WO2019107195A1 - Substrat antimicrobien et son procédé de fabrication - Google Patents

Substrat antimicrobien et son procédé de fabrication Download PDF

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Publication number
WO2019107195A1
WO2019107195A1 PCT/JP2018/042576 JP2018042576W WO2019107195A1 WO 2019107195 A1 WO2019107195 A1 WO 2019107195A1 JP 2018042576 W JP2018042576 W JP 2018042576W WO 2019107195 A1 WO2019107195 A1 WO 2019107195A1
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Prior art keywords
metal
cellulose nanofibers
oxidized cellulose
less
substrate
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PCT/JP2018/042576
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English (en)
Japanese (ja)
Inventor
曽根　篤
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日本ゼオン株式会社
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Priority to JP2019557155A priority Critical patent/JP7264061B2/ja
Publication of WO2019107195A1 publication Critical patent/WO2019107195A1/fr

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    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K31/00—Medicinal preparations containing organic active ingredients
    • A61K31/70—Carbohydrates; Sugars; Derivatives thereof
    • A61K31/715—Polysaccharides, i.e. having more than five saccharide radicals attached to each other by glycosidic linkages; Derivatives thereof, e.g. ethers, esters
    • A61K31/716—Glucans
    • A61K31/717—Celluloses
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/34—Shaped forms, e.g. sheets, not provided for in any other sub-group of this main group
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
    • A01N59/16—Heavy metals; Compounds thereof
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
    • A01N59/16—Heavy metals; Compounds thereof
    • A01N59/20—Copper
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
    • A61P17/00—Drugs for dermatological disorders
    • A61P17/04—Antipruritics
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
    • A61P31/00—Antiinfectives, i.e. antibiotics, antiseptics, chemotherapeutics
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y5/00—Nanobiotechnology or nanomedicine, e.g. protein engineering or drug delivery
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D101/00—Coating compositions based on cellulose, modified cellulose, or cellulose derivatives
    • C09D101/02—Cellulose; Modified cellulose
    • C09D101/04—Oxycellulose; Hydrocellulose
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/14—Paints containing biocides, e.g. fungicides, insecticides or pesticides
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
    • Y02A50/30—Against vector-borne diseases, e.g. mosquito-borne, fly-borne, tick-borne or waterborne diseases whose impact is exacerbated by climate change

