WO2022239761A1 - 繊維材料及び複合材料、並びにそれらの製造方法 - Google Patents

繊維材料及び複合材料、並びにそれらの製造方法 Download PDF

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WO2022239761A1
WO2022239761A1 PCT/JP2022/019766 JP2022019766W WO2022239761A1 WO 2022239761 A1 WO2022239761 A1 WO 2022239761A1 JP 2022019766 W JP2022019766 W JP 2022019766W WO 2022239761 A1 WO2022239761 A1 WO 2022239761A1
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nanocellulose
oxidized cellulose
mass
kneading
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French (fr)
Japanese (ja)
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じゆん ▲高▼田
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Toagosei Co Ltd
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Toagosei Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C08J5/06—Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
    • D06M13/325—Amines
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/50—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with organometallic compounds; with organic compounds containing boron, silicon, selenium or tellurium atoms
    • D06M13/51—Compounds with at least one carbon-metal or carbon-boron, carbon-silicon, carbon-selenium, or carbon-tellurium bond
    • D06M13/513—Compounds with at least one carbon-metal or carbon-boron, carbon-silicon, carbon-selenium, or carbon-tellurium bond with at least one carbon-silicon bond
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H11/00—Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only
    • D21H11/16—Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only modified by a particular after-treatment
    • D21H11/18—Highly hydrated, swollen or fibrillatable fibres
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H11/00—Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only
    • D21H11/16—Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only modified by a particular after-treatment
    • D21H11/20—Chemically or biochemically modified fibres
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/02—Natural fibres, other than mineral fibres
    • D06M2101/04—Vegetal fibres
    • D06M2101/06—Vegetal fibres cellulosic

Definitions

  • nanocellulose Because nanocellulose has a large number of hydrophilic functional groups, it has a low affinity with resin, and problems such as not being able to obtain a sufficient reinforcing effect even if it is kneaded with resin as it is have been pointed out.
  • Patent Document 1 proposes a method of mixing nanocellulose with a resin in a state where the nanocellulose is present on the surface of the resin particles, instead of directly mixing the nanocellulose with the resin. It is
  • Patent Document 2 discloses a resin modifier containing cellulose nanofibers reacted with an amine or a quaternary ammonium salt compound and a polymer of ethylenically unsaturated monomers in order to enhance the resin modification effect.
  • a plaster is disclosed.
  • Patent Document 3 discloses a composite material containing a thermoplastic resin, a cationic surfactant, cellulose nanofibers, and a silicon atom-containing hydrophobizing agent.
  • the resin-modifying additive of Patent Document 1 contains nanocellulose obtained by reacting an N-oxyl compound on natural cellulose fibers and/or a derivative of the nanocellulose, and resin particles. It does not disclose the use of oxidized cellulose obtained by using chlorous acid or a salt thereof as an oxidizing agent, or the inclusion of a silicon atom-containing hydrophobizing agent or a water-soluble solvent as other components in the resin modifier.
  • oxidized cellulose obtained by using hypochlorous acid or a salt thereof having an effective chlorine concentration of 14% by mass to 43% by mass as an oxidizing agent for a cellulosic raw material is dissolved.
  • hypochlorous acid or a salt thereof having an effective chlorine concentration of 14% by mass to 43% by mass as an oxidizing agent for a cellulosic raw material is dissolved.
  • a silicon atom-containing hydrophobizing agent or a water-soluble solvent as other components in the resin modifier.
  • TEMPO oxidized cellulose nanofibers are used as nanocellulose in the composite material of Patent Document 3, the use of nanocellulose derived from oxidized cellulose obtained by using hypochlorous acid or a salt thereof as an oxidizing agent is disclosed. It has not been.
  • An object of the present invention is to provide a composite material of nanocellulose and resin that has excellent strength.
  • the present invention is as follows. [1] nanocellulose; a nanocellulose modifier; a water-soluble solvent; A fibrous material comprising the nanocellulose contains an oxide of a cellulosic raw material with hypochlorous acid or a salt thereof and is substantially free of N-oxyl compounds; fiber material. [1-1]
  • the nanocellulose modifier contains at least one selected from the group consisting of cationic surfactants and silicon atom-containing hydrophobizing agents, The fiber material according to [1].
  • the nanocellulose modifier comprises a cationic surfactant and a silicon atom-containing hydrophobizing agent, The fiber material according to [1] or [1-1].
  • the cationic surfactant contains at least one selected from the group consisting of primary to tertiary amine salts and quaternary ammonium salts, The fiber material according to any one of [1] to [1-2].
  • the cationic surfactant contains at least one selected from the group consisting of primary to tertiary amine salts having 1 to 40 carbon atoms and quaternary ammonium salts having 1 to 40 carbon atoms, The fiber material according to any one of [1] to [1-3].
  • the cationic surfactant contains at least one selected from the group consisting of primary to tertiary amine salts having 2 to 20 carbon atoms and quaternary ammonium salts having 2 to 20 carbon atoms, The fiber material according to any one of [1] to [1-4].
  • the cationic surfactant contains at least one selected from the group consisting of primary to tertiary amine salts having 8 to 18 carbon atoms and quaternary ammonium salts having 8 to 18 carbon atoms, The fiber material according to any one of [1] to [1-5].
  • the silicon atom-containing hydrophobizing agent has the following formula (1): R2mSi(OR1) 4-m ( 1 ) [In formula (1), R 1 is a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms, R 2 is an unsubstituted or substituted hydrocarbon group having 1 to 10 carbon atoms, m is 0, 1 or 2] Including at least one selected from the group consisting of a compound represented by and a partial hydrolysis condensate thereof, The fiber material according to any one of [1] to [1-6]. [1-8] The boiling point of the water-soluble solvent is 100° C. or higher and 300° C. or lower under 1 atmosphere. The fiber material according to any one of [1] to [1-7].
  • the boiling point of the water-soluble solvent is 150° C. or higher and 250° C. or lower under 1 atmosphere.
  • the amount of the water-soluble solvent dissolved in 100 g of water at 20° C. is 20 g or more.
  • [1-11] The amount of the water-soluble solvent dissolved in 100 g of water at 20° C. is 50 g or more.
  • the production method wherein the oxidized cellulose contains an oxide of a cellulosic raw material produced by hypochlorous acid or a salt thereof and does not substantially contain an N-oxyl compound.
  • the production method wherein the oxidized cellulose contains an oxide of a cellulosic raw material produced by hypochlorous acid or a salt thereof and does not substantially contain an N-oxyl compound.
  • the oxidized cellulose is in the form of a dispersion dispersed in an aqueous solvent, further comprising a drying step of removing the aqueous solvent from the second mixture;
  • an elastic kneader is used in the kneading step, The production method according to [9].
  • the elastic kneader is an open roll, The production method according to [10].
  • the kneading step is A step of first kneading the fiber material and the thermoplastic resin according to any one of [1] to [3] to obtain a masterbatch; a step of second kneading the masterbatch; The production method according to any one of [9] to [11], comprising
  • FIG. 4 shows a graph used for determination of kneading temperature by viscoelasticity measurement
  • the fibrous material of the present invention contains nanocellulose, a nanocellulose modifier, and a water-soluble solvent.
  • the nanocellulose contained in the fiber material of the present invention contains oxides of cellulosic raw materials by hypochlorous acid or salts thereof, and does not substantially contain N-oxyl compounds.
  • the fiber material of the present invention is a composition containing nanocellulose, a nanocellulose modifier, and a water-soluble solvent, and can be used to obtain a composite material with a resin. Accordingly, one aspect of the invention is a composite resin made from the fibrous material of the invention.
  • a thermoplastic resin is preferable as the resin to be combined with the fiber material of the present invention.
  • the composite material of the present invention includes a thermoplastic resin, nanocellulose, and a nanocellulose modifier.
  • the nanocellulose contained in the composite material of the present invention contains oxides of cellulosic raw materials by hypochlorous acid or salts thereof, and does not substantially contain N-oxyl compounds.
  • Nanocellulose used in the present invention is obtained by nanoizing a cellulosic raw material.
  • the main component of plants is cellulose, and bundles of cellulose molecules are called cellulose microfibrils.
