Barrier coating composition of sugar fatty acid ester latex

Abstract

The present disclosure describes methods for treating cellulosic materials with barrier coating compositions that allow for surface modification, including such surfaces exhibiting barrier functionality, such as oil and grease resistance, water resistance, etc. The disclosed methods provide for combining at least one sugar fatty acid ester (SFAE) with a polymer and applying such a combination onto a substrate comprising a cellulose-based material. Compositions comprising a combination of an SFAE and a polymer are also disclosed, including the use of such compositions to reduce the blocking effect of the polymer without affecting the barrier performance or folding of an article of manufacture coated with the composition. Furthermore, blocking rating data for SFAE-polymer compositions may be used to identify conditions under which adhesion properties can be developed to produce a composition that allows for effective heat sealing of an article of manufacture.

Description

Technical Field

[0001] The present invention relates primarily to treating surfaces with barrier coatings, and more specifically to treating such surfaces with a barrier coating composition comprising a sugar fatty acid ester (SFAE) combined with a polymer and further optional pigments and other functional chemicals, and to methods that can be extended to control adhesion, including the type and amount of polymer applied and the temperature and pressure that can be used in its application.

Background Art

[0002] Many oil- and grease-resistant (OGR) applications that require significant oil and grease resistance rely on chemical means of holdout, particularly the use of fluorochemicals (FCs). FC chemistry is very specific in its performance and effectiveness in both direct low-solids size press coating and wet end coating on fibers. These coating methods can provide a high level of grease holdout that is maintained when products made using this chemistry are folded or creased in any way that might damage the surface. In the paper and packaging industries, despite years of working on alternative chemistries, there is currently nothing that has the effectiveness of FCs.

[0003] As an alternative approach, there may be the formation of a physical barrier through the surface treatment of the substrate by means of several coating methods. Several chemistries and coating methods have been tested. With the correct selection of multiple "coating" layers and materials, it becomes possible to form a physical barrier that is free of defects (pinholes) against grease (and also against water). However, many OGR applications require the product to be folded, creased, or formed in a way that can easily "crack" the coating, resulting in defects in the physical barrier and entry points for oil and grease. One solution to such problems is to select a very soft and flexible barrier material and to use a coating that does not contain (or contains a low level of) pigment / inorganic materials. A very flexible coating will withstand folding and not crack. Barrier coatings containing a relatively high level of latex are among the most successful of these approaches.

[0004] Many polymer-based coatings, including latex-containing coatings, are formulated materials that are applied to a substrate on a coater and then wound into a roll (for example, in the application to paper and paperboard). In subsequent operations, under certain conditions, the polymer therein may function like an adhesive that binds the two surfaces together. A problem that may occur with such latex-containing coatings is that they may become blocked when wound into a roll. This is essentially an unintended adhesion, forming a log that cannot be unrolled even when the coated material is in roll form, rendering the roll completely unusable.

[0005] The causes of such blocking are diverse and include, but are not limited to, inefficient curing, substrates that are not properly adapted to the environment, flexible binders with high adhesion characteristics at low temperatures, high ambient humidity, coating films that are too heavy or have too high a viscosity resulting in slow or incomplete drying, coating films that are too weak or have too low a viscosity resulting in ineffective complete wetting, coatings that are too cold or are contaminated, insufficient or inadequate air flow passing through the drying system, substrates that absorb and retain excessive moisture throughout the drying process, and re-softening of the coating due to high heat from the back side of the substrate.

[0006] Detackifiers may be used to solve these problems. Commonly used pigments include mica, talc, calcium carbonate, white carbon, or corn starch. Also, detackifiers include, but are not limited to, lycoposium powder, inorganic fillers such as titanium dioxide, silica powder, alumina, common metal oxides, baking powder, diatomaceous earth, etc. Polymers and other additives with low surface energy may also be used, including various fluoropolymers, silicone additives, polyolefins and thermoplastics, waxes, compounds with alkyl side chains such as those having 16 or more carbons, and debonding agents known in the paper industry. On the other hand, these detackifiers tend to have a negative impact on the coating performance by affecting the barrier properties of the coating or its ability to withstand folding.

[0007] Existing latex companies and many specialty chemical companies have tested "barrier" products. However, approaches that exhibit good performance through folding tend to result in high adhesiveness and blocking.

[0008] Nevertheless, while loss of tack is often desired, modulating the adhesion properties of the polymer is also a valuable process. Thus, coated articles having improved non-blocking properties are highly desired, coating compositions that provide improved non-blocking properties without affecting the barrier properties, and methods of applying such compositions to create adjustable adhesion are needed. SUMMARY OF THE INVENTION

[0009] The present disclosure relates to a method of treating a surface with a barrier coating composition that imparts water resistance and / or oil / grease resistance to such treated surfaces. The disclosed method provides a step of combining at least one sugar fatty acid ester (SFAE) and a polymer, and a step of applying such a combination onto a substrate comprising a cellulose-based material. Such compositions also include reducing the tendency of the polymer-containing barrier coating to block, and providing resistance to the treated surface against the formation of cracks in folding while leaving the barrier functional properties intact. Also provided are means for advantageously modulating or adjusting the adhesion properties of the polymer through modifying process variables by developing the observed adhesion properties of such compositions.

[0010] In one embodiment, a barrier coating composition comprising at least one sugar fatty acid ester (SFAE) and a polymer is disclosed, wherein when the composition is applied to a substrate, the tack of the polymer is reduced without affecting the barrier function of the coating as compared to a similar composition except that the sugar fatty acid ester is absent.

[0011] In one aspect, the coated substrate exhibits improved foldability.

[0012] In another aspect, examples of polymers include PvOH, starch, styrene-butadiene latex, styrene-acrylate latex, carboxylated styrene-butadiene latex, oligomer-stabilized styrene-acrylic copolymer latex, surfactant-stabilized styrene-acrylic copolymer latex, polyvinyl acetate, ethylene-vinyl acetate, acrylics, and combinations thereof.

[0013] In a related aspect, the polymer is styrene-butadiene latex or styrene-acrylate latex.

[0014] In another aspect, the sugar fatty acid ester is a sucrose fatty acid ester. In a related aspect, examples of the composition include blends of two or more sugar fatty acid esters having different HLB values. In another related aspect, examples of the sugar fatty acid ester include saturated fatty acid moieties, unsaturated fatty acid moieties, or combinations thereof.

[0015] In one aspect, the polymer is a latex. In another aspect, examples of at least one sugar fatty acid ester include saturated sucrose fatty acid esters. In a related aspect, examples of the sucrose fatty acid ester include mono-esters having a content of about 10% to about 25%.

[0016] In one embodiment, a detackified polymer composition comprising a sugar fatty acid ester (SFAE) and a polymer, wherein the SFAE is a saturated SFAE, and the polymer includes styrene-butadiene latex, styrene-acrylate latex, carboxylated styrene-butadiene latex, oligomer-stabilized styrene-acrylic copolymer latex, surfactant-stabilized styrene-acrylic copolymer latex, polyvinyl acetate, ethylene-vinyl acetate, acrylics, and combinations thereof, and optionally, examples of one or more agents include mica, talc, calcium carbonate, white carbon, or corn starch, kudzu powder, titanium dioxide, silica powder, alumina, metal oxides, diatomaceous earth, and combinations thereof, is disclosed.

[0017] In related aspects, articles of manufacture are disclosed that include the above-described non-stick polymer composition.

[0018] In one embodiment, a method of making a polymer non-stick includes the step of mixing a sugar fatty acid ester with a polymer including styrene butadiene latex, styrene acrylate latex, carboxylated styrene butadiene latex, oligomer stabilized styrene acrylic copolymer latex, surfactant stabilized styrene acrylic copolymer latex, polyvinyl acetate, ethylene vinyl acetate, acrylics, and combinations thereof, and optionally one or more agents including mica, talc, calcium carbonate, white carbon, or corn starch, kudzu powder, titanium dioxide, silica powder, alumina, metal oxides, diatomaceous earth, and combinations thereof.

[0019] In related aspects, the method further includes the step of applying the mixture to a substrate and the step of determining the blocking degree of the polymer.

[0020] In another aspect, the coating formed on the substrate exhibits low tack of the polymer and equivalent or improved foldability without negatively affecting the barrier function of the coating as compared to a substrate coated with a similar polymer mixture except that it does not contain a sugar fatty acid ester.

[0021] In one aspect, examples of applying the mixture include normal size presses (vertical, inclined, horizontal), gate roll size presses, metering size presses, offset printing, calendar size coating, tube sizing, on-machine, off-machine, single-sided coaters, double-sided coaters, short dwell, simultaneous double-sided coaters, blade or rod coaters, gravure coaters, gravure printing, spraying, flexographic printing, inkjet printing, laser printing, supercalendering, and combinations thereof.

[0022] In related aspects, the coating is applied to the entire outer surface of the substrate, the entire inner surface of the substrate, or a combination thereof. In a further related aspect, the coating is applied to the substrate by masking.

[0023] In another aspect, examples of the substrate include cellulose-based materials. In related aspects, examples of cellulose-based materials include paper, paper sheets, cardboard, papermaking pulp, heat-sealable bags, heat-sealable containers, heat-sealable pouches, food storage cartons, parchment paper, cake cardboard, meat wrapping paper, release paper / liners, food storage bags, shopping bags, transport bags, bacon cardboard, insulating materials, tea bags, coffee or tea containers, compost bags, tableware, hot or cold beverage containers, cups, lids, plates, bottles for storing carbonated liquids, gift cards, bottles for storing non-carbonated liquids, food wrap films, food waste treatment containers, food handling utensils, fabric fibers (e.g., cotton or cotton blends), water storage and transport utensils, alcoholic or non-alcoholic beverage containers, external casings or screens for electrical products, internal or external components of furniture, curtains, and interior decoration items.

[0024] In a further related aspect, examples of the barrier function include oil and grease resistance, water resistance, moisture resistance, oxygen resistance, and combinations thereof. 2

[0025] In one embodiment, a method for determining the blocking rating of a SFAE-polymer combination is disclosed that includes the steps of applying a mixture comprising SFAE and a polymer to coat a substrate surface, the mixture having different ratios of SFAE to polymer on a dry matter basis; contacting opposing coated surfaces of the substrate with each other and / or contacting a coated substrate surface with an uncoated substrate for a selected period of time over a range of temperatures and / or pressures; and measuring the blocking resistance for the mixture, which defines a range of blocking ratings for a particular ratio of SFAE to polymer.

[0026] In a related embodiment, the blocking rating further includes a comparison to a control composition that does not contain SFAE, where the amount of the polymer on a dry matter basis in the control is the same. In a further related embodiment, the blocking rating defines the range of conditions under which the mixture will or will not adhere to opposing coated or uncoated surfaces for the same substrate.

[0027] In one embodiment, the effect on the barrier properties of the blocking-rated mixture is also determined.

[0028] In one embodiment, a method for manufacturing a heat-sealed product, comprising: applying a blocked-rated mixture comprising at least one SFAE and a polymer to a surface of a substrate to coat the surface; exposing the substrate coated with the mixture to a first condition, wherein the applied heat and pressure would result in polymer adhesion in the absence of the SFAE; collecting the exposed substrate; contacting the surface of the collected exposed substrate with the opposing surface of a separate collected exposed substrate or the surface of an uncoated substrate; and exposing the contacted surfaces to a second condition, wherein the applied heat and pressure would result in polymer adhesion in the presence of the SFAE and form a seal between the contacted surfaces.

[0029] In related aspects, the blocked-rated mixture can be applied to partially coat the surface of the substrate. In one aspect, the blocked-rated mixture can be applied onto a surface selected by masking or printing.

[0030] In one embodiment, a product manufacturable by the above method is disclosed.

Brief Description of the Drawings

[0031]

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Embodiments for Carrying Out the Invention

[0032] Before describing the compositions, methods, and methodologies, it should be understood that the present invention is not limited to the specific compositions, methods, and experimental conditions described, as such compositions, methods, and conditions may vary. The scope of the present invention is limited only by the appended claims, and it should also be understood that the terminology herein is for the purpose of describing particular embodiments only and is not intended to be limiting.

[0033] In this specification and the appended claims, the singular forms "a," "an," and "the" include the referents of plural references unless the context clearly dictates otherwise. For example, reference to "sugar fatty acid esters" includes one or more sugar fatty acid esters and / or compositions of the type described herein that would be apparent to one of ordinary skill in the art upon reading the present disclosure.

[0034] Unless defined otherwise, all scientific and technical terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. It is understood that any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention, as modifications and variations are intended to be encompassed within the spirit and scope of the present disclosure.

