixing the second auxiliary with the pulp premix to form a pulp mixture; and (d) thermoforming the pulp mixture to form a packaging material (see, e.g., U.S. Patent Application Publication No. 2005 / 0211405, the entire contents of which are incorporated herein by reference).

[0005] Although current methods are effective in providing water / oil resistance to fiber-based substrates / surfaces, the use of fluorochemicals has more recently come under scrutiny due to environmental and health concerns. Thus, it would be desirable to have compositions and methods that can achieve barrier performance (e.g., water / oil resistance) on cellulosic fiber-based molded substrates without the use of fluorochemicals. Summary of the Invention

[0006] The present disclosure relates, inter alia, to a method for treating molded surfaces with carrier particles that impart water and / or oil / grease resistance to such treated surfaces. The disclosed method involves combining at least one sugar fatty acid ester (SFAE) with a polymer, such as a latex, in particulate form and applying such particles to a substrate comprising a cellulosic material. Such compositions can also include inorganic minerals / pigments.

[0007] In one embodiment, a method for producing a cellulose-containing article is disclosed, the method comprising the steps of adding an emulsion or slurry to a cellulosic fiber furnish, the emulsion or slurry comprising one or more sucrose fatty acid esters and one or more carrier particles; draining the furnish through one or more meshes or screens; thermoforming the mixture in a mold into a product; and removing the product from the mold, wherein the product exhibits water, oil, and grease resistance compared to a cellulosic product not treated with the emulsion or slurry. In a related aspect, the method relates to a cellulosic fiber furnish comprising fibers from wheat, wheat stalk, wood, sugarcane bagasse, reed, edge paper, and combinations thereof.

[0008] In one aspect, the product is a bowl, plate, bottle, pouch, package, or insert. In another aspect, the carrier includes sucrose fatty acid esters, polymers, solid latex polymer beads, hollow polymer shells, resin beads, pigment particles, and combinations thereof. In a related aspect, the pigment particles include calcium carbonate, titanium dioxide, kaolin clay, silica, silicates, talc, mica, and combinations thereof.

[0009] In one embodiment, the particles further comprise raw corn starch, rice starch, wheat starch, potato starch, or tapioca starch granules, oat hulls, rice hulls, ground nut shells, or combinations thereof. In another embodiment, the particles are coated with one or more sucrose esters and dispersed in an aqueous emulsion or slurry.

[0010] In one embodiment, the aqueous emulsion or slurry is mixed with the cellulosic fiber slurry at a concentration of about 5% to about 50% of the total dry weight prior to wet forming.

[0011] In another aspect, the carrier is a polymer, and the polymer exhibits a low glass transition temperature. In a related aspect, the polymer is a latex. In another related aspect, the product exhibits reduced tack.

[0012] In one embodiment, a composition is disclosed that includes sucrose fatty acid ester particles containing one or more cargo materials. In one aspect, the cargo molecules are selected based on the properties to be modified. In a related aspect, such properties can be tunable (e.g., resulting in a range of 3M kit values ​​and / or a range in water contact angle). In another related aspect, different portions of a product made using the composition can exhibit different properties by selecting various cargo molecules and / or the means of making the particles (e.g., varying heating temperature, heating time, heating-cooling cycle, mixing method, buffer, surfactant, emulsifier, continuous / discontinuous phase composition, pH, emulsion method, etc.).

[0013] In one embodiment, the one or more cargo materials include polymers, solid latex polymer beads, resin beads, calcium carbonate, titanium dioxide, kaolin clay, silica, silicates, talc, mica, and combinations thereof.

[0014] In a further embodiment, the composition comprises thymol, lecithin, an alkyl glucoside, and combinations thereof.

[0015] In one embodiment, the particle is a micelle, microcapsule, or nanocapsule.

[0016] In another embodiment, the sucrose fatty acid ester is a mono- or diester.

[0017] In a further embodiment, the sucrose fatty acid ester comprises all saturated fatty acids or is a mixture of saturated and unsaturated fatty acids.

[0018] In a related embodiment, the sucrose fatty acid ester particles comprise one or more sucrose fatty acid esters.

[0019] In one embodiment, an emulsion is disclosed comprising the composition described above. In a related aspect, the one or more cargo materials comprise latex.

[0020] In another embodiment, an article of manufacture produced by the above-described method is disclosed. [Brief explanation of the drawings]

[0021] [Figure 1] FIG. 1 shows a scanning electron micrograph (SEM) (58x magnification) of untreated medium porosity Whatman filter paper. [Figure 2] FIG. 1 shows an SEM (1070x magnification) of untreated medium porosity Whatman filter paper. [Figure 3]Side-by-side comparison of SEM (27x magnification) of paper made from recycled pulp before (left) and after (right) coating with microfibrillated cellulose (MFC). [Figure 4] Side-by-side comparison of SEM (98x magnification) of paper made from recycled pulp before (left) and after (right) coating with MFC. [Figure 5] FIG. 1 shows the water penetration in paper treated with different coating formulations: Polyvinyl alcohol (PvOH), ◇; SEFOSE® + PvOH, 1:1 (v / v), □; Ethylex (starch), △; SEFOSE® + PvOH, 3:1 (v / v), ×. [Figure 6] FIG. 1 shows water beading on paper treated with an aqueous composition containing two sucrose fatty acid esters with different HLB values ​​and precipitated calcium carbonate. DETAILED DESCRIPTION OF THE INVENTION

[0022] Before describing the present compositions, methods, and methodologies, it is to be understood that this invention is not limited to the particular compositions, methods, and experimental conditions described, as such compositions, methods, and conditions may vary. It is also to be understood that the scope of the present invention will be limited only by the claims, and that the terminology used herein is for the purpose of describing particular embodiments only, and is not intended to be limiting.

[0023] As used herein and in the appended claims, the singular forms "a," "an," and "the" include plural referents unless the context clearly dictates otherwise. Thus, for example, reference to "sugar fatty acid esters" includes one or more sugar fatty acid esters and / or compositions of the type described herein that would become apparent to one of ordinary skill in the art upon reading this disclosure and so forth.

[0024] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this disclosure belongs. Any methods and materials similar or equivalent to those described herein can be used in the practice or testing of this disclosure, with the understanding that modifications and variations are within the spirit and scope of the disclosure.

[0025] As used herein, the terms "about," "approximately," "substantially," and "largely" will be understood by those of ordinary skill in the art and will vary to some extent depending on the context in which they are used. If there are uses of terms that are not clear to persons of ordinary skill in the art given the context in which the terms are used, "about" and "approximately" will mean plus or minus <10% of the particular term, and "substantially" and "largely" will mean plus or minus >10% of the particular term. "Comprising" and "consisting essentially of" have their accustomed meanings in the art.

[0026] Barrier coatings on surfaces typically function to prevent inclusions (e.g., liquids / gases) from passing through the surface or to reduce the release of such inclusions. Various materials that make up the coating can improve the performance of a particular base component. For example, latex is a very good film former and can serve as the primary component of a base coat that seals a porous base sheet, to which a top coat can be added to improve the performance of the base coat. In such a base and top coat configuration, the latex acts as a physical barrier, and polymers, for example, can be added to improve performance metrics such as Cobb value.

[0027] While not a polymer in itself, as disclosed herein, SFAE has been found to aid in modifying the Cobb value of substrates containing a barrier coating that includes latex. Without being bound by any theory, it is possible that a latex coating leaves pores that allow water / water vapor to enter the interstices of a porous substrate such as paper: the SFAE can fill the pores, and because the SFAE has a hydrophobic surface, the water / water vapor is repelled from the pores, resulting in an improved Cobb value. This combination works well, providing improved levels of performance, including allowing for lower Cobb values ​​without compromising product quality.

[0028] In addition, inorganic pigments can be added, and mixtures of inorganic particles, latex, and SFAE provide improved fine-tuning of various sheet properties. For example, such sheets may contain wood fibers and bioplastic fibers in combination to make them waterproof and grease-resistant. This potential combination allows for the use of cheaper, more common materials, such as mechanical or recycled pulp, as a large percentage of the sheet's mass. In such cases, the addition of a calcium carbonate-latex-SFAE mixture, for example, provides an improvement that allows for control of the sheet's density.

[0029] In one embodiment, a method for producing a water-resistant, and / or oil- and grease-resistant cellulose-containing article is disclosed, comprising adding an emulsion or slurry containing one or more sucrose fatty acid esters and one or more carrier particles to a cellulose fiber furnish and draining the furnish through one or more meshes or screens. In one aspect, the wet-formed cellulose fibrous article is then heated to remove remaining water and produce a finished article, such as a bowl, plate, or packaging container or insert.

[0030] In a related aspect, the carrier particles include, but are not limited to, solid latex polymer beads, hollow polymer shells, resin beads, or pigment particles such as calcium carbonate, titanium dioxide, kaolin clay, silica or silicates, talc, or mica. In another related aspect, the particles may be organic particles such as raw corn starch, rice starch, wheat starch, potato starch, or tapioca starch granules, oat hulls, rice hulls, ground nut shells, or other similar particles or combinations thereof.

[0031] In one embodiment, particles can be coated with one or more sucrose fatty acid esters and dispersed in an aqueous emulsion or slurry. In a related aspect, the aqueous emulsion or slurry can then be mixed with a cellulose fiber slurry at a concentration of about 5% to about 10%, about 10% to about 20%, about 20% to about 30%, about 30% to about 40%, or about 40% to about 50% of the total dry weight prior to wet-molding. Without being bound by any theory, the sucrose fatty acid esters overcome the sticking problem encountered with the use of many polymer particles, such as latex. This is particularly true for polymers or latexes with low glass transition temperatures.

[0032] In a related aspect, the size and distribution of the coated particles can be selected by those skilled in the art so that they can migrate toward the surface of the article during the forming process. Without being bound by any theory, this increases the concentration of the coated particles on the surface relative to the bulk of the article, improving the cost-benefit of adding the coated particles. In another related aspect, the increased concentration of the coated particles allows for film formation and melting of the sucrose fatty acid ester and / or polymer on the surface of the article during the heating and drying process, and also allows for catalytic or chemical reactions with optional additives to initiate bonding with the cellulose substrate, crosslinking of components, or otherwise chemically modify the surface of the article to develop water, oil, and / or grease resistance.

[0033] In another related aspect, the release properties of one or more sucrose fatty acid esters allow for the use of potentially tacky or adhesive additives in the present compositions, overcoming deficiencies in the prior art while contributing to the barrier properties of the article.

[0034] Use of the present disclosure eliminates or greatly reduces the need to coat, dip, or spray additional materials onto the surface of an article to impart water, oil, and / or grease resistance.

