Manufactured articles containing nanocellulose elements

Abstract

The present invention includes a simple NCE-based material comprising a simple NCE-based matrix, the simple NCE-based matrix comprising a population of redispersible NCEs treated with a drying / dispersing additive; the matrix provides a structural framework for the simple NCE-based material; and the simple NCE-based material comprises a barrier formulation. The present invention also includes a composite NCE-containing material comprising a composite NCE-containing matrix, the composite NCE-containing matrix comprising a population of redispersible NCEs treated with a drying / dispersing additive, and an existing matrix; the redispersible NCEs are incorporated into the existing matrix, the existing matrix provides a structural framework for the composite NCE-containing material; and the composite NCE-containing material comprises a barrier formulation. The present invention further includes a plastic substrate, a manufactured article, and a method for manufacturing the aforementioned NCE-containing material.

Description

Technical Field

[0001] Related Applications This application claims the benefit of U.S. Provisional Application No. 63 / 458,269, filed Apr. 10, 2023. The entire teachings of the above application are incorporated herein by reference.

[0002] Field of the Invention This application relates to a formulation comprising a nanocellulose material for use in synthetic or natural bioplastic products.

Background Art

[0003] Background of the Invention Synthetic plastics are materials made of long polymer chains that have chemical and physical properties determined by the types of monomers involved in the polymerization process, such as how they link to each other in the polymer backbone and what side chains they have. Most plastics have a carbon-based backbone, with or without the incorporation of heteroatoms. Synthetic ("artificial") plastics are formed by chemical reactions such as condensation, addition, and crosslinking. Representative plastic categories include acrylics, polyesters, polyurethanes, halogenated polymers, and bioplastics. This last category, bioplastics, refers to synthetic plastics formed from biogenic monomers such as proteins, polysaccharides, and sugar derivatives. However, most synthetic plastics are petroleum-based polymers formed from petrochemical sources.

[0004] In 2021, approximately 400 million metric tons of synthetic plastics were produced. Six major polymer types, all derived from petrochemical products: polyethylene terephthalate (PET), high-density polyethylene (HDPE), low-density polyethylene (LDPE), polyvinyl chloride (PVC), polypropylene (PP), and polystyrene (PS), account for approximately 70% of global plastic production. If current trends continue with the increasing demand for plastics and the expansion of production capacity, global plastic production per year is estimated to exceed 1.1 billion tons.

[0005] The ubiquity of synthetic plastics presents two major environmental challenges. First, they are overwhelmingly made from petrochemical raw materials, requiring significant energy inputs for their production, which typically involves the generation of greenhouse gases. Second, conventional synthetic plastics are resistant to decomposition, posing a formidable obstacle to effective disposal and often remaining in the environment for centuries. While recycling can recover certain components of plastic waste, it is not adequately adapted due to its high cost and complexity: in 2015, 6.3 billion tons of plastic waste were generated, of which only 9% were recycled, another 79% were left in landfills or dumped into the environment (including the oceans), and another 12% were incinerated, resulting in the release of greenhouse gases and potentially toxic fumes. Despite the environmental impacts associated with synthetic plastics, plastics are ubiquitous in commerce, partly due to their durability. Because they do not decompose, they can be used to form articles that are intended to be nearly permanent, robust, and unbreakable. Other properties such as flexibility, moldability (plasticity), low cost for production, and lightweight are added to the appeal of plastics.

[0006] Concerns about the environmental impact of discarded and broken-down plastic materials are prompting manufacturers to consider bio-based alternatives. Materials that are composed of whole or significant parts of biological products or renewable agricultural or forestry materials are designated “bio-based” by the USDA. Biopolymers derived from bio-based materials can be used to form bioplastic materials that offer alternatives to conventional petroleum-based plastics.

[0007] Biopolymers can be produced by biological systems (microorganisms, plants, animals) or chemically synthesized from biological materials such as proteins, starches, and sugars. The primary sources of biopolymers are renewable materials such as agricultural feedstocks or waste products. Many biopolymers are biodegradable, meaning they can be broken down into carbon dioxide, water, and other organic compounds via the enzymatic action of microorganisms. These bio-based plastics, made from precursors such as polylactic acid (PLA), polyhydroxyalkanoates (PHA), and cellulose, are typically considered biodegradable and can be broken down in the environment by microorganisms under certain conditions (e.g., high heat and long duration for PLA). Certain biodegradable materials are further considered "compostable," meaning they can be broken down by microorganisms to form nutrient-rich organic materials that can enrich the soil, producing end products similar to those produced during natural compost formation.

[0008] While these bio-based plastic alternatives, such as polylactic acid plastics, starch-derived plastics, or cellulosic plastics, are of great interest as substrates for the manufacture of plastic materials, their use in general consumer applications, such as durable forming articles, containers, and packaging, remains limited, partly due to performance limitations. These materials tend to be hydrophilic and / or lipophilic, and have a high affinity for water and / or lipids. Therefore, these materials can become waterlogged or immersed in oils, making them unsuitable as containers for food and beverages and other products containing water or oil. When water or oil penetrates durable articles, they begin to solvate the container or packaging material, affecting their mechanical properties, thus making them structurally weak and prone to inadequacy. These limitations of bio-based plastics are often overcome by coating bioplastic materials with substances that have strong hydrophobic and oleophobic properties, usually petroleum-derived organic substances, such as polyethylene, polyethyleneimine, PVC, or fluorocarbons, materials with well-recognized environmental impacts. Furthermore, while such coatings improve water and oil resistance in bio-based materials, these materials still lack rigidity and mechanical strength.

[0009] To address these limitations, manufacturers are adding inorganic and organic materials as granular or fibrous fillers to bio-based formulations to improve their mechanical properties and streamline their processing. Compared to these materials using inorganic fillers, alternative bioplastics incorporating natural particles or fibers offer advantages such as renewability, high strength, relatively easy processing, and other desired properties. Nanoscale and microscale cellulose fibers, such as nanofiberized cellulose (NFC), microfiberized cellulose (MFC), nanocrystalline cellulose (NCC), and microcrystalline cellulose (MCC), are particularly attractive fillers for improving strength. These nanoscale and microscale cellulose fibers and crystals (collectively referred to as “nanocellulose elements,” “NC elements,” or “NCE”) have potential for use in biopolymer products, but with limitations. Firstly, since NCE fibers themselves are hydrophilic, they do not contribute to the water resistance of the resulting product. Therefore, water-repellent treatment is still necessary for articles containing NCE. More importantly, NCE requires to be transported to its intended use in a highly diluted suspension (<1–10 wt%) to prevent it from entangling with itself. This entanglement leads to hardening into a dense, viscous mass that resists redispersion; if this tightly packed network of aggregated cellulose elements is further dehydrated, it hardens further in a process called hornification. Complete drying of an NCE suspension forms a solid, brick-like mass that is substantially nondispersible. Therefore, in order to maintain an NCE suspension in a usable state so that the properties of the NCE it contains are available for use in other materials, the NCE must be maintained in a highly diluted form.

[0010] Despite a decade of academic and industrial efforts, the success of low-cost and effective drying and redispersion of NCE has not been found by commercial nanocellulose manufacturers. Two difficulties arise from two factors: (a) drying or concentrating aqueous media in which NCE is suspended and (b) subsequently redispersing them: (1) the properties of cellulose polymers in NCE that form hydrogen bonds with each other, causing adjacent cellulose elements to adhere to irreversible aggregates consisting of aggregates of particles that permanently bond to each other and resist redispersion; and (2) the large surface area per unit weight associated with the size and morphology of NCE, which greatly increases the exposure of NCE surfaces to each other and worsens adhesion due to hydrogen bonding. These two factors combined result in keratinization associated with concentrated and dried NCE suspensions. The tendency of NCE suspensions toward keratinization necessitates that these materials be transported in large volumes of water, significantly adding to the costs associated with their transport and use. Drying techniques such as freeze-drying, spray-drying, supercritical fluid drying, and atomization have been investigated by researchers, but these techniques have yielded, at best, small samples of redispersed NC elements, with high costs, energy requirements, and the need for specialized equipment preventing their widespread adoption. This resistance to redispersion has hindered the adoption of NCE as an additive for other bio-based materials.

[0011] Therefore, there remains a need in the technical field for methods and formulations that provide bioplastics with satisfactory mechanical strength and water / oil resistance, a need that could provide commercially viable alternatives to petroleum-derived plastics for manufactured articles. There is a need to enable their commercial implementation at low cost, without excessive energy requirements, without the need for special equipment, and to the extent that NCE is incorporated into bio-based materials for such articles. To achieve these latter goals, there remains an unaddressed need to make nanocellulose-containing formulations redispersible, keratinization-resistant, and capable of economically transporting and efficiently and cost-effectively incorporating these formulations into bio-based composites. [Overview of the Initiative]

[0012] Summary of the Invention In some embodiments, a simple NCE material comprising a simple NCE matrix is ​​disclosed herein, the simple NCE matrix comprising a population of redispersed NCEs, and the simple NCE matrix providing a structural framework for the simple NCE material. In some embodiments, the simple NCE material comprising a plurality of submatrices. In some embodiments, pulp or pulp-based material is incorporated into the simple NCE matrix; the simple NCE matrix may be pulp-dominant. In some embodiments, the simple NCE matrix further comprises a reinforcing agent or barrier formulation. In some embodiments, the matrix comprises a reinforcing agent which may contain a further amount of NCE. In some embodiments, the matrix comprises a barrier formulation which may contain methylcellulose and produce oleophobicity. In other embodiments, the matrix comprises a barrier formulation which may contain a resin acid or a combination of resin acids and produce hydrophobicity. Manufactured articles comprising the simple NCE materials described above are also disclosed herein. In some embodiments, the manufactured articles further comprise a barrier formulation. In some embodiments, the articles are formed into a shaped article which can be formed into a container.

[0013] Methods for producing a simple NCE system material are also disclosed herein, comprising the steps of (a) providing a redispersed suspension containing redispersed NC elements, wherein the redispersed suspension is produced by (i) providing an initial NCE suspension containing NC elements suspended in a liquid or other fluid medium; (ii) adding a drying / dispersing additive to the initial NCE suspension to form a suspension of redispersible NCE; (iii) drying the suspension of redispersible NCE to produce a dried material containing redispersible NCE; and (iv) suspending the dried material in a resuspension fluid to produce a redispersed suspension; (b) drying or concentrating the redispersed suspension to produce a simple NCE system matrix, wherein the simple NCE system matrix provides a structural framework for a simple NCE system material; and (c) adding an additive substance before or after the drying or concentrating step to thereby produce a simple NCE system material. In embodiments, the simple NCE system matrix comprises a plurality of submatrices. In one embodiment, the additive substance is a bulking agent that may contain pulp or pulp-based materials. In another embodiment, the additive substance is a barrier formulation that produces oleophobicity, which may contain methylcellulose. In yet another embodiment, the additive substance is a barrier formulation that produces hydrophobicity, which may contain resin acids or combinations of resin acids. In yet another embodiment, the additive substance is an appearance modifier such as a pigment.

[0014] In embodiments, composite NCE-containing materials comprising a composite NCE-containing matrix are further disclosed herein, the composite NCE-containing matrix comprising a group of additive NCEs and an existing matrix, the additive NCEs being incorporated into the existing matrix, and the existing matrix providing a structural framework for the composite NCE-containing material. In embodiments, the existing matrix is ​​biobased. In embodiments, the composite NCE-containing material further comprises one or more additive substances, each additive substance selected from the group consisting of reinforcing agents, barrier formulations and fillers. Manufactured articles comprising the composite NCE-containing materials described above are also disclosed herein. Manufactured articles may be selected from the group consisting of transaction cards, liquid containers, packaging materials for consumer products, thin films and sheets, and hollow cylinders for flexible tubes. Also disclosed herein are methods for producing composite NCE-containing materials, comprising the steps of: providing a group of additive NCEs, incorporating the group into an existing matrix to form a composite NCE-containing matrix; and adding additive substances to the composite NCE-containing matrix to produce a composite NCE-containing material.

[0015] In further embodiments, simple NCE materials comprising a simple NCE matrix are disclosed herein, the simple NCE matrix comprising a population of redispersible NCEs treated with a drying / dispersing additive comprising a low critical solution temperature (LCST) polymer; the simple NCE matrix provides a structural framework for the simple NCE material; and the simple NCE material comprises a barrier formulation or barrier substance. In embodiments, the barrier formulation comprises a substance selected from the group consisting of cellulose polymers, lipids, proteins, fillers, fatty acids, resin acids, and combinations of resin acids. In some aspects, the NCE material comprises a barrier substance, the barrier substance selected from the group consisting of cellulose polymers, lipids, proteins, fillers, fatty acids, resin acids, and combinations of resin acids. In embodiments, the barrier formulation comprises a resin acid or combination of resin acids. In one embodiment, the barrier formulation comprises an oleophobic substance selected from the group consisting of MC, HPMC, CMC, NaCMC, CA, CAB, chitosan, rosin, lignin, pea protein, and zein; in another embodiment, the barrier formulation comprises a hydrophobic substance selected from the group consisting of MC, CA, CAB, chitosan, rosin, hydrophobized starch, lignin, pea protein, and zein. In a specific further embodiment, the barrier substance is an oleophobic substance selected from the group consisting of MC, HPMC, CMC, NaCMC, CA, CAB, chitosan, rosin, lignin, and plant protein; in another embodiment, the barrier substance is a hydrophobic substance selected from the group consisting of MC, CA, CAB, chitosan, rosin, hydrophobized starch, lignin, and plant protein. In an embodiment, the NCE-based material further comprises one or more additive substances: in one aspect, one or more additive substances are selected from fillers, reinforcing agents, or appearance modifiers or combinations thereof. In some aspects, one or more additive substances are fillers that may contain pulp or pulp-based materials; in embodiments, the simple NCE matrix is ​​pulp-dominant. In embodiments, the fillers are filler particles that may contain plant-derived organic materials. One or more additive substances are reinforcing agents that may contain further amounts of NCE.Furthermore, plastic substrates containing these simple NCE-based materials are disclosed herein as manufactured articles containing such plastic substrates that are formed into molded articles such as containers or food containers.

[0016] In embodiments, a method for producing a plastic article containing a simple NCE material is also disclosed herein, comprising the steps of (a) producing a simple NCE material containing redispersible NC elements, wherein the simple NCE material is produced by: (i) providing an initial suspension containing NC elements suspended in a fluid medium; (ii) combining a drying / dispersing additive with the initial suspension to form a flexible suspension of redispersible NCE; for example, the drying / dispersing additive includes an LCST polymer; and (iii) adding an additive substance to the flexible suspension of redispersible NCE while maintaining its flexibility, thereby forming the simple NCE material in a flexible state; and (b) forming or shaping the flexible simple NCE material into a desired configuration, thereby producing a plastic article. The additive substance may be selected from the group consisting of reinforcing agents, barrier formulations, barrier substances, and fillers. In embodiments, the forming or shaping step includes extrusion molding.

[0017] In some embodiments, composite NCE-containing materials comprising a composite NCE-containing matrix are further disclosed herein, the composite NCE-containing matrix comprising a population of redispersible NCEs treated with a drying / dispersible additive comprising a low critical solution temperature (LCST) polymer and an existing matrix; the redispersible NCEs are incorporated into the existing matrix, the existing matrix providing a structural framework for the composite NCE-containing material; the composite NCE-containing material comprises a barrier formulation or barrier substance. In some embodiments, the existing matrix comprises a bio-based polymer which may include a cellulose derivative which may be a polyhydroxyalkanoate. In some embodiments, the existing matrix comprises a petroleum-derived polymer which may be derived from recycled plastic materials. In some embodiments, the barrier formulation comprises a substance selected from the group consisting of cellulose polymers, lipids, proteins, fillers, fatty acids, resin acids and combinations of resin acids. In some aspects, the NCE-containing material comprises a barrier substance which is selected from the group consisting of cellulose polymers, lipids, proteins, fillers, fatty acids, resin acids and combinations of resin acids. In one embodiment, the barrier formulation comprises an oleophobic substance selected from the group consisting of MC, HPMC, CMC, NaCMC, CA, CAB, chitosan, rosin, lignin, and plant proteins; in another embodiment, the barrier formulation comprises a hydrophobic substance selected from the group consisting of MC, CA, CAB, chitosan, rosin, hydrophobized starch, lignin, and plant proteins. In a specific further embodiment, the barrier substance is an oleophobic substance selected from the group consisting of MC, HPMC, CMC, NaCMC, CA, CAB, chitosan, rosin, lignin, and plant proteins; in another embodiment, the barrier substance is a hydrophobic substance selected from the group consisting of MC, CA, CAB, chitosan, rosin, hydrophobized starch, lignin, and plant proteins. In one embodiment, the barrier formulation comprises a resin acid or a combination of resin acids. In an embodiment, the NCE-containing material further comprises one or more additive substances selected from fillers, reinforcing agents, or appearance modifiers. In one embodiment, one or more additive substances give the composite NCE-containing material properties selected from the group consisting of structural strength, resilience, elasticity, water resistance, and oil and grease resistance.Furthermore, plastic substrates containing these composite NCE-containing materials are disclosed herein as manufactured articles containing such plastic substrates, which are formed into articles such as transaction cards, liquid containers, food containers, food kitchen products, packaging materials for consumer products, thin films and sheets, and hollow cylinders for flexible tubes.

[0018] In embodiments, the composite NCE-containing material is produced by a sub-step of (a) producing a composite NCE-containing material containing redispersible NC elements, wherein the composite NCE-containing material is produced by (i) providing an initial suspension containing NC elements suspended in a fluid medium; (ii) combining a drying / dispersing additive with the initial suspension to form a flexible suspension of redispersible NCE; for example, the drying / dispersing additive includes an LCST polymer; (iii) incorporating the flexible suspension into an existing matrix to form a flexible composite NCE-containing matrix; and (iv) adding an additive substance to at least one of the initial suspension, the flexible suspension, the existing matrix, and the composite NCE-containing matrix to maintain its flexibility and thereby form a flexible composite NCE-containing material; and (b) forming or shaping the flexible composite NCE-containing material into a desired configuration to produce a formed article. The additive substance may be selected from the group consisting of reinforcing agents, barrier formulations, barrier substances, and fillers. In embodiments, the forming or shaping step includes extrusion molding. [Brief explanation of the drawing]

[0019] Brief explanation of the drawing [Figure 1] Figure 1 is a block diagram showing the process for creating a matrix containing redispersed nanocellulose elements. [Figure 2] Figure 2 is a block diagram showing the process for creating a matrix containing redispersed nanocellulose elements. [Figure 3]FIG. 3 is a block diagram showing a process for creating a matrix containing redispersed nanocellulose elements.