Definitions

  • the present invention relates to an antibacterial substrate using metal-containing oxidized cellulose nanofibers having good antibacterial properties, and a method for producing the same.
  • oxidized cellulose nanofiber when the oxidized cellulose nanofiber is applied to various applications such as a composite material, it is important to further improve the performance of the oxidized cellulose nanofiber depending on the application.
  • desired properties for example, deodorizing properties
  • Patent Documents 2 and 3 various studies have been made to impart desired properties (for example, deodorizing properties) to oxidized cellulose nanofibers while maintaining the dispersibility of the oxidized cellulose nanofibers.
  • the present invention provides an antimicrobial base material that effectively and continuously disinfects bacteria that occur in living environments and the like, and a method for producing the same.
  • the inventors diligently studied to achieve the above-mentioned purpose. Then, the inventors have conceived of imparting a high antibacterial effect to individual oxidized cellulose fibers by incorporating the metal other than sodium into the well-dispersed oxidized cellulose fiber.
  • the inventors of the present invention oxidize natural cellulose in the presence of an oxidation catalyst such as an N-oxyl compound and then mechanically disperse the obtained oxidized cellulose to obtain water. And the like. It is possible to obtain a dispersion liquid in which highly crystalline microfibers (metal-containing oxidized cellulose nanofibers) having a number average fiber diameter of 30 nm or less are favorably dispersed in a dispersion medium such as The metal in the oxidized cellulose nanofibers is replaced with a metal other than sodium so that the content of metals other than sodium per gram of cellulose nanofibers falls within a predetermined range, so that the average density falls within a predetermined range.
  • metal-containing oxidized cellulose nanofibers containing other metals in the form of a salt to a substrate having a contact angle within a predetermined range It found that antimicrobial substrate is obtained which exhibit antimicrobial, and completed the present invention.
  • the present invention aims to advantageously solve the above-mentioned problems, and the antibacterial substrate of the present invention is a substrate comprising metal-containing oxidized cellulose nanofibers containing metal other than sodium in the form of a salt. It is an antibacterial base material attached on top,
  • the number average fiber diameter of the metal-containing oxidized cellulose nanofiber is 30 nm or less, and the content of metal other than sodium per 1 g of the metal-containing oxidized cellulose nanofiber is 0.
  • the average density of the metal-containing oxidized cellulose nanofibers deposited on said substrate is at 0.000001 mg / mm 2 or more 0.1 mg / mm 2 or less, the base material And a contact angle of 5 ° or more and 90 ° or less.
  • the antibacterial substrate is a metal-containing oxidized cellulose nanofiber containing metal other than sodium in the form of a salt attached to the substrate, and the number average fiber diameter of the metal-containing oxidized cellulose nanofiber is 30 nm or less, the content of metal other than sodium per 1 g of the metal-containing oxidized cellulose nanofibers is 0.1 mmol / g or more and 2.5 mmol / g or less, and the metal-containing oxidized cellulose nanofibers attached on the substrate the average density of not more than 0.000001 mg / mm 2 or more 0.1 mg / mm 2, if the contact angle of the substrate 5 ° to 90 °, life such as cells that occur in an effective and sustainable environmental It can be antibacterial.
  • the “number-average fiber diameter” of the metal-containing oxidized cellulose nanofibers is the fiber diameter measured by measuring the fiber diameter of five or more metal-containing oxidized cellulose nanofibers using an atomic force microscope. It can be determined by calculating the number average. Specifically, the “number-average fiber diameter” of the metal-containing oxidized cellulose nanofibers can be determined, for example, using the measurement method described in the examples of the present specification. Further, in the present invention, the “average density” of the metal-containing oxidized cellulose nanofibers deposited on the substrate can be specifically determined using, for example, the measurement method described in the examples of the present specification.
  • the “content” of metals other than sodium per 1 g of metal-containing oxidized cellulose nanofibers can be specifically determined, for example, using the measurement method described in the examples of the present specification.
  • the “contact angle” of the substrate can be specifically determined, for example, using the measurement method described in the examples of the present specification.
  • the metal-containing oxidized cellulose nanofibers are preferably metal-containing carboxylated cellulose nanofibers. If the metal-containing oxidized cellulose nanofiber is a metal-containing carboxylated cellulose nanofiber, the metal-containing oxidized cellulose nanofiber is excellent in dispersibility, and the antibacterial base can sufficiently exhibit antibacterial properties even if the compounding amount is small.
  • the number average fiber length of the metal-containing oxidized cellulose nanofibers is preferably 50 nm or more and 2000 nm or less.
  • the “number-average fiber length” of metal-containing oxidized cellulose nanofibers is the fiber length measured by measuring the fiber length of five or more metal-containing oxidized cellulose nanofibers using an atomic force microscope. It can be determined by calculating the number average.
  • the “number-average fiber length” of the metal-containing oxidized cellulose nanofibers can be determined, for example, using the measurement method described in the examples of the present specification.
  • the average degree of polymerization of the metal-containing oxidized cellulose nanofibers is preferably 100 or more and 2000 or less. If the average degree of polymerization of the metal-containing oxidized cellulose nanofibers is 100 or more and 2000 or less, the metal-containing oxidized cellulose nanofibers do not adhere to the antibacterial substrate and are not peeled off, and the durability can be further improved. .
  • the “average degree of polymerization” of the metal-containing oxidized cellulose nanofibers can be determined using a viscosity method. Specifically, the “average degree of polymerization” of the metal-containing oxidized cellulose nanofibers can be determined, for example, using the measurement method described in the examples of the present specification.
  • the metal other than sodium is at least one selected from metals of Groups 2 to 14 and Period 3 to Period 6 in the long period table. It is more preferably at least one selected from the group consisting of magnesium, aluminum, calcium, titanium, chromium, manganese, iron, cobalt, nickel, copper, zinc, silver, tin, barium and lead, aluminum, It is particularly preferable to be at least one selected from the group consisting of calcium, iron, cobalt, copper, zinc and silver, and most preferable to be at least one selected from the group consisting of copper, zinc and silver. If the metal other than sodium is the above-described metal, it is possible to easily impart desired antibacterial properties to the antibacterial substrate.
  • the manufacturing method of the antibacterial base material of this invention manufactures the antibacterial base material which manufactures either of the antibacterial base materials mentioned above And applying a dispersion in which the metal-containing oxidized cellulose nanofibers are dispersed in a dispersion medium to the substrate, and a drying step of drying the applied dispersion.
  • a dispersion liquid in which the metal-containing oxidized cellulose nanofibers are dispersed in a dispersion medium is applied to the base material and the applied dispersion liquid is dried, an antibacterial base material excellent in antibacterial property is manufactured. can do.
  • the dispersion medium is preferably water.
  • the metal-containing oxidized cellulose nanofibers can be well dispersed in the dispersion.
  • bacteria generated in the living environment and the like can be antibacterially effectively and continuously.
  • an antimicrobial substrate having excellent antimicrobial properties can be produced.
  • the antibacterial substrate of the present invention is used for antibacterial of bacteria generated in living environment etc., and metal-containing oxidized cellulose nanofibers containing metal other than sodium in the form of a salt adhere on the substrate 2.
  • the antibacterial base material wherein the number average fiber diameter of the metal-containing oxidized cellulose nanofibers is 30 nm or less, and the content of metals other than sodium per 1 g of the metal-containing oxidized cellulose nanofibers is 0.1 mmol / g or more.
  • the average density of the metal-containing oxidized cellulose nanofibers deposited on a substrate is not more than 0.000001 mg / mm 2 or more 0.1 mg / mm 2, the contact angle of the substrate 5 ° or more 90 It is characterized by being less than or equal to °.
  • the antibacterial base material of this invention can be manufactured using the manufacturing method of the antibacterial base material of this invention. Then, the manufacturing method of the antibacterial substrate of the present invention and the antibacterial substrate of the present invention which can be manufactured using the manufacturing method will be sequentially described below.
  • the antibacterial base material of this invention is not specifically limited, For example, it can be used for antimicrobials of the microbe generate
  • the salt is preferably a metal ion bonded to a negative ion, more preferably a negative ion derived from an organic acid, and particularly preferably an organic acid derived from a carboxylic acid structure.
  • One example of the preparation method of the metal-containing carboxylated cellulose nanofiber in the antibacterial base material of the present invention contains metal other than sodium in the form of a salt, the number average fiber diameter is 30 nm or less, 1 g of metal-containing oxidized cellulose nanofiber It is a method of preparing metal-containing oxidized cellulose nanofibers having a content of a metal other than sodium per unit of 0.1 mmol / g or more and 2.5 mmol / g or less.
  • the oxidized cellulose nanofiber containing the first metal in the form of a salt is used as a raw material, and the method of the following (i) or (ii) is used to
