Binder composition for fine particles, processing liquid, and textile product

Abstract

The present invention provides: a binder composition for fine particles, said composition containing nanocellulose; a processing liquid which contains fine particles and the binder composition for fine particles; and a fiber product.

Description

[Technical Field]

[0001] The present invention relates to a binder composition for fine particles, a processing liquid, and a textile product. [Background technology]

[0002] Conventionally, there have been proposed filters having various functions such as antibacterial, antiviral, deodorizing, etc. In the above filters, for example, by binding inorganic fine particles to fibers, it is possible to exhibit functions such as antibacterial, antiviral, and deodorizing.

[0003] When inorganic fine particles are bound to fibers, for example, a resin binder such as an aqueous resin binder is used as a binder. It is known that in the case of inorganic fine particles having antibacterial, antiviral, and deodorizing functions, the above functions are mainly exhibited by the particles exposed from the resin binder.

[0004] For example, Patent Document 1 describes a deodorizing filter having a deodorizing fiber layer containing fibers and a deodorizing agent bound to the surface of the fibers. Patent Document 1 also discloses that in the deodorizing fiber layer of the deodorizing filter, the deodorizing agent is bound to the fibers with a resin binder. If the amount of deodorizing agent is increased to improve the deodorizing effect, the amount of resin binder that binds the filter and deodorizing agent must also be increased. Increasing the amount of resin binder buries the deodorizing agent, which means that the expected deodorizing effect cannot be achieved with an increase in the deodorizing agent content, and breathability also decreases. To solve this problem, Patent Document 1 proposes a method for the deodorizing filter in which the thickness and basis weight of the deodorizing fiber layer and the breathability of the deodorizing filter are set within specified ranges. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Patent Publication No. 2018-134449 Summary of the Invention [Problem to be solved by the invention]

[0006] As described above, when inorganic fine particles are bound to, for example, fibers, increasing the amount of inorganic fine particles requires increasing the amount of resin binder, which results in the problem that the functions of the inorganic fine particles cannot be exerted due to the embedded inorganic fine particles. Therefore, when fine particles are bound to a substrate such as fibers, it is required to make the functions of the fine particles more highly exerted. Furthermore, when adjusting the substrate to which inorganic particles are bound in order to enhance the functionality of the inorganic particles, as in the method of Patent Document 1, there are limitations to the applicable fiber substrates, and therefore a more versatile method is required.

[0007] The particles are attached to the substrate by, for example, applying a processing liquid containing the particles and a binder to the substrate, but there is a problem in that the particles tend to settle in the processing liquid containing the particles and the binder, making the process difficult to work with.

[0008] Therefore, an object of the present invention is to provide a binder composition that allows for high workability when binding fine particles to a substrate and allows the fine particles to exhibit their functions to a high degree. [Means for solving the problem]

[0009] As a result of extensive research, the inventors discovered that a composition containing nanocellulose is easy to work with when binding microparticles to a substrate and can enhance the functionality of the microparticles, leading to the completion of the present invention.

[0010] That is, the present invention is as follows. [1] A binder composition for fine particles containing nanocellulose. [2] Used to bind fine particles and fibers, [1] The binder composition for fine particles according to the present invention. [3] The nanocellulose comprises oxidized nanocellulose; [1] or [2], the binder composition for fine particles. [4] The average fiber length of the nanocellulose is 100 nm or more and 700 nm or less, The binder composition for fine particles according to any one of [1] to [3]. [5] The nanocellulose is substantially free of N-oxyl compounds; The binder composition for fine particles according to any one of [1] to [4]. [6] The nanocellulose is oxidized nanocellulose produced by defibrating oxidized cellulose obtained by oxidizing raw cellulose with hypochlorous acid or a salt thereof, The binder composition for fine particles according to any one of [1] to [5]. [7] The fine particles are inorganic fine particles. The binder composition for fine particles according to any one of [1] to [6]. [8] The fine particles are ceramics. The binder composition for fine particles according to any one of [1] to [6]. [9] The fine particles are at least one selected from the group consisting of deodorants, antiallergens, antiviral agents, antibacterial agents, antifungal agents, and sustained-release materials. The binder composition for fine particles according to any one of [1] to [8].

[10] A processing liquid comprising the binder composition for fine particles according to any one of [1] to [9] and fine particles.

[11] A textile product produced using the binder composition for fine particles according to any one of [1] to [9].

[12] A textile product produced using the processing solution described in

[10] . [Effects of the Invention]

[0011] According to the present invention, it is possible to provide a binder composition that allows for high workability when binding fine particles to a substrate and allows the fine particles to exhibit their functions to a high degree. DETAILED DESCRIPTION OF THE INVENTION

[0012] DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described in detail below with reference to the preferred embodiments. However, the present invention is not limited to the following embodiments and can be practiced in various modified forms within the scope of the present invention.

[0013] The composition of the present invention is a binder composition for fine particles containing nanocellulose. The binder composition for fine particles of the present invention refers to a composition for binding fine particles. The dried coating film obtained from the binder composition for fine particles of the present invention is formed by the binder component nanocellulose, and fine particles such as inorganic fine particles can be bound to the object to be coated via the binder. Furthermore, it is believed that the binder composition for fine particles of the present invention increases the contact efficiency of the fine particles with the object on which they act, allowing the fine particles to exhibit high functions such as deodorizing, antiviral, antiallergenic, antibacterial, and antifungal properties. In addition, nanocellulose has high dispersibility and can prevent the settling of fine particles in the processing liquid, so it is thought that the binder composition for fine particles will have high workability.

[0014] The substrate to which the binder composition for fine particles is applied is not particularly limited, and can be an article containing an inorganic material, an organic material, or a combination thereof. The substrate here refers to the object to which the fine particles are to be applied. The shape of the substrate is also not particularly limited. Examples of the substrate include resin molded products (including foamed resin molded products) such as films, granules, and general molded products; fibers; and sheet-like articles such as nonwoven fabrics and woven fabrics containing fibers. When the substrate is a nonwoven fabric, preferred are nonwoven fabrics entangled by needle punching or hydroentanglement, nonwoven fabrics produced by thermal bonding, and nonwoven fabrics produced by spunbonding. The binder composition for fine particles of the present invention can be suitably used to bind fine particles and fibers.

[0015] The components constituting the fiber as the substrate are not particularly limited, and examples thereof include resins such as polyester, polyethylene, polypropylene, polyvinyl chloride, polyacrylic acid, polyamide, polyvinyl alcohol, polyurethane, polyvinyl ester, polymethacrylic acid ester, rayon, and acetate. The fiber may contain only one type of resin or multiple types of resins. The fiber may also contain cotton, silk, wool, etc. Furthermore, the fiber may contain cellulose or viscose fiber. The fiber may also be a blend of polyester and cotton, for example. The fiber diameter of the fiber used as the substrate is not particularly limited, but is usually 1 μm or more and 1 mm or less.

[0016] <Nanocellulose> The nanocellulose used in the present invention can be commercially available nanocellulose, or nanocellulose obtained by preparing it yourself from a cellulosic raw material such as softwood pulp. When preparing nanocellulose, it can be prepared by referring to, for example, Cellulose Commun., 14(2), 62(2007) and the pamphlet of International Publication No. 2018 / 230354. Nanocellulose in the present invention is a general term for cellulose that has been nanosized, and includes cellulose nanofibers, cellulose nanocrystals, and the like. Nanocellulose is fibrous cellulose obtained by micronizing fibrous cellulose, and is therefore also called "microfine cellulose fiber."

[0017] A specific example of a suitable method for producing nanocellulose in the present invention is a nanocellulose production method comprising the steps of: oxidizing a cellulosic raw material using hypochlorous acid or a salt thereof having an effective chlorine concentration of 6% by mass or more and 43% by mass or less, preferably 7% by mass or more and 43% by mass or less, to produce oxidized cellulose; and defibrating the oxidized cellulose to nanosize it. Therefore, the nanocellulose of the present invention preferably includes oxidized nanocellulose.Furthermore, the nanocellulose of the present invention is preferably oxidized nanocellulose produced by defibrating oxidized cellulose obtained by oxidizing raw cellulose with hypochlorous acid or a salt thereof. The oxidized cellulose of the present invention can also be said to be oxidized cellulose that is an oxide of starting cellulose. Furthermore, when oxidized cellulose is obtained by oxidizing starting cellulose with hypochlorous acid or a salt thereof, the oxidized cellulose can also be said to be oxidized cellulose that is an oxide of starting cellulose with hypochlorous acid or a salt thereof.

