Polyol fatty acid ester carrier composition

Abstract

To provide methods for treating cellulosic fibrous materials with sucrose fatty acid ester-containing particles (carrier systems) that allow modification of the surface, and to provide a method which includes making such surfaces water-resistant and / or oil / grease-resistant.SOLUTION: The disclosed method provides forming micelle particles by combining at least one sugar fatty acid ester (SFAE) with a polymer (e.g., latex), and applying such particles to a substrate containing a cellulose fiber-based material (e.g., pulp), particularly to form a molded article. Compositions comprising combinations of SFAE, latex, and optionally a mineral or other additives are also disclosed.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] Background of the Disclosure The present disclosure relates generally to treating fiber-containing substrates, and more particularly to treating latex and other fiber-containing substrates. and optionally minerals, e.g., compositions containing such combinations. Treating the substrate with particles containing combined sugar fatty acid esters (SFAE) More particularly, the present disclosure relates to the use of said particles as carriers for coatings, and To provide barrier properties to moldings made from such substrates, carrier coatings This relates to a method of applying the [Background technology]

[0002] In the conventional method, raw materials for producing cellulose fiber-based molded products include wheat, Materials may include culms, wood, sugarcane bagasse, reeds, and edge paper. It can be pulped by chemical pulping to form a mixture that is then hardened in a metal mold. This includes water-soluble acrylic, latex, resin or EVA (ethyl vinyl acetate). The surface can be treated with a coating agent having the above properties.

[0003] In the past decade, such methods have been applied to (a) straw, grain, waste residues and dens (b) selecting a raw material comprising non-toxic rice husks containing phytosan-rich plants; Washing the shell raw material with water to remove dust, soil and contaminants; (d) grinding the raw material consisting of rice husks into powder; (e) Mix the powder thoroughly with the additional premix and water to form a mixture. a step in which an additional premix contains specific food gums, sulfates, hard acids, and processing agents; Certain edible gums are made of latex, pectin and protein gels, and are processed (f) a mixture of a specific edible gum, calcium chloride, and alum; (g) thermally forming the mixture into a product; and (g) removing the product from the mold. (h) a drying step (e.g., all of which are incorporated herein by reference). (See Taiwan Patent Publication No. 500746, which is incorporated herein by reference.) .

[0004] Recent methods include (a) the use of anionic materials (e.g., aluminum silicate and natural waxes) a first auxiliary agent containing a cellulose emulsion) and a nonionic and cationic substance (e.g., Fluorochemical resins, polymer compounds, aliphatic polyamines and alkyl acrylic copolymers (b) separately preparing a pulp using a second auxiliary agent containing a polymer; ) uniformly mixing the pulp, the first adjuvant, and water to form a pulp premix. and (c) mixing a second adjuvant with the pulp premix to form a pulp mixture. and (d) thermoforming the pulp mixture to form a packaging material (e.g., See, for example, U.S. Patent Application Publication No. 2004 / 019999, which is incorporated herein by reference in its entirety. See specification 05 / 0211405).

[0005] Recent methods have been effective in providing water / oil resistance to textile substrates / surfaces. However, more recently, the use of fluorochemicals has been restricted due to environmental and health concerns. This is under strict scrutiny. Compositions and methods for achieving barrier properties (e.g., water / oil resistance) on fiber-based molding substrates It is preferable to use Summary of the Invention

[0006] The present disclosure provides, inter alia, a method for making such treated surfaces water and / or oil resistant / A method for treating a molded surface with carrier particles that impart grease resistance is disclosed. The method comprises mixing at least one sugar fatty acid ester (SFAE) with a polymer such as latex. It is proposed to combine the compound in particulate form and apply such particles to a substrate containing cellulosic material. Such compositions may also include inorganic minerals / pigments.

[0007] In one embodiment, a method for producing a cellulose-containing article comprises the steps of: to a cellulosic fiber furnish, wherein the emulsion or slurry is one of or a step comprising a plurality of sucrose fatty acid esters and one or more carrier particles. and; draining the furnish through one or more meshes or screens. thermoforming the mixture into a product in a mold; and removing the product from the mold. wherein the product has a characteristic that, compared to a cellulosic product not treated with said emulsion or slurry, A method for exhibiting water, oil, and grease resistance is disclosed. Loin fiber furnishes include wheat, wheat stalk, wood, sugarcane bagasse, reeds, and edge and methods involving fibers from paper and combinations thereof.

[0008] In one embodiment, the product is a bowl, plate, bottle, pouch, package, or insert. In another embodiment, the carrier may be a sucrose fatty acid ester, a polymer, a solid latex, or the like. Polymer beads, hollow polymer shells, resin beads, pigment particles, and combinations thereof In a related aspect, the pigment particles include calcium carbonate, titanium dioxide, Examples of suitable inorganic fillers include phosphate clay, silica, silicates, talc, mica and combinations thereof.

[0009] In one embodiment, the particles are made from raw corn starch, rice starch, wheat starch, potato starch, or the like. starch or tapioca starch granules, oat hulls, rice hulls, crushed nut shells, or In another embodiment, the particles further comprise one or more sucrose enzymes. coated with ester and dispersed in an aqueous emulsion or slurry.

[0010] In one embodiment, the aqueous emulsion or slurry is subjected to total drying prior to wet forming. It is mixed with a cellulose fiber slurry at a concentration of about 5% to about 50% by dry weight.

[0011] In another embodiment, the carrier is a polymer, the polymer exhibiting a low glass transition temperature. In a related aspect, the polymer is latex. In another related aspect, the product is low This indicates reduced tack.

[0012] In one embodiment, sucrose fatty acid ester granules containing one or more cargo materials In one aspect, the cargo molecule is selected based on the property to be modified. In a related aspect, such properties may be adjustable (e.g., 3M kits). In another related aspect, Various cargo molecules and / or means for preparing said particles (e.g., heating temperature, heating time, heating Heat-cool cycles, mixing methods, buffers, surfactants, emulsifiers, continuous / discontinuous phase composition, of products made using the composition by selecting the appropriate Different portions may exhibit different properties.

[0013] In one embodiment, the one or more cargo materials include polymers, solid latex polymers, -Beads, resin beads, calcium carbonate, titanium dioxide, kaolin clay, silica, silica Examples of suitable silica gel include talc, mica, and combinations thereof.

[0014] In a further embodiment, the composition comprises thymol, lecithin, alkyl glucosides and their Includes combinations.

[0015] In one embodiment, the particle is a micelle, microcapsule, or nanocapsule.

[0016] In another embodiment, the sucrose fatty acid ester is a mono- or diester.

[0017] In a further embodiment, the sucrose fatty acid ester comprises all saturated fatty acids or saturated and It is a mixture of saturated and unsaturated fatty acids.

[0018] In a related aspect, the sucrose fatty acid ester particles comprise one or more sucrose fatty acids. Contains fatty acid esters.

[0019] In one embodiment, an emulsion comprising the above-described composition is disclosed. Or the plurality of cargo materials comprises latex.

[0020] In another embodiment, an article of manufacture produced by the above-described method is disclosed. [Brief explanation of the drawings]

[0021] [Figure 1] FIG. 1 shows a scanning electron micrograph (SEM) (58x magnification) of untreated medium porosity Whatman filter paper. [Figure 2] FIG. 1 shows an SEM (1070x magnification) of untreated medium porosity Whatman filter paper. [Figure 3] Side-by-side comparison of SEM (27x magnification) of paper made from recycled pulp before (left) and after (right) coating with microfibrillated cellulose (MFC). [Figure 4] Side-by-side comparison of SEM (98x magnification) of paper made from recycled pulp before (left) and after (right) coating with MFC. [Figure 5] FIG. 1 shows the water penetration in paper treated with different coating formulations: Polyvinyl alcohol (PvOH), ◇; SEFOSE® + PvOH, 1:1 (v / v), □; Ethylex (starch), △; SEFOSE® + PvOH, 3:1 (v / v), ×. [Figure 6] FIG. 1 shows water beading on paper treated with an aqueous composition containing two sucrose fatty acid esters with different HLB values ​​and precipitated calcium carbonate. DETAILED DESCRIPTION OF THE INVENTION

[0022] Before describing the present compositions, methods, and methodologies, it is important to note that the present invention is not limited to the specific compositions, methods, and methods described. Such compositions, methods, and conditions are not intended to be limiting, as methods and experimental conditions may vary. It should be understood that the scope of the present invention is limited only by the claims and not by the scope of the present specification. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting. It should also be understood that this is not intended to

[0023] As used in this specification and the appended claims, the singular forms "a," "an," and "the" " includes the reference of several instructions unless the context makes clear otherwise. Thus, for example, reference to "sugar fatty acid ester" includes any reference to a sugar fatty acid ester that would be apparent to one of ordinary skill in the art upon reading this disclosure. one or more sugar fatty acid esters of the type described herein, The composition includes:

[0024] Unless otherwise defined, all technical and scientific terms used herein are within the meaning of the present disclosure. It has the same meaning as commonly understood by a person skilled in the art. As understood to be within the spirit and scope of the present disclosure, Any methods and materials similar or equivalent can be used in the practice or testing of this disclosure.

[0025] As used herein, the terms "about," "approximately," "substantially," and "largely" are used to refer to the same or similar terms as would be understood by one of ordinary skill in the art. The terms are understood as follows and vary to some extent depending on the context in which they are used. If there are uses of the terms that are not clear to a person skilled in the art in light of the context, the terms "about" and "approximately" should be used interchangeably. means plus or minus <10% of the specified term, and "substantially" and "significantly" " means plus or minus >10% of a particular term. "Contains" and " "Consisting essentially of" has their accustomed meaning in the art.

[0026] Barrier coatings on surfaces typically prevent foreign matter (e.g., liquids / gases) from passing through the surface. It functions to prevent the release of foreign substances or to reduce the release of such foreign substances. Various materials that make up the coating can improve the performance of a particular base component. Tex is a very good film former and provides a base coat that seals onto the porous base sheet. It can serve as the main component of the base coat, to which the top coat is added. In this configuration of base and top coats, the latex It acts as a thermal barrier and, for example, polymers can be added to improve performance metrics such as Cobb value.

[0027] Although not a polymer in itself, as disclosed herein, SFAEs are polymers that are based on latex. It has been found to aid in modifying the Cobb value of substrates containing barrier coatings containing Without being bound by any theory, it is believed that latex coatings are produced by the action of water / water vapor on the paper. SFAE can fill the pores and leave pores for penetration into the interstices of porous substrates such as Since SFAE has a hydrophobic surface, water / water vapor is repelled from the pores, improving This combination works well and provides an improved level of performance. This allows for a low Cobb value without compromising product quality.

[0028] In addition, inorganic pigments can be added to the mixture of inorganic particles, latex and SFAE. This allows for improved fine tuning of various properties of the seat. For example, such a seat , together with a combination containing wood fibers to make such sheets waterproof / greaseproof. The sheet may contain bioplastic fibers. Uses cheaper and more common materials such as mechanical or recycled pulp, which is a percentage In such a case, for example, calcium carbonate-latex-SFA The addition of E-mixture provides an improvement that allows for control of the density of the sheet.

[0029] In one embodiment, a cellulose ester having water resistance and / or oil and grease resistance is used. A method for producing a sucrose-containing article, comprising: and one or more carrier particles, and adding the furnish to the paper stock and passing the furnish through one or more meshes or screens. and draining the water. The fibrous article is then heated to remove any remaining water and placed in a bowl, plate, or container. A finished article such as a packaging container or insert is produced.

[0030] In a related aspect, carrier particles include solid latex polymer beads, hollow polymer Shells, resin beads, or calcium carbonate, titanium dioxide, kaolin clay, silica These include pigment particles such as silicate, talc, or mica. In another related aspect, the particles are made of raw corn starch, rice starch, wheat starch, or the like. Starch, potato starch or tapioca starch granules, oat hulls, rice Organic particles such as hulls, crushed nut shells, or other similar particles or combinations thereof. It is also possible.