[0035] In one embodiment, one or more sucrose fatty acid esters can form micelles / microcapsules / nanocapsules and can themselves be used as carriers, which can be combined with thymol, lecithin, or alkyl glucosides to encapsulate solid latex polymer beads, resin beads, or pigment particles such as calcium carbonate, titanium dioxide, kaolin clay, silica or silicates, talc, or mica. Also, changes in particle size can be affected by using longer aliphatic groups (i.e., micelles / microcapsules / nanocapsules are smaller with longer acyl groups). Furthermore, due to the high DS, bilayer structures similar to cell membranes can be formed.

[0036] In one embodiment, the present disclosure provides that by treating a cellulose fiber-based substrate with the disclosed carrier combination, the resulting material can be, among other things, highly oil / grease-resistant, hydrophobic, and exhibit low Cobb values. Furthermore, these sugar fatty acid esters, once removed by, for example, bacterial enzymes, are readily digested as such. The derivatized surface can exhibit very high heat resistance, withstanding temperatures as high as 250°C, and can be more impermeable to gases than the underlying base substrate. Therefore, such materials are an ideal solution to the problem of derivatizing the hydrophilic surface of cellulose in any embodiment in which cellulose materials may be utilized.

[0037] Advantages of the products and methods disclosed herein include that the coating compositions are made from renewable agricultural resources—sugars and vegetable oils; have a low toxicity profile and are suitable for food contact; are tailored to reduce the coefficient of friction of the paper / paperboard surface even at high water resistance levels (i.e., do not make the paper too slippery for downstream processing or end use); can be used with or without special emulsifying equipment or emulsifiers; and are compatible with traditional paper recycling programs: i.e., do not adversely affect recycling operations like, for example, polyethylene, polylactic acid, or wax-coated paper. Also, the expanded use of inorganic chemicals such as PCC / GCC takes advantage of the inherent properties of fillers (e.g., low abrasion).

[0038] Other benefits of the coating formulation include: - Relative ease of fabrication; - Base coating is performed well at high speeds at the target coat weight; - No roll blocking; - No problems with purification; - the coating can be carried out at a solids content of 60-75% with a viscosity of 220-350 cps, which can be adjusted lower for blade coating; - Higher solids content indicates lower dryer costs, including that SFAE did not adversely affect viscosity; - Eliminates or greatly reduces the need to coat, dip, or spray additional materials onto the surface of the article to impart water, oil, and / or grease resistance. Includes:

[0039] As used herein, "bio-based" refers to a material that is intentionally made from substances derived from living (or formerly living) organisms. In a related aspect, a material that contains at least about 50% of such substances is considered bio-based.

[0040] As used herein, "bind," including grammatical variations thereof, means to adhere or cause to adhere as essentially a single mass.

[0041] As used herein, "support" means a material used to support or carry another material, such as a polymer, pigment, or catalyst.

[0042] As used herein, "cargo" refers to the substance or material delivered by the carrier.

[0043] As used herein, "furnish" means the defined mixture of fibrous and non-fibrous materials, such as fillers, sizing agents, and dyes, in aqueous suspension from which paper is made.

[0044] As used herein, "cellulosic" refers to a natural, synthetic, or semi-synthetic material that can be formed or extruded into an object (e.g., bag, sheet) or film or filament and can be used to make such an object, film, or filament, and that is structurally and functionally similar to cellulose, for example, coatings and adhesives (e.g., carboxymethylcellulose). In another example, cellulose is a complex carbohydrate (CH) composed of glucose units that forms the main component of cell walls in most plants. 10 O5) n The cellulose is cellulosic.

[0045] As used herein, "capsule" means a substance or material that contains another substance or material (e.g., a closed container). In a related aspect, micro- and nano- refer to units on the micrometer and nanometer scales.

[0046] As used herein, "coating weight" is the weight of material (wet or dry) applied to a substrate. It is expressed in pounds per ream or grams per square meter as specified.

[0047] As used herein, "Cobb value" refers to the water absorption (as weight of water per unit area) of a sample. The procedure for determining "Cobb value" is performed according to TAPPI Standard 441-om. The Cobb value is calculated by subtracting the initial weight of the sample from the final weight of the sample, then dividing by the area of ​​the sample that is covered by water. The reported value represents the grams of water absorbed per square meter of paper.

[0048] As used herein, "compostable" means that the solid product is biodegradable in soil.

[0049] As used herein, "edge wicking" refers to the absorption of water in a paper structure at the outer limits 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, coatings containing sugar fatty acid esters described herein prevent edge wicking in treated products. In one aspect, a similar problem exists where grease / oil gets trapped in creases that may be present in paper or paper products. The "grease creasing effect" created by folding, pressing, or crushing the paper structure can be defined as the absorption of grease in the paper structure.

[0050] As used herein, "effect," including grammatical variations thereof, means imparting a particular property to a particular material.

[0051] As used herein, "hydrophobic material" refers to a material 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 materials.

[0052] As used herein, "hydrophobic" means the property of being water repellent and tending to repel and not absorb water.

[0053] As used herein, "lipid resistance" or "oleophobicity" refers to the property of being lipid repellent and tending to repel and not absorb lipids, grease, fats, etc. In a related embodiment, grease resistance can be measured by the "3M Kit" test or the TAPPI T559 Kit test. In another related embodiment, the "second oleophobic material," if any, is a material that has lipid resistance, such as perfluoroalkyl or polyfluoroalkyl.

[0054] As used herein, "micelle," including grammatical variations, refers to an aggregate of molecules in a colloidal solution.

[0055] As used herein, "emulsion" means a mixture of two or more liquids that are normally immiscible (cannot be mixed or blended). In a related aspect, an emulsion can be water-in-oil (w / o), oil-in-water (o / w), or a double emulsion (e.g., w / o / w).

[0056] As used herein, "cellulose-containing material" or "cellulose-based material" refers to a composition consisting essentially of cellulose, including, but not limited to, paper, paper sheets, paperboard, paper pulp, food storage cartons, parchment paper, cake board, butcher paper, release paper / liners, food storage bags, shopping bags, shipping bags, bacon board, insulation materials, tea bags, coffee or tea containers, compost bags, tableware, containers for holding hot or cold beverages, cups, lids, plates, carbonated liquid storage bottles, gift cards, non-carbonated liquid storage bottles, food wrap, garbage disposal containers, food handling equipment, fabric fibers (e.g., cotton or cotton blends), water storage and transport equipment, alcoholic or non-alcoholic beverages, outer casings or screens for electronic products, interior or exterior components of furniture, curtains, and upholstery.

[0057] As used herein, "release paper" refers to a paper sheet used to prevent a tacky surface from prematurely adhering to an adhesive or mastic. In one aspect, the coatings disclosed herein can be used to replace or reduce the use of silicon or other coatings to produce materials with low surface energy. Determining surface energy can be easily accomplished by measuring the contact angle (e.g., Optical Tensiometer and / or High Pressure Chamber; Dyne Testing, Staffordshire, United Kingdom) or by using Surface Energy Test Pens or Inks (see, e.g., Dyne Testing, Staffordshire, United Kingdom).

[0058] As used herein, with respect to SFAE, "peelable" means that the SFAE coating, once applied, can be removed from the cellulose-based material (e.g., removable by manipulating physical properties). As used herein, with respect to SFAE, "non-peelable" means that the SFAE coating, once applied, is substantially irreversibly bonded to the cellulose-based material (e.g., removable by chemical means).

[0059] As used herein, "fluffy" refers to a fluffy, solid material having the appearance of raw cotton or Styrofoam® peanuts. In one embodiment, the fluffy material can be made from nanocellulose fibers (e.g., MFC), cellulose nanocrystals, and / or cellulose filaments and sugar fatty acid esters, and the resulting fibers or filaments or crystals are hydrophobic (and dispersible) and can be used in composite materials (e.g., concrete, plastics, etc.).

[0060] As used herein, "fibers in solution" or "pulp" refers to lignocellulosic fibrous material prepared by chemical or mechanical separation of cellulose fibers from wood, fiber crops, or waste paper. In related embodiments where cellulose fibers are treated by the methods disclosed herein, the cellulose fibers themselves contain bound sugar fatty acid esters as isolated entities, and the bound cellulose fibers have properties that are distinct and different from free fibers (e.g., pulp or cellulose fibers or nanocellulose or microfibrillated cellulose-sugar fatty acid ester bound materials do not form hydrogen bonds between fibers as readily as unbound fibers).

[0061] As used herein, "repulpable" means rendering the paper or paperboard product suitable for being crushed into an amorphous, flexible mass for reuse in the manufacture of paper or paperboard.

[0062] As used herein, "adjustable," including grammatical variations thereof, means adjusting or adapting a method to achieve a particular result.

[0063] As used herein, "water contact angle" refers to the angle, measured through a liquid, at which the liquid / vapor interface meets a solid surface. It quantifies the wettability of a solid surface by a liquid. The contact angle reflects the strength with which liquid and solid molecules interact, compared to the strength with which each interacts with its own species. On many highly hydrophilic surfaces, a water droplet exhibits a contact angle between 0° and 30°. Generally, a solid surface is considered hydrophobic if the water contact angle is greater than 90°. Water contact angles can be easily obtained using an optical tensiometer (see, e.g., Dyne Testing, Staffordshire, United Kingdom).

[0064] As used herein, "breathability" refers to breathability, or the ability of a textile to transport moisture. There are at least two different measurement methods. One, the MVTR (Moisture Vapor Transmission Rate) test according to ISO 15496, indicates the breathability (WVP) of a fabric and therefore its ability to transport sweat to the outside air. The measurement determines the number of grams of moisture (water vapor) that pass through one square meter of fabric in 24 hours (the higher the level, the more breathable it is).

[0065] In one embodiment, the TAPPI T 530 Hercules Sizing Test (i.e., Paper Sizing Test by Ink Resistance) may be used to determine waterfastness. Ink resistance by the Hercules method is best classified as a test that directly measures the extent of penetration. Others classify it as a speed of penetration test. There is no single test that "measures sizing" best. Test selection depends on the end use and mill control needs. This method is particularly suitable for use as a mill control sizing test to accurately detect changes in sizing levels. It provides the sensitivity of the ink float test while providing reproducible results, reducing test time, and automatically determining the endpoint.

[0066] Sizing, measured by the resistance to the penetration of aqueous liquids through or absorption by the paper, is an important characteristic of many papers, typical of which are bag, container board, meat wrap, writing, and some printing grades.

[0067] Such a method may be used to monitor the production of paper or paperboard for a particular end-use, provided that an acceptable correlation is established between the test value and the end-use performance of the paper. Due to the nature of the test and the penetrant, it may not correlate sufficiently well to be applicable to all end-use requirements. This method measures sizing by penetration. Other methods measure sizing by surface contact, surface penetration, or absorption. Size tests are selected based on their ability to simulate the means of water contact or absorption in the end-use. This method can also be used to optimize sizing chemical usage costs.

