Hybrid materials based on nanocellulose

Abstract

The present invention provides a sustainable alternative nanocellulose-based hybrid material that has improved strength and flexibility as compared to known biopolymer and leather substitutes. The invention further provides a method of producing the nanocellulose-based hybrid material.

Description

Technical Field

[0001] This disclosure relates to cellulose nanoparticle-based hybrid materials and methods for their preparation. Cellulose nanoparticle-based hybrid materials can be used in a variety of applications, including textiles incorporating said materials for clothing, footwear, wearable accessories, interior furniture, automotive and aerospace upholstery, interior decoration, packaging, and medical applications. Background Technology

[0002] In the fashion industry, sheet / film materials used for footwear and accessories are typically made of animal leather, polyurethane, or PVC. These materials are durable, thick, flexible, and soft to the touch, but present ethical and sustainability challenges.

[0003] Cellulose-based nonwoven sheets or films are known to be used in the production of paper materials for applications such as filters, absorbent cleaning materials, packaging, or disposable products. These materials are often too stiff or too weak for textile applications.

[0004] Bacterial cellulose materials known in the art lack the flexural strength of animal or synthetic leather, which limits their applications.

[0005] The purpose of this invention is to provide an alternative, sustainable, bio-based material with unique tensile strength and flexibility for textile applications. Summary of the Invention

[0006] This invention provides a sustainable alternative bio-based material that exhibits improved strength and flexibility compared to known biopolymers and leather alternatives.

[0007] The present invention provides a bio-based material composition comprising: (a) cellulose; (b) anionic polysaccharide; and (c) cationic polysaccharide; wherein the composition is cross-linked.

[0008] In some embodiments, cellulose is nanocellulose. In some embodiments, cellulose is bacterial nanocellulose.

[0009] In some embodiments, the anionic polysaccharide is one or more anionic polysaccharides selected from the group consisting of: pectin, alginate, gellan gum, carboxymethyl cellulose, hyaluronic acid, and polyglutamic acid (PGA). In some embodiments, the anionic polysaccharide is pectin.

[0010] In some embodiments, the cationic polysaccharide comprises or is composed of cationic microfibrillated cellulose (MFC) and / or cationic starch.

[0011] In some embodiments, the composition is crosslinked via one or more tricarboxylic acids selected from the group consisting of citric acid, isocitric acid, aconitic acid, propane-1,2,3-tricarboxylic acid, muscaric acid, and benzotriic acid. In some embodiments, the composition is crosslinked via chemical crosslinking and / or via physical crosslinking.

[0012] In some embodiments, the composition comprises a humectant. In some embodiments, the composition comprises a humectant comprising or consisting of one or more humectants selected from the group consisting of glycerol, sorbitol, xylitol, mannitol, erythritol, maltitol, isomaltitol, lactitol, hydrogenated starch hydrolysate (HSH), and polyhydroxyols. In some embodiments, the composition comprises glycerol.

[0013] In some embodiments, the composition comprises one or more fillers.

[0014] In some embodiments, the composition comprises cellulose: anionic polysaccharide: cationic polysaccharide in a ratio of 4:1:5.

[0015] The present invention further provides a method for producing a bio-based material composition, the method comprising the steps of: (a) providing a mixture comprising cellulose, anionic polysaccharides and cationic polysaccharides; (b) crosslinking the polysaccharides of step (a); and thereby obtaining a bio-based material composition.

[0016] In some embodiments, the method of the present invention comprises providing a mixture of cellulose, anionic polysaccharide and cationic polysaccharide, wherein the weight ratio of cellulose to anionic polysaccharide to cationic polysaccharide in step (a) is approximately 4:1:5.

[0017] In some embodiments, the method of the present invention further includes a step (i) of blending the cellulose, wherein step (i) is performed prior to step (a). In some embodiments, step (i) includes blending the cellulose with a wetting agent and / or water. In some embodiments of the method of the present invention, the wetting agent comprises or consists of one or more wetting agents selected from the group consisting of glycerol, sorbitol, xylitol, mannitol, erythritol, maltitol, isomaltitol, lactitol, hydrogenated starch hydrolysate (HSH), and polyhydroxyols. In some embodiments, the wetting agent comprises glycerol.

[0018] In some embodiments of the method of the present invention, the method further includes a step (c) of heating and / or stirring the mixture. In some embodiments of the method of the present invention, the method further includes a step (d) of casting and / or coating the mixture into a mold, on a support, and / or on a substrate. In some embodiments of the method of the present invention, the method further includes a step (e) of drying the cast mixture. In some embodiments of the method of the present invention, the method further includes a step (ii) of adding one or more fillers to the mixture, wherein step (ii) may be performed before or after step (b). In some embodiments of the method of the present invention, the method further includes a step (iii) of adding one or more dyes to the mixture, wherein step (iii) may be performed before, after, after, or after step (d) or step (e). In some embodiments of the method of the present invention, the method further includes a step (iv) of subjecting the composition to plasma treatment, surface coating, and / or surface functionalization, wherein step (iv) may be performed after, after, or after step (e).

[0019] In some embodiments of the method of the present invention, the method for producing the composition is a green method, wherein (a) all reagents and products used in the method are biologically based; (b) the method does not contain petrochemical products; (c) the method utilizes only non-toxic chemicals; and / or (d) the method is sustainable.

[0020] This invention provides a hybrid material based on nanocellulose, comprising bacterial cellulose (BC), pectin, cationic microfibrillated cellulose (MFC), and glycerol.

[0021] In some embodiments, the material comprises cationic MFC, pectin, and BC in a ratio of 1:8:11 (cationic MFC: pectin: BC).

[0022] In some embodiments, the material comprises cationic MFC, pectin and BC in a ratio of 1:5:4 (cationic MFC: pectin: BC).

[0023] In some embodiments, the material comprises approximately 15% to 80% by weight of BC, approximately 10% to 70% by weight of pectin, approximately 1% to 10% by weight of cationic MFC, approximately 5% to 60% by weight of glycerol, and / or approximately 3% to 20% by weight of water. In some embodiments, the material comprises approximately 0.5% to 50% by weight of BC, approximately 0.5% to 70% by weight of pectin, approximately 1% to 10% by weight of cationic MFC, approximately 0.5% to 60% by weight of glycerol, and / or approximately 3% to 20% by weight of water. In one embodiment, the material comprises approximately 27.5% by weight of BC, approximately 20% by weight of pectin, approximately 2.5% by weight of cationic MFC, approximately 40% by weight of glycerol, and / or approximately 10% by weight of water. In one embodiment, the material comprises approximately 18.2% by weight of BC, approximately 22% by weight of pectin, approximately 4.5% by weight of cationic MFC, approximately 40.3% by weight of glycerol, and / or approximately 15% by weight of water.

[0024] In one embodiment, the material of the present invention is coated onto the support. In another embodiment, the material of the present invention is cast and / or coated onto the support and / or substrate.

[0025] In one embodiment, the material further comprises inorganic fillers, such as ceramic fillers (e.g., calcium carbonate).

[0026] In some embodiments, the tensile strength of the material is approximately 180 N or 18.5 kg. In some embodiments, the maximum elongation of the material is 8.7%. In some embodiments, the material has flexural strength such that it does not break after 25,000 flexures when measured by a flexometer (such as a Bally flexometer) and / or according to ISO 5402-1.

[0027] The present invention further provides materials of the present invention for use in textiles. The present invention further provides clothing, footwear, wearable accessories, interior furniture, automotive and aerospace upholstery, interior decoration, packaging, and medical applications incorporating materials of the present invention.

[0028] The present invention further provides a method for producing the nanocellulose material of the present invention. In one embodiment, the method comprises the following steps: (1) obtaining and processing bacterial cellulose; (2) mixing the bacterial cellulose, pectin, cationic microfibrillated cellulose (MFC), glycerol and optionally an inorganic filler together to produce a slurry; (3) pouring the slurry into a mold; (4) optionally drying the resulting slurry material; and (5) thereby obtaining the final bio-based textile material of the present invention.

[0029] In another embodiment, the present invention provides a method for producing the nanocellulose material of the present invention using a scaffold. The method comprises the following steps: (1) obtaining and processing bacterial cellulose; (2) mixing the bacterial cellulose, pectin, cationic microfibrillated cellulose (MFC), glycerol and optionally an inorganic filler together to produce a slurry; (3) pouring the slurry into a mold; (4) placing the scaffold within the slurry; (5) optionally pouring additional slurry such that the scaffold is encapsulated within the slurry; (6) optionally drying the resulting scaffold-slurry material; and (7) thereby obtaining the final bio-based textile material of the present invention.

[0030] The mixing step of the method can be carried out in a top-mounted agitator. The drying step of the method can be carried out in an oven.

[0031] Within the scope of this disclosure, it is expressly intended that the various aspects, embodiments, examples, and alternatives listed in the foregoing paragraphs, claims, and / or the following description and drawings, and in particular their various features, may be employed independently or in any combination. That is, all embodiments and / or features of any embodiment may be combined in any way and / or in any combination unless such features are incompatible. Attached Figure Description

[0032] Figure 1 Scanning electron microscope (SEM) images of the materials according to the invention are depicted. Imaging was performed as described in Example 5. The structure of the cellulose nanoparticle-based hybrid material is shown. A finely interwoven network of blended biopolymer fibers is visible, in which fibers of varying thicknesses surround an aggregated biopolymer encapsulation.

[0033] Figures 2A to 2H The stress test results of the formulation in Table 5 of Example 7 are depicted. Figure 2A Involves formulation B1; Figure 2B Involves formulation B2; Figure 2C Involves formulation B3; Figure 2D Involves formulation B4; Figure 2E Involves formulation B5 (prepared at pH 4); Figure 2F Involves formulation B6; Figure 2G This involves formulation B5 (prepared at pH 10); Figure 2H This involves formulation B7. Figures 2A to 2H The stress test results shown are illustrated in Table 5 of Example 7.

[0034] Figures 3A to 3D SEM images of the bio-based material composition according to the invention, namely, the cross-linked cellulose nanofiber-based hybrid material of formulation B6 according to Example 7, produced according to the method of Example 6, are depicted. Imaging was performed as described in Example 8. Detailed Implementation

[0035] definition

[0036] To aid in understanding this invention, several terms are defined herein.

[0037] As used herein, the term 'comprising' means that any of the elements set forth must be included, and other elements may optionally be included. 'substantially constitutes' means that any of the elements set forth must be included, excluding elements that would substantially affect the essential and novel characteristics of the listed elements, and other elements may optionally be included. 'consisting of' means excluding all elements other than those listed. Embodiments defined by each of these terms are within the scope of this invention.

[0038] As used herein, the terms 'bacterial cellulose', 'nanocellulose', 'bacterial nanocellulose', 'bacterial-derived cellulose', and 'bacterial-derived nanocellulose' are equivalent and refer to cellulose macromolecules produced by bacteria, such as those from the genus *Komagataeibacter* (formerly known as *Gluconacetobacter* or *Acetobacter*), characterized by high tensile strength, high tensile stiffness, high chemical purity, biocompatibility, and a high water-to-cellulose ratio. Suitablely, such bacterial nanocellulose will be substantially free of related molecules, such as lignin, typically found in plant-derived cellulose.

