Bio-based barrier coatings

Abstract

To provide a barrier coating that provides increased oil and / or grease resistance to cellulosic materials without sacrificing the biodegradability thereof.SOLUTION: A barrier coating comprises a prolamine and at least one polyol fatty acid ester (PFAE), where the polyol comprises a cyclic structure and 1 to 2 fatty acid moieties or 3 to 5 fatty acid moieties, and where the fatty acid is a saturated fatty acid.SELECTED DRAWING: Figure 5

Description

[Technical field]

[0001] The present invention relates generally to a method for treating cellulosic-containing materials, and more particularly to a method for treating cellulosic-containing materials. The present invention is a bio-based barrier coating containing polyol fatty acid ester and prolamin. and / or compositions to enhance the hydrophobicity / oleophobicity of cellulose-based materials. The method comprises the steps of: mixing the polyol fatty acid ester with a known prolamin solvent or plasticizer; Such barrier coatings or compositions and methods may be used in place of are useful in modifying the surfaces of cellulose-based materials, including paper, paperboard and packaging products This relates to a method. [Background technology]

[0002] The industry has adopted fluorocarbons for their ability to lower the surface energy of articles. Compounds based on orocarbon chemistry have been available for many years to combat the penetration of oil and / or grease. The use of perfluorinated hydrocarbons has been raised. One issue that has been growing is environmental persistence. The EPA and FDA have recently The latest research has revealed that school children are at increased risk of developing pulmonary embolism. The occurrence of perfluorooctane sulfonate in blood samples taken from >90%). The costs and potential environmental liability of these compounds have been Therefore, manufacturers are required to manufacture articles that are resistant to penetration by oil and / or grease. The government was forced to explore alternatives.

[0003] Reducing the surface energy improves the penetration resistance of the article, but has several disadvantages. For example, textile fabrics treated with fluorocarbons have good stain resistance. However, once soiled, the cleaning composition penetrates and thus removes the stain from the fabric. The ability to remove stains may be affected, thereby permanently soiling the fabric and shortening its useful life. Another example is grease-resistant paper, which is then printed on and and / or coated with adhesive, in which case the required grease resistance This is achieved by treating with fluorocarbons, but the low surface energy of the paper makes it difficult to block the Printing ink or ink problems, including kinking, backtrap mottle, poor adhesion and alignment Problems related to adhesive acceptance can occur. If you are planning to use grease-resistant paper, the low surface energy may reduce adhesion. Low surface energy articles can be exposed to corona radiation to improve printability, coatability, or adhesion. They can be treated by post-molding processes such as electrical, chemical, and flame treatment. Such processes increase the cost of manufacturing the article and may have other disadvantages.

[0004] Prolamins are proteinaceous compounds present as storage proteins in cereal grains. For example, zein is found in corn gluten meal, a by-product of corn milling. Zein is a prolamine found in foods with a higher proline content and is hydrolyzed by aqueous fatty alcohols. Zein properties can be modified using some plasticizers. The primary use of locosi gluten meal is as an animal feed, which is typically sold at a low price. There has been interest in developing value-added products from zein in the past. However, the solvent and Many plasticizers are not suitable for use in the food industry.

[0005] New interest in zein as a polymeric material has led to a focus on solid plastic waste treatment Zein is also used in films, coatings and plastics. Zein offers several potential advantages as a feedstock for many applications: it is biodegradable and can be recycled annually. It is renewable. The annual corn surplus provides a substantial source of raw material. However, There are also concerns about the use of zein as a dermal filler. Zein is a biological material and is largely Like other biological materials, they are affected by water. To this end, zein-containing compositions are modified to make the desired prolamin properties less susceptible to water. It would be desirable to combine Summary of the Invention

[0006] The present disclosure provides a method for treating cellulosic material, comprising: The base components are treated with a composition that enhances oleophobicity while maintaining their biodegradability / recyclability. The disclosed method comprises the step of synthesizing prolamines and polyols, e.g., sugars. A barrier coating containing a fatty acid ester (SFAE or PFAE) and a cellulose The method includes applying the composition to the substrate.

[0007] In an embodiment, a barrier comprising a prolamine and at least one PFAE, such as an SFAE. A coating that is resistant to oil and / or grease on the surface of the article to which the coating is exposed. A barrier coating is present in a concentration sufficient to render the coating substantially resistant to application of In a related embodiment, the prolamins include zein, hordein, glial Gin, kafirin and combinations thereof.

[0008] In one embodiment, the at least one PFAE comprises a cyclic compound. In one embodiment, at least one PFAE comprises a carbohydrate. In one embodiment, the at least one PFAE comprises an oligosaccharide. In an embodiment, the at least one PFAE comprises a disaccharide. In an embodiment, the at least one PFAE comprises sucrose or lactose. In one embodiment, the polyol comprises 1 to 2 fatty acid moieties or 3 to 5 fatty acid moieties. In one embodiment, the fatty acid portion comprises a saturated fatty acid or a saturated and an unsaturated fatty acid. It is combined with acid.

[0009] In one embodiment, the coating is made of polyvinyl alcohol (PvOH), polylactic acid (P LA), clay, precipitated calcium carbonate, ground calcium carbonate ), natural and / or synthetic latex, TiO2, talc, glyoxyl (glyo xyl), as well as combinations thereof.

[0010] In one embodiment, the fatty acid moiety is obtained from a natural source. are oilseeds, including soybeans, peanuts, rapeseed, barley, and canola. , sesame seeds, cotton seeds, palm kernels, grape seeds, olives, safflowers, sunflowers, copra, Corn, coconut, flaxseed, hazelnut, wheat, rice, potato, cassia Examples of suitable oils include peas, legumes, camelina seeds, mustard seeds, and combinations thereof.

[0011] In one embodiment, the PFAE is a monoester, diester, triester, tetraester, The ester may be a ter, a pentaester, or a mixture thereof.

[0012] In another embodiment, the barrier coating is biodegradable and / or compostable. In a related aspect, the article is paper, paperboard, paper pulp, food storage cartons, food Storage bags, shipping bags, coffee or tea containers, tea bags, bacon board, diapers , weed block / barrier fabric or film, mulching film, flower pots, pa Packing beads, bubble wrap, oil absorbing materials, laminates, envelopes, gift cards, credit cards Cards, gloves, raincoats, oil and grease resistant (OGR) paper, shopping bags, compost bags Bags, release paper, tableware, containers for holding hot or cold beverages, cups, paper towels , plates, bottles for storing carbonated liquids, insulating materials, bottles for storing non-carbonated liquids, food wrap Films, food waste disposal containers, food handling equipment, cup lids, fabric fibers, water storage storage and transport equipment, storage and transport equipment for alcoholic or non-alcoholic beverages, electronic External casings or screens for products, internal or external components of furniture, curtains, indoor Decorative items, films, boxes, sheets, trays, pipes, water pipes, pharmaceutical packaging, Clothing, medical devices, contraceptives, camping equipment, molded cellulosic materials, and their This is a combination of:

[0013] In one embodiment, the cellulose-based material is a mixture of prolamines and sugar fatty acid esters (S and at least one polyol fatty acid ester (PFAE), The cellulose-based material is contacted with a barrier coating, and the contacted cellulose-based material is then subjected to Heat, radiation, a catalyst, or a combination thereof, for a period of time sufficient to cause adhesion to the cellulose-based material. and exposing the cellulose-based material to a solvent to tweak the oleophobic resistance. A method for derivatizing a barrier coating is disclosed. In a related aspect, the method includes removing excess barrier coating. In another related aspect, the method includes removing the barrier coating. The coating is applied at the size press.

[0014] In one embodiment, at least one sugar fatty acid ester (SFAE) and a prolamine In a related aspect, the coating comprises: The surface of the article is resistant to the application of oil and / or grease in the absence of the second oleophobic material. In another related embodiment, the barrier is present on the article in a concentration sufficient to render it qualitatively resistant. Coatings include clay, talc, precipitated calcium carbonate, ground calcium carbonate, TiO 2, and combinations thereof. [Brief description of the drawings]

[0015] [Figure 1] FIG. 1 shows a scanning electron micrograph (SEM) (58x magnification) of untreated medium porosity Whatman filter paper. [Diagram 2] FIG. 1 shows an SEM (1070x magnification) of untreated medium porosity Whatman filter paper. [Diagram 3] Side-by-side comparison 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. [Diagram 5] FIG. 1 shows 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), ×. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0016] Before describing the compositions, methods, and methodologies, the present invention is directed to the specific compositions described, Since methods and experimental conditions may vary, the present invention is not limited to such compositions, methods and conditions. It should be understood that the scope of the present invention is limited only by the appended claims. However, 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 be the case.

[0017] As used in this specification and the appended claims, the singular forms "a," "a "n" and "the" are plural unless the context clearly indicates otherwise. Thus, for example, a reference to "sugar fatty acid esters" includes the One or more of the types described herein that will become apparent to those of skill in the art upon reading the disclosure, etc. Sugar fatty acid esters and / or compositions are included.

[0018] Unless otherwise defined, all technical and scientific terms used herein belong to the present invention. The terms and expressions used in the present invention have the same meaning as commonly understood by those of ordinary skill in the art. It is understood that the present disclosure is within the spirit and scope of the present invention. Any methods and materials similar or equivalent to those described herein may be used in the practice or testing of the present invention. It can be used.

[0019] As used herein, the terms "about," "approximately," "substantially," and "largely" are used interchangeably herein. As will be understood by those of skill in the art, will vary to some extent depending on the context in which the term is used. If there are uses of a term that are not clear to a person of ordinary skill in the art given the context in which it is used, the terms "about" and "about" shall be used interchangeably. and "approximately" means plus or minus <10% of the particular term, and "substantially" and and "significantly" means plus or minus >10% of a particular term. " and "consisting essentially of" have the meaning accustomed to in the art.

[0020] The present disclosure provides a method for producing a stable water-based barrier coating and / or composition. The present invention provides compositions and methods for producing value-added products from prolamins such as zein, including When applied to a surface or substrate, the composition provides oil and / or glaze resistance. The composition produces an article having high surface energy. As a result, the compositions achieve their barrier properties while lowering the surface energy of the article. This avoids the disadvantages associated with the use of barrier compositions that

[0021] In embodiments, the barrier coating or composition according to the present disclosure comprises one or more Prolamins are found in corn, wheat, barley, rice and sorghum. It is a proteinaceous compound present as a storage protein in all cereal grains. Examples of amino acids include zein, hordein, gliadin and kafirin. In a related embodiment, the prolamine can be zein. Zein is a member of the Glob Al Protein Products, Fairfield, ME and various other manufacturers. It is commercially available from manufacturers.

[0022] In an embodiment, the barrier coating or composition comprises a sucrose fatty acid ester. The fatty acid esters may also include one or more polyols or sugars, including fatty acid esters of polyols or sugars. In one embodiment, the composition includes zein and a polyol fatty acid ester.

[0023] In one embodiment, the polyol fatty acid ester is a glycol, sulfonamide, amide Contains well-known primary and secondary plasticizers such as glycol, sorbitol, and ethylene glycol. They are sometimes used to replace the more commonly known zein plasticizers (e.g., Lawton JW, Cerea (see Table IV in l Chem (2002) 79(1): 1-18).

[0024] In an embodiment, the present disclosure provides a method for treating a surface of a substrate with a zein-polyol fatty acid ester combination. By treating the surface with a barrier composition containing the compound, the resulting surface is oil-resistant and / or Polyol fatty acid esters and zein are known to be resistant to bacteria, e.g. When removed by enzymes, it is digested, and therefore the biodegradability of the substrate is improved by the barrier coating. The barrier compositions disclosed herein therefore have high surface energy An ideal solution for derivatizing the surface of cellulosic substrates to produce articles with energy In addition, polyol fatty acid esters can counteract the zein-specific properties of moisture (water) (e.g. For example, film formation, tensile strength, etc.

[0025] In embodiments, it has a low range degree of substitution (DS) of 1 to 2 or a medium range DS of 3 to 5. , using polyol fatty acid esters containing saturated fatty acid moieties directly with prolamines; In one embodiment, a sucrose fatty acid ester having a DS of 1 to 5 is heated to a melting point. Upon heating, the zein can be directly blended. In a related embodiment, the zein is then Such mixtures are converted into aqueous zein dispersions by the application of kinetic energy (mixing) and water. In another related embodiment, such a dispersion can be converted to a It is stable for a while.

[0026] DS relates to the number of fatty acid moieties attached to the polyol. In embodiments, DS The metric represents the average of a population of molecules. Fatty acids can be obtained from natural sources, e.g., animal sources. and therefore represents a population of fatty acids rather than a pure source of only one fatty acid species. The starting fatty acids are also heterogeneous, so when complexes such as PFAE are formed, Depending on the polyol used, a mixed population of products may be obtained. Objects often contain a range of DS rather than a population with a single DS.

