Method for producing modified substances

Abstract

To provide a method for producing a modified substance.SOLUTION: A method for producing a modified substance includes the steps of: (1) providing a substance with a hydrophobic surface, (2) making cellulose fibers coexist with water-soluble polysaccharides, thereby fibrillating the cellulose fibers, and (3) subjecting the substance to the cellulose fibers fibrillated in coexistence with the water-soluble polysaccharides, thereby modifying the hydrophobic surface of the substance.SELECTED DRAWING: None

Description

Technical Field

[0001] The present disclosure relates to a method for producing a modified substance and a method for producing a functional fiber.

Background Art

[0002] Regarding the technology for producing cellulose nanofibers by defibrating cellulose fibers, mainly chemical methods such as TEMPO oxidation and phosphorylation using plant-derived pulp as a raw material, and enzymatic hydrolysis methods, as well as grinders, homogenizers, and underwater counter-collision methods, are known.

[0003] It is expected that high-quality cellulose fibers with low paper texture can be obtained by defibrating bacterial cellulose. For example, after treating bacterial cellulose with a pulp defibrator, a pressure defibrating treatment is performed with a homogenizer, and it is known to add it to chocolate drinks, clam paste, ice cream, tofu, kamaboko, hamburger patties, sausages, and fillings. Also, methods such as treating nata de coco with a blender at 20,000 rpm for 10 minutes and then performing high-pressure homogenization treatment (passing through at a maximum of 600 bar 10 times), or defibrating with a high-shear blender and further treating with an ultrasonic device are known.

[0004] Regarding the cellulose defibrated product obtained by defibrating cellulose in this way, various applications are expected in the food field. Also, by defibrating water-insoluble carbohydrates such as plant stems and leaves mainly composed of cellulose, and chitin and the outer shells of crustaceans mainly composed of it, the usability is improved not only in the food industry but also in non-food industries such as plastics, fibers, films, and paper, and thus it has attracted high attention.

Summary of the Invention

Means for Solving the Problems

[0005] The inventors analyzed the properties of suspensions prepared by defibrating cellulose fibers in the presence of various water-soluble polysaccharides and found that they have a high degree of interaction with materials having hydrophobic surfaces, such as plastics.

[0006] Therefore, this disclosure provides the following: (Item 1) A method for producing a modified substance, (1) A step of providing a material having a hydrophobic surface, (2) A step of defibrating cellulose fibers by having cellulose fibers and water-soluble polysaccharides coexist, (3) A step of modifying the hydrophobic surface of the substance by applying cellulose fibers that have been defibrated in the presence of the water-soluble polysaccharide to the substance, Methods that include... (Item 2) The method according to the above item, wherein the defibrillation of the cellulose fibers is carried out by adding the water-soluble polysaccharide to the cellulose fibers to obtain a mixture. (Item 3) The method according to any one of the above items, wherein the defibrated cellulose fibers include fibers having a fiber length of at least 2 μm. (Item 4) The method according to any one of the above items, wherein step (3) is carried out in the presence of a water-soluble polysaccharide. (Item 5) The method according to any one of the above items, wherein the water-soluble polysaccharide present in step (3) is the same as or different from the water-soluble polysaccharide used in step (2). (Item 6) The method according to any one of the above items, wherein the concentration of water-soluble polysaccharides present in step (3) is approximately 0.1 wt% or less. (Item 7) The method according to any one of the above items, wherein the water-soluble polysaccharide comprises xylan or a derivative thereof, β-glucan or a derivative thereof, mannan or a derivative thereof, chitosan or a derivative thereof, or any combination thereof. (Item 8) The method according to any one of the above items, wherein the substance having the hydrophobic surface includes a synthetic resin substrate, the leaves, stems, flowers, fruits, and roots of plants, the body surface of animals, and hair. (Item 9) The method according to any one of the above items, wherein the synthetic resin substrate comprises polyethylene, polypropylene, polyethylene terephthalate, polystyrene, polyvinyl alcohol, polylactic acid, polyglycolic acid, polybutylene succinate, polybutylene succinate adipate, polyethylene terephthalate succinate, polybutylene adipate terephthalate, poly(3-hydroxybutyrate-co-3-hydroxyhexanoate), or any combination thereof. (Item 10) The method according to any one of the above items, wherein the modification includes imparting hydrophilicity, imparting electric charge, imparting antibacterial properties, or any combination thereof. (Item 11) The method according to any one of the above items, further comprising the step of bonding functional molecules to a substance to which the cellulose fibers are applied. (Item 12) The method according to any one of the above items, wherein the functional molecule includes a dye, fluorescent dye, luminescent dye, oxidizing agent, conductive substance, metal, ionic substance, enzyme, organism, polysaccharide, protein, or any combination thereof. (Item A1) A method for producing fibers for modifying hydrophobic surfaces, (A) A step of defibrating cellulose fibers by coexisting them with water-soluble polysaccharides, (B) A step of bonding functional molecules to the defibrated cellulose fibers. Methods that include... (Item A2) The method according to the above item, wherein the defibrillation of the cellulose fibers is carried out by adding the water-soluble polysaccharide to the cellulose fibers to obtain a mixture. (Item A3) The method according to any one of the above items, wherein the defibrated cellulose fibers include fibers having a fiber length of at least 2 μm. (Item A4) The method according to any one of the above items, wherein the water-soluble polysaccharide comprises xylan or a derivative thereof, β-glucan or a derivative thereof, mannan or a derivative thereof, chitosan or a derivative thereof, or any combination thereof. (Item A5) The method according to any one of the above items, wherein the functional molecule includes a dye, a fluorescent dye, a fermentation dye, an oxidizing agent, a conductive substance, a metal, an ionic substance, an enzyme, an organism, a polysaccharide, a protein, or any combination thereof. (Item B1) A modifier comprising cellulose fibers and / or water-soluble polysaccharides for modifying substances having a hydrophobic surface. (Item B2) The modifier described above, wherein the cellulose fibers are defibrated in the presence of a water-soluble polysaccharide. (Item B3) The modifier according to any one of the above items, wherein the defibrillation of the cellulose fibers is carried out by adding the water-soluble polysaccharide to the cellulose fibers to obtain a mixture. (Item B4) The modifier according to any one of the above items, wherein the defibrated cellulose fibers include fibers having a fiber length of at least 2 μm. (Item B5) The modifier according to any one of the above items, wherein the modification is carried out in the presence of a water-soluble polysaccharide. (Item B6) The modifier according to any one of the above items, wherein the water-soluble polysaccharide present during the aforementioned modification is the same as or different from the water-soluble polysaccharide present during fibrillation. (Item B7) A modifier according to any one of the above items, wherein the concentration of water-soluble polysaccharides present during the aforementioned modification is approximately 0.01 wt% or less. (Item B8) The modifier according to any one of the above items, wherein the water-soluble polysaccharide comprises xylan or a derivative thereof, β-glucan or a derivative thereof, mannan or a derivative thereof, chitosan or a derivative thereof, or any combination thereof. (Item B9) The substance having the hydrophobic surface is the modifier according to any one of the above items, including a synthetic resin substrate, a leaf, stem, flower, fruit, root of a plant, the body surface of an animal, and hair. (Item B10) The synthetic resin substrate is the modifier according to any one of the above items, including polyethylene, polypropylene, polyethylene terephthalate, polystyrene, polyvinyl alcohol, polylactic acid, polyglycolic acid, polybutylene succinate, polybutylene succinate adipate, polyethylene terephthalate succinate, polybutylene adipate terephthalate, poly(3-hydroxybutyrate-co-3-hydroxyhexanoate), or any combination thereof. (Item B11) The modification includes imparting hydrophilicity, imparting charge, imparting antibacterial properties, or any combination thereof, and is the modifier according to any one of the above items. (Item C1) A substance produced by the method according to any one of the above items. (Item CC1) A fiber produced by the method according to any one of the above items.