[0035] As used herein, "about," "approximately," "substantially," and "significantly" are understood by those of ordinary skill in the art and vary to some extent depending on the context in which they are used. In cases where the use of a term is not clear to one of ordinary skill in the art considering the context in which the term is used, "about" and "approximately" mean plus or minus <10% of the particular term, and "substantially" and "significantly" mean plus or minus >10% of the particular term. "Comprising" and "consisting essentially of" have their conventional meanings in the art.

[0036] Surface barriers typically function to prevent external substances (e.g., liquids / gases) from passing through the surface or to reduce the release of such external substances. The various polymers that make up the coating can improve the performance of a particular base component. For example, latex can be a very good film former and can serve as a major component of a base coating to seal a porous base sheet, and a top coating can be added to improve the performance of the base coating. In such a configuration of the base and top coatings, the latex functions as a physical barrier and, for example, polymers can be added to improve performance metrics such as bumps and / or 3M kit values.

[0037] Effective barrier coatings require three important properties: 1) the need to prevent external substances (e.g., liquids / gases) from passing through the surface, 2) the need to withstand cracking (i.e., foldability) when the substrate containing the coating is sharply bent, and 3) the need to resist blocking. As shown in FIGS. 7(a) - 7(d), this can be illustrated by a pyramid. Currently, for typical polymer combinations, only two of these properties (FIGS. 7(b), 7(c)) may show significant improvement simultaneously. That is, when the barrier function is improved or modified, either blocking or foldability is sacrificed and all three are not maintained.

[0038] As described above, polymer compositions having tested barrier properties show that good performance by folding can be achieved, but the positive properties are accompanied by high tack and result in blocking. As shown in the present disclosure, in order to achieve good folding / barrier performance, blocking resistance should not be sacrificed. In other words, the addition of SFAE to the polymer enables the simultaneous achievement of the three important properties of the barrier coating (FIG. 7(d)). In one embodiment, the addition of SFAE enables the expansion of the range and types of polymers for use in barrier compositions.

[0039] Furthermore, as blocking is reduced, coatings containing the polymer at a higher percentage can result in coatings containing a softer polymer. In related aspects, the SFAE functions as an anti-blocking agent.

[0040] As used herein, the SFAE has been found to be useful in modifying a substrate that includes a barrier coating containing a polymer, although it is not itself a polymer. Without being bound by theory, for example, a polymer coating may leave pores to water / water vapor and move into the gaps of a porous substrate, such as paper. The SFAE can fill the pores, and since the SFAE has a hydrophobic surface, water / water vapor is repelled from the pores, resulting in an improved barrier function (e.g., cob). The combination performs well, enabling effective barrier performance without blocking or negatively affecting foldability.

[0041] In one embodiment, the present disclosure demonstrates that by treating a cellulosic material with a combination of a polymer and a sugar fatty acid ester, the resulting material can be made highly hydrophobic, show little or no blocking, and at the same time maintain good foldability. Furthermore, these sugar fatty acid esters are readily digestible themselves when removed, for example, by bacterial enzymes. The derivatized surface exhibits very high heat resistance and can withstand high temperatures of 250 °C and may be less permeable to gas than the underlying base substrate. Thus, in an optional embodiment where a cellulosic material may be used, this material is an ideal solution to the problem of derivatizing the hydrophilic surface of cellulose.

[0042] Advantages of the products and methods using the SFAE described herein include that the SFAE is made from renewable agricultural resources - sugars and vegetable oils, has a low toxicity profile and is suitable for food contact, can be adjusted to reduce the coefficient of friction of the paper / board surface even at high water resistance levels (i.e., not making the paper too slippery for downstream processing or end use), may or may not be used with special emulsification equipment or emulsifiers, is compatible with traditional paper recycling programs, i.e., does not adversely affect recycling operations such as those performed on polyethylene, polylactic acid, or wax-coated paper.

[0043] Other advantages regarding the coating formulation include - being relatively easy to prepare; - the base coating being well performed at high speed at the target coating weight; - the coating may be carried out at a solids content between 60 - 75% with a viscosity of 220 - 350 cps that can be adjusted to the lower side for blade coating; - the high solids content includes that the SFAE did not have a negative impact on the viscosity, indicating a reduction in dryer costs, among others.

[0044] Another advantage is that the combination of SFAE and polymer indicates that the adhesive properties of the combination can be developed and the usefulness of such properties can be achieved depending on process variables, including but not limited to temperature, pressure, and time. For example, such an advantage allows the blocking rating of a particular SFAE-polymer ratio to be determined and used to produce a heat-sealable product. In one embodiment, a method for determining the blocking rating of a SFAE-polymer combination is disclosed, comprising the steps of applying a mixture comprising SFAE and polymer to coat a substrate surface, the mixture having a different ratio of SFAE to polymer on a dry matter basis, contacting opposing coated surfaces of the substrate with each other and / or contacting the coated substrate surface with an uncoated substrate for a selected period of time over a range of temperatures and / or pressures, and measuring the blocking resistance for the mixture, which defines a range of blocking ratings for a particular ratio of SFAE to polymer. In a related aspect, the blocking rating further comprises comparing the composition without SFAE as a control, the control having the same amount of the polymer on a dry matter basis. In a further related aspect, the blocking rating defines the range of conditions under which the mixture will or will not adhere to opposing coated or uncoated surfaces for the same substrate. In one aspect, the effect on the barrier properties of the blocking-rated mixture is also determined.

[0045] In one embodiment, a method for manufacturing a heat-sealed product, comprising: applying a blocked-rated mixture comprising at least one SFAE and a polymer to a surface of a substrate to coat the surface; exposing the substrate coated with the mixture to a first condition, wherein the applied heat and pressure would result in adhesion of the polymer in the absence of the SFAE; collecting the exposed substrate; contacting a surface of the collected exposed substrate with an opposing surface of a separate collected exposed substrate or a surface of an uncoated substrate; and exposing the contacted surfaces to a second condition, wherein the applied heat and pressure would result in adhesion of the polymer in the presence of the SFAE and form a seal between the contacted surfaces. In related aspects, the blocked-rated mixture may be applied to partially cover the surface of the substrate. For example, only the surface exposed to the ambient atmosphere may be covered with the blocked-rated mixture, or only the surface not exposed to the ambient atmosphere may be covered with the blocked-rated mixture. In related aspects, the blocked-rated mixture may be applied on a surface selected by masking or printing. Also, in one embodiment, a product manufacturable by the above method is disclosed.

[0046] As used herein, "adhere" means the act of sticking to something, including its grammatical variants.

[0047] As used herein, "bio-based" means a material intentionally made from substances derived from living (or once-living) organisms. In related aspects, a material containing at least about 50% of such substances is considered bio-based.

[0048] As used herein, "bind" means to adhere or cause to adhere as an essentially single mass, including its grammatical variations.

[0049] As used herein, "blocking" includes its grammatical variants and means the tendency for two coated materials in close contact (e.g., coated paper sheets) to adhere to each other, which, for example, in the case of paper sheets, may result in the sheets tearing or developing holes when separated.

[0050] As used herein, "blocking resistance" means the ability of a given material to resist the adhesion effects of temperature, pressure, time, and humidity. The MAP-4 material test software may be programmed to conduct a blocking test using the ASTM D3354 or ASTM D918 standard. This result reflects the ability of the material to adhere to itself when separated. Samples can be rated from 0 to 5 based on the following scale: 5 = complete blocking, the paper cannot be completely separated; 4 = significant blocking, it is difficult to separate the paper and fibers tear during the process; 3 = moderate blocking, it is difficult to separate the paper, there is damage to the coating, and fibers may slightly tear during the process; 2 = slight blocking, the paper separates fairly easily but the coating adheres to itself noticeably; 1 = the paper separates easily without damaging the coating, there may be some slight adhesion near the edges; 0 = zero adhesion. In one embodiment, adding SFAE reduces blocking from 5 to 0.

[0051] As used herein, "blocking rating" includes its grammatical variants and means the assigned blocking resistance score determined for a coating composition having a specific ratio to the polymer of SFAE.

[0052] As used herein, "cellulosic" means a natural, synthetic, or semi-synthetic material that can be formed or extruded into an object (e.g., a bag, sheet) or a film or filament and can be used to make such an object or film or filament, and that is structurally and functionally similar to cellulose, such as coatings and adhesives (e.g., carboxymethyl cellulose). In another example, cellulose, which is a complex carbohydrate (C 6 H 10 O 5 ) n composed of glucose units and that is the main component of cell walls in most plants, is cellulosic.

[0053] As used herein, "clamp pressure" means the amount of force in pounds per square inch (psi) applied to two or more surfaces by a brace, band, or clasp used to hold the two or more surfaces together.

[0054] As used herein, "clamp time" means the amount of time that the clamp pressure is applied to two or more surfaces.

[0055] As used herein, "coating weight" is the weight of the material (wet or dry) applied to a substrate. It is expressed in pounds per specified run or grams per square meter.

[0056] As used herein, "Cobb value" means the water absorption (as the weight of water per unit area) of a sample. The procedure for determining the "Cobb value" is carried out in accordance with TAPPI standard 441-om. The Cobb value is calculated by subtracting the initial weight of the sample from the final weight of the sample and then dividing by the area of the sample that is covered with water. The reported value represents the grams of water absorbed per square meter of paper.

[0057] As used herein, "compostable" means that these solid products are biodegradable in soil.

[0058] As used herein, "anti-tack additive" means a process chemical that reduces the adhesiveness of other substances.

[0059] As used herein, "defining a range" means indicating the boundaries of a range, including its grammatical variations.

[0060] As used herein, "edge wicking" means the absorption of water at the outer limit points of a paper structure by one or more mechanisms including, but not limited to, capillary penetration of pores between fibers, diffusion through fibers and bonds, and surface diffusion of fibers in the paper structure. In related aspects, edge wicking in a product treated with a coating containing the sugar fatty acid esters described herein is prevented. In one aspect, there is a similar problem where grease / oil can penetrate into the folds that may be present in paper or paper products. The "grease creasing effect" created by folding, pressing, or crushing the paper structure can be defined as the absorption of grease in the paper structure.

[0061] As used herein, "effect" means imparting specific properties to a specific material, including its grammatical variations.

[0062] As used herein, "hydrophobic substance" means a substance that does not attract water. For example, wax, rosin, resin, sugar fatty acid ester, diketene, shellac, vinyl acetate, PLA, PEI, oil, fat, lipid, other water-repellent chemicals, or combinations thereof are hydrophobic substances.

[0063] As used herein, "hydrophobicity" means water-repellency and the property of tending to repel and not absorb water.

[0064] As used herein, "lipid resistance" or "oleophobicity" means the property of being lipid-repellent and tending to repel and not absorb lipids, greases, fats, etc. In related aspects, grease resistance can be measured by the "3M Kit" test or the TAPPI T559 Kit test.

[0065] As used herein, "polymer" means a chemical compound or mixture of compounds formed by polymerization and consisting essentially of repeating structural units.

[0066] As used herein, "cellulose-containing material" or "cellulose-based material" means a composition consisting essentially of cellulose. For example, such materials can include, but are not limited to, paper, paper sheets, cardboard, papermaking pulp, food storage cartons, parchment paper, cakeboard, meat wrapping paper, release paper / liner, food storage bags, shopping bags, transport bags, bacon board, insulation materials, tea bags, coffee or tea containers, compost bags, tableware, containers for holding hot or cold beverages, cups, lids, plates, bottles for storing carbonated liquids, gift cards, bottles for storing non-carbonated liquids, films for food wrapping, household waste treatment containers, food handling utensils, fabric fibers (e.g., cotton or cotton blends), water storage and transport utensils, alcoholic or non-alcoholic beverages, external casings or screens for electronic products, internal or external components of furniture, curtains, and interior decoration items.

[0067] As used herein, "release paper" means a paper sheet used to prevent an adhesive surface from adhering prematurely to an adhesive or mastic. In one aspect, the coatings described herein can be used to produce materials with low surface energy in place of or to reduce the use of silicon or other coatings. Determination of surface energy can be readily achieved by measurement of the contact angle (e.g., Optical Tensiometer and / or High Pressure Chamber; Dyne Testing, Staffordshire, United Kingdom) or use of Surface Energy Test Pens or Inks (see, e.g., Dyne Testing, Staffordshire, United Kingdom).

[0068] As used herein, "removable" in relation to the SFAE means that once the SFAE coating is applied, it can be removed from the cellulose-based material (e.g., removable by manipulating physical properties). As used herein, "non-removable" in relation to the SFAE means that once the SFAE coating is applied, it binds substantially irreversibly to the cellulose-based material (e.g., removable by chemical means).

[0069] As used herein, "fluffy" means a soft, solid material having the appearance of raw cotton or Styrofoam® peanuts. In one embodiment, the fluffy material can be made from nanocellulose fibers (e.g., MFC), cellulose nanocrystals, and / or cellulose filaments and sugar fatty acid esters, and the resulting fibers or filaments or crystals are hydrophobic (and dispersible) and can be used in composites (e.g., concrete, plastics, etc.).

