Combination of sugar fatty acid ester inorganic particles

Abstract

The present disclosure describes a method for treating cellulosic materials with a composition that allows for better retention of inorganic particles on cellulosic substrates. The disclosed method provides for combining sugar fatty acid esters (SFAEs) with such inorganic particles and applying such a combination to the cellulosic materials to eliminate or reduce the use of retention aids or binders for fillers in papermaking processes. Also disclosed are compositions containing such combinations of SFAEs and inorganic particles.

Description

[Technical Field]

[0001] [CROSS-REFERENCE TO RELATED APPLICATIONS] This application claims priority to U.S. Patent Application Publication No. 16 / 456,433, filed with the U.S. Patent and Trademark Office on June 28, 2019, which is incorporated herein by reference in its entirety.

[0002] The present invention relates generally to treating cellulosic-based materials, and specifically to treating such materials with sugar fatty acid esters (SFAEs) in combination with inorganic particles, e.g., with compositions containing such combinations. [Background technology]

[0003] Inorganic particles, such as kaolin, talc, calcium carbonate, and TiO2, are typically used as fillers in the papermaking process. For example, calcium carbonate is used as a filler material in the alkaline papermaking process of paper mills. Currently, calcium carbonate is more prevalent than other papermaking filter materials (e.g., kaolin). The primary reason for calcium carbonate's preference is the demand for brighter, bulkier paper. The use of calcium carbonate in the alkaline papermaking process offers significant advantages (e.g., calcium carbonate is inexpensive, has high brightness, creates a porous surface on the paper sheet, improves printability, reduces binder demand, increases machine speed and productivity, improves drainage, improves machine runnability, is cost-effective in the papermaking process, reduces fiber consumption, and achieves high retention compared to other paper fillers).

[0004] Calcium carbonate typically occurs in three natural forms: limestone, chalk, and marble. It is produced by the reaction between calcium salts and carbon dioxide. There are two types of calcium carbonate used in paper mills: ground calcium carbonate (GCC) and precipitated calcium carbonate (PCC).

[0005] Ground calcium carbonate is produced by crushing limestone or marble and finds use due to its high brightness and purity. Typically, the particle shape of ground calcium carbonate is rhombohedral. This filler material is used in alkaline, wood-free papermaking processes. The brightness of GCC is approximately 86-95%.

[0006] The coarse particle shape and small amounts of quartz frequently found in GCC cause problems as it is highly abrasive and reduces the life of paper machine forming wires and press felts.

[0007] Precipitated calcium carbonate is a form of CaCO3, which is produced by a chemical reaction known as carbonation. PCC overcomes the shortcomings of GCC, thereby imparting superior gloss and opacity properties to paper. The structure of PCC differs from that of GCC. The crystal structure of PCC can be controlled and includes acicular, rhombohedral (cubic), scalenohedral (triangular), and prismatic. The brightness of PCC is approximately 90-97%. However, PCC formulations containing paper sheets may be less viable than GCC formulations containing paper sheets.

[0008] On modern, high-speed twin-wire paper machines, the turbulence required to obtain good formation often leads to poor filler retention. Also, both types of calcium carbonate do not adhere to cellulose by themselves and require a retention aid or binder to bind to the pulp. Typically, such retention aids or binders include papermaker's alum, synthetic polymers, polyacrylamide, microparticle systems, latex, starch, and polyvinyl alcohol (PvOH), which can increase costs or make the product less "green" if desired (e.g., synthetic polymers).

[0009] It would be desirable to bind the calcium carbonate to eliminate the need for retention aids or binders or to reduce the amount of retention aid or binder needed to bind the inorganic particles to the cellulosic surface. Summary of the Invention

[0010] The present disclosure relates, inter alia, to a method for treating cellulosic materials with a composition that enhances the retention of inorganic particles (i.e., fillers). The disclosed method provides for combining sugar fatty acid esters (SFAEs) with such fillers and applying such a combination onto cellulose to eliminate or reduce the use of retention aids or binders for the fillers in papermaking processes. Compositions including the combination of SFAEs and inorganic particles are also disclosed.

[0011] In one embodiment, a composition is disclosed comprising a sugar fatty acid ester (SFAE) and inorganic particles, wherein the SFAE is present at a concentration sufficient to cause the inorganic particles to be retained on a cellulose-based material, and wherein a substrate comprising the composition exhibits superior water and / or grease resistance compared to a substrate comprising a composition comprising only the inorganic particles or one or more SFAEs.

[0012] In one embodiment, the SFAE comprises all unsaturated fatty acids, all saturated fatty acids, or a mixture of saturated and unsaturated fatty acids, and optionally further comprises one or more binders selected from PvOH or starch.

[0013] In another embodiment, the SFAE is a mixture of two or more different SFAEs, wherein the two or more different SFAEs comprise all saturated fatty acids.

[0014] In one embodiment, the inorganic particles include clay, ground calcium carbonate, precipitated calcium carbonate, talc, titanium dioxide, and combinations thereof, and the inorganic particles comprise at least 1% of the composition on a dry basis (db).

[0015] In another embodiment, the SFAE comprises at least one sugar and at least one aliphatic group containing 8 to 30 carbons. In one embodiment, the inorganic particles are calcium carbonate and the substrate exhibits water resistance. In a related embodiment, the inorganic particles are clay and the substrate exhibits grease resistance.

[0016] In one embodiment, the cellulose-based substrates include paper, paperboard, paper pulp, food storage cartons, food storage bags, shipping bags, coffee or tea containers, tea bags, bacon board, diapers, weed blocking / barrier fabric or film, mulching film, plant pots, packing beads, bubble wrap, oil absorbent materials, laminates, envelopes, gift cards, credit cards, gloves, raincoats, OGR paper, shopping bags, compost bags, release paper, tableware, hot or cold beverage containers, cups, paper towels, plates, carbonated liquid storage bottles, insulating materials, carbonated Examples of suitable cellulosic fiber applications include: container-free liquid storage bottles, food wrap films, food waste disposal containers, food handling equipment, cup lids, formable paper cup lid screws, paper straws, fabric fibers, water storage and transport equipment, paperboard for pharmaceutical applications, release paper, alcoholic or non-alcoholic beverage storage and transport equipment, casings, external screens for electronic products, interior or exterior furniture components, curtains, upholstery, films, boxes, sheets, trays, pipes, water conduits, pharmaceutical packaging, clothing, medical devices, contraceptives, camping equipment, formed cellulosic fiber materials, and combinations thereof.

[0017] In one embodiment, an article of manufacture is disclosed that includes a coating comprising one or more sugar fatty acid esters (SFAEs), inorganic particles, a cellulose-based substrate, and optionally one or more binders, wherein the inorganic particles are present in the coating at a concentration of at least 1% on a dry basis (db). In a related aspect, the cellulose-based substrate may be any of the following: paper, paperboard, paper pulp, food storage cartons, food storage bags, shipping bags, coffee or tea containers, tea bags, bacon board, diapers, weed blocking / barrier fabric or film, mulching film, plant pots, packing beads, bubble wrap, oil absorbent material, laminate, envelopes, gift cards, credit cards, gloves, raincoats, OGR paper, shopping bags, compost bags, release paper, tableware, hot or cold beverage containers, cups, paper towels, plates, carbonated liquid storage bottles, insulating materials, charcoal, etc. Examples include acid-free liquid storage bottles, food wrap films, food waste disposal containers, food handling equipment, cup lids, formable paper cup lid screws, paper straws, fabric fibers, water storage and transport equipment, paperboard for pharmaceutical applications, release papers, alcoholic or non-alcoholic beverage storage and transport equipment, casings, external screens for electronic products, interior or exterior furniture components, curtains, upholstery, films, boxes, sheets, trays, pipes, water conduits, pharmaceutical packaging, clothing, medical devices, contraceptives, camping equipment, formed cellulosic fibrous materials, and combinations thereof.

