CN114258445A - Sugar fatty acid ester inorganic particle combination - Google Patents

Abstract

The present disclosure describes methods of treating cellulosic materials with compositions that provide inorganic particles with greater retention on the cellulosic substrate. The disclosed method provides: combining Sugar Fatty Acid Esters (SFAE) with such inorganic particles and applying such combinations to cellulosic materials eliminates or reduces the use of retention aids or binders for fillers in the papermaking process. Compositions comprising a combination of SFAE and inorganic particles are also disclosed.

Description

Sugar fatty acid ester inorganic particle combination

Background

Cross Reference to Related Applications

This application claims priority from U.S. patent application No.16/456,433 filed by the U.S. patent and trade Office on 28/6/2019, which is incorporated herein by reference in its entirety.

Technical Field

The present application relates generally to the treatment of cellulosic based materials, and more particularly to the treatment of such materials with Sugar Fatty Acid Esters (SFAE) in combination with inorganic particles, including compositions comprising such combinations.

Background

Inorganic particles such as kaolin, talc, calcium carbonate and TiO₂Are commonly used as fillers in papermaking processes. For example, calcium carbonate is used in paper mills as a filler material in alkaline papermaking processes. Currently, calcium carbonate dominates over other papermaking filler materials (e.g., kaolin). The main reason behind the popularity of calcium carbonate is the need for brighter and thicker heavier papers. The use of calcium carbonate in alkaline papermaking processes has significant benefits (e.g., calcium carbonate is less expensive and can also form a porous surface on the paper if it has high brightness, improves printability, reduces binder requirements, increases machine speed and productivity, improves drainage, improves machine runnability, is cost effective in papermaking, can reduce fiber consumption, and can achieve more retention (retentivity) than other paper fillers).

Typically, calcium carbonate exists in three natural forms, such as limestone, chalk and marble. In nature, it is formed in the reaction of calcium salts and carbon dioxide. Two types of calcium carbonate are used in paper mills: ground Calcium Carbonate (GCC) and Precipitated Calcium Carbonate (PCC).

Ground calcium carbonate is made by milling limestone or marble and is used for its high brightness and purity. Generally, the particle shape of ground calcium carbonate is rhombohedral. The filler material is used in alkaline, wood-free papermaking processes. The GCC had a brightness of about 86-95%.

The coarse particle shape and small amount of quartz common in GCC can cause problems; it is more abrasive and shortens the life of paper machine forming wires and press felts.

The precipitated calcium carbonate being CaCO produced by chemical reaction₃In form, and this process is referred to as the carbonation process. PCC ameliorates the disadvantages of GCC, which provides better gloss and opacity characteristics to the paper. The structure of PCC is different from that of GCC. The crystal structure of PCC can be controlled and includes acicular, rhombohedral (cubic), scalenohedral (triangular), and prismatic. The brightness of the PCC is about 90-97%. However, PCC-containing paper may have poorer formation than GCC-containing paper.

On modern high-speed gap paper machines (twin-wire paper machines), the turbulence required to obtain good formation often results in low retention of the filler. Furthermore, for both types of calcium carbonate, they do not adhere to cellulose themselves and require retention aids (binders) or binders to adhere to the pulp. Typically, such retention aids or binders include paper alum, synthetic polymers, polyacrylamides, particulate systems, latex, starch, and polyvinyl alcohol (PvOH), which can add cost or make the product less "green" (e.g., synthetic polymers) if desired.

It is desirable to bind the calcium carbonate so that the use of a retention aid or binder is unnecessary or to reduce the amount of retention aid or binder required to adhere the inorganic particles to the cellulosic surface.

Disclosure of Invention

The present disclosure relates to methods of treating cellulosic materials with compositions that, in particular, increase the retention of inorganic particles (i.e., fillers). The disclosed method provides: the combination of Sugar Fatty Acid Esters (SFAE) with such fillers and the application of such combinations to cellulose eliminates or reduces the use of retention aids or binders for fillers in the papermaking process. Compositions comprising a combination of SFAE and inorganic particles are also disclosed.

In embodiments, compositions are disclosed comprising Sugar Fatty Acid Esters (SFAEs) and inorganic particles, wherein the SFAEs are present in a sufficient concentration to retain the inorganic particles on the cellulose-based material, and wherein a substrate comprising the composition exhibits greater water resistance and/or greater oil resistance than a substrate comprising the composition comprising the inorganic particles or one or more SFAEs alone.

In one aspect, 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.

In another aspect, the SFAE is a mixture of two or more different SFAEs, wherein the two or more different SFAEs are all saturated fatty acids.

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

In another aspect, the SFAE comprises at least one saccharide and at least one aliphatic group comprising 8 to 30 carbon atoms. In one aspect, the inorganic particle is calcium carbonate, wherein the substrate exhibits water resistance. In a related aspect, the inorganic particles are clays, wherein the substrate exhibits resistance to grease.

In one aspect, the cellulose-based substrate comprises paper, paperboard, pulp, carton for storing food, bag for storing food, shipping bag, coffee or tea container, tea bag, bacon board (bacon board), diaper, weed-blocking/barrier fabric or film (weed-block/barrier fabric or film), mulching film, planting pot, packing bead (packing bead), bubble-film wrapper (bubble wrap), oil absorbent material, laminate, envelope, gift card, credit card, glove, raincoat, OGR paper, shopping bag, compost bag, release paper, tableware, container for holding hot and cold beverages, cup, paper towel, tray, bottle for storing carbonated liquid, insulation, bottle for storing non-carbonated liquid, film for packaging food, disposal container, food disposal container, cup cover, screw thread on plastic paper, paper straws, woven fabrics, water storage and delivery devices, medical cardboard, release paper, devices for storing and delivering alcoholic or non-alcoholic beverages, casings (casting), electronic product screens, internal or external parts of furniture, curtains, upholstery, films, boxes, sheets, trays, tubes, water pipes, medical product packaging, garments, medical devices, contraceptives, camping equipment, molded cellulosic fibrous materials, and combinations thereof.

In embodiments, articles of manufacture are disclosed that include a coating comprising one or more Sugar Fatty Acid Esters (SFAE), 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 related aspects, the cellulose-based substrate includes paper, paperboard, paper pulp, cartons for storing food, bags for storing food, shipping bags, coffee or tea containers, tea bags, bacon boards, diapers, weed-obscuring/barrier fabrics or films, mulching films, planting pots, packaging beads, bubble-film packaging materials, oil absorbent materials, laminates, envelopes, gift cards, credit cards, gloves, raincoats, OGR paper, shopping bags, compost bags, release paper, tableware, containers for holding hot and cold beverages, cups, paper towels, trays, bottles for storing carbonated liquids, insulation materials, bottles for storing non-carbonated liquids, films for packaging food, garbage disposal containers, food disposal appliances, cup covers, threads on plastic paper cup covers, paper straws, fabric fibers, water storage and delivery appliances, medical cardboard, release paper, paper pouches, paper bags, paper pouches, paper, an appliance for storing and delivering alcoholic or non-alcoholic beverages, a housing, an electronics screen, an interior or exterior part of furniture, a curtain, upholstery, a film, a box, a sheet, a tray, a tube, a water pipe, a medical product packaging, a garment, a medical device, a contraceptive, a camping equipment, a molded cellulosic fibrous material, and combinations thereof.

In embodiments, 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 curing for a time sufficient to cause the mixture to adhere to the at least one surface, wherein the cured surface is more hydrophobic and/or oleophobic than a surface treated with the at least one SFAE alone or the composition including only inorganic particles.

In one aspect, the treated cellulosic surface is hydrophobic. In another aspect, the treated cellulosic surface is oleophobic.

In one aspect, SFAE includes all saturated fatty acids or mixtures of saturated and unsaturated fatty acids. SFAE, on the other hand, is a mixture of two or more different SFAEs.

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

In one aspect, the inorganic particles comprise calcium carbonate, wherein the calcium carbonate comprises greater than or equal to about 30% of the mixture on a dry basis (db).

In another aspect, the cellulosic substrate comprises paper, paperboard, pulp, cartons for storing food, bags for storing food, shipping bags, coffee or tea containers, tea bags, bacon boards, diapers, weed-obscuring/barrier fabrics or films, mulching films, planting pots, packaging beads, bubble-film packaging, oil absorbent materials, laminates, envelopes, gift cards, credit cards, gloves, raincoats, OGR paper, shopping bags, compost bags, release paper, tableware, containers for hot and cold beverages, cups, tissues, trays, bottles for carbonated liquids, insulation materials, bottles for non-carbonated liquids, films for packaging food, garbage disposal containers, food disposal appliances, cup covers, threads on plastic cup covers, paper straws, fabric fibers, water storage and delivery appliances, medical paperboard, release paper, appliances for storing and delivering alcoholic or non-alcoholic beverages, electronic housings or screens, internal or external parts of furniture, curtains, upholstery, films, boxes, sheets, trays, tubes, water pipes, medical product packaging, clothing, medical devices, contraceptives, camping equipment, molded cellulosic fibrous materials, and combinations thereof.

Drawings

Figure 1 shows a Scanning Electron Micrograph (SEM) of untreated medium porosity Whatman filter paper (58 x magnification).

Figure 2 shows the SEM of untreated medium porosity Whatman filter paper (1070 x magnification).

Figure 3 shows a side-by-side comparison of SEM of paper made from recycled pulp before (left) and after (right) (27 x magnification) coating using microfibrillated cellulose (MFC).

Figure 4 shows a side-by-side comparison of SEM of paper made from recycled pulp before (left) and after (right) (98 x magnification) coating using MFC.

Fig. 5 shows water penetration in paper treated with various coating formulations: polyvinyl alcohol (PvOH), rhombus;

+ PvOH at a ratio of 1:1(v/v), square; ethyl lex (starch), triangular;

+ PvOH at a ratio of 3:1(v/v), cross.

Detailed Description

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

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 "a sugar fatty acid ester" includes one or more sugar fatty acid esters and/or compositions of the type described herein, which will become apparent to those skilled in the art upon reading this disclosure and so forth.

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

As used herein, "about," "substantially," and "significantly" will be understood by those of ordinary skill in the art and will vary to some extent depending on the context in which they are used. If the use of this term is not clear to one of ordinary skill in the art given its context of use, "about" and "approximately" means plus or minus < 10% of the particular term, and "substantially" and "significantly" means plus or minus > 10% of the particular term. "comprising" and "consisting essentially of … …" have their customary meaning in the art.

All pigments must remain uniformly on the paper to be acted upon. Paper can become less expensive when fillers are used that are less costly than fibers. However, the proportion of filler in the paper is limited by the extent to which it leads to a reduction in strength, bulk and sizing quality. While the trend is certainly toward higher filler content, barrier properties are significantly reduced once the pigment concentration in any barrier coating exceeds 10% or 20%.

Although not polymeric per se, SFAE contributes to the retention of fillers or inorganic particles such as PCC. While not being bound by any theory, SFAE may crosslink or provide a network with fines and surfaces on the fiber. The combination performs well and allows for higher levels of adhesion without compromising product quality, including providing increased levels of performance.

In addition, organic particles such as uncooked starch, wood particles, oat hulls, etc. provide bulk and can increase the caliper (caliper) which is highly desirable in some products, while inorganic materials increase density. Furthermore, for hydrophobic polymers, including wood resins (wood resins), hot melt waxes, bio-plastics, etc., that can produce undesirable particulates and/or sticky substances or deposits, the use of SFAE-inorganic particulate combinations can address these undesirable aggregates.

