阅读说明：本技术 多元醇脂肪酸酯载体组合物 (Polyol fatty acid ester carrier compositions ) 是由 J·斯宾德 M·A·比洛多 S·米凯尔 于 2020-01-24 设计创作，主要内容包括：本发明描述了用含有蔗糖脂肪酸酯的颗粒(载体系统)处理纤维状纤维素材料的方法,所述颗粒使得能进行表面改性,包括使所述表面具有耐水性和/或耐油/油脂性。所公开的方法提供将至少一种糖脂肪酸酯(SFAE)与聚合物(例如胶乳)组合以形成胶束颗粒,并将这种颗粒施加到包括纤维状纤维素基材料(例如纸浆)的基材以形成尤其是模制品。还公开了包含SFAE、胶乳和任选的矿物或其他添加剂的组合的组合物。(The invention describes a method for treating fibrous cellulose material with particles (carrier system) containing sucrose fatty acid esters, which particles enable surface modification, including imparting water and/or oil/grease resistance to the surface. The disclosed method provides for combining at least one Sugar Fatty Acid Ester (SFAE) with a polymer (e.g., latex) to form micellar particles, and applying such particles to a substrate comprising a fibrous cellulose-based material (e.g., pulp) to form, inter alia, a molded article. Also disclosed are compositions comprising a combination of SFAE, latex, and optionally minerals or other additives.)

1. A method of producing a molded cellulose-containing article comprising:

adding an emulsion or slurry to a cellulosic fiber furnish, wherein the emulsion or slurry comprises one or more sucrose fatty acid esters and one or more carrier particles;

draining the furnish through one or more screens or screens;

hot forming the mixture into a product in a mold; and

the product is peeled off from the mould,

wherein the product exhibits water, oil and/or grease resistance as compared to a cellulosic product not treated with the emulsion or slurry.

2. The method of claim 1, wherein the product is a bowl, tray, bottle, bag, packaging container, or insert.

3. The method of claim 1, wherein the carrier is selected from the group consisting of sucrose fatty acid esters, polymers, solid latex polymer beads, hollow polymer shells, resin beads, pigment particles, and combinations thereof.

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

5. The method of claim 1, wherein the pellets further comprise uncooked corn starch, rice starch, wheat starch, potato starch, or tapioca starch pellets, oat hulls, rice hulls, ground nut shells, or combinations thereof.

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

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

8. The method of claim 1, wherein the support is a polymer, and wherein the polymer exhibits a low glass transition temperature.

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

10. The method of claim 9, wherein the product exhibits reduced stickiness.

11. A composition comprising sucrose fatty acid ester particles, said particles comprising one or more loading materials.

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

13. The composition of claim 11, further comprising thymol, lecithin, alkyl glucosides, and combinations thereof.

14. The composition of claim 11, wherein the particle is a micelle, microcapsule, or nanocapsule.

15. The composition of claim 11, wherein the sucrose fatty acid ester is a mono-or di-ester.

16. The composition of claim 11, wherein said sucrose fatty acid ester comprises both saturated fatty acids or a mixture of saturated and unsaturated fatty acids.

17. The composition of claim 11, wherein the fatty acid ester particles comprise one or more sucrose fatty acid esters.

18. An emulsion comprising the composition of claim 11.

19. The emulsion of claim 18, wherein the one or more load bearing materials comprise latex.

20. An article produced by the method of claim 1.

Technical Field

The present invention relates generally to the treatment of fiber-containing substrates, and more particularly to the treatment of such substrates with particles comprising a combination of Sugar Fatty Acid Esters (SFAE) with polymers (e.g., latex) and optionally minerals, including compositions containing such combinations. In particular, the invention relates to the use of said particles as a carrier for coatings and to a method of applying the carrier coating to produce barrier properties on moulded products made from said substrate.

Background information

In general, raw materials for manufacturing cellulose fiber-based molded products may include wheat, wheat straw, wood, bagasse, reed, and edge paper (edge paper). The material is slurried by a hydrodynamic pulping process to form a mixture, which can then be cured on a metal mold. Subsequently, surface treatment with water-soluble acrylic, latex, resin, or coating agent containing EVA (ethyl vinyl acetate) may be performed.

Over the past decade, these methods have included (a) selecting non-toxic, chaff-rich materials, including straw, grain, waste residues and starch-rich plants; (b) washing the raw material with much chaff with water to remove dust, soil and pollutants; (c) centrifugal drying; (d) grinding the raw materials with much coarse bran into powder; (e) uniformly mixing the powder with an additive premix and water to form a mixture, the additive premix containing a specific edible gum, a sulfate, a stearic acid, and a treating agent, wherein the specific edible gum consists of a latex, a pectin, and a protein gel, and the treating agent consists of a specific edible gum, calcium chloride, and alum; (f) thermoforming the mixture into a product; (g) stripping the product from the mold; and (h) drying (see, e.g., taiwan patent publication No. 500746, herein incorporated by reference).

More recent methods include: (a) separately preparing pulp using a first auxiliary agent containing an anionic substance (e.g., an aluminum silicate and a natural wax emulsion) and a second auxiliary agent containing a nonionic and cationic substance (e.g., a fluorochemical series resin, a polymer compound, an aliphatic polyamine, and an alkylacryloyl copolymer); (b) uniformly mixing paper pulp, a first auxiliary agent and water to form a paper pulp premix; (c) mixing a second aid with the pulp pre-mix to form a pulp mixture; and (d) thermoforming the pulp mixture to form a packaging material (see, e.g., U.S. publication No. 20050211405, incorporated herein by reference).

While the latter approach is effective for creating water/oil resistance on fiber-based substrates/surfaces, the use of fluorochemicals has recently been under strict scrutiny due to environmental and health concerns. It is therefore desirable to use compositions and methods that can achieve barrier properties (e.g., water/oil resistance) to cellulosic fiber-based molded substrates without the use of fluorochemicals.

Disclosure of Invention

The present invention relates to a process for treating molding surfaces with carrier particles which impart, inter alia, water and/or oil/grease resistance to surfaces so treated. The disclosed method provides for combining at least one Sugar Fatty Acid Ester (SFAE) with a polymer (e.g., latex) in particulate form and applying such particulates to a substrate comprising a cellulose-based material. Such compositions may also include inorganic minerals/pigments.

In embodiments, a method of making a cellulose-containing article is disclosed, comprising adding an emulsion or slurry to a cellulosic fiber furnish, wherein the emulsion or slurry comprises one or more sucrose fatty acid esters and one or more carrier particles; draining the furnish through one or more screens or screens; hot forming the mixture into a product in a mold; and stripping the product from the mold, wherein the product exhibits water, oil, and grease resistance as compared to a cellulosic product not treated with the emulsion or slurry. In a related aspect, the cellulosic fiber furnish includes fibers from wheat, wheat straw, wood, bagasse, reed, border paper, and combinations thereof.

In one aspect, the product is a bowl, tray, bottle, bag, packaging container, or insert. In another aspect, the carrier comprises sucrose fatty acid esters, polymers, solid latex polymer beads, hollow polymer shells, resin beads, pigment particles, and combinations thereof. In related aspects, the pigment particles comprise calcium carbonate, titanium dioxide, kaolin clay, silica, silicates, talc, mica, and combinations thereof.

In one aspect, the pellets further comprise uncooked corn starch, rice starch, wheat starch, potato starch or tapioca starch pellets, oat hulls, rice hulls, ground nut shells, or combinations thereof. In another aspect, the particles are coated with one or more sucrose esters and dispersed into an aqueous emulsion or slurry.

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

In another aspect, the support is a polymer, and the polymer exhibits a low glass transition temperature. In a related aspect, the polymer is a latex. In another related aspect, the product exhibits reduced stickiness.