[0018] In one embodiment, a method of treating a cellulosic substrate is disclosed, comprising: adding at least one sugar fatty acid ester (SFAE) to a composition comprising inorganic particles to form a mixture; applying the mixture to at least one surface of the cellulosic substrate; and allowing to cure for a sufficient period of time to adhere the mixture to the at least one surface, wherein the hardened surface exhibits increased hydrophobicity and / or oleophobicity compared to a surface treated with a composition comprising only the at least one SFAE or inorganic particles.

[0019] In one embodiment, the treated cellulosic surface is hydrophobic. In another embodiment, the treated cellulosic surface is oleophobic.

[0020] In one embodiment, the SFAE comprises all saturated fatty acids or a mixture of saturated and unsaturated fatty acids, hi another embodiment, the SFAE is a mixture of two or more different SFAEs.

[0021] In one embodiment, the inorganic particles include clay, ground calcium carbonate, precipitated calcium carbonate, talc, titanium dioxide, and combinations thereof, and the inorganic particles are present in the mixture at a concentration of at least about 1% on a dry basis (db). In a related embodiment, the composition further comprises polyvinyl alcohol or starch.

[0022] In one embodiment, the inorganic particles include calcium carbonate, and the calcium carbonate comprises about 50% or more of the mixture on a dry basis (db).

[0023] In another aspect, the cellulosic substrate may be any suitable material, including paper, paperboard, paper pulp, food storage cartons, food storage bags, shipping bags, coffee or tea containers, tea bags, bacon board, diapers, weed blocking / barrier fabric or film, mulching film, plant pots, packing beads, bubble wrap, oil absorbent materials, laminates, envelopes, gift cards, credit cards, gloves, raincoats, OGR paper, shopping bags, compost bags, release paper, tableware, containers for holding hot or cold beverages, cups, paper towels, plates, bottles for storing carbonated liquids, insulating materials, carbonated Examples include empty liquid storage bottles, food wrap films, food waste disposal containers, food handling equipment, lids for cups, screws for formable paper cup lids, paper straws, fabric fibers, water storage and transport equipment, paperboard for pharmaceutical applications, release paper, storage and transport equipment for alcoholic or non-alcoholic beverages, exterior casings or screens for electrical appliances, interior or exterior components of furniture, curtains, upholstery, films, boxes, sheets, trays, pipes, water conduits, pharmaceutical packaging, clothing, medical devices, contraceptives, camping equipment, formed cellulosic materials, and combinations thereof. [Brief explanation of the drawings]

[0024] [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), ×. DETAILED DESCRIPTION OF THE INVENTION

[0025] Before describing the compositions, methods, and methodologies of the present invention, it is to be understood that this invention is not limited to the particular compositions, methods, and experimental conditions described, as these may vary. It is also to be understood that the terminology used herein describes particular embodiments only, and that the scope of the present invention will be limited only by the appended claims, and is not intended to be limiting.

[0026] As used in this specification and 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.

[0027] 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 invention belongs. It will be understood that any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention, since modifications and variations are within the spirit and scope of this disclosure.

[0028] 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.

[0029] All pigments must be uniformly held in the sheet to be effective. Paper can be made more cheaply if fillers that are less expensive than fiber are used. However, the percentage of filler in the sheet is limited by the resulting loss in strength, bulk, and sizing quality. While there is certainly a trend toward increasing filler content, above 10 or 20% pigment concentration in any barrier coating, the barrier properties decrease significantly.

[0030] SFAE is not a polymer itself, but rather aids in the retention of fillers or inorganic particles, such as PCC. Without being bound by any theory, SFAE may crosslink or provide a network with the fines and fiber surfaces. The combination works well, allowing for increased levels of adhesion without compromising product quality, including improved performance levels.

[0031] Organic particles such as uncooked starch, wood particles, oat hulls, etc. may also be added to provide much-needed bulk and thickness in some products, while inorganic materials increase density. Furthermore, with respect to hydrophobic polymers, including wood resins, hot melt waxes, bioplastics, etc., which may produce undesirable particles and / or sticky clumps or deposits, the use of a SPAE-inorganic particle combination may overcome such undesirable agglomeration.

[0032] Furthermore, the addition of a composition containing a mixture of inorganic particles and SFAE improves the fine-tuning of various sheet properties. For example, such sheets may contain wood fibers, and a combination of bioplastic fibers and SFAE may be used to waterproof such sheets. This 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-SFAE mixture, for example, improves the control of the sheet's density.

[0033] In one embodiment, the present disclosure demonstrates that treating a cellulosic material with a combination of inorganic particles and sugar fatty acid esters can render the resulting material, among other things, highly hydrophobic and / or oleophobic. Furthermore, these sugar fatty acid esters are themselves easily digestible when removed, for example, by bacterial enzymes. The derivatized surface exhibits very high heat resistance, can withstand temperatures as high as 250°C, and can be more impermeable to gases than the underlying base substrate. Therefore, the material is an ideal solution to the problem of derivatizing the hydrophilic surface of cellulose in any embodiment in which a cellulosic material may be used.

[0034] Advantages of the products and methods disclosed herein include that the coating compositions are made from renewable agricultural resources—sugars and vegetable oils; are biodegradable; have a low toxicity profile, making them suitable for food contact; can be tailored to reduce the coefficient of friction of the paper / paperboard surface even with high levels of water resistance (i.e., making the paper less slippery for downstream processing or end use); can be used with or without special emulsifying equipment or emulsifiers; are compatible with conventional paper recycling programs; i.e., do not adversely affect recycling operations like polyethylene, polylactic acid, or wax-coated papers. Additionally, the expanded use of inorganics, such as PCC, takes advantage of the inherent properties of fillers (e.g., low abrasion).

[0035] 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.

[0036] As used herein, "bind," including grammatical variations thereof, means to adhere or cause to adhere as essentially a single mass.

[0037] As used herein, "cellulosic" refers to a natural, synthetic, or semi-synthetic material that can be molded or extruded into objects (e.g., bags, sheets) or films or filaments, and can be used to make such objects, films, or filaments, and that is structurally and functionally similar to cellulose, e.g., coatings and adhesives (e.g., carboxymethyl cellulose). In another example, complex carbohydrates (CH) composed of glucose units are 16 O5) n , and the cellulose that forms the main component of the cell wall in most plants is cellulosic.

[0038] As used herein, "coating weight" is the weight of material (wet or dry) applied to a substrate, given in pounds per ream or grams per square meter.

[0039] As used herein, "Compostable" means that these solid products are biodegradable in soil.

[0040] As used herein, "dry basis" is a measure of the mass of all components (eg, solids) excluding water.