[0068] As used herein, "oxygen permeability" refers to the degree to which a polymer allows the passage of a gas or fluid. The oxygen permeability (Dk) of a material is a function of the diffusivity (D) (i.e., how quickly oxygen molecules traverse the material) and the solubility (k) (or the amount of oxygen molecules absorbed per volume of material). The oxygen permeability (Dk) value is typically between 10 and 150 x 10 -11 (cm 2 ml O2 / (s ml mmHg). A semi-logarithmic relationship has been demonstrated between hydrogel water content and oxygen permeability (units: Barrer). The International Organization for Standardization (ISO) specifies permeability using the SI unit of hectopascal (hPa) for pressure. Therefore, Dk = 10 -11 (cm 2 ml O2) / (s ml hPa). Barrer units can be converted to hPa by multiplying them by the constant 0.75.

[0069] As used herein, "biodegradable," including grammatical variations thereof, means capable of being broken down by the action of living organisms (eg, by microorganisms), especially into harmless products.

[0070] As used herein, "recyclable," including grammatical variations thereof, means a material that can be treated or processed (for second-hand and / or scrap materials) to make said material suitable for reuse.

[0071] As used herein, "latex" refers to a stable dispersion (emulsion) of polymeric particles in an aqueous medium. Latex is found in nature, but synthetic latex can be made by polymerizing monomers such as styrene that have been emulsified with surfactants. Naturally occurring latex is a milky fluid found in 10% of all flowering plants (angiosperms). It is a complex emulsion of proteins, alkaloids, starches, sugars, oils, tannins, resins, and gums that coagulates when exposed to air.

[0072] As used herein, "filler" means a finely divided white mineral (or pigment) added to a papermaking furnish to improve the optical and physical properties of the sheet. The particles serve to fill the spaces and interstices between the fibers, thus producing a sheet with increased brightness, opacity, smoothness, gloss, and printability, but generally reduced bond and tear strength. Common papermaking fillers include clay (kaolin, bentonite), calcium carbonate (both GCC and PCC), talc (magnesium silicate), and titanium dioxide.

[0073] As used herein, "tackiness" refers to the quality or tendency of a material to remain adhered to a surface that comes into contact with said material, as measured by ASTM D4501.

[0074] As used herein, "Gurley second" or "Gurley number" is a unit of measurement indicating the number of seconds required for 100 cubic centimeters (deciliters) of air to pass through 1.0 square inch of a given material at a pressure differential of 4.88 inches (0.176 psi) of water (ISO 5636-5:2003) (porosity). Furthermore, for stiffness, the "Gurley number" is a unit of measurement for a portion of a material that measures the force required to deflect a given amount (1 milligram force) of the material when held vertically. Such values ​​can be measured with a Gurley Precision Instruments device (Troy, New York).

[0075] 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 molecule.

[0076] Griffin's method for nonionic surfactants, described in 1954, HLB=20*M h / M [In the formula, M h where M is the molecular mass of the hydrophilic portion of the molecule, and M is the molecular mass of the entire molecule. The results are expressed 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.

[0077] The HLB value can be used to predict the surfactant properties of a molecule. <10: Fat-soluble (water-insoluble) >10: Water-soluble (fat-insoluble) 1.5~3: Defoamer 3-6: W / O (water-in-oil) emulsifier 7-9: Wetting and spreading agent 13-15: Cleaning agent 12-16: O / W (oil-in-water) emulsifier 15-18: Solubilizers or hydrotropes

[0078] In some embodiments, the HLB values ​​of the sugar fatty acid esters (or compositions comprising the esters) disclosed herein can be in the lower range. In other embodiments, the HLB values ​​of the sugar fatty acid esters (or compositions comprising the esters) disclosed herein can be in the medium to higher range. In one embodiment, a mixture of SFAEs having different HLB values ​​can be utilized.

[0079] As used herein, "SEFOSE®" refers to a sucrose fatty acid ester containing one or more unsaturated fatty acids (soybean oil fatty acid ester) made from soybean oil and commercially available from Procter & Gamble Chemicals (Cincinnati, Ohio) under the trade name SEFOSE® 1618U (see polysoybean oil fatty acid sucrose below). As used herein, "OLEAN®" refers to a sucrose fatty acid ester of the formula C n+12 H 2n+22 O 13 SFAE is the name for sucrose fatty acid esters in which all fatty acids are saturated and is available from Procter & Gamble Chemicals. SFAE can also be purchased from Mitsubishi Chemical Foods Corporation (Tokyo, Japan), which offers a variety of such SFAEs.

[0080] As used herein, "soybean oil fatty acid ester" refers to a mixture of salts of fatty acids derived from soybean oil.

[0081] As used herein, "oilseed fatty acids" refers to 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, flaxseed, hazelnut, wheat, rice, potato, cassava, legumes, camelina seed, mustard seed, and combinations thereof.

[0082] As used herein, "wet strength" refers to a measure of how well the web of fibers holding paper together can resist breaking forces when the paper is wet. Wet strength can be measured using a Finch Wet Strength Device from Thwing-Albert Instrument Company (West Berlin, NJ). In this case, wet strength is typically provided by wet strength additives such as kymene, cationic glyoxylated resins, polyamidoamine-epichlorohydrin resins, polyamine-epichlorohydrin resins, including epoxide resins. In one embodiment, cellulose-based materials coated with the SFAE disclosed herein provide such wet strength in the absence of such additives.

[0083] As used herein, "wet" means filled with or saturated with water or another liquid.

[0084] In one embodiment, the method disclosed herein includes mixing a latex with inorganic particles (e.g., clay, talc, calcium carbonate) to form a slurry, blending the slurry with a sugar fatty acid ester to form an aqueous coating, and applying the coating to a cellulosic material, optionally including exposing the contacted cellulosic material to heat, radiation, a catalyst, or a combination thereof for a time sufficient to bond the coating to the cellulosic 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. Additionally, the resulting cellulosic material surface exhibits a lower Cobb value compared to the surface of a cellulosic material that has not been so treated.

[0085] As disclosed herein, all sugar fatty acid esters, including mono-, di-, and trisaccharides, are suitable for use in connection with this aspect of the disclosure. In a related aspect, the sugar fatty acid ester can be a mono-, di-, tri-, tetra-, penta-, hexa-, hepta-, or octa-ester, and combinations thereof, including that the fatty acid moiety can be saturated, unsaturated, or a combination thereof.

[0086] Without being bound by any theory, the interaction between the sugar fatty acid ester and the cellulose-based material can be due to ionic, hydrophobic, van der Waals interactions, or covalent bonds, or a combination thereof. In a related aspect, the binding of the sugar fatty acid ester to the cellulose-based material can be substantially irreversible (e.g., using an SFAE that includes a combination of saturated and unsaturated fatty acids).

[0087] Also, the sugar fatty acid ester bond alone in sufficient concentration is sufficient to render the cellulosic material hydrophobic, i.e., hydrophobicity is achieved through the sugar fatty acid ester bond alone, including other properties such as strengthening, stiffening, and bulking of the cellulosic material, among others, without the addition of waxes, rosins, resins, diketenes, shellacs, vinyl acetates, PLA, PEI, oils, other water-repellent chemicals, or combinations thereof (i.e., second hydrophobic materials).

[0088] An advantage of the present disclosure is that multiple fatty acid chains react with cellulose and two sugar molecules in the structure, for example, the disclosed sucrose fatty acid esters, resulting in a tight crosslinked network and improved strength in fibrous webs such as paper, paperboard, airlaid and wet-laid nonwovens, and textiles, thus overcoming the potentially undesirable effects of some fillers (e.g., calcium carbonate and reduced bond and tear strength). This is not typically seen with other sizing or hydrophobic treatment chemistries. The disclosed sugar fatty acid esters also develop / increase wet strength, a property not present when using many other water-resistant chemistries.

[0089] Another advantage is that the disclosed sugar fatty acid esters soften fibers and increase the space between them, thereby increasing bulk without substantially increasing weight. Fibers and cellulose-based materials modified as disclosed herein may also be repulped. Furthermore, water, for example, cannot easily "push" through the low surface energy barrier and penetrate into the sheet.

[0090] Saturated SFAEs are typically solid at nominal processing temperatures, while unsaturated SFAEs are typically liquid. Therefore, it is possible to form uniform and stable dispersions of saturated SFAEs in aqueous coatings without significant interaction or incompatibility with other coating components, which are typically hydrophilic. Such dispersions also allow for the preparation of high concentrations of saturated SFAEs without adversely affecting coating rheology, uniform coating application, or coating performance characteristics. Upon heating, drying, and compounding of the coating layer, the saturated SFAE particles melt and spread, rendering the coating surface hydrophobic. In one embodiment, a method for producing a bulky fibrous structure that retains strength even when exposed to water is disclosed. The dried fiber slurry typically forms a dense structure that disintegrates easily upon exposure to water. Molded fibrous products made using the disclosed method include paper plates, drink holders (e.g., cups), lids, food trays, and packaging that are lightweight, strong, and resistant to exposure to water and other liquids.

[0091] In one embodiment, sugar fatty acid esters can be mixed with polyvinyl alcohol (PvOH) to produce a size for water-resistant coatings. As disclosed herein, a synergistic relationship between sugar fatty acid esters and PvOH has been identified, including the ability to reduce the amount of PvOH in inorganic mixtures. PvOH is known in the art to be a good film former and to form strong hydrogen bonds with cellulose, but it has poor resistance to water, especially hot water. In one aspect, the use of PvOH aids in emulsifying the sugar fatty acid esters into aqueous coatings. In one aspect, PvOH provides the sugar fatty acid esters with an abundant source of OH groups for crosslinking along the fiber, increasing paper strength, particularly wet strength, and water resistance, beyond what is possible with PvOH alone. For saturated sugar fatty acid esters with free hydroxyls on the sugar, crosslinkers such as dialdehydes (e.g., glyoxal, glutaraldehyde, etc.) can also be used.

[0092] 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 of the present disclosure, and it is believed that all such methods are applicable for use within the scope of the present disclosure. For example, in some embodiments, it may be preferable to synthesize the fatty acid ester by esterifying sugar with one or more fatty acid moieties obtained from oilseeds, including, but not limited to, soybean oil, sunflower oil, olive oil, canola oil, peanut oil, and mixtures thereof.