[0070] As used herein, "fibers in solution" or "pulp" means a lignocellulosic fiber material prepared by chemically or mechanically separating cellulose fibers from wood, fiber crops, or paper waste. In related aspects where cellulose fibers are treated by the methods described herein, the cellulose fibers themselves contain the bound sugar fatty acid esters as discrete entities, and the bound cellulose fibers have different properties from the free fibers (e.g., a pulp or cellulose fiber or nanocellulose or microfibrillated cellulose-sugar fatty acid ester binding material does not form hydrogen bonds between fibers as readily as unbound fibers).

[0071] As used herein, "repulpable" means making a paper or paperboard product suitable for being crushed into a shapeless soft mass for reuse in the manufacture of paper or paperboard.

[0072] As used herein, "adjustable", including its grammatical variations, means adjusting or adapting a method to achieve a particular result.

[0073] As used herein, "tackiness" means the appearance of defects in an applied coating and having a slight stickiness when contacted. Such properties may be tested by using an inverted probe machine (ASTM D2979).

[0074] As used herein, "water contact angle" means the angle measured through a liquid where the liquid / vapor interface meets the solid surface. It quantifies the wettability of the solid surface by the liquid. The contact angle reflects the strength of the interaction between the molecules of the liquid and the solid, compared to the strength of each interacting with molecules of its own kind. On many highly hydrophilic surfaces, water droplets exhibit contact angles in the range of 0° to 30°. Generally, when the water contact angle is greater than 90°, the solid surface is considered hydrophobic. The water contact angle can be easily obtained using an optical tensiometer (see, for example, Dyne Testing, Staffordshire, United Kingdom).

[0075] As used herein, "water vapour permeability" means breathability, or the ability of a textile to transfer moisture. There are at least two different measurement methods. One of them, the MVTR (moisture vapor transmission rate) test conducted in accordance with ISO 15496, indicates the water vapour permeability (WVP) of the fabric, i.e., the degree of sweat transport to the outside air. The measurement determines the number of grams of moisture (water vapor) passing through one square meter of the fabric in 24 hours (the higher the level, the higher the breathability).

[0076] In one aspect, the TAPPI T 530 Hercules sizing test (i.e., the sizing test of paper by ink resistance) may be used to determine water resistance. The ink resistance by the Hercules method is best classified as a direct measurement test of the degree of penetration. Otherwise, it is classified as the rate of the penetration test. There is no single best test for "measuring sizing". The test selection depends on the end use and the needs of mill control. This method is particularly suitable for use as a mill control sizing test that accurately detects changes in sizing levels. It provides the sensitivity of the ink float test while yielding reproducible results, shortening the test time, and automatically determining the end point.

[0077] Sizing, measured by resistance to the passage of aqueous liquids through paper or absorption of aqueous liquids into paper, is an important feature of many papers. These are typically bags, boxboard for containers, meat wrapping, writing, and some printing grades.

[0078] Such methods may be used to monitor the manufacture of paper or board for a particular end use, provided that an acceptable correlation has been established between the test values and the end use performance of the paper. Because of the nature of the tests and the penetrants, it does not always show a sufficient correlation to be applicable to all end use requirements. This method measures sizing by the degree of penetration. Other methods measure sizing by surface contact, surface penetration, or absorption. A size test is selected based on the ability to simulate the means of water contact or absorption in the end use. This method can also be used to optimize the cost of using size chemicals.

[0079] As used herein, "oxygen permeability" means the degree to which a polymer allows the passage of gases or fluids. The oxygen permeability (Dk) of a material is a function of the diffusion rate (D) (i.e., the speed at which oxygen molecules cross the material) and the solubility (k) (or the amount of oxygen molecules absorbed per volume of the material). The value of the oxygen permeability (Dk) typically falls within the range of 10 - 150×10 -11 (cm 2 ml O 2 ) / (s ml mmHg). A semi-logarithmic relationship has been shown between the hydrogel water content and the oxygen permeability (in Barrers). The International Organization for Standardization (ISO) has specified permeability using the SI unit of pressure, hectopascal (hPa). Thus, Dk = 10 -11 (cm 2 ml O 2 ) / (s ml hPa). The Barrer unit can be converted to the hPa unit by multiplying it by the constant 0.75.

[0080] As used herein, "biodegradable" means, including its grammatical variations, capable of being decomposed by the action of living organisms (e.g., by microorganisms) into particularly harmless products.

[0081] As used herein, "recyclable" means, including its grammatical variations, a material that is processable to produce the said material suitable for reuse, or can be processed (for used and / or waste products).

[0082] As used herein, "latex" means a stable dispersion (emulsion) of polymer microparticles in an aqueous medium. It occurs in nature, but synthetic latex can be produced by polymerizing monomers emulsified with surfactants, such as styrene. Natural latex is a milky fluid found in 10% of all flowering plants (angiosperms). It is a complex emulsion consisting of proteins, alkaloids, starch, sugars, oils, tannins, resins, and rubber, and coagulates when exposed to air.

[0083] As used herein, "filler" means a micronized white mineral (or pigment) added to the papermaking furnish to improve the optical and physical properties of the sheet. The particles fill the spaces and gaps between the fibers, and thus serve to produce a sheet with increased brightness, opacity, smoothness, gloss, and printability, but generally with decreased bonding and tear strength. Common papermaking fillers include clay (kaolin, bentonite), calcium carbonate (both GCC and PCC), talc (magnesium silicate), and titanium dioxide.

[0084] As used herein, "Gurley second" or "Gurley number" is a unit that indicates the number of seconds required for 100 cubic centimeters (deciliters) of air to pass through a given material of 1.0 square inch under a water pressure difference of 4.88 inches (0.176 psi) (ISO 5636-5:2003) (porosity). Also, with respect to rigidity, "Gurley number" is a unit of a portion of the material that measures the force required to bend a vertically held material by a given amount (a force of 1 milligram). Such values can be measured with an apparatus of Gurley Precision Instruments (Troy, New York).

[0085] The hydrophilic-lipophilic balance (HLB) of a surfactant is a measure of the degree to which it is hydrophilic or lipophilic, determined by calculating values for different regions of its molecules.

[0086] The Griffin method for nonionic surfactants, described in 1954, is as follows: [Chemical formula] [where M h is the molecular mass of the hydrophilic part of the molecule and M is the molecular mass of the whole molecule.], and the result is shown on a scale of 0 to 20. An HLB value of 0 corresponds to a completely lipophilic / hydrophobic molecule, and an HLB value of 20 corresponds to a completely hydrophilic / lipophobic molecule.

[0087] The HLB value can be used to predict the surfactant properties of a molecule. <10: Lipophilic (water-insoluble) >10: Water-soluble (lipid-insoluble) 1.5 - 3: Defoaming agent 3 - 6: W / O (water-in-oil type) emulsifier 7 - 9: Wetting and spreading agent 13 - 15: Detergent 12 - 16: O / W (oil-in-water type) emulsifier 15 - 18: Solubilizing agent or hydrotrope

[0088] In some embodiments, the HLB value of the sugar fatty acid ester (or the composition containing said ester) described herein can be in a lower range. In other embodiments, the HLB value of the sugar fatty acid ester (or the composition containing said ester) described herein can be in a medium to higher range. In one embodiment, mixed SFAEs having different HLB values may be used.

[0089] As used herein, "SEFOSE®" is the name of a sucrose fatty acid ester (soybean oil fatty acid ester) containing one or more unsaturated fatty acids made from soybean oil, and is commercially available from Procter & Gamble Chemicals (Cincinnati, OH) under the trade name SEFOSE® 1618U (see the following polysoybean oil fatty acid sucrose). As used herein, "OLEAN®" is the formula C n+12 H 2n+22 O 13 and is the name of a sucrose fatty acid ester in which all fatty acids are saturated fatty acids, and is available from Procter & Gamble Chemicals. Further, the SFAE may be purchased from Mitsubishi Chemicals Foods Corporation (Tokyo, Japan) which offers various SFAEs.

[0090] As used herein, "soybean oil fatty acid ester" means a mixture of salts of fatty acids derived from soybean oil.

[0091] As used herein, "oilseed fatty acids" means fatty acids derived from plants including, but not limited to, soybean, peanut, rapeseed, barley, canola, sesame seed, cottonseed, palm kernel, grape seed, olive, safflower, sunflower, copra, corn, coconut, linseed, hazelnut, wheat, rice, potato, cassava, bean fruit, camelina seed, mustard seed, and combinations thereof.

[0092] As used herein, "wet strength" means a measure of how well the fiber web holding the paper together can resist the force of breakage when the paper is in a wet state. Wet strength can be measured using a Finch Wet Strength Device from Thwing-Albert Instrument Company (West Berlin, NJ). In that case, wet strength is typically provided by wet strength additives such as gums, cationic glyoxylated resins, polyamidoamine-epichlorohydrin resins, polyamine-epichlorohydrin resins, including epoxide resins. In one embodiment, the cellulose-based material coated with the SFAE described herein provides such wet strength in the absence of such additives.

[0093] As used herein, "wet" means being covered or saturated with water or another liquid.

[0094] In one embodiment, the method described herein includes mixing a latex and a sugar fatty acid ester to form an aqueous coating, and applying the coating to a cellulosic material, and the method optionally includes exposing the contacted cellulose-based material to heat, radiation, a catalyst, or a combination thereof for a time sufficient to bond the coating to the cellulose-based material. In related aspects, such radiation can include, but is not limited to, UV, IR, visible light, or a combination thereof. In another related aspect, the reaction may be carried out at room temperature (i.e., 25 °C) to about 150 °C, about 50 °C to about 100 °C, or about 60 °C to about 80 °C. Further, the resulting surface of the cellulosic material will exhibit a lower bump value compared to the surface of a cellulosic material not so treated.

[0095] In this specification, fatty acid esters of all sugars, including monosaccharides, disaccharides, and trisaccharides, are applicable to the uses associated with such aspects in the present invention. In related aspects, the sugar fatty acid esters can be mono-, di-, tri-, tetra-, penta-, hexa-, hepta-, or octa-esters, and combinations thereof, including that the fatty acid moiety may be saturated, unsaturated, or a combination thereof.

[0096] Without being bound by any theory, the interaction between the sugar fatty acid ester and the cellulose-based material can be by ionic, hydrophobic, van der Waals interactions, or covalent bonds, or a combination thereof. In related aspects, the sugar fatty acid ester bound to the cellulose-based material can be substantially irreversible (e.g., using SFAE including a combination of saturated and unsaturated fatty acids).

[0097] Furthermore, the binding of the sugar fatty acid ester at a sufficient concentration is sufficient to make the cellulose-based material hydrophobic. That is, the hydrophobicity is achieved without adding wax, rosin, resin, diketene, shellac, vinyl acetate, PLA, PEI, oil, other water-repellent chemicals, or combinations thereof (i.e., a second hydrophobic substance), including that other properties such as strengthening, stiffening, and bulking of the cellulose-based material are achieved only by the sugar fatty acid ester binding.

[0098] The advantages of the present invention disclosed are that multiple fatty acid chains react with cellulose and two sugar molecules in the structure, for example, the disclosed sucrose fatty acid esters result in a rigid cross-linked network, improving the strength of fibrous webs such as paper, paperboard, airlaid and wetlaid nonwovens, and textiles, and thus overcoming the potential undesirable effects of some fillers (such as calcium carbonate and the decrease in bonding and tear strength). This is not usually seen in the chemical properties of other sizing or hydrophobic treatments. The sugar fatty acid esters described herein also generate / increase wet strength, a property that does not exist when using many other water-resistant chemical properties.

[0099] Another advantage is that the disclosed sugar fatty acid esters soften the fibers, increasing the space between them, and thus increasing the bulk without substantially increasing the weight. Further, the fibers and cellulose-based materials modified as described herein may be repulped. Also, for example, water cannot enter the sheet by easily "pushing" through a low surface energy barrier.

[0100] Saturated SFAEs are typically solids at the nominal processing temperature, while unsaturated SFAEs are typically liquids. This allows for the formation of a uniform and stable dispersion of saturated SFAEs in an aqueous coating, typically without significant interaction or incompatibility with other coating components that are typically hydrophilic. Further, such dispersions allow for the preparation of high concentrations of saturated SFAEs without adversely affecting the rheology of the coating, uniform coating application, or coating performance characteristics. When the particles of saturated SFAE melt and spread during heating, drying, and compounding of the coating layer, the coating surface becomes hydrophobic. In one embodiment, a method is disclosed for producing a bulky fibrous structure that retains strength even when exposed to water. Generally, a dried fiber slurry forms a dense structure that easily degrades when exposed to water. Examples of shaped fiber products produced using the disclosed method include paper plates, drink holders (e.g., cups), lids, food trays, and packaging that are lightweight, strong, and resistant to exposure to water and other liquids.