In one embodiment, a composition is disclosed comprising sucrose fatty acid ester particles containing one or more loading (cargo) materials. In one aspect, the cargo molecule is selected based on the property to be improved. In a related aspect, such characteristics may be adjustable (e.g., to provide a range of 3M kit values and/or a range of water contact angles). In another related aspect, different characteristics may be exhibited by different portions of a product made using compositions obtained by selecting various loading molecules and/or the manner in which the particles are made (e.g., varying heating temperatures, heating times, heating-cooling cycles, mixing methods, buffers, surfactants, emulsifiers, continuous/discontinuous phase compositions, pH, emulsion processes, etc.).

In one aspect, the one or more load bearing materials comprise a polymer, solid latex polymer beads, resin beads, calcium carbonate, titanium dioxide, kaolin, silica, silicates, talc, mica, and combinations thereof.

In another aspect, the composition comprises thymol, lecithin, an alkyl glucoside, and combinations thereof.

In one aspect, the particle is a micelle, microcapsule, or nanocapsule.

In another aspect, the sucrose fatty acid ester is a monoester or a diester.

In another aspect, the sucrose fatty acid esters comprise all saturated fatty acids or a mixture of saturated and unsaturated fatty acids.

In a related aspect, the sucrose fatty acid ester particles comprise one or more sucrose fatty acid esters.

In one embodiment, an emulsion comprising the above composition is disclosed. In a related aspect, the one or more load bearing materials includes latex.

In another embodiment, an article made by the above method is disclosed.

Drawings

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

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

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

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

Fig. 5 shows the water permeability of paper treated with various coating formulations: polyvinyl alcohol (PvOH), rhombus; 1:1(v/v)+ PvOH, square; ethyl lex (starch), triangular; 3:1(v/v)+ PvOH, cross shape.

Fig. 6 shows water droplets on paper treated with an aqueous composition comprising 2 sucrose fatty acid esters having different HLB values and precipitated calcium carbonate.

Detailed Description

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

As used in this specification and the appended claims, the singular forms "a", "an", and "the" include plural referents unless the context clearly dictates otherwise. Thus, for example, reference to "a sugar fatty acid ester" includes one or more sugar fatty acid esters, and/or compositions of the type described herein, as will be apparent to those skilled in the art upon reading the disclosure.

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

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

Barrier coatings on surfaces are often used to prevent passage of foreign substances (e.g., liquids/gases) through the surface, or to reduce egress of such foreign substances. The various materials comprising the coating may improve the properties of a particular base component. For example, latex is a very good film former that can be used as a major component of a primer to seal porous substrates, to which a topcoat can be added to improve the properties of the primer. In the construction of such base and top coats, the latex serves as a physical barrier, for example, where polymers may be added to improve performance metrics such as Cobb value.

While not polymeric, the SFAE disclosed herein itself has been found to contribute to changing the Cobb value of a substrate that contains a barrier coating comprising latex. While not being bound by theory, latex films may leave voids that allow water/water vapor to enter the interstices of a porous substrate (e.g., paper): SFAE can fill the pores and because SFAE has a hydrophobic surface, water/water vapor drains from the pores, thereby improving the Cobb value. This combination performs well and allows for reduction of Cobb values without affecting product quality, including providing increased performance levels.

Furthermore, the mixture of inorganic particles, latex and SFAE provides an improvement in the fine tuning of various properties of the sheet, as inorganic pigments can be added. For example, such sheets may contain wood fibers and include a combination of bio-plastic fibers and such sheets that are water/grease resistant. Contemplated combinations will allow the use of cheaper, more common materials, such as mechanical pulp or recycled pulp will account for a greater percentage of the sheet mass. In this case, the addition of, for example, a calcium carbonate-latex-SFAE mixture will provide an improvement that allows control of the sheet density.

In embodiments, a method of making a cellulose-containing article having water and/or oil and grease resistance is disclosed, the method comprising adding an emulsion or slurry comprising one or more sucrose fatty acid esters and one or more carrier particles to a cellulosic fiber furnish and draining the furnish through one or more screens. In one aspect, the wet molded cellulosic fibrous product is then heated to remove residual water and produce a finished product, such as a bowl, tray, or packaging container or insert.

In related aspects, the carrier particles can include, but are not limited to, solid latex polymer beads, hollow polymer shells, resin beads, or pigment particles (e.g., calcium carbonate, titanium dioxide, kaolin clay, silica or silicates, talc, or mica). In another related aspect, the pellets may also be organic pellets, such as uncooked corn starch, rice starch, wheat starch, potato starch or tapioca pellets, oat hulls, rice hulls, ground nut shells or other similar pellets, or combinations thereof.

In embodiments, the particles may be coated with one or more sucrose fatty acid esters and dispersed into an aqueous emulsion or slurry. In a related aspect, the aqueous emulsion or slurry can then be mixed with the cellulosic fiber slurry at a concentration of about 5% to about 10%, about 10% to about 20%, about 20% to about 30%, about 30% to about 40%, or about 40% to about 50% of the total dry weight prior to wet forming. Without being bound by theory, the sucrose fatty acid ester overcomes the adhesion problems encountered with the use of many polymer particles such as latex. This is particularly true for polymers or latexes having low glass transition temperatures.

In a related aspect, one skilled in the art can select the size and dispersion of the coated particles so that they can migrate to the surface of the article during the molding process. Without being bound by theory, this increases the concentration of coated particles on the surface as compared to the bulk of the article, increasing the cost effectiveness of adding the coated particles. In another related aspect, the increased concentration of coated particles causes the sucrose fatty acid ester and/or polymer to film and melt on the surface of the article during heating and drying, and also causes the catalyst or chemical reaction with the optional additives to be initiated to bond with the cellulosic substrate, form crosslinks for the components, or chemically modify the surface of the article to form water, oil, and/or grease resistance.

In another related aspect, the release characteristics of one or more sucrose fatty acid esters allows the use of latent tack or adhesive additives in the composition, overcoming the deficiencies of the prior art while contributing to the barrier characteristics of the article.

The use of the present invention eliminates or greatly reduces the need to coat, impregnate or spray additional materials onto the surface of the article to impart water, oil and/or grease resistance.

In embodiments, one or more sucrose fatty acid esters may form micelles/microcapsules/nanocapsules and may themselves serve as carriers that may be combined with thymol, lecithin, alkyl glucosides to encapsulate solid latex polymer beads, resin beads or pigment particles (e.g., calcium carbonate, titanium dioxide, kaolin, silica or silicates, talc or mica). Furthermore, the variation in particle size can be achieved by using longer aliphatic groups (i.e., micelles/microcapsules/nanocapsules become more compact due to longer acyl groups). Furthermore, for larger DS, a cell membrane-like bilayer structure can be formed.

In embodiments, the present invention shows that by treating a substrate based on cellulose fibres with the above disclosed carrier composition, the resulting material can be made very resistant to oil/grease, hydrophobic and exhibits low Cobb values, among other things. Furthermore, these sugar fatty acid esters are easily digested, for example, once removed by bacterial enzymes. The derivatized surface exhibits great thermal resistance, can withstand temperatures up to 250 ℃, and may be more gas impermeable than the underlying substrate. Thus, in any embodiment where a cellulosic material may be used, the material is an ideal solution to the problem of hydrophilic surface derivatization of cellulose.

Advantages of the products and methods disclosed herein include: the coating composition is made from renewable agricultural resources, sugars and vegetable oils; has low toxicity characteristics and is suitable for food contact; even with high water resistance standards, adjustments can be made to reduce the coefficient of friction of the paper/paperboard surface (i.e., without making the paper too slippery to be useful for downstream processing or end use); may or may not be used with specific emulsifying equipment or emulsifiers; and is compatible with conventional paper recycling projects: i.e. without adversely affecting the recycling operation as with polyethylene, polylactic acid or wax coated paper, and furthermore the extended use of inorganics (e.g. PCC/GCC) takes advantage of the inherent properties of fillers (e.g. less abrasive).