[0093] 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 have been replaced by an ester moiety. In a related aspect, the disaccharide ester is represented by formula I

[0094] [ka]

[0095] [ka]

[0096] wherein "R" is a linear, branched, or cyclic, saturated or unsaturated aliphatic or aromatic moiety having from about 8 to about 40 carbon atoms. wherein at least one "A", at least one, at least two, at least three, at least four, at least five, at least six, at least seven, and all eight "A" moieties of the formula correspond to Structure I. In a related aspect, the sugar fatty acid esters described herein can be mono-, di-, tri-, tetra-, penta-, hexa-, hepta-, or octa-esters, and combinations thereof, and the aliphatic groups can be all saturated aliphatic groups or can include saturated and / or unsaturated groups, or combinations thereof.

[0097] Suitable "R" groups include any form of aliphatic moiety, including those containing one or more substituents, which may occur on any carbon in the moiety. Also included are aliphatic moieties that contain functional groups within the aliphatic moiety, such as ether, ester, thio, amino, phospho, etc. Also included are oligomeric and polymeric aliphatic moieties, such as sorbitan, polysorbitan, and polyalcohol moieties. Examples of functional groups that can be added to an aliphatic (or aromatic) moiety containing an "R" group include, but are not limited to, halogen, alkoxy, hydroxy, amino, ether, and ester functional groups. In one embodiment, the moiety may have crosslinkable functionality. In another embodiment, the SFAE (e.g., activated clay / pigment particles) may be crosslinked to a surface. In another embodiment, the double bonds present on the SFAE may be used to facilitate reaction with other surfaces.

[0098] Suitable disaccharides include raffinose, maltodextrose, galactose, sucrose, glucose combinations, fructose combinations, maltose, lactose, mannose combinations, erythrose combinations, isomaltose, isomaltulose, trehalose, trehalulose, cellobiose, laminaribiose, chitobiose, and combinations thereof.

[0099] In one embodiment, the substrate for adding the fatty acid includes starch, hemicellulose, lignin, or a combination thereof.

[0100] In one embodiment, the composition comprises 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.

[0101] More particularly, the starch can be unmodified starch or starch that has been modified by chemical, physical or enzymatic processes.

[0102] Chemical processing includes the optional treatment of starch with chemical agents to produce modified starch (e.g., plastarch materials). Chemical processing includes, but is 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 starches include the reaction of alkenyl succinic anhydrides, especially octenyl succinic anhydride, with starch to produce hydrophobically esterified starch; the reaction of 2,3-epoxypropyltrimethylammonium chloride with starch to produce cationic starch; the reaction of ethylene oxide with starch to produce hydroxyethyl starch; the reaction of hypochlorite with starch to produce oxidized starch; the reaction of acid with starch to produce acid-depolymerized starch; and the defatting of starch with solvents such as methanol, ethanol, propanol, methylene chloride, chloroform, and carbon tetrachloride to produce defatted starch.

[0103] Physically modified starch is starch that has been physically processed in a manner that provides the physically modified starch. Physical processing includes, but is not limited to, heat treatment of starch in the presence of water, heat treatment of starch in the absence of water, breaking down starch granules by any mechanical means, and treating starch under pressure to melt the starch granules. Physically modified starch can also be prepared by using a combination of any physical treatments. Examples of physically modified starch include heat treatment of starch in an aqueous environment to swell the starch granules without granule rupture; heat treatment of anhydrous starch granules to cause polymer rearrangement; fragmentation of starch granules by mechanical degradation; and pressure treatment of starch granules in an extruder to cause melting of the starch granules.

[0104] Enzymatically modified starch is optionally starch that has been treated with an enzyme to provide the enzymatically modified starch. Enzymatic processing includes, but is not limited to, the reaction of starch with α-amylase, the reaction of starch with protease, the reaction of starch with lipase, the reaction of starch with phosphorylase, the reaction of starch with oxidase, etc. Enzymatically modified starch can be prepared by using any combination of enzyme treatments. Examples of enzymatic processing of starch include reacting alpha-amylase enzymes with starch to produce depolymerized starch; reacting alpha-amylase debranching enzymes with starch to produce debranched starch; reacting protease enzymes with starch to produce starch with reduced protein content; reacting lipase enzymes with starch to produce starch with reduced lipid content; reacting phosphorylase enzymes with starch to produce enzymatically modified phosphated starch; and reacting oxidase enzymes with starch to produce enzymatically oxidized starch.

[0105] The disaccharide fatty acid ester can be a sucrose fatty acid ester according to Formula I, where the "R" groups are aliphatic, linear or branched, saturated or unsaturated, and have from about 8 to about 40 carbon atoms.

[0106] As used herein, the terms "sugar fatty acid ester" and "sucrose fatty acid ester" include compositions of varying purity and mixtures of compounds of any purity level. For example, a sugar fatty acid ester compound can be a substantially pure material, i.e., a compound having a given number of "A" groups substituted with only one type of moiety of Structure I (i.e., all "R" groups are the same and all of the sucrose moieties are substituted to the same degree). It also includes compositions containing blends of two or more sugar fatty acid ester compounds with different degrees of substitution, but all of the substituents having the same "R" group structure. It also includes compositions that are mixtures of compounds with different degrees of substitution of the "A" groups, where the substituent moieties of the "R" groups are independently selected from two or more "R" groups of Structure I. In a related aspect, the "R" groups can be the same or different, including the sugar fatty acid esters in a composition that can be the same or different (i.e., a mixture of different sugar fatty acid esters).

[0107] In the compositions of the present disclosure, the composition may comprise a sugar fatty acid ester compound having a high degree of substitution. In one embodiment, the sugar fatty acid ester is sucrose polysoybean fatty acid.

[0108] [ka]

[0109] Sugar fatty acid esters can be prepared by esterification with substantially pure fatty acids using known esterification methods.They can also be prepared by transesterification using sugar and fatty acid esters in the form of fatty acid glycerides derived from natural sources, such as oils extracted from oilseeds, such as soybean oil.The transesterification reaction of using fatty acid glycerides to provide sucrose fatty acid esters is described in, for example, 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 WO 1992 / 004361 (A1), all of which are incorporated herein by reference.

[0110] In addition to making hydrophobic sucrose esters via transesterification, similar hydrophobicity can be achieved in cellulosic fibrous articles by directly reacting acid chlorides with polyols containing ring structures similar to sucrose.

[0111] As noted 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, e.g., U.S. Patent No. 6,995,232, incorporated herein by reference in its entirety). As a result of the source of the fatty acids, the feedstock used to prepare sucrose fatty acid esters contains a variety of saturated and unsaturated fatty acid methyl esters having fatty acid moieties containing 12 to 40 carbon atoms. This is reflected in the product sucrose fatty acid esters made from such sources, because the sucrose moiety containing product contains a mixture of ester moiety substituents; 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 esters. To further illustrate this point, sucrose esters derived from soybean oil are a mixture of species with "R" group structures reflecting the fact that soybean oil contains 26% by weight triglyceride of oleic acid (HC—CH]—CH═CH—[CH]—C(O)OH), 49% by weight triglyceride of linoleic acid (HC—[CH]—[—CH—CH═CH]—[—CH—]—C(O)OH), 11% by weight triglyceride of linolenic acid (HC—[—CH—CH═CH—]—[—CH—]—C(O)OH), and 14% by weight of various saturated fatty acid triglycerides listed in the Seventh Ed. of the Merck Index, which is incorporated herein by reference in its entirety. All of these fatty acid moieties are represented in the "R" groups of the substituents of the product sucrose fatty acid esters. Thus, when referring herein to sucrose fatty acid esters as products of reactions employing fatty acid feedstocks derived from natural sources, e.g., soybean oil fatty acid 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 sugar fatty acid ester may exhibit low viscosity (e.g., about 10-2000 centipoise at room temperature or standard pressure). In another aspect, the unsaturated fatty acid may have one, two, three, or more double bonds.

[0112] In one embodiment of the present disclosure, the sugar fatty acid ester, in particular the disaccharide ester, is formed from a fatty acid having an average of 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, or about 20 to about 40 carbon atoms.

[0113] 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 attached to the cellulose-based material as a coating, the SFAE is applied to the surface of the cellulose-based material in a concentration of at least about 0.1 g / m 2 ~Approx. 1.0g / m 2 , about 1.0g / m 2 ~about 2.0g / m 2 , about 2g / m 2 ~about 3g / m 2 In a related aspect, it is present at a coating weight of about 3 g / m 2 ~approx. 4g / m 2 , approximately 4 g / m 2 ~about 5g / m 2 , about 5g / m 2 ~about 10g / m 2 , about 10g / m 2 ~about 20g / m 2In another embodiment, when the cellulose-based material is a solution containing cellulose fibers, the SFAE is present at a concentration of at least about 0.025% (wt / wt) of the total fibers present. In related aspects, it can be present at about 0.05% (wt / wt) to about 0.1% (wt / wt), about 0.1% (wt / wt) to about 0.5% (wt / wt), about 0.5% (wt / wt) to about 1.0% (wt / wt), about 1.0% (wt / wt) to about 2.0% (wt / wt), about 2.0% (wt / wt) to about 3.0% (wt / wt), about 3.0% (wt / wt) to about 4.0% (wt / wt), about 4.0% (wt / wt) to about 5.0% (wt / wt), about 5.0% (wt / wt) to about 10% (wt / wt), or about 10% (wt / wt) to about 50% (wt / wt) of the total fiber present. In another related aspect, the amount of SFAE can be equal to the amount of fiber present. In some embodiments, the SFAE can coat the entire exterior surface of the cellulose-based material (e.g., coat the entire paper piece or cellulose-containing article).

[0114] 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), or about 40% to about 50% (wt / wt) of the sugar fatty acid ester by weight of the coating. In a related aspect, the coating can contain about 25% to about 35% (wt / wt) of the sugar fatty acid ester by weight of the coating.

[0115] In one embodiment, cellulose-based materials include, but are not limited to, paper, paperboard, paper sheets, paper pulp, cups, boxes, trays, lids, release paper / liners, compost bags, shopping bags, shipping bags, bacon board, tea bags, insulation, coffee or tea containers, pipes and conduits, food-grade disposable cutlery, plates and bottles, TV and mobile device screens, clothing (e.g., cotton or cotton blends), bandages, pressure-sensitive labels, pressure-sensitive tapes, feminine products, and medical devices used on or within the body such as contraceptives, drug delivery devices, containers for pharmaceutical materials (e.g., pills, tablets, suppositories, gels, etc.), etc. The disclosed coating technology can also be used on furniture and upholstery, outdoor camping equipment, etc.

[0116] In one aspect, the coatings described herein are resistant to a pH ranging from about 3 to about 9. In related aspects, the pH can be from about 3 to about 4, from about 4 to about 5, from about 5 to about 7, or from about 7 to about 9.

