Method for modifying polymer barrier film

Abstract

To provide a method to modify dried polymer films using printed crosslinking agents, including that the crosslinked polymer resulting from the method exhibits greater insolubility compared to crosslinked polymers made where the crosslinking agent and the polymer are combined and applied as a homogenous solution.SOLUTION: A method of preparing a crosslinked film, comprising the steps of: a) applying a polymer solution to a substrate; b) drying the polymer solution on the substrate; c) printing a crosslinking agent on the dried substrate; and d) heating the printed substrate for a sufficient time to achieve crosslinking to form a crosslinked polymeric film, wherein the resulting crosslinked polymer exhibits greater insolubility relative to a crosslinked polymer generated by application of the same polymer and crosslinking agent combined in solution.SELECTED DRAWING: Figure 1

Description

[Technical field]

[0001] The present invention relates generally to barrier films, and in particular to a method for making a crosslinked film. , compositions for forming such films, and articles of manufacture made with such films The present invention relates to a method comprising the steps of: [Background technology]

[0002] Film-based barrier coatings prevent contact between the contents of a package and the permeant. It is widely used in packaging materials to prevent the passage of liquids, gases, odorous substances, etc. The improved barrier properties are being used in a wide range of applications, including packaging for food, cosmetics, pesticides, and pharmaceuticals. This is an important goal for manufacturers of films sold in the United States. The use of plastic materials is typical. Traditionally, these coatings have been a part of such coatings, but in recent years, they have been used in plastics, especially fossil fuel-based The use of plastics in the home is coming under consumer / market pressure due to their lasting impact on the environment. It has fallen out of favor because of this.

[0003] Thermoplastic resin films include polypropylene, polyester, and polyamide. Mido's oriented films generally have excellent mechanical properties, heat resistance, and transparency, and are used as packaging materials. Typical barrier materials are polymeric monolayers, coextrusions or laminates. Bilayer polymer films, coated monolayers, or films with one or both surfaces The barrier coating is a bilayer or multilayer film with one or more coatings. The technology includes the application of thin aluminum sheets using vacuum deposition onto a variety of base film structures. This includes metallization by plating.

[0004] Polyvinyl alcohol (hereinafter sometimes abbreviated as "PvOH") is a water-soluble synthetic polymer known as such. PvOH is particularly excellent in strength and film forming properties compared to other synthetic polymers. Therefore, PvOH is used as a material for films and fibers, an additive for paper and fiber processing, an adhesive, a stabilizer for emulsion polymerization and suspension polymerization, a binder for inorganic substances, etc. Thus, PvOH is frequently used in various applications.

[0005] There are many processes for film formation, including aqueous coating and / or metering, calendering, extrusion, plastisol casting systems, as well as organosol casting systems. Extrusion and calendering are processes that melt the polymer before solidification and form plastics. Also, the casting processes of plastisol and organosol include melting the polymer in a plasticizer matrix and then forming a film by the solvent action of the plasticizer.

[0006] In conventional methods and apparatuses, the solution containing the base polymer and secondary components such as plasticizers, fillers, surfactants, activators, and colorants, which is finally cast onto a moving surface, is prepared by combining the base polymer and secondary components with water in a tank and then mixing them. Subsequently, the homogeneous solution or suspension is pumped through one or more operations including degassing and filtration and then supplied to a solution casting die for casting onto a moving surface such as a moving belt.

[0007] ​​​​​​​​​​In recent years, a method has been developed for continuously producing a solvent cast film by using a pressurized stream of a PvOH solution, combining it with a stream of a fluid containing a crosslinking agent, in-line mixing the combination of the PvOH solution stream and the crosslinking agent stream, applying the resulting homogeneous mixture of the PvOH solution and the crosslinking agent to a moving surface, and then evaporating the solvent from the mixture (see, for example, U.S. Patent Application Publication No. 2007 / 0085235, which is hereby incorporated by reference in its entirety). However, such methods require the use of complex machinery and multiple solvents. Thus, there is a desire to devise a method that uses a simpler process step / device to obtain a film having desired barrier coating properties.

SUMMARY OF THE INVENTION

[0008] The present disclosure relates to a method of making a film that includes modifying a polymer film using a printed crosslinking agent such that the resulting crosslinked polymer has reduced solubility compared to a crosslinked polymer made by combining the crosslinking agent and the polymer in solution. Also disclosed are articles of manufacture produced by such methods.

[0009]

[0010] In one embodiment, a method of making a crosslinked film includes applying a polymer solution to a substrate, drying the polymer solution on the substrate, printing a crosslinking agent on the dried substrate, and heating the printed substrate for a time sufficient to achieve crosslinking, wherein the resulting crosslinked polymer has reduced solubility compared to application of the same polymer and crosslinking agent combined in solution.​​​​​​​​​​​​​A method is disclosed that exhibits greater insolubility compared to the cross-linked polymer produced. In a related aspect, the method optionally further comprises evaporating an optional solvent from a heated substrate to form a cross-linked polymer film.

[0011] In one aspect, the polymers include polyvinyl alcohol, polyethylene oxide, dextrin, starch, cellulose derivatives (e.g., hemicellulose, hydroxyethyl cellulose, hydroxypropyl cellulose and other cellulose ethers), lignin, polyvinyl pyrrolidone, polyacrylamide, polyacrylic acid, polyacrylate, pectin, alginate, protein, derivatized protein (e.g., gelatin, corn zein, whey protein), and combinations thereof. In a related aspect, the polymer is polyvinyl alcohol.

[0012]

[0013] In another aspect, the substrate is a cellulosic material.

[0014] In one aspect, the cross-linking agents include aldehydes, aldehyde-containing resins, polyfunctional carboxylic acids, difunctional methacrylates, N-lactam carboxylates, dithiols, dimethyl urea, diisocyanates, borates, salts of polyvalent anions, inorganic polyions, Group 1B salts, polyamine-epichlorohydrin resins, and combinations thereof.

[0014] In a related aspect, the cross-linking agents include aldehydes, aldehyde-containing resins, dicarboxylic acids, and combinations thereof. In a related aspect, the cross-linking agent includes an aldehyde. In a related aspect, the cross-linking agent includes a dialdehyde. In another related aspect, the cross-linking agents include glutaraldehyde. It contains Rioxal, glutaraldehyde, or a mixture thereof. Further related In an embodiment, the crosslinking agent is glyoxal.

[0015] In one embodiment, the crosslinking agent is present in an amount of up to about 10% by weight based on the weight of the polymer . In another embodiment, the polymer is present in an amount in the range of about 50% to 90% by weight based on the weight of the polymer solution %.

[0016] In another embodiment, printing includes flexographic printing, gravure printing, inkjet printing, ind igo printing, and offset printing.

[0017] In one embodiment, the cellulosic materials include paper, cardboard, pulp for papermaking, cartons for food storage, bags for food storage, transport bags, containers for coffee or tea, tea bags, cardboard for bacon , diapers, weed-inhibiting / barrier fabrics or films, weed control films, flower pots, packaging beads, bubble wrap, oil-absorbing substances, laminates, envelopes, gift cards, credit cards, gloves, raincoats, greaseproof paper, shopping bags, compost bags, release paper, tableware, containers for holding hot or co ld beverages, cups, paper towels, plates, bottles for storing carbonated liquids, insulating materials, bottles for storing non-carbonated liquids, films for food wrap, containers for raw garbage disposal, food handling utensils, lids for cups, paper straws, fabric fibers, utensils for storing and transporting water , cardboard for medical use, release paper, utensils for storing and transporting alcoholic or non-alcoholic beverages , external casings or screens for electronic products, internal or external components of furniture, curtains , interior decoration supplies, films, boxes, sheets, trays, pipes, aqueducts, packaging for pharmaceutical products, Clothing, medical devices, contraceptives, camping equipment, formed cellulose-based materials, and combinations thereof are included. are included.

