SACCHARIDE FA TTY ESTER INORGANIC PARTICLE COMBINATIONS

CROSS REFERENCE TO RELATED APPLICATIONS

[0001] This application claims priority from U.S. Patent Application No. 16/456,433 filed June 28, 2019, In the U.S. Patent and Trademark Office, which is incorporated herein by reference in its entirety.

PB .R OF THE INVENTION

| ⁾ 02J The present invention relates generally to treating cellulosk-bssed materials, and more specifically to treating such materials with saccharide fatty acid esters iSFAE) in combination with inorganic particles, including compositions containing such combinations.

BACKGROUND INFORMATION

Inorganic particles such as kaolin, talc, calcium carbonate, and TiO _¾ are typically used in paper making processes as filler. Calcium carbonate, for example, is used in paper mills as a filler materia] in the alkaline papermaking process. Presently, calcium carbonate dominates over other papermaking filter materials <e.g„ kaolin). The main reason behind the preference for calcium carbonate is the demand for brighter and bulkier paper. There are significant benefits to the use of calcium carbonate in the alkaline papennaklng process (e.g., calcium carbonate is cheaper and if has high brightness, creates a porous surface on the paper sheet, improves

prmtabi!ity, lowers binder demand, Increases machine speed arid productivity’, improves water drainage, improves machine rumability, is cost-effective in papermaking processes, it can reduce fiber consumption, and can obtain more retention compared to other paper fillers).

|¾&84] Usually calcium carbonate occurs in three natuial forms such as limestone, chalk and marble. Naturally, it forms between the reactions of calcium salt and carbon dioxide. There are two types of calcium carbonate used in paper mills: ground calcium carbonate (GCC) Mid precipitated calcium carbonate (FCC). 10005| Ground calcium carbonate is manufactured by grinding limestone or marble and finds use because of its high brightness and purity. Generally, tire particle shape of ground calcium carbonate is rhombOhedrai. This filler material is used in alkaline, wood free papentiaking processes. The brightness of GCC is about 86-95%

10006! The rough particle shape and small amounts of quartz often found m GCC create a problem; it is more abrasive and shortens the life of paper machine forming wires and press felts.

100 71 precipitated calcium carbonate is the form of CaCCfe which is manufactured by chemical reactions and the process is known a the carbonation process. PCC improves the drawback of GCC, it provides better gloss and opacity properties for the paper. The structure of PCC is different from the structure of GCC. The crystal structure of PCC can be controlled and includes needle-shaped, rhombohedral (cubic), scalenohedral (triangular) and prismatic. The brightness of PCC is abo ut 90-97%. However, PCC containing paper sheets can have poorer formation than GCC containing paper sheets. f0008| On modern high-speed, twin-wire paper machines, the turbulence needed to obtain good formation often causes low retention of fillers. In addition, for both types of calcium carbonates, the _} have no adhesion on their own to cellulose, and require a retention aid or binder to atach to pulp. Typically, such retention aids or hinders include paperniaker's alum, synthetic polymers, polyacrylamides, microparticle systems, latex, starch, and polyvinyl alcohol (Fv0!¾ which retention aids or binders can increase costs, or make products less "green" (e,g., synthetic polymers) where desired.

J6009J if would be desirable to bind calcium carbonates to make use of retention aids or binders unnecessary or re uce the amount of retention aid or binder needed to attach inorganic particles to celluiosic surfaces.

SUMMARY OF THE INVENTION f il ί> The present disclosure relates to methods of treating celluiosic aterials with a composition that allows, infer alie, greater retention of inorganic particles (ie., fillers). The methods as disclosed provide combining saccharide fatty acid esters (SFAE) with such fillers and applying such combinations on cellulose to eliminate or reduce the use of retention aids or binders for fiber in the paper making process. Compositions comprising combinations of SFAE and inorganic particles are also disclosed.

1 _. 001 IJ In embodiments, a composition comprising a saccharide fatty acid ester (SFAE) and inorganic particles is disclosed, where the SFAE is present at a sufficient concentration to cause the inorganic particles to be retained on the cellulose-based material and where the substrate containing the composition exhibits greater water resistance and/or grease resistance compared to a substrate containing the compositi n comprising the inorganic particles or one or more SF AE alone

|M12j In one aspect, the SFAE include all ««saturated" fatty acids, all saturated fatty acids or a mixture of saturated and ««saturated fatty acids, and optionally, further includes one or more binders selected from PvOH or starch. fOOD| In. another aspect, the SFAE is a mixture of two or more different SFAFA, where the two or more different SF AE contain all: saturated fatty acids.

10fi!4| in one aspect the inorganic particles include clay, ground calcium carbonate, precipitate calcium carbonate, talc, titanium dioxide and combinations thereof, and where the inorganic particles comprise at least 1 % of the composition on a dry basis fdb)

|00I5j In another aspect, the SFAE contains at least one saccharide and at least one aliphatic group comprising 8 to 30 carbons. In one aspect, fee inorganic particle is calcium carbonate, where the substrate exhibits water resistance in a related aspect, the inorganic particle is clay, where the substrate exhibits grease resistance. fOOMf In one aspect, the cellulose based substrate includes paper, paperboard, paper pulp, a food storage cation, a food storage bag, a shipping bag, a coffee or tea container, a tea bag, bacon board, diapers, weed-block/barrier fabric or film, mulching film, plant pots, packing beads, bubble wrap oil absorbent material, laminates, envelops, gift cards, credit cards, gloves, raincoats, OGR paper, a shopping bag, a compost bag, release paper, eating utensil, a hot or cold beverage container, cup, paper towels, plate, a carbonated liquid storage bottle, insulating material, a non-carbonated liquid storage bottle, wrapping food film, a garbage disposal container, a food handling· implement, a cup lid, a screw on cup lid of moldable paper, paper straws a fabric fibre, a water storage and conveying implement, medical MSS paperboard release paper, an alcoholic or mn- alcoholic drink storage and conveying implement casing, an electronic good outer screen, an internal or external piece of furniture, a curtain, upholstery, film, box, sheet, tray, pipe, water conduit pharmaceutical product packaging, clothing, medical device, contraceptive, camping equipment, molded cellulosic fiber material and combinations thereof

10Oi7j In embodiments, an article of manufacture is disclosed including a coating containing one or more saccharide fatty acid esters (SFAE), inorganic policies, a cellulose based substrate, and optionally, one or more binders, where the inorganic particles are present in the coating at a concentration of at least 1 % on a dry basis (db) in a related aspect, the cellulose based substrate includes paper, paperboard, paper pulp, a food storage carton, a food storage bag, a shipping bag, a coffee or tea container, a tea bag, bacon board, diapers, weed-block/barrier fabric or film, mulching film, plant pots, packing beads, bubble wrap, oil absorbent material laminates, envelops, gift cards, credit cards, gloves, raincoats _* OCR paper, a shopping bag, a compost bag,release paper* eating utensil, a hot or cold beverage container, cup, paper towels, plate, a carbonated liquid storage bottle, Insulating material, a nou-carbonated liquid storage bottle, wrapping food film, a. garbage disposal container, a food handling implement, a cup lid, a screw on cup lid of mo!dable paper, paper straws, a fabric fibre, a water storage and conveying implement, medical use paperboard, release paper, an alcoholic or non-alcoholic drink storage and conveying implement, casing, an electronic good outer screen, an internal or external piece of furniture, a curtain, upholstery, film, box, sheet, tray, pipe, water conduit, pharmaceutical product packaging, clothing, medical device, contraceptive, camping equipment, molded cellulosic fiber material and combinations thereof.

J0Q18J In embodiments, a method of treating a cellulosic substrate is disclose includingadding at least one saccharidefatty acid ester (SFAE) to a composition comprising inorganicparticles to form a mixture; applying said mixture to at least one surface of said cellulosic substrate; and curing for a sufficient lime to allow the mixture to adhere io the at least one surface, where the cured surface exhibits higher hydrophobicity and/or Jipophohicity compared to a surface treated with the at least one SFAE or the composition comprising the inorganic particles alone. In one aspect, the treated celiulosic surface is hydrophobic. In another aspect, the treated eelMosic surface is lipophobic.

(0020} In one aspect, the SFAE includes all saturate fatty adds or a mixture of saturated and unsaturated fatty acids, in another aspect, the SFAE is a mixture of two or more different SFAEs,

{002IJ In one aspect, the inorganic particles include day, ground calcium carbonate, precipitated calcium carbonate talc* titanium dioxide and combinations thereof, where the inorgani c particles are present in the mixture at a concentration of at least about 1 % on a dry basis (db). In a related aspect, the composition further comprises poly vinyl alcohol or starch

{00221 in one aspect, the inorganic particles include calcium carbonate, where the calcium carbonate comprises greater than or equal to about 30% of the mixture on a dry basis (db).

|00231 ¾h another aspect, the eeUiilosk substrate includes paper, paperboard, paper pulp, a carton for food storage, a hag for food storage, a shi ping hag, a container for coffee or tea, a lea bag, bacon hoard, diapers, weed-blockfoamer fabric or film, mulching film, plant pots, packing beads, bubble wrap, oil absorbent material, laminates, envelops, gift cards, credit cards, gloves, raincoats, OGR paper, a shopping bag, a compost bag, release paper, eating utensil, container for holding hot or cold beverages, cup, paper towels, plate, a bottle for carbonated liquid storage, insulating material, a bottle for non-earbonafed liquid storage, film for wrapping food, a garbage disposal container, a food handling implement, a lid for a cup, a screw on cup lid of moklable paper, paper straws, a fabric fibre, a water storage and conveying implement _* medical use paperboard, release paper, a storage and con veying implement for alcoholic or non-alcoholic drinks, an outer easing or screen for electronic goods, an internal or external piece of furniture, a. curtain, upholsters', film, box, sheet, tray, pipe, water conduit, packaging for pharmaceuticalproducts, clothing, medical device, contraceptive, camping equipment _* celiulosic material that is molded an combinations thereof

BRIEF « iPTKM OF THE BgAWMGS

{ 0241 HO, 1 shows spanning electron micrograph (SEM) of untreated, medium porosity Whatman Filter Paper (58x magnification). 100 51 FIG. 2 shows an SEM of untreated, medium porosity Whatman Filter Paper (i G70xmagnification); f0026f FIG. 3 shows a side-by-side comparison of SEMs of paper made from recycled pulp before (left) and after (right) coating with mierofibriifated cellulose (MFC): (2?x magnification).

10027 _. J FIG, 4 shows a side-by-side comparison of SEMs of paper made from recycled pulp before (left) and after (right) coating with MFC (98x magnification). p028j FIG. 5 show s water penetration in paper treated with various coating formulations: polyvinyl alcohol (PvOH), diamonds; SEF0SE& -* PvOH at 1 : 1 (y/v), squares; Ethylex (starch), triangles, SEFQSE& + PvOH at 3: 1 ( v), crosses

f002P) Before ibe preseit composition, methods, and methodologies are described, it is to be understood that this invention is not limited to particular compositions, methods, and experimental conditions described as such compositions, methods, and conditions max vary. It is also to be understood that the terminology used herein is for purposes of describing particular embodiments only, an is not intende to be limiting, since the scope of the present invention will be limited only in the appended claims. O03O| As used in this specification and the appended claims, the singular forms "a", "an” and “the" include plural references unless the context clearly dictates otherwise. Thus, for example, references to "a saccharide fatty aci ester” includes one or more saccharide fatly acid esters, and/or compositions of the typo described herein which wi ll become apparent to those persons skilled in the art upon reading this disclosure and so forth.