  • the second metal is contained in the form of a salt by replacing the metal ion of 1 with the ion of the second metal, and the number average fiber diameter is 30 nm or less, per 1 g of metal-containing oxidized cellulose nanofibers
  • a metal-containing oxidized cellulose nanofiber is prepared, which has an ion content of the second metal of 0.1 mmol / g or more and 2.5 mmol / g or less.
  • the metal-containing oxidized cellulose nanofibers are preferably metal-containing carboxylated cellulose nanofibers.
  • the second metal means a metal other than the first metal.
  • An oxidized cellulose nanofiber containing a first metal in the form of a salt is contacted with a strong acid in the state of being dispersed in a solvent, and the ion of the first metal contained in the form of a salt is substituted by a hydrogen atom And then a method of contacting the oxidized cellulose nanofiber in which the ion of the first metal is replaced by hydrogen atom with the salt of the second metal in a dispersed state in a solvent (the second preparation method).
  • oxidized cellulose nanofibers containing the first metal in the form of a salt are brought into contact with a salt of the second metal in a state of being dispersed in a solvent, and oxidized cellulose nano At least a part, preferably all, of the ions of the first metal of the fiber are replaced by the ions of the second metal (metal substitution step).
  • the metal-containing oxidized cellulose nanofibers containing the second metal in the form of a salt, which are obtained in the above-mentioned metal substitution step, are washed (washing step), and further optionally in a dispersion medium
  • the second metal is contained in the form of a salt, the number average fiber diameter is 30 nm or less, and the content of the second metal per 1 g of the metal-containing oxidized cellulose nanofiber is The metal-containing oxidized cellulose nanofiber which is 0.1 mmol / g or more and 2.5 mmol / g or less is obtained.
  • oxidized cellulose nanofiber which contains the said 1st metal which can be used in a metal substitution process in the form of a salt, it is obtained by oxidizing cellulose and contains the 1st metal in the form of a salt If, for example, any oxidized cellulose nanofibers such as those disclosed in WO 2011/074301 can be used. Among them, as oxidized cellulose nanofibers containing a first metal in the form of a salt, it is preferable to use carboxylated cellulose nanofibers containing the first metal in the form of a salt. If carboxylated cellulose nanofibers are used, metal-containing oxidized cellulose nanofibers having excellent dispersibility can be obtained.
  • the carboxylated cellulose nanofiber containing the first metal in the form of a salt is not particularly limited, and the primary hydroxyl group at the 6-position of ⁇ -glucose unit, which is a constitutional unit of cellulose, is selectively oxidized And carboxylated cellulose nanofibers.
  • a method for selectively oxidizing the primary hydroxyl group at the 6-position of the ⁇ -glucose unit for example, an oxidation method using an N-oxyl compound such as TEMPO catalytic oxidation method described below as an oxidation catalyst can be mentioned. .
  • natural cellulose is used as a raw material and TEMPO (2,2,6,6-tetramethyl-1-piperidine-N-oxyl) or a derivative thereof is caused to act as an oxidation catalyst in an aqueous solvent as an oxidation catalyst
  • natural cellulose is oxidized.
  • the natural cellulose after the oxidation treatment is optionally washed and then dispersed in an aqueous medium such as water, whereby the number average fiber diameter is, for example, 30 nm or less, preferably 10 nm or less, and a carboxylate type
  • An aqueous dispersion of cellulose nanofibers having carboxyl groups (carboxylated cellulose nanofibers) is obtained.
  • natural cellulose used as a raw material
  • the purified cellulose isolated from the biosynthesis system of celluloses such as a plant, an animal, and a bacteria production gel
  • natural cellulose includes softwood pulp, hardwood pulp, cotton pulp such as cotton linter and cotton lint, non-wood pulp such as straw pulp and bagasse pulp, bacterial cellulose, cellulose isolated from sea squirt, seaweed And cellulose etc. isolated from From the viewpoint of enhancing the efficiency of the oxidation reaction and enhancing the productivity of the carboxylated cellulose nanofibers, the isolated and purified natural cellulose may be subjected to a treatment for expanding the surface area such as beating.
  • TEMPO 2,2,6,6-tetramethyl-1-piperidine-N-oxyl
  • TEMPO derivatives having various functional groups at the 4-position carbon are to be used Can.
  • TEMPO derivatives include 4-acetamide TEMPO, 4-carboxy TEMPO, 4-phosphonooxy TEMPO and the like.
  • excellent reaction rates are obtained when TEMPO or 4-acetamido TEMPO is used as an oxidation catalyst.
  • hypohalous acid or a salt thereof hypohalous acid or a salt thereof (hypochlorous acid or a salt thereof, hypobromous acid or a salt thereof, hypoiodite acid or a salt thereof, etc.), or a hypohalous acid or a salt thereof (chlorous acid or Its salt, brominated acid or its salt, iodine acid or its salt etc., perhalogenated acid or its salt (perchloric acid or its salt, periodic acid or its salt etc.), halogen (chlorine, bromine, iodine etc.) ), Halogen oxides (ClO, ClO 2 , Cl 2 O 6 , BrO 2 , Br 3 O 7 etc.), nitrogen oxides (NO, NO 2 , N 2 O 3 etc.), peracids (hydrogen peroxide, hydrogen peroxide, etc.) Acetic acid, persulfuric acid, perbenzoic acid and the like are included. These oxidizing agents can be used alone or in combination of two or more. Also, it
  • bromide and iodide may be used as a co-oxidant.
  • ammonium salts ammonium bromide, ammonium iodide
  • alkali metal bromides or iodides alkaline earth metal bromides or iodides
  • bromides and iodides can be used alone or in combination of two or more.
  • the metal constituting the metal salt is usually contained in the form of a salt in the carboxylated cellulose nanofibers. That is, the metal constituting the metal salt is the first metal.
  • a sodium salt as the oxidizing agent, more preferably sodium hypochlorite, more preferably sodium hypochlorite and bromide It is particularly preferred to use a sodium co-oxidant.
  • a sodium salt is used as an oxidizing agent, the carboxylated cellulose nanofiber which contains sodium in the form of a salt as a 1st metal normally is obtained.
  • the conditions and method of the oxidation treatment are not particularly limited, and known conditions and methods used in the TEMPO catalyzed oxidation method can be adopted.
  • the primary hydroxyl group at the 6-position of the ⁇ -glucose unit is oxidized to the carboxyl group via the aldehyde group, but the metal-containing oxidized cellulose nanofiber obtained using the carboxylated cellulose nanofiber as a raw material
  • the proportion to be oxidized to a carboxyl group is preferably 50 mol% or more, more preferably 70 mol% or more, and 90 mol% or more. More preferable.
  • a dispersion apparatus used when disperse
  • a disintegrating apparatus such as a household mixer, an ultrasonic homogenizer, a high pressure homogenizer, a twin-screw kneading apparatus, a millstone or the like can be used.
  • a defibrating device that is generally used for home use or industrial production.
  • an aqueous dispersion of carboxylated cellulose nanofibers with a narrow fiber diameter can be obtained more efficiently by using a strong and beatable defibrillator such as various homogenizers or various refiners.
  • the carboxylated cellulose nanofibers after the oxidation treatment after repeating the water washing and the solid-liquid separation to increase the purity.
  • the unbroken-down component remains in the aqueous dispersion after dispersion treatment, it is preferable to remove the un-broken-down component using centrifugation or the like.
  • the substitution of metal ions by the contact between the oxidized cellulose nanofibers containing the first metal in the form of a salt and the salt of the second metal was obtained by the above-mentioned TEMPO catalytic oxidation method etc.
  • a solution or solid of a second metal salt can be added to the dispersion of oxidized cellulose nanofibers, and the resulting mixture can be stirred.
  • the metal substitution step the oxidized cellulose nanofibers dispersed well as described above are brought into contact with the salt of the second metal to replace the metal ions, whereby the single oxidized cellulose nanofibers are obtained.
  • the second metal is effectively contained in the metal-containing oxidized cellulose nanofibers excellent in the antibacterial effect.
  • the salt of the second metal can be a salt of a metal according to the properties desired to be imparted to the obtained metal-containing oxidized cellulose nanofibers.
  • the salt of the second metal is not particularly limited, for example, when the first metal is sodium (that is, when a sodium salt is used as the oxidizing agent), preferably in the long period table.
  • the metal-containing oxidized cellulose nanofiber (copper-containing oxidized cellulose nanofiber) obtained by using a salt of copper, zinc, or silver as a second metal salt is particularly excellent in antibacterial property.
  • the form of the salt of the second metal added to the dispersion of oxidized cellulose nanofibers is not particularly limited, and may be any form such as a halide, an acetate, a sulfate, or a nitrate.
  • the second metal salt is preferably a weak acid salt, and more preferably an acetate salt, from the viewpoint of improving the metal ion substitution efficiency.
  • the first metal is contained in the form of a salt.
  • the solvent for the oxidized cellulose nanofibers is preferably water.
  • the concentration of the oxidized cellulose nanofibers in the solvent is preferably 0.005% by mass or more, more preferably 0.01% by mass or more, still more preferably 0.05% by mass or more
  • the content is preferably 5% by mass or less, more preferably 3% by mass or less, and still more preferably 2% by mass or less. If the concentration of oxidized cellulose nanofibers is too low, reaction efficiency and productivity will deteriorate. Moreover, it is because the viscosity of a solvent becomes high and uniform stirring becomes difficult when the density
  • the time for stirring the mixture of the oxidized cellulose nanofibers and the salt of the second metal can be a time sufficient for metal ion substitution, for example, 1 hour or more and 10 hours or less.
  • the temperature at the time of stirring a mixture can be 10 degreeC or more and 50 degrees C or less, for example.
  • the oxidized cellulose nanofiber containing the first metal in the form of a salt and the salt of the second metal are brought into contact with each other in the solution, the oxidized cellulose nanofiber gels.