[0018] In one aspect, the method is to adjustably induce the substrate for hydrophobic and / or oleophobic resistance to embody. In a related aspect, the resulting substrate is hydrophobic. Also in a related aspect the resulting substrate is oleophobic. In another related aspect, the resulting substrate exhibits a 3M Grease KIT test value between 3 and 1 12.

[0019] In one aspect, the polymer solution is provided as an emulsion.

[0020] In another aspect, the polymer solution contains one or more of clay, carbonate, calcium carbonate, titanium dioxide, plastic pigments, binders, starch, proteins, polymer emulsions, latex, zirconium salts, calcium stearate, lecithin oleate, polyethylene emulsions, carboxymethyl cellulose, acrylic polymers, alginates, polyacrylate rubbers, polyacrylates, microbicides, oil-based defoamers, silicone-based defoamers, stilbene, direct dyes or acid dyes.

[0021] is included.

[0021] In one embodiment, a manufactured article includes a substrate having a crosslinked polymer coating layer, wherein the crosslinking is substantially limited to the upper surface of the layer and there is substantially no crosslinking contained within the layer. The manufactured article is disclosed. is shown.

[0022] In a related aspect, the crosslinked polymer layer contains substantially the same crosslinking agent and polymer, but provides the manufactured article with higher flexibility, lower rigidity, and / or greater elongation compared to a manufactured article in which substantial crosslinking is contained within the layer.

Brief Description of the Drawings

[0023]

Figure 1

Modes for Carrying Out the Invention

[0024] Before describing the present composition, method, and methodology, it should be understood that the present invention is not limited to such specific compositions, methods, and experimental conditions, as the specific compositions, methods, and conditions may vary. The scope of the present invention is limited to the appended claims, and it should also be understood that the terminology described herein is for the purpose of describing specific embodiments only and is not intended to be limiting.

[0025] As used in this specification and the appended claims, the singular forms "a", "an", " and "the" include plural referents unless the context clearly indicates otherwise. For example, reference to "a polymer" includes one or more polymers and / or compositions of the type described herein that would be apparent to those of ordinary skill in the art upon reading the present disclosure. compositions as would be apparent to those of ordinary skill in the art upon reading the present disclosure.

[0026] Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Modifications and It is understood that equivalent and alternative embodiments fall within the spirit and scope of the present disclosure, and accordingly, any methods and materials similar or equivalent to those described herein can be used in the practice and testing of the present invention. As used herein, the terms "about," "substantially," and "significantly" are understood by those of ordinary skill in the art and vary to some extent depending on the context in which they are used. In the context in which a term is used, if the usage of the term is not clear to those of ordinary skill in the art, "about" and "approximately" mean plus or minus 10% of the particular term, and "substantially" and "significantly"

[0027] mean plus or minus greater than 10% of the particular term. "Comprising" and "consisting essentially of" have their conventional meanings in the art. Conventional methods and systems for producing crosslinked films, particularly crosslinked PvOH, have been carried out by combining a crosslinking agent and a polymer in solution (Figure 1, upper reaction). In contrast, the methods described herein involve printing one or more crosslinking agents onto a previously applied base polymer to form the final film (Figure 1, lower reaction). Advantages obtainable by various embodiments of the method include the adaptability and efficiency of the method in producing more insoluble films by more effectively reaching the -OH groups on the film surface.

[0028]

[0029] As described herein, the crosslinking agent is applied onto the polymer film surface by printing or by using the crosslinking agent in a manner similar to overcoating varnish. Without being bound by any theory, ​​​​​​​​​​Rather, after the polymer film is set / dried, the crosslinking agent is printed on the dried / hardened surface and is most likely to react with the -OH groups most available on the surface. Coating, and rapid (e.g., less than 1 minute) heating after coating causes a reaction on the surface to form a crosslinked network that insolubilizes the surface while assisting with gloss.

[0030] Advantages include, but are not limited to, ag film applications where lower solubility and slower in-situ material degradation are ensured (resulting in overall savings as less PvOH content is required to achieve the desired functionality). Similarly, (In a parallel vein), the disclosed method may be useful for products that require an insoluble PvOH outer layer (e.g., providing improved tactile and appearance in paper straws).

[0031] (In a parallel vein), the disclosed method may be useful for products that require an insoluble PvOH outer layer (e.g., providing improved tactile and appearance in paper straws).

[0031] By optimizing the amounts of polymer and crosslinking agent, the number of products containing such films can be increased. The disclosed method shows a distinct difference from the mixing of polymer and crosslinking agent in solution. When such a mixture is applied to paper and then dried at a high temperature sufficient to ensure crosslinking, it results in a film that is much more soluble when immersed in water compared to products manufactured by the disclosed method. Without being bound by theory, due to the resulting structural differences (see Figure 1), the mechanical properties of the films by the disclosed method are different and include, but are not limited to, higher flexibility, lower rigidity, and greater elongation.

[0032] ​​​​​​​​​ As used herein, "aqueous" means that water is normally used as a solvent or medium, or contains water. It means.

[0033] As used herein, "biobased" means a material intentionally made from substances derived from living (or once living) organisms. In related aspects , a material containing at least about 50% of such substances is considered to be biobased. It is.

[0034] As used herein, "bind" means to adhere or cause to adhere to essentially a single mass, including its grammatical variations. It means to adhere or cause to adhere to essentially a single mass, including its grammatical variations.

[0035] As used herein, "cellulosic" refers to natural, synthetic, or semi-synthetic materials that can be formed or extruded into objects (e.g., bags, sheets) or films or filaments, and that can be used to make such objects or films or filaments, and materials that are structurally and functionally similar to cellulose, such as coatings and adhesives (e.g., carboxymethylcellulose). Another example is cellulose, which is a complex carbohydrate (C6H O5) composed of glucose units and forms the main component of cell walls in most plants. It is 10 O5) n It is Cellulose is cellulosic.

[0036] As used herein, "coating weight" is the weight of the material (wet or dry) applied to a substrate. Coating weight is expressed in pounds per specified linear yard or grams per square meter. It is the weight of the material (wet or dry) applied to a substrate. Coating weight is expressed in pounds per specified linear yard or grams per square meter. It is expressed.

[0037] ​As used herein, "Cobb value" means the water absorption rate (the weight of water per unit area) of a sample. The procedure for obtaining the Cobb value is carried out in accordance with TAPPI standard 441-om. The Cobb value is calculated by subtracting the initial weight of the sample from the final weight of the sample and then dividing by the area of the sample covered with water. The reported value represents the number of grams of water absorbed per square meter of paper. As used herein, "compostable" means that a solid product is biodegradable in soil. As used herein, "crosslinking" means a bond that links one polymer chain to another polymer chain, including its grammatical variations. Such a linkage can take the form of a covalent bond or an ionic bond, and the polymer can be either a synthetic polymer or a natural polymer (such as a protein). A crosslinking agent forms such a linkage and includes, but is not limited to, aldehydes, aldehyde-containing resins, polyfunctional carboxylic acids, difunctional methacrylates, N-lactam carboxylates, dithiols, dimethylurea, diisocyanates, borate salts, salts of polyvalent anions, inorganic polyions, Group 1B salts, polyamide-epichlorohydrin resins, and combinations thereof. In one embodiment, the crosslinking agent can be present in an amount of up to about 10% by weight, for example, about 1% to about 10% by weight, or 5% to about 10% by weight, based on the weight of the water-soluble polymer. As used herein, "crosslinking density" means the number of chemical crosslinks per unit volume within a polymer. When the crosslinking density is defined as the reciprocal of the molecular weight between crosslinks (Mc), the crosslinking density is

[0038]

[0039]

[0040] ​​​​​​​​​​​​​​​, can be obtained by the following formula. Ge = pRT / Mc

[0041] In the formula, Ge is the equilibrium elastic modulus obtained by temperature sweep of dynamic mechanical analysis, p is the density (which may be obtained by the Archimedes method), R is the universal gas constant in J / mol*K units, and T is the absolute temperature in Kelvin units. Once Ge and p are experimentally found, M c can be calculated, and finally the crosslink density can be calculated. In related aspects, the film obtained by the method described herein may have a lower crosslink density compared to the film obtained by the crosslinking agent and polymer in solution.