[0041] 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.

[0042] As used herein, "effect," including grammatical variations thereof, means imparting a particular property to a particular material.

[0043] 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.

[0044] As used herein, "hydrophobic" means the property of being water repellent and tending to repel and not absorb water.

[0045] 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 aspect, grease resistance can be measured by the "3M Kit" test or the TAPPI T559 Kit test.

[0046] As used herein, "cellulose-containing material" or "cellulose-based material" refers to a composition consisting essentially of cellulose. Such materials include, for example, paper, paperboard, paper pulp, food storage cartons, food storage bags, shipping bags, coffee or tea containers, tea bags, bacon board, diapers, weed blocking / barrier fabric or film, mulching film, plant pots, packing beads, bubble wrap, oil absorbent materials, laminates, envelopes, gift cards, credit cards, gloves, raincoats, OGR paper, shopping bags, compost bags, release paper, tableware, containers for holding hot or cold beverages, cups, paper towels, plates, bottles for storing carbonated liquids, insulating materials, carbonated beverages, and the like. Examples of cellulosic materials that may be used include, but are not limited to, uncoated liquid storage bottles, food wrap films, food waste disposal containers, food handling equipment, lids for cups, paper straws, fabric fibers, water storage and transport equipment, paperboard for pharmaceutical applications, release paper, storage and transport equipment for alcoholic or non-alcoholic beverages, exterior casings or screens for electrical appliances, interior or exterior furniture components, curtains, upholstery, films, boxes, sheets, trays, pipes, water lines, pharmaceutical packaging, clothing, medical devices, contraceptives, camping equipment, formed cellulosic materials, and combinations thereof.

[0047] 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 readily 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).

[0048] As used herein, "peelable" with respect to an SFAE 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, "non-peelable" with respect to an SFAE means that the SFAE coating, once applied, is substantially irreversibly bonded to the cellulose-based material (e.g., removable by chemical means).

[0049] As used herein, "fibers in solution" or "pulp" refers to lignocellulosic fibrous material prepared by chemically or mechanically separating cellulose fibers from wood, fiber crops, or waste paper. In 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).

[0050] As used herein, "repulpable" means rendering the paper or paperboard product suitable for being crushed into a shapeless, flexible mass for reuse in the manufacture of paper or paperboard.

[0051] As used herein, "adjustable," including grammatical variations thereof, means adjusting or adapting a method to achieve a particular result.

[0052] As used herein, "water contact angle" refers to the angle, measured through a liquid, at which a liquid / vapor interface meets a solid surface. It quantifies the wettability of a solid surface by a liquid. The contact angle reflects the strength with which liquid and solid molecules interact, relative 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 may be readily obtained using an optical tensiometer (see, e.g., Dyne Testing, Staffordshire, United Kingdom).

[0053] As used herein, "water vapor permeability" refers to breathability, or the ability of a textile to transport moisture. There are at least two different measurement methods. One of these, the MVTR (Water 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).

[0054] 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 reproducible results, reduces test time, and provides the sensitivity of the ink float test while providing automatic endpoint determination.

[0055] 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.

[0056] This method may be used to monitor the production of paper or paperboard for a specific 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 well enough 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.

[0057] 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 its diffusivity (D) (i.e., how quickly oxygen molecules traverse the material) and its solubility (k) (or the amount of oxygen molecules absorbed per volume of material). Oxygen permeability (Dk) values ​​are typically in the range of 10 to 150 x 10 -11 (cm 2 ml O2 / (s ml mmHg). A semi-logarithmic relationship was 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.

[0058] 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.

[0059] 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.

[0060] 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.

[0061] 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).

[0062] 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.

[0063] Griffin's method for nonionic surfactants, described in a 1954 study, HLB=20*M h / M [In the formula, M h where M is the molecular weight of the hydrophilic portion of the molecule, and M is the molecular weight 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 a value of 20 corresponds to a completely hydrophilic / lipophobic molecule.

[0064] The HLB value can be used to predict the surfactant properties of a molecule. <10: Lipid-soluble (water-insoluble) >10: Water soluble (nonlipid) 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

[0065] In some embodiments, the HLB values ​​for the sugar fatty acid esters (or compositions comprising the esters) disclosed herein may be in the lower range. In other embodiments, the HLB values ​​for the sugar fatty acid esters (or compositions comprising the esters) disclosed herein may be in the medium to high range. In one embodiment, a step of mixing SFAEs having different HLB values ​​may be used.

[0066] 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 13is the name of a sucrose fatty acid ester having the formula (I), in which all fatty acids are saturated fatty acids, and is available from Procter & Gamble Chemicals. Additionally, SFAE can be purchased from Mitsubishi Chemical Foods Corporation (Tokyo, Japan), which offers a variety of such SFAEs.

[0067] As used herein, "soybean oil fatty acid ester" refers to a mixture of salts of fatty acids derived from soybean oil.

[0068] 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.

[0069] 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 manufactured by 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 achieve such wet strength in the absence of such additives.

[0070] As used herein, "wet" means covered or saturated with water or another liquid.

[0071] In one embodiment, the process disclosed herein includes mixing a sugar fatty acid ester with inorganic particles (e.g., clay, talc, calcium carbonate) and applying the mixture to a cellulosic material to adhere the particles to the cellulosic material, and the process further includes contacting the cellulose-based material with the combination and exposing the contacted cellulose-based material to heat, radiation, a catalyst, or a combination thereof for a sufficient time to bond the combination to the cellulose-based material. In a related aspect, such radiation may include, but is not limited to, UV, IR, visible light, or a combination thereof. In another related aspect, the reaction may be carried out at room temperature (i.e., 25°C) to about 150°C, about 50°C to about 100°C, or about 60°C to about 80°C.

[0072] Additionally, the binding reaction between the mixture and the cellulosic material may be carried out with or substantially reduced in the presence of a retention aid (i.e., binder, such as PvOH or starch). In one embodiment, the mixture may include a mixture of mono-, di-, tri-, tetra-, penta-, hexa-, hepta-, or octaesters. In another embodiment, the mixture may also include proteins, polysaccharides, and lipids, including, but not limited to, milk proteins (e.g., casein, whey protein, etc.), wheat gluten, gelatin, prolamins (e.g., corn zein), soy protein isolate, starch, modified starch, acetylated polysaccharides, alginates, carrageenans, chitosan, inulin, long chain fatty acids, waxes, and combinations thereof.

[0073] In one embodiment, the cellulosic material may be rendered oleophobic by the addition of polyvinyl alcohol (PvOH) and / or prolamins. In one aspect, the prolamins include zein, gliadin, hordein, secalin, cathilin, and avenin. In a related aspect, the prolamin is zein.

[0074] In one embodiment, catalysts and organic supports (e.g., volatile organic compounds) are not required to carry out the bonding reaction, including the fact that the disclosed methods are not contemplated for laminating materials. In a related aspect, the reaction time is substantially instantaneous (i.e., less than 1 second). Furthermore, the resulting materials exhibit low blocking.

[0075] As used herein, all sugar fatty acid esters, including monosaccharides, disaccharides, and trisaccharides, are applicable for use in connection with this aspect of the invention. In a related aspect, the sugar fatty acid ester may be a mono-, di-, tri-, tetra-, penta-, hexa-, hepta-, or octaester, and combinations thereof, including that the fatty acid moiety may be saturated, unsaturated, or combinations thereof.