[0031] In one embodiment, the particles are coated with one or more sucrose fatty acid esters. and can be dispersed in an aqueous emulsion or slurry. The slurry is then mixed with a mixture of about 5% to about 10%, about 10% to about 10% of the total dry weight of the slurry prior to wet forming. At concentrations of 20%, approximately 20% to approximately 30%, approximately 30% to approximately 40%, or approximately 40% to approximately 50% , may be mixed with a cellulose fiber slurry. Without being bound by any theory, However, sucrose fatty acid esters are often encountered in the use of polymer particles such as latex. Overcomes adhesion problems. This is due to the use of polymers with low glass transition temperatures, or latex. This is especially true in the case of

[0032] In a related aspect, the size and distribution of the coated particles may be determined by the size and distribution of the coated particles as they form. Any suitable material may be selected by one skilled in the art to move towards the surface of the article during the process. Without wishing to be bound by theory, this is due to the amount of coating on the surface compared to the bulk of the item. Increased concentration of coated particles improves the cost benefit of adding coated particles In another related aspect, the increased concentration of coated particles allows for heating and drying. Sucrose fatty acid esters and / or polymers on the surface of the article during the drying process film formation and melting, and catalytic or chemical reactions with optional additives. This allows for bonding to the cellulose substrate, initiating cross-linking of the components, or otherwise Chemically modifying the surface of an article to develop water, oil, and / or grease resistance Can.

[0033] In another related aspect, the exfoliating properties of one or more sucrose fatty acid esters This allows for the use of potentially tacky or adhesive additives in the composition, and improves the ballast properties of the article. It overcomes the shortcomings of the prior art while contributing to rear characteristics.

[0034] Use of the present disclosure may be used to provide water, oil, and / or grease resistance. This eliminates the need to coat, dip, or spray additional materials onto the surface of the article. be eliminated or greatly reduced.

[0035] In one embodiment, the one or more sucrose fatty acid esters are present in micelles / microcapsules. Capsules / nanocapsules can be formed and can be used as carriers themselves, and the carriers is combined with thymol, lecithin, and alkyl glucoside to form a solid latex polymer beads, resin beads, or calcium carbonate, titanium dioxide, kaolin clay, silica It can encapsulate pigment particles such as silicates, talc, or mica. Also, changes in particle size can be affected by using longer aliphatic groups. (i.e., micelles / microcapsules / nanocapsules have longer acyl groups and smaller Furthermore, due to the high DS, a bilayer structure similar to that of the cell membrane can be formed.

[0036] In one embodiment, the present disclosure provides a method for treating a cellulosic fiber-based substrate with the disclosed carrier combination. This makes the resulting material, among other things, highly oil / grease resistant and hydrophobic, These sugar fatty acid esters can be easily digested by bacterial enzymes, for example. If removed, as such it is easily digested. Derivatized surfaces are very It has high heat resistance and can withstand temperatures up to 250°C, and is more resistant to heat than the base material underneath. Such materials can be more impermeable to the body. In all of the embodiments that may be utilized, the problem of derivatizing the hydrophilic surface of cellulose is addressed. This is an ideal solution.

[0037] Advantages of the products and methods disclosed herein include that the coating composition is reproducible. Agricultural sources - made from sugars and vegetable oils; has a low toxicity profile and is suitable for food contact Reduces the coefficient of friction of the paper / paperboard surface even at high water resistance levels (i.e., paper is Special emulsification adjusted to avoid making the surface too slippery for processing or end use Can be used with or without equipment or emulsifiers; traditional paper recycling programs Compatible with: e.g. polyethylene, polylactic acid, or wax-coated paper This includes not affecting playback operations in a negative way, such as PCC / GCC. The growing use of inorganic chemicals takes advantage of the inherent properties of fillers (eg, low abrasiveness).

[0038] Other benefits of the coating formulation include: - Relative ease of fabrication; - Base coating is performed well at high speeds at the target coat weight; - No roll blocking; - No problems with purification; - The coating can be adjusted lower for blade coating Viscosity: 22 It can be made at 60-75% solids with 0-350 cps; - High solids content includes that SFAE did not adversely affect viscosity. Demonstrating lower dryer costs; - On the surface of an article to impart water, oil, and / or grease resistance The need to coat, dip, or spray additional materials is eliminated or greatly reduced. Significantly reduce Includes:

[0039] As used herein, "bio-based" refers to living (or formerly living) organic matter. means a material intentionally made from substances derived from the body. Materials containing at least about 50% of such substances are considered biobased.

[0040] As used herein, "bind," including its grammatical variations, essentially means a single It means to adhere or to be made to adhere as a mass.

[0041] As used herein, a "support" refers to a material that supports or supports another material, such as a polymer, pigment, or catalyst. means the substance used to carry.

[0042] As used herein, "cargo" refers to the substance or material delivered by a carrier. do.

[0043] As used herein, "furnish" refers to the raw materials in a water suspension from which paper is made. It refers to a predetermined mixture of fibrous and non-fibrous materials such as fillers, sizes, and dyes. Taste.

[0044] As used herein, "cellulosic" refers to an object (e.g., bag, sheet) or film. The material can be formed or extruded into a material such as a film or filament. means any natural, synthetic or semi-synthetic material that can be used to make filaments, Structurally and functionally similar to cellulose, e.g., in coatings and adhesives (e.g., calcines). Another example is the main component of the cell walls of most plants. Complex carbohydrates (C6H) composed of glucose units 10 O5) n The cellulose is , and is cellulose-based.

[0045] As used herein, "capsule" means a substance or material that contains another substance or material. In a related aspect, micro- and nano- refer to micro- and nano-. Refers to units on the chromate and nanometer scales.

[0046] As used herein, "coat weight" refers to the weight of material (wet or dry) applied to a substrate. It is the weight in pounds per ream or grams per square meter specified. It is expressed in mu.

[0047] As used herein, the "Cobb value" refers to the weight of water (per unit area) of a sample. The procedure for determining "Cobb value" is in accordance with TAPPI Standard 441-om. The Cobb value is calculated by subtracting the initial weight of the sample from the final weight of the sample, then covering it with water. The value reported is calculated by dividing by the area of ​​the sample being used. The absorbed water mass is expressed as grams of water absorbed per torr.

[0048] As used herein, "compostable" means that the solid product is biodegradable in soil. do.

[0049] As used herein, "edge wicking" refers to the formation of pores between fibers in a paper structure. limited to capillary penetration of pores in the fiber, diffusion through fibers and bonds, and surface diffusion of the fiber. Absorption of water at the outer limits of the structure by one or more mechanisms including but not limited to: In a related aspect, the present invention relates to a coating containing a sugar fatty acid ester as described herein. This prevents edge wicking in the treated product. A similar problem exists where grease / oil gets trapped in folds that may be present in paper or paper products. The paper structure is created by folding, pressing, or crushing the paper structure. The "grease creasing effect" refers to the effect of grease in the paper structure. It can be defined as the absorption of

[0050] As used herein, "effect," including its grammatical variations, refers to the specific property of a particular material. It means to give.

[0051] As used herein, "hydrophobic material" means a material that does not attract water. rosin, resin, sugar fatty acid ester, diketene, shellac, vinyl acetate, PL A, PEI, oils, fats, lipids, other water-repellent chemicals, or a combination of these are hydrophobic substances. be.

[0052] As used herein, "hydrophobic" refers to the property of being water-repellent and tending to repel and not absorb water. means.

[0053] As used herein, "lipid-resistant" or "oleophobic" refers to the ability to repel lipids, such as fats, grease, It refers to the property of tending to repel and not absorb fat, etc. In a related manner, grease resistance The activity can be measured by the "3M kit" test or the TAPPI T559 kit test. In another related aspect, the "second oleophobic material," if any, may be, for example, a perfluoroalkyl or These are substances that are lipid-resistant, such as polyfluoroalkyl.

[0054] As used herein, "micelle" refers to an aggregate of molecules in a colloidal solution, including grammatical variations. means.

[0055] As used herein, an "emulsion" refers to a liquid that is normally immiscible (unmixable or blendable). In a related aspect, an emulsion refers to a mixture of two or more liquids (which cannot be blended). water-in-water (w / o), oil-in-water (o / w) or double emulsions (e.g., w / o / w) Ugh.

[0056] As used herein, "cellulose-containing material" or "cellulose-based material" refers to a material that is Such materials include, for example, paper, paper sheets, and the like. Paperboard, paper pulp, food storage cartons, parchment, cake board, Butcher paper, release paper / liner, food storage bags, shopping bags, shipping bags, bacon board, insulating Rimming materials, tea bags, coffee or tea containers, compost bags, tableware, hot or Containers for holding cold drinks, cups, lids, plates, bottles for storing carbonated liquids, Gift cards, still liquid storage bottles, food wrap, food waste disposal containers, food handling equipment, fabric fibers (e.g., cotton or cotton blends), water storage and and transport equipment, alcoholic or non-alcoholic beverages, outer casings or containers for electronic products Examples include screens, interior or exterior furniture components, curtains, and upholstery items. Examples include, but are not limited to:

[0057] As used herein, a "release paper" is a sticky surface that readily adheres to an adhesive or mastic. In one aspect, the present disclosure refers to a paper sheet used to prevent the The coatings used replace or reduce the use of silicon or other coatings. This can be used to create materials with low surface energy. is measured by contact angle measurement (e.g., Optical Tensiometer and / or High Pressure Chamber;Dyne Testing, Staff ordshire, United Kingdom) or Surface Energy Use of Test Pens or Inks (e.g., Dyne Testing, Staffordshire, United Kingdom) It's easily achievable.

[0058] As used herein, in relation to SFAE, "peelable" means that once the SFAE coating is Once applied, it should be removable from the cellulose-based material (e.g., by virtue of its physical properties). In this specification, in relation to SFAE, "Non-peelable" means that once the SFAE coating is applied, it will not peel off from cellulose-based materials. By "substantially irreversibly bound" is meant to bind to the material (e.g., removable by chemical means).

[0059] As used herein, "fluffy" refers to raw cotton or Styrofoam (registered trademark). "peanut" refers to a fluffy solid material having the appearance of peanuts. In one embodiment, Fluffy materials include nanocellulose fibers (e.g., MFC), cellulose nanocrystals, and and / or cellulose filaments and sugar fatty acid esters, and the resulting fibers or The filaments or crystals are hydrophobic (and dispersible), and the composite (e.g., It can be used on materials such as steel, plastic, etc.

[0060] As used herein, "fibers in solution" or "pulp" refers to cellulose fibers in wood, fiber, Lignocellulosic acid prepared by chemical or mechanical separation from crops or waste paper The term "cellulose-based fiber material" refers to a material in which cellulose fibers are treated by the methods disclosed herein. In a related manner, the cellulose fibers themselves isolate the sugar fatty acid esters attached to them. The bound cellulose fibers have properties that are separate and distinct from the free fibers. (e.g., pulp or cellulose fibers or nanocellulose or microcellulose) If the material is a cellulose-sugar fatty acid ester bonded material, it is easier to bond than unbonded fibers. (In this case, hydrogen bonds do not form between fibers.)

[0061] As used herein, "repulpable" refers to a paper or paperboard product that can be recycled for use in the manufacture of paper or paperboard. This means making it suitable for being crushed into an amorphous, soft mass for reuse.

[0062] As used herein, "adjustable" means, including grammatical variations thereof, an amount of material that can be adjusted to achieve a particular result. This means adjusting or adapting the method so that

[0063] As used herein, the term "water contact angle" refers to the angle at which a liquid / vapor interface meets a solid surface. The angle measured through the liquid at which the solid surface is encountered by the liquid. Quantifying wettability. Contact angle measures the strength of interaction between liquid and solid molecules, respectively. This reflects the comparison of their respective types and strengths of action. On a surface, a water droplet exhibits a contact angle of 0° to 30°. Generally, when the water contact angle is greater than 90°, The water contact angle is measured using an optical tensiometer (e.g., a Dyne See Testing, Staffordshire, United Kingdom can be easily obtained using

[0064] As used herein, "breathable" refers to the breathability or ability of a textile to transport moisture. There are at least two different measurement methods. One of them, ISO 15496, The compliant MVTR (Moisture Vapor Transmission Rate) test measures the breathability (WVP) of the fabric and therefore the It measures the amount of sweat that passes through one square meter of fabric in 24 hours. Determines the number of grams of moisture (water vapor) that pass through (the higher the level, the more breathable it is) .