[0042] In one embodiment, a method of making a crosslinked film, comprising applying a polymer solution to a substrate, drying the polymer solution on the substrate, printing a crosslinking agent on the dried substrate, and heating the printed substrate for a time sufficient for crosslinking to be achieved, wherein the resulting crosslinked polymer exhibits greater insolubility compared to the crosslinked polymer produced by application of the same polymer and crosslinking agent combined in solution. In related aspects, the method optionally further comprises evaporating an optional solvent from the heated substrate to form a crosslinked polymer film.

[0043] In related aspects, one or more polymers may be blended prior to deposition onto the substrate, including where different polymers are crosslinked together and the one or more polymers may be different. In another aspect, the polymer is linked to smaller molecules, and the smaller molecules are added for functionality (e.g., to obtain water resistance and / or grease resistance). Use as a crosslinking agent for attaching a sucrose ester with a low degree of substitution to a substrate).

[0044] In one embodiment, crosslinking is substantially limited to the upper surface of the layer, and the layer substantially does not contain crosslinking, and a manufactured article including a substrate having a crosslinked polymer coating layer is disclosed. In one aspect, the manufactured article exhibits a lower crosslink density compared to a manufactured article produced by a method of depositing a mixture of a crosslinking agent and a polymer as a solution onto a substrate. In one aspect, the crosslinked polymer layer contains substantially the same crosslinking agent and polymer, but provides the manufactured article with higher flexibility, lower rigidity, and / or greater elongation compared to a manufactured article in which substantial crosslinking is contained within the layer.

[0045] In one embodiment, as used herein, "edge wicking" means the absorption of water at the outer edge of a paper structure by one or more mechanisms including capillary penetration of pores between fibers, diffusion through fibers and bonds, and surface diffusion on the fibers, but not limited to these. In a related aspect, the polymer films described herein prevent edge wicking of the treated product. In one aspect, there is a similar problem of grease / oil entering the folds that may be present in paper or paper products. Such a "grease creasing effect" can be defined as the absorption of grease in the paper structure created by folding, pressing, or compressing the paper structure. / or greater elongation to the manufactured article.

[0046] In one embodiment, as used herein, "effect", including its grammatical variations, refers to attributing a specific property to a specific material In one embodiment, "effect" as used herein, including its grammatical variations, refers to attributing a specific property to a specific material In one embodiment, "effect" as used herein, including its grammatical variations, refers to attributing a specific property to a specific material In one embodiment, "effect" as used herein, including its grammatical variations, refers to attributing a specific property to a specific material In one embodiment, "effect" as used herein, including its grammatical variations, refers to attributing a specific property to a specific material In one embodiment, "effect" as used herein, including its grammatical variations, refers to attributing a specific property to a specific material In one embodiment, "effect" as used herein, including its grammatical variations, refers to attributing a specific property to a specific material In one embodiment, "effect" as used herein, including its grammatical variations, refers to attributing a specific property to a specific material In one embodiment, "effect" as used herein, including its grammatical variations, refers to attributing a specific property to a specific material

[0047] In this specification, "effect", including its grammatical variations, refers to attributing a specific property to a specific material means to do with.

[0048] In this specification, "hydrophobic substance" means a substance that does not attract water. For example, hydrophobic substances include wax, rosin, resin, sugar fatty acid ester, diketene, shellac, vinyl acetate, PLA, PEI, oil, fat, lipid, other water-repellent chemicals, or combinations thereof.

[0049] In this specification, "hydrophobic" means water-repellent, a property that tends to repel and not absorb water.

[0050] In this specification, "lipid resistance" or "oleophobicity" means lipophobicity, a property that tends to repel and not absorb lipids, greases, fats, etc. In related aspects, grease resistance can be measured by the "3M KIT" test or the TAPPI T559 Kit test.

[0051] In this specification, "laminated structure" means a manufactured product constructed from multiple layers of sheet materials joined together by an adhesive. For example, paper tubes, drinking paper straws, and cardboard are all laminated structures.

[0052] In this specification, "cellulose-containing material" or "cellulose-based material" means a composition consisting essentially of cellulose. For example, such materials include paper, paper sheets, paperboard, pulp for papermaking, food storage cartons, tracing paper, cakeboard, meat wrapping paper, release paper / liner, paper straws, food storage bags, drinking paper straws, paper tubes, cardboard, shopping bags, shipping bags, bacon board, insulating materials, tea bags, coffee or tea containers, compost bags Mugs, tableware, containers for holding hot or cold beverages, cups, lids, plates, carbonated liquid storage bottles, gift cards, non-carbonated liquid storage bottles, food wrap films, food waste disposal containers, food handling utensils, fabric fibers (e.g., cotton or cotton blends), water storage and transportation utensils, alcoholic or non-alcoholic beverages, external casing or screen for electronic products, interior or exterior components of furniture, curtains, and interior decoration items may be included, but are not limited thereto.

[0053] As used herein, "release paper" means a paper sheet used to prevent the adhesive surface from adhering quickly to an adhesive or mastic. In one aspect, the film described herein can be used to replace or reduce the use of silicon or other coatings to produce materials with low surface energy. Surface energy can be readily determined by measuring the contact angle (e.g., using an Optical Tensiometer and / or High Pressure Chamber; Dyne Testing, Staffords hire, United Kingdom) or by using Surface Energ y Test Pens or Inks (see, e.g., Dyne Testing, Staffordshire, United Kingdom). It can be readily determined.

[0054] As used herein, "substrate" means a material that provides a surface on which something is deposited or engraved.

[0055] As used herein, "fibers in solution state" or "pulp" means cellulose fibers from wood, fibers Lignocellulose prepared by chemically or mechanically separating from crops or paper waste means a cellulosic fiber material. In related aspects where cellulose fibers are treated by the methods described herein the cellulose fibers themselves contain the bound film as an isolated entity and the bound cellulose fibers have different properties distinct from the free fibers.

[0056] As used herein, "repulpable" means making paper or paperboard products suitable for crushing into a shapeless soft mass for reuse in the manufacture of paper or paperboard.

[0057] As used herein, "adjustable" means adjusting or adapting a process, including its grammatical variations, to obtain a particular result.

[0058] As used herein, "water contact angle" means the angle measured through a liquid where the liquid / vapor interface contacts a solid surface. The water contact angle quantifies the wettability of a solid surface by a liquid. The contact angle reflects how strongly the molecules of the liquid and solid interact with each other compared to how strongly each interacts with its own kind. On many highly hydrophilic surfaces, water droplets exhibit a contact angle of 0° - 30°. Generally, when the water contact angle is greater than 90°, the solid surface is considered hydrophobic. The water contact angle can be easily obtained using an optical tensiometer (see, for example, Dyne Testing, Staffordshire, United Kingdom). When the water contact angle is greater than 90°, the solid surface is considered hydrophobic. The water contact angle can be easily obtained using an optical tensiometer (see, for example, Dyne Testing, Staffordshire, Un ited Kingdom).