BRIEF DESCRIPTION OF THE DRAWINGS

[0020] DETAILED DESCRIPTION OF THE INVENTION 1. Components of the Redispersible Nanocellulose Element Formulation a. General Redispersible Nanocellulose Elements Nanocellulose elements (NCEs) can be processed to be redispersible in formulations for making useful manufactured articles using formulations and methods as described herein and as described in U.S. Patent Application Publication No. 20220412010A1 (U.S. Patent Application No. 17 / 834,521, filed June 7, 2022; the ‘521 application), the contents of which are hereby incorporated by reference in their entirety. It has unexpectedly been discovered that using the methods of these inventions, formulations can be prepared that contain NCEs, are concentrated or dried, and can then be redispersed without keratinization. Such formulations containing the redispersed NCEs can then be used for the manufacture of useful articles. The formulation itself can be dried and formed to make a manufactured article, or the formulation can be incorporated into an existing matrix to form a composite having improved properties relative to the existing matrix itself or a composite having additional properties not present in the existing matrix.

[0021] Suitable substrates for processing by the systems and methods disclosed herein (i.e., NFCs and MFCs, as well as NCCs and MCCs, collectively known as NCEs) can be derived from all types of cellulose raw materials, particularly plant-derived cellulose raw materials. Plant-derived cellulose raw materials include lignocellulose materials: lignocellulose materials consist of cellulose polymers bound together with a variable amount of lignin. All types of lignocellulose materials are suitable for producing NCEs or other lignocellulose materials, such as pulp. Plants having use as lignocellulose materials may be woody (e.g., trees with hard trunks and perennial growth cycles) or non-woody with weak trunks and annual or limited perennial growth cycles. Lignocellulose materials may include special-purpose grains such as switchgrass and elephantgrass, which are cultivated for applications such as biofuels and are capable of multiple harvests. Suitable materials for pulp production may, without limitation, originate from industries such as agriculture (e.g., corn stalks and leaves after the kernels have been removed and corn cobs, sugarcane bagasse, straw, bundles of empty oil palm fruits, pineapple leaves, apple stalks, coir fiber, mulberry bark, rice hulls, bean pods, soybean pods (or "soy hulls")), cotton linters, blue agave waste, North African grass, banana pseudo stem residue, American groundnut hulls, pistachio nut shells, grape pomace, shea butter nut shells, passion fruit peels, fique fiber waste, sago seed shells, kelp waste, rush stalks, etc.) or forestry (sawmill and paper mill waste).

[0022] In some embodiments, NCE is conventionally prepared from precursor lignocellulose material or other plant-derived cellulose raw materials by a series of mechanical and / or chemical procedures performed in an aqueous medium, where the aqueous suspension loosens the hydrogen bonds between the cellulose filaments to facilitate delamination, resulting in the formation of NCE. Since NFCs and MFCs are extracted from plants by different techniques, their forms and properties differ. NFCs and MFCs can be distinguished from each other based on their size and shape: cellulose nanofibers are considerably smaller in diameter than cellulose microfibers and can be straight and rod-shaped, while cellulose microfibers are larger in diameter, more flexible, and have a more varied and irregular appearance. While the literature cites a range of dimensions for NFCs and MFCs, NFC fibers are nanoscale (e.g., have a diameter of 4–20 nm), and MFCs are even larger, but typically in the nano range, with a diameter of 20–100 nm or more. After forming NCE from precursor cellulose material, the NCE is dispersed in an aqueous medium at low concentrations (<10 wt%) because, as mentioned above, their high water absorption capacity and tendency to form hydrogen bonds cause entanglement due to hydrogen bonding in high aspect ratio NC elements, resulting in the formation of highly viscous suspensions even at low solid concentrations.

[0023] As described in the '521 application, additives have been discovered that can be used to prepare NCEs and are redispersible after being formulated in solution. Such additives are referred to herein as "dry / dispersible additives". Without being bound by theory, these additives function to inhibit or disrupt hydrogen bonding with each other and with the NCE at certain, usually high, reaction temperatures, preventing curing and keratinization while retaining their high inherent hydrophobicity that allows for easy redispersion in an aqueous medium. As used herein, the terms "redispersion" and its grammatical derivatives and cognates refer to the process by which a dry or concentrated NCE prepared to be redispersible as described herein is suspended in a fluid medium, referred to as a resuspension fluid (either aqueous or non-aqueous), and there is substantial complete dissolution of the suspension of the dry or concentrated NCE to release its NCE components suspended in the resuspension fluid. In embodiments, an aqueous resuspension fluid can be used; in other embodiments, a non-aqueous resuspension fluid such as a fluid having hydrophobic or amphiphilic properties can be used.

[0024] As used herein, the term “redispersible” means these NCEs treated with a drying / dispersing additive as disclosed herein, which makes the NCEs redispersible. Formulations containing such redispersible NCEs may exist in liquid, dry, or partially dry states. In a fully dry or partially dry state, NCEs in a formulation are redispersible by suspending them in a resuspension fluid. Redispersible NCEs (i.e., NCEs treated with a drying / dispersing additive as disclosed herein) are present in a liquid formulation before they are dried; the presence of the drying / dispersing additive makes such NCEs redispersible, so they may subsequently experience redispersion when dried or concentrated. Redispersible NCEs also exist in a liquid formed by adding a redispersion fluid to a dry or concentrated formulation containing redispersible NCEs; their presence when resuspended in such a liquid indicates that they are indeed redispersible and therefore redispersible. To avoid any doubt, this last group of redispersible NCEs, which are formulated to be redispersible and resuspended in a resuspension fluid that actually redisperses them, may more specifically be called “redispersed NCEs”; all redispersed NFCs are redispersible by definition, but not all redispersible NFCs are redispersible.

[0025] In one embodiment, the redispersion results in suspensions of NCEs, which are formed as individual NCEs or amorphous aggregates of individual NCEs (both referred to herein as “resuspended particles”), and such resuspended particles have an aspect ratio greater than 10. In one embodiment, the resuspended particles have an aspect ratio of about 10 to about 300 or about 10 to about 200. In one embodiment, the resuspended particles have an aspect ratio of about 50 to about 150. In one embodiment, the resuspended particles have an aspect ratio of about 25 to about 75. In another embodiment, the resuspended particles have an aspect ratio of about 75 to about 125.

[0026] These formulations and methods include several different categories of drying / dispersing additives: (1) certain temperature-responsive polymers that can introduce spaces between NC elements during drying, thereby preventing their aggregation; (2) certain volatile small molecules that can create spaces between NC elements during drying; and (3) certain non-volatile small or large molecules ("blocking agents") that disrupt hydrogen bonding between or within NC elements during drying. The drying / dispersing additives include, but are not limited to, temperature-responsive polymers, volatile small molecule additives, and blocking agents. All of these materials act to disrupt hydrogen bonding at high temperatures or otherwise, while creating gaps between or within NC elements, allowing for subsequent redispersion by further drying.

[0027] Certain additives (e.g., the specific LCST polymers listed below) are suitable for use as single agents to facilitate drying and redispersion, while other additives are intended for use as adjuvants in combination with the main drying / dispersing additive, either when administered to the initial NC suspension simultaneously with the main additive, or as a pretreatment to the initial NC suspension or any of its precursors before the addition of the main additive, or as a posttreatment to the initial NC suspension after the addition of the main drying / dispersing additive.

[0028] b. Drying / dispersing additives It is understood that the drying / dispersing additives disclosed herein, individually or in combination, may be introduced into initial NCE-containing suspensions to improve the drying process of NCE and facilitate their redispersion. Drying / dispersing additives may also be used in combination with other agents that enhance their efficiency, even if these other agents are not effective as drying / dispersing additives when used alone; such agents used in combination with drying / dispersing additives to enhance their efficiency are referred to as “adjuvants.” It is further understood that one or more drying / dispersing additives and / or adjuvants may act together in a synergistic manner. Furthermore, combinations of drying / dispersing additives may be introduced sequentially, with or without the addition of adjuvants, during and / or before, after, or during the process used to prepare initial NC suspensions from feedstock materials of a cellulose source. For example, nonpolymeric additives may be added during the process used to prepare initial NC suspensions from feedstock materials, but preferably after the chemical pretreatment of initial NCE derived from cellulose or lignocellulose precursor material.

[0029] i. Temperature-responsive polymers In some embodiments, certain temperature-responsive polymers may be used to create spaces between NC elements during drying, thereby preventing the NC elements from aggregating during the drying process. By preventing high-density aggregation and curing of NCEs, temperature-responsive polymers redisperse them upon contact with a resuspended fluid. Temperature-responsive polymers particularly suitable for this purpose are those that exhibit a phenomenon known as LCST (Low Critical Solution Temperature) phase behavior. Certain LCST polymers are understood to be hydrophilic below their LCST transition temperature and reversibly hydrophobic above their LCST transition temperature. That is, below the LCST point, the polymer exhibits a high affinity for water, consistent with its intrinsic molecular hydrophilicity. However, above the LCST point, the polymer repels water and avoids hydrogen bonding. This is evident from the observed thermogelation of polymer solutions above this transition temperature. When polymeric or oligomeric LCST additives self-assemble on the surface of NC elements (in the form of monolayers or layers of several particles), the drying of the NC elements and the resulting form of the NC-containing material in the dry state are influenced to facilitate the final redispersion of such NCEs.

[0030] For use in this setup, the LCST polymer can be added to the initial NC suspension at a temperature below the transition temperature of the LCST polymer. The initial NC suspension is then heated to allow it to dry. As water evaporates from the initial NC suspension during drying, its temperature rises to the boiling point of water, exceeding the transition temperature of the LCST polymer, at which point the LCST polymer loses its hydrophilic properties and becomes hydrophobic. Once it becomes hydrophobic, the behavior of the LCST polymer changes: it interferes with the hydrogen bonding that would otherwise occur between the NC elements. Here, the hydrophobic nature of the LCST polymer drives the aggregation or disaggregation of the NC elements instead of these processes driven by the interaction of the hydrophilic cellulose units of the NC elements.

[0031] In some embodiments, the selected LCST polymer can significantly or completely prevent high-density aggregation and curing of NC elements during drying. In some embodiments, the ability of the selected LCST polymer to disrupt high-density aggregation and curing of NC elements is independent of the selection of equipment and the mode of drying. For example, a suspension containing the LCST polymer and NC elements may remain stationary during drying. A wide range of drying temperatures and pressures can be applied to the initial NC suspension in the presence of the selected LCST polymer to achieve drying without aggregation. Dried NC materials incorporating the selected LCST polymer described herein can be easily redispersed in water by gentle agitation or stirring, with minimal or no clumping, or with any remaining high-density aggregation or curing identified in the redispersed suspension. These features allow for a wide tolerance in parameters for redispersion and for handling the material being redispersed.

[0032] In this embodiment, the following list provides examples of LCST polymers and their analog short-chain oligomers that can be used as drying / dispersing additives to prevent high-density aggregation and hardening of NC elements, thereby facilitating the subsequent redispersion of NC elements. Methylcellulose Carboxymethylcellulose • Sodium carboxymethylcellulose • Hydroxyethylcellulose • Hydroxypropylcellulose Hydroxypropylmethylcellulose Ethyl hydroxyethyl cellulose • Polyvinyl caprolactam • Poly(methyl vinyl ether) • Poly(N-isopropylacrylamide) • Poly(N,N-diethylacrylamide) • Block copolymer of poly(ethylene oxide) and poly(propylene oxide) • Poly(pentapeptide) of elastin

[0033] Note that the thermal gelation temperatures of the specific additives listed above depend on the type and degree of substitution and are adjustable by structural design. Advantageously, LCST polymers selected for use as drying / dispersing additives may have transition temperatures higher than ambient temperature (e.g., >25°C), so the polymer remains in solution until the drying process begins.

[0034] ii. Volatile small molecule additive systems In some embodiments, a volatile system containing small molecule additives may be used, alone or in combination with other additives, to act as a drying / dispersing additive by creating spaces between NC elements during drying, thereby preventing the NC elements from aggregating during the drying process. Selected small molecule additives for use in volatile systems are miscible with water and have a boiling point higher than that of coexisting water. Small molecule additives useful in volatile systems are further characterized by their considerably lower hydrogen bonding tendency compared to water. When an additive-loaded volatile system containing NCE and the selected small molecule additive undergoes drying, water molecules preferentially evaporate, while the small molecule additive remains due to its high boiling point, thereby increasing the concentration of the additive in the remaining solution between adjacent NC elements. In some embodiments, the molecular segmentation of the volatile small molecule additive includes both polar and nonpolar functional groups. Without being constrained by theory, it is conceivable that adhesion between and within NC elements is reduced, as the polar segmentation is attracted to cellulose hydroxyl groups, and the nonpolar segmentation simultaneously interferes with hydroxy-hydroxyl interactions. Subsequently, as the temperature in the system rises, the additives evaporate, leaving behind the NC elements surrounded by air, and thus separating from each other. The resulting dry material, containing NC elements separated from each other by air, can be readily redispersed without forming any indicators of aggregation, hardening, or concentration change, such as observable aggregates / clumps. The redispersed suspension contains resuspended NC particles with a uniform distribution in the suspension, where the NC elements retain their nanoscale characteristics, and redispersion can be achieved by very gentle stirring / agitation only.

[0035] In this embodiment, the following list provides examples of small molecule additives that can be used as drying / dispersing additives in the aforementioned volatile systems to prevent high-density aggregation and hardening, thereby facilitating the subsequent redispersion of NC elements. The exemplary additives can be divided into two categories: nonionic and cationic compounds.

[0036] Without limitation, nonionic candidates include: • Tri(propylene glycol) butyl ether (TPnB) • Di(propylene glycol) propyl ether (DPnP) • Propylene glycol butyl ether (PnB) • Propylene glycol propyl ether (PnP) • Ethylene glycol monobutyl ether • Propylene glycol monomethyl ether acetate • Propylene glycol diacetate • Ethylene glycol diacetate Benzyl alcohol · 1-heptanol · 1-Hexanol These could be cited.

[0037] Without limitation, cationic candidates include: Ethylenediamine • Diethylenetriamine • Tetraethylenepentaamine • 1,3-pentanediamine • Piperazine • 1,2-Cyclohexanediamine Aniline Pyridine • Piperazine These could be cited.

[0038] In some embodiments, the small molecule additive may completely evaporate from the initial NC suspension, leaving only the NC elements in suspended or dry form, without any residue of the additive. However, in other embodiments, trace amounts of the small molecule additive may remain. For example, certain cationic additives may have cationic groups that adhere to cellulose molecules, so that after complete drying, trace amounts of the additive remain adhered to the cellulose. For most industrial applications, the residue of these additives does not pose health or environmental problems. However, in some embodiments, biodegradable cationic small molecules, such as 1,3-pentanediamine, may be selected to avoid such problems.

[0039] iii. Blocking agent In some embodiments, non-volatile small or large molecular additives may be used separately from the volatile systems described above to prevent hydrogen bonding and / or create spaces between NC elements during drying, thereby preventing interaction between NC elements and thus preventing aggregation of NC elements during the drying process. In some embodiments, surface-functionalized nanoscale particles may be used in the same manner. Such non-volatile small or large molecular additives and nanoscale particles used to perform this blocking function are referred to herein as blocking agents or barriers. As used herein, the terms “blocking agent” or “barrier” include any non-volatile chemical additive or nanoscale granular material that, whether the substance is inserted between or into NC elements, or whether the substance provides a transient competitive bonding site for NC elements, or otherwise, prevents hydrogen bonding or creates spaces within NC elements.

[0040] As an example, caffeine and other xanthine derivatives are small molecule blockers that can be advantageously used to facilitate the isolation of NC elements from each other and their subsequent redispersion during drying or concentration processes. Without being constrained by theory, it is conceivable that certain purines (e.g., caffeine and other xanthines or xanthine derivatives) and aromatic nitrogen atoms in pyrimidines can hydrogen bond with the hydroxyl groups of cellulose, presenting a flat, relatively nonpolar, molecularly smooth outer surface for water-screening to the NCE, thus preventing adhesion between and within NC elements. Caffeine and other xanthines and xanthine derivatives can typically be used in amounts that do not pose health or environmental problems, even when used in doses sufficient to facilitate NC dispersion.

[0041] As another example, certain wetting agents can be used as blocking molecules. Wetting agents have multiple hydrophilic sites, such as hydroxyl, ester, and ammonium groups, that can form hydrogen bonds with the surface of NC elements, thereby shielding the interaction of these elements with each other via hydrogen bonding, and thus preventing high-density aggregation and hardening. Furthermore, these hygroscopic substances are biocompatible and are already widely used in the pharmaceutical, cosmetic, and food industries. Examples of short and long wetting agent candidates, though not limited to these, include glycerin, caprylyl glycol, ethylhexylglycerin, tribehenin, hydrolyzed soy protein, various amino acids, propylene glycol, methyl gluceth-20, phenyl trimethicone, hyaluronic acid, sorbitol, and gelatin.

[0042] As yet another example, fatty acids can also be used as blocking agents. Fatty acids include a hydrophilic moiety and a hydrophobic tail. The hydrophilic moiety can form hydrogen bonds with the surface of the NC elements, thereby shielding the interaction of these elements with each other via hydrogen bonding and preventing aggregation. Preferably, fatty acids that do not contain too many hydrophilic moieties and where excessive hydrogen bonding occurs between the NCE particles and the fatty acid may be selected. However, in embodiments where a very large number of hydrogen moieties can cause high-density aggregation and hardening, the hydrophobic tail of the fatty acid blocking agent may act to physically prevent high-density aggregation and hardening of the NC elements by preventing or hindering hydrogen bonding. In embodiments, the blocking agent may be fatty acids, such as stearic acid, palmitic acid, myristic acid, lauric acid, capric acid, caprylic acid, caproic acid, etc. Water-soluble fatty acids may be selected to facilitate the dispersion of fatty acids in aqueous solutions of NC elements.