[0065] In one embodiment, the TAPPI T 530 Hercules size test (i.e., resistance to The ink-based paper sizing test may be used to determine waterfastness. Ink resistance by the ules method is best classified as a test for direct measurement of the degree of penetration. Others classify it as a speed of penetration test. The best test is "measuring sizing." No test has been performed. Test selection depends on end use and mill control needs. Suitable for use as a mill control sizing test to accurately detect changes in sizing levels It is particularly suitable for providing reproducible results, reducing test time and automating endpoint determination. This provides the sensitivity of the ink float test while determining the

[0066] It is measured by the resistance to the penetration of aqueous liquids through the paper or the absorption of aqueous liquids into the paper. Sizing is an important feature of many papers. Typical of these are bags, container boards, Paper, meat wrap, writing, and some printing grades.

[0067] Such methods are used to monitor the production of paper or paperboard for specific end uses. may be used, provided that an acceptable correlation between the test values ​​and the end-use performance of the paper is established. Due to the nature of the test and the permeant, it is This method does not necessarily correlate sufficiently to be applicable to the application requirements. Other methods measure sizing by surface contact, surface penetration, or absorption. Ability to simulate water contact or absorption means in end use This method optimizes sizing chemical usage costs. It can also be used for

[0068] As used herein, "oxygen permeability" refers to the degree to which a polymer allows the passage of gases or fluids. The oxygen permeability (Dk) of a material is determined by the diffusivity (D) (i.e., the rate at which oxygen molecules can cross a material). is a function of the rate at which oxygen is absorbed per volume of material and the solubility (k) of the material. The oxygen permeability (Dk) value is typically 10 to 150 x 10 -11 (cm 2 ml The hydrogel water content and oxygen permeability (units) are within the range of (s ml mmHg) / (s ml mmHg). A semi-logarithmic relationship is shown between the saturation and the barrer units. (ISO) specifies permeability using the SI unit of hectopascal (hPa) for pressure. Therefore, Dk=10 -11 (cm 2 ml O2) / (s ml hPa). The units of pressure in hPa can be converted to units of pressure in hPa by multiplying them by the constant 0.75.

[0069] As used herein, "biodegradable" means, including grammatical variations thereof, decomposition by the action of living organisms (e.g., It means that it can be broken down (e.g., by microorganisms) into particularly harmless products.

[0070] As used herein, "recyclable" means a material suitable for reuse, including grammatical variations thereof. Can be processed to produce the material, or (for used and / or scrap materials) It means a material that can be processed.

[0071] As used herein, "latex" refers to a stable dispersion of polymer particles in an aqueous medium. Latex is found in nature, but it is emulsified using surfactants. Synthetic latex can be made by polymerizing monomers such as styrene. Latex is a milky fluid found in 10% of all flowering plants (angiosperms). It contains proteins, alkaloids, starches, sugars, oils, tannins, resins, and gums. It is a complex emulsion consisting of cellulose, which solidifies when exposed to air.

[0072] As used herein, "fillers" refer to additives used in papermaking to improve the optical and physical properties of the sheet. The term "particles" refers to finely divided white minerals (or pigments) added to paper furnishes for papermaking. Fills gaps and voids, thus improving brightness, opacity, smoothness, gloss, and printability. This serves to produce a sheet with increased, but generally reduced, bond and tear strength. Common papermaking fillers include clay (kaolin, bentonite), calcium carbonate, These include cellulose (both GCC and PCC), talc (magnesium silicate), and titanium dioxide. It can be obtained.

[0073] As used herein, "tackiness" refers to the quality of a material that remains adhered to a surface that comes into contact with said material. It can be measured by ASTM D4501.

[0074] As used herein, the term "Gurley second" or "Gurley number" refers to a number ) is the pressure that 100 cubic centimeters (deciliters) of air expends in a given volume of 1.0 square inch. The number of seconds required for water to pass through the material at a pressure differential of 4.88 inches (0.176 psi) It is a unit that indicates the porosity (ISO 5636-5:2003). The "Gurley number" is the force required to deflect a material held vertically by a given amount (1 milligram of force). is a unit of measurement of the force required to measure a portion of the material. Such a value is called Gu Instruments from Ryley Precision Instruments (Troy, New York) ork).

[0075] The hydrophilic-lipophilic balance (HLB) of a surfactant is calculated based on the values ​​of different regions of the molecule. The viscosity of a substance is a measure of the degree to which it is hydrophilic or lipophilic, as determined by the viscosity of that substance.

[0076] Griffin's method for nonionic surfactants, described in 1954, HLB=20*M h / M [In the formula, M h is the molecular mass of the hydrophilic portion of the molecule, and M is the molecular mass of the entire molecule The results are expressed on a scale of 0 to 20. An HLB value of 0 indicates a completely lipophilic / hydrophobic mixture. An HLB value of 20 corresponds to a completely hydrophilic / lipophobic molecule.

[0077] The HLB value can be used to predict the surfactant properties of a molecule. <10: Fat-soluble (water-insoluble) >10: Water-soluble (fat-insoluble) 1.5~3: Defoamer 3-6: W / O (water-in-oil) emulsifier 7-9: Wetting and spreading agent 13-15: Cleaning agent 12-16: O / W (oil-in-water) emulsifier 15-18: Solubilizers or hydrotropes

[0078] In some embodiments, the sugar fatty acid esters disclosed herein (or the esters) In other embodiments, the HLB value of the composition (including the composition) may be in the lower range. HLB values ​​of the sugar fatty acid esters (or compositions containing said esters) disclosed herein In one embodiment, S with different HLB values ​​can be in the medium to higher range. Mixing of FAEs is available.

[0079] As used herein, "SEFOSE®" refers to a type or mixture of soybean oil and sesame oil. Sucrose fatty acid ester (soybean oil fatty acid ester) containing multiple unsaturated fatty acids The name is Procter & Gamble Chemicals (Cincinnati It is commercially available from Pharmacy, OH under the trade name SEFOSE® 1618U. (See polysoybean oil sucrose below.) As used herein, "OLEAN (registered trademark)" is a compound of formula C n+12 H 2n+22 O 13 and all fatty acids are saturated fatty acids is the name of sucrose fatty acid esters, and is a Procter & Gamble SFAE also offers a variety of these SFAEs. It can be purchased from Mitsubishi Chemical Foods Corporation (Tokyo, Japan), which provides

[0080] As used herein, "soybean oil fatty acid ester" refers to a mixture of salts of fatty acids derived from soybean oil. means.

[0081] As used herein, "oilseed fatty acids" refers to fatty acids derived from soybeans, peanuts, rapeseed, barley, canola, and La, sesame seeds, cotton seeds, palm kernels, grape seeds, olives, safflowers, sunflowers, copra , corn, coconut, flaxseed, hazelnuts, wheat, rice, potato, Including but not limited to mackerel, legumes, camelina seeds, mustard seeds, and combinations thereof The term "fatty acids of plant origin" refers to fatty acids of plant origin including those of the above.

[0082] As used herein, "wet strength" refers to the ability of a paper to hold together when it is wet. It is a measure of how well a web of fibers can resist breaking forces. Wet strength is measured by the Thwing-Albert Instrument Company (W Finch Wet Strength Device in Berlin, NJ) e, in which case wet strength is typically measured using epoxy resins, including Benzene, cationic glyoxylated resin, polyamidoamine-epichlorohydrin resin, poly This is provided by wet strength additives such as triamine-epichlorohydrin resins. In some embodiments, the SFAE-coated cellulose-based materials disclosed herein may , which provides such wet strength in the absence of such additives.

[0083] As used herein, "wet" means filled or saturated with water or another liquid. means.

[0084] In one embodiment, the method disclosed herein involves mixing latex and inorganic particles (e.g., clay). mixing the slurry with sugar, talc, and calcium carbonate to form a slurry; blending the fatty acid ester with the aqueous coating to form a water-based coating; and applying a coating of the contacted cellulose-based material to the cellulosic material, the method comprising: Cellulose-based materials are subjected to heat, radiation, catalysts, or a combination of these, and coatings are applied to cellulosic materials. In a related aspect, the method further comprises exposing the compound to a sufficient amount of time to allow binding. Such radiation may include UV, IR, visible light, or a combination thereof. In another related embodiment, the reaction is carried out at room temperature (i.e., 25°C). The reaction can be carried out at a temperature of from about 50°C to about 150°C, from about 50°C to about 100°C, or from about 60°C to about 80°C. The surface of the resulting cellulosic material is similar to that of a cellulosic material that has not been treated in this way. It shows a lower Cobb value compared to the surface.

[0085] As disclosed herein, fatty acid esters of all sugars, including monosaccharides, disaccharides, and trisaccharides, are The sugars and fats are suitable for use in connection with this aspect of the disclosure. The acid esters may be saturated, unsaturated, or a combination of the two. including mono-, di-, tri-, tetra-, penta-, hexa-, hepta-, or octa- ter-esters, and combinations thereof.

[0086] Without being bound by any theory, it is believed that the sugar fatty acid ester and cellulose-based material The interactions between the materials can be ionic, hydrophobic, van der Waals interactions, or covalent bonds. In a related aspect, the cellulose Sugar fatty acid esters attached to base materials (e.g., saturated and unsaturated fatty acids) The reaction may be substantially irreversible (using an SFAE containing a combination of acids).

[0087] Furthermore, the binding of sugar fatty acid esters alone at sufficient concentrations can make cellulosic materials hydrophobic. That is, the hydrophobicity is provided by the sugar-fatty acid ester bond alone, and in particular by the Other properties such as strengthening, stiffening, and bulking of cellulose-based materials can be achieved. Wax, rosin, resin, diketene, shellac, vinyl acetate, PLA, PE I, oil, other water-repellent chemicals, or a combination thereof (i.e., a second hydrophobic material) This is achieved without any additional effort.

[0088] An advantage of the present disclosure is that multiple fatty acid chains react with cellulose and two sugar molecules in the structure. For example, the disclosed sucrose fatty acid esters produce a rigid crosslinked network, making them suitable for use in paper, paperboard, and elastomeric products. Improved strength and durability of fibrous webs such as fabrics, wet-laid nonwovens, and textiles. Therefore, the potential undesirable effects of some fillers (e.g., calcium carbonate and The advantage of this is that it can overcome the drawbacks of other sizing or This is not seen in hydrophobic treatment chemistries. Also, the sugar fatty acid esters disclosed are different from other It also develops / increases wet strength, a property that is not present when using many water-resistant chemistries. Make it big.

[0089] Another advantage is that the disclosed sugar fatty acid esters soften the fibers and increase the space between them. This increases the bulk without substantially increasing the weight. Repulping the fibers and cellulose-based materials modified as disclosed herein Furthermore, water, for example, can easily "push" through low surface energy barriers. ed)" and into the seat.

[0090] Saturated SFAEs are typically solid at the nominal processing temperature, and unsaturated SFAEs are typically Therefore, a uniform and stable dispersion of saturated SFAE in the aqueous coating can be achieved by Without significant interaction or incompatibility with other coating components, which are typically hydrophilic Such dispersions also allow for the formation of coating rheology. without adversely affecting coating application, uniformity, or coating performance characteristics. It is possible to prepare a saturated SFAE with a high concentration. During the composite process, when the saturated SFAE particles melt and spread, the coating surface becomes hydrophobic. In one embodiment, a method for producing a bulky fibrous structure that retains strength even when exposed to water is used. Generally, dried fiber slurries are easily decomposed when exposed to water. Forming a dense structure. Molded fiber products made using the disclosed methods include: They are lightweight, strong, and resistant to exposure to water and other liquids, making them ideal for paper plates, drink holders, and more. These include holders (e.g., cups), lids, food trays and packaging.

[0091] In one embodiment, the sugar fatty acid ester is mixed with polyvinyl alcohol (PvOH) to form As disclosed herein, inorganic sizing agents can be used to produce water-resistant coatings. Sugar fatty acid ester and PvOH, including the possibility of reducing the amount of PvOH in the case of a mixture PvOH is a good film former by itself and is a good additive to cellulose. It is known in the art that cellulose forms strong hydrogen bonds with water, but not with hot water. In one embodiment, the use of PvOH emulsifies the sugar fatty acid esters to In one aspect, PvOH crosslinks along the fiber, helping to form a water-based coating. This provides the sugar fatty acid ester with an abundant source of OH groups for improving the strength of the paper, e.g., especially the wet strength, and Increases water resistance and durability beyond that possible with PvOH alone. The saturated sugar fatty acid esters that are used include dialdehydes (e.g., glyoxal, glutaraldehyde, Crosslinking agents such as aldehydes can also be used.