Furthermore, the addition of a composition comprising a mixture of inorganic particles and SFAE improves the fine-tuning of various properties of the paper. For example, such paper may comprise wood fibers, and bioplastic fibers in combination with SFAE to render such paper impervious to water. The contemplated combination allows for the use of cheaper, more common materials, such as mechanical or recycled pulp, to make up a larger proportion of the paper mass. In this case, the addition of, for example, a calcium carbonate-SFAE mixture provides an improvement in controlling the density of the paper.

In embodiments, the present disclosure demonstrates that by treating cellulosic materials with a combination of inorganic particles and sugar fatty acid esters, the resulting materials themselves can become strongly hydrophobic and/or lipophobic. Furthermore, these sugar fatty acid esters are themselves easily digested, for example, once removed by bacterial enzymes. The derivatized surface appears very heat resistant, can withstand temperatures up to 250 ℃, and may be more gas impermeable than the underlying substrate. Thus, in any embodiment where a cellulosic material may be employed, the material is an ideal solution to the problem of derivatizing the hydrophilic surface of cellulose.

Advantages of the products and methods disclosed herein include: the coating composition is made from renewable agricultural resources-sugar and vegetable oil; is biodegradable; has low toxicity and is suitable for food contact; can be adjusted to reduce the coefficient of friction of the paper/paperboard surface (i.e., not to make the paper too slippery to accommodate downstream processing or end use), even with high water resistance; may or may not be used with special emulsifying equipment or emulsifiers; and is compatible with conventional paper recycling programs, i.e., does not adversely affect the recycling operation as polyethylene, polylactic acid, or waxed paper. In addition, the extended use of inorganics (such as PCC) takes advantage of the inherent properties of fillers (e.g., lower abrasiveness).

As used herein, "biobased" means a material that is intentionally made from a substance derived from a living (or once living) organism. In a related aspect, materials comprising at least about 50% of such substances are considered to be biobased.

As used herein, "bonded" includes grammatical variations thereof meaning bonded or resulting in substantial bonding as a single mass.

As used herein, "cellulosic" means a natural, synthetic, or semi-synthetic material that can be molded or extruded into objects (e.g., bags, sheets) or films or filaments that can be used to make such objects or films or filaments that are similar in structure and function to cellulose, such as coatings and adhesives (e.g., carboxymethylcellulose). In another example, cellulose, a complex carbohydrate (C) composed of glucose units₆H₁₀O₅)_nIt forms the major component of the cell wall in most plants-it is cellulosic.

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

As used herein, "compostable" means that these solid products can biodegrade into the soil.

As used herein, "dry basis" is a measure of the quality of all ingredients but excluding water (e.g., solids).

As used herein, "edge wicking" means absorption of water in a paper structure at the outer edges of the structure by one or more mechanisms including, but not limited to, capillary penetration in the inter-fiber pores, diffusion through the fibers and adhesive, and surface diffusion on the fibers. In a related aspect, a coating comprising a sugar fatty acid ester as described herein prevents edge wicking in a treated product. On the one hand, similar problems exist with grease/oil ingress into the crease (which may be present in the paper or paper product). This "grease creasing effect" may be defined as the adsorption of grease in a paper structure by folding, pressing or crushing the paper structure.

As used herein, "effect" including grammatical variations thereof means imparting a particular characteristic to a particular material.

As used herein, "hydrophobe" means a substance that does not absorb water. For example, waxes, rosins, resins, sugar fatty acid esters, diketene, shellac, vinyl acetate, PLA, PEI, oils, fats, lipids, other water-proofing chemicals, or combinations thereof are hydrophobes.

As used herein, "hydrophobic" means the characteristic of being water repellent, tending to repel water and not absorbing water.

As used herein, "lipid resistance" or "lipophobicity" means the property of being fat repellent, tending to repel without absorbing lipids, grease, fat, etc. In related aspects, oil and grease resistance can be measured by the "3M KIT" test or TAPPI T559 KIT test.

As used herein, "cellulose-containing material" or "cellulose-based material" means a composition consisting essentially of cellulose. For example, such materials can include, but are not limited to, paper, cardboard, paper pulp, cartons for storing food, bags for storing food, shipping bags, coffee or tea containers, tea bags, bacon boards, diapers, weed-obscuring/barrier fabrics or films, mulching films, planting pots, packaging beads, bubble film packaging, oil absorbent materials, laminates, envelopes, gift cards, credit cards, gloves, raincoats, OGR paper, shopping bags, compost bags, release paper, tableware, containers for holding hot and cold beverages, cups, paper towels, trays, bottles for storing carbonated liquids, insulating materials, bottles for storing non-carbonated liquids, films for packaging food, garbage disposal containers, food handling implements, paper straws, fabric fibers, water storage and delivery implements, medical cardboard, release paper, implements for storing or delivering alcoholic or non-alcoholic beverages, disposable bottles for storing carbonated liquids, disposable bottles for storing non-carbonated liquids, disposable bottles for storing food, disposable bottles for storing water, or for storing water for storing a disposable beverages, for storing a disposable beverage, for storing a disposable food for use in a disposable food for use in a disposable bottle, for use in a disposable bottle for use for a disposable bottle for use for a disposable bottle for the, Housings or screens for electronic products, internal or external parts of furniture, curtains and upholstery, films, boxes, sheets, trays, tubes, pipes, medical product packaging, garments, medical devices, contraceptives, camping equipment, molded cellulosic materials, and combinations thereof.

As used herein, "release paper" means a sheet of paper used to prevent premature adhesion of an adhesive surface to an adhesive or cohesive. In one aspect, the coatings disclosed herein may be used to replace or reduce the use of silicon or other coatings for producing materials with low surface energy. The determination of the surface energy is effected by measuring the contact angle (for example, Optical Tensiometer and/or High Pressure Chamber; dye Testing, Staffordshire, United Kingdom) or by using a surface energy test pen or ink (see, for example, dye Testing, Staffordshire, United Kingdom).

As used herein, "strippable" with respect to an SFAE means that the SFAE coating, once applied, can be removed from the cellulose-based material (e.g., can be removed by manipulation of physical properties). As used herein, "non-strippable" with respect to the SFAE means that the SFAE coating, once applied, is substantially irreversibly bound to the cellulose-based material (e.g., removable by chemical means).

As used herein, "fiber in solution" or "pulp" refers to lignocellulosic fiber material prepared by chemical or mechanical separation of cellulosic fibers from wood, fiber crops, or waste paper. In a related aspect, when the cellulosic fibers are treated by the methods disclosed herein, the cellulosic fibers themselves comprise the bound sugar fatty acid ester as a separate entity, and wherein the bound cellulosic fibers have independent and distinct properties relative to free fibers (e.g., pulp fiber-sugar fatty acid ester or cellulosic fiber-sugar fatty acid ester or nanocellulose or microfibrillated cellulose-sugar fatty acid ester binding material does not form hydrogen bonds between fibers as readily as unbound fibers).

As used herein, "repulpable" means that the paper or paperboard product is adapted to be crushed into a soft, amorphous mass for reuse in the production of paper or paperboard.

As used herein, "tunable" includes grammatical variations thereof that mean adjusting or adapting a process to achieve a particular result.

As used herein, "water contact angle" refers to an angle measured through a liquid where the liquid/vapor interface is in contact with a solid surface. It quantifies the wettability of a liquid to a solid surface. The contact angle reflects the strength of the interaction of a liquid and a solid molecule with each other relative to the strength of the interaction of the molecule with its same class of molecules. On many highly hydrophilic surfaces, a water droplet will exhibit a contact angle of 0 ° to 30 °. Generally, a solid surface is considered hydrophobic if the water contact angle is greater than 90 °. The water contact angle can be readily obtained using an Optical Tensiometer (Optical tensometer) (see, e.g., Dyne Testing, Staffordshire, United Kingdom).

As used herein, "water vapor permeability" means breathability or the ability of a textile to transport moisture. There are at least two different measurement methods. One is the MVTR test (Moisture vapor Transmission Rate) according to ISO 15496, which describes the Water Vapor Permeability (WVP) of the fabric and thus also the degree of evaporative Transmission to the outside air. Measurements determined how many grams of moisture (water vapor) passed through one square meter of fabric in 24 hours (the higher the level, the higher the air permeability).

In one aspect, TAPPI T530 Hercules sizing test (size test) (i.e., sizing test paper by ink resistance) may be used to determine water resistance. The ink resistance of the Hercules method is best classified as a direct measurement of penetration. Others classify it as a permeability test. There is no optimal test method for "sizing (sizing)" measurement. Test selection depends on the end use and mill control requirements. This method is particularly suitable for mill-controlled sizing tests to accurately detect changes in sizing levels. It provides sensitivity to the float test while providing repeatable results, shorter test times and automatic endpoint determination.

Sizing is an important feature of many papers as measured by resistance to the penetration or absorption of aqueous liquids through or into the paper. Typical of these are bags, cartonboard, meat wrapping, writing paper and some printing grades.

The method can be used to monitor the production of paper or board for a particular end use, provided that an acceptable correlation has been established between the test values and the end use properties of the paper. Due to the nature of the test and penetrant, it does not have to be of sufficient relevance to suit all end use requirements. This method measures sizing by permeability. Other methods measure sizing by surface contact, surface penetration or absorption. Sizing tests were selected based on their ability to simulate the water contact or absorption pattern in the end use. The method can also be used to optimize the cost of sizing chemicals used.

As used herein, "oxygen permeability" means 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 both the diffusivity (D), i.e., the speed at which oxygen molecules pass through the material, and the solubility (k), or the molecular weight of oxygen absorbed per volume in the material. Oxygen permeability (Dk) values typically range from 10 to 150x 10^-11(cm² ml O₂) /(s ml mmHg) range. The relationship between the water content of the hydrogel and the oxygen permeability (unit: Barrer unit) has been shown to be semilogarithmic. The international organization for standardization (ISO) has specified permeability in terms of pressure using SI units of hectopascal (hPa). Thus Dk 10^-11(cm² ml O₂) /(s ml hPa). Barrer units can be converted to hPa units by multiplying them by a constant of 0.75.

As used herein, "biodegradable" including grammatical variations thereof means capable of being specifically broken down into harmless products by the action of an organism (e.g., by a microorganism).

As used herein, "recyclable" includes grammatical variations thereof, meaning a material that can be processed or manipulated (with used and/or discarded articles) to render the material suitable for reuse.

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 paper. The particles are used to fill spaces and gaps between fibers to produce paper with increased brightness, opacity, smoothness, gloss, and printability, but generally have lower bond strength and tear strength. Common papermaking fillers include clay (kaolin, bentonite), calcium carbonate (GCC and PCC), talc (magnesium silicate) and titanium dioxide.

As used herein, "Gurley seconds" or "Gurley number" is a unit (ISO5636-5:2003) (porosity) that describes the number of seconds required for 100 cubic centimeters (deciliters) of air to pass through a given material of 1.0 square inches at a pressure differential of 4.88 inches of water (0.176 psi). Further, for stiffness, "gurley number" is the unit of force (1 milligram force) required to deflect a given amount of material measured for a piece of material placed vertically. Such values can be measured on a Gurley Precision Instruments' device (Troy, New York).