[0027] In contrast, those containing unsaturated fatty acid moieties with a DS of >5 (i.e., low HLB value) Polyol fatty acid esters and polyols containing saturated fatty acid moieties with a DS of >5 The fatty acid esters of prolamines are not compatible with prolamines under the same conditions. Although these esters (i.e., high degree of substitution, low HLB value) are not hydrophobic, It is believed that the amphipathic / hydrophobic proteins cannot be emulsified due to the high viscosity of the emulsion. Among these polyol fatty acid esters, when used alone, they have good grease resistance. The compatibility disclosed herein could potentially be commercially viable. As disclosed herein, the use of mid-range polyols at the surface of the paper is more useful. The use of esters alone also results in high contact angles and low kit values. In the case of Under the conditions disclosed herein, the oil It was observed that these esters beaded up instead of spreading on the treated surfaces. Additionally, the zein and esters are combined to the extent that the zein forms a film. The ester then readily allows the oil to penetrate in response to pressure applied to the droplets, A corresponding increase in kit value is observed.

[0028] Because of the high molecular weight of prolamines, a significant amount of " A "solvent" is required. Known prolamine solvents include aniline, acetic acid, ethylene glycol, etc. These include cholesteryl, ethylenediamine, glycerol, lactic acid, methanol, and pyridine. Other solvents include mixtures with water, such as acetone or ethanol; lower aliphatic aldehydes; and mixtures with alcohols, such as acetone, benzene and furfural. In one embodiment, the mass of the solvent must be equal to or greater than the mass of the prolamine. In this case, an excess of polyol ester is needed to stabilize the protein, and water is Upon addition, a stable aqueous dispersion is produced. repels grease through the formation of an insoluble high surface energy film, so it does not dissolve or Once the dispersed protein is evenly distributed and the water is removed, a proper film formation is achieved. It is essential that the formation occurs on the substrate.

[0029] Advantages of the products and methods disclosed herein include that the coating compositions are renewable. Made from zein, polyols and vegetable oils, which are naturally sourced from agricultural sources, they are biodegradable and have low toxicity. It has a thermal conductivity profile suitable for food contact and increases the coefficient of friction of paper / board surfaces to a high level of water resistance. Even the slipperiness is reduced (i.e., making the paper too slippery for downstream processing or end use). may be adjusted to account for applied oil and / or grease. It can be used with or without special emulsifying equipment or emulsifiers, and is a traditional paper recycling method. Compatible with bio-production programs, i.e. polyethylene, PLA or wax composites This includes not being adversely affected by recycling operations, as is the case with paper.

[0030] Additional benefits include: a) Some polyol esters exhibit significant kit and are effective on treated surfaces (i.e. , high surface energy) in the absence of a second oleophobic material exhibiting bead formation of oil; b) Polyol esters have no effect even when carbonate is added in limited amounts. The present invention provides a kit comprising a barrier coating comprising calcium carbonate and and grease resistance (i.e., the presence of calcium carbonate in any form The formulation overcomes the problems of grease resistance, which usually destroys the paper's resistance to grease. To enable savings of c) The polyol ester can be used in place of known zein solvents (e.g., all See Lawton, supra (2006), which is incorporated herein by reference in its entirety. 02) Table I) d) All (except water) of the barrier coating materials (PFAE, zein, calcium carbonate, etc.) Inorganic particles / pigments (such as ammonium nitrate, clay, etc.) may provide distinct functionality in formulations. What can be made, e) The PFAE barrier coating makes zein less susceptible to water; f) Several PFAEs or combinations of PFAEs (i.e., low-range DS to mid-range DS 1-2 fatty acid moieties and 3-5 fatty acid moieties, respectively) are Convenient for blending min Including, but not limited to:

[0031] As used herein, "adhere" refers to the ability to adhere to, for example, a surface, substrate, or substance. This means that

[0032] As used herein, a "barrier coating" or "barrier composition" refers to a Blocks or prevents contact between the undesirable element and one or more of the coated surfaces, but to prevent contact of the undesirable elements, such as oil or grease, with the coated surface of the substrate. means a material applied to a surface (or surfaces) of a substrate that stops or prevents do.

[0033] As used herein, "bio-based" means any material that is living (or was once living) It means a material that is intentionally produced from substances derived from living organisms. Related Aspects In the United Nations Convention on Biotechnology and Food Safety, materials that contain at least about 50% of such substances are considered biobased. will be done.

[0034] As used herein, "combining" refers essentially to a single entity, including its grammatical variations. It means to adhere or to be adhered to as a single mass.

[0035] As used herein, "cellulosic" refers to an object (e.g., bag, sheet) or The material can be molded or extruded into a film or filament, and such objects or can be used to make films or filaments. It means a semi-synthetic material that is structurally and functionally similar to cellulose and is used, for example, in coatings and and adhesives (e.g., carboxymethylcellulose). In another example, most plants Complex carbohydrates (C6H) composed of glucose units that form the main component of cell walls in yeast. 10 O5 ) n The cellulose is cellulosic.

[0036] As used herein, "coating weight" refers to the weight of material (wet) applied to a substrate. or dry weight. It is the number of pounds per specified ream or square meter. It can be expressed in grams per gallon.

[0037] As used herein, "compostable" means that the solid product is biodegradable in soil. It means something.

[0038] As used herein, "edge wicking" refers to the formation of pores between fibers in a paper structure. The diffusion is limited to the capillary permeation 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 embodiment, the polyol fatty acid esters described herein are The coating contains prevents edge wicking in the treated product In one embodiment, grease / oil gets into the folds that may be present in paper or paper products. Similar problems exist when folding, pressing, or squashing the paper structure. The "grease creasing effect" created by this is due to the grease in the paper structure. It can be defined as the absorption of a substance.

[0039] As used herein, "effect" refers to a specific characteristic, including grammatical variations thereof. It means to give to a specific material.

[0040] As used herein, "hydrophobic material" means a material that does not attract water. For example, wax, rosin, resin, polyol fatty acid ester, diketene, shellac, Vinyl acetate, PLA, polyethyleneimine (PEI), oil, fat, lipids, and other water repellents The chemical, or combination thereof, is a hydrophobic material.

[0041] As used herein, "hydrophobic" means water repellent, repelling water, and not absorbing water. It means a characteristic that tends to

[0042] As used herein, "high surface energy" refers to a surface energy of at least about 32 dynes / cm m, usually refers to an article having a surface energy of at least about 36 dynes / cm. Anything below this is considered to have a "low surface energy." The surface energy may be any suitable By methods such as contact angle measurements and the relationship between surface energy using Young's equation The higher the surface energy, the stronger the molecular attraction between different materials. Reflect what is to come.

[0043] As used herein, "lipid resistance" or "oleophobicity" refers to the ability to repel lipids and oils. The term refers to the property of tending to repel and not absorb substances, grease, fat, etc. In the , grease resistance is tested by "3M kit" test or TAPPI T559 kit test In another related embodiment, a "second oleophobic material" is For example, perfluoroalkyl and polyfluoroalkyl substances that are lipid-resistant can be used. be.

[0044] As used herein, "cellulose-containing material" or "cellulose-based material" refers to a "Material" means a composition consisting essentially of cellulose. For example, such a material may be paper, paper sheets, paperboard, paper pulp, food storage cartons, parchment, cake board, Butcher paper, Release paper / liner, Food storage bags, Shopping bags, Shipping bags, Bacon board, Insulating edging materials, tea bags, coffee or tea containers, compost bags, tableware, hot or cold Containers for holding green beverages, cups, lids, plates, bottles for storing carbonated liquids, gift To cards, bottles for storing non-carbonated liquids, food wrap films, food waste disposal containers, food handling Equipment, fabric fibers (e.g., cotton or cotton blends), water storage and transport equipment, alcoholic or non-alcoholic beverages, external casings or screens for electronic products, home Examples of such items include interior and exterior components of furniture, curtains, and upholstery items. Not limited to these.

[0045] As used herein, a "release paper" is a paper that has a sticky surface that is attached to an adhesive or mastic. It means a sheet of paper used to prevent premature adhesion. The coatings disclosed herein may be used in place of or as an alternative to silicon or other coatings. can be used to reduce its use and produce materials with low surface energy. The determination of surface energy can be done by measuring the contact angle (e.g., Optical Tensile Strength). meter and / or High Pressure Chamber;Dyne Testing, Staffordshire, United Kingdom) Use Surface Energy Test Pens or Inks (e.g. , Dyne Testing, Staffordshire, United Kingdom This can be achieved by

[0046] As used herein, "peelable" in reference to PFAE means that the PFAE coating Once applied, the coating is removable from cellulose-based materials (e.g. As used herein, "removable" means "capable of being removed, for example, by manipulating a physical property." Thus, "non-removable" in the context of PFAE means that the PFAE coating, once applied, For example, by substantially irreversibly binding (e.g., by chemical means) to cellulose-based materials. more removable).

[0047] As used herein, "fluffy" refers to raw cotton or styrofoam. It means an airy solid material having the appearance of foamed peanuts. In the study, the fluffy material is nanocellulose fiber (e.g., MFC), cellulose nano It is made from cellulose crystalline and / or cellulose filaments and polyol fatty acid esters. and the resulting fibers or filaments or crystals are hydrophobic (and dispersible). It can be used in composite materials (e.g. concrete, plastics, etc.) do.

[0048] As used herein, "solution fiber" or "pulp" refers to cellulosic fibers. It is prepared by chemical or mechanical separation of fibers from wood, fiber crops or waste paper. The term "lignocellulosic fiber material" refers to a lignocellulosic fiber material produced by the method disclosed herein. In a related embodiment in which cellulose fibers are treated, the cellulose fibers themselves are treated with bound polyolefins. It contains cellulose fatty acid esters as isolated entities and has free cellulose fibers bound to it. It has distinct and different properties from fibers (e.g. pulp, cellulose fibers, nanocellulose Alternatively, if the material is a microfibrillated cellulose-polyol fatty acid ester bonded material, (They do not form hydrogen bonds between fibers as readily as bonded fibers).

[0049] As used herein, "repulpable" refers to a paper or paperboard product that is suitable for crushing into shapeless, flexible masses for reuse in the manufacture of paperboard. This means that...

[0050] As used herein, a "stable aqueous composition" refers to a composition that is contained in a closed container and maintained at a temperature of from about 0° C. to about No viscosity change, coagulation or sedimentation for at least 8 hours when stored at temperatures in the range of 60°C. Some embodiments of the composition include at least one aqueous composition that is substantially resistant to water. It is stable for 24 hours and often for at least 6 months.

[0051] As used herein, "adjustable" refers to a particular outcome, including grammatical variations thereof. This means adjusting or adapting a method to achieve a desired result, e.g., E in combination with a specific substrate exposed to a specific oil and / or a specific grease, To make the treated substrate resistant to the particular oil and / or the particular grease. It is possible.

[0052] As used herein, "water contact angle" refers to the angle at which a liquid / vapor interface meets a solid surface. The term refers to the angle measured through a liquid at which the surface is wetted by the liquid. It defines the wettability of a solid surface by a liquid. The contact angle is a measure of the strength of interaction between liquid and solid molecules, each of which corresponds independently to the other. On most highly hydrophilic surfaces, the water droplets move at 0° to This shows a contact angle of 30°. In general, if the water contact angle is greater than 90°, the solid surface is hydrophobic. The water contact angle is measured using an optical tensiometer (e.g., Dyne Testing, S taffordshire, United Kingdom) to It can be easily obtained.

[0053] As used herein, "moisture permeability" refers to the ability of a textile to breathe or transfer moisture. It means the ability to move something. There are at least two different ways of measuring it. One of them is ISO The MVTR (Moisture Vapor Transmission Rate) test according to 15496 measures the moisture vapor transmission rate (WVP) of fabrics. , and therefore indicates the degree of sweat transport to the outside air. The number of grams of moisture (water vapor) that pass through the material in 24 hours is determined (the higher the level, the better the ventilation). (The effect is more pronounced.)

[0054] Other test methods for measuring MVTR include ASTM E96 and ASTM F12 49 is listed.

[0055] A variation of ASTM E96 employs a chamber to measure moisture resistance. The chamber is The chambers are vertically separated by the substrate / barrier material. One chamber contains dry air. The other chamber has humid air. A 24-hour test is run to determine the amount of moisture that escapes into the "dry" chamber. ASTM E96 refers to one of five combinations of temperature and humidity for a "wet" chamber. The most stringent conditions are 100°F / RH (relative humidity) 95%. The method can be time consuming and pressure changes can affect the actual results. .

[0056] ASTM F1249 uses an infrared (IR) detector to measure the concentration of fluoride in the ASTM E96 method. The change in RH on the dry side of the film was measured in a chamber similar to that used in This is a method for measuring MVTR. Water is placed at the bottom of the chamber to create an atmosphere of 100% RH. A barrier material is used to separate the bottom and top. The top side of the chamber is flushed with dry air. The air is ventilated and the change in RH is measured with an IR detector. The disadvantage of this method is that it is difficult to control the RH. RH is limited to 100% unless special equipment is used that allows do.

[0057] In one embodiment, the TAPPI T 530 Hercules size test (i.e., A paper sizing test (Ink Fastness Test) is sometimes used to determine water fastness. The Hercules method of ink resistance is best classified as a direct measurement test of the degree of penetration. Others classify the assay as a rate of penetration test. There is no one best test. Test selection depends on end use and mill control needs. The Hercules method is a mill controlled sizing test that detects changes in sizing levels. The test provides reproducible results, reduces test time and has a precise endpoint. Provides automatic determination of the sensitivity of the ink float test.