[0007] In the present disclosure, it is intended that one or more of the above features may be provided in combination in addition to the explicitly stated combinations. Further embodiments and advantages of the present disclosure will be recognized by those skilled in the art upon reading the following detailed description as needed.

[0008] In addition to the above, the features and remarkable effects of the present disclosure will be clear to those skilled in the art by referring to the sections of the embodiments of the invention and the drawings below.

Advantages of the Invention

[0009] A suspension prepared by defibrating cellulose fibers in the presence of water-soluble polysaccharides can be applied to various substances, and in particular can be used as a hydrophilic agent for substances with hydrophobic surfaces. It can exhibit functions such as controlling ink penetration by altering the water contact angle, suppressing water droplet adhesion, providing a scaffold for bonding and chemical derivatization through surface interactions, and providing a scaffold for hydrophilic substances such as enzymes, microorganisms, and titanium dioxide. Therefore, the method disclosed herein is expected to be applied to surface processing and high-performance processes for plastics and the like.

[0010] Furthermore, according to the method disclosed herein, by modifying the surface of hydrophobic materials such as plastics and imparting hydrophilicity, it is possible to improve printability and label suitability, control adhesion with other components such as oil droplets, and coat and fix oxidizing agents, ethylene decomposing agents, etc., thereby increasing the added value of materials and expanding their applications.

[0011] Furthermore, this technology is expected to have applications in modifying the surface of materials and imparting bio-related functions (such as sensor functions, enzyme functions, and antibacterial properties), as well as electrical conductivity and electrostatic properties, through the use of hydrophilic materials. [Brief explanation of the drawing]

[0012] [Figure 1] Figure 1 is a photograph showing the state of adsorption of cellulose fibers onto a substrate in a method according to one embodiment of the present disclosure. BWX: Birchwood xylan, TMG: Tamarind seed gum, Chitosan: Chitosan [Figure 2] Figure 2 is a graph showing the amount of cellulose fibers adsorbed onto a substrate in a method according to one embodiment of the present disclosure. BC: Bacterial cellulose, BWX: Birchwood xylan, TMG: Tamarind seed gum, Chitosan: Chitosan, CMC: Carboxymethylcellulose, Guargum: Guar gum, Sodium alginate: Sodium alginate [Figure 3]Figure 3 is a graph showing the amount of cellulose fibers adsorbed onto each substrate when water-soluble polysaccharides are added before or after defibration of cellulose fibers. BWX: Birchwood xylan, TMG: Tamarind seed gum, Chitosan: Chitosan, CMC: Carboxymethylcellulose, Guargum: Guar gum, Sodium alginate: Sodium alginate [Figure 4] Figure 4 is a photograph showing the effect of tamarind seed gum (TMG) concentration on the adsorption effect. [Figure 5] Figure 5 shows the results of a cleaning effect on a cellulose / polysaccharide composite bonded to a substrate in a method according to one embodiment of the present disclosure. BWX: Birchwood xylan, TMG: Tamarind seed gum, Chitosan: Chitosan [Figure 6] Figure 6 shows the results when fine pulp (FP) is used as the cellulose fiber in a method according to one embodiment of the present disclosure. [Figure 7] Figure 7 shows the results of measuring the contact angle of a substrate surface to which defibrated cellulose fibers bound in the presence of a water-soluble polysaccharide are attached, in a method according to one embodiment of the present disclosure. BWX: Birchwood xylan, TMG: Tamarind seed gum, Chitosan: Chitosan [Figure 8] Figure 8 is a magnified photograph of the substrate surface to which cellulose fibers, defibrated in the presence of a water-soluble polysaccharide, are bound in a method according to one embodiment of the present disclosure. [Figure 9] Figure 9 is a photograph visualizing xyloglucan in a defibrated cellulose fiber / water-soluble polysaccharide complex in one embodiment of this disclosure. Tamarind seed gum was used as the water-soluble polysaccharide in the defibrated cellulose fiber / water-soluble polysaccharide complex. Since xyloglucan is the main component of tamarind seed gum, xyloglucan was visualized in this embodiment. BC: Bacterial cellulose, TMG: Tamarind seed gum [Figure 10] Figure 10 is a photograph of a ginkgo leaf treated with a defibrated cellulose fiber / water-soluble polysaccharide composite in a method according to one embodiment of the present disclosure. BC: Bacterial cellulose, TMG: Tamarind seed gum [Figure 11] Figure 11 is a photograph of a tomato treated with a defibrated cellulose fiber / water-soluble polysaccharide complex according to one embodiment of the present disclosure. The image shows the skin of a cherry tomato. BC: Bacterial cellulose, TMG: Tamarind seed gum, Chitosan: Chitosan [Figure 12] Figure 12 is a magnified photograph of a tomato in which a defibrated cellulose fiber / water-soluble polysaccharide composite is applied according to a method in one embodiment of the present disclosure. The image shows the skin of a cherry tomato. [Figure 13] Figure 13 is a photograph showing the application of a defibrated cellulose fiber / water-soluble polysaccharide complex to a tomato in a method according to one embodiment of the present disclosure. The top row shows a whole cherry tomato, and the bottom row shows a cherry tomato cut in half. BC: Bacterial cellulose, TMG: Tamarind seed gum, Chitosan: Chitosan [Figure 14] Figure 14 is a photograph showing the application of a defibrated cellulose fiber / water-soluble polysaccharide composite to hair in a method according to one embodiment of the present disclosure. BC: Bacterial cellulose, TMG: Tamarind seed gum, Chitosan: Chitosan [Modes for carrying out the invention]

[0013] The present disclosure is described below in best form. Throughout this specification, singular expressions should be understood to include the concept of their plural form unless otherwise specified. Accordingly, singular articles (e.g., "a," "an," "the" in English) should be understood to include the concept of their plural form unless otherwise specified. Furthermore, terms used herein should be understood to have the meaning commonly used in the art unless otherwise specified. Accordingly, unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by those skilled in the art to which this disclosure pertains. In case of any conflict, this specification (including definitions) shall prevail.

[0014] The following provides definitions of terms used specifically in this specification and / or basic technical concepts as appropriate.

[0015] In this specification, "approximately" means ±10% of the following number.

[0016] In this specification, "defibration" refers to the process of breaking down water-insoluble carbohydrates, such as bacterial cellulose and pulp fibers, into a slurry.

[0017] In this specification, "polysaccharide" means a polymer of multiple monosaccharides, and in this disclosure, it typically includes any five or more monosaccharides. The monosaccharides used in polysaccharides are not particularly limited, but include, for example, glucose, galactose, fructose, xylose, arabinose, galacturonic acid, glucuronic acid, mannose, glucosamine, N-acetylglucosamine, rhamnose, anhydrogalactose, etc., and may include one or more of these with modified side chains. The bonding modes of monosaccharides include linear, branched, and cyclic, as well as multiple of these modes, and may also include those bonded to other sugars, proteins, or non-sugar substances such as lipids.