  • the dispersion step is carried out after the optional washing step, the obtained oxidized cellulose nanofibers are well dispersed again, and metal-containing oxidized cellulose having a number average fiber diameter of 30 nm or less Nanofibers can be obtained.
  • washing step optionally carried out after the metal substitution step, for example, using a known washing method such as repetition of centrifugation and an operation of replacing the supernatant with a washing liquid, or washing with a large amount of washing liquid, etc. Wash the oxidized cellulose nanofibers after metal replacement.
  • any cleaning solution such as water can be used, but from the viewpoint of further enhancing the metal replacement efficiency of the oxidized cellulose nanofiber obtained in the metal replacement step, the salt of the second metal first It is preferable to carry out washing using water as a washing liquid after carrying out washing using an aqueous solution of
  • Dispersing step In the dispersing step, known dispersing devices such as household mixers, ultrasonic homogenizers, high-pressure homogenizers, twin-screw kneaders, millstones and the like of oxidized cellulose nanofibers containing the second metal in the form of salts Use to disperse. Then, if necessary, the unfibrillated component is removed using centrifugation or the like to obtain a dispersion of metal-containing oxidized cellulose nanofibers.
  • known dispersing devices such as household mixers, ultrasonic homogenizers, high-pressure homogenizers, twin-screw kneaders, millstones and the like of oxidized cellulose nanofibers containing the second metal in the form of salts Use to disperse. Then, if necessary, the unfibrillated component is removed using centrifugation or the like to obtain a dispersion of metal-containing oxidized cellulose nanofibers.
  • the number average fiber diameter of the metal-containing oxidized cellulose nanofibers is not particularly limited as long as it is 30 nm or less, but it is 10 nm or less from the viewpoint of highly dispersing Is preferably 4 nm or less, more preferably 3.5 nm or less, preferably 2 nm or more, and more preferably 3 nm or more. Therefore, if the said dispersion liquid is used, even if it is a small amount, the antimicrobial base material which is excellent in antimicrobial property will be obtained.
  • the content of metals other than sodium per 1 g of metal-containing oxidized cellulose nanofibers obtained as described above is not particularly limited as long as it is 0.1 mmol / g or more and 2.5 mmol / g or less. It is preferably 0.3 mmol / g or more, more preferably 0.7 mmol / g or more, and preferably 2.3 mmol / g or less. If content of metals other than sodium per 1 g of metal-containing oxidized cellulose nanofibers is 0.3 mmol / g or more, the antimicrobial activity can be improved. Moreover, if content of metals other than sodium per gram of metal oxide cellulose nanofibers is 2.3 mmol / g or less, precipitation and sedimentation of metal can be suppressed.
  • the metal-containing oxidized cellulose nanofibers obtained as described above preferably have a number average fiber length of 50 nm or more, more preferably 70 nm or more, and still more preferably 100 nm or more, 400 nm or more is particularly preferable, 550 nm or more is most preferable, 2000 nm or less is preferable, 1500 nm or less is more preferable, 1000 nm or less is more preferable, and 600 nm or less Is particularly preferred. If the number average fiber length is 50 nm or more, the metal-containing oxidized cellulose nanofibers do not adhere to the substrate and are not peeled off, and the durability can be improved.
  • the number average fiber length of the metal-containing oxidized cellulose nanofibers is, for example, the number average fiber length of natural cellulose used as a raw material, the oxidation treatment conditions, and the conditions for dispersing carboxylated cellulose nanofibers after oxidation treatment (disaggregation) Or, it can be adjusted by changing the conditions for dispersing (disintegration) after the metal substitution step. Specifically, the number average fiber length can be shortened by prolonging the time of dispersion treatment (fibrillation treatment).
  • the metal-containing oxidized cellulose nanofibers preferably have an average degree of polymerization (average value of the number of glucose units contained in cellulose molecules) of 100 or more, more preferably 300 or more, and 500 or more. Is more preferably 600 or more, particularly preferably 2000 or less, more preferably 1500 or less, still more preferably 1000 or less, particularly preferably 700 or less preferable.
  • the average degree of polymerization is 100 or more, the metal-containing oxidized cellulose nanofibers do not adhere to the substrate and are not peeled off, and the durability can be improved.
  • the average degree of polymerization is 2000 or less, the metal-containing oxidized cellulose nanofibers do not adhere to the substrate and are not peeled off, and the durability can be improved.
  • the average degree of polymerization of metal-containing oxidized cellulose nanofibers is, for example, the average degree of polymerization of natural cellulose used as a raw material, the oxidation treatment conditions, the conditions for dispersing carboxylated cellulose nanofibers after oxidation treatment (disintegration), metal It can adjust by changing the conditions made to disperse
  • Second preparation method In the second preparation method, first, oxidized cellulose nanofibers containing a first metal in the form of a salt are contacted with a strong acid in a state of being dispersed in a solvent, and the first metal of oxidized cellulose nanofibers At least a part, preferably all of the ions are replaced with hydrogen atoms (hydrogen replacement step). Next, optionally, the oxidized cellulose nanofibers obtained in the hydrogen substitution step are washed (first washing step) and further dispersed in a dispersion medium (first dispersion step).
  • the oxidized cellulose nanofibers in which ions of the first metal are substituted by hydrogen atoms are contacted with a salt of the second metal in a dispersed state in a solvent, and hydrogen atoms and hydrogen atoms introduced in the hydrogen substitution step At least a part of, preferably all of the ions of the first metal not substituted by at least one of the ions of the second metal (metal substitution step).
  • the metal-containing oxidized cellulose nanofibers containing a second metal in the form of a salt, which are obtained in the metal substitution step are washed (second washing step), and, if necessary, a dispersion medium (The second dispersion step), the second metal is contained in the form of a salt, the number average fiber diameter is 30 nm or less, and the second per 1 g of the metal-containing oxidized cellulose nanofibers A metal-containing oxidized cellulose nanofiber having a metal content of 0.1 mmol / g to 2.5 mmol / g is obtained.
  • the metal substitution step is carried out after the hydrogen substitution step, so that the first preparation method described above (the method of directly substituting the first metal with the second metal) and In comparison, the rate at which the first metal is replaced by the second metal can be increased.
  • the strong acid is not particularly limited as long as it can replace the ion of the first metal with a hydrogen atom (that is, replace the carboxyl group of the oxidized cellulose nanofiber with a carboxylic acid type).
  • hydrochloric acid, sulfuric acid, nitric acid and the like can be used, and among them, it is preferable to use hydrochloric acid.
  • the time which stirs the mixture of an oxidized cellulose nanofiber and strong acid can be made into sufficient time, for example, 10 minutes or more and 5 hours or less time, for substitution with a metal ion and a hydrogen atom.
  • the temperature at the time of stirring a mixture can be 10 degreeC or more and 50 degrees C or less, for example.
  • First cleaning step In the first washing step optionally performed after the hydrogen substitution step, for example, repeating centrifugation and an operation of replacing the supernatant with a washing solution, or known washing such as filtration and washing with a large amount of washing solution, etc.
  • the method is used to wash oxidized cellulose nanofibers after hydrogen substitution to remove strong acid.
  • the strong acid can be removed, and the residual carboxylic acid type carboxyl group can be suppressed in the metal substitution step described later.
  • the metal substitution step the hydrogen atom introduced in the hydrogen substitution step and the ion of the first metal not substituted by the hydrogen atom can be sufficiently substituted by the second metal ion.
  • washing solution such as water can be used as the washing solution used in the first washing step, but from the viewpoint of further enhancing the efficiency of substituting the carboxyl group of the oxidized cellulose nanofiber with the carboxylic acid type.
  • washing is preferably carried out using water as a washing solution.
  • first dispersion step In the first dispersion step, oxidized cellulose nanofibers in which a carboxyl group is substituted to a carboxylic acid type are dispersed in a dispersion medium such as water, and ions of a first metal are substituted by hydrogen atoms. A dispersion of fibers is obtained. In the first dispersion step, it is not necessary to completely disperse the oxidized cellulose nanofibers in which the carboxyl group is substituted to the carboxylic acid type, using a known dispersion device (disintegration device) or the like.
  • dispersion device disintegration device
  • the metal substitution step of the second preparation method is the same as that of the first preparation method described above except that the oxidized cellulose nanofiber in which the ion of the first metal is replaced by a hydrogen atom is brought into contact with the salt of the second metal. It can be carried out in the same manner as the metal replacement step.
  • the suitable aspect of the metal substitution process of a 2nd preparation method is also the same as the suitable aspect of the metal substitution process of a 1st preparation method.
  • the second washing step and the second dispersion step in the second preparation method can be carried out in the same manner as the washing step and the dispersion step of the first preparation method described above. Furthermore, preferred embodiments of the second washing step and the second dispersion step of the second preparation method are the same as the preferred embodiments of the washing step and the dispersion step of the first preparation method.
