WO2022118883A1 - Particules de cellulose poreuse et procédé de production associé - Google Patents

Particules de cellulose poreuse et procédé de production associé Download PDF

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WO2022118883A1
WO2022118883A1 PCT/JP2021/044097 JP2021044097W WO2022118883A1 WO 2022118883 A1 WO2022118883 A1 WO 2022118883A1 JP 2021044097 W JP2021044097 W JP 2021044097W WO 2022118883 A1 WO2022118883 A1 WO 2022118883A1
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cellulose
cellulose particles
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water
alcohol
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Japanese (ja)
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貢平 山田
知也 和田
和友 大崎
祐輝 林
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花王株式会社
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B1/00—Preparatory treatment of cellulose for making derivatives thereof, e.g. pre-treatment, pre-soaking, activation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B1/00—Preparatory treatment of cellulose for making derivatives thereof, e.g. pre-treatment, pre-soaking, activation
    • C08B1/08—Alkali cellulose
    • 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
    • C08J3/12—Powdering or granulating
    • C08J3/16—Powdering or granulating by coagulating dispersions

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  • the present invention relates to cellulose particles and a method for producing the same.
  • Spherical particles are used in cosmetics, for example, to improve slipperiness.
  • Patent Document 1 describes a step of supplying a cellulose solution into an air stream of a gas inert to the cellulose solution to atomize the cellulose solution into fine particles in a gas phase; and a liquid.
  • Patent Document 2 describes a step of supplying a cellulose solution into an air stream of a gas inert to the cellulose solution to atomize the cellulose solution into fine particles in a gas phase; and a liquid.
  • a method for producing regenerated cellulose spherical particles is described, which comprises a step of bringing droplets into contact with a coagulating liquid to form regenerated cellulose spherical particles.
  • Patent Document 2 describes a step of cooling a cellulose dope prepared by mixing an alkaline aqueous solution and a raw material cellulose powder to a temperature lower than -12 ° C., and after the step of cooling.
  • a method for producing porous cellulose beads is described, which comprises a step of adjusting the cellulose dope to a temperature higher than 15 ° C.
  • the present invention comprises a step of mixing a water-in-oil emulsion containing cellulose and an alcohol having an octanol / water partition coefficient of 0.5 or more to precipitate the cellulose to obtain cellulose particles.
  • the present invention also relates to cellulose particles having a sphericity of 0.80 or more and a pore volume of 0.3 mL / g or less.
  • FIG. 1 It is a figure which shows the appearance and the SEM image of the fracture surface of the cellulose particle obtained in Example 1.
  • FIG. 1 shows the appearance and the SEM image of the fracture surface of the cellulose particle obtained in Example 1.
  • Patent Document 1 has a problem in terms of simplicity, and it cannot be said that the method of Patent Document 2 has been sufficiently studied from the viewpoint of spherical shape.
  • One embodiment of the present invention relates to providing a production method capable of easily producing cellulose particles having a high degree of sphericity.
  • the present inventors have been able to provide a production method capable of easily producing cellulose particles having a high degree of sphericity by contacting a specific alcohol with a water-in-oil emulsion of cellulose to precipitate cellulose. I found it.
  • one embodiment of the present invention relates to the following [1] and [2].
  • [1] Cellulose particles comprising a step of mixing a water-in-oil emulsion containing cellulose and an alcohol having an octanol / water partition coefficient of 0.5 or more and precipitating the cellulose to obtain cellulose particles. Production method.
  • [2] Cellulose particles having a sphericity of 0.80 or more and a pore volume of 0.3 mL / g or less.
  • a water-in-oil emulsion containing cellulose and an alcohol having an octanol / water partition coefficient ClogP of 0.5 or more are mixed to precipitate the cellulose.
  • a water-in-oil emulsion containing cellulose and an organic solvent is mixed with an alcohol having an octanol / water partition coefficient ClogP of 0.5 or more to obtain the cellulose. It includes a step of precipitating to obtain cellulose particles.
  • the method for producing cellulose particles according to the embodiment of the present invention preferably includes the following steps (A) to (C) in this order.
  • the octanol / water partition coefficient ClogP refers to a scale showing the distribution of a substance between the octanol phase and the water phase, and is an index showing the hydrophobicity of a chemical substance.