[0101] In one embodiment, a sugar fatty acid ester may be mixed with polyvinyl alcohol (PvOH) to produce a sizing agent for a water-resistant coating. As disclosed herein, a synergistic relationship between the sugar fatty acid ester and PvOH has been revealed, including the ability to reduce the amount of PvOH in the case of an inorganic mixture. PvOH is itself a good film-forming agent and is known in the art to form strong hydrogen bonds with cellulose, but has limited resistance to water, particularly hot water. In an aspect, the use of PvOH helps to emulsify the sugar fatty acid ester into an aqueous coating. In one aspect, PvOH provides the sugar fatty acid ester with a rich source of OH groups for crosslinking along the fibers, increasing the strength of the paper, such as particularly the wet strength, and the water resistance beyond what is possible with PvOH alone. For saturated sugar fatty acid esters having free hydroxyls on the sugar, crosslinking agents such as dialdehydes (e.g., glyoxal, glutaraldehyde, etc.) can also be used.

[0102] In one embodiment, the sugar fatty acid ester comprises or consists essentially of sucrose esters of fatty acids. Many methods are known and available for making or otherwise providing the sugar fatty acid esters according to the present invention, and all such methods are considered to be available for use within the broad scope of the present invention. For example, in some embodiments, the fatty acid ester is preferably synthesized by esterifying a sugar with one or more fatty acid moieties obtained from fatty seeds including but not limited to soybean oil, sunflower oil, olive oil, canola oil, peanut oil, and mixtures thereof.

[0103] In one embodiment, the sugar fatty acid ester comprises a sugar moiety including but not limited to a sucrose moiety in which one or more of the hydroxyl hydrogens are replaced by ester moieties. In a related aspect, the disaccharide ester has the following formula I: [Chemical formula] [wherein, "A" is hydrogen or the following structure I [Chemical formula] (wherein, "R" is a linear, branched, or cyclic saturated or unsaturated aliphatic or aromatic moiety having from about 8 to about 40 carbon atoms), and at least one "A", at least one, at least two, at least three, at least four, at least five, at least six, at least seven, and all eight "A" moieties of the formula are in accordance with structure I. ] has the structure of. In a related aspect, the sugar fatty acid esters described herein can be mono-, di-, tri-, tetra-, penta-, hexa-, hepta-, or octa-esters, and combinations thereof, and the aliphatic groups can all be saturated aliphatic groups, or can include saturated and / or unsaturated groups, or combinations thereof.

[0104] Suitable "R" groups include aliphatic moieties in any form, including those containing one or more substituents, and these substituents may occur on any carbon in the moiety. Aliphatic moieties containing functional groups within the aliphatic moiety, such as ether, ester, thio, amino, phospho, etc., are also included. Oligomeric and polymeric aliphatic moieties, such as sorbitan, polysorbitan, and polyalcohol moieties, are also included. Examples of functional groups that can be added to the aliphatic (or aromatic) moiety containing the "R" group include, but are not limited to, halogen, alkoxy, hydroxy, amino, ether, and ester functional groups. In one embodiment, the moiety may have a crosslinkable functional group. In another embodiment, SFAE (e.g., activated clay / pigment particles) may be crosslinked to the surface. In another embodiment, the double bonds present on the SFAE may be used to facilitate reactions with other surfaces.

[0105] Suitable disaccharides include raffinose, maltodextrose, galactose, sucrose, combinations of glucose, combinations of fructose, maltose, lactose, combinations of mannose, combinations of erythrose, isomaltose, isomaltulose, trehalose, trehalulose, cellobiose, laminaribiose, chitobiose, and combinations thereof.

[0106] In one embodiment, substrates for adding fatty acids can include starch, hemicellulose, lignin, or combinations thereof.

[0107] In one embodiment, the composition includes a starch fatty acid ester, and the starch can be derived from any suitable source such as dent corn starch, waxy corn starch, potato starch, wheat starch, rice starch, sago starch, tapioca starch, sorghum starch, sweet potato starch, and mixtures thereof.

[0108] More specifically, the starch can be unprocessed starch or starch processed by chemical, physical, or enzymatic processing.

[0109] Chemical processing includes the optional treatment of starch with chemicals to produce modified starch (e.g., plasticizer materials). Within the scope of chemical processing are included, but not limited to, the depolymerization of starch, the oxidation of starch, the reduction of starch, the etherification of starch, the esterification of starch, the nitration of starch, the degreasing of starch, the hydrophobization of starch, etc. Chemically modified starch can also be prepared by using any combination of chemical treatments. Examples of chemically modified starch include the reaction of alkenyl succinic anhydride, particularly octenyl succinic anhydride, with starch to produce hydrophobic esterified starch; the reaction of 2,3-epoxypropyltrimethylammonium chloride with starch to produce cationic starch; the reaction of ethylene oxide with starch to produce hydroxyethyl starch; the reaction of hypochlorite with starch to produce oxidized starch; the reaction of an acid with starch to produce acid-depolymerized starch; and the reaction of starch with a solvent such as methanol, ethanol, propanol, methylene chloride, chloroform, carbon tetrachloride, etc. to degrease the starch and produce degreased starch.

[0110] Physically modified starch is starch that has been physically treated in a form that provides physically modified starch. Within the scope of physical processing are included, but not limited to, the heat treatment of starch in the presence of water, the heat treatment of starch in the absence of water, the fragmentation of starch granules by any mechanical means, the pressurization of starch to melt the starch granules, etc. Physically modified starch can also be prepared by using any combination of physical treatments. Examples of physically modified starch include the heat treatment of starch in an aqueous environment to swell the starch granules without granule breakage; the heat treatment of anhydrous starch granules to cause polymer rearrangement; the fragmentation of starch granules by mechanical disintegration; and the pressurization of starch granules by an extruder to cause melting of the starch granules.

[0111] Enzymatically processed starch is any starch treated with an enzyme in any form that provides enzymatically processed starch. Within the scope of enzymatic processing, it includes, but is not limited to, the reactions of α-amylase with starch, protease with starch, lipase with starch, phosphorylase with starch, oxidase with starch, etc. Enzymatically processed starch can be prepared by using any combination of enzyme treatments. Examples of the enzymatic processing of starch include the reaction of an alpha-amylase enzyme with starch to produce depolymerized starch; the reaction of an alpha-amylase debranching enzyme with starch to produce debranched starch; the reaction of a protease enzyme with starch to produce starch with a reduced protein content; the reaction of a lipase enzyme with starch to produce starch with a reduced lipid content; the reaction of a phosphorylase enzyme with starch to produce enzymatically processed phosphorylated starch; and the reaction of an oxidase enzyme with starch to produce enzymatically oxidized starch.

[0112] The disaccharide fatty acid ester can be a sucrose fatty acid ester according to Formula I [wherein the "R" group is aliphatic, straight-chain or branched, saturated or unsaturated, and has about 8 to about 40 carbon atoms].

[0113] As used herein, the terms "sugar fatty acid ester" and "sucrose fatty acid ester" include compositions having different purities and mixtures of compounds at optional purity levels. For example, a sugar fatty acid ester compound can be a substantially pure material, i.e., it can include a compound having a predetermined number of "A" groups substituted by only one type of the structural I moiety (i.e., all "R" groups are the same and all of the sucrose moieties are substituted to an equal extent). It also includes a composition containing a blend of two or more sugar fatty acid ester compounds having different degrees of substitution but all of the substituents having the same "R" group structure. It also includes a composition which is a mixture of compounds having different degrees of substitution of the "A" group and the substituent portions of the "R" groups independently selected from two or more of the "R" groups of structural I. In a related aspect, the "R" groups can be the same or different, including the case where the sugar fatty acid esters in the composition are the same or different (i.e., a mixture of different sugar fatty acid esters).

[0114] In the composition according to the present invention, the composition may be composed of a sugar fatty acid ester compound having a high degree of substitution. In one embodiment, the sugar fatty acid ester is sucrose polysoybean oil fatty acid.

[0115]

Chemical formula

[0116] Sugar fatty acid esters can be prepared by esterification with a substantially pure fatty acid by known esterification methods. They can also be prepared by transesterification using a sugar and a fatty acid ester in the form of a fatty acid glyceride derived from, for example, a natural source, such as an oil extracted from fatty seeds, such as soybean oil. The transesterification reaction for providing sucrose fatty acid esters using fatty acid glycerides is described, for example, in U.S. Patent Nos. 3,963,699; 4,517,360; 4,518,772; 4,611,055; 5,767,257; 6,504,003; 6,121,440; 6,995,232, and International Publication No. 1992 / 004361 (A1), each of which is hereby incorporated by reference in its entirety as part of this specification.

[0117] In addition to producing hydrophobic sucrose esters via transesterification, similar hydrophobicity can be achieved in cellulosic fiber articles by reacting an acid chloride directly with a polyol containing a ring structure similar to sucrose.

[0118] As described above, sucrose fatty acid esters can be prepared by transesterification of sucrose with a methyl ester feedstock prepared from glycerides derived from natural sources (see, for example, U.S. Patent No. 6,995,232, which is incorporated herein by reference in its entirety). As a result of the fatty acid source, the feedstocks used to prepare sucrose fatty acid esters contain various saturated and unsaturated fatty acid methyl esters having fatty acid moieties containing 12 to 40 carbon atoms. This is reflected in the sucrose fatty acid esters, which are products made from such sources, because the sucrose moiety containing the product contains a mixture of ester moiety substituents. Referring to Structure I above, the "R" group is a mixture having 12 to 26 carbon atoms in a ratio that reflects the feedstock used to prepare the sucrose ester. To further illustrate this point, sucrose esters derived from soybean oil are such that soybean oil is 26 wt% oleic acid (H 3 C-CH 2 7 -CH=CH-[CH 2 7 -C(O)OH) triglyceride, 49 wt% linoleic acid (H 3 C-[CH 2 3 -[-CH 2 -CH=CH] 2 -[-CH 2 -] 7 -C(O)OH) triglyceride, 11 wt% linolenic acid (H 3 C-[-CH 2 -CH=CH-] 3 -[-CH 2 -] 7 ​​​-C(O)OH) triglycerides, and a mixture of species having an "R" group structure that reflects the inclusion of 14 wt% of various saturated fatty acid triglycerides, all of which are described in the Seventh Ed. Of the Merck Index, which is hereby incorporated by reference in its entirety. All of these fatty acid moieties are representative in the "R" group of the substituents of the sucrose fatty acid ester product. Thus, when referring to sucrose fatty acid esters herein as the product of a reaction employing a fatty acid feedstock derived from a natural source, e.g., soybean oil fatty acids sucrose, the term is intended to include all of the various components typically found as a result of the source from which the sucrose fatty acid ester is prepared. In a related aspect, the disclosed sugar fatty acid esters may exhibit low viscosities (e.g., about 10 to 2000 centipoise at room temperature or standard atmospheric pressure). In another aspect, the unsaturated fatty acids may have one, two, three, or more double bonds.

[0119] In one embodiment, the sugar fatty acid esters, and in one aspect the disaccharide esters, are formed from fatty acids having on average more than about 6 carbon atoms, about 8 to 16 carbon atoms, about 8 to about 18 carbon atoms, about 14 to about 18 carbon atoms, about 16 to about 18 carbon atoms, about 16 to about 20 carbon atoms, about 20 to about 40 carbon atoms.

[0120] In one embodiment, the sugar fatty acid ester can be present in various concentrations as a means to achieve non-sticking properties or to adjust the adhesion properties of the polymer. In one aspect, when the sugar fatty acid ester (SFAE) is mixed with the polymer, the SFAE can be present at about 0.1% to about 1%, 1% to about 5%, about 5% to about 10%, about 20%, about 30%, about 40%, about 50%, about 60%, about 70%, about 80%, about 90%, about 95%, about 99% of the mixture on a dry matter basis. In a related aspect, the polymer can be present at about 0.1% to about 1%, 1% to about 5%, about 5% to about 10%, about 20%, about 30%, about 40%, about 50%, about 60%, about 70%, about 80%, about 90%, about 95%, or about 99% of the mixture on a dry matter basis. In one embodiment, examples of the polymer include, but are not limited to, PvOH, starch, styrene butadiene latex, styrene acrylate latex, carboxylated styrene butadiene latex, oligomer stabilized styrene acrylic copolymer latex, surfactant stabilized styrene acrylic copolymer latex, polyvinyl acetate, ethylene vinyl acetate, acrylics, and combinations thereof. In one aspect, the SFAE and polymer composition does not contain other anti-blocking agents.