10031 J 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 may be used in the practice or testing of the in vention, as it will be understood that modifications and variations are encompassed wi thin the spirit and scope of the instant disclosure. }ΐM>32| As used herein, "about,” "approximately." "substantially" and "significantly" will be understood by a person of ordinary skill in the art and will vary in some extent depending on the context in which they are used if there are uses of the term which are not clear to persons of ordinary skill in the an given the context in which it is used, "about'' and "approximately" will mean plus Or minus <10% Gf particular term and "substantially" and "significantly” will mean plus or minus >10% of the particular term. "Comprising" and "consisting essentially of’ have their customary meaning in the art f0033J All pigments must be uniformly retained in the sheet to be effective. Pape can he made cheaper when using fillers that are less costly than fibers. However the proportion of filler in the sheet is limited by the resultant reduction in strength, bulk and sizing quality. While the trend is definitely toward higher filler contents, once the pigment concentratio is abo ve 10 or 20% in any harrier coating, barrier properties are significantly reduced, fil634f Although not a polymer, per co, SFAEs aid in retention of filler or inorganic particles such as PCC, While not being bound by theory; the SFAEs may crosslink or provide a network with surfaces on the fines and fibers. The combination performs well and allows a higher l vel of attachment without compromising product quality including providing, an increased level of performance,

JG03SI Also, organic particles such as uncooked starch, particles of wood, oaf hulls and the like oiler hulk and caliper which are greatly needed in some products may be added, whereas the inorganics increase density'. Further for hydrophobic polymers that might create unwanted particles and/or sticky masses or deposits, including wood resin, hot melt waxes. hiopSastics and the like, the use of SPAB-moiganie particle combinations may overcome such unwanted agglomerations.

} 036| Moreover, the addition of a composition comprising a mixture of inorganic particles and SFAEs would offer the i mprovement of fi ne tuning of the various properties of a sheet. For example, such sheets may contain wood fiber, and include a bioplastie fiber along with SFAE combinations to waterproof such a sheet. The combinations as envisaged would allow the use of cheaper, more common materials, such as mechanical or recycled pulp to be a larger percentage of the mass of the sheet In such a case, the addition of, for example, a calcium carbonate- SFAE mixture would offer the improvement of allowing the control of the density of the sheet. fO037j In e bodiments:, the present disclosure sho ws that by treating the eellulosic materials with a combination of inorganic particles and saccharide fatty add esters the resulting material, inter alia, can he mads strongly hydrophobic and/or !ipophobic. to addition, these saccharide faty acid esters, for example, once removed by bacterial enzymes, are easily digested as such The fieri vatteed surface displays a great deal of heat resistance, being able to withstand temperatures as high as 250°C and may he more i per eant to gases than the base substrate underneath. The material is therefore an ideal solution to the problem of derivat ng the hydrophilic surface of cellulose in any embodiment in which cellulose materials ma be employed, 003S| Advanta e of the products arid methods as disclosed herein include that the coating composition is made from renewable agricultural resources ~ saccharides and vegetable oils; is biodegradable; has a low toxicity profile and suitable for food contact; can be tuned to reduce the coefficient of friction of the paper/paperboard surface (i,e, , does not mate the paper too slippery fordownstrea processing or end use), even at high levels of water resistance; may or may not be used with special emulsification equipment or emulsification agents, and is compatible with traditional paper recycling programs; i.e., poses no adverse impact on recycling operations, like polyethylene, poiyktoiic acid, or wax coated papers do Further, the extended use of inorganics, such as PCC, takes advantage of the inherent property of the filler (e.g., less flbrasrve) f003 f As used herein, "biobased" mam a materia! intentionally made from substances derived from living (or once-living) organisms. In a related aspect material containing at least about 50% of such substances is considered biobased.

100401 As used herein, "bind", including grammatical variations thereof means to cohere or cause to cohere essentially as a single mass.

(00411 As used herein, "eellulosic” means natural, synthetic or semisyothetie materials that can be molded or extruded into objects (e.g., bags, sheets) or films or filaments, which may he used for making such objects or .films or filaments, that is structurally and functionally similar to cellulose, a.g. coatings and adhesi ves (e g., carboxyraethyleeiiulose). In another example cellulose, a complex eart>ohydraie (CsB oDi),, that is composed of glucose units, which forms the main constituent of the ceil wall in most lants, is cellulosie

|0042l As used herein, "coating weight'’ is the weight of a _: material (wet or dry) applied to a substrate. It is expressed in pounds per specified ream or grams per square meter.

(0043J As use herein, ''compostable" means these solid products are biodegradable into the sod.

(60441 As used herein, "dry basis" is the measure of the mass of all constituents excluding water (e.g. solids), fOMSf As used herein, "edge wicking" means th sorption of water in a paper structure at the outside limit of said structure by one or more mechanisms including, but not limited to, capillary penetration in the pores between fibers, diffusion through fibers and bonds, and surface diffusion on the fibers, In a related aspect the saccharide fatty acid ester containing coating as described herein prevents edge wicking in treated products in one aspect, a similar problem exists withgrease/oil entering creases that may be present in paper or paper products. Such a "grease creasing effect” may be defined as the sorption of grease in a paper structure drat is created by folding, pressing or crushing said paper structure.

(664$) As used herein, "effect", including grammatical variations thereof, means to impart particular property to a specific material

(6G47| As used here! a "hydrophobe" means a substance that does not attract water. Forexample, waxes, rosins, resins, saccharide fatty acid esters, diketenes, shellacs, vinyl acetates,

FI, A, PEI, oils, fats, lipids, other water re cl!ant chemicals or combinations thereof are hydrophobes.

(60481 As used herein, "hydrophobiesiy" means the property of being water-repellent tending to repel and not absorb water. }1M349| As used herein, "lipid resistance* or "lipophobicity” means die property o f being lipid- repellent tending to repel and tioi absorb lipids, grease, fats: an the like. In a related aspect, the grease resistance may be measured by a "3M KIT" test of a APPl T559 Kit test, fOOSOj As used herein, "cellulose-containing material" or "cellulose-based material" means acomposition which consists essentially of cellulose. For example, such material may include* but is not limited to, paper paperboard, paper pulp, a carton for food storage, a bag for food storage, a shipping bag, a container for coffee or tea. a tea bag, bacon board, diapers weed-block/barrier fabric or film, mulching film, plant pots, packing heads, bubble wrap, oil absorbent material, laminates, envelops, gift cards, credit cards, gloves, raincoats, OGR paper, a shopping hag, a compost bag, release paper, eating utensil, container for holding hot or cold beverages, cup, paper towels, plate, a bottle for carbonated liquid storage, insulating materia! _* a bottle for non- carbonated liquid storage, film for wrapping food, a garbage disposal container, a food, handling implement a lid fora cup, paper straws, a fabric fibre, a water storage and conveying implement, paperboard from medical use, release paper, a storage and conveying implement lor alcoholic or non-alcoholic drinks, aft outer easing or screen for electronic goods, aft internal or external piece of furniture, a Curtain, upholstery, film, box, sheet, tray, pipe, water con uit, packaging for pharmaceutical products, clothing, medical device, contraceptive, camping equipment, celfolosic material that is molded and combinations thereof. fiKiSI 1 As used herein,“release paper" mean a paper sheet used to prevent a sticky surface from prematurely adhering to an adhesive or a mastic. In one aspect, the coatings as disclosed herein can be used to replace or reduce the use of silicon or other coatings to produce a material .having a low surface energy. Determining the surface energ may be readily achieved by measuring contact angle (e.g., Optical Tensiometer and/or High Pressure Chamber, Dyne Testing, Staffordshire, United Kingdom) or by use of S urface Energy Test Pets or Inks (see, e.g.. Dyne Testing, Staffordshire, United Kingdom), 0052| As used herein "releasable" with reference to the SFAE means that the; SFAE coating, once applied, may he removed from the cellulose-based material (e.g., removeabie by manipulating physical properties) As used herein "non-releasahle" with reference 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). }00S3| As used herein,“fibers in solution" or "pulp” means a lignocellulosic fibrous material prepared by chemically or mechanically separating cellulose fibers from wood, fiber crops or waste paper. In a related aspect, where cellulose fibers are treate by the methods as disclosed herein, the cellulose fibers themselves contain bound saccharide fatty acid esters as isolated entities, and where the bound cellulose fibers have separate and distinct properties from free fibers (e.g., pulp- or cellulose fiber- or nanoeeliulose ormscrofibrillated cellulose-saccharide fatty acid ester bound material would not form hyd rogen bonds between fibers as readily as unbound fibers}

10054] As used herein, "repalpable" means -to «take a paper or paperboard product suitable for crushing into a soft, shapeless mass for reuse in the production of paper or paperboard.

100551 As used herein, "tunable", including grammatical variations thereof means to adjust or adapt a process to achieve a particular result

100561 As used herein, "water contact angle" means the angle measured through a liquid, where a liquid/vapor interface meets a solid surface. It quantifies the wettability of the solid surface by the liquid. The contact angle is a reflection of how strongly the liquid and solid molecules interact with each other, relative to how strongly each interacts with its own kind. On many highly hydrophilic surfaces, water droplets will exhibit contact angles of 0° to 30 ^s .

Generally, if the water contact angle is huger than 90% the solid surface is considered hydrophobic. Water contact angle may be readily obtained using an Optical Tensiometer (see, e.g, . Dyne Testing, Staffordshire, United Kingdom).

J0O57J As used herein, ^" water vapour permeability" means breaihabiliiy or a textile’s ability to transfer moisture, There are at least two different measurement methods. One, ihe MVTR Test (Moisture Vapour Transmission Rate) ih accordance with ISO 15496., describes the water vapor permeability (WVP) of a fabric and therefore the degree of perspiration transport to the outside air. The measurements determine how many grams of moisture (water vapor) pass through a square meter of fabric in 24 hours (the higher the level, the higher the breathabiiity).

(0058J In one aspect, TAPP! T 530 Hercules si¾e test (i. e.. size test for paper by ink resistance) may be used to determine water resistance, ink resistance by the Hercules method is best classified as a direct measurement test for the degree of penetration. Others classify it as a rate of penetration test There is -no one best test for "measuring sizing," Test selection depends on end use and mill control needs. This method is especially suitable lot use as a tnill control Si ing test t o accurately detect changes in sizin level it offers t he sensiti vity of die ink float test while providing reproducible results, shorter test times and automatic end point determination.

10059 Sizing, as measured by resistance to permeation through or absorption into paper of aqueous liquids, is an important characteristic of many papers. Typical of these are bag.

cantainerboard, butcher's wrap, writing, and some printing grades.

|t)060| This method may be used to monitor paper or board production for specific end uses provided acceptable correlation has been establishe between test values and the paper's end use performance. Due to the nature of the test and the penetrant, it will not necessarily correlate sufficiently to be applicable to all end use requirements. This method measures siring by rate of penetration. Other methods measure sizing by surface contact, surface penetration, or absorption. Size tests are, selected based on the ability to simulate the means of water contact or absorption in end use. This method can also be used to optimize size chemical usage costs.

10061) As used herein, "oxygen permeability" means the degree to which a polymer allows the passage of a gas or fluid. Oxygen permeability (Dk) of a material is a function of the diffusivity (D) (i.e.. the speed at which oxygen molecules traverse the material) and the solubility (k) (or the amount of oxygen molecules absorbed _* per volume, in the material). Values of oxygenpermeability (Dk) typically fall within the range 10- 150 x 10 (corf mi ©2}.% ml mmKg). A semi-logarithmic relationship .has been demonstrated between hydrogel water content and oxygen permeability (Unit; Barrel unit). The international Organization for Standardization (ISO) has specified permeability using the Si unit heciopascdl (hPa) for pressure. Hence Dk ~ 10 (cnri ml Oj) /(s ml hPa). The Barrer unit can be converted to hPa unit by multiplying it by the constant 0.73, f{HK»2| As used herein "biodegradable", including grammatical variations thereof, means capable of being broken down especially into innocuous products by the action of living tilings (e.g., by microorganisms). }ΐM>ΐ>3| As used herein, "recyclable”, incl uding grammatical variations thereof means a material that is treatable or that can be processed (with used and/or waste items) so as to mate said materi l suitable for reuse.