  • the number average fiber diameter of the metal-containing oxidized cellulose nanofiber containing the second metal in the form of a salt is not particularly limited as long as it is 30 nm or less. From the viewpoint of high dispersion, it is preferably 10 nm or less, more preferably 4 nm or less, particularly preferably 3.5 nm or less, preferably 2 nm or more, and more preferably 3 nm or more preferable. Therefore, if the said dispersion liquid is used, even if it is a small amount, the antimicrobial base material which is excellent in antimicrobial property will be obtained.
  • the content of metals other than sodium per 1 g of metal-containing oxidized cellulose nanofibers obtained as described above is not particularly limited as long as it is 0.1 mmol / g or more and 2.5 mmol / g or less. It is preferably 0.3 mmol / g or more, more preferably 0.7 mmol / g or more, and preferably 2.3 mmol / g or less. If content of metals other than sodium per 1 g of metal-containing oxidized cellulose nanofibers is 0.3 mmol / g or more, the antimicrobial activity can be improved. Moreover, if content of metals other than sodium per gram of metal oxide cellulose nanofibers is 2.3 mmol / g or less, precipitation and sedimentation of metal can be suppressed.
  • number average fiber length is 50 nm or more
  • the metal-containing oxidized cellulose nanofiber which contains a 2nd metal in the form of a salt obtained as mentioned above is 50 nm or more.
  • the thickness is preferably 100 nm or more, more preferably 400 nm or more, most preferably 550 nm or more, and preferably 2000 nm or less, more preferably 1500 nm or less, and 1000 nm or less Is more preferably, and particularly preferably 600 nm or less. If the number average fiber length is 50 nm or more, the metal-containing oxidized cellulose nanofibers do not adhere to the substrate and are not peeled off, and the durability can be improved.
  • the number average fiber length of the metal-containing oxidized cellulose nanofibers containing the second metal in the form of a salt is, for example, the number average fiber length of natural cellulose used as a raw material, oxidation treatment conditions, carboxylation after oxidation treatment It can be adjusted by changing the conditions for dispersing (disintegrating) cellulose nanofibers or the conditions for dispersing oxidized cellulose nanofibers containing a second metal in the form of a salt after metal substitution step (disintegrating) . Specifically, the number average fiber length can be shortened by prolonging the time of dispersion treatment (fibrillation treatment).
  • the metal-containing oxidized cellulose nanofiber containing the second metal in the form of a salt preferably has an average degree of polymerization (average value of the number of glucose units contained in the cellulose molecule) of 100 or more, and 300
  • the above is more preferable, 500 or more is more preferable, 600 or more is particularly preferable, 2000 or less is preferable, 1500 or less is more preferable, and 1000 or less Is more preferable, and 700 or less is particularly preferable.
  • the average degree of polymerization is 100 or more, the metal-containing oxidized cellulose nanofibers do not adhere to the substrate and are not peeled off, and the durability can be improved.
  • the metal-containing oxidized cellulose nanofibers do not adhere to the substrate and are not peeled off, and the durability can be improved.
  • the average degree of polymerization of metal-containing oxidized cellulose nanofibers is, for example, the average degree of polymerization of natural cellulose used as a raw material, the oxidation treatment conditions, the conditions for dispersing carboxylated cellulose nanofibers after oxidation treatment (disintegration), metal It can adjust by changing the conditions made to disperse
  • the method for producing an antimicrobial substrate according to the present invention comprises the steps of applying to the substrate a dispersion in which the metal-containing oxidized cellulose nanofibers prepared by the above-mentioned preparation method are dispersed in a dispersion medium, and the applied dispersion And d) drying.
  • the application step is a step of applying a dispersion in which the metal-containing oxidized cellulose nanofibers described above are dispersed in a dispersion medium to a substrate.
  • the coating method may, for example, be spray coating, dip coating, blade coating, spin coating, roll coating, beam coating, spiral coating, etc. From the viewpoint of high dispersibility, spray coating is preferred.
  • the contact angle of the substrate as the application target is not particularly limited as long as it is 5 ° or more and 90 ° or less, and is preferably 10 ° or more, and more preferably 88 ° or less. If the contact angle of the substrate is 10 ° or more, it is possible to suppress the flow-down and penetration. In addition, if the contact angle of the substrate is 88 ° or less, the dispersion can be compatible with the substrate.
  • a base material glass, an acrylic resin, polycarbonate resin, a polyethylene terephthalate, ceramics etc. are mentioned, for example.
  • the base materials may be used alone or in combination of two or more.
  • glass is preferable in that it is transparent and easily adheres.
  • the solid content concentration of the dispersion is not particularly limited, but is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and preferably 5% by mass or less And 3% by mass or less is more preferable. If the solid content concentration of the dispersion is 0.01% by mass or more, the working efficiency can be improved. In addition, when the solid content concentration of the dispersion is 5% by mass or less, coating and spraying can be facilitated.
  • dispersion medium in the dispersion liquid examples include water; organic solvents such as methanol and ethanol; and the like, but water is preferable in that metal-containing oxidized cellulose nanofibers can be favorably dispersed in the dispersion liquid.
  • the average density of the metal-containing oxidized cellulose nanofibers is 0.0001 mg / mm 2 or more, a more sufficient antibacterial effect can be exhibited.
  • the average density of the metal-containing oxidized cellulose nanofibers is 0.07 mg / mm 2 or less, it can be more reliably suppressed that the metal-containing oxidized cellulose nanofibers form a film and are peeled off from the base material.
  • the drying step is a step of drying the applied dispersion. Through the drying step, the metal-containing oxidized cellulose nanofibers can be deposited substantially uniformly on the substrate.
  • the drying temperature is preferably 10 ° C. or more, more preferably 20 ° C. or more, preferably 60 ° C. or less, and more preferably 50 ° C. or less. If the drying temperature is 10 ° C. or more, the water can be evaporated. Moreover, if the drying temperature is 60 ° C. or less, it is possible to suppress the drying roughness.
  • the drying time is preferably 30 minutes or more, more preferably 60 minutes or more, preferably 300 minutes or less, and more preferably 120 minutes or less. If the drying time is 30 minutes or more, it can be dried completely. In addition, if the drying time is 300 minutes or less, the working efficiency can be improved.
  • the antibacterial base material that can be manufactured using the manufacturing method described above has a number average fiber diameter of 30 nm or less, and a content of metal other than sodium is 0.1 mmol / g or more per 1 g of the metal-containing oxidized cellulose nanofibers. Metal-containing oxidized cellulose nanofibers containing 5 mmol / g or less are contained. And, since this antibacterial base material uses metal-containing oxidized cellulose nanofibers containing metal effectively in the form of salt with respect to each single oxidized cellulose nanofiber, excellent antibacterial performance can be obtained. Demonstrate.
  • the average density of the metal-containing oxidized cellulose nanofibers in the antimicrobial substrate is not particularly limited, 0.0001 mg / Mm 2 or more is preferable, 0.0002 mg / mm 2 or more is more preferable, and 0.07 mg / mm 2 or less is preferable, and 0.05 mg / mm 2 or less more preferably, particularly preferably at 0.010 mg / mm 2 or less, and most preferably 0.0007 mg / mm 2 or less.
  • the metal-containing oxidized cellulose nanofibers in the antibacterial substrate preferably have a number-average fiber length of 50 nm or more, more preferably 70 nm or more, and more preferably 100 nm or more. Is more preferably 400 nm or more, particularly preferably 550 nm or more, and is preferably 2000 nm or less, more preferably 1500 nm or less, and still more preferably 1000 nm or less. , 600 nm or less is particularly preferable.
  • the metal-containing oxidized cellulose nanofibers in the antibacterial substrate preferably have an average degree of polymerization of 100 or more, more preferably 300 or more, still more preferably 500 or more, and 600 or more. In particular, it is preferably 2000 or less, more preferably 1500 or less, still more preferably 1000 or less, and particularly preferably 700 or less.
  • the contact angle of the substrate as the application target is not particularly limited as long as it is 5 ° or more and 90 ° or less, and is preferably 10 ° or more, more preferably 33 ° or more, and 88 ° or less Is preferably, 87 ° or less is more preferable, and 57 ° or less is particularly preferable. If the contact angle of the substrate is 10 ° or more, it is possible to suppress the flow-down and penetration. In addition, if the contact angle of the substrate is 88 ° or less, the dispersion can be compatible with the substrate.
  • a base material glass, an acrylic resin, polycarbonate resin, a polyethylene terephthalate, ceramics etc. are mentioned, for example.
  • the base materials may be used alone or in combination of two or more.
  • glass is preferable in that it is transparent and easily adheres.
  • ⁇ Carboxyl group content of oxidized cellulose nanofibers From a pulp sample of oxidized cellulose nanofibers whose dry weight was precisely weighed, 60 mL of a dispersion having a concentration of 0.5% by mass to 1% by mass of the oxidized cellulose nanofibers was prepared. Next, the pH of the dispersion was adjusted to about 2.5 with 0.1 M hydrochloric acid, and then a 0.05 M aqueous solution of sodium hydroxide was added dropwise to observe changes in conductivity until the pH reached 11. .