[0058] It is measured by the resistance of water-based liquids to permeation through the paper or to absorption by the paper. Sizing is an important feature of many papers. Typical of these are bags, container boards, etc. Paper, meat wrap, writing and some printing grades.

[0059] The method is used to monitor the production of paper or paperboard for a specific end use. However, an acceptable correlation between the test values ​​and the end-use performance of the paper must be established. Due to the nature of the test and the permeant, the test is The methods may not necessarily be sufficiently interrelated to be applicable to the application requirements. Other methods measure sizing by surface contact, surface penetration or absorption. The ability to simulate the means of water contact or absorption in the end use The method is chosen to optimize sizing chemical usage costs. It can also be used for

[0060] As used herein, "oxygen permeability" refers to the ability of a polymer to allow the passage of gas or fluid. The oxygen permeability (Dk) of a material is determined by its diffusivity (D) (i.e., the rate at which oxygen the speed at which oxygen molecules move across a material) and the solubility (k) (or the number of oxygen molecules per volume of material) The oxygen permeability (Dk) is a function of the amount of oxygen absorbed. The oxygen permeability (Dk) value is typically in the range of 10 to 150 × 10 -11 ( cm 2 ml O2) / (s ml mmHg). Hydrogel water content and permeability A semi-logarithmic relationship was shown between the oxygen content (unit: Barrer unit) and the international standard The ISO uses the SI unit of pressure, hectopascal (hPa), to measure permeability. Therefore, Dk=10 -11 (cm 2 ml O2) / (s ml hP a) Barrer units can be converted to hPa units by multiplying the Barrer value by a constant 0.75. can.

[0061] As used herein, "biodegradable," including its grammatical variations, refers to the action of living organisms. can be broken down by (e.g., by microorganisms), especially into harmless products .

[0062] As used herein, "recyclable" means to recycle, including its grammatical variations. Processable or (used and / or) capable of making said material suitable for use (For waste materials) means materials that can be processed.

[0063] As used herein, "Gurley seconds" or "Gurley number" means the number of 100 cubic seconds. inch (deciliter) of air pushes 1.0 square inch of a given material through water with a pressure difference of 4. It is a unit of measurement that indicates the number of seconds required to pass 88 inches (0.176 psi) SO 5636-5:2003) (porosity). Furthermore, regarding stiffness, the "Gurley number" is , the force required to deflect a material held vertically a given amount (1 milligram force) The unit of measurement for the portion of the material that is being measured. Such values ​​are expressed in Gurley Precision. The measurements were performed using a 3D printer (Troy, New York). This can be done.

[0064] HLB is related to the hydrophilic-lipophilic balance of a molecule and is calculated for different regions of the molecule. is a measure of the degree to which a moiety is hydrophilic or lipophilic, as determined by

[0065] 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. ] and the results are expressed on a scale of 0 to 20. An HLB value of 0 represents a completely lipophilic / hydrophobic molecule. and an HLB value of 20 corresponds to a completely hydrophilic / oleophobic molecule.

[0066] The HLB value can be used to predict the surface active 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) emulsifiers 7~9: Wetting and spreading agent 13-15: Cleaning agent 12-16: O / W (oil-in-water) emulsifier 15-18: Solubilizers or hydrotropes

[0067] In embodiments, the polyol fatty acid esters disclosed herein (or the esters) The HLB value of the composition containing the ether can be in the lower range of 1 to 3. In the present specification, the polyol fatty acid ester (or the polyol fatty acid ester containing the polyol fatty acid ester) is The HLB value of the composition can be in the mid to higher range. The combination of PFAE and zein to form the aqueous composition has an HLB value in the mid-range of 4-10. The use of such esters having the formula:

[0068] As used herein, "SEFOSE®" is a syrup made from soybean oil. Sucrose fatty acid esters (soybean oil fats) containing one or more unsaturated fatty acids Procter & Gamble Chemicals ( (Cincinnati, OH) under the trade name SEFOSE® 1618U (See Polysucrose Soybean Acid Below).

[0069] As used herein, “OLEAN®” refers to a compound of formula C n+12 H 2n+ 22 O 13 The name of sucrose fatty acid ester having all fatty acids being saturated fatty acids. and is available from Procter & Gamble Chemicals.

[0070] Other PFAEs with various HLB values ​​and different fatty acid moieties are available from Mitsubishi Chemical. The compound can be obtained from Ries Corporation (Tokyo, Japan) under the trade name RYOTO™.

[0071] As used herein, "soybean oil fatty acid esters" refer to fatty acids derived from soybean oil. "Method of Solvent Preparation" means a mixture of salts of

[0072] As used herein, "oilseed fatty acids" refers to fatty acids derived from soybean, peanut, canola, and other , barley, canola, sesame seeds, cotton seeds, palm kernels, grape seeds, olives, safflower, corn Hemp, copra, corn, coconut, linseed, hazelnut, wheat, rice, zucchini Limited to potatoes, cassava, legumes, camelina seeds, mustard seeds, and combinations thereof. The term "fatty acids" refers to fatty acids of plant origin, including but not limited to:

[0073] As used herein, a "plasticizer" is an agent that increases the plasticity or decreases the viscosity of a material. Additives are substances that are added to modify physical properties. They are low volatility liquids, or perhaps even solids. Plasticizers are used to dissolve polymers in water. It reduces the attractive forces between the chains and promotes flexibility.

[0074] In embodiments, "fatty acid" includes carboxylic acids containing an aliphatic chain which may be branched. The aliphatic chain may be a saturated aliphatic chain or may have one or more carbon:carbon bilayers. The aliphatic chain may contain unsaturated bonds such as aryl bonds and may be cis or trans. , a short chain of 5 carbons or less; a medium chain of 6 to 12 carbons; a long chain of 13 to 21 carbons; or It can be even longer, up to 22 or more carbon atoms.

[0075] As used herein, a "polyol" is a polymer containing multiple hydroxyl groups. The term "polyol" refers to an organic compound. The polyols are biodegradable and recyclable. In the above, the polyols are furan, pyran, ribose, deoxyribose, ribonucleoside, Ring structures of nucleotides, deoxynucleosides, ribonucleotides, deoxyribonucleotides, etc. In embodiments, the polyol comprises a carbohydrate. In an embodiment, the polyol comprises a sugar. In an embodiment, the polyol comprises a monosaccharide, a disaccharide, or a trisaccharide. In embodiments, the polyol includes a glycosaminoglycan, a mucopolysaccharide, and the like. In an embodiment, the polyol is glucose, fructose, galactose, ribonuclease, or the like. ose, deoxyribose, arabinose, xylose, mannose, sucrose, lactose This includes services, etc.

[0076] As used herein, "wet strength" refers to the ability of paper to hold together when it is wet. It is a measure of how well a web of fibers can resist the force of breaking. The strength of the material is provided by Thwing-Albert Instrument Company (We The Finch Wet Strength Device (St. Berlin, NJ) In this case, wet strength can be measured using kymene, cationic glyoxyl Polyamide resins, including polyamidoamine-epichlorohydrin resins and epoxide resins In embodiments, the present invention is provided by additives such as dimethyl-epichlorohydrin resins. The PFAE-coated cellulose-based materials disclosed herein are Such wet strength is achieved in the absence of any additives.

[0077] As used herein, "wet" means filled with or saturated with water or another liquid. This means that

[0078] In embodiments, the methods disclosed herein comprise providing a barrier coating on a cellulosic The step of attaching to a surface or bonding to a cellulosic surface. the method comprising contacting the barrier coating with a cellulose contacting the base material with a coating comprising a polyol fatty acid ester and a prolamine; and exposing the contacted cellulose-based material to heat, radiation, a catalyst, or a combination thereof. The barrier coating is exposed to the cellulose-based material for a period of time sufficient to bond the barrier coating to the cellulose-based material. In a related embodiment, such radiation includes UV, IR, visible light, Other related examples include, but are not limited to, In some embodiments, the reaction is carried out at room temperature (i.e., 25° C.) to about 150° C., about 50° C. to about 100° C. The reaction can be carried out at about 60°C to about 80°C.

[0079] In one embodiment, the polyol fatty acid ester-prolamine barrier composition comprises a monoester. esters, diesters, triesters, tetraesters, pentaesters, or combinations thereof In another embodiment, the barrier coating comprises a mixture of milk proteins. Proteins (e.g., casein, whey protein, etc.), wheat gluten, gelatin, soybean Protein isolates, starches, modified starches, acetylated polysaccharides, alginates, carrageenans, These include, but are not limited to, chitosan, inulin, long chain fatty acids, waxes, and combinations thereof. It may contain other proteins, polysaccharides and lipids, including those listed above.

[0080] In embodiments, the coating may further contain PvOH.

[0081] In embodiments, it is contemplated that the disclosed methods can be used to enhance materials. In order to adhere the coating to the surface of the article, the catalyst may also be supported on an organic carrier (e.g., In a related embodiment, the reaction time is substantially Furthermore, the resulting material exhibits low blocking properties.

[0082] As disclosed herein, all polyol lipids, including monosaccharides, disaccharides, and trisaccharides, are Fatty acid esters are suitable for use in the present invention. The fatty acid moiety of the ester of aryl fatty acids may be saturated, unsaturated, or a combination thereof. Including monoesters, diesters, triesters, tetraesters, pentesters, and combinations thereof.

[0083] Without being bound by theory, it is believed that the polyol fatty acid ester and the cellulose-based material The interactions between the materials are ionic, hydrophobic, hydrogen, van der Waals interactions, and covalent bonds. In a related aspect, the cell The polyol fatty acid esters attached to the cellulose-based material may be (e.g., saturated fatty acids Without being bound by theory, the PFAEs used in this study (including combinations of PFAEs containing unsaturated fatty acids and unsaturated fatty acids) are virtually irreversible. Although not desired to be bundled, the unsaturated fatty acids are covalently bound to the surface.

[0084] Furthermore, the binding of polyol fatty acid esters at sufficient concentrations alone can produce a cellulose-based The properties of the material are sufficient to make it resistant to oil and / or grease, i.e. oleophobic. PFAE bonding alone can enhance the reinforcement, stiffening, and bulking of cellulose-based materials. Other properties may be achieved, including waxes, rosins, resins, diketenes, silsesquioxanes, and the like. Shellac, vinyl acetate, natural and / or synthetic latex, PLA, PEI, Oil, other oil / grease repellent chemicals, or a combination thereof (i.e., a second oleophobic This is achieved without the addition of any additives (e.g., phosphate ions).

[0085] The advantage of the disclosed invention is that multiple fatty acid chains are present in the cellulose, as well as in the structure or group The polyol and cyclic molecules in the backbone of the material, such as the disclosed sucrose fatty acid esters, It reacts with cellulose to form a rigid crosslinked network and is used in paper, paperboard, airlaid and wet-laid nonwovens, and The strength of textiles and other fibrous webs is improved. It is usually the result of a process that is different from other sizing processes. In embodiments, the barrier coatings described above are used to A method of manufacturing an article, comprising the steps of: A method is disclosed for producing an article that is resistant to permeation.

[0086] The present invention also relates to an article comprising the above composition applied to a substrate. Resistant to energy, and to penetration by oil and / or grease. In such a case, the barrier coating disclosed herein is applied at the size press. but not other prolamine-containing coatings.

[0087] Another advantage is that the disclosed polyol fatty acid esters soften the fibers and fill the voids between the fibers. The advantage of this approach is that it increases the spacing and therefore the bulk without substantially increasing the weight. Additionally, the fibers and cellulose-based materials modified as disclosed herein can be recycled. In addition, oil and / or grease, for example, can easily cause the barrier to break down. It is not possible for them to "push through" and into sheets treated with the barrier coating described. It is not possible.

[0088] Saturated PFAEs are typically meltable solids at nominal processing temperatures, while unsaturated PFAEs are , typically liquid, thereby allowing for uniform and stable dispersal of saturated PFAE in the aqueous coating. The ability to form suitable dispersions without significant interactions or incompatibilities with other coating ingredients. Furthermore, such dispersions allow for improved rheology, uniformity, and The coating application or coating performance properties, therefore, High concentration saturation without adversely affecting the ability to use a size press for coating It is possible to prepare PFAE. The coating layer is heated, dried and composited. When the Loramine and saturated PFAE particles melt and spread, the coating surface becomes oleophobic. In an embodiment, the prolamin contained in the coating is blocked with the ester. A method for producing a bulky fibrous structure that retains its strength even when exposed to water because it is covered Molded fiber products made using the disclosed methods include lightweight, Strong and resistant to exposure to oil, grease, water and other liquids, paper plates, drinks These include holders (e.g., cups), lids, food trays, and packaging. do.

[0089] In embodiments, the polyol fatty acid ester is mixed with a prolamine to provide oil resistance and and / or to produce a sizing agent for a grease-based coating. Thus, the synergistic relationship between polyol fatty acid esters and prolamins has become clear. Prolamines are known in the art to be film-forming agents, but they are not water-sensitive. In an embodiment, the use of polyol fatty acid esters emulsifies the prolamin to It aids in making water-based coatings.