(00641 As used herein, "filler" means finely divided white mineral (or pigments) added to paper making furnishes to improve the optical and physical properties of the sheet. The particle serve to fill in the spaces and crevices between the fibers, thus, producing a sheet with increased brightness, opacity, smoothness, gloss, and prittiability, but generally, lower bonding and tear strength. Common paper making fillers include clay (kaolin, bentonite), calcium carbonate (both GCC and PCC), talc (magnesium silicate), and titanium dioxide.

(BOSS! As use herein, "Gurley second" or "Gurley number" is a unit describing the number of seconds required for 100 cubic centimeters (deciliter) of air to pass through .0 square inch of a gi ven material at a pressure d ifferential of 4 88 inches of water (0. 176 psi) (ISO 5636- 5;2003){PQrosity). In addition, for stiffness, "Gurley number” is a unit for a piece of vertically held matenal measuring the force required to deflect said materia! a given amount (1 milligram of force) Such values may be measured cm a Gurle .Precision Instruments' device (Troy, New York).

|0066| HLB-The hydrophilk-lipophiS.ic balance of a surfactant is a measure of the degree to which it is hydrophilic or lipophilic, determined by calculating values fo the different regions of the molecule.

|006?| Griffin's method for non-ionic surfactants as described in 1954 works as follows:

(006§! where is the molecular mass of the hydrophilic portion of the molecule, and M is the molecular mass of the whole molecule giving a result on a scale of 0 to 20. An HLB value of 0 corresponds to a completely hpophi!ic/hydrophobic molecule, and a value of 20 corresponds to a completely hydropbiiie/!tpophobie molecule.

(0069J The HLB value can be used to predict she surfactant properties of a molecule: < 10 : Lipid-SOlubie (water -insoluble)

> 10 : Water-soluble (lipid-insoluble)

.1.5 to 3: anti -foaming agent 3 to 6: W/O (water in oil) emulsifier

7 to 9: wetting and spreading agent 13 to 15: detergent

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

15 to 18: solubiliser or hydrotrope

P(I7(11 In some embodiments _: , the MLB values for the saccharide fatty add esters (or composition comprising said ester) as disclosed herein may be in the lower range in other embodiments, the HLB values for the saccharide faty acid esters (or composition comprising said ester) as disclosed herein may be in the middle to higher ranges. In embodiments, mixing SFAEs with different HLB values may be used fO(37 l 1 As used herein, "SEPOSE* denotes a sucrose taty acid ester made from soybean oil (soyaie) which Is commercially available from Procter & Gamble Chemicals (Cincinnati, Old)under the trade name SEFOSE 161811 (see sucrose poiysoyate belo w), which contains one ormore fatty acids that are unsaturated. As used herein, "GLEAN ⁴ denotes a sucrose fatty acid ester which is available from Procter & Gamble Chemicals having the formula C nF jjOw, where all fatty acids are saturated. In addition, SFAEs may be purchased from Mitsubishi Chemicals Foods Corporation (Tokyo, JP), which offers a variety of such SFAEs.

(00721 As used herein, "soyate" means a mixture of sails of fatty acid from soybean oil. f0073| As used herein, "oilseed fatty acids" means fatty acids from plants, including but not limited to soybeans, peanuts, rapeseeds, barley, canola sesame seeds, cottonseeds, palm kernels, grape seeds, olives, safflowers sunflowers, copra, corn, coconuts, linseed, hazelnuts, wheat, rice, potatoes, cassavas, legumes, camel ina seeds, mustard seeds, and combinations thereof. JiM)74j As used herein "wet strength" means the measure ofhow well the web of fibers holding fee paper together can resist a force of rupture when the paper is wet. The wet strength may be measured using a Finch Wet Strength Device from Thwtng* Albert Instrument Company (West Berlin, Ni). Where the wet strength is typically effected by wet strength additives such as kyraene, cationic g!yoxv!ated resins, polvamidoamine-epiciilorohydrin resins, polyamine- epichlofohydrin resins, including epoxide resins. In embodiments, SFAE coated cellulose base material as disclosed herei n effects such wet strength in the absence of such additives.

P07S1 As used herein "wet" means covered or saturated with water or Mother liquid.

|t)076| In embodiments, a process as disclosed herein includes mixing of a saccharide fatt acid ester with an inorganic panicles (e.g., clay, talc, calcium carbonate) an applying said mixture to a ceiMosie material which can allows said particles to adhere to said ceiluiosic material, where said process comprises contacting a cellulose-based material with the combination and exposing fee contacted ceiiulose-based material to heat radiation, a catalyst or a combination thereof fee a sufficient time to bind tire combination to the cellulose based material. In a related aspect, such radiation ay include, but is not limited to UV, IR, visible light or a combination thereof. In another related aspect, the reaction may be carried out at room temperature (i.e,, 25’C) to about 1 0 ^® C, about 50 ^® G id about 100°C, or about 60°C to about

8f ⁾ °e.

|007T| Further, fee binding reaction between the mixture and fee ceiluiosic material may be carried out with or substantially reduced retention aids (be., binders such as PvOH or starch) in one aspect, the mixture may contain a mixture of mono-, di~, tri- tetra-, penta-, hexa-, hepta-. or octaesiers. In another spect the may also may contain proteins, polysaccharides and lipids, including but not limited to, milk proteins (e.g.. casein, whey protein and the like), whe t glutens, gelatins, prolamines (e.g., com zeins), soy protein isolates, starches, modified starches, acetylated polysaccharides, alginates, carrageenans, chi iosans, irad ns, long chain fatty adds, waxes, and combinations thereof.

J0078J In embodiments, ceiluiosic material may be made lipophobic by the addition of polyvinyl alcohol (PvOH) and/or prolamines. In one aspect, the prolamines include zein, gifedin, hordein, secaito, katirin and avenin, in a related aspect, the prolamine is zein. lu embodiments, no catalysts and no organic carriers (e.g., volatile organic compounds) am require to carry out the binding reaction, including that no build-up of material is contemplated using the method as disclosed. In a related aspect, the reaction time is substantially instantaneous f t. e., less than i second). Further, the resulting material exhibits low blocking. 00801 As disclosed herein, fatty acid esters of all saccharides, including mono-, di- saccharides and tri-saccharides, are adaptable for use in connection with this aspect of the present invention. In a related aspect, the saccharide fatty acid ester may be a mono-, di~, iri , tetra-, pentiK hexa-, hepta-, oroctaester, and combinations thereof, including that the fatty acid moieties may he saturated, unsaturated or a combination thereof.

I008l| While not being bound by theory, the Interaction between the saccharide .fatly acid ester and the cellulose-based material may be by ionic, hydrophobic, van der Wards interaction, or covalent bonding, or a combination thereof in a related aspect, the saccharide fatty acid ester binding to the cellulose- based material may be substantially irreversible (e.g., using an SFAB comprising a combi nation of saturated and unsaturated fatty acids) .

|il(1821 Further, at a sufficient concentration, the binding of the saccharide fatty acid ester alone is enough to make the ceihilose-based material hydrophobic i.e., hydropbobicily is achieved in the absence of the addition of waxes, rosins, resins, dikelenes, shellacs, vinyl acetates, PLA, PEI, ods, other waiter repehant chemicals or combinations thereof (t.e., secondary hydrophobes), including that other properties such as, inter alia, strengthening _;, stiffening, and bulking of the cell uiose-based material is achieved by saccharide fatty acid ester binding alone.

100831 An advantage of the invention as disclosed is that multiple fatty add chains are reactive with the cellulose and with the two saccharide molecules in the structure, for example the sucrose fatly acid esters as disclosed gi ve rise to a stiff cross! inking network, leading to strength improvements in fibrous webs such as paper, paperboard, air-laid and wet-laid non- wovens, and textiles, thus may overcome potential unwanted effects of some fillers (e.g., calcium carbonates aid lower bonding and teas strength). This is typically not foun in other sizing or hydrophobic treatment chemistri es _: The saccharide fatty acid esters as disclosed .herein also generaterincrease wet strength, a property absen t when using many other water resistan chemistries. f0084j Another ad vantage is that the saccharide fatty acid esters as disclosed soften the fibers, increasing the space between them, tiros, increasing bulk without substantially increasing weight. In addition, fibers and cellulose-based material modified as disclosed herein, may be repulped. Further, for example, water cannot be easily "pushed" past the low surface energy barrier into the sheet. iOOSSj Saturated SFAE are typically solids at nominal processing temperatures, whereas unsaturated SFAE are typically liquids. This permits the formation of uniform, stable dispersions of saturated SFAE in aqueous coatings without significant interactions or incompatibilities with other coating components, which are typically hydrophilic In addition, this dispersion allows for high concentrations of saturated SFAE to he prepared without adversely affecting coaling rheology, uniform coating application, or coating performance characteristics. The coatingsurface will become hydrophobic when the particles of saturated. SFAE melt and spread open heating, drying and consolidation of the coating layer. In embodiments, a method of producing bulky, fibrous structures that retain strength even when exposed to water is disclosed. Generally fibrous slurries that are dried form dense structures that are easily broken down upon exposure to water. Formed fiber products made usin th method as disclosed may include paper plates, drink holders (e.g.. cups}, lids, food trays and packaging that would be light weight, strong, and he resistant to exposure to water ai other liquids

10086] In embodiments, saccharide fatty acid esters may be mixed with polyvinyl alcohol (PvOH) to produce sizing agents for water resistant Coatings. As disclosed herein, a synergistic relationshi between saccharide fatty acid esters and PvOH has been demonstrated, including that with inorganic mixtures, the amount of PvOH may be reduced. While it is known in the art that PvOH is itself a good film former, and forms strong hydrogen bonds with cellulose, it is not very resistant to water, particularly hot water in aspects, the use of PvOH helps to emulsify saccharide fatty aci esters into an aqueous coating, in one aspect, PvOH provides a rich source of OH groups for saccharide fatty acid esters to crosslink along the fibers, which increases the strength of paper, for example, particularly wet strength, and water resistance beyond what is possible with PvOH alone. For saturated saccharide fatty acid esters with free hydroxyls on the saccharide, a cresslmking agent such as a dialdehyde (e.g,, glyoxai, giuiafaidehyde, and the like) may also be. used. f0087| In embodiments, the saccharide fatty acid esters comprise or consist essentially of sucrose esters of fatty acids. Matty methods are known and available for making or otherwise providing the saccharide fatty actd ester of the present invention, and all such methods are believed to be available for use within the broad scope of the present invention. For example, in certain embodiments it may be preferred that the fatty acid esters are synthesized by esterifying a saccharide with one or more fatty arid moieties o btained from oil seeds including but not limited to, soybean oik sunflower oil olive oil, canola oil peanut oil, aid mixtures thereof )0881 in embodiments, the saccharide fatty acid esters comprise a saccharide moiety, including but not limited to a sucrose moiety, which has been substituted by an ester moiety at one or more of its hydroxyl hydrogens in a related aspect, disaccharide esters have the structure of Formula I.