[0117] In one embodiment, there is provided a method for treating the surface of a cellulose-containing (or cellulosic) material, comprising the step of: R-CO-X formula (II) X-CO-R-CO-X1 Formula (III) wherein R is a linear, branched, or cyclic aliphatic hydrocarbon group having 6 to 50 carbon atoms, and X and X1 are independently Cl, Br, R-CO-OR, or O(CO)OR. A method is disclosed that includes applying to a surface a composition containing an alkanoic acid derivative having the formula (III), where X or X1 are the same or different, and the SFAE disclosed herein is a carrier, and the method does not require an organic base, gaseous HCl, VOCs, or a catalyst.

[0118] 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.

[0119] In one embodiment, the sugar fatty acid ester can be an emulsifier and can include a mixture of one or more mono-, di-, tri-, tetra-, penta-, hexa-, hepta-, or octa-esters. In another aspect, the fatty acid portion of the sugar fatty acid ester can include saturated groups, unsaturated groups, or combinations thereof. In one aspect, the sugar fatty acid ester-containing emulsion can contain proteins, polysaccharides, and / or lipids, including, but not limited to, milk proteins (e.g., casein, whey protein, etc.), wheat gluten, gelatin, prolamins (e.g., corn zein), soy protein isolate, starch, acetylated polysaccharides, alginates, carrageenans, chitosan, inulin, long-chain fatty acids, waxes, and combinations thereof.

[0120] In one embodiment, the sugar fatty acid ester emulsifiers disclosed herein may be used to carry coatings or other chemicals used in papermaking, including, but not limited to, agarite, esters, diesters, ethers, ketones, amides, nitriles, aromatics (e.g., xylene, toluene), acid halides, anhydrides, alkyl ketene dimer (AKD), alabaster, alganic acid, alum, alvanic, glue, barium carbonate, barium sulfate, chlorine dioxide, dolomite, diethylenetriamine pentaacetate, EDTA, enzymes, formamidine sulfate, guar gum, gypsum, lime, magnesium bisulfate, milk of lime, milk of magnesia, polyvinyl alcohol (PvOH), rosin, rosin soap, satin, soap / fatty acids, sodium bisulfate, soda ash, titania, surfactants, starch, modified starch, hydrocarbon resins, polymers, waxes, polysaccharides, proteins, latex, and combinations thereof. In one embodiment, the disclosed mixtures can contain one or more SFAEs and one or more of the following inorganic particles: clay (kaolin, bentonite), calcium carbonate (both GCC and PCC), talc (magnesium silicate), and titanium dioxide.

[0121] In one embodiment, the cellulose-containing material produced by the methods disclosed herein exhibits increased hydrophobicity or water resistance compared to the untreated cellulose-containing material. In a related aspect, the treated cellulose-containing material exhibits increased oleophobicity or grease resistance compared to the untreated cellulose-containing material. 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).

[0122] In one embodiment, the treated cellulose-containing material may have improved mechanical properties compared to the same untreated material. For example, paper bags treated with the methods disclosed herein exhibit increased burst strength, Gurley number, tensile strength, and / or maximum load energy. In one aspect, the burst strength increases by about 0.5 to 1.0 times, about 1.0 to 1.1 times, about 1.1 to 1.3 times, or about 1.3 to 1.5 times. In another aspect, the Gurley number increases by about 3 to 4 times, about 4 to 5 times, about 5 to 6 times, or about 6 to 7 times. In yet another aspect, the tensile strain increases by about 0.5 to 1.0 times, about 1.0 to 1.1 times, about 1.1 to 1.2 times, or about 1.2 to 1.3 times. In yet another aspect, the maximum load energy increases by about 1.0 to 1.1 times, about 1.1 to 1.2 times, about 1.2 to 1.3 times, or about 1.3 to 1.4 times.

[0123] In one embodiment, the cellulose-containing material is a base paper containing microfibrillated cellulose (MFC) or cellulose nanofibers (CNF), as described, for example, in U.S. Patent Application Publication No. 2015 / 0167243 (incorporated herein by reference in its entirety), where the MFC or CNF is added during the forming and papermaking process and / or added to a preformed layer as a coating or secondary layer to reduce the porosity of the base paper. In a related aspect, the base paper is contacted with the sugar fatty acid ester described above. In another related aspect, the contacted base paper is further contacted with polyvinyl alcohol (PVOH). In one embodiment, the resulting contacted base paper is controllably water- and oil-resistant. In a related aspect, the resulting base paper may exhibit a Gurley value of at least about 10-15 (i.e., Gurley air resistance (seconds / 100 cc, 20 oz. cylinder)), or at least about 100, or at least about 200 to about 350. In one aspect, the sugar fatty acid ester coating can be a laminate of one or more layers, or one or more layers can be formed as a laminate, or the amount of one or more layers of coating can be reduced to achieve the same performance effect (e.g., water resistance, grease resistance, etc.). In a related aspect, the laminate can include a biodegradable and / or configurable heat seal or adhesive.

[0124] In one embodiment, the sugar fatty acid ester may be formulated as an emulsion, and the selection of the emulsifier and the amount used will be dictated by the nature of the composition and the ability of the emulsifier to promote dispersion of the sugar fatty acid ester. In one aspect, the emulsifier includes, but is not limited to, water, buffers, polyvinyl alcohol (PVOH), carboxymethylcellulose (CMC), latex, milk protein, wheat gluten, gelatin, prolamin, soy protein isolate, starch, acetylated polysaccharides, alginate, carrageenan, chitosan, inulin, long-chain fatty acids, waxes, agar, alginate, glycerol, gums, lecithin, poloxamer, monoglycerol, diglycerol, monosodium phosphate, monostearate, propylene glycol, detergents, cetyl alcohol, and combinations thereof. In other embodiments, the ratio of sugar ester to 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 one skilled in the art that the ratio may be varied depending on the desired characteristics of the final product.

[0125] In one embodiment, the sugar fatty acid esters can be combined with one or more coating ingredients (singly or in combination) for internal and surface sizing, including but not limited to binders (e.g., starch, soy protein, polymer emulsions, PvOH, latex), and additives (e.g., glyoxal, glyoxalated resins, zirconium salts, calcium stearate, lecithin oleate, polyethylene emulsions, carboxymethyl cellulose, acrylic polymers, alginates, polyacrylate rubbers, polyacrylates, microbicides, oil-based antifoams, silicone-based antifoams, stilbenes, direct dyes, and acid dyes). In a related aspect, such ingredients can provide one or more properties, including but not limited to, building a microporous structure, providing a light-scattering surface, improving ink acceptance, improving gloss, binding pigment particles, bonding the coating to the paper, base sheet support, filling the pores of the pigment structure, reducing water sensitivity, resisting wet pick in offset printing, preventing blade scratching, improving gloss in supercalendering, reducing dusting, adjusting coating viscosity, achieving water retention, dispersing pigments, maintaining coating dispersion, preventing coating / coating colorant degradation, controlling foaming, reducing entrained air and coating craters, increasing whiteness and brightness, controlling color and hue, etc. It will be apparent to one skilled in the art that the combinations may vary depending on the properties desired in the final product.

[0126] In one embodiment, the method employing the sugar fatty acid ester 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 Bio-PBS, a PEI layer, etc.), providing a layer of material that exhibits desired properties (e.g., water resistance, low surface energy, etc.), thereby reducing the amount of primary / secondary layer required to achieve the same 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.

[0127] 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 temperatures from 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 temperatures from about 200°C to about 300°C.

[0128] The substrate can be treated with the modifying composition, for example, by immersion, exposing the surface to the composition for less than 1 second, although the substrate may be dried (e.g., at about 80-150°C) before application. The substrate can be heated to dry the surface, after which the modified material is ready for use. In one aspect, in accordance with the methods disclosed herein, the substrate can be treated with any suitable coating / sizing method typically practiced in paper mills (e.g., see Smook, G., Surface Treatments, Handbook for Pulp & Paper Technologists, (2016), 4 th Ed., Cpt. 18, pp. 293-309, TAPPI Press, Peachtree Corners, GA USA).

[0129] In some applications, the material may be dried before processing, but no special preparation of the material is necessary when practicing the present disclosure. 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 can be applied by conventional size presses (vertical, inclined, horizontal), gate roll size presses, metering size presses, calendar size application, tube sizing, on-machine, off-machine, single-sided coaters, double-sided coaters, short dwell, simultaneous double-sided coaters, blade or rod coaters, gravure coaters, gravure printing, flexographic printing, inkjet printing, laser printing, supercalendering, and combinations thereof.

[0130] 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, other non-wood fibers (such as sisal, jute or hemp, flax or straw), cellulose nanocrystals, or nanofibrillated cellulose.

[0131] In one embodiment, the sugar fatty acid ester coating is applied in an amount sufficient to completely coat 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 a container, the entire inner surface of a container, or a combination thereof, or to one or both sides of a base paper. In other embodiments, the entire upper surface of a film may be coated with the sugar fatty acid ester coating, or the entire lower surface of a film may be coated with the sugar fatty acid ester coating, or a combination thereof. In some embodiments, the holes of an instrument / meter may be coated with the coating, or the outer surface of an instrument / meter may be coated with the sugar fatty acid ester coating, or a combination thereof. In one embodiment, the sugar fatty acid ester coating is applied in an amount sufficient to partially coat at least one surface of the cellulose-containing material. For example, only the surface exposed to the ambient atmosphere may be coated with the sugar fatty acid ester coating, or only the surface not exposed to the ambient atmosphere may be coated with the sugar fatty acid ester coating (e.g., masked). As will be apparent to one skilled in the art, the amount of the sugar fatty acid ester coating applied may depend on the use of the material to be coated. In one aspect, one surface may be coated with a sugar fatty acid ester coating, and the opposite surface may be coated with an agent including, but not limited to, proteins, wheat gluten, gelatin, prolamins, soy protein isolates, starches, modified starches, acetylated polysaccharides, alginates, carrageenans, chitosan, inulin, long chain fatty acids, waxes, and combinations thereof. In a related aspect, an SFAE can be added to the furnish, and the resulting material on the web may be provided with an additional coating of the SFAE.

[0132] Suitable coating methods may be used to deliver any of the various sugar fatty acid ester coatings and / or emulsions applied in the course of practicing this aspect of the method. In one embodiment, sugar fatty acid ester coating methods include dipping, spraying, painting, printing, and optional combinations of any of these methods, alone or in conjunction with other coating methods adapted to practice the disclosed method.

[0133] For example, by increasing the concentration of sugar fatty acid ester, the compositions disclosed herein can react more broadly with the cellulose being treated, and the end result still exhibits improved water / lipid repellency properties. However, higher coat weights do not necessarily equate to increased water resistance. In one aspect, various catalysts allow for faster "curing," allowing the quality of the sugar fatty acid ester to be precisely tailored to meet specific applications.