[0076] Without being bound by any theory, the interaction between the sugar fatty acid ester and the cellulose-based material may be due to ionic, hydrophobic, van der Waals interactions, or covalent bonds, or a combination thereof. In a related aspect, the binding of the sugar fatty acid ester to the cellulose-based material may be substantially irreversible (e.g., using an SFAF containing a combination of saturated and unsaturated fatty acids).

[0077] Furthermore, sufficient concentrations of sugar fatty acid ester linkages alone are sufficient to render the cellulose-based material hydrophobic, i.e., hydrophobicity is achieved without the addition of waxes, rosins, resins, diketenes, shellacs, vinyl acetates, PLA, PEI, oils, other water-repellent chemicals, or combinations thereof (i.e., second hydrophobic substances), including that other properties, such as, inter alia, strengthening, stiffening, and bulking of the cellulose-based material, are achieved solely through the sugar fatty acid ester linkages.

[0078] An advantage of the present invention is that the multiple fatty acid chains are reactive with cellulose and two sugar molecules within the structure, for example, the disclosed sucrose fatty acid esters produce a tight crosslinked network, improving the strength of 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 observed with other sizing or hydrophobic treatment chemistries. The sugar fatty acid esters disclosed herein also provide / increase wet strength, a property not present when using many other water-resistant chemistries.

[0079] Another advantage is that the disclosed sugar fatty acid esters soften fibers, increasing the space between them and thus increasing bulk without substantially increasing weight. Furthermore, the processed fibers and cellulose-based materials disclosed herein may be repulped. Furthermore, for example, water cannot easily "push through" the low surface energy barrier and penetrate into the sheet.

[0080] Saturated SFAEs are typically solid at nominal processing temperatures, while unsaturated SFAEs are typically liquid. This allows for the formation of uniform, stable dispersions of saturated SFAEs in aqueous coatings without significant interaction or incompatibility with other coating components, which are typically hydrophilic. Furthermore, this dispersion allows for the preparation of high concentrations of saturated SFAEs without adversely affecting coating rheology, uniform coating application, or coating performance properties. If the saturated SFAE particles melt and spread during heating, drying, and solidification of the coating layer, the coating surface will become 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 generally forms a dense structure that easily disintegrates when exposed to water. Molded fibrous products made using the disclosed method can include paper plates, drink holders (e.g., cups), lids, food trays, and packaging that are lightweight, strong, and resistant to exposure to water and other liquids.

[0081] 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 by itself 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 helps emulsify 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.

[0082] In one embodiment, the sugar fatty acid ester comprises or consists essentially of a sucrose ester of a fatty acid. Many methods are known and available for making or providing the sugar fatty acid esters of the present invention, and all such methods are considered to be available for use within the broad scope of the present invention. For example, in certain embodiments, it may be preferred that the fatty acid ester be synthesized by esterification of a sugar with one or more fatty acid moieties obtained from oilseeds, including, but not limited to, soybean oil, sunflower oil, olive oil, canola oil, peanut oil, and mixtures thereof.

[0083] 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 has the structure of Formula I: [ka] wherein "A" is hydrogen or the following structure 1 [ka]

[0084] wherein "R" is a straight, branched, or cyclic, saturated or unsaturated, aliphatic or aromatic moiety of from about 8 to about 40 carbon atoms, and the "A" portion of the formula is according to Structure 1 when at least one "A" is at least 1, at least 2, at least 3, at least 4, at least 5, at least 6, at least 7, and all 8. In a related aspect, the sugar fatty acid esters described herein may be mono-, di-, tri-, tetra-, penta-, hexa-, hepta-, or octa-esters, and combinations thereof, and the aliphatic groups may be all saturated groups, or may contain saturated and / or unsaturated groups, or combinations thereof.

[0085] Suitable "R" groups include any form of aliphatic moiety, including those containing one or more substituents, which may appear 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 aliphatic (or aromatic) moieties 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.

[0086] 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.

[0087] In one embodiment, the substrate for adding the fatty acid may include starch, hemicellulose, lignin, or a combination thereof.

[0088] In one embodiment, the composition comprises a starch fatty acid ester, and the starch may be 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.

[0089] More particularly, the starch can be unmodified starch or starch that has been modified by chemical, physical or enzymatic processes.

[0090] Chemical processing includes any treatment of starch with chemicals that results in 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 may also be prepared by using any combination of chemical treatments. Examples of chemically modified starches include the reaction of starch with alkenyl succinic anhydrides, especially octenyl succinic anhydride, to produce hydrophobically esterified starches; the reaction of starch with 2,3-epoxypropyltrimethylammonium chloride to produce cationic starches; the reaction of starch with ethylene oxide to produce hydroxyethyl starch; the reaction of starch with hypochlorite to produce oxidized starch; the reaction of starch with acid to produce acid-depolymerized starch; and the defatting of starch with solvents such as methanol, ethanol, propanol, methylene chloride, chloroform, carbon tetrachloride, etc. to produce defatted starch.

[0091] 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.

[0092] Enzymatically modified starch is any starch that has been treated with an enzyme in any manner to provide an 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.

[0093] The disaccharide fatty acid ester may be a sucrose fatty acid ester according to Formula I, where the "R" groups are aliphatic, linear or branched, saturated or unsaturated, and have between about 8 and about 40 carbon atoms.

[0094] As used herein, the terms "sugar fatty acid ester" and "sucrose fatty acid ester" include compositions of varying purity, as well as mixtures of compounds at 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 Structure 1 moiety (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, and where the substituent moieties of the "R" groups are independently selected from two or more "R" groups of Structure 1. 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).

[0095] In the compositions of the present invention, 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.

[0096] [ka] Polysoybean oil sucrose (SEFOSE® 1618U)

[0097] Sugar fatty acid esters can be prepared by esterification with substantially pure fatty acids through known esterification processes.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 those found in oil extracted from oilseeds, for example, soybean oil.The transesterification reaction of using fatty acid glycerides to provide sucrose fatty acid esters is described in, for example, U.S. Patent No. 3,963,699; U.S. Patent No. 4,517,360; U.S. Patent No. 4,518,772; U.S. Patent No. 4,611,055; U.S. Patent No. 5,767,257; U.S. Patent No. 6,504,003; U.S. Patent No. 6,121,440; and U.S. Patent No. 6,995,232, and International Publication No. 1992,004,361 (A1), all of which are incorporated herein by reference.

[0098] In addition to creating hydrophobic sucrose esters via transesterification, similar hydrophobic properties may be achieved in fibrous cellulosic articles by directly reacting acid chlorides with polyols containing ring structures similar to sucrose.

[0099] 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., US Pat. 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 1 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 as set forth in the Seventh Ed. of the Merck Index, incorporated herein by reference. 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 to sucrose fatty acid esters herein as products of reactions employing fatty acid feedstocks derived from natural sources, such as 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 esters are prepared. In a related aspect, the disclosed sugar fatty acid esters can exhibit low viscosities (e.g., about 10-2000 centipoise at room temperature or standard pressure).In another embodiment, the unsaturated fatty acid may have one, two, three or more double bonds.

[0100] In one embodiment of the invention, the sugar fatty acid ester, in some embodiments 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.