Other advantages of the coating formulation include:

relatively easy to prepare;

the base coating performs well at high speed at the target coating weight;

-does not block the reel;

no problems with cleaning;

the coating can be run between 60 and 75% solids and the viscosity can be adjusted to a lower value for the draw-down: 220-350 cps;

high solids content means lower dryer cost, including SFAE does not adversely affect viscosity;

the need to coat, impregnate or spray additional materials on the surface of the article to impart water, oil and/or grease resistance is eliminated or greatly reduced.

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

As used herein, "bonded," including grammatical variations thereof, means bonded or caused to be bonded into substantially a single substance.

As used herein, "carrier" means a substance used to carry or transport another substance, such as a polymer, pigment, or catalyst.

As used herein, "cargo" means a substance or material that is delivered by a carrier.

As used herein, "furnish" means a predetermined mixture of fibrous and non-fibrous materials (such as fillers, sizes, and dyes) in an aqueous suspension for making paper.

As used herein, "cellulosic" means a natural, synthetic or semi-synthetic material that can be molded or extruded into an object (e.g., bag, sheet) or film or monofilament, which can be used to make such an object or filmOr a filament: i.e., similar in structure and function to cellulose, such as coatings and adhesives (e.g., carboxymethyl cellulose). In another example, cellulose is cellulosic, which is a complex carbohydrate (C) composed of glucose units₆H₁₀O₅)_nIt is the major component of the cell wall in most plants.

As used herein, "capsule" means a substance or material (e.g., a closed container) that encapsulates another substance or material. In a related aspect, micron and nanometer refers to the unit micron and nanometer scale.

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

As used herein, "Cobb value" means the water absorption (by weight of water per unit area) of a sample. The procedure for determining the "Cobb value" complies with TAPPI standard 441-om. The Cobb value is calculated as follows: the initial weight of the sample was subtracted from the final weight of the sample and then divided by the area of the sample covered by water. The reported values represent grams of water absorbed per square meter of paper.

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

As used herein, "edge wicking" means absorption of water in a paper structure at the outer edges of the structure by one or more mechanisms including, but not limited to, capillary penetration in pores between fibers, diffusion through fibers and bonds (bonds), and surface diffusion over fibers. In a related aspect, the coatings containing sugar fatty acid esters described herein prevent edge wicking in the treated product. On the one hand, there may be similar problems of grease/oil entering the folds in paper or paper products. This "grease creasing effect" may be defined as the absorption of grease in a paper structure produced by folding, pressing or crumpling the paper structure.

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

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

As used herein, "hydrophobic" means water-repellent, water-repellent and non-absorbing properties.

As used herein, "grease resistance" or "oleophobic" means the property of being grease repellent, prone to repel, and not absorbing lipids, grease, fat, and the like. In a related aspect, oil and grease resistance can be measured by the "3M KIT" test or TAPPI T559 KIT test.

As used herein, "micelle," including grammatical variations thereof, means an aggregate of molecules in a colloidal solution.

As used herein, "emulsion" means a mixture of two or more liquids that are generally immiscible (incompatible or immiscible). In related aspects, the emulsion can be a water-in-oil (w/o), oil-in-water (o/w), or double emulsion (e.g., w/o/w).

As used herein, "cellulose-containing material" or "cellulose-based material" means a composition consisting essentially of cellulose. For example, such materials may include, but are not limited to, paper, cardboard, paper pulp, cartons for food storage, parchment, cake board, meat paper (butcher paper), release paper/liner, bags for food storage, shopping bags, shipping bags, bacon pads, insulation, tea bags, containers for coffee or tea, compost bags, eating utensils, containers for hot or cold beverages, cups, lids, trays, bottles for carbonated liquids, gift cards, bottles for non-carbonated liquids, films for wrapping food, garbage disposal containers, food handling tools, textile fibers (e.g., cotton or cotton blends), tools for storing and transporting water, alcoholic or non-alcoholic beverages, housings or screens for electronic products, parts inside or outside furniture, curtains, and upholstery.

As used herein, "release paper" means paper used to prevent an adhesive surface from prematurely adhering to an adhesive or sticking (mastic). In one aspect, the coatings disclosed herein may be used to replace or reduce the use of silicon or other coatings to make materials with low surface energy. Determination of surface energy can be readily accomplished by measuring contact angles (e.g., optical tensiometers and/or hyperbaric chambers; Dyne Testing, Staffordshire, United Kingdom) or by using surface energy test pens or inks (see, e.g., Dyne Testing, Staffordshire, United Kingdom).

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

As used herein, "fluffy" means a light (air) solid material having the appearance of raw cotton or polystyrene foam particles (Styrofoam peanout). In embodiments, the loft material may be made of nanocellulose fibers (e.g., MFC) cellulose nanocrystals and/or cellulose filaments and sugar fatty acid esters, wherein the resulting fibers or filaments or crystals are hydrophobic (and dispersible) and may be used in composite materials (e.g., concrete, plastic, etc.).

As used herein, "fiber in solution" or "pulp" means lignocellulosic fibrous material prepared by chemical or mechanical separation of cellulosic fibers from wood, fiber crops, or waste paper. In a related aspect, where the cellulose fibers are treated by the methods disclosed herein, the cellulose fibers themselves contain bound sugar fatty acid esters as separate entities, and where the bound cellulose fibers have different and unique characteristics from free fibers (e.g., pulp cellulose or cellulose fibers or nanocellulose or microfibrillated cellulose-sugar fatty acid ester bound materials do not form hydrogen bonds between fibers as readily as unbound fibers).

As used herein, "repulpable" means the manufacture of a paper or paperboard product that is suitable for crushing into soft, shapeless lumps for reuse in the manufacture of paper or paperboard.

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

As used herein, "water contact angle" means the angle measured through a liquid where the liquid/vapor interface contacts the surface of a solid. It quantifies the wettability of a liquid to a solid surface. The contact angle reflects how strongly the liquid and solid molecules interact with each other compared to the strength of their respective interactions with themselves. On many highly hydrophilic surfaces, water droplets exhibit contact angles of 0 ° to 30 °. Generally, a solid surface is considered hydrophobic if the water contact angle is greater than 90 °. Water contact angles can be readily obtained using an optical surface tensiometer (see, e.g., Dyne Testing, Staffordshire, United Kingdom).

As used herein, "water vapor permeability" means breathability or the ability of a textile to transfer moisture. There are at least two different measurement methods. One is the MVTR test (moisture vapor transmission rate) according to ISO 15496, which describes the water vapor transmission rate (WVP) of the fabric, and thus the degree of sweat transport to the outside air. These measurements determine how many grams of moisture (water vapor) pass through a square meter of fabric in 24 hours (the higher the level, the higher the air permeability).

In one aspect, water resistance can be determined using TAPPI T530 Hercules sizing (size) test (i.e., sizing test of paper by ink resistance). Ink resistance as measured by the Hercules method is best classified as a direct test of penetration. Other classification methods classify them as penetration rate tests. There is no best test for "measuring sizing". The choice of test depends on the end use and plant (mill) control requirements. The method is particularly suitable for use as a factory controlled sizing test to accurately detect changes in sizing levels. It provides sensitivity to the float test while providing repeatable results, shorter test times and automatic endpoint determination.

The degree of sizing is an important characteristic of many papers, as measured by the resistance to penetration or absorption of aqueous liquids into the paper. Typical of these papers are bags, container board, butcher's wrap, writing and certain printing grades.

The method can be used to monitor the production of paper or paperboard for a particular end use if an acceptable correlation has been established between the test values and the paper end use properties. Due to the nature of the test and penetrant, it may not necessarily be of sufficient relevance to suit all end-use requirements. The method measures the degree of sizing by the rate of permeation. Other methods measure sizing by surface contact, surface penetration or absorption. The sizing test is selected based on its ability to simulate the manner in which water contacts or absorbs in the end use. The method can also be used to optimize the cost of the sizing chemicals used.