The HLB-hydrophilic-lipophilic balance-of a surfactant is a measure of its degree of hydrophilicity or lipophilicity, and is determined by calculating the values of different regions of the molecule.

The Griffin process for nonionic surfactants described in 1954 is as follows:

HLB＝20*M_h/M

wherein M is_hIs the molecular mass of the hydrophilic part of the molecule and M is the molecular mass of the whole molecule, giving results in the range of 0 to 20. An HLB value of 0 corresponds to a fully lipophilic/hydrophobic molecule and a value of 20 corresponds to a fully hydrophilic/lipophobic molecule.

HLB values can be used to predict surfactant properties of molecules:

< 10: fat-soluble (water-insoluble)

> 10: water solubility (lipid insolubility)

1.5-3: defoaming agent

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

7 to 9: wetting and spreading agent

13 to 15: detergent composition

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

15 to 18: solubilizers or hydrotropes

In some embodiments, the HLB value of the sugar fatty acid esters disclosed herein (or compositions comprising the esters) may be in a lower range. In other embodiments, the HLB value of the sugar fatty acid esters (or compositions comprising the esters) as disclosed herein may range from intermediate to higher. In embodiments, mixed SFAEs with different HLB values may be used.

As used herein，

Denotes a sucrose fatty acid ester (soyate) made from soybean oil, available from Procter&Gamble Chemicals (Cincinnati, OH) is commercially available under the trade name sefse 1618U (see sucrose soyate, infra), which contains one or more unsaturated fatty acids. As used herein, the term "a" or "an" refers to,

the representation is available from Procter&Formula C obtained from Gamble Chemicals_n+12H_2n+22O₁₃The sucrose fatty acid ester of (1), wherein all the fatty acids are saturated. In addition, SFAEs are available from Mitsubishi Chemicals Foods Corporation (Tokyo, JP), which offers a variety of such SFAEs.

As used herein, "fatty acid soyate" means a mixture of salts of fatty acids from soybean oil.

As used herein, "oilseed fatty acid" refers to fatty acids from plants, including, but not limited to, soybean, peanut, rapeseed, barley, canola (canola), sesame seed, cottonseed, palm kernel, grape seed, olive, safflower, sunflower, copra kernel, corn, coconut, linseed, hazelnut, wheat, rice, potato, cassava, alfalfa, camellia seed (camelina seed), mustard seed, and combinations thereof.

As used herein, "wet strength" means a measure of the extent to which a web that holds paper together can resist failure forces when the paper is wet. The Wet Strength can be measured using a Finch Wet Strength Device from the Thwing-Albert Instrument Company (West Berlin, NJ). Wherein wet strength is typically affected by wet strength additives such as alkaline curing cationic resins (kymene), cationic glyoxylated resins, polyamidoamine-epichlorohydrin resins, polyamine-epichlorohydrin resins, including epoxy resins. In embodiments, the SFAE coated cellulose-based materials disclosed herein achieve such wet strength without such additives.

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

In embodiments, the methods disclosed herein comprise mixing a sugar fatty acid ester and an inorganic particle (e.g., clay, talc, calcium carbonate) and applying the mixture to a cellulosic material, which can adhere the particle to the cellulosic material, wherein the method comprises contacting the cellulosic based material with the combination and exposing the contacted cellulosic based material to heat, radiation, a catalyst, or a combination thereof for a sufficient time to bond the combination to the cellulosic based material. In related aspects, such radiation may include, but is not limited to, UV, IR, visible light, or combinations thereof. In another related aspect, the reaction can be carried out at room temperature (i.e., 25 ℃) to about 150 ℃, about 50 ℃ to about 100 ℃, or about 60 ℃ to about 80 ℃.

Furthermore, the bonding reaction between the mixture and the cellulosic material can be carried out with a retention aid (i.e., a binder such as PVOH or starch) or a significantly reduced retention aid. In one aspect, the mixture can comprise monoesters, diesters, triesters, tetraesters, pentaesters, hexaesters, heptaesters, or octaesters. On the other hand, it may also comprise proteins, polysaccharides and lipids, including but not limited to milk proteins (e.g., casein, whey protein, etc.), wheat proteins, gelatin, prolamines (e.g., zein), isolated soy protein, starch, modified starch, acetylated polysaccharides, alginates (alginates), carrageenan, chitosan, inulin, long chain fatty acids, waxes and combinations thereof.

In embodiments, the cellulosic material may be lipophobic by the addition of polyvinyl alcohol (PvOH) and/or prolamine. In one aspect, the prolamines include zein, gliadin, hordein, secalin, katirin, and avenin. In a related aspect, the prolamine is zein.

In embodiments, no catalyst and organic carrier (e.g., volatile organic compound) are required to perform the combination reaction, including: material build-up is not considered using the disclosed methods. In a related aspect, the reaction time occurs substantially instantaneously (i.e., less than 1 second). Furthermore, the resulting material exhibits low blocking.

As disclosed herein, all fatty acid esters of saccharides (including monosaccharides, disaccharides, and trisaccharides) are suitable for use in connection with this aspect of the invention. In related aspects, the sugar fatty acid ester can be a monoester, diester, triester, tetraester, pentaester, hexaester, heptaester, or octaester, and combinations thereof, including fatty acid moieties that can be saturated, unsaturated, or combinations thereof.

While not being bound by theory, the interaction between the sugar fatty acid ester and the cellulose-based material may be achieved by ionic, hydrophobic, van der waals interactions, or covalent bonds, or combinations 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 SFAE comprising a combination of saturated and unsaturated fatty acids).

Furthermore, at sufficient concentrations, the combination of only sugar fatty acid esters is sufficient to make the cellulose-based material hydrophobic: that is, hydrophobicity is achieved without adding: waxes, rosins, resins, diketene, shellac, vinyl acetate, PLA, PEI, oils, other water repellent chemicals, or combinations thereof (i.e., secondary hydrophobes), including other properties such as, in particular, strengthening, stiffening, and bulking of cellulose-based materials is achieved solely by the combination of sugar fatty acid esters.

An advantage of the disclosed invention is that the plurality of fatty acid chains can react with cellulose and with two sugar molecules in the structure, e.g., the disclosed sucrose fatty acid esters create a rigid cross-linked network, resulting in increased strength of fibrous webs such as paper, paperboard, air-laid and wet-laid nonwovens, and textiles, and thus can overcome the potential adverse effects of certain fillers such as calcium carbonate and lower bond strength and tear strength. This is not typically present in other sizing or hydrophobic treatment chemicals. The sugar fatty acid esters disclosed herein also produce/increase wet strength, a property not present when many other water-resistant chemicals are used.

Another advantage is that the disclosed sugar fatty acid esters soften the fibers, increasing the space between them, thereby increasing volume without significantly increasing weight. Further, the modified fibers and cellulose-based materials as disclosed herein may be repulped. Further, for example, water cannot be easily "squeezed" into the sheet by a low surface energy barrier.

Saturated SFAEs are typically solid at nominal processing temperatures, while unsaturated SFAEs are typically liquid. This enables the formation of a uniform, stable dispersion of saturated SFAE in an aqueous coating without significant interaction or incompatibility with other coating components, which are typically hydrophilic. In addition, such dispersions allow the preparation of high concentrations of saturated SFAE without adversely affecting coating rheology, uniform coating application, or coating performance characteristics. When particles saturated with SFAE melt and spread when the coating is heated, dried and consolidated, the coating surface will become hydrophobic. In embodiments, a method of making a lofty fibrous structure that retains strength even when exposed to water is disclosed. Typically, the dried fiber slurry forms a dense structure that readily disintegrates when exposed to water. Shaped fiber products made using the disclosed methods can include paper trays, beverage containers (e.g., cups), lids, food trays, and packaging, which are lightweight, strong, and resistant to exposure to water and other liquids.

In embodiments, the sugar fatty acid ester may be mixed with polyvinyl alcohol (PvOH) to make a sizing agent for water-resistant coatings. As disclosed herein, a synergistic relationship between sugar fatty acid esters and PvOH has been demonstrated, with inorganic mixtures, to reduce the amount of PvOH. Although it is known in the art that PvOH is a good film former by itself and forms strong hydrogen bonds with cellulose, it is not very water resistant, especially hot water. In some aspects, the use of PvOH helps emulsify the sugar fatty acid esters into aqueous coatings. In one aspect, PvOH provides an abundant source of OH groups for the sugar fatty acid esters to crosslink along the fibers, which increases the strength (e.g., especially wet strength) of the paper and water resistance over that possible with PvOH alone. For saturated fatty acid esters of sugars containing free hydroxyl groups, crosslinking agents such as dialdehydes (e.g., glyoxal, glutaraldehyde, etc.) may also be used.

In embodiments, the sugar fatty acid ester comprises or consists essentially of a sucrose ester of a fatty acid. A number of processes are known and can be used to prepare or provide the sugar fatty acid esters of the present invention and all such processes are believed to be useful within the broad scope of the present invention. For example, in certain embodiments, fatty acid esters may be synthesized, preferably by esterifying sugars with one or more fatty acid moieties obtained from oil seeds, including but not limited to soybean oil, sunflower oil, olive oil, canola oil, peanut oil, and mixtures thereof.

In embodiments, the sugar fatty acid ester comprises a sugar moiety, including but not limited to a sucrose moiety, which has been substituted at one or more of its hydroxyl hydrogens with an ester moiety. In a related aspect, the disaccharide ester has the structure of formula I.

Wherein "a" is hydrogen or structure I below:

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 wherein at least one "a" is at least one, at least two, at least three, at least four, at least five, at least six, at least seven, and all eight "a" moieties of the formula are in accordance with structure I. In related aspects, the sugar fatty acid esters as described herein can be monoesters, diesters, triesters, tetraesters, pentaesters, hexaesters, heptaesters, or octaesters, and combinations thereof, wherein the aliphatic groups can be fully saturated or can comprise saturated and/or unsaturated groups, or combinations thereof.

Suitable "R" groups include any form of aliphatic moiety, including those containing one or more substituents that may be present on any carbon of the moiety. Also included are aliphatic moieties having functional groups therein, such as ether, ester, thio, amino, phospho, and the like. Also included are oligomeric and polymeric aliphatic moieties such as sorbitan, polysorbitan and polyol moieties. Examples of functional groups that can be attached to the aliphatic (or aromatic) moiety comprising the "R" group include, but are not limited to, halogen, alkoxy, hydroxyl, amino, ether, and ester functional groups. In one aspect, the moiety can have crosslinking functionality. In another aspect, SFAE can be crosslinked to a surface (e.g., activated clay/pigment particles). On the other hand, the double bonds present on SFAE can be used to facilitate reactions on other surfaces.

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

In embodiments, the substrate for adding fatty acids may comprise starch, hemicellulose, lignin, or a combination thereof.

In embodiments, the composition comprises a starch fatty acid ester, wherein the starch may be derived from any suitable source, such as dent corn starch, waxy corn starch, potato starch, wheat starch, rice starch, sago starch, tapioca starch, sorghum starch, sweet potato starch, and mixtures thereof.

In more detail, the starch may be unmodified starch, or starch that has been modified by chemical, physical or enzymatic modification methods.