[0039] As used herein, the terms 'crosslinking', 'crosslink', or 'crosslinked' should be understood to encompass any chemical or physical intermolecular interaction (hereinafter referred to as chemical crosslinking and physical crosslinking). Non-limiting examples of 'chemical crosslinking' are covalent bonds, ionic bonds, and coordinate bonds. Non-limiting examples of 'physical crosslinking' are hydrogen bonding, van der Waals forces, dipole-dipole interactions, ion-dipole interactions, ion-ion interactions, electrostatic interactions, London dispersion forces, and π-π interactions. As used herein, the term 'chemical crosslinking' may refer to a chemical bond or an intermolecular bond. As used herein, the term 'physical crosslinking' may refer to an electrostatic interaction or a steric interaction. As used herein, the terms 'crosslinking', 'crosslink', or 'crosslinked' may encompass both chemical crosslinking and physical crosslinking.

[0040] This document should be understood to mean that when a material or composition is 'crosslinked' (or any other variation thereof) by means of a 'crosslinking agent', it can be understood as subjecting the material to a crosslinking reaction promoted by, involving, consisting of, or containing a crosslinking agent, thereby forming a crosslink. A non-limiting example of such a crosslinking agent is a tricarboxylic acid selected from the group consisting of citric acid, isocitric acid, aconitic acid, propane-1,2,3-tricarboxylic acid, muscaric acid, and benzoic acid. The crosslinking agent can promote crosslinking. Crosslinking can consist of or contain a crosslinking agent.

[0041] As used herein, the terms 'bio-based material composition', 'composition', 'bio-based material', 'biomaterial', 'material' and 'nanocellulose-based hybrid material' are equivalent and interchangeable terms.

[0042] As used herein, the term 'anionic polysaccharide' can be considered to refer to any one or more anionic polysaccharides. Anionic polysaccharides are polysaccharides that carry a negative charge.

[0043] As used herein, the term 'cationic polysaccharide' can be considered to refer to any one or more cationic polysaccharides. Cationic polysaccharides can comprise natural cationic and / or cationic-modified polysaccharides. Cationic polysaccharides are polysaccharides carrying a positive charge.

[0044] "Wetting agent" is any substance or compound that has hygroscopic properties, capable of absorbing and retaining moisture from the surrounding environment. As used herein, the term "wetting agent" may be considered to refer to one or more wetting agents. As used herein, a wetting agent may be a plasticizer.

[0045] As used herein, the term 'strength' (or its variations) can be considered to refer to one or more strength properties tested by the International Organization for Standardization (ISO) standards ISO 13934-1:2013, BS EN ISO 5402-1:2022, BS EN ISO 4674-1:2016, BS EN ISO 13936-3:2007, BS EN ISO 13935-2:2014, and BS EN ISO 3377-1:2011. Therefore, 'strength' can also refer to the tensile strength of a material. The term 'tensile strength' is interchangeable with the terms 'Young's Modulus', 'Young's Modulus Value', or 'YM'. As used herein, the term 'strength' may also relate to the durability of any of the aforementioned properties; that is, a robust material may possess tensile strength that does not significantly decrease over time.

[0046] As used herein, the term 'flexibility' (or its variations) may be considered to refer to flexibility in dynamic cyclic testing, such as the Bally flexure test (e.g., according to ISO 5402-1:2022) or any other suitable equivalent flexibility test. As used herein, the term 'flexibility' may also relate to the persistence of a material's flexibility properties, i.e., a flexible material may possess Bally flexure that does not significantly decrease over time.

[0047] As used herein, the term 'nanocellulose' is defined as cellulose comprising fibers or composed of fibers with widths in the nanometer range.

[0048] Microfibrillated cellulose (MFC) is a type of cellulose in which the outer layer of fibers is peeled off by mechanical shearing, exposing the protofibrillary bundles.

[0049] As used herein, the term 'non-toxic' or 'non-toxic chemical' can be defined as a chemical, chemical substance, or chemical process that is substantially permitted under the Control of Substances Hazardous to Health Regulations (COSHH) guidelines. As used herein, the term 'non-toxic' or 'non-toxic chemical' can also be defined as a chemical, chemical substance, or chemical process that is not considered highly hazardous (e.g., to humans, animals, or the environment).

[0050] Unless otherwise stated, any composition component ratios defined herein shall be interpreted as including or excluding the wet weight of the composition. Unless otherwise stated, any composition component ratios defined herein shall be interpreted as calculated on a weight basis.

[0051] As used herein, the term 'a' (an abbreviated as 'a') is used to indicate that a particular element, component, or feature may refer to both the singular and plural forms. Throughout the specification and claims, 'a' (an abbreviated as 'a') covers instances where the mentioned element, component, or feature may appear once or multiple times.

[0052] It should be understood that, within the scope of this invention, any or all of the various embodiments described herein may be combined.

[0053] Properties of hybrid materials based on nanocellulose

[0054] This invention provides a nanocellulose-based hybrid material that exhibits improved strength and flexibility compared to other known leather alternatives.

[0055] The material of this invention has been shown to have a tensile strength of 127 MPa (NB. MPa and N / mm). 2(These are equivalent units). Compared to other leather alternatives in the prior art, the material of the present invention not only has superior tensile strength, but also improved tensile strength relative to leather itself.

[0056] The material of this invention achieves tensile strength far superior to known materials without compromising flexibility. The material of this invention has been shown to exhibit resistance to flexural stress (as determined using BS EN ISO 5402-1:2022) without cracking after 25,000 cycles. This level of flexibility makes the material suitable for the wide range of applications envisioned herein. Surprisingly, despite its high tensile strength, the material maintains such high flexibility. This high level of flexibility is further demonstrated at industrially relevant thicknesses. For example, the flexural stress values ​​reported herein were tested at a thickness of 0.8 mm. The material also maintains the same high level of flexibility at other thicknesses, for example, between about 0.1 mm and 3.0 mm.

[0057] The materials of this invention have increased tensile strength compared to leather and / or leather substitutes. In some embodiments, the Young's modulus of the material is at least 50 MPa, at least 75 MPa, at least 100 MPa, at least 125 MPa, at least 150 MPa, or at least 175 MPa. In some embodiments, the Young's modulus of the material is 127 MPa. The Young's modulus value of the tensile strength of the material can be measured using ISO 13934-1:2013 or any equivalent or suitable method in the art.

[0058] The material of the present invention exhibits high flexibility and / or flexural strength. In some embodiments, the material exhibits flexural strength and / or shows no breakage after 15,000, 20,000, 25,000, 30,000, 35,000, 40,000, 45,000, or 50,000 cycles. In some embodiments, the material exhibits flexural strength and / or shows no breakage after 25,000 cycles. The flexibility and / or flexural strength of the material can be measured using a flexometer according to BS EN ISO 5402-1:2022 or any equivalent or suitable method in the art.

[0059] The materials of this invention possess tear resistance suitable for a variety of applications contemplated herein. In some embodiments, the tear resistance of the material is at least 3 N, at least 5 N, at least 6 N, at least 7 N, at least 8 N, at least 9 N, or at least 10 N. In some embodiments, the tear resistance of the material is at least 5 N. The tear resistance of the material can be measured using BS EN ISO4674-1:2016 or any equivalent or suitable method in the art.

[0060] The materials of this invention possess resistance to seam slippage suitable for a variety of applications contemplated herein. In some embodiments, the resistance to seam slippage of the material is at least 40 N, at least 50 N, at least 60 N, at least 70 N, at least 80 N, at least 90 N, or at least 100 N. In some embodiments, the resistance to seam slippage of the material is at least 60 N. The resistance to seam slippage of the material can be measured using BS EN ISO 13936-3:2007 or any equivalent or suitable method in the art.

[0061] The materials of this invention have seam strengths suitable for a variety of applications contemplated herein. In some embodiments, the warp seam strength of the material is at least 10 N, at least 20 N, at least 30 N, at least 40 N, or at least 50 N. In some embodiments, the warp seam strength of the material is at least 22 N. In some embodiments, the weft seam strength of the material is at least 50 N, at least 60 N, at least 70 N, at least 80 N, at least 90 N, or at least 100 N. In some embodiments, the weft seam strength of the material is at least 58 N. The resistance to seam slippage of the material can be measured using BS EN ISO 13935-2:2014 or any equivalent or suitable method in the art.

[0062] The materials of this invention have tear loads suitable for a variety of applications contemplated herein. In some embodiments, the tear load of the material is at least 2 N, at least 3 N, at least 4 N, at least 5 N, at least 6 N, at least 7 N, at least 8 N, at least 9 N, or at least 10 N. In some embodiments, the tear load of the material is at least 3.7 N. The tear load of the material can be measured using BS EN ISO 3377-1:2011 or any equivalent or suitable method in the art.

[0063] The materials of this invention overcome the ethical and ecological problems associated with animal-based materials such as leather. The materials of this invention are substantially biological-based, optionally up to 100% biological-based, sustainable, biodegradable, and suitably free of petrochemical products. The chemicals used to produce the materials are of low toxicity, and suitably are non-toxic. Furthermore, unlike other leather alternatives (such as 'fruit leather'), the materials of this invention have defined starting materials, resulting in more predictable end products and thus suitability for industrial manufacturing and quality control.

[0064] The strength and flexibility of the material can be attributed to novel crosslinking within the material, resulting in a surprisingly significant increase in both strength and flexibility. The chemical linkages (e.g., via covalent bonding) of the cellulose, anionic polysaccharides, and cationic polysaccharides in the material of the present invention enhance the material strength beyond what is typically expected. Furthermore, the use of cationic polysaccharides (such as cationic MFCs) also improves the tensile strength of the material of the present invention by promoting ionic crosslinking within the material. Due to this covalent crosslinking by the covalent crosslinking agent (such as citric acid) and the ionic interactions between (at least) the anionic and cationic polysaccharides, the material exhibits unexpectedly high strength and flexibility. The combined effect of cationic polysaccharides and covalent crosslinking is beyond additive in improving strength and flexibility properties. The material of the present invention can be covalently crosslinked and / or ionicly crosslinked. The material of the present invention can be chemically crosslinked and / or physically crosslinked. Further details of these improved properties of the material of the present invention can be found in examples, such as Examples 3, 4, 7, and / or 9.

[0065] The use of cationic MFCs instead of non-cationic MFCs resulted in an unexpectedly high increase in the tensile strength of the material. This can be attributed to the strong chemical crosslinking between the cationic MFCs and the crosslinking agent. Such a high degree of crosslinking was not observed in the presence of non-ionic MFCs, suggesting that the high tensile strength of the material of the present invention may be attributed to the presence of cationic groups (e.g., quaternary ammonium groups) on the cationic MFCs. The chemical crosslinking and (at least) the physical crosslinking established between the cationic MFCs and cellulose work synergistically, for example, through electrostatic interactions, to achieve the high tensile strength of the material of the present invention.

[0066] Hybrid materials based on nanocellulose

[0067] This invention provides a bio-based material composition comprising: cellulose, anionic polysaccharides, and cationic polysaccharides, wherein the composition is cross-linked. In some embodiments, the cellulose is nanocellulose. In some embodiments, the cellulose is bacterial cellulose. In some embodiments, the cellulose is bacterial nanocellulose. In some embodiments, the anionic polysaccharide is selected from the group consisting of: pectin, alginate, gellan gum, carboxymethyl cellulose, hyaluronic acid, and polyglutamic acid (PGA). In some embodiments, the anionic polysaccharide is pectin. In some embodiments, the cationic polysaccharide is cationic microfibrillated cellulose (MFC) and / or cationic starch. The cationic polysaccharide may comprise natural cationic and / or cationic modified polysaccharides. For example, in some embodiments, the cationic polysaccharide comprises quaternary ammonium cationic modified MFC and / or quaternary ammonium cationic modified starch. Suitably, the polysaccharides used in this invention can be modified with alternative cationic groups known to those skilled in the art.