  • ClogP represents the calculated value of the octanol-water-partition coefficient (logP) defined by the following formula, which is obtained according to ChemDraw Professional 19.1. Of Perkin Elmer.
  • logP log ([substance] octanol / [substance] water)
  • [substance] octanol indicates the molar concentration of the substance in the 1-octanol phase
  • [substance] water indicates the molar concentration of the substance in the aqueous phase.
  • the step (A) is a step of mixing an alkaline aqueous solution and cellulose to obtain a cellulose aqueous solution in which cellulose is dissolved in the alkaline aqueous solution.
  • the “cellulose-dissolved” state means a state in which the aqueous cellulose solution is visually transparent, and a part of the cellulose may be in a dispersed state.
  • raw material cellulose chemically pure cellulose
  • wood such as various wood chips, pruned branches of various trees, thinned wood, branch wood, construction waste wood, factory waste wood
  • wood pulp produced from wood, fibers around cotton seeds Pulps such as cotton linter pulp obtained from; Papers such as newspapers, cardboards, magazines, and high-quality papers; Plant stems and leaves such as rice straw and corn stalks; Various celluloses such as rice husks, palm husks, and coconut husks.
  • the contained raw material can be used.
  • wood such as various wood chips, pruned branches of various trees, thinned wood, branch wood, construction waste, and factory waste; Pulps such as wood pulp produced from wood and cotton linter pulp obtained from the fibers around cotton seeds are preferred.
  • the shape of the raw material cellulose include powder, sheet, and cotton. Among these, it is preferably in the form of powder from the viewpoint of excellent solubility in an alkaline aqueous solution.
  • the degree of polymerization of the raw material cellulose is preferably 1000 or less, more preferably 500 or less, still more preferably 300 or less from the viewpoint of improving the solubility in an alkaline aqueous solution, and the mechanical strength and sphericity of the obtained cellulose particles can be determined. From the viewpoint of further improvement, it is preferably 10 or more, more preferably 50 or more, still more preferably 100 or more, still more preferably 150 or more.
  • the average diameter equivalent to the circumference circle of the raw material cellulose is preferably 1 ⁇ m or more, more preferably 2 ⁇ m or more, still more preferably 5 ⁇ m or more, still more preferably, from the viewpoint of handleability and productivity.
  • Is 10 ⁇ m or more and is preferably 500 ⁇ m or less, more preferably 300 ⁇ m or less, still more preferably 200 ⁇ m or less, still more preferably 100 ⁇ m or less, from the viewpoint of improving the solubility in an alkaline aqueous solution.
  • the perimeter-equivalent diameter according to the present embodiment is the diameter of a circle having the same perimeter as the perimeter of the particles.
  • the perimeter circle equivalent average diameter according to the present embodiment is a number average value of the perimeter circle equivalent diameters of 50 randomly selected particles.
  • the diameter equivalent to the perimeter circle of the particles can be calculated from an electron microscope (SEM) image using, for example, image analysis type particle size distribution measurement software Mac-View ver.4.
  • the alkaline aqueous solution according to the present embodiment is not particularly limited as long as it exhibits alkalinity and can dissolve cellulose.
  • “can dissolve cellulose” means, for example, that cellulose is mixed with an alkaline aqueous solution in an amount such that the concentration becomes a 4% by mass solution, and the dissolution can be visually confirmed.
  • Examples of the basic compound in the alkaline aqueous solution according to the present embodiment include alkali metal hydroxides such as sodium hydroxide, potassium hydroxide and lithium hydroxide; and tertiary amines such as trimethylamine and triethylamine.
  • alkali metal hydroxides are preferable, at least one selected from sodium hydroxide and potassium hydroxide is more preferable, and sodium hydroxide is further preferable from the viewpoint of availability.
  • the above basic compounds can be used alone or in combination of two or more.
  • the concentration of the basic compound in the alkaline aqueous solution is preferably 5% by mass or more, more preferably 6% by mass or more, further preferably 7% by mass or more, and preferably 20% by mass from the viewpoint of improving the solubility of cellulose. Below, it is more preferably 15% by mass or less, further preferably 12% by mass or less, still more preferably 10% by mass or less. Further, the concentration of the basic compound in the alkaline aqueous solution may be adjusted so as to be finally within the above range by adding alkaline aqueous solutions having different concentrations separately.