  • Cellulose in cellulosic raw materials is also contained in the form of cellulose microfibrils.
  • Nanocellulose in the present invention is a general term for cellulose made into nano, and includes fine cellulose fibers, cellulose nanocrystals, and the like. Fine cellulose fibers are also referred to as cellulose nanofibers (also referred to as CNF).
  • nanocellulose can be used as the nanocellulose in the present invention, and nanocellulose obtained by preparing from cellulosic raw materials such as softwood pulp can also be used.
  • the nanocellulose in the present invention is nanoized oxidized cellulose obtained by oxidizing cellulosic raw materials. That is, the nanocellulose in the present invention includes oxidized nanocellulose.
  • the oxidation method is oxidation using hypochlorous acid or a salt thereof.
  • oxidation using hypochlorous acid or a salt thereof refers to oxidation that occurs when hypochlorous acid or a salt thereof acts on a cellulosic raw material.
  • the nanocellulose in the present invention is nanoized oxidized cellulose obtained by oxidizing a cellulosic raw material with hypochlorous acid or a salt thereof.
  • the oxidized cellulose can also be referred to as an oxide of a cellulosic raw material.
  • Nanocellulose in the present invention includes oxides of cellulosic raw materials with hypochlorous acid or salts thereof.
  • the nanocellulose in the present invention is obtained by oxidizing a cellulosic raw material with hypochlorous acid or a salt thereof, and does not use an N-oxyl compound such as TEMPO in this oxidation. Therefore, the nanocellulose in the present invention is substantially free of N-oxyl compounds. Therefore, nanocellulose is highly safe because the effects of N-oxyl compounds on the environment and the human body are sufficiently reduced.
  • the nanocellulose (or oxidized cellulose) "substantially does not contain N-oxyl compounds” means that the nanocellulose does not contain any N-oxyl compounds or means that the content of is 2.0 mass ppm or less, preferably 1.0 mass ppm or less, relative to the total amount of nanocellulose.
  • the N-oxyl compound when the content of the N-oxyl compound is preferably 2.0 ppm by mass or less, more preferably 1.0 ppm by mass or less as an increase from the cellulosic raw material, "the N-oxyl compound is substantially means “not including”.
  • the content of the N-oxyl compound can be measured by known means. Known means include a method using a trace total nitrogen analyzer (for example, manufactured by Nitto Seiko Analyticc Co., Ltd., device name: TN-2100H).
  • the nanocellulose in the present invention contains a carboxy group, but the carboxy group may be of H type (--COOH), or in a salt form (--COO - X + : X + is a cation that forms a salt form). It may be in a modified form by reacting the carboxyl group with another compound to form a covalent bond.
  • the type of salt is not particularly limited, but alkali metal salts such as lithium, sodium, and potassium; alkaline earth metal salts such as calcium salts and barium salts; other metal salts such as magnesium salts and aluminum salts; amine salts and the like.
  • Preferred examples of the other compounds include primary, secondary, and tertiary amines.
  • the cellulosic raw material in the present invention is not particularly limited as long as it is a material mainly composed of cellulose, and examples thereof include pulp, natural cellulose, regenerated cellulose, and fine cellulose obtained by depolymerizing a cellulose raw material by mechanical treatment. be done.
  • the cellulosic raw material a commercially available product such as crystalline cellulose made from pulp can be used as it is.
  • unused biomass containing a large amount of cellulose components, such as bean curd refuse and soybean hulls may be used as a raw material.
  • the cellulosic raw material may be treated with an alkali of an appropriate concentration for the purpose of facilitating penetration of the oxidizing agent into the raw pulp.
  • the carboxy group content of nanocellulose and oxidized cellulose in the present invention is preferably 0.20 to 2.0 mmol/g.
  • the amount of carboxyl groups is 0.20 mmol/g or more, the oxidized cellulose can be imparted with sufficient defibration properties.
  • the amount of carboxyl groups is 2.0 mmol/g or less, it is possible to obtain nanocellulose with a low proportion of particulate cellulose and uniform quality. It is believed that this improves the dispersibility of nanocellulose and makes it easier to obtain a fibrous material.
  • the amount of carboxy groups in the nanocellulose and oxidized cellulose in the present invention is more preferably 0.30 mmol/g or more, still more preferably 0.35 mmol/g or more, and even more preferably 0.40 mmol/g. g or more, still more preferably 0.42 mmol/g or more, still more preferably 0.50 mmol/g or more, still more preferably over 0.50 mmol/g, even more preferably 0.55 mmol / g or more.
  • the upper limit of the amount of carboxyl groups may be less than 2.0 mmol/g, may be 1.5 mmol/g or less, may be 1.2 mmol/g or less, or may be 1.0 mmol/g or less.
  • a preferable range of the amount of carboxyl groups can be determined by appropriately combining the above-mentioned upper limit and lower limit.
  • the amount of carboxyl groups in nanocellulose is more preferably 0.30 mmol/g or more and less than 2.0 mmol/g, still more preferably 0.35 to 2.0 mmol/g, still more preferably 0.35 to 1 .5 mmol/g, still 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 between 0.55 and 1.0 mmol/g.
  • the oxidized cellulose in the present invention is obtained by, for example, oxidizing a cellulosic raw material under conditions in which the available chlorine concentration of hypochlorous acid or a salt thereof in the reaction system is relatively high (for example, 6% by mass to 43% by mass). It can be obtained by The oxidized cellulose in the present invention can also be produced by appropriately controlling reaction conditions such as available chlorine concentration, pH during reaction, and reaction temperature.
  • the oxidized cellulose thus obtained preferably has a structure in which at least two of the hydroxyl groups of the glucopyranose rings constituting the cellulose are oxidized. It preferably has a structure in which the hydroxyl group at the 3-position is oxidized and a carboxy group is introduced.
  • the hydroxyl group at the 6th position of the glucopyranose ring in the oxidized cellulose is not oxidized and remains as the hydroxyl group.
  • the position of the carboxy group in the glucopyranose ring of oxidized cellulose can be analyzed by solid-state 13 C-NMR spectrum.
  • Rayon has the same chemical structure as cellulose, and its oxide (rayon oxide) is water soluble.
  • rayon oxide rayon oxide
  • a carbon peak attributed to a carboxy group is observed at 165 to 185 ppm.
  • two signals appear in this chemical shift range.
  • solution two-dimensional NMR measurement it can be determined that the carboxy groups were introduced at the 2- and 3-positions.
  • carboxyl groups are introduced at the 2nd and 3rd positions by evaluating the spread of peaks appearing at 165 to 185 ppm in the solid-state 13 C-NMR spectrum. That is, after drawing a baseline to the peaks in the range of 165 ppm to 185 ppm in the solid-state 13 C-NMR spectrum and obtaining the overall area value, the two peak area values obtained by vertically dividing the area value at the peak top are calculated. A ratio (large area value/small area value) is obtained, and if the ratio of the peak area values is 1.2 or more, it can be said that the peak is 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 top of the peak to the baseline. That is, if the ratio L'/L is 0.1 or more, it can be determined that a broad peak exists.
  • the ratio L'/L may be 0.2 or more, 0.3 or more, 0.4 or more, or 0.5 or more.
  • the upper limit of the ratio L'/L is not particularly limited, it is usually 3.0 or less, may be 2.0 or less, or may be 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.
  • the nanocellulose in the present invention is an aggregate of single unit fibers.
  • the nanocellulose in the present invention only needs to contain at least one nanocellulose, and nanocellulose is preferably the main component.
  • nanocellulose is the main component means that the proportion of nanocellulose in nanocellulose is more than 50% by mass, preferably more than 70% by mass, more preferably more than 80% by mass. Point. Although the upper limit of the above ratio is 100% by mass, it may be 98% by mass or 95% by mass.
  • the average fiber length of the nanocellulose in the present invention is preferably 50 to 2000 nm, more preferably 100 to 1000 nm, even more preferably 100 to 700 nm, still more preferably 100 to 500 nm, still more preferably. is between 100 and 400 nm.
  • the average fiber length exceeds 2000 nm, the dispersion containing nanocellulose tends to increase in viscosity.