[0068] The bio-based material compositions of the present invention can be chemically or physically cross-linked, such as covalently, ionicly, and / or electrostatically cross-linked. The cross-linking of the polysaccharides in the composition improves its flexibility and strength. In some embodiments, the composition is cross-linked via one or more tricarboxylic acids selected from the group consisting of citric acid, isocitric acid, aconitic acid, propane-1,2,3-tricarboxylic acid, muscaric acid, and benzoic acid. In some embodiments, the composition is cross-linked via citric acid.

[0069] Humectants can be incorporated into the materials of the present invention to improve moisture management, prevent electrostatic adsorption, and / or enhance comfort. In some embodiments, the composition comprises a humectant. In some embodiments, the compositions of the present invention comprise one or more humectants selected from the group consisting of glycerol, sorbitol, xylitol, mannitol, erythritol, maltitol, isomaltitol, lactitol, hydrogenated starch hydrolysate (HSH), and polyols. In some embodiments, the composition comprises glycerol.

[0070] Polymers can be incorporated into the composition to achieve further desired properties for the purposes envisioned herein. In some embodiments, the composition may comprise polymers selected from the group consisting of: polylactic acid (PLA), polyhydroxyalkanoates (PHA), chitosan, polyglycolic acid, polyhydroxypolyurethane (PHU), poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV), polydioxanone (PDO), poly-ε-caprolactone (PCL), alginate, hyaluronic acid, poly(lactic-co-glycolic acid) (PLGA), carrageenan, gum arabic, xyloglucan, and polyethylene glycol (PEG).

[0071] Proteins can be incorporated into the composition to achieve further desired properties for the purposes contemplated herein. In some embodiments, the composition may comprise a protein selected from the group consisting of gelatin, silk, or elastin.

[0072] Fillers can be further incorporated into the composition to achieve further desired properties for the intended uses described herein. It is envisioned that ceramic and / or natural short fiber fillers be incorporated into the materials of the present invention. In some embodiments, the composition comprises one or more fillers selected from the group consisting of: hydroxyapatite (HA), tricalcium phosphate (TCP), zirconium oxide, alumina, silica, glass ceramics, bioglass, calcium phosphate, calcium, cotton fiber, flax fiber, hemp fiber, jute fiber, bamboo fiber, silk fiber, wool fiber, kenaf fiber, ramie fiber, coconut fiber (coconut shell fiber), banana fiber, bagasse fiber, regenerated cellulose fiber, and wood fiber.

[0073] The composition may further comprise surface functionalization, such as treatment with a sizing agent, coating with a surface coating, or plasma treatment. In some embodiments, the sizing agent used in this invention is an alkylated ketene dimer, silane chemicals, and acetylation. In some embodiments, the composition may be coated in one or more surface coatings selected from the group consisting of: natural waxes, bioplastics, polylactic acid (PLA), polyhydroxyalkanoates (PHA), polyhydroxybutyrate (PHB), cellulose, esters (e.g., acetate, cellulose acetate butyrate, or other suitable esters), plant proteins, soy protein, pea protein, corn protein, ceramics, liquid nanoglass, and nanoglass. In some embodiments, the composition comprises nanoparticles that absorb and / or emit electromagnetic radiation.

[0074] The compositions of the present invention may further comprise a scaffold and / or a substrate. In some embodiments, the scaffold and / or substrate comprises one or more materials selected from the group consisting of yarns, textiles, electrospun nanofibers, nonwoven fabrics, knitted fabrics, woven fabrics, braided structures, fiber webs, felts, and porous textiles. In some embodiments, the composition further comprises a backing material, such as a textile. In some embodiments, the composition is adhered to the backing material.

[0075] The composition can be used as a bio-based material. The composition can be used as a leather substitute. The composition can be formulated into sheets. The composition can be embossed and / or stamped. The thickness of the composition can be less than 10 mm, less than 5 mm, less than 3 mm, less than 2 mm, or less than 1 mm. The thickness of the composition can be greater than 0.01 mm, greater than 0.05 mm, greater than 0.1 mm, or greater than 1 mm.

[0076] Articles comprising the said compositions are also envisioned. For example, clothing articles, accessories, home furnishings, automotive upholstery, automotive trim materials, or packaging materials comprising or composed of the compositions of the present invention are all within the scope of the present invention. Such examples include, but are not limited to: shoes, boots, sandals, socks, jackets, hats, gloves, shirts, T-shirts, sweaters, trousers, underwear, bags, handbags, jewelry, sunglasses, eyeglasses, suitcases, wallets, purses, pencil cases, cosmetic bags, phone cases, earphones, watch straps, cushion covers, upholstery suitable for sofas or chairs, curtains, blinds, lampshades, carpets, floor mats, doormats, tablecloths, and yoga mats.

[0077] It is also envisioned to use dyes in the composition to impart technical and / or aesthetic benefits to the composition. In some embodiments, the composition further comprises or has been stained. In some embodiments, the dye is a natural dye. In some embodiments, the dye is bacterially produced. In some embodiments, the dye is a color-changing and / or responsive dye, such as an electrochromic, thermochromic, or photochromic dye.

[0078] In some embodiments, a nanocellulose-based hybrid material is further provided, comprising bacterial cellulose (BC), a heteropolysaccharide, a cationic MFC, and a humectant. The heteropolysaccharide may be one or more heteropolysaccharides selected from the group consisting of pectin, agar, gelatin, guar gum, and corn starch. The humectant may be one or more humectants selected from the group consisting of glycerol, polyethylene glycol (PEG), hyaluronic acid, and alpha-hydroxy acids (such as glycolic acid, lactic acid, and citric acid).

[0079] In one embodiment, the nanocellulose-based hybrid material of the present invention comprises bacterial cellulose (BC), pectin, cationic MFC, and glycerol.

[0080] In some embodiments, the material comprises cationic MFC, pectin and BC in a weight ratio of 1:8:11 (cationic MFC: pectin: BC).

[0081] In some embodiments, the material comprises cationic MFC, pectin and BC in a weight ratio of 1:5:4 (cationic MFC: pectin: BC).

[0082] In one embodiment, the material of the present invention is coated onto a scaffold. The scaffold may comprise one or more materials selected from the group consisting of: yarns, textiles, electrospun nanofibers, nonwoven fabrics, knitted fabrics, woven fabrics, braided structures, fiber webs, felts, and porous textiles. In some embodiments, the material is used as a textile or leather substitute.

[0083] In one embodiment, the material further comprises an inorganic filler, such as a ceramic filler (e.g., calcium carbonate). In one embodiment, the material comprises one or more fillers selected from the group consisting of: hydroxyapatite (HA), tricalcium phosphate (TCP), zirconium oxide, alumina, silica, glass ceramics, bioglass, calcium phosphate, calcium sulfate, cotton fiber, flax fiber, hemp fiber, jute fiber, bamboo fiber, silk fiber, wool fiber, kenaf fiber, ramie fiber, coconut fiber (coconut shell fiber), banana fiber, bagasse fiber, and wood fiber.

[0084] In some embodiments, the material comprises about 15% to 80% by weight of BC, about 10% to 70% by weight of pectin, about 1% to 10% by weight of cationic MFC, about 5% to 60% by weight of glycerol, and / or about 3% to 20% by weight of water. In one embodiment, the material comprises about 27.5% by weight of BC, about 20% by weight of pectin, about 2.5% by weight of cationic MFC, about 40% by weight of glycerol, and / or about 10% by weight of water.

[0085] In some embodiments, the material comprises about 0.5% to 50% by weight of BC, about 0.5% to 70% by weight of pectin, about 1% to 10% by weight of cationic MFC, about 0.5% to 60% by weight of glycerol, and / or about 3% to 20% by weight of water. In one embodiment, the material comprises about 18.2% by weight of BC, about 22% by weight of pectin, about 4.5% by weight of cationic MFC, about 40.3% by weight of glycerol, and / or about 15% by weight of water.

[0086] Materials derived from bacterial cellulose, as known in the art, do not exhibit sufficient flexural strength and are unsuitable for use as textiles, such as leather substitutes. A key problem addressed by this invention is improving the flexibility of materials derived from bacterial cellulose while maintaining strength. Therefore, the materials of this invention are abrasion-resistant, durable, and suitable for the applications envisioned herein.

[0087] Adding heteropolysaccharides such as pectin to (plasticized) BC improves flexibility, but at the cost of tensile strength. However, in some embodiments, the addition of cationic MFCs in the preparation of the material of the present invention maintains a certain level of tensile strength and elongation, while also maintaining resistance to flexural deformation.

[0088] The material of this invention has a high Bally flexural value (i.e., high flexural strength). Results reported in Example 3 show that the unique formulation of this invention, combined with the production method of this invention, transforms the material from a wet hydrogel into a dry sheet, producing a novel material that not only possesses tensile strength comparable to commercial textiles but also exhibits increased flexibility in textile testing scenarios. When tested according to EN ISO 17694 (ISO 54021:2022 Bally flexural strength), the material of this invention did not exhibit cracking after 25,000 flexes.

[0089] The material of the present invention further possesses high tensile strength suitable for use as textiles and for all applications contemplated herein. When tested according to ISO 13934-1:2013, the tensile strength of the material of the present invention can be approximately 180 N or 18.5 kg. Suitably, when tested according to ISO 13934-1:2013, the material of the present invention can exhibit an elongation of approximately 8.7%.

[0090] As can be seen from Figure 2, the cellulose-based hybrid material of the present invention has a finely interwoven fiber network structure of blended biopolymers, wherein fibers of varying thicknesses surround aggregated biopolymer encapsulations. The nanostructure of the material supports the properties and technical advantages described herein.

[0091] The advantage of the bio-based materials of this invention lies in their ability to mimic or replace a wide variety of textiles, from nonwoven films to soft leather. Furthermore, the materials of this invention possess material properties that are at least equivalent to or even superior to those of such textiles.

[0092] Compared to BC and glycerol slurry formulations alone, the materials of the present invention exhibit improved rheological properties.

[0093] Methods for generating hybrid materials based on nanocellulose

[0094] The present invention further provides a method for producing biological-based material compositions. The improved properties of the materials of the present invention are a result of polysaccharide crosslinking. This is achieved by using a crosslinking agent to induce crosslinking within the composition. Crosslinking imparts surprisingly improved mechanical properties in the form of tensile strength and flexibility.

[0095] Furthermore, according to specific embodiments, the method of the present invention is a 'green' method, meaning that substantially all reagents and products used in the method can be bio-based; the method may be petrochemical-free; the method may use only low-toxicity or non-toxic chemicals; and / or the method is sustainable. In this context, 'reagent' can be considered to mean anything used in the method. In this context, 'petrochemical-free' can be considered to mean not using petrochemicals as reagents, not having reagents derived from petrochemicals, and / or not using petrochemicals in the production of any reagents used in the method. In this context, 'non-toxic chemicals' can be considered to mean not using toxic or polluting reagents, and / or the method does not produce, in part or as a result of, toxic or polluting products or byproducts. In this context, 'sustainable' can be considered to mean that, compared to conventional methods for manufacturing leather, leather substitutes, or other existing textiles, the method is low in energy intensity, low in carbon intensity, low in water intensity, low in land intensity, low in resources, produces more durable products, produces biodegradable products, and / or produces a lower carbon footprint.