[0018] In this specification, "water-soluble polysaccharide" means polysaccharides that are water-soluble. Many types of compounds exist as natural products, but in this specification, artificially synthesized polysaccharides may also be used in addition to natural products. In this specification, water-soluble polysaccharides also include polysaccharides that are not water-soluble in their original state but become water-soluble after treatment with an acid or alkali, or after heat treatment. For example, but not limited to these, the following may be included: xylan or its derivatives (including those substituted with glucuronic acid residues, arabinose residues, etc.), β-glucan or its derivatives ((1-3), (1-4)β-glucan, xyloglucan, xanthan gum, tamarind seed gum (main component: xyloglucan), etc.), mannan or its derivatives (galactomannan, etc.), water-soluble cellulose derivatives or their salts (including carboxymethylcellulose salts, methylcellulose, hydroxypropylmethylcellulose, and other polysaccharides chemically modified from cellulose), chitosan or its derivatives (partially deacetylated chitin, etc.), alginic acid or its salts or derivatives thereof, carrageenan, gellan gum, pectin or its substructures or derivatives thereof, and any combination thereof.

[0019] In this specification, "cellulose fiber" refers to water-insoluble carbohydrates and may include, for example, plant tissues mainly composed of water-insoluble cellulose such as bacterial cellulose (nata de coco), peptidoglycan, plant cellulose (fine pulp), and plant fiber (vegetable flour, etc.), as well as crab shells, shrimp shells, animal tissues, insect powders, algal cells, filamentous fungal cells, yeast cells, and bacterial cells (natto bacteria cells, lactic acid bacteria cells, etc.). Cellulose fiber may also be a water-insoluble substance composed of multiple types of carbohydrates.

[0020] In this specification, "fiber length" refers to the length of a fiber along its long axis, and means the straight-line distance between the two ends of a fiber, assuming that the fiber can be arranged in a straight line along its long axis without collapsing.

[0021] In this specification, "carbohydrate" basically refers to a substance whose main component is monosaccharides, and edible carbohydrates include digestible sugars and dietary fiber. Although there are many types of compounds that are naturally occurring carbohydrates, the carbohydrates used in this specification may be artificially synthesized or may exist in a state that includes substances other than carbohydrates. In addition, non-edible plant cell walls, polysaccharides inside or outside microbial cells, storage polysaccharides in seeds, roots, tubers, etc., polysaccharides in animal cartilage, extracellular matrix polysaccharides in animal cells, and extracellular skeleton polysaccharides are also included in the definition of carbohydrates in this specification.

[0022] In this specification, "coexistence" means that cellulose fibers and water-soluble polysaccharides are present simultaneously in the same system, and that the water-soluble polysaccharides are present in a dissolved state when the defibration operation of cellulose fibers is performed according to this disclosure. When the defibration operation of cellulose fibers is performed according to this disclosure, at least a portion of the coexisting water-soluble polysaccharides is in a state in which it can newly form a complex with the cellulose fibers. Adding water-soluble polysaccharides after the defibration operation of cellulose fibers does not constitute "coexistence" as defined herein, nor does defibrating materials in which water-soluble polysaccharides have already formed a complex with the cellulose fibers constitute defibration under "coexistence" as defined herein.

[0023] In this specification, "modification" of a substance means changing or improving any property of the substance to be modified compared to before the modification operation. For example, modification of a substance having a hydrophobic surface may impart hydrophilicity, improve antibacterial properties, or impart an electric charge to the substance. "Antibacterial properties" include antibacterial, antifungal, antiviral, growth inhibitory properties for plants and animals, and repellency against them.

[0024] In this specification, "hydrophobic surface" is interpreted broadly to mean a surface that does not mix with water and / or a surface that repels water droplets. One definition is a surface whose contact angle with water is at least about 90° or more, and this usually applies to surfaces made of plastic or synthetic resin. In this specification, the contact angle with water is the angle between the tangent line of the contour curve of the liquid at the intersection of the contour curve and the horizontal surface, when the member having a horizontal surface is in contact with water (droplet) dropped onto the horizontal surface. The contact angle can be measured, for example, by the droplet method in a measurement environment with a temperature of about 20 to about 30°C and a relative humidity of about 30 to about 70%.

[0025] In this specification, "substance having a hydrophobic surface" means a substance having the above-mentioned hydrophobic surface over at least part or the whole thereof, and the degree of hydrophobicity is not particularly limited. For example, substances having a hydrophobic surface can include synthetic resin substrates such as plastics, plant materials such as leaves, stems, flowers, fruits, and roots, animal materials such as skin, feathers, hair, and exoskeletons, microbial materials such as bacterial cells and biofilms, or living organisms themselves that contain them, metals such as iron and aluminum, tar-like petroleum-related substances, bio-oils obtained by high-temperature treatment of biomass, and films made of oils and fats. Animal materials can include bird feathers and sheep's wool, and the skin and feathers of arthropods, insects, and other organisms.

[0026] In this specification, "functional molecule" refers to a molecule that can impart any desired function to a target substance. By attaching, binding to, or mixing the functional molecule with the substance, the substance can acquire properties corresponding to the function of the functional molecule. Examples of functional molecules include dyes, fluorescent dyes, fermentation dyes, oxidizing agents, conductive substances, metals, ionic substances, enzymes, biological substances, polysaccharides, proteins, or any combination thereof.

[0027] In this specification, "to apply..." means any means of bringing one substance into contact with another, for example, the techniques for application may include, but are not limited to, brushing, rolling, spraying, injecting, painting, absorbing, adsorbing, immersion, saturating, penetrating, immersing, or a combination thereof.

[0028] In this specification, "mixture" means a state in which multiple constituent units are mixed, dispersed, or swollen, or a state in which one constituent unit is dissolved in other constituent units.

[0029] (Preferred embodiment) Preferred embodiments of the Disclosure are described below. The embodiments provided below are provided for a better understanding of the Disclosure, and the scope of the Disclosure should not be limited to the descriptions below. It will be apparent that those skilled in the art can make appropriate modifications within the scope of the Disclosure, taking into consideration the descriptions herein. Furthermore, the embodiments of the Disclosure below can be used individually or in combination.

[0030] In one aspect of the present disclosure, a method is provided for producing a modified substance, comprising: (1) providing a substance having a hydrophobic surface; (2) defibrating cellulose fibers in the presence of cellulose fibers and a water-soluble polysaccharide; and (3) modifying the hydrophobic surface of the substance by applying the defibrated cellulose fibers in the presence of the water-soluble polysaccharide to the substance.

[0031] The method disclosed herein is characterized by modifying a substance having a hydrophobic surface by utilizing the properties of defibrated cellulose fibers in the presence of water-soluble polysaccharides. That is, the method disclosed herein is based on the hypothesis that the appearance of new cellulose surfaces that may occur during the cellulose dissociation process causes association between nearby celluloses, promoting entanglement of fibers and thus hindering the dissociation process. The method disclosed herein is based on the discovery that the coexistence of polysaccharides that interact with cellulose during the cellulose dissociation process provides useful defibrated cellulose fibers, and that these defibrated cellulose fibers function as modifiers for substances having a hydrophobic surface.

[0032] In one embodiment, when defibrating cellulose fibers, it is preferable that the water-soluble polysaccharide exists as a solution, for example, dissolved in water, a mixed solvent of water and other substances, alcohol, or a hydrophilic solvent. Cellulose fibers can be mixed with such a solution of water-soluble polysaccharide and defibrated in its presence. In another embodiment, when applying the defibrated cellulose fibers to a substance having a hydrophobic surface, the substance may exist as itself, and the defibrated cellulose fibers or a solution thereof can be applied (e.g., by spraying), or the substance may be put into a solution, for example, dissolved in water, a mixed solvent of water and other substances, alcohol, or a hydrophilic solvent, and then the defibrated cellulose fibers may be brought into contact with the substance. In this way, the substance having a hydrophobic surface can be modified using the defibrated cellulose fibers.