  • the viscosity which is a feature of nanocellulose, tends to be difficult to develop and the binding property tends to decrease.
  • the average fiber width of nanocellulose is preferably 1 to 200 nm, more preferably 1 to 15.0 nm, more preferably 1 to 10 nm, still more preferably 1 to 5 nm.
  • the image processing conditions are arbitrary, but there are cases where the values calculated for the same image differ depending on the conditions.
  • the range of difference in values depending on the conditions is preferably within the range of ⁇ 100 nm for the average fiber length.
  • the range of difference in values depending on conditions is preferably within the range of ⁇ 10 nm for the average fiber width.
  • Method for producing nanocellulose An example of a method for producing nanocellulose that can be used in the fiber material or composite material of the present invention, specifically, a cellulosic raw material using hypochlorous acid or a salt thereof in the substantial absence of an N-oxyl compound
  • a production method of obtaining oxidized cellulose by oxidation of also referred to as step A
  • obtaining nanocellulose from the oxidized cellulose also referred to as step B
  • Hypochlorous acid or salts thereof used for oxidizing cellulosic raw materials include hypochlorous acid water, sodium hypochlorite, potassium hypochlorite, calcium hypochlorite, and ammonium hypochlorite. is mentioned. Among these, sodium hypochlorite is preferable from the viewpoint of ease of handling.
  • a method of producing oxidized cellulose by oxidation of a cellulosic raw material includes a method of mixing a cellulosic raw material with a reaction solution containing hypochlorous acid or a salt thereof.
  • the solvent contained in the reaction solution is preferably water because it is easy to handle and hardly causes side reactions.
  • the amount of hypochlorous acid or its salt used is not particularly limited, but it is preferable to use hypochlorous acid or its salt having an available chlorine concentration of 6% by mass or more and 43% by mass or less.
  • hypochlorous acid or a salt thereof with an available chlorine concentration of 6% by mass or more and 43% by mass or less, the amount of carboxyl groups in the oxidized cellulose can be sufficiently increased, the fineness is sufficiently advanced, and after the oxidation reaction can omit the mechanical defibration process.
  • the effective chlorine concentration of hypochlorous acid or its salt in the reaction solution (reaction system) is preferably in the range of 6 to 43% by mass.
  • the effective chlorine concentration of the reaction solution is more preferably 14% by mass or more, still more preferably 18% by mass or more, and even more preferably 20% by mass or more. is.
  • the effective chlorine concentration of the reaction solution is more preferably 40% by mass or less, and still more preferably 38% by mass or less.
  • the range of effective chlorine concentration of the reaction liquid the aforementioned lower limit and upper limit can be appropriately combined.
  • the effective chlorine concentration range is more preferably 16 to 43% by mass, more preferably 18 to 40% by mass.
  • the effective chlorine concentration range is preferably 6% by mass or more and less than 14% by mass, more preferably 7% by mass or more and less than 14% by mass. It is more preferably 7% by mass or more and 13% by mass or less, and even more preferably 8% by mass or more and 13% by mass or less.
  • hypochlorous acid is a weak acid that exists as an aqueous solution
  • hypochlorites are compounds in which hydrogen in hypochlorous acid is replaced with other cations.
  • sodium hypochlorite which is hypochlorite
  • the concentration is measured as the amount of available chlorine in the solution, not the concentration of sodium hypochlorite. .
  • the oxidation reaction of cellulosic raw materials with hypochlorous acid or its salts should be carried out while adjusting the pH within the range of 5.0 to 14.0. Within this range, the oxidation reaction of the cellulosic raw material can be sufficiently advanced, and the amount of carboxyl groups in the oxidized cellulose can be sufficiently increased. This makes it possible to easily defibrate the oxidized cellulose.
  • the pH of the reaction system is more preferably 7.0 or higher, still more preferably 8.0 or higher, even more preferably 8.5 or higher, still more preferably 9.0 or higher, and still more preferably 9.5 or higher.
  • the upper limit of the pH of the reaction system is not particularly limited, and is preferably 14.5 or less, more preferably 14.0 or less, still more preferably 13.0 or less, still more preferably 12.5 or less, and still more preferably 12.5 or less. It is preferably 12.0 or less, more preferably 11.5 or less.
  • the pH range of the reaction system is more preferably 7.0 to 14.0, still more preferably 8.0 to 13.5, still more preferably 8.5 to 13.0.
  • an alkaline agent such as sodium hydroxide
  • an acid such as hydrochloric acid
  • the method for producing oxidized cellulose will be further described below, taking as an example the case where sodium hypochlorite is used as hypochlorous acid or a salt thereof.
  • the reaction solution is preferably an aqueous sodium hypochlorite solution.
  • the effective chlorine concentration of the sodium hypochlorite aqueous solution to the desired concentration (for example, the desired concentration: the range of 6% by mass to 43% by mass)
  • hypochlorite with a lower effective chlorine concentration than the desired concentration A method of concentrating a sodium hypochlorite aqueous solution, a method of diluting a sodium hypochlorite aqueous solution with a higher effective chlorine concentration than the target concentration, and sodium hypochlorite crystals (e.g., sodium hypochlorite pentahydrate) Examples include a method of dissolving in a solvent.
  • the method of stirring includes, for example, a stirrer with stirring blades, a homomixer, a disper-type mixer, a homogenizer, external circulation stirring, and the like.
  • shear type stirrers such as homomixers and homogenizers, stirrer with stirring blades, and A method using one or more of disper-type mixers is preferred, and a method using a stirrer with stirring blades is particularly preferred.
  • stirrer with stirring blades When using a stirrer with stirring blades, propeller blades, paddle blades, turbine blades, swept blades, anchor blades, gate blades, Maxblend blades, full zone blades, helical ribbon blades, screw blades (with draft tubes, etc.) ) or the like can be used. When using a stirrer with stirring blades, it is preferable to stir at a rotational speed of 50 to 300 rpm. In addition, multi-screw kneaders such as single-screw kneaders and twin-screw kneaders can also be used.
  • the reaction temperature in the oxidation reaction is preferably 15°C to 100°C, more preferably 20°C to 90°C.
  • the reaction time of the oxidation reaction can be set according to the degree of progress of the oxidation, but is preferably about 15 minutes to 50 hours.
  • the pH of the reaction system is set to 10 or higher, it is preferable to set the reaction temperature to 30° C. or higher and/or the reaction time to 30 minutes or longer.
  • a treatment may be performed to stop the oxidation reaction.
  • the treatment for stopping the oxidation reaction is not particularly limited, but examples thereof include a method of adding an acid or a metal catalyst. Moreover, the method of reducing hypochlorous acid or its salt is suitably mentioned. Specific examples of the treatment for stopping the oxidation reaction include a method of adding a reducing agent such as sodium sulfite. The amount of the reducing agent to be added may be appropriately adjusted according to the amount of hypochlorous acid or its salt (effective chlorine concentration).
  • Oxidized cellulose can be obtained as an oxide of In the isolation treatment, some or all of the carboxyl groups in the oxidized cellulose may be converted to H-type (--COOH) by adjusting the pH of the solution containing the oxidized cellulose to 4 or less.
  • the solution containing oxidized cellulose obtained by the above reaction may be used as it is, or may be subjected to the following fibrillation step, for example.
  • reducing agent used in the above reduction reaction common reducing agents can be used, and examples include borates, sulfites, and the like. Coloring can be prevented by using these reducing agents.
  • the borates are a generic term for borates and boronates.
  • the borate in the present invention refers to a salt composed of an anion derived from boric acid (B(OH) 3 ) and a monovalent metal ion.
  • borates are M 3 [BO 3 ], M 2 [HBO 3 ], M[H 2 BO 3 ], M 2 [R-BO 2 ] or M[R-BO 2 H].
  • M is a monovalent metal ion
  • R is a monovalent hydrocarbon group
  • These borates may be present in the composition of the invention as a solid, ionized, or reacted with the functional groups of the nanocellulose.