[0092] In one embodiment, the sugar fatty acid ester comprises or is a sucrose ester of a fatty acid. Numerous methods are available for making or disposing of the sugar fatty acid esters of the present disclosure. is known and available for providing other methods, and all such methods are within the scope of this disclosure. For example, in some embodiments, the lipid Fatty acid esters are sugars, soybean oil, sunflower oil, olive oil, canola oil, peanut oil, and One or more species obtained from oilseeds, including but not limited to, and mixtures thereof It may be preferable to synthesize it by esterifying multiple fatty acid moieties.

[0093] In one embodiment, the sugar fatty acid ester is an ester in which one or more of the hydroxyl hydrogens are esterified. The term "sugar moiety" includes sugar moieties including, but not limited to, sucrose moieties substituted with a moiety. In a related embodiment, the disaccharide ester is represented by formula I

[0094] [ka]

[0095] [ka]

[0096] (wherein "R" is a straight, branched, or cyclic saturated hydrocarbon group having from about 8 to about 40 carbon atoms. (The term "aliphatic" refers to a cyclic or unsaturated aliphatic or aromatic moiety.) and at least one "A", at least one, at least two, at least three of the formula one, at least four, at least five, at least six, at least seven, and all Eight "A" moieties match structure I.] In a related aspect, the sugar fatty acid esters described herein have the structure: -, tri-, tetra-, penta-, hexa-, hepta-, or octa-esters, and and combinations thereof, and the aliphatic groups may all be saturated aliphatic groups; Alternatively, it may contain saturated and / or unsaturated groups, or a combination thereof.

[0097] Suitable "R" groups include any form of aryl, including those containing one or more substituents. Aliphatic moieties are also included, and these substituents may occur on any carbon in the moiety. It is possible to include functional groups within the aliphatic portion, such as ether, ester, thio, amino, phospho, etc. Oligomeric and polymeric aliphatic moieties, such as sorbitan, polyisoprene, and the like, are also included. Also included are resorbitan and polyalcohol moieties. Aliphatic (or aromatic) compounds containing an "R" group Examples of functional groups that can be added to the (aromatic) moiety include halogen, alkoxy, hydroxy, , amino, ether and ester functional groups. In one embodiment, the moiety may have a crosslinkable functional group. Alternatively, the SFAE may be surface-crosslinked. The double bonds present may be used to facilitate reaction with other surfaces.

[0098] Suitable disaccharides include raffinose, maltodextrose, galactose, and sucrose. combinations of glucose, combinations of fructose, maltose, lactose, mannose combinations of erythrose, isomaltose, isomaltulose, trehalose, Trehalulose, cellobiose, laminaribiose, chitobiose, and combinations thereof Examples include:

[0099] In one embodiment, the substrate for adding the fatty acid includes starch, hemicellulose, lignin, or a combination thereof.

[0100] In one embodiment, the composition comprises a starch fatty acid ester, wherein the starch is Dentco Corn starch, waxy corn starch, potato starch, wheat starch, rice starch sago starch, tapioca starch, sorghum starch, sweet potato starch, and It may come from any suitable source, including mixtures of these.

[0101] More particularly, the starch may be unmodified starch or a starch that has been chemically, physically or enzymatically modified. The starch may be modified by a process.

[0102] Chemical processing involves the use of chemicals to produce modified starches (e.g., plaster starch materials). Included within the scope of chemical processing are optional treatments of starch such as depolymerization of starch. , starch oxidation, starch reduction, starch etherification, starch esterification, de These include, but are not limited to, starch nitrification, starch degreasing, starch hydrophobization, etc. Chemically modified starch is prepared by using any combination of chemical treatments. Examples of chemically modified starches include alkenyl succinic anhydrides, especially octenyl succinic acid. Reaction of citric anhydride with starch to produce hydrophobic esterified starch; 2, 3-epoxypropyltrimethylammonium chloride is reacted with starch to give cationic Reaction to form hydroxylated starch; ethylene oxide is reacted with starch to form hydroxylated Reaction to produce oxidized starch; hypochlorite reacts with starch to produce oxidized starch The reaction that produces; The reaction that produces acid depolymerized starch by reacting acid with starch; Starch Methanol, ethanol, propanol, methylene chloride, chloroform, carbon tetrachloride, etc. A reaction in which starch is degreased with a solvent such as 1,2-dichloro-2,4-dichloro-1,4 ...

[0103] Physically modified starch is starch that has been physically treated in a way that provides physically modified starch. Physical processing includes heat treatment of starch in the presence of water, heat treatment of starch in the presence of heat, crushing of starch granules by any mechanical means, These include, but are not limited to, pressure treatment to melt the starch granules. Physically modified starches can also be prepared by using any combination of physical treatments. Examples of physically modified starches include starches that have been modified to swell the starch granules without granule rupture. Heat treatment of starch in an aqueous environment; anhydrous starch granules to induce polymer rearrangement Heat treatment of the granules; fragmentation of starch granules by mechanical degradation; and melting of starch granules. Examples of such methods include the pressure treatment of starch granules in an extruder to raise the temperature.

[0104] Enzymatically modified starch is a starch that has been treated with an enzyme, optionally in a manner to provide an enzymatically modified starch. Enzymatic processing includes the addition of α-amylase and starch. Reaction of proteases with starch, reaction of lipases with starch, phosphorylase These include, but are not limited to, reactions of hydroxylase with starch, reactions of oxidase with starch, etc. Enzymatically modified starch is prepared by using any combination of enzyme treatments. An example of enzymatic processing of starch is the reaction of starch with alpha-amylase enzyme. The reaction produces depolymerized starch; the reaction produces debranched starch by reacting alpha-amylase with starch. reacting protease enzymes with starch to produce debranched starch; A reaction that produces starch with reduced protein content; a lipase enzyme is reacted with starch a reaction to produce starch with reduced lipid content; reacting to produce enzymatically modified phosphated starch; and One example is the reaction of a starch with an enzyme to produce enzymatically oxidized starch.

[0105] The disaccharide fatty acid esters are represented by formula I, wherein the "R" groups are aliphatic and may be linear or branched. and is saturated or unsaturated and has about 8 to about 40 carbon atoms. The ester may be a fatty acid ester.

[0106] As used herein, the terms "sugar fatty acid ester" and "sucrose fatty acid ester" includes compositions with different purities and mixtures of compounds at optional purity levels. For example, the sugar fatty acid ester compound can be a substantially pure material, i.e., having a given number of "A" groups substituted with only one type of structural moiety (i.e., all the "R" groups are the same and all of the sucrose moieties are substituted to an equal extent) It can contain different degrees of substitution, but all of the substituents have the same "R" group structure. Also included are compositions containing a blend of two or more sugar fatty acid ester compounds, which are "A" The degree of substitution of the "R" groups varies, and the substituent moieties of the "R" groups are independently selected from two or more "R" groups of Structure I. In a related aspect, the sugars in the composition are selected from the group consisting of: The fatty acid esters may be the same or different (i.e., different sugar fatty acid esters). The "R" groups may be the same or different, including mixtures thereof.

[0107] In the compositions of the present disclosure, the composition comprises sugar fatty acid ester compounds having a high degree of substitution. In one embodiment, the sugar fatty acid ester is sucrose polysoybean fatty acid.

[0108] [ka]

[0109] Sugar fatty acid esters can be prepared by known esterification methods using substantially pure fatty acids. These can be made by the polymerization of sugars and saccharides extracted from natural sources, e.g., oilseeds. Fatty acid esters in the form of fatty acid glycerides derived from oils such as those found in soybean oil It can also be prepared by interesterification using fatty acid glycerides. Transesterification reactions to provide esterified fatty acid esters are described, for example, in U.S. Pat. No. 3,963,699. Specification of No. 4517360; Specification of No. 4518772; No. 46110 Specification No. 55; Specification No. 5767257; Specification No. 6504003; Specification No. 612 1440; 6995232, and WO 1992 / 00436 No. 1 (A1), the entire contents of which are incorporated herein by reference. do.

[0110] In addition to creating hydrophobic sucrose esters via transesterification, acid chlorides can also be converted to sucrose. Cellulose can be obtained by reacting it directly with polyols containing a ring structure similar to cellulose. Similar hydrophobicity can be achieved in fiber-based articles.

[0111] As mentioned above, sucrose fatty acid esters are prepared from glycerides derived from natural sources. It can be prepared by transesterification of sucrose from a methyl ester feedstock (e.g., See US Pat. No. 6,995,232, which is incorporated herein by reference in its entirety. As a result of the source of fatty acids, sucrose fatty acid esters can be prepared using The feedstocks used are a variety of saturated and esterified fatty acids with fatty acid moieties containing 12 to 40 carbon atoms. Contains unsaturated fatty acid methyl esters. This is a product made from such sources. This is reflected in certain sucrose fatty acid esters, because the sucrose moiety containing product This is because the compound contains a mixture of ester moiety substituents, and with reference to Structure I above, The "R" groups are in a ratio of 12, reflecting the feedstocks used to prepare the sucrose esters. To further illustrate this point, soybean oil is a mixture of 26 to 30 carbon atoms. The sucrose esters derived from soybean oil are 26% by weight of oleic acid (H3C-CH2] 7-CH=CH-[CH2]7-C(O)OH) triglyceride, 49% by weight of linoleic acid acid (H3C-[CH2]3-[-CH2-CH=CH]2-[-CH2-]7-C(O )OH) triglyceride, 11% by weight of linolenic acid (HC—[—CH—CH═CH -]3-[-CH2-]7-C(O)OH), and 14% by weight of Seventh Ed. Of the Contains a variety of saturated fatty acid triglycerides as listed on the Merck Index All of these fatty acid moieties are a mixture of species with "R" group structures that reflect This is a typical example of the "R" group of the substituent of the product sucrose fatty acid ester. Therefore, fatty acid feedstocks derived from natural sources, such as soybean oil fatty acid sucrose, are employed. When referring to sucrose fatty acid esters herein as products of reactions involving The various components typically found as a result of the source from which the cellulose fatty acid esters are prepared are: In a related aspect, the sugar fatty acid ester is a low viscosity (e.g., It may also be one that exhibits a resistance of about 10 to 2000 centipoise at room temperature or standard atmospheric pressure. In the above, unsaturated fatty acids may have one, two, three or more double bonds.

[0112] In one embodiment of the present disclosure, the sugar fatty acid ester, in particular the disaccharide ester, has an average more than about 6 carbon atoms, about 8 to 16 carbon atoms, about 8 to about 18 carbon atoms, about 1 4 to about 18 carbon atoms, about 16 to about 18 carbon atoms, about 16 to about 20 carbon atoms, It is formed from fatty acids having about 20 to about 40 carbon atoms.

[0113] In one embodiment, the sugar fatty acid esters are hydrophobic depending on the form of the cellulose-based material. The sugar fatty acid ester (S When FAE is bonded to a cellulose-based material as a coating, SFAE is at least about 0.1 g / m on the surface of the cellulose-based material. 2 ~Approx. 1.0g / m 2 , Approximately 1.0g / m 2 ~about 2.0g / m 2 , about 2g / m 2 ~about 3g / m 2 Coating weight of In a related aspect, it is present at about 3 g / m 2 ~approx. 4g / m 2 , approximately 4 g / m 2 ~ Approximately 5g / m 2 , about 5g / m 2 ~about 10g / m 2 , about 10g / m 2 ~about 20g / m 2 exists In another embodiment, the cellulose-based material can be a melt-blown material containing cellulose fibers. When in a liquid form, the SFAE comprises at least about 0.025% (wt / wt) of the total fiber present. t) In a related aspect, it is present at a concentration of about 0.05% of the total fiber present. (wt / wt) ~ approx. 0.1% (wt / wt), approx. 0.1% (wt / wt) ~ approx. 0.5% ( wt / wt), approx. 0.5%(wt / wt) ~ approx. 1.0%(wt / wt), approx. 1.0%(w t / wt) ~ approx. 2.0% (wt / wt), approx. 2.0% (wt / wt) ~ approx. 3.0% (wt) / wt), approx. 3.0%(wt / wt) ~ approx. 4.0%(wt / wt), approx. 4.0%(wt / wt) ~ approx. 5.0% (wt / wt), approx. 5.0% (wt / wt) ~ approx. 10% (wt / wt) ), which can be present at about 10% (wt / wt) to about 50% (wt / wt). In some embodiments, the amount of SFAE may be equal to the amount of fiber present. In the present invention, the SFAE coats the entire outer surface of the cellulose-based material (e.g., The entire paper piece or cellulose-containing article can be coated.