[0043] 2. Redispersibility of NC elements and redispersed suspensions The block diagram in Figure 1 schematically shows process 100 involved in the preparation of a redispersible suspension of NC elements, which can be further processed to produce a redispersible suspension of NC elements and materials made therefrom. As shown in Figure 1, process 100 for producing a suspension of redispersed NC elements comprises four steps.

[0044] Step 1 involves suspending a collection of NCE 102 in a suspension fluid 104 to produce an initial NCE suspension 108. Processes for forming an initial NCE suspension suitable for further processing using the formulations and methods disclosed herein are well known in the art. To form such an NCE-containing suspension, a cellulose source may be treated using conventional mechanical techniques and any chemical treatments to extract the constituent cellulose nanomaterials (i.e., NCEs) and hold them as suspensions in a liquid or other fluid medium. The NC elements thus extracted form an initial NC suspension, which may be treated to make them redispersible in subsequent steps using the formulations and methods disclosed.

[0045] In step 2, the drying / dispersing additive 110 described above is added to the initial NCE suspension 108 to produce a suspension of redispersible NCE 112. As previously discussed, the drying / dispersing additive 110 makes the NCE in the initial NCE suspension 108 redispersible. The redispersible suspension of NCE 112 is dried in step 3 to produce a dry material 114 containing the redispersible NCE. The dry material 114 containing the redispersible NCE is then either ground / minced and used as a dry component, or suspended in the resuspension fluid 118 in step 4 to produce a suspension 120 of the redispersible NCE produced as described above at a desired concentration; such redispersible NCE treated by suspension in the resuspension fluid as described in step 4 may also be referred to as “redispersed NCE”. In one embodiment, the subsequently redispersed suspension 120 of NCE may be treated alone by drying or concentrating, for example, as shown in step 5a, to form a simple NCE system matrix 122 of dried, resuspended NCE, which is formed as a continuous sheet. At the microscopic level, the structure is three-dimensional, highly porous, and typically forms a large, structurally amorphous network structure; however, when nanocrystalline elements are used and / or when crosslinking strategies such as the incorporation and esterification of carboxylic acids into the surface of NCE are employed, semi-crystalline NCE matrices may be synthesized. As used herein, the term “amorphous” refers to any solid formation in which the constituent elements are not organized into a distinct repeating lattice pattern. Amorphous structures usually enhance degradability. Additionally, additive substances (not shown) can be readily integrated into the amorphous simple NCE system matrix 122 to produce advantageous features such as malleability, processability, heat resistance, strength, or oleophobic or hydrophobic properties.

[0046] To reduce the amount of NCE required to produce the desired properties for the matrix, NCE-free pulp-based or pulp-containing additives may also be added. As used herein, the term “pulp-based” means these materials derived from pulp, obtained by processing, forming, or treating them while retaining pulp or pulp derivatives within them.

[0047] Pulp is understood to be produced from materials containing cellulose or lignocellulose fibers, such as wood, non-wood raw materials, special-purpose grains, paper waste, recycled paper, agricultural residues, etc. Non-wood raw materials such as bagasse, grain straw, bamboo, reeds, African sedge, jute, flax, and sisal hemp are well known in the art as sources of cellulose fibers; certain non-limiting examples of materials containing lignocellulose fibers are also provided herein. Wood and other plant materials used to produce pulp contain three main non-aqueous components: cellulose, lignin, and hemicellulose. Chemical and / or mechanical processes for producing pulp are intended to break down the mass structure of the plant material source into constituent fibers, thereby producing a fibrous, cellulose-containing material known in the art as pulp. Pulp can also be formed from previously processed materials such as paper scraps or recycled paper or certain fabrics; such materials may lack some or all of the components found in wood or other pulp materials, but can be subjected to appropriate chemical or mechanical processes to form them into pulp.

[0048] Pulp and pulp-based materials may be used in conjunction with the formulations, compositions, and methods disclosed herein to form or shape as components or substrates for manufactured articles of any useful shape, such as sheets, fibers, solid articles, and molded articles. Such additives may act as low-cost fillers to add volume to a matrix so that a larger amount of simple NCE-based matrix is ​​produced; in such a matrix, redispersible or redispersed NCE may be added in combination with a filler (e.g., conventional pulp or other pulp-based material) so that the final matrix has desired mechanical properties.

[0049] NCE is understood to be an additive substance that causes the organizational and structural characteristics of the matrix having the performance properties to be obtained, and other additives may be added to the matrix to produce any of the advantageous properties or other desired properties described above. For example, appearance-modifying additives, such as dyes or other colorants, may be added to the matrix, or other additives may be intended to provide desired properties such as odor-related agents, emollients, cosmetics, pharmaceuticals, medical and agricultural active ingredients, fragrances and scents. Other relevant additives may be included in the matrix to enable a particular additive to achieve its intended purpose. For example, an NCE matrix may contain odor-blocking chemicals or natural scents that are adapted for release in enclosed, confined spaces with high levels of odoriferant material in items such as gym bags and suitcases, or adapted for use in personal items that may emit odors (e.g., shoe insoles or linings). NCE matrices adapted for these purposes may incorporate plasticizers or other additives (e.g., shoe linings that release odor-controlling substances when in contact with body-temperature feet) to regulate the release of deodorants or adapt their release to specific environmental conditions. Similarly, NCE matrices may be formulated with deodorant or antiperspirant substances in the matrix interstitial spaces, and the NCE matrices work to allow for more durable application of such products to the skin. As a further example, various fragrances may be used by the systems disclosed herein. The term “fragrance,” as used herein, means various odors that may be intentionally incorporated into and delivered by the matrices described herein. For example, pleasant fragrances may be used for cosmetic or aesthetic purposes, or to mask unpleasant odors. Fragrances may be used for medical, veterinary, or agricultural purposes to act as insect repellents, pesticides, pheromones, growth hormones, etc. Aromas can be supplied from volatile aromatic compounds, such as essential oils, hydrosols, or aromatic microcapsules. Exemplary supplies may incorporate biological and chemical supplies suspended in solution for easy application or mixing. Other sources for aromas may be aqueous systems, such as hydrosols.Other examples of fragrance-based technologies based on the formulations disclosed herein include, but are not limited to, insecticides for agricultural use, fragrances and odor neutralizers for household use, and pet hormones to promote calming behavior around the home. By controlling the rate of release through careful manipulation of the base technology, applications can be personalized for agricultural products that release insecticides rapidly, for example, during planting season and more slowly when plants are fully grown, to suit the needs of various consumers. The technologies disclosed herein can be readily adapted for agricultural purposes, for example, by using pheromones as agricultural active ingredients. Pheromones are understood to be secreted or excreted chemical substances that elicit social responses in members of the same species. Although they may not have the “odor” as the term is commonly understood, pheromone receptors are typically located in the olfactory epithelium or vomeronasal organ, indicating that they are processed in a similar pathway as conventionally. Thus, pheromones are considered odor-related activators for the purposes of this disclosure; they are known to be useful in the agricultural industry as pesticides or artificial growth hormones. The examples described herein are illustrative and not limiting. Other examples of additive substances useful with the matrices disclosed herein can be readily conceived by those skilled in the art.

[0050] Additive substances may be integrated into or added to the simple NCE system matrix 122 before, during, or after processing in step 5a: the additive substance(s) may be added to the NCE suspension 120 which has been redispersed before processing step 5a, and / or added so that the suspension 120 is dried or concentrated, and / or they may be added to the simple NCE system matrix 122. A material comprising a simple NCE system matrix 122 which provides a structural framework to the material, and further comprising any additive substances, may be referred to as a “simple NCE system material.” When the term “matrix” is used herein as in “simple NCE system matrix,” it is understood that the matrix formation process described above does not require the creation of a single continuous simple NCE system matrix, but instead may create multiple simple NCE system matrices which are more loosely linked to each other or discontinuous. When multiple simple NCE system matrices are created by the process disclosed herein, the interrelationships of the matrices thus formed provide an organization and structure which may be carried over to the final simple NCE system material. More specifically, when redispersed, NCE can form entanglements or adhesions with one or more matrices that make up one or more matrices. Physical mixing of a liquid formulation containing redispersed NCE can fragment one or more matrices into smaller ones that are more loosely bound to one another. This bonding of smaller matrices can provide desirable structural stability for simple NCE-based materials. This alignment is compatible with the addition of pulp or pulp-based materials that can act as fillers, etc. The structure of the simple NCE-based matrix allows pulp or pulp-based materials to be incorporated into the overall matrix without substantially impairing their strength, stability, and / or durability.

[0051] In another embodiment, the suspension 120 may be added to another existing matrix 124, as shown in step 5b, to form a composite NCE-containing matrix 128. The redispersed NCE in the suspension 120 may be referred to as “additive NCE” when used in step 5b to be added to the existing matrix 124. In this embodiment, the existing matrix 124 provides a structural framework for the composite NCE-containing matrix, and the NCE is integrated into the composite NCE-containing matrix 128. The existing matrix 124 may provide an amorphous host matrix or produce a more recognizable ordered pattern of atoms or molecules in a regular lattice-like array, as may be found in crystals. In the composite NCE-containing matrix 128, the NCE is inserted into the existing matrix 124 to form the composite NCE-containing matrix 128. The more additive NCE the composite NCE-containing matrix 128 contains, the more the performance of the composite NCE-containing material 128 exhibits the performance that can be contributed to by the NCE. For example, formulations containing additive NCE and pulp-based extenders may provide significant strength to the composite NCE-containing matrix 128, and the presence of pulp-based extenders adds volume to the composite NCE-containing matrix 128, potentially making its production less expensive. Other properties of the composite NCE-containing matrix 128 may be provided in interaction with any structural organization or other properties provided by the existing matrix 124 alone or by the additive NCE.

[0052] In some embodiments, other additive substances may be included in the composite NCE-containing matrix to add or improve desired properties such as malleability, processability, heat resistance, strength, or oleophobic or hydrophobic properties. Such additive substances may be available to or added to the composite NCE-containing matrix 128 before, during, or after the addition of the NCE population redispersed from the suspension 120 to the existing matrix 124. In some embodiments, the existing matrix 124 already contains some or all of the desired additive substances, and their presence is carried over to the composite NCE-containing matrix 128. In other embodiments, the additive substances are included when the redispersed NCE and the existing matrix 124 are combined in step 5b to form the composite NCE-containing matrix 128. In yet another embodiment, the additive substances may be introduced into the composite NCE-containing matrix 128 after it has been formed. The composite NCE-containing matrix 128 having its included additive substances provides a material that can be further processed, shaped, or otherwise formed into a manufactured article. A material containing a composite NCE-containing matrix 128 that provides a structural framework to the material, and further containing any additive substances, may be referred to as a "composite NCE-containing material".

[0053] Both the simple NCE matrix 122 and the composite NCE-containing matrix 128 may be used to provide a structural framework to a material containing redispersible NCE as shown in this figure, such material may be formed or shaped to produce a manufactured article. In other embodiments not shown in this figure, the simple NCE matrix or the composite NCE-containing matrix may be used to provide a structural framework to a material containing redispersible NCE.

[0054] 3. Redispersibility and redispersed nanocellulose elements in plastic substrates for manufacturing articles. As described above, redispersible or redispersed NC elements produced according to the systems and methods disclosed herein may be included in matrices used to form NCE-containing materials, both as components of simple NCE-system materials formed preferentially from redispersible or redispersed NCE, either alone or without another existing matrix, and as components of composite NCE-containing materials including a composite NCE-containing matrix having redispersible or redispersed NCE inserted into an existing matrix. Both simple NCE-system materials and composite NCE-containing materials may be used as components of plastic substrates or plastic substrates that can be formed in other manufactured articles. As used herein, the term “plastic” means a material that incorporates a three-dimensional framework (or “matrix”), retains flexibility, and thus results in a flexible NCE-system or NCE-containing material. Such a plastic material may be formed or shaped from its flexible state into a desired structure, and further fixed in the desired structure, which is held for a specified period. The process of shaping or forming a material from a flexible state into a desired structure can be achieved by many techniques well known in the art, such as extrusion, calendering, injection molding, thermoforming, and blow molding. Similarly, the process of fixing the material into a desired structure can be achieved by many techniques well known in the art, such as heating, application of extended pressure and / or hardening, and incorporation of additives that enable fixing or curing. The specified period for holding the material in a desired structure is determined based on its intended use in the manufactured article and the intended use of the manufactured article itself (e.g., temporary vs. relatively permanent use), as well as the intended process for the disposal of the material and the disposal of the manufactured article at the end of its lifespan.

[0055] a. Simple NCE-based materials Simple NCE-based materials can be used as plastic substrates for forming articles of various shapes, and the mechanical properties of such formed articles depend on the structural framework provided by the matrix of dry, redispersible, or redispersed NCE, which is at least partially incorporated into the simple NCE-based material. Therefore, simple NCE-based materials can be used to form articles that have advantageous mechanical properties such as strength and stability, but can also be remodeled to be dissolvable or decomposable within a reasonable time for consumer use. Such articles are conceived to have relatively temporary durability and can be disposed of by biodegradation or composting.

[0056] For example, this combination of mechanical properties and solubility / degradability allows containers to be sufficiently durable to hold their contents during consumer use, but also to be constructed from materials that are easily degradable at the end of their intended lifespan. As used herein, the term “container” is broadly interpreted to mean any storage container, vessel, or partial or complete enclosure that can be used in conjunction with an item or product to hold, disperse, deliver, separate, suspend, construct, package, store or divide an item or product, or to provide similar functions derived from the partial or complete enclosure of an item or product therein. Exemplary containers include storage containers, vessels or enclosures of any shape and geometry, whether rigid or flexible, and intended for either temporary or permanent use. Non-limiting examples include cylindrical containers such as bottles, jars, cups, straws, barrels, cans, drums, and tubs; containers enclosed in straight lines such as boxes, crates, cartons, and cases; flat storage containers such as plates, trays, dishes, lids, and holders; and delivery systems such as pill capsules or soluble foams for delivering pharmaceuticals, pesticides, or other active ingredients to targeted areas for application, protection, or treatment. Advantageously, containers can provide protection from impact, collision, and mechanical damage, as well as from external environmental elements such as weather, pests, and microorganisms; furthermore, containers can provide protection from the ingress of oil, grease, and water, as well as from leakage of fluids seeping out due to the products they contain. For these reasons, containers are particularly useful for protecting food.

[0057] This combination of mechanical properties and biodegradability also allows containers to be constructed from simple NCE-based materials for intentionally short-term purposes, such as containers for fertilizers or agricultural products intended to decompose over a very short period of time to release the products into the environment. This combination of properties also allows containers to be constructed for delivering activators for purposes such as laundry or other household care, as they dissolve rapidly or immediately upon contact with water. Simple NCE-based materials, whose structure is based on a three-dimensional array of NCE alone, are bio-based overall because they are formed from NC elements. Therefore, they offer a significant alternative to petroleum-derived formulations used to produce conventional manufactured articles used for similar purposes and provide vehicles for remaking combinations of mechanical properties and solubility to match the specific purpose of the article.

[0058] A significant limitation to the use of simple NCE-based materials is their vulnerability to oils, greases, and water: simple NCE-based materials tend to offer virtually no inherent resistance to the ingress and passage of water or oils / greases into the material, and are often made from NCE in combination with other, often cheaper filler materials, such as pulp and pulp-derived materials. This vulnerability is exacerbated by the cost of NCE itself: NCE can be mixed with cheaper extenders or fillers to reduce the overall cost of the NCE-based material. Pulp or pulp-derived materials are frequently used for this purpose. However, such materials, referred to as "pulp-dominant," are particularly susceptible to the effects of water and greases. In pulp-dominant materials without any other treatment, exposure to water or oils / greases can result in a loss of structural strength or an actual loss of integrity of the formed articles made from such materials.

[0059] As used herein, the term “pulp-dominant” means a matrix or material in which pulp or pulp-based material is present in sufficient quantity to have a substantial effect on the material’s mechanical properties. A pulp-dominant matrix may require further NCE or other reinforcement to make it as strong, stable, or durable as a non-pulp-dominant simple NCE-based material, depending on the material’s final intended use; further, such material may be treated with barrier formulations to make them resistant to the effects of water, oil, and grease, depending on the NCE-based material’s final intended use. For example, a pulp-dominant simple NCE-based material may be used to form sheets for personal care items such as cosmetic paper or toilet paper with little or no further reinforcement, while a similar material intended for use as paper towels may require more reinforcement because its final intended use requires greater strength and resilience. A pulp-dominant material may also benefit from treatments to improve its oil and grease resistance and / or its water resistance, depending on the final intended use for such material.

[0060] Therefore, simple NCE matrix can be treated with formulations that impart oil and grease resistance (oleophobicity) and / or water resistance (hydrophobicity) to the matrix itself or to these materials containing such a matrix. Water resistance in a material is often measured by the water vapor transfer rate, which is expressed as gm / m 2 Units are / day or g / 100in 2 The permeability of a material to water vapor is measured daily; therefore, the term “water resistance” (WR) includes resistance to liquid water and resistance to water vapor. Thus, oil and grease resistance (OGR) and water resistance (WR, and together with OGR, “OGWR”) properties can be incorporated into the material itself or articles formed therefrom. These OGWR properties may also be called “barrier properties,” and the substance or formulation that produces barrier properties may be called a “barrier-producing formulation” or “barrier formulation.” A “barrier substance” refers to a substance that produces barrier properties. Both oil / grease resistance (or oleophobicity) and water resistance (or hydrophobicity) may be individually referred to as barrier properties.

[0061] Barrier properties can be tuned within a simple NCE-containing material to allow differential permeability of the material to various fluids (whether oil, grease, or water). For example, in some embodiments, a barrier-forming formulation can impart both OGR and WVR properties to the article it processes, and the relative intensity of each property can be adjusted by adjusting a component selected for the formulation itself and / or by adjusting the relative amount of that component, for example, to emphasize hydrophobicity or oleophobicity.