[0018] Furthermore, when the nanocellulose of the present invention is produced using hypochlorous acid or its salt with the above-mentioned predetermined effective chlorine concentration, it can be obtained without using N-oxyl compounds such as 2,2,6,6-tetramethyl-1-piperidine-N-oxyl radical (hereinafter referred to as TEMPO). N-oxyl compounds have been identified as harmful, and when nanocellulose is produced using them, N-oxyl compounds are contained in the nanocellulose. Therefore, it is preferable that the nanocellulose of the present invention is substantially free of N-oxyl compounds. As used herein, "substantially free of N-oxyl compounds" means that no N-oxyl compounds are used in producing the oxidized cellulose, or that the content of nitrogen derived from N-oxyl compounds in the oxidized cellulose is 2.0 ppm or less, preferably 1.0 ppm by mass or less. Furthermore, "substantially free of N-oxyl compounds" also means that the content of N-oxyl compounds, as an increase from the cellulosic raw material, is preferably 2.0 ppm by mass or less, more preferably 1.0 ppm by mass or less. The residual nitrogen component can be measured using a trace total nitrogen analyzer, and more specifically, can be measured by the method described in the Examples.

[0019] When the nanocellulose of the present invention is produced using hypochlorous acid or a salt thereof having the above-mentioned predetermined effective chlorine concentration, the fluidity of the resulting composition tends to be higher, and the workability when binding the fine particles to the substrate is further improved.

[0020] The cellulosic raw material in the present invention is not particularly limited as long as it is a material primarily composed of cellulose, and examples thereof include pulp, natural cellulose, regenerated cellulose, and fine cellulose obtained by depolymerizing a cellulose raw material through mechanical treatment. Commercially available products such as crystalline cellulose derived from pulp can be used as is as the cellulosic raw material. Alternatively, unused biomass containing a large amount of cellulose components, such as soybean pulp refuse or soybean hulls, may also be used as the raw material. Furthermore, the cellulosic raw material may be treated with an alkali of an appropriate concentration in order to facilitate the penetration of the oxidizing agent used in the next step into the raw pulp.

[0021] One example of the method for producing nanocellulose in the present invention is a production method comprising the steps of: oxidizing a cellulosic raw material with hypochlorous acid or a salt thereof having an available chlorine concentration of 6 to 43% by mass, preferably 7 to 43% by mass, to produce oxidized cellulose; and defibrating the oxidized cellulose to nanosize particles. The available chlorine concentration in the oxidizing agent, hypochlorous acid or a salt thereof, is preferably 14% to 43% by mass, and even more preferably 18% to 43% by mass. By keeping the effective chlorine concentration at 43% by mass or less, the progress of self-decomposition tends to be suppressed, making handling easier.

[0022] The available chlorine concentration in hypochlorous acid or its salts is a well-known concept and is defined as follows: Hypochlorous acid is a weak acid that exists as an aqueous solution, and hypochlorite is a compound in which the hydrogen of hypochlorous acid is replaced by another cation. Although hypochlorite can exist as a solid with water of crystallization, it is a deliquescent and very unstable substance, and is generally handled as an aqueous solution. For example, sodium hypochlorite, a hypochlorite salt, exists only in solution, so the amount of available chlorine in the solution is measured rather than the concentration of sodium hypochlorite. The available chlorine in sodium hypochlorite is the oxidizing power of the divalent oxygen atom produced by the decomposition of sodium hypochlorite, which is equivalent to two atomic equivalents of monovalent chlorine. Therefore, the combined chlorine atoms in sodium hypochlorite (NaClO) have the same oxidizing power as two uncombined chlorine (Cl2) atoms, and available chlorine = 2 x (chlorine in NaClO). To measure the specific available chlorine concentration, the sample is weighed accurately, water, potassium iodide, and acetic acid are added, and the sample is left to stand. The liberated iodine is then titrated with a sodium thiosulfate solution using an aqueous starch solution as an indicator.

[0023] Examples of hypochlorous acid or salts thereof include hypochlorous acid water, sodium hypochlorite, potassium hypochlorite, calcium hypochlorite, ammonium hypochlorite, etc. Among these, sodium hypochlorite is preferred from the viewpoint of ease of handling. Hereinafter, one method for producing nanocellulose used in the present invention will be described using sodium hypochlorite as an example of hypochlorous acid or a salt thereof.

[0024] (1) A process for producing oxidized cellulose by oxidizing a cellulosic raw material using an aqueous sodium hypochlorite solution having an available chlorine concentration of 6% by mass or more and 43% by mass or less. As a method for adjusting the effective chlorine concentration of sodium hypochlorite aqueous solution to 6% by mass or more and 43% by mass or less, there are a method for concentrating the sodium hypochlorite aqueous solution whose effective chlorine concentration is less than 6% by mass, and a method for adjusting the effective chlorine concentration of sodium hypochlorite pentahydrate crystals of about 43% by mass by using them as they are or by diluting them with water.Among these, it is preferable to use sodium hypochlorite pentahydrate to adjust the effective chlorine concentration as an oxidizing agent, because it has little self-decomposition, that is, the effective chlorine concentration is less reduced, and adjustment is easy.

[0025] The amount of the aqueous sodium hypochlorite solution having an available chlorine concentration of 6% by mass to 43% by mass, which is the oxidizing agent, used can be selected within a range that promotes the oxidation reaction. There are no particular limitations on the method for mixing the cellulosic raw material and the aqueous sodium hypochlorite solution, but from the viewpoint of ease of operation, it is preferable to add the cellulosic raw material to the aqueous sodium hypochlorite solution and mix them.

[0026] The reaction temperature in the oxidation reaction is preferably 15° C. or higher and 40° C. or lower, and more preferably 20° C. or higher and 35° C. or lower. To efficiently promote the oxidation reaction, the pH of the reaction system is preferably maintained at 7 or higher and 14 or lower, and more preferably at 10 or higher and 14 or lower. To adjust the pH, an alkaline agent such as sodium hydroxide or an acid such as hydrochloric acid can be added. The reaction time for the oxidation reaction can be set according to the degree of progress of the oxidation, but it is preferable to carry out the reaction for, for example, about 15 minutes to 6 hours.

[0027] In the oxidation reaction, hydroxyl groups in the cellulosic raw material are oxidized to carboxyl groups to produce oxidized cellulose. While the amount of carboxyl groups in the oxidized cellulose is not particularly limited, it is preferable that the amount of carboxyl groups per gram of oxidized cellulose be 0.1 mmol / g or more and 3.0 mmol / g or less when the oxidized cellulose is defibrated and nano-sized to produce nanocellulose in the subsequent step. The amount of carboxyl groups is more preferably 0.2 mmol / g or more and 2.0 mmol / g or less, even more preferably 0.35 to 2.0 mmol / g, even more preferably 0.35 to 1.5 mmol / g, even more preferably 0.40 to 1.5 mmol / g, even more preferably 0.50 to 1.2 mmol / g, even more preferably greater than 0.50 to 1.2 mmol / g, and even more preferably 0.55 to 1.0 mmol / g. The oxidation reaction may also be carried out in two stages.

[0028] The amount of carboxy groups in oxidized cellulose can be measured by the following method. Pure water is added to a 0.5% by mass slurry of oxidized cellulose to make a total volume of 60 ml, and 0.1 M aqueous hydrochloric acid is added to adjust the pH to 2.5. 0.05 N aqueous sodium hydroxide is then added dropwise, and the electrical conductivity is measured until the pH reaches 11. The amount of carboxy groups in oxidized cellulose is calculated using the following formula from the amount of sodium hydroxide (a) consumed in the neutralization stage of the weak acid, where the change in electrical conductivity is gradual. The amount of carboxy groups in oxidized cellulose can be adjusted by changing the reaction time, reaction temperature, pH of the reaction solution, etc. of the oxidation reaction. Amount of carboxyl groups (mmol / g oxidized cellulose) = a (ml) × 0.05 / mass of oxidized cellulose (g)

[0029] (2) The process of defibrating oxidized cellulose to nanosize it The nanocellulose used in the present invention can be produced, for example, by defibrating the oxidized cellulose obtained in the above process to nanosize it. The defibration method may be limited to weak stirring in a solvent using a stirrer or the like, or mechanical defibration may be performed. Mechanical defibration can shorten the defibration time.