[0059] As used herein, "water vapour permeability" means breathability, or The kiss style means the ability to transfer moisture. There are at least two different measurement methods . One of them is the MVTR (moisture vapor transmission rate) test in accordance with ISO 15496, which describes the moisture vapor permeability (WVP) of the fabric, that is, the degree of sweat transport to the outside air. For the measurement , it is required to determine how many grams of moisture (water vapor) pass through one square meter of fabric in 24 hours (the higher the level, the higher the breathability).

[0060] In one aspect, the TAPPI T 530 Hercules sizing test (i.e., the sizing test of paper by ink resistance) may be used to determine water resistance . The ink resistance by the Hercules method is best classified as a direct measurement test of the penetration degree . It may also be classified as a penetration rate test. There is no one test that is best for "measuring sizing". The test selection depends on the end use and the requirements of mill control . Such a method is particularly suitable for use as a mill control sizing test that can accurately detect changes in the sizing level. This method provides reproducible results, a shorter test time, and automatic end point determination, while providing the sensitivity of the ink float test .

[0061] Sizing measured by the resistance to the penetration or absorption of aqueous liquids into or by paper is an important characteristic of many papers. Typical of these are bags, boxboard for containers, meat wrapping films, writing papers, and some printing grades .

[0062] Such a method has an acceptable correlation established between the test value and the end-use performance of the paper ​​​​​​Used to monitor the production of paper or paperboard for a particular end use, provided that May be used for all end-use requirements depending on testing and permeant properties This method does not necessarily correlate well enough to be Other methods measure sizing by surface contact, surface penetration, or absorption. Substitute materials are selected based on their ability to simulate the means of water contact or absorption in the end use application. Such a method reduces the cost of using size chemicals. It can also be used to optimize the cost of ownership.

[0063] Tests performed include bond strength, curing time, smoothness, paper stiffness, water resistance (hot water and and cold water), printability, beam strength, ease of cutting, molding, and putty adhesion. However, this is not limited to these.

[0064] As used herein, "oxygen permeability" refers to the ability of a polymer to permeate gases or liquids. The oxygen permeability (Dk) of a material is determined by its diffusion rate (D) (i.e. the rate at which oxygen molecules cross the material) and the solubility (k) (or the volumetric The oxygen permeability (Dk) is a function of the amount of oxygen molecules absorbed per unit of blood. The oxygen permeability (Dk) value is usually between 10 and 150. ×10 -11 (cm 2 ml O2) / (s ml mmHg). A semi-logarithmic relationship was observed between the water content of the gel and the oxygen permeability (unit: Barrer). The International Organization for Standardization (ISO) uses the SI unit hectopascal (hPa) for pressure. Therefore, Dk = 10 -11 (cm2 ml O2) / (s ml hPa). The bar unit can be converted to the hPa unit by multiplying it by the constant 0.75 to be.

[0065] As used herein, "printing" means, including its grammatical variations, engraving something in or on the surface of a substrate stamp. In related aspects, the methods described herein may include, but are not limited to, flexographic printing, U V printing, gravure printing, inkjet printing, Indigo printing, and offset printing including, but not limited to, aqueous printing techniques.

[0066] As used herein, "polymer" means a substance having a molecular structure consisting mainly or entirely of a large number of similar units bonded together . For example, such polymers include polyvinyl alcohol, polyethylene oxide, dextran, starch, cellulose derivatives (e.g such as hemicellulose, hydroxyethyl cellulose, hydroxypropyl cellulose and other cellulose ethers), lignin, polyvinylpyrrolidone, polyacrylamide, polyacrylic acid, polyacrylate, pectin, alginate, protein, derivatized protein (e.g such as gelatin, corn zein, whey protein), and combinations thereof, but are not limited thereto. In related aspects, the polymer is poly vinyl alcohol.

[0067] As used herein, "biodegradable" means, including its grammatical variations, being decomposable by the action of living organisms (e.g by microorganisms) into particularly harmless products.

[0068] As used herein, "recyclable" means, including its grammatical variations, being suitable for reuse of materials is meant to be (processable with (used and / or waste) and / or) processable or processible said material.

[0069] As used herein, "latex" means a stable dispersion of polymer microparticles in an aqueous medium (emulsion). Although latex is found in nature, synthetic latex can be produced by polymerizing monomers such as styrene emulsified with a surfactant . The latex found in nature is a milky fluid found in 10% of all flowering plants (angiosperms). Latex is a complex emulsion consisting of proteins, alkaloids, starches, sugars, oils, tannins , resins, and rubber, and coagulates when exposed to air.

[0070] As used herein, "filler" means a micronized white mineral (or pigment) added to the finished paper stock for papermaking to improve the optical and physical properties of the sheet. The particles fill the spaces and gaps between the fibers , thereby increasing brightness, opacity, smoothness, gloss, and printability, but usually serving to produce a sheet with reduced bond and tear strength. Common papermaking fillers include clay (kaolin, bentonite), calcium carbonate (both GCC and PCC ), talc (magnesium silicate), and titanium dioxide. ).

[0071] As used herein, "Gurley second" or "Gurley number" means the time in seconds or the number of seconds required for 100 cubic centimeters (deciliters) of air to pass through a given 1.0 square inch area of material at a pressure differential of 4.88 inches of water column (0.176 psi) . The unit that represents the number of seconds required (ISO 5636-5:2003) (porosity) . Also, regarding rigidity, the “Gurley number” is, in a single piece of material held vertically, the unit for measuring the force required to deflect the material by a given amount (the force of 1 milligram). Such values can be measured with the apparatus of Gurley Precision Instruments (Troy, New York).

[0072] As used herein, “wet strength” means a measure of how well the web of fibers that holds the paper together can resist the force of breakage when the paper is in a wet state. Wet strength can be measured using the Finch Wet Strength Device of Thwing-Albert Instrument Company (West Berlin, NJ). In such cases, wet strength is typically provided by wet strength additives such as polyamideamine-epichlorohydrin resins, poly amine-epichlorohydrin resins, polyamideamine-epichlorohydrin resins containing glyoxalated resin, epoxide resin, and the like, including cationic starch. In one embodiment, the films described herein provide such wet strength in the absence of such additives.

[0073] As used herein, “wet” means being covered with or soaked with water or another liquid.

[0074] As described herein, the method by printing has demonstrated that an insoluble film can be produced by reducing the amount of PvOH. PvOH itself is an excellent film-forming agent and is known in the art to form strong hydrogen bonds with cellulose, but water, especially warm water ​​​​​​​ In one embodiment, PvOH has abundant cross-linking properties along the fiber. This provides a source of OH groups that increases the strength of the paper beyond that possible with PvOH alone. , e.g., to increase wet strength and water resistance in particular. Crosslinking agents include dialdehydes (e.g., may contain aryl oxal, glutaraldehyde, etc.

[0075] In one embodiment, the substrate may comprise starch, the starch being dent corn starch. , waxy corn starch, potato starch, wheat starch, rice starch starch, sago starch, tapioca starch, sorghum starch, sweet potato starch, and It may come from any source, including mixtures of these.

[0076] More particularly, the starch may be unmodified starch or modified by chemical, physical or enzymatic means. It may also be a starch that has been modified by processing.

[0077] Chemical processing involves the addition of chemicals to produce modified starches (e.g., plaster starch materials). Within the scope of chemical processing, starch depolymerization is included. , starch oxidation, starch reduction, starch etherification, starch esterification, de These include, but are not limited to, starch nitrification, starch degreasing, starch hydrophobization, etc. Chemically modified starch can be produced by using any combination of chemical treatments. Examples of chemically modified starches include alkenes which produce hydrophobic esterified starches. Reaction of octenylsuccinic anhydrides, especially octenylsuccinic anhydride, with starch; cationic decacyclic Starch-producing 2,3-epoxypropyltrimethylammonium chloride Reaction with; reaction of starch with ethylene oxide to produce hydroxyethyl starch; Reaction of starch with hypochlorite to produce oxidized starch; producing acidolysis polymerized starch Reaction of starch with acid; methanol, ethanol, propanol, methylene chloride, chloroform, carbon tetrachloride, etc. of starch to produce defatted starch Defatting with solvents such as is included.