[0096] In particular, compared with the crosslinking agents based on petrochemical products commonly used in the art, the materials and methods of the present invention use green crosslinking agents, such as organic crosslinking agents.

[0097] This invention provides a method for producing a bio-based material composition, the method comprising the steps of: (a) providing a mixture comprising cellulose, anionic polysaccharides, and cationic polysaccharides; (b) crosslinking the polysaccharides of step (a); and thereby producing a bio-based material composition. In some embodiments, the mixture of step (a) further comprises a humectant. In some embodiments, the cellulose is nanocellulose. In some embodiments, the cellulose is bacterial nanocellulose. In some embodiments, the anionic polysaccharide is selected from the group consisting of pectin, alginate, gellan gum, carboxymethyl cellulose, hyaluronic acid, and polyglutamic acid (PGA). In some embodiments, the anionic polysaccharide is pectin. In some embodiments, the cationic polysaccharide is cationic microfibrillated cellulose (MFC) and / or cationic starch. The cationic polysaccharide may comprise natural cationic and / or cationic modified polysaccharides. For example, in some embodiments, the cationic polysaccharide comprises quaternary ammonium cationic modified MFC and / or quaternary ammonium cationic modified starch. In some embodiments, the weight ratio of the cellulose:the anionic polysaccharide:the cationic polysaccharide in step (a) is approximately 4:1:5. In some embodiments, the mixture (a) further comprises a humectant. In some embodiments, the weight ratio of cellulose:anionic polysaccharide:cationic polysaccharide in step (a) is approximately 2:1:5, 8:1:5, 4:2:5, 4:4:5, 4:1:10, or 4:1:2.5. In some embodiments, mixture (a) further comprises a wetting agent. Exemplary wetting agents are provided throughout the application.

[0098] In some embodiments, the method of the present invention comprises providing a mixture of cellulose, anionic polysaccharides, and cationic polysaccharides, wherein the weight ratio of cellulose to anionic polysaccharides to cationic polysaccharides in step (a) is approximately 2:1:5, 8:1:5, 4:2:5, 4:4:5, 4:1:10, or 4:1:2.5. In some embodiments, the method of the present invention comprises providing a mixture of cellulose, anionic polysaccharides, and cationic polysaccharides, wherein the weight ratio of cellulose to anionic polysaccharides to cationic polysaccharides in step (a) is approximately 4:1:5.

[0099] In some embodiments, step (b) of the method comprises adding a crosslinking agent. Crosslinking can be chemical or physical, such as covalent, ionic, and / or electrostatic crosslinking. Crosslinking of the polysaccharides in the composition improves the flexibility and strength of the composition. In some embodiments, the crosslinking is covalent, and the crosslinking agent comprises a tricarboxylic acid. In some embodiments, the crosslinking is covalent, and the crosslinking agent comprises one or more crosslinking agents selected from the group consisting of citric acid, isocitric acid, aconitic acid, propane-1,2,3-tricarboxylic acid, muscaric acid, and benzotriic acid. In some embodiments, the crosslinking agent is citric acid. In some embodiments, the crosslinking agent is added to the mixture of step (a) in an amount of about 0.05% w / w, about 0.1% w / w, about 0.2% w / w, about 0.3% w / w, about 0.4% w / w, or about 0.5% w / w.

[0100] In some embodiments, the method further includes a step (i) of blending the cellulose, wherein step (i) is performed prior to step (a). In some embodiments, step (i) includes blending the cellulose with a wetting agent and / or water. Blending may include mixing, shearing, combining in an overhead mixer, or any other suitable method.

[0101] In some embodiments, the method further includes a step (c) of heating and / or stirring the mixture. Step (c) is performed after step (b). In some embodiments, the mixture is heated to a temperature of about 50°C, about 60°C, about 70°C, about 80°C, or about 90°C. In some embodiments, the mixture is stirred at about 250 rpm, about 500 rpm, about 750 rpm, about 1000 rpm, about 1250 rpm, about 1500 rpm, or about 1750 rpm.

[0102] In some embodiments, the method further includes step (d) of pouring and / or coating the mixture into a mold, onto a support, and / or onto a substrate. Step (d) is performed after step (b) or step (c). In some embodiments, the support and / or substrate comprises one or more materials selected from the group consisting of: yarns, textiles, electrospun nanofibers, nonwoven fabrics, knitted fabrics, woven fabrics, braided structures, fiber webs, felts, and porous textiles.

[0103] In some embodiments, the method further includes a step (e) of drying the casting mixture. Step (e) is performed after step (d).

[0104] In some embodiments, the method further includes a step (ii) of adding one or more fillers to the mixture, wherein step (ii) may be performed before or after step (b).

[0105] In some embodiments, the method further includes a step (iii) of adding one or more dyes to the mixture, wherein step (iii) may be performed before, after, after (c), after (d), or after (e).

[0106] In some embodiments, the method further includes step (iv) of subjecting the composition to plasma treatment, surface coating and / or surface functionalization, wherein step (iv) may be performed after step (b), after step (c), after step (d) or after step (e).

[0107] The present invention further provides a method for producing the nanocellulose material of the present invention. In one embodiment, the method comprises the following steps: (1) obtaining and processing bacterial cellulose; (2) mixing the bacterial cellulose, pectin, cationic microfibrillated cellulose (MFC), glycerol and optionally an inorganic filler together to produce a slurry; (3) pouring the slurry into a mold; (4) optionally drying the resulting slurry material; and (5) thereby obtaining the final bio-based textile material of the present invention.

[0108] In another embodiment, the present invention provides a method for producing the nanocellulose material of the present invention using a scaffold. The method comprises the following steps: (1) obtaining and processing bacterial cellulose; (2) mixing the bacterial cellulose, pectin, cationic microfibrillated cellulose (MFC), glycerol and optionally an inorganic filler together to produce a slurry; (3) pouring the slurry into a mold; (4) placing the scaffold within the slurry; (5) optionally pouring additional slurry such that the scaffold is encapsulated within the slurry; (6) optionally drying the resulting scaffold-slurry material; and (7) thereby obtaining the final bio-based textile material of the present invention.

[0109] Bacterial cellulose is used as a starting material to produce the nanocellulose-based hybrid materials of this invention. Bacterial cellulose is a fermented biopolymer and can be used as a primary base material in combination with one or more other bio-based additives to produce the bio-based materials of this invention. The resulting bio-based material is a bio-based textile alternative that meets defined material testing standards. Bacterial cellulose can suitably meet material testing parameters such as thickness, tensile strength of approximately 180 N, and flexural strength of approximately 25,000 cycles. Bacterial cellulose can be statically grown bacterial nanocellulose sheets.

[0110] As part of the step of obtaining and processing bacterial cellulose in the method for producing the nanocellulose-based hybrid material of the present invention, the bacterial cellulose is processed. The bacterial cellulose can be prepared into cubes. The cubes can be of any size, for example, approximately 15 × 15 × 15 mm. The bacterial cellulose cubes can be compressed as part of the processing step or prior to the processing step. The dry weight content of the bacterial cellulose cubes can be approximately 3% to 5% by weight.

[0111] Bacterial cellulose may be used as part of the processing steps of the method or subjected to a cleaning step prior to the processing steps. The cleaning process may include one or more disinfection and / or washing steps. The disinfection step may include soaking in a bleach solution. Soaking may last at least approximately 12 hours. The bleach solution may contain approximately 1% by volume of bleach. The weight ratio of bacterial cellulose to the bleach solution is approximately 1:8. Any suitable solvent can be used as the washing solution for the washing step, such as water, including deionized water, distilled water, pure water, or tap water. The washing step may include soaking in a washing solution. Soaking may last at least approximately 12 hours. The weight ratio of bacterial cellulose to the washing solution is approximately 1:8.

[0112] In the final processing step, the bacterial cellulose obtained from the cleaning step can be mixed with water to form a mixture for subsequent steps. The bacterial cellulose may swell after the washing step. The weight ratio of bacterial cellulose to water is 3:8. Suitably, 3 kg of washed bacterial cellulose is combined with 8 kg of water to form a mixture weighing 11 kg. Optionally, the water used in this step can be cold drinking water. The dry weight of the mixed bacterial nanocellulose can be from approximately 0.5% to 2% by weight.

[0113] A method for producing the nanocellulose material of the present invention includes a mixing step. In the mixing step, processed bacterial cellulose, a wetting agent (such as glycerol), pectin, and cationic MFC are mixed. Optionally, an inorganic filler, such as a ceramic filler (e.g., calcium carbonate), is included in the mixing step. The amount of glycerol added in the mixing step can be calculated based on the weight of water added during the final processing step of the bacterial cellulose processing step. The weight of the added glycerol can be 5% by weight of the water added in the final processing step.

[0114] The mixing step can be further divided into sub-steps. In the first mixing sub-step, glycerol and processed bacterial cellulose are mixed using a high-shear mixing process (such as blending). The mixture can be processed by high-shear mixing at a constant rate or a varying rate. The mixture can be subjected to high-shear mixing at a constant temperature between approximately 20 and 30°C. The high-shear mixing can last between approximately 1 minute and 10 minutes. Therefore, the slurry produced by the first mixing sub-step is a substantially homogeneous or completely homogeneous mixture.

[0115] In the second mixing sub-step, the slurry may be allowed to stand to allow a wetting agent (e.g., glycerol) to penetrate the bacterial cellulose. This causes plasticization of the slurry. The second mixing sub-step may last approximately 12 hours. Optionally, the second mixing sub-step may include intermittent mixing.

[0116] In an optional third mixing sub-step, the slurry is filtered to dewater it. Dewatering the slurry can remove approximately 50% to 60% of its total weight. In some embodiments, filtration is gravity filtration. In some embodiments, the filter is a mesh filter with a fixed pore size. The fixed pore size can be approximately 400 micrometers. In some embodiments, the slurry is separated and then filtered, then dewatered and reassembled. The product of the third mixing sub-step is a dewatered slurry.

[0117] In the fourth mixing sub-step, cationic MFCs are added to the slurry. The weight of the added cationic MFCs can be calculated as a weight percentage of the slurry produced in the second or third mixing sub-step. In some embodiments, approximately 4% by weight of cationic MFCs equivalent to the slurry can be added. The mixture of cationic MFCs and slurry can then be stirred. Stirring can be performed in any suitable mixing vessel, such as a top-mounted stirrer. Stirring in this sub-step can be low-shear. Stirring rates between approximately 50 rpm and 200 rpm or between 50 rpm and 1000 rpm can be used. In some embodiments, the stirring rate is 100 rpm. In some embodiments, the stirring rate is 600 rpm. In some embodiments, stirring can be performed under vacuum conditions.

[0118] In the fifth mixing sub-step, pectin is added to the slurry. The pectin may be added in powder form. The weight of the added pectin may be calculated as a percentage of the weight of the slurry produced in the second or third mixing sub-step. In some embodiments, approximately 0.7% by weight of pectin equivalent to the slurry may be added. The mixture of pectin and slurry may then be stirred to prevent pectin aggregation. Stirring may be performed in any suitable mixing vessel, such as a top-mounted agitator. Stirring in this sub-step may be low-shear. A stirring rate between approximately 50 rpm and 200 rpm may be used. In some embodiments, the stirring rate is 100 rpm.