  • the dissolution of cellulose in an alkaline aqueous solution is preferably carried out, for example, by adding cellulose to an alkaline aqueous solution and stirring and mixing.
  • the temperature at which cellulose is dissolved in an alkaline aqueous solution is preferably ⁇ 20 ° C. or higher, more preferably ⁇ 10 ° C. or higher, still more preferably ⁇ 5 ° C. or higher, from the viewpoint of improving the solubility of cellulose without freezing. Yes, preferably 10 ° C. or lower, more preferably 5 ° C. or lower, still more preferably 0 ° C. or lower.
  • the stirring time depends on the scale of production, the concentration of the alkaline aqueous solution, the addition amount, and the temperature, and is appropriately set. Therefore, the stirring time is not particularly limited, and is usually carried out until the cellulose is visually dissolved.
  • the cellulose concentration of the cellulose aqueous solution may be appropriately determined in consideration of the solubility of cellulose, the handleability of the cellulose aqueous solution, the particle size of the target cellulose particles, etc., but is preferably 0.5% by mass or more, more preferably. 1% by mass or more, more preferably 2% by mass or more, and preferably 20% by mass or less, more preferably 15% by mass or less, still more preferably 12% by mass or less, still more preferably 10% by mass or less, still more preferably. It is 8% by mass or less, more preferably 6% by mass or less.
  • the step (B) is a step of mixing the aqueous cellulose solution obtained in the step (A) with an organic solvent to obtain a water-in-oil emulsion of cellulose.
  • the organic solvent preferably excludes alcohols having an octanol / water partition coefficient ClogP of 0.5 or more.
  • a water-in-oil emulsion in which the aqueous cellulose solution is emulsified in the organic solvent can be prepared.
  • the organic solvent is not particularly limited as long as it can prepare a water-in-oil emulsion of an aqueous cellulose solution and can keep the state of the emulsion stable.
  • the octanol / water partition coefficient ClogP of the organic solvent is preferably 0.70 or more, more preferably 0.70 or more, from the viewpoint of obtaining a water-in-oil emulsion in the step (B) and further increasing the sphericality of the obtained cellulose particles. It is 0.90 or more, more preferably 1.0 or more, still more preferably 1.2 or more, still more preferably 2.0 or more, still more preferably 3.0 or more.
  • the upper limit of the octanol / water partition coefficient ClogP of the organic solvent is not particularly limited, but is preferably 6.0 or less, more preferably 5.0 or less, and further, for example, from the viewpoint of solubility in alcohol in the step (C).
  • the organic solvent is a mixed solvent
  • the octanol / water partition coefficient ClogP of the organic solvent can adopt the weighted average value of ClogP of each solvent constituting the mixed solvent.
  • organic solvent examples include aliphatic hydrocarbons such as n-hexane, n-heptane, dichloromethane, dichloroethane and chloroform; alicyclic hydrocarbons such as cyclohexane, methylcyclohexane, cycloheptane and methylcycloheptane; toluene, xylene and the like.
  • Aromatic hydrocarbons such as dichlorobenzene; esters such as ethyl acetate and fatty acid glycerin ester may be mentioned. These organic solvents may be used alone or in combination of two or more.
  • the aliphatic hydrocarbon, the alicyclic hydrocarbon, the aromatic hydrocarbon and the ester also include a partially halogenated halide.
  • the preferred organic solvent is one or more selected from hydrocarbons and esters, which may have a halogen atom.
  • the number of carbon atoms of the hydrocarbon and the ester is preferably 4 or more, more preferably 6 or more, and preferably 22 or less, more preferably 12 or less.
  • aliphatic hydrocarbons having 6 or more and 10 or less carbon atoms aliphatic hydrocarbons having 6 or more and 10 or less carbon atoms
  • alicyclic hydrocarbons having 6 or more and 10 or less carbon atoms aromatic hydrocarbons having 6 or more and 10 or less carbon atoms, and 4 or more and 10 carbon atoms.
  • At least one selected from the following esters is preferred, and at least one selected from ethyl acetate, dichloromethane, chloroform, toluene, dichlorobenzene and n-hexane is more preferred, from dichloromethane, chloroform, toluene, dichlorobenzene and n-hexane.