[0101] In one embodiment, the sugar fatty acid ester may be present at different concentrations to achieve hydrophobic / oleophobic properties 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).

[0102] In other embodiments, the coating can comprise 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.

[0103] 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.

[0104] 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.

[0105] 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.

[0106] 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.

[0107] In one embodiment, the sugar fatty acid esters disclosed herein may be used in coating with other chemicals used in papermaking, including, but not limited to, agarite, esters, diesters, ethers, ketones, amides, nitriles, aromatic compounds (e.g., xylene, toluene), acid halides, anhydrides, alkyl ketene dimer (AKD), alabaster, alganic acid, alum, alvanin, 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 mixture may include one or more SFAEs and one or more of the following inorganic particles: clay (kaolin, bentonite), calcium carbonate (both GGC and PCC), talc (magnesium silicate), and titanium dioxide. In a related aspect, the inorganic particles may be present in the coating composition at between about 1% and about 2%, about 2% and about 5%, about 5% and about 10%, about 10% and about 20%, about 20% and about 30%, about 30% and about 40%, about 40% and about 50%, about 50% and about 60%, or about 60% and about 70%. In a further related aspect, the SFAEs may be present in the same, higher, or lower proportions relative to the amount of inorganic particles in the coating. In one aspect, the coating including one or more SFAEs includes all saturated fatty acids.

[0108] 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).

[0109] In one embodiment, the treated cellulose-containing material may have improved mechanical properties compared to the same untreated material. For example, paper bags treated using the methods disclosed herein exhibit increased burst strength, Gurley number, tensile strength, and / or maximum load energy. In one aspect, the burst strength is increased by about 0.5 to 1.0 times, about 1.0 to 1.1 times, about 1.1 to 1.3 times, or about 1.3 to 1.5 times. In another aspect, the Gurley number is increased by about 3 to 4 times, about 4 to 5 times, about 5 to 6 times, or about 6 to 7 times. In yet another aspect, the tensile strain is increased by about 0.5 to 1.0 times, about 1.0 to 1.1 times, about 1.1 to 1.2 times, or about 1.2 to 1.3 times. In yet another aspect, the maximum load energy is increased by about 1.0 to 1.1 times, about 1.1 to 1.2 times, about 1.2 to 1.3 times, or about 1.3 to 1.4 times.

[0110] In one embodiment, the cellulose-containing material is a base paper containing microfibrillated cellulose (MFC) or cellulose nanofibers (CNF), such as those described in U.S. Patent Application Publication No. 2015 / 0167243 (the entire contents of which are incorporated herein by reference), where the MFC or CNF is added during the forming and papermaking process and / or added to a pre-formed layer as a coating or second 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 a further related aspect, the contacted base paper is further contacted with polyvinyl alcohol (PVOH). In one embodiment, the resulting contacted base paper is controllably water- and oil-resistant. In a related aspect, the resulting base paper may exhibit a Gurley value of at least about 10-15 (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 may be a laminate with respect to one or more layers, or may provide one or more layers as a laminate, or may reduce the amount of coating in one or more layers to achieve the same performance effect (e.g., water resistance, grease resistance, etc.). In a related aspect, the laminate may include a biodegradable and / or composable heat seal or adhesive.

[0111] 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 may include, 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.

[0112] In one embodiment, the sugar fatty acid ester 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, or 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, and controlling color and hue. It will be apparent to those skilled in the art that the combinations may vary depending on the properties desired in the final product.

[0113] 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.

[0114] 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.

[0115] The substrate may be treated with the modifying composition, e.g., 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 may be heated to dry the surface, after which the modified material is ready for use. In one embodiment, in accordance with the methods disclosed herein, the substrate may 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.

[0116] In some applications, the material may be dried before processing, but no special preparation of the material is necessary when practicing the present invention. In one embodiment, the disclosed method can be used on any cellulose-based surface, including, but not limited to, films, rigid containers, fibers, pulp, fabrics, etc. In one aspect, the sugar fatty acid ester or coating 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 coater, double-sided coater, short dwell, simultaneous double-sided coater, blade or rod coater, gravure coater, gravure printing, flexography, inkjet printing, laser printing, supercalendering, and combinations thereof.

[0117] 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 and straw), cellulose nanocrystals, or nanofibrillated cellulose.

[0118] In one embodiment, the amount of the sugar fatty acid ester coating applied is 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 amount of the sugar fatty acid ester coating applied is 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.

[0119] Any suitable coating method 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 any combination of any of these methods alone or in combination with other coating methods adapted to practice the disclosed method.

[0120] 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 "cure" to precisely tailor the quality of the sugar fatty acid ester to meet specific applications.

[0121] 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.

[0122] The derivatized materials have altered physical properties that can be defined and measured using appropriate tests known in the art. For hydrophobicity, analytical protocols can 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 follow are defined by the American Society for Testing and Materials (Protocol ASTM D7334-08).

[0123] 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).

[0124] 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.

[0125] Various methods are available for determining and testing biodegradability, including the shake flask method (ASTM E1279-89(2008)) and the Zahn-Wellens test (OECD TG 302 B).

[0126] A variety of methods are available for determining and testing compostability, including but not limited to ASTM D6400.

[0127] Materials suitable for treatment with the method of the present invention include various forms of cellulose, including plant fibers such as cotton and flax, wood fibers, regenerated cellulose (rayon and cellophane), partially alkylated cellulose (cellulose ethers), partially esterified cellulose (acetate rayon), and other modified cellulose materials, all of which have a significant percentage of 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 may include, but is not limited to, cellulose triacetate, cellulose propionate, cellulose acetate propionate, cellulose acetate butyrate, nitrocellulose (cellulose nitrate), cellulose sulfate, celluloid, methylcellulose, ethylcellulose, ethylmethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, cellulose nanocrystals, hydroxyethylmethylcellulose, hydroxypropylmethylcellulose, ethylhydroxyethylcellulose, carboxymethylcellulose, and combinations thereof.

[0128] 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.

[0129] Among the possible uses of the coating technology, such items include, but are not limited to, containers for all purposes, such as paper, paperboard, paper pulp, cups, lids, boxes, trays, release papers / liners, compostable bags, shopping bags, pipes and water lines, disposable cutlery for food, plates and bottles, screens for TVs and mobile devices, clothing (e.g., cotton or cotton blends), bandages, pressure-sensitive labels, pressure-sensitive tape, 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.

[0130] The following examples are intended to illustrate, but not limit, the present invention. [Example]

[0131] [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.

[0132] <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 removal 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, but sheets coated with various amounts of SEFOSE® exhibited increasing levels of water resistance as the coat weight increased (see Table 1).

[0133] [Table 1]

[0134] It was observed that the heavier sheets had poor water resistance and that water resistance was not achieved unless the sheets were dry.

[0135] <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 samples were coated and placed in an oven at 105°C for 15 minutes. 10-15 test droplets were placed on the coated side of the paperboard and the water holdout time was measured and recorded in the table below. Water penetration of the untreated paperboard control was instantaneous (see Table 2).

[0136] [Table 2]

[0137] <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.

[0138] Further investigation 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. The 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.

[0139] [Table 3]

[0140] [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. 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.