[0033] <Cellulose fibers defibrated in the presence of water-soluble polysaccharides> Cellulose fibers that can be used in the method disclosed herein include plant tissues mainly composed of water-insoluble cellulose such as bacterial cellulose (nata de coco), starch, chitin, chitosan, paramylon, peptidoglycan, mannan, plant cellulose (fine pulp), and plant fibers (vegetable flour, etc.), as well as crab shells, shrimp shells, animal tissues, insect powders, algal cells, filamentous fungal cells, yeast cells, and bacterial cells (natto bacteria cells, lactic acid bacteria cells, etc.). Cellulose fibers such as plant cellulose and bacterial cellulose tend to entangle during defibrillation and have low dissociability. Therefore, when cellulose fibers are suspended in water, they cannot be defibrillated using food blenders or food mixers, and require the use of special equipment such as high-power grinders, homogenizers, high-pressure treatment devices, and ultrasonic treatment devices for the pulp industry. This disclosure provides a technology for easily defibrating cellulose fibers, which could previously only be defibrated using such special equipment, by coexisting them with water-soluble polysaccharides, and for modifying materials having a hydrophobic surface by utilizing the properties of these defibrated cellulose fibers.

[0034] In one embodiment, the cellulose fibers used in the method of this disclosure may be natural cellulose fibers that have not had functional groups introduced by chemical reactions or the like. While it is possible to modify any substance by introducing functional groups into cellulose fibers by chemical reactions and then using such functionally grouped cellulose fibers, the method of this disclosure provides a technology that can modify substances having hydrophobic surfaces using natural cellulose fibers without the use of such chemical reactions. With cellulose fibers into which functional groups have been introduced by chemical reactions, it is necessary to consider the chemical structure itself, the partial chemical structure, or the chemical, biological, and physical effects of coexisting or residual substances, and it may be necessary to conduct verification from the standpoint of safety and quality stability in advance.

[0035] Bacterial cellulose exhibits a gel-like state, as it is produced as nata de coco, and if necessary, materials can be used that have been cleaned and cut to remove coexisting substances such as bacterial cells, according to known methods. In the case of materials distributed as cut products in a stabilizer such as sugar solution, materials that have been desaccharified and washed can be used if necessary. Furthermore, it is desirable that raw materials distributed as dried products be in a water-absorbed state during the dissociation process. Plant cellulose (pulp) is cut plant tissue derived from wood, herbs, algae, etc. More preferably, it is desirable that at least some of the components coexisting with cellulose, such as cell wall components and intracellular components, have been removed to improve the cellulose content. Similarly, with other cellulose fibers, it is desirable to cut them into a shape suitable for crushing and to improve the defibrillation efficiency by increasing the carbohydrate content.

[0036] In one embodiment of the present disclosure, cellulose fibers can be defibrated using a food blender or food mixer by coexisting with water-soluble polysaccharides dissolved in water during defibration, and the resulting composite contains a mixture of cellulose fibers and water-soluble polysaccharides. In one embodiment, the defibration of cellulose fibers in the method of the present disclosure may be carried out under harsher conditions using industrial machinery such as a ball mill. In another embodiment, the composite obtained by defibrating cellulose fibers in the presence of water-soluble polysaccharides dissolved in water using a food blender or food mixer can be further processed with industrial machinery such as a ball mill to obtain even finer disintegrated material.

[0037] In one embodiment of the present disclosure, one or more types of water-soluble polysaccharides can be added during the defibrillation of cellulose fibers. In one embodiment of the present disclosure, the water-soluble polysaccharide is preferably a polysaccharide that interacts with the surface, such as water-insoluble cellulose, and may include, but is not limited to, xylan or its derivatives (including those substituted with glucuronic acid residues, arabinose residues, acetyl groups, 4-O-methylglucuronic acid residues, feruloyl groups, etc.), β-glucan or its derivatives ((1-3), (1-4)β-glucan, xyloglucan, xanthan gum, tamarind seed gum (main component: xyloglucan), etc.), mannan or its derivatives (galactomannan, etc.), water-soluble cellulose derivatives or salts thereof (including polysaccharides chemically modified from cellulose, such as carboxymethylcellulose salt, methylcellulose, hydroxypropylmethylcellulose, etc.), chitosan or its derivatives (partially deacetylated chitin, etc.), alginic acid or its salts or derivatives thereof, carrageenan, gellan gum, pectin or its substructures or derivatives thereof, and any combination thereof. In one embodiment, the β-glucan or its derivatives may include (1-3),(1-4)β-glucan, and not only purified (1-3),(1-4)β-glucan but also extracts containing (1-3),(1-4)β-glucan from barley, wheat, oats, etc., can be used as water-soluble polysaccharides in this disclosure. When obtaining such extracts, it is necessary to inactivate the (1-3),(1-4)β-glucan-degrading enzymes inherent in barley, etc. Effective methods include roasting and then grinding the barley, etc. to obtain an extract, or grinding and then heat-treating to obtain an extract. In addition, the extract may also contain water-soluble polysaccharides other than (1-3),(1-4)β-glucan, such as derivatives of xylan. While some water-soluble polysaccharides are readily available as thickening and stabilizing agents, extracts containing (1-3),(1-4)β-glucan from barley, wheat, and oats, and extracts containing xylan derivatives from rice bran and wheat bran, are water-soluble polysaccharides that can be easily obtained from food materials. Therefore, the method disclosed herein can be easily carried out at home or in small-scale manufacturing facilities.

[0038] In one embodiment of this disclosure, these water-soluble polysaccharides can be dissolved or highly swollen by adding acids or alkalis as needed, or by heating, before being included in the defibrillation of cellulose fibers. In another embodiment of this disclosure, the shelf life can be improved and quality maintained by applying sterilization techniques for wet foods, such as autoclave sterilization or retort sterilization, to the water-soluble polysaccharides. The effective weight ratio of water-soluble polysaccharides to cellulose fibers during defibrillation varies depending on the characteristics of the interaction between the water-soluble polysaccharides and cellulose fibers, the characteristics of the substructures of the water-soluble polysaccharides involved in the interaction, the purity of the carbohydrates in the cellulose fibers, the potential amount of surface exposure related to the interaction in the cellulose fibers, the degree of surface exposure depending on the processing conditions during defibrillation, and the influence of coexisting substances in the system during defibrillation. In one embodiment, it is sufficient that the cellulose fibers and the water-soluble polysaccharides dissolved in water coexist during the defibrillation of cellulose fibers, and other substances can be added as needed.

[0039] In one embodiment of this disclosure, cellulose fibers can be defibrated by coexisting with water-soluble polysaccharides dissolved in water using a food blender or food mixer, with a processing time of approximately 1 second to approximately 120 minutes, preferably approximately 5 seconds to approximately 60 minutes, and more preferably approximately 10 seconds to approximately 10 minutes. In this specification, "food blender" or "food mixer" refers to a so-called household blender or mixer available through general distribution channels, for example, one with a processing capacity of approximately 20 liters or less per processing cycle and approximately 50 liters or less per hour when processing continuously, and includes those sold to households, cake shops, food manufacturers, restaurants, small-scale food manufacturers, etc., at home electronics retailers and online sales sites. Examples of food blenders or food mixers include devices or equipment for blending and / or mixing food for one to more than ten servings.

[0040] In one embodiment, processing with a food blender or food mixer can be performed in multiple steps of approximately 10 seconds, 20 seconds, or 30 seconds each, for a total of approximately 1 minute, 5 minutes, 7 minutes, or 10 minutes, in order to avoid overheating of the machine. In one embodiment, the processing temperature can be appropriately changed depending on the properties of the coexisting water-soluble polysaccharides. In one embodiment, when water-insoluble cellulose is used as the cellulose fiber to be defibrated, it is stable in the range of approximately 0°C to 100°C where water molecules are liquid, and if the effects of water-soluble polysaccharides and other additives are not considered, processing can be performed in this temperature range.