  • the metal-containing oxidized cellulose nanofiber dispersion was diluted to prepare a dispersion having a concentration of the metal-containing oxidized cellulose nanofiber of 0.0001%. Thereafter, the obtained dispersion was dropped onto mica and dried to obtain an observation sample. And atomic force microscope (Dimension The observation sample is observed using FastScan AFM, manufactured by BRUKER, Tapping mode), and in the image in which the metal-containing oxidized cellulose nanofibers can be confirmed, the fiber diameter of five or more metal-containing oxidized cellulose nanofibers is measured and the average value Was calculated. The results are shown in Table 1.
  • the metal-containing oxidized cellulose nanofiber dispersion was diluted to prepare a dispersion having a concentration of the metal-containing oxidized cellulose nanofiber of 0.0001%. Thereafter, the obtained dispersion was dropped onto mica and dried to obtain an observation sample. Then, an observation sample is observed using an atomic force microscope (Dimension FastScan AFM, manufactured by BRUKER, Tapping mode), and in an image in which metal-containing oxidized cellulose nanofibers can be confirmed, five or more metal-containing oxidized cellulose nanofibers The fiber length was measured and the average value was calculated.
  • the degree of polymerization of metal-containing oxidized cellulose nanofibers was determined by the viscosity method.
  • Metal content of metal-containing oxidized cellulose nanofibers The metal in the metal-containing oxidized cellulose nanofibers was characterized and quantified by the ICP-AES method. In addition, SPS5100 (made by SII nanotechnology) was used for the measurement. In addition, the amount of each ion was quantified by ion chromatography. In addition, DX500 (made by DIONEX) was used for the measurement. The results are shown in Table 1. Then, from each measurement result, the amount of metal forming a salt with the carboxyl group of the oxidized cellulose nanofiber was determined.
  • ⁇ Contact angle of base material The contact angle of the substrate (glass, acrylic resin, polycarbonate resin, melamine resin, cotton) was measured by a liquid angle method ⁇ / 2 method using a contact angle meter (Drop Master 100, manufactured by Kyowa Interface Science). The solvent used was water, and the value of 1 second after the droplet was taken as the measurement value. Only when the substrate is cotton, a value of 0.1 seconds after the droplet was taken as the measurement value. The results are shown in Table 1.
  • Antibacterial performance of antibacterial substrate The prepared metal-containing oxidized cellulose nanofiber aqueous dispersion was uniformly sprayed on one side of a 50 mm long, 50 mm wide, and 1.8 mm thick substrate, and then the substrate was dried at room temperature. The antibacterial performance after the drying was evaluated according to JIS Z 2801. The results are shown in Table 1. In Table 1, antimicrobial activity values against Staphylococcus aureus and E. coli are shown. Here, if the antimicrobial activity value is 2 or more, it is considered to have an antimicrobial performance.
  • Example 1 Preparation of Oxidized Cellulose Nanofiber Dispersion> 1 weight of softwood bleached kraft pulp by dry weight, 5 mmol of sodium hypochlorite, 0.1 g (1 mmol) of sodium bromide and 0.016 g (1 mmol) of TEMPO dispersed in 100 mL of water, 4 at room temperature The mixture was gently stirred for a while and washed with distilled water to obtain TEMPO catalyzed oxidized pulp (oxidized cellulose). The carboxyl group content of the obtained TEMPO catalyst oxidized pulp was 1.4 mmol / g.
  • aqueous dispersion having a solid concentration of 0.1%. Then, using an ultrasonic homogenizer (Nissei, Ultrasonic Generator) for 2 minutes at 7.5 ⁇ 1000 rpm using a homogenizer (Microtech Nichion, Hiscotron) for the aqueous dispersion, with ice around the container An aqueous dispersion containing carboxylated cellulose nanofibers as oxidized cellulose nanofibers was obtained by performing defibration treatment with V-LEVEL 4 and TIP 26 D for 4 minutes while cooling.
  • Ultrasonic homogenizer Neissei, Ultrasonic Generator
  • a homogenizer Microtech Nichion, Hiscotron
  • the carboxylated cellulose nanofiber aqueous dispersion was obtained by the above to obtain an aqueous dispersion of carboxylated cellulose nanofibers having a concentration of 0.1%, which is a transparent liquid.
  • the carboxylated cellulose nanofibers contained sodium (first metal) derived from a co-oxidant in the form of a salt.
  • aqueous dispersion of hydrogen-substituted carboxylated cellulose nanofibers having a concentration of 0.1% in which the hydrogen-substituted carboxylated cellulose nanofibers were dispersed (first dispersion step).
  • the carboxyl group on the surface of hydrogen-substituted carboxylated cellulose nanofibers is measured by FT-IR (FT / IR-6100, manufactured by JASCO Corporation) according to Biomacromolecules (2011, Volume 12, 518-522). As a result, 90% or more were substituted with the carboxylic acid type.
  • centrifugation (12000 G (120 ⁇ 100 rpm / g), 10 using a centrifuge (manufactured by SAKUMA, M201-1VD, angle rotor 50F-8AL) from the aqueous dispersion of carboxylated cellulose nanofibers substituted with copper, 10
  • the unfibrillated component was removed by 12 ° C. for a minute to obtain an aqueous dispersion of a metal-containing carboxylated cellulose nanofiber having a concentration of 0.1%, which is a transparent liquid (dispersion step).
  • the obtained metal-containing carboxylated cellulose nanofiber contains 0.7 mmol / g of copper (Cu), and the amount of sodium is Was found to be 1 mass ppm or less.
  • the amount of ions by ion chromatography using DX500 it was found that the amount of acetate ions was 0.5 mass ppm or less and the amount of chloride ions was 0.1 mass ppm or less.
  • the metal-containing carboxylated cellulose nanofibers sodium ions of the carboxylated cellulose nanofibers are substituted by copper ions, and one copper ion is bound to two carboxyl groups. It is guessed that The number average fiber length of the metal-containing carboxylated cellulose nanofibers was 550 nm. The average degree of polymerization of the metal-containing carboxylated cellulose nanofibers was 600. And the obtained metal-containing carboxylated cellulose nanofiber aqueous dispersion was sprayed on soda glass (contact angle 33 °), dried, and the antibacterial performance was evaluated according to the method for evaluating the antibacterial performance. The average density of the metal-containing carboxylated cellulose nanofibers on soda glass at that time was 0.0002 mg / mm 2 . The evaluation results are shown in Table 1 as Example 1.
  • Example 2 ⁇ Preparation of Oxidized Cellulose Nanofiber Dispersion>
  • Example 2 ⁇ Preparation of Oxidized Cellulose Nanofiber Dispersion>
  • an aqueous dispersion of carboxylated cellulose nanofibers having a concentration of 0.1% was obtained.
  • metal-containing oxidized cellulose nanofiber dispersion 50 g of the above-mentioned aqueous dispersion of hydrogen-substituted carboxylated cellulose nanofibers having a concentration of 0.1% is stirred, 19.5 g of an aqueous solution of zinc (II) having a concentration of 0.1% is added thereto, Stirring was continued for 3 hours (metal substitution step).
  • the carboxylated cellulose nanofibers gelated by the addition of an aqueous solution of zinc (II) acetate is centrifuged (12000 G (120 ⁇ 100 rpm / using a centrifuge (M made by SAKUMA, M201-1VD, angle rotor 50F-8AL)). g) after 10 minutes at 12 ° C.) wash the recovered cellulose nanofibers with a 0.1% aqueous solution of zinc (II) acetate, and then collect the recovered cellulose nanofibers in a large amount of distilled water (Washing step).
  • the obtained metal-containing carboxylated cellulose nanofiber contains 0.7 mmol / g of zinc (Zn), and the amount of sodium is Was found to be 1 mass ppm or less.
  • Zn zinc
  • the amount of ions was 0.5 mass ppm or less and the amount of chloride ions was 0.1 mass ppm or less.
  • the metal-containing carboxylated cellulose nanofibers sodium ions of the carboxylated cellulose nanofibers are substituted with zinc ions, and one zinc ion is bonded to two carboxyl groups. It is guessed that The number average fiber length of the metal-containing carboxylated cellulose nanofibers was 550 nm. The average degree of polymerization of the metal-containing carboxylated cellulose nanofibers was 600. And the obtained metal-containing carboxylated cellulose nanofiber aqueous dispersion was sprayed on soda glass (contact angle 33 °), dried, and the antibacterial performance was evaluated according to the method for evaluating the antibacterial performance. The average density of the metal-containing carboxylated cellulose nanofibers on soda glass at that time was 0.0002 mg / mm 2 . The evaluation results are shown in Table 1 as Example 2.
  • Example 3 ⁇ Preparation of Oxidized Cellulose Nanofiber Dispersion>
  • Example 3 ⁇ Preparation of Oxidized Cellulose Nanofiber Dispersion>
  • an aqueous dispersion of carboxylated cellulose nanofibers having a concentration of 0.1% was obtained.
  • 50 g of the above-mentioned aqueous dispersion of hydrogen-substituted carboxylated cellulose nanofibers having a concentration of 0.1% is stirred, 18 g of an aqueous solution of silver acetate (I) having a concentration of 0.1% is added thereto, and 3 hours at room temperature Stirring was continued (metal replacement step).
  • the carboxylated cellulose nanofibers gelated by the addition of an aqueous solution of silver (I) acetate is centrifuged (12000 G (120 x 100 rpm / using a centrifuge (M made by SAKUMA, M201-1VD, angle rotor 50F-8AL)) g) after 10 minutes at 12 ° C.) wash the recovered cellulose nanofibers with an aqueous solution of silver acetate (I) at a concentration of 0.1%, and then collect the recovered cellulose nanofibers in a large amount of distilled water (Washing step).
  • the obtained metal-containing carboxylated cellulose nanofiber contains 1.4 mmol / g of silver (Ag), and the amount of sodium is Was found to be 1 mass ppm or less.
  • the amount of ions by ion chromatography using DX500 it was found that the amount of acetate ions was 0.5 mass ppm or less and the amount of chloride ions was 0.1 mass ppm or less.
  • the metal-containing carboxylated cellulose nanofibers sodium ions of the carboxylated cellulose nanofibers are substituted with silver ions, and one silver ion is bound to one carboxyl group. It is guessed that The number average fiber length of the metal-containing carboxylated cellulose nanofibers was 550 nm. The average degree of polymerization of the metal-containing carboxylated cellulose nanofibers was 600. And the obtained metal-containing carboxylated cellulose nanofiber aqueous dispersion was sprayed on soda glass (contact angle 33 °), dried, and the antibacterial performance was evaluated according to the method for evaluating the antibacterial performance. The average density of the metal-containing carboxylated cellulose nanofibers on soda glass at that time was 0.0007 mg / mm 2 . The evaluation results are shown in Table 1 as Example 3.