  • the above sulfites include sulfite (M 2 SO 3 : M is a monovalent cation moiety), hydrogen sulfite (MHSO 3 : M is a monovalent cation moiety), pyrosulfite (M 2 S 2 O 5 or M'S 2 O 5 : M is a monovalent cation moiety, M' is a divalent cation moiety), hyposulfite (M 2 S 2 O 4 or M'S 2 O 4 : M is a monovalent (M' is a divalent cation moiety), or hydrates thereof.
  • M include alkali metal ions and ammonium ions
  • examples of M′ include alkaline earth metal ions.
  • sulfites include sodium hydrogen sulfite, potassium hydrogen sulfite, ammonium hydrogen sulfite, sodium sulfite, potassium sulfite, ammonium sulfite, sodium hyposulfite, potassium hyposulfite, calcium hyposulfite, sodium pyrosulfite, and potassium pyrosulfite. , magnesium pyrosulfite, calcium pyrosulfite and the like.
  • the amount of sulfites is preferably 0.1 to 15% by mass, more preferably 1 to 15% by mass, still more preferably 1.0 to 12% by mass, and 3.0 to 10% by mass relative to the absolute dry mass of oxidized cellulose. % by mass is even more preferred.
  • the reduction treatment temperature should be about 10 to 90°C in terms of the efficiency of the reduction treatment and suppression of fiber deterioration.
  • the pH at the reduction treatment may be appropriately adjusted depending on the reducing agent to be used, and is usually in the range of pH 2-12.
  • the reaction time in the reduction reaction can be appropriately set according to the degree of progress of the reduction, and is not particularly limited.
  • the oxidized cellulose is preferably in the form of a dispersion.
  • the dispersion as used herein is a suspension containing oxidized cellulose.
  • the dispersion liquid may contain the solvent used in the oxidation. Alternatively, a dispersion medium may be appropriately added to form a dispersion liquid. Since the oxidized cellulose is a dispersion liquid, it is easy to handle, and tends to facilitate the progress of miniaturization.
  • the amount of the oxidized cellulose is usually in the range of 0.1% by mass or more and 95% by mass or less, preferably 1% by mass, when the total amount of the dispersion is 100% by mass. % or more and 50 mass % or less, more preferably 1 mass % or more and 30 mass % or less.
  • Oxidized cellulose includes fibrous cellulose obtained by oxidizing a cellulosic raw material using hypochlorous acid or a salt thereof. Oxidized cellulose is also referred to as oxidized cellulose fiber. That is, oxidized cellulose includes oxides of cellulosic raw materials with hypochlorous acid or salts thereof. The main component of plants is cellulose, and bundles of cellulose molecules are called cellulose microfibrils. Cellulose in cellulosic raw materials is also contained in the form of cellulose microfibrils.
  • Nanocellulose can be obtained by fibrillating the oxidized cellulose obtained above to make it nano, if necessary.
  • methods for defibrating oxidized cellulose include weak stirring using a magnetic stirrer and the like, mechanical fibrillation, and the like.
  • Mechanical fibrillation methods include, for example, a screw type mixer, a paddle mixer, a disper type mixer, a turbine type mixer, a homogenizer under high speed rotation, a high pressure homogenizer, an ultrahigh pressure homogenizer, a double cylindrical homogenizer, and an ultrasonic homogenizer. , water jet counter-collision disperser, beater, disc refiner, conical refiner, double disc refiner, grinder, single or multi-screw kneader, rotation or revolution stirrer, vibration stirrer, etc. method.
  • Nanocellulose can be produced by nanoizing oxidized cellulose by using one or more of these devices, preferably by treating oxidized cellulose in a dispersion medium.
  • a method using an ultra-high-pressure homogenizer can be preferably used in that it can produce nanocellulose with more advanced fibrillation.
  • the pressure during fibrillation treatment is preferably 100 MPa or higher, more preferably 120 MPa or higher, and still more preferably 150 MPa or higher.
  • the number of defibration treatments is not particularly limited, it is preferably two or more, more preferably three or more, from the viewpoint of sufficiently progressing defibration.
  • the oxidized cellulose can be sufficiently fibrillated by gentle stirring using a rotation/revolution stirrer, a vibrating stirrer, or the like. Examples of vibratory stirrers include vortex mixers (touch mixers). That is, according to the oxidized cellulose, uniform nanocellulose can be obtained even when the defibration treatment is performed under mild defibration conditions.
  • alcohols include methanol, ethanol, isopropanol, isobutanol, sec-butyl alcohol, tert-butyl alcohol, methyl cellosolve, ethylene glycol and glycerin.
  • Ethers include ethylene glycol dimethyl ether, 1,4-dioxane and tetrahydrofuran.
  • Ketones include acetone and methyl ethyl ketone.
  • the nanocellulose in the present invention preferably satisfies the following zeta potential and light transmittance.
  • the nanocellulose in the present invention preferably has a zeta potential of ⁇ 30 mV or less.
  • the zeta potential is ⁇ 30 mV or less (that is, the absolute value is 30 mV or more)
  • sufficient repulsion between microfibrils is obtained, and nanocellulose with a high surface charge density is likely to be produced during mechanical fibrillation.
  • the dispersibility of the nanocellulose is improved, and the dispersion tends to have excellent viscosity stability.
  • the upper limit of the zeta potential is not particularly limited, it is usually -100 mV or less.
  • the zeta potential is -100 mV or more (that is, the absolute value is 100 mV or less)
  • oxidative cutting in the fiber direction tends to be suppressed as oxidation progresses, so nanocellulose with a uniform size can be obtained.
  • the adhesiveness tends to be higher.
  • the zeta potential of nanocellulose is preferably ⁇ 35 mV or less, more preferably ⁇ 40 mV or less, and even more preferably ⁇ 50 mV or less.
  • the lower limit of the zeta potential is preferably ⁇ 90 mV or more, more preferably ⁇ 85 mV or more, further preferably ⁇ 80 mV or more, even more preferably ⁇ 77 mV or more, even more preferably ⁇ 70 mV or more, and more preferably ⁇ 65 mV or more. More preferred.
  • the aforementioned lower limit and upper limit can be appropriately combined.
  • the zeta potential is preferably ⁇ 90 mV or more and ⁇ 30 mV or less, more preferably ⁇ 85 mV or more and ⁇ 30 mV or less, still more preferably ⁇ 80 mV or more and ⁇ 30 mV or less, still more preferably ⁇ 77 mV or more and ⁇ 30 mV or less. more preferably ⁇ 70 mV or more and ⁇ 30 mV or less, still more preferably ⁇ 65 mV or more and ⁇ 30 mV or less, and still more preferably ⁇ 65 mV or more and ⁇ 35 mV or less.
  • the zeta potential is a value measured under conditions of pH 8.0 and 20° C.
  • a cellulose aqueous dispersion in which nanocellulose and water are mixed to have a nanocellulose concentration of 0.1% by mass. be. Specifically, it can be measured according to the following method. Pure water is added to the nanocellulose aqueous dispersion to dilute the nanocellulose concentration to 0.1%. A 0.05 mol/L sodium hydroxide aqueous solution is added to the diluted nanocellulose aqueous dispersion to adjust the pH to 8.0, and a zeta potential measuring device such as a zeta potential meter (ELSZ-1000) manufactured by Otsuka Electronics Co., Ltd. The zeta potential is measured at 20° C. by
  • the nanocellulose in the present invention has few aggregates, and the nanocellulose dispersion dispersed in the dispersion medium tends to exhibit high light transmittance with little light scattering of the fine cellulose fibers.
  • the nanocellulose in the present invention preferably has a light transmittance of 95% or more in a liquid mixture obtained by mixing with water to a solid content concentration of 0.1% by mass.
  • the light transmittance is more preferably 96% or higher, still more preferably 97% or higher, and even more preferably 99% or higher.
  • the light transmittance is a value measured with a spectrophotometer at a wavelength of 660 nm. Also, light transmittance can be measured using an aqueous dispersion containing nanocellulose.
  • aqueous dispersion of nanocellulose is placed in a quartz cell with a thickness of 10 mm, and the light transmittance at a wavelength of 660 nm is measured using a spectrophotometer such as JASCO V-550.