Formula I

0M)891 where "A" is hydrogen or of Structure 1 below;

Structure I }1M390| where "R” is a linear branched, or cyclic, saturated or unsaturated, aliphatic or aromatic moiety of about eight to about 40 carbon atoms, and where at feast one "A," is at feast one, at least two, at least three, at least four. at least five, at least six, at least seven, and ait eight ’’A’ moieties of Formula are in accordance with Structure 1. hi a related aspect the saccharide fatty acid esters as described herein may be motto-, di~, in-, leira-, petita-, hexii-, hepta , or oeta- esters, and combinations thereof where the aliphatic groups may be all saturated or may contain saturated and/or unsaturated groups or combinations thereof,

1009*11 Suitable "R" groups include any form of aliphatic moiety, including those which contain one or more substituents, winch may occur on any carbon in the moiety. Also included are aliphatic moieties which include functional groups within the moiety, for example, an ether, ester, thio, amino, phpspho, or Ac like. Also included are oligomer and polymer aliphatic moieties, for exam le sorbitmi polysorbitan and polyalcohol moieties. Examples of functional groups which may be: appended to the aliphatic (or aromatic) moiety comprising the "R" group include, but are not limited to, halogens, alkoxy. hydroxy, amino, ether and ester functional groups. In one aspect, said oieties may have erossUnking functionalities. In another aspect, the SFAE may be crosslinked to a surface (e.g., activated clay/ pigment particles). In another aspect, double bonds present on the SFAE may be used to facilitate reactions onto other surfaces.

J0092J Suitable disaccharides include raffinose, malto extrose, galactose, sucrose, combinations of glucose, combinations of fructose, maltose, lactose, combinations of mannose, combinations of etythrose, isoma!tose, isomalrulose, trehalose, irehaiulose, celiobiose,

lamiaaribiose, chitobiose and combinations thereof.

|O093| In embodiments, the substrate for addition of fatty acids ma include starches, hemiceliuloses, lignins or combinations thereof

}0094j In embodiments, a composition comprises a starch fatty acid ester, where the starch may be derived from any suitable source such as dent com starch, waxy corn starch, potato starch, wheat starch, rice starch, sago starch, tapioca starch, sorghum starch, sweet potato starch, and mixtures thereof. 1009S| In more detail, the starch may be an unmodified starch, or a starch that has been modified by a chemical, physical or enzymatic modification.

}0096f Chemical modification includes any treatment of a starch with a chemical that results in a modified starch (e.g. , plastsrch material). Within chemical modification are included, but not limited to, epoiy merization of a starch, oxidation of a starch, reduction of a starch, etherification of a starch, esterification of a starch, nitrification of a starch, defatting of a starch,

hydrophobizatibn of a starch, and the like. Chemically modified starches may al o be prepared by using a combination of any of tire chemical treatments. Examples of chemically modified starches include the reaction of alkenyl succinic anhydride, particularly octenyi succinic anhydride, with starch to produce a hydrophobic esteriiled starch; the reaction of 2,3- epoxy propyltri methyl ammonium chloride with starch to produce a cationic starch; the reaction of ethylene oxide with starch to produce by droxyethyi starch; the reaction of hypochlorite with starch to produce an oxidized starch; the reaction of an acid with starch to produce an acid depolymarizsd starch; defatting of a starch with a Solvent such as methanol, ethanol propanol, methylene chloride, chloroform, carbon tetrachloride, and the like, to produce a defated starch.

}0097| Physically modified starches are any starches that are physically treated in any manner to provide physically modified starches. Within physical modification are included, but not limited to, thermal treatment of the starch in the presence of water, thermal treatment of the starch in the absence of water, fracturing the starch granule by any mechanical means pressure treatment of starch to melt the starch granules, and the like. Physically modified starches may also be prepared by using a combination of any of the physical treatments. Examples of physically modified starches include the thermal treatment of starch in an aqueous environment to cause the starch granules to swell without granule rupture; the thermal treatment of anhydrous starch granules to cause polymer rearrangement; fragmentation of the starch granules by mechanical disintegration; and pressure treatment of starch granules by means of an extruder to cause melting of the starch granules.

100981 Enzymatically modified starches are any starches that are enzymatically treated in anymanner to provide enzymatically modified starches. Within enzymatic modification are included, but not limited to, the reaction of m alpha amylase with starch, the reaction of a protease with Starch, the reaction of a lipase with starch, the reaction of a pbospborylase with starch, the reaction of at oxidase with starch, a d the like. Enzymatically modified starches may be.

prepared by using a combination of any of the enzymatic treatments. Examples of enzymatic modification of starch include the reaction of alpha-amylase enzyme with starch to produce a depot ymerized starch; the reaction of alpha amylase debranching enzyme with starch to produce a debraochad starch; the reaction of a protease enzyme with starch to produce a starch with reduced protein content; the reaction of a lipase enzyme with starch to produce a starch with reduced lipid content; the reaction of a phosphorylass enzyme with starch to produce an enzyme modified phosphated starch; and the reaction of art oxidase enzyme with starch to produce an enzyme oxidized starch, f0099| Disacehatide fatty acid esters may be sucrose fatty acid esters in accordance withFormula 1 wherein the: "R" groups are aliphatic and are linear or branched, saturated or

uosaiyrateti and have between about % and about 4.0 carbon atoms, fOO !Offj As used herein the terms "saccharide fatty acid esters" mi "sucrose fatty acid ester" include compositions possessing different degrees of purity as well as mixtures of compounds of any purity level. For example, the saccharide fatty acid ester compound can be a substantially pure material that is, it can compris a compound having a given number of the "A" groups s ubs tituted by only one species of Structure f moiety (that is, all "R" groups are the same and all of the sucrose moieties are substituted to an equal degree) h also incl udes a composition comprising a blend of two or more saccharide fatty acid osier compounds, which differ in their degrees of substitution, but wherein all of the substituents have the same ^>r R" gro up structure, it also includes compositions which are a mixture o.f compounds- .having differing degrees of "A” group substitution, and wherein the "R" group substituent moieties are independently selected from two or mote”R” groups of Structure G. In a related aspect, "R" groups may be the same or may be different, including that said saccharide fatty acid esters in a composition may be the same or may be different: (i.e., a mixture of different saccharide .fatty acid esters).

|0ti l 01| For compositions of the present invention, the composition may be comprised o f saccharide fatty acid ester compounds having a high degree of substitution. In embodiments, the saccharide fatty acid ester is a sucrose po!ysoyate.

A Sucrose Polysoyate (SEFOSE®

1618U)

|00102| Saccharide fatly acid esters may be made by esterification with substantially pure fatty acids by known processes of esterification. They can he prepared also by trans-esterification using saccharide and fatty arid esters in the form of fatty acid glycerides derived, for example, from natural sources, for example, those found in oil extracted from oil seeds, for example soybean oil Trans-esterification reactions providing sucrose fatty arid esters using fatty arid glycerides are described, for example, in U.S. Pat Nos. 3,963,699; 4,517,360; 4, 518,772;

4,61 1 ,055; 5,767,257; 6,504,003; 6.1 21.440; and 6,995,232, and WQ199200436! Al, herein incorporated by reference in their entireties.

!bb103| in addition to making hydrophobic sucrose esters via tm sesterification, similar hydrophobic properties may be achieved in fibrous, celiulosic articles by directly reacting arid chlorides with polyols containing analogous ring structures to sucrose. fii(S|04{ As mentioned above, sucrose fatty acid esters may be prepared by trans-esterification of sucrose .from methyl ester feedstocks which have been prepared from glycerides derived from natural sources (see, e.g:, 6,995,232, herein incorporated by reference in its entirety). As a conseq uence of the sou rce of the fully acids, the feedstock used to prepare the sucrose laity acid ester contains a range of saturated and «maturated fatty acid methyl esters having faty acidmoieties containing between 12 and 40 carbon atoms. This wilt be reflected in the product sucrose fatty acid esters made from such a source in that the sucrose moieties comprising the product will contain a mixture of ester moiety substituents, wherein, with reference to Structure I abo ve, the”R” groups will he a mixture havin between 12 and 26 carbon atoms with a ratio that reflects the feedstock used to prepare the sucrose ester. Further to illustrate this point, sucrose esters deri ved from soybean. oil will be a mi xt ure of species having ¾" group structures which reflect that soybean oil comprises 26 wt % triglycerides of oleic acid (l¾C-CHjj _? -CH ^:::: CH-

[CH;> -C(0)0H), 49 wt % triglycerides of Imoleie acid (H^CHCHaJH-O-fe ^. CH-CHjri>CB _; b~€(G)OH), I I wt. % of triglycerides of linoiemc acid

€iO}0H}, and, 14 wt. % of triglycerides of various saturated fatty acids, as described in the Seventh Ed. Of the Merck index, which is incorporated herein by reference. All of these fatty acid moieties ate represented in the“R" groups of the substituents in the product sucrose fatty acid ester. Accordingly, when referring to a sucrose fatty acid ester herein as the product of a reaction employing a fatty acid feed stock deri ved from a natural source, for example, sucrosesoyate, the term is intended to include all of the various constituents which are typical ly found as a consequence of the source ifom which the sucrose fatty acid ester is prepared. In a related aspect, the saccharide fatty acid esters as disclosed ma exhibit low viscosity {e g., between about .10 to 2000 eentipoke at room temperature or under standard atmospheric pressure). Inanother aspect, the urisaturated fatty a ds, may have one, two, three or more double bonds.

(00105] In embodiments of the present invention, She saccharide fatty acid ester, and in aspects, the disaccharide ester, is formed from faty acids having greater than about 6 carbon atoms, from about 8 to 16 carbon atoms, from about 8 to about 18 carbon atoms, from about 14 to about 18 carbons atoms, from about 16 to about 18 carbon atoms, from about 16 to about 20 carbon atoms, and from about 20 to about 40 carbon atoms, on verage, 001.06] In embodiments, the saccharide fatty acid ester may be present in different concentrations to achieve hydrophobicity/lipophohicily depending on the form of the cellulose- based material In one aspect, when a saccharide fatty acid ester (SFAE) is bound as a coating on the cellulose-based material, the 8PAE is present at a coating weight of at least about 0. Ig/m ⁱ to about 1.0g/nr, about l.Og/nr to about 2.0g4ir. about 2g/nr to about 3g/nri on a surface of the cellulose-based material, lb a related aspect, it may be present from about 3g/nr to about 4g/my about 4g/m ² to about Sg/tn ² about Sg/m* to about lOg/tn ² , about 1 Og/m ² to about 20g/m ² In another aspect when the cellulose-based material is a solution containing cellulose fiber, the SFAB is present at a concentration of at least about 0.025% (wi/wt) of the total fiber present. In a related aspect, it may be present at about 0.05% (wt/wt) to abort! 0.1 % (wt/wt). about 0.1 % (wt/wt) to about 0.5% (wi/wt), about 0.5% (wt/wt) to about 1 .0% (wt/wl), about 1.0% (wt/wt) to about 2.0% (wt/wt). about 2 0% (wt/wt) to about 3.0% (wt/wt), about 3.0% (wt/wt) to about 4 0% (wi/wt), about 4.0% (wt/wt) to about 5,0% (wi/wt), about 5,0%(wt/wf) to about 10% (wi/wt), about 10% (wt/wt) to about 50% (wt/wt) of the total fiber present. In a further related aspect, the amount of SPAT may be equal to the amount of fiber present. In some embodiments, the SFAE may coat the entire outer surface of a cellulose-based materia! (e.g , coat an entire piece of paper or ceSlulose-coniairring article).

1001.07] In other embodiments. a coating may comprise between about 0 9% to about 1.0%, about 1.0% to about 5 0%, about 5.0 to about 10%. about 10% to about 20%, about 20% to about 30%, about 40% to about 50% saccharide fatty acid ester by weight of the coating (wt/wt). fn a related aspect, the coating may contain between about 25% to about 35% saccharide fatty acid ester by weight of the coating (wt/wl).

|00M>Sf In embodiments, the cellulose-based material includes, but is not limited to, paper,, paperboard, paper sheets, paper pulp, cups, boxes, trays, Ms, release papers/liners, compost bags, shopping bags, shipping bags, bacon board, tea ags, insulating material, containers for coffee or tea, pipes and water conduits, food grade disposable cutlery, plates and bottles, screens for TV and mobile devices, clothing (e.g., cotton or cotton blends), bandages, pressure sensitive labels, pressure sensitive tape, feminine products, and medical devices to be used on the body or inside it such as contraceptives, drug delivers ^1, devices, container for pharmaceutical materials e.g., pills, tablets, suppositories, gels, etc. ), and the like. Also, the coating technology as disclosed may be used on furniture and upholstery, outdoors camping equipment and the like.