  • At least one selected is more preferred, at least one selected from dichlorobenzene and n-hexane is even more preferred, and n-hexane is even more preferred.
  • the mixing amount of the organic solvent may be an amount that can sufficiently emulsify the aqueous cellulose solution and may be appropriately determined in consideration of the particle size of the target cellulose particles and the like, but it improves the emulsification stability of the water-in-oil emulsion. From the viewpoint of making the solvent, it is preferably 100 parts by mass or more, more preferably 200 parts by mass or more, still more preferably 300 parts by mass or more, still more preferably 400 parts by mass or more, and preferably 400 parts by mass or more with respect to 100 parts by mass of the cellulose aqueous solution. It is 1000 parts by mass or less, more preferably 800 parts by mass or less, still more preferably 600 parts by mass or less.
  • the surfactant include nonionic surfactants, anionic surfactants and cationic surfactants. Among these, nonionic surfactants are preferable from the viewpoint of further improving the emulsion stability of the water-in-oil emulsion.
  • nonionic surfactant examples include sorbitan fatty acid esters such as sorbitan monooleate, sorbitan monostearate, sorbitan sesquioleate, sorbitan coconut oil fatty acid, sorbitan monopalmitate, sorbitan tristearate, and sorbitan trioleate.
  • sorbitan fatty acid esters such as sorbitan monooleate, sorbitan monostearate, sorbitan sesquioleate, sorbitan coconut oil fatty acid, sorbitan monopalmitate, sorbitan tristearate, and sorbitan trioleate.
  • Polyoxyethylene sorbitan fatty acid esters such as polyoxyethylene sorbitan monooleate and polyoxyethylene sorbitan trioleate; polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene oleyl ether, and polyoxyethylene stearyl ether; Polyoxyethylene glycerin fatty acid ester such as monooleic acid polyoxyethylene glyceryl; polyoxyethylene sorbitol fatty acid ester such as tetraoleic acid polyoxyethylene sorbit; polyoxyethylene cured castor oil; polyglycerin fatty acid ester; sucrose fatty acid ester; poly Examples thereof include ether-modified silicone.
  • At least one selected from polyoxyethylene alkyl ether, sorbitan fatty acid ester, sucrose fatty acid ester and polyether-modified silicone is preferable from the viewpoint of further improving the emulsion stability of the water-in-oil emulsion, and polyoxy At least one selected from ethylene lauryl ether and sorbitan monooleate is more preferable.
  • anionic surfactant examples include an alkylbenzene sulfonate such as sodium alkylbenzene sulfonate; an alkyl sulfate such as sodium alkyl sulfate; and an alkyl ether sulfate such as sodium alkyl ether sulfate.
  • examples of the cationic surfactant include alkyltrimethylammonium chloride and dialkyldimethylammonium chloride.
  • the surfactant may be added to at least one of the cellulose aqueous solution and the organic solvent before mixing, or may be added to the liquid after mixing the cellulose aqueous solution and the organic solvent, but it may be added to the organic solvent before mixing. It is preferable to dissolve it.
  • the amount of the surfactant added is preferably 0.1 part by mass or more with respect to 100 parts by mass of the organic solvent from the viewpoint of improving the emulsion stability of the water-in-oil emulsion. It is more preferably 0.5 parts by mass or more, further preferably 1.0 part by mass or more, and preferably 20 parts by mass or less, more preferably 10 parts by mass or less, still more preferably 5 parts by mass or less.
  • the water-in-oil emulsion of cellulose is preferably prepared, for example, by adding an aqueous solution of cellulose to an organic solvent in which a nonionic surfactant is dissolved and stirring and mixing the mixture.
  • a method of mixing and stirring in a range of ⁇ 20 ° C. or higher and 60 ° C. or lower using a mixer such as a high-speed emulsification / disperser can be mentioned. Since the diameter of the droplets formed becomes smaller as the rotation speed during stirring increases, the rotation speed of the mixer can be appropriately adjusted according to the particle size of the target cellulose.
  • Step (C) is a step of mixing a water-in-oil emulsion and an alcohol having an octanol / water partition coefficient of 0.5 or more to precipitate cellulose and obtain cellulose particles.
  • alcohol and a water-in-oil emulsion are mixed, and the water in the emulsion replaces the solvent, so that cellulose is precipitated and cellulose particles are obtained.