Chemical modification includes any treatment of starch with chemicals that produce modified starch (e.g., plastic starch materials). Chemical modifications include, but are not limited to, depolymerization of starch, oxidation of starch, reduction of starch, etherification of starch, esterification of starch, nitration of starch, degreasing of starch, hydrophobization of starch, and the like. Chemically modified starches may also be prepared by using a combination of any chemical treatments. Examples of chemically modified starches include alkenyl succinic anhydrides, particularly octenyl succinic anhydride, reacted with starch to produce hydrophobic esterified starch; 2, 3-epoxypropyl trimethyl ammonium chloride reacts with starch to generate cationic starch; ethylene oxide reacts with starch to generate hydroxyethyl starch; hypochlorite reacts with starch to produce oxidized starch; acid reacts with starch to generate acid hydrolyzed starch; the starch is defatted with a solvent such as methanol, ethanol, propanol, dichloromethane, chloroform, carbon tetrachloride, etc., to obtain defatted starch.

Physically modified starch is any starch that has been physically treated in any manner to provide a physically modified starch. Physical modifications include, but are not limited to, heat treating the starch in the presence of water, heat treating the starch in the absence of water, breaking the starch granules by any mechanical means, pressure treating the starch to melt the starch granules, and the like. Physically modified starches can also be prepared by using a combination of any physical treatments. Examples of physically modified starches include heat treating the starch in an aqueous environment to swell the starch granules without cracking; heat treating the anhydrous starch granules to cause rearrangement of the polymer; breaking up the starch granules by mechanical disintegration; the starch granules are subjected to a pressure treatment by means of an extruder in order to melt the starch granules.

Enzymatically modified starch is any starch that has been enzymatically treated in any manner to provide an enzymatically modified starch. Enzymatic modifications include, but are not limited to, reactions of alpha-amylase with starch, proteases with starch, lipases with starch, phosphorylases with starch, oxidases with starch, and the like. Enzymatically modified starches can be prepared by using any combination of enzymatic treatments. Examples of enzymatic modification of starch include reaction of an alpha-amylase with starch to produce depolymerized starch; reacting alpha amylase debranching enzyme with starch to produce debranched starch; reacting the protease with starch to produce a starch having a reduced protein content; reacting the lipase with starch to produce starch having reduced fat content; reacting a phosphorylase with starch to produce an enzyme-modified phosphorylated starch; the oxidase reacts with the starch to produce enzymatically oxidized starch.

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

As used herein, the terms "sugar fatty acid ester" and "sucrose fatty acid ester" include compositions having different purities as well as mixtures of compounds of any purity level. For example, the sugar fatty acid ester compound can be a substantially pure material, i.e., it can comprise a compound having a given number of "a" groups substituted with only one moiety of structure I (i.e., all "R" groups are the same, and all sucrose moieties are substituted to the same extent). It also includes compositions comprising blends of two or more sugar fatty acid ester compounds that differ in their degree of substitution, but wherein all substituents have the same "R" group structure. It also includes compositions that are mixtures of compounds differing in the degree of substitution of the "a" groups, and wherein the "R" group substituent moieties are independently selected from two or more "R" groups of structure I. In related aspects, the "R" groups may be the same or different, including that the sugar fatty acid esters in the composition may be the same or different (i.e., a mixture of different sugar fatty acid esters).

For the composition of the present invention, the composition may contain a sugar fatty acid ester compound having a high degree of substitution. In embodiments, the sugar fatty acid ester is sucrose soyate.

Sucrose Glycine max oil fatty acid ester: (

1618U)

The sugar fatty acid esters can be prepared by esterification with substantially pure fatty acids by known esterification methods. They may also be prepared by transesterification using fatty acid esters in the form of sugars and fatty acid glycerides, for example those derived from natural sources, such as those present in oils extracted from oilseeds, such as soybean oil. Transesterification reactions using fatty acid glycerides to provide sucrose fatty acid esters are described, for example, in U.S. Pat. nos.3,963,699, 4,517,360, 4,518,772, 4,611,055, 5,767,257, 6,504,003, 6,121,440 and 6,995,232 and WO1992004361 a1, which are incorporated herein by reference in their entirety.

In addition to the preparation of hydrophobic sucrose esters by transesterification, similar hydrophobicity can be achieved in fibrous cellulosic articles by directly reacting an acid chloride with a polyol containing a ring structure similar to sucrose.

As mentioned above, sucrose fatty acid esters can be prepared by transesterification of sucrose from a methyl ester feedstock that has been prepared from glycerides derived from natural sources (see, e.g., 6,995,232, incorporated herein by reference in its entirety). Depending on the source of the fatty acids, the starting material for the preparation of sucrose fatty acid esters comprises a series of saturated and unsaturated fatty acid methyl esters having fatty acid moieties containing from 12 to 40 carbon atoms. This will be reflected in the sucrose fatty acid ester product prepared from this source, since the sucrose portion that makes up the product will contain a mixture of ester moiety substituents, wherein, with reference to structure I above, the "R" group will be a mixture having from 12 to 26 carbon atoms in a proportion that reflects the starting material used to prepare the sucrose ester. To further illustrate this point, sucrose esters derived from soybean oil will be a mixture of materials having an "R" group structure reflecting that soybean oil contains 26% by weight oleic triglyceride (H)₃C-CH₂]₇-CH＝CH-[CH₂]₇-C (O) OH), 49% by weight linoleic acid triglyceride (H)₃C-[CH₂]₃-[-CH₂-CH＝CH]₂-[-CH₂-]₇-C (O) OH), 11% by weight of linolenic acid triglyceride (H)₃C-[-CH₂-CH＝CH-]₃-[-CH₂-]₇-c (o) OH), and 14% by weight triglycerides of various saturated fatty acids, as described in the Merck Index seventh edition, which is incorporated herein by reference. All of these fatty acid moieties are represented in the "R" group of substituents in the sucrose fatty acid ester product. Thus, sucrose fatty acid esters are referred to herein as reaction products using fatty acid feedstocks derived from natural sources (e.g., sucrose soy oil fatty acid esters)) When used, the term is intended to include all the different components that are typically produced as a result of the preparation of the sucrose fatty acid ester source. In a related aspect, the disclosed sugar fatty acid esters can exhibit low viscosity (e.g., about 10 to 2000 centipoise at room temperature or standard atmospheric pressure). In another aspect, the unsaturated fatty acid can have one, two, three, or more double bonds.

In embodiments of the invention, the sugar fatty acid ester, and in some aspects, the disaccharide ester, is formed from fatty acids having an average of greater 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 20 carbon atoms, and about 20 to about 40 carbon atoms.

In embodiments, the sugar fatty acid ester may be present in different concentrations to achieve hydrophobicity/oleophobicity depending on the form of the cellulose-based material. In one aspect, when the Sugar Fatty Acid Ester (SFAE) is incorporated as a coating on a cellulose-based material, the SFAE is at least about 0.1g/m²To about 1.0g/m²About 1.0g/m²To about 2.0g/m²About 2g/m²To about 3g/m²Is present on the surface of the cellulose-based material. In a related aspect, it can be about 3g/m²To about 4g/m²About 4g/m²To about 5g/m²About 5g/m²To about 10g/m²About 10g/m²To about 20g/m²Are present. In another aspect, when the cellulose-based material is a solution comprising cellulose fibers, the SFAE is present at a concentration of at least about 0.025% (weight/weight) of the total fibers present. In related aspects, it can be present at about 0.05% (w/w) to about 0.1% (w/w), about 0.1% (w/w) to about 0.5% (w/w), about 0.5% (w/w) to about 1.0% (w/w), about 1.0% (w/w) to about 2.0% (w/w), about 2.0% (w/w) to about 3.0% (w/w), about 3.0% (w/w) to about 4.0% (w/w), about 4.0% (w/w) to about 5.0% (w/w), about 5.0% (w/w) to about 10% (w/w), about 10% (w/w) to about 50% (w/w) of the total fibers present. In addition toIn a related aspect, the amount of SFAE can be equal to the amount of fiber present. In some embodiments, SFAE may coat the entire outer surface of a cellulose-based material (e.g., coat the entire paper or cellulose-containing article).

In other embodiments, the coating may comprise from about 0.9% to about 1.0%, from about 1.0% to about 5.0%, from about 5.0% to about 10%, from about 10% to about 20%, from about 20% to about 30%, from about 40% to about 50% of the sugar fatty acid ester, by weight (w/w) of the coating. In a related aspect, the coating can comprise from about 25% to about 35% of the sugar fatty acid ester, based on the weight of the coating (weight/weight).

In embodiments, the cellulose-based material includes, but is not limited to, paper, cardboard, paper, pulp, cups, boxes, trays, lids, release papers/liners, compost bags, shopping bags, shipping bags, bacon boards, tea bags, insulation, coffee or tea containers, pipes and tubs, food grade disposable tableware, plates and bottles, screens for televisions and mobile devices, clothing (e.g., cotton or cotton blends), bandages, pressure sensitive labels, pressure sensitive tapes, feminine products, and medical devices for use on or in the body, such as contraceptives, drug delivery devices, containers for pharmaceutical materials (e.g., pills, tablets, suppositories, gels, and the like), and the like. In addition, the disclosed coating techniques can be used for furniture and upholstery, outdoor camping equipment, and the like.

In one aspect, the coatings described herein are resistant to a pH in the range of 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, from about 7 to about 9.

In embodiments, the alkanoic acid derivative is mixed with the sugar fatty acid ester to form an emulsion, wherein the emulsion is used to treat the cellulose-based material.

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

In embodiments, the sugar fatty acid esters as disclosed herein may be used in coatings with other chemicals used in papermaking including, but not limited to, talc, esters, diesters, ethers, ketones, amides, nitriles, aromatics (e.g., xylene, toluene), acid halides, anhydrides, Alkyl Ketene Dimers (AKD), alabaster, alginic acid, alum, albarine, gums, barium carbonate, barium sulfate, chlorine dioxide, dolomite, diethylenetriamine pentaacetate, EDTA, enzymes, formamidine sulfuric acid, guar gum, gypsum, lime, magnesium hydrogen sulfate, milk of lime, milk of magnesium oxide, polyvinyl alcohol (PvOH), rosin soaps, satin, soaps/fatty acids, sodium bisulfate, soda ash (soda-ash), titanium dioxide, surfactants, starch, modified starch, hydrocarbon resins, polymers, waxes, polysaccharides, proteins, Latexes, and combinations thereof. In embodiments, the disclosed mixtures may comprise one or more SFAEs and one or more of the following inorganic particles: clay (kaolin, bentonite), calcium carbonate (GCC and PCC), talc (magnesium silicate) and titanium dioxide. In related aspects, the inorganic particles can be present in the coating composition from about 1% to about 2%, from about 2% to about 5%, from about 5% to about 10%, from about 10% to about 20%, from about 20% to about 30%, from about 30% to about 40%, from about 40% to about 50%, from about 50% to about 60%, or from about 60% to about 70%. In another related aspect, SFAB may be present in a proportion equal to, higher than, or lower than the amount of inorganic particles in the coating. In one aspect, the coating comprising one or more SFAEs comprises all saturated fatty acids.

In embodiments, the cellulose-containing material produced by the methods disclosed herein exhibits greater hydrophobicity or water resistance relative to untreated cellulose-containing material. In a related aspect, the treated cellulose-containing material exhibits greater lipophobicity or grease resistance relative to an untreated cellulose-containing material. In another related aspect, the treated cellulose-containing material can be biodegradable, compostable, and/or recyclable. In one aspect, the treated cellulose-containing material is hydrophobic (water resistant) and oleophobic (grease resistant).