[0119] In an optional sixth mixing sub-step, inorganic filler is added to the slurry. The inorganic filler may be added in powder form. The weight of the added inorganic filler may be calculated as a weight percentage of the final mixture after the addition of the inorganic filler. In some embodiments, approximately 0.5% to 10% by weight of the final slurry of inorganic filler may be added. The mixture of inorganic filler and slurry may then be stirred to prevent the inorganic filler from agglomerating. Stirring may be performed in any suitable mixing vessel, such as a top-mounted agitator. The stirring in this sub-step may be low-shear. A stirring rate of approximately 50 rpm to 200 rpm may be used. In some embodiments, the stirring rate is 100 rpm.

[0120] In the seventh mixing sub-step, the slurry is continuously agitated. Agitation can be carried out in any suitable mixing vessel, such as a top-mounted agitator. Agitation in this sub-step can be low-shear. An agitation rate between approximately 50 rpm and 200 rpm can be used. In some embodiments, the agitation rate is 100 rpm. Agitation in this sub-step can be sustained between 4 hours and 20 hours. In some embodiments, agitation in this sub-step can be sustained between 16 hours and 20 hours.

[0121] In some embodiments, the fourth, fifth, and sixth mixing sub-steps can be performed in any order. In one embodiment, the mixing sub-steps can be performed in numerical order. In another embodiment, the fourth, fifth, and sixth mixing sub-steps can be performed simultaneously.

[0122] A method for producing the nanocellulose material of the present invention includes the step of pouring a slurry into a mold. The slurry layer produced in the mixing step can be coated onto a solid substrate. The substrate may have dimensions matching the desired size of the final material. In some embodiments, the slurry may be extruded into the desired final shape. The slurry may be heated using any suitable method (e.g., a water bath) prior to coating. The slurry may be heated to approximately 20 to 80°C. The slurry may be coated onto the substrate with a thickness of approximately 0.5 mm to 20 mm. The slurry may be coated onto the substrate using any suitable tool (e.g., a doctor blade or a removable coating knife) to achieve the coating. In one embodiment, the coating may be of uniform thickness. Alternatively, the coating thickness may vary between approximately 0.5 mm and 20 mm. Optionally, the coated substrate may be dried in this step. The substrate may be dried using an oven. The substrate may be dried to remove approximately 90% of the moisture from the coating.

[0123] In some embodiments, a method of producing the nanocellulose material of the present invention includes the step of placing a scaffold within a slurry. The scaffold may be a textile scaffold comprising woven, nonwoven, or sheet material containing yarns or fibers. The thickness of the textile scaffold may be approximately 0.1 mm to 1 mm. The material may comprise one or more materials selected from the group consisting of cotton, regenerated cellulose, flax, hemp, wool, and silk. The textile scaffold may be tension-clamped within a frame larger than the final sheet material and placed on top of a first layer of cast slurry. The tensioned frame may then be clamped to a solid substrate platform. Alternatively, the textile scaffold, tension-clamped within a frame, may be placed on a solid substrate platform, followed by coating with a biopolymer layer and then coating thereon with a slurry layer.

[0124] In some embodiments, the textile support is fed in by a roller, and the slurry is directly applied to the textile by air knife coating, roller coating, transfer coating, or die coating.

[0125] In some embodiments, a method of producing the nanocellulose material of the present invention includes the step of casting an additional slurry such that the scaffold is encapsulated within the slurry. The material having the scaffold and a single-sided slurry coating (produced in a previous step of placing the scaffold within the slurry) can be placed on a flat substrate platform, with the scaffold positioned on the top side. A second slurry layer is cast over the top of the scaffold material to form a scaffold textile coated on both sides with the biopolymer material. The second slurry layer may have a similar or the same thickness as the first slurry layer coated on a solid substrate.

[0126] In some embodiments, the method for producing the nanocellulose material of the present invention may optionally include a step of drying the resulting material, which, depending on the embodiment, may be a slurry or a scaffold-slurry. If a scaffold is used, during the drying step, a tensioning device is used to hold the coated scaffold under tension, for example, by holding the scaffold in a frame. The material may be dried for approximately 60 to 720 minutes, or until the material loses approximately 90% of its moisture content. The material may be dried at a temperature of approximately 30 to 80°C. In some embodiments, the material may be dried at a temperature of approximately 20 to 100°C. During drying, the thickness of the slurry layer may decrease by approximately 5 to 10 times. Depending on the height of the wet slurry layer, the final material thickness may be approximately 0.3 mm to 1.5 mm. If a scaffold is used, the tensioning device may be removed after drying.

[0127] Some embodiments of the invention described herein may be defined according to any of the following numbered clauses:

[0128] 1. A biological-based material composition comprising:

[0129] (a) Cellulose;

[0130] (b) Anionic polysaccharides; and

[0131] (c) Cationic polysaccharides;

[0132] The composition therein is cross-linked.

[0133] 2. The composition according to Clause 1, wherein the cellulose is nanocellulose.

[0134] 3. The composition according to clause 1 or 2, wherein the cellulose is bacterial cellulose.

[0135] 4. The composition according to any one of the preceding clauses, wherein the anionic polysaccharide comprises or consists of one or more anionic polysaccharides selected from the group consisting of: pectin, alginate, gellan gum, carboxymethyl cellulose, hyaluronic acid and polyglutamic acid (PGA).

[0136] 5. The composition according to any one of clauses 1 to 3, wherein the anionic polysaccharide is pectin.

[0137] 6. The composition according to any one of the preceding clauses, wherein the cationic polysaccharide comprises or is composed of cationic microfibrillated cellulose (MFC) and / or cationic starch.

[0138] 7. The composition according to any one of the preceding clauses, wherein the composition is crosslinked by one or more tricarboxylic acids selected from the group consisting of: citric acid, isocitric acid, aconitic acid, propane-1,2,3-tricarboxylic acid, muscaric acid, and benzoic acid.

[0139] 8. The composition according to any one of the preceding clauses, wherein the composition is cross-linked by chemical cross-linking and / or by physical cross-linking.

[0140] 9. The composition according to Clause 8, wherein the chemical crosslinking comprises or consists of covalent and / or ionic bonds.

[0141] 10. The composition according to clause 8 or 9, wherein the physical crosslinking comprises or is composed of electrostatic interactions, such as hydrogen bonding, van der Waals forces, dipole-dipole interactions, ion-dipole interactions, ion-ion interactions, electrostatic interactions, London dispersion forces and / or π-π interactions.

[0142] 11. The composition according to any one of the preceding clauses, wherein the composition further comprises a wetting agent.

[0143] 12. The composition according to Clause 11, wherein the wetting agent comprises or consists of one or more wetting agents selected from the group consisting of glycerol, sorbitol, xylitol, mannitol, erythritol, maltitol, isomaltitol, lactitol, hydrogenated starch hydrolysate (HSH), and polyhydroxyol.

[0144] 13. The composition according to any one of the preceding clauses, wherein the composition further comprises one or more polymers selected from the group consisting of: polylactic acid (PLA), polyhydroxyalkanoate (PHA), chitosan, polyglycolic acid, polyhydroxypolyurethane (PHU), poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV), polydioxanone (PDO), poly-ε-caprolactone (PCL), alginate, hyaluronic acid, poly(lactic acid-co-glycolic acid) (PLGA), carrageenan, gum arabic, xyloglucan, and polyethylene glycol (PEG).

[0145] 14. The composition according to any one of the preceding clauses, wherein the composition further comprises one or more proteins selected from the group consisting of gelatin, silk, or elastin.

[0146] 15. The composition according to any one of the preceding clauses, wherein the composition further comprises one or more bio-based elastomers selected from the group consisting of: rubber, natural rubber, and epoxidized vegetable oils.

[0147] 16. The composition according to any one of the preceding clauses, wherein the composition further comprises one or more fillers.

[0148] 17. The composition according to Clause 16, wherein the one or more fillers comprise ceramic fillers selected from the group consisting of: hydroxyapatite (HA), tricalcium phosphate (TCP), zirconium oxide, alumina, silica, glass ceramics, bioglass, calcium phosphate, and calcium sulfate.

[0149] 18. The composition according to Clause 16 or 17, wherein said one or more fillers comprise natural short fiber fillers selected from the group consisting of: cotton fiber, flax fiber, hemp fiber, jute fiber, bamboo fiber, silk fiber, wool fiber, kenaf fiber, ramie fiber, coconut fiber (coconut shell fiber), banana fiber, bagasse fiber, regenerated cellulose fiber, and wood fiber.

[0150] 19. The composition according to any one of the preceding clauses, used as a biological-based material.

[0151] 20. The composition according to Clause 19, wherein the bio-based material is a leather substitute.

[0152] 21. The composition according to any one of the preceding clauses further comprises surface functionalization.

[0153] 22. The composition according to Clause 21, wherein the surface functionalization is achieved by a sizing agent such as an alkylated ketene dimer, a silane chemical, and / or acetylation.

[0154] 23. The composition according to any one of the foregoing clauses further comprises a surface coating.

[0155] 24. The composition according to Clause 23, wherein the surface coating comprises or consists of one or more of the group selected from: natural waxes, bioplastics, polylactic acid (PLA), polyhydroxyalkanoates (PHA), polyhydroxybutyrate (PHB), cellulose, esters (e.g., esters of acetate, cellulose acetate butyrate or other suitable esters), plant proteins, soy proteins, pea proteins, corn proteins, ceramics, liquid nanoglasses and nanoglasses.

[0156] 25. The composition according to any one of the preceding clauses, wherein the surface has been treated with plasma.

[0157] 26. The composition according to any one of the preceding clauses further comprises a support and / or a substrate.

[0158] 27. The composition according to Clause 26, wherein the scaffold and / or substrate comprises one or more materials selected from the group consisting of: yarns, textiles, electrospun nanofibers, nonwoven fabrics, knitted fabrics, woven fabrics, braided structures, fiber webs, felts, and porous textiles.

[0159] 28. The composition according to any one of the preceding clauses, further comprising a backing material, such as a textile, optionally wherein the backing material is adhered to the composition by means of adhesion.

[0160] 29. The composition according to any one of the preceding clauses, wherein the composition has been dyed with a dye.

[0161] 30. The composition according to Clause 29, wherein the dye is a natural dye, and optionally wherein the dye is produced by bacteria.

[0162] 31. The composition according to clause 29 or 30, wherein the dye is a color-changing and / or responsive dye, such as an electrochromic, thermochromic, or photochromic dye.

[0163] 32. The composition according to any one of the preceding clauses further comprises nanoparticles that absorb electromagnetic radiation.

[0164] 33. The composition according to any one of the preceding clauses further comprises nanoparticles that emit electromagnetic radiation.

[0165] 34. The composition according to any one of the preceding clauses, wherein the composition has been embossed and / or stamped.

[0166] 35. The composition according to any one of the preceding clauses, wherein the composition is a sheet.

[0167] 36. The composition according to any one of the preceding clauses, wherein the thickness of the composition is less than 10 mm, less than 5 mm, less than 3 mm, less than 2 mm or less than 1 mm.

[0168] 37. The composition according to any one of the preceding clauses, wherein the thickness of the composition is greater than 0.01 mm, greater than 0.05 mm, greater than 0.1 mm, or greater than 1 mm.

[0169] 38. The composition according to any one of the preceding clauses, wherein the thickness of the composition is 0.8 mm.

[0170] 39. A garment article comprising or consisting of any one of the compositions according to Clauses 1 to 33.