As used herein, "oxygen permeability" means the degree to which a polymer allows the passage of a gas or fluid. The oxygen permeability (Dk) of a material is a function of the diffusivity (D), i.e., the speed at which oxygen molecules pass through the material, and the solubility (k), or the amount of oxygen molecules absorbed per volume in the material. The oxygen permeability (Dk) values typically fall between 10 and 150x10^-11(cm²ml O₂) /(s ml mmHg). A semilogarithmic relationship has been demonstrated between hydrogel water content and oxygen permeability (units: Barrer units). The international organization for standardization (ISO) specifies permeability using SI units "hectopascal (hPa)" for pressure. Thus, Dk is 10^-11(cm²ml O₂) /(s ml hPa). Barrer units can be converted to hPa units by multiplying them by a constant of 0.75.

As used herein, "biodegradable," including grammatical variations thereof, means capable of being broken down into, inter alia, harmless products by the action of organisms (e.g., by microorganisms).

As used herein, "recyclable," including grammatical variations thereof, means a material (used and/or waste) that can be processed or processed to render the material suitable for reuse.

As used herein, "latex" means a stable dispersion (emulsion) of polymeric microparticles in an aqueous medium. It exists in nature, but synthetic latexes can also be made by polymerizing monomers (e.g., styrene) that have been emulsified with a surfactant. Latex found in nature is a milky white liquid found in 10% of the flowering plants (angiosperms). It is a complex emulsion of proteins, alkaloids, starches, sugars, oils, tannins, resins and gums that coagulates upon exposure to air.

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

As used herein, "tack" means the quality or tendency of a material to remain adhered to a surface in contact with the material. Can be measured by ASTM D4501.

As used herein, "Gurley seconds" or "Gurley number" is a unit (ISO 5636-5:2003) (Porosity) that describes the number of seconds required for 100 cubic centimeters (deciliters) of air to pass 1.0 square inch of a given material under a pressure differential of 4.88 inches of water (0.176 psi). In addition, for stiffness, "Gurley number" is the unit of force (1 milligram of force) required to deflect a given amount of a material measured against a piece of material held vertically. This value can be measured on a Gurley Precision Instruments device (Troy, New York).

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

The Griffin method for nonionic surfactants described in 1954 was calculated as follows:

HLB＝20*M_h/M

where Mh is the molecular weight of the hydrophilic portion of the molecule and M is the molecular weight of the entire molecule, resulting in values of 0 to 20. An HLB value of 0 corresponds to a fully lipophilic/hydrophobic molecule, while a value of 20 corresponds to a fully hydrophilic/lipophobic molecule.

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

< 10: fat-soluble (water-insoluble)

> 10: water solubility (lipid insolubility)

1.5 to 3: defoaming agent

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

7 to 9: wetting and spreading agent

13 to 15: detergent composition

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

15 to 18: solubilizer or hydrotrope (hydrotope)

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

As used herein, the term "a" or "an" refers to,represents a sucrose fatty acid ester (soyate) made from soybean oil, available from Procter under the trade name SEFOSE 1618U&Gamble Chemicals (Cincinnati, OH) are commercially available (see sucrose soyate below) and contain one or more unsaturated fatty acids. As used herein, the term "a" or "an" refers to,the representation is available from Procter&Commercially available from Gamble Chemicals having formula C_{n+ 12}H_2n+22O₁₃The sucrose fatty acid ester of (1), wherein all the fatty acids are saturated. In addition, SFAEs are commercially available from Mitsubishi Chemicals Foods Corporation (Tokyo, JP), which offers a variety of such SFAEs.

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

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

As used herein, "wet strength" means a measure of the degree to which a web holding paper together resists breaking forces when the paper is wet. The Wet Strength can be measured using a Finch Wet Strength Device (Finch Wet Strength Device) from Thwing-Albert Instrument Company (West Berlin, NJ). Wherein wet strength is generally affected by wet strength additives such as alkaline cured cationic resins (kymene), cationic glyoxalated resins, polyamidoamine-epichlorohydrin resins, polyamine-epichlorohydrin resins including epoxy resins. In embodiments, the SFAE coated cellulose-based materials disclosed herein achieve such wet strength in the absence of such additives.

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

In embodiments, the methods disclosed herein comprise mixing a latex with inorganic particles (e.g., clay, talc, calcium carbonate) to form a slurry, mixing the slurry with a sugar fatty acid ester to form an aqueous coating, and applying the coating to a cellulosic material, wherein the method optionally comprises exposing the contacted cellulosic-based material to heat, radiation, a catalyst, or a combination thereof for a sufficient time to bond the coating to the cellulosic-based material. In related aspects, such radiation may include, but is not limited to, UV, IR, visible light, or combinations thereof. In another related aspect, the reaction can be carried out at room temperature (i.e., 25 ℃) to about 150 ℃, about 50 ℃ to about 100 ℃, or about 60 ℃ to about 80 ℃. Further, the surface of the resulting cellulosic material exhibits a lower Cobb value as compared to the surface of a cellulosic material that has not been so treated.

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

Without being bound by theory, the interaction between the sugar fatty acid ester and the cellulose-based material may be by ionic, hydrophobic, van der waals interactions, or covalent bonds, or combinations thereof. In a related aspect, the binding of the sugar fatty acid ester to the cellulose-based material is substantially irreversible (e.g., using a SFAE comprising a combination of saturated and unsaturated fatty acids).

Furthermore, at sufficient concentrations, the combination of only sugar fatty acid esters is sufficient to make the cellulose-based material hydrophobic: that is, hydrophobicity, including other properties such as, inter alia, strengthening, stiffening, and bulking of cellulose-based materials, is achieved without the addition of waxes, rosins, resins, diketene, shellac, vinyl acetate, PLA, PEI, oils, other water repellant chemicals, or combinations thereof (i.e., a second hydrophobic agent).

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

Another advantage is that the disclosed sugar fatty acid esters soften the fibers, increasing the distance between them, thus increasing the volume without significantly increasing the weight. Additionally, the modified fiber and cellulose-based materials disclosed herein may be repulped. Further, for example, water cannot easily "rush" too low a surface energy barrier into the paper.

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

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

In embodiments, the sugar fatty acid ester comprises or consists essentially of a sucrose fatty acid ester. Many methods are known for preparing or providing the sugar fatty acid esters of the present invention, and all such methods are believed to be useful within the broad scope of the present invention. For example, in certain embodiments, it may be preferred to synthesize fatty acid esters by esterifying sugars with one or more fatty acid moieties obtained from oil seeds including, but not limited to, soybean oil, sunflower oil, olive oil, canola oil, peanut oil, and mixtures thereof.

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

Wherein "a" is hydrogen or the following structure I:

wherein "R" is a straight, branched, or cyclic, saturated or unsaturated, aliphatic or aromatic moiety having from about 8 to about 40 carbon atoms, and wherein at least one "a" is at least one, at least two, at least three, at least four, at least five, at least six, at least seven, and all eight "a" moieties of formula (la) conform to structure I. In a related aspect, the sugar fatty acid esters described herein can be monoesters, diesters, triesters, tetraesters, pentaesters, hexaesters, heptaesters, or octaesters, and combinations thereof, wherein the aliphatic groups can be fully saturated or can contain saturated and/or unsaturated groups, or combinations thereof.

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

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

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

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

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

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

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

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

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

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

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

Sucrose soyabean oil fatty acid ester (C)1618U)

The sugar fatty acid esters can be prepared by esterification with substantially pure fatty acids by known esterification methods. They may also be prepared by transesterification using sugars and fatty acid esters in the form of fatty acid glycerides from, for example, natural sources, such as those found in oils extracted from oilseeds (e.g., soybean oil). Transesterification reactions to provide sucrose fatty acid esters using fatty acid glycerides are described, for example, in U.S. patent No. 3,963,699; U.S. Pat. No. 4,517,360; nos. 4,518,772; 4,611,055 No; 5,767,257 No; 6,504,003 No; 6,121,440 No; and 6,995,232, and WO 1992004361A 1, all of which are incorporated herein by reference in their entirety.