[0090] In an embodiment, the polyol fatty acid ester is a polyol fatty acid ester comprising a sugar, such as sucrose, an ester of a fatty acid, Many methods can be used to prepare polyol fatty acids of the present invention. It is known and available to make or otherwise provide esters, and such All such methods are available for use within the scope of the present invention. For example, in embodiments: Fatty acid esters are made by mixing polyols with soybean oil, sunflower oil, olive oil, canola oil, and oats. A type of oil obtained from oilseeds, including but not limited to flowering oils, or mixtures thereof or synthesized by esterification with multiple fatty acid moieties.

[0091] In embodiments, the cyclic polyol fatty acid ester comprises a disaccharide moiety, such as a sucrose moiety. The sugar moiety includes, but is not limited to, one or more hydroxyl hydrogens are esterified. In one embodiment, the disaccharide ester is represented by formula I

[0092] [ka] [wherein "A" is hydrogen or the following structure I [ka] (wherein "R" is a straight chain, branched, or cyclic saturated fatty acid having from about 8 to about 40 carbon atoms. (saturated or unsaturated aliphatic or aromatic moieties) and at least one "A" is at least one, at least two, at least at least 3, at least 4, at least 5, at least 6, at least 7, or All eight "A" moieties match structure I. In one embodiment, the disaccharide fatty acid esters described herein have the structure: esters, diesters, triesters, tetraesters, pentaesters, and their Combinations are possible, and the R groups may be saturated or saturated and unsaturated groups.

[0093] Suitable "R" groups include any form, including those containing one or more substituents. Also included are aliphatic moieties of the formula: where the substituents may occur on any carbon in the moiety. Aliphatic groups containing functional groups within the aliphatic portion, such as ether, ester, thio, amino, phospho, etc. Aliphatic moieties are also included. Oligomeric and polymeric aliphatic moieties, such as sorbitan, polyisocyanate, Also included are ruthenium and polyalcohol moieties. Aliphatic (or aromatic) containing "R" groups Examples of functional groups that can be added to the moiety include halogen, alkoxy, hydroxy, and a These functional groups include, but are not limited to, amino, ether and ester functional groups. In another embodiment, the moiety may have a crosslinkable functional group. For example, activated clay / pigment particles) may be crosslinked to the surface. The double bonds present on the FAE are used to facilitate reactions to and with surfaces. This may be the case.

[0094] In an embodiment, the polyol comprises a carbohydrate. In an embodiment, the polyol comprises a sugar. In an embodiment, the polyol comprises a disaccharide. Suitable sugars and oligosaccharides include , raffinose, maltodextrose, galactose, sucrose, glucose combination combination of fructose, combination of maltose, lactose, and mannose, erythritol, A combination of isomaltulose, trehalose, trehalulose, cellulose Examples of suitable saccharides include saccharide stearate, ...

[0095] In embodiments, the polyol base or backbone for the addition of fatty acids includes dendrimer, The cellulose may include cellulose, hemicellulose, lignin, or a combination thereof.

[0096] In an embodiment, the composition comprises a starch fatty acid ester, the starch being Dentco Corn starch, waxy corn starch, potato starch, wheat starch, rice starch Punch, sago starch, tapioca starch, sorghum starch, sweet potato starch, and The compounds may be derived from any suitable source, including but not limited to, sodium phosphate esters, sodium phosphate diphosphate esters, and mixtures thereof.

[0097] In embodiments, the starch may be unmodified starch or may be chemically modified, physically modified or otherwise processed. The starch may be modified by enzyme modification.

[0098] Chemical modification involves the use of chemical agents to produce modified starches (e.g., plastarch materials). Chemical modifications include any treatment of starch that results in starch depolymerization, ... Oxidation of starch, reduction of starch, etherification of starch, esterification of starch, These include, but are not limited to, nitrification, starch degreasing, starch hydrophobization, etc. Chemically modified starches may also be prepared using any combination of chemical treatments. Examples of chemically modified starches include alkenyl succinic anhydrides, especially octenyl Reaction of succinic anhydride with starch to produce hydrophobic esterified starch; 2 ,3-epoxypropyltrimethylammonium chloride was reacted with starch to produce cationic Reaction to form hydroxylic starch; ethylene oxide is reacted with starch to form hydroxylic Reaction to produce ethyl starch; reaction of hypochlorite with starch to produce oxidized starch reaction to produce acid depolymerized starch; reaction to produce acid depolymerized starch; starch Methanol, ethanol, propanol, methylene chloride, chloroform, carbon tetrachloride Examples of reactions include those in which starch is degreased with a solvent to produce defatted starch.

[0099] Physically modified starch is starch that has been physically treated in a way to provide physically modified starch. Within the scope of physical processing are heat treatment of starch in the presence of water, heat treatment of starch in water; crushing starch granules by any mechanical means; These include, but are not limited to, pressure treatment to melt the starch granules. Physically modified starches may also be prepared by using any combination of physical treatments. Examples of physically modified starches include starch granules that are swollen without granule rupture. Heat treatment of starch in an aqueous environment to induce polymer rearrangement; Heat treatment of starch granules, fragmentation of starch granules by mechanical degradation, and melting of starch granules Examples of methods include pressure treatment of starch granules in an extruder to cause

[0100] Enzyme modified starch is any starch that has been treated with an enzyme in any manner to provide an enzyme modified starch. The enzymatic modification of starch includes the reaction of starch with α-amylase, proteases, and Reaction of lipase with starch, reaction of lipase with starch, reaction of phosphorylase with starch, These include, but are not limited to, the reaction of starch with oxidase. The pun can be prepared by using any combination of enzyme treatments. An example of enzymatic modification of starch is the reaction of α-amylase enzyme with starch to depolymerize it. The reaction that produces starch; the debranching enzyme α-amylase reacts with starch to produce debranched starch. The reaction that produces starch; the reaction of protease enzyme with starch to produce starch with low protein content. A reaction that produces reduced starch; the lipid content is reduced by reacting the lipase enzyme with starch. A reaction to produce reduced starch; reacting a phosphorylase enzyme with starch to produce the enzyme Reactions to produce modified phosphate starch; and reactions involving the reaction of starch with oxidase enzymes. The reaction produces enzymatically oxidized starch.

[0101] The disaccharide fatty acid esters are represented by formula I, where the "R" groups are aliphatic and may be linear or branched. and is saturated or both saturated and unsaturated and has from about 8 to about 40 carbon atoms. It is possible to obtain a sucrose fatty acid ester by the above method.

[0102] As used herein, "polyol fatty acid ester" means The terms "sucrose fatty acid ester" and "sucrose fatty acid ester" refer to compositions having different purities. and mixtures of compounds at any purity level. For example, sugar fatty acid ester compounds can be a substantially pure material, i.e., replaced by only one type of Structure I moiety. A given number of "A" groups are substituted (i.e., all "R" groups are the same and All of the triol moieties may be substituted to the same degree. These terms refer to two or more groups having different degrees of substitution, but all of the substituents having the same "R" group structure. Also included are compositions containing blends of polyol fatty acid ester compounds. The degree of substitution 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 poly(A) and / or poly(B) are each independently selected from the group consisting of a mixture of compounds. The all fatty acid esters may be the same or different (i.e., different polyol fatty acids). The "R" groups may be the same or different, including mixtures of fatty acid esters.

[0103] In the composition of the present invention, the composition contains a polyol fatty acid ester compound having a lower DS. In an embodiment, the polyol fatty acid ester may be composed of polysoybean oil. It is a fatty acid sucrose.

[0104] [ka] Sucrose polysoyate (SEFOSE® 1618U)

[0105] Polyol fatty acid esters are prepared by mixing a polyol with a fatty acid ester extracted from a natural source, such as an oil seed. fatty acids in the form of fatty acid glycerides derived from oxidized oils, such as those found in soybean oil Substantially pure fatty acids can be prepared by known esterification methods, such as transesterification using It can be prepared by esterification with fatty acid glycerides. Transesterification reactions to provide aryl fatty acid esters are described, for example, in U.S. Pat. No. 3,963,699. No. 4,517,360, No. 4,518,772, No. 4,611,055 , No. 5,767,257, No. 6,504,003, No. 6,121,440, No. 6,995,232 and International Publication No. WO 1992004361. , each of which is incorporated herein by reference in its entirety.

[0106] In addition to creating hydrophobic polyol esters via transesterification, acid chlorides can also be used to In cellulosic fiber articles, by reacting directly with polyols containing ring structures, Similar hydrophobicity can be achieved by using

[0107] As mentioned above, the polyol fatty acid esters are prepared from glycerides derived from natural sources. can be prepared by transesterification of polyols from methyl ester feedstocks (See, e.g., U.S. Pat. No. 6,349,363, which is incorporated herein by reference in its entirety. (See, e.g., U.S. Pat. No. 995,232). As a result of the source of fatty acid, polyol fatty acid esters The feedstock used to prepare the oleic acid contains fatty acid moieties containing 12 to 40 carbon atoms. It contains various saturated and unsaturated fatty acid methyl esters having such a source. This is reflected in the polyol fatty acid esters, which are products made from This is because the polyol portion containing the compound contains a mixture of ester moiety substituents. With reference to Structure I of the present invention, the "R" group represents the feed used to prepare the polyol ester. It is a mixture of 12 to 26 carbon atoms in a ratio that reflects the raw materials. As shown in Fig. 1, the polyol ester derived from soybean oil is oleic acid ester containing 26% soybean oil by weight. Triglyceride of phosphate (H3C-CH2]7-CH=CH-[CH2]7-C(O)OH) 49% by weight of linoleic acid (H3C-[CH2]3-[-CH2-CH=CH]2-[ -CH2-]7-C(O)OH), 11% by weight of linoleic acid (H3C- Triglyceride of [-CH2-CH=CH-]3-[-CH2-]7-C(O)OH), and 14% by weight of S, which is incorporated herein by reference in its entirety. Various articles listed in the eventh Ed. Of the Merck Index It is a mixture of species with "R" group structures reflecting the inclusion of saturated fatty acid triglycerides. All of these fatty acid moieties are part of the desired product, the polyol fatty acid ester. It is representative of the "R" group of the substituents. Thus, natural sources, such as soybean oil, Polysaccharides are herein produced as products of reactions employing fatty acid feedstocks derived from sucrose fatty acids. When referring to all fatty acid esters, the natural source feedstock is one in which the polyol fatty acid esters are It is intended to include all of the various components typically found as a result of the source being prepared. In a related aspect, the disclosed polyol fatty acid esters have low viscosity (e.g. For example, it may show a value of about 10 to 2000 centipoise at room temperature or standard atmospheric pressure. In the same manner, unsaturated fatty acids may have one, two, three or more double bonds. There is.

[0108] In an embodiment of the invention, the polyol fatty acid ester, in an aspect a disaccharide ester, , an average of more than about 6 carbon atoms, about 8 to 16 carbon atoms, about 8 to about 18 carbon atoms 14 to 18 carbon atoms, 16 to 18 carbon atoms, 16 to 20 carbon atoms It is formed from fatty acids having about 20 to about 40 carbon atoms.

[0109] In an embodiment, the polyol fatty acid ester and prolamine in the barrier coating The ratio varies depending on the form of the cellulose-based material, the oil and / or grease to which the material is exposed, etc. In one embodiment, the PFAE can be adjusted (modified) to achieve oleophobicity. The ratios of glycerol to prolamin were 1:1, 2:1, 3:1, and 4:1 on a weight-to-weight (wt / wt) basis. In a related embodiment, the polyol fatty acid ester may be 1:1 or 5:1. When prolamins are mixed as a coating on cellulose-based materials, At least about 0.1 g / m2 of the surface of the loin-based material 2 ~Approx. 1.0g / m 2 ,about 1.0g / m 2 ~about 2.0g / m 2 , about 2g / m 2 ~about 3g / m 2 The coating weight of In a related embodiment, the coating mixture may be about 3 g / m 2 ~ Approximately 4g / m 2 , about 4g / m 2 ~about 5g / m 2 , about 5g / m 2 ~about 10g / m 2 , about 10g / m 2 ~about 20g / m 2 In another embodiment, a cellulose-based When the material is a solution containing cellulose fibers, the coating is applied to all of the fibers present. The compound may be present in a concentration of at least about 0.025% (wt / wt). In this embodiment, the coating composition comprises about 0.05% (wt / wt) of the total fibers present. ~0.1%(wt / wt), approx. 0.1%(wt / wt)~0.5%(wt / wt), Approx. 0.5% (wt / wt) ~ approx. 1.0% (wt / wt), approx. 1.0% (wt / 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), approximately 5.0% (wt / wt) ~ approximately 10% (wt / wt), approximately 10% ( It can be present at about 50% (wt / wt) to about 50% (wt / wt).

[0110] In embodiments, the coating comprises from about 0.9% to about 1. 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), Containing about 40% to about 50% (wt / wt) or more of polyol fatty acid ester. In a related embodiment, the coating may be about 2% by weight of the coating. It may contain from 5% to about 35% (wt / wt) of polyol fatty acid ester.