[0171] 40. The garment articles as described in Clause 39, wherein said articles are selected from the group consisting of: shoes, boots, sandals, socks, jackets, hats, gloves, shirts, T-shirts, sweaters, trousers and underwear.

[0172] 41. An accessory comprising or consisting of any one of the compositions according to Clauses 1 to 38.

[0173] 42. The accessories as described in Clause 41, wherein the accessories are selected from the group consisting of: bags, handbags, jewelry, sunglasses, eyeglasses, suitcases, wallets, purses, pencil cases, cosmetic bags, phone cases, earphones, and watch straps.

[0174] 43. A household article comprising or consisting of any one of the compositions according to Clauses 1 to 38.

[0175] 44. The home furnishings as described in Clause 43, wherein the home furnishings are selected from the group consisting of: cushion covers, upholstery suitable for sofas or chairs, curtains, blinds, lampshades, carpets, floor mats, doormats, placemats, tablecloths and yoga mats.

[0176] 45. An automotive soft furnishing or automotive trim material comprising or consisting of any composition according to any one of clauses 1 to 38.

[0177] 46. ​​A method for producing a biological-based material composition, the method comprising the steps of:

[0178] (a) Provide a mixture comprising cellulose, anionic polysaccharides and cationic polysaccharides;

[0179] (b) Crosslinking the cellulose, the anionic polysaccharide and the cationic polysaccharide of step (a);

[0180] And this leads to biological-based material compositions.

[0181] 47. The method according to Clause 46, wherein the mixture of step (a) further comprises a wetting agent.

[0182] 48. The method according to clause 46 or 47, wherein the cellulose is nanocellulose.

[0183] 49. The method according to any one of clauses 46 to 48, wherein the cellulose is bacterial cellulose.

[0184] 50. The method according to any one of clauses 46 to 49, wherein the anionic polysaccharide is one or more anionic polysaccharides selected from the group consisting of: pectin, alginate, gellan gum, carboxymethyl cellulose, hyaluronic acid and polyglutamic acid (PGA).

[0185] 51. The method according to any one of clauses 46 to 50, wherein the anionic polysaccharide is pectin.

[0186] 52. The method according to any one of clauses 46 to 51, wherein the cationic polysaccharide is cationic microfibrillated cellulose and / or cationic starch.

[0187] 53. The method according to any one of clauses 46 to 52, wherein the weight ratio of the cellulose:the anionic polysaccharide:the cationic polysaccharide in step (a) is about 2:1:5, 8:1:5, 4:2:5, 4:4:5, 4:1:10 or 4:1:2.5.

[0188] 54. The method according to any one of clauses 46 to 52, wherein the weight ratio of the cellulose:the anionic polysaccharide:the cationic polysaccharide in step (a) is approximately 4:1:5.

[0189] 55. The method according to any one of clauses 46 to 54, further comprising step (i) of blending the cellulose, wherein step (i) is performed prior to step (a).

[0190] 56. The method according to Clause 55, wherein step (i) comprises blending the cellulose with a wetting agent and / or water.

[0191] 57. The method according to any one of clauses 46 to 56, wherein the mixture in step (a) further comprises a wetting agent.

[0192] 58. The method according to clause 56 or 57, wherein the wetting agent comprises or is composed of one or more wetting agents selected from the group consisting of glycerol, sorbitol, xylitol, mannitol, erythritol, maltitol, isomaltitol, lactitol, hydrogenated starch hydrolysate (HSH), and polyhydroxyol.

[0193] 59. The method according to any one of clauses 46 to 58, wherein step (b) comprises adding a crosslinking agent.

[0194] 60. The method according to Clause 59, wherein the crosslinking agent is a tricarboxylic acid.

[0195] 61. The method according to Clause 60, wherein the crosslinking agent is one or more tricarboxylic acids selected from the group consisting of: citric acid, isocitric acid, aconitic acid, propane-1,2,3-tricarboxylic acid, muscaric acid, and benzoic acid.

[0196] 62. The method according to any one of clauses 59 to 61, wherein the crosslinking agent is citric acid.

[0197] 63. The method according to any one of clauses 59 to 62, wherein the crosslinking agent is added to the mixture of step (a) in an amount of about 0.05% w / w, about 0.1% w / w, about 0.2% w / w, about 0.3% w / w, about 0.4% w / w or about 0.5% w / w.

[0198] 64. The method according to any one of clauses 46 to 63, further comprising the step (c) of heating and / or stirring the mixture.

[0199] 65. The method according to Clause 64, wherein the mixture is heated to a temperature of about 50°C, about 60°C, about 70°C, about 80°C, or about 90°C.

[0200] 66. The method according to clause 64 or 65, wherein the mixture is stirred at about 250 rpm, about 500 rpm, about 750 rpm, about 1000 rpm, about 1250 rpm, about 1500 rpm or about 1750 rpm.

[0201] 67. The method according to any one of clauses 46 to 66, wherein the method further comprises the step (d) of casting and / or coating the mixture into a mold, on a support and / or on a substrate.

[0202] 68. The method according to Clause 67, wherein the support and / or substrate comprises one or more materials selected from the group consisting of: yarns, textiles, electrospun nanofibers, nonwoven fabrics, knitted fabrics, woven fabrics, braided structures, fiber webs, felts, and porous textiles.

[0203] 69. The method according to clause 67 or 68, wherein the method further comprises the step of drying the casting mixture (e).

[0204] 70. The method according to any one of clauses 46 to 70, wherein the method further comprises the step (ii) of adding one or more fillers to the mixture, wherein step (ii) may be performed before or after step (b).

[0205] 71. The method according to Clause 70, wherein the one or more fillers comprise ceramic fillers selected from the group consisting of: hydroxyapatite (HA), tricalcium phosphate (TCP), zirconium oxide, alumina, silica, glass ceramics, bioglass, calcium phosphate, and calcium sulfate.

[0206] 72. The composition according to clause 70 or 71, wherein the one or more fillers comprise natural short fiber fillers selected from the group consisting of: cotton fiber, flax fiber, hemp fiber, jute fiber, bamboo fiber, silk fiber, wool fiber, kenaf fiber, ramie fiber, coconut fiber (coconut shell fiber), banana fiber, bagasse fiber, regenerated cellulose fiber, and wood fiber.

[0207] 73. The method according to any one of clauses 46 to 72, wherein the method further comprises the step (iii) of adding one or more dyes to the mixture, wherein step (iii) may be performed before, after, after, or after step (e).

[0208] 74. The method according to Clause 73, wherein the one or more dyes are selected from the group consisting of electrochromic, thermochromic and photochromic dyes.

[0209] 75. The method according to clause 73 or 74, wherein the dye is produced by bacteria.

[0210] 76. The method according to any one of clauses 46 to 75, wherein the method further comprises step (iv) subjecting the composition to plasma treatment, surface coating and / or surface functionalization, wherein step (iv) may be performed after step (b), after step (c), after step (d) or after step (e).

[0211] 77. The method according to Clause 76, wherein the surface functionalization is achieved by treating the composition with a sizing agent.

[0212] 78. The method according to clause 76 or 77, wherein the composition is subjected to a surface coating selected from the group consisting of: natural waxes, bioplastics, polylactic acid (PLA), polyhydroxyalkanoates (PHA), polyhydroxybutyrate (PHB), cellulose, esters, acetates, cellulose acetate butyrate, plant proteins, soy proteins, pea proteins, corn proteins, ceramics, liquid nanoglasses, and nanoglasses.

[0213] 79. The method according to any one of clauses 46 to 78, wherein the method further comprises a final step of embossing and / or stamping the composition.

[0214] 80. The method according to any one of clauses 46 to 79, wherein the method is a green method, wherein

[0215] (a) All reagents used in the method are biologically based reagents;

[0216] (b) The method does not contain petrochemical products;

[0217] (c) The method uses only non-toxic chemicals; and / or

[0218] (d) The method described is sustainable.

[0219] 81. The method according to any one of Clauses 46 to 80, wherein the bio-based material composition is a bio-based material composition according to any one of Clauses 1 to 45.

[0220] 82. A nanocellulose-based hybrid material comprising bacterial cellulose (BC), pectin, cationic microfibrillated cellulose (MFC), and glycerol.

[0221] 83. The nanocellulose-based hybrid material as described in Clause 82, wherein the ratio of cationic MFC:pectin:BC is approximately 1:5:4.

[0222] 84. The nanocellulose-based hybrid material according to Clause 82, wherein the ratio of cationic MFC:pectin:BC is approximately 1:8:11.

[0223] 85. A biological-based material composition comprising:

[0224] (a) Bacterial nanocellulose;

[0225] (b) Pectin;

[0226] (c) Cationic MFCs; and

[0227] (d) Glycerin;

[0228] The composition is cross-linked by citric acid.

[0229] Example

[0230] The invention described herein is further illustrated by the following examples, but these examples should not in any way be construed as further limitations.

[0231] Example 1 - Production process for preparing cellulose nanoparticle-based hybrid materials

[0232] Obtaining and processing bacterial cellulose (BC)

[0233] Fermented biopolymers, serving as the primary substrate, are combined with one or more additional bio-based additives to produce a bio-based material. The resulting bio-based material is a bio-based textile alternative that meets defined material testing standards. The material testing parameters meet the following requirements: thickness of 0.5 mm, tensile strength of 180 N, and flexural strength ≥ 25,000 cycles.

[0234] Fermented biopolymers are statically grown bacterial nanocellulose sheets. The nanocellulose sheets are prepared into 15 × 15 × 15 mm cubes, compressed at a 1:10 ratio, with a dry weight content of 3-5%.

[0235] The cellulose cubes undergo a two-step cleaning process before processing. The first step is a disinfection step using a 1% bleach solution, which involves soaking in the solution for at least 12 hours, with the weight ratio of the cellulose cubes to the bleach solution being 1:8. The second and final disinfection step is a washing step using pure water, which also involves soaking for at least 12 hours, with the weight ratio of the cellulose cubes to the water being 1:8.

[0236] The cellulose cubes discharged from the washing step swelled to approximately three times their original weight. The swollen cellulose cubes were weighed and the weight was corrected to 3 kg using cold drinking water. The 3 kg of swollen cellulose cubes were combined with 8 kg of cold drinking water to form a mixture of 11 kg in total. The dry weight of nanocellulose in the solution was 0.5% to 2% by weight.

[0237] Combine the core ingredients in the top-mounted blender.

[0238] At this stage, glycerin (also known as a wetting agent) is added to 8 kg of water. The optimal amount of glycerin is added based on the weight of the added water, typically 5%.

[0239] The cellulose cube-water-glycerol mixture was processed by high-shear (blending). The mixture was processed by high-shear (blending) at a constant rate. The high-shear processing was carried out at a constant temperature of 20 to 30°C for a fixed duration of 1 to 10 minutes. The high-shear (blending) process produced a homogeneous mixture, referred to herein as a slurry. The slurry was allowed to stand for 12 hours with intermittent stirring. This 12-hour period was established as wetting agent soaking and was crucial for the plasticization of the cellulose polymer matrix.

[0240] The slurry is separated into portions and optionally subjected to gravity filtration. Gravity filtration is accomplished using a mesh with a fixed pore size, for example, approximately 400 micrometers. The slurry is filtered to remove 50% to 60% of its weight by removing water. The degree of dewatering is determined by the weight of the dewatered slurry and the weight of the filtrate.

