WO2018216474A1 - Nanofibres de cellulose oxydée, dispersion de nanofibres de cellulose oxydée, et procédé de production de dispersion de nanofibres de cellulose oxydée - Google Patents

Nanofibres de cellulose oxydée, dispersion de nanofibres de cellulose oxydée, et procédé de production de dispersion de nanofibres de cellulose oxydée Download PDF

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WO2018216474A1
WO2018216474A1 PCT/JP2018/018029 JP2018018029W WO2018216474A1 WO 2018216474 A1 WO2018216474 A1 WO 2018216474A1 JP 2018018029 W JP2018018029 W JP 2018018029W WO 2018216474 A1 WO2018216474 A1 WO 2018216474A1
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oxidized cellulose
cellulose nanofiber
oxidized
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mmol
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PCT/JP2018/018029
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Japanese (ja)
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伸治 佐藤
眞 松本
武史 中山
賢志 高市
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日本製紙株式会社
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B15/00—Preparation of other cellulose derivatives or modified cellulose, e.g. complexes
    • C08B15/02—Oxycellulose; Hydrocellulose; Cellulosehydrate, e.g. microcrystalline cellulose
    • C08B15/04—Carboxycellulose, e.g. prepared by oxidation with nitrogen dioxide

Definitions

  • the present invention relates to an oxidized cellulose nanofiber, a dispersion containing the oxidized cellulose nanofiber, and a method for producing the oxidized cellulose nanofiber dispersion.
  • nanofibers nanofibers
  • This nanofiber is expected to have an effect of increasing the strength of a high-performance filter, resin or coating film that does not allow extremely fine foreign substances to pass through.
  • Patent Document 1 discloses a fine cellulose fiber (cellulose nanofiber having a number average fiber diameter of 2 to 150 nm in which a part of hydroxyl groups of cellulose is carboxylated). Fiber).
  • This cellulose nanofiber has the property that the viscosity at a low shear rate is high and the viscosity at a high shear rate is low. For this reason, for example, a coating containing cellulose nanofibers is expected to be easy to apply at the time of coating and not to drip after coating.
  • the present invention provides the following (1) to (6).
  • the oxidized cellulose nanofiber according to (1) wherein the amount of carboxyl groups of the oxidized cellulose nanofiber is 0.4 to 0.8 mmol / g with respect to the absolute dry mass of the oxidized cellulose nanofiber.
  • the amount of carboxyl groups of the oxidized cellulose nanofiber is 0.2 to 2.0 mmol / g with respect to the absolute dry mass of the oxidized cellulose nanofiber, and the oxidized cellulose nanofiber obtained by the following formula (1)
  • Ratio of carboxyl group (%) (total amount of carboxyl group amount / carboxyl group amount and carboxylate group amount) ⁇ 100 (4)
  • the amount of carboxyl groups of the oxidized cellulose nanofibers is 0.2 to 2.0 mmol / g with respect to the absolute dry mass of the oxidized cellulose nanofibers, and the amount of carboxyl groups of the oxidized cellulose nanofibers is large.
  • the oxidized cellulose nanofiber according to (1) containing 40 to 100 mol% of a valent metal.
  • (6) a preparation step of preparing an oxidized cellulose nanofiber dispersion having a carboxyl group amount of 0.2 to 2.0 mmol / g with respect to the absolutely dry mass of the oxidized cellulose nanofiber; and the oxidized cellulose nanofiber dispersion;
  • an addition / mixing step of adding 40 to 100 mol% of a polyvalent metal with respect to the amount of carboxyl groups of the oxidized cellulose nanofibers and mixing them to the oxidized cellulose nanofiber dispersion obtained by the addition / mixing step
  • the dispersion was stirred for 24 hours using a stirrer having a rotation speed of 1000 rpm, and then allowed to stand for 6 hours, and the rate of decrease in viscosity at a shear rate of 0.1 / s was 50% or less.
  • an oxidized cellulose nanofiber that suppresses a decrease in viscosity in a low shear rate region.
  • the dispersion containing this oxidized cellulose nanofiber and the manufacturing method of this dispersion can be provided.
  • 2 is a graph showing changes in viscosity of an oxidized CNF aqueous dispersion in a stability test (Examples 1-1 and 1-2, Comparative Example 1-1). 2 is a graph showing changes in viscosity of an oxidized CNF aqueous dispersion in a stability test (Example 2-1 and Comparative Examples 2-1, 2-2, and 2-3).
  • the oxidized cellulose nanofiber (oxidized CNF) of the present invention is characterized by satisfying the following conditions.
  • the oxidized cellulose nanofiber of the present invention is not particularly limited as long as the above-mentioned viscosity reduction rate is satisfied.