[0111] In embodiments, the cellulose-based material includes paper, paperboard, paper sheets, paper pulp, paperboard ... bags, cups, boxes, trays, lids, release paper / liners, compostable bags, shopping bags, shipping bags, Bacon board, tea bags, insulating materials, coffee or tea containers, pipes and water conductions tubes, food grade disposable cutlery, plates and bottles, screens for televisions and portable devices Clothing (e.g., cotton or cotton blends), bandages, pressure sensitive labels, pressure sensitive tapes, feminine products , as well as medical devices, drug delivery devices, and medicines used on or inside the body, such as contraceptives. These include, but are not limited to, containers for materials (e.g., pills, tablets, suppositories, gels, etc.). The disclosed coating technology may also be used on furniture and interior décor, outdoor It can also be used for camping equipment.

[0112] In one embodiment, the coatings described herein have a pH range of about 3 to about 9. In related embodiments, the pH is about 3 to about 4, about 4 to about 5, about 5 to about 7. , can be about 7 to about 9.

[0113] In an embodiment, a method for treating the surface of a cellulose-containing (or cellulosic) material 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 or X1 are the same. In contrast, the PFAE disclosed herein is the carrier and the method comprises the steps of: Cl), volatile organic compounds (VOCs) or catalysts are not required.

[0114] In an embodiment, the alkanoic acid derivative is mixed with the polyol fatty acid ester to form an emulsion. and using the emulsion to treat the cellulose-based material.

[0115] In embodiments, the polyol fatty acid ester can be an emulsifier, and can be one or Multiple monoesters, diesters, triesters, tetraesters and pentaesters In one embodiment, the polyol fatty acid ester is used as an emulsifier. and one or more of triesters, tetraesters and pentaesters. It may contain a mixture of one or both monoesters and diesters. In another embodiment, the fatty acid portion of the polyol fatty acid ester is a saturated group or It may contain a combination of saturated and unsaturated fatty acids. Stell-containing emulsions contain milk proteins (e.g., casein, whey protein, etc.), gelatin, , soy protein isolate, starch, acetylated polysaccharides, alginate, carrageenan, These include, but are not limited to, chitosan, inulin, long chain fatty acids, waxes, and combinations thereof. It may contain other proteins, polysaccharides and / or lipids, including those listed above.

[0116] In embodiments, the polyol fatty acid ester emulsifier disclosed herein is or agarite, ester, diester, ether, ketone, amide, nitrile aromatic compounds (e.g., xylene, toluene), acid halides, anhydrides, talc, Alkyl ketene dimer (AKD), alabaster, alganic acid cid), alum, albaline, glue, barium carbonate, barium sulfate, precipitated calcium carbonate Calcium, ground calcium carbonate, titanium dioxide, clay, dolomite, diethylenetriamine amine pentaacetate, ethylenediaminetetraacetic acid (EDTA), enzymes, formamidine sulfur Acid, Guar Gum, Gypsum, Lime, Magnesium Bisulfate, Milk of Lime, Milk of Magnesia, Pv OH, rosin, rosin soap, satin, soap / fatty acid, sodium bisulfate, soda ash, Titania, surfactants, starch, modified starch, hydrocarbon resins, polymers, waxes,

[0013] 2. The composition of the present invention includes, but is not limited to, polysaccharides, proteins, and combinations thereof, which are used in papermaking. It may also be used to transport other chemicals that are

[0117] In embodiments, the cellulose-containing material produced by the methods disclosed herein The material exhibits increased hydrophobicity or water resistance compared to untreated cellulose-containing materials. In a related embodiment, the treated cellulose-containing material is a cellulose-containing material that is In another related aspect, the present invention provides a method for producing a coating composition comprising the steps of: The processed cellulose-containing materials are biodegradable, compostable, and / or recyclable. In one embodiment, the treated cellulose-containing material can be hydrophobic (water-resistant) and and oleophobic (grease resistant).

[0118] In embodiments, the treated cellulose-containing material has a reduced cellulose content compared to the same material that is untreated. For example, the materials treated in the manner disclosed herein may have improved mechanical properties. The paper bags have 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, about In another embodiment, the Gurley number is increased by about 1.1 to 1.3 times, about 1.3 to 1.5 times. , about 3-4 fold, about 4-5 fold, about 5-6 fold, and about 6-7 fold. , tensile strain or strength is about 0.5 to 1.0 times, about 1.0 to 1.1 times, about 1.1 to 1.2 times In another embodiment, the maximum load energy is increased by about 1.2 to 1.3 times. .0-1.1x, approx. 1.1-1.2x, approx. 1.2-1.3x, and approx. 1.3-1.4x It increased.

[0119] In embodiments, the cellulose-containing material may be, for example, any of the cellulose-containing materials described in U.S. Patent Application Publication No. 2015 / 013666. No. 67243, which is incorporated herein by reference in its entirety. Microfibrillated cellulose (MFC) or cellulose nanofibers ( CNF) is added to the base paper during the molding and papermaking process. and / or added to a preformed layer as a coating or secondary layer to In a related embodiment, the base paper is treated with the polyol fatty acid ester as described above to reduce the porosity of the paper. In another related embodiment, the contacted base paper is further contacted with PvOH. In embodiments, the resulting contacted base paper has controllably water and oil resistance. In a related embodiment, the resulting base paper has a melting point of at least about 10 to 15 (i.e., Gurley Air Resistance (sec / 100cc, 20 oz cylinder), or at least approx. In one embodiment, the polymer may exhibit a Gurley value of at least about 200 to about 350. The prolamine-polyol fatty acid ester coating is a laminate of one or more layers. or one or more layers may be formed as a laminate; and It is possible to reduce the amount of one or more coating layers while still achieving the same performance effect (e.g., water resistance, In a related embodiment, the laminate can achieve biodegradability. May contain non-removable and / or compostable heat seals or adhesives.

[0120] In embodiments, the polyol fatty acid ester may be formulated as an emulsion. The choice of emulsifier and the amount used will depend on the nature of the composition and whether the emulsifier is capable of dispersing the polyol fatty acid ester. In one embodiment, the emulsifiers include water, a buffer, PvOH, carboxymethylcellulose (CMC), milk protein, wheat gluten, gelatin Chin, soy protein isolate, starch, acetylated polysaccharides, alginate, carrageenan , chitosan, inulin, long chain fatty acids, wax, agar, alginate, glycerol, galactose , lecithin, poloxamer, monoglycerol, diglycerol, monosodium phosphate , monostearate, propylene glycol, detergent, cetyl alcohol, and In one embodiment, the polynucleotide may include, but is not limited to, a combination of the above. The ratio of ester to emulsifier is about 0.1:99.9, about 1:99, about 10:90, about 20: The ratio may be about 80, about 35:65, about 40:60 or about 50:50. It will be apparent to one skilled in the art that the ratio may be varied depending on the properties desired.

[0121] In embodiments, the prolamine-polyol fatty acid ester coating comprises a pigment (e.g. clay, calcium carbonate, titanium dioxide, plastic pigments), binders (e.g. starch, soy protein, polymer emulsion, PvOH), and additives (e.g., Rioxal, glyoxalated resin, zirconium salts, calcium stearate, carbonate Calcium, lecithin oleate, polyethylene emulsion, carboxymethylcellulose, Acrylic polymers, alginates, polyacrylate gums, polyacrylates, microbicidal Antifoaming agents, oil-based antifoaming agents, silicone-based antifoaming agents, stilbenes, direct dyes and acids One or more types of coatings for internal and surface sizing, including but not limited to dyes In a related embodiment, the compound may be combined with any of a number of ingredients (singly or in combination). Ingredients such as these are believed to build a microporous structure, provide a light scattering surface, and improve ink receptivity. improve gloss, bind pigment particles, and apply coatings to paper, base sheet reinforcements binding, filling pores in pigment structure, reducing water sensitivity, Resists hot picking, prevents blade scratching, and is super calendering Improve gloss, reduce dust generation, adjust coating viscosity, and realize water retention. Disperse pigments, maintain coating dispersion, and improve coating / coating color Prevents deterioration, controls foaming, reduces entrained air and coating craters, These include, but are not limited to, increasing whiteness and brightness, controlling color and shade. Depending on the desired properties of the final product, one or more properties may be obtained, including It will be apparent to one skilled in the art that other combinations may be used.

[0122] In an embodiment, the method of employing the prolamine-polyol fatty acid ester comprises the steps of: Subsequent / secondary coatings (e.g. silicone-based layers, starch-based layers, claves, etc.) It is often used to reduce the cost of applying layers of plastic (such as a base layer, PLA layer, PEI layer, etc.) Yes, the desired properties (e.g., oil and / or grease resistance, water resistance, low surface energy By providing a layer of a material that exhibits high surface area, low surface tension, high surface energy, etc., the same properties can be achieved. In one embodiment, the amount of material (e.g., heat shield) required to form the primary / secondary layer is reduced. A coating of a PFAE layer (a polymerizable agent) may be coated on the PFAE layer. In this case, the composition is fluorocarbon-free and silicone-free.

[0123] In embodiments, 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 one embodiment, the surface of the cellulose-based material has a water contact angle of about 60° to about 120°. In one embodiment, the surface treatment is chemically stable at temperatures of about 200° C. to about 300° C. be.

[0124] The substrate to which the prolamine / PFAE composition has been added may be pre-coated (e.g., for about 80-150 min) prior to application. The surface may be immersed in the modified composition and dried at 35° C. for 1 hour. The substrate can be heated to dry the surface. Afterwards the modified material is ready for use. In accordance with the methods disclosed herein, the substrate can be processed using any suitable papermaking process typically performed in a paper mill. may be treated with suitable coating / sizing methods (e.g., cited in its entirety). Smook, G., "Surface T reatments”,“Handbook for Pulp & Paper Te chnologists” (2016), 4 th Ed., Chap. 18, pp. 293-309, TAPPI Press, Peachtree Corn ers, GA USA).

[0125] In some applications, the material may be dried before processing; however, in the practice of the present invention, No special preparation is necessary. In embodiments, the disclosed method can be used to prepare a film, a rigid container, or a Any cellulose, including but not limited to glass, fiber, pulp, fabric, etc. In one embodiment, the prolamine / polyol fat may be used on the surface of the base. Acid ester or coating agent is applied by conventional size press (vertical, inclined, horizontal), gate Roll size press, Metering size press, Calendar size application, Tube sizing, On-machine, off-machine, single-sided coater, double-sided coater, short dwell, simultaneous double-sided coater coater, blade or rod coater, gravure coater, gravure printing, flexographic printing , inkjet printing, laser printing, supercalendering, and combinations thereof. It can be applied by

[0126] Depending on the source, cellulose can be found in paper, paperboard, pulp, softwood fibers, hardwood fibers, or any combination thereof. combinations of nanocellulose, cellulose nanofibers, whiskers or microfibrils; Microfibrillated cotton or cotton blends, cellulose nanocrystals, or nanofibrillated It may be cellulose.

[0127] In embodiments, the application amount of the prolamine-polyol fatty acid ester coating is A sufficient amount to completely coat at least one surface of the cellulose-containing material. For example, in an embodiment, the prolamine-polyol fatty acid ester coating is The complete exterior surface, the complete interior surface of the container, or a combination thereof, or even one side of the base paper In embodiments, the entire top surface of the film may be coated with It may be coated with a prolamine-polyol fatty acid ester coating or The complete lower surface of the film was coated with a prolamine-polyol fatty acid ester coating. In some embodiments, the instrument / gauge hole may be covered on both sides. The exterior of the device / instrument may be coated with prolamin-poly It may be covered with a thiol fatty acid ester coating or the outer and Both inner surfaces are coated. In an embodiment, the prolamine-polyol fatty acid ester The amount of coating applied is sufficient to partially cover at least one surface of the cellulose-containing material. For example, in the ambient atmosphere or in the product, composition, chemical, or chemical in the target end use. Only the surfaces exposed to the mixture or material are coated with prolamine-polyol fatty acid ester coating. Only surfaces that are covered by glycerol or are not exposed to the ambient atmosphere are exposed to prolamin-polysaccharides. The coating is covered with a triol fatty acid ester coating (e.g., masking). As will be apparent to those skilled in the art, the amount of prolamine-polyol fatty acid ester coating applied The amount of adhesion may depend on the material being coated. In one embodiment, one surface is Coated with prolamin-polyol fatty acid ester (prolamin-PFAE) The opposite surface is made of protein, wheat gluten, gelatin, and soy protein isolate. starch, modified starch, acetylated polysaccharides, alginate, carrageenan, chitosan, Including, but not limited to, inulin, long chain fatty acids, waxes, and combinations thereof In one embodiment, the prolamin-PFAE is It can be added to the paper stock and the resulting material on the web contains PFAE or prolamin- An additional coating of PFAE may be applied.

[0128] Any suitable coating method may be applied in the course of carrying out that aspect of the method. Various prolamine-polyol fatty acid ester coatings and / or emulsions are available. In an embodiment, prolamin-poliomyelitis may be used to deliver either The methods of coating fatty acid esters include dipping, spraying, painting, printing, and the like. Any of the methods may be used alone or in any combination to practice the disclosed methods. Along with other applicable coating methods.