(00109] In one aspect, the coatings as described herein are resistant to pH in. the range of between about 3 to about 9. In a related aspect, the pH may be from about 3 to about 4, about 4 to about 5, about 5 to about 7. about 7 to about 9 JtMltii ⁾ ] In embodiments, an alkanoic acid derivative is mixed with a saccharide fatty acid -ester to form an emulsion, where the emulsion is used to treat the cellulose-based material. fOOl ll¾ hi embodiments, the saccharide fatty acid ester may he an emulsifying agent and may comprise a mixture of one or more mono-, dk irk tetra-, penta-, hexa-, hepta-, or octaesters In another aspect, the fatty acid moiety of the saccharide fatty acid ester may contain saturated groups, umaturated groups or a combination thereof. In one aspect, the saccharide fatty acid ester-containing emulsion may contain proteins, polysaccharides and/or lipids, including but not limited to milk proteins (e.g., casein, whey protein and the like), wheat glutens, gelatins, prolamines (e.g., com zeinX soy protein isolates, starches, acetylated polysaccharides, alginates, eamageenans, chuosans, inulins, long chain fatty acids, waxes, and combinations thereof. Q0I.I2] In embodiments the saccharide fatty acid ester as disclosed herein may he used in coatings with o ther chemicals used for paper manufacturing including, but not limited to, agalite, esters, diesters, ethers, ketones, amides, nitriles, aromatics (e.g , xylenes, toluenes), acid halides, {«hydrides, alkyl ketene dimer ( A D), alabaster, aig nic acid, alum albarine, glues, barium carbonate, barium sulfate, chlorine dioxide, dolomite, diethylene triamine penta acetate, EDTA, enzymes, fo iamidme sulfuric acid, guar gum, gypsum, lime, magnesium bssuliate, milk of lime, milk of magnesia, polyvmayl alcohol (PvOFI), rosins, rosin soaps, satins, soaps/fatty acids sodium bisulfate, soda-ash, titania, surfactants, starches, modified starches, hydrocarbon resins, polymers, waxes, polysaccharides, proteins, latex, and combinations thereof. In embodiments, the mixture as disclosed may contain one or more SFAEs and one or more ofthe following inorganic particles; day (kaolin, bentonite), calcium carbonate (both GGC and PCC), talc

(magnesium silicate), and titanium dioxide. In a related aspect, the inorganic particles may fee present at between about !% to about 2%, about 2% to about 5%, about 5% to about 10%, about 10% to about 20%, about 20% to about 30%, about 30% to about 40%, about 40% to about 5034, about 50% to about 6034, or about 60% to about 70% in a coating composition in a further related aspect the SFABs may be present in an equal, .higher or lower proportion compared to the amounts of inorganic parti cles in a coating. In one aspect, coatings containing one or more

SFAEs comprise- all saturated fatty acids, jOOIfSf In embodiments, the cellulose-containing material generated by the methods as disclosed herein exhibits greater hydrophobiciiy or water-resistance relative to the cellulose- contuiring material without the treatment In a related aspect, the treated cellulose-containing material exhibits greater lip op hob t city or grease test stance relativ to the cellulose-containing material without the treatment. In a further related aspect, tile treated cellulose-containing matedai may be biodegradable, compostable, and/or recyclable In oils aspect the treated cellulose-containing material is hydrophobic (water resistant) and lipophohic (grease resistant). 001.14} In embodiments, the treated cellulose-containing material may have improved mechanical properties compared to that same material untreated. For example, paper bags treated by the process as disclosed herein show increased hurst strength, Gurley Number, Tensile Strength and/or Energy of Maximum Load, In one aspect, the burst strength is increased by a factor of between about 0,5 to 1 ,0 fold, between about 1.0 and 1.1 fold, between about LI and 1.3 fold, between about 1 .3 to 1,5 fold. In another aspect the Gurley Number increased by a factor of between about 3 to 4 fold, between about 4 to 5 fold, between about 5 to 6 fold and about 6 to 7 fold. In still another aspect, the Tensile Strain increased by a factor of between about 0.5 to 1.0 fold, between about 1.0 to 1.1 fold, between about 1. 1 to 1 ,2 fold and between about 1.2 to 1.3 fold. And in another aspect, the Energy of Max Load increased by a factor of between about 1 ,0 io 1.1 fold, between about 1.1 to 1.2, fold, between about 1.2 to 1 ,3 fold, and between about 1 ,3 io 1.4 fold.

|«011"5J In embodiments, the cellulose-containing material is a base paper comprising raicroilbri Hated cellulose (MFC) of cellulose nariofibe (CNF) as described for example in U S. Fob. No. 2015/0167243 (herein incorporated by reference in its entirety), where the MFC or CNF is added during the forming process an paper making process and/or added as a coating or asecondary’ layer to a prior forming layer to decrease the porosity of said base paper io a related aspect, the base paper is contacted with the saccharide fatty acid ester as described above In a further related aspect, the contacted base paper is further contacted with a polyvinyl alcohol (PvOH). In embodiments, the resulting contacted base paper is tuoeably water and lipid resistant in a related aspect, the resulting base paper ma exhibit a Gurley value of at least about 10-15 (i e., Gurley Air Resistance (sec/i 00 oc, 20 o.r. eyl. )), or at least about 100, at least about 200 to about 350. in one aspect, the saccharide faty acid ester coating may be a laminate for one or more layers or may provide one or more layers as a laminate or may reduce the amount of coating of one or more layers to achieve the same performance effect (e.g.. water resistance. grease resistance arid the like) i a related aspect the laminate may comprise a biodegradable and/or composable heat seal or adhesive, f _.001 161 In embodiments, the saccharide fatty acid esters may be formulated as emulsions, where the choice emulsifying agent and the amount employed is dictated by the nature of thecomposition and the ability of the agent to facilitate the dispersion of the saccharide fatty acid ester. In one aspect, the emulsifying agents may include, but are not limited to, water, buffers, polyvinyl alcohol (PvOH), carboxymethy! cellulose (CMC), latex, milk proteins, wheat gluteus, gelatins, prolamines, soy protein isolates, starches, acetyiated polysaccharides, alginates, carrageenans, chitosans, inulins, long chain tatty acids, waxes, agar, alginates, glycerol, gums, lecithins, poloxamers, mono-, di-glycerols, mosiosodmra phosphates, monostearate, propylene glycols, detergents, cetyl lcohol, and combinations thereof. 1ft another aspect, the saccharide ester: emulsifying agent ratios may be from about 0.1 :99,9, from shoot 1.* .>. from about 10:90, iTo about 20: H , fiom about 35:65. from about 40:60, and from about 50: 50. It will be apparent to one of skill in the art" that ratios may be varied depending on the property (ses) desired for the final product.

{00117} In embodiments, the saccharide fatty acid esters may be combined with one or more coating components for internal and surface siting (alone or in combination), including but notlimited to, binders (eg., starch, soy protein, polymer emulsions, PvOH, latex), and additi ves (e.g., glyoxal, glyoxalated resins, zirconium salts, calcium stearate, lecithin oleate, polyethylene emulsion, cirboxymethyi cellulose, acrylic polymers, alginates, polyacrylate gums,

polyacryistes, rmcrobiocides, oil based defoamers, silicone based defoamers, shibenes, direci dyes and add dyes), In ¾ related aspect, snob components may provide one or more properties, including but not limited to, building a fine porous structure, pro tiding light scattering surface, improving ink receptivity, improving gloss, binding pigment particles, binding coatings to paper, base sheet reinforcement, filling pores in pigment structure, reducing water sensitivity, resisting wet pick in offset printing, preventing blade scratching, improving gloss in supercalendering, reducing dusting, adj usting coating viscosity, providing water holding, dispersing pigments, maintaining coating dispersion, preventing spoilage of coafing/coating color, controlling foaming, reducing entrained air and coating craters, increasing whi teness and brightness, and controlling color and shade. It; will be apparent to one of skill m the art that combinations may be varied depending on the property(ies) desired for the final product f _. 00118| In embodiments, the methods employing said saccharide fatty acid esters may be used to tower the cost of applications of pri ary/secondary coating (e.g,, silicone-based las er, starch- based layer, clay-based layer, PLA-layer, Bio-PBS. PEI -layer and the like) by providing a layer of material that exhibits a necessary property (e.g. , water resistance, low surface energy, and the like), thereby reducing the amount of primaxy/seeondary layer necessar to achieve that same property. In one aspect, materials may be coated on top of an SFAE layer (e.g. heal sealable agents). In embodiments, the composition is fluorocarbon and silicone free.

|IM ⁾ 1 19) In embodiments, the compositions increase both mechanical and thermal stability of the treated product in one aspec t, the surface treatment is thermostable at temperatures between about -Kit PC to about SOOT hi further related aspect, the surface of the cellulose-based material exhibits a water contact angle of between about bO’’ to about 12(ri. In another related aspect, the surface treatment is chemically stable at temperatures of between about 20CFC to about 3b( ^)y C.

{001201 The substrate which ma be dried prior to application (e.g., at about 8(M50T), ma be treated with the modifying composition by dipping, for example, and allowing the surface to be exposed to the composition for less than I second. he substrate may be heated to dry the s rface, after which the modified material is ready for use. in one aspect, according to the method as disclosed herein the substrate may be treated by any suitable coating/ sizing process typically carried ur in a paper mill (see, e g., Smoob, G , Surface Treatments in Ha dhookfor 293-309, TAPP! Press,. Peachtree Corners, GA USA, herein incorporated by reference in its entirety}.

100121J No special preparation of the material is necessary in practicing this invention, although for some applications, the material may be dried before treatment . In embodiments, the methods as disclosed may be used on any cellulose-based surface, including but. not limited to, a film, a rigid container, fibers, pulp, a fabric or the like. In one aspect, the saccharide fatly acid esters or coating agents may be applied by conventional size press (vortical, inclined, horizontal), gate roll size press, metering size press, calender size application, tube sizing, on-machine, off- machine, single-sided coater. double-sided coater, short dwell simultaneous two-side coater, blade or rod coaier, grav ure coater, gravure printing, flexographic printing, ink-jet printing, laserprinting, supereaSenderi.ng, and combinations thereof

(001221 Depending on the source, the cellulose may be paper, paperboard, pulp, softwood fiber, hardwood fiber, or combinations thereof,; rtanoceSlulose, cellulose nanofibres, whiskers or rmeroibrii, microiibril ted, cotton or coton blends, other non-wood fibers, (such as sisal jute or hemp, flax and straw) cellulose narrocrystals, or nanofibiilaied cellulose

(00 23! In embodiments, die amount of saccharide fat ty acid ester coating applied is sufficient to completely cover at least one surface of a cellulose-containing material. For example, in embodiments, the saccharide fatty add ester coating may be applied to the complete outer surface of a container, the complete inner surface of a container, or a combination thereof, or one or bo th sides of a base paper. In other embodiments, the complete upper surface of a film may he covered by the saccharide fatty acid ester coating, or the complete under surface of a film may be covered by tire saccharide fatty acid ester coating, or a combination thereof In some

embodiments, the lumen of a device/instrument may be covered by the coating or the outer surface of the deviceriasirumeot may be covered. by the saccharide fatly acid ester coating, or a combination thereof. In embodiment, the amount of saccharide fatly acid ester coating applied is sufficient to partially cover at least one surface f a cellulose-containing material. For example, only those surfaces expose to the ambient atmosphere are co vered by the saccharide fatty acid ester coaling, or only those surfaces that are hot exposed to the ambient atmosphere are covered by the saccharide fatty acid ester coaling (e.g , masking). As will be apparent to one of skill in the art, the amount of saccharide fatty acid ester coating applied may be dependent on the use of the material to be covered. In one aspect, one surface may b coated with a saccharide fatty acid ester and the opposing surface may be coated with an agent including, but not limited to, proteins, wheat glutens, gelatins, prolamines, soy protein isolates, starches, modified starches, acetylated polysaccharides, alginates, carrageenans, ehitosans, malms, long chain fatty acids, waves, and combinations thereof. In a related aspect, the SFAE can be added to a furnish, and the resulting material on the web irmy be provided with an additional coating of SFAE.