[0030] The method of mechanical defibration is not particularly limited, and can be selected appropriately depending on the purpose, for example, after thoroughly washing the oxidized cellulose with a solvent. Examples include known mixing and stirring devices such as a screw mixer, paddle mixer, disperser mixer, turbine mixer, homomixer under high speed rotation, high-pressure homogenizer, ultra-high-pressure homogenizer, double cylinder homogenizer, ultrasonic homogenizer, water jet collision type disperser, beater, disk refiner, conical refiner, double disk refiner, grinder, and single-shaft or multi-shaft kneader. By treating the oxidized cellulose in a solvent using one of these devices alone or in combination of two or more types, the oxidized cellulose can be nanosized to produce nanocellulose.

[0031] The solvent used in the defibration treatment is not particularly limited and can be appropriately selected depending on the purpose, and examples include water, alcohols, ethers, ketones, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, etc. These may be used alone or in combination of two or more.

[0032] Examples of the alcohols include methanol, ethanol, isopropanol, isobutanol, sec-butyl alcohol, tert-butyl alcohol, methyl cellosolve, ethylene glycol, and glycerin. Examples of the ethers include ethylene glycol dimethyl ether, 1,4-dioxane, and tetrahydrofuran. Examples of the ketones include acetone and methyl ethyl ketone.

[0033] By selecting an organic solvent as the solvent, it becomes easier to isolate the oxidized cellulose obtained in the above process and the nanocellulose obtained by defibrating it. In addition, because the nanocellulose is obtained as a dispersion in the organic solvent, it becomes easier to mix it with resins that dissolve in the organic solvent and the raw material monomers for those resins.

[0034] The average fiber length of nanocellulose is preferably 100 nm or more and 700 nm or less, more preferably 100 nm or more and 400 nm or less. When the average fiber length is 100 nm or more and 700 nm or less, the processing liquid during coating is uniform and workable, and since appropriate fluidity is obtained, uniform coating is possible. In addition, there is a tendency for the binding to the substrate to be excellent, and when it is 100 nm or more and 400 nm or less, these tend to be even better. The average fiber width of nanocellulose is preferably 2 nm to 10 nm, more preferably 2.5 nm to 6 nm. By having an average fiber width of 2 nm to 10 nm, the processing liquid during coating is uniform, workability is high, uniform coating is possible, and there is a tendency for the binding to the substrate to be excellent. Methods for adjusting the average fiber length and average fiber width of nanocellulose to fall within the above ranges include, for example, adjusting the conditions in the process of defibrating and nano-sizing the oxidized cellulose described above.

[0035] The average fiber width and average fiber length were calculated by mixing nanocellulose with water to a nanocellulose concentration of approximately 1 to 10 ppm, air-drying the resulting diluted cellulose aqueous dispersion on a mica substrate, observing the shape of the nanocellulose using a scanning probe microscope, randomly selecting any number of fibers from the obtained image, and calculating the cross-sectional height of the shape image = fiber width and the perimeter ÷ 2 = fiber length. Image processing software can be used to calculate these average fiber widths and lengths. While the image processing conditions are arbitrary, differences in calculated values ​​may occur even for the same image depending on the image processing conditions. The range of difference in values ​​depending on the image processing conditions is preferably within ±100 nm for average fiber length. The range of difference in values ​​depending on the conditions is preferably within ±10 nm for average fiber width. More detailed measurement methods follow the methods described in the Examples below.

[0036] The nanocellulose or oxidized cellulose used in the present invention preferably has a structure in which at least two of the hydroxyl groups on the glucopyranose ring that constitutes the cellulose are oxidized. More specifically, it has a structure in which the hydroxyl groups at the second and third positions on the glucopyranose ring are oxidized and a carboxyl group is introduced. Furthermore, it is preferable that the hydroxyl group at the sixth position on the glucopyranose ring in the nanocellulose or oxidized cellulose is not oxidized and remains as a hydroxyl group. The position of the carboxyl group on the glucopyranose ring can be determined by the solution NMR spectrum using oxidized rayon as a model molecule and the solid NMR spectrum of oxidized cellulose. 13 It can be analyzed by comparing C-NMR spectra.

[0037] Rayon has the same chemical structure as cellulose, and its oxide (rayon oxide) is water-soluble. 13C-NMR measurements reveal a carbon peak attributable to carboxy groups at 165 to 185 ppm. In one embodiment of the oxidized cellulose or nanocellulose used in the present invention, obtained by oxidizing raw cellulose with hypochlorous acid or its salt, two signals appear within this chemical shift range. Furthermore, solution two-dimensional NMR measurements reveal that carboxy groups have been introduced at the 2- and 3-positions.

[0038] Oxidized cellulose or nanocellulose solid obtained by oxidizing raw cellulose with hypochlorous acid or its salts 13 In C-NMR, when the amount of carboxyl groups introduced is large, two signals appear at 165 to 185 ppm, and when the amount of carboxyl groups introduced is small, a very broad signal may appear. As can be seen from the results for oxidized rayon, the signals of the carboxyl group carbons introduced at the 2nd and 3rd positions are close to each other, and this is difficult to achieve with low-resolution solid state spectroscopy. 13 In C-NMR, the separation of the two signals is insufficient. Therefore, when the amount of carboxyl group introduced is small, a broad signal is observed. 13 In the C-NMR spectrum, the introduction of carboxy groups at the 2nd and 3rd positions can be confirmed by evaluating the broadening of the peaks appearing at 165 to 185 ppm. That is, solid 13 A baseline is drawn around the peak in the range of 165 ppm to 185 ppm in the C-NMR spectrum to determine the overall area value, and then the area value is vertically divided at the peak top to determine the ratio of the two peak area values ​​(large area value / small area value). If the ratio of the peak area values ​​is 1.2 or more, the peak can be said to be broad. The presence or absence of the broad peak can be determined by the ratio of the length L of the baseline in the range of 165 ppm to 185 ppm to the length L' of the perpendicular line from the peak top to the baseline. That is, if the ratio L' / L is 0.1 or more, it can be determined that a broad peak is present. The ratio L' / L may be 0.2 or more, 0.3 or more, 0.4 or more, or even 0.5 or more. There is no particular upper limit to the ratio L' / L, but it is usually 3.0 or less, and may be 2.0 or less, or 1.0 or less. The structure of the glucopyranose ring can also be determined by analysis according to the method described in Sustainable Chem. Eng. 2020, 8, 48, 17800-17806.

[0039] When the nanocellulose or oxidized cellulose used in the present invention contains a carboxyl group, it may be in the salt form, proton form, or modified form with a modifying group. The modifying group is not particularly limited, as long as it is a compound capable of forming an ionic or covalent bond with the carboxyl or hydroxyl group of the nanocellulose or oxidized cellulose. The physical properties of the nanocellulose or oxidized cellulose can be adjusted by adjusting the form of the carboxyl group. Examples of compounds having a modifying group capable of forming an ionic bond include primary amines, secondary amines, tertiary amines, quaternary ammonium compounds, and phosphonium compounds. Examples of compounds having a modifying group capable of forming a covalent bond include alcohols, isocyanate compounds, and epoxy compounds.

[0040] <Dispersion medium> The binder composition for fine particles of the present invention may contain a dispersion medium for dispersing nanocellulose. Therefore, one embodiment of the present invention is a binder composition for fine particles containing nanocellulose and a dispersion medium. The dispersion medium used in the binder composition for fine particles of the present invention is not particularly limited as long as it disperses nanocellulose.

[0041] Examples of the dispersion medium include water, alcohols, ethers, ketones, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, etc. These may be used alone or in combination of two or more.

[0042] Examples of the alcohols include methanol, ethanol, isopropanol, isobutanol, sec-butyl alcohol, tert-butyl alcohol, methyl cellosolve, ethylene glycol, and glycerin. Examples of the ethers include ethylene glycol dimethyl ether, 1,4-dioxane, and tetrahydrofuran. Examples of the ketones include acetone and methyl ethyl ketone.