[0062] In some embodiments, NCE alone, or NCE modified with barrier-forming materials such as lignin, wax, or fatty acids, can impart some degree of oleophobicity or hydrophobicity to simple NCE-based materials, and their concentrations can be adjusted to optimize these barrier properties. Without being constrained by theory, it is believed that dense encapsulation of NCE can enhance the barrier properties they provide. Furthermore, regardless of their inherent hydrophilicity, NCE (either alone or modified with barrier-forming materials) can be sufficiently densely encapsulated in simple NCE-based materials under certain conditions, imparting water-resistant or water vapor-resistant barrier properties to these materials.

[0063] In some embodiments, a wide range of additive components may be combined to provide desired barrier properties. For example, a barrier-forming formulation suitable for use with a simple NCE matrix may contain cellulose ethers such as methylcellulose and / or resin acids. Alternative cellulose components for barrier-forming formulations include, but are not limited to, CMC (carboxymethylcellulose), CMCNa (sodium carboxymethylcellulose salt), CA (cellulose acetate), CDA (cellulose diacetate), cellulose triacetate (CTA), CAB (cellulose acetate butyrate), CAPh (cellulose acetate phthalate), CAP (cellulose acetate propionate), EC (ethylcellulose), HEC (hydroxyethylcellulose), EHEC (ethyl hydroxyethylcellulose), HPC (hydroxypropylcellulose), HPMC (hydroxypropyl methylcellulose), HPMCP (hydroxypropyl methylcellulose phthalate), and HPMCAS (hydroxypropyl methylcellulose acetate). Methylcellulose is particularly advantageous in barrier formulations for simple NCE-based matrices due to its oil and grease resistance, high viscosity, and its characteristic low critical solution temperature (LCST) that causes gelation when heated. Resin acids and their combinations (rosin, gum rosin, pitch, etc.) can be used alone or in combination with methylcellulose to provide water resistance. Cellulose acetate is also a particularly advantageous component in barrier formulations, especially food and beverage containers, assuming that it can produce both oleophobic and hydrophobic properties.

[0064] More specifically, resin acids are bio-derived rubbers that are sticky and water-insoluble in their natural state, and are based on empirical formula C 19 H 29These are characterized as unsaturated diterpene carboxylic acids having a COOH group and a phenanthrene ring structure. Examples of resin acids include abietic acid, pulstolic acid, levopimaric acid, neoabietic acid, dehydrogenated ibuptic acid, pimaric acid, isopimaric acid, and sandaracopimalic acid. They can be divided into two categories, abietic-type resin acids and pimaric-type resin acids, according to their chemical structure. The monomeric molecules of abietic-type resin acids have two conjugated double bonds and one isopropyl group. Dehydrogenated abietic acid, abietic acid, pulstolic acid, and levopimaric acid are examples of abietic-type resins. The monomeric molecules of pimaric-type resins have methyl and vinyl at the C13 position and two independent double bonds. This type of structure is mainly found in the resins and pine resins of pine, such as pimaric acid, isopimaric acid, sandaracopimalic acid, and pimaric resin acids.

[0065] The carboxyl groups (one or more) of resin acids can react with polyols (e.g., glycerol, erythritol, etc.) to form esters (thus, three or four resin acid molecules can bond together to form basic resin acid construct blocks, e.g., "oligomers" of abietic acid). Resin acids tend to be glassy and rigid at room temperature. Depending on plasticization, they can soften with increasing temperature and the amount of plasticizer used. Resin acids are compatible and miscible with various oils / waxes to modulate their thermal or physical properties (e.g., glass transition temperature, malleability, and hydrophobicity, but not limited to these). For example, beeswax and carnauba wax are soluble in certain resin acids, thus affecting their melting point and glass transition temperature, while also decreasing their solubility in the solvent. Other examples of suitable oils and waxes for mixing with resin acids include, but are not limited to: • Mineral oil and wax (paraffin) Beeswax Carnauba wax • Linseed wax Candelilla ·lard • Coconut oil Flaxseed oil • Eucalyptus essential oil • Cocoa butter ·Sweet tonsil oil ·olive oil Palm oil Castor oil • Sunflower oil Canola oil These are some examples.

[0066] The proportions of these components in the barrier-forming formulation are adjusted to optimize its OGR and WVR properties, so that the desired amount of OGWR in the simple NCE-based material formed by adding a specific barrier-forming formulation to a simple NCE-containing matrix can be skillfully managed.

[0067] The block diagram in Figure 2 schematically illustrates how barrier-forming formulations may be added during the formation of a simple NCE system matrix and its subsequent processing. Process 200 in Figure 2 begins by providing a dry material 202 containing redispersible NCE, therein prepared substantially as described with respect to Figure 1. The dry material 202 containing redispersible NCE is then ground / minced and used as a dry component or suspended in a resuspension fluid 204 to resuspend the NCE in the dry material 202 and form a suspension 208 of redispersed NCE of a desired concentration, substantially as described with respect to Figure 1. The suspension 208 of redispersed NCE is then subjected to drying 210 to produce a simple NCE system matrix 212, which can then be used to form a simple NCE system material substantially as described with respect to Figure 1. Barrier-forming formulations 214 may be added at points A, B, C and / or D. More specifically, the barrier-forming formulation 214 may be added as part of step 206, and the dried material 202 containing redispersible NCE is treated with the resuspension fluid 204 to produce a suspension of redispersed NCE 208. For example, the barrier-forming formulation 214 may be added to the redispersion fluid 204 as indicated by its introduction at point A. The barrier-forming formulation 214 may also be added to the suspension of redispersed NCE 208 as indicated by its introduction at point B. The barrier-forming formulation 214 may also be added during the drying step 210 in which the suspension of redispersed NCE 208 is treated, ultimately forming a simple NCE-based material 212 as indicated by its introduction at point C. Finally, the barrier-forming formulation may be added to the simple NCE-based material 212 as indicated by its introduction at point D. Although a single barrier-forming formulation 214 is shown in this figure, it will be understood that multiple barrier-forming formulations or barrier-forming formulation components may be added at different introduction points. The first barrier-forming formulation may be added at one introduction point, and the second barrier-forming formulation may be added at a second introduction point. The barrier-forming formulations and combinations of their components may be introduced at any point during the process using methods well known in the art, such as (without limit) mixing them in the formulation, spraying them onto or into a designated substrate, or coating them onto its surface.Such barrier-forming formulations may contain redispersed NCE to enhance performance and act as a pore-closing agent in their interaction with the surface of existing NCE-containing materials to which the coating is deposited. Barrier-forming formulations without redispersed NCE may also be applied to impart enhanced performance.

[0068] Examples of formulations for spraying onto or into a substrate include:

[0069] Exemplary formulations (by weight relative to the total weight of 100g of formulation) for creating oil, grease, and water-resistant barriers used as coatings are: • Cellulose acetate butyrate (CAB): 10g Rosin: 10g Acetone: 79g • Plasticizer (e.g., but not limited to triacetin, triethyl citrate, triethyl acetyl citrate, tributyl citrate): 1g Includes.

[0070] Exemplary formulations (by weight relative to the total weight of 100g of formulation) for creating oil, grease, and water-resistant barriers used as coatings are: Methylcellulose (MC): 3g • Redistributed NCE (NFC or MFC or a combination of them): 1g ·Water: 54g • Rosin: 4g • Ethanol or acetone: 38g This includes the following: Here, MC is solubilized in water and then combined with redispersed NCE. Simultaneously, rosin is solubilized in either ethanol or acetone. The two solutions can then be combined to create an OGWR barrier.

[0071] An example formulation for hydrophobic coatings includes the following components (by weight relative to the total weight of 100g of the formulation) that are combined to form a solution in acetone: Cellulose acetate (CA): 3.5g Ethanol: 7g Acetone: 82.5g • Gum rosin (GR): 7g Includes.

[0072] An example formulation for an oleophobic coating is the following components (by weight relative to the total weight of 100g of the formulation) that are combined to form an aqueous solution in water: Methylcellulose (or any cellulose ether): 75g • Redistributed NCE (NFC or MFC or a combination of them): 25g Includes.

[0073] More specifically, exemplary simple NCE-based materials having OGWR properties can be prepared as follows, and the barrier-forming formulation is added to a redispersible or redispersed suspension of NCE. A redispersible (in this case, redispersed) suspension of NCE prepared as described above is provided, to which methylcellulose (MC) is added with or without a sugar alcohol plasticizer (glycerol, xylitol, maltitol, sorbitol, erythritol, mannitol, etc.). The addition of these components is intended to produce oleophobicity. Such a redispersible or redispersed suspension of NCE may contain NFC, MFC, or both. Such a redispersible or redispersed suspension of NCE may also contain fillers, such as pulp or pulp-based components, to provide a larger volume to the final simple NCE-based matrix and the resulting material. Separately, rosin solutions are prepared by mixing rosin with an alcohol or ketone solvent (e.g., ethanol or acetone) to achieve a 10-100 wt% (wt rosin / wt solvent) rosin solution in the solvent. After preparing this solution, the solution can be emulsified in water using the properly dissolved rosin, preferably using a linear homogenizer with polyethylene glycol (PEG) at 1-25% relative to the weight of the rosin, or the solution can be directly mixed with a redispersible or redispersed MC-containing suspension of NCE. A small amount of solvent used to prepare the mixture may be added to the NCE suspension before adding the rosin mixture to facilitate homogenization. The mixing process can be carried out vigorously, for example, by slowly pouring the rosin-based formulation onto the NCE-containing resuspension with moderate to high shear force, or by spraying the solution as a fine mist with relatively low shear force, so that the fine rosin suspensions in the liquid phase aggregate through the MC-NCE-containing suspension. It is advantageous to add a rosin solution as a high-pressure flow or to prepare an aqueous emulsion, and the rosin granular size is small. After combining these components, the resulting mixture can be dried and processed to produce a simple NCE matrix, which can yield a simple NCE material.

[0074] Rosin addition improves the hydrophobicity of the matrix. The hydrophobicity of rosin can be increased by heat-treating the rosin before dissolving it in the solvent, for example, by heating the rosin at about 200°C for about 10-30 minutes to remove impurities such as terpentine. Heat treatment also increases the softening point of the rosin from 45°C to 59°C, making it more elastic when subjected to heat during the later stages of treatment. In some embodiments, rosin may be loaded in an amount of about 35 wt% relative to the dry pulp weight, but amounts of rosin in the range of about 1 wt% to about 50 wt%, about 1 wt% to about 10 wt%, about 8 wt% to about 25 wt%, about 20 wt% to about 40 wt%, or about 35 wt% to about 55 wt% relative to the dry pulp weight may be used. In some embodiments, the ratio of redispersible or redispersed NCE to MC is about 1:3. Other ratios of NCE to MC in the range of 5:1 to 1:3 may be used.

[0075] A simple NCE matrix with OGWR properties can be prepared by combining the above-mentioned components. This matrix can then be formed into a simple NCE material that can be used to produce manufactured articles. Retention aids can be added to the simple NCE matrix to improve the retention of other additives in the simple NCE material. Retention aids, which are typically cationic polymers or surfactants, are well known in the paper industry; for example, substances such as chitosan or PDADMAC can be used as retention aids.

[0076] In exemplary embodiments, the OGR and WVR materials disclosed herein may be used as barrier-forming formulations together with simple NCE-based materials, either as coatings applied to the surface of a material or as mixed additives. More specifically, the OGR and / or WVR formulations may be used as coatings or mixed with simple NCE-based materials as described above, which may then be formed into a product (e.g., thermoformed).

[0077] As an example, a container or part of a container formed from a simple NCE-based material having OGR and / or WVR properties is prepared, enabling the container to reliably contain liquids, gels, or wet solids for delivery to consumers for other purposes. Such simple NCE-based materials may be pulp-dominant, and appropriate adjustments of the amounts of NCE and barrier-forming formulations are made based on the amount of pulp or pulp-based material they contain. In embodiments, the barrier-forming formulation may also be applied to the surface of the simple NCE-based material before its formation or shaping into a formed article, or the barrier-forming formulation may be applied to a formed article after formation or shaping has taken place. For example, the barrier-forming formulation may be applied surfacely to a precursor material or a manufactured article using conventional coating procedures such as paint or blade coating, curtain coating, or by spraying if the formulation has a viscosity that is compatible with a selected spraying apparatus. In other embodiments, the barrier-forming formulation may be incorporated into a simple NCE-based formulation at any concentration (as described above); the mixture may then be heated to slightly above the low critical solution temperature of the LCST polymer components of the barrier-forming formulation before molding / thermoforming. This procedure involves dispersing the LCST polymer within the mixture and allowing it to precipitate (or fall) onto the fibers or surface of a simple NCE-containing matrix structure.

[0078] In some embodiments, a filler, such as pulp or a pulp-based material, may be added to a simple NCE matrix to form a pulp-dominant simple NCE material as described above. In such a material, NCE may interact with the pulp or pulp-based filler so that it coats them or fills the pores between the pulp fibers or the fibers of the pulp-based material. In this capacity, the simple matrix(s) formed within the simple NCE material may act as a pore-closing agent, filling gaps in the pulp material. This pore closing allows this type of simple NCE material to be used with pulp or a pulp-based material to form high-value special paper products having properties that reflect the behavior of the NCE matrix. As an example, since an embedded NCE matrix blocks pores in the paper material that would otherwise allow oils to pass into the product, a paper product with an NCE matrix embedded in its pores may provide or improve oil and grease resistance (particularly with respect to other barrier materials). As another example, a paper product with NCE embedded in its pores may be remodeled to form a releasable label backing or selective adhesive. In one embodiment, the barrier-forming formulation described above may be added to a simple NCE-based material to enhance the effect of the NCE matrix as a pore-closing agent by imparting, for example, oleophobic or hydrophobic properties to the material, which can then be carried over to a product of the type of pulp-dominant paper produced therefrom.

[0079] In some embodiments, filler particles may be added to simple NCE-based matrices and materials to provide a bulking effect and / or to act as pore-closing agents. These filler particles may be used in addition to or in place of barrier-forming formulations; in either case, the filler particles may interact with pulp fibers and simple NCE matrices to impart barrier properties such as oleophobicity and / or hydrophobicity; furthermore, the filler particles may influence mechanical properties such as strength, toughness, flexibility, and elasticity.

[0080] Such filler particles may include, but are not limited to, large or small particles of any shape made from natural or artificial materials and produced by any processing method (e.g., physical grinding, precipitation, emulsification), or mixtures of different sizes and shapes, such as organic or inorganic components; for example, particles useful for this purpose may include, but are not limited to, sand particles, ceramic particles, biomass materials or particles, mineral particles, resin materials, glass materials, polymeric materials, rubber materials, composite granular materials, chemically active materials such as fatty acids, surfactants, and sugar alcohols, organic materials such as wood or nut shells that have been finely ground, crushed, pulverized or broken to an appropriate size (e.g., walnuts, pecans, coconuts, almonds, ivory palms, Brazil nuts, etc.), seed shells or fruit kernels that have been finely ground, crushed, pulverized or broken to an appropriate size (e.g., plums, olives, etc.) Finely ground, crushed, pulverized or broken materials of other plant origin such as peaches, cherries, apricots, etc., coffee grounds, pine cone pollen, sisal hemp, rice husk ash, rice husks, coconut shells, cotton stalks, corn cobs, etc., certain inorganic particles, such as solid glass, glass microspheres, fly ash, silica, alumina, fumigated carbon, carbon black, graphite, mica, boron, zirconia, talc, kaolin, titanium dioxide. This may include, but is not limited to, halogenated (chlorinated or bromised), phosphorus-based, nitrogen-based, inorganic / mineral-based flame retardants such as hexabromocyclododecane (HBCD), triphenyl phosphate (TPP), tricresyl phosphate (TCP), isopropylated phenol, phosphate 3:1 (PIP 3:1), etc., as well as combinations or composites of these or similar different materials.In some embodiments, plant-derived organic materials, such as (without limiting) wood or nut shells that have been finely ground, crushed, pulverized or broken to an appropriate size (e.g., walnuts, pecans, coconuts, almonds, ivory palms, Brazil nuts, etc.); seed shells or fruit kernels that have been finely ground, crushed, pulverized or broken to an appropriate size (e.g., plums, olives, peaches, cherries, apricots, etc.); coffee grounds, pine cone pollen, sisal, rice husk ash, rice husks, coconut shells, cotton stalks, etc.; and other plant-derived finely ground, crushed, pulverized or broken materials such as corn cobs are particularly advantageous for use as filler particles.

[0081] Advantageously, in one embodiment, filler particles may be selected that are naturally hydrophobic or can be made hydrophobic by linking or coating the particles with a hydrophobic material, such as stearic acid or oleic acid (e.g., functionalized PCCs). In one embodiment, the filler particles may contain wax either as the substance of the particles themselves or as a coating for other particles, and these waxes may be in wax form or emulsion form (oil-in-water wax emulsion). For example, waxy substances such as beeswax, soy wax, and carnauba wax may be used either as substrate particles or as a coating for other filler particles. As used herein, the term “wax” means any hydrocarbon that is a lipophilic and malleable solid having a melting point typically higher than about 40°C near ambient temperature. Examples of waxes include long-chain aliphatic hydrocarbons having typically 20 to 40 carbon atoms per molecule or fatty acid / alcohol esters having typically 12 to 32 carbon atoms per molecule, such as myricyl cellotates found in beeswax and carnauba wax. The filler particles can be mixed into a barrier-forming formulation to impart a pore-sealing function.

[0082] b. Composite NCE-containing material Composite NCE-containing materials, formed from composite materials in which redispersible or redispersed NCE is integrated into an existing matrix, can be used as plastic substrates for forming a variety of products. After mixing them with the existing matrix, the additive NCE can be utilized as particles or as more elongated fibrous structures, aligning themselves in a straight or randomly oriented manner, and combined with the existing matrix embedded within the composite NCE-containing material to form a network or other internal structure. In some embodiments, the three-dimensional matrix framework of the existing matrix material is coated with and / or immersed therein to form a composite NCE-containing matrix, and the presence of the additive NCE imparts specialized properties that exceed or are not found in the existing matrix. For example, composite NCE-containing materials can exhibit specialized mechanical properties such as strength, hardness, toughness, brittleness, rigidity, cohesiveness, durability, impact resistance, and light transmittance, where the presence of NCE in the composite NCE-containing material produces or enhances these specialized mechanical properties.