[0134] It will be apparent to one skilled in the art that the choice of cellulose to be treated, sugar fatty acid ester, reaction temperature, and exposure time are process parameters that may be optimized by routine experimentation to suit any particular application of the final product.

[0135] The derivatized materials have altered physical properties that can be defined and measured using appropriate tests known in the art. For hydrophobicity, analytical protocols include, but are not limited to, contact angle measurements and moisture uptake. Other properties include stiffness, WVTR, porosity, tensile strength, lack of substrate degradation, burst and tear properties. Specific standardized protocols to be followed are defined by the American Society for Testing and Materials (Protocol ASTM D7334-08).

[0136] The permeability of surfaces to various gases, such as water vapor and oxygen, can also be modified by sugar fatty acid ester coating methods to enhance the barrier function of the material. The standard unit for measuring permeability is the barrer, and protocols for measuring these parameters are available in the public domain (ASTM Standard F2476-05 for water vapor and ASTM Standard F2622-8 for oxygen).

[0137] In one embodiment, materials treated according to the procedures of the present disclosure exhibit complete biodegradability as measured by degradation in an environment under microbial attack.

[0138] Various methods are available to define and test biodegradability, including the shake flask method (ASTM E1279-89(2008)) and the Zahn-Wellens test (OECD TG 302 B).

[0139] Various methods are available for determining and testing compostability, including but not limited to ASTM D6400.

[0140] Materials suitable for treatment with the methods of the present disclosure include various forms of cellulose, such as cotton fibers, plant fibers such as flax, wood fibers, regenerated cellulose (rayon and cellophane), partially alkylated cellulose (cellulose ethers), partially esterified cellulose (acetate rayon), and other modified cellulose materials, all of which have a significant percentage of surface area available for reaction / bonding. As noted above, the term "cellulose" encompasses these materials as well as others with similar polysaccharide structures and similar properties. Of these, the relatively new material microfibrillated cellulose (cellulose nanofibers) (see, e.g., U.S. Pat. No. 4,374,702; U.S. Patent Application Publication Nos. 2015 / 0167243; and 2009 / 0221812, all of which are incorporated herein by reference) is particularly suited to this application. In other embodiments, the 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.

[0141] In addition to increasing its hydrophobicity, the modifications of cellulose disclosed herein may also increase its tensile strength, flexibility, and stiffness, thereby further broadening its range of uses. Biodegradable and partially biodegradable products made from or by using the modified cellulose disclosed herein, including recyclable and compostable products, are all within the scope of this disclosure.

[0142] Among the possible uses of the coating technology, such items include, but are not limited to, containers for all purposes, paper, paperboard, paper pulp, cups, lids, boxes, trays, release paper / liners, compost bags, shopping bags, pipes and water lines, disposable food cutlery, plates and bottles, screens for TVs and mobile devices, clothing (e.g., cotton or cotton blends), 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. The disclosed coating technology can also be used on furniture and upholstery, outdoor camping equipment, etc.

[0143] The following examples are intended to illustrate, but not limit, the present disclosure. [Example]

[0144] [Example 1] (Sugar fatty acid ester blend) SEFOSE® is a liquid at room temperature, and all coatings / emulsions containing this material were applied at room temperature using a benchtop drawdown device. Rod types and sizes were varied to produce different coat weights.

[0145] (Formulation 1) 50 ml of SEFOSE® was added to a solution containing 195 ml of water and 5 grams of carboxymethylcellulose (FINNFIX® 10; CP Kelco, Atlanta, GA). The formulation was mixed for 1 minute using a Silverson homogenizer set at 5000 rpm. The emulsion was coated onto a 50-gram base sheet made from bleached hardwood pulp and an 80-gram sheet composed of unbleached softwood. Both papers were placed in an oven (105°C) for 15 minutes to dry. After removing from the oven, the sheets were placed on a lab bench and 10 drops of room-temperature water were pipetted onto each sheet. The base sheet selected for this test readily absorbed the water droplets, while sheets coated with various amounts of SEFOSE® exhibited increasing levels of water resistance as the coat weight increased (see Table 1).

[0146] [Table 1]

[0147] It was observed that water resistance was poor with the heavier sheets and that water resistance was not achieved unless the sheets were dry.

[0148] (Formulation 2) Addition of SEFOSE® to cup stock: (Note this is a single ply stock without MFC treatment. 110 grams of paperboard made with eucalyptus pulp). 50 grams of SEFOSE® was added to 200 grams of 5% cooked ethylated starch (Ethylex 2025) and mixed for 30 seconds using a benchtop caddy mill. The paper sample was 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 holdout time was measured and recorded in the table below. Water penetration of the untreated paperboard control was instantaneous (see Table 2).

[0149] [Table 2]

[0150] (Formulation 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 examples, as well as to a piece of fiberboard and a quantity of cotton fabric. When a drop of water was placed on the sample, penetration into the substrate occurred within 30 seconds, but after drying in an oven at 105°C for 15 minutes, the drop evaporated before being absorbed into the substrate.

[0151] Further investigations concerned whether SEFOSE® could be compatible with compounds used in oil- and grease-resistant coatings. SEFOSE® is useful for water resistance and stiffness improvement. 240 g of paperboard stock was used to conduct the stiffness tests. Results are shown in Table 3 below. These data were obtained at a single coat weight of 5 grams per square meter and are reported as an average of five samples. Results are in Taber stiffness units recorded using our V-5 Taber stiffness tester, Model 150-E.

[0152] [Table 3]

[0153] [Example 2] (Binding of sugar esters to cellulosic substrates) To determine whether SEFOSE® reversibly binds to cellulosic materials, pure SEFOSE® was mixed with pure cellulose in a 50:50 ratio. The SEFOSE® was reacted at 300°F for 15 minutes, and the mixture was extracted with methylene chloride (a non-polar solvent) or distilled water. The samples were refluxed for 6 hours, and a gravimetric analysis of the samples was performed.

[0154] [Table 4]

[0155] [Example 3] (Survey of cellulosic surfaces) Scanning electron microscope images of base paper with and without MFC demonstrate that a less porous base potentially requires far less waterproofing agent to react with the surface. Figures 1-2 show untreated, medium-porosity Whatman filter paper. Figures 1 and 2 demonstrate the relatively large exposed surface area available for derivatization. However, the highly porous sheet also provides ample escape routes for water. Figures 3 and 4 show a side-by-side comparison of a paper made from recycled pulp before and after coating with MFC (these are two magnifications of the same sample; the left side of the image clearly does not contain MFC). Tests show that derivatization of a much less porous sheet offers greater promise for long-term water / vapor barrier performance. The final two images are, for comparison, close-ups of the average "pores" of a single filter paper and a CNF-coated paper at similar magnification.

[0156] From the above data, it is clear that there is a critical point, with the addition of more material, with a corresponding increase in performance. Without being bound by any theory, the reaction appears to be faster with unbleached paper, suggesting that the presence of lignin may facilitate the reaction.

[0157] In fact, products like SEFOSE® are liquid and can be easily emulsified, suggesting that they could be easily adapted to work with coating equipment commonly used in paper mills.

[0158] [Example 4] "Phluphi" Liquid SEFOSE® was mixed and reacted with bleached hardwood fibers to produce various formulations that yielded waterproof handmade sheets. It was found that when sucrose esters were mixed with the pulp prior to sheet formation, the majority of the sucrose esters were retained with the fibers. After sufficient heating and drying, brittle, fluffy, yet highly hydrophobic handmade sheets were 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 manually stirred, and the water was poured into a standard handmade sheet mold. The resulting fiber mat was removed and dried at 325°F for 15 minutes. The resulting sheets exhibited significant hydrophobicity and significantly reduced hydrogen bonding between the fibers themselves (water contact angles greater than 100 degrees were observed). An emulsifier can be added. The ratio of SEFOSE® to fiber can be approximately 1:100 to 2:1.

[0159] Subsequent testing showed that talc was the only spectator in this and was excluded from further testing.

[0160] [Example 5] Environmental Effects on SEFOSE® Coating Properties In an attempt to better understand the reaction mechanism between sucrose esters and fibers, low viscosity coatings were applied to bleached kraft sheet that had been treated with wet strength resin but was not water resistant (no sizing). All coatings were below 250 cps as measured using a Brookfield viscometer at 100 rpm.

[0161] SEFOSE® was emulsified with Ethylex 2025 (starch) and applied to paper via gravure roll. For comparison, SEFOSE® was also emulsified with Westcote 9050 PvOH. As shown in Figure 5, oxidation of the double bonds in SEFOSE® is enhanced by the presence of heat and additional chemical environments that enhance the oxidative chemistry (see also Table 5).

[0162] [Table 5]

[0163] [Example 6] (Effect of unsaturated vs. saturated fatty acid chains) SEFOSE® was reacted with bleached softwood pulp and dried to form sheets. The extent of reaction with the pulp was then determined by extraction with CHCl, toluene, and water. Extraction was performed for at least 6 hours using Soxhlet extraction glassware. The extraction results are shown in Table 6 below.

[0164] [Table 6]

[0165] The data shows that essentially all of the SEFOSE® remains on the sheet. To further verify this, the same procedure was performed on pulp alone, and the results show that approximately 0.01 g was obtained per 10 g of pulp. Without being bound by any theory, this could easily be explained as residual pulping chemicals that had not been completely removed, or more likely extractables.

[0166] The experiment was repeated using pure fibers of cellulose (e.g., α-cellulose from Sigma Aldrich, St. Louis, MO). As long as the SEFOSE® loading level remained below about 20% of the fiber mass, more than 95% of the SEFOSE® mass was retained with the fiber and was not extracted with either polar or nonpolar solvents. Without being bound by any theory, optimizing the baking time and temperature may further enhance the sucrose esters remaining with the fiber.

[0167] As the data show, it is generally clear that SEFOSE® cannot be extracted from the material after drying. On the other hand, when a fatty acid containing all saturated fatty acid chains (e.g., OLEAN®, available from Procter & Gamble Chemicals, Cincinnati, Ohio) is used in place of SEFOSE®, nearly 100% of the OLEAN® in the material can be extracted using hot water (above 70°C). OLEAN® is identical to SEFOSE®, the only change being that saturated fatty acids are attached (OLEAN®) instead of unsaturated fatty acids (SEFOSE®).

[0168] Another notable aspect is that the multiple fatty acid chains are reactive with cellulose and the two sugar molecules in the structure, allowing SEFOSE® to form a tight crosslinked network, leading to improved strength in fibrous webs such as paper, paperboard, airlaid and wetlaid nonwovens, and textiles.