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

As described above, sucrose fatty acid esters can be prepared from methyl ester feedstocks prepared from glycerides derived from natural sources by transesterifying sucrose (see, e.g., 6,995,232, incorporated herein by reference in its entirety). Due to the source of the fatty acids, the raw materials used to prepare sucrose fatty acid esters contain a range of saturated and unsaturated fatty acid methyl esters having fatty acid moieties containing 12 to 40 carbon atoms. This will be reflected in the product sucrose fatty acid ester made from this source, since the sucrose moiety comprising this product will contain a mixture of ester moiety substituents, wherein for formula I above, the "R" group will be a mixture having from 12 to 26 carbon atoms in a ratio that reflects the starting material used to make the sucrose ester. To further illustrate this, sucrose esters from soybean oil would be a mixture of materials with an "R" group structure that reflects a soybean oil containing 26% by weight of oleic acid triglyceride (H)₃C-[CH₂]₇-CH＝CH-[CH₂]₇-C (O) OH), 49% by weight of linoleic acid triglyceride (H)₃C-[CH₂]₃-[-CH₂-CH＝CH]₂-[CH₂]₇-C (O) OH), 11% by weight of linolenic acid triglyceride (H)₃C-[-CH₂-CH＝CH-]₃-[-CH₂]₇-C (O) OH) and 14% by weight of triglycerides of various saturated fatty acids, as described in the seventh edition of Merck Index, which is incorporated herein by reference. All of these fatty acid moieties are represented in the "R" group of substituents in the product sucrose fatty acid ester. Thus, when a sucrose fatty acid ester is referred to herein as the product of a reaction using a fatty acid feedstock derived from a natural source (e.g., sucrose soya oil fatty acid ester), the term is intended to include all of the various ingredients typically found as a result of preparing the source of the sucrose fatty acid ester. In a related aspect, the disclosed sucrose fatty acid esters can exhibit low viscosities (e.g., about 10 to 2000 centipoise at room temperature or at standard atmospheric pressure). In another aspect, the unsaturated fatty acid can have one, two, three, or more double bonds.

In embodiments of the invention, the sugar fatty acid ester, and in certain aspects, disaccharide ester, is formed from fatty acids having an average of greater than about 6 carbon atoms, about 8 to 16 carbon atoms, about 8 to about 18 carbon atoms, about 14 to about 18 carbon atoms, about 16 to about 20 carbon atoms, and about 20 to about 40 carbon atoms.

In embodiments, depending on the form of the cellulose-based material, the sugar fatty acid ester may be present in different concentrations to achieve hydrophobicity. In one aspect, when combining a Sugar Fatty Acid Ester (SFAE) as a coating on a cellulose-based material, the SFAE is at least about 0.1 g/m on the surface of the cellulose-based material²To about 1.0g/m²About 1.0g/m²To about 2.0g/m²About 2g/m²To about 3g/m²The coating weight of (a) is present. In a related aspect, it can be about 3g/m²To about 4g/m²About 4g/m²To about 5g/m²About 5g/m²To about 10g/m²About 10g/m²To about 20g/m²Are present. In another aspect, when the cellulose-based material is a solution containing cellulose fibers, the coating can be present at a concentration of at least about 0.025% (wt/wt) of the total fibers present. In related aspects, it can be present from about 0.05% (wt/wt) to about 0.1% (wt/wt), from about 0.1% (wt/wt) to about 0.5% (wt/wt), about 0.5% (wt/wt) of the total fibersWt% (wt/wt) to about 1.0% (wt/wt), about 1.0% (wt/wt) to about 2.0% (wt/wt), about 2.0% (wt/wt) to about 3.0% (wt/wt), about 3.0% (wt/wt) to about 4.0% (wt/wt), about 4.0% (wt/wt) to about 5.0% (wt/wt), about 5.0% (wt/wt) to about 10% (wt/wt), about 10% (wt/wt) to about 50% (wt/wt). In another related aspect, the amount of SFAE may be equal to the amount of fiber present. In some embodiments, SFAE may coat the entire outer surface of a cellulose-based material (e.g., coat the entire paper or cellulose-containing article).

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

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

In one aspect, the coatings described herein are resistant to a pH of between about 3 and about 9. In related aspects, the pH can be from about 3 to about 4, from about 4 to about 5, from about 5 to about 7, from about 7 to about 9.

In an embodiment, a method is disclosed for treating a surface of a cellulose (or cellulosic) containing material, the method comprising applying to the surface a composition comprising an alkanoic acid derivative having formula (II) or (III):

R-CO-X formula (II)

X-CO-R-CO-X₁A compound of the formula (III),

wherein R is a linear, branched OR cyclic aliphatic hydrocarbon group having 6 to 50 carbon atoms, and wherein X and X1 are independently Cl, Br, R-CO-OR OR O (CO) OR, wherein X OR X is X when the alkanoic acid derivative comprises formula (III)₁The same or different, wherein the SFAE disclosed herein is a support, and the process does not require an organic base, gaseous HCl, VOC, or a catalyst.

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

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

In some embodiments, the sugar fatty acid ester emulsifiers disclosed herein can be used in load-bearing coatings or other chemicals used in papermaking including, but not limited to, talc, esters, diesters, ethers, ketones, amides, nitriles, aromatics (e.g., xylene, toluene), acid halides, acid anhydrides, Alkyl Ketene Dimers (AKD), alabaster, algainic acid, alum, albarine, gum (glue), barium carbonate, barium sulfate, chlorine dioxide, dolomite, diethylenetriamine pentaacetate, EDTA, enzymes, formamidine sulfate, guar gum, gypsum, lime, magnesium bisulfate, milk of lime, milk of magnesium oxide, polyvinyl alcohol (PvOH), rosin soap, satin, soap/fatty acid, sodium bisulfate, soda ash (soda ash), titanium dioxide, surfactants, starch, modified starch, hydrocarbon resins, polymers, waxes, polysaccharides, Proteins, latexes, and combinations thereof. In embodiments, the disclosed mixtures may contain one or more SFAEs and one or more of the following inorganic particles: clay (kaolin, bentonite), calcium carbonate (GCC and PCC), talc (magnesium silicate) and titanium dioxide.

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

In embodiments, the treated cellulose-containing material may have improved mechanical properties compared to the same material without treatment. For example, paper bags treated by the methods disclosed herein exhibit increased burst strength, Gurley number, tensile strength, and/or energy to maximum load. In one aspect, the burst strength is increased by a factor of about 0.5 to 1.0, about 1.0 to 1.1, about 1.1 to 1.3, about 1.3 to 1.5. In another aspect, the Gurley number is increased by about 3 to 4 times, about 4 to 5 times, about 5 to 6 times, and about 6 to 7 times. In another aspect, the tensile strain is increased by a factor of about 0.5 to 1.0, about 1.0 to 1.1, about 1.1 to 1.2, and about 1.2 to 1.3. And in another aspect, the maximum load energy is increased by a factor of about 1.0 to 1.1, about 1.1 to 1.2, about 1.2 to 1.3, and about 1.3 to 1.4.

In embodiments, the cellulose-containing material is a base paper (base paper) comprising microfibrillated cellulose (MFC) or Cellulose Nanofibers (CNF), described, for example, in U.S. patent application publication No. 2015/0167243 (incorporated herein by reference in its entirety), wherein MFC or CNF is added during the forming and papermaking processes and/or as a coating or secondary layer to a previously formed layer to reduce the porosity of the base paper. In a related aspect, the base paper is contacted with a sugar fatty acid ester as described above. In another related aspect, the contacted base paper is further contacted with polyvinyl alcohol (PvOH). In embodiments, the resulting contacted base paper is adjustably water and lipid resistant. In a related aspect, the resulting base paper can exhibit a Gurley value (i.e., Gurley air resistance (seconds/100 cc, 20oz. cyl.)) of at least about 10-15, or at least about 100, at least about 200 to about 350. In one aspect, the sugar fatty acid ester coating can be a laminate of one or more layers, or one or more layers can be provided as a laminate, or the amount of coating of one or more layers can be reduced to achieve the same performance effect (e.g., water resistance, grease resistance, etc.). In related aspects, the laminate may comprise a biodegradable and/or compostable heat sealer or adhesive.