  • the amount of carboxyl groups of oxidized CNF is 0.4 to 0 with respect to the absolutely dry mass of oxidized CNF.
  • the amount of carboxyl groups in the oxidized CNF is 0.2 to 2.0 mmol / g with respect to the absolute dry mass of the oxidized CNF. Mention may be made of oxidized CNF having a carboxyl group ratio of 50% or more.
  • Formula (1): Ratio of carboxyl group (%) (total amount of carboxyl group amount / carboxyl group amount and carboxylate group amount) ⁇ 100
  • the carboxyl group represents a group represented by —COOH
  • the carboxylate group represents a group represented by —COO 2 — .
  • the counter cation of the carboxylate group is not particularly limited, and examples thereof include alkali metal ions such as sodium ions and potassium ions.
  • the oxidized cellulose nanofiber of the present invention is not particularly limited as long as the above-mentioned viscosity reduction rate is satisfied, but the carboxyl group amount is 0.2 to 2.0 mmol / wt with respect to the absolutely dry mass of oxidized CNF. and oxidized CNF containing 40 to 100 mol% of a polyvalent metal with respect to the amount of carboxyl groups of oxidized CNF.
  • the oxidized CNF of the present invention can be obtained by defibrating oxidized cellulose obtained by introducing a carboxyl group into a cellulose raw material.
  • cellulose raw materials include plant materials (for example, wood, bamboo, hemp, jute, kenaf, farmland waste, cloth, pulp (coniferous unbleached kraft pulp (NUKP), coniferous bleached kraft pulp (NBKP), hardwood not yet).
  • plant materials for example, wood, bamboo, hemp, jute, kenaf, farmland waste, cloth, pulp (coniferous unbleached kraft pulp (NUKP), coniferous bleached kraft pulp (NBKP), hardwood not yet).
  • NUKP unbleached kraft pulp
  • NKP coniferous bleached kraft pulp
  • Bleached kraft pulp LLKP
  • hardwood bleached kraft pulp LLKP
  • softwood unbleached sulfite pulp NUSP
  • softwood bleached sulfite pulp NBSP
  • thermomechanical pulp TMP
  • recycled pulp waste paper, etc.
  • animal nature examples include materials (for example, ascidians), algae, microorganisms (for example, acetic acid bacteria (Acetobacter)), those originating from microbial products, and any of them can be used, preferably plants or microorganisms It is a cellulose raw material derived from, and more preferably a plant-derived cellulose raw material.
  • a carboxyl group can be introduced into the cellulose raw material by oxidizing (carboxylation) the above cellulose raw material by a known method.
  • oxidation there is a method in which a cellulose raw material is oxidized in water using an oxidizing agent in the presence of an N-oxyl compound and bromide, iodide, or a mixture thereof.
  • an oxidized cellulose having an aldehyde group and a carboxyl group (—COOH) or a carboxylate group (—COO ⁇ ) on the surface can be obtained.
  • concentration of the cellulose at the time of reaction is not specifically limited, It is preferable that it is 5 mass% or less.
  • N-oxyl compound refers to a compound capable of generating a nitroxy radical.
  • any compound can be used as long as it promotes the target oxidation reaction.
  • TEMPO 2,2,6,6-tetramethylpiperidine-1-oxy radical
  • its derivatives for example, 4-hydroxy TEMPO
  • the amount of N-oxyl compound used is not particularly limited as long as it is a catalytic amount capable of oxidizing cellulose as a raw material. 0.01 mmol to 10 mmol is preferable, 0.01 mmol to 1 mmol is more preferable, and 0.05 mmol to 0.5 mmol is more preferable with respect to 1 g of absolutely dry cellulose.
  • the concentration is preferably about 0.1 mmol / L to 4 mmol / L with respect to the reaction system.
  • Bromide is a compound containing bromine and contains alkali metal bromide that can dissociate and ionize in water.
  • An iodide is a compound containing iodine, and includes an alkali metal iodide.
  • the amount of bromide or iodide used can be selected within a range that can promote the oxidation reaction.
  • the total amount of bromide and iodide is preferably 0.1 mmol to 100 mmol, more preferably 0.1 mmol to 10 mmol, and still more preferably 0.5 mmol to 5 mmol with respect to 1 g of absolutely dry cellulose.
  • oxidizing agent known ones can be used, and examples thereof include halogen, hypohalous acid, halous acid, perhalogen acid or salts thereof, halogen oxide, peroxide and the like.
  • halogen hypohalous acid
  • halous acid halous acid
  • perhalogen acid or salts thereof halogen oxide
  • peroxide peroxide
  • sodium hypochlorite is preferable because it is inexpensive and has a low environmental impact.