[0043] The binder composition for fine particles of the present invention can be blended with fine particles to form a processing liquid. Therefore, one aspect of the present invention is a processing liquid containing the binder composition for fine particles of the present invention and fine particles. It can also be said that the processing liquid of the present invention contains nanocellulose, a dispersion medium, and fine particles. When the binder composition for fine particles of the present invention contains a dispersion medium, the ratio of the dispersion medium to the nanocellulose is not particularly limited. In addition, the ratio of the dispersion medium to the nanocellulose in the processing solution of the present invention is not particularly limited. In this case, the amount of nanocellulose in the processing solution can be appropriately adjusted depending on the type of substrate and the amount of fine particles by adding or removing the dispersion medium.

[0044] The proportion of nanocellulose in the processing solution of the present invention can be adjusted appropriately depending on the type of substrate and the amount of fine particles, but it is usually 0.01% by mass or more, preferably 0.1% by mass or more, and more preferably 0.3% by mass or more, based on the total amount of the processing solution. A nanocellulose proportion of 0.01% by mass or more tends to enable fine particles, such as inorganic fine particles, to be efficiently bound to fibers. Furthermore, a nanocellulose proportion of 0.01% by mass or more can suppress the settling of fine particles in the processing solution, and the fine particle binder composition tends to be more workable. The upper limit of the proportion of nanocellulose in the processing fluid of the present invention is not particularly limited, and is usually 50% by mass or less, preferably 20% by mass or less, and more preferably 10% by mass or less. By keeping the proportion of nanocellulose at 50% by mass or less, the functions of fine particles such as inorganic fine particles tend to be fully exhibited.

[0045] <Fine particles> The fine particles in the present invention include particles having a particle size of 1 nm or more and 1000 μm or less. The fine particles in the present invention are preferably inorganic fine particles. The median diameter of the fine particles in the present invention is preferably 0.01 μm or more and 100 μm or less, more preferably 0.05 μm or more and 50 μm or less, and even more preferably 0.1 μm or more and 20 μm or less. 2 / g or more 2000m 2 / g or less, and 2 / g or more 1000m 2 / g or less is more preferable, and 50m 2 / g or more 1000m 2 It is more preferable that the saturation coefficient is 1 / g or less. By ensuring that the median diameter and BET specific surface area are within the above ranges, sedimentation of the fine particles in the processing liquid can be further suppressed, and the binding ability to the substrate tends to be further improved. The median diameter can be measured using a laser diffraction particle size distribution analyzer. The BET specific surface area can be measured using a specific surface area pore size distribution analyzer. More specifically, the median diameter and BET specific surface area can be measured by the methods described in the Examples.

[0046] The inorganic fine particles are not particularly limited and include, for example, simple metals such as copper, silver, nickel, palladium, carbon, silicon, aluminum, zinc, and platinum, as well as metal compounds containing at least one of these metals. The metal compounds may be oxides, chlorides, halides (bromides, fluorides, etc.), inorganic acid salts (nitrates, sulfates, hydrochlorides, phosphates, phosphites, etc.), and organic acid salts (carboxylates such as formates and acetates, and oxycarboxylates such as lactates and malates, etc.). Examples of metal compounds include alumina, zirconia, titanium oxide, barium titanate, alumina nitride, silicon nitride, boron nitride, silicate glass, lead glass, inorganic glass, ruthenium oxide, yttrium oxide, cerium oxide, aluminum silicate, zinc oxide, and copper silicate. Carbon-containing compounds also include carbon black and carbon nanotubes. As the inorganic fine particles, the above-mentioned materials may be used alone or in combination of two or more kinds.

[0047] Ceramics are also suitable examples of the fine particles used in the present invention. Ceramics herein refers to sintered bodies obtained by heat-treating and sintering inorganic materials. Examples of inorganic materials include, but are not limited to, elemental materials such as carbon; oxide materials such as alumina, zirconia, titania, barium titanate, and silica; hydroxide materials such as hydroxyapatite; carbide materials such as silicon carbide; carbonate materials; nitride materials such as silicon nitride; halide materials such as fluorite; and phosphate materials. These inorganic materials may be used alone or in combination of two or more. Among ceramics, ceramics that emit far-infrared rays are preferred. The use of ceramics that emit far-infrared rays tends to be able to exhibit antibacterial, deodorizing, and temperature-raising effects. Ceramics that emit far-infrared rays are preferably made from inorganic materials that have infrared radiation properties, such as alumina, zirconia, titania, and silica, as raw materials.

[0048] The fine particles can be those with a deodorizing effect (also called deodorants). Examples of deodorants include chemical adsorption types that adsorb malodorous components by chemical adsorption or form chemical bonds with malodorous components, activated carbon types that adsorb malodorous components by physical adsorption, and photocatalysts that decompose malodorous components on contact. Specific examples of malodorous components to be deodorized include basic compounds such as ammonia and amines, acidic compounds such as acetic acid and isovaleric acid, aldehydes such as formaldehyde, acetaldehyde and nonenal, and sulfur compounds such as hydrogen sulfide and methyl mercaptan.

[0049] Deodorizers for these malodorous components include inorganic deodorizers and organic deodorizers. Specific examples of inorganic deodorants include phosphates of tetravalent metals, zeolites, amorphous composite oxides, composites containing at least one atom selected from Al, Ag, Cu, Zn, and Mn, zirconium compounds selected from hydrated zirconium oxide and zirconium oxide, hydrotalcite compounds, and amorphous active compounds. Examples of organic deodorants include amine compounds. From the viewpoint of safety and resistance to deterioration, inorganic deodorants that are insoluble or poorly soluble in water are preferred.

[0050] These deodorants may be used alone or in combination of two or more. Using multiple deodorants with different targets for deodorization (malodorous components) can sometimes produce a synergistic effect. For example, a combination of a basic gas deodorant and a sulfur-based gas deodorant is suitable for excrement odors or putrid odors (such as odors from food waste) containing ammonia, trimethylamine, hydrogen sulfide, methyl mercaptan, dimethyl disulfide, etc. For example, a combination of a basic gas deodorant and an acidic gas deodorant is suitable for body odors such as sweat odors containing acetic acid and isovaleric acid, etc. Furthermore, a combination of a basic gas deodorant, an acidic gas deodorant, and an aldehyde gas deodorant is suitable for tobacco odors containing basic gases, acetaldehyde, acetic acid, etc. When two or more deodorants are used in combination, the ratio of the amounts used is preferably selected based on the deodorizing performance, such as the deodorizing capacity and deodorizing speed, of the deodorants used and the gas concentration (concentration of malodorous components) of the target environment. For example, when two types of deodorizers are used to deodorize a malodorous gas containing multiple malodorous components, the mass ratio to obtain a sufficient deodorizing effect is 20:80 to 80:20. Note that deodorizing capacity refers to the amount (mL) of malodorous components under standard conditions that 1 g of deodorizer can deodorize, and the larger this value, the longer the deodorizing effect of the deodorizing filter can be sustained. Next, deodorants that can be suitably used in the present invention are as follows.

[0051] (A) phosphates of tetravalent metals The phosphate of a tetravalent metal is preferably a compound represented by the following general formula (1): This compound is insoluble or poorly soluble in water, and has an excellent deodorizing effect against basic gases. H a M b (PO4) c nH2O (1) (In the formula, M is a tetravalent metal atom, a, b, and c are integers satisfying the formula: a+4b=3c, and n is 0 or a positive integer.) Examples of M in the general formula (1) include Zr, Hf, Ti, and Sn. Preferred specific examples of tetravalent metal phosphates include zirconium phosphate (Zr(HPO4)2·H2O), hafnium phosphate, titanium phosphate, tin phosphate, etc. These compounds include crystalline compounds with various crystal systems such as α-type crystals, β-type crystals, and γ-type crystals, as well as amorphous compounds, and either can be preferably used.

[0052] (B) Amine compounds The amine compound is preferably a hydrazine compound or an aminoguanidine salt. These compounds react with aldehyde gases and therefore have excellent deodorizing effects against aldehyde gases. Examples of hydrazine compounds include adipic acid dihydrazide, carbohydrazide, succinic acid dihydrazide, and oxalic acid dihydrazide. Examples of aminoguanidine salts include aminoguanidine hydrochloride, aminoguanidine sulfate, and aminoguanidine bicarbonate. These amine compounds can be used to form deodorizers supported on a carrier. In this case, the carrier is typically an inorganic compound, specifically, zeolite, amorphous composite oxides, silica gel, and the like, which will be described later. Both zeolite and amorphous composite oxides have deodorizing effects against basic gases, so when used as a carrier, they are effective against both aldehyde gases and basic gases.