In embodiments, the sugar fatty acid ester may be formulated as an emulsion, wherein the selection and amount of emulsifier is determined by the nature of the composition and the ability of the agent to promote dispersion of the sugar fatty acid ester. In one aspect, the emulsifier can include, but is not limited to, water, buffers, polyvinyl alcohol (PvOH), carboxymethylcellulose (CMC), latex, milk protein, wheat gluten, gelatin, prolamine, isolated soy protein, starch, acetylated polysaccharide, alginate, carrageenan, chitosan, inulin, long chain fatty acids, wax, agar, alginate, glycerol, gum, lecithin, poloxamer, monoglycerol, diglycerol, monosodium phosphate, monostearate, propylene glycol, detergents, cetyl alcohol, and combinations thereof. In another aspect, the ratio of sugar ester to emulsifier can be about 0.1:99.9, about 1:99, about 10:90, about 20:80, about 35:65, about 40:60, and about 50: 50. It will be apparent to those skilled in the art that the proportions may vary depending on the desired characteristics of the final product.

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

In embodiments, methods of using the sugar fatty acid esters can be used to reduce the cost of application of primary/secondary coatings (e.g., silicone-based layers, starch-based layers, clay-based layers, PLA layers, bioppbs, PEI layers, etc.) by: a layer of material exhibiting the necessary characteristics (e.g., water resistance, low surface energy, etc.) is provided, thereby reducing the amount of primary/secondary layers required to achieve the same characteristics. In one aspect, a material may be coated on top of the SFAE layer (e.g., a heat sealer). In embodiments, the composition is free of fluorocarbon compounds and silicones.

In embodiments, the composition increases both the mechanical and thermal stability of the treated product. In one aspect, the surface treatment is thermally stable at temperatures between about-100 ℃ to about 300 ℃. 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 ℃ to about 300 ℃.

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

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

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

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

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

For example, by increasing the concentration of sugar fatty acid esters, the compositions disclosed herein can react more broadly with the treated cellulose, again with the end result exhibiting improved water/grease resistance properties. However, higher coating weights do not necessarily mean increased water resistance. In one aspect, various catalysts may result in faster "curing" to precisely adjust the amount of sugar fatty acid ester to meet a particular application.

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

The derived material has altered physical properties that can be defined and measured using appropriate tests known in the art. For hydrophobicity, analytical protocols may include, but are not limited to, contact angle measurements and moisture absorption. Other properties include stiffness, WVTR, porosity, tensile strength, insufficient substrate degradation, fracture and tear properties. The American Society for Testing and Materials (protocol ASTM D7334-08) defines a specific standardized protocol to be followed.

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

In embodiments, the materials treated according to the presently disclosed methods exhibit complete biodegradability, as measured by degradation in the environment under microbial attack.

Biodegradability can be defined and tested using a variety of methods, including the shake flask method (ASTM E1279-89(2008)) and the Zahn-Wellens test (OECD TG 302B).

Compostability may be defined and tested using a variety of methods, including but not limited to ASTM D6400.

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

Modification of cellulose as disclosed herein, in addition to increasing hydrophobicity, can also increase its tensile strength, flexibility and stiffness, thereby further expanding its range of use. Both fully biodegradable products and partially biodegradable products, including recyclable and compostable products, made from or by using the modified cellulose disclosed herein are within the scope of the present application.

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

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

Examples

Example 1 sugar fatty acid ester formulation

At room temperatureThe following is a liquid and all coatings/emulsions containing the material were applied at room temperature using a bench-top draw down apparatus. The type and size of the rod is varied to produce a range of coating weights.

Preparation 1

Mixing 50ml ofAdding to a solution containing 195ml of water and 5g of carboxymethylcellulose10; CP Kelco, Atlanta, GA). This formulation was mixed for 1 minute using a Silverson homogenizer set at 5000 rpm. This emulsion was coated on 50 grams of base paper made from bleached hardwood pulp and 80 grams of paper consisting of unbleached softwood. The two sheets were placed in an oven (105 ℃) for 15 minutes to dry. After removal from the oven, the papers were placed on a lab bench and 10 drops of water (room temperature) were applied to each paper by pipette. The base paper chosen for this test immediately absorbed water droplets, but was coated in different amountsThe papers of (a) show an increased water resistance level with increasing coating weight (see table 1).

TABLE 1 useBase paper of

It was observed that the water resistance was small in the heavier sheet, and water resistance could not be obtained unless the sheet was dried.

Preparation 2

Will be provided withAddition to cup stock (cup stock): (Note thatThis is a single layer feedstock that is not MFC treated. 110 grams of cardboard made from eucalyptus pulp). 50 g of the powderAdded to 200 grams of 5% cooked ethylated starch (Ethylex 2025) and stirred for 30 seconds using a bench Kedy Mill (kady mill). The paper samples were coated and placed in an oven at 105 ℃ for 15 minutes. 10-15 drops of the test drops were placed on the coated side of the paperboard and the water retention time was measured and recorded in the table below. Water penetration on the untreated paperboard control was instantaneous (see table 2).

TABLE 2. channelsHot water penetration of treated cup stock

Preparation 3

Will be pureWarm to 45 ℃ and place in spray bottle. The paper stock listed in the previous example was uniformly sprayed with a piece of fiberboard and a measured amount of cotton. When a drop of water is placed on the sample, it penetrates into the substrate within 30 seconds. However, after drying in an oven at 105 ℃ for 15 minutes, the water droplets evaporate before being absorbed into the substrate.

Continuing research interestWhether it is compatible with compounds used in oil and grease resistant coatings.Can be used for water resistance and rigidity improvement. 240 grams of paperboard stock was used for the stiffness test. Table 3 shows the results. These data are based on the weight of the individual coatings: obtained at 5g/mThe average of 5 samples was reported. The results are reported in our type 150-E V-5Taber stiffness tester in Taber stiffness units.

TABLE 3 rigidity test

EXAMPLE 2 binding of sugar esters to cellulosic substrates

To determineWhether or not reversibly bound to a cellulosic material will be pureMixed with pure cellulose in a ratio of 50: 50. Make itThe reaction was carried out at 300 ℃ F. for 15 minutes, and then the mixture was extracted with dichloromethane (non-polar solvent) or distilled water. The sample was refluxed for 6 hours and analyzed gravimetrically.

TABLE 4 extraction from cellulosic materials

Example 3 detection of cellulosic surface

Scanning electron microscope images of base papers with and without MFC demonstrated that base papers with lower porosity may require much less water repellent to react with the surface. Figures 1-2 show untreated medium porosity Whatman filters. Fig. 1 and 2 show a relatively high exposed surface area for reaction with the derivatizing agent. However, it also shows a highly porous sheet material with sufficient space for water to escape. Figures 3 and 4 show a side-by-side comparison of paper made from recycled pulp before and after coating with MFC. (they are two magnifications of the same sample, with no MCF evident to the left of the image). Tests have shown that derivatization of sheets with much lower porosity shows a greater potential for long-term water/vapor barrier performance. The last two images are close-ups of the average "well" on one filter paper and on CNF coated paper at similar magnification for the control.

The above data indicate a key point: adding more material will correspondingly improve performance. While not being bound by theory, the unbleached paper appears to react faster, indicating that the presence of lignin can accelerate the reaction.

Such asThe fact that the product of (a) is a liquid, it can be easily emulsified, indicates that it can be easily adapted to the coating equipment normally used in paper mills.