  • the zeta potential and light transmittance can be controlled by oxidizing with hypochlorous acid or a salt thereof, and in particular by adjusting the reaction time, reaction temperature, stirring conditions, etc. of the oxidation reaction. Specifically, as the reaction time is lengthened and/or the reaction temperature is raised, oxidation of the cellulose microfibril surface in the cellulosic raw material progresses, and repulsion between fibrils occurs due to electrostatic repulsion and osmotic pressure. Strengthening tends to result in smaller average fiber widths.
  • the zeta potential can be increased by setting one or more of the oxidation reaction time, reaction temperature, and stirring conditions (e.g., lengthening the reaction time) so that oxidation proceeds more (i.e., increases the degree of oxidation). It tends to be higher.
  • the degree of polymerization of the oxidized cellulose used in the present invention is preferably 600 or less.
  • the degree of polymerization of oxidized cellulose exceeds 600, a large amount of energy tends to be required for defibration, and sufficient fibration property cannot be expressed, resulting in a decrease in the dispersibility of nanocellulose and, in turn, a decrease in strength.
  • the lower limit of the degree of polymerization of oxidized cellulose is not particularly set.
  • the degree of polymerization of the oxidized cellulose is less than 50, the proportion of particulate cellulose rather than fibrous cellulose is increased, and the effect as nanocellulose may be reduced.
  • the degree of polymerization of oxidized cellulose is preferably in the range of 50 or more and 600 or less.
  • the degree of polymerization of oxidized cellulose is more preferably 580 or less, still more preferably 560 or less, still more preferably 550 or less, still more preferably 500 or less, still more preferably 450 or less, and More preferably, it is 400 or less.
  • the lower limit of the degree of polymerization is more preferably 60 or more, still more preferably 70 or more, still more preferably 80 or more, and still more preferably 90 or more. It is more preferably 100 or more, still more preferably 110 or more, and particularly preferably 120 or more.
  • a preferred range of the degree of polymerization can be determined by appropriately combining the above-mentioned upper limit and lower limit.
  • the degree of polymerization of oxidized cellulose is more preferably 60 to 600, still more preferably 70 to 600, even more preferably 80 to 600, still more preferably 80 to 550, and still more preferably 80 to 600. 500, more preferably 80-450, particularly preferably 80-400.
  • the degree of polymerization of oxidized cellulose is the average degree of polymerization (viscosity average degree of polymerization) measured by a viscosity method. Details follow the method described in Examples.
  • the nanocellulose modifier included in the present invention is an agent that has the effect of interfering with the hydrogen bonds formed by the hydroxyl groups contained in the glucopyranose skeleton that constitutes the nanocellulose, or an agent that has the effect of hydrophobizing the nanocellulose.
  • a nanocellulose modifier it adheres to the surface of the nanocellulose such that the nanocellulose modifier physically blocks the surface hydroxyl groups of the nanocellulose from contact with adjacent nanocelluloses, thereby:
  • the effect of hydrogen bonding between adjacent nanocellulose hydroxyl groups can be substantially weakened.
  • the nanocellulose modifier may also contain functional groups that chemically bond with hydroxyl and carboxy groups on the surface of the nanocellulose so as to prevent the formation of hydrogen bonds between the hydroxyl groups of different nanocelluloses.
  • nanocellulose modifiers include cationic surfactants; silicon atom-containing hydrophobizing agents; sugars such as saccharin, saccharose and trehalose; polyamine compounds; cations; , a combination of anionic and nonionic surfactants; Berocell 587K, 584, 509, 509HA and 614 from EKA Chemical Inc. (Marietta GA) and EMCOL CC-42 from Witco Chemical Inc. (Greenwich, Connecticut) (i.e., poly[oxy(methyl-1,2-ethanediyl)], a-[2-(diethylmethylammonio)methylethyl]-w-hydroxychloride) and Quake 3190 and 2028 from Herculer Inc.
  • kalamazoo commercial compounds commonly known in the paper manufacturing industry as fluff pulp debonders
  • Amide compounds such as N-methyl- ⁇ -valerolactam, ⁇ -caprolactam, N-methyl- ⁇ -caprolactam, N-acetyl- ⁇ -caprolactam, undecanelactam and laurolactam
  • glycols sulfoxides; halogenated acetic acids
  • Polyphenol urea; formamide
  • alkalis such as sodium hydroxide, potassium hydroxide, lithium hydroxide, beryllium hydroxide, calcium oxide, sodium silicate, sodium carbonate
  • Inorganic acids such as pyrophosphoric acid, primary chlorous acid perchlorate, chlorous acid, nitrous acid, and sulfurous acid
  • salts such as lithium chloride, calcium thiocyanate, ammonium thiocyanate, and sodium thi
  • nanocellulose modifiers it is preferable to include cationic surfactants and silicon atom-containing hydrophobizing agents, and it is more preferable to include them in combination.
  • the cationic surfactant contained in the present invention can suppress aggregation due to hydrogen bonding between nanocelluloses in fiber materials and composite materials.
  • the cationic surfactant has the effect of suppressing aggregation of nanocellulose in the fiber material after the drying process described below.
  • Cationic surfactants include primary to tertiary amine salts and quaternary ammonium salts. These may be used individually by 1 type, and may be used in combination of 2 or more type. It should be noted that the primary to tertiary "amine salts" may be in either the form of an amine or the form of an ammonium salt, or may be in both forms. means.
  • amines and ammonium salts tend to coexist before reacting with nanocellulose, and tend to become ammonium salts after reacting with nanocellulose.
  • Cationic surfactants include primary to tertiary amine salts having a long-chain alkyl group preferably having a carbon number (C number) of 1 to 40, more preferably 2 to 20, and still more preferably 8 to 18.
  • C number carbon number
  • quaternary ammonium salts can be suitably used. It can be assumed that the larger the number of carbon atoms, the higher the effect of suppressing aggregation due to hydrogen bonding between adjacent nanocelluloses.
  • the salt is not particularly limited, and examples thereof include chlorides, bromides, and the like.
  • the amount of cationic surfactant compounded is not particularly limited, but it is usually in the range of 0.1 to 2.5 parts by weight per 1 part by weight of nanocellulose. preferable.
  • the mass ratio is 0.1 times or more, it is possible to act on the carboxyl groups on the nanocellulose surface, suppress reaggregation of nanocellulose, and tend to obtain a good fibrillation state in the thermoplastic resin. . If the mass ratio exceeds 2.5 times, the amount of surfactant in the composite tends to be large, resulting in deterioration of workability and various physical properties of the composite material.
  • the cationic surfactant may range from 0.1 to 1.0 parts by weight per part by weight of nanocellulose.
  • the silicon atom-containing hydrophobizing agent suppresses aggregation due to hydrogen bonding between nanocelluloses in the composite material.
  • a silicon atom-containing hydrophobizing agent is used as a nanocellulose surface treatment agent to hydrophobize nanocellulose.
  • the nanocellulose aqueous dispersion exists as nanocellulose in a state in which some of the hydroxyl groups are carboxylated and defibrated by charge repulsion. Nano cellulose is aggregated again by hydrogen bonding.
  • the silicon atom-containing hydrophobizing agent binds to hydroxyl groups of nanocellulose in the composite material, or suppresses hydrogen bonding between nanocelluloses in the composite material by being present between adjacent nanocelluloses.
  • silicon atom-containing hydrophobizing agents are excellent in adhesion to thermoplastic resins in composite materials. This is because the functional group of the silicon atom-containing hydrophobizing agent chemically bonds with the thermoplastic resin.
  • the silicon atom-containing hydrophobizing agent can be selected according to the type of thermoplastic resin used in the composite material, having an appropriate functional group that easily bonds with the thermoplastic resin.
  • silicon atom-containing hydrophobizing agents examples include alkylalkoxysilanes, alkoxysilanes, and halogenated organosilanes.
  • Specific examples of silicon atom-containing hydrophobizing agents include organosilanes comprising silane compounds having two or more hydroxyl groups or alkoxy groups in one molecule represented by the following formula (1) and/or partial hydrolysis condensates thereof. compounds, organosilazane compounds, and the like. These may be used singly or in combination of two or more.