[0053] (C) Zeolite The zeolite is preferably a synthetic zeolite. The zeolite is insoluble or poorly soluble in water and has an excellent deodorizing effect against basic gases. Zeolite structures are diverse, but any known zeolite can be used, including A-type, X-type, Y-type, α-type, β-type, ZSM-5, amorphous, etc.

[0054] (D) Amorphous composite oxide The amorphous composite oxide is a compound other than the above-mentioned zeolite, and is preferably an amorphous composite oxide composed of at least two selected from Al2O3, SiO2, MgO, CaO, SrO, BaO, ZnO, ZrO2, TiO2, WO2, CeO2, Li2O, Na2O, and KO. This composite oxide is insoluble or slightly soluble in water and has excellent deodorizing effects against basic gases. Amorphous composite oxides represented by the formula X2O-Al2O3-SiO2 (where X is at least one alkali metal atom selected from Na, K, and Li) are particularly preferred due to their excellent deodorizing performance. Being amorphous means that no clear diffraction signals based on crystal planes are observed when powder X-ray diffraction measurements are performed. Specifically, an X-ray diffraction chart plotting diffraction angle on the horizontal axis and diffraction signal intensity on the vertical axis shows almost no highly kurtotic (so-called sharp) signal peaks.

[0055] (E) A composite containing at least one atom selected from Ag, Cu, Zn, and Mn This composite is insoluble or slightly soluble in water and has an excellent deodorizing effect against sulfur-based gases. This composite is a composite material composed of at least one atom selected from Ag, Cu, Zn, and Mn, and at least one compound containing such an atom, and other materials. The compound containing at least one atom of Ag, Cu, Zn, and Mn is preferably an oxide, hydroxide, salt of an inorganic acid such as phosphoric acid or sulfuric acid, or salt of an organic acid such as acetic acid, oxalic acid, or acrylic acid. Therefore, the deodorizer (E) can be a water-insoluble composite in which at least one metal selected from Ag, Cu, Zn, and Mn, or the compound, is supported on a carrier made of an inorganic compound as the other material. Preferred inorganic compounds for the carrier include silica, phosphates of tetravalent metals, and zeolites. Furthermore, since phosphates of tetravalent metals and zeolites have a deodorizing effect on basic gases, when phosphates of tetravalent metals and zeolites are used as carriers, they are effective against both sulfur-based gases and basic gases.

[0056] (F) Zirconium compounds The zirconium compound is hydrated zirconium oxide or zirconium oxide, preferably an amorphous compound. These compounds are insoluble or slightly soluble in water and have an excellent deodorizing effect against acidic gases. Hydrated zirconium oxide is a compound synonymous with zirconium oxyhydroxide, zirconium hydroxide, hydrous zirconium oxide, and zirconium oxide hydrate.

[0057] (G) Hydrotalcite-based compounds The hydrotalcite compound has a hydrotalcite structure and is preferably a compound represented by the following general formula (2): This compound is insoluble or poorly soluble in water and has an excellent deodorizing effect against acidic gases. M1 (1-x) M2 x (OH)2An - (x / n) mH2O (2) (In the formula, M1 is a divalent metal atom, M2 is a trivalent metal atom, x is a number greater than 0 and equal to or less than 0.5, An- is an n-valent anion such as a carbonate ion or a sulfate ion, and m is a positive integer.) Examples of the hydrotalcite-based compounds include magnesium-aluminum hydrotalcite and zinc-aluminum hydrotalcite. Of these, magnesium-aluminum hydrotalcite is particularly preferred because it has a more excellent deodorizing effect on acidic gases. Calcined hydrotalcites, i.e., compounds obtained by calcining a hydrotalcite compound at a temperature of about 500°C or higher to eliminate carbonate groups and hydroxyl groups, are also included in the hydrotalcite-based compounds.

[0058] (H) Amorphous active oxide This amorphous active oxide is a compound that does not contain the above-mentioned amorphous complex oxides, and is preferably insoluble or poorly soluble in water and has excellent deodorizing effects against acidic gases or sulfur-based gases. Specific examples of amorphous active oxides include Al2O3, SiO2, MgO, CaO, SrO, BaO, ZnO, CuO, MnO, ZrO2, TiO2, WO2, and CeO2. Surface-treated active oxides can also be used. Specific examples of surface-treated oxides include active oxides surface-treated with organopolysiloxane, and active oxides surface-coated with oxides or hydroxides of aluminum, silicon, zirconium, or tin. Surface treatment with organic materials such as organopolysiloxane is preferable because it provides better deodorizing performance than surface treatment with inorganic materials.

[0059] As the fine particles, fine particles having an antiallergen effect (also referred to as an antiallergen agent) can be used. Suitable examples of the antiallergen agent include inorganic substances with a high concentration of acid sites. In this specification, an inorganic substance with a high concentration of acid sites refers to a solid having many acid sites on its surface. Examples of inorganic substances with a high concentration of acid sites include, but are not limited to, amorphous magnesium silicate, α-type zirconium phosphate, layered titanium phosphate, activated alumina, and activated titania. These may be used alone or in combination of two or more.

[0060] Specific examples of the anti-allergen effect include the effects of Dermatophagoides farinae allergen (commonly called Derf2 allergen) and cedar pollen allergen (commonly called Cryj1 allergen), etc. The anti-allergen effect can be evaluated by the sandwich method of the ELISA method using the above allergens. The test procedure when using Dermatophagoides farinae allergen is as follows. Antibody-coated wells were prepared using a Dermatophagoides farinae allergen (Derf2)-specific antibody (15E11 antibody, Asahi Breweries, Ltd.) according to standard procedures. Next, 3 mg of sample was weighed out, and 500 μL of Dermatophagoides farinae allergen (Derf2) diluted to 40 ng / mL with antigen diluent was added. The mixture was thoroughly stirred to bring the sample and allergen into contact, then centrifuged. The supernatant was collected and added to the 15E11 antibody-coated wells that had been treated with a blocking agent and allowed to stand at room temperature. After 1 hour, the sample was discarded, each well was washed with washing buffer, and horseradish peroxidase-labeled anti-Derf2 monoclonal antibody 13A4PO (Asahi Breweries, Ltd.) diluted to 200 ng / mL in washing buffer was added to each well and allowed to stand at room temperature. After 1 hour, the antibody solution is discarded, each well is washed with washing buffer, and substrate solution is added to each well and allowed to stand at room temperature. After 5 minutes, 2N sulfuric acid is added to stop the reaction, and the absorbance at 490 nm is measured. The results are expressed as the allergen inactivation rate (%) of each sample by determining the relationship between the amount of allergen and absorbance by performing an evaluation without using a sample, and then determining the amount of remaining allergen from the absorbance when various samples are evaluated, and calculating using <Equation 1>: Allergen inactivation rate (%) = (1 - amount of remaining allergen / initial amount of allergen) x 100 <Equation 1>

[0061] As the fine particles, fine particles having antiviral activity (also called antiviral agents) can be used. The antiviral agent is not particularly limited as long as it has an antiviral effect, and examples of the antiviral agent include silver, copper, zinc, platinum, zinc compounds, silver compounds, copper compounds, metal oxide particles carrying a metal or metal oxide, zeolite ion-exchanged with metal ions, and copper complexes.

[0062] The antiviral activity can be evaluated by dip-coating the composition or treatment solution of the present invention onto a polyester fabric to evaluate the antiviral product (antiviral treated fabric). Specifically, a virus infectivity titer of 2 × 10 was measured on 0.4 g of the antiviral treated fabric before or after washing (washing means after three washes according to the JIS L0217 103 method).4 0.2 mL of influenza A virus solution (PFU / mL) is inoculated by penetration and allowed to stand at 25°C for 2 hours. The virus solution is then recovered and subjected to the plaque count method to measure the virus infectivity. The virus infectivity of the contact solution before being left to stand for 2 hours is also measured. The antiviral effect can be evaluated using the antiviral activity value obtained by the following formula. Antiviral activity value = Log (virus infectivity immediately after inoculation) - Log (virus infectivity after 2 hours)

[0063] The antibacterial agent is not particularly limited, and examples thereof include inorganic antibacterial microparticles in which metal ions having antibacterial properties, such as silver ions, copper ions, zinc ions, and tin ions, are encapsulated in an inorganic carrier such as zeolite, and titanium oxide-based inorganic antibacterial microparticles, and one or more of these may be used.