Example 4 "Phluphi"

Mixed liquidAnd reacted with bleached hardwood fibers to produce a variety of methods for making water-repellent handsheets. When the sucrose ester is mixed with the pulp before sheet formation, it is found to remain mostly in the fiber. Upon sufficient heating and drying, a brittle, fluffy but very hydrophobic handsheet formed. In this example, 0.25 grams would be usedMixed with 4.0 grams of bleached hardwood fibers in 6 liters of water. The mixture was stirred by hand and the water was drained into a standard handsheet mold. The resulting fiber mat was removed and dried at 325 ° F for 15 minutes. The resulting sheet exhibits significant hydrophobicity and greatly reduces hydrogen bonding between the fibers themselves. (water contact angles greater than 100 degrees were observed.) emulsifiers may be added.The ratio to fiber may be about 1:100 to 2: 1.

Subsequent tests showed that talc was only one non-participating material (separator) in the process, and was excluded from the other tests.

Example 5 environmental PairEffect of coating Properties

To better understand the mechanism of the reaction of sucrose esters with fiber, low viscosity coatings were applied to bleached kraft paper to which wet strength resins had been added, but which had no water resistance (no sizing). The coatings were each less than 250cps as measured using a Brookfield viscometer at 100 rpm.

Emulsified with ethyl 2025 (starch) and applied to paper by a gravure roll. For comparison, also emulsified with Westcote 9050PvOHAs shown in fig. 5, the enhancement may be achieved by heating and other chemical environments that enhance the oxidizing chemistryOxidation of the medium double bond (see table 5).

TABLE 5 environmental pairsInfluence of (to number of minutes of failure)

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

Make itReacted with bleached softwood pulp and dried to form a sheet. Subsequently, with CH₂Cl₂Toluene and water were extracted to determine the extent of reaction with the pulp. Extraction was carried out using a glass soxhlet extractor for at least 6 hours. The extraction results are shown in table 6.

Table 6.Combined pulp extraction

The data indicate that substantially allRemain in the sheet. To further confirm this, the same procedure was carried out on the pulp alone, and the results showed that about 0.01 g per 10g of pulp could be obtained. While not being bound by theory, it can be readily interpreted as residual pulping chemicals or more likely incompletely removed extractives.

Pure fibers of cellulose (e.g., alpha-cellulose from Sigma Aldrich, st. louis, MO) were used and the experiment was repeated. As long asIs maintained below about 20% of the mass of the fiber, more than 95% of the mass will remain in the fiberAnd cannot be extracted with either polar or non-polar solvents. Without being bound by theory, optimizing the baking time and temperature may further increase the sucrose esters retained in the fiber.

As shown, numberIt has been shown that after drying it is generally not extractable from the materialOn the other hand, when fatty acids comprising fully saturated fatty acid chains are used instead(e.g. inAvailable from Procter&Gamble Chemicals (Cincinnati, OH), approximately 100% of the material can be extracted with hot water (70 ℃ or above 70 ℃).Andthe only difference being that it has a saturated fatty acid attached to itRather than unsaturated fatty acids

Another notable aspect is that the multiple fatty acid chains react with cellulose and, through two sugar molecules in the structure,a rigid cross-linked network is created, thereby increasing the strength of fibrous webs, such as paper, paperboard, air-laid and wet-laid nonwovens, and textiles.

Example 7 additionTo achieve water resistance

Hardwood and softwood kraft pulps were used to make 2 grams and 3 grams of handsheets. When will beWhen added to 1% pulp in an amount of 0.1% or more and the moisture is drained to form a handsheet,remain in the fiber, giving it water resistance. From 0.1% to 0.4%The water beads on the surface for a few seconds or less.After the loading of (a) exceeds 0.4%, the water-resistant time increases rapidly to several minutes, then to several hours as the loading level increases to greater than 1.5%.

Example 8 preparation of fluffy fiber Material

Adding into pulpThe fibers can be softened, increasing the spacing between them, increasing the volume. For example, 3% hardwood pulp containing 125g (dry) pulp was drained and dried and found to have a volume of 18.2 cubic centimeters. Mixing 12.5gAdded to the same 3% hardwood pulp slurry also containing 125g dry fibers. After draining, the resulting felt was 45.2 cubic centimeters.

With heat already at 60 DEG C30g of standard bleached hardwood kraft pulp (from Old Town Fuel and Fiber, LLC, Old Town, ME) was sprayed. The 4.3cm³Placed in a 10,000rpm shredder and essentially re-pulped. The mixture was poured into a handsheet mold and dried at 105 ℃. The volume of the resulting hydrophobic pulp was 8.1cm³. A 2 inch square piece of the material was cut and placed in a hydraulic press and 50 tons of pressure applied for 30 seconds. The volume of the squares had been significantly reduced, but still had over 50% more volume than the 2 inch squares cut for the control without applied pressure.

Importantly, not only is an increase in bulk and softness observed, but the mat that is forcibly repulped after drainage produces a fiber mat that retains all of the hydrophobicity. This property is also valuable in addition to the observation that water cannot easily "rush" through a low surface energy barrier into the sheet. The linked fatty acid hydrophobic single chains do not show this property.

While not being bound by theory, this represents additional evidence —Reacts with the cellulose and the OH groups of the cellulose fiber surface are no longer available for subsequent hydrogen bonding. Other hydrophobic materials interfere with the original hydrogen bonding, but upon repulping, this effect is reversed and the OH groups on the cellulose are free to participate in hydrogen bonding upon re-drying.

Example 9 pouch paper test data

The following table (Table 7) illustrates the results at 5-7g/m on unbleached kraft paper bag stock (control)²Is/are as followsAnd polyvinyl alcohol (PvOH) mixture. Reference also includes commercial bags.

TABLE 7 pouch paper test

As shown in the table, with useIncreased tensile and burst strength with PvOH coated control base paper。

Example 10 Wet/Dry tensile Strength

The bleached pulp was used to make 3 grams of handsheets. As follows comparesWet and dry tensile strengths at different addition levels. Note that, for these handsheets,without emulsifying into any coating, it was merely mixed into the pulp and drained without adding other chemicals (see table 8).

TABLE 8 Wet/Dry tensile Strength

It is also noted that the 5% addition rate produced a wet strength that was not significantly lower than the dry strength of the control.

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

Multiple experiments were performed with sucrose esters prepared having less than 8 fatty acids attached to the sucrose moiety. Samples SP50, SP10, SP01, and F20W (available from siterna, The Netherlands) contained 50, 10, 1, and substantially 0% monoester, respectively. While these commercially available products are made by reacting sucrose with saturated fatty acids, making them less useful for further crosslinking or similar chemical action, they can be used to test emulsification and water resistance properties.

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

Example 12 HST data and moisture uptake

To prove thatProviding the observed water repellency properties individually, in varying amounts(emulsified with either PvOH or Ethylex 2025, applied by knife coating) porous Twins River (Matawaska, ME) basepapers were treated and analyzed by the Hercules sizing test. The results are shown in Table 9.

TABLE 9 useHST data of (a).

As can be seen from Table 9, the addition of the additive to the surface of the paperIncreasing the water tolerance (as shown by the increasing HST in seconds).

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

Table 10 HST data F20W.

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

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

Water resistance is not only due to the presence of fatty acids that form ester linkages with cellulose, but also the loading of softwood handsheets (bleached softwood kraft)Oleic acid is added directly to the pulp, wherein the oleic acid is in contact with the pulpThe cellulose in (1) forms an ester bond. The mass at time zero represents the "completely dry" mass of the handsheet taken from the oven at 105 ℃. The samples were placed in a controlled humidity chamber maintained at 50% RH. The change in mass over time (in minutes) was recorded. The results are shown in tables 11 and 12.

Table 11.The moisture is absorbed.

Table 12 moisture uptake of oleic acid.

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

Note this difference here: the addition of oleic acid directly to the pulp to form ester linkages greatly slows the absorption of moisture. In contrast, only 2% ofAbsorption of moisture is slowed, and at higher concentrations,will not. Thus, while not being bound by theoryThe structure of the binding material cannot be explained only by the structure formed by the simple fatty acid ester and cellulose.

Example 13 saturated SFAE

Saturated esters are waxy solids at room temperature and, due to saturation, are less reactive with the sample matrix or itself. These materials are melted and can be applied in liquid form using elevated temperatures (e.g., at least 40 ℃, and for all those tested, above 65 ℃), 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 hydrophobicity.