[0129] For example, by increasing the concentration of polyol fatty acid ester, The prolamines that are more readily dissolved and form more uniform films. Various catalysts allow for a more rapid "cure" of the coating to meet specific applications. Prolamin: The nature (composition) or amount of polyol fatty acid esters can be precisely controlled. There is a gender.

[0130] Selection of cellulose to be treated, prolamine-polyol fatty acid ester coating, Reaction temperatures and exposure times are routinely adjusted to suit any particular application of the final product. It will be apparent to one of skill in the art that these are parameters that can be optimized empirically.

[0131] In an embodiment, the prolamine is zein. Zein was purchased commercially (see above). (see Lawton JW, Cereal Chem (2002) 7 9(1): 1-18, at pages 1-4 (please refer to this document in its entirety). The present invention can be prepared by the method described in US Pat. No. 6,399,323, which is incorporated herein by reference.

[0132] Derivatized materials are defined and characterized using appropriate tests known in the art. Hydrophobicity has altered physical properties that can be measured and analyzed. Col can include, but is not limited to, contact angle measurements and moisture uptake. Other properties include stiffness, moisture vapor transmission rate (WVTR), porosity, tensile strength, and lack of matrix degradation. , rupture and tear properties. The specific standardization protocols that should be followed are those of the United States Materials Testing Association. It is defined by the Institute (Protocol ASTM D7334-08).

[0133] The permeability of the surface to various gases such as water vapor and oxygen is improved by enhancing the barrier function of the material. The polyol fatty acid ester coating method may also be changed to achieve the desired permeability. The standard unit for measuring these parameters is the barrer, and the protocol for measuring these parameters is is also available in the public domain (for water vapor, ASTM standard F2476-05 , and ASTM standard F2622-8 for oxygen).

[0134] In embodiments, biodegradable materials treated according to the procedures of the present disclosure are resistant to microbial attack. It exhibits complete biodegradability as measured by degradation in the environment.

[0135] Shake flask method (ASTM E1279-89(2008)) and Zahn-Wel Various methods are available to define and evaluate biodegradability, including the lens test (OECD TG 302 B). are available for inspection and testing.

[0136] Various methods, including but not limited to ASTM D6400, define compostability. and available for testing.

[0137] In embodiments, the barrier coating compositions disclosed herein are applied to a substrate or surface. When applied to a surface, it results in an article that is resistant to penetration of oil and / or grease. Resistance to oil and / or grease penetration is achieved by using a variety of oil, grease and wax coatings. Resists immersion in solvents such as toluene and heptane, as well as other oily substances. Resistance to oil and / or grease penetration is rated by 3M In one embodiment, the composition comprises at least 3, At least 5, at least 7, at least 9 kits.

[0138] In an embodiment, a method of making an article includes applying a barrier coating composition to a substrate. Apply to surfaces with high surface energy and resistance to penetration of oil and / or grease In a related aspect, a method is disclosed for producing an article comprising: The rear composition is placed in intimate contact with one or more surfaces of the substrate to allow penetration of the surface. In one embodiment, the barrier coating comprises at least one It may be applied to one or more surfaces, or in an application, the coating may be applied to the It may be absorbed internally and applied so that it comes into contact with more surfaces.

[0139] In an embodiment, the barrier composition is applied to the substrate as a coating. By any suitable method, such as rolling, spreading, spraying, brushing or pouring. The composition can then be coated onto a substrate, which can then be dried and the barrier composition can be combined with other materials. , co-extrusion onto a preformed substrate, or melt / extrusion coating onto a preformed substrate. In one embodiment, the coating may be applied at a size press. In this case, the substrate may be coated with a barrier composition on one, both or all sides. In one embodiment, the barrier composition is moved along a roller to uniformly spread the barrier composition on the substrate. Coating knives such as "doctor blades" are sometimes used which allow In one embodiment, the barrier coating is applied by continuously operating a spread coater. They may be applied to textiles, nonwovens, foils, paper, paperboard and other sheet materials.

[0140] The barrier compositions disclosed herein are resistant to penetration of oil and / or grease. The material may be used to manufacture a wide variety of different articles having the following properties: Paper, cardboard, cardboard, container board, gypsum board, wood, wood composites, furniture, masonry , leather, automotive finishes, furniture polishes, plastics, non-stick cookware and foams These include, but are not limited to:

[0141] In embodiments, the barrier compositions disclosed herein are used in fast food packaging. It is often used in food packaging paper and paperboard. We offer fast food packaging, food bags, snack bags, grocery bags, cups, trays, Cartons, boxes, bottles, crates, food packaging films, blister pack packaging materials, microwave safe Applications include popcorn bags, release paper, pet food containers, beverage containers, OGR paper, etc. In embodiments, textile fibers, such as natural or synthetic textile fibers, are used. In a related aspect, the textile fibers can be used to make clothing, linens, tile articles, and the like. It may be further processed into carpets, draperies, wallpaper, and upholstery items.

[0142] In embodiments, the substrate is formed into an article either before or after application of the desired barrier composition. In one embodiment, the container may be made from a flat coated paperboard, press formed, molded, or molded into a molded article. Produced by blank forming or by folding and gluing paperboard into the desired final shape Flat coated paperboard stock can be, for example, As disclosed in U.S. Pat. No. 4,900,594, the entire disclosure of which is incorporated herein by reference. formed into a tray by the application of heat and pressure to the No. 5,294,483, the entire disclosure of which is hereby incorporated by reference. They may be vacuum formed into food and beverage containers as described above.

[0143] Materials suitable for treatment by the method of the present invention include those that have a significant surface area available for reaction / bonding. Cotton fiber, plant fibers such as flax, wood fiber, regenerated cellulose (rayon, etc.) and cellophane), partially alkylated cellulose (cellulose ether), partially esterified Cellulose (rayon acetate) and other modified cellulose materials in various forms As mentioned above, the term "cellulose" refers to these materials. , as well as all others having similar polyol structures and similar properties. Among these, microfibrillated cellulose (cellulose nanofiber) is a relatively new material. -) (e.g., each of which is incorporated herein by reference in its entirety) U.S. Patent No. 4,374,702, U.S. Patent Application Publication No. 2015 / 0167243 and and 2009 / 0221812) are particularly suited to the implementation of the intended subject matter. In an embodiment, the cellulose may be cellulose triacetate, cellulose propionate, or the like. Cellulose acetate propionate, cellulose acetate butyrate, nitrocellulose (cellulose nitrate) cellulose, cellulose sulfate, celluloid, methylcellulose, ethylcellulose, ethylmeth ethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, cellulosic Nanocrystals, Hydroxyethyl Methylcellulose, Hydroxypropyl Methylcellulose cellulose, ethylhydroxyethylcellulose, carboxymethylcellulose, and their Combinations may include, but are not limited to:

[0144] When cellulose is modified with the barrier coatings disclosed herein, it becomes more resistant to oil and / or In addition to increasing resistance to grease, it also has increased tensile strength, flexibility and rigidity. This may further broaden the scope of use. Biodegradable and partially biodegradable products made from or by using Including cyclable and compostable products are all within the scope of this disclosure.

[0145] Among the available uses of coating technology, such items include: Containers for paper, paperboard, paper pulp, cups, lids, boxes, trays, release paper / lights, etc. containers, compost bags, shopping bags, pipes and water pipes, disposable cutlery for food, plates and bottles, screens for televisions and mobile devices, clothing (e.g. cotton or cotton blends), Bandages, pressure sensitive labels, pressure sensitive tapes, feminine products, and medical devices such as contraceptives, drug delivery The coating methods disclosed herein include, but are not limited to, coating apparatus. The coating technology can also be used in furniture and interior decoration, outdoor camping equipment, etc. .

[0146] The following examples are intended to illustrate, but not limit, the present invention. Intend. EXAMPLES

[0147] [Example 1] Sugar fatty acid ester blend SEFOSE® is a liquid at room temperature and can be dissolved using a benchtop drawdown device. All coatings / emulsions containing the material were applied at room temperature. Various coat weights The rod type and size were changed to produce

[0148] Formulation 1 Add 50ml of SEFOSE® to 195ml of water and 5 grams of carboxylate. Methylcellulose (FINNFIX® 10; CP Kelco, Atlant The mixture was added to a solution containing 100% ethanol (100% ethanol, 100% ethanol, 100% ethanol) and the remaining ethanol was added to a solution containing 100% ethanol (100% ethanol, ...). The formulation was mixed for 1 minute using a homogenizer. The emulsion was made with bleached hardwood pulp. The 50 gram base sheet is made from 100% unbleached softwood, and the 80 gram sheet is made from 100% unbleached softwood. Both papers were placed in an oven (105°C) for 15 minutes to dry. After removing the sheets from the oven, place them on the laboratory bench and pipette 10 drops of water (room temperature) onto each sheet. The untreated base sheet absorbed the water droplets immediately, whereas various amounts of SEFOSE For sheets coated with POLY(R), water resistance increases with increasing coat weight. Elevated levels were observed (see Table 1).

[0149] [Table 1]

[0150] Water resistance is less pronounced in the heavier sheets and will only last if the sheets are dry. It was observed that aqueous compatibility was not achieved.

[0151] Formulation 2 Addition of SEFOSE® to cup stock: (single layer stock without MFC treatment) (110 grams of paperboard made from eucalyptus pulp). 50 grams of SEFOSE (registered trademark) (registered trademark) was added to 200 grams of 5% heat ethylated starch (Ethylex 2025). The paper samples were then coated with 100% ethanol and mixed for 30 seconds using a benchtop caddy mill. The test droplets (10-15) were applied to the coated paperboard. The untreated pieces were placed on their coated sides and the water hold out times were measured and recorded in the table below. Water penetration for the paperboard control was instantaneous (see Table 2).

[0152] [Table 2]

[0153] Formulation 3 Pure SEFOSE® was warmed to 45°C and placed in a spray bottle. The water droplets were applied to the paper stock from the previous example, as well as to a piece of fiberboard and a quantity of cotton fabric. When placed in a 105°C oven, penetration into the substrate occurred within 30 seconds. After drying for 5 minutes, the water droplets evaporated before being absorbed into the substrate.

[0154] Continuing research shows that SEFOSE® is an oil and / or grease resistant coating. The issue was whether the compound used in the coating could be compatible with SEFOSE (registered trademark). ) is useful for improving water resistance and stiffness. Paperboard stock (240g) was subjected to stiffness test. The results are shown in Table 3. Data is for a single coat weight of 5 grams per square meter. The results were obtained on a V-5 Tab 100 and the average of five samples is reported. The stiffness is in Taber stiffness units recorded using a er stiffness tester model 150-E.

[0155] [Table 3]

[0156] [Example 2] Attachment of sugar esters to cellulosic substrates Determine if SEFOSE® is reversibly bound to cellulosic materials I tried mixing pure SEFOSE® with pure cellulose in a 50:50 ratio. The SEFOSE® was reacted at 300° F. for 15 minutes and the mixture was mixed with methyl chloride. The samples were then extracted with ethylene (a non-polar solvent) or distilled water. The samples were refluxed for 6 hours and the weight of the samples was analyzed. went.

[0157] [Table 4]

[0158] [Example 3] Investigation of cellulosic surfaces Scanning electron microscope images of base paper with and without MFC show that the base paper has fewer pores. This shows that much less waterproofing agent may be required to react with the surface. Figure 1 shows the untreated medium porosity Whatman filter paper. Figures 1 and 2 show the reaction of the derivatizing agent. However, the highly porous sheet does not allow water to escape. Figures 3 and 4 show the structure of the pulp-made composite. The papers were compared before and after coating with MFC. (There are two magnifications of the same sample, the left side of the image does not contain the MCF.) Derivatization of the sheet with much less pores would be more effective for long-term water / vapor barrier performance. The last two images are from a single filter for contrast and comparison. A close-up of the average "pore" of the paper and a photo of the CNF-coated paper taken at a similar magnification. Here is a close-up.

[0159] From the data above, it is clear that there is a critical point, that with the addition of more material, there is a corresponding increase in performance. Without being bound by theory, it is clear that the reaction is more rapid on unbleached paper. The reaction appears to be fast, suggesting that the presence of lignin may enhance the reaction. is.

[0160] Liquid SEFOSE® can be easily emulsified. The fluids are adapted to work in coating equipment commonly used in paper mills. It is possible.

[0161] [Example 4] "Phluphi" Liquid SEFOSE® is mixed and reacted with bleached hardwood fibers to create waterproof handmade paper. Various forms were produced that yielded sheets. Sucrose esters were mixed with the pulp prior to sheet formation. When the fibers were mixed together, most of the PFAE was retained with the fibers. In this example, 0.2 mm thick handmade sheets were formed that were brittle and fluffy, but hydrophobic. Add 5 grams of SEFOSE® to 4.0 grams of bleached hardwood fiber in 6 liters of water. The mixture was stirred by hand and the water was poured into a standard handmade sheet mold. The fiber mat was removed and dried for 15 minutes at 325° F. The resulting sheet was highly hydrophobic. The fiber showed excellent water contact angle of more than 100° and significantly reduced hydrogen bonds between fibers. (Observed). Emulsifiers can be added. SEFOSE® and fiber are approximately It can be 1:100~2:1.