(001241 Any suitable, coating process may be used to deliver any of the v ario us saccharide fatty acid ester coatings and/or emulsions applied in the course of practicing this aspect of the method. In embodiments, saccharide fatty acid ester coatin processes include immersion, spraying. painting, printing, and any combination of any of these processes, alone or with other costingprocesses adapted for practicing the methods as disclosed.

{00125} By increasing the concentration of saccharide fatty add ester, for example, the composition as disclosed herein may react more extensi vely with the cellulose being treated with the net result that again improved water-repellent lipid resistance characteristics are exhibited. However, higher coat weights do not necessarily translate to increased water resistance. In one aspect, various catalysis might: allow for speedier "curing" to precisely tune the quantity of saccharide laity acid ester to meet specific applications.

{00126} It will be apparent to one of skill in the art that the selection of cellulose to he treated, the saccharide fatty acid ester, the reaction temperature, and the exposure time are process parameters that may be optimized by routine experimentation to suit any particular application for the final product.

|00l2?f The derivarized materials have altered physical properties which may be defined and measured using appropriate tests known in the art. For hydrophobicity the analytical protocol may include, but is not li mited to, the contact angle measurement: and moisture pick-up. Other properties include, stiffness, WVTR, porosity, tensile strength, lack of substrate degradation, hurst and tear properties A specific standardized protocol, to follow is defined by the American Society for Testing and Materials {protocol ASTM 07334 - 08).

{00128} The permeability of a surface to various gases such as water vapour and oxygen may also be al tered by the saccharide fatty acid ester coating process as the hairier function of the material i$ enhanced. The standard unit measuring permeability is the Barter and protocols to measure these parameters are also available in the public domain (AS'TM std F2476-05 for water vapour and ASTM std F 2622-8 for oxygen).

{00129} In embodiments, materials treated according to the presently disclosed procedure display a complete biodegradability as measured by the degradation in the environment under nucroofganismal attack.

100130] Various methods are available to define nd test biodegradabilit including the shake- flask method (ASTM El 2? 9 - 89(2008» and the Zahn-Wellens test (OECD TG 302 B). Various methods are available to define and test compostabil ity incl «ding, box no t limited to, ASTM D6400. f00132| Materials suitable for treatment by the process of ibis invention include various forms of cellulose, such as cotton libers, plant fibers such as .flax, wood fibers, regenerated cellulose (rayon and cellophane), partially alkylated cellulose (cellulose ethers), partially esieri!ied cellulose (acetate rayon), and other modified cellulose materials which have a substantial portion Of their surfaces available for readion/hindtng. As state above, the term "cellulose" includes all of these materials and others of similar polysaccharide stmcfine and having similar properties Among these the relati vely no vel material micrpfibrtllated cellulose (cellulose nanofiber) (see e.g,, US patent US4 _j 374,702 and US Pub. Nos. 2015/0167243 and 20093)221812 herein incorporated by reference in their entireties) is particularly suitable fox this application, In other embodiments, celluloses may include: but are not limited to, cellulose triacetate, cellulose propionate cellulose acetate propionate, cellulose acetate butyrate nitrocellulose (cellulose nitrate), cellulose sulfate, celluloid, methylcell ulose, ethyl cellulose, ethyl methyl cellulose, hydroxyethyi cellulose, hydroxypropvl cellulose, cellulose aanoervstals, hy roxy ethyl methyl cellulose, hydroxypropyl methyl cellulose ethyl hvdroxyethyl cellulose, csrbOxyniethyl cellulose, and combinations thereof.

|00I33J The modification of the cellulose as disclosed herein, in addition to increasing its hydrophobicity, ma also increase its tensile strength, flexibility and stiffness, thereby further widening its spectrum of use. All biodegradable and partially biodegradable products made from or by usi ng the modified cellulose disclosed in this application are within t he scope of the disclosure, including recyclable and compostable products,

1001341 Amon the possible applications of the coating technology such items include, but are not limited to, containers for all purpose such as paper, paperboard, paper pulp, cups, lids, boxes trays, release papers/liners, compost bags, shopping bags, pipes and water conduits, food grade disposable cutlery, plates and bottles, screens for TV and mobile devices, clothing (e.g,, cotton or cotton blends), bandages, pressure sensitive labels, pressure sensitive tape, feminine products, and medical devices to be used on the body or inside it such as contraceptives, drug deli very devices, and the tike. Also, the coating technology as disclosed may be used on furniture and upholstery, outdoors camping equipment and the like. f¾0!.3S] The following examples are intended to illustrate but not limit the invention

EXAMPLES fOOl f Example 1. Saccharide Faty Acid Ester Formulations

|00:I 37j SBPOSE® is a liquid at mom temperature and all coaiings/emutsions containing this material were applied at room temperature using a bench top drawdown device. Ro type and s^e were varied to create a range of coat weights.

Formulation 1

100138 _. 1 50 ml of SEFOSB® were added to a solution containing 195 mi of water and 5 grams of carboxYmethyleelh ose (FINNFJX 10; CP Kelco, Atlanta GA) This formulation was mixed using a Silverson Homogenizer set to 5000 rpm for I. minute This emulsion was coated on a SO gram base sheet made of bleached hardwood pulp and an 80 gram sheet composed of unbleached softwood. Both papers were placed into an oven (lOSX) for 15 minutes to dry. Upon removal from the oven, sheeis were placed on the lab bench and 10 drops of water (room temperature) applied via pipette to each sheet. The base sheets selected tor this testing would absorb a droplet of water immediately, whereas sheets coated with varying amounts of SEFOSE& showed increasing le vels of water resistance as coat weight increased (see Table 1).

Table 1. Base Sheet Results with SEFOSB®

1001391 It was observed that water resistance was less in the heavier sheet and no water resistance was achieved unless the sheet was dry.

Formulation 2 {G01.4GJ Addition of SEFOSE® to cup stock: {note this is single layer stock with no MFC treatment 1 10 gram board made Of Eucalyptus pulp). 50 grams of SEP OS£& was added to 200 grams of 5% cooked ethylated starch (Ethylex 2025) and stirred using a bench top kady mill for "30 seconds. Paper samples were coated and placed in the oven at 105 *0 for 15 minutes. 10-15 test droplets were placed on the coated side of the hoard and water holdout time as measured and recorded in the table below. Water penetration on the untreated board control was instant (see Table 2).

Table 2, Penetration of Hot Water ' Treated Cup Stock

Formulation 3

}G01 11 Pure SEFOSE® was warmed to 45°C and placed in a spray botle. A uniform spray was applied to the paper stock listed in the previous example, as well as to a piece offiberboard and an amount of cotton cloth. When water drops were placed on the samples, penetration into the substrate occurred within 30 seconds, however after drying in the oven for 15 minutes at !05°C beads of water evaporated before being absorbed into the substrate.

{00:1421 Continued investigation concerned whether SEFOSE® might be compatible with compounds used for oil and grease resistant coatings. SEFOSE® is useful for water resistance as well as stiffness improvements, 240 gram board stock was used to do stiffness tests. Table 3 shows the results. These data were obtained at a single coat weight: 5 grams/ square meter with a 5 sample average being reported. Results are in Taber stiffness units recorded with our V-5 Taber stiffness tester Mode! J5G-E. Table 3. Stillness Test

|00143| Example 2, Bonding of Saccharide Ester to Ceiluiosic Substrate

|Q0:l 4j In an effort to determine whether SBFOSB was reversibly bound to a ceiluiosic material, pure SEF0SE3P was mixed with pure cellulose at ratio of 50:50. The SEFOSES was allowed to read for 15 min at 300 ^¾ F and the mixture was extracted with methylene chloride (non-polar solvent) or distilled water. The samples were refluxed for 6 hours, and gravimetric analysis of the samples was carried out.

Table 4. Extraction of SEFOSE® from Ceiluiosic Material

1001451 Example 3. Examination of Ceiluiosic Surfaces 00146 Scanning electron microscope i mages of base papers with and witho ut MFC il lustrate how a less porous base has potential to require far less waterproofing agents reacted to the surface. FIGs. 1-2 sho untreated medium porosity Whatman filter paper. FIGs. 1 and 2 show the relative high surface area exposed for a derix itiziog agent to react with, however, it also shows a highly porous sheet with plenty of room for water to escape. FIGs. 3 and 4 show a side by side comparison of paper ade with recycled pulp before and after coating with MFC. (They are two magnifications of the same samples, no MCF obviously on the left side of image). The testing shows that dermrizaiion of a much less porous sheet shows more premise for long term water/ vapor barrier performance. The last two images are just close ups taken of an average "pore” in a sheet of fi l ter paper as well as a similar magnification of CNF coated paper for contrast purposes. f0014?l The data above demonstrate a critical oint: that addition of more material results in a corresponding increase in performance. While not being bound by theory, the reaction appears to be faster with unbleached papers, suggesting that the presence of lignin may speed the reaction.

[00148] The fact that a product like the SEFOSE# is a liquid, it can readily emulsify, suggesting that it can easily be adapted to work in coating equipment commonly used in. paper mills.

Example 4. "PhSuphi"

[00149] Liquid SEFOSE# was mixed and reacted with bleached hardwood fiber to generate a variety of ways to create a waterproof handsheet. When the sucrose ester was ixed with pulp prior to sheet formation it was found that the majori ty of it is retained with the fiber. Withsufficient heating and drying, a brittle, fluffy but very hydrophobic handsheet was formed. In this example, 0.25 grams SEFOSE® was mixed with 4.0 grams bleached hardwood Fiber in 6 liters of water. This mixture was stirred by baud and the water drained in a standard handsheet mold. The resulting fiber mat was removed and dried for 15 minutes at 325"F. The produced sheer exhibited significant hydrophobicity as well as greatly reduced hydrogen bonding between the fibers themselves. (Water contact angle was observed to be greater than 100 degrees) An emulsifier may he added. SEFOSE# to fiber may be from about 1:100 to :1.

[00150] Subsequent testing shows that tale is only a spectator in this and was left out of additional testing.

Example 5. Environmental Effects on SEFOSE# Coating Properties

[001 _: 51] In an effort to better understand the mechanism of sucrose esters reaction with fi ber, lo viscbsify coatings were applied to a bleach kraft sheet that had wet strength resin added, but no water resistance (no siting). Coatings were all less than 250 cps as measured using a

Brookfield Viscometer at 100 rpm |Q0152] SEFOSE® was emulsified with Ethylex 2025 (starch) and applied to the paper via a gravure roll. For comparison, SEFOSE® was also emulsified w th Wesleote 9050 PvGH. As shown in FIG. 5, Oxidation of the double bonds in SEFOSE® is enhanced by the presence of heat and a ditional chemical environments that enhance oxidative chemistry (see also. Table .5).