  • the organosilane compound includes a silane compound having two or more hydroxyl groups or alkoxy groups represented by the following formula (1) in one molecule and/or a partially hydrolyzed condensate thereof.
  • R2mSi(OR1) 4-m ( 1 ) (In formula (1), R 1 is a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms, R 2 is an unsubstituted or substituted hydrocarbon group having 1 to 10 carbon atoms, and m is 0. , 1 or 2.)
  • m may be 1 or 2.
  • the organosilane compound in which m is 2 is more than the organosilane compound in which m is 1. It is preferable to mix them.
  • R 1 is a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms, such as methyl, ethyl, propyl and butyl. Among these, a methyl group and an ethyl group are preferable.
  • OR 1 is a hydrolyzable group and can chemically bond with the hydroxyl group of nanocellulose. Furthermore, in the above formula (1), OR 1 can also form a chemical bond with metal fillers and inorganic fillers that can be blended in the composite material.
  • R 2 is an unsubstituted or substituted hydrocarbon group having 1 to 10 carbon atoms.
  • Substituents include, for example, amino groups, epoxy groups, unsaturated groups, and (meth)acryl groups.
  • the hydrocarbon group may be linear, branched, or cyclic (including heterocyclic). Examples of the hydrocarbon group include alkyl groups such as methyl group, ethyl group, propyl group, butyl group, hexyl group and octyl group, cycloalkyl groups such as cyclohexyl group, vinyl group, allyl group, propenyl group and butenyl group.
  • R 2 can chemically bond with the thermoplastic resin that forms the matrix of the composite material.
  • organosilazane compounds include hexamethyldisilazane and 1,3-divinyl-1,1,3,3-tetramethyldisilazane.
  • the amount of the silicon atom-containing hydrophobizing agent is usually preferably 0.05 parts by mass or more, more preferably 0.05 parts by mass or more and 30.0 parts by mass or less, relative to 1 part by mass of nanocellulose. preferable.
  • the amount of the silicon atom-containing hydrophobizing agent is preferably 30.0 parts by mass or less, more preferably 0.05 parts by mass or more and 30.0 parts by mass or less per 100 parts by mass of the thermoplastic resin. .
  • the amount of the silicon atom-containing hydrophobizing agent is 0.05 parts by mass or more, reaggregation due to hydrogen bonding between nanocelluloses tends to be suppressed.
  • both an organosilane compound (M2) in which m is 2 in the above formula (1) and an organosilane compound (M1) in which m is 1 in the above formula (1) are blended in a thermoplastic resin as silicon atom-containing hydrophobizing agents.
  • the mass ratio (M2:M1) of the blending amounts of both compounds can be 4:1.
  • the organosilane compound in which m is 1 in the above formula (1) can be 0.05 to 0.5 parts by mass with respect to 1 part by mass of nanocellulose in the composite material.
  • the organosilane compound in which m is 2 in the above formula (1) can be 0.2 to 2.0 parts by mass with respect to 1 part by mass of nanocellulose in the composite material.
  • the water-soluble solvent used in the present invention refers to a solvent that is soluble in water.
  • the water-soluble solvent can inhibit reaggregation of nanocellulose after dehydration and drying by preventing hydrogen bonding between nanocelluloses even after the aqueous solvent is removed in the drying step described later.
  • the water-soluble solvent functions as a displacing agent for the aqueous solvent of the nanocellulose dispersion. In addition, the disentanglement of nanocellulose in the mixing step can be facilitated.
  • the water-soluble solvent used in the present invention preferably has a boiling point of 100° C. or more and 300° C. or less under 1 atmosphere, and a solubility of 20 g or more in 100 g of water at 20° C., and a boiling point of 1 atmosphere. is 150° C. or more and 250° C. or less, and the amount dissolved in 100 g of water at 20° C. is more preferably 50 g or more.
  • water-soluble solvents examples include 1,2-butanediol, ethylene glycol, dipropylene glycol dimethyl ether, 3-methoxy-3-methyl-1-butanol, propylene glycol monomethyl ether, diethylene glycol, triethylene glycol, propylene glycol, Neopentyl glycol, glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, diglycerin, N-methylpyrrolidone, diethylene glycol monoethyl acetate, diethylene glycol monobutyl ether and the like. These water-soluble solvents can be used alone or in combination of two or more.
  • the blending amount of the water-soluble solvent is preferably in the range of 2.0 to 20.0 parts by mass per 1 part by mass of nanocellulose.
  • the mass ratio of the water-soluble solvent is 2.0 times or more, there is a tendency that nanocellulose can be defibrated when the fibrous material after the drying process described below is used to form a composite with a thermoplastic resin.
  • the mass ratio of the water-soluble solvent is 20.0 times or more, there is a tendency that the processing becomes difficult at the time of compositing.
  • the blending amount of the water-soluble solvent may be in the range of 2.5 to 10.0 parts by mass with respect to 1 part by mass of nanocellulose, and is 2.5 parts by mass or more and less than 10.0 parts by mass. good too.
  • thermoplastic resins include polyolefins such as polyvinyl chloride, polyvinylidene chloride, polyvinyl acetate, polystyrene, polyethylene, and polypropylene; acrylic resins such as polyacrylic acid and polymethacrylic acid; polyamides, polyethylene terephthalate, polylactic acid, and polyurethane; , rubber-modified styrenic resins, polycarbonates, and the like. These can be used individually or in combination of 2 or more types. When two or more resins are used in combination, a mixture of these different resins, a melt blend of different resins, or a copolymer can be used.
  • thermoplastic resins examples may include resins commonly called thermoplastic elastomers.
  • Thermoplastic elastomers can be roughly divided into styrene (TPS: SBS (styrene-butylene-styrene block copolymer), SEBS (styrene-ethylene-butylene-styrene), olefin (TPO), vinyl chloride (TPVC), and urethane (TPU).
  • TPS styrene
  • SEBS styrene-ethylene-butylene-styrene
  • TPO olefin
  • TPVC vinyl chloride
  • TPU urethane
  • ester type (TPEE), amide type (TPAE), etc. can be used alone or in combination of two or more.
  • TPEE ester type
  • TPAE amide type
  • the thermoplastic resin may contain polar and reactive functional groups, such as epoxy groups, anhydride groups, amino groups, cyanate groups, carboxyl groups, to enhance interaction with the cationic surfactant-treated nanocellulose. It may also be a modified thermoplastic resin having reactive functional groups selected from groups and combinations thereof. Examples of such thermoplastic resins include maleic anhydride-modified polyolefins, maleic anhydride-modified linear low-density polyethylene (modified LLDPE), and maleic anhydride-modified polypropylene. .
  • the thermoplastic resin may be recycled plastic that is recycled from discarded plastic after being used.
  • recycled plastics include thermoplastic resins obtained by sorting, washing, pulverizing, and pelletizing waste plastics such as food containers, beverage containers, and trays.
  • the polyolefin resin component of the recycled plastic may be 80% by mass or more, and may be 90% by mass or more.
  • the main resin may be 50% by mass or more, more preferably 70% by mass or more, and particularly 80% by mass or more.
  • Additives such as antioxidants, plasticizers and flame retardants may be added to the thermoplastic resin as long as the effects of the present invention are not impaired.
  • the fiber material of the present invention is produced by, for example, preparing a dispersion containing nanocellulose, a nanocellulose modifier, and a water-soluble solvent dispersed in an aqueous solvent, drying the dispersion, and removing the dispersion from the dispersion. It can be produced by a production method including a step of obtaining a fibrous material by removing the aqueous solvent (hereinafter also referred to as a drying step).
  • the nanocellulose used in the production method may not be dispersed in an aqueous solvent, and may be in a dried form, for example.
  • the drying process is the process of removing the aqueous solvent from the dispersion to obtain the fiber material.
  • a method for removing the aqueous solvent from the dispersion a known method can be used.
  • the dispersion may be dried by heating or by a spray drying method.
  • the CNF dispersion may be poured into a container (such as a vat) and the container placed in an oven at 30°C to 100°C to evaporate the aqueous solvent.
  • the aqueous solvent may be completely removed from the dispersion, or a small amount of the aqueous solvent may remain to the extent that it can be removed in the later-described mixing step. Note that the drying step may be omitted when dry nanocellulose is used (that is, it does not contain an aqueous solvent).