[0078] Physically processed starch is any starch that has been physically treated in any manner that provides physically processed starch Any starch that has been physically processed. Within the scope of physical processing, heat treatment of starch in the presence of water, heat treatment of starch in the absence of water, fragmentation of starch granules by optional mechanical means, pressure treatment of starch to melt starch granules, etc. are included, but are not limited to these. Physically processed starch can also be prepared by using any combination of physical treatments. Examples of physically processed starch include heat treatment of starch in an aqueous environment to swell starch granules without granule breakage; heat treatment of anhydrous starch granules to cause polymer rearrangement; fragmentation of starch granules by mechanical dissociation; and pressure treatment of starch granules by an extruder to cause melting of starch granules. Heat treatment of starch in an aqueous environment to swell starch granules without granule breakage; heat treatment of anhydrous starch granules to cause polymer rearrangement; fragmentation of starch granules by mechanical dissociation; and pressure treatment of starch granules by an extruder to cause melting of starch granules.

[0079] Enzymatically processed starch is any optional starch that has been treated with enzymes in any manner that provides enzymatically processed starch Within the scope of enzymatic processing, reactions of alpha - amylase with starch, reactions of protease with starch, reactions of lipase with starch, reactions of phosphorylase with starch, reactions of oxidase with starch, etc. are included, but are not limited to these. Enzymatically processed starch can be prepared by using any combination of enzymatic treatments. It can be prepared by. Examples of the enzymatic processing of starch include the reaction of amyloglucosidase with starch to produce depolymerized starch; the reaction of alpha-amylase debranching enzyme with starch to produce debranched starch; the reaction of protease enzyme with starch to produce starch with reduced protein content; the reaction of lipase enzyme with starch to produce starch with reduced lipid content; the reaction of phosphorylase enzyme with starch to produce enzymatically processed phosphorylated starch; and the reaction of oxidase enzyme with starch to produce enzymatically oxidized starch. The reaction of amyloglucosidase with starch; the reaction of alpha-amylase debranching enzyme with starch to produce debranched starch; the reaction of protease enzyme with starch to produce starch with reduced protein content; the reaction of lipase enzyme with starch to produce starch with reduced lipid content; the reaction of phosphorylase enzyme with starch to produce enzymatically processed phosphorylated starch; and the reaction of oxidase enzyme with starch to produce enzymatically oxidized starch. The reaction of phosphorylase enzyme with starch to produce enzymatically processed phosphorylated starch; and the reaction of oxidase enzyme with starch to produce enzymatically oxidized starch. The reaction of oxidase enzyme with starch to produce enzymatically oxidized starch. are included.

[0080] In one embodiment, the polymer solution can contain from about 10% to about 90%, from about 10% to about 20%, from about 30% to about 40%, from about 50% to about 60%, from about 70% to about 80%, from about 80% to about 90% polymer (weight / weight) based on the weight of the solution. In related aspects, the coating can contain from about 80% to about 99% polymer (weight / weight) based on the weight of the coating. % to about 20%, about 30% to about 40%, about 50% to about 60%, about 70% to about 80%, about 80% % to about 90% polymer (weight / weight). In related aspects, the coating can contain from about 80% to about 99% polymer (weight / weight) based on the weight of the coating. can contain from about 80% to about 99% polymer (weight / weight) based on the weight of the coating. based on the weight of the coating.

[0081] In one embodiment, the crosslinking agent is present in an amount of up to about 10 wt% based on the weight of the polymer. In related aspects, the crosslinking agent is present in an amount in the range of about 1 wt% to about 2 wt%, about 2 wt% to about 3 wt%, about 3 wt% to about 4 wt%, about 4 wt% to about 5 wt%, about 5 wt% to about 6 wt%, about 6 wt% to about 7 wt%, about 7 wt% to about 8 wt%, about 8 wt% to about 9 wt%, about 9 wt% to about 10 wt% based on the weight of the polymer. In related aspects, the crosslinking agent is present in an amount in the range of about 1 wt% to about 2 wt%, about 2 wt% to about 3 wt%, about 3 wt% to about 4 wt%, about 4 wt% to about 5 wt%, about 5 wt% to about 6 wt%, about 6 wt% to about 7 wt%, about 7 wt% to about 8 wt%, about 8 wt% to about 9 wt%, about 9 wt% to about 10 wt% based on the weight of the polymer. %, about 2 wt% to about 3 wt%, about 3 wt% to about 4 wt%, about 4 wt% to about 5 wt%, about 5 wt% % to about 6 wt%, about 6 wt% to about 7 wt%, about 7 wt% to about 8 wt%, about 8 wt% to about 9 wt%, about 9 wt% to about 10 wt% based on the weight of the polymer.

[0082] In one embodiment, the cellulose-based materials include paper, paperboard, paper sheets, papermaking pulp, cups, boxes, trays, lids, release paper / liners, compost bags, shopping bags, transport bags, paper st Low, paper tubes, cardboard, bacon paper, tea bags, insulating materials, coffee or tea containers, pipes and aqueducts, disposable cutlery for food, dishes and bottles, TV and screens for portable devices, clothing (e.g., cotton or cotton blends), bandages, pressure-sensitive labels, pressure tapes, feminine products, and contraceptives, drug delivery devices, containers for pharmaceutical materials (e.g., pills, tablets, suppositories, gels, etc.) and other medical devices used on or inside the body, etc. are included but not limited to these. Further, the disclosed coating technology can also be used for furniture and interior decoration products, outdoor camping equipment, etc.

[0083] In one aspect, the coating described herein is resistant to pH in the range of about 3 to about 9. In related aspects, the pH can be about 3 to about 4, about 4 to about 5, about 5 to about 7, about 7 to about 9. In one aspect, the polymer solution can contain adhesives, proteins, polysaccharides and / or lipids (including but not limited to milk proteins, (e.g., casein, whey protein, etc.)), gluten, gelatin, prolamin (e.g., zein), protein, protein isolate, starch, acetylated polysaccharide, alginate, latex, carrageenan,

[0084] chitosan, inulin, long-chain fatty acids, waxes, and combinations thereof. In one embodiment, the polymer solution described herein contains agarite, esters, diesters, ethers, ketones, amides, nitriles, aromatic compounds (e.g., xylene, toluene ), acid halides, anhydrides, alkyl ketene dimer (AKD), alum, and aluminum. chitosan, inulin, long-chain fatty acids, waxes, and combinations thereof.

[0085] In one embodiment, the polymer solution described herein contains agarite, esters, diesters, ethers, ketones, amides, nitriles, aromatic compounds (e.g., xylene, toluene ), acid halides, anhydrides, alkyl ketene dimer (AKD), alum, and aluminum. Alganic acid, alum, albumin, glue, barium carbonate, barium sulfate Barium, chlorine dioxide, dolomite, diethylenetriaminepentaacetate, EDTA, enzyme Formamidine sulfate, guar gum, gypsum, lime, magnesium bisulfate, lime milk, magnesia milk Rosin, rosin soap, satin, soap / fatty acid, sodium bisulfate, soda ash Titania, surfactant, starch, modified starch, hydrocarbon resin, polymer, wax Including, but not limited to, polysaccharides, proteins, latex, and combinations thereof, can be used to carry other chemicals used in papermaking. In one embodiment, the disclosed polymer solution is one or more polymers, and the following inorganic particles Kaolin (kaolin, bentonite), calcium carbonate (both GCC and PCC), talc ( Magnesium silicate), and one or more of titanium dioxide.