[0169] [Example 7] (Addition of SEFOSE® to achieve water resistance) Both hardwood and softwood kraft pulp were used to prepare 2-gram and 3-gram handsheets. When SEFOSE® was added to a 1% pulp slurry at levels above 0.1%, the water was drained, and handsheets were formed; the SEFOSE® was retained with the fibers, imparting water resistance. At 0.1% to 0.4% SEFOSE®, water beaded on the surface for a few seconds or less. At SEFOSE® loadings above 0.4%, the time to water resistance increased rapidly to minutes, then hours, for loading levels above 1.5%.

[0170] [Example 8] (Manufacturing bulky fiber materials) When SEFOSE® is added to pulp, it acts to soften the fibers, increasing the space between them and increasing bulk. For example, a 3% slurry of hardwood pulp containing 125 g (dry) of pulp was found to occupy a volume of 18.2 cubic centimeters when drained and dried. 12.5 g of SEFOSE® was added to the same 3% hardwood pulp slurry containing an equal amount of 125 g of dry fiber. Upon draining and drying, the resulting mat occupy 45.2 cubic centimeters.

[0171] 30 g of standard bleached hardwood kraft pulp (manufactured by Old Town Fuel and Fiber, LLC, Old Town, ME) was sprayed with SEFOSE®, which had been warmed to 60° C. 3 The mixture was poured into a handsheet mold and dried at 105°C. The resulting hydrophobic pulp was 8.1 cm 3 This material was cut into 2-inch squares and placed in a hydraulic press where 50 tons of pressure was applied for 30 seconds. The volume of the squares was significantly reduced, but still occupied a volume 50% higher than the same 2-inch squares cut for the no-pressure control.

[0172] Not only was an increase in bulk and softness observed, but it was also important to note that the forced repulping of the mat upon draining resulted in a fiber mat that retained all of its hydrophobic properties. This quality is valuable in addition to the knowledge that water cannot easily "squeeze" through the low surface energy barrier and penetrate the sheet. Hydrophobic single fatty acid chain attachments do not exhibit this property.

[0173] Without being bound by any theory, this represents further evidence that SEFOSE® is reacting with cellulose, making the OH groups on the surface of the cellulose fibers no longer available to participate in subsequent hydrogen bonding. Other hydrophobic materials interfere with the initial hydrogen bonding, but upon repulping, this effect is reversed, and the OH groups on the cellulose are free to participate in hydrogen bonding upon redrying.

[0174] [Example 9] (Bag paper test data) The table below (Table 7) shows the range of 5 to 7 g / m 2 The figures show the properties imparted by coating a mixture of SEFOSE® and polyvinyl alcohol (PvOH) onto unbleached kraft bag stock (control). Also included for reference are commercially available bags.

[0175] [Table 7]

[0176] As shown in the table, coating the control base paper with SEFOSE® and PvOH increases the tensile and burst.

[0177] [Example 10] (wet / dry tensile strength) Three gram handmade sheets were made from bleached pulp. Wet and dry tensile strengths were compared at different SEFOSE® loading levels as follows: Note that for these handmade sheets, SEFOSE® was not emulsified into any coating; it was simply mixed into the pulp and drained without any other chemistry added (see Table 8).

[0178] [Table 8]

[0179] It should also be noted that the wet strength is not significantly lower than the dry strength of the control with the 5% addition.

[0180] [Example 11] (Use of esters containing less than 8 saturated fatty acids) Several experiments were performed using sucrose esters formed by attaching fewer than eight fatty acids to the sucrose moiety. Samples SP50, SP10, SP01, and F20W (Sisterna, The Netherlands) contained 50%, 10%, 1%, and essentially 0% monoesters, respectively. These commercially available products were made by reacting sucrose with saturated fatty acids, and therefore would not be useful for further cross-linking or similar chemistries, but were useful in investigating emulsification and water repellency properties.

[0181] For example, 10 g of SP01 was mixed with 10 g of glyoxal in a 10% hot PvOH solution. The mixture was "heated" at 200°F for 5 minutes and applied by drawdown to a porous base paper made from bleached hardwood kraft. The result was a cross-linked wax-based coating on the surface of the paper, exhibiting good hydrophobicity. A minimum of 3 g / m 2 When the sucrose ester was applied, the resulting contact angle was greater than 100°. Because glyoxal is a well-known crystallizer used with compounds containing OH groups, this method is a promising means for attaching fairly unreactive sucrose esters to surfaces by bonding the remaining alcohol group on the sucrose ring with available alcohol groups on the substrate or other coating materials.

[0182] [Example 12] (HST data and moisture absorption) To demonstrate the waterproofing properties observed with SEFOSE® alone, porous Twins River (Matawaska, ME) base paper was treated with various amounts of SEFOSE® (and PvOH or Ethylex 2025 emulsified and applied by drawdown) and assayed in the Hercules Sizing Test. The results are shown in Table 9 below.

[0183] [Table 9]

[0184] As shown in Table 9, increasing amounts of SEFOSE® applied to the surface of the paper increased water resistance (as indicated by an increase in HST (in seconds)).

[0185] This can also be seen using coatings of saturated sucrose ester products. As a specific example of this, a product called F20W (available from Sisterna, The Netherlands) is described as having a very low % monoester with most molecules in the 4-8 substitution range. It should be noted that when a stable emulsion is made using equal parts of the F20W product with PvOH, the add-on of the F20W product is only 50% of the total coating. Thus, add-on of 0.5 g / m 2 ", the same add-on weight of PvOH is also present, 1.0 g / m 2 The results are shown in Table 10 below.

[0186] [Table 10]

[0187] Again, the water resistance of the porous sheet increased with increasing F20W, as shown in Table 10. Therefore, the applied sucrose fatty acid ester itself makes the paper water resistant.

[0188] Because water resistance is not simply due to the presence of fatty acids that form ester bonds with cellulose, softwood handmade sheets (bleached softwood kraft) were loaded with SEFOSE®, and oleic acid, which forms ester bonds with the cellulose in the pulp, was added directly to the pulp. The mass at time 0 represents the "bone dry" mass of the handmade sheet removed from a 105°C oven. The sample was placed in a humidity chamber maintained at 50% RH. The change in mass over time (in minutes) was recorded. The results are shown in Tables 11 and 12 below.

[0189] [Table 11]

[0190] [Table 12]

[0191] Note that the difference here is that when oleic acid is added directly to the pulp and forms ester bonds, it greatly slows moisture absorption. In contrast, only 2% SEFOSE® slows moisture absorption, and at higher concentrations, SEFOSE® does not. Therefore, without being bound by any theory, the structure of the SEFOSE® binding material cannot be explained solely by the structure formed by simple fatty acid esters and cellulose.

[0192] [Example 13] (Saturated SFAE) The saturated ester class is a waxy solid at room temperature, and because it is saturated, it is less likely to react with the sample matrix or with itself. When used at elevated 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.

[0193] The data presented here represent HST (Hercules Size Test) readings obtained from papers coated with various amounts of saturated SFAE.

[0194] #45 bleached hardwood kraft sheet obtained from Turner Falls Paper was used for the test coatings. Gurley porosity was measured at approximately 300 seconds, representing a fairly tight base sheet. S-370, obtained from Mitsubishi Foods (Japan), was emulsified with xanthan gum (up to 1% by weight of the saturated SFAE formulation) prior to coating.

[0195] Coat weight (pounds per ton) HST of saturated SFAE formulation (average of 4 measurements per sample).

[0196] [Table 13]

[0197] The available experimental data also supports that limited amounts of saturated SFAE can enhance the water resistance of coatings designed for other purposes / uses. For example, when saturated SFAE was blended with Ethylex starch and polyvinyl alcohol-based coatings, increased water resistance was observed in both cases.

[0198] The following examples were coated onto a #50 bleached lithocycle base with a Gurley porosity of 18 seconds.

[0199] 100 grams of Ethylex 2025 was heated at 10% solids (1 liter volume), and 10 grams of S-370 was added hot and mixed using a Silverson homogenizer. The resulting coating was applied using a conventional benchtop drawdown apparatus, and the paper was dried under a heat lamp.

[0200] At a coat weight of 300# / ton, starch alone had an average HST of 480 seconds. A mixture of starch and saturated SFAE at a similar coat weight increased the HST to 710 seconds.

[0201] Sufficient polyvinyl alcohol (Selvol 205S) was dissolved in hot water to form a 10% solution. When this solution was coated onto the same #50 paper as above, the average HST was 225 at a coat weight of 150 lb / ton. Using the same solution, S-370 was added to form a mixture containing 90% PVOH / 10% S-370 on a dry basis (i.e., 90 ml water, 9 grams PVOH, 1 gram S-370). The average HST increased to 380 seconds.

[0202] Saturated SFAEs are compatible with prolamins (specifically, zein; see U.S. Pat. No. 7,737,200, incorporated herein by reference in its entirety). The addition of saturated SFAEs helps in this way, since one of the major barriers to commercial production of the subject matter of that patent is the water solubility of the formulations.

[0203] [Example 14] (Other saturated SFAE) Size press evaluations of saturated SFAE-based coatings were conducted on bleached lightweight sheets (approximately 35#) that had no sizing and were relatively poorly formed. All evaluations were performed using Exceval HR 3010 PvOH, which was heated to emulsify the saturated SFAE. Sufficient saturated SFAE was added to account for 20% of the total solids. The focus was on evaluating samples of S-370 vs. C-1800 (available from Mitsubishi Foods, Japan). Both of these esters performed better than the control. Table 14 below shows some of the key data.

[0204] [Table 14]

[0205] Note that the saturated compounds appear to result in an increase in Kit, with both S-370 and C-1800 increasing HST by approximately 100%.

[0206] [Example 15] (wet strength additive) Laboratory testing has shown that the chemistry of sucrose esters can be tailored to achieve a variety of properties, including their use as wet-strength additives. When sucrose esters are created by attaching saturated groups to each alcohol functional group of sucrose (or other polyols), the result is a hydrophobic, waxy material with low miscibility / solubility in water. These compounds can be added to cellulosic materials to impart water resistance, either internally or as a coating, but because they do not chemically react with each other or any part of the sample matrix, they are susceptible to removal by solvents, heat, and pressure.

[0207] When waterproofing and higher levels of water resistance are desired, sucrose esters containing unsaturated functional groups may be made and added to cellulosic materials to achieve oxidation and / or crosslinking that helps anchor the sucrose ester in the matrix and make it more resistant to removal by physical means. By adjusting the number and size of the unsaturated groups on the sucrose ester, a means has been provided to use a molecule that is not optimal for imparting water resistance, but which can be crosslinked to impart strength.

[0208] The data presented here is derived 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).