[0041] When cellulose fibers are defibrated, a shearing force is applied to the cellulose fibers, causing them to tear into two or more clumps. In other words, in this disclosure, when cellulose fibers such as bacterial cellulose, which are in a state where water-insoluble cellulose chains are associated as described above, are defibrated, a substance that interacts with the cellulose fibers (e.g., a water-soluble polysaccharide) is present. This prevents the suppression of defibration by the re-association of carbohydrates constituting the cellulose fibers during defibration, and allows for the easy acquisition of defibrated cellulose fibers. When re-association of defibrated cellulose fibers occurs, for example, in bacterial cellulose, it is thought that amorphous carbohydrates are released during defibration, and these amorphous carbohydrates interact with the hydrophobic surface of carbohydrate crystals located at or near the detached site. In this disclosure, based on the hypothesis that even if amorphous carbohydrates are released, if the hydrophobic surface of the crystal is protected by another substance, interactions that lead to re-association will be less likely to occur, a substance that interacts with cellulose fibers (e.g., a water-soluble polysaccharide) is added, and it has been confirmed that defibration is promoted as hypothesized.

[0042] In one embodiment, the water-soluble polysaccharides present during the defibration of cellulose fibers can be those added to the cellulose fibers from an external source. In this way, a mixture of cellulose fibers and water-soluble polysaccharides can be obtained, and the cellulose fibers can be defibrated in their presence. Polysaccharides originally bound to cellulose fibers or their raw materials are hydrophobic polysaccharides and therefore cannot be used as water-soluble polysaccharides in the method disclosed herein.

[0043] In one embodiment of the present disclosure, such defibration treatment of cellulose fibers may result in defibration of cellulose fibers having fiber lengths of at least approximately 2 μm, approximately 3 μm, approximately 4 μm, approximately 5 μm, approximately 6 μm, approximately 7 μm, approximately 8 μm, approximately 9 μm, or approximately 10 μm. When defibrating cellulose fibers, if strong collision energy is applied to the cellulose fibers, such as in a counter-impact treatment, many fibers become nano-sized fibers. In the defibration treatment used in the method of the present disclosure, defibration is achieved simply by stirring with a food blender or food mixer in the presence of water-soluble polysaccharides, so only a very small amount of nano-sized fibers are present, and most fibers have the above-mentioned fiber lengths.

[0044] <Cellulose fibers defibrated in the presence of water-soluble polysaccharides> In one embodiment of this disclosure, the defibrated cellulose fibers obtained as described above can be applied to a substance having a hydrophobic surface to modify the substance.

[0045] In a method according to one embodiment of this disclosure, when applying defibrated cellulose fibers to coat a substance having a hydrophobic surface, the method is not particularly limited. For example, the substance having a hydrophobic surface can be impregnated or immersed in a solution containing defibrated cellulose fibers, or the solution containing defibrated cellulose fibers can be applied to the surface of the substance having a hydrophobic surface. In one embodiment, impregnation and application may be performed in combination, or each may be performed repeatedly. The application means is not particularly limited and can be an air spray, brush, roller, etc.

[0046] In one embodiment, the material having a hydrophobic surface after the application of defibrated cellulose fibers may be dried as needed. Drying can be carried out, for example, by heat drying, forced drying, and / or room temperature drying.

[0047] The substances to be modified are not particularly limited as long as they have a hydrophobic surface, but may include, for example, synthetic resin substrates such as plastics, plant materials such as leaves, stems, flowers, fruits, and roots, animal materials such as skin, feathers, hair, and exoskeletons, microbial materials such as bacterial cells and biofilms, or living organisms containing these materials, and metals such as iron and aluminum. In one embodiment, animal materials may include bird feathers, sheep's wool, and the skin and feathers of arthropods, insects, and other organisms. By using vegetables and fruits as the substances to be modified, antibacterial components, preservatives, or insecticidal components can be imparted to vegetables and fruits, and by using insects and leaves as the substances to be modified, insecticides can be effectively sprayed on insects and leaf surfaces. In one embodiment, the method disclosed herein can also be used to enhance the functionality of various rinses and skin moisturizers.

[0048] In one embodiment, the substance to be modified can include tar-like petroleum-related substances, bio-oil obtained by high-temperature treatment of biomass, and oil-based films. By modifying such substances using the method of the present disclosure, oil-assimilating bacteria can be attached to these substances.

[0049] In one embodiment, the synthetic resin substrate can be polyethylene, polypropylene, polyethylene terephthalate, polystyrene, polyvinyl alcohol, polylactic acid, polyglycolic acid, polybutylene succinate, polybutylene succinate adipate, polyethylene terephthalate succinate, polybutylene adipate terephthalate, poly(3-hydroxybutyrate-co-3-hydroxyhexanoate), or any combination thereof.

[0050] In one embodiment, when the defibrated cellulose fibers of this disclosure are applied to a synthetic resin substrate having a hydrophobic surface such as polyethylene, the surface of the substrate can be modified to be hydrophilic, for example. The properties imparted by the defibrated cellulose fibers of this disclosure may vary depending on the type of water-soluble polysaccharide and cellulose fiber, or a combination thereof. In one embodiment, the desired properties can also be imparted by appropriately combining the properties of the water-soluble polysaccharide used during defibration and the water-soluble polysaccharide that can be optionally added after defibration. For example, the properties imparted by the defibrated cellulose fibers of this disclosure may include the imparting of hydrophilicity, the imparting of electric charge, the imparting of antibacterial properties, or any combination thereof.

[0051] In one embodiment, when the defibrated cellulose fibers of the present disclosure are applied to a material having a hydrophobic surface, the amount of cellulose fibers adsorbed can be determined, for example, by cellulose staining. Specifically, a dispersion of defibrated cellulose fibers is dropped onto a material having a hydrophobic surface (e.g., a PP film) and left to stand at room temperature for 10 minutes or more. After that, the cellulose fibers are removed, the material is immersed in pure water about 5 times to wash away any unadsorbed fibers, and then air-dried at 60°C for 10 minutes or more. 1 × 10⁻⁶ of this material is then treated with phosphate buffer (pH 7.5). -3Fluorescent staining is performed by dropping Calcofluor white diluted to % and allowing it to stand for at least 10 minutes. Next, the fluorescently stained sample is observed under a fluorescence microscope to obtain a fluorescence image. Background fluorescence is removed from the fluorescence image using image processing software (imagej / Fiji), and after adjusting the brightness and contrast, the binarized image is used to evaluate the amount of adsorption. The proportion of white areas on the screen of the nine binarized images can be calculated, and the mean and standard deviation can be determined.

[0052] In one embodiment, when the defibrated cellulose fibers are applied to a substance having a hydrophobic surface, the process can be carried out in the presence of water-soluble polysaccharides. As described above, in the method of this disclosure, the cellulose fibers are defibrated in the presence of water-soluble polysaccharides, so the cellulose fibers immediately after defibration are in the presence of water-soluble polysaccharides. In one embodiment of this disclosure, when these defibrated cellulose fibers are applied to a substance having a hydrophobic surface for modification, the modification process may be carried out after removing the water-soluble polysaccharides, or the modification process may be carried out in the presence of water-soluble polysaccharides.