[0083] As another example, composite NCE-containing materials may exhibit specialized barrier properties, such as OGWR properties, that may be present in the existing matrix but are enhanced in the composite NCE-containing material, or that are absent in the existing matrix but provided in the composite NCE-containing material. In some embodiments, NCE alone or NCE modified with barrier-forming materials, such as lignin, wax, or fatty acids, may impart some degree of oleophobicity or hydrophobicity to the composite NCE-containing material, and their concentrations may be adjusted to optimize these barrier properties. Without being constrained by theory, it is thought that dense packing of NCE can enhance the barrier properties they provide. Furthermore, regardless of their inherent hydrophilicity, NCE (either alone or modified with barrier-forming materials) can be packed sufficiently densely in a composite NCE-containing material to impart water-resistant or water vapor-resistant barrier properties to these materials under certain circumstances.

[0084] Combining redispersible or redispersed NCE with an existing matrix may allow the presence of NCE to act as a pore-closing agent in its interaction with the existing matrix. Under these circumstances, redispersible or redispersed NCE may interact with the existing matrix, either coating it or filling pores or gaps in the network structure provided by the existing matrix. In some embodiments, these pore-closing effects may be enhanced when used in combination with other oil- and grease-repellent additives. In this ability, NCE and any matrix they form may act as pore-closing agents, filling gaps in the existing matrix, thereby acting as a plug to prevent certain molecules, such as oils and greases, from passing through the composite NCE-containing matrix. This mechanism is similar for simple NCE-based materials as it is for NCE itself in terms of behavior or as a pore-closing agent. Furthermore, filler particles may be added to the composite NCE-containing matrix in the same way that filler particles may be added to a simple NCE-based matrix. The role of filler particles has been described in detail above with respect to simple NCE-based materials; this description may be applied to the use of filler particles for composite NCE-containing materials with necessary modifications. Briefly, filler particles may be added to composite NCE-containing matrices for bulking effect and / or act as pore-closing agents for simple pulp-based matrices, either alone or in combination with other barrier materials. In various embodiments, filler particles may be used in addition to or in place of barrier-forming formulations; in any case, filler particles may interact with existing matrices and / or composite NCE-containing matrices to impart barrier properties such as oleophobicity and / or hydrophobicity.

[0085] More generally, the process of preparing composite NCE-containing materials from composite NCE-containing matrices can be modified to produce desired material properties. The generation of OGWR properties by incorporating barrier-forming formulations in such materials is one example of how composite NCE-containing matrices can be modified to produce such material properties. Existing matrices can be prepared to be particularly suitable for combining with redispersible or redispersed NCE in order to form composite NCE-containing matrices and to produce composite NCE-containing materials. For example, the degree of flexibility in products formed from composite NCE-containing materials can be finely tuned by changing the composition of the existing matrix, the amount of additive NCE used in the existing matrix to form the composite NCE-containing matrix, and / or the amount of various additives intended to optimize the properties of the final composite NCE-containing material. By selecting appropriate additives and polymers for the existing matrix into which the NCE is integrated to form the composite material, such additives, along with biodegradability, can produce properties such as structural strength, resilience, elasticity, water resistance, oil and grease resistance in the manufactured articles formed therefrom.

[0086] The block diagram in Figure 3 schematically illustrates how barrier-forming formulations may be added during the formation of the composite NCE-containing matrix and subsequent processing. Process 300 in Figure 3 begins with providing a dry material 302 containing redispersible NCE, such dry material 302 is prepared substantially as described with respect to Figure 1. The dry material 302 is then treated with a resuspension fluid 304 in a resuspension step 306 to form a suspension 308 of redispersed NCE, substantially as described with respect to Figure 1. The suspension 308 of redispersed NCE is then combined with an existing matrix 310 to produce a composite NCE-containing matrix 312, substantially as shown in step 5a of Figure 1. The composite NCE-containing matrix 312 may be combined with additives and / or further processed to form a composite NCE-containing material 314. The barrier-forming formulation 318 may be added at points A and B, substantially as described with respect to Figure 1. Alternatively or additionally, the barrier-forming formulation 318 may be added at one or more points W, X, Y, and Z. More specifically; the barrier-forming formulation 318 may be added so that the suspension 308 of redispersed NCE 308 is mixed with the existing matrix 310, as indicated by point W; the barrier-forming formulation 318 may be added to the existing matrix 310 before it is mixed with the suspension 308 of redispersed NCE, as indicated by point X; the barrier-forming formulation 310 may be added to the composite NCE-containing matrix 312 so that it is treated to become the composite NCE-containing material 314, as indicated by point Y; and / or the barrier-forming formulation 310 may be added to the composite NCE-containing material 314, as indicated by point Z. Advantageously for this last type of application, the barrier-forming formulation may be sprayable to allow for easy application to either the surface of the composite NCE-containing material 314 or the surface of a formed article manufactured therefrom (not shown). Although this figure shows a single barrier-forming formulation 318, it is understood that multiple barrier-forming formulations or components of barrier-forming formulations may be added at different introduction points W, X, Y, or Z. A first barrier-forming formulation may be added at one introduction point, and a second barrier-forming formulation may be added at a second introduction point.A combination of formulation and / or barrier-forming formulation components may be introduced at any point during the process.

[0087] In this embodiment, barrier-forming formulations containing biopolymers may be prepared as additives to impart OGWR properties or other useful properties to composite NCE-containing materials, as well as how additives may be used in conjunction with barrier-forming formulations combined with simple NCE-based materials. Such additives may be added to barrier-forming formulations, which may then be combined with composite NCE-containing matrices as described above. Examples of biopolymers include biopolyesters such as polyhydroxy-alkanoates and polylactic acid derivatives. Advantageously, certain exopolysaccharides, such as pullulan, kefiran, cellulose, levan, guerane, etc., may be used to form films, which may be advantageous for these barrier-forming formulations and useful articles produced therefrom, which are used as coatings for composite NCE-containing materials. Such biopolymers may also include, but are not limited to, exopolysaccharides such as bacterial cellulose, kefiran, pullulan, levan, guerane, other naturally occurring polysaccharides such as arginine, lignin, carrageenan, gum arabic, starch, and plant glucomannan-like locust bean gum, mannan, guar gum, etc., and cellulose derivatives. As used herein, these products prepared by modification of natural cellulose polysaccharides are referred to as “cellulose derivatives,” “cellulose polymers,” or “cellulose-derived products (cellulosic).” Such modifications may include chemical modifications, such as cellulose degradation and derivatization of -OH groups. Acids / bases, oxidizing agents, biopharmaceuticals, and mechanical treatments are all examples of degradation reactions. Modifications that introduce novel functional groups to the cellulose backbone include carboxymethylation, oxidation, and addition reactions. Other reactions such as esterification, acylation, transplantation, and esterification can also produce cellulose derivatives. Other examples of reactions that produce cellulose derivatives are well known in the art.

[0088] While various specialized properties of composite materials using NCE have already been envisioned in industry, their use has been hindered by the previously mentioned redispersion problems. The redispersion techniques disclosed herein facilitate the transport of NCE compositions that can be concentrated or dried and then resuspended to combine with an existing matrix to produce a composite NCE-containing material. In some embodiments, these redispersion techniques can produce a homogeneous mixture of high-aspect-ratio NCE within the main matrix-forming material, enabling the enhancement of desired specialized properties of the final composite, including mechanical properties such as those described above. In other embodiments, NCE formulations prepared using the redispersion techniques disclosed herein can be prepared to introduce or enhance specialized properties, such as barrier properties, which enable the composite NCE-containing material to have a desired degree of oil and grease resistance and / or water vapor resistance.

[0089] Redispersible or redispersed NCEs prepared as described herein can act as fillers in composite NCE-containing matrices. Fillers are understood to improve the mechanical and barrier properties of materials such as organics and plastics, and / or make them more economical to manufacture or transport, for example, by requiring less expensive components or by making them lighter. Redispersible and redispersed NCEs prepared as described herein can also be combined with other fillers, such as pulp or pulp-based materials, to increase the final volume of composite NCE-containing matrices while maintaining strength during the presence of additive NCEs. Although NCEs are already used as fillers in plastics, their use is limited by their resistance to redispersibility.

[0090] The methods for NCE redispersion disclosed herein may enable a wider range of applications for NCE, such as reinforcement of composite materials and plastic substrates, and may further allow for a dramatic expansion of novel applications. As used herein, the term “reinforcement” means an improvement in mechanical properties found in an existing matrix, belonging to strength, hardness, toughness, brittleness, rigidity, cohesiveness, flexibility, durability, or impact resistance, or the provision of such mechanical properties if they are not already present in the existing matrix. A composite NCE-containing matrix having improved mechanical properties compared to an existing matrix may be referred to as “reinforced” by the reinforcement of the composite NCE-containing matrix due to the presence of NCE. NCE can be used as a filler in a variety of environments, as the examples above illustrate.

[0091] In one embodiment, the composite NCE-containing matrix is ​​formed from an existing petroleum-derived matrix into which redispersible or redispersed NCE is incorporated. In another embodiment, the composite NCE-containing matrix is ​​formed from an existing bio-based matrix into which redispersible or redispersed NCE is incorporated.

[0092] i. Existing petroleum-derived matrix In some embodiments, petroleum-derived polymers are used to form an existing matrix that is combined with an additive (redispersible or redispersed) NCE to form a composite NCE-containing matrix having advantageous properties. Various petroleum-derived polymers can be used as existing matrices to form a composite matrix using NCEs such as polyvinyl alcohol, high-density polyethylene, low-density polyethylene, polyvinyl chloride, acrylonitrile butadiene styrene, polypropylene, polylactic acid, polybutylene succinate, polyethylene succinate, and polypropylene succinate. The addition of NCEs to these matrices can provide specialized properties such as increased mechanical properties, such as increased strength and / or flexibility, or barrier properties, such as oleophobic or hydrophobic properties or water vapor resistance properties. Furthermore, redispersible or redispersed NCEs can be added to the matrix as components in a formulation that also includes a filler, such as pulp or pulp-based material. Such a formulation can provide an additional volume of NCE components to the resulting composite NCE-containing matrix while retaining or improving their mechanical properties compared to the existing matrix. The use of such formulations containing redispersible or redispersed NCE and bulking agents may reduce the need for other expensive components, thereby lowering the overall cost of the resulting composite NCE-containing matrix and the materials produced therefrom.

[0093] However, the use of redispersible or redispersed NCE as an additive NCE combined with an existing hydrophobic matrix presents difficulties because NCE itself is hydrophilic. Incorporation of additive NCE into an existing hydrophobic matrix may present problems due to the weak interfacial strength between the hydrophobic polymer matrix and the hydrophilic NC elements, but redispersible or redispersed NCE can be further modified to become more hydrophobic, resulting in a stronger interface. For use in hydrophobic environments, NCE can be surface-modified to match the properties of the existing hydrophobic matrix into which they are incorporated, so that they become compatible with the existing matrix and can be regularly dispersed within it. In some embodiments, surface modification of additive NCE prepared according to the methods disclosed herein can be carried out, for example, by using a hydrophobic monolayer on the NCE. Methods for this modification may include silane coupling, alkali treatment, acetylation, carbonylation, TEMPO oxidation, polymer transplantation, bacterial modification, surfactant addition, and the like. In some embodiments, hydrophobized NCEs for use in hydrophobic matrices may be prepared such that they are not only redispersible upon drying but also compatible with various existing hydrophobic polymeric matrices, such as thermoplastic and thermosetting matrices (e.g., polypropylene, polyethylene, polystyrene, polyester, poly(acrylate / methacrylate), rubber, silicone, urethane, epoxy, etc.), for their hydrophobic coating, resulting in strong, lightweight composite NCE-containing materials for further processing to provide manufactured articles. Other modifications may include the incorporation of other additives having polar heads and nonpolar tails (e.g., fatty acids or surfactants) that enhance interfacial adhesion between the hydrophobic matrix and the hydrophilic NCE; it is understood that these additives may interact with both the hydrophobic matrix and the hydrophilic NCE to improve their adhesion to each other.

[0094] As previously described, other additives to obtain desired properties may be added to a composite NCE-containing matrix to produce a composite NCE-containing material useful as a plastic substrate. Such additives may be added at any stage in the production of a composite NCE-containing material, for example, to an existing matrix or composite NCE-containing matrix or composite NCE-containing material. For example, plasticizers such as phthalates may be used to make the material more flexible and versatile. Such a composite NCE-containing material containing plasticizers can then be formed by conventional techniques such as extrusion, calendering, injection molding, thermoforming, and blow molding to produce formed articles. The redispersed NCE embedded in the composite NCE-containing matrix acts as a reinforcing agent, such as a filler, particle, or fiber, to improve the mechanical properties of the material softened by the plasticizer.

[0095] In this embodiment, redispersed NCE may be added to improve the mechanical properties of recycled petroleum-derived plastics, i.e., plastic materials containing petroleum-derived polymers, which are derived from recycled plastic materials. Thus, plastic waste can be repurposed to produce various forms of articles, but significant deterioration of material properties can occur during the recycling process, largely due to high heat and mechanical stress. Furthermore, contamination of the recycling stream generally occurs due to a lack of consumer awareness about proper recycling practices and misclassification at recycling facilities. Both deterioration (molecular weight reduction, chain breakage, defects, etc.) and the presence of impurities contribute to a reduction in the strength of recycled plastics compared to their unused counterparts. Incorporating redispersed NCE into recycled plastic feedstock can increase the weakened matrix. NCE can be combined with recycled plastics in powder, flake, or other forms. The recycled plastic feedstock can be a mixture of specific polymers or copolymers, and it can also be a mixture of various recycled plastics. Redispersed NCE can be combined with recycled feedstock before or during heat treatment. For example, the redispersed NCE can be fed into an extruder for mixing and dispersion, and the recycled molten polymer feed material is processed through a screw. The resulting articles may be suitable for single-use applications such as food and kitchenware (e.g., table cutlery, plates, and straws) or consumer product packaging, or for long-term applications such as furniture like tables, chairs, and cabinets.

[0096] ii. Existing bio-based matrices In some embodiments, a bio-based polymer is used to form an existing matrix that is combined with additive NCE to form a composite NCE-containing matrix having advantageous properties. Under these circumstances, all structural components of the composite NCE-containing matrix are bio-based, as are the composite NCE-containing material formed from the composite NCE-containing matrix. This composite NCE-containing material can be used as a plastic substrate formed in manufactured articles. Fabricating this plastic substrate from bio-based components (i.e., redispersible or redispersed (additive) NCE and a bio-based existing matrix) offers sustainability advantages in both eliminating reliance on petrochemical raw materials and facilitating the decomposition and disposal of products formed from such plastic materials.

[0097] In these embodiments where bio-based polymers are used to form an existing matrix, the constitutive bio-based polymer forming the existing matrix may be a homopolymer, copolymer, polymer mixture, or any combination thereof. Additive components may be combined with the constitutive bio-based polymer to optimize the properties of the existing matrix. For example, cellulose acetate (CA) and cellulose butyrate (CAB) may be mixed together in an acetone solution or mixed together in a molten state under high shear forces such as extrusion to form an existing matrix; alternatively, one of the two cellulose polymers may be used independently. Additional or alternative cellulose polymers that may be used in the existing matrix include cellulose acetate propionate, methylcellulose, hydroxypropyl methylcellulose, hydroxypropyl cellulose, sodium carboxymethylcellulose, carboxymethylcellulose, cellulose acetate phthalate, hydroxyethylcellulose, chitosan, and the like. Polyhydroxyalkanoates (PHAs), including poly-3-hydroxybutyrate (PHB), polyhydroxyvalerate (PHV), and polygydroxyhexanoate (PHH), may also be used to form a matrix. Polybutylene succinate (PBS), polybutylene succinate co-adipate (PBSA), and the like, made from biomass, may also be used to form a matrix. In some embodiments, one or more plasticizers may be added to an existing matrix to soften it and increase its flexibility. Bio-based plasticizers may be added to an existing matrix and may include fatty acids, polyols, epoxidized triglyceride vegetable oils, alkyl esters of adipic acid and citrate, etc.; examples of such plasticizers, without limitation, include triglycerin, tributyl citrate, triethyl citrate, triethyl acetyl citrate, polyethylene glycol, epoxidized soybean oil, oleic acid, etc.Bio-based resinous materials, such as gum rosin, may be added to an existing matrix to hydrophobize, harden, and / or bond it to limit its degree of flexibility; such materials have other advantages, such as acting as an adhesive-like substance to fix matrix fragments together or to form crosslinks between them. Such materials may have the further advantage of aiding the hydrophobicity of the matrix and any subsequent materials derived therefrom, if water resistance is desired for the final application. Further additives may be included to optimize the material properties for the final use application. For example, fillers and bulking agents may be included: pulp may be added to an existing matrix as a filler or bulking agent to reduce costs and improve composition; wood flour, sawdust, ash, mineral powder, lignin, and other low-cost filler granules may be used to reduce costs and / or to close pores in the matrix; precipitated calcium carbonate and stearic acid may be added to an existing matrix to improve hardness and hydrophobicity; precipitated calcium carbonate may be added alone to act as a nucleating agent or to provide brightness. Alternatively, or in combination with other additives, oil-glue-resistant and / or water-resistant (OGWR) formulations can be incorporated into existing matrices to obtain hydrophobic and oleophobic properties as desired. Biodegradation-promoting additives can be used to aid in the rapid decomposition of materials after disposal; for example, silica particles can be incorporated into CAB plasticizing matrices.