[0064] The antifungal agent is not particularly limited, and examples thereof include antifungal agents containing metal components, zeolite, hydroxyapatite, silica, antibacterial glass, etc. These can be used alone or in combination of two or more. Examples of metal components in antifungal agents include titanium, zirconium, chromium, molybdenum, cobalt, nickel, platinum, copper, silver, zinc, cadmium, and mercury. These metal components can be used alone or in combination of two or more. Among these metal components, silver, copper, and zinc are preferred. The metal components may be supported on a carrier such as a porous carrier. Examples of carriers include zeolite, silica, glass, hydroxyapatite, hydrotalcite, silicates (e.g., calcium silicate), and phosphates (e.g., calcium phosphate and zirconium phosphate).

[0065] The microparticles can be microparticles (also called sustained-release materials) that have the effect of sustained-release of a functional agent. The sustained-release material here refers to a material that gradually releases the functional agent contained in the sustained-release material. Examples of sustained-release materials include a form in which the functional agent is supported on a carrier, and a form in which the functional agent is encapsulated in nano- or microcapsules. The carrier in the embodiment in which the functional agent is supported on the carrier is not particularly limited, and examples thereof include layered inorganic compounds, porous particles, and interlayer-modified layered inorganic compounds having crosslinking groups and / or modifying groups between layers of the layered inorganic compound. Examples of the layered inorganic compounds include graphite, layered metal chalcogenides, layered metal oxides (e.g., titanium oxide, layered perovskite compounds mainly composed of niobium oxide, titanium niobate, molybdate, etc.), layered metal oxyhalides, layered metal phosphates (e.g., layered antimony phosphate, etc.), layered clay minerals, layered silicates (e.g., mica, smectites (montmorillonite, saponite, hectorite, fluorohectorite, etc.), kaolins (kaolinite, etc.), magadiite, Kenyaite, kanemite, etc.), and layered double hydroxides. Examples of interlayer-modified layered inorganic compounds include interlayer-crosslinked layered inorganic compounds having an organic-inorganic hybrid crosslinked structure between layers of layered inorganic compounds, as described in WO 2019 / 146304, and interlayer-modified layered inorganic compounds in which the interlayer space between layered inorganic compounds is modified with an organic-inorganic hybrid group such as a silyl group. Nano- or microcapsules are composed of a core substance encapsulated in the capsule and a wall material encapsulating the core substance, and the functional agent corresponds to the core substance. The components constituting the wall material may be appropriately selected depending on the conditions such as the core substance to be encapsulated in the microcapsule and the sustained release time. The functional agent that may be contained in the sustained-release material may be any of inorganic components, organic components, and mixtures thereof, and examples thereof include, but are not limited to, deodorizers, antiallergens, antiviral agents, antibacterial agents, antifungal agents, fragrances, air fresheners, pesticides, plant hormones, herbicides, repellents for pests and vermin, insecticides, bactericides, insect repellents, preservatives, dust repellents, fertilizers, pharmaceuticals, quasi-drugs, cosmetics, antioxidants, lubricants, moisturizers, and food additives.

[0066] The proportion of the microparticles in the processing fluid of the present invention may be adjusted as appropriate depending on the type of substrate and the application, but is usually 0.01% by mass or more, preferably 0.1% by mass or more, and more preferably 0.3% by mass or more, based on the total amount of the processing fluid. By having a proportion of the microparticles of 0.01% by mass or more, binding tends to be possible. The upper limit of the proportion of fine particles in the working fluid of the present invention is not particularly limited, and is usually 50% by mass or less, preferably 20% by mass or less, and more preferably 10% by mass or less. When the proportion of fine particles is 50% by mass or less, the fine particles are dispersed in the working fluid without settling, which tends to improve workability.

[0067] The mass ratio of nanocellulose to microparticles in the present invention (ratio of nanocellulose mass to microparticle mass: nanocellulose / microparticles) can be adjusted appropriately depending on the type of microparticles used, but is usually in the range of 0.01 to 50. The mass ratio is preferably 0.05 to 20, more preferably 0.05 to 10, and even more preferably 0.05 to 5.

[0068] The binder composition or processing liquid for fine particles of the present invention may contain other additives. Examples of such additives include multifunctional crosslinking agents. The multifunctional crosslinking agent is not particularly limited as long as it reacts with functional groups contained in the nanocellulose and / or binder composition to form a crosslinked structure. Examples of multifunctional crosslinking agents include polyisocyanates, carbodiimide compounds, epoxy compounds, oxazoline compounds, polyvalent metal compounds (aluminum chloride, zinc acetate, etc.), urea-formaldehyde resins and / or melamine-formaldehyde resins, water-dispersible phenolic resins, N-methylol compounds, metaxylenediamine, methylolmelamine compounds, hydrazide compounds, glyoxal compounds, and vinyl sulfone compounds.

[0069] Examples of the polyisocyanate include water-dispersible polyisocyanates, specifically 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, 4,4'-diphenylether diisocyanate, 2-nitrodiphenyl-4,4'-diisocyanate, 2,2'-diphenylpropane-4,4'-diisocyanate, 3,3'-dimethyldiphenylmethane-4,4'-diisocyanate, 4,4'-diphenylpropane diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, naphthylene-1,4-diisocyanate, and naphthylene-1,5 aromatic isocyanates such as 1,6-hexamethylene diisocyanate, 1,4-tetramethylene diisocyanate, and lysine diisocyanate; aromatic aliphatic diisocyanates such as xylylene-1,4'-diisocyanate and xylylene-1,3'-diisocyanate; isophorone diisocyanate, hydrated tolylene diisocyanate, hydrated xylylene diisocyanate, hydrated diphenylmethane diisocyanate, hydrated tetramethylxylylene diisocyanate, alicyclic diisocyanates; and NCO group-terminated compounds obtained by reacting these compounds with active hydrogen group-containing compounds. Furthermore, instead of polyisocyanates in which an isocyanurate ring structure has been introduced by adding a polyol to an organic isocyanate and an isocyanurate catalyst, prepolymer-like isocyanate compounds obtained by reacting a diisocyanate polymer or a di- or higher functional polyol with a diisocyanate or a polymeric substance may be used. These polyisocyanates can be used alone or in a mixture of two or more types.

[0070] Examples of the epoxy compounds include bifunctional glycidyl ether epoxy resins such as bisphenol A, bisphenol F, brominated bisphenol A, hydrogenated bisphenol A, bisphenol S, bisphenol AF, biphenyl, naphthalene, fluorene, polyalkylene glycol, and alkylene glycol; and multifunctional glycidyl ethers such as phenol novolac, orthocresol novolac, DPP novolac, trifunctional, tris-hydroxyphenylmethane, and tetraphenylolethane. These include epoxy resins of the type; glycidyl ester type epoxy resins of synthetic fatty acids such as dimer acids; glycidylamine type epoxy resins such as TGDDM, TGIC, hydantoin type, TETRAD-D type, aminophenol type, aniline type, and toluidine type; alicyclic epoxy resins; epoxy resins having sulfur atoms in the epoxy resin main chain, such as FLEP 10 manufactured by Toray Fine Chemicals Co., Ltd.; urethane-modified epoxy resins having urethane bonds; and rubber-modified epoxy resins containing polybutadiene, liquid polyacrylonitrile-butadiene rubber, or NBR. Among these, bisphenol A type is preferred. These may be used alone or in combination of two or more. The epoxy compound may also be a water-dispersible epoxy resin, specific examples of which include 1,4-butanediol diglycidyl ether, propylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, glycerin polyglycidyl ether, diglycerin polyglycidyl ether, polyglycerin polyglycidyl ether, and sorbitol-based polyglycidyl ether.

[0071] The carbodiimide compound is preferably a carbodiimide compound in which a terminal isocyanate group is blocked with a hydrophilic group, which is obtained by subjecting a diisocyanate to a carbon dioxide-free condensation reaction. The carbodiimide compound can be synthesized, for example, by the method shown in the examples of JP-A-10-316930. The carbodiimide compound may be commercially available. For example, the carbodiimide compound is commercially available from Nisshinbo under the trade name "Carbodilite" (registered trademark). Commercially available carbodilites include, for example, carbodilite V-02, V-02-L2, V-04, V-06, and SV-02.