  • Example 4 Preparation of Oxidized Cellulose Nanofiber (TOCN) Dispersion
  • TOCN Oxidized Cellulose Nanofiber
  • 50 g of the aqueous dispersion of carboxylated cellulose nanofibers having a concentration of 0.1% is stirred, and 18 g of an aqueous solution of copper (II) acetate having a concentration of 0.1% is added thereto as an aqueous solution of copper salt. Stirring was continued for 3 hours (metal substitution step).
  • the carboxylated cellulose nanofibers gelated by the addition of a copper (II) acetate aqueous solution are centrifuged (12000 G (120 ⁇ 100 rpm / using a centrifuge (M made by SAKUMA, M201-1VD, angle rotor 50F-8AL)). g) after 10 minutes at 12 ° C.) wash the recovered cellulose nanofibers with a 0.1% aqueous solution of copper (II) acetate, and then collect the recovered cellulose nanofibers in a large amount of distilled water (Washing step).
  • the obtained metal-containing carboxylated cellulose nanofiber contains 0.7 mmol / g of copper (Cu), and the amount of sodium is Was found to be 1 mass ppm or less.
  • the amount of acetate ions was 0.5 mass ppm or less.
  • the metal-containing carboxylated cellulose nanofibers sodium ions of the carboxylated cellulose nanofibers are substituted by copper ions, and one copper ion is bound to two carboxyl groups. It is guessed.
  • the number average fiber length of the metal-containing carboxylated cellulose nanofibers was 550 nm.
  • the average degree of polymerization of the metal-containing carboxylated cellulose nanofibers was 600.
  • the obtained metal-containing carboxylated cellulose nanofiber aqueous dispersion was sprayed on soda glass (contact angle 33 °), dried, and the antibacterial performance was evaluated according to the method for evaluating the antibacterial performance.
  • the average density of the metal-containing carboxylated cellulose nanofibers on soda glass at that time was 0.0002 mg / mm 2 .
  • the evaluation results are shown in Table 1 as Example 4.
  • Example 5 In Example 4, in place of using soda glass (contact angle 33 °) as the base material, in the same manner as in Example 4 except that an acrylic resin (contact angle 57 °) was used, “oxidized cellulose nano Preparation of fiber (TOCN) dispersion, "preparation of metal-containing oxidized cellulose nanofiber dispersion”, and "performance evaluation of metal-containing oxidized cellulose nanofiber and antimicrobial substrate” were performed.
  • TOCN oxidized cellulose nano Preparation of fiber
  • preparation of metal-containing oxidized cellulose nanofiber dispersion preparation of metal-containing oxidized cellulose nanofiber dispersion
  • performance evaluation of metal-containing oxidized cellulose nanofiber and antimicrobial substrate were performed.
  • the average density of the metal-containing carboxylated cellulose nanofibers on the acrylic resin at that time was 0.0002 mg / mm 2 .
  • the evaluation results are shown in Table 1 as Example 5.
  • Example 6 In Example 4, in place of using soda glass (contact angle of 33 °) as the base material, in the same manner as in Example 4 except that polycarbonate resin (contact angle of 87 °) was used, “oxidized cellulose nano Preparation of fiber (TOCN) dispersion, "preparation of metal-containing oxidized cellulose nanofiber dispersion", and "performance evaluation of metal-containing oxidized cellulose nanofiber and antimicrobial substrate” were performed. The average density of the metal-containing carboxylated cellulose nanofibers on the polycarbonate resin at that time was 0.0002 mg / mm 2 . The evaluation results are shown in Table 1 as Example 6.
  • Example 7 In Example 4, instead of using an antibacterial substrate having an average density of 0.0002 mg / mm 2 of metal-containing carboxylated cellulose nanofibers on soda glass, it is possible to use metal-containing carboxylated cellulose nanofibers on soda glass "Preparation of oxidized cellulose nanofiber (TOCN) dispersion", “dispersion of metal-containing oxidized cellulose nanofiber” as in Example 4 except that an antibacterial substrate having an average density of 0.05 mg / mm 2 was used. "Preparation of solution” and “performance evaluation of metal-containing oxidized cellulose nanofibers and antibacterial substrate” were performed. The evaluation results are shown in Table 1 as Example 7.
  • TOCN oxidized cellulose nanofiber
  • the obtained metal-containing carboxylated cellulose nanofiber contains 1.4 mmol / g of sodium (Na) .
  • one sodium ion is bound to one carboxyl group of the carboxylated cellulose nanofibers.
  • the number average fiber length of the metal-containing carboxylated cellulose nanofibers was 570 nm.
  • the average degree of polymerization of the metal-containing carboxylated cellulose nanofibers was 610.
  • the recovered TEMPO-catalyzed oxidized pulp was washed with a large amount of distilled water, and then 50 mL of distilled water was added to obtain a TEMPO-catalyzed oxidized pulp aqueous dispersion with a concentration of 0.1% (dispersion step).
  • 50 g of the aqueous dispersion of hydrogen-substituted carboxylated cellulose nanofibers having a concentration of 0.1% is stirred, 1 g of an aqueous solution of copper (II) acetate having a concentration of 0.1% is added thereto, and 3 hours at room temperature Stirring was continued (metal replacement step).
  • the carboxylated cellulose nanofibers gelated by the addition of a copper (II) acetate aqueous solution are centrifuged (12000 G (120 ⁇ 100 rpm / using a centrifuge (M made by SAKUMA, M201-1VD, angle rotor 50F-8AL)). g) after 10 minutes at 12 ° C.) wash the recovered cellulose nanofibers with a 0.1% aqueous solution of copper (II) acetate, and then collect the recovered cellulose nanofibers in a large amount of distilled water (Washing step).
  • the obtained metal-containing carboxylated cellulose nanofiber contains 0.05 mmol / g of copper (Cu), and the amount of sodium is Was found to be 1 mass ppm or less.
  • the amount of ions by ion chromatography using DX500 it was found that the amount of acetate ions was 0.5 mass ppm or less and the amount of chloride ions was 0.1 mass ppm or less.
  • 50 g of the aqueous dispersion of hydrogen-substituted carboxylated cellulose nanofibers having a concentration of 0.1% is stirred, 18 g of an aqueous solution of copper (II) acetate having a concentration of 0.1% is added thereto, and 3 hours at room temperature Stirring was continued (metal replacement step).
  • the carboxylated cellulose nanofibers gelated by the addition of a copper (II) acetate aqueous solution are centrifuged (12000 G (120 ⁇ 100 rpm / using a centrifuge (M made by SAKUMA, M201-1VD, angle rotor 50F-8AL)). g) after 10 minutes at 12 ° C.) wash the recovered cellulose nanofibers with a 0.1% aqueous solution of copper (II) acetate, and then collect the recovered cellulose nanofibers in a large amount of distilled water (Washing step). The pH was 5.5.
  • the obtained metal-containing carboxylated cellulose nanofiber contains 0.7 mmol / g of copper (Cu), and the amount of sodium is Was found to be 1 mass ppm or less.
  • the amount of ions by ion chromatography using DX500 it was found that the amount of acetate ions was 0.5 mass ppm or less and the amount of chloride ions was 0.1 mass ppm or less.
  • Example 5 In Example 4, in place of using soda glass (contact angle of 33 °) as the base material, in the same manner as in Example 4 except that a melamine resin (contact angle of 100 °) was used, Preparation of fiber (TOCN) dispersion, "preparation of metal-containing oxidized cellulose nanofiber dispersion", and "performance evaluation of metal-containing oxidized cellulose nanofiber and antimicrobial substrate” were performed.
  • the average density of the metal-containing carboxylated cellulose nanofibers on the melamine resin at that time was 0.0002 mg / mm 2 .
  • the evaluation results are shown in Table 1 as Comparative Example 5. However, metal-containing carboxylated cellulose nanofibers were sparsely distributed on the melamine resin.
  • Example 6 In Example 4, in place of using soda glass (contact angle of 33 °) as the base material, in the same manner as in Example 4 except that cotton (contact angle of 3 °) was used, “oxidized cellulose nanofibers Preparation of (TOCN) dispersion, "preparation of metal-containing oxidized cellulose nanofiber dispersion", and "performance evaluation of metal-containing oxidized cellulose nanofiber and antibacterial substrate” were performed.
  • the average density of the metal-containing carboxylated cellulose nanofibers on cotton at that time was 0.0000006 mg / mm 2 .
  • the evaluation results are shown in Table 1 as Comparative Example 6. Here, the dispersion penetrated into cotton, and the abundance (average density) of the cotton surface of the metal-containing carboxylated cellulose nanofibers became low.
  • Example 7 filter paper (manufacturer name: ADVANTEC, trade name: qualitative filter paper No. 2, ⁇ 150 mm) (contact angle 4 °) is used instead of using soda glass (contact angle 33 °) as the base material Similar to Example 4, “Preparation of oxidized cellulose nanofiber (TOCN) dispersion”, “Preparation of metal-containing oxidized cellulose nanofiber dispersion”, and “Metal-containing oxidized cellulose nanofiber and "Performance evaluation of antibacterial base material” was performed. The average density of the metal-containing carboxylated cellulose nanofibers on the filter paper at that time was 0.0000007 mg / mm 2 . The evaluation results are shown in Table 1 as Comparative Example 7. Here, the dispersion penetrated into the filter paper, passed through the filter paper, and the abundance (average density) of the metal-containing carboxylated cellulose nanofibers on the filter paper surface decreased.
  • the antimicrobial substrates of Examples 1 to 7 are antimicrobial substrates in which metal-containing oxidized cellulose nanofibers containing metal other than sodium in the form of a salt are adhered on the substrate, and metal-containing oxidized cellulose
  • the number average fiber diameter of the nanofibers is 30 nm or less, and the content of the metal other than sodium per 1 g of the metal-containing oxidized cellulose nanofibers is 0.1 mmol / g or more and 2.5 mmol / g or less, on the substrate the average density of the deposited metal-containing oxidized cellulose nanofibers 0.000001 mg / mm 2 or more 0.1 mg / mm 2 or less, the contact angle of the substrate is 5 ° to 90 °, generating such in living environment It can be seen that the bacteria (eg, Staphylococcus aureus, E. coli) can be effectively and persistently antibacterially treated.
  • the bacteria eg, Staphylococcus aureus, E. coli
  • produces in a living environment etc. effectively and continuously can be provided, and its manufacturing method.