Table 5. Environmental Effects on SEFOSE® (Minutes to Failure)

SEFOSE#

Time FVOi! -FVOH Et ylex 3: 1

0 0,08 0.07 0.15

1 0 083 0.11 0, 15 1.8

2 0,08 0.18 0.13 1.8

5 0.09 0 25 0.1 1,3

10 0.08 0.4 0,1 0 9

30 0.08 1.1 0.08 0.8

60 0.08 3 8 0.08 0.8

120 0.08 8 0.08 0 7

500 0 07 17 0.07 0.4

Example 6. Effect of Unsaturated vs. Saturated Fatty Acid Chains

1 _. 00153! SEFOSE® was reacte with bleached softwood pulp and dried to form a sheet.

Subsequently, extractions: were carried out with CHjC¾, toluene and water to determine the extent of the reaction with pulp. Extractions were performed for at least 0 hours using Soxh!ei extraction glassware. Results: of the extractions are shown in Table 6,

1001541 The data indicate that essentially ah of the SEFOSE® remains in the sheet. To further verity this, the same procedure was carried out on (he pulp alone, and results shows that approximately 0.01 g per lOg of pulp was obtained. While not being hound by theory, this could easily be accounted i¾r as residual pulping chemicals or more likely extracti ves that had not bean completely removed.

}001S5| Pure fibers of cellulose (e,g,, «-cellulose from Sigma Aldrich. St Louis, MO) were used, and the experiment repeated. As long as the loading levels of SEFOSE® remained below about 20% of the mass of the fibers, over 95% ofthe mass of SEF05E® was retained with the fibers and not extractable with either polar on hόh-polar solvents. While not being bound by theory, optimizing bakin time and temperature rosy further enhance the sucrose esters remaining with the fibers. fMlStSf As shown, the data demonstrate a general inability to extract: SEFGSE® out ofthe material after drying. On the other band, when the fatty acids containing all saturated fatty acid chains are used instead of SFFOSB® (e.g , GLEAN®, available from Procter & Gamble Chemicals (Cincinnati, OH}), nearly 100% of tire of the material can be extracted using hot water (at or abo ve 7 ⁽ EC). CLEAN# is identical to SEFOSE® with the only change being saturated fatty acids attached (CLEAN®) instead of unsaturated fatty acids (SEFOSE#).

|00i$71 Another noteworth aspect is that multiple My acid chains are reactive with the cellulose, _: an with the two saccharide molecules in the structure, the SEFOSE® gives rise to: a stiff crosslinking network leading to strength improvements in fibrous webs such as paper,paperboard, air-laid and wet-laid non-wo vens, and textiles.

Example 7, SEFOSE#· Additions to Achieve Water Resistance

100158] 2 and 3 gram handsheets were made using both hardwood and softwood krnft pulps. When SEFOSE# wa added to the l.% pulp slurry ai a level of 0. i% _> or greater and water was drained forming the handsheet, SEFOSE® was retained with the fibers, where it imparted water resistance. From 0.1 % to 0.4% SEFOSE®, water beaded on the surface for a fe seconds or less. After SEFOSE# loading went abo ve 0 4%. the time of water resistance quickly increased to minutes and then to hours for loading levels greater than I .of f.

Example 8 Production of Bulky Fibrous Material 1¾K ⁾ 159] Addition of SEFOSEyf to pulp acts to soften the fibers, increase space between them increasing bulk. For example, a 3% slurry of hardwood pulp containing ! 25g (dry) of pulp as drained, dried and found to occupy ! 8.2 cubic centimeters volume. 12.3g oi ^' SEFOSE# was added to the same 3% hardwood pulp slurr that contained an equivalent of i ^: 2Sg dry fiber Upon draining the water and drying, the resulting at occupied 45.2 cubic centimeters.

(iiCit6G| 30g of a standard bleached hardwood braft pulp (produced by Old Town Fuel and Fiber. LLC, Old Town, ME) was sprayed widi SEFOSB# that had been wanned to 00*€. This 4.3 cm' was placed in a disintegrator for 10,000 tpm and essentially repulped. The mixture was poured through a handsheet mold and dried at 105T. The resulting hydrophobic pulp occupied a volume of Hi era'. A 2 inch square of this material was cut and placed iu a hydraulic press with 50 tons of pressure applied for 30 seconds. The volume of the square was reduced significantly but still occupie 50% more volume than the same 2 inch square cut for the control with no pressure applied.

(OO.I61| it is significant that not only is an Increase in bulk and softness observed, but that aforcibly repulped mat when the water w as drained resulted in a fiber mat where all of die hydrophobicity was retained. This quality, in addition to the observations that water cannot he easily '’pushed/' past the low surface energy barrie into the sheet is of value. Attachment of hydrophobic Single-chains of faty acids do not exhibit this property

1001621 While not being bound by theory, this represent additional evidence that SEFOSB·! ⁾ is reacting with the cellulose and that the OH groups on the surface of the cellulose fibers are no longer available to participate in subsequent hydrogen bonding. Other hydrophobic materials interfere with initial hydrogen bonding, but upon repulping this effect is reversed and the OHgroups on the cellulose are free to participate in hydrogen bonding upon redrying.

Example 9, Bag Paper Testing Data

100163} The following table (Table 7) illustrates properties imparted by coaling 5-?g/«r with a SEFQSE# and polyvinyl alcohol (PvOH) mixture onto an unbleached kraft bag stock (control). Also included for reference are commercial bags.

Table ?. Bag Paper Tests f 00164} As may be seen in the Table, tensile and burst increase with the coating of the control base paper with SETOSE# and PyOH.

Example 1.0. Wet Dry Tensile Strength fOO Sf 3 gram handsheets were made from bleached pulp. The following compares wet and dry tensile strength at different lex eJa of SEFOSE® addition. Note that" with these handsheets SEFGSE® was not emulsified into any coating, it was simply mixed into the pulp and drained with no other chemistry added (see Table 8).

Table 8. Wet/Dry Tensile Strength

{00166} Note also, that the 5% addition for th wet strength is hot far below the dry strength of the control.

Example 1,1. Use of .Esters Containing L ess Than 8 Saturated Fatty Acids

{00167} A number of experiments were carried out: w ith sucrose esters produced having less than 8 fatty acids attached to the sucrose moiety. Samples of SP50, SP10, SPO.1 and F20W (from Sistema, The Netherlands) which contain 50, 10, 1 and essentially 0¾ monoeBters, respectively, Whiiethese commerciall available products are made by reacting sucrose with saturated fatly acids, thus relegating them less useful for further erosslinking or similar chemistries, they have been useful in. examining emulsification and water repelling properties,

|00168] For example, lOg of SP01 was mixed with iOg of lyoxal in a 10% cooked PvOH solution. The mixture was "cooked" at 200% ^' for 5 mins and applied via drawdown to a porous base paper made from bleached hardwood krdft. The result was a crossiinked waxy coating on the surface of the paper that exhibited good hydrophobicity. Where a minimum of 3g/nf was applied, the resulting contact angle was greater than 100° Since the glyoxaf is a well -known crystallizer used on compounds having Off groups, this method is a potential means to affix fairly unreactive sucrose esters to a surface by bonding leftover alcohol groups on the sucrose ring with an alcohol group made available in the substrate or other coating materials:

Example 12. HST Data and Moisture Uptake

106169] To demonstrate that SEFOSE® alone provides the water proofing properties observed, porous Twins River (Matawaska, ME) base paper was treated with various amounts ofSEFOSE (and PvOH or Ethylex 2025 to emulsify, applied by drawdown) and assayed by Hercules Size Test The results are shown in Table 9.

Table 9, HST Bala with SBFOSE&

100170 j As can be seen in Table 9, increased SEFOSE applied to the surface of the paper lead to increased wafer resistance (as shown by increased HST in seconds). |¾0!.7I] This may also be seen using coatings of a saturated sucrose ester product. For this particular example, the product, F20W (available from Sistema, The Netherlands) is described as a very !ow% monoester with most molecules in the 4-8 substitution range. Note that the F20W product picku is only 50% of the total coating, as it was emulsified with PvOH using equal parts of each to make a stable emulsion. So, where the pickup is labeled "0.5 g/nT" there is also the same pickup of PvOH giving a total pickup of 1.0 g/nr. Results are shown in T able 10.

Table 10 HST Data F20W.

|O0172| As can be seen from Table 10, again, increase F20W increases the water resistance of the orous _: sheet Thus, the applied sucrose faty acid ester itself is making the paper water resistance,

100173} That the water resistance is not simply ue to the presence of a faty acid forming an ester bond with the cellulose, softwood handsheets {bleached softwood kraft) were loaded with SEFOSE and oleic acid was directly added to the pulp where the oleic acid forms an ester bond with the cellulose in the pulp. The mass at time zero represents th "bone dry " ^' mass of the handsheets taken out of the oven at lOS . The samples were placed in a controlled humidity room maintained at 50% KM. The change in mass is noted over time (in minutes). The results are shown in Tables 11 and 12.

Table 11. Moisture Uptake

Table 12. Moisture Uptake Oleic Acid.

00174] Note the difference hare where oleic . acid is directly added to the pulp forming an ester bond greatly slows moisture uptake. In contrast, only 2% SEFOSE& slows moisture uptake, at higher concentrations, SEFOSEt ⁾ does not. As such, while not being bound by theory, the structure of the SEFOSE® bound material cannot be simply explained by the structure formed by simple fatty acid esters and cellulose.

Example 13, Saturated SFAEs fOOt 75] The saturated class of esters are waxy solids at room temperature which, due to saturation, are less reactive with the sample matrix or itself. Using elevated temperatures (e.g., at least 40°C and for all the ones tested above 65°C) these material melt and may be applied as a liquid which then cools and solid ifies forming a hydrophobic coating Alternatively, these materials may be emulsified in solid form and applied as an aqueous coating to impart hydrophobic characteristics.

}00176| The data shown here represent HST (Hercules Size test) readings obtained from papers coated with varying quantities of saturated Sf AEs.

(00177) A #45, bleached, hardwood kraft sheet obtained from Turner Falls paper was used for lest coatings. The Gurley porosity measured approximately 300 seconds, representing a fairly light base sheet S-370 obtained from Mitsubishi Foods (Japan) as emulsified with Xanthan Gum (op to 1% of the mass of saturated SFAE formulation) before coating

(00J78| Coat weight of saturated SFAE formulation (pounds per ton) HST (average of 4 measurements per sample).

Table 1

|(K3t:79) Lab data generated also supports that limited amounts of saturated SFAE may enhance water resistance of coalings that are designed for other purposes/apph cations. For example, saturated SFAE was blended with Ethylex starch and polyvinyl alcohol based coatings and increased water resistance was observed in each case,

100180) The examples below were coated on a #50, bleached recycled base with a Gurley porosity of 18 seconds.

(00181) 100 grams of Ethylex 2025 were cooked at 1044 solids (1 liter volume) and 10 grants of S-370 were added in hot and mixed using a Sllverson homogenizer. The resul ting coating as applied using a common benchtop drawdown device and the papers were dried under heat lamps. I00t82{ At 3OO /t0iT coat weight, ie starch alone had an average H$T of 480 seconds. With the same coat weight of the starch and sat arm d SFAE mixtur , the HST increased to 710 seconds.

}Gt)183| Enough polyvinyl alcohol (Selvo! 205 S) w dissolved in hot water to achieve a 10% solution. This solution was coated on the same #50 paper described above and had an average HST of 225 at ISO pounds/ton of coat weight Using this same solution, S-370 was added to achieve a mixture in which contained 90% PVOH «10% S-370 on a dry basis (i.e. , 90 nil water, 9 grams PvOH, 1 gram S-370); average HST increased to 380 seconds.

|M184f Saturated SFAEs are compatible with prolamines (specifically’, xeift; see U.S. Fat No. 7,737,200, herein incorporate by reference in its entirety). Since one of the major barriers to commercial production of the subject matter of said patent is that the formulation be water soluble; the addition of saturated SFAEs assists in this manner.