[0072] Examples of the oxazoline compound include 2-vinyl-2-oxazoline, 2-vinyl-4-methyl-2-oxazoline, 2-vinyl-5-methyl-2-oxazoline, 2-isopropenyl-2-oxazoline, 2-isopropenyl-4-methyl-2-oxazoline, and 2-isopropenyl-5-ethyl-2-oxazoline. These compounds may be used alone or in combination. Among these compounds, 2-isopropenyl-2-oxazoline is preferred because it is easily available industrially.

[0073] The oxazoline compound may be an oxazoline-based polymer, and examples of such oxazoline-based polymers include water-soluble types such as EPOCROS (registered trademark) WS-500 and WS-700, and emulsion types such as EPOCROS K-2010, K-2020, and K-2030 (manufactured by Nippon Shokubai Co., Ltd.).

[0074] The functional groups in both urea-formaldehyde resin and melamine-formaldehyde resin react with hydroxyl groups and can form bonds between polymer binder molecules or between nanocellulose and the polymer binder.

[0075] The above-mentioned meta-xylenediamine, methylolmelamine compounds, hydrazide compounds, glyoxal compounds, and vinyl sulfone compounds are water-soluble crosslinking agents. Among these, compounds having multiple vinyl sulfone groups are preferred because the reaction proceeds relatively slowly. As the vinyl sulfone compound, commercially available products such as VS-B (K-FJC) and VS-C (K-FJD) (manufactured by Fujifilm Corporation) can also be used.

[0076] The amount of other additives such as a polyfunctional crosslinking agent to be added is not particularly limited and may be adjusted as appropriate.

[0077] As described above, the binder composition or processing liquid for fine particles of the present invention can be suitably used for binding fine particles and fibers. One aspect of the present invention is a textile product produced using the binder for fine particles of the present invention. Another aspect of the present invention is a textile product produced using the processing liquid of the present invention.

[0078] The textile product of the present invention can be produced, for example, by mixing the binder composition for microparticles of the present invention and microparticles in any quantitative ratio to prepare a processing liquid, then applying the processing liquid to a textile product and drying it at any temperature. Also, the textile product of the present invention can be produced, for example, by mixing the binder composition for microparticles of the present invention and microparticles in any quantitative ratio to prepare a processing liquid, then immersing the textile product in the processing liquid and drying it at any temperature. [Example]

[0079] EXAMPLES The present invention will be specifically explained below with reference to examples and comparative examples, but the present invention is not limited to these examples.

[0080] (Method for measuring the average fiber length and width of nanocellulose) The obtained nanocellulose dispersion was diluted 1,000 to 1,000,000 times with pure water, allowed to dry naturally on a mica substrate, and the shape of the nanocellulose was observed in AC mode using an Oxford Asylum scanning probe microscope "MFP-3D infinity." The obtained images were binarized using the image processing software "ImageJ" and analyzed for fiber length. For 100 or more fibers, the average fiber length was calculated as fiber length = "perimeter" ÷ 2. Regarding the fiber width, the software attached to the "MFP-3D infinity" was used to calculate the average fiber width for 50 or more fibers, taking the cross-sectional height of the shape image as the fiber width.

[0081] (dispersion stability) 100 mL of the processing solution was placed in a 100 mL measuring cylinder and left to stand at 25°C for 24 hours, after which the formation of a supernatant was visually evaluated. Dispersion stability was evaluated according to the following evaluation criteria. A: A supernatant was observed. C: No supernatant was observed.

[0082] (Deodorization test) The test was carried out by passing ammonia gas adjusted to 200 ppm or hydrogen sulfide adjusted to 120 ppm as a malodorous component from one side of the deodorizing filter to the other side. Specifically, the malodorous components contained in a bag were sucked in using a Gastec Corporation gas extractor "MODEL GV-100," and a 5cm area was collected along the path. 2 After passing the gas through the deodorizing filter, the concentration of malodorous components in the passing gas was measured using a gas detector tube. The deodorizing rate was calculated using the following formula. Deodorization rate = (Concentration of malodorous components contained in the bag - Concentration of malodorous components in the passing gas) / Concentration of malodorous components contained in the bag x 100

[0083] (condition of machining fluid) After lightly stirring the machining fluid with a spatula, the fluidity of the fluid was evaluated by scooping it up and tilting it from horizontal to vertical, and the presence or absence of settling after leaving it undisturbed for 7 days was evaluated visually. A: The liquid started flowing immediately after tilting, and there was no settling. B: The liquid started flowing within 5 seconds of tilting, and there was no settling. C: No liquid flowed even after 10 seconds of tilting, and no sedimentation occurred.

[0084] (Processing uniformity) The treated woven fabric was visually evaluated for uneven coating (processing irregularities). A: No unevenness in the processing was visible to the naked eye. C: Unevenness in processing was visible to the naked eye.

[0085] (cohesiveness) The treated woven fabric was flicked with a finger 10 times and the amount of powder that fell off was evaluated. A: There was no powder falling off. B: Powder fell off at less than 10% of the applied amount. C: More than 10% of the applied amount of powder fell off.

[0086] Example 1 As a cellulosic raw material, softwood pulp (Sigma-Aldrich NIST RM 8495, bleached kraft pulp) was cut into 5 mm squares with scissors and processed at 25,000 rpm for 1 minute in a Wonder Blender WB-1 (Osaka Chemical Co., Ltd.) to mechanically defibrate the material into a flocculent state. 350 g of sodium hypochlorite pentahydrate crystals with an effective chlorine concentration of 42% by mass were placed in a beaker, and pure water was added and stirred to adjust the effective chlorine concentration to 21% by mass. 35% by mass of hydrochloric acid was added thereto and stirred to obtain a sodium hypochlorite aqueous solution with a pH of 11. The aqueous sodium hypochlorite solution was heated to 30°C in a constant temperature water bath while being stirred at 200 rpm using a propeller-type stirring blade in a stirrer manufactured by Shinto Scientific Co., Ltd. (Three-One Motor, BL600), and then 50 g of the above-mentioned cellulosic raw material was added. After supplying the cellulosic raw material, the mixture was kept at 30°C in the same thermostatic water bath, and the pH during the reaction was adjusted to 11 by adding 48% by mass of sodium hydroxide, followed by stirring under the same conditions for 30 minutes using a stirrer. After the reaction was completed, the product was subjected to solid-liquid separation by suction filtration using a PTFE mesh filter with 134 μm openings, and the resulting oxidized cellulose was washed with pure water. Pure water was added to the oxidized cellulose to prepare a 5% dispersion, which was then processed 10 times at 200 MPa using an ultra-high pressure homogenizer "Starburst Lab" manufactured by Sugino Machine Co., Ltd. (hereinafter referred to as "Starburst Lab") to obtain a nanocellulose aqueous dispersion (binder composition for microparticles). In the ultra-high pressure homogenizer, oxidized cellulose aqueous dispersion is circulated through the built-in ultra-high pressure defibrating section to proceed with defibration. One pass of the liquid through the defibrating section is called one pass. The residual nitrogen content of nanocellulose derived from N-oxyl compounds was 1.0 ppm or less. The residual nitrogen content was measured as the amount of nitrogen using a trace total nitrogen analyzer (manufactured by Nitto Seiko Analytech Co., Ltd., device name: TN-2100H) and calculated as the increase from the raw pulp. To determine the position of carboxyl groups introduced by oxidation of cellulose, we first performed oxidation on rayon as a model and investigated the solid state of oxidized rayon. 13 C-NMR spectrum data was obtained. 13 The C-NMR spectrum data showed two signals at 165 to 185 ppm, which correspond to the carboxy groups introduced at the 2- and 3-positions. Next, the nanocellulose derived from the oxidized cellulose obtained in Example 1 was freeze-dried, and then the solid of the sample was left at 23°C and 50% RH for 24 hours or more. 13 C-NMR was measured and the spectral data was compared with that of oxidized rayon. As a result, two signals were observed at 165-185 ppm in the nanocellulose derived from the oxidized cellulose, confirming that the hydroxyl groups at the 2nd and 3rd positions of the glucopyranose ring had been oxidized and carboxyl groups had been introduced.13 The measurement conditions for C-NMR are as follows: (1) Sample tube: Zirconia tube (4 mm diameter) (2) Magnetic field strength: 9.4T (1H resonance frequency: 400MHz) (3) MAS rotation speed: 15 kHz (4) Pulse sequence: CPMAS method (5) Contact time: 3 ms (6) Waiting time: 5 seconds (7) Accumulation count: 10,000 to 15,000 times (8) Measuring device: JNM ECA-400 (manufactured by JEOL Ltd.)