In embodiments, the treated cellulose-containing material may have improved mechanical properties compared to the same material that was not treated. For example, paper bags treated by the methods disclosed herein exhibit increased burst strength (burst strength), gurley number, tensile strength, and/or Energy at Maximum Load (Energy of Maximum Load). In one aspect, the burst strength is increased by a factor of about 0.5 to 1.0, about 1.0 to 1.1, about 1.1 to 1.3, about 1.3 to 1.5. In another aspect, the gurley number is increased about 3 to 4 fold, about 4 to 5 fold, about 5 to 6 fold, and about 6 to 7 fold. In yet another aspect, the tensile strain is increased by a factor of about 0.5 to 1.0, about 1.0 to 1.1, about 1.1 to 1.2, and about 1.2 to 1.3. And in another aspect, the maximum load energy is increased by a factor of about 1.0 to 1.1, about 1.1 to 1.2, about 1.2 to 1.3, and about 1.3 to 1.4.

In embodiments, the cellulose-containing material is a base paper comprising microfibrillated cellulose (MFC) or Cellulose Nanofibers (CNF), such as described in u.s.pub.no.2015/0167243 (which is incorporated herein by reference in its entirety), wherein MFC or CNF is added during the forming process and papermaking process and/or as a coating or second layer to a previously formed layer to reduce the porosity of the base paper. In a related aspect, the base paper is contacted with a sugar fatty acid ester as described above. In another related aspect, the contacted base paper is further contacted with polyvinyl alcohol (PvOH). In embodiments, the resulting contacted base paper is adjustably water and grease resistant. In related aspects, the resulting base paper can exhibit a gurley number (i.e., gurley air resistance (sec/100cc,20oz. cyl.)) of at least about 10 "15, or a gurley number of at least about 100, at least about 200, to about 350. In one aspect, the sugar fatty acid ester coating can be a laminate of one or more layers, or one or more layers can be provided as a laminate, or the amount of coating of one or more layers can be reduced 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 compostable heat seal or adhesive.

In embodiments, the sugar fatty acid ester may be formulated as an emulsion, wherein the choice of emulsifier and the amount used is determined by the nature of the composition and the ability of the agent to facilitate dispersion of the sugar fatty acid ester. In one aspect, the emulsifier can include, but is not limited to, water, buffers, polyvinyl alcohol (PvOH), carboxymethylcellulose (CMC), latex, milk protein, wheat gluten, gelatin, prolamine, soy protein isolate, starch, acetylated polysaccharide, alginate, carrageenan, chitosan, inulin, long chain fatty acids, wax, agar, alginate, glycerol, gum, lecithin, poloxamer, monoglycerol, diglycerol, monosodium phosphate, monostearate, propylene glycol, detergents, cetyl alcohol, and combinations thereof. In another aspect, 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 those skilled in the art that the proportions may vary depending on the desired characteristics of the final product.

In embodiments, the sugar fatty acid ester may be combined with one or more coating components (alone or in combination) for internal and surface sizing, including but not limited to adhesives (e.g., starch, soy protein, polymer emulsions, PvOH, latex), additives (e.g., glyoxal resins, zirconium salts, calcium stearate, oleolecithin, polyethylene emulsions, carboxymethylcellulose, acrylic polymers, alginates, polyacrylate gums, polyacrylates, biocides, oil-based defoamers, silicone defoamers, stilbene (stilbene), direct dyes, and acid dyes). In related aspects, such components can provide one or more properties including, but not limited to, building pore structures, providing light scattering surfaces, improving ink receptivity, improving gloss, binding pigment particles, binding coatings to paper, reinforcing substrates, filling pores in pigment structures, reducing water sensitivity, resisting wet pick in offset, preventing doctor blade scratching, increasing supercalender gloss, reducing dust, adjusting coating viscosity, providing water retention, dispersing pigments, keeping coatings dispersed, preventing coating/coating color deterioration, controlling foaming, reducing entrapped air and coating cratering, increasing whiteness and brightness, controlling color and hue. It will be apparent to those skilled in the art that the combination may vary depending on the desired characteristics of the final product.

In embodiments, the methods of using the sugar fatty acid esters can be used to reduce the cost of applying primary/secondary coatings (e.g., silicone-based, starch-based, clay-based, PLA-based, Bio-PBS, PEI layers, etc.) by providing a layer of material that exhibits the necessary properties (e.g., water resistance, low surface energy, etc.) to reduce the amount of primary/secondary layers necessary to achieve that same property. In one aspect, the material may be coated on top of the SFAE layer (e.g., a heat sealable agent). In embodiments, the composition is free of fluorocarbon and silicone.

In embodiments, the composition increases the mechanical and thermal stability of the treated product. In one aspect, the surface treatment is thermally stable at a temperature of about-100 ℃ to about 300 ℃. In a further related aspect, the cellulose-based material surface exhibits a water contact angle of about 60 ° to about 120 °. In another related aspect, the surface treatment is chemically stable at a temperature of about 200 ℃ to about 300 ℃.

The substrate can be dried (e.g., at about 80-150 ℃) prior to application, and can be treated with the modifying composition, for example, by dipping and exposing the surface to the composition for less than 1 second. The substrate may be heated to dry the surface and the modified material is then ready for use. In one aspect, according to the methods disclosed herein, the substrate may be treated by any suitable coating/sizing process typically performed in a Paper mill (see, e.g., Smook, g., Surface Treatments in Handbook for Pulp & Paper technologies, (2016), 4 th edition, chapter 18, page 293-.

No special preparation of the material is required in the practice of the invention, although for some applications the material may be dried prior to processing. In embodiments, the disclosed methods may be used on any cellulose-based surface, including but not limited to films, rigid containers, fibers, pulp, fabrics, and the like. In one aspect, the sugar fatty acid ester or coating agent may be applied by: conventional size presses (vertical, inclined, horizontal), gate roll size presses, metered size presses, calender size application, tube size application, on-machine (on-machine), off-machine (off-machine), single-side coater, double-side coater, short dwell (short dwell), simultaneous double-side coater, knife or bar coater, gravure, flexo, ink jet, laser printing, supercalendering, and combinations thereof.

Depending on the source, the cellulose may be paper, cardboard, pulp, softwood fibers, hardwood fibers, or combinations thereof, nanocellulose, cellulose nanofibers, whiskers or microfibers, microfibrillated cotton or cotton blends, other non-wood fibers (such as sisal, jute or hemp, flax, and straw), cellulose nanocrystals, or nanofibrillated cellulose.

In embodiments, the amount of sugar fatty acid ester coating applied is sufficient to completely cover at least one surface of the cellulose-containing material. For example, in embodiments, the sugar fatty acid ester coating may be applied to the entire outer surface of the container, the entire inner surface of the container, or a combination thereof, or one or both sides of the base paper. In other embodiments, the entire upper surface of the film may be covered by the sugar fatty acid ester coating, or the entire lower surface of the film may be covered by the sugar fatty acid ester coating, or a combination thereof. In some embodiments, the inner lumen of the device/instrument may be covered by a coating, or the outer surface of the device/instrument may be covered by a sugar fatty acid ester coating, or a combination thereof. In embodiments, the amount of sugar fatty acid ester coating applied is sufficient to partially cover at least one surface of the cellulose-containing material. For example, only those surfaces exposed to the ambient atmosphere are covered by the sugar fatty acid ester coating, or only those surfaces not exposed to the ambient atmosphere are covered (e.g., masked) by the sugar fatty acid ester coating. It will be apparent to those skilled in the art that the amount of sugar fatty acid ester coating applied may depend on the use of the material to be covered. In one aspect, one surface may be coated with a sugar fatty acid ester, while the opposing surface may be coated with an agent including, but not limited to, protein, wheat gluten, gelatin, prolamine, soy protein isolate, starch, modified starch, acetylated polysaccharide, alginate, carrageenan, chitosan, inulin, long chain fatty acids, waxes, and combinations thereof. In a related aspect, SFAE may be added to the furnish (furnish) and an additional coating of SFAE may be provided to the resulting material on the web (web).

Any of the various sugar fatty acid ester coatings and/or emulsions applied during performance of this aspect of the method may be delivered using any suitable coating process. In embodiments, the sugar fatty acid ester coating process comprises immersion, spraying, painting, printing, and any combination of any of these processes, alone or with other coating processes suitable for performing the disclosed methods.

By increasing the concentration of sugar fatty acid esters, for example, the compositions disclosed herein can react more extensively with the cellulose being treated, which again exhibits the net result of improved water/grease resistance properties. However, higher coating weights do not necessarily mean increased water resistance. In one aspect, various catalysts may allow for faster "curing" to precisely adjust the amount of sugar fatty acid ester to meet a particular application.

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

The derivatized material has altered physical properties, which can be defined and measured using appropriate tests known in the art. For hydrophobicity, analytical methods may include, but are not limited to, contact angle measurement and moisture absorption. Other properties include stiffness, WVTR, porosity, tensile strength, lack of substrate degradation (lack of substrate degradation), burst properties, and tear properties. The specific standardized method to be followed is defined by the American Society for Testing and Materials (ASTM D7334-08 method).

The permeability of the surface to various gases, such as water vapor and oxygen, may also be changed by the sugar fatty acid ester coating process as the barrier function of the material is enhanced. The standard unit for measuring permeability is Barrer and methods for measuring these parameters are also available in the public domain (ASTM std F2476-05 for water vapor and ASTM std F2622-8 for oxygen).

In embodiments, the materials treated according to the methods of the present disclosure exhibit complete biodegradability when measured by degradation in the environment under microbial attack.

Various methods can be used to define and test biodegradability, including the shake flask method (ASTM E1279-89 (2008)) and the Zahn-Wellens test (OECD TG 302B).

A variety of methods may be used to define and test compostability, including but not limited to ASTM D6400.

Materials suitable for treatment by the process of the present invention include cellulose in various forms, such as cotton fibers, plant fibers such as flax, wood fibers, regenerated cellulose (rayon and cellophane), partially alkylated cellulose (cellulose ethers), partially esterified cellulose (cellulose acetate) and other modified cellulose materials, most of their surface being available for reaction/bonding. As noted above, the term "cellulose" includes all of these materials as well as other materials having similar polysaccharide structures and having similar properties. Of these, the relatively novel material microfibrillated cellulose (cellulose nanofibers) (see, e.g., U.S. Pat. No. 4,374,702 and U.S. publication nos. 2015/0167243 and 2009/0221812, incorporated herein by reference in their entirety) is particularly suitable for this application. In other embodiments, the cellulose may include, but is not limited to, cellulose triacetate, cellulose propionate, cellulose acetate butyrate, nitrocellulose (cellulose nitrate), cellulose sulfate, celluloid, methyl cellulose, ethyl methyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, cellulose nanocrystals, hydroxyethyl methyl cellulose, hydroxypropyl methyl cellulose, ethyl hydroxyethyl cellulose, carboxymethyl cellulose, and combinations thereof.

The modification of the cellulose disclosed herein, in addition to increasing its hydrophobicity, can also increase its tensile strength, flexibility and stiffness, further widening its range of use. All biodegradable and partially biodegradable products made from or by using the modified cellulose disclosed in this application are within the scope of the present disclosure, including recyclable and compostable products.