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Abstract

La présente invention concerne un substrat antimicrobien susceptible de réguler efficacement et de manière continue les micro-organismes générés dans un environnement vivant, etc. et un procédé de fabrication du substrat antimicrobien. Le substrat antimicrobien comprend des nanofibres de cellulose oxydée contenant du métal, qui contiennent un métal autre que le sodium sous la forme d'un sel, qui a adhéré à un substrat, où : le diamètre de fibre moyen en nombre des nanofibres de cellulose oxydée contenant du métal est de 30 nm ou moins ; la teneur du métal autre que le sodium est de 0,1 à 2,5 mmole inclus par gramme de nanofibres de cellulose oxydée contenant du métal ; la densité moyenne des nanofibres de cellulose oxydée contenant du métal qui ont adhéré au substrat est de 0,000001 à 0,1 mg/mm2 inclus ; et l'angle de contact du substrat étant de 5 à 90 ° inclus.
PCT/JP2018/042576 2017-11-29 2018-11-16 Substrat antimicrobien et son procédé de fabrication WO2019107195A1 (fr)

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Publication number Priority date Publication date Assignee Title
WO2021123773A1 (fr) * 2019-12-16 2021-06-24 Oxy Solutions As Compositions antimicrobiennes

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CN112176725A (zh) * 2020-10-28 2021-01-05 上海威露美生物科技有限公司 羧基酯化络合抗菌纤维、制备方法及应用

Citations (4)

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WO2010089948A1 (fr) * 2009-02-06 2010-08-12 花王株式会社 Suspension de fibres de cellulose et son procédé de production
JP2014070158A (ja) * 2012-09-28 2014-04-21 Toppan Printing Co Ltd 抗菌性微細セルロース、その製造方法ならびに抗菌性コーティング剤
WO2016125497A1 (fr) * 2015-02-04 2016-08-11 日本ゼオン株式会社 Dispersion de nanofibres de cellulose oxydée contenant un métal et procédé de préparation associé
JP2017149103A (ja) * 2016-02-26 2017-08-31 凸版印刷株式会社 抗菌消臭シートの製造方法及び抗菌消臭シート

Patent Citations (4)

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Publication number Priority date Publication date Assignee Title
WO2010089948A1 (fr) * 2009-02-06 2010-08-12 花王株式会社 Suspension de fibres de cellulose et son procédé de production
JP2014070158A (ja) * 2012-09-28 2014-04-21 Toppan Printing Co Ltd 抗菌性微細セルロース、その製造方法ならびに抗菌性コーティング剤
WO2016125497A1 (fr) * 2015-02-04 2016-08-11 日本ゼオン株式会社 Dispersion de nanofibres de cellulose oxydée contenant un métal et procédé de préparation associé
JP2017149103A (ja) * 2016-02-26 2017-08-31 凸版印刷株式会社 抗菌消臭シートの製造方法及び抗菌消臭シート

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021123773A1 (fr) * 2019-12-16 2021-06-24 Oxy Solutions As Compositions antimicrobiennes

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