[0121] In one embodiment, examples of the cellulosic material include, but are not limited to, paper, paperboard, paper sheet, papermaking pulp, cup, box, tray, lid, release paper / liner, compost bag, shopping bag, transport bag, bacon paperboard, tea bag, insulating material, coffee or tea container, pipe and aqueduct, food-grade disposable cutlery, plate and bin, screen for TV and portable devices, clothing (e.g., cotton or cotton blend), bandage, pressure-sensitive label, pressure-sensitive tape, feminine product, and medical devices, drug delivery devices, pharmaceutical materials (e.g., pills, tablets, suppositories, gels, etc.) containers used on or inside the body such as contraceptives. Also, the disclosed coating technology can be used for furniture and interior decoration items, outdoor camping equipment, etc.

[0122] In one aspect, the coating described herein is resistant to pH in the range of about 3 to about 9. In related aspects, the pH can be about 3 to about 4, about 4 to about 5, about 5 to about 7, or about 7 to about 9.

[0123] In one embodiment, an alkanoic acid derivative is mixed with a sugar fatty acid ester to form an emulsion, and the emulsion is used to treat a cellulose-based material.

[0124] In one embodiment, the sugar fatty acid ester can be an emulsifier and can include a mixture of one or more mono-, di-, tri-, tetra-, penta-, hexa-, hepta-, or octa-esters. In another aspect, the fatty acid moiety of the sugar fatty acid ester can include saturated groups, unsaturated groups, or combinations thereof. In one aspect, the sugar fatty acid ester-containing emulsion can contain proteins, polysaccharides, and / or lipids including, but not limited to, milk proteins (e.g., casein, whey protein, etc.), wheat gluten, gelatin, prolamins (e.g., zein), soy protein isolate, starch, acetylated polysaccharides, alginates, carrageenans, chitosan, inulin, long-chain fatty acids, waxes, and combinations thereof.

[0125] In one embodiment, the sugar fatty acid ester emulsifier described herein can be used to carry other chemicals used in papermaking, which are not limited to but include coating, or agarite, ester, diester, ether, ketone, amide, nitrile, aromatic compounds (e.g., xylene, toluene), acid halide, anhydride, alkyl ketene dimer (AKD), alum, alganic acid, alum, albumin, glue, barium carbonate, barium sulfate, chlorine dioxide, dolomite, diethylenetriaminepentaacetate, EDTA, enzyme, formamidine sulfate, guar gum, alum, lime, magnesium bisulfate, lime milk, magnesia milk, polyvinyl alcohol (PvOH), rosin, rosin soap, satin, soap / fatty acid, sodium bisulfate, soda ash, titania, surfactant, starch, modified starch, hydrocarbon resin, polymer, wax, polysaccharide, protein, latex, and combinations thereof. In an embodiment, the disclosed mixture may include one or more SFAEs and one or more of inorganic particles of clay (kaolin, bentonite), calcium carbonate (both GCC and PCC), talc (magnesium silicate), and titanium dioxide.

[0126] In one embodiment, the cellulose-containing material provided by the method described herein exhibits higher hydrophobicity or water resistance compared to the cellulose-containing material without treatment. In a related aspect, the treated cellulose-containing material exhibits higher oleophobicity or grease resistance compared to the cellulose-containing material without treatment. In another related aspect, the treated cellulose-containing material can be biodegradable, compostable, and / or recyclable. In one aspect, the treated cellulose-containing material is hydrophobic (water resistant) and oleophobic (grease resistant).

[0127] In one embodiment, the processed cellulose-containing material may have improved mechanical properties compared to the same unprocessed material. For example, paper bags processed by the methods described herein exhibit increased burst strength, Gurley number, tensile strength, and / or maximum load energy. In one aspect, the burst strength is increased by about 0.5 to 1.0 times, about 1.0 to 1.1 times, about 1.1 to 1.3 times, about 1.3 to 1.5 times. In another aspect, the Gurley number is increased by about 3 to 4 times, about 4 to 5 times, about 5 to 6 times, and about 6 to 7 times. In yet another aspect, the tensile strain is increased by about 0.5 to 1.0 times, about 1.0 to 1.1 times, about 1.1 to 1.2 times, and about 1.2 to 1.3 times. In still another aspect, the maximum load energy is increased by about 1.0 to 1.1 times, about 1.1 to 1.2 times, about 1.2 to 1.3 times, and about 1.3 to 1.4 times.

[0128] In one embodiment, the cellulose-containing material is a base paper containing microfibrillated cellulose (MFC) or cellulose nanofiber (CNF), such as described in U.S. Patent Application Publication No. 2015 / 0167243 (which is hereby incorporated by reference in its entirety and made a part of this specification). MFC or CNF is added during the forming process and the papermaking process, and / or added to the prior forming layer as a coating or a secondary layer to reduce the porosity of the base paper. In a related aspect, the base paper is contacted with the above sugar fatty acid ester. In another related aspect, the contacted base paper is further contacted with polyvinyl alcohol (PvOH). In an embodiment, the obtained contacted base paper is adjustably water-resistant and lipid-resistant. In a related aspect, the obtained base paper may exhibit a Gurley air permeability resistance of at least about 10 to 15 (i.e., seconds / 100 cc, 20-ounce cylinder), or at least about 100, or at least about 200 to about 350 Gurley values. In one aspect, the sugar fatty acid ester coating can be a single-layer or multi-layer laminate, or a single-layer or multi-layer can be formed as a laminate, or the amount of the single-layer or multi-layer coating can be reduced to achieve similar performance effects (e.g., water resistance, grease resistance, etc.). In a related aspect, the laminate may include biodegradability and / or a heat-sealable or adhesive that can be formed.

[0129] In one embodiment, the sugar fatty acid ester may be formulated as an emulsion, and the choice of emulsifier and its amount used is dictated by the nature of the composition and the ability of the emulsifier to promote the dispersion of the sugar fatty acid ester. In one aspect, examples of emulsifiers include, but are not limited to, water, buffer, polyvinyl alcohol (PvOH), carboxymethyl cellulose (CMC), latex, milk protein, wheat gluten, gelatin, prolamin, soy protein isolate, starch, acetylated polysaccharide, alginate, carrageenan, chitosan, inulin, long-chain fatty acid, wax, agar, alginate, glycerol, gum, lecithin, poloxamer, monoglycerol, diglycerol, monosodium phosphate, monostearate, propylene glycol, detergent, cetyl alcohol, and combinations thereof. In another aspect, the ratio of sugar ester:emulsifier can be about 0.1:99.9, about 1:99, about 10:90, about 20:80, about 35:65, about 40:60, and about 50:50. It will be apparent to those skilled in the art that the ratio may be varied according to the desired properties of the final product.

[0130] In one embodiment, the sugar fatty acid ester can be combined with one or more coating components (alone or in combination) for internal and surface sizing, including but not limited to binders (e.g., starch, soybean protein, polymer emulsion, PvOH, latex), and additives (e.g., glyoxal, glyoxalated resin, zirconium salt, calcium stearate, lecithin oleate, polyethylene emulsion, carboxymethyl cellulose, acrylic polymer, alginate, polyacrylate rubber, polyacrylate, microbicide, oil-based defoamer, silicone-based defoamer, stilbene, direct dye, and acid dye). In related aspects, such components can build a microporous structure, provide a light-scattering surface, improve ink receptivity, improve glossiness, bind pigment particles, bind the coating to paper and base sheet reinforcement, fill the pores of the pigment structure, reduce water sensitivity, resist wet pick in offset printing, prevent blade scratching, improve glossiness in supercalendering, reduce dust generation, adjust coating viscosity, achieve water retention, disperse pigments, maintain coating dispersion, prevent degradation of the coating / coating colorant, control foaming, reduce entrained air and coating craters, increase whiteness and brightness, and control color and color tone, among other properties, including but not limited to these. It will be apparent to those skilled in the art that the combination can be varied according to the desired properties of the final product.

[0131] In one embodiment, the method of employing the sugar fatty acid ester may be used to reduce the cost of applying a primary / secondary coating (e.g., a silicone-based layer, a starch-based layer, a clay-based layer, a PLA layer, Bio-PBS, a PEI layer, etc.), providing a layer of material that exhibits the required properties (e.g., water resistance, low surface energy, etc.), thereby reducing the amount of primary / secondary layers required to achieve similar properties. In one aspect, a material (e.g., a heat-sealable agent) can be coated on top of the SFAE layer. In one embodiment, the composition is fluorocarbon and silicone-free.

[0132] In one embodiment, the composition enhances both the mechanical and thermal stability of the treated product. In one aspect, the surface treatment is thermally stable at a temperature of about -100°C to about 300°C. In another related aspect, the surface of the cellulose-based material exhibits a water contact angle of about 60° to about 120°. In another related aspect, the surface treatment is chemically stable at a temperature of about 200°C to about 300°C.

[0133] The substrate may be dried (e.g., at about 80 - 150°C) before coating, but can be treated using the modified composition, for example, by dipping and exposing the surface to the composition for less than 1 second. The substrate can be heated to dry the surface, and then the modified material is immediately ready for use. In one aspect, the substrate may be treated according to the methods described herein using any suitable coating / sizing method typically practiced in a paper mill (e.g., Smook, G., Surface Treatments, Handbook for Pulp & Paper Technologists, (2016), 4 th Ed., Cpt. 18, pp. 293 - 309, TAPPI Press, Peachtree Corners, GA USA, which is hereby incorporated by reference in its entirety).

[0134] In some applications, the material may be dried before processing, but no special preparation of the material is required when implementing the present invention. In one embodiment, the disclosed method can be used on any cellulose-based surface, including but not limited to films, rigid containers, fibers, pulp, fabrics, etc. In one aspect, the sugar fatty acid ester or coating agent can be applied by conventional size presses (vertical, inclined, horizontal), gate roll size presses, metering size presses, calendar size coating, tube sizing, on-machine, off-machine, single-sided coater, double-sided coater, short dwell, simultaneous double-sided coater, blade or rod coater, gravure coater, gravure printing, flexographic printing, inkjet printing, laser printing, supercalendering, and combinations thereof.

[0135] Depending on the source, the cellulose can be paper, paperboard, pulp, softwood fibers, hardwood fibers, or combinations thereof, nanocellulose, cellulose nanofibers, whiskers or microfibrils, microfibrillated cotton or cotton blends, other non-wood fibers (e.g., sisal, jute or hemp, flax and straw), cellulose nanocrystals, or nanofibrillated cellulose.

[0136] In one embodiment, the application amount of the sugar fatty acid ester coating is an amount sufficient to completely cover at least one surface of the cellulose-containing material. For example, in one embodiment, the sugar fatty acid ester coating may be applied to the entire outer surface of the container, the entire inner surface of the container, or a combination thereof, or one or both sides of the base paper. In other embodiments, the entire upper surface of the film may be covered with the sugar fatty acid ester coating, or the entire lower surface of the film may be covered with the sugar fatty acid ester coating, or a combination thereof. In some embodiments, the holes of the device / instrument may be covered with the coating, or the outer surface of the device / instrument may be covered with the sugar fatty acid ester coating, or a combination thereof. In one embodiment, the application amount of the sugar fatty acid ester coating is an amount sufficient to partially cover at least one surface of the cellulose-containing material. For example, only the surface exposed to the ambient atmosphere is covered with the sugar fatty acid ester coating, or only the surface not exposed to the ambient atmosphere is covered with the sugar fatty acid ester coating (e.g., masking). As will be apparent to those skilled in the art, the application amount of the sugar fatty acid ester coating may depend on the use of the material to be coated. In one aspect, one surface may be coated with the sugar fatty acid ester, and the opposite surface may be coated with an agent including, but not limited to, proteins, wheat gluten, gelatin, prolamin, soy protein isolate, starch, modified starch, acetylated polysaccharide, alginate, carrageenan, chitosan, inulin, long-chain fatty acids, waxes, and combinations thereof. In a related aspect, the SFAE can be added to the finished paper stock, and the resulting material on the web may be provided with an additional coating of the SFAE.

[0137] Any suitable coating method may be used to deliver any of the various sugar fatty acid ester coatings and / or emulsions applied during the process of implementing this aspect of the method. In one embodiment, sugar fatty acid ester coating methods include dipping, spraying, painting, printing, and any combination of any of these methods alone or in combination with other coating methods adapted to implement the disclosed method.

[0138] For example, by increasing the concentration of the sugar fatty acid ester, the compositions described herein can react more extensively with the cellulose being treated, and in the final result, improved water / oil repellent properties are also shown. However, it is not necessarily the case that the higher the coat weight, the greater the water resistance. In one aspect, various catalysts enable faster "curing" and precisely adjust the quality of the sugar fatty acid ester to meet specific applications.