In the possible applications of coating technology, such items include, but are not limited to, containers for all purposes, such as paper, cardboard, pulp, cups, lids, boxes, trays, release paper/liners, compost bags, shopping bags, pipes and tubs, food grade disposable tableware, plates and bottles, screens for televisions and mobile equipment, clothing (e.g., cotton or cotton blends), bandages, pressure sensitive labels, pressure sensitive tapes, feminine products, and medical devices for on or in the body such as contraceptives, drug delivery devices, and the like. In addition, the disclosed coating techniques can be used for furniture and upholstery, outdoor camping equipment, and the like.

The following examples are intended to illustrate, but not limit, the present invention.

Examples

Example 1 sugar fatty acid ester formulation

Liquid at room temperature and all coatings/emulsions containing this material were applied at room temperature using a bench top draw down device. The rod type and size were varied to create a range of coating weights.

Preparation 1

Mixing 50ml of

Adding to a solution containing 195ml of water and 5g of carboxymethylcellulose

10; CP Kelco, Atlanta, GA). The formulation was mixed for 1 minute using a Silverson homogen set at 5000 rpm. The emulsion was coated on 50g base paper made of bleached hardwood pulp and 80g paper consisting of unbleached softwood. The two sheets were placed in an oven (105 ℃) for 15 minutes to dry. After removal from the oven, the sheets were placed on a laboratory bench and 10 drops of water (room temperature) were added dropwise to each sheet via a dropper. The base paper selected for this test immediately absorbed a drop of water, but was not coatedSame amount of

The paper of (a) shows an increasing level of water resistance with increasing coating weight (see table 1).

TABLE 1 use

Base paper of

Lower waterfastness of heavier paper was observed and until the paper was dry, waterfastness could not be achieved.

Preparation 2

Will be provided with

Adding into cup raw materials: (note this is a single ply stock without MFC treatment-110 grams of board made from eucalyptus pulp). 50g of the powder

Added to 200 grams of 5% cooked ethylated starch (Ethyllex 2025) and stirred for 30 seconds using a bench-top kady mill. The paper samples were coated and placed in an oven at 105 ℃ for 15 minutes. 10-15 test droplets were placed on the coated side of the paperboard and the water retention time was measured and recorded in the table below. The water penetration on the untreated control plate was transient (see table 2).

Table 2.

Hot Water Permeability of treated cup stock

Preparation 3

Will be pure

Heated to 45 ℃ and placed in a spray bottle. Evenly sprayed onto the paper stock listed in the previous example, as well as a piece of fiberboard and a certain amount of cotton. When a drop of water was dropped on the sample, it penetrated into the substrate within 30 seconds, whereas after drying in an oven at 105 ℃ for 15 minutes, the drop of water evaporated before being absorbed into the substrate.

Continued research is directed to

Whether it is possible to be compatible with the compounds used for oil and grease resistant coatings.

Can be used for improving water resistance and rigidity. The stiffness test was performed using 240 grams of paperboard stock. Table 3 shows the results. These data were obtained at a single coating weight: 5 grams per square meter, the average of 5 samples is reported. The results are reported in Taber stiffness units using our V-5Taber stiffness tester model 150-E.

TABLE 3 rigidity test

EXAMPLE 2 binding of sugar esters to cellulosic substrates

To determine

Whether or not reversibly bound to a cellulosic material will be pure

Mixed with pure cellulose in a ratio of 50: 50. Make it

The reaction was carried out at 300 ℃ F. for 15 minutes and the mixture was extracted with dichloromethane (non-polar solvent) or distilled water. Returning the sampleFlow for 6 hours and sample was gravimetrically analyzed.

TABLE 4 extraction from cellulosic materials

EXAMPLE 3 inspection of cellulosic surfaces

Scanning electron microscope images of base papers with and without MFC illustrate how the less porous base papers have this potential: which requires much less water repellent to react with the surface. Figures 1-2 show untreated medium porosity Whatman filters. FIGS. 1 and 2 show a relatively high exposed surface area for the derivatizing agent to react with; however, it also shows that highly porous paper has a lot of space for water to leave. Figures 3 and 4 show a side-by-side comparison of papers made with recycled pulp before and after coating with MFC. (they are two magnifications of the same sample, no MCF is evident on the left side of the image). Tests have shown that derivatization of paper with much lower porosity shows a greater desire for long-term water/vapor barrier properties. The last two pictures are only a close-up of the average "hole" in one filter paper and similar magnification of the CNF coated paper for comparison purposes.

The above data demonstrate a focus: adding more material results in a corresponding increase in performance. While not being bound by theory, the reaction of unbleached paper appears to be faster, indicating that the presence of lignin may accelerate the reaction.

In fact, e.g.

Such a product is a liquid which can be easily emulsified, which means that it can be easily adapted to the coating equipment normally used in paper mills.

Example 4 "fluffing (Phluphi)"

Mixing liquid

Mixed with bleached hardwood fibers and reacted to produce a variety of methods for making water repellent handsheets. When the sucrose ester is mixed with the pulp prior to forming the paper, it is found to be largely retained in the fibers. Upon sufficient heating and drying, a brittle, fluffy but very hydrophobic handsheet was formed. In this example, 0.25 grams

Mixed with 4.0 grams of bleached hardwood fibers in 6 liters of water. The mixture was stirred manually and the water was drained in a standard handsheet mold. The resulting fiber mat was removed and dried at 325 ° f for 15 minutes. The paper prepared shows significant hydrophobicity and greatly reduced hydrogen bonding between the fibers themselves. (water contact angles greater than 100 degrees were observed). Emulsifiers may be added.

The ratio to fiber may be about 1:100 to 2: 1.

Subsequent testing indicated that talc was not a participant in this test and was excluded from other tests.

Example 5 environmental Pair

Effect of coating Properties

To better understand the mechanism of the sucrose ester reaction with the fiber, a low viscosity coating was applied to bleached kraft paper with wet strength resin added but without water resistance (no sizing). The coatings were each less than 250cps as measured using a Brookfield viscometer at 100 rpm.

Emulsifying with Ethyllex 2025 (starch)

And coated onto paper by gravure roll. For the sake of comparison purposes,

also emulsified with Westcote 9050 PvOH. As shown in FIG. 5As shown in the figure, the material of the steel wire,

the oxidation of the medium double bond is enhanced by the presence of heat and other chemical environments that enhance the oxidation chemistry (see table 5).

TABLE 5 environmental pairs

Influence of (to number of minutes of failure)

Example 6 comparison of the Effect of unsaturated saturated fatty acid chains and saturated fatty acid chains

Reacted with bleached softwood pulp and dried to form paper. Subsequently, with CH₂Cl₂Toluene and water were extracted to determine the extent of reaction with the pulp. The extraction was performed using a soxhlet extraction glass vessel for at least 6 hours. The extraction results are shown in Table 6.

Table 6.

Combined with extraction of pulp

The data indicate that substantially all

Remain in the paper. To further verify this, the same procedure was carried out only on the pulp, and the results showed that about 0.01 gram was obtained per 10 grams of pulp. While not being bound by theory, it can be easily interpreted as residual pulping chemicals or more likely an extract that has not been completely removed.

Pure cellulose fiber (e.g., alpha-cellulose from Sigma Aldrich, st. As long as

Is maintained at a loading level of less than about 20% of the mass of cellulose, then

More than 95% of the mass will remain in the fiber and cannot be extracted with polar or non-polar solvents. Without being bound by theory, optimizing the bake time and temperature may further increase the sucrose ester retained to the fiber.

As shown, the data indicate that after drying, it is generally not possible to extract from the material

On the other hand, when fatty acids containing all saturated fatty acid chains are used instead of

(for example,

available from Procter&Gamble Chemicals (Cincinnati, OH), nearly 100% of the material can be extracted using hot water (equal to or higher than 70 ℃).

And

the only change being the attachment of saturated fatty acids

Rather than unsaturated fatty acids

Another notable aspect is multiple fatsThe acid chain can react with cellulose and by having two sugar molecules in the structure,

a rigid cross-linked network is created, resulting in increased strength of fibrous webs such as paper, paperboard, air-laid and wet-laid nonwovens, and textiles.

Example 7 addition

To achieve water resistance

Hardwood and softwood kraft pulps were used to make 2 grams and 3 grams of handsheets. When in use

When added to 1% pulp at a level of 0.1% or more and the water drained to form a handsheet,

remain in the fiber, thereby imparting water resistance. From 0.1% to 0.4%

The water beads on the surface for a period of a few seconds or less.

The water-resistance time increases rapidly to a few minutes after a loading of more than 0.4% and then to a few hours when the loading exceeds 1.5%.

Example 8 preparation of fluffy fiber Material

Will be provided with

The addition to the pulp serves to soften the fibers, increasing the space between them to increase the volume. For example, a slurry of 3% hardwood pulp containing 125 grams (dry) pulp was drained and dried, and found to occupy a volume of 18.2 cubic centimeters. Mixing the mixture with 12.5 g

Added to the same 3% hardwood pulp slurry also containing 125 grams dry fiber. After draining and drying, the resulting felt (mat) occupied 45.2 cubic centimeters.

With heat already at 60 DEG C

30g of standard bleached hardwood kraft pulp (made by Old Town Fuel and Fiber, LLC, Old Town, ME) was sprayed. The 4.3cm³Placed in a 10,000rpm mill and essentially repulped. The mixture was poured into a handsheet mold and dried at 105 ℃. The volume of the obtained hydrophobic pulp was 8.1cm³. This material was cut 2 inches square and placed in a hydraulic press and 50 tons of pressure applied for 30 seconds. The volume of the square was significantly reduced, but still occupied more than 50% of the volume of the same 2 inch square cut for control without applied pressure.

Importantly, not only is an increase in bulk and softness observed, but upon drainage, the forcibly repulped mat produces a fiber mat that retains all of the hydrophobicity. This property is also valuable in addition to the observation that water cannot be easily "squeezed" into the paper with a low surface energy barrier. The attachment of hydrophobic fatty acid single chains does not exhibit this property.

While not being bound by theory, this represents

Additional evidence that OH groups on the surface of cellulose fibers are no longer available to participate in subsequent hydrogen bonding are reacted with cellulose. Other hydrophobic materials interfere with the inherent hydrogen bonding, but upon repulping, this effect is reversed and the OH groups on the cellulose are free to participate in hydrogen bonding upon re-drying.

Example 9 pouch paper test data

The following table (Table 7) shows the results of the test

And polyVinyl alcohol (PvOH) mixture at 5-7g/m²The properties imparted by coating on unbleached kraft paper bag stock (control). Reference is also made to commercial bags.

TABLE 7 pouch paper test

As can be seen from the table, the tensile and rupture strengths are dependent on the application

And PvOH coating the control base paper.

Example 10 Wet/Dry tensile Strength

3 grams of handsheets were made from bleached pulp. The differences are compared as follows

Wet and dry tensile strength at add-on level. Note that, for these handsheets,

without emulsifying into any of the coatings, the emulsion,

only mix into the pulp and drain without addition of other chemicals (see table 8).

TABLE 8 Wet/Dry tensile Strength

Note also that the wet strength at 5% addition is not much lower than the dry strength of the control.