[0114] In other embodiments, the coating may comprise from about 0.9% to about 1.0% by weight of the coating. 0% (wt / wt), about 1.0% to about 5.0% (wt / wt), about 5.0 to about 10% (w t / wt), about 10% to about 20% (wt / wt), about 20% to about 30% (wt / wt), It may contain about 40% to about 50% (wt / wt) of sugar fatty acid ester. The coating may contain about 25% to about 35% (wt / wt) of sugar based on the weight of the coating. It may contain fatty acid esters.

[0115] In one embodiment, the cellulose-based material includes paper, paperboard, paper sheets, paper pulp, Cups, boxes, trays, lids, release paper / liners, compostable bags, shopping bags, shipping bags, Conveyor board, tea bags, insulating materials, coffee or tea containers, pipes and conductors Water pipes, food grade disposable cutlery, plates and bottles, screens for TVs and mobile devices clothing (e.g., cotton or cotton blends), bandages, pressure-sensitive labels, pressure-sensitive tapes, feminine products , as well as medical devices used on or inside the body, such as contraceptives, drug delivery devices, and pharmaceuticals Containers for ingredients (e.g., pills, tablets, suppositories, gels, etc.), but are not limited to these. The disclosed coating technology is also applicable to furniture and interior decoration, outdoor camping, and other outdoor activities. It can also be used for pumping equipment.

[0116] In one aspect, the coatings described herein have a pH ranging from about 3 to about 9. In a related aspect, the pH is about 3 to about 4, about 4 to about 5, about 5 to about 7, about 7 to about 8, or about 8 to about 9. It can be about 9.

[0117] In one embodiment, the method for treating the surface of a cellulose-containing (or cellulosic) material comprises: and formula (II) or (III) R-CO-X formula (II) X-CO-R-CO-X1 Formula (III) [wherein R is a straight-chain, branched-chain, or cyclic aliphatic hydrocarbon having 6 to 50 carbon atoms] X and X1 are independently Cl, Br, R-CO-OR, or O(CO ) OR. The method includes applying to a surface a composition containing an alkanoic acid derivative having the formula: When the alkanoic acid derivative contains the formula (III), X and X1 are the same. Alternatively, the SFAE disclosed herein is the carrier and the method involves the addition of an organic base, gaseous HCl No VOCs or catalysts required.

[0118] In one embodiment, an alkanoic acid derivative is mixed with a sugar fatty acid ester to form an emulsion; The emulsion is used to treat a cellulose-based material.

[0119] In one embodiment, the sugar fatty acid ester can be an emulsifier and can be one or more mono- or di-esters. No-, di-, tri-, tetra-, penta-, hexa-, hepta-, or octa-ester In another embodiment, the fatty acid portion of the sugar fatty acid ester may comprise a mixture of saturated fatty acids. In one embodiment, the sugar fatty acid ester may include a group of the formula: The emulsion contains milk proteins (e.g., casein, whey protein, etc.), wheat gluten, , gelatin, prolamins (e.g., corn zein), soy protein isolate, Starch, acetylated polysaccharides, alginate, carrageenan, chitosan, inulin, long-chain fatty acids Proteins, polysaccharides, including but not limited to, cellulose, waxes, and combinations thereof. It may contain sugars and / or lipids.

[0120] In one embodiment, the sugar fatty acid ester emulsifiers disclosed herein are used in coatings or or agarite, ester, diester, ether, ketone, amide, nitrile, aromatic Compounds (e.g., xylene, toluene), acid halides, anhydrides, alkyl ketene dimers AKD, snowdrop, alganic acid, alum, alba Glue, barium carbonate, barium sulfate, chlorine dioxide, dolomite, diethylenetriamine Aminopentaacetate, EDTA, enzymes, formamidine sulfate, guar gum, gypsum, Lime, magnesium bisulfate, milk of lime, milk of magnesia, polyvinyl alcohol (PvOH ), rosin, rosin soap, satin, soap / fatty acid, sodium bisulfate, soda ash, chi starch, modified starch, hydrocarbon resins, polymers, waxes, poly including, but not limited to, sugars, proteins, latex, and combinations thereof , and other chemicals used in papermaking. The mixture to be prepared comprises one or more SFAEs and the following inorganic particles: clay (cabon). Phosphorus, Bentonite), Calcium Carbonate (Both GCC and PCC), Talc (Magnesium Silicate) The composition may contain one or more of: methacrylate (methacrylate methacrylate), methacrylate (methacrylate methacrylate), and titanium dioxide.

[0121] In one embodiment, the cellulose-containing material produced by the methods disclosed herein The cellulose-containing material exhibits increased hydrophobicity or water resistance compared to untreated cellulose-containing materials. In this manner, the treated cellulose-containing material has a lower cellulose content than the untreated cellulose-containing material. In another related aspect, the treated cellulose exhibits high oleophobicity or grease resistance. The biodegradable, compostable, and / or recyclable material may be biodegradable, compostable, and / or recyclable. In this way, the treated cellulose-containing materials become hydrophobic (water-resistant) and oleophobic (grease-resistant) (gender).

[0122] In one embodiment, the treated cellulose-containing material has improved properties compared to the same material that is untreated. For example, papers treated with the methods disclosed herein may have improved mechanical properties. The bags exhibit increased burst strength, Gurley number, tensile strength and / or maximum load energy. In one embodiment, the burst strength is about 0.5 to 1.0 times, about 1.0 to 1.1 times, or about 1.1 to 1. In another embodiment, the Gurley number is increased by about 3 to 4 times, or about 4 to 6 times. In another embodiment, the tensile strain is increased by about 0. 5 to 1.0 times, approximately 1.0 to 1.1 times, approximately 1.1 to 1.2 times, and approximately 1.2 to 1.3 times increase In another embodiment, the maximum load energy is increased by about 1.0 to 1.1 times, or by about 1.1 to 1. 0.2 times, approximately 1.2 to 1.3 times, and approximately 1.3 to 1.4 times.

[0123] In one embodiment, the cellulose-containing material is a material such as that described in, for example, U.S. Patent Application Publication No. 2015 / 016 No. 7243, the entire contents of which are incorporated herein by reference. Microfibrillated cellulose (MFC) or cellulose nanofibers (CN F), and MFC or CNF is added during the molding and papermaking processes. and / or added to a preformed layer as a coating or secondary layer to enhance the properties of said base paper. In a related aspect, the base paper is contacted with the sugar fatty acid ester described above. In another related embodiment, the contacted base paper is further contacted with polyvinyl alcohol (PvOH). In one embodiment, the resulting contacted base paper is controllably water- and oil-resistant. In a related aspect, the resulting base paper has a viscosity of at least about 10-15 (i.e., Rayleigh air resistance (seconds / 100cc, 20 oz cylinder), or at least about 10 0, or at least about 200 to about 350. The ester coating may be a single layer or a multi-layer laminate, or may be a single layer or Alternatively, multiple layers may be formed as a laminate, or one or more coating layers may be formed. The amount of coating can be reduced to achieve the same performance benefits (e.g., water resistance, grease resistance, etc.). In a related aspect, the laminate may be biodegradable and / or configurable heat sealed or bonded. It may also contain an adhesive.

[0124] In one embodiment, the sugar fatty acid ester may be formulated as an emulsion, and the emulsifier and The amount used will depend on the nature of the composition and the ability of the emulsifier to promote dispersion of the sugar fatty acid ester. In one embodiment, the emulsifier may be water, a buffer, polyvinyl alcohol ( PvOH), carboxymethyl cellulose (CMC), latex, milk protein, wheat Gluten, gelatin, prolamin, soy protein isolate, starch, acetylated polysaccharides , alginate, carrageenan, chitosan, inulin, long chain fatty acids, wax, agar, alginate Glycerol, Gum, Lecithin, Poloxamer, Monoglycerol, Diglycerol Roll, Monosodium Phosphate, Monostearate, Propylene Glycol, Detergent, Cetearyl Alcohol Other suitable ethanolic compounds include, but are not limited to, ethyl alcohol, methyl ... In this embodiment, the ratio of sugar ester to emulsifier is about 0.1:99.9, about 1:99, about 10:9 0, approximately 20:80, approximately 35:65, approximately 40:60, and approximately 50:50 It will be apparent to those skilled in the art that the ratio may be varied depending on the properties desired in the final product. There will be.

[0125] In one embodiment, the sugar fatty acid ester is used in combination with a binder (e.g., starch, soy protein). , polymer emulsions, PvOH, latex), and additives (e.g., glyoxal, Glyoxalated resin, zirconium salt, calcium stearate, lecithin oleate , polyethylene emulsion, carboxymethyl cellulose, acrylic polymer, alginate Polyacrylate rubber, polyacrylate, microbicides, oil-based defoamers, silicones These include, but are not limited to, stilbenes, direct dyes and acid dyes. One or more coating components for internal and surface sizing, including (but not limited to) In a related aspect, such components may be combined with microporous Builds a tough structure, provides a light scattering surface, improves ink acceptance, improves gloss, Binding pigment particles, bonding coatings to paper, base sheets, reinforcements, pigment structure Fills pores, reduces water sensitivity, resists wet pick in offset printing, Prevents blade scratching and improves gloss in supercalendering , reduce dust generation, adjust coating viscosity, achieve water retention, disperse pigments, Maintain coating dispersion, prevent deterioration of coating / coating colorants, and reduce foaming. Control, reduce entrained air and coating craters, increase whiteness and brightness including, but not limited to, controlling color and shade The combination can be varied depending on the properties desired in the final product. It will be apparent to those skilled in the art that other methods may be used.

[0126] In one embodiment, the method employing the sugar fatty acid ester is a primary / secondary coating ( For example, silicone-based layer, starch-based layer, clay-based layer, PLA layer, B It is sometimes used to reduce the cost of coating layers (e.g., io-PBS, PEI layer, etc.) a layer of material that exhibits the desired properties (e.g., water resistance, low surface energy, etc.) The amount of primary / secondary layer required to achieve the same properties is reduced. For example, a heat sealable agent can be coated onto the SFAE layer. In one embodiment, the composition is fluorocarbon and silicone free.

[0127] In one embodiment, the composition enhances both the mechanical and thermal stability of the treated product. In one embodiment, the surface treatment is thermally stable at temperatures from about -100°C to about 300°C. In a related aspect, the surface of the cellulose-based material is in contact with water at an angle of about 60° to about 120°. In another related aspect, the surface treatment is performed by chemically treating the surface at a temperature of about 200°C to about 300°C. It is generally stable.

[0128] The substrate may be dried (for example, at about 80 to 150°C) before application, but the modifying composition may be applied to the substrate. The surface can be treated with, for example, immersion, exposing the surface to the composition for less than one second. The substrate can be heated to dry the surface, after which the modified material can be readily In one aspect, the substrate is prepared according to the methods disclosed herein. It may be treated with any suitable coating / sizing method typically performed in a paper mill. (See, e.g., Smook, G., incorporated herein by reference in its entirety. ., Surface Treatments, Handbook for Pulp & Paper Technologists, (2016), 4 th Ed., Cpt. 18, pp. 293-309, TAPPI Press, Peac (See Htree Corners, GA USA).

[0129] In some applications, the material may be dried before processing, but in practicing this disclosure, No special preparation is required. In one embodiment, the disclosed method can be used to prepare films, rigid containers, fibers, Any cellulose-based material, including but not limited to, pulp, fabric, etc. In one embodiment, the sugar fatty acid ester or coating agent can be used on the surface of a conventional surface. Size press (vertical, inclined, horizontal), gate roll size press, measuring size press, Kare Undersize application, tube sizing, on-machine, off-machine, single-sided coater, double-sided Coater, short dwell, simultaneous double-sided coater, blade or rod coater, gravure Coater, gravure printing, flexographic printing, inkjet printing, laser printing, super The coating may be applied by calendering, or by combinations thereof.