[0139] It will be apparent to those skilled in the art that the selection of the cellulose to be treated, the sugar fatty acid ester, the reaction temperature, and the exposure time are parameters of the method that can be optimized by routine experimental methods to be suitable for any specific application of the final product.

[0140] The derivatized materials have modified physical properties that can be defined and measured using appropriate tests known in the art. For hydrophobicity, analysis protocols can include, but are not limited to, contact angle measurement and moisture absorption. Other properties include rigidity, WVTR, porosity, tensile strength, absence of substrate degradation, rupture, and tear properties. The specific standardized protocol to follow is defined by the American Society for Testing and Materials (Protocol ASTM D7334-08).

[0141] The permeability to various gases such as water vapor and oxygen on the surface may also be changed by the sugar fatty acid ester coating method so that the barrier function of the material is enhanced. The standard unit for measuring permeability is the burer, and the protocols for measuring these parameters are also available in the public domain (ASTM standard F2476-05 for water vapor and ASTM standard F2622-8 for oxygen).

[0142] In one embodiment, the material processed according to the procedures of the present disclosure exhibits complete biodegradability as measured by degradation in an environment under microbial attack.

[0143] Various methods, including the flask shaking method (ASTM E1279-89(2008)) and the Zahn-Wellens test (OECD TG 302 B), are available for defining and testing biodegradability.

[0144] Various methods, including but not limited to ASTM D6400, are available for defining and testing compostability.

[0145] Suitable materials for processing by the method according to the present invention include various forms of cellulose such as cotton fiber, plant fibers such as linen, wood fiber, regenerated cellulose (rayon and cellophane), partially alkylated cellulose (cellulose ether), partially esterified cellulose (acetate rayon), and other modified cellulose materials, which have a considerable proportion of surfaces available for reaction / bonding. As described above, the term "cellulose" includes all of these materials, as well as others having a similar polysaccharide structure and similar properties. Among these, microfibrillated cellulose (cellulose nanofiber) of relatively new materials (for example, see U.S. Patent No. 4,374,702, U.S. Patent Application Publication No. 2015 / 0167243 and No. 2009 / 0221812, which are hereby incorporated by reference in their entirety) is particularly suitable for this application. In other embodiments, cellulose may include, but is not limited to, cellulose triacetate, cellulose propionate, cellulose acetate propionate, cellulose acetate butyrate, nitrocellulose (cellulose nitrate), cellulose sulfate, celluloid, methylcellulose, ethylcellulose, ethylmethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, cellulose nanocrystals, hydroxyethylmethylcellulose, hydroxypropylmethylcellulose, ethylhydroxyethylcellulose, carboxymethylcellulose, and combinations thereof.

[0146] The modification of cellulose described herein, in addition to increasing its hydrophobicity, also enhances its tensile strength, flexibility and rigidity, thereby possibly further expanding its range of use. Biodegradable and partially biodegradable products made from or using the modified cellulose described herein, including recyclable and compostable products, are all within the scope of this disclosure.

[0147] Among the available applications of the coating technology, such items include containers for all purposes, such as paper, paperboard, pulp for papermaking, cups, lids, boxes, trays, release paper / liners, compost bags, shopping bags, pipes and aqueducts, disposable cutlery for food, dishes and bottles, screens for TVs and portable devices, clothing (e.g., cotton or cotton blend), bandages, pressure-sensitive labels, pressure-sensitive tapes, feminine products, and medical devices used on or inside the body such as contraceptives, drug delivery devices, etc., but are not limited thereto. Also, the disclosed coating technology can be used for furniture and interior decoration items, outdoor camping equipment, etc.

[0148] The following examples are for illustrative purposes of the present invention and are not limiting.

Examples

[0149] [Example 1] <Sugar fatty acid ester formulation> SEFOSE (registered trademark) is liquid at room temperature, and all coatings / emulsions containing this material were applied at room temperature using a bench-top type drawdown apparatus. The type and size of the rod were changed to produce various coat weights.

[0150] (Formulation 1) 50 ml of SEFOSE® was added to a solution containing 195 ml of water and 5 grams of carboxymethyl cellulose (FINNFIX® 10; CP Kelco, Atlanta, GA). The formulation was mixed for 1 minute using a Silverson homogenizer set at 5000 rpm. This emulsion was coated onto a 50-gram base sheet made of bleached hardwood pulp and an 80-gram sheet composed of unbleached softwood. Both papers were placed in an oven (105 °C) for 15 minutes to dry. After removing from the oven, the sheets were placed on a bench and 10 drops of water (room temperature) were added to each sheet with a pipette. The base sheet selected for this test immediately absorbs the water droplets, but it was observed that for the sheets coated with various amounts of SEFOSE®, the level of water resistance increased as the coat weight increased (see Table 1).

[0151]

Table 1

[0152] It was observed that water resistance was lacking in the heavier sheets and that water resistance was not achieved if the sheets were not dry.

[0153] (Formulation 2) Addition of SEFOSE® to the cup stock: (Note that this is a single-layer stock without MFC treatment. 110-gram paperboard made from eucalyptus pulp). 50 grams of SEFOSE® was added to 200 grams of 5% heat-ethylated starch (Ethylex 2025) and stirred for 30 seconds using a bench-top Kadimill. The paper samples were coated and placed in an oven at 105 °C for 15 minutes. 10 - 15 test droplets were placed on the coated side of the paperboard and the water hold-out time was measured and recorded in the table below. Water penetration of the untreated paperboard control was instantaneous (see Table 2).

[0154]

Table 2

[0155] (Complex 3) Pure SEFOSE® was warmed to 45 °C and placed in a spray bottle. A uniform spray was applied to the paper stock listed in the previous example, as well as to a single piece of fiberboard and a quantity of cotton cloth. When water droplets were placed on the samples, penetration into the substrate occurred within 30 seconds, but after drying in an oven at 105 °C for 15 minutes, the water droplets evaporated before being absorbed into the substrate.

[0156] Ongoing investigations were related to whether SEFOSE® could be compatible with compounds used in oil-resistant and greasiness coatings. SEFOSE® was useful for improving water resistance and rigidity. To conduct the rigidity test, 240 g of paperboard stock was used. The results are shown in Table 3. These data were obtained at a single coat weight of 5 grams per square meter, and the average of five samples is reported. The results are in Taber rigidity units, recorded using the inventors' V-5 Taber rigidity tester model 150-E.

[0157]

Table 3

[0158] [Example 2] <Binding of Sugar Esters to Cellulosic Substrates> To determine whether SEFOSE® binds reversibly to cellulosic materials, pure SEFOSE® was mixed with pure cellulose in a 50:50 ratio. SEFOSE® was reacted at 300 °F for 15 minutes, and the mixture was extracted with methylene chloride (a nonpolar solvent) or distilled water. The samples were refluxed for 6 hours, and a gravimetric analysis of the samples was performed.

[0159]

Table 4

[0160] [Example 3] <Investigation of the Cellulose-based Surface> Scanning electron microscope images of the base paper with and without MFC indicate that a base with fewer pores has the potential to require much less waterproofing agent reacting on the surface. Figures 1 and 2 show untreated Whatman filter paper with void fraction. Also, Figures 1 and 2 show that the exposed surface area where the derivatizing agent can react is relatively large. On the other hand, it is also shown that there are sufficient places for water to escape in the highly porous sheet. Figures 3 and 4 show a comparison of paper made from recycled pulp before and after coating with MFC (they are two magnifications of the same sample, and the left side of the image clearly does not contain MCF). Tests show that derivatization of sheets with far fewer pores shows higher promise for long-term water / vapor barrier performance. The last two images are a precise close-up of the average "pores" of a single filter paper and a precise close-up of CNF-coated paper taken at the same magnification for comparison.

[0161] From the above data, it became clear that at the critical point, with the addition of more materials, the performance correspondingly improved. Without being bound by any theory, it seems that the reaction is faster in unbleached paper, suggesting that the presence of lignin may promote the reaction.

[0162]

[0163] [Example 4] 「Phluphi」 Liquid SEFOSE® was mixed and reacted with bleached hardwood fibers to produce various forms that created a waterproof handcrafted sheet. When sucrose esters were mixed with pulp before sheet formation, most of it was found to be retained with the fibers. With sufficient heating and drying, a brittle and fluffy but highly hydrophobic handcrafted sheet was formed. In this example, 0.25 grams of SEFOSE® was mixed with 4.0 grams of bleached hardwood fibers in 6 liters of water. This mixture was manually stirred and the water was poured into a standard handcrafted sheet mold. The resulting fiber mat was removed and dried at 325°F for 15 minutes. The produced sheet exhibited significant hydrophobicity and greatly reduced hydrogen bonding between the fibers themselves (a water contact angle greater than 100 degrees was observed). Emulsifiers could be added and the ratio of SEFOSE® to fiber could be about 1:100 to 2:1.

[0164] Subsequent tests showed that talc was the only spectator in this case and was removed from further tests.

[0165] [Example 5] <Environmental Effects on SEFOSE® Coating Properties> As an attempt to better understand the reaction mechanism between sucrose esters and fibers, a low-viscosity coating was applied to a bleached kraft sheet that had wet strength resin added but no water resistance (no sizing). All coatings were measured using a Brookfield viscometer at 100 rpm and had a viscosity of less than 250 cps.

[0166] SEFOSE® was emulsified with Ethylex 2025 (starch) and applied to paper via a gravure roll. For comparison, SEFOSE® was also emulsified with Westcote 9050 PvOH. As shown in Figure 5, the oxidation of the double bonds in SEFOSE® is enhanced by heat and the presence of additional chemical environments that enhance its oxidative chemical properties (see also Table 5).

[0167]

Table 5

[0168] [Example 6] [Effect of unsaturated fatty acid chain on saturated fatty acid chain] SEFOSE (registered trademark) was reacted with bleached softwood pulp, dried, and formed into a sheet. Then, CH 2 Cl 2 , toluene, and water were used for extraction to determine the degree of reaction with the pulp. Extraction was carried out for at least 6 hours using a Soxhlet extraction glass apparatus. The extraction results are shown in Table 6.

[0169] [Table 6]

[0170] The data showed that essentially all of SEFOSE (registered trademark) remained in the sheet. To further verify, the same procedure was carried out with pulp alone, and it was found from the results that about 0.01 g was obtained per 10 g of pulp. Without being bound by any theory, this can be easily explained as residual pulping chemicals that were not completely removed or more likely extracts.

[0171] The experiment was repeated using pure cellulose fibers (e.g., α - cellulose from Sigma Aldrich (St. Louis, MO)). As long as the loading level of SEFOSE (registered trademark) remained less than about 20% of the mass of the fibers, more than 95% of the mass of SEFOSE (registered trademark) was retained with the fibers and was not extracted by either polar or non - polar solvents. Without being bound by any theory, optimizing the baking time and temperature may further enhance the sucrose ester remaining with the fibers.

[0172] It has been found that, generally, SEFOSE® cannot be extracted from the material after drying. On the other hand, when fatty acids containing all saturated fatty acid chains (e.g., OLEAN® available from Procter & Gamble Chemicals (Cincinnati, OH)) are used instead of SEFOSE®, almost 100% of the OLEAN® in the material can be extracted using hot water (at 70 °C or higher). OLEAN® is identical to SEFOSE®, except that the only change is that saturated fatty acids are bonded (in OLEAN®) instead of unsaturated fatty acids being bonded (in SEFOSE®).

[0173] Another aspect worthy of note is that multiple fatty acid chains are reactive with cellulose and two sugar molecules in the structure, resulting in SEFOSE® forming a rigid crosslinked network, leading to an improvement in the strength of fiber webs such as paper, paperboard, airlaid and wet nonwovens, and textiles.

[0174] [Example 7] <Addition of SEFOSE® to Achieve Water Resistance> Using both hardwood and softwood kraft pulp, 2-gram and 3-gram hand-made sheets were produced. When SEFOSE® was added to the 1% pulp slurry at a level of 0.1% or more and the water was drained to form the hand-made sheet, SEFOSE® was retained with the fibers, imparting water resistance. With 0.1% - 0.4% of SEFOSE®, the water became beaded on the surface in less than a few seconds. When the SEFOSE® loading exceeded 0.4%, the water resistance time increased rapidly to several minutes and then to several hours towards a loading rate level higher than 1.5%.

[0175] [Example 8] <Production of Bulky Fiber Materials> When SEFOSE (registered trademark) was added to the pulp, it softened the fibers, increased the space between them, and caused them to become bulky. For example, when a 3% slurry of softwood pulp containing 125 g (dry state) of pulp was drained and dried, it was found to occupy a volume of 18.2 cubic centimeters. 12.5 g of SEFOSE (registered trademark) was added to a similar 3% softwood pulp slurry containing an equal amount of 125 g of dry fibers. When drained and dried, the resulting mat occupied 45.2 cubic centimeters.