Example 11 use of esters containing less than 8 saturated fatty acids

Multiple experiments were performed with sucrose esters prepared having less than 8 fatty acids attached to the sucrose moiety. Samples SP50, SP10, SP01 and F20W (from siterna, the netherlands) contained 50, 10, 1 and essentially 0% monoester, respectively. While these commercial products are prepared by reacting sucrose with saturated fatty acids and thus reduce their usefulness for further crosslinking or similar chemistry, they can be used to examine emulsification and water-resistance properties.

For example, 10g of SP01 was mixed with 10g of glyoxal in a 10% cooked PvOH solution. The mixture was "cooked" at 200 ° f for 5 minutes and then coated by knife coating onto a porous base paper made from bleached hardwood kraft paper. The result is a crosslinked waxy coating on the surface of the paper which exhibits good hydrophobicity. At a minimum amount of 3g/m²In the case of (2), the contact angle generated is greater than 100 °. Since glyoxal is a well-known crystallization agent for compounds having OH groups, this method is a potential means to fix the sucrose esters, which are rather inactive, to the surface by bonding the remaining alcohol groups on the sucrose rings with the alcohol groups available in the substrate or other coating materials.

Example 12 HST data and hygroscopicity

To prove

The observed water repellency properties were provided separately and were determined by the Hercules sizing Test (Hercules Size Test) by treating porous Twins River (Matawaska, ME) basepapers with different amounts of SEFOSE (emulsified with either PvOH or ethlex 2025, coated by knife coating). The results are shown in table 9.

Table 9.

HST data of

As can be seen from Table 9, the coating to the paper surface was increased

Resulting in an increase in water resistance (e.g. in seconds)Indicated by increased HST counted).

This can also be seen by using a coating of the saturated sucrose ester product. For this particular example, product F20W (available from Sisterna, the Netherlands) is described as a very low% monoester with most molecules in the 4-8 degree of substitution range. Note that the amount of F20W product added was only 50% of the total coating, since F20W was emulsified with PvOH in equal parts to each other to make a stable emulsion. Therefore, when the addition amount is marked as "0.5 g/m²"when the same amount of PvOH added is also present, this gives a total addition of 1.0g/m². The results are shown in table 10.

TABLE 10 HST data F20W

HST-sec	Sisterna F20W addition
		<1	0
2.0	0.5g/m2
		17.8	1.7g/m2
175.3	2.2g/m2
		438.8	3.5g/m2
2412	4.1g/m2

It can also be seen from table 10 that increasing F20W increased the waterfastness of the porous paper sheet. Therefore, the sucrose fatty acid ester itself applied imparts water resistance to the paper.

The water resistance is not only due to the presence of fatty acids forming ester bonds with cellulose, but the softwood handsheets (bleached softwood kraft) are loaded with

And oleic acid is added directly to the pulp, wherein the oleic acid forms ester linkages with cellulose in the pulp. The mass at time zero represents the "completely dry" mass of the handsheet taken out of the oven at 105 ℃. The samples were placed in a controlled humidity space maintained at 50% RH. Changes in mass were recorded over time (in minutes). The results are shown in tables 11 and 12.

TABLE 11 moisture absorption

Table 12 hygroscopicity-oleic acid.

Time (hours)	30% oleic acid	50% oleic acid	Control
				0	4.018	4.014	4.356
0.5	4.067	4.052	4.48
				2	4.117	4.077	4.609
3	4.128	4.08	4.631
				5	4.136	4.081	4.647
21	4.142	4.083	4.661

Note the difference here where oleic acid is added directly to the pulp to form ester linkages greatly slows moisture absorption. In contrast, only 2% of

Can slow down moisture absorption and can be used in higher concentration

Does not slow down moisture absorption. Thus, while not being bound by theory,

the structure of the binding material cannot be explained simply by the structure formed by simple fatty acid esters and cellulose.

Example 13 saturated SFAE

Saturated esters are waxy solids at room temperature and, due to saturation, are less reactive with the sample matrix or itself. Using elevated temperatures (e.g., at least 40 ℃, and above 65 ℃ for all materials tested), these materials melt and can be coated as a liquid, then cooled and solidified to form a hydrophobic coating. Alternatively, these materials may be emulsified in solid form and applied as an aqueous coating to impart hydrophobic character.

The data shown here represent HST (hercules sizing test) readings obtained from paper coated with different amounts of saturated SFAE.

A #45 bleached hardwood kraft paper from Turner Falls paper was used for the test coatings. The gurley porosity was measured at about 300 seconds, indicating a fairly tight base paper. S-370 from Mitsubishi Foods (japan) was emulsified with xanthan gum (up to 1% of the mass of a saturated SFAE formulation) prior to coating.

Coating weight (pounds/ton) HST of saturated SFAE formulation (average of 4 measurements per sample).

Watch 13

S-370 coating weight (pounds/ton)	HST (average of four measurements per sample)
		Control group #0 alone	4 seconds
#45	140 seconds
		#65	385 seconds
#100	839 seconds
		#150	1044 seconds
#200	1209 seconds

The resulting laboratory data also demonstrate that a limited amount of saturated SFAE can improve the water resistance of coatings designed for other purposes/applications. For example, mixing saturated SFAE with ethyl-lex starch and a polyvinyl alcohol-based coating, an increase in water resistance was observed in each case.

The following examples were coated on #50 bleached recycled base paper with a gurley porosity of 18 seconds.

100 grams of Ethylex2025 was cooked at 10% solids (1 liter volume) and 10 grams of S-370 was added while hot and mixed using a Silverson homogenizer. The resulting coating was applied using a common bench-top doctor blade and the paper was dried under a heating lamp.

At 300 #/ton coating weight, starch alone has an average HST of 480 seconds. Using the same coat weight of starch and saturated SFAE mixture, the HST increased to 710 seconds.

Sufficient polyvinyl alcohol (Selvol 205S) was dissolved in hot water to obtain a 10% solution. This solution was coated on the same #50 paper described above and had an average HST of 225 at 150 lbs/ton coating weight. Using the same solution, S-370 was added to give a mixture containing 90% PVOH/10% S-370 (on a dry basis) (i.e. 90 ml water, 9 g PvOH, 1g S-370): the average HST increased to 380 seconds.

Saturated SFAEs are compatible with prolamines (specifically, zein; see U.S. patent No.7,737,200, which is incorporated herein by reference in its entirety). One of the major obstacles to commercial production due to the subject of said patent is that the formulation is water soluble: the addition of saturated SFAE therefore provides assistance in this respect.

Example 14 other saturated SFAEs

Size press evaluation of saturated SFAE-based coatings was performed on bleached light weight paper (about # 35) which was not sized and formed relatively poorly. All evaluations used cooked Exceval HR 3010PvOH to emulsify saturated SFAE. Enough saturated SFAE was added to account for 20% of total solids. The focus was to evaluate S-370 and C-1800 samples (available from Mitsubishi Foods, Japan). Both esters performed better than the control, and some key data are shown in table 14:

TABLE 14

	Average HST	Kit value
			Only 10% polyvinyl alcohol	38 seconds	2
PVOH and S-370	85 seconds	3
			PVOH and C-1800	82 seconds	5

Note that saturated compounds appear to increase kit values, with both S-370 and C-1800 producing about a 100% increase in HST.

Example 15 Wet Strength additive

Laboratory tests have shown that the chemistry of sucrose esters can be tailored to achieve a variety of properties, including use as wet strength additives. When sucrose esters are prepared by attaching a saturated group to each alcohol functional group on sucrose (or other polyol), the product is a hydrophobic waxy substance with low water miscibility/solubility. However, these compounds may be added to cellulosic materials to impart water resistance internally or as a coating; they are easily removed by solvents, heat and pressure, since they do not chemically react with each other, nor with any part of the sample matrix.

In the case where water repellency and a higher level of water resistance are desired, sucrose esters containing unsaturated functional groups can be prepared and added to the cellulosic material to effect oxidation and/or crosslinking, which helps to immobilize the sucrose esters in the matrix and render them highly resistant to removal by physical means. By adjusting the number of unsaturated groups and the size of the sucrose ester, a method is obtained to carry out crosslinking to impart strength with molecules that are not optimal for imparting water resistance.

The data shown here is by

Added to bleached kraft paper at various levels and obtained with wet tensile data. The percentages shown in the table represent the percentage of sucrose esters of treated 70# bleached paper (see table 15).

Watch 15

This data illustrates a trend that the addition of unsaturated sucrose esters to paper increases wet strength with increasing loading levels. Dry stretch shows the maximum strength of the paper as a reference point.

Example 16. method for producing sucrose esters using acid chlorides.

In addition to the preparation of hydrophobic sucrose esters by transesterification, similar hydrophobicity can be achieved in fibrous articles by directly reacting an acid chloride with a polyol containing a ring structure similar to sucrose.

For example, 200 grams of palmitoyl chloride (CAS 112-67-4) was mixed with 50 grams of sucrose and mixed at room temperature. After mixing, the mixture was raised to 100 ° f and held at this 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-13NMR showed that a large amount of hydrophobic sucrose ester had been prepared.

Although it has been shown (by BT3 and others) that the addition of fatty acid chlorides to cellulosic materials can impart hydrophobicity, the reaction itself is not desirable on site because the gaseous HCl liberated as a by-product can create a number of problems including corrosion of surrounding materials, harm to workers and the surrounding environment. Another problem resulting from the production of hydrochloric acid is that as more hydrochloric acid is formed, i.e. more polyol sites are reacted, the fiber composition becomes weaker. As the amount of palmitoyl chloride reacted with the cellulose and cotton materials increases, the hydrophobicity increases and the strength of the article decreases.

This reaction was repeated multiple times using 200 grams of R-CO-chloride to react with 50 grams each of other similar polyols including corn starch, birchwood xylan, carboxymethyl cellulose, glucose and extracted hemicellulose.

EXAMPLE 17 Peel Test (Peel Test)

Peel testing the force required to Peel the tape from the paper surface at a reproducible angle was measured using a wheel between the two jaws of a tensile Tester (ASTM D1876; e.g., 100Series Multidurar Peel Tester, Testresources, Shakopeee, MN).

For this work bleached kraft paper from Turner Falls paper (MA) with high gurley number (600 seconds) was used. This paper of #50 lbs represents a relatively tight but highly absorbent paper.

When #50 pound paper was coated with 15% ethyllex starch as a control, the average force required (5 samples) was 0.55 pounds/inch. When treated with the same coating but with

Replace 25% of Ethyllex starch (so 25% of the added amount is

75% still ethyl), the average force was reduced to 0.081 lbs/inch. By 50% of

Instead of ethyllex, the force required was reduced to less than 0.03 pounds per inch.

The paper is prepared in accordance with TAPPI standard method 404 for determining the tensile strength of the paper.

Finally, the same paper is used with S-370 at a load rate of 750 lbs/ton-this effectively fills all the holes in the paper, creating a complete physical barrier. This does pass the TAPPI kit 12 on a flat surface. This brief experiment shows that grease resistance can be achieved using saturated SFAE varieties.

Example 18 saturated SFAE and inorganic particles (fillers)

Saturated Sucrose Fatty Acid Esters (SFAE) include hydrophilic and hydrophobic depending on the number (and chain length) of fatty acid chains attached to the sucrose molecule. These are not considered highly reactive compounds.