[0130] Depending on the source, cellulose can be found in paper, paperboard, pulp, softwood fibers, hardwood fibers, or any of these. combinations thereof, nanocellulose, cellulose nanofibers, whiskers or microfibrils , microfibrillated cotton or cotton blends, other non-wood fibers (sisal, jute or hemp, flax, straw, etc.), cellulose nanocrystals, or nanofibrillated cellulose can be done.

[0131] In one embodiment, the amount of sugar fatty acid ester coating applied is less than the amount of the cellulose-containing material. The amount is sufficient to completely cover at least one surface. For example, in one embodiment, The fatty acid ester coating may be applied to the entire exterior surface of the container, the entire interior surface of the container, or may be applied to one or both sides of the base paper, or in combinations thereof. In some cases, the entire top surface of the film may be coated with a sugar fatty acid ester coating. or the entire lower surface of the film is coated with a sugar fatty acid ester coating, or In some embodiments, the holes in the instrument / meter may be coated with a combination of coatings. The outer surface of the equipment / instrument may be coated with a sugar fatty acid ester coating. In one embodiment, the sugar fatty acid ester may be coated with a saccharide, a saccharide fatty acid ester ... The amount of steril coating applied is such that it partially covers at least one surface of the cellulose-containing material. For example, only the surfaces exposed to the ambient atmosphere are coated with sugar fatty acid esters. Only surfaces that are covered by coatings or are not exposed to the ambient atmosphere, It is covered by an ester coating (e.g., masking). As such, the amount of sugar fatty acid ester coating applied will depend on the use of the material being coated. In one embodiment, one surface is coated with a sugar fatty acid ester coating. The opposite surface may be coated with proteins, wheat gluten, gelatin, prolamin, Soy protein isolate, starch, modified starch, acetylated polysaccharides, alginate , carrageenan, chitosan, inulin, long chain fatty acids, waxes, and combinations thereof. The composition may be coated with agents including, but not limited to, SFAE can be added to the furnish and the resulting material on the web can contain the added SFAE. Additional coatings may be applied.

[0132] Suitable coating methods include the various sugars and fats that are applied in the course of carrying out this aspect of the method. Whether used to deliver either a fatty acid ester coating and / or emulsion In one embodiment, the sugar fatty acid ester coating method is a method of dipping, spraying, painting, printing, etc. and any combination of these methods, either alone or in combination with the disclosed methods. This includes, along with other coating methods that are suitable for carrying out the method.

[0133] For example, by increasing the concentration of sugar fatty acid esters, the compositions disclosed herein is able to react more extensively with the cellulose being treated, and the end result is Improved water / oil repellency properties are exhibited. However, higher coat weights do not necessarily mean improved water resistance. In one aspect, various catalysts allow for faster "curing" This allows the quality of sugar fatty acid esters to be precisely adjusted to meet specific applications.

[0134] The choice of cellulose to be treated, sugar fatty acid ester, reaction temperature, and exposure time determine the final The method may be optimized by routine experimentation to suit any particular use of the product. It will be clear to those skilled in the art that the parameters are

[0135] The derivatized material can be defined and measured using appropriate tests known in the art. Hydrophobicity has altered physical properties that can be determined by the analytical protocol. Examples of such methods include, but are not limited to, contact angle measurements and moisture uptake. Properties include stiffness, WVTR, porosity, tensile strength, lack of substrate degradation, burst and tear properties The specific standardized protocols to be followed are defined by the American Society for Testing and Materials. (Protocol ASTM D7334-08).

[0136] The permeability of the surface to various gases such as water vapor and oxygen is enhanced by the barrier function of the material. The sugar fatty acid ester coating method may also be modified so that the permeability is measured. The quasi-unit is a barrer, and the protocols for measuring these parameters are published. Also available in standard versions (ASTM standard F2476-05 for water vapor and A for oxygen) STM standard F2622-8).

[0137] In one embodiment, materials treated according to the procedures of the present disclosure are resistant to microbial attack in an environment. It shows complete biodegradability as measured by breakdown in water.

[0138] Shake flask method (ASTM E1279-89(2008)) and Zahn-Welle Various methods are available to define and test biodegradability, including the ns test (OECD TG 302 B). available for testing.

[0139] Various methods assess compostability, including but not limited to ASTM D6400. Available to define and test.

[0140] Materials suitable for treatment by the methods of the present disclosure have a significant surface area available for reaction / bonding. Cotton fiber, plant fiber such as flax, wood fiber, regenerated cellulose (rayon and and cellophane), partially alkylated cellulose (cellulose ether), partially esterified cellulose Cells of various shapes, such as cellulose (rayon acetate), and other modified cellulose materials As mentioned above, the term "cellulose" refers to these materials, and all others having similar polysaccharide structures and similar properties. A relatively new material, microfibrillated cellulose (cellulose nanofibers) (e.g. , U.S. Pat. No. 437,470, which is incorporated herein by reference in its entirety. No. 2, U.S. Patent Application Publication Nos. 2015 / 0167243 and 2009 12 / 0221812) are particularly suited to the present application. So, cellulose is cellulose triacetate, cellulose propionate, cellulose acetate, Cellulose phosphate, cellulose acetate butyrate, nitrocellulose (cellulose nitrate), sulfuric acid cell Rose, celluloid, methylcellulose, ethylcellulose, ethylmethylcellulose, Hydroxyethyl cellulose, hydroxypropyl cellulose, cellulose nanocrystals, Hydroxyethyl methylcellulose, Hydroxypropyl methylcellulose, Ethyl hydro hydroxyethyl cellulose, carboxymethyl cellulose, and combinations thereof. However, it is not limited to these.

[0141] The modifications of cellulose disclosed herein, in addition to increasing its hydrophobicity, also improve its tensile strength, It may also have increased flexibility and rigidity, thereby further widening its range of uses. Biodegradable and biodegradable polymers made from or by using the disclosed modified celluloses. Biodegradable and partially biodegradable products, including recyclable and compostable products, are all within the scope of the present disclosure. It is within range.

[0142] Among the available uses of coating technology, such items include: containers for paper, paperboard, paper pulp, cups, lids, boxes, trays, release paper / liners, stacks Fertilizer bags, shopping bags, pipes and water pipes, disposable cutlery for food, plates and bottles, Screens for TVs and mobile devices, clothing (e.g., cotton or cotton blends), bandages, pressure sensitive Medical products used on or inside the body, such as labels, pressure sensitive tapes, feminine products, and contraceptives These include, but are not limited to, medical devices, drug delivery devices, and the like. The coating technology can also be used on furniture and interior decorations, outdoor camping equipment, etc.

[0143] The following examples are intended to illustrate, but not limit, the present disclosure. Intend. [Example]

[0144] [Example 1] (Sugar fatty acid ester blend) SEFOSE® is a liquid at room temperature and can be dispensed using a benchtop drawdown device. All coatings / emulsions containing this material were applied at room temperature. The rod type and size were changed to produce more volume.

[0145] (Formulation 1) Add 50 ml of SEFOSE® to 195 ml of water and 5 grams of carboxymethylcellulose. Methylcellulose (FINNFIX® 10; CP Kelco, Atlanta, GA) a, GA). The blend was mixed for 1 minute using a homogenizer. A 50 gram base sheet made of unbleached softwood and an 80 gram base sheet made of unbleached softwood. Both papers were placed in an oven (105°C) for 15 minutes to dry. After removing from the oven, place the sheets on the lab bench and pipette room temperature water onto each sheet. The base sheet selected for this test readily absorbs the water droplets, For sheets coated with various amounts of SEFOSE®, the coat weight As the amount of water added increased, the level of water resistance increased (see Table 1). .

[0146] [Table 1]

[0147] Water resistance is poor in the heavier sheets and cannot be achieved unless the sheets are dry. It was observed that there was no

[0148] (Formulation 2) Addition of SEFOSE® to cup stock: (This is a simple addition without MFC treatment. (Note: This is a 110g paperboard made from eucalyptus pulp.) 50 grams of SEFOSE® with 200 grams of 5% cooked ethyl starch ( Ethylex 2025) and simmered for 30 seconds using a benchtop cadmium mill. The paper samples were coated and placed in an oven at 105°C for 15 minutes. Test droplets were placed on the coated side of the paperboard and the water holdout time was measured. The results are recorded in the table below. Water penetration for the untreated paperboard control was instantaneous (see Table 2). I want to be.

[0149] [Table 2]

[0150] (Formulation 3) Pure SEFOSE® was warmed to 45°C and placed in a spray bottle. The paper stock listed in the previous examples was applied to a piece of fiberboard and a quantity of cotton cloth. When a water droplet was placed on the sample, penetration into the substrate occurred within 30 seconds, but in the oven, 105 After drying at 0°C for 15 minutes, the water droplets evaporated before being absorbed into the substrate.

[0151] Continuing research shows that SEFOSE® is used in oil and grease resistant coatings. The question was whether the compound could be compatible with the compound being used. Useful for improving water resistance and stiffness. To perform the stiffness test, 240 g of paperboard stock was used. The results are shown in Table 3 below. These data are for a single coat weight of 5 grams. The results are reported in units per square meter and are the average of five samples. Taber stiffness measured using our V-5 Taber stiffness tester, model 150-E. r is the stiffness unit.

[0152] [Table 3]

[0153] [Example 2] (Binding of sugar esters to cellulosic substrates) Determine whether SEFOSE® reversibly binds to cellulosic materials To achieve this, pure SEFOSE® and pure cellulose were mixed in a 50:50 ratio. The SEFOSE® was reacted at 300°F for 15 minutes to chloride the mixture. Extraction was performed with methylene (a non-polar solvent) or distilled water. The sample was refluxed for 6 hours and then subjected to gravimetric analysis. was carried out.

[0154] [Table 4]

[0155] [Example 3] (Survey of cellulosic surfaces) Scanning electron microscope images of base paper with and without MFC show that the base has fewer pores. This indicates that much less waterproofing agent may be required to react with the surface. 1-2 show untreated medium-porosity Whatman filter paper. However, the highly porous sheet has a relatively large exposed surface area where water can react. Figures 3 and 4 show that there are sufficient places for the particles to escape. The papers were compared before and after coating with MFC. (These are two magnifications of the same sample, with the left side of the image clearly showing the MCF.) Tests have shown that derivatization of the much less porous sheet is more resistant to long-term water / steam exposure. It can be seen that the barrier performance is more promising. The last two images are shown for comparison. A close-up of the average pore size of a single filter paper and a CNF-coated paper. This is a precise close-up taken at a similar magnification.

[0156] From the data above, it is clear that the critical point is reached when more material is added, resulting in a corresponding increase in performance. Without being bound by any theory, it is clear that the reaction appears to be faster, which suggests that the presence of lignin may accelerate the reaction. It suggests.

[0157] In fact, products like SEFOSE® are liquids and can be easily emulsified. and easily adapt it to work with coating equipment commonly used in paper mills It has been suggested that this may be possible.

[0158] [Example 4] "Phluphi" Liquid SEFOSE® is mixed and reacted with bleached hardwood fibers to create waterproof handmade sheets. Sucrose esters were mixed with the pulp before sheet formation. It was found that most of the particles were retained with the fibers. This resulted in brittle, fluffy, but very hydrophobic handmade sheets. In this example, 0.25 grams of SEFOSE® was dissolved in 6 liters of water at 4.0 The mixture was mixed with 100 grams of bleached hardwood fiber. The mixture was stirred by hand and the water was passed through a standard handsheet. The resulting fiber mat was removed and dried at 325°F for 15 minutes. The resulting sheets exhibited significant hydrophobicity and significantly reduced hydrogen bonding between the fibers themselves (1 A water contact angle greater than 0° was observed.) Emulsifiers can be added. SEFO The ratio of SE (registered trademark) to fiber can be about 1:100 to 2:1.

[0159] Subsequent testing showed that talc was the only spectator in this study, and additional testing was required. It is clear that this was excluded from the experiment.

[0160] [Example 5] Environmental Effects on SEFOSE® Coating Properties In an attempt to better understand the reaction mechanism between sucrose esters and fibers, wet strength resins were added. Bleached kraft sheet that is not waterproof (without sizing) Low viscosity coatings were applied. All coatings were measured using a Brookfield viscometer. It was measured using 00 rpm and was less than 250 cps.

[0161] SEFOSE® was emulsified with Ethylex 2025 (starch) and gravimetrically For comparison, SEFOSE® was applied to paper via a Westc As shown in Figure 5, the emulsion was also emulsified with SEFOSE (registered trademark). The oxidation of the double bond in ) occurs when heat and the presence of additional chemical environments enhance the oxidative chemical properties. (See also Table 5).