[0176] 30 g of standard bleached softwood kraft pulp (manufactured by Old Town Fuel and Fiber, LLC, Old Town, ME) was sprayed with SEFOSE (registered trademark) warmed to 60 °C. This 4.3 cm 3 was placed in a disintegrator at 10,000 rpm and essentially repulped. The mixture was poured through a hand-laid sheet mold and dried at 105 °C. The resulting hydrophobic pulp occupied a volume of 8.1 cm 3 This material was cut into 2-inch squares and placed in a hydraulic press, and a pressure of 50 tons was applied for 30 seconds. Although the volume of the squares was significantly reduced, it still occupied 50% more volume than similar 2-inch squares cut for the control without pressure applied.

[0177] It is also important that not only an increase in bulk and softness was observed, but also that a fiber mat was obtained in which all of the hydrophobicity was retained by the forced repulped mat when drained. Such a quality is valuable in addition to the finding that water cannot easily "push through" the low surface energy barrier and enter the sheet. A single fatty acid chain bond of hydrophobicity does not exhibit this property.

[0178] While not being restricted by any theory, this shows additional evidence that SEFOSE (registered trademark) reacts with cellulose and the OH groups on the surface of cellulose fibers are no longer available for subsequent hydrogen bonding. Other hydrophobic materials interfere with the initial hydrogen bonding, but during repulping, this effect is reversed and the OH groups of cellulose are free to participate in hydrogen bonding during redrying.

[0179] [Example 9] <Paper bag test data> The following table (Table 7) shows the properties imparted by coating unbleached kraft bag stock (control) with a mixture of 5 - 7 g / m 2 of SEFOSE (registered trademark) and polyvinyl alcohol (PvOH). Also included for reference are commercially available bags.

[0180]

Table 7

[0181] As shown in the table, coating the control base paper with SEFOSE (registered trademark) and PvOH increased the tensile and burst strength.

[0182] [Example 10] <Wet / dry tensile strength> Three - gram handmade sheets were made from bleached pulp. Below, the wet and dry tensile strengths were compared at different addition levels of SEFOSE (registered trademark). Note that in these handmade sheets, SEFOSE (registered trademark) was not emulsified in any coating, but simply mixed into the pulp and drained without adding other chemical properties (see Table 8).

[0183]

Table 8

[0184] Also note that for the wet strength, with a 5% addition, it does not fall much below the dry strength of the control.

[0185] [Example 11] [Use of esters containing less than eight saturated fatty acids] Several experiments were conducted using sucrose esters in which less than eight fatty acids were bonded to the sucrose moiety. Samples of SP50, SP10, SP01 and F20W (Sisterna, The Netherlands) contain 50%, 10%, 1%, and essentially 0% monoesters, respectively. These commercial products are made by reacting sucrose with saturated fatty acids, which renders them no longer useful for further crosslinking or useful for similar chemical properties, but useful when investigating emulsifying and water repellent properties.

[0186] For example, 10 g of SP01 was mixed with 10 g of glyoxal in a 10% heated PvOH solution. The mixture was "heated" at 200 °F for 5 minutes and applied by drawdown onto a porous base paper made from bleached hardwood kraft. The result was a crosslinked wax-based coating on the surface of the paper that exhibited good hydrophobicity. When applying a minimum of 3 g / m 2 The contact angle obtained was greater than 100°. Since glyoxal is a well-known crystallization agent used with compounds having OH groups, this method is a promising means of attaching fairly non-reactive sucrose esters to the surface by bonding the remaining alcohol groups of the sucrose ring to available alcohol groups in the substrate or other coating materials.

[0187] [Example 12] [HST data and moisture absorption] To demonstrate that waterproof properties are observed with SEFOSE® alone, porous Twins River (Matawaska, ME) base paper was treated with various amounts of SEFOSE® (and PvOH or Ethylex 2025 which is emulsified and applied by drawdown) and assayed in the Hercules sizing test. The results are shown in Table 9.

[0188]

Table 9

[0189] As shown in Table 9, the water resistance increased (as indicated by the increase in HST (unit: second)) with the increase in SEFOSE (registered trademark) applied to the surface of the paper.

[0190] This was also observed when using the coating of the saturated sucrose ester product. As a specific example, the product F20W (available from Sisterna, The Netherlands) is described as having a very low monoester % in most of the molecules in the 4 - 8 substitution range. It should be noted that when a stable emulsion was prepared using the F20W product and PvOH in equal parts by volume, the impregnation amount of the F20W product was only 50% of the total coating. Thus, when the impregnation amount is labeled as "0.5 g / m 2 ", there is also PvOH with a similar impregnation amount, and a total impregnation amount of 1.0 g / m 2 is obtained. The results are shown in Table 10.

[0191]

Table 10

[0192] As shown in Table 10, the water resistance of the porous sheet increased with the increase in F20W. Therefore, the applied sucrose fatty acid ester itself makes the paper water - resistant.

[0193] Since the water resistance is not simply due to the presence of fatty acids that form ester bonds with cellulose, SEFOSE (registered trademark) was loaded onto the softwood hand - made sheet (bleached softwood kraft), and oleic acid that forms an ester bond with cellulose in the pulp was directly added to the pulp. The mass at time 0 represents the "bone - dry" mass of the hand - made sheet taken out from an oven at 105°C. The sample was placed in a humidity - controlled chamber maintained at RH50%. The change in mass was recorded over time (unit: minute). The results are shown in Table 11 and Table 12.

[0194]

Table 11

[0195]

Table 12

[0196] It should be noted that the difference here when oleic acid is directly added to the pulp to form an ester bond is that it greatly slows down moisture absorption. In contrast, as little as 2% SEFOSE® slows down moisture absorption, and at higher concentrations, SEFOSE® does not slow it down. Without being bound by any theory, the structure of the SEFOSE® binder should not be explainable by the structure formed by simple fatty acid esters and cellulose alone.

[0197] [Example 13] <Saturated SFAE> The class of saturated esters is a waxy solid at room temperature and, being saturated, is less reactive with the sample matrix or itself. When used at high temperatures (e.g., at least 40°C for all tested ones, above 65°C), these materials melt and can be applied as a liquid, then cooled and solidified to form a hydrophobic coating. Alternatively, these materials can be emulsified in solid form and applied as an aqueous coating to impart hydrophobic characteristics.

[0198] The data shown here represent the HST (Hercules size test) readings obtained from papers coated with various amounts of saturated SFAE.

[0199] The #45 bleached hardwood kraft sheet obtained from Turner Falls paper was used for the test coating. The Gurley porosity was measured at about 300 seconds, representing a fairly tight base sheet. S-370 obtained from Mitsubishi Foods (Japan) was emulsified with xanthan gum (up to 1% of the mass of the saturated SFAE formulation) before coating.

[0200] Coating weight of saturated SFAE complex (pounds per ton) HST (average of 4 measurements per sample).

[0201]

Table 13

[0202] The experimental data obtained also confirmed that a limited amount of saturated SFAE may enhance the water resistance of coatings designed for other purposes / applications. For example, blending saturated SFAE with coatings based on Ethylex starch and polyvinyl alcohol resulted in an increase in water resistance in all cases.

[0203] The following examples were coated on #50 bleached recycled base with a Gurley porosity of 18 seconds.

[0204] 100 grams of Ethylex 2025 was heated at 10% solids (1 liter by volume), 10 grams of S-370 was added while hot, and mixed using a Silverson homogenizer. The resulting coating was applied using a common bench-top drawdown apparatus, and the paper was dried under a heating lamp.

[0205] At a coating weight of 300 # / ton, starch alone had an average HST of 480 seconds. For a mixture of starch and saturated SFAE at a similar coating weight, the HST increased to 710 seconds.

[0206] Sufficient polyvinyl alcohol (Selvol 205S) was dissolved in hot water to form a 10% solution. When this solution was coated on #50 paper as above, the average HST was 225 at a coating weight of 150 pounds / ton. Using such a similar solution and adding S-370 formed a mixture containing 90% PVOH / 10% S-370 on a dry weight basis (i.e., 90 ml of water, 9 grams of PvOH, 1 gram of S-370). The average HST increased to 380 seconds.

[0207] Saturated SFAE is compatible with prolamin (specifically, zein; see U.S. Patent No. 7,737,200, which is incorporated herein by reference in its entirety). One of the main barriers to the commercial production of the subject matter of the patent is that the formulation is water-soluble, so the addition of saturated SFAE serves in this form.

[0208] [Example 14] <Other saturated SFAE> The size press evaluation of the saturated SFAE-based coating was performed on a bleached lightweight sheet (about 35#) without sizing and with relatively poor formation. All evaluations were carried out using Exceval HR 3010 PvOH heated to emulsify the saturated SFAE. Sufficient saturated SFAE was added to account for 20% of the total solids. Samples of S-370 vs. C-1800 (available from Mitsubishi Foods (Japan)) were focused on for evaluation. Both of these esters performed better than the control. Table 14 shows some of the important data.

[0209]

Table 14

[0210] The saturated compounds appear to result in an increase in the kit, and it should be noted that both S-370 and C-1800 have an increase in HST of approximately 100%.

[0211] [Example 15] <Wet strength additive> Laboratory tests have shown that the chemical properties of sucrose esters can be adjusted to achieve various characteristics, including their use as wet strength additives. When sucrose esters are prepared by bonding saturated groups to each alcohol functional group of sucrose (or other polyols), the result is a hydrophobic wax-like substance that is poorly miscible / soluble in water. Although adding these compounds to cellulose-based materials can impart water resistance either internally or as a coating, they do not chemically react with each other or with any part of the sample matrix and are thus easily removed by solvents, heat, and pressure.

[0212] When higher levels of water repellency and water resistance are desired, sucrose esters containing unsaturated functional groups are prepared and added to cellulose-based materials with the aim of fixing the sucrose esters in the matrix and achieving oxidation and / or crosslinking that will help make them highly resistant to removal by physical means. By adjusting the number and size of the unsaturated groups in the sucrose esters, means are obtained for crosslinking molecules that are not optimal for imparting water resistance but are used to impart strength.

[0213] The data presented here were obtained by adding SEFOSE® at various levels to bleached kraft sheets and obtaining wet tensile data. The percentages shown in the table represent the sucrose ester (%) of the treated 70# bleached paper (see Table 15).

[0214]

Table 15

[0215] The data show that when unsaturated sucrose esters are added to paper, the wet strength tends to increase as the loading level increases. Dry tensile is shown relative to the maximum strength of the sheet.

[0216] [Example 16] <Method for Producing Sucrose Esters Using Acid Chlorides> In addition to producing hydrophobic sucrose esters via transesterification, similar hydrophobicity in fibrous articles could be achieved by reacting acid chlorides directly with polyols containing a ring structure similar to sucrose.

[0217] For example, 200 grams of palmitoyl chloride (CAS 112 - 67 - 4) was mixed with 50 grams of sucrose at room temperature. After mixing, the mixture was brought to 100°F and maintained at that temperature overnight (ambient pressure). The resulting material was washed with acetone and deionized water to remove any unreacted or hydrophilic materials. Analysis of the remaining material using C - 13 NMR showed that a significant amount of hydrophobic sucrose esters had been produced.

[0218] It has been shown that adding fatty acid chlorides to cellulosic materials can impart hydrophobicity (BT3 and others), but the reaction itself causes several problems including the corrosive gaseous HCl by - product released, which is undesirable in the field as it is harmful to workers and the surrounding environment. One additional problem caused by the generation of hydrochloric acid is that as more is formed, i.e., as more polyol sites react, the fiber composition becomes weaker. Palmitoyl chloride was reacted with cellulose and cotton materials while increasing their amounts. As the hydrophobicity increased, the strength of the articles decreased.

[0219] The above reaction was repeated several times using 200 grams of R - CO - chloride reacted with 50 grams each of other similar polyols including corn starch, xylan from birch, carboxymethyl cellulose, glucose, and extracted hemicellulose.

[0220] [Example 17] <Peel Test> The peel test measures the force required to peel tape from the surface of paper as an angle of reproducibility, using a wheel between the two jaws of a tensile tester (ASTM D1876; e.g., 100 Series Modular Peel Tester, TestResources, Shakopee, MN).

[0221] For this work, bleached kraft paper derived from Turners Falls paper (Turners Falls, MA) with a high Gurley (600 seconds) was used. This #50 pound sheet represents a fairly tight but highly absorbent sheet.

[0222] When the #50 pound paper was coated with 15% Ethylex starch as a control, the average force required (for five samples) was 0.55 pounds per inch. When treated with a similar coating (thus, 25% impregnation with SEFOSE® instead of 25% Ethylex starch and 75% still Ethylex), the average force decreased to 0.081 pounds per inch. When SEFOSE® was used instead of 50% of Ethylex, the force required decreased to less than 0.03 pounds per inch.