[0241] The addition of cationic microfibrillated cellulose (MFC) was calculated based on the weight percentage of the original undehydrated slurry. Cationic microfibrillated cellulose will be referred to herein as Cat. MFC. The inclusion rate of Cat. MFC was 4% of the original undehydrated slurry weight. Cat. MFC was weighed and added to a large stock of dehydrated slurry. The slurry mixture was stirred at 100 rpm using an immersion top-mounted agitator.

[0242] The addition of pectin is calculated based on the weight percentage of the original undehydrated slurry. The pectin inclusion rate is 0.7% of the original undehydrated slurry weight. The weighed pectin is slowly incorporated into the stirred slurry mixture to avoid pectin powder agglomeration. Once the pectin is evenly incorporated into the slurry mixture, the bulk mixture is continuously stirred at 100 rpm for 16-20 hours.

[0243] Optionally, inorganic fillers, such as ceramic fillers like calcium carbonate, can be added in dry powder form at this step. Stir until the final product contains 0.5% to 10% by weight.

[0244] Therefore, a mixed slurry with approximately 50% by weight dry polymer and 50% by weight water and glycerol is obtained.

[0245] Pour the mixed slurry into the mold.

[0246] A layer of mixed slurry is coated onto a solid substrate platform, the size of which is matched to the size of the final sheet material.

[0247] Before coating, heat the slurry to a temperature of 20 to 80°C in a water bath. The coating thickness can vary between 0.5 mm and 20 mm. Different tools can be used to form the layer—a doctor blade to distribute the slurry evenly, or a movable coating blade can be used to form the coating. The coating height can be adjusted by the distance between the platform and the coating blade and can vary between 0.5 and 20 mm.

[0248] The first layer can optionally be dried in an oven (using the same method described in the drying steps below) to remove approximately 90% of the moisture before adding the yarn support.

[0249] Place the support inside the slurry (optional)

[0250] A textile scaffold is incorporated into the material. The scaffold is selected from woven, nonwoven, or knitted sheet materials containing yarns. The thickness of the textile ranges from 0.1 to 1 mm. Preferred materials are natural yarns such as cotton, regenerated cellulose, flax, hemp, wool, and silk. The textile is tensioned within a frame larger than the final sheet material and placed on top of the first layer of slurry. The tensioned frame is then clamped to a solid substrate platform. Alternatively, the textile material, tensioned within the frame, is placed on a solid substrate platform, followed by coating with a biopolymer layer and then with a slurry layer thereon.

[0251] Material with a scaffold and a single-sided slurry coating is placed on a flat substrate platform, with the scaffold positioned on the top side. A second slurry layer, with the same height range as the first slurry layer, is poured over the top of the scaffold material to form a scaffold textile coated with biopolymer material on both sides.

[0252] The material obtained by drying in an oven

[0253] This step is essential if a support is included; otherwise, it is optional.

[0254] The coated support (if used) is held under tension during drying by holding it on the frame.

[0255] Dry the material at 30 to 80°C for 60 to 720 minutes, until it feels dry to the touch and has lost approximately 90% of its moisture. Dry the slurry layer and reduce its thickness by 5 to 10 times. Depending on the height of the wet slurry layer, the final sheet material thickness will then be 0.3 mm to 1.5 mm.

[0256] If tension is involved on the support, it can be eliminated by releasing it from the clamping frame.

[0257] result

[0258] The final product weight composition (including residual moisture) produced by the above method is shown in Table 1 below.

[0259] Bacterial cellulose (BC) preferably comprises approximately 50% by weight of the final biopolymer (excluding wetting agents and water). The optimal formulation has a cationic MFC:pectin:BC ratio of 1:8:11.

[0260] Table 1 .

[0261]

[0262] Example 2 - Alternative Formulations Based on Nanocellulose Hybrid Materials

[0263] The method of Example 1 can also be used to produce the nanocellulose-based hybrid material of the present invention, having a final formulation different from that shown in Table 1. For example, the method of Example 1 produces a nanocellulose-based hybrid material having a formulation listed in Table 2.

[0264] Table 2 lists the weight composition of the final product produced by the method in Example 1, including residual moisture.

[0265] In this example, the optimal formulation has a cationic MFC:pectin:BC ratio of 1:5:4.

[0266] Table 2

[0267]

[0268] Example 3 - Properties of Hybrid Materials Based on Nanocellulose

[0269] Different compositions of nanocellulose-based hybrid materials were tested to determine tensile strength, elongation, and Bally flexural properties. The results are shown in Table 3. The percentage compositions shown in Table 3 do not include moisture. Formulation 3 illustrates the properties of the material according to the invention.

[0270] Thickness of each component was measured according to ISO 2286-3:2016. Tensile strength and elongation were measured according to ISO 13934-1:2013. Bally flexural properties were measured according to EN ISO 17694 (ISO 5402-1:2022 Bally flexural properties).

[0271] Surprisingly, the material of this invention was found to have a high Bally flexural value. The results show that the unique formulation of this invention, combined with the production method of this invention, transforms the material from a wet hydrogel into a dry sheet, producing a novel material that not only possesses tensile strength comparable to commercial textiles but also exhibits increased flexibility in textile testing scenarios.

[0272] Adding heteropolysaccharides such as pectin to plasticized BC improves flexibility, but at the cost of tensile strength. Surprisingly, the addition of cationic MFCs maintained a certain level of tensile strength and elongation, while also preserving flexural strength.

[0273] It can be seen that formulation 3, as the preferred composition of the present invention, exhibits improved properties compared to other tested formulations. Formulation 1 is known in the art but lacks flexural strength. Blends of BC and heteropolysaccharides such as pectin have high flexural strength but low elongation and tensile strength per unit thickness, such as formulation 2.

[0274] Table 3

[0275]

[0276] Example 4 - Characteristics of alternative formulations based on nanocellulose hybrid materials

[0277] The material properties of alternative formulations of cellulose nanoparticle-based hybrid materials (produced using the method of Example 1) as described in Example 2 were tested using the methods listed in Example 3. The results are shown in Table 4.

[0278] Thickness of each component was measured according to ISO 2286-3:2016. Tensile strength and elongation were measured according to ISO 13934-1:2013. Bally flexural properties were measured according to EN ISO 17694 (ISO 5402-1:2022 Bally flexural properties).

[0279] Surprisingly, the material of the present invention was found to have a high Bally flexural value. The results show that the formulation of the present invention, combined with the production method of the present invention, transforms the material from a wet hydrogel into a dry sheet, producing a novel material that not only possesses tensile strength comparable to commercial textiles but also exhibits increased flexibility in textile testing scenarios.

[0280] Adding heteropolysaccharides such as pectin to plasticized BC improves flexibility, but at the cost of tensile strength. Surprisingly, the addition of cationic MFCs maintained a certain level of tensile strength and elongation, while also preserving flexural strength.

[0281] It can be seen that formulation 6, as the preferred composition of the present invention, exhibits improved properties compared to other tested formulations. Formulation 4 is known in the art but lacks flexural strength. Blends of BC and heteropolysaccharides such as pectin have high flexural strength but low elongation and tensile strength per unit thickness, such as formulation 5.

[0282] Table 4

[0283]

[0284] Example 5 - Structural Microscopy Examination of Hybrid Materials Based on Nanocellulose

[0285] Scanning electron microscopy was used to examine the nanocellulose-based hybrid materials to obtain structural information. Samples of nanocellulose-based hybrid materials containing a cationic MFC:pectin:BC ratio of 1:8:11 were analyzed.

[0286] The sample solvent was replaced with ethanol, followed by critical point drying to remove moisture. The sample was mounted on a metal base and sputter-coated with silver to reduce charge interruption, and then imaged at 8000x magnification.

[0287] The imaging results can be seen in Figure 1 middle. Figure 1 The structure of the cellulose nanoparticle-based hybrid material is shown. A finely interwoven network of blended biopolymer fibers is visible, in which fibers of varying thicknesses surround an aggregated biopolymer encapsulation.

[0288] Example 6 - Generation of cross-linked cellulose nanofiber-based hybrid materials

[0289] This article describes a method for producing the crosslinked nanocellulose-based hybrid material of the present invention, the hybrid material containing bacterial cellulose, cat MFC, pectin, glycerol and citric acid.

[0290] The raw materials used in the method are: nanocellulose, pectin, cationic microfibrillated cellulose (Cat MFC), glycerol, citric acid, and water. Nanocellulose may be bacterial nanocellulose (BC). Bacterial nanocellulose can be produced as a primary bacterial cellulose sheet with the introduction of additives. Pectin may be pectin (CAS: 57-50-1), optionally standardized with sucrose (CAS: 9000-69-5). Pectin is obtained from CP Kelco. Cat MFC may be cellulose 2-hydroxy-3-trimethylammonium chloride propyl ether. Cat MFC is obtained from Weidmann. Glycerin may be vegetable glycerin or vegetable glycerol, and may be pharmaceutical grade and / or food grade. Glycerin is obtained from Special Ingredients. Glycerin can be used as a plasticizer. Citric acid may be 100% pure, food-grade citric acid formulated into fine crystals. Citric acid is obtained from Intralabs. Citric acid is used as a crosslinking agent.

[0291] The production process is as follows:

[0292] - A slurry was prepared by blending nanocellulose in 1 part (g) of hydrated BC and 3 parts (mL) of water containing 5% glycerol.

[0293] - Soak the slurry again in 1.5 liters of water containing 5% glycerin overnight;

[0294] - Use a HEPA filter to dewater 1000 g of slurry until 650 g of slurry remains;

[0295] - Calculate the amount of Cat MFC (65 g) and pectin (5.85 g) to be added using 650 g of dehydrated slurry;

[0296] -Then the dehydrated slurry, Cat MFC, and pectin are mixed for 2 hours to form a slurry mixture;

[0297] - Add citric acid (1.5 g) to the slurry mixture;

[0298] - Heat the resulting mixture to 80°C using a temperature regulator and stir at 1000 rpm for 2 hours;

[0299] -Then, allow the mixture to return to ambient temperature and stir overnight;

[0300] - Cast the slurry into samples in an A7 mold, each sample containing 150 g of wet weight of the processed slurry;

[0301] - The sample was air-dried in a dehydration oven in the presence of an interface.

[0302] Example 7 - Tensile Strength of Alternative Formulations

[0303] Tensile strength was tested for various alternative formulations. Tensile strength and elongation were measured according to ISO 13934-1:2013. Table 5 shows the tensile strength test results for different formulations. All formulations were plasticized with glycerol in the same manner as described in Example 6. Formulation B5 was prepared at two different pH values: 4 and 10. The formulation was produced using a method similar to that listed in Example 6. Formulation B6 was produced by the method listed in Example 6 and is therefore an example of a crosslinked cellulose nanoparticle-based hybrid material. Young's modulus is provided in MPa. MPa and N / mm are well known. 2 These are equivalent units, where 1 MPa equals 1 N / mm². 2 .

[0304] Tensile testing machine SOP: Cut the sample into 90 mm × 40 mm strips. Clamp 20 mm of the sample at either end of the strip to obtain a test sample with a width of 40 mm and a length of 50 mm. The sample is tested in equilibrium with standard atmosphere and otherwise in accordance with ISO 13934-1:2013.

[0305] The Young's modulus value is independent of the sample thickness measured according to ISO 13934-1:2013. Table 5 provides the thickness of the test compositions for reference and completeness purposes only.