[0098] For example, photocatalysts, pro-oxidants, and enzymes can be used to accelerate the decomposition of NCE-containing materials such as plastics once they enter a landfill. Using the example of enzymes, and without being constrained by theory, it is understood that the activity of certain biodegradable accelerators can be explained by the following mechanisms: To decompose different cellulose derivatives, it may be necessary to first decompose the functional groups, and then further decompose the β-1,4-bonds in the cellulose backbone. Unmodified cellulose can be decomposed by cellulase and β-glucosidase enzymes. Lipase or acetylesterase are examples of enzymes that can be used to hydrolyze acetyl groups in cellulose acetate. By incorporating enzymes into a plastic matrix, the activity of the enzymes can accelerate the decomposition of plastics, for example, while it is present in a waste facility or landfill. Methods for incorporating enzymes into a matrix may include physical adsorption, covalent bonding, crosslinking, and encapsulation. Furthermore, enzymes can be immobilized on particles and then incorporated into an existing matrix for better retention and distribution. In addition, enzyme loading and enzyme selection can be adjusted to accelerate or slow the decomposition rate under different circumstances. For example, enzymes that are active within a specific temperature range and pH environment may be selected to initiate decomposition when NCE-containing plastic materials are to be composted or soiled, or when the plastic materials are intended for a slower decomposition process, such as when they are to be sent to landfills.

[0099] Ultraviolet (UV) resistance can also be imparted to existing matrices or composite NCE-containing matrices using additives that absorb or stabilize UV ​​irradiation. For example, carbon black or other dyes that absorb UV light can be added as pigments. In one embodiment, bio-based materials containing different UV functional groups, such as lignin, phenolic units, ketones, chromophores, and conjugated double bonds, which can impart UV resistance, can be incorporated into polymer matrices as UV-absorbing additives to enhance long-term stability. In one embodiment, lignin can be combined with NCE-containing matrices in manufactured articles that are typically exposed to UV light (e.g., sunglass frames).

[0100] In some embodiments, an existing matrix or a composite NCE-containing matrix may be magnetized with an additive such as gamma iron oxide. Although it has been stated that the additives are added to the existing matrix, it is understood that they may be introduced directly into the composite matrix formulation (i.e., after the additive NCE is combined with the existing matrix) in addition to or instead of introducing them into the existing matrix.

[0101] In one embodiment, a composite NCE-containing matrix for use in composite NCE-containing materials may be prepared as follows. In this embodiment, a bio-based existing matrix is ​​prepared to contain performance-enhancing additives, and this existing matrix is ​​then combined with redispersible or redispersed (additive) NCE. In one embodiment, to prepare a bio-based existing matrix, the matrix-forming components are dissolved in a solution of acetone or water, depending on the solubility parameter of the matrix, to form a solution containing about 2 wt% to about 25 wt%, about 5 wt% to about 15 wt%, about 5 wt% to about 50 wt%, or about 20 wt% to about 75 wt%, for example, a 12 wt% solution of these components; in another embodiment, a solvent may not be required. Heat treatment and high-shear force mixing may be used to produce a hot melt of the matrix material. The matrix powder, pellets, or other forms may be fed into a twin-screw extruder, heated to a softened state, and combined with redispersible NCE and other additives.The matrix-forming components include constitutive polymer components (e.g., cellulose acetate (CA), cellulose acetate butyrate (CAB), etc.) and other cellulose ethers (e.g., methylcellulose, carboxymethylcellulose, hydroxypropylcellulose, carboxymethylcellulose, sodium carboxymethylcellulose, hydroxymethylcellulose, etc.), polyhydroxyalkanoates (PHA), such as poly-3-hydroxybutyrate (PHB), polyhydroxyvalerate (PHV), and polyhydroxyhexanoates (polyhydroxyhexanoates) e) (PHH), polybutylene succinate (PBS), etc., or combinations of such polymer components) may be included and combined with rosin or its derivatives, fillers, e.g., calcium carbonate or silica, bulking agents, e.g., pulp or pulp-based materials, and / or fatty acids (preferably saturated), e.g., stearic acid, lauric acid, palmitic acid, oleic acid, etc., along with plasticizers (e.g., triacetin, triethyl citrate, triethyl acetyl citrate, glycerol, xylitol, trehalose, sorbitol, mannitol, polyethylene glycol, polypropylene glycol, epoxidized soybean oil, castor oil, palm oil, etc.). For example, CAB or other biopolymers may be added in the range of about 55% to about 95%; plasticizers may be added in the range of about 0.1% to about 20%; gum rosin may be added in the range of about 10% to about 40%. As another example, CAB or other biopolymers may be added in the range of approximately 60% to approximately 90%; plasticizers may be added in the range of approximately 0.1% to approximately 20%; stearic acid may be added in the range of approximately 5% to approximately 25%; calcium carbonate may be added in the range of approximately 3% to approximately 17%, with a stearic acid to calcium carbonate ratio of approximately 3:2. In yet another example, HPC or other biopolymers may be added in the range of approximately 55% to approximately 95%; plasticizers may be added in the range of approximately 5% to approximately 40%; gum rosin may be added in the range of approximately 10% to approximately 40%. In yet another example, HPC or other biopolymers may be added in the range of approximately 5% to approximately 50%; plasticizers may be added in the range of approximately 0.5% to approximately 30%.

[0102] For example, components containing rosin, plasticizers, and cellulose acetate butyrate (or any other biopolymer or combination of biopolymers) are combined with other additives; under certain circumstances, the order of combination may be important. In one embodiment, the least viscous components are combined first (rosin, PCC, stearic acid), then CAB is added, followed by the plasticizer. The solution is stirred until the mixture is homogeneous and no aggregates remain. The solution is thickened to provide an existing matrix into which the additive NCE is incorporated.

[0103] In parallel, the additive NCE is prepared. In one embodiment, a selected amount of the dry, redispersible NC-containing material prepared as described above is resuspended in a resuspension fluid such as water and thoroughly mixed by an overhead mixer.

[0104] In this method, a formulation of the redispersed additive NCE is prepared. In this embodiment, the formulation of the redispersed NCE may contain an amount of redispersed NCE suitable for achieving the desired properties in the composite NCE-containing material. The amount of redispersed NCE in the range of about 1% to about 50% (wt%) of the total composite NCE-containing matrix may be used, with a range of about 5% to about 40% being preferable. The use of less water in this formulation facilitates the drying of the material into which the additive NCE is incorporated and aids in its moldability. This formulation of the additive NCE is then combined with an existing matrix to prepare a composite NCE-containing matrix. In this embodiment, since suitable components have already been added to the existing matrix, no further components are added to the composite NCE-containing matrix. Surfactants such as caprylic glycosides may be added; not bound by theory, it is understood that such additives may crosslink polar and nonpolar components during mixing and processing. Next, the composite NCE-containing matrix and any other desired components may be mixed with high shear force using an overhead stirrer, high-shear-force mixer, twin-screw extruder, etc., to produce a composite NCE-containing material. This initial forming process may be adjusted based on the viscosity requirements for the manufacturing process used to produce articles formed from the composite NCE-containing material.

[0105] 4. Manufactured articles having OGWR characteristics a. General OGWR characteristics In some embodiments, barrier-forming formulations may be prepared to emphasize OGR properties, WVR properties, or both; in some embodiments, barrier-forming formulations may contain both types of properties, and formulation components may be adjusted to further enhance either the OGR or WVR properties or to balance them. For example, since there is a range of cellulose polymers with varying degrees of hydrophobicity or oleophobicity, a cellulose polymer may be selected to produce a desired degree of OGR and / or WVR. Barrier-forming formulations for producing water resistance may include various cellulosic polymers and those that are more hydrophobic in particular. Overall, since cellulosic polymers tend to be oleophobic (hydrophilic), it may be beneficial to include other materials in the barrier-forming formulation when higher water resistance is desired. For example, methylcellulose provides good oil / grease resistance, though not as high as water resistance. Mixtures of methylcellulose (MC) and cellulose acetate (CA) may be provided to adjust both OGR and WVR properties. While the LCST polymers discussed perform well in terms of oil resistance, the films / coatings made using them are soluble at room temperature, resulting in a less pronounced effect on water resistance. Cellulose acetate and lipids are some examples of additives that can be used to adjust barrier formulations to be more hydrophobic, and combinations of these components with more oleophobic materials can provide both oil and water resistance. Notably, cellulose acetate can provide both hydrophobic and oleophobic properties. Cellulose acetate and other cellulose acetate derivatives (e.g., cellulose acetate butyrate, without limitation) are unique in that they possess some degree of oleophobicity in addition to strong hydrophobicity. Similarly, certain fillers have more hydrophobic or oleophobic properties: for example, fillers such as waxes can be selected to increase hydrophobicity, or, for example, a lot of excess NCE can be added as a pore-blocking agent to increase oleophobicity. Fatty acids can also be used to increase hydrophobicity, either by themselves or paired with charge-binding agents such as minerals (e.g., calcium carbonate paired with stearic acid).

[0106] In an embodiment, substances such as NCE, MC, HPMC, CMC, NaCMC, CA, CAB, chitosan, rosin, lignin, plant proteins (e.g., pea protein, zein, etc.) and / or any combination thereof may be used as oleophobic substances to provide oil resistance; in an embodiment, substances such as NCE, MC, CA, CAB, chitosan, rosin, hydrophobized starch, lignin, pea protein, zein and / or any combination thereof may be used as hydrophobic substances to provide water and / or water vapor resistance.

[0107] More specifically, depending on the balance and quantity of components, barrier formulations can be classified into three general categories: 1) those that provide balanced OGR and WVR properties; 2) those that provide some degree of hydrophobicity or not hydrophobic but substantially oleophobic; and 3) those that provide some degree of oleophobicity or not oleophobic but substantially hydrophobic. Articles incorporating Category 1 barrier formulations may be used in applications such as food packaging where both oil and water repulsion are advantageous. Articles incorporating Category 2 barrier formulations may be used for applications where oil repulsion is a more important property, such as for oil or grease materials, for packaging of a given amount of oily products such as salad dressing or cosmetic lotion, or for use in containers as more durable containers that may contain motor oil and similar fluids instead of metal containers for this purpose. Articles incorporating Category 3 barrier-forming formulations may be used for applications where water repulsion (and even waterproofing) is a more important property, such as in six-pack holders for coffee cups and beverage cans, or in grocery bags and other containers (e.g., cardboard boxes) or packaging intended to be substantially water-resistant or leak-proof.

[0108] b. Exemplary oleophobic and hydrophobic manufactured articles The ubiquity of plastic products presents a wide range of other opportunities for the alternative NCE-containing materials described herein to conventional petroleum-derived plastics currently in use. Given the environmental challenges associated with the production and disposal of conventional petroleum-derived plastics, the composite NCE-containing materials disclosed herein offer good alternatives. Exemplary examples include, but are not limited to, transaction cards, plastic bottles, packaging and wrapping, space fillers (impact, sound and thermal insulation), films and sheets, drinking straws and dining kitchen products, such as cutlery, paper products with enhanced OGWR and strength (e.g., corrugated cardboard, cardboard and any fibrous products), structural plastics, nail polish and foam, etc. Bio-based NCE-containing materials for producing useful manufactured articles can be customized and modified to produce desired performance characteristics and biodegradability.

[0109] i. Transaction card Transaction cards, well-known in everyday commercial applications, are small, lightweight, and easily portable devices used to accomplish administrative processes such as payment transfers, entry / exit procedures, and identity verification. Such transaction cards are common in modern commerce. Examples include credit cards, debit cards, prepaid gift cards (collectively "payment cards"), transit passes, identification cards, insurance cards, and hotel keys. These are typically formed from petroleum-derived materials that provide a lightweight and durable substrate for printing and embedding, forming specialized components such as iron oxide for magnetic stripes, inks, dyes, and chips. They are typically manufactured as laminates of PVC, a petroleum-derived plastic that takes hundreds of years to decompose. As of 2020, it is estimated that 6 billion payment cards are issued annually; 30 million kg of PVC are used for issuing these cards each year.

[0110] While these transaction cards are understood to contain other materials such as metals, glass, silicon, and resins in addition to petroleum-derived plastics, converting them from petroleum-derived plastic sources to bio-based alternatives may offer additional advantages in the disposal of these cards. For example, if the cards or their fragmented remnants are incinerated at a recycling facility, bio-based materials produce fewer toxic gases than petroleum-derived alternatives. Furthermore, biodegradable bio-based materials can undergo programmed decomposition at waste management facilities, thus avoiding their incineration.

[0111] Using the methods described above, more environmentally friendly alternative substrates for transaction cards can be fabricated by combining existing bio-based matrices with redispersed (additive) NCE to create composite NCE-containing matrices. As discussed earlier, composite NCE-containing matrices combined with any desired additives constitute a composite NCE-containing material that can be used as a plastic substrate for forming transaction cards. For such products, it is advantageous to include water-resistant additives so that the card maintains its integrity throughout its lifespan.

[0112] The basic formulation for composite NCE-containing materials useful for forming transaction cards consists of the following components (by weight relative to the total weight of 100g of the formulation): 5 wt% to 50 wt%, e.g., 12 wt%, of the following components, which are combined as a solid in a high-shear-force heat mixer such as a hot-melt extruder: Cellulose acetate butyrate (CAB): 36g • Redistributed NCE (NFC or MFC or a combination of them): 36g Gum rosin (GR): 26g • Plasticizer (triacetin, triethyl citrate, or triethyl acetyl citrate): 2g It may include.

[0113] While specific amounts of these components are provided for the exemplary formulations described above, it is understood that a range of these components may be added to create other formulations with favorable properties. For example, nanocellulose components may be added in the range of approximately 5% to 50%; CABs in the range of approximately 30% to 70%; plasticizers in the range of approximately 0.1% to 15%; and gum rosin in the range of approximately 5% to 45%. In this formulation, CABs combined with gum rosin and plasticizers may combine with additive NCEs to form an existing matrix that produces a composite NCE-containing material. In these composite NCE-containing materials with relatively large amounts of CAB, CABs have a greater influence on the overall properties of the composite NCE-containing material compared to the influence of NCEs; conversely, in these composite NCE-containing materials with relatively large amounts of redispersed NCEs, NCEs have a greater influence on the overall properties of the composite NCE-containing material compared to the influence of CABs. In one embodiment, the redispersed NCE can be combined with an extender such as pulp or a pulp-based material and added to an existing CAB matrix.

[0114] The basic formulation for composite NCE-containing materials useful for forming transaction cards consists of the following components (by weight relative to the total weight of 100g of the formulation), which are combined as a solution in 5wt% to 50wt%, for example, 12wt%, acetone, or as a solid in a high-shear-force heating mixer, for example, a hot-melt extruder: • Cellulose derivatives, e.g., cellulose acetate butyrate (CAB): 41g • Redistributed NCE (NFC or MFR or a combination of both): 28g Pulp: 9g Capryl glucoside: 2g • Plasticizer (triacetin, triethyl citrate, or triethyl acetyl citrate): 4g Gumrosin: 16g It may include.

[0115] This basic formulation can be modified to produce a composite NCE-containing material that produces a flexible card with enhanced hardness. Such a formulation is prepared by combining the following components (by weight relative to the total weight of 100 g of the formulation) in a solution in 5 wt% to 50 wt%, for example, 12 wt%, of acetone, or as a solid in a high-shear-force heating mixer, for example, a hot-melt extruder: • Cellulose derivatives, e.g., cellulose acetate butyrate (CAB): 36g • Redistributed NCE (NFC or MFC or a combination of them): 36g • Plasticizer (triacetin, triethyl citrate, or triethyl acetyl citrate): 2g • Stearic acid: 16g • Precipitated calcium carbonate (PCC): 10g It may include.

[0116] While specific amounts of these components are provided for the exemplary formulations described above, it is understood that a range of these components may be added to create other formulations with favorable properties. For example, nanocellulose components may be added in the range of approximately 5% to approximately 50%; CAB may be added in the range of approximately 30% to approximately 70%; plasticizers may be added in the range of approximately 0.1% to approximately 15%; stearic acid may be added in the range of approximately 1% to approximately 12%; calcium carbonate (PCC) may be added in the range of approximately 0.6% to approximately 8%, with a desired stearic acid:PCC ratio of approximately 3:2. In these composite NCE-containing materials with a relatively large amount of CAB, CAB has a greater influence on the overall properties of the composite NCE-containing material compared to the influence of NCE; conversely, in these composite NCE-containing materials with a relatively large amount of redispersed NCE, NCE has a greater influence on the overall properties of the composite NCE-containing material compared to the influence of CAB. In one embodiment, the redispersed NCE can be combined with a bulking agent, such as pulp or a pulp-based material, and added to an existing CAB matrix. In this formulation, the CAB combined with gum rosin and a plasticizer can be combined with the additive NCE to create an existing matrix that produces a composite NCE-containing material. Without being constrained by theory, it is understood that the addition of a fatty acid (e.g., stearic acid) is amphiphilic, thus providing hydrophobic properties to the matrix and facilitating the incorporation of hydrophilic PCC particles into the matrix; the PCC particles can act as a hardening reinforcer in the CAB matrix.

[0117] Barrier-forming formulations can be incorporated into composite NCE-containing materials used to form transaction cards to produce OGWR properties. In one embodiment, hydrophobic properties are imparted to the composite NCE-containing material by including a hydrophobic agent in the existing matrix or composite NCE-containing material so that the final transaction card product is more water-resistant and durable. In another embodiment, a bio-based hydrophobic and / or oleophobic coating can be applied to the surface of the formed transaction card product or to the surface of one or more layers of the composite NCE-containing material that are laminated together to form a transaction card. Suitable hydrophobic agents include, but are not limited to, organic compounds having highly polar and non-polar regions, which allow the compound to bind or complex with hydrophilic NCE to provide a non-polar, outward-facing surface. Examples of hydrophobic agents include fatty acids such as stearic acid, lauric acid, palmitic acid, and oleic acid; surfactants such as fatty acid amines or fatty acid alcohols; rosin components such as abietic acid, neoabietic acid, pulsed toruic acid, pimaric acid, isopimaric acid, and dehydroabietic acid; and natural waxes such as lanolin, beeswax, and carnauba. Examples of hydrophobic agents include silanes, siloxanes, or silica micro / nanoparticles, but these are less favorable than the materials disclosed herein due to their environmental impact.