[0162] Subsequent testing showed that talc was the only bystander in the method and was excluded from further testing. It can be seen that.

[0163] [Example 5] Environmental Effects on SEFOSE® Coating Properties To better understand the reaction mechanism between sucrose ester and fiber, wet strength resins were added. Bleached kraft sheet that is not waterproof (no sizing) but has a low viscosity. A Brookfield viscometer was used at 100 rpm to measure the viscosity of the coating. The coating viscosity was measured.

[0164] SEFOSE® was emulsified with Ethylex 2025 (ethylated starch). The paper was coated with SEFOSE® via a gravure roll. It was also emulsified with estcote 9050 PvOH. As shown in Figure 5, SEFOSE ( The oxidation of the double bond of ethylene glycol tetrahydrofuran (EPO) produces heat and additional chemical rings that enhance the oxidative chemistry. This is enhanced by the presence of a boundary (see also Table 5).

[0165] [Table 5]

[0166] [Example 6] Effect of unsaturated versus saturated fatty acid chains SEFOSE® was reacted with bleached softwood pulp and dried to form a sheet. It was then extracted with CH2Cl2, toluene, and water to determine the extent of reaction with the pulp. The extraction was performed for at least 6 hours using Soxhlet extraction glassware. is shown in Table 6.

[0167] [Table 6]

[0168] Data shows that essentially all of the SEFOSE® remains on the sheet. The same procedure was performed on pulp alone, and the results showed that the concentration of pulp was approximately 0.01 per 10 g of pulp. Without being bound by theory, it can be seen that the These could be explained as residual pulping chemicals or more likely extractables. can.

[0169] Pure fibers of cellulose (e.g., from Sigma Aldrich (St. Louis, The experiment was repeated using α-cellulose (SEFOSE®). As long as the loading level remains below about 20% of the fiber's mass, SEFOSE® More than 95% of the mass of the cellulose was retained with the fiber and was not extracted with either polar or non-polar solvents. Without being bound by theory, it is believed that optimizing the baking time and temperature results in a better adhesion between the fibers and the This may further enhance residual sucrose esters in the sucrose extract.

[0170] As shown, the data generally reveals that SEFOSE® is lost from the material after drying. On the other hand, it is clear that all the fatty acids in PFAE are saturated fatty acid chains. The results showed that Procter & Gamble C, which accounts for almost 100% of the PFAEs in the material, OLEAN® available from Hemicals, Cincinnati, Ohio ) can be extracted using hot water (above 70°C). is identical to SEFOSE®, with the only change being the addition of unsaturated fatty acids to the sucrose. Instead of being bound to fatty acids (SEFOSE®), saturated fatty acids are bound to fatty acids (O LEAN (registered trademark) point.

[0171] Another notable aspect is that multiple fatty acid chains are attached to the cellulose and two sugar molecules in the structure. reacts with cellulose, forming a tightly crosslinked network that is used in paper, board, and airlay. This leads to improved strength in fiber webs such as wet-laid nonwovens and textiles. be.

[0172] [Example 7] SEFOSE® added to achieve water resistance 2 and 3 gram hand-made sheets made from both hardwood and softwood kraft pulp. A test was made. SEFOSE® was added to a 1% pulp slurry at a level of 0.1% or more. When the water is drained off and handsheets are formed, SEFOSE® dissolves in the fibers and Both were retained and provided water resistance. The surface beaded up for less than a few seconds. SEFOSE® loading was greater than 0.4%. For loading levels above 1.5%, the time to water resistance is in minutes and then hours. increased rapidly during

[0173] [Example 8] Manufacturing of bulky fiber materials Adding SEFOSE® to pulp softens the fibers and increases the space between the fibers. For example, a pulp-containing 125g (dry weight) A 3% slurry of hardwood pulp, when drained and dried, has a volume of 18.2 cubic centimeters. After draining and drying, 12.5 g of SEFOSE® ) to the same 3% hardwood pulp slurry containing an equal amount of 125 g dry fiber. The resulting mat occupied 45.2 cubic centimeters.

[0174] 30 grams of standard bleached hardwood kraft pulp (Old Town Fuel and F iber, LLC, Old Town, ME) in a container heated to 60°C. The spray was performed with 4.3 cm 3 The mixture was placed in a 10,000 rpm disintegrator. The mixture was poured through a hand sheet mould and dried at 105°C. The resulting hydrophobic pulp was 8.1 cm 3 The material was cut into 2-inch cubes. The square was then placed in a hydraulic press and subjected to 50 tons of pressure for 30 seconds. The volume of the square was significantly reduced. but still 50% higher than the same 2 inch square cut for the no pressure control. It took up volume.

[0175] Not only was an increase in bulk and softness observed, but the forced repulping of the maize after draining was also observed. It is also important to note that the resulting fiber mat retained all of its hydrophobic properties. The quality of this material allows water to easily "squeeze" through the low surface energy barrier and into the sheet. This is in addition to the knowledge that the binding of hydrophobic single fatty acid chains is unlikely to occur. Does not exhibit that characteristic.

[0176] Without being bound by theory, it is believed that SEFOSE® is a cellulose The OH groups on the surface of the cellulose fibers are no longer able to participate in subsequent hydrogen bonds. This represents further evidence that other hydrophobic materials may interfere with the initial hydrogen bonding. However, during repulping, the effect is reversed, and the OH groups of cellulose are hydrogen-bonded during redrying. Freely participate in such cases.

[0177] [Example 9] Bag paper test data The following table (Table 7) shows the range of 5 to 7 g / m 2 Mixture of SEFOSE® and PvOH The properties imparted by coating the blend onto unbleached kraft bag stock (control) were Also included for reference are commercial bags.

[0178] [Table 7]

[0179] As can be seen in Table 7, the control base paper was treated with SEFOSE® and PvOH. When coated with , the tensile and burst are increased.

[0180] [Example 10] Wet / Dry Tensile Strength Three gram hand sheets were made from bleached pulp. The following data indicate that SEFOS The wet and dry tensile strengths of the different E® loading levels are compared. For handmade sheets, SEFOSE® is not emulsified in any coating but is applied alone. Note that the mixture was mixed into the pulp and drained without adding any other chemical properties. (See Table 8).

[0181] [Table 8]

[0182] The 5% addition rate also resulted in wet strength that was not significantly lower than the dry strength of the control. Please take note.

[0183] [Example 11] Use of esters containing less than eight saturated fatty acids Using sucrose esters formed by attaching less than eight fatty acids to the sucrose moiety Several experiments were carried out. Samples SP50, SP10, SP01 and F20W (Si sterna, The Netherlands) are 50%, 10%, 1%, and and essentially 0% monoesters. These commercial products are sucrose saturated The compound is prepared by reacting it with a saturated fatty acid, thus making it more suitable for further cross-linking. The compounds are no longer useful or are no longer useful for similar chemical properties, but the compounds are still useful for emulsification and This is useful for investigating the water repellency and hydrophobicity properties of the material.

[0184] 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 sheet made from bleached hardwood kraft. The coating was applied by drawing down onto a porous base paper. The results showed that the cross-linked polymer 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 contact angle obtained was was greater than 100°. Glyoxal is a well-known Since the crystallizer is a sucrose crystallizer, the method involves converting the remaining alcohol groups of the sucrose ring into a substrate or other By combining with the alcohol groups available in the coating material, It is a promising means to attach non-reactive sucrose esters to surfaces.

[0185] [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 modified starch emulsified and applied by drawdown ( Ethylex 2025) and assayed in the Hercules size test. The results are shown in Table 9.

[0186] [Table 9]

[0187] As can be seen in Table 9, increasing amounts of SEFOSE® applied to the surface of the paper Addition of this compound results in increased water resistance (as indicated by an increase in HST (in seconds)).

[0188] This can also be seen using coatings of saturated sucrose ester products. F20W (Sisterna, The Netherlands) has a 4-8 substitution range. The percentage of monoester in most molecules is described as very low. was emulsified using equal parts of each with PvOH to create a stable emulsion. Note that only 50% of the total coating was applied. Therefore, the wet pick-up is "0. 5g / m 2 ", the same add-on weight of PvOH is also present, 1.0 g / m 2 of The total pick-up is obtained and the results are shown in Table 10.

[0189] [Table 10]

[0190] As can be seen from Table 10, the water resistance of the porous sheet increases with increasing F20W. Thus, the applied sucrose fatty acid ester makes the paper water resistant.

[0191] Water resistance is not simply due to the presence of fatty acids that form ester bonds with cellulose. To achieve this, softwood handmade sheets (bleached softwood kraft) were loaded with SEFOSE® and Oleic acid, which forms an ester bond with the cellulose in the pulp, was added directly to the pulp. The mass at 0 is the "bone dry" mass of the 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 ( The results are shown in Tables 11 and 12.

[0192] [Table 11]

[0193] [Table 12]

[0194] The difference when oleic acid is added directly to the pulp to form an ester bond is that it greatly increases moisture absorption. In contrast, only 2% SEFOSE® At higher concentrations, 30% SEFOSE® does not slow down the wetting. Thus, without wishing to be bound by theory, the structure of the SEFOSE® bonding material is This cannot be explained by the structure formed by simple fatty acid esters and cellulose. do not have.

[0195] [Example 13] Saturation SFAE Saturated esters are waxy solids at room temperature and, because they are saturated, do not react with the sample matrix. or difficult to react between molecules. High temperatures (e.g., at least 40°C, all tested , above 65°C), the material can be melted and applied as a liquid and then cooled and solidifies to form a hydrophobic coating. Alternatively, the material may be used as a water-based coating. The emulsion can be emulsified and applied to impart hydrophobic characteristics.

[0196] The data shown in Table 13 was obtained from papers coated with various amounts of saturated SFAE. Represents the HST (Hercules Size Test) reading.

[0197] Bleached hardwood kraft sheets from Turner Falls Paper #45 were used as test coats. The Gurley porosity was measured at about 300 seconds and was found to be a fairly tight base sheet. S-370 (3-5) obtained from Mitsubishi Foods (Japan) DS) was added to xanthan gum (up to 1% by weight of the saturated PFAE formulation) prior to coating. ) and emulsified.

[0198] Coat weight (pounds per ton) and HST (pounds per sample) of saturated PFAE formulations The results (average of four measurements) are shown in Table 13.

[0199] [Table 13]

[0200] Data shows that limited amounts of saturated PFAEs are used in products designed for other purposes / uses. It has been shown that saturated PFAE can enhance the water resistance of coatings. Water resistance when blended with Ethylex starch and PvOH based coatings An increase in was observed in both cases.

[0201] The following examples were run on a bleached Lisa cycle base #50 with a Gurley porosity of 18 seconds. It was done.

[0202] 100 grams of modified starch (Ethylex 2025) was added to 10% solids (1 liter by volume). Heat at 375°C (220°F) and add 10 grams of S-370 while hot. The resulting mixture was mixed using a common benchtop drawdown device. The coating was applied and the paper was dried under a heat lamp.

[0203] At a coat weight of 300# / ton, starch alone had an average HST of 480 seconds. For the mixture of starch and saturated PFAE at the same coat weight, the HST increased to 710 seconds. .

[0204] Sufficient PvOH (Selvol 205S) was dissolved in hot water to form a 10% solution. When the solution was coated onto the same #50 paper as above, the coating yielded 150 lb / ton coat weight. The average HST was 225. Using that same solution, the addition of S-370 reduced the drying By volume, 90% PVOH / 10% S-370 (i.e., 90 ml of water, 9 grams of PVOH) A mixture containing 1 g of S-370 (OH) was formed and the average HST increased to 380 seconds. Added.

[0205] Some insoluble cold polymers, such as starch, are composed of prolamines (e.g., zein; taken as a whole). See U.S. Pat. No. 7,737,200, which is incorporated herein by reference. One of the main barriers to commercial production of the subject matter of said patents is the formulation The addition of saturated PFAE is useful in that manner since the material is water soluble.

[0206] [Example 14] Other saturated SFAEs Size press evaluation of saturated PFAE-based coatings was performed without sizing and with good forming properties. The experiment was carried out on a relatively insufficiently bleached lightweight sheet (approximately 35#). All evaluations were performed using a pretreated Exceval HR 3010 PvOH. Sufficient saturated PFAE was added to account for 20% of the total solids. The focus was on evaluating samples (available from Mitsubishi Foods, Japan). Both of these esters performed better than the control. Some of the key data are: Shown in Table 14.

[0207] [Table 14]

[0208] Saturated compounds appear to result in increased kits, with both S-370 and C-1800 Note that in both cases, the increase in HST is approximately 100%.

[0209] [Example 15] Wet Strength Additives Laboratory testing has demonstrated that polyol ester chemistry is suitable for use as a wet strength additive. It has been found that the saturated groups can be tuned to achieve a variety of properties, including By attaching the amine to each alcohol functional group of the ester (or other polyol), Once the diol ester is made, the result is a hydrophobic wax that is poorly miscible / soluble in water. Compounds are added to cellulosic materials to form cellulose-based materials either internally or as a coating. However, the compounds can be used together to provide water resistance to the sample matrix. Does not chemically react with any part, making it easily removable with solvents, heat and pressure .