  • the octanol / water partition coefficient ClogP of alcohol is 0.5 or more, preferably 0.6 or more, more preferably 0.7 or more, still more preferably 0.8 or more, from the viewpoint of further increasing the sphericality of the obtained cellulose particles. From the same viewpoint, it is preferably 4.0 or less, more preferably 3.5 or less, still more preferably 3.0 or less, still more preferably 2.5 or less, still more preferably 2.3 or less.
  • the octanol / water partition coefficient ClogP of the alcohol can adopt the weighted average value of the ClogP of each alcohol constituting the mixed alcohol.
  • the octanol / water partition coefficient ClogP of the organic solvent is preferably larger than the octanol / water partition coefficient ClogP of alcohol from the viewpoint of further increasing the sphericality of the obtained cellulose particles, and [octanol / water partition coefficient ClogP of the organic solvent is preferable.
  • ]-[Alcohol octanol / water partition coefficient ClogP] is preferably 0.5 or more, more preferably 1.0 or more, still more preferably 1.5 or more, and from the same viewpoint, preferably 4.5 or less. It is more preferably 4.0 or less, still more preferably 3.5 or less, still more preferably 3.4 or less.
  • the solubility of alcohol in water at 25 ° C. is preferably 0.1 g / 100 mL or more, more preferably 0.3 g / 100 mL or more, still more preferably 0.5 g / 100 mL or more, from the viewpoint of productivity of cellulose particles. From the viewpoint of further increasing the sphericality of the obtained cellulose particles, it is preferably 100 g / 100 mL or less, more preferably 50 g / 100 mL or less, still more preferably 30 g / 100 mL or less, still more preferably 20 g / 100 mL or less.
  • the carbon number of the alcohol is preferably 4 or more, preferably 8 or less, more preferably 7 or less, still more preferably 6 or less, from the viewpoint of further increasing the sphericity of the obtained cellulose particles.
  • the alcohol preferably contains at least one selected from 1-butanol, 2-butanol, 2-methyl-1-propanol, 1-hexanol and 1-pentanol.
  • the mixing amount of the alcohol is preferably 500 parts by mass or more, more preferably 700 parts by mass or more with respect to 100 parts by mass of the water-in-oil emulsion from the viewpoint of suppressing aggregation of the obtained cellulose particles and further increasing the sphericality. It is more preferably 900 parts by mass or more, preferably 2000 parts by mass or less, more preferably 1500 parts by mass or less, still more preferably 1200 parts by mass or less.
  • the acid may be further mixed.
  • the amount of alcohol used can be reduced.
  • the reason for this is considered to be that the discharge of water in the emulsion can be promoted by mixing the acid.
  • the acid may be an inorganic acid or an organic acid, and specifically, it may contain an organic acid, and may contain at least one selected from acetic acid, citric acid, malic acid, lactic acid, and succinic acid. preferable. It is desirable that the acid used in that case be compatible with alcohol.
  • the mixed amount of the acid used is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, still more preferably 30 parts by mass or more, and preferably 70 parts by mass or less, based on 100 parts by mass of the alcohol.
  • the alcohol and the acid may be mixed simultaneously or sequentially with the water-in-oil emulsion, but the alcohol and the acid may be mixed at the same time. It is preferable to do so.
  • the mixing of the alcohol and the water-in-oil emulsion is preferably carried out, for example, by adding the water-in-oil emulsion to the alcohol and stirring and mixing.
  • adding the water-in-oil emulsion to the alcohol it is preferable to add the water-in-oil emulsion in a state where the alcohol is agitated so that the droplets do not bond with each other.
  • the temperature at which the alcohol and the water-in-oil emulsion are mixed is preferably 0 ° C. or higher, more preferably 5 ° C. or higher, still more preferably 15 ° C. or higher, and is preferably 50 ° C. from the viewpoint of further increasing the sphericity. Below, it is more preferably 40 ° C. or lower, still more preferably 30 ° C. or lower.
  • the obtained cellulose particles can be separated and recovered by using known methods such as centrifugation, filtration, decantation, and drying. Further, the recovered cellulose particles may be washed with water, alcohol or the like. The obtained cellulose particles may be classified using a sieve or the like in order to adjust the particle size.