[0223] Paper preparation followed TAPPI standard method 404 for determining the tensile strength of paper.

[0224] Finally, similar paper was used with S-370 at a loading rate of 750 pounds per ton. This effectively fills all the pores of the sheet and forms a complete physical barrier. Indeed, this passes the TAPPI kit 12 in-plane. This short experiment shows that it is possible to obtain grease resistance using a saturated SFAE variant.

[0225] [Example 18] [Saturated SFAE and Inorganic Particles (Filler)] Saturated sucrose fatty acid esters range from hydrophilic to hydrophobic depending on the number (and chain length) of fatty acid chains attached to the sucrose molecule. These are not considered highly reactive compounds.

[0226] A variety of substituted SAFEs with side chains 16 or 18 carbon atoms in length have been investigated. The materials investigated are waxy solids with a melting point below 150 °C. When coated on paper, highly substituted esters impart a significant level of water resistance depending on the coating weight and sheet porosity. Finally, similar paper was used with S-370 at a loading rate of 750 pounds per ton. This effectively fills all the pores of the sheet and forms a complete physical barrier. The paper so treated was found to have a TAPPI kit 12. This short-term experiment shows that it is possible to obtain grease resistance using saturated SFAE variants.

[0227] (Observation results) More hydrophobic esters tend to aggregate in aqueous emulsions / dispersions, making it difficult to achieve a uniform coating on paper.

[0228] The low melting point of many of these molecules results in "penetration" of the coating into the sheet.

[0229] When hydrophobic SAFEs are mixed with polymers to aid in the stabilization of the dispersion, these polymers (i.e., latex, starch, polyvinyl alcohol) tend to surround these esters in such a way as to weaken the desired hydrophobic properties.

[0230] When mixed with calcium carbonate (e.g., precipitated calcium carbonate), unexpected attractions are observed. SAFE does not penetrate into the paper under similar drying conditions.

[0231] Calcium carbonate is thought to aid in the dispersion of SAFE, and the adhesion is such that SAFE acts as a binder to bind the calcium carbonate particles to the surface of the coated paper. This uniform dispersion is thought to result in enhanced water resistance for a given amount of ester.

[0232] [Example 18] <Pigment-containing coating formulation> (Method) Analysis of SEFOSE® with a number of MALLARDCREEK samples (TYKOTE® 1019, 1004, 6160, 1005, 6152) and DOW 620® as well as some BASF samples is thought to support the chemical compatibility of the latex with SEFOSE®. The order of addition is not considered important and the viscosity is not thought to change significantly.

[0233] (Cup paper stock) MALLARD CREEK TYKOTE® 1019 was blended with IMERYSLX® clay slurry. SEFOSE® was blended into this mixture and the resulting ratios were latex: 70%, LX® clay: 20%, SEFOSE®: 10% (top coating) or 75%, GCC: 75%, SEFOSE®: 3%, TYKOTE® 1019: 21.5% (base coating). The base coating blend had a pH of about 7.6, a viscosity of 215 cps, and a solids content of 60 - 70%. The top coating had a pH of 7.8, a solids content of about 57%, and a viscosity of about 240 cps. The reported coating weight was approximately 8 g / m 2 when applied via a blade to a pre-coated board paper. Rolls of hot cup stock, cold cup stock, and cup bottom stock were made with two different coatings.

[0234] Table 16 shows the effect on the cob value of SEFOSE® curing in a pigment-containing coating formulation.

[0235]

Table 16

[0236] As shown in the table, when SEFOSE (registered trademark) (10% by weight) was added to the coating of the latex-coated paperboard having 39 cob values, the number decreased to 3.

[0237] SEFOSE (registered trademark) is not considered an effective film-forming agent to the same extent as latex. Therefore, without being bound by theory, it is assumed that latex forms a barrier film and SEFOSE (registered trademark) acts synergistically by adding hydrophobicity to any voids / pinholes in the latex film.

[0238] (Plastic substrate) To further understand the cob effect, a plastic substrate was coated with DOW620 (registered trademark) latex, dried (on the plastic substrate), and the cob was measured (cob value = 10.5). This data point reflects the fact that the cob reading is affected not only by the water that penetrates the paper itself, but also by the fact that water soaks or is absorbed by the coating itself. When this experiment was repeated by adding 10% SEFOSE (registered trademark) to the latex (also coating on the plastic substrate), the cob value dropped to 3.8, reflecting the hydrophobicity in the film itself.

[0239] [Example 19] <Anti-blocking effect> To determine the anti-blocking effect of SFAE on latex, a series of tests were conducted using a paper substrate. The test paper substrates were either lightweight OGR sheets, 35# or 18pt cup stock, or bleached kraft. All papers were about 9 g / m 2Coating was performed using a bench-top draw-down device at the coating weight of

[0240] Each test was performed using 1 square inch samples, simulating blocking conditions more suitable from the front to the back while the coated sides faced each other. Blocking was judged using a 5-point scale as follows.

[0241] 5 = Complete blocking. The paper cannot be completely separated.

[0242] 4 = Significant blocking. It is difficult to separate the paper, and fibers tear when separating.

[0243] 3 = Moderate blocking. It is difficult to separate the paper, and there is damage to the coating, including slight fiber tearing when separating.

[0244] 2 = Slight blocking. The paper separates quite easily, but the coating adheres noticeably to itself.

[0245] 1 = The paper separates easily without damaging the coating. There may be some slight adhesion near the edges.

[0246] 0 = Adhesion is zero.

[0247] As shown in Table 17, when SFAE was added, the degree of blocking decreased significantly for both SB latex and SA latex, and the folding and 3M kit values remained unchanged.

[0248]

Table 17

[0249] Tests showing resistance to blocking over various pressures and times can be seen in Figures 8 and 9.

[0250] Figure 8 shows the effect of SFAE on the degree of blocking as a function of the clamp pressure (in the range of 500 - 900 psi) at 100 °C for SB. As shown in Figure 8, SFAE combined with SB completely prevented blocking (showing a blocking point of about 1 - 1.5), while SB alone showed moderate to complete blocking (showing a blocking point of about 3.5 - 5) over the same clamp pressure range.

[0251] Figure 9 shows the effect of SFAE on the degree of blocking as a function of the clamp time at 100 °C for SA. Again, as can be seen in Figure 9, in the absence of SFAE, the latex showed low resistance to blocking (upper right, oval cluster), while in the presence of SFAE, it showed significant resistance to blocking (lower circle).

[0252] The results show that for both SB or SA latex, the addition of SFAE achieves the following three important properties required for an effective barrier coating: 1) prevent foreign substances from passing through the surface (e.g., maintaining the 3M kit); 2) resist cracking when the substrate containing the coating is bent suddenly (i.e., maintain foldability); and 3) resist blocking.

[0253] [Example 20] <Determination of Blocking Evaluation> To determine the blocking assessment for combinations of SFAE-polymers, esters are mixed with polymers over a variety of concentrations from about 60% SFAE to 40% polymer to about 3% SFAE to 97% polymer on a dry matter basis. The various mixtures are then applied as a coating to cover at least one surface of a paper substrate sample. Either the opposing coated surfaces of the sample or the coated surface and the uncoated surface of the sample are brought into contact with each other, maintaining one or more process variables (e.g., time, pressure, temperature) constant while simultaneously selecting other process variables to vary over a specific range. The blocking resistance for each set of conditions is determined as described in Example 19, and the data is tabulated or plotted. As a control, a comparison is made with a composition without SFAE, and at the same time, the amount of polymer is similarly maintained on a dry matter basis over the concentration range being tested. Barrier properties (e.g., water resistance, oil resistance, and grease resistance, folding, etc.) are also determined.

[0254] Based on the data created for any series of SFAE-polymer combinations, conditions were identified for effectively adjusting the adhesion properties of barrier coatings made from such combinations for various applications.

[0255] Although the invention has been described with reference to the above embodiments, it will be understood that modifications and variations are included within the spirit and scope of the invention. Accordingly, the invention is limited only by the following claims. All references cited herein are hereby incorporated by reference in their entirety as part of this specification.

Claims

1. A barrier coating composition consisting essentially of at least one sugar fatty acid ester (SFAE) and a polymer, wherein the polymer is selected from the group consisting of latex, polyvinyl acetate, ethylene vinyl acetate, and combinations thereof, wherein the at least one SFAE is present in the composition at 0.1% to 99% of the mixture of the SFAE and the polymer on a dry matter basis, wherein the polymer is present in the composition at 0.1% to 99% of the mixture of the SFAE and the polymer on a dry matter basis, the composition when applied to a substrate, when tested according to ASTM D2979, has a reduced tack of the polymer without negatively affecting the barrier function of the coating as compared to a similar composition except for the absence of the sugar fatty acid ester. A barrier coating composition.

2. The barrier coating composition according to claim 1, wherein the coated substrate exhibits improved foldability.

3. The barrier coating composition according to claim 1, wherein the polymer is latex.

4. The barrier coating composition according to claim 1, wherein the sugar fatty acid ester is a sucrose fatty acid ester.

5. The barrier coating composition according to claim 1, wherein the sugar fatty acid ester comprises a saturated fatty acid moiety, an unsaturated fatty acid moiety, or a combination thereof.

6. The barrier coating composition according to claim 1, wherein the at least one sugar fatty acid ester comprises a saturated sucrose fatty acid ester, and further wherein the sucrose fatty acid ester comprises a monoester content of about 10% to about 25%.

7. The barrier coating composition according to claim 1, wherein the SFAE is a saturated SFAE.

8. The barrier coating composition according to any one of claims 1, 3, and 7, wherein the composition is a non-tacky polymer composition.

9. A manufactured article comprising the non-tacky polymer according to claim 8.

10. A method for making a polymer non-sticky, comprising the step of mixing a sugar fatty acid ester (SFAE), a polymer, and an optional one or more non-sticking agents, wherein the polymer is selected from the group consisting of styrene-butadiene latex, styrene-acrylate latex, carboxylated styrene-butadiene latex, oligomer-stabilized styrene-acrylic copolymer latex, surfactant-stabilized styrene-acrylic copolymer latex, polyvinyl acetate, ethylene-vinyl acetate, and combinations thereof, the SFAE is present at 0.1% to 99% of the mixture of the SFAE and the polymer on a dry matter basis, and the polymer is present at 0.1% to 99% of the mixture of the SFAE and the polymer on a dry matter basis.

11. The method according to claim 10, wherein the one or more non-sticking agents are selected from the group consisting of mica, talc, calcium carbonate, white carbon, or corn starch, Dioscorea powder, titanium dioxide, silica powder, alumina, metal oxides, diatomaceous earth, and combinations thereof.

12. The method according to claim 10, further comprising the step of applying the mixture to a substrate and determining the blocking degree of the polymer.

13. The method according to claim 12, wherein the coating is applied to the entire outer surface of the substrate, the entire inner surface of the substrate, or a combination thereof, or the coating is applied to the substrate by masking.

14. The method according to claim 12, wherein the substrate comprises a cellulose-based material.

15. The barrier function is selected from the group consisting of oil resistance, grease resistance, water resistance, moisture resistance, ozone resistance, and combinations thereof, according to the method of claim 12. ２ ​

16. A method for manufacturing a heat-sealed product, comprising: a) applying the barrier coating composition according to claim 1 to the surface of a substrate to coat the surface; b) exposing the coated substrate to a first condition, wherein the heat and pressure applied in the first condition result in adhesion to the polymer in the absence of the SFAE; c) collecting the exposed substrate; d) contacting the surface of the collected exposed substrate with the opposite surface of a separate collected exposed substrate or the surface of an uncoated substrate; e) exposing the two contacted surfaces to a second condition, wherein the heat and pressure applied in the second condition result in adhesion to the polymer in the presence of the SFAE and form a seal between the two contacted surfaces; comprising; the polymer is selected from the group consisting of latex, polyvinyl acetate, ethylene vinyl acetate, and combinations thereof; the at least one SFAE is present at 0.1% to 99% by dry matter basis of the mixture of the SFAE and the polymer; the polymer is present at 0.1% to 99% by dry matter basis of the mixture of the SFAE and the polymer. **Claim 17** The method according to claim 16, wherein the composition is applied to partially coat the surface of the substrate. **Claim 18** The SFAE is present at 0.1% to 1%, 1% to 5%, 5% to 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, 95%, or 99% by dry matter basis of the mixture, and / or the polymer is present at 0.1% to 1%, 1% to 5%, 5% to 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, 95%, or 99% by dry matter basis of the mixture, of the barrier coating composition according to any one of claims 1 and 8, the article of manufacture according to claim 9, the method according to claim 10, and the method according to claim 16.

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