[0141] [Table 4]

[0142] [Example 3] <Investigation of cellulose-based 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. Meanwhile, 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 MCF). Tests show that derivatization of a much less porous sheet offers greater promise for long-term water / vapor barrier performance. The final two images provide a close-up of the average "pores" of a single filter paper and a close-up of a CNF-coated paper at similar magnification for comparison.

[0143] The above data reveal that there is a critical point, where the addition of more material results in 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.

[0144] In fact, products like SEFOSE® are liquid and can be easily emulsified, suggesting that they can be easily adapted to work with coating equipment commonly used in paper mills.

[0145] [Example 4] "Phluphi" Liquid SEFOSE® was mixed and reacted with bleached hardwood fibers to produce various forms that created a waterproof handmade sheet. When sucrose ester was mixed with pulp before sheet formation, most of it was found to be retained with the fibers. With sufficient heating and drying, a very hydrophobic handmade sheet was formed, although it was brittle and fluffy. In this example, 0.25 grams of SEFOSE® was mixed with 4.0 grams of bleached hardwood fibers in 6 liters of water. This mixture was stirred manually 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 produced sheet showed significant hydrophobicity and greatly reduced hydrogen bonding between the fibers themselves. (A water contact angle greater than 100 degrees was observed.). An emulsifier could be added. SEFOSE® and the fibers could be in a ratio of about 1:100 to 2:1.

[0146] Subsequent tests revealed that talc was the only spectator in this case and was removed from further tests.

[0147] [Example 5] [Environmental Effects on SEFOSE® Coating Properties] As an attempt to better understand the reaction mechanism between sucrose ester and fibers, a low-viscosity coating was applied to bleached kraft sheets that had wet strength resin added but no water resistance (no sizing). All coatings were measured to be less than 250 cps using a Brookfield viscometer at 100 rpm.

[0148] SEFOSE® was emulsified with Ethylex 2025 (starch) and applied to paper via a gravure roll. For comparison, SEFOSE® was also emulsified with Westcote 9050 PvOH. As shown in Figure 5, the oxidation of the double bonds of SEFOSE® was enhanced by heat and the presence of an additional chemical environment that enhanced its oxidative chemical properties (see also Table 5).

[0149] [Table 5]

[0150] [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 carried out for at least 6 hours using Soxhlet extraction glassware. The extraction results are shown in Table 6 below.

[0151] [Table 6]

[0152] The data showed that essentially all of the SEFOSE® remained on the sheet. To further verify this, the same procedure was performed on pulp alone, and the results showed 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.

[0153] 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.

[0154] As the data show, it was generally not possible to extract SEFOSE® from the material after drying. However, when a fatty acid containing all saturated fatty acid chains (e.g., OLEAN®, available from Procter & Gamble Chemicals, Cincinnati, Ohio) was used in place of SEFOSE®, nearly 100% of the OLEAN® in the material could 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®).

[0155] 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.

[0156] [Example 7] Addition of SEFOSE® to Achieve Water Resistance Both hardwood and softwood kraft pulp were used to make 2-gram and 3-gram handsheets. When SEFOSE® was added to a 1% pulp slurry at levels above 0.1%, the water was drained off, 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%.

[0157] [Example 8] <Manufacturing bulky fiber materials> The addition of SEFOSE® to pulp acted 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 occupied 45.2 cubic centimeters.

[0158] 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.

[0159] 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, a property not exhibited by hydrophobic single fatty acid chain bonds.

[0160] 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.

[0161] [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). A commercially available bag is also included for reference.

[0162] [Table 7]

[0163] As shown in the table, coating the control base paper with SEFOSE® and PvOH increased the tensile and burst.

[0164] [Example 10] <Wet and dry tensile strength> Three gram handmade sheets were made from bleached pulp. Below, the wet and dry tensile strengths are compared at different SEFOSE® loading levels. Note that these handmade sheets were not emulsified with SEFOSE® in any coating; it was simply mixed into the pulp and drained without the addition of other chemicals (see Table 8).

[0165] [Table 8]

[0166] Note that for wet strength, with an addition of 5%, it does not fall much below the dry strength of the control.

[0167] [Example 11] <Use of esters containing less than 8 saturated fatty acids> Several experiments were conducted using sucrose esters in which less than 8 fatty acids were bound to the sucrose moiety. Samples of SP50, SP10, SP01 and F20W (Sisterna, The Netherlands) contained 50%, 10%, 1%, and essentially 0% monoesters, respectively. These commercial products were made by reacting sucrose with saturated fatty acids and were thus no longer useful for further crosslinking or for similar chemical properties, but were useful when investigating emulsifying and water repellent properties.

[0168] For example, 10 g of SP01 was mixed with 10 g of glyoxal in a 10% heated PvOH solution. The mixture was "heated" at 200°F for 5 minutes and applied by drawdown onto porous base paper made from bleached hardwood kraft. The result was a crosslinked wax-based coating on the surface of the paper that exhibited good hydrophobicity. When a minimum of 3 g / m 2 was applied, the contact angle obtained was greater than 100°. Since glyoxal is a well-known crystallization agent used with compounds having OH groups, this method is a promising means of attaching fairly non-reactive sucrose esters to the surface by bonding the remaining alcohol groups of the sucrose ring to available alcohol groups in the substrate or other coating materials.

[0169] [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.

[0170] [Table 9]

[0171] As shown in Table 9, increasing the amount of SEFOSE® applied to the surface of the paper increased water resistance (as indicated by an increase in HST (in seconds)).

[0172] This can also be seen using coatings of saturated sucrose ester products. As a specific example, 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.

[0173] [Table 10]

[0174] As shown in Table 10, the water resistance of the porous sheet increased with increasing F20W. Thus, the applied sucrose fatty acid ester itself makes the paper water resistant.

[0175] 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.

[0176] [Table 11]

[0177] [Table 12]

[0178] Note the difference here when oleic acid is added directly to the pulp and forms ester bonds, which 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.

[0179] [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.

[0180] The data presented here represent HST (Hercules Size Test) readings obtained from papers coated with various amounts of saturated SFAE.

[0181] #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.

[0182] Coat weight (pounds per ton) HST of saturated SFAE formulation (average of 4 measurements per sample).

[0183] [Table 13]

[0184] The experimental data also confirmed that limited amounts of saturated SFAE can enhance the water resistance of coatings designed for other purposes / applications. For example, when saturated SFAE was blended with Ethylex starch and polyvinyl alcohol-based coatings, increased water resistance was observed in both cases.

[0185] The following examples were coated onto a #50 bleached lithocycle base with a Gurley porosity of 18 seconds.

[0186] 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.

[0187] At a coat weight of 300# / ton, starch alone had an average HST of 480 seconds. A mixture of starch and saturated SFAE at the same coat weight increased the HST to 710 seconds.

[0188] Sufficient polyvinyl alcohol (Selvol 205S) was dissolved in hot water to form a 10% solution. This solution, when coated onto the same #50 paper described above, resulted in an average HST of 225 at a coat weight of 150 lbs / ton. Using this 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.

[0189] Saturated SFAEs are compatible with prolamins (specifically, zein; see U.S. Pat. No. 7,737,200, the entire contents of which are incorporated herein by reference.) The addition of saturated SFAEs helps in this manner, since one of the major barriers to commercial production of the subject matter of that patent is the water solubility of the formulations.