  • Cellulose particles According to the method for producing cellulose particles according to the present embodiment, cellulose particles having a high degree of sphericity can be obtained. Further, according to the method for producing cellulose particles according to the present embodiment, it is not necessary to chemically modify cellulose with an acetyl group or the like, so that cellulose particles having no chemically modifying group can be obtained.
  • the sphericity of the cellulose particles according to the present embodiment is preferably 0.80 or more, more preferably 0.85 or more, still more preferably 0.88 or more, still more preferably 0.90 or more, from the viewpoint of improving slipperiness. Is. The higher the sphericity of the cellulose particles according to the present embodiment, the more preferable it is.
  • the upper limit thereof is not particularly limited, but is, for example, 1.0 or less.
  • the sphericity of the cellulose particles is the number average value of the circularity of 50 randomly selected cellulose particles.
  • the circularity of the cellulose particles can be calculated from an electron microscope (SEM) image using, for example, image analysis type particle size distribution measurement software Mac-View ver.4.
  • the average diameter equivalent to the perimeter circle of the cellulose particles according to the present embodiment is not particularly limited because an appropriate range is selected depending on the application, but is preferably 1 ⁇ m or more, more preferably 1 ⁇ m or more from the viewpoint of handleability and productivity. It is 2 ⁇ m or more, more preferably 5 ⁇ m or more, preferably 300 ⁇ m or less, more preferably 200 ⁇ m or less, still more preferably 100 ⁇ m or less, still more preferably 50 ⁇ m or less, still more preferably 30 ⁇ m or less, still more preferably 20 ⁇ m or less.
  • the method of calculating the average diameter equivalent to the perimeter circle is as described above.
  • the pore volume of the cellulose particles according to the present embodiment can be obtained by the mercury intrusion method described in the examples.
  • the pore volume of the cellulose particles according to the present embodiment is preferably 0.3 mL / g or less, more preferably 0.2 mL / g or less, still more preferably 0, from the viewpoint of preventing deformation due to compression and improving slipperiness. .1 mL / g or less, more preferably 0.05 mL / g or less.
  • Cellulose particles according to this embodiment can be blended or used in, for example, cosmetics, toiletry products, oral care products, quasi-drugs, pharmaceutical products, household products, agricultural products and the like. Further, since the cellulose particles according to the present embodiment have high sphericity and excellent slipperiness, they can be suitably used for cosmetics, toiletry products, oral care products, quasi-drugs and the like. Further, since the cellulose particles according to the present embodiment have a high degree of sphericity, they are suitably used as, for example, various chromatographic fillers, polymer carriers, bioreactor carriers, test agent carriers, body fluid purification carriers, and the like. Can be done. Further, since the cellulose particles according to the present embodiment are composed of cellulose derived from a natural plant, they are environmentally friendly and can be suitably used as a substitute material for microplastics.
  • Cellulose comprising a step of mixing a water-in-oil emulsion containing cellulose and preferably an organic solvent with an alcohol having an octanol / water partition coefficient of 0.5 or more and precipitating the cellulose to obtain cellulose particles. How to make particles.
  • the production method according to any one of [1] to [6], wherein [octanol / water partition coefficient ClogP of organic solvent]-[octanol / water partition coefficient ClogP of alcohol] is 4.5 or less.
  • [34] The cellulose particles according to [33], which have a sphericity of 0.85 or more.
  • [36] The cellulose particle according to any one of [33] to [35], which has a pore volume of 0.1 mL / g or less.
  • [37] The cellulose particle according to any one of [33] to [36], which has a pore volume of 0.05 mL / g or less.
  • Example 1 (1) Step (A) As the raw material cellulose, cellulose powder (Theoras (registered trademark) PH-101 manufactured by Asahi Kasei Corporation, degree of polymerization: 170, average diameter equivalent to a peripheral circle: 50 ⁇ m) was used. 10.6 g of cellulose powder was added to 189.4 g of an aqueous solution having a NaOH concentration of 4% by mass, and the mixture was cooled to -2 ° C. Then, while maintaining ⁇ 2 ° C., 50 g of an aqueous solution having a NaOH concentration of 22% by mass was added, and the mixture was swiftly stirred with a spatula to dissolve cellulose. The obtained aqueous cellulose solution has a cellulose concentration of 4% by mass and a NaOH concentration of 7.6% by mass.