[0053] In one embodiment, when the modification step is carried out in the presence of a water-soluble polysaccharide, the water-soluble polysaccharide present may be the same water-soluble polysaccharide used in the defibration step, or it may be a different water-soluble polysaccharide from the one used in the defibration step. That is, cellulose fibers can be defibrated in the presence of a water-soluble polysaccharide, then the water-soluble polysaccharide can be removed, and a different type of water-soluble polysaccharide can be added to the defibrated cellulose fibers for use in the modification step. In another embodiment, cellulose fibers can be defibrated in the presence of a water-soluble polysaccharide, and a different type of water-soluble polysaccharide can be added without removing the water-soluble polysaccharide. As described above, in the method of this disclosure, the properties imparted by the modification step may change depending on the type of water-soluble polysaccharide and cellulose fiber, or a combination thereof. Therefore, any water-soluble polysaccharide may be added to impart the desired properties, and the removal or addition of water-soluble polysaccharide can be carried out by any method.

[0054] In one embodiment, the concentration of water-soluble polysaccharide present in the modification process can be appropriately set depending on the type of water-soluble polysaccharide and the type of substance to be modified. For example, it can be about 1.0 wt% or less, about 0.5 wt% or less, about 0.1 wt% or less, about 0.05 wt% or less, about 0.01 wt% or less, about 0.005 wt% or less, or about 0.001 wt% or less. The lower limit can be, for example, about 0.0001 wt% or more, about 0.0005 wt% or more, about 0.001 wt% or more, or about 0.005 wt% or more.

[0055] In one embodiment of this disclosure, functional molecules can be further attached to a material to which defibrated cellulose fibers have been applied. Such functional molecules can be any type, but examples include dyes, fluorescent dyes, fermentation dyes, oxidizing agents, conductive substances, metals, ionic substances, enzymes, biological substances, polysaccharides, proteins, or any combination thereof.

[0056] Such functional molecules can be mixed with defibrated cellulose fibers to modify the physical properties and characteristics of the cellulose fibers. For example, when using a substance having a hydrophobic surface as a coating for food materials using the method disclosed herein (e.g., coating the surface of tomatoes), seasonings, sugars, starches, oils and fats, proteins, inorganic salts, gelling agents, other foods and their processed products, nutritional components, functional components, etc., can be added. Cellulose fibers have high compatibility with these functional molecules, but the compatibility of these molecules with water-soluble polysaccharides, or the effect on the interaction between the cellulose fibers constituting the complex and the water-soluble polysaccharides, varies depending on the type of water-soluble polysaccharide and the defibration conditions, so it is preferable to determine the scope of application on a case-by-case basis. For example, the effects of salt and pH can affect the electrostatic effect and the associated dispersion effect depending on the water-soluble polysaccharide, and the dispersion state can be controlled.

[0057] In other aspects of this disclosure, a method for producing functional fibers is provided, comprising the steps of: defibrating cellulose fibers in the presence of cellulose fibers and a water-soluble polysaccharide; and binding functional molecules to the defibrated cellulose fibers. Such a method may have the features described elsewhere in this specification.

[0058] In other aspects of this disclosure, a modifier comprising cellulose fibers and / or water-soluble polysaccharides for modifying a substance having a hydrophobic surface is provided. The modifier of this disclosure may have the features described elsewhere in this specification.

[0059] In other aspects of this disclosure, materials produced by methods described elsewhere in this specification are provided. In yet another aspect, fibers produced by methods described elsewhere in this specification are provided. Such materials and fibers may have the characteristics described elsewhere in this specification. [Examples]

[0060] The defibrated cellulose fibers were prepared as follows: 3 kg of bacterial cellulose (BC, domestically produced nata de coco (commercial use), Morinaga & Co., Ltd.) was placed in a 20 L container, and 15 L of tap water was added and gently stirred. Desaccharification was performed by changing the water five times every 24 hours. 20 g of this was taken by wet weight, 27 g of 0.35% polysaccharide solution was added, and then it was disintegrated by grinding it in a household mixer (Food Mill TML180, Tescom) at a speed of 25,000 rpm for 30 seconds x 4 times.

[0061] In the following examples, the product was prepared using a small mixer system. Furthermore, the fine pulp used in Example 5 was prepared as described below.

[0062] Whatman Qualitative Filter Paper No. 1 was mixed with 10g of tamarind seed gum aqueous solution (w / w), placed in a 50mL stainless steel jar, and a 25mm diameter stainless steel ball. The mixture was then ground in a ball mill (Varder Scientific Co., Ltd. (Japan Headquarters: Tokyo) Mixer Mill MM301) at 15 reciprocations / second for 4 minutes, and this was used as fine pulp.

[0063] (Example 1: Measurement of the amount of cellulose fibers adsorbed onto the substrate) In this example, we confirmed the extent to which defibrated cellulose fibers were adsorbed onto the substrate. Details are shown below.

[0064] The circuit boards used were those listed in the table below. [Table 1]

[0065] A solution containing cellulose fibers was dropped onto the substrate and left to stand at room temperature for 10 minutes. After removing the droplets, pure water was gently dropped onto the substrate and immediately removed. This process was repeated five times to remove any cellulose fibers that were not adsorbed onto the substrate. After the above cleaning procedure, the substrate was dried in a 60°C oven for 10 minutes.

[0066] After the above treatment, a calcofluor white solution was added dropwise to the substrate and allowed to stand at room temperature for 10 minutes to stain the cellulose fibers. After removing the calcofluor white solution, phosphate buffer (pH 7.5) was gently added dropwise and immediately removed. This process was repeated three times to remove any excess calcofluor white solution.

[0067] After the above staining, a very small amount of phosphate buffer (pH 7.5) was added dropwise, and the samples were observed using a fluorescence microscope (Olympus BX51). The results are shown in Figure 1. Bacterial cellulose (BC) was used as the cellulose fiber in all cases. In Figure 1, "No water-soluble polysaccharide" indicates that no water-soluble polysaccharide was added during defibrillation. In the four rightmost panels of Figure 1, BC was defibrillated with the addition of birchwood xylan (BWX), tamarind seed gum (TMG), and chitosan, respectively, as water-soluble polysaccharides. From these results, it can be seen that the amount of adsorption to the substrate was higher when defibrillation was performed with water-soluble polysaccharides than when bacterial cellulose alone was adsorbed, indicating that the hydrophobic surface can be modified by coexisting cellulose fibers and water-soluble polysaccharides during defibrillation.

[0068] Figure 2 shows a graph of the amount of cellulose fibers adsorbed onto the substrate. BC represents bacterial cellulose, TMG represents tamarind seed gum, BWX represents birchwood xylan, and CMC represents carboxymethylcellulose. This graph also shows that the amount of adsorption to the substrate is higher when bacterial cellulose is defibrated together with a water-soluble polysaccharide than when bacterial cellulose is adsorbed alone. When tamarind seed gum is used as the water-soluble polysaccharide, the adsorption to PET is significantly higher. Chitosan also exhibits high adsorption to PET. On the other hand, when used as the water-soluble polysaccharide for polystyrene, the amount of adsorption is high. With birchwood xylan, the adsorption to PP is high.

[0069] (Example 2: Verification of the timing of polysaccharide addition) In this example, we investigated whether there was a change in the amount of adsorption to the substrate when water-soluble polysaccharides were added before defibration of cellulose fibers and when they were added after defibration. The adsorption experiment to the substrate was conducted in the same manner as in Example 1. The results are shown in Figure 3. BC represents bacterial cellulose, TMG represents tamarind seed gum, BWX represents birchwood xylan, and CMC represents carboxymethyl cellulose. Figure 3 is a graph obtained by subtracting the area fraction when water-soluble polysaccharides were added before defibration from the area fraction when they were added after defibration, using the same method as in Figure 2. In other words, the more negative this value is, the greater the increase in adsorption by adding water-soluble polysaccharides before defibration. From these results, it can be seen that, on various hydrophobic substrates, the amount of adsorption to the hydrophobic substrate is greater when water-soluble polysaccharides are added before defibration of cellulose fibers than when they are added after defibration.