[0162] [Table 5]

[0163] [Example 6] (Effect of unsaturated vs. saturated fatty acid chains) SEFOSE® was reacted with bleached softwood pulp and dried to form a sheet. Subsequent extractions with CH2Cl2, toluene, and water were performed to determine the extent of reaction with the pulp. Extraction was carried out for at least 6 hours using Soxhlet extraction glassware. , the results of the extraction are shown.

[0164] [Table 6]

[0165] The data shows that essentially all of the SEFOSE® remains on the sheet. To further verify this, the same procedure was carried out on pulp alone, and the results showed that It can be seen that about 0.01g was obtained per 10g of pulp. This is not to say that residual pulping chemicals or more likely pulping chemicals were not completely removed. It can be easily described as a highly potent extract.

[0166] Pure fibers of cellulose (e.g., from Sigma Aldrich (St. Louis, MO) The experiment was repeated using α-cellulose (MO). As long as the loading level remains below about 20% of the fiber mass, SEFOSE® More than 95% of the mass was retained with the fiber and was not extracted with either polar or non-polar solvents. Without being bound by any theory, it is believed that optimizing the baking time and temperature can Residual sucrose esters with the fiber may be further enhanced.

[0167] As the data show, it is generally difficult to remove SEFOSE® from the material after drying. On the other hand, instead of SEFOSE®, Fatty acids containing saturated fatty acid chains (e.g., Procter & Gamble Chemical OLEAN® (available from Pharmacy, Inc., Cincinnati, OH) was used. When this is done, hot water (above 70°C) is used to remove approximately 1% of the OLEAN® in the material. OLEAN® is the same as SEFOSE®. The only change is that unsaturated fatty acids are attached (SEFOSE®). Instead, saturated fatty acids are attached (OLEAN®).

[0168] Another notable aspect is that multiple fatty acid chains are attached to the cellulose and two sugar molecules in the structure. reacts with the SEFOSE® polymer to form a rigid crosslinked network, making it ideal for paper, paperboard, and airlay applications. This leads to improved strength of fiber webs such as dry and wet-laid nonwovens, and textiles. is.

[0169] [Example 7] (Addition of SEFOSE® to achieve water resistance) 2-gram and 3-gram handmade sheets made from both hardwood and softwood kraft pulp SEFOSE® was added to a 1% pulp slurry at a level of 0.1% or greater. When added, the water is drained off, and the handsheets are formed, SEFOSE® is absorbed into the fibers. At 0.1% to 0.4% SEFOSE®, , water beaded up on the surface for a few seconds or less. SEFOSE® load was 0. Above 4%, the water resistance time in minutes increases for load levels higher than 1.5%. It increased rapidly over the course of several hours.

[0170] [Example 8] (Manufacturing bulky fiber materials) When SEFOSE® is added to pulp, it softens the fibers and fills the spaces between them. For example, if 125g (dry weight) of pulp is A 3% slurry of hardwood pulp is drained and dried to yield 18.2 cubic centimeters. It was found that 12.5 g of SEFOSE® was mixed with an equal amount of 125 g of dry fiber was added to the same 3% hardwood pulp slurry. , the resulting mat occupied 45.2 cubic centimeters.

[0171] 30g of standard bleached hardwood kraft pulp (Old Town Fuel and Fibre) er, LLC, Old Town, ME) in a preheated SEFO This 4.3 cm 3 into a 10,000 rpm disintegrator The mixture was poured through a hand sheet mold and dried at 105°C. The resulting hydrophobic pulp was 8.1 cm 3 This material occupied a volume of 2 inches square. The squares were cut into pieces and placed in a hydraulic press, where a pressure of 50 tons was applied for 30 seconds. The pressure was reduced but still 50% less than the same 2 inch square cut for the no pressure control. % occupied a higher volume.

[0172] Not only is an increase in bulk and softness observed, but forced repulping upon draining is also observed. It is also important to note that the mat resulted in a fiber mat that retained all of its hydrophobic properties. The quality of this material allows water to easily "squeeze" through the low surface energy barrier and penetrate the sheet. This is valuable in addition to the knowledge that it is impossible to obtain a single hydrophobic fatty acid chain. Bonds do not exhibit this property.

[0173] Without being bound by any theory, this is because SEFOSE® The OH groups on the surface of the cellulose fibers are involved in the subsequent hydrogen bonding. This represents further evidence that other hydrophobic materials are no longer available for use in the early stages. However, during repulping, this effect is reversed and the OH groups of cellulose , which is free to participate in hydrogen bonding upon redrying.

[0174] [Example 9] (Bag paper test data) The table below (Table 7) shows the range of 5 to 7 g / m 2 SEFOSE® and polyvinyl alcohol A mixture of PvOH and ethanol was coated onto unbleached kraft bag stock (control). The figures show the properties imparted by the bag. A commercially available bag is also included for reference.

[0175] [Table 7]

[0176] Control base paper was coated with SEFOSE® and PvOH as shown in the table. With increasing the strain, the tensile strength and burst strength increase.

[0177] [Example 10] (wet / dry tensile strength) Three gram handsheets were made from bleached pulp. The wet and dry tensile strengths of these handmade papers were compared at different addition levels of PEG-400. In the coated sheets, SEFOSE® is not emulsified into any coating; Note that this was simply mixed into the pulp and drained without any other chemicals added. (See Table 8).

[0178] [Table 8]

[0179] It should also be noted that the wet strength was not significantly lower than the dry strength of the control at 5% addition. I want to be done that.

[0180] [Example 11] (Use of esters containing less than 8 saturated fatty acids) Using sucrose esters formed by attaching less than eight fatty acids to the sucrose moiety Several experiments were carried out. RNA (The Netherlands) samples were 50%, 10%, 1%, and and contains essentially 0% monoesters. These commercially available products are It is made by reacting cellulose with saturated fatty acids, thus allowing for further cross-linking. No longer useful or useful for similar chemical properties, but emulsifying and repellent It was useful in investigating water characteristics.

[0181] For example, 10g of SP01 was mixed with 10g of glyoxal in a 10% heated PvOH solution. The mixture was "cooked" at 200°F for 5 minutes and mixed with a polypropylene blend made from bleached hardwood kraft. The coating was applied by drawing down onto porous base paper. The results showed that the cross-linked coating on the surface of the paper exhibited good hydrophobicity. It was a wax-based coating. The minimum thickness was 3g / m 2 When the coating was applied, the resulting contact angle was greater than 100°. Glyoxal is a well-known compound used in compounds with OH groups. Since the crystallizer is a sucrose crystallizer, this method does not require the remaining alcohol groups on the sucrose ring to be transferred to the substrate or other By combining with the alcohol groups available in the coating material, This is a promising approach for attaching reactive sucrose esters to surfaces.

[0182] [Example 12] (HST data and moisture absorption) To demonstrate that SEFOSE® alone exhibits waterproofing properties, Porous Twins River (Matawaska, ME) base paper was mixed with various amounts of SEFO. SE® (and PvOH or Ethylex® emulsified and applied by drawdown) 2025) and assayed in the Hercules size test. The results are shown in Table 9 below. Shows.

[0183] [Table 9]

[0184] As shown in Table 9, increasing amounts of SEFOSE® applied to the surface of the paper This resulted in increased water resistance (as indicated by an increase in HST (in seconds)).

[0185] This can also be seen using a coating of saturated sucrose ester products. As a specific example, F20W (Sisterna, The Netherlands) The product (available at www.mcg-mcg-mcg.com) has a very high percentage of monoesters with most molecules in the 4-8 substitution range. The F20W product was mixed with PvOH in equal parts. When used to make a stable emulsion, the add-on weight of the F20W product was 50% of the total coating. Please note that the impregnation rate is only 0.5 g / m. 2 " When the same amount of PvOH is present, 1.0 g / m 2 The total impregnation amount is obtained. The results are shown in Table 10.

[0186] [Table 10]

[0187] As shown in Table 10, the water resistance of the porous sheet increased with increasing F20W. Therefore, the applied sucrose fatty acid ester itself makes the paper water-resistant. .

[0188] Water resistance is not simply due to the presence of fatty acids that form ester bonds with cellulose. Therefore, we loaded SEFOSE® onto softwood handmade sheets (bleached softwood kraft). In this case, oleic acid, which forms an ester bond with the cellulose in the pulp, was added directly to the pulp. The mass at time 0 is the "bone dry" mass of a handmade sheet taken out of a 105°C oven. The sample was placed in a humidity chamber maintained at 50% RH. The change in mass was recorded over time. (unit: minutes) The results are shown in Tables 11 and 12 below.

[0189] [Table 11]

[0190] [Table 12]

[0191] The difference here is that when oleic acid is added directly to the pulp and forms an ester bond, Note that this significantly slows moisture absorption. In contrast, only 2% SEFOS E® slows moisture absorption, and at higher concentrations, SEFOSE® slows it down. Therefore, without being bound by any theory, SEFOSE (registered trademark) The structure of the binder is formed by simple fatty acid esters and cellulose. There's no way that can be explained by that alone.

[0192] [Example 13] (Saturated SFAE) The saturated ester class is a waxy solid at room temperature and is saturated, so it is difficult to distinguish the sample matrix. High temperature (e.g., at least 40°C, When used at temperatures above 65°C (all tested), these materials melt and are applied as a liquid. These materials can then be cooled and solidified to form a hydrophobic coating. The material can be emulsified in solid form and applied as a water-based coating to impart hydrophobic characteristics.

[0193] The data presented here are H values ​​obtained from papers coated with various amounts of saturated SFAE. Represents the ST (Hercules Size Test) reading.

[0194] #45 bleached hardwood kraft sheet obtained from Turner Falls Paper was used as the test coat. The Gurley porosity was measured at approximately 300 seconds and was found to be a fairly tight base sheet. S-370 obtained from Mitsubishi Foods (Japan) was used as a coating. Before mixing, the mixture was emulsified with xanthan gum (maximum 1% by weight of the saturated SFAE formulation).

[0195] Coat weight (pounds per ton) of saturated SFAE formulation HST (4 times per sample) the average of the measurements).

[0196] [Table 13]

[0197] Based on the experimental data obtained, the limited amount of saturated SFAE is suitable for other purposes / uses. There is also evidence that it may enhance the water resistance of coatings designed for this purpose. For example, saturated SFAE is mixed with Ethylex starch and polyvinyl alcohol based coatings. When blended with the coating, increased water resistance was observed in both cases.

[0198] The following examples were applied to a #50 bleached lithocycle base with a Gurley porosity of 18 seconds. It was done.

[0199] 100 grams of Ethylex 2025 at 10% solids (volume 1 liter) was heated, Add 10 grams of S-370 hot and use a Silverson homogenizer The resulting coating was then mixed using a common benchtop drawdown device. Once coated, the paper was dried under a heat lamp.

[0200] At a coat weight of 300# / ton, starch alone had an average HST of 480 seconds. For starch and saturated SFAE mixtures with similar coat weights, the HST increased to 710 seconds. Ta.

[0201] Dissolve enough polyvinyl alcohol (Selvol 205S) in hot water to make a 10% solution. This solution was coated onto the same #50 paper as above, producing a coating of 150 lb / tonne. The average HST was 225 at the same coat weight. Then, on a dry basis, 90% PVOH / 10% S-370 (i.e., 90 ml of water, 9 A mixture containing 1 gram of PvOH, 1 gram of S-370 was formed. The average HST increased to 380 seconds.

[0202] Saturated SFAEs are prolamins (specifically, zein; all of which are incorporated herein by reference). See U.S. Patent No. 7,737,200, which is incorporated herein by reference. One of the major barriers to commercial production of the subject matter of said patents is that the formulations are water soluble. So, adding saturated SFAE is helpful in this way.

[0203] [Example 14] (Other saturated SFAE) Size press evaluation of saturated SFAE-based coatings was performed without sizing and with This was done with a relatively insufficiently bleached lightweight sheet (approximately 35#). All evaluations were performed using pre-treated Exceval HR 3010 PvOH. A sufficient amount of saturated SFAE was added to account for 20% of the total solids. The study focused on evaluating the ingredients (available from Mitsubishi Foods, Japan). Both of these esters performed better than the control. Table 14 below lists the key data. A portion of the data is shown.