  • the process of preparing the dispersion can also be performed using oxidized cellulose before nanoization.
  • the nanocellulose contained in the present invention is obtained by oxidizing a cellulosic raw material with hypochlorous acid or a salt thereof, and the oxidized cellulose obtained by the above oxidation has excellent fibrillation properties, and a shearing force is applied by stirring or the like. This makes it easy to nanoize. Therefore, the dispersion can be obtained by using oxidized cellulose instead of nanocellulose.
  • One aspect of the present invention is a method of producing the fibrous material of the present invention using oxidized cellulose.
  • the oxidized cellulose is defibrated by stirring a first mixture containing oxidized cellulose and materials other than the nanocellulose of the fibrous material of the present invention. and obtaining a second mixture containing nanocellulose, and optionally a drying step of removing the aqueous solvent from the second mixture.
  • the oxidized cellulose is stirred and a material other than the nanocellulose of the fiber material is continuously added to defibrate the oxidized cellulose and obtain nanocellulose. and, optionally, a drying step of removing the aqueous solvent from the second mixture.
  • the oxidized cellulose contains an oxide of a cellulosic raw material by hypochlorous acid or a salt thereof, and does not substantially contain an N-oxyl compound.
  • nanocellulose, oxidized cellulose, and fibrous material are as described above.
  • Materials other than nanocellulose in the fiber material are materials other than nanocellulose that can be contained in the fiber material, such as nanocellulose modifiers and water-soluble solvents, but are not limited to these.
  • continuous addition of materials means performing in succession the pulverization of oxidized cellulose by stirring and the addition of materials.
  • a specific embodiment in which stirring and addition are performed in series includes, for example, a mode in which the oxidized cellulose is stirred to make it finer and the above materials are added in one pot; Mode of adding material; and the like, but not limited to these.
  • the fiber material obtained by the drying process contains nanocellulose, a nanocellulose modifier, and a water-soluble solvent.
  • the nanocellulose modifier suppresses aggregation due to hydrogen bonding between nanocelluloses in the fibrous material.
  • a water-soluble solvent facilitates dispersion of nanocellulose in the mixing step described later. Therefore, by using the fiber material in the mixing step described later, the nanocellulose can be combined with the thermoplastic resin without aggregating. Moreover, since most of the water-based solvent has been removed from the fibrous material, the later-described mixing step can be carried out even if the thermoplastic resin is not an emulsion.
  • the aqueous solvent may not be completely removed in the drying step, and a small amount of the aqueous solvent may remain.
  • the composite material of the present invention can be produced by a step of mixing a fibrous material with a thermoplastic resin to obtain a composite material (also referred to as a mixing step).
  • a high shearing force is applied to the thermosetting resin, and the elastic restoring force of the thermosetting resin is utilized to defibrate the nanocellulose and disperse it in the thermosetting resin.
  • Examples of the method of applying a high shearing force to the thermosetting resin in the mixing step include a method of kneading using an elastic kneader such as an open roll or closed kneader, an extruder, an injection molding machine, or the like.
  • the kneading process using the open roll method will be described below.
  • the kneading step using the open roll method can be performed with reference to JP-A-2021-014510.
  • the fibrous material in the mixing step is preferably mixed so that 0.5 to 120 parts by mass of nanocellulose is mixed with 100 parts by mass of the thermoplastic resin.
  • the temperature at which the processing region appears in the storage elastic modulus of the composite material near the melting point (Tm ° C.) of the thermoplastic resin is increased by 1 from the flat region appearance temperature (T3 ° C.) in the storage elastic modulus.
  • the kneading temperature is in the range of 0.06 times (T3 ° C. ⁇ 1.06) and the roll interval is set to more than 0 mm and 0.5 mm or less using an open roll.
  • the kneading temperature can be set from the storage elastic modulus using the glass transition point instead of the melting point.
  • an apparatus for melting and molding a thermoplastic resin such as an open roll, a closed kneader, an extruder, an injection molding machine, etc., can be used, but the method using an open roll will be explained. do.
  • the surface speed ratio (V1/V2) between the two in this step can be 1.05 to 3.00. .
  • the desired high shear force can be obtained.
  • the mixture extruded from such a narrow roll gap has moderate elasticity at the kneading temperature and has a moderate viscosity in the temperature range, so the restoring force due to the elasticity of the thermoplastic resin is large.
  • the nanocellulose can be greatly moved along with the deformation of the thermoplastic resin at that time. The rubber elastic region will be described later.
  • the kneading temperature is the surface temperature of the mixture in the low temperature kneading step, not the set temperature of the processing equipment. It is desirable to measure the actual surface temperature of the resin as much as possible for the kneading temperature, but if it cannot be measured, measure the surface temperature of the resin immediately after taking out the composite material from the processing equipment, and use that temperature as the kneading temperature during processing. be able to. For open rolls, the surface temperature can be measured using a non-contact thermometer on the mixture wrapped around the first roll.
  • the low-temperature kneading step is a flat region from a temperature near the melting point (a flat region where the storage elastic modulus (E') hardly decreases even after the melting point in the results of a dynamic viscoelasticity test (hereinafter referred to as a DMA test), That is, by using up to a part of the rubber elastic region like an elastomer), nanocellulose, which tends to aggregate, is defibrated so as to be loosened and dispersed in a thermoplastic resin.
  • a DMA test a dynamic viscoelasticity test
  • the kneading temperature range in the low-temperature kneading step is preferably lower than the boiling point of the water-soluble solvent.
  • the residual amount of the water-soluble solvent in the low-temperature kneading step can be 20% by mass or less with respect to the amount of the water-soluble solvent in the nanocellulose dispersion.
  • the fiber material in the mixing step may be mixed so that the nanocellulose is usually 0.5 parts by mass to 120 parts by mass with respect to 100 parts by mass of the thermoplastic resin, and may be 1 part by mass or more and less than 50 parts by mass. It may be 5 parts by mass to 30 parts by mass.
  • the fiber material in the mixing step may be mixed so that the water-soluble solvent is 500 parts by mass or less with respect to 100 parts by mass of the thermoplastic resin.
  • the mixing ratio of the mixture obtained in the first kneading step and the thermoplastic resin in the second kneading step may be adjusted so that the composite material of the present invention has a desired nanocellulose concentration.
  • the amount of nanocellulose may be in the range of more than 0.1 parts by mass and 50 parts by mass or less.
  • the second kneading step can use a known molding machine such as an open roll, closed kneading machine, extruder, injection molding machine that can be used in the first kneading step.
  • a known molding machine such as an open roll, closed kneading machine, extruder, injection molding machine that can be used in the first kneading step.
  • the same molding machine as used in the process may be used.
  • the mixture obtained in the first kneading step and, if necessary, the thermoplastic resin are put into the above-described known molding machine and molded.
  • a general processing temperature for thermoplastic resins can be selected.
  • the water-soluble solvent is removed at a temperature below the decomposition temperature of nanocellulose (confirmed by thermogravimetric/differential calorimetric analysis) and at a temperature at which the water-soluble solvent can be sufficiently evaporated. It can also be carried out by repeating kneading.
  • the heat treatment in the removal step can be accelerated, for example, by reducing pressure.
  • cellulose As a system raw material, 50 g of pulp powder (VP-1) manufactured by TDI Co., Ltd. was added. After supplying the cellulosic raw material, while maintaining the temperature at 30°C in the same constant temperature water bath, the pH during the reaction was adjusted to 11 while adding 48% by mass sodium hydroxide, and the mixture was stirred under the same conditions with a stirrer for 2 hours. did After completion of the reaction, centrifugation (1000 G, 10 minutes), decantation, and addition of pure water in an amount corresponding to the removed liquid were repeated to recover oxidized cellulose (solid concentration: 13%). Here, the solid content concentration was calculated by drying the obtained oxidized cellulose at 110° C.
  • the oxidized cellulose of Production Example 1 had a carboxy group content of 0.7 mmol/g and a degree of polymerization of 89.
  • the liberated iodine was titrated with a 0.1 mol/L sodium thiosulfate solution (indicator, starch test solution), and the titration amount was 34.55 ml.