[0086] In one embodiment, the film produced by the method described herein exhibits greater insolubility compared to a film not produced by the disclosed method. In a related Aspect, the resulting film may exhibit higher oleophobicity or grease resistance compared to a film made with a solution containing a combination of a crosslinking agent and a polymer. Further In related aspects, the resulting film may be biodegradable, compostable, and / or recyclable. In one aspect, the resulting film is hydrophobic (water resistant) and / or Is oleophobic (grease resistant).

[0087] In one embodiment, the film obtained as described herein by this method It may have improved mechanical properties as compared to an unmade film. For example, the paper bag processed by the process described in the present specification has increased burst strength, Gurley number, tensile strength and / or energy at maximum load. In one aspect, the burst strength is about 0. Between 5 and 1.0 times, between about 1.0 and 1.1 times, between about 1.1 and 1.3 times, between about 1.3 and 1. Increases at a magnification between 5 times. In another aspect, the Gurley number is between about 3 and 4 times, between about 4 and 5 times Between, between about 5 and 6 times, and increases at a magnification of about 6 to 7 times. In yet another aspect, the tensile Strain is between about 0.5 and 1.0 times, between about 1.0 and 1.1 times, between about 1.1 and 1.2 times, and Increases at a magnification between about 1.2 and 1.3 times. In yet another aspect, the energy at maximum load Increases at a magnification between about 1.0 and 1.1 times, between about 1.1 and 1.2 times, between about 1.2 and 1.3 times, and

[0088] In one embodiment, the cellulose-containing material is, for example, U.S. Patent Application Publication No. 2015 / 016 7243 (incorporated herein by reference in its entirety), microfibrillated cellulose (MFC) or cellulose nanofiber ) is a base paper containing (CNF), and MFC or CNF is added during the forming process and the papermaking process And / or added to a previously formed layer as a coating or secondary layer to reduce the porosity of the base paper. In a related aspect, the base paper is contacted with a polymer solution And printed as described above. In a further related aspect, the polymer in the contacted base paper Is PvOH. In one embodiment, the obtained contacted base paper is adjustably water-resistant and Lipid-resistant. In a related aspect, the obtained base paper has at least about 10-15 (i.e., ), and And That is, it may exhibit Gurley permeability (seconds / 100 cc, 20-ounce cylinder), or at least about 100, at least about 200 to about 350 Gurley values. In one aspect, the film can act as a laminate of one or more layers, or can comprise one or more layers as a laminate, or reduce the amount of coating of one or more layers to obtain the same performance effects (e.g., water resistance, grease resistance, etc.). In a related aspect, the laminate can include a biodegradable and / or compostable heat seal or adhesive.

[0089] In one embodiment, the polymer solution may be formulated as an emulsion, and the choice of emulsifier and its amount is determined by the nature of the composition and the ability of the emulsifier to promote the dispersion of the polymer. In one aspect, the emulsifier can include water, buffer, carboxymethyl cellulose (CMC), latex es, milk proteins, wheat gluten, gelatin, prolamin, soy protein isolate, starch, acetylated polysaccharides, alginates, carrageenans, chitosan, inulin, long-chain fatty acids, fatty acid esters, sucrose esters, waxes, agar, alginates, glycerol rolls, gums, lecithin, poloxamers, monoglycerols, diglycerols, monosodium phosphate, monostearate, propylene glycol, detergents, cetyl alcohol, and combinations thereof, but is not limited thereto. In another aspect, the polymer :emulsifier ratio can be about 0.1:99.9, about 1:99, about 10:90, about 20:80, about 3 5:65, about 40:60, and about 50:50. It will be apparent to those skilled in the art that the ratio may be varied according to the desired characteristics of the final product.

[0090] In one embodiment, the polymer is combined with a binder (e.g., starch, protein, latex, polymer emulsion), additives (e.g., zirconium salts, calcium stearate, lecithin oleate, polyethylene emulsion, carboxymethyl cellulose, acrylic polymers alginates, polyacrylate rubbers, polyacrylates, microbicides, oil-based defoamers, silicone-based defoamers, stilbenes, direct dyes and acid dyes), and one or more coating components (alone or in combination) for internal and surface sizing, including but not limited to these. In related aspects, such components can build a microporous structure, provide a light-scattering surface, improve ink receptivity, improve gloss, bind pigment particles, bind the coating to paper, board sheet reinforcement, fill pores in the pigment structure, reduce water sensitivity, resist wet pick in offset printing, prevent blade scratching, improve gloss in super calendering, reduce dusting, adjust coating viscosity, achieve water retention, disperse pigments, maintain coating dispersion, prevent degradation of the coating / coating colorant, control foaming, reduce entrained air and coating craters, increase whiteness and brightness, and control color and shade, including but not limited to these one or more properties. It will be apparent to those skilled in the art that the combinations may be varied according to the desired properties of the final product. The disclosed methods provide materials that exhibit the required properties (e.g., water resistance, low surface energy, etc.).

[0091] ​ By providing a layer of material, the cost of applying a primary / secondary coating (e.g., a silicone base layer, a starch base layer, a clay base layer, a PLA layer, Bio-PBS, PE I layer, etc.) is reduced, thereby reducing the amount of primary / secondary layer required to obtain the same properties. In one embodiment, the composition is free of fluorocarbons and silicones. In one embodiment, the composition enhances both the mechanical and thermal stability of the treated product. In one aspect, the surface treatment is thermally stable at temperatures between about -100 °C and about 300 °C.

[0092] In one embodiment, the composition enhances both the mechanical and thermal stability of the treated product. In one aspect, the surface treatment is thermally stable at temperatures between about -100 °C and about 300 °C. In a further related aspect, the surface of the cellulose-based material exhibits a water contact angle between about 60° and about 120°. In another related aspect, the surface treatment is chemically stable at temperatures between about 200 °C and about 300 °C. In a further related aspect, the surface of the cellulose-based material exhibits a water contact angle between about 60° and about 120°. In another related aspect, the surface treatment is chemically stable at temperatures between about 200 °C and about 300 °C.

[0093] A substrate that is dried (e.g., at about 80 - 150 °C) before coating can be treated with a crosslinking agent by printing. The substrate can be heated to dry the surface, and then the modified material is immediately ready for use. In one aspect, according to the method described herein, the substrate can be treated by an optional suitable coating / sizing process typically carried out in a paper mill (e.g., Smook, G., Surface Treatments, Handbook for Pulp&Paper Technologists, (2016), 4th Ed., Cpt.18, pp.293 - 309, TAPPI Press, Peacht which is hereby incorporated by reference in its entirety and made a part of this specification), (e.g., by reference to Smook, G., Surface Treatments, Handbook for Pulp&Paper Technologists, (2016), 4th Ed., Cpt.18, pp.293 - 309, TAPPI Press, Peacht which is hereby incorporated by reference in its entirety and made a part of this specification), (See Lee Corners, GA USA).

[0094] In one embodiment, the disclosed method is for producing films, rigid containers, fibers, pulp, fabrics, For use on any cellulose-based surface, including but not limited to cellulose lacquers, etc. can.

[0095] Depending on the source, cellulose can be used in paper, paperboard, pulp, softwood fibers, hardwood fibers, or other applications. Combinations of these, nanocellulose, cellulose nanofibers, whiskers or microfibers Fibrilled, microfibrillated cotton or cotton blends, other non-wood fibers (sisal, jute) or hemp, flax and straw), cellulose nanocrystals, or nanofibrillated cells It can be loin.