[0306] Table 5

[0307]

[0308] Three tensile stress tests were performed on the formulations in Table 5. Figures 2A to 2H The stress test results of the formulations in Table 5 are presented. Figure 2A Involves formulation B1; Figure 2B Involves formulation B2; Figure 2C Involves formulation B3; Figure 2D Involves formulation B4; Figure 2E Involves formulation B5 (prepared at pH 4); Figure 2F Involves formulation B6; Figure 2G This involves formulation B5 (prepared at pH 10); Figure 2H This involves formulation B7.

[0309] Formulation B1 was prepared from BC slurry with the addition of 0.5 wt% citric acid and 5% glycerol plasticizer. The addition of citric acid as a crosslinking agent to the BC slurry had a generally poor effect on the mechanical strength of the resulting casting composition, exhibiting a low Young's modulus value of approximately 8.3 MPa. This indicates that citric acid alone cannot effectively act as a crosslinking agent for this slurry modification under these conditions.

[0310] Formulation B2 was prepared from BC slurry with the addition of 0.5 wt% citric acid, 5% glycerol plasticizer, and 0.7% pectin filler. In this formulation, the addition of pectin increased the mechanical strength compared to BC slurry alone, but the increase was less than 25 MPa. This indicates that the additional pectin caused this quality improvement, rather than promoting the crosslinking of citric acid, thus suggesting that crosslinking had not yet occurred.

[0311] Formulation B3 was prepared from BC slurry with the addition of 5% glycerol plasticizer, microfibrillated cellulose (MFC), and 0.7% pectin filler. This formulation serves as a control for citric acid crosslinking of slurry containing both MFC and pectin filler but without cationic MFC. The similar Young's modulus value to that of formulation B2 confirms the hypothesis that citric acid crosslinking does not occur in slurry mixtures containing only BC, glycerol, and pectin.

[0312] Formulation B4 was prepared from BC slurry with the addition of 5% glycerol plasticizer, cationic microfibrillated cellulose (Cat MFC), and 0.7% pectin filler. This formulation also serves as a control for the addition of cationic MFC. Compared to Formulation B3 (the same mixture but containing MFC), substitution with cationic MFC resulted in a doubling of the overall mechanical strength. The cationic MFC interacts with the bacterial cellulose component in the mixture; since BC carries a partially negative charge, this interaction is assumed to be an electrostatic interaction of ionic crosslinking.

[0313] Formulation B5 (prepared at pH 4) was made from BC slurry with the addition of 0.5 wt% citric acid, 5% glycerol plasticizer, microfibrillated cellulose (MFC), and 0.7% pectin filler. In this formulation, the addition of citric acid to the MFC-containing BC slurry (prepared at pH 4) increased the mechanical strength by approximately 5 MPa relative to formulation B3. This indicates that, in this case, the citric acid interaction is not actually a covalent crosslinking but rather acts as an additive to increase mechanical strength.

[0314] Formulation B6 was prepared from BC slurry with the addition of 0.5 wt% citric acid, 5% glycerol plasticizer, cationic microfibrillated cellulose (Cat MFC), and 0.7% pectin filler. In this formulation, the inclusion of cationic MFC significantly increased the average Young's modulus by over 90 MPa compared to previously reported values. The increased properties and strength resulting from the inclusion of cationic MFC indicate a novel interaction between the cationic MFC and citric acid in the form of crosslinking. The hypothetical electrostatic interaction between BC and the cationic MFC further explains the increased material properties of this formulation. The exact nature of the crosslinking aspect of this mixture is unknown but can be attributed to both the citric acid and cationic MFC components, as the mechanical strength decreases in both the MFC-containing and non-citric acid-containing formulations. The positive charge of the quaternary ammonium groups present on the MFC is hypothesized to accelerate the crosslinking process, thus explaining the significant increase in mechanical strength.

[0315] Formulation B5 (prepared at pH 10) was made from BC slurry with the addition of 0.5 wt% citric acid, 5% glycerol plasticizer, microfibrillated cellulose (MFC), and 0.7% pectin filler. In this formulation, changing the reaction conditions from pH 4 to alkaline (pH 10) to provide reaction catalysis did indeed improve the mechanical strength and properties of the film compared to the same formulation without alkaline catalysis. However, while the mechanical strength was significantly improved, the performance increase was not equivalent to that exhibited by formulation B6, where MFC was replaced with cationic MFC. Although alkaline catalysis did improve the degree of citric acid crosslinking, it could not achieve the same level of mechanical strength as the formulation containing cationic MFC. This further supports the hypothesis that novel interactions lie between cationic MFC and citric acid, as the performance of the alkaline-catalyzed equivalent cannot mimic the aforementioned properties.

[0316] Formulation B7 was prepared from BC slurry with the addition of 0.5 wt% citric acid, 5% glycerol plasticizer, microfibrillated cellulose (MFC), 0.7% pectin filler, and 0.3 wt% sodium hypophosphite (for catalytic purposes). This formulation was tested as a control. The presence of the catalyst sodium hypophosphite adversely affected the mechanical strength of the composition of this formulation. The evidence suggests that catalytic chemicals such as sodium hypophosphite do not enhance the crosslinking between MFC and citric acid. Therefore, this supports the hypothesis that a novel crosslinking mechanism occurs between citric acid and cationic MFC. The data provided in this example support this hypothesis.

[0317] Conclusion: The use of cationic MFCs instead of non-cationic MFCs resulted in a surprisingly high increase in the tensile strength of the material. This increase in tensile strength can be attributed to the strong covalent crosslinking between the cationic MFCs and the citric acid crosslinking agent. Such a high degree of crosslinking was not observed in the presence of non-ionic MFCs, suggesting that the increase in tensile strength seen in the above experimental data may be attributed to the presence of quaternary ammonium groups (i.e., cationic groups) on the cationic MFCs. The covalent crosslinking and the ionic crosslinking established between the cationic MFCs and BC work synergistically through electrostatic interactions to achieve the high tensile strength of the material of this invention.

[0318] Example 8 - Structural microscopy examination of cross-linked cellulose nanofiber-based hybrid materials

[0319] The cellulose nanoparticle-based hybrid materials were examined by scanning electron microscopy to obtain structural information. The cellulose nanoparticle-based hybrid material sample prepared according to formulation B6 of Examples 6 / 7 was imaged.

[0320] The sample solvent was replaced with ethanol, followed by critical point drying to remove moisture. The sample was mounted on a metal base and sputter-coated with silver to reduce charge interruption, and then imaged at 8000x magnification.

[0321] The imaging results can be seen in Figures 3A to 3D middle. Figures 3A to 3D The structure of the cellulose nanoparticle-based hybrid material is shown. A finely interwoven network of blended biopolymer fibers is visible, in which fibers of varying thicknesses surround an aggregated biopolymer encapsulation.

[0322] Example 9 - Mechanical properties of cross-linked cellulose nanoparticle-based hybrid materials

[0323] The mechanical properties of the cross-linked cellulose nanofiber hybrid material according to the present invention were tested according to tests conducted by several international standardization organizations, and the results are shown in Table 6. The tested material was approximately 0.8 mm thick.

[0324] Table 6

[0325]

[0326] Bally flexural properties of BC + citric acid: fractured after < 20,000 cycles. Bally flexural properties were measured according to EN ISO 17694 (ISO5402-1:2022 Bally flexural properties).

Claims

1. A bio-based material composition comprising: (a) cellulose; (b) an anionic polysaccharide; and (c) a cationic polysaccharide; wherein the composition is cross-linked.

2. The composition according to claim 1, wherein the cellulose is nanocellulose, optionally wherein the cellulose is bacterial cellulose.

3. The composition of claim 1 or claim 2, wherein the anionic polysaccharide comprises or consists of one or more anionic polysaccharides selected from the group consisting of: pectin, alginate, gellan gum, carboxymethyl cellulose, hyaluronic acid, and polyglutamic acid (PGA).

4. The composition according to any one of the preceding claims, wherein the cationic polysaccharide comprises or consists of cationic microfibrillated cellulose (MFC) and / or cationic starch.

5. The composition according to any one of the preceding claims, wherein the composition is cross-linked by one or more tricarboxylic acids selected from the group consisting of citric acid, isocitric acid, aconitic acid, propane-1,2,3-tricarboxylic acid, grifolic acid, and trimesic acid.

6. The composition according to any one of the preceding claims, wherein the composition is cross-linked by chemical cross-linking and / or by physical cross-linking.

7. The composition according to any one of the preceding claims, wherein the composition further comprises a humectant.

8. The composition according to any one of the preceding claims, wherein the composition further comprises one or more fillers.

9. A method of producing a bio-based material composition, the method comprising the steps of: (a) providing a mixture comprising cellulose, an anionic polysaccharide, and a cationic polysaccharide; (b) cross-linking the cellulose, the anionic polysaccharide, and the cationic polysaccharide of step (a); and thereby producing a bio-based material composition.

10. The method according to claim 9, wherein the mixture of step (a) further comprises a humectant.

11. The method according to claim 9 or 10, wherein the cellulose is nanocellulose.

12. The method according to any one of claims 9 to 11, wherein the anionic polysaccharide is one or more anionic polysaccharides selected from the group consisting of pectin, alginate, gellan gum, carboxymethyl cellulose, hyaluronic acid, and polyglutamic acid (PGA).

13. The method according to any one of claims 9 to 12, wherein the cationic polysaccharide is cationic microfibrillated cellulose and / or cationic starch.

14. The method according to any one of claims 9 to 13, wherein the weight ratio of the cellulose: the anionic polysaccharide: the cationic polysaccharide in step (a) is about 4:1:

5.

15. The method according to any one of claims 9 to 14, further comprising a step (i) of blending the cellulose, wherein step (i) is performed prior to step (a).

16. The method according to any one of claims 9 to 15, wherein step (b) comprises adding a cross-linking agent.

17. The method according to claim 16, wherein the cross-linking agent is a tricarboxylic acid selected from the group consisting of citric acid, isocitric acid, aconitic acid, propane-1,2,3-tricarboxylic acid, grifolic acid, and trimesic acid.

18. The method according to any one of claims 9 to 17, further comprising a step (c) of heating and / or stirring the mixture.

19. The method according to any one of claims 9 to 18, wherein the method further comprises a step (d) of casting and / or coating the mixture into a mold, onto a scaffold and / or onto a substrate.

20. The method according to any one of claims 9 to 19, wherein the method further comprises a step (ii) of adding one or more fillers to the mixture, wherein step (ii) can be performed before or after step (b).

21. The method according to any one of claims 9 to 20, wherein the method further comprises a step (iii) of adding one or more dyes to the mixture, wherein step (iii) can be performed before step (b), after step (b), after step (c), after step (d) or after step (e).

22. The method according to any one of claims 9 to 21, wherein the method further comprises a step (iv) of subjecting the composition to a plasma treatment, a surface coating and / or a surface functionalization, wherein step (iv) can be performed after step (b), after step (c), after step (d) or after step (e).

23. The method according to any one of claims 9 to 22, wherein the method is a green method, wherein (a) all reagents used in the method are bio-based reagents; (b) the method is free of petrochemical products; (c) the method only utilizes non-toxic chemicals; and / or (d) the method is sustainable.

24. The method according to any one of claims 9 to 23, wherein the bio-based material composition is the bio-based material composition according to any one of claims 1 to 8.

25. A bio-based material composition comprising: (a) bacterial nanocellulose; (b) pectin; (c) cationic MFC; and (d) glycerol; wherein the composition is cross-linked by citric acid.

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