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

A #45 bleached hardwood kraft Paper obtained from Turner Falls Paper was used for the test coatings. The Gurley porosity was measured for about 300 seconds and represents a fairly compact base paper. S-370 from Mitsubishi foods (Japan) was emulsified with xanthan gum (up to 1% by mass of a saturated SFAE formulation) prior to coating.

Coating weight (lb/ton) and HST (average of 4 measurements per sample) for saturated SFAE formulations.

Watch 13

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

The generated laboratory data also demonstrates that a limited amount of saturated SFAE can enhance the water resistance of coatings to be used for other purposes/applications. For example, saturated SFAE was blended with ethyl lex starch and polyvinyl alcohol based coatings and in each case an increase in water resistance was observed.

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

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

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

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

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

Example 14 other saturated SFAEs

Sizing press evaluations of saturated SFAE-based coatings were performed on bleached light weight paper (about 35#) without sizing and relatively poor forming properties. All evaluations were performed by using Exceval HR 3010 PvOH cooked to emulsify saturated SFAE. Sufficient saturated SFAE was added to account for 20% of total solids. Emphasis was placed on evaluating comparative S-370 samples to C-1800 samples (available from Mitsubishi Foods, Japan). The performance of both esters was superior to the control, and some key data are shown in table 14:

TABLE 14

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

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

Example 15 Wet Strength additive

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

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

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

Watch 15

The data demonstrate a tendency that the addition of unsaturated sucrose esters to paper increases wet strength with increasing loading levels. The dry tensile strength shows the maximum strength of the paper as a reference point.

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

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

For example, 200 grams of palmitoyl chloride (CAS 112-67-4) was mixed with 50 grams of sucrose and mixed at room temperature. After mixing, the mixture was raised to 100 ° F and held at this temperature overnight (ambient pressure). The resulting material was washed with acetone and deionized water to remove any unreacted or hydrophilic material. Use of C¹³NMR analysis of the remaining material showed that a large amount of hydrophobic sucrose esters had been prepared.

Although it has been demonstrated (by BT3, etc.) that the addition of fatty acid chlorides to cellulosic materials can impart hydrophobicity, the reaction itself is undesirable in the field because the gaseous HCl released as a by-product can cause a number of problems including corrosion of surrounding materials and is harmful to workers and the surrounding environment. Another problem caused by the generation of hydrochloric acid is that as hydrochloric acid is formed more (i.e., more polyol sites are reacted), the fibrous composition becomes more brittle. Palmitoyl chloride reacts more with cellulose and cotton materials and the strength of the article decreases with increasing hydrophobicity.

The reaction was repeated several times using 200 g of R-CO-Cl each reacted with 50 g of other similar polyols including corn starch, birch xylan, carboxymethyl cellulose, glucose and extracted hemicellulose.

EXAMPLE 17 Peel test

Peel testing the force required to Peel the tape from the surface of the paper at a reproducible angle was measured using a wheel between the jaws of a tensile Tester (ASTM D1876; e.g., the 100 series Modular Peel Tester, test resources, shakope, MN).

To do this, high Gurley (600 sec) bleached kraft paper from Turners Falls papers (turn's Falls, MA) was used. This #50 pound sheet represents a fairly compact but very absorbent sheet.

When #50 pound paper was coated with 15% ethyl lex starch as a control, the average force required (over 5 samples) was 0.55 pounds per inch. When treated with the same coating but withWhen 25% of the ethyllex starch is replaced (in this way,was added at 25%, 75% was still ethyl), the average force dropped to 0.081 lbs/inch. By usingInstead of 50% ethyllex, the force required dropped to less than 0.03 lbs/inch.

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

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

Example 18 saturated SFAE and inorganic particles (fillers)

Saturated sucrose fatty acid esters 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.

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

And (4) observation:

more hydrophobic esters tend to aggregate in aqueous emulsions/dispersions and thus forming a uniform coating on paper is challenging.

The low melting point of several of these molecules causes the coating to "melt" into the paper.

If hydrophobic SAFE is mixed with polymers to help stabilize the dispersion, these polymers (i.e., latex, starch, polyvinyl alcohol) tend to surround the esters in a way that diminishes the desired hydrophobicity.

When mixed with calcium carbonate (e.g., precipitated calcium carbonate), this can produce unexpected attractiveness. Under the same drying conditions, SAFE does not melt into the paper.

The calcium carbonate appears to aid in the dispersion of the SAFE and the adhesion forces cause the SAFE to act as an adhesive to attach the calcium carbonate particles to the surface of the coated paper. It is believed that this uniform dispersion results in enhanced water resistance for a given amount of ester.

EXAMPLE 18 pigmented coating formulation

Method

With some MALLARD CREEK samples (1019. 1004, 6160, 1005, 6152) and DOWAnd analysis of some BASF samples (Epotal NX 4430, Epotal s440) appeared to support chemically the latex withAnd (4) compatibility. The order of addition does not appear to be critical nor does the viscosity show a significant change.

Cup paper raw material

MALLARD CREEK will be mixed1019 and IMERYSAnd mixing the clay slurry. Will be provided withMixed into the mixture in the proportions obtained for the latex: 70 percent of the total weight of the mixture,clay: 20 percent of the total weight of the mixture,10% (top coat) or 75%, GCC: 75 percent;3％；1019: 21.5% (base coat). The basecoat blend has a pH of about 7.6, a viscosity of 215cps, and a solids content of 60-70%. The topcoat had a pH of 7.8, a solids content of about 57%, and a viscosity of about 240 cps. The reported coating weight is about 8g/m²Applied to the pre-coated paperboard by a doctor blade. The hot cup stock roll, cold cup stock roll and cup bottom stock roll were made of 2 different paints.

Table 16 shows the color coating formulationsEffect of curing on Cobb value.

TABLE 16 curing time and Cobb value

Curing time at 90 DEG C	Cobb value (30 minutes)
		0 minute	39
30 minutes	26
		1 hour	21
3 hours	15
		6 hours	7
12 hours	3

As can be seen from the table, latex coated paperboard (Cobb value 39) was added to the coatingAfter (10 wt.%), the value was reduced to 3.

It does not appear to be an effective film former as latex, therefore, without being bound by theory, it is hypothesized that latex forms a barrier film, andby adding to any holes/pinholes in the latex filmHydrophobicity to act synergistically.

Plastic substrate

To further understand the Cobb effect, the plastic substrate was treated with DOWLatex coating, drying (on plastic substrate) and measuring Cobb (Cobb value 10.5). This data point reflects that the Cobb reading is affected not only by the water permeability of the paper itself, but also by the water immersion or absorption into the coating itself. When 10% is added to the latexWhen the experiment was repeated (also coated onto a plastic substrate), the Cobb value dropped to 3.8, reflecting the hydrophobicity of the film itself.

EXAMPLE 19 SFAE encapsulation of solid latex Polymer beads and addition to cellulose fibers

SFAE was mixed with latex in aqueous propylene glycol by a temperature cycling method involving heating to 90 ℃ for 20 minutes, cooling to 21 ℃ for 1 minute, heating at 90 ℃ for 5 minutes, and cooling to 21 ℃. SFAE may be kneaded with latex.

Prior to wet forming, the particles are dispersed into an aqueous emulsion or slurry, which is then mixed with the cellulosic fiber slurry at a concentration of about 5% to about 50% of the total dry weight. The emulsion may be kneaded with the fiber slurry. The fiber slurry is then applied to a machine comprising a mesh or screen to remove water, and optionally heated. The resulting fibrous material is then applied to a mold and heated until dry. After drying, the resulting product is removed from the mold.

Although the present invention has been described with reference to the above embodiments, it should be understood that modifications and variations are included within the spirit and scope of the present invention. Accordingly, the invention is not to be restricted except in light of the attached claims. All references disclosed herein are incorporated by reference in their entirety.