[0096] In one embodiment, the amount of polymer solution applied is at least one surface of the cellulose-containing material. For example, in one embodiment, the polymer solution is applied to the The complete exterior surface, the complete interior surface of the container, or a combination of both, or a strip of base paper In other embodiments, the entire upper surface of the substrate may be coated with a polyimide. The entire lower surface of the substrate may be coated with the polymer solution. In some embodiments, the coating may be a fluororesin, a fluororesin, a fluororesin coating ... The lumen of the device / instrument may be coated with the polymer solution or the outside of the device / instrument may be coated with the polymer solution. The surface may be coated with a polymer solution, or a combination thereof. In one embodiment, the amount of polymer solution applied is at least one surface of the cellulose-containing material. For example, only the surfaces exposed to the ambient atmosphere are covered with a polymer. - Only the surface that is coated by a solution or not exposed to the ambient atmosphere, the polymer solution (e.g., masking). As will be apparent to those skilled in the art, the application amount of the polymer sol ution may depend on the use of the material to be coated. In one aspect, one surface may be coated with a polymer - solution, and the opposite surface may be coated with an agent including but not limited to proteins, wheat gluten, ze - latin, prolamin, protein isolate, starch, modified starch, acetylated polysaccharide, a - luginate, carrageenan, chitosan, inulin, long-chain fatty acid, wax, and combinations thereof. In a related - aspect, the polymer solution can be added to the finished furnish, and the resulting material on the web may - be provided with an additional coating of the polymer solution.

[0097] The selection of the cellulose, polymer, crosslinking agent, reaction temperature, and exposure time to be treated can be optimized by routine experimental methods so as to be suitable for the optional specific use of the final - product. It will be apparent to those skilled in the art that these are process parameters.

[0098] The derivatized material has modified physical properties that can be defined and measured using appropriate tests known in the art. For hydrophobicity, the analysis protocol may include but is not limited to contact - angle measurement and moisture absorption. Other properties include stiffness, WVTR, porosity, tensile strength, lack of substrate degradation, rupture, and tear properties. The specific - standardized protocol to follow is defined by the American Society for Testing and Materials (Protocol ASTM - D7334-08).

[0099] The surface permeability to various gases such as water vapor and oxygen can also be changed when the barrier function of the material is enhanced by the disclosed processes. The standard unit for measuring permeability is the barr, and the protocols for measuring these parameters are also available in the public domain (ASTM standard F2476-05 for water vapor and ASTM standard F2622-8 for oxygen). In one embodiment, the materials processed according to the procedures of the present disclosure exhibit complete biodegradability as measured by degradation in an environment under microbial corrosion. Various methods, including the flask shaking method (ASTM E1279-89(2008)) and the Zahn-Wellens test (OECD TG 302 B), are available for defining and testing biodegradability. ASTM D6400 and other methods, including but not limited to this, are available for defining and testing compostability.

[0100] Materials suitable for processing by the process according to the present invention include various forms of cellulose such as cotton fiber, plant fibers such as linen, wood fiber, regenerated cellulose (rayon and cellophane), partially alkylated cellulose (cellulose ether), partially esterified cellulose (acetate rayon), and other modified cellulose materials, which have a substantial proportion of surfaces available for reaction / bonding. As described above, the term "cellulose" includes all of these materials as well as others with similar polysaccharide structures and similar properties. Among these, the ratio

[0101]

[0102]

[0103] ​​​​​​​​​​​​​Relatively new materials such as microfibrillated cellulose (cellulose nanofibers) (e.g., , incorporated herein by reference in its entirety, U.S. Patent No. 43 74702, U.S. Patent Application Publication No. 2015 / 0167243, and 2009 / 0221812) are particularly suitable for such applications. In other embodiments, the cellulose may include, but is not limited to, cellulose triacetate, cellulose propionate, cellulose acetate propionate, cellulose acetate butyrate, nitrocellulose (cellulose nitrate), cellulose sulfate, celluloid, methylcellulose, ethylcellulose, ethylmethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, cellulose nanocrystals, hydroxyethylmethylcellulose, hydroxypropylmethylcellulose, ethylhydroxyethylcellulose, carboxymethylcellulose, and combinations thereof.

[0104] In addition to increasing its hydrophobicity, the modification of the cellulose described herein also enhances its tensile strength, flexibility, and rigidity, thereby further expanding its range of use. Biodegradable and partially biodegradable products made from or using the modified cellulose disclosed in this application are all within the scope of this disclosure, including recyclable and compostable products.

[0105] Among the possible uses of coating technology, such items include containers for any purpose such as paper, cardboard, paper pulp for papermaking, cups, lids, boxes, trays, release paper / liners, compost bags, shopping bags, pipes, and ducts, disposable food cutlery, plates, and bottles. Screens for TVs and portable devices, clothing (e.g., cotton or cotton blend), bandages, pressure-sensitive labels, pressure-sensitive tapes, feminine products, and medical devices used physically or internally such as contraceptives and drug delivery devices are included, but not limited thereto. The disclosed coating technology can also be used for furniture and interior decoration products, outdoor camping equipment, etc. .

[0106] The following examples are for illustrative purposes and are not intended to be limiting.

Example

[0107] [Example 1] Using a rod coater, polyvinyl alcohol (PvOH) was coated onto 20# bleached hardwood sheets. A PvOH (Selvol 425 from Sekisui Chemical, Japan) film was applied at 5 g / m and dried. Glyoxal 2 was applied by offset rotary printing (heat set) to test the water resistance of the film. 5 mL of water was placed on both the untreated paper and the glyoxal-treated paper PvOH films and left for 15 minutes. After 15 minutes, the untreated PvOH film dissolved in water and the water penetrated into the paper substrate. The treated paper retained an insoluble Pv OH film on the surface, as indicated by the water pooled on the film.

[0108] [Example 2] Fully hydrolyzed PvOH was coated onto the first base paper to finally obtain a film that makes the paper particularly water-resistant. The PvOH was applied at 6 g / m 2 to obtain the desired properties. In the second base paper, 4 g / m2 Using PvOH at the coating weight of and then printing glyoxal to crosslink the -OH groups on the surface, it has been found that almost the same properties can be obtained. It has been found.

[0109] The present invention has been described with reference to the above embodiments, but it will be understood that modifications and variations are included within the spirit and scope of the present invention. The present invention is limited only by the following claims. All references described in this specification are hereby incorporated by reference in their entirety and are hereby made a part of this specification. The present invention is limited only by the following claims. All references described in this specification are hereby incorporated by reference in their entirety and are hereby made a part of this specification. The present invention is limited only by the following claims. All references described in this specification are hereby incorporated by reference in their entirety and are hereby made a part of this specification.