[0070] (Example 3: Effect of tamarind seed gum (TMG) concentration on adsorption effect) In this example, we investigated whether the amount of adsorption to the substrate changes depending on the concentration of tamarind seed gum used as the water-soluble polysaccharide. The adsorption experiment to the substrate was performed in the same manner as in Example 1. The results are shown in Figure 4. From these results, it can be seen that the amount of bacterial cellulose adsorbed to the substrate changes depending on the concentration of tamarind seed gum defibrated in the presence of tamarind seed gum. Furthermore, it can be seen that when the total concentration of water-soluble polysaccharide and cellulose fiber is high, the accessibility of the cellulose fiber / water-soluble polysaccharide complex to the substrate decreases, and that adsorption to the substrate is better when the concentration of water-soluble polysaccharide and cellulose fiber is low. When the effect of tamarind seed gum concentration on adsorption was investigated, it was suggested that when the tamarind seed gum concentration is about 0.01% or higher, the adsorbed fibers peel off when washed with water. A concentration of about 0.001% is desirable for adsorption.

[0071] (Example 4: Cleaning effect on cellulose fiber / water-soluble polysaccharide composite bonded to a substrate) In this example, we confirmed the change in adsorption amount when a cellulose fiber / water-soluble polysaccharide composite that had been dropped onto a substrate was washed.

[0072] The substrate used was the one shown in Table 1 of Example 1.

[0073] A solution containing cellulose fibers was dropped onto the substrate and allowed to stand at room temperature for 10 minutes. After removing the droplets, pure water was gently added and immediately removed. This process was repeated five times to remove any cellulose fibers that were not adsorbed onto the substrate. Subsequently, the substrate was immersed in deionized water or EtOH for 30 minutes as a washing procedure.

[0074] After the above treatment, a calcofluor white solution was added dropwise to the substrate and allowed to stand at room temperature for 10 minutes to stain the cellulose fibers. After removing the calcofluor white solution, phosphate buffer (pH 7.5) was gently added dropwise and immediately removed. This process was repeated three times to remove any excess calcofluor white solution.

[0075] After the staining described above, a very small amount of phosphate buffer (pH 7.5) was added dropwise, and the results were observed using a fluorescence microscope (Olympus BX51). The results are shown in Figure 5. From these results, it can be seen that, depending on the type of water-soluble polysaccharide, the amount of adsorption decreases or remains unchanged after the washing process. Furthermore, when chitosan was used as the water-soluble polysaccharide, it can be seen that even after washing, the cellulose fiber / water-soluble polysaccharide complex remained dispersed and bound to the substrate surface without agglomerating.

[0076] (Example 5: Verification using fine pulp (FP)) In this example, the amount of adsorption to a substrate was confirmed when cellulose fibers other than bacterial cellulose (fine pulp) were defibrated in the presence of water-soluble polysaccharides. The results are shown in Figure 6. In this example, TMG was uniformly 10 g of 0.2 wt% TMG solution. Figure 6 shows the experimental results when 0.5 g of FP was added to this TMG and when 0.125 g of FP was added and defibrated, respectively. From these results, it can be seen that increasing the amount of TMG relative to the amount of FP (0.125 g FP / TMG) results in finer filtration. Furthermore, from these results, it can be seen that even when using fine pulp (FP) as the cellulose fiber, not just bacterial cellulose, defibration in the presence of water-soluble polysaccharides (tamarind seed gum) increases the amount of adsorption to polypropylene and polyethylene terephthalate. When tamarind seed gum was added to polypropylene, it was suggested that a higher ratio of tamarind seed gum to fine pulp resulted in thinner and shorter fibers.

[0077] For PET film, almost no adsorption was observed without the addition of tamarind seed gum. On the other hand, adsorption was observed when tamarind seed gum was added. This suggests that the morphology of the adsorbed fibers may differ depending on the ratio of tamarind seed gum added to the pulp.

[0078] (Example 6: Measurement of the contact angle on the substrate surface to which defibrated cellulose fibers are bound in the presence of water-soluble polysaccharides) In this example, the contact angle of cellulose fibers bound to a substrate surface in the presence of water-soluble polysaccharides was measured. The contact angle was measured as follows: First, a dispersion of cellulose fibers was dropped onto each substrate, left to stand at room temperature for 10 minutes, and then washed with pure water. The samples were then air-dried at 60°C for 30 minutes to be used as contact angle measurement samples. 5 μl of pure water was dropped onto the sample, and the droplet was photographed horizontally with a camera. From the captured image, the contact angle between the droplet and the substrate was measured using image processing software (imageJ / Fiji). The measurement was performed three times, and the average value and standard deviation were calculated.

[0079] The results are shown in Figure 7. Generally, materials with a contact angle greater than 90° can be said to repel water. Therefore, these results show that the hydrophilicity of a substrate can be improved by bonding defibrated cellulose fibers to the substrate in the presence of water-soluble polysaccharides. Although PET is not inherently very hydrophobic, it can be shown that its degree of hydrophilicity can be increased when it is defibrated using Chitosan.

[0080] Figure 8 shows a magnified photograph of the substrate surface to which defibrated cellulose fibers were bound in the presence of water-soluble polysaccharides. In this photograph, cellulose fibers are adsorbed only in the area where the letter "P" is written with the defibrated cellulose fibers. From this photograph, it can be seen that on the substrate surface to which defibrated cellulose fibers were bound in the presence of water-soluble polysaccharides, the cellulose fibers are adsorbed in a relatively uniform network shape, and extreme aggregation is not observed. This suggests that the fibers were fixed by adsorption, and aggregation was suppressed.

[0081] (Example 7: Visualization of xyloglucan in defibrated cellulose fiber / water-soluble polysaccharide complex) In this example, xyloglucan was visualized in a defibrated cellulose fiber / water-soluble polysaccharide complex. Tamarind seed gum was used as the water-soluble polysaccharide in the defibrated cellulose fiber / water-soluble polysaccharide complex. Since xyloglucan is the main component of tamarind seed gum, xyloglucan was visualized in this example.

[0082] A dispersion of cellulose fibers was dropped onto each substrate, allowed to stand at room temperature for 10 minutes, washed with pure water, and then blocked with blocking buffer (Blocking One (Nacalai Tesque)). Anti-xyloglucan antibody (LM15), diluted 100-fold with blocking buffer, was used as the primary antibody. The LM15 primary antibody solution was dropped onto the substrate with adsorbed cellulose fibers, allowed to stand at room temperature for 1 hour, and then washed five times with phosphate buffer (pH 7.5). Next, the secondary antibody solution containing FITC against LM15 was dropped onto the substrate, allowed to stand at room temperature for 1 hour, and then washed five times with phosphate buffer. Finally, 1 × 10⁻⁶-3 Cellulose fibers were fluorescently stained with % calcofluor white and observed under a fluorescence microscope.

[0083] The results are shown in Figure 9. This figure shows that xyloglucan contained in TMG added during defibration is present in the same location as the cellulose fibers of bacterial cellulose. It can be seen that cellulose and xyloglucan are present in the same location, form a complex, and that this complex is bound to the substrate.