[0118] Formulations for hydrophobization, such as those that can be added to a complex NCE-containing matrix and those that can be coated onto the surface of one or more layers of a complex NCE-containing material, may contain components ranging from about 25% to about 70% cellulose acetate (CA); from about 25% to about 70% gum rosin (GR); and from about 1% to about 20% plasticizers, such as triacetin, triethyl citrate, or triethyl acetyl citrate. To prepare a formulation for hydrophobization, the aforementioned components can be dissolved in an ethanol / alcohol solvent mixture in a ratio of about 0.1% to about 20% hydrophobizing component (wt%) to about 10% to about 50% ethanol (wt%) to about 50% to about 70% acetone (wt%).

[0119] An exemplary formulation of such hydrophobic and oleophobic coatings is composed of the following components (by weight relative to the total weight of 100 g of the formulation) that are combined to form a solution in acetone: Cellulose acetate (CA): 7g Ethanol: 14g Acetone: 71g • Gum rosin (GR): 7g • Plasticizer (triacetin, triethyl citrate, or triethyl acetyl citrate): 1g It may include.

[0120] Exemplary formulations for creating oil, grease, and water-resistant barriers used as coatings (by weight relative to the total weight of 100g of the formulation) are: Methylcellulose (MC): 3g • Redistributed NCE (NFC or MFC or a combination of them): 1g ·Water: 54g • Rosin: 4g • Ethanol or acetone: 38g Includes.

[0121] An example formulation for an oleophobic coating is the following components (by weight relative to the total weight of 100g of the formulation) that are combined to form an aqueous solution in water: Methylcellulose (or any cellulose ether): 75g • Redistributed NCE (NFC or MFC or a combination of them): 25g Includes.

[0122] ii. Plastic bottles Plastic bottles are traditionally made from many types of petroleum-derived polymers, including, but not limited to, polyethylene terephthalate, polyethylene, polypropylene, and polycarbonate. Such manufactured goods are widely used commercially and serve as containers for a virtually endless number of liquid and solid substances, such as food and beverages (e.g., spices, cooking oils, salad dressings, etc.), soaps, shampoos, household products, industrial products, personal care items, cosmetics, and pharmaceuticals. A significant environmental challenge is presented by their durability after the end of their useful life: the materials from which these items are formed take hundreds or thousands of years to decompose. Plastic bottles used as containers for drinking water exemplify the environmental burden these items place on the environment. More than 80% of the plastic water bottles produced end up in landfills; it is estimated that more than 2 million tons of discarded water bottles currently remain in landfills, and they may remain reasonably intact for centuries.

[0123] Using the methods disclosed herein, a bio-based flexible plastic substrate for the manufacture of plastic bottles can be produced by combining an existing matrix formed of bio-derived polymers with the aforementioned collection of redispersed NCEs. Thus, the redispersed NCEs combined with the existing matrix can form a bio-based composite NCE-containing matrix that can be used to replace currently formed non-biodegradable plastics in plastic bottles and similarly formed containers. The use of redispersed NCEs in the composite matrix has the further advantage of creating a physical barrier to prevent oxygen molecules from passing through the material. Such a plastic substrate can be remodeled to maintain its integrity during a given lifespan while being adapted for decomposition (e.g., through biodegradation or composting) at the end of its designated useful life.

[0124] An example formulation for making a plastic bottle is the following components (by weight relative to the total weight of 100g of the formulation), which are combined as solids in an acetone solution or in a high-shear-force heating mixer, such as a hot-melt extruder: Cellulose acetate butyrate (CAB): 60g • Redistributed NFC: 10g • Gum rosin (GR): 25g • Plasticizer (triacetin, triethyl citrate, or triethyl acetyl citrate): 5g It may include.

[0125] An example formulation for making a plastic bottle is the following components (by weight relative to the total weight of 100g of the formulation), which are combined as solids in an acetone solution or in a high-shear-force heating mixer, such as a hot-melt extruder: Cellulose acetate butyrate (CAB): 52g • Redistributed NFC: 17g • Pulp fiber: 6g • Gum rosin (GR): 20g • Plasticizer (triacetin, triethyl citrate, or triethyl acetyl citrate): 5g It may include.

[0126] While specific amounts of these components are provided for the exemplary formulations described above, it is understood that a range of these components may be added to create other formulations with advantageous properties. For example, nanocellulose components may be added in the range of about 1% to about 30%; CABs may be added in the range of about 30% to about 90%; plasticizers may be added in the range of about 1% to about 35%, preferably in the range of about 15% to about 25%; and rosin may be added in the range of about 5% to about 25%. In these composite NCE-containing materials with a relatively large amount of CAB, CAB has a greater influence on the overall properties of the composite NCE-containing material compared to the influence of NCE; conversely, in these composite NCE-containing materials with a relatively large amount of redispersed NCE, NCE has a greater influence on the overall properties of the composite NCE-containing material compared to the influence of CAB.

[0127] In the preparation of a suitable composite NCE-containing matrix, the components listed above may be added to the extent intended to optimize specific desired properties. For example, lower concentrations of nanocellulose (e.g., about 1% to about 15%; less nanocellulose results in better visual clarity) may be used to achieve a desired degree of mechanical strength and visual clarity. Higher concentrations of plasticizers compared to transaction card formulations, for example, amounts of plasticizer higher than 5 wt% of the total formulation, help to achieve desired external properties such as gloss or smoothness, in addition to introducing higher flexibility into the formed object. For products requiring a more durable structure (e.g., shampoo bottles or pill containers), formulations with less plasticizer may be used, and the walls of the container may be made thicker. To manufacture plastic bottles from composite NCE-containing materials, they may be heated and shaped using conventional techniques such as blow molding.

[0128] When used to contain aqueous fluids, plastic bottles made from composite NCE-containing materials require hydrophobic properties to prevent leakage. When used to contain oily liquids such as cooking oils, oleophobic properties are required to prevent leakage. Barrier-forming formulations can be incorporated into the composite NCE-containing material used to form the plastic bottle to produce the required OGWR properties. In one embodiment, hydrophobic properties are imparted to the composite NCE-containing material by including a hydrophobic agent in the existing matrix or composite NCE-containing material so that the product is more water-resistant and durable. In another embodiment, a bio-based hydrophobic coating can be painted onto the surface of the transaction card product to be formed or onto the surface of one or more layers of composite NCE-containing material that are laminated together to form a transaction card.

[0129] iii. Packaging for consumer products While there are similarities between the requirements for manufacturing plastic bottles and those for manufacturing other types of packaging for consumer products, the properties of these different product categories differ because they are used for different purposes. For example, plastic bottles can have a considerably longer lifespan compared to other types of containers, and they must remain water and / or oil impermeable throughout their entire lifespan, whereas packaging for other products may be designed for a shorter lifespan or to have less demanding performance requirements, and the materials forming them may be tailored accordingly. Typically, plastic bottles require great structural strength to allow them to be transported and stacked while protecting their liquid contents. Petroleum-derived polymers have been remarkably suitable for meeting such performance requirements. However, when these materials are made from petroleum-derived polymers, once manufactured and discarded regardless of their original intended use, petroleum-derived polymers impose a significant burden on the environment because they make these materials long-lasting and resistant to disposal.

[0130] Composite NCE-containing materials can be modified to offer further programmable decomposition to address specific container performance requirements (e.g., a balance of flexibility, strength, and lightweight). For example, composite NCE-containing materials with higher concentrations of NCE reinforcement in a bio-based matrix may be provided to replace PVC in highly rigid shell-shaped packaging and rigid boxes. As another example, substitutes for PET used in more flexible food product containers may include composite NCE-containing materials with lower concentrations of NFC reinforcement and higher plasticizer content. Methods for forming composite NCE-containing materials into container and packaging materials include (without limiting) those commonly known in industry, such as thermoforming, vacuum forming, injection molding, and extrusion molding.

[0131] In some embodiments, composite matrices may be fabricated from existing biodegradable matrices having a combination of specialized properties such as advantageous mechanical and barrier properties. For example, packaging materials may be formed from existing natural polymeric matrices previously described, such as starch or derivatized cellulose (cellulose ether or cellulose acetate), reinforced with redispersed NCE, to which barrier-forming materials may be optionally added. In some embodiments, small NCE particles, shaped, for example, as rolled balls of fibers or longer reinforced NCE fibers, may be incorporated into the overall packaging material matrix for increased shock absorption. The NCE chains for this purpose may have inherent hydrophobicity and may optionally be treated with materials to improve their oil and grease resistance. Overall, these existing bio-based matrices incorporating redispersed NCE reinforcements (e.g., NCE fibers and / or NCE-reinforced polymer fibers) may be used in a variety of packaging applications, such as packing peanuts, bags, and corrugated boxes.

[0132] Generally, packaging has requirements for OGWR properties suitable for use. Packages or containers intended for use with food products must contain any food-related fluids within their contents and must protect the contents from exposure to external humidity, greases, and oils. Packages or containers must remain structurally intact even when exposed to humidity, greases, or oils. Therefore, the OGWR properties of a package or container contribute to its structural stability by preventing oil, grease, or water from impairing its strength or resilience. Barrier-forming formulations can also be used to produce OGWR properties in simple NCE-based materials and composite NCE-containing materials used as packages or containers.

[0133] For example, OGR or WVR pouches, pods, or other packaging articles formed from NCE as described herein may serve as containers for spices, dressings, or other liquid or gel-like food substances, allowing consumers to open the package and, if desired, dispense the food substance. Such packaging can conveniently contain and dispense water-based or oil-based food substances such as soy sauce, ketchup, mustard, mayonnaise, salad dressings, and dairy products, thereby reducing the plastic waste associated with conventional packaging for such food substances.

[0134] An exemplary formulation for making a container for non-oxygen-sensitive substances (e.g., salt / pepper) is the following ingredients (by weight relative to the total weight of 100g of the formulation): Methylcellulose (MC): 85.5g Xylitol: 4.5g • NCE: 10g It may include.

[0135] An exemplary formulation for making a container for oxygen-sensitive material (e.g., see-through film for meat trays) includes the following components (by weight relative to the total weight of 100g of the formulation): • Polyvinyl alcohol (PVA): 23.75g • Polyvinyl acetate (PVAc): 23.75g Methylcellulose (MC): 42.75g • Maltitol: 4.75g • NCE: 5g It may include.

[0136] Exemplary formulations for creating a water-resistant barrier to be mixed into a slurry to be molded and thermoformed (by weight relative to the total weight of 1000 g of dry formulation): • 0.4 wt% water-based pulp slurry: 8325g (33.33g dry wt) • Redispersible NCE: 7.9175g (NCE) and 23.7525g (MC) Rosin: 35g (50g in ethanol)

[0137] Exemplary formulations for creating oils, greases, and water-resistant barriers to be mixed in or used as a coating (by weight relative to the total weight of 100 g of the formulation) • Cellulose acetate butyrate (CAB): 10g Rosin: 10g Acetone: 79g • Plasticizer (e.g., but not limited to triacetin, triethyl citrate, triethyl acetyl citrate, tributyl citrate): 1g

[0138] An example formulation for such a hydrophobic coating is the following components (by weight relative to the total weight of 100g of the formulation) which are combined to form a solution in acetone: Cellulose acetate (CA): 7g Ethanol: 14g Acetone: 71g • Gum rosin (GR): 7g • Plasticizer (triacetin, triethyl citrate, or triethyl acetyl citrate): 1g Includes.

[0139] Adding barrier-forming formulations for the purpose of OGWR is particularly useful in the preparation of versatile simple NCE materials: their mechanical properties are mainly provided by the simple NCE matrix itself, which is vulnerable to oil, grease, and water permeability, especially when pulp-dominant. Adding barrier-forming formulations to such simple NCE materials can provide intrinsic oil, grease, or water resistance, thereby protecting the contents from such intrusion and further protecting the integrity of the material itself or the packaging or containers made from it.

[0140] iv. Thin films and sheets For example, thin films and sheets used as wraps or containers (e.g., stretchable wraps, plastic bags, garbage bags, etc.) have requirements for flexibility, elasticity, oil and water resistance, as well as strength. Currently, these are typically made from polyethylene. As an alternative, bio-based composite NCE-containing matrices can be made using cellulosic polymers as matrix-forming elements in existing matrices, and this matrix or the final composite NCE-containing matrix can be modified to produce the desired elasticity. Potential cellulose derivatives include, but are not limited to, CMC (carboxymethylcellulose), CMCNa (sodium carboxymethylcellulose salt), CA (cellulose acetate), CDA (cellulose diacetate), cellulose triacetate (CTA), CAB (cellulose acetate butyrate), CAPh (cellulose acetate phthalate), CAP (cellulose acetate propionate), EC (ethylcellulose), HEC (hydroxyethylcellulose), EHEC (ethyl hydroxyethylcellulose), HPC (hydroxypropylcellulose), HPMC (hydroxypropyl methylcellulose), HPMCP (hydroxypropyl methylcellulose phthalate), and HPMCAS (hydroxypropyl methylcellulose acetate). To achieve high elasticity, significant entanglement of polymer chains can occur in the existing matrix. By incorporating long-chain crosslinking agents into the natural polymer backbone through esterification, a highly entangled and linked structure can be formed, providing the desired elasticity. For example, any mono- or dicarboxylic acid (e.g., sebacic acid, but not limited to sebacic acid) can be crosslinked to a cellulosic polymer (e.g., cellulose diacetate) in the presence of an acid catalyst. The existing matrix thus prepared can be combined with redispersed NFCs to form a composite NCE-containing matrix with appropriate strength and elasticity. Other components can be incorporated into the existing matrix or composite NCE-containing matrix to form a final composite NCE-containing material that can be used to form specific manufactured articles using current industrial methods.

[0141] Composite films or sheets formed from composite NCE-containing materials can be transparent or translucent as desired and possess excellent mechanical properties such as tear resistance along with biodegradability. In contrast, conventional transparent or translucent films and sheets, such as those used in Ziplock bags, garbage bags, food bags, etc., are typically formed from petroleum-derived, slow-degrading polyolefins such as polyethylene and polypropylene. In embodiments, films and sheets formed by incorporating NCE as described herein can be used in many other packaging applications where strength is desired and provide a biodegradable alternative to conventional polyolefin-based packaging materials.

[0142] Films or sheets having barrier properties such as OGWR properties offer significant advantages when used in commercial settings. For example, for this purpose, films or sheets can be used as packaging or wrapping with optimized resistance to oils and greases and / or water or water vapor, and can be used as packaging or wrapping for delicate products. In embodiments, films or sheets can be further modified to improve oil resistance when encountering oil or oily suspensions, to optimize water resistance when encountering aqueous solutions or suspensions, to add strength, or to reduce gas permeability to produce more airtight packaging properties. In embodiments, composite NCE-containing materials having OGWR properties disclosed herein can be modified by adding further polymers or particles to a matrix material (e.g., PVA, PVOH, hydroxyethyl butyrate, release clay, etc.) to improve their airtight properties.

[0143] For example, a film or sheet having OGWR properties formed from a composite NCE-containing material may be used as a component or as part of a container for liquids such as milk (e.g., a milk carton that can be stored at room temperature) and may be sterilizable by techniques such as ultraviolet sterilization and other methods well known to those skilled in the art. In embodiments, such a film or sheet may be transparent or translucent, have excellent mechanical properties such as tear resistance or rigidity, and provide a feasible alternative to conventional packaging and sealing films made of polyolefins.

[0144] As another example, films and sheets with OGWR properties formed from composite NCE-containing materials can be used as packaging for food. Existing matrices contributing to composite NCE-containing materials used for these purposes may include conventional biodegradable, naturally derived polymers, such as cellulose ethers, cellulose esters, starch ethers, starch esters, polyvinyl alcohol, hydroxyethyl butyrate, or any combination thereof. In these composite NCE-containing materials, NCE can impart improved mechanical strength, stiffness, and tear resistance to the material, which can be enhanced by including dispersant additives in the material. OGWR properties in films or sheets can be achieved by including barrier-forming formulations having oleophobic and / or hydrophobic properties. In embodiments, additive NCE may be prepared to provide OGWR properties to composite NCE-containing materials, for example, when these fibers are coated with a film that produces these properties. Appropriate plasticizers can be added to cellulose acetate or other hydrophobic, resilient materials to impart elasticity to the coated fibers, or incorporated into polymer matrices to provide flexibility and stretchability to the product. For products intended to be gas-impermeable, polyvinyl alcohol or polyvinyl acetate / polyvinyl alcohol copolymers may be used.

[0145] More specifically, composite NCE-containing films or sheets may be prepared from existing matrices containing biodegradable materials such as cellulose ethers, cellulose esters, starch ethers, starch esters, polyvinyl alcohol, hydroxyethyl butyrate, polyvinyl acetate, or any combination thereof; then, additives may be provided to produce specific properties for specific commercial needs. As previously described, OWGR properties are particularly advantageous; some of the additives mentioned above may act as barrier-making formulations to produce these properties. Other additives may be included in the composite NCE-containing material to produce other properties. For example, a film or sheet requiring gas barrier properties may be made from a composite NCE-containing material containing polyvinyl alcohol, polyvinyl acetate, its copolymers, or mixtures thereof.

[0146] The proportions of components in composite NCE-containing matrices and composite NCE-containing materials may also be adjusted to improve specific properties. In some embodiments, NCE may be added at concentrations ranging from 1 wt% to 10 wt% to improve mechanical strength. In some embodiments, existing matrices may be prepared to increase the physical integrity of the resulting composite NCE-containing matrices by using polymers selected for their physical integrity and by selecting their high molecular weight versions (e.g., tens of thousands of g / mol to millions of g / mol, e.g., molecular weight ranges of hundreds of thousands of g / mol to millions of g / mol). Plasticizers may be incorporated at concentrations ranging, for example, from about 1 wt% to about 50 wt% or about 1 wt% to about 10 wt% or about 5% to about 15% to impart flexibility. Useful plasticizers include, but are not limited to, 1,2-propanediol, xylitol, erythritol, maltitol, and mannitol, or fatty acids such as caprylic acid and caproic acid. Fatty acids used as plasticizers may be beneficial in barrier applications due to their hydrophobic properties. For large-scale processing, the complete formulation (including redispersed NCE, existing matrix(s), plasticizer, barrier-forming formulation and other desired additives) may be mixed in a large tank and pumped to an extruder with slot dies. The extruded sheets may then be compressed and / or perforated by rollers. After drying (heated rollers or oven), the compressed sheets may be collected on rolls or further formed into bags or sachets.