[0204] [Table 14]

[0205] Saturates appear to result in increased kits, whereas S-370 and C-1800 Note that both increase HST by approximately 100%.

[0206] [Example 15] (wet strength additive) Laboratory testing has confirmed the chemical properties of sucrose esters as wet strength additives. It has been found that the use of saturated groups can be tailored to achieve a variety of properties, including the use of to each alcohol functional group of sucrose (or other polyol) Once the sucrose ester is made, the result is a hydrophobic compound that is less miscible / soluble in water. These compounds were added to cellulosic materials to or coatings can provide water resistance, but they are mutually exclusive and can be used to It does not chemically react with any part of the brix and is therefore easily removed by solvents, heat and pressure. It is easy to get caught.

[0207] If waterproofing and a higher level of water resistance are desired, the matrix may contain sucrose esters. oxidation and / or oxidation reactions that help immobilize the ter and make it highly resistant to removal by physical means Alternatively, sucrose esters containing unsaturated functional groups may be prepared for the purpose of achieving cross-linking. The number of unsaturated groups in the sucrose ester and the amount of unsaturated groups in the sucrose ester may be adjusted to 100% by weight and then added to the cellulosic material. By adjusting the size, it is possible to obtain a molecule that is not optimal for imparting water resistance. provided a means of cross-linking to provide strength.

[0208] The data presented here demonstrates the application of SEFOSE® to bleached kraft sheet at various levels. The percentages shown in the table are derived by adding 100g of ethylenediaminetetraacetic acid to the treated sample and obtaining wet tensile data. The results show the sucrose esters (%) of 70# bleached paper prepared using the method described above (see Table 15).

[0209] [Table 15]

[0210] The data show that the addition of unsaturated sucrose esters to paper increases the loading level. The wet strength tends to increase with increasing strength. and show.

[0211] [Example 16] (Method of producing sucrose esters using acid chlorides) In addition to creating hydrophobic sucrose esters via transesterification, acid chlorides , by directly reacting with a polyol containing a ring structure similar to sucrose, Similar hydrophobicity can be achieved with other products.

[0212] For example, 200 grams of palmitoyl chloride (CAS 112-67-4) can be mixed with 50 grams of The mixture was mixed with 100°F of sucrose and mixed at room temperature. The resulting material was washed with acetone and deionized water to obtain Any unreacted or hydrophilic material was removed. C-13 NMR was used to determine the remaining Analysis of the material showed that a significant amount of hydrophobic sucrose esters had been produced.

[0213] It has been shown that the addition of fatty acid chlorides to cellulosic materials can impart hydrophobic properties. However, the reaction itself (BT3 and others) is such that the released by-product, gaseous HCl, reacts with the surrounding material. This causes several problems, including corrosion of the One additional drawback of generating hydrochloric acid is that it is undesirable in the field. The main problem is that as more are formed, i.e., as more polyol moieties are reacted, Palmitoyl chloride is used in combination with cellulose and cotton materials, and the resulting fiber composition is weakened. Increasing amounts of these compounds were reacted. As the hydrophobicity increased, the strength of the article decreased. .

[0214] Corn starch, birch xylan, carboxymethyl cellulose, gluten and 50 g each of other similar polyols, including coacervate and extracted hemicellulose. The above reaction was repeated several times using 200 grams of reacted R-CO-chloride.

[0215] [Example 17] (peel test) Peel testing is required to peel the tape from the paper surface at a reproducible angle. To measure the force applied, a wheel was used between the two jaws of the tensile tester (ASTM D1876; e.g., 100 Series Modular Peel Tester r, TestResources, Shakopee, MN).

[0216] This work was supported by the Turners Falls Paper (Turners Falls, MA). This #50 pon paper was made from bleached kraft paper with a high Gurley ratio (600 seconds). The sheet shows a fairly compact but very absorbent sheet.

[0217] When #50 pound paper was coated with 15% Ethylex starch as a control, The average force required (for five specimens) was 0.55 lbs / in. A similar mixture was prepared except that 25% of the starch was replaced with SEFOSE®. ting (thus 25% add-on is SEFOSE® and 75% is When treated with Ethylex, the average force is reduced to 0.081 lb / in. Substituting SEFOSE® for 50% of the Ethylex The force required was reduced to less than 0.03 pounds per inch.

[0218] The paper preparation followed TAPPI Standard Method 404 for determining the tensile strength of paper.

[0219] Finally, the same paper was used with S-370 at a loading rate of 750 pounds per ton. This effectively filled all of the pores in the sheet, creating a complete physical barrier. Indeed, this passes TAPPI Kit 12 on a flat surface. This short experiment shows that saturation It has been shown that it is possible to obtain grease resistance using the SFAE variant.

[0220] [Example 18] (Saturated SFAE and inorganic particles (fillers)) Saturated sucrose fatty acid esters are those that vary in the number of fatty acid chains attached to the sucrose molecule (approximately Depending on the molecular weight and chain length, they range from hydrophilic to hydrophobic. These are not considered highly reactive compounds. It is not done.

[0221] Various substituted SAFEs with side chains of 16 or 18 carbons in length have been investigated. The test material is a waxy solid with a melting point below 150°C. When coated onto paper, it The substituted esters provide significant levels of water resistance depending on coat weight and sheet porosity. Finally, the same paper in S-370 effectively fills all the pores in the sheet, giving a complete It was used at a loading rate of 750 pounds per ton to create a physical barrier. The paper was found to have TAPPI Kit 12. This short-term experiment was performed using saturated SFA Variants of E were used to demonstrate grease resistance.

[0222] (Observation results) The more hydrophobic esters tend to aggregate in aqueous emulsions / dispersions, which Achieving a uniform coating on the paper becomes difficult.

[0223] The low melting points of some of these molecules allow for the "melting" of the coating into the sheet. )"

[0224] When hydrophobic SAFE and polymers are mixed together to help stabilize the dispersion, these Polymers (i.e., latex, starch, polyvinyl alcohol) are This tends to surround the terpene in a way that weakens the desired hydrophobic properties.

[0225] When mixed with calcium carbonate (e.g., precipitated calcium carbonate), it has unexpected appeal. SAFE does not dissolve in paper under similar drying conditions.

[0226] The calcium carbonate appears to aid in the dispersion of SAFE, and the adhesion is due to the fact that SAFE acts as a binder. It acts as a catalyst to adhere calcium carbonate particles to the surface of the coated paper. This uniform dispersion is believed to enhance water resistance for a given amount of ester. can be done.

[0227] [Example 18] (Pigmented coating formulations) (method) SEFOSE® and some Mallard Creek samples (TYKO TE® 1019, 1004, 6160, 1005, 6152) and DOW 620® and some BASF samples (Epotal NX 4430, The analysis of Epotal s440 shows that the latex is chemically compatible with SEFOSE (registered The order of addition does not appear to matter. The viscosity does not appear to change appreciably.

[0228] (cup paper stock) Mallard Creek Tykote® 1019 with Imerys L The mixture was blended with SEFOSE X® clay slurry. The resulting ratio was 70% latex, 20% LX® clay, SEFOSE®: 10% (top coat) or 75%, GCC: 75%;S EFOSE®: 3%; Tykote® 1019: 21.5% (base The basecoat blend had a pH of about 7.6, a viscosity of 215 cps, and The top coat had a pH of 7.8, a solids content of approximately 57%, and a viscosity of approximately The reported coat weight was 240 cps. Apply through a spray gun and apply approximately 8g / m 2 The two different coatings Rolls of cup stock, cold cup stock, and cup bottom stock were produced. Ta.

[0229] Table 16 below shows the effectiveness of SEFOSE® cure in pigmented coating formulations. The effect on Cobb scores is shown.

[0230] [Table 16]

[0231] As shown in the table, SEFOSE® (10% by weight) was added to the coating, The latex coated board had a Cobb score of 39, but the score dropped to 3. It decreased.

[0232] SEFOSE® is not believed to be as effective a film former as latex. Therefore, without being bound by any theory, latex is a barrier. The SEFOSE® latex film forms a film that fills any voids in the latex film. It was hypothesized that adding hydrophobicity to pinholes would act synergistically.

[0233] (Plastic substrate) To further understand the Cobb effect, the plastic substrate was treated with Dow 620 ) coated with latex, dried (on plastic substrate), and measured for cob (Cobb value = 10.5). This data point indicates that the Cobb reading is affected by water penetrating the paper itself. This not only reflects the water being absorbed into the coating, but also reflects the water being absorbed into the coating itself. This reflects the fact that 10% SEFOSE® was added to the latex (also When this experiment was repeated (coating on a plastic substrate), the Cobb value dropped to 3.8. This reflects the hydrophobicity of the film itself.

[0234] [Example 19] (SFAE encapsulation of solid latex polymer beads and their addition to cellulose fibers) SFAE was heated in aqueous propylene glycol at 90°C for 20 minutes and then cooled to 21°C for 1 minute. 5 minutes, then heat again at 90°C for an additional 5 minutes, and cool to 21°C. The SFAE was mixed with the latex by the cycle method. stomach.

[0235] The particles are dispersed in an aqueous emulsion or slurry, and the aqueous emulsion or slurry is then Prior to wet molding, the cellulose fiber slurry is mixed at a concentration of about 5% to about 50% of the total dry weight. The emulsion may be mixed with a fiber slurry. The fiber slurry is then heated. Optionally, the mixture was applied to a machine equipped with a mesh or screen to remove water. The fibrous material was then applied to a mold and heated until dry. Once dry, the resulting product The article was removed from the mold.

[0236] While the disclosure has been described with reference to the above examples, modifications and variations are within the spirit and scope of the disclosure. It will be understood that the present invention is within the spirit and scope of the following claims. The invention is limited only by the scope of the claims. All of which are incorporated herein by reference.

Claims

1. 1. A method for producing a molded cellulose-containing article, comprising: adding an emulsion or slurry to a cellulosic fiber furnish, The emulsion or slurry comprises one or more sucrose fatty acid esters and one or more a plurality of carrier particles; draining the furnish through one or more meshes or screens. Pu and, thermoforming the mixture into an article in a mold; removing the product from the mold; Including, The product has a higher resistance to corrosion than a cellulosic product that has not been treated with the emulsion or slurry. The method exhibits water, oil, and / or grease resistance.

2. The product is a bowl, plate, bottle, pouch, package or insert. The method according to claim 1.

3. The carrier may be a sucrose fatty acid ester, a polymer, a solid latex polymer bead, Selected from the group consisting of hollow polymer shells, resin beads, pigment particles, and combinations thereof The method of claim 1 .

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

5. The particles are selected from raw corn starch, rice starch, wheat starch, potato starch, or tapioca starch granules, oat hulls, rice hulls, crushed nut shells, or The method of claim 1 further comprising the steps of:

6. The particles are coated with one or more sucrose esters and dissolved in an aqueous emulsion or 10. The method of claim 1, wherein the cellulose is dispersed in a solution or a slurry.

7. The aqueous emulsion or slurry may comprise from about 5% to about 50% of the total dry weight of the composition prior to wet-forming.

7. The method of claim 6, wherein the cellulose fiber slurry is mixed with the cellulose fiber slurry at a concentration of

8. 2. The method of claim 1, wherein the carrier is a polymer, and the polymer exhibits a low glass transition temperature. How to post.

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

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

11. A composition comprising sucrose fatty acid ester particles containing one or more cargo materials.

12. The one or more cargo materials may be polymers, solid latex polymer beads, resins, Beads, calcium carbonate, titanium dioxide, kaolin clay, silica, silicates, talc, 12. The composition of claim 11, wherein the inorganic filler is selected from the group consisting of mica and combinations thereof.

13. 10. The method of claim 1 further comprising thymol, lecithin, alkyl glucosides, and combinations thereof.

1. The composition described in 1.

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

15. 12. The method of claim 11, wherein the sucrose fatty acid ester is a mono- or diester. Composition of.

16. The sucrose fatty acid ester contains all saturated fatty acids, or a mixture of saturated and unsaturated fatty acids. The composition of claim 11 which is a mixture of fatty acids.

17. the fatty acid ester particles comprise one or more sucrose fatty acid esters. Item 12. The composition according to item 11.

18. An emulsion comprising the composition of claim 11.

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

20. 10. An article made by the method of claim 1.

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