  • a blank test was performed separately and corrected. Since 1 ml of 0.1 mol/L sodium thiosulfate solution corresponds to 3.545 mg Cl, the effective chlorine concentration in the sodium hypochlorite aqueous solution is 21% by mass.
  • solid-state 13 C-NMR of a sample left at 23° C. and 50% RH for 24 hours or more was measured. It was confirmed to have a structure in which the hydroxyl group at the position was oxidized and a carboxyl group was introduced. Measurement conditions for solid-state 13 C-NMR are shown below.
  • the degree of polymerization was measured by the following method. (Measurement of viscosity average degree of polymerization) Oxidized cellulose was added to an aqueous solution of sodium borohydride adjusted to pH 10, and reduction treatment was performed at 25° C. for 5 hours. The amount of sodium borohydride was 0.1 g per 1 g of oxidized cellulose fibers. After the reduction treatment, solid-liquid separation and water washing were performed by suction filtration, and the obtained oxidized cellulose fibers were freeze-dried. After adding 0.04 g of dried oxidized cellulose fiber to 10 ml of pure water and stirring for 2 minutes, 10 ml of 1M copper ethylenediamine solution was added and dissolved.
  • Example 1 (Preparation of fiber material) The oxidized cellulose (13%) of Production Example 1 was diluted with water to form a 0.1-1% aqueous dispersion. Dimethoxydimethylsilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-22: described as "OS" in the table) is added to the aqueous dispersion as a nanocellulose modifier, and stirred using a stirrer or propeller stirrer. to obtain a mixture.
  • Dimethoxydimethylsilane manufactured by Shin-Etsu Chemical Co., Ltd., KBM-22: described as "OS” in the table
  • Diethylene glycol (denoted as “DEG” in the table) as a water-soluble solvent and monododecylamine (denoted as “MDA” in the table) as a nanocellulose modifier were further added to the above mixture, and "TK Robomix” manufactured by Primix Co., Ltd. was stirred at 10,000 rpm for 10 minutes. As a result, the oxidized cellulose was fibrillated to obtain an aqueous dispersion containing nanocellulose. Commercially available diethylene glycol and monododecylamine were used. The aqueous dispersion containing nanocellulose was analyzed by the following [method for measuring fiber length and fiber width], and the nanocellulose had an average fiber length of 154 nm and an average fiber width of 3.4 nm.
  • a fiber material A was obtained by pouring a nanocellulose aqueous dispersion into a vat, heating a ventilated oven to 50° C., and drying for 24 hours to remove water.
  • the composition of fiber material A is as shown in Table 1.
  • a ratio is a ratio when the mass of nanocellulose is set to 1.
  • a kneader manufactured by Toyo Seiki Seisakusho was set at 127° C., and the ABS resin was added to start kneading.
  • the fiber material obtained in the above (preparation of fiber material) was gradually added thereto and kneaded so that the torque did not exceed 200 Nm.
  • a masterbatch of nanocellulose and ABS was thus obtained.
  • the kneader used was Laboplastomill 10S100 with a mixer R60H and a roller type. The temperature of 127 ° C.
  • thermoplastic resin (here, ABS resin) to be kneaded. , heating rate: 2°C/min).
  • Example 2 The procedure was carried out in the same manner as in Example 1, except that the amount of the oxidized cellulose aqueous dispersion was adjusted so that the nanocellulose content was as shown in Table 3.
  • the TEMPO-oxidized nanocellulose used for the fiber material B was prepared as follows.
  • As a cellulosic raw material the same pulp powder as in Production Example 1 was prepared. 0.16 g of TEMPO and 1.0 g of sodium bromide were placed in a beaker, pure water was added and stirred to form an aqueous solution, and 10.0 g of pulp powder was added. After heating the above aqueous solution to 25° C. in a constant temperature water bath while stirring with a stirrer, 0.1 M sodium hydroxide was added and stirred to obtain an aqueous solution with a pH of 10.0.
  • Pure water was added to this oxidized cellulose to prepare a dispersion with a concentration of 2% by mass, followed by 20 passes at 200 MPa with an ultra-high pressure homogenizer "Starburst Lab” manufactured by Sugino Machine Co., Ltd. to obtain an aqueous dispersion of nanocellulose. rice field.
  • an ultra-high pressure homogenizer "Starburst Lab” manufactured by Sugino Machine Co., Ltd. to obtain an aqueous dispersion of nanocellulose. rice field.
  • defibration was advanced by circulating the oxidized cellulose aqueous dispersion through a built-in ultrahigh-pressure disentanglement unit. One pass of liquid passing through the fibrillation section is called one pass.
  • the contained nanocellulose had an average fiber length of 860 nm and an average fiber width of 3.6 nm.
  • a composite material was prepared using the fiber material B in the same manner as in Example 1 (composite material preparation by two-stage kneading).
  • Comparative Example 2 The procedure was carried out in the same manner as in Comparative Example 1, except that the addition amount of the TEMPO-oxidized nanocellulose aqueous dispersion was adjusted so that the nanocellulose content was as shown in Table 3.
  • Comparative Example 3 The composite material of Comparative Example 3 was produced with reference to WO2020/184177. Specifically, it was produced by the following procedure. 0.52 g of 0.5M hydrochloric acid was added to 36.9 g of the dispersion liquid containing nanocellulose obtained from the oxidized cellulose of Production Example 1 and stirred to precipitate nanocellulose. 0.034 g of monododecylamine (including 5 g of ethanol, the same shall apply hereinafter) and 4.13 g of pure water are added thereto, stirred, filtered, and filtered while washing with 10 g of pure water in this order to convert nanocellulose into amine. reacted.
  • monododecylamine including 5 g of ethanol, the same shall apply hereinafter
  • the impact strength preferably exceeds 20 kJ/m 2 , and more preferably exceeds 25 kJ/m 2 .
  • Reference Example 1 in the table is the result of a test piece obtained from ABS resin.
  • CNF-1 refers to nanocellulose obtained from the oxidized cellulose of Production Example 1
  • CNF-2 refers to TEMPO-oxidized nanocellulose.
  • MDA monododecylamine
  • DEG diethylene glycol ABS: polymer alloy composed of acrylonitrile, butadiene and styrene OS: dimethoxydimethylsilane
  • MDA, DEG, ABS and OS were used.

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US12163282B2 (en) * 2022-07-29 2024-12-10 Zhejiang A & F University Powder-assembled composite micro-nano fiber and preparation method thereof
WO2025058020A1 (ja) * 2023-09-15 2025-03-20 東亞合成株式会社 変性セルロース

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2017193814A (ja) * 2016-04-13 2017-10-26 関東電化工業株式会社 セルロースナノファイバーの分散液およびその製造方法
WO2018230354A1 (ja) * 2017-06-16 2018-12-20 東亞合成株式会社 セルロースナノファイバーの製造方法
WO2020066537A1 (ja) * 2018-09-26 2020-04-02 森　良平 セルロースナノファイバー（ｃｎｆ）およびそれを含む複合材料の製造方法
JP2021014510A (ja) * 2019-07-11 2021-02-12 株式会社富山環境整備 複合材料及び複合材料の製造方法

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Publication number Priority date Publication date Assignee Title
JP2017193814A (ja) * 2016-04-13 2017-10-26 関東電化工業株式会社 セルロースナノファイバーの分散液およびその製造方法
WO2018230354A1 (ja) * 2017-06-16 2018-12-20 東亞合成株式会社 セルロースナノファイバーの製造方法
WO2020066537A1 (ja) * 2018-09-26 2020-04-02 森　良平 セルロースナノファイバー（ｃｎｆ）およびそれを含む複合材料の製造方法
JP2021014510A (ja) * 2019-07-11 2021-02-12 株式会社富山環境整備 複合材料及び複合材料の製造方法

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US12163282B2 (en) * 2022-07-29 2024-12-10 Zhejiang A & F University Powder-assembled composite micro-nano fiber and preparation method thereof
WO2025058020A1 (ja) * 2023-09-15 2025-03-20 東亞合成株式会社 変性セルロース

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