Example 14 Other Saturated SFAEs fOOt 85] Sixe press evaluations of saturated SFAE based coatings were done on a bleached lightweight sheet (approx. 35 ) that had no sizing and relatively poor formation. All evaluations were done using Exceval HR 3010 PvOH cooked to emulsify the saturated SFAE. Enough saturated SFAE was added to account for 20% of the total solids. The focus was on evaluating the S-370 vs the C-1800 samples (available front Mitsubishi Foods, Japan). Both of these esters performed better than the control, some of the key data are shown in Table 14;

foot 86] Note that the saturated compounds appear to give an increase in kit, with both the S-370 and the C~1 800 yielding a -100% increase in HST.

Example 13. Wet Strength Additi ve l¾01:87| Laboratory testing has shown that the chemistry of the sucrose esters can be tuned to achie ve a variety of properties, including use as a wet strength additive. When the sucrose esters are made by attaching saturated groups to each alcohol functionality on the sucrose (or other polyol), the result is a hydrophobic, waxy substance having low miscibihty/solubihty in water. These compounds may he added to ceiMosie materials to impart water resistance either internally or as a coating, however; since they are not chemically reacted to each other or any part of the sample matrix they are susceptible to remo val by solvents, heat and pressure. fOOlSSj Where waterproofing and higher levels of water resistance are desired, sucrose esters containing unsaturated functional groups may be made and added to the cellulose material with the goal of achieving oxidation and/or cross! inking which helps fix toe sucrose ester in toe mar and render it highly resistant to removal by physical means. El tuning the number of unsaturated groups as well as the size of ⁽ he sucrose: esters a means is obtained for crosslinking to impart strength, yet with a molecule that is not optimal for imparting water resistance.

| ⁽ MHd9{ The data shown here is taken by adding SEFOSE® to a bleached, kraft sheet at varying , levels and obtaining wet tensile data. The percentages shown in the table represent the percent sucrose ester of toe treated 70# bleached paper (see Table 15).

Table 15

{001901 The data illustrate a trend in that adding unsaturated sucrose esters to pa ers increases the wet strength as loading level increases. The dry tensile shows toe maximum strength: of the sheet as a point of reference.

Example 16. Method of producing sucrose esters using acid chlorides. in addition to making hydrophobic sucrose esters via iransesterification, similar hydrophobic properties cart be achieved in fibrous articles by directly reacting acid chlorides with polyols containing analogous ring structures to sucrose.

|00192] For example, 200 grains of paJotitoyi chloride (CAS 1 12-67-4) were mixed with 50 grams of sucrose add mixed at room temperature. After mixing the mixtur was brought to FOOT and maintaine at that temperature overnight (ambient pressure). The resulting material was washed with acetone and deionized water to remove any unreacied or hydrophilic materials. Analysis of remaining material using C- 13 NMR showed a significant uantity of hydrophobic sucrose ester had been made.

0 ⁾ 0193] While it has been shown (by BT3 and others) that the addition of fatty acid chlorides to c lulosic materials could impart hydrophobic properties, the reaction itself is undesirable on site as the by-product given off. gaseous HO, creates a number of problems including corrosion of surrounding materials and is hazardous to workers and surrounding environment One additional problem created by the productions of hydrochloric acid is that: as more is formed. i,e. _: , more polyol sites are reacted. the weaker the fibrous composition becomes. Paimitoyl chloride was. reacted in increasing amounts with cellulose and cotton materials and as hydiophobieity increased, strength of the article decreased.

1661 41 The reaction above was repeated several times using 200 grams of R-۩ chloride reacted with 50 grams each of other similar polyols, including corn starch, xyiat from birch, carboxymethylcelliilose, glucose and extracted hemkelhUoSes.

Example 17. Peel Test

(60195] Peel test utilizes a wheel between the two jaws of the tensile tester to measure force needed to peel tape off from a papers surface as a reproducible angle (ASTM D1876; e.g, . 100 Series Modula Peel Tester, TestResources, Shakopee, MM).

16 196] For this work, bleached krai! paper with high Gurley (600 seconds) front Turner

Falls paper (Turner's Falls, MA) was used This #50 pound sheet represents a fairly tight, but quite ahsorbant sheet. When the #30 ound paper was coated with 13% Ethylex starch as a control, the average force (over 5 samples) that was needed was 0,55 ponodrineh, When treated -with the same coating but with SEF0SE€s substituted for 25% of the Ethylex starch (so 23% pickup is SEFOSE#, 75% is still Ethylex) the average force ecreased to 0.081 pounds/ inch With a 5(1% substitution of SBPOS£% for the Ethylex, the force needed decreased to less than 0.03 pounds per inch.

100198 J The preparaliofi of this paper is in accord with TAPPI standard method 404 for determining tensile strength of papers.

|M199f Finally, the same paper was used with. S-370 at a loading rate of 750 pounds per ton - which effectively fills all the pours in the sheet creating a complete physical barrier. This indeed passes a TAFPt kit 12 on the flat. This brief experiment shows that it is possible to get grease resistance using saturated SFAE varieties.

Example IS. Saturated SFAE and Inorganic Particles (Fillers) fOO200] Saturated sucrose laity acid, esters (SFAE) range from hydrophilic to hydrophobic depending on the number of fatty acid chains (and the chain length) attached to the sucrose molecule. These are not: considered to be highly reactive compounds.

1002011 A range of substituted SF AEs has been investigated, side chains being 16 or 18 carbons in length. The examined materials a waxy solids with melting points below 15CE€, When coated on paper the highly substituted esters impart significant levels of water resistance depending on coat weight and sheet porosity. For this example, the same paper was used with S- 370 at a loading rate of 750 pounds per ton - which effectively ill Is all the pores in the sheet creating a complete physical barrier. Hie paper treated so was found to possess a TAPPI kit 12. This brief experiment shows that it is possible to get grease .resistance using saturated SFAE varieties.

1002021 Observations:

1002031 More hydrophobic esters tend to aggregate in aqueous emuisions/dispersions and so uniform coatings on the paper become challenging The low melting point of a numbe of these molecules results oruhe coating "melting” into the sheet. If hydrophobic §FAE arc mixed wi th polymers to help stabilize the dispersion _» these polymers (i.e,, latex, starch: polyvinyl alcohol) tend to surroun these esters in a way that mutes the desired hydrophobic properties,

100204] When mixed with calcium carbonate ( e.g.. precipitated calcium carbonate) there Is an attraction which is unexpected. The SFAE does hot melt into the paper under the same drying: conditions. Calcium carbonate appears to aid n dispersion of the SFAE and adherence is such that the SFAE acts as a hinder to attach the calcium carbonate pat1icles to the surface of coated papers. While not being bound by theory, it is thought that this uniform dispersion results in. enhanced water resistance for a gi ven amount of ester

(60205] Table 16 shows water resistance as measured by Hercules Size Test (FIST) increasing with the formulations containing 50% calcium carbonate. An unsized, porous 40-pound sheet was coated by hand drawdowns. Coat weights were 7-10 g/mf

Table 16.

(00206] The advantages to the combinations as demonstrated include reduced cost of coating via use of carbonate as well as more efficient use of the SFAE molecules as they are more evenly distributed across the surface of the paper substrate.

Example 17. Saturated SFAE Blends and inorganic Particles (Fillers and Clays)

(002Q7] A. This Example was designed to examine the interaction between saturated sucrose fatty acid ester blends and calcium carbonate.

(60208] A paper coating was made having the following composition (on a dry basis): 10% PVOH; 20% sucrose ester (SE-.15/I 803 blend, SFAEs in eq ual proportions; SE-I5 is available from Hangzhou Union Biotechnology Co. , Ltd , Hangzhou China and C- 1.803 is available from Itochu Chemicals America, Inc,, While Plains, NY) and 70% precipitated calcium carbonate (available from OMYA Inc., Blue Ash, OH). This mixture was applie to a 05» bleached kraft sheet at a coat weight of 8 g/m" Calcium carbonate slum· by itself exhibi ts no water contact angle and no HST when coated on papers. The results using the coating

composition are shown in Table 17,

Table 1 7

1002091 This example serves to illustrate that the ester-carbonate interaction is significant enough that the carbonate helps hold the uniformly' distributed ester on the surface of the shee where maximum effect can be observed. Further, the data demonstrates that a bio-based material has been identified that c be used with CaCO _? that results in a coated sheet exhibiting high contact angle when fhe CaCO* is present as the majority component of the composition. White not being bound by theory, this effect becomes more apparent when heavy coal weights of a high pigment composition may be applied.

[00210] B: This Example was designed to examine th interaction between saturated sucrose fatty acid esters and pigments (e.g. , clays).

[0621 If Kaolin-based materials have very different properties from calcium

carbonate. Table 18: shows the results using another SPAE blend, 80 0:E (available from Tensac, SJi, Tucuman, Argentina) and SE-15 in equal parts, and 80 OB, SE-15 and iinerys CA?IM ^!¾ (kaolin-based material, available from Imerys Clay, hie. , Roswell, GA) in equal parts, to produce an QGR coating. "The folio wing formulations were prepared at 10% solids and coated at 5 g/m ² Table 18.

[(10212) Once th pigment is present above U>~20%, using CAPIM ^ alone die paper exhibits no kit, and as stated above, once the concentration is abov 10 or 20% pigment in any barrier coating. typically barrier properties are significantly reduced (e.g. , grease is able to find pores to penetrate) The observation that esters give better grease resistance with less net ester in the formulation is significant

Other uses

(00213 j Cup base stock was found to be .heavily treated with rosin to increase ater resistance. However, the Guriev on this board was found to be 51 ⁾ seconds indicating a fairly porous board. ^' Ibis material is repnipabie and steam quickly penetrates to soften it. Pure SEFOSBK was applied to this board and dried in an oven at i OfrtC overnight. The resulting material bad a plastic like fee! and was completely waterproof By mass, it was 50% (wt/wt) cel!uiose/50% (wt/wt) SEFOSEif The Gurley was too high to measure. Submerging a sample in water for 7 days did not significantly soften the material, however, from greenhouse data it seems to biodegrade in approximately 150 days Common tapes and glues would not stick to this composite material

(06214} Experiments with saturated SFAB and vein have been carried out as zeisi has been shown to impart grease resistance to paper Stable aqueous dispersions ofzein (up to 25% in water) to which saturated SFAE was added from 2 to 5% were generated. Observations

demonstrated that saturated SFAE“locks down" zein on paper by imparting water resistance (in addition to grease resistance) to the formulation.

(00215] The combination of SFAEs, inorganic particles and bioplastie may be mixed to produce a moMabie paper for the d esign of a biodegradable coffee cup Sid. Using wood fiber, and sufficient bioplastic fiber (e.g., polybutylene succinate (Bio-PBS) or poiylactic acid (PLA)) along with SFAE, the resulting paper base would be water resistant, where SFAE concentration is optimized to ensure water resistance of the article, and ^" where use of cheaper more common materials, such as regular pulp represents a larger percentage of the mass of the fid. Thus, a relatively small amount (e.g., less than 10%) of the mass of the article would be other materials like bio-polymers, thereby allowing for addition of other additives that may be used to give flexibility, improve tear or stretch properties and the like. }ΐM>23€s) The addition o f a calcium carhanate/ SF AE mixture allows for the control of the density of the lid.

1 _. 002171 Al though foe invention has been described with referenc to the above xamines it will be understood that modifications and variations are encompassed within the spirit and scope of the invention. Accordingly, the in vention is limited only by the following claims. Ail references disclosed herein are hereby incorporated by reference in their entireties.