  • cellulose powder Theoras (registered trademark) PH-101 manufactured by Asahi Kasei Corporation, degree of polymerization: 170, average diameter equivalent to a peripheral circle:
  • Step (B) 2.52 g of a nonionic surfactant (Emulgen 102KG manufactured by Kao Corporation, polyoxyethylene lauryl ether) was added to 180 g of an organic solvent (n-hexane), and the mixture was preliminarily stirred with a spatula.
  • a nonionic surfactant Emulgen 102KG manufactured by Kao Corporation, polyoxyethylene lauryl ether
  • an organic solvent n-hexane
  • 40 g of the cellulose aqueous solution obtained in the step (A) was added, and the mixture was stirred and mixed for 10 minutes at 20 ° C. and 4000 rpm using a homomixer MARK II type 2.5 (manufactured by Primix Co., Ltd.).
  • emulsified to obtain a water-in-oil emulsion of cellulose Emulgen 102KG manufactured by Kao Corporation, polyoxyethylene lauryl ether
  • step (C) The emulsion obtained in step (B) was added to an alcohol (1-butanol) for precipitating cellulose particles to precipitate cellulose particles. It was precipitated with 500 g of alcohol per 50 g of the emulsion. When the emulsion was added to the alcohol, the alcohol was stirred using a stirrer under the condition of 500 rpm. The temperature of the alcohol was room temperature (20 ° C.). After precipitating the cellulose particles, the obtained liquid was filtered under reduced pressure (700 hPa) using a filter paper (OMNIPORE DISC PTFE PHILIC 1.0UM 90MM WH PLN 25 / PK, mesh opening 1 ⁇ m manufactured by Millipore).
  • FIG. 1 shows an SEM image of the appearance and fracture surface of the obtained cellulose particles.
  • the pore volume of the obtained cellulose particles was 0.0011 mL / g.
  • the obtained cellulose particles were evaluated by the above method. The results are shown in Table 1.
  • Examples 2-9 and Comparative Examples 1-5 Cellulose particles were produced by the same method as in Example 1 except that the conditions of steps (A) to (C) were changed to the conditions shown in Table 1, and evaluation was performed by the above method.
  • the results are shown in Table 1.
  • SPAN80 in Table 1 is a surfactant (monooleate sorbitan) manufactured by Tokyo Kasei Kogyo Co., Ltd.
  • Leodor SP-O10V is a surfactant (monooleate sorbitan) manufactured by Kao Co., Ltd., modified silicone KF-6048. Is a surfactant manufactured by Shin-Etsu Chemical Industry Co., Ltd.
  • sucrose fatty acid ester ER-290 is a surfactant manufactured by Mitsubishi Chemical Co., Ltd. Sugar oleic acid ester
  • acetic acid was used instead of alcohol in an amount of 1000 parts by mass with respect to 100 parts by mass of the emulsion.
  • Example 10 is the same as Example 9 except that acetic acid (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) was used together with 1-butanol in step (C) by 40 parts by mass per 100 parts by mass of 1-butanol. Then, cellulose particles were produced and evaluated by the above method. The results are shown in Table 1.
  • cellulose particles having a high degree of sphericity could be produced.
  • the production method of the present invention is excellent in convenience because it can be mass-processed in a liquid state.

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Abstract

La présente invention concerne [1] un procédé de production de particules de cellulose qui comprend une étape dans laquelle une émulsion eau-dans-huile contenant de la cellulose est mélangée avec un alcool présentant un coefficient de partage octanol-eau ClogP de 0,5 ou plus pour précipiter la cellulose et ainsi obtenir des particules de cellulose et [2] des particules de cellulose présentant un degré de sphéricité supérieur ou égal à 0,80 et un volume de pore de 0,3 ml/g ou moins.
PCT/JP2021/044097 2020-12-02 2021-12-01 Particules de cellulose poreuse et procédé de production associé WO2022118883A1 (fr)

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JP2020200261 2020-12-02
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WO2015046473A1 (fr) * 2013-09-27 2015-04-02 株式会社カネカ Procédé de production de perles de cellulose poreuses par utilisation d'une solution aqueuse alcaline, support pour immobilisation de ligands, et adsorbant
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