A series of substituted SAFEs have been studied, with side chains of 16 or 18 carbons in length. The material tested was a waxy solid with a melting point below 150 ℃. When coated on paper, highly substituted esters impart significant water resistance depending on the coat weight and paper porosity. In this example, the same paper is used with S-370 at a load rate of 750 lbs/ton-this effectively fills all the holes in the paper, creating a complete physical barrier. The paper so treated was found to pass the TAPPI kit 12. This brief experiment shows that grease resistance can be achieved using saturated SFAE types.

And (4) observation:

more hydrophobic esters tend to aggregate in aqueous emulsions/dispersions and thus it becomes difficult to form a uniform coating on paper. Many of these molecules have low melting points, resulting in the coating "melting" into the paper. If hydrophobic SAFE is mixed with polymers to help stabilize the dispersion, these polymers (i.e., latex, starch, polyvinyl alcohol) tend to surround the esters in a way that diminishes the desired hydrophobicity.

When mixed with calcium carbonate (e.g., precipitated calcium carbonate), this can produce unexpected attractiveness. SAFE does not melt into the paper under the same drying conditions. The calcium carbonate appears to aid in the dispersion of the SAFE and the adhesion force is such that the SAFE acts as an adhesive to attach the calcium carbonate particles to the surface of the coated paper. While not being bound by any theory, it is believed that this uniform dispersion results in enhanced water resistance for a given amount of ester.

Table 16 shows the improvement in water resistance as measured by the Hercules Sizing Test (HST) with the formulation containing 50% calcium carbonate. The unsized porous 40 pound paper was hand coated (hand drawn down). The weight of the coating is 7-10g/m²。

Table 16.

The advantages of the demonstrated combination include reduced coating costs by using carbonates and more efficient use of SFAE molecules as they are more evenly distributed over the surface of the paper substrate.

Example 17 saturated SFAE blends and inorganic particles (Filler and Clay)

A. This example is designed to examine the interaction between a saturated sucrose fatty acid ester blend and calcium carbonate.

The paper coating was made to have the following composition (on a dry basis): 10% PVOH; 20% sucrose ester (SE-15/1803 blend, SFAE in equal proportions; SE-I5 from Hangzhou Union Biotechnology Co., Ltd, Hangzhou, China, and C-1803 from Itochu Chemicals America, Inc., While Plains, NY) and 70% precipitated calcium carbonate (from OMYA Inc., Blue Ash, OH). The mixture was added at 8g/m²Coating weight of (2) was applied to a No. 65 bleached Kraft paper. The calcium carbonate slurry, when coated on paper, does not show water contact angle and HST by itself. The results using the coating composition are shown in table 17.

TABLE 17

Sample (I)	HST (second)
		Base paper	0
Base paper + CaCO3	0
		Base paper and sucrose ester blend	35
Base paper + CaCO3+ sucrose ester blend	118

This example serves to illustrate that the ester-calcium carbonate interaction is sufficiently pronounced that the carbonate helps to maintain an even distribution of the ester on the paper surface, where the greatest effect is observed. In addition, the data demonstrate that biological substrates have been identifiedThe material can be mixed with CaCO₃When used together as CaCO₃When present as a major component of the composition, produces a coated paper exhibiting a high contact angle. While not being bound by theory, this effect becomes more pronounced when high coating weight high pigment compositions can be applied.

This example is designed to detect the interaction between saturated sucrose fatty acid ester and pigment (e.g., clay).

Kaolin-based materials have very different properties than calcium carbonate. Table 18 shows the use of another SFAE blend-equal parts of 80OE (available from Tenac, S.h., Tucuman, Argentina) and SE-15, and equal parts of 80OE, SE-15 and Imerys CAPIM^TM(Kaolin-based materials, available from Imerys Clay, Inc., Roswell, GA) -results of making QGR coatings. The following formulations were prepared at 10% solids and at 5g/m²And (4) coating.

Table 18.

Composition comprising a metal oxide and a metal oxide	Kit
		CAPIMTM	0
SE-15	3
		80OE	3
80OE/SE 15	4
		80OE/SE-15/CAPIMTM	5/6

CAPIM alone once the pigment is present at greater than 10-20%^TMPaper does not show kit and as noted above, once in any barrier coating, the concentration is above 10 or 20% pigment, the typical barrier performance is significantly reduced (e.g., grease can find pore penetration). It is clearly observed that esters provide better oil resistance with less net ester (net ester) in the formulation.

Other uses

The cup base stock was found to be heavily treated with rosin to increase water resistance. However, the Gurley on the plate was found to be 50 seconds, indicating that the plate is quite porous. The material can be repulped and steam rapidly penetrates to soften it. Will be pure

Applied to the plate and dried in an oven at 100 ℃ overnight. The resulting material had a plastic-like feel and was completely waterproof. It was 50% (weight/weight) cellulose/50% (weight/weight)

Gurley is too high to measure. Immersion of the sample in water for 7 days did not significantly soften the material, however, from greenhouse data it appeared to biodegrade within approximately 150 days. Ordinary tapes and glues do not stick to such composites.

Examples with saturated SFAE and zein have been performed, as zein has been shown to impart oil and grease resistance to paper. Stable aqueous dispersions of zein (up to 25% in water) were produced with 2% to 5% saturated SFAE added. Observations demonstrate that saturated SFAE "lock" zein to paper by imparting water (and grease) resistance to the formulation.

The combination of SFAE, inorganic particles and bioplastic can be blended to produce a 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)) along with SFAE, the resulting paper substrate will have water resistance, with the SFAE concentration optimized to ensure water resistance of the article and a greater percentage of the lid mass in the case of cheaper, more common materials (e.g., common pulp) being used. Thus, other materials such as biopolymers will account for a relatively small amount (e.g., less than 10%) of the mass of the article, allowing for the addition of other additives to provide flexibility, improve tear or tensile properties, and the like.

The addition of the calcium carbonate/SFAE mixture allows control of the density of the lid.

While the invention has been described with reference to the above embodiments, it is to be understood that modifications and variations are also encompassed within the spirit and scope of the invention. Accordingly, the invention is limited only by the following claims. All documents disclosed herein are incorporated by reference in their entirety.

Claims (20)

1. A composition comprising one or more Sugar Fatty Acid Esters (SFAEs) and inorganic particles, wherein the SFAEs are present in a sufficient concentration to adhere the inorganic particles to a cellulose-based substrate, and wherein the substrate containing the composition exhibits greater water and/or grease resistance than a substrate containing the composition comprising the inorganic particles or one or more spas alone.

2. The composition of claim 1, wherein the SPAE 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.

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

4. 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, and wherein the inorganic particles comprise at least 1% of the composition on a dry basis (db).

5. The composition of claim 1, wherein the SFAE comprises at least one saccharide and at least one aliphatic group comprising 8 to 30 carbon atoms.

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

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

8. The composition of claim 1, wherein the cellulose-based substrate is selected from the group consisting of paper, paperboard, pulp, cartons for storing food, bags for storing food, shipping bags, coffee or tea containers, tea bags, bacon boards, diapers, weed-blocking/barrier fabrics or films, mulching films, planting pots, packaging beads, bubble film packaging, oil absorbent materials, laminates, envelopes, gift cards, credit cards, gloves, raincoats, OGR paper, shopping bags, compost bags, release paper, tableware, containers for cold or hot beverages, cups, paper towels, trays, bottles for storing carbonated liquids, insulation materials, bottles for storing non-carbonated liquids, films for packaging food, garbage disposal containers, food handling appliances, cup covers, threads on plastic paper cup covers, paper straws, textile fibers, water storage and water delivery appliances, Medical cardboard, release paper, appliances for storing and delivering alcoholic or non-alcoholic beverages, housings, electronic product screens, internal or external parts of furniture, curtains, upholstery, films, boxes, sheets, trays, tubes, water pipes, medical product packaging, clothing, medical devices, contraceptives, camping equipment, molded cellulosic fibrous materials and combinations thereof.

9. An article comprising a coating comprising one or more Sugar Fatty Acid Esters (SFAE), 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).

10. The article of claim 9, wherein the cellulose-based substrate is selected from the group consisting of paper, paperboard, pulp, cartons for storing food, bags for storing food, shipping bags, coffee or tea containers, tea bags, bacon boards, diapers, weed-obscuring/barrier fabrics or films, mulching films, planting pots, packaging beads, bubble film packaging, oil absorbent materials, laminates, envelopes, gift cards, credit cards, gloves, raincoats, OGR paper, shopping bags, compost bags, release paper, tableware, containers for cold or hot beverages, cups, paper towels, trays, bottles for storing carbonated liquids, insulation materials, bottles for storing non-carbonated liquids, films for packaging food, garbage disposal containers, food handling appliances, cup covers, threads on plastic paper cup covers, paper straws, textile fibers, water storage appliances, and water transport appliances, Medical cardboard, release paper, appliances for storing and delivering alcoholic or non-alcoholic beverages, housings, electronic product screens, internal or external parts of furniture, curtains, upholstery, films, boxes, sheets, trays, tubes, water pipes, medical product packaging, clothing, medical devices, contraceptives, camping equipment, molded cellulosic fibrous materials and combinations thereof.

11. A method of 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; and is

c) Curing for a time sufficient to cause the mixture to adhere to the at least one surface,

wherein the cured surface is more hydrophobic and/or oleophobic than a surface treated with at least one SFAE or composition comprising inorganic particles alone.

12. The method according to claim 11, wherein the treated cellulosic surface is hydrophobic.

13. A method according to claim 11, wherein the treated cellulosic surface is oleophobic.

14. The method of claim 11, wherein the SFAE comprises all saturated fatty acids or comprises a mixture of saturated and unsaturated fatty acids.

15. The method according to claim 11, wherein said SFAE is a mixture of two or more different SFAEs.

16. The method of claim 11, wherein the inorganic particles are selected from the group consisting of clay, ground calcium carbonate, precipitated calcium carbonate, talc, titanium dioxide, and combinations thereof, wherein the inorganic particles are present in the mixture at a concentration of at least about 1% on a dry basis (db).

17. The method according to claim 16, wherein the composition further comprises polyvinyl alcohol or starch.

18. The method according to claim 11, wherein the inorganic particles comprise calcium carbonate, and wherein the calcium carbonate comprises greater than or equal to about 50% of the mixture on a dry basis (db).

19. The method according to claim 16, wherein the calcium carbonate is precipitated calcium carbonate.

20. The method of claim 11, wherein the cellulosic substrate is selected from the group consisting of paper, paperboard, pulp, cartons for storing food, bags for storing food, shipping bags, coffee or tea containers, tea bags, bacon boards, diapers, weed-blocking/barrier fabrics or films, mulching films, planting pots, packaging beads, bubble film packaging, oil absorbent materials, laminates, envelopes, gift cards, credit cards, gloves, raincoats, OGR paper, grocery bags, compost bags, release paper, tableware, containers for containing cold or hot beverages, cups, paper towels, trays, bottles for storing carbonated liquids, insulation materials, bottles for storing non-carbonated liquids, films for packaging food, garbage disposal containers, food handling appliances, cup covers, screw threads on plastic paper cup covers, paper straws, textile fibers, water storage and water transport appliances, Medical cardboard, release paper, appliances for storing and delivering alcoholic or non-alcoholic beverages, housings, electronic product screens, internal or external parts of furniture, curtains, upholstery, films, boxes, sheets, trays, tubes, water pipes, medical product packaging, clothing, medical devices, contraceptives, camping equipment, molded cellulosic fibrous materials and combinations thereof.

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