[0210] If waterproofing and a higher level of water resistance are desired, the matrix should contain sucrose esters. Oxidation and oxidation processes that help immobilize esters and make them resistant to removal by physical means. Polyol esters containing unsaturated functional groups are prepared for the purpose of achieving crosslinking and / or The number of unsaturated groups in the sucrose ester is and size control provide a means of cross-linking to impart strength; The molecules can be modified to make them more water resistant.

[0211] The data in Table 15 shows the effect of applying SEFOSE® to bleached kraft sheet at various levels. The percentages shown in the table are the percentages of the treated The results show the sucrose esters (%) of 70# bleached paper prepared using the method described above (see Table 15).

[0212] [Table 15]

[0213] The data shows a trend for increasing wet strength as loading level increases. Tensile strength is shown using the maximum strength of the sheet as a reference point.

[0214] [Example 16] Method for producing sucrose esters using acid chlorides In addition to creating hydrophobic polyol esters via transesterification, acid chlorides can also be used to Similar hydrophobicity can be achieved in textile articles by reacting directly with polyols containing ring structures. Sexual characteristics can be achieved.

[0215] For example, 200 grams of palmitoyl chloride (CAS 112-67-4) to 50 grams The mixture was brought to 100°F and kept at that temperature overnight. The resulting material was washed with acetone and deionized water to remove any Any unreacted or hydrophilic material was also removed. 13 NMR was used to analyze the remaining material. Analysis revealed that a significant amount of hydrophobic sucrose ester was produced.

[0216] The addition of fatty acid chlorides to cellulosic materials can impart hydrophobicity. The reaction produces a number of problems, including the corrosion of surrounding materials due to the gaseous HCl by-product. This is undesirable as it is harmful to workers and the surrounding environment. One additional problem that arises is that as more are formed, i.e., more poly As the ol sites react, the fiber composition weakens. For example, palmitic chloride When an increased amount of toil is reacted with cellulose or cotton materials, the hydrophobicity increases, and the The strength decreased.

[0217] Corn starch, birch xylan, carboxymethylcellulose, glutamic acid, 50 grams each of other similar polyols, including coacervate and extracted hemicellulose The above reaction was repeated several times using 200 grams of R-CO-chloride reacted with , with similar results.

[0218] [Example 17] Peel test A peel test is required to peel the tape from the paper surface at a reproducible angle. To measure the force applied, a wheel is placed between the two jaws of the tensile tester (ASTM D1876; For example, 100 Series Modular Peel Tester r, TestResources, Shakopee, MN).

[0219] Turners Falls Newspaper (Turners Falls, MA) The bleached kraft paper used had a viscosity of 600 seconds. The #50 lb. sheets were This represents a tighter, yet highly absorbent sheet.

[0220] #50 pound paper was coated with 15% modified starch (Ethylex starch) as a control. When the specimens were subjected to the same pressure, the average force required (for five specimens) was 0.55 lbs / in. The use of SEFOSE® instead of 25% of the Ethylex starch Except for the same coating (hence 25% add-on is SEFOSE®) When treated with 100% Ethylex (also 75% Ethylex), the average force was 0.081 lbs. / inch. SEFOSE® was substituted for 50% of the Ethylex. When used, the force required was reduced to less than 0.03 pounds per inch.

[0221] The paper preparation follows TAPPI Standard Method 404 for determining the tensile strength of paper.

[0222] Finally, the same paper was used with S-370 at a loading rate of 750 pounds per ton. This effectively fills all of the pores in the sheet, creating a complete physical barrier. The paper passes TAPPI Kit 12 on a flat surface. The saturated PFAE variants are used to improve the resistance to grease. It is possible to obtain a high degree of stability.

[0223] [Example 18] Zein-SFAE Composition A. Mid-range DS Sucrose contains a saturated fatty acid moiety and has about 3-4 saturated fatty acid chains attached to a sucrose molecule. Clostridium glyceride fatty acid ester (Fooding Group Ltd., Shanghai, 100 grams of ethyl acetate (CA) was weighed into a beaker. The ester changed from a white powder to a highly viscous molten wax. Heat was applied until it turned into a powdery substance. 30 grams of pure zein (Freeman The ester was supplied by Epoxy Industries LLC, Tuckahoe, NY. Once the powder was dissolved in the ester, the heat was removed. The mixture was allowed to stand for 10 minutes. Ventilate. The mixture was stirred using a pip homogenizer while adding warm water. Addition of 0.01 g of water resulted in a free-flowing homogenous zein-ester mixture with at least There was no visible solid, precipitate or phase separation for 100 hours.

[0224] The same ester was blended with hot water and coated onto 35#, 18 Gurley bleached base paper. .4g / m 2 With this coat weight, TAPPI Kit 4 was achieved. By increasing the coat weight, When PFAE was used alone, the kit value did not seem to increase, but the ester The grease beaded up on the paper. Using esters mixed with calcium carbonate, was reproduced and applied to the same paper. 2 So, I completed kit 3.

[0225] The Zein-SFAE combination was applied to various bases via a benchtop drawdown coater. When applied to a sheet, a TAPPI kit value in the range of 2 to 6 was observed. The results depended on the tightness of the sheet and the coat weight applied. For example, a 250 Gurley wash At least 4g / m2 using a white base sheet 2 When the coating was applied, Other additives were added to eliminate air bubbles, inhibit bacterial degradation, and improve the It is expected that this may help optimize protein characterization, i.e. particle size.

[0226] Sucrose fatty acid esters containing saturated fatty acid moieties with an HLB of about 3 and a DS of 3-5. Stel (RYOTO™ S370 from Mitsubishi Chemical Corporation, Tokyo, Japan) Weigh 100 grams of B370) into each of two beakers. Heat the sample until it melts. 30 grams of zein (Freeman Industrial A yellow powder was added to each beaker. Once completely melted, remove from heat. Allow mixture to stand for 10 minutes. Benchtop homogenizer Use a stirrer to stir the mixture while adding warm water to each beaker. -Water is added until an ester mixture is obtained.

[0227] The combined zein-PFAE mixture was applied to various substrates via a benchtop drawdown coater. When applied to a paper sheet, the result is a treated paper with higher kit value and oil repellency. do.

[0228] Zein is necessary to achieve medium to high levels of kit value. However, due to the zein-ester synergy, a low kit in the range of 3-4 is required. This may enable new formulation methods for those who do not have access to a coater on-site. It is worth noting that, in addition, it is now possible to achieve kits with some level of pigmentation. Ugh.

[0229] B. Low range DS Sucrose contains a saturated fatty acid moiety and has about 1-2 saturated fatty acid chains attached to a sucrose molecule. Weigh 100 grams of cellulose fatty acid ester into a beaker. Heat until the ester is melted. Add 30 grams of pure zein to the ester. When blending, heat. Remove the mixture. Allow the mixture to stand. Using a benchtop homogenizer, stir the mixture. Upon stirring and adding warm water, a free flowing zein-SFAE mixture results.

[0230] The combined Zein-SFAE was applied to various base systems via a benchtop drawdown coater. When applied to a sheet, a treated paper was obtained in which the grease and oil beaded up. .

[0231] It has an HLB of 16 and has one or two saturated fatty acid chains attached to a sucrose molecule. This suggests that sucrose fatty acid esters containing saturated fatty acid moieties (Mitsubishi Chemical Corporation (Tokyo 100 grams of RYOTO L1695 and P1670 (both from Kyoto, Japan) Weigh into each of the two beakers. Heat the samples until the ester melts. 3 0 grams of zein (Freeman Industries LLC, Tuckahoe , NY) is introduced into each beaker. Once the yellow powder has dissolved in the ester, the heat is removed. Allow the mixture to sit for 10 minutes. Use a benchtop homogenizer to agitate the mixture. Add hot water to each beaker while mixing until a homogenous zein-ester mixture is obtained. And add water.

[0232] The combined zein-PFAE mixture was applied to various substrates via a benchtop drawdown coater. When applied to a paper sheet, the treated paper had higher kit values ​​and obvious oil repellency. is obtained.

[0233] [Example 19] Cup base stock is often heavily treated with rosin to make it more water resistant. Okay. But it turns out that the Gurley of that board is 50 seconds. This is pretty This suggests that the material is a highly porous cardboard. The material is repulpable and steam can It penetrates quickly and softens the material. Pure SEFOSE® is applied to the board. The mixture was then dried overnight in an oven at 100°C. The resulting material felt like plastic to the touch. By weight, the material is 50% (wt / wt) cellulose. / 50% (wt / wt) of SEFOSE®. Gurley was too expensive and Immersion of the samples in water for 7 days did not significantly soften the material. Greenhouse data revealed that the material will biodegrade in approximately 150 days. Common tapes and glues will not stick to this composite material.

[0234] Zein has been shown to impart grease resistance to paper, so saturated PFAE and zein Experiments were carried out using stable aqueous dispersions of zein with 2-5% saturated PFAE. (up to 25% in water). Observations indicate that saturated PFAEs contribute to the formulation (grease resistance). It has been shown that this "seals" the zein in the paper by making it water-resistant (in addition to its elasticity). It became.

[0235] Although the invention has been described with reference to the above examples, modifications and variations are within the spirit and scope of the invention. It will be understood that the present invention is within the spirit and scope of the following claims. The present invention is limited only by the scope of the claims. All references disclosed herein are incorporated by reference in their entirety. The entire disclosure is incorporated herein by reference.

Claims

1. A barrier coating comprising a prolamin and at least one polyol fatty acid ester (PFAE), wherein the polyol comprises a cyclic structure and one to two fatty acid moieties or three to five fatty acid moieties, and when applied to a substrate or surface, the barrier coating provides an article resistant to the penetration of oil and / or grease, wherein the polyol is sucrose and the prolamin is zein.

2. The barrier coating according to claim 1, wherein the fatty acid is a saturated fatty acid.

3. The barrier coating according to claim 1, wherein the fatty acid is an unsaturated fatty acid.

4. An article comprising the coating described in claim 1, wherein the coating is present in a concentration sufficient to make the surface of the article substantially resistant to the application of oil and / or grease.

5. A barrier coating according to claim 1 or an article according to claim 4, wherein the article comprises a cellulose-based material, and the weight of the coating on the surface of the cellulose-based material is at least about 0.1 g / m². ２ ~Approx. 1.0g / m ２ , about 1.0g / m ２ ~Approx. 2.0g / m ２ , about 2g / m ２ ~About 3g / m ２ A barrier coating or article.

6. The barrier coating according to claim 1, further comprising one or more materials selected from the group consisting of polyvinyl alcohol (PvOH), polylactic acid (PLA), clay, talc, precipitated calcium carbonate, pulverized calcium carbonate, natural and synthetic latex, glyoxyl, and combinations thereof.

7. The barrier coating according to claim 1, wherein the fatty acid is obtained from a natural source.

8. The barrier coating according to claim 1, wherein the fatty acid is obtained from oilseeds, and preferably the oilseeds are selected from the group consisting of soybeans, peanuts, rapeseed, barley, canola, sesame seeds, cotton seeds, palm kernels, grape seeds, olives, safflower, sunflower, copra, corn, coconut, flaxseed, hazelnuts, wheat, rice, potatoes, cassava, legumes, camelina seeds, mustard seeds, and combinations thereof.

9. The barrier coating according to claim 1, wherein the polyol is sucrose and contains fatty acids obtained from oilseeds.

10. Paper, cardboard, papermaking pulp, food storage cartons, food storage bags, transport bags, coffee or tea containers, tea bags, bacon cardboard, diapers, weed blocks / barrier fabrics or films, mulching films, flower pots, packing beads, bubble wrap, oil absorbent materials, laminates, envelopes, gift cards, credit cards, gloves, raincoats, OGR paper, shopping bags, compost bags, release paper, tableware, containers for holding hot or cold beverages, cups, paper towels, plates, carbonated liquid storage bottles, insulating materials, non-carbonated liquids The article according to claim 4, selected from the group consisting of bottles for body storage, films for food wrap, food waste disposal containers, food handling utensils, lids for cups, fabric fibers, water storage and transport equipment, alcoholic or non-alcoholic beverage storage and transport equipment, external casings or screens for electronic products, internal or external components of furniture, curtains, upholstery items, films, boxes, sheets, trays, pipes, water conduits, pharmaceutical packaging, clothing, medical devices, contraceptives, camping equipment, molded cellulose materials, and combinations thereof.

11. A method for controllably derivatizing a cellulose-based material for oleophobicity, comprising the steps of contacting the cellulose-based material with a barrier coating comprising a prolamin and at least one polyol fatty acid ester (PFAE), wherein the polyol comprises a cyclic structure and one to two fatty acid moieties or three to five fatty acid moieties, the polyol is sucrose, and the prolamin is zein, and then exposing the contacted cellulose-based material to heat, radiation, a catalyst, or a combination thereof for a time sufficient to cause the barrier coating to adhere to the cellulose-based material.

12. The method according to claim 11, further comprising the step of removing an excess barrier coating.

13. The method according to claim 11, wherein the barrier coating is applied by a size press.

14. Clay, talc, precipitated calcium carbonate, pulverized calcium carbonate, TiO ２ The barrier coating according to claim 1, further comprising inorganic particles selected from the group consisting of the and combinations thereof.

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