[0147] v. Hollow cylinders for flexible tubes such as drinking straws An application combining biodegradability, strength, and barrier properties is the use of NCE material to form hollow cylinders that can be used to create flexible tubes for use as biodegradable drinking straws, for example. Straws tend to use more durable, non-biodegradable plastics because they are intended for use with various liquids such as alcohol, fats, and acids at various temperatures, and because straws require sufficient strength to resist deformation during normal use; biodegradable materials alone lack the liquid resistance and strength to withstand the pressures that straws typically encounter. The use of NCE material alone or in combination with other biodegradable materials can provide the necessary liquid resistance and strength while allowing the product to be biodegradable.

[0148] The simple NCE-based materials described above can be formed as a sheath and wound around a hollow cylinder to function as a straw. Since such materials may be pulp-dominant, they can be economically formed in combination with a simple NCE-based matrix using pulp or a pulp-based filler as the main component. Barrier-forming formulations are advantageous in providing the hydrophobicity or oleophobicity required for the expected end use of hollow cylinders such as drinking straws. For example, bagasse or other fibrous agricultural waste products may be sources of NCE that are redispersed according to the methods disclosed herein; such NCE can then be mixed with formulations containing CA, rosin, and plasticizers to produce composite NCE-containing materials that can be extruded to form drinking straws.

[0149] In another embodiment, a composite NCE-containing material having desired OGWR properties may be formed by using a cellulosic material, such as methylcellulose for an existing matrix, in combination with additive NCE. In such a composite, cellulose acetate or other material may be selected to produce hydrophobicity. For example, certain biodegradable LCST polymers or hydrophobic cellulosic polymers, such as CA or CAB or other materials or copolymers thereof, such as polyvinyl acetate / polyvinyl alcohol, lipids, waxes, hydrophobic starch, fatty acids, or any other similar hydrophobic polymers may be included in the composite NCE-containing material to increase its hydrophobicity.

[0150] In one embodiment, a composite NCE-containing material having OGWR properties may be mixed with an aqueous vehicle to produce a viscous mixture, which may then be formed as a sheet or extruded as a hollow cylinder. Reinforcing materials, such as spun hydrogel fibers, may be added to the composition to improve strength and flexibility. For embodiments having OGWR properties, the ratio of OGR or WVR component to NCE may be about 1:1 to about 12:1 or about 3:1 to about 9:1. In another embodiment, a 2-3% suspension of NCE may be mixed with an MC or other cellulose derivative-containing suspension. In one embodiment, the NCE formulation may contain CMF and CNF, or contain more CMF than CNF, or consist essentially of CMF, and the CMF to CNF ratio is adjusted to optimize the strength of the final formulation. In one embodiment, standard pulp may be used in the mixture in addition to or instead of derivatized cellulose. The stiffness of the straw product may be improved by eliminating or reducing the amount of glycerol or other plasticizers used in the formulation. [Examples]

[0151] Examples Example 1: Preparation of a redispersible NCE sheet The redispersible NCE sheet was prepared by combining a drying / dispersing additive with an NCE slurry and then drying it at a high temperature in an oven. There are various combinations and many ratios of additives that can be used to prepare a sheet of dried redispersible NCE. In this specific example, LCST polymer hydroxypropyl methylcellulose (HPMC) was used as the dispersing additive in combination with nanofiberized cellulose (NFC) in a 5:1 NFC:HPMC ratio. The components were combined in an aqueous solution consisting of 1.25 wt% NFC. [Table 1]

[0152] First, 0.25 g of HPMC was added to 58.08 g of water in a beaker while stirring at medium to high speed for approximately 15 minutes. Then, the stirring speed was reduced to its lowest setting, and mixing continued until all bubbles on the surface disappeared. After removing the beaker from the stirring plate, 41.67 g of 3 wt% L NFC (1.25 g of dry weight NFC) was added. Next, these components were mixed using an overhead stirrer at 250 rpm for 15 minutes. The well-mixed sample was then scooped onto a silicone mat and spread evenly on the mat using a doctor blade set to a thickness of 1.5 mm. The mat with the sample was placed in an oven and dried at 60°C until the sample was completely dry (approximately 2 hours). The dried sheet was slowly removed from the silicone mat. As a result of these procedures, the previously non-dispersible NFC was modified with a drying / dispersing additive so that it could be redispersed when combined with water. Dry sheets containing such redispersible NFC were prepared using these procedures.

[0153] Example 2: Preparation and manufacture of a composite NCE-containing transaction card sheet The materials used in this example are: • Cellulose acetate butyrate (Sigma Aldrich) • Gumrosin (Sigma Aldrich) • Calcium carbonate (Sigma Aldrich) • Stearic acid (Sigma Aldrich) • Triacetin (Sigma Aldrich) • Triethyl 2-acetyl citrate (Sigma Aldrich) • Hydroxymethylpropylcellulose: Sigma Aldrich • Acetone (McMaster Carr) • Caprylglucoside (Berkley Green) It may include.

[0154] The equipment used in this embodiment is: Corning stirring plate • ONiLAB Overhead Stirrer CRUSHANUG Ultimate Design 5-ton hydraulic heat press machine with two 3x5 inch heating plates • Dia Vac pump Binder forced convection oven It may include.

[0155] This experiment tested an initial formulation for creating a credit card with the structure of a composite NCE-containing material, where the composite NCE-containing material contained a matrix with redispersed NCE. This process had three main stages: matrix preparation, reinforcing material addition, and heat press manufacturing.

[0156] Matrix preparation: Each of the desired components was added one at a time to a beaker of acetone while mixing the beakers with a magnetic stirring bar to form an acetone solution containing 12 wt% of the matrix components. The matrix components were added in the specified order, and the mixture was homogenized for a sufficient amount of time, after which the next component was added. Then, CAB, CA, or a combination of the two was added and stirred until no lumps remained (approximately 30 minutes to 1 hour). Selectively but finally, the plasticizer was added to the mixture and stirred for at least 15 minutes to obtain a homogeneous mixture.

[0157] The following components were used to create three different matrices. The components are listed in the order they were added to the acetone beaker. Table 1 below provides a summary of the specific amounts of each component used. Matrix 1: Rosin, Capryl Glucoside (CG), CAB, TEA • Matrix 2: Stearic acid, CC, CAB, TEA Matrix 3: Rosin, stearic acid, CC, CAB, triacetin [Table 2]

[0158] The following components were used to create three different matrices. The components are listed in the order they were added to the acetone beaker. Table 2 below provides a summary of the specific amounts of each component used.

[0159] Addition of redispersed NCE-containing formulation: A sheet of redispersible NCE prepared as described in Example 1 was added to a large beaker and vigorously mixed for 30 minutes using an overhead stirrer. In these experiments, the inventors used an equal amount of dry NCE to CAB. Acetone was added along with the well-dispersed fibers and thoroughly mixed using a stirring rod. The amount of acetone included was 40% of the weight of the redispersed NFC solution. Once the mixture was homogenized, the reinforcing material was readily added to the matrix. The following table (Table 2) lists the amounts of NCE and acetone required for addition to matrices 1, 2, and 3. [Table 3]

[0160] The redispersed NCE acetone mixture was then added to a beaker containing the matrix components and mixed using a turbine stirrer on an overhead stirrer for 10 minutes until homogeneous.

[0161] Heat Press Manufacturing: The final step of this experiment involved using a heat press to form the newly created composite mixture into a thin structure suitable for use in transaction cards. Before inserting the material into the heat press, excess acetone was removed using a sieve and a vacuum filtration pump. The filtration system consisted of a vacuum pump and two Erlenmeyer flasks, all connected by piping. The sieve was taped to a funnel and connected to the first flask using piping. The composite material was then placed on the sieve and the vacuum was turned on. The liquid was removed from the composite material through the sieve and then the funnel; the liquid was then collected in the first Erlenmeyer flask through the piping. This step was complete when no more liquid could be removed through the funnel. The composite NCE-containing material was solid after this excess liquid was removed. This was the desired state for holding the material together until it was compressed in the heat press, without being completely dry.

[0162] The heat press was turned on and set to 110°C. Five grams of composite NCE-containing material was pressed by hand into a flat rectangle (approximately 3 mm thick) and placed between two pieces of a silicone mat. As the press heated up, the silicone mat containing the composite material was positioned on the lower plate of the press. The upper plate was then lowered, making slight contact with the upper silicone mat, to begin heating the material. After two minutes, the plate was lowered slightly, applying some more pressure to the material. These processes were repeated until sufficient pressure was applied to press the material to the desired thickness, such as a 1 mm thick sheet that could be further cut into shapes useful for transaction cards such as credit cards.

[0163] Example 3: Preparation and manufacture of a composite NCE-containing transaction card sheet Matrix Preparation: An acetone solution containing 10 wt% of the matrix component was formed by adding each of the desired components one by one to a beaker of acetone while mixing the beaker with a magnetic stirring bar. The matrix components were added in the specified order, and the mixture was homogenized for a sufficient amount of time before the next component was added. Rosin was added to the acetone first, then CAB or CA, and finally the plasticizer. Mixing was continued until the solution was homogenized, and then further components were added.

[0164] A sheet of redispersible NCE prepared as described in Example 1 was added to a large beaker and vigorously mixed in an overhead stirrer for 30 minutes. The amount of NCE used depended on the desired final stiffness of the material. Cards with a higher NFC load of approximately 28% and a lower load of approximately 17% were prepared. Pulp was then added to the redispersed NCE solution and mixed. Acetone was then added to the solution.

[0165] Acetone was added to thoroughly disperse the fibers and then completely mixed with a stirring rod. The amount of acetone included was 40% of the weight of the redispersed NFC solution. Once the mixture was homogenized, the reinforcing material was readily added to the matrix at a load of 23x relative to the solid fibers (1:23 pulp + NCE:acetone). The addition of acetone assisted in the addition of hydrophilic cellulose fibers to the hydrophobic solution. It was ideal to use pulp with a low solid content in water and redispersed NCE to aid in homogeneous mixing. After the addition of acetone, the solution was further mixed with high shear force using an overhead stirrer. Capryl glucoside was also added to this solution to assist in crosslinking of polar and nonpolar components during mixing in the next step. After both the matrix and reinforcing material were completely mixed, the two solutions were readily combined. The reinforcing material solution was slowly added to the matrix solution and mixed vigorously under high shear force conditions.

[0166] The following table (Table 3) lists exemplary formulations of cards produced using CAB. The ratios of these formulations may also apply to samples produced by extrusion molding. [Table 4]

[0167] Heat Press Manufacturing: The final step of this experiment involved using a heat press to form the newly fabricated composite mixture into a thin structure suitable for use in transaction cards or other rigid packaging applications. Before heat pressing the material, it was heated uniformly in an oven at 50-70°C for 5-30 minutes to evaporate some of the solvent. The heat press was turned on and set to 120°C. A rectangular mold was placed on the press with an upper silicone mat and filled with the composite material. A mesh net and a second silicone mat were placed on top of the mold. The upper plate was then lowered, slightly in contact with the upper silicone mat, to begin heating the material. After 2 minutes, the plate was lowered further to apply more pressure to the material. These processes were repeated until sufficient pressure was applied to evaporate the solvent, compressing the material into a 1mm thick sheet that could be further cut into shapes useful for transaction cards, such as credit cards, for example.

[0168] While the present invention is particularly shown and described in relation to its preferred embodiments, it will be understood by those skilled in the art that various variations in form and detail can be made in the present invention without departing from the scope of the invention as encompassed in the appended claims. All U.S. patents and published or unpublished U.S. patent applications cited herein are incorporated by reference. All published foreign patents and patent applications cited herein are incorporated by reference. All other published references, documents, manuscripts and scientific literature cited herein are incorporated by reference. All relevant teachings in all patents, published applications and references cited herein are incorporated by reference in their entirety.

Claims

1. A simple NCE-based material containing a simple NCE-based matrix, A simple NCE matrix comprises a population of redispersible NCEs treated with a drying / dispersing additive containing a low critical solution temperature (LCST) polymer; A simple NCE matrix provides a structural framework for simple NCE materials; Simple NCE-based materials further include barrier formulations. Simple NCE-based material.

2. The simple NCE-based material according to claim 1, wherein the barrier formulation comprises a substance selected from the group consisting of cellulose polymers, lipids, proteins, fillers, fatty acids, resin acids, and combinations of resin acids.

3. The simple NCE-based material according to claim 2, wherein the barrier formulation comprises a resin acid or a combination of resin acids.

4. The simple NCE-based material according to claim 1, wherein the barrier formulation comprises an oleophobic substance selected from the group consisting of MC, HPMC, CMC, NaCMC, CA, CAB, chitosan, rosin, lignin, and plant proteins.

5. The simple NCE-based material according to claim 1, wherein the barrier formulation comprises a hydrophobic substance selected from the group consisting of MC, CA, CAB, chitosan, rosin, hydrophobic starch, lignin, and plant protein.

6. The simple NCE material according to claim 1, further comprising one or more additive substances selected from the group consisting of bulking agents, reinforcing agents, or appearance modifiers, or combinations thereof.

7. The simple NCE material according to claim 6, wherein one or more additive substances are fillers.

8. The simple NCE material according to claim 7, wherein the bulking agent comprises pulp or a pulp-based substance.

9. The simple NCE-based material according to claim 8, wherein the simple NCE-based matrix is ​​predominantly pulp.

10. The simple NCE material according to claim 7, wherein the bulking agent includes filler particles.

11. The simple NCE-based material according to claim 10, wherein the filler particles contain a plant-derived organic material.

12. The simple NCE-based material according to claim 6, wherein one or more additive substances are reinforcing agents, and the reinforcing agents contain a further amount of NCE.

13. A plastic substrate comprising the simple NCE material described in claim 1.

14. A manufactured article comprising a plastic substrate according to claim 13, formed into a molded article.

15. The manufactured article according to claim 14, wherein the formed article is a container.

16. The manufactured article according to claim 15, wherein the container is a food container.

17. a. A process for producing a simple NCE system material containing redispersible NC elements, where the simple NCE system material is: i. To provide an initial suspension containing NC elements suspended in a fluid medium; ii. Combining the drying / dispersing additive with the initial suspension to form a flexible suspension of redispersible NCE; and iii. To form a simple NCE-based material in a flexible state by adding one or more additive substances to a flexible suspension of redispersible NCE while maintaining the flexibility of the redispersible NCE. It is manufactured by the following sub-processes; b. A process of forming or shaping a flexible, simple NCE-based material into a desired form, thereby manufacturing a plastic article. A method for manufacturing a plastic article containing a simple NCE-based material in a flexible state.

18. The method according to claim 17, wherein one or more additive substances are selected from the group consisting of reinforcing agents, barrier formulations, and bulking agents, and combinations thereof.

19. The manufacturing method according to claim 17, wherein the forming or shaping step includes extrusion molding.

20. A composite NCE-containing material comprising a composite NCE-containing matrix, The composite NCE-containing matrix comprises a population of redispersible NCEs and the existing matrix, treated with a drying / dispersing additive containing a low critical solution temperature (LCST) polymer; Redispersible NCE is incorporated into an existing matrix, and the existing matrix provides a structural framework for the composite NCE-containing material; The composite NCE-containing material further contains a barrier formulation. Composite NCE-containing material.

21. The composite NCE-containing material according to claim 20, wherein the existing matrix contains a bio-based polymer.

22. The composite NCE-containing material according to claim 21, wherein the bio-based polymer contains a cellulose derivative.

23. The composite NCE-containing material according to claim 22, wherein the cellulose derivative is a polyhydroxyalkanoate.

24. The composite NCE-containing material according to claim 20, wherein the existing matrix contains a petroleum-derived polymer.

25. The composite NCE-containing material according to claim 24, wherein the petroleum-derived polymer is derived from recycled plastic materials.

26. The composite NCE-containing material according to claim 20, wherein the barrier formulation comprises a substance selected from the group consisting of cellulose polymers, lipids, proteins, fillers, fatty acids, resin acids, and combinations of resin acids.

27. The composite NCE-containing material according to claim 26, wherein the barrier formulation comprises a resin acid or a combination of resin acids.

28. The composite NCE material according to claim 20, further comprising one or more additive substances selected from the group consisting of bulking agents, reinforcing agents, or appearance modifiers, or combinations thereof.

29. The composite NCE-containing material according to claim 20, wherein one or more additive substances produce properties selected from the group consisting of structural strength, resilience, elasticity, water resistance, and oil and grease resistance in the composite NCE-containing material.

30. A plastic substrate comprising the composite NCE-containing material according to claim 20.

31. A manufactured article comprising a plastic substrate according to claim 30, formed into a molded article.

32. The manufactured article according to claim 31, wherein the formed article is selected from the group consisting of transaction cards, liquid containers, food containers, packaging materials for consumer products, thin films and sheets, and hollow cylinders for flexible tubes.

33. a. A process for producing a composite NCE-containing material containing redispersible NC elements, wherein the composite NCE-containing material is: i. To provide an initial suspension containing NC elements suspended in a fluid medium; ii. Combining the drying / dispersing additive with the initial suspension to form a flexible suspension of redispersible NCE; iii. Incorporating flexible suspensions into an existing matrix to form a flexible composite NCE-containing matrix; iv. Adding an additive substance to at least one of the initial suspension, the flexible suspension, the existing matrix, and the composite NCE-containing matrix to maintain its flexibility, thereby forming a flexible composite NCE-containing material. It is produced by the sub-process of; and b. A process of forming or shaping a flexible composite NCE-containing material into a desired form, thereby manufacturing a formed article. A method for manufacturing a plastic article containing a flexible composite NCE-containing material.

34. The method according to claim 33, wherein the additive substance is selected from the group consisting of reinforcing agents, barrier formulations, and bulking agents.

35. The method according to claim 33, wherein the step of forming or shaping includes extrusion molding.

Images