Claims

**Claim 1** A method for producing a crosslinked film, comprising: a) applying a polymer solution to a substrate; b) drying the polymer solution on the substrate; c) printing a crosslinking agent on the dried substrate; d) heating the printed substrate for a time sufficient to achieve crosslinking to form a crosslinked polymer film, wherein the resulting crosslinked polymer exhibits greater insolubility compared to a crosslinked polymer produced by coating the same polymer and crosslinking agent combined in solution. **Claim 2** The method according to claim 1, wherein the polymer is selected from the group consisting of polyvinyl alcohol, polyethylene oxide, dextran, starch, hemicellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, cellulose ether, lignin, polyvinyl pyrrolidone, polyacrylamide, polyacrylic acid, polyacrylate, pectin, alginate, protein, gelatin, zein, whey protein, and combinations thereof. **Claim 3** The method according to claim 2, wherein the substrate is a cellulose-based material. **Claim 4** The method according to claim 3, wherein the polymer is polyvinyl alcohol. **Claim 5** The method according to claim 1, wherein the crosslinking agent is selected from the group consisting of aldehyde, aldehyde-containing resin, polyfunctional carboxylic acid, difunctional methacrylate, ammonium zirconium carbonate, N-lactam carboxylate, dithiol, dimethyl urea, diisocyanate, borate, salt of polyvalent anion, inorganic polyion, salt of Group 1B, polyamide-epichlorohydrin resin, and combinations thereof. **Claim 6** The method according to claim 5, wherein the crosslinking agent is selected from the group consisting of aldehyde, aldehyde-containing resin, dicarboxylic acid, and combinations thereof. **Claim 7** The method according to claim 6, wherein the crosslinking agent contains aldehyde. **Claim 8** The method according to claim 7, wherein the crosslinking agent contains dialdehyde. **Claim 9** The method according to claim 8, wherein the crosslinking agent contains glyoxal, glutaraldehyde, or a mixture thereof. **Claim 10** The method according to claim 9, wherein the crosslinking agent is glyoxal. **Claim 11** The method according to claim 1, wherein the crosslinking agent is present in an amount up to about 10% by weight based on the weight of the polymer. **Claim 12** ​ ​ ​ ​ ​ ​ ​ ​ ​ ​ ​ ​ ​ ​ ​ The polymer is present in an amount in the range of about 50 wt% to 90 wt% based on the weight of the polymer solution. The method according to claim 11, wherein the polymer is present in an amount in the range of about 50 wt% to 90 wt% based on the weight of the polymer solution. **Claim 13** The printing is selected from the group consisting of flexographic printing, gravure printing, inkjet printing, indigo printing, and offset printing, according to the method of claim 1. The method according to claim 1, wherein the printing is selected from the group consisting of flexographic printing, gravure printing, inkjet printing, indigo printing, and offset printing. **Claim 14** The cellulosic material is paper, paperboard, pulp for papermaking, carton for food storage, bag for food storage, bag for transportation, container for coffee or tea, tea bag, paperboard for bacon, diaper, weed-inhibiting / barrier fabric or film, weeding film, flowerpot, packing beads, bubble wrap, oil-absorbing substance, laminate, envelope, gift card, credit card, glove, laminate coat, greaseproof paper, shopping bag, compost bag, release paper, tableware, container for holding hot or cold beverages, cup, paper towel, plate, bottle for storing carbonated liquid, insulating material, bottle for storing non-carbonated liquid, film for food wrap, domestic waste treatment container, tool for food handling, lid for cup, paper straw, fabric fiber, tool for storing and transporting water, paperboard for medical use, release paper, tool for storing and transporting alcoholic or non-alcoholic beverages, external casing or screen for electronic products, internal or external components for furniture, curtain, interior decoration supplies, film, box, sheet, tray, pipe, aqueduct, packaging for pharmaceutical products, clothing, medical equipment, contraceptive, camping equipment, formed cellulosic material, and combinations thereof, according to the method of claim 2. The method according to claim 2, wherein the cellulosic material is selected from the group consisting of paper, paperboard, pulp for papermaking, carton for food storage, bag for food storage, bag for transportation, container for coffee or tea, tea bag, paperboard for bacon, diaper, weed-inhibiting / barrier fabric or film, weeding film, flowerpot, packing beads, bubble wrap, oil-absorbing substance, laminate, envelope, gift card, credit card, glove, laminate coat, greaseproof paper, shopping bag, compost bag, release paper, tableware, container for holding hot or cold beverages, cup, paper towel, plate, bottle for storing carbonated liquid, insulating material, bottle for storing non-carbonated liquid, film for food wrap, domestic waste treatment container, tool for food handling, lid for cup, paper straw, fabric fiber, tool for storing and transporting water, paperboard for medical use, release paper, tool for storing and transporting alcoholic or non-alcoholic beverages, external casing or screen for electronic products, internal or external components for furniture, curtain, interior decoration supplies, film, box, sheet, tray, pipe, aqueduct, packaging for pharmaceutical products, clothing, medical equipment, contraceptive, camping equipment, formed cellulosic material, and combinations thereof. **Claim 15** The method according to claim 1, wherein the substrate is adjustably derivatized for hydrophobic and / or oleophobic resistance. The method according to claim 1, wherein the substrate is adjustably derivatized for hydrophobic and / or oleophobic resistance. **Claim 16** The method according to claim 15, wherein the obtained substrate is hydrophobic. **Claim 17** The method according to claim 15, wherein the obtained substrate is oleophobic. **Claim 18** The method according to claim 17, wherein the obtained substrate exhibits a 3M Grease KIT test value between 3 and 12. The method according to claim 17, wherein the obtained substrate exhibits a 3M Grease KIT test value between 3 and 12. **Claim 19** The method according to claim 1, wherein the polymer solution is provided as an emulsion. **Claim 20** The polymer solution comprises clay, calcium carbonate, titanium dioxide, plastic pigment, binder, starch, protein, polymer emulsion, latex, zirconium salt, stearyl salt, according to the method of claim 1. Calcium phosphate, lecithin oleate, polyethylene emulsion, carboxymethyl cellulose , acrylic polymer, alginate, polyacrylate rubber, polyacrylate, bactericidal agent, oil-based defoamer, silicone-based defoamer, stilbene, direct dye or acid dye, the method according to claim 1, comprising one or more of them.

21. A manufactured product containing a substrate including a crosslinked polymer coating layer, wherein the crosslinking is substantially limited to the upper surface of the foregoing layer, and there is substantially no crosslinking contained in the foregoing layer.

22.

23. The crosslinked polymer layer contains substantially the same crosslinking agent and polymer, but gives the manufactured product higher flexibility, lower rigidity, and / or greater elongation as compared with a manufactured product in which substantial crosslinking is contained in the foregoing layer, the manufactured product according to claim 21.

24.

25. The polymer is selected from the group consisting of polyvinyl alcohol, polyethylene oxide, dextran, dextrin, hemicellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, cellulose ether, lignin, polyvinyl pyrrolidone, polyacrylamide, polyacrylic acid, polyacrylate, pectin, alginate, protein, gelatin, zein, whey protein, and combinations thereof, the manufactured product according to claim 21.

26.

27. The layer is crosslinked with a crosslinking agent selected from the group consisting of aldehyde, aldehyde-containing resin, polyfunctional carboxylic acid, difunctional methacrylate, ammonium zirconium carbonate, N-lactam carboxylate, dithiol, dimethyl urea, diisocyanate, borate, salt of polyvalent anion, inorganic polyion, salt of Group 1B, polyamide-epichlorohydrin resin, and combinations thereof, the manufactured product according to claim 21.

28.

29.

30. The substrate is a cellulosic material, the manufactured product according to claim 21.

31. The cellulosic material is paper, paperboard, pulp for papermaking, carton for food storage, bag for food storage, bag for transportation, container for coffee or tea, tea bag, paperboard for bacon, diaper, weed-inhibiting / barrier fabric or film, weeding film, flowerpot, packing beads, bubble wrap, oil-absorbing substance, laminate, envelope, gift card, credit card, glove, lay

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220.

221. 【 Encote, oil-resistant paper, shopping bags, compost bags, release paper, tableware, hot or cold beverages Containers for holding, cups, paper towels, plates, bottles for storing carbonated liquids, insulating materials, carbonated Bottles for storing non-carbonated liquids, films for food wrapping, household waste disposal containers, food handling Utensils, lids for cups, paper straws, fabric fibers, water storage and transportation utensils, cardboard for medical use Release paper, storage and transportation utensils for alcoholic or non-alcoholic beverages, external casings or screens for electronic products Internal or external components of furniture, curtains, interior decoration Articles, films, boxes, sheets, trays, pipes, aqueducts, packaging for pharmaceutical products, clothing, medical Equipment, contraceptives, camping utensils, formed cellulose-based materials, and combinations thereof The manufactured product according to claim 25, selected from the group consisting of

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