[0209] [Table 15]

[0210] The data show that the addition of unsaturated sucrose esters to paper tends to increase wet strength as load level increases. Dry tensile is shown using the maximum strength of the sheet as a reference point.

[0211] [Example 16] (Method of producing sucrose esters using acid chlorides) In addition to making hydrophobic sucrose esters via transesterification, similar hydrophobicity can be achieved in textile articles by directly reacting acid chlorides with polyols containing ring structures similar to sucrose.

[0212] For example, 200 grams of palmitoyl chloride (CAS 112-67-4) was combined with 50 grams of sucrose and mixed 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 material. Analysis of the remaining material using C-13 NMR revealed that a significant amount of hydrophobic sucrose ester had been produced.

[0213] While the addition of fatty acid chlorides to cellulosic materials has been shown to impart hydrophobicity (BT3 and others), the reaction itself is undesirable in the field because the released by-product, gaseous HCl, poses several problems, including corrosion of surrounding materials and is harmful to workers and the surrounding environment. One additional problem posed by the evolution of hydrochloric acid is that the fiber composition weakens as more is formed, i.e., as more polyol moieties react. Palmitoyl chloride was reacted with increasing amounts of cellulose and cotton materials. As hydrophobicity increased, the strength of the article decreased.

[0214] 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, birch-derived xylan, carboxymethyl cellulose, glucose, and extracted hemicellulose.

[0215] [Example 17] (peel test) The peel test utilized a wheel between the two jaws of a tensile tester to measure the force required to peel the tape from the paper surface at a reproducible angle (ASTM D1876; e.g., 100 Series Modular Peel Tester, TestResources, Shakopee, MN).

[0216] A high Gurley (600 seconds) bleached kraft paper from Turners Falls Paper (Turners Falls, MA) was used in this work. This #50 lb. sheet demonstrates a fairly tight, yet extremely absorbent, sheet.

[0217] When #50 pound paper was coated with 15% Ethylex starch as a control, the average force required (for five samples) was 0.55 lb / in. When treated with a similar coating except that SEFOSE® replaced 25% of the Ethylex starch (so 25% add-on was SEFOSE® and 75% was still Ethylex), the average force was reduced to 0.081 lb / in. When SEFOSE® was used to replace 50% of the Ethylex, the force required was reduced to less than 0.03 lb / in.

[0218] The paper preparation followed TAPPI Standard Method 404 for determining the tensile strength of paper.

[0219] Finally, the same paper was used with S-370 at a loading rate of 750 pounds per ton. This effectively filled all of the pores in the sheet, creating a complete physical barrier. Indeed, it passed TAPPI Kit 12 on a flat surface. This short experiment demonstrated that it is possible to obtain grease resistance using saturated SFAE variants.

[0220] [Example 18] (Saturated SFAE and inorganic particles (fillers)) Saturated sucrose fatty acid esters range from hydrophilic to hydrophobic depending on the number (and length) of fatty acid chains attached to the sucrose molecule. They are not considered highly reactive compounds.

[0221] Various substituted SAFEs with side chains 16 or 18 carbons long have been investigated. The test materials are waxy solids with melting points below 150°C. When coated onto paper, the highly substituted esters impart significant levels of water resistance depending on the coat weight and sheet porosity. Finally, the same paper in S-370 was used at a loading rate of 750 pounds per ton, which effectively filled all of the sheet's pores and created a complete physical barrier. The paper so treated was found to have a TAPPI Kit 12. This short-term experiment demonstrated that grease resistance could be achieved using a saturated SAFE variant.

[0222] (Observation results) The more hydrophobic esters tend to aggregate in aqueous emulsions / dispersions, making uniform coating on paper difficult.

[0223] The low melting points of some of these molecules result in the "melting" of the coating into the sheet.

[0224] When polymers are mixed with the hydrophobic SAFE to help stabilize the dispersion, these polymers (i.e., latex, starch, polyvinyl alcohol) tend to surround these esters in a way that weakens the desired hydrophobic properties.

[0225] When mixed with calcium carbonate (e.g., precipitated calcium carbonate), SAFE has an unexpected appeal: it does not dissolve in paper under similar drying conditions.

[0226] The calcium carbonate appeared to aid in the dispersion of SAFE, and the adhesion was such that SAFE acted as a binder, adhering the calcium carbonate particles to the surface of the coated paper. This uniform dispersion is believed to enhance water resistance for a given amount of ester.

[0227] [Example 18] (Pigmented Coating Formulations) (method) Analysis of SEFOSE® with several MALLARD CREEK samples (TYKOTE® 1019, 1004, 6160, 1005, 6152) as well as DOW 620® and several BASF samples (Epotal NX 4430, Epotal s440) appears to confirm that the latexes are compatible with SEFOSE® from a chemical standpoint. The order of addition does not appear to matter, and the viscosity does not appear to change appreciably.

[0228] (cup paper stock) Mallard Creek Tykote® 1019 was blended with Imerys LX® clay slurry. SEFOSE® was blended into this mixture, resulting in a ratio of 70% latex, 20% LX® clay, 10% SEFOSE® (topcoat) or 75% GCC; 3% SEFOSE®; and 21.5% Tykote® 1019 (basecoat). The basecoat blend had a pH of approximately 7.6, a viscosity of 215 cps, and 60-70% solids. The topcoat had a pH of 7.8, a viscosity of approximately 57% solids, and a viscosity of approximately 240 cps. The reported coat weight was approximately 8 g / m2 when applied via blade to the precoated board. 2 Rolls of hot cup stock, cold cup stock, and cup bottom stock were made with two different coatings.

[0229] Table 16 below shows the effect of SEFOSE® cure on Cobb value in pigmented coating formulations.

[0230] [Table 16]

[0231] As shown in the table, the addition of SEFOSE® (10% by weight) to the coating reduced the Cobb value from 39 for the latex coated board to 3.

[0232] SEFOSE® does not appear to be as effective a film former as latex. Therefore, without being bound by any theory, it was hypothesized that latex forms a barrier film and SEFOSE® acts synergistically by adding hydrophobicity to any voids / pinholes in the latex film.

[0233] (Plastic substrate) To further understand the Cobb effect, a plastic substrate was coated with Dow 620® latex, dried (on the plastic substrate), and the Cobb was measured (Cobb value = 10.5). This data point reflects the fact that the Cobb reading is not only affected by water penetrating into the paper itself, but also reflects water soaking into or absorbing into the coating itself. When this experiment was repeated with 10% SEFOSE® added to the latex (also coated onto a plastic substrate), the Cobb value dropped to 3.8, reflecting hydrophobicity in the film itself.

[0234] [Example 19] (SFAE encapsulation of solid latex polymer beads and their addition to cellulose fibers) The SFAE was mixed with the latex in aqueous propylene glycol by a temperature cycle method that included heating at 90° C. for 20 minutes, cooling to 21° C. for 1 minute, heating again at 90° C. for an additional 5 minutes, and cooling to 21° C. The SFAE may be kneaded with the latex.

[0235] The particles are dispersed in an aqueous emulsion or slurry, and the aqueous emulsion or slurry is then mixed with a cellulose fiber slurry at a concentration of about 5% to about 50% of the total dry weight prior to wet-forming. The emulsion may be kneaded with the fiber slurry. The fiber slurry is then applied to a machine equipped with a mesh or screen, optionally with heat, to remove water. The resulting fibrous material is then applied to a mold and heated until dry. Once dry, the resulting product is removed from the mold.

[0236] Although the present disclosure has been described with reference to the above examples, it will be understood that modifications and variations are encompassed within the spirit and scope of the disclosure. Accordingly, the present invention is limited only by the following claims. All references disclosed herein are incorporated by reference in their entirety.

Claims

1. 1. A method for producing a molded cellulose-containing article, comprising: adding an emulsion or slurry to a cellulosic fiber furnish, said emulsion or slurry comprising one or more sucrose fatty acid esters and one or more carrier particles; draining the furnish through one or more meshes or screens; thermoforming the mixture into an article in a mold; removing the product from the mold; Including, at least one carrier particle of the one or more carrier particles is a raw starch particle; The method, wherein the product exhibits water, oil, and / or grease resistance compared to a cellulosic product that has not been treated with the emulsion or slurry.

2. 10. The method of claim 1, wherein the product is a bowl, plate, bottle, pouch, package, or insert.

3. 10. The method of claim 1, wherein another carrier of the one or more carrier particles is selected from the group consisting of polymers, solid latex polymer beads, hollow polymer shells, resin beads, pigment particles, and combinations thereof.

4. 4. The method of claim 3, wherein the pigment particles are selected from the group consisting of calcium carbonate, titanium dioxide, kaolin clay, silica, silicates, talc, mica, and combinations thereof.

5. 10. The method of claim 1, wherein another carrier of the one or more carrier particles comprises raw rice starch, wheat starch, potato starch, or tapioca starch granules, oat hulls, rice hulls, ground nut shells, or combinations thereof.

6. 10. The method of claim 1, wherein the one or more carrier particles are coated with one or more sucrose esters and dispersed in an aqueous emulsion or slurry.

7. 7. The method of claim 6, wherein the aqueous emulsion or slurry is mixed with a cellulosic fiber slurry at a concentration of about 5% to about 50% of the total dry weight prior to wet forming.

8. The method of claim 3 wherein the polymer is a latex.

9. 10. The method of claim 8, wherein the product exhibits reduced tack as measured by ASTM D4501.

10. 10. A composition for use in the method of any one of claims 1 to 9, comprising sucrose fatty acid ester particles containing one or more materials to be delivered by said one or more carrier particles, said one or more carrier particles containing said one or more materials, and at least one of said one or more carrier particles being a raw starch particle.

11. 11. The composition of claim 10, wherein the one or more materials delivered by the one or more carrier particles are selected from the group consisting of polymers, solid latex polymer beads, resin beads, calcium carbonate, titanium dioxide, kaolin clay, silica, silicates, talc, mica, and combinations thereof.

12. 11. The composition of claim 10, further comprising thymol, lecithin, alkyl glucoside, and combinations thereof.

13. The composition of claim 10 , wherein the sucrose fatty acid ester particles are micelles, microcapsules, or nanocapsules.

14. The composition of claim 10, wherein the sucrose fatty acid ester is a mono- or diester.

15. 11. The composition of claim 10, wherein the sucrose fatty acid ester comprises all saturated fatty acids or a mixture of saturated and unsaturated fatty acids.

16. The composition of claim 10 , wherein the fatty acid ester particles comprise one or more sucrose fatty acid esters.

17. An emulsion comprising the composition of claim 10.

18. 20. The emulsion of claim 17, wherein the one or more materials delivered by the one or more carrier particles comprises latex.

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