[0190] [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 heated, saturated SFAE-emulsified Exceval HR 3010 PvOH. 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. Some of the key data is shown below in Table 14.

[0191] [Table 14]

[0192] It should be noted that the saturated compounds appear to result in an increase in Kit, with both S-370 and C-1800 resulting in an increase in HST of approximately 100%.

[0193] [Example 15] Wet Strength Additives 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 easily removed by solvents, heat, and pressure.

[0194] When waterproofing and higher levels of water resistance are desired, sucrose esters containing unsaturated functional groups can 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. Adjusting the number and size of the unsaturated groups on the sucrose ester provides a molecule that is not optimal for imparting water resistance, but which can be used to crosslink to impart strength.

[0195] 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 below represent the % sucrose esters of the treated 70# bleached paper (see Table 15).

[0196] [Table 15]

[0197] The data show a trend of increasing wet strength with increasing load level when unsaturated sucrose esters are added to the paper. Dry tensile is shown with the maximum strength of the sheet as the reference point.

[0198] [Example 16] <Method for producing sucrose esters using acid chlorides> In addition to creating hydrophobic sucrose esters via transesterification, similar hydrophobicity could be achieved in textile articles by directly reacting acid chlorides with polyols containing ring structures similar to sucrose.

[0199] 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.

[0200] 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 generation 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.

[0201] 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.

[0202] [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).

[0203] For this work, a bleached kraft paper with a high Gurley (600 seconds) from Turners Falls Paper (Turners Falls, MA) was used. This #50 lb. sheet represents a fairly tight, yet extremely absorbent, sheet.

[0204] 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 the same 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.

[0205] The paper preparation followed TAPPI Standard Method 404 for determining the tensile strength of paper.

[0206] 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 was possible to achieve grease resistance using a saturated SFAE variant.

[0207] [Example 18] <Saturated SFAE and inorganic particles (fillers)> Saturated sucrose fatty acid esters (SFAEs) range from hydrophilic to hydrophobic depending on the number (and length) of fatty acid chains attached to the sucrose molecule. They are not considered to be highly reactive compounds.

[0208] Various substituted SFAEs with side chains 16 or 18 carbons in length have been investigated. Test materials were 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. For this example, 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. Papers treated in this manner were found to have a TAPPI Kit 12. This short-term experiment demonstrated that grease resistance could be achieved using a variant of a saturated SFAE.

[0209] <Observation results> More hydrophobic esters tend to aggregate in aqueous emulsions / dispersions, thus making uniform coating on paper more difficult. The low melting points of some of these molecules result in the coating "melting" into the sheet. When hydrophobic SFAEs are mixed with polymers 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.

[0210] When mixed with calcium carbonate (e.g., precipitated calcium carbonate), it has unexpected appeal. SFAE does not dissolve in paper under the same drying conditions. The calcium carbonate appears to aid in the dispersion of the SFAE, and the adhesion is such that the SFAE acts as a binder to adhere the calcium carbonate particles to the surface of the coated paper. Without being bound by any theory, it is believed that such uniform dispersion enhances water resistance for a given amount of ester.

[0211] Table 16 below shows the water resistance measured by the Hercules Size Test (HST) and increased for formulations containing 50% calcium carbonate. Unsized porous 40 lb sheets were coated by hand drawdown. Coating weights ranged from 7 to 10 g / m². 2 It was.

[0212] [Table 16]

[0213] Demonstrated benefits of the combination include reduced coating costs through the use of carbonates, as well as more efficient use of the SFAE molecules as they are more evenly distributed across the paper substrate surface.

[0214] [Example 17] <Saturated SFAE Blends and Inorganic Particles (Fillers and Clays)> A. This example was designed to study the interaction between saturated sucrose fatty acid ester blends and calcium carbonate.

[0215] A paper coating was prepared with the following composition (dry basis): 10% PVOH; 20% sucrose ester (SE-15 / 1803 blend, equal ratios of SFAE; SE-15 available from Hangzhou Union Biotechnology Co., Ltd., Hangzhou China, and C-1803 available from Itochu Chemicals America, Inc., While Plains, NY), and 70% precipitated calcium carbonate (available from OMYA Inc., Blue Ash, OH). This mixture was applied at 8 g / m². 2 The coating weight was applied to 65# bleached kraft sheet. The calcium carbonate slurry itself does not exhibit a water contact angle or HST when coated on paper. The results of using the coating composition are shown in Table 17 below.

[0216] [Table 17]

[0217] This example serves to illustrate that the ester-carbonate interaction is important enough that the carbonate helps keep the ester evenly distributed on the surface of the sheet, allowing for maximum observed effectiveness. Furthermore, the data demonstrates that bio-based materials have been identified that can be used with CaCO3 to provide coated sheets that exhibit high contact angles when CaCO3 is present as a major component of the composition. Without being bound by any theory, this effect is more pronounced when heavy coating weights of highly pigmented compositions may be applied.

[0218] B: This example was designed to examine the interaction between saturated sucrose fatty acid esters and pigments (e.g., clay).

[0219] Kaolin-based materials have very different properties than calcium carbonate. Table 18 shows the results of producing OGR coatings using equal amounts of another SFAE blend, 80OE (available from Tensac, Sh, Tucuman, Argentina) and SE-15, and equal amounts of 80OE, SE-15, and Imerys CAPIM™ (a kaolin-based material available from Imerys Clay, Inc., Roswell, GA). The following formulations were prepared at 10% solids and applied at 5 g / m². 2 The coating was carried out.

[0220] [Table 18]

[0221] In either barrier coating, when the pigment was present at more than 10-20% using CAPIM™ alone, the paper did not exhibit kit, and as noted above, when the pigment concentration exceeded 10 or 20%, the barrier properties typically decreased significantly (e.g., grease could find pores to penetrate). It is important to observe that the ester provides excellent grease resistance with less net ester in the formulation.

[0222] <Other uses> The cup base stock was found to be heavily treated with rosin to enhance water resistance. However, the Gurley of this paperboard was found to be 50 seconds, indicating a highly porous paperboard. This material is repulpable, and steam penetrates and softens it quickly. Pure SEFOSE® was applied to the paperboard and dried overnight in a 100°C oven. The resulting material had a plastic-like feel and was completely waterproof. It was 50% (wt / wt) cellulose / 50% (wt / wt) SEFOSE® by mass. The Gurley was too high to measure. Submerging a sample in water for 7 days did not significantly soften the material, but greenhouse gas data suggests it will biodegrade in approximately 150 days. Common tapes and glues will not adhere to this composite material.

[0223] Because zein has been shown to impart grease resistance to paper, experiments were conducted with saturated SFAE and zein. Stable aqueous dispersions (up to 25% in water) of zein were produced with 2-5% saturated SFAE. Observations demonstrated that saturated SFAE "locks" the zein onto the paper by imparting water resistance to the formulation (in addition to grease resistance).

[0224] Combinations of SFAE, inorganic particles, and bioplastics may be mixed to produce moldable paper for designing biodegradable coffee cup lids. Using wood fibers and sufficient bioplastic fibers (e.g., polybutylene succinate (Bio-PBS) or polylactic acid (PLA)) with SFAE can make the resulting paper base water-resistant. It has been shown that optimizing the SFAE concentration to ensure water resistance of the article and using inexpensive, common materials, such as standard pulp, can increase the mass percentage of the lid. Therefore, relatively small amounts (e.g., less than 10%) of the article can be made of other materials, such as biopolymers, thereby allowing for the addition of other additives that may be used to provide flexibility, improve tear or extension properties, etc.