[0087] <Example 2> Except for the 15-pass treatment, the nanocellulose was produced under the same conditions as in Example 1. The residual nitrogen component derived from N-oxyl compounds in the nanocellulose was 1.0 ppm or less.

[0088] Example 3 Except for the 20-pass treatment, the nanocellulose was produced under the same conditions as in Example 1. The residual nitrogen component derived from N-oxyl compounds in the nanocellulose was 1.0 ppm or less.

[0089] Example 4 Except for the 25-pass treatment, the nanocellulose was produced under the same conditions as in Example 1. The residual nitrogen component derived from N-oxyl compounds in the nanocellulose was 1.0 ppm or less.

[0090] < refer to Example 5> As a cellulose-based raw material, cotton-like softwood pulp obtained using the same raw materials and mechanical processing conditions as in Example 1 was added to water to form a 0.5% aqueous dispersion, which was then pre-defibrated using a Masuko Sangyo fine grinder (Supermass Colloider) at 1500 rpm for 10 passes. This was then processed in a Starburst Lab at 200 MPa for 40 passes to obtain a nanocellulose aqueous dispersion (binder composition for microparticles). This was heated and concentrated in an evaporator as needed before use. The residual nitrogen content of the nanocellulose derived from N-oxyl compounds was 1.0 ppm or less.

[0091] Example 6 A beaker was charged with 0.8 g of TEMPO (Sigma-Aldrich) and 5 g of sodium bromide (Fujifilm Wako Pure Chemical Industries, Ltd.), and 5,000 mL of purified water was added. The mixture was stirred at 200 rpm using a propeller-type stirring blade in a Shinto Scientific agitator (Three-One Motor, BL600) to dissolve the mixture. After heating to 25°C in a constant-temperature water bath, 50 g of cotton-like softwood pulp obtained using the same raw materials and mechanical processing conditions as in Example 1 was added as a cellulosic raw material, and 0.1 M sodium hydroxide solution was added to adjust the pH to 10. Next, 131.5 g of sodium hypochlorite aqueous solution (industrial grade, effective chlorine concentration 13.5% by mass) was added to initiate the reaction. After the sodium hypochlorite aqueous solution was added, the mixture was kept at 25°C in the same constant-temperature water bath. The pH during the reaction was adjusted to 10 by adding 0.1 M sodium hydroxide, and the mixture was stirred for 120 minutes under the same conditions. After the reaction was completed, the product was subjected to solid-liquid separation by suction filtration using a PTFE mesh filter with 20 μm openings, and the resulting oxidized cellulose was washed with pure water. A 0.5% dispersion was prepared by adding purified water to the oxidized cellulose, and this was passed through three passes at 200 MPa in a Starburst Lab to obtain a nanocellulose aqueous dispersion (binder composition for fine particles). This was then heated and concentrated in an evaporator as needed before use. The residual nitrogen component derived from N-oxyl compounds in the nanocellulose was 5 ppm.

[0092] [Production Examples 1 and 2] The nanocellulose aqueous dispersions (binder compositions for fine particles) of Examples 1 and 4 were mixed with water to give 1 wt% aluminum silicate powder and 1 wt% nanocellulose, respectively, and stirred to prepare processing solutions. The processing amount of aluminum silicate powder was 1.0 g / m 2The processing solution was applied to a woven fabric (100% polyester) and dried so that the median diameter of the aluminum silicate powder was 20 μm as measured with a Malvern laser diffraction particle size distribution analyzer "MS2000" (hereinafter referred to as MS2000), and the BET specific surface area was 600 m as measured with a Quantachrome Instruments specific surface area and pore distribution analyzer "AUTOSORB-1" (hereinafter referred to as AUTOSORB-1). 2 The particles were 0.1g / g. The processing liquid was subjected to a dispersion stability test, and the treated woven fabric was subjected to a deodorization test with ammonia gas.

[0093] [Comparative Manufacturing Example 1] The same procedure as in Production Example 1 was carried out, except that an acrylic binder manufactured by Toagosei Co., Ltd. (hereinafter referred to as NW-7090) was used as the binder.

[0094] [Table 1]

[0095] [Production Examples 3 and 4, Comparative Production Example 2] Except for using copper silicate powder instead of aluminum silicate powder and for conducting a deodorization test with hydrogen sulfide gas, the procedures were the same as in Production Examples 1 and 2 and Comparative Production Example 1. The copper silicate powder had a median diameter of 3 μm as measured with an MS2000 and a BET specific surface area of ​​500 m as measured with an AUTOSORB-1. 2 The particles were 0.1g / g.

[0096] [Table 2]

[0097] [Production Examples 5 and 6, Comparative Production Example 3] The conditions were the same as those in Production Examples 1 and 2 and Comparative Production Example 1, except that zinc oxide powder was used instead of aluminum silicate powder and a deodorization test with hydrogen sulfide gas was conducted. The zinc oxide powder had a median diameter of 2 μm as measured with MS2000 and a BET specific surface area of ​​100 m as measured with AUTOSORB-1. 2 The particles were 0.1g / g.

[0098] [Table 3]

[0099] [Production Example 7 ~10, 12, Reference Manufacturing Example 11 ] Example 1 ~4, 6, Manufacturing Example 5 The nanocellulose aqueous dispersions were mixed with water to make the aluminum silicate powder 5 wt% and nanocellulose 0.5 wt% and stirred to prepare processing solutions. 2 The processing solution was applied to a woven fabric (100% polyester) and then dried. The processing solution was subjected to a dispersion stability test, and the treated fabric was subjected to a deodorization test. In addition, the nanocellulose aqueous dispersion was used as a binder to test the state of the processing solution, processing uniformity, and binding ability.

[0100] [Comparative Manufacturing Example 4] The same procedures as in Production Example 3 were carried out, except that an acrylic binder (NW-7090) manufactured by Toagosei Co., Ltd. was used as the binder composition.

[0101] [Table 4]

[0102] The scores in the table are based on the state of the processing liquid, uniformity of processing, binding ability, and deodorizing rate, with 4 points for a deodorizing rate of 95% or more, 2 points for 90% to less than 95%, 1 point for 80% to less than 90%, and D for 80% or less, with A being 2 points, B being 1 point, and C being 0 point. The score rankings were based on the following criteria. A:8~10 points B: 5~7 points C: 2~4 points D: Less than 1 point or deodorization rate of 80% or less [Industrial Applicability]

[0103] The binder composition for fine particles of the present invention has industrial applicability in the field of adhering fine particles.

Claims

1. A composition for binding microparticles, comprising nanocellulose, The average fiber length of the nanocellulose is 100 nm or more and 700 nm or less, The fine particles include particles having a particle size of 1 nm or more and 1000 μm or less. The composition.

2. Used to bind fine particles and fibers, The composition of claim 1.

3. The nanocellulose comprises oxidized nanocellulose; The composition according to claim 1 or 2.

4. The nanocellulose has a structure in which the second and third hydroxyl groups of the glucopyranose ring are oxidized and carboxyl groups are introduced, The composition according to any one of claims 1 to 3.

5. The fine particles are inorganic fine particles. The composition according to any one of claims 1 to 4.

6. The fine particles are ceramics. The composition according to any one of claims 1 to 5.

7. the fine particles are at least one selected from the group consisting of deodorants, antiallergens, antiviral agents, antibacterial agents, antifungal agents, and sustained-release materials; The composition according to any one of claims 1 to 6.

8. A processing fluid comprising the composition according to any one of claims 1 to 7 and fine particles, The fine particles include particles having a particle size of 1 nm or more and 1000 μm or less. Processing fluid.

9. A textile product made using the composition according to any one of claims 1 to 7.

10. A textile product produced using the processing liquid according to claim 8.

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