[0084] (Example 8: Adsorption test of defibrated cellulose fiber / water-soluble polysaccharide composite on a bio-derived hydrophobic surface) In this example, we confirmed whether the defibrated cellulose fiber / water-soluble polysaccharide composite adsorbed to a hydrophobic surface of biological origin. A biological sample (e.g., ginkgo leaf) was cut into 10 mm squares, immersed in a suspension of cellulose fibers, and shaken for 2 minutes. After washing with pure water, the sample was dried at 50°C for 10 minutes, and 1 × 10⁶ of the composite was applied. -3 Cellulose fibers were fluorescently stained by dropping a % Calcofluor white aqueous solution onto them. These samples were then UV excited and observed using a fluorescence microscope. The biological samples used were those listed in the table below. Figure 10 shows a photograph of the samples adsorbed onto ginkgo leaves.

[0085] [Table 2]

[0086] These results indicate that when ginkgo leaves were used, the defibrated cellulose fiber / water-soluble polysaccharide complex was well adsorbed, causing the leaf surface to repel water. The adsorption of the defibrated cellulose fiber / water-soluble polysaccharide complex may be related to the degree of cuticle layer development.

[0087] Furthermore, by changing the type of water-soluble polysaccharide, some substances were adsorbed well, indicating that the relationship between the target biological sample and the water-soluble polysaccharide is also important. For tomatoes, the tomatoes were immersed in a suspension of cellulose fibers, shaken for 2 minutes, and then washed with pure water. 1 × 10⁻⁶-3 Cellulose fibers were fluorescently stained by dropping a % aqueous solution of Calcofluor white onto them. These samples were then UV excited and observed using a fluorescence microscope.

[0088] Commercially available cherry tomatoes were dipped in defibrated BC only, defibrated with TMG, and defibrated with Chitosan, and then immersed in water again. It was observed that the defibrated tomatoes with Chitosan had increased wettability (Figures 11-13). The lower part of Figure 13 shows photographs of untreated and defibrated cherry tomatoes cut in half, stained with Calcofluor white, and irradiated with UV light. The surface of the cherry tomatoes treated with Chitosan showed a bluish-white color due to the Calcofluor white bound to the cellulose, indicating that cellulose / chitosan was bound to the surface of the cherry tomatoes. Chitosan has antibacterial properties and is therefore useful in the food industry.

[0089] Figure 14 shows a photograph of the results when using hair. It can be seen that when using hair, both tamarind seed gum and chitosan are adsorbed well as water-soluble polysaccharides.

[0090] (Example 9: Confirmation of antibacterial properties) By using chitosan as a water-soluble polysaccharide, antibacterial properties can be imparted to the resulting defibrated fibers. Antibacterial properties are evaluated by culturing appropriate microorganisms on agar plates in a plastic petri dish, placing a substrate fragment treated with antibacterial agents on the plate, and observing the formation of an inhibition zone due to the suppression of microbial growth. Alternatively, antibacterial properties can be evaluated by dropping the microbial culture solution onto the surface of the substrate, culturing it for a certain period of time, then immersing the substrate in water to release the microorganisms, and then allowing a portion of that water to stand on an agar plate for static cultivation and counting the number of colonies.

[0091] (Example 10: Color development of defibrated fibers) A fluorescent dye is adsorbed as a functional molecule onto the defibrated fibers or the material to which the fibers are applied. Calcofluor white is prepared as the fluorescent dye, and the defibrated fibers or the material to which the fibers are applied are labeled with the fluorescent dye in the same manner as in Example 7. In this case, the dye (Calcofluor White) can be adsorbed onto the cellulose bound to the substrate surface. Also, as shown in Figure 10, antibodies can be attached to the tamarind seed gum used in the modification process to induce color development.

[0092] (Note) As described above, while the present disclosure has been illustrated using preferred embodiments thereof, it is understood that the scope of this disclosure should be interpreted solely by the claims. Patents, patent applications and other documents cited herein should be incorporated herein by reference as if their contents were specifically described herein. [Industrial applicability]

[0093] According to this disclosure, by modifying the surface of hydrophobic materials such as plastics and imparting hydrophilicity, it is possible to improve printability and label suitability, control adhesion with other components such as oil droplets, and coat and fix oxidizing agents, ethylene decomposing agents, etc., thereby increasing the added value of materials and expanding their applications.

Claims

1. A method for producing a modified substance, (1) A step of providing a material having a hydrophobic surface, (2) A step of defibrillating cellulose fibers, which are bacterial cellulose or plant cellulose, by coexisting them with a water-soluble polysaccharide containing xylan or its derivatives, β-glucan or its derivatives, mannan or its derivatives, chitosan or its derivatives, or any combination thereof. (3) A step of modifying the hydrophobic surface of the substance by applying the defibrated cellulose fibers to the substance. Methods that include...

2. The method according to claim 1, wherein the defibrillation of the cellulose fibers is carried out by adding the water-soluble polysaccharide to the cellulose fibers to obtain a mixture and stirring it.

3. The method according to claim 1 or 2, wherein the defibrated cellulose fibers include fibers having a fiber length of at least 2 μm.

4. The method according to claim 1, wherein step (3) is carried out in the presence of a water-soluble polysaccharide.

5. The method according to claim 4, wherein the water-soluble polysaccharide present in step (3) is the same as the water-soluble polysaccharide used in step (2).

6. The method according to claim 4, wherein the concentration of the water-soluble polysaccharide present in step (3) is 0.1 wt% or less.

7. The method according to claim 1, wherein the water-soluble polysaccharide comprises xylan or a derivative thereof, β-glucan or a derivative thereof, mannan or a derivative thereof, chitosan or a derivative thereof, or any combination thereof.

8. The method according to claim 1, wherein the substance having the hydrophobic surface includes a synthetic resin substrate, the leaves, stems, flowers, fruits, and roots of plants, the body surface of an animal, and hair.

9. The method according to claim 8, wherein the synthetic resin substrate comprises polyethylene, polypropylene, polyethylene terephthalate, polystyrene, polyvinyl alcohol, polylactic acid, polyglycolic acid, polybutylene succinate, polybutylene succinate adipate, polyethylene terephthalate succinate, polybutylene adipate terephthalate, poly(3-hydroxybutyrate-co-3-hydroxyhexanoate), or any combination thereof.

10. The method according to claim 1, wherein the modification includes imparting hydrophilicity, imparting electric charge, imparting antibacterial properties, or any combination thereof.

11. The method according to claim 1, further comprising the step of binding functional molecules to a substance to which the cellulose fibers are applied.

12. The method according to claim 11, wherein the functional molecule includes a dye, a fluorescent dye, a luminescent dye, an oxidizing agent, a conductive substance, a metal, an ionic substance, an enzyme, a biological substance, a polysaccharide, a protein, or any combination thereof.

13. A method for producing fibers for modifying hydrophobic surfaces, (A) A step of defibrillating cellulose fibers, which are bacterial cellulose or plant cellulose, by coexisting them with a water-soluble polysaccharide containing xylan or its derivatives, β-glucan or its derivatives, mannan or its derivatives, chitosan or its derivatives, or any combination thereof. (B) A step of bonding functional molecules to the defibrated cellulose fibers. Methods that include...

14. The method according to claim 13, wherein the defibrillation of the cellulose fibers is carried out by adding the water-soluble polysaccharide to the cellulose fibers to obtain a mixture and stirring it.

15. A modifier comprising cellulose fibers, which are bacterial cellulose or plant cellulose, and / or water-soluble polysaccharides, including xylan or its derivatives, β-glucan or its derivatives, mannan or its derivatives, chitosan or its derivatives, or any combination thereof, for modifying substances having a hydrophobic surface.

16. The modifier according to claim 15, wherein the cellulose fibers are defibrated in the presence of a water-soluble polysaccharide.

17. A substance produced by the method described in claim 1.

18. A fiber produced by the method described in any one of claims 13 or 14.

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