[0225] The addition of the calcium carbonate / SFAE mixture allowed for control of the density of the lid.

[0226] Although the invention 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 invention. Accordingly, the invention is limited only by the following claims. All references disclosed herein are incorporated by reference.

Claims

1. 1. A composition comprising one or more sugar fatty acid esters (SFAEs) and inorganic particles, wherein the SFAEs are applied to a surface of a cellulosic substrate in an amount of 0.1 g / m ２ ~20g / m ２ wherein the substrate comprising the composition exhibits superior water and / or grease resistance compared to a substrate comprising the composition comprising only the inorganic particles or one or more SFAEs, and wherein the inorganic particles comprise at least 50 wt % of the composition on a dry basis.

2. 10. The composition of claim 1, wherein all of the SFAEs comprise unsaturated fatty acids, saturated fatty acids, or a mixture of saturated and unsaturated fatty acids, and optionally further comprises one or more binders selected from PvOH or starch.

3. 2. The composition of claim 1, wherein the SFAE is a mixture of two or more different SFAEs, all of which contain saturated fatty acids.

4. 10. The composition of claim 1, wherein the inorganic particles are selected from the group consisting of clay, ground calcium carbonate, precipitated calcium carbonate, talc, titanium dioxide, and combinations thereof.

5. 10. The composition of claim 1, wherein the SFAE comprises at least one sugar and at least one aliphatic group containing from 8 to 30 carbons.

6. The composition of claim 4 , wherein the inorganic particles are calcium carbonate and the substrate exhibits water resistance.

7. 5. The composition of claim 4, wherein the inorganic particles are clay and the substrate exhibits grease resistance.

8. The cellulosic substrate may be paper, paperboard, paper pulp, food storage cartons, food storage bags, shipping bags, coffee or tea containers, tea bags, bacon board, diapers, weed blocking / barrier fabric or film, mulching film, plant pots, packing beads, bubble wrap, oil absorbent material, laminates, envelopes, gift cards, credit cards, gloves, raincoats, OGR paper, shopping bags, compost bags, release paper, tableware, hot or cold beverage containers, cups, paper towels, plates, carbonated liquid storage bottles, insulating materials, non-carbonated liquid storage bottles, 10. The composition of claim 1, wherein the composition is selected from the group consisting of food wrap films, food waste disposal containers, food handling equipment, cup lids, formable paper cup lid screws, paper straws, fabric fibers, water storage and transport equipment, paperboard for pharmaceutical applications, release paper, alcoholic or non-alcoholic beverage storage and transport equipment, casings, exterior screens for electronic products, interior or exterior furniture components, curtains, upholstery, films, boxes, sheets, trays, pipes, water conduits, pharmaceutical packaging, clothing, medical devices, contraceptives, camping equipment, formed cellulosic fibrous materials, and combinations thereof.

9. 1. An article of manufacture comprising a cellulosic substrate and a coating on the cellulosic substrate, wherein the coating comprises one or more sugar fatty acid esters (SFAEs), inorganic particles, and optionally one or more binders, wherein the inorganic particles are present in the coating at a concentration of at least 50% by weight on a dry basis; The cellulosic substrate may be any suitable material, including paper, paperboard, paper pulp, food storage cartons, food storage bags, shipping bags, coffee or tea containers, tea bags, bacon board, diapers, weed blocking / barrier fabric or film, mulching film, plant pots, packing beads, bubble wrap, oil absorbent materials, laminates, envelopes, gift cards, credit cards, gloves, raincoats, OGR paper, shopping bags, compost bags, release paper, tableware, hot or cold beverage containers, cups, paper towels, plates, carbonated liquid storage bottles, insulating materials, non-carbonated liquid storage bottles, and the like. an article of manufacture selected from the group consisting of storage bottles, food wrap films, food waste disposal containers, food handling equipment, cup lids, formable paper cup lid screws, paper straws, fabric fibers, water storage and transport equipment, paperboard for pharmaceutical applications, release paper, alcoholic or non-alcoholic beverage storage and transport equipment, casings, exterior screens for electronic products, interior or exterior furniture components, curtains, upholstery, films, boxes, sheets, trays, pipes, water conduits, pharmaceutical packaging, clothing, medical devices, contraceptives, camping equipment, formed cellulosic fibrous materials, and combinations thereof.

10. 1. A method for treating a cellulosic substrate, comprising: a) adding at least one sugar fatty acid ester (SFAE) to a composition comprising inorganic particles to form a mixture; b) applying the mixture to at least one surface of the cellulosic substrate; c) allowing a sufficient time for the mixture to harden and adhere to the at least one surface; Including, the cured surface exhibits increased hydrophobicity and / or oleophobicity compared to a surface treated with a composition comprising only at least one SFAE or said inorganic particles; The method wherein said inorganic particles comprise at least 50% by weight of said mixture on a dry basis.

11. The method of claim 10, wherein the treated cellulosic surface is hydrophobic.

12. The method of claim 10, wherein the treated cellulosic surface is oleophobic.

13. 11. The method of claim 10, wherein all of the SFAEs comprise saturated fatty acids or a mixture of saturated and unsaturated fatty acids.

14. The method of claim 10, wherein the SFAE is a mixture of two or more different SFAEs.

15. 11. The method of claim 10, wherein the inorganic particles are selected from the group consisting of clay, ground calcium carbonate, precipitated calcium carbonate, talc, titanium dioxide, and combinations thereof.

16. 16. The method of claim 15, wherein the composition further comprises polyvinyl alcohol or starch.

17. 11. The method of claim 10, wherein the inorganic particles comprise calcium carbonate, and the calcium carbonate comprises about 50% or more of the mixture on a dry basis (db).

18. 18. The method of claim 17, wherein the calcium carbonate is precipitated calcium carbonate.

19. Cellulosic substrates are used in a wide variety of applications including paper, paperboard, paper pulp, food storage cartons, food storage bags, shipping bags, coffee or tea containers, tea bags, bacon board, diapers, weed blocking / barrier fabric or film, mulching film, plant pots, packing beads, bubble wrap, oil absorbent materials, laminates, envelopes, gift cards, credit cards, gloves, raincoats, OGR paper, shopping bags, compost bags, release paper, tableware, hot or cold beverage containers, cups, paper towels, plates, carbonated liquid storage bottles, insulating materials, non-carbonated liquid storage bottles, food 11. The method of claim 10, wherein the cellulosic fiber material is selected from the group consisting of food wrap films, food waste disposal containers, food handling equipment, cup lids, formable paper cup lid screws, paper straws, fabric fibers, water storage and transport equipment, paperboard for pharmaceutical applications, release paper, alcoholic or non-alcoholic beverage storage and transport equipment, casings, external screens for electronic products, interior or exterior furniture components, curtains, upholstery, films, boxes, sheets, trays, pipes, water conduits, pharmaceutical packaging, clothing, medical devices, contraceptives, camping equipment, formed cellulosic fiber materials, and combinations thereof.

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