  • the amount of the oxidizing agent used is preferably 0.5 mmol to 500 mmol, more preferably 0.5 mmol to 50 mmol, and even more preferably 1 mmol to 25 mmol, 3 mmol to 10 mmol with respect to 1 g of absolutely dry cellulose. Further, for example, 1 mol to 40 mol is preferable with respect to 1 mol of the N-oxyl compound.
  • the reaction temperature is preferably 4 ° C. to 40 ° C., and may be a room temperature of about 15 ° C. to 30 ° C.
  • carboxyl groups are generated in the cellulose, so that the pH of the reaction solution decreases.
  • an alkaline solution such as an aqueous sodium hydroxide solution is added during the reaction to maintain the pH of the reaction solution at about 8 to 12, preferably about 10 to 11.
  • the reaction medium is preferably water for reasons such as ease of handling and the difficulty of side reactions.
  • the reaction time in the oxidation reaction can be appropriately set according to the progress of oxidation, and is usually 0.5 to 6 hours, and preferably 0.5 to 4 hours.
  • the oxidation reaction may be carried out in two stages.
  • the carboxylated cellulose obtained by filtration after the completion of the first-stage reaction is oxidized again under the same or different reaction conditions without being subjected to reaction inhibition by the salt generated as a by-product in the first-stage reaction, It can be oxidized efficiently.
  • the ozone concentration in the gas containing ozone is preferably 50 g / m 3 to 250 g / m 3 , and more preferably 50 g / m 3 to 220 g / m 3 .
  • the amount of ozone added to the cellulose raw material is preferably 0.1 parts by mass to 30 parts by mass, and more preferably 5 parts by mass to 30 parts by mass when the solid content of the cellulose raw material is 100 parts by mass. .
  • the ozone treatment temperature is preferably 0 ° C. to 50 ° C., more preferably 20 ° C. to 50 ° C.
  • the ozone treatment time is not particularly limited, but is about 1 minute to 360 minutes, preferably about 30 minutes to 360 minutes. When the conditions for the ozone treatment are within these ranges, the cellulose can be prevented from being excessively oxidized and decomposed, and the yield of oxidized cellulose is improved.
  • an additional oxidation treatment may be performed using an oxidizing agent.
  • the oxidizing agent used for the additional oxidation treatment is not particularly limited, and examples thereof include chlorine compounds such as chlorine dioxide and sodium chlorite, oxygen, hydrogen peroxide, persulfuric acid, peracetic acid and the like.
  • these oxidizing agents can be dissolved in a polar organic solvent such as water or alcohol to prepare an oxidizing agent solution, and a cellulose raw material can be immersed in the solution for additional oxidation treatment.
  • the amount of carboxyl groups in the oxidized cellulose can be adjusted by controlling the reaction conditions such as the amount of the oxidant added and the reaction time.
  • the amount of carboxyl groups is about 0.2 to 2.0 mmol / g with respect to the absolutely dry mass of oxidized cellulose. If it is less than 0.2 mmol / g, a great deal of energy is required to defibrate to oxidized CNF. Moreover, when the oxidized cellulose exceeding 2.0 mmol is used as a raw material, the obtained oxidized CNF does not have a fiber form.
  • the apparatus used for defibration is not particularly limited, and examples thereof include high-speed rotation type, colloid mill type, high pressure type, roll mill type, ultrasonic type and the like, high pressure or ultra high pressure homogenizer is preferable, wet high pressure or An ultra-high pressure homogenizer is more preferable. It is preferable that the apparatus can apply a strong shearing force to the cellulose raw material or oxidized cellulose (usually a dispersion).
  • the pressure that can be applied by the apparatus is preferably 50 MPa or more, more preferably 100 MPa or more, and still more preferably 140 MPa or more.
  • the apparatus is preferably a wet high-pressure or ultrahigh-pressure homogenizer capable of applying the above pressure to a cellulose raw material or oxidized cellulose (usually a dispersion) and applying a strong shearing force. Thereby, defibration can be performed efficiently.
  • the number of treatments (passes) in the defibrating device may be one time, two times or more, and preferably two times or more.
  • oxidized cellulose is dispersed in a solvent.
  • a solvent will not be specifically limited if an oxidized cellulose can be disperse
  • distributed For example, water, organic solvents (for example, hydrophilic organic solvents, such as methanol), and those mixed solvents are mentioned. Since the cellulose raw material is hydrophilic, the solvent is preferably water.
  • the solid content concentration of oxidized cellulose in the dispersion is usually 0.1% by mass or more, preferably 0.2% by mass or more, more preferably 0.3% by mass or more. Thereby, the liquid quantity with respect to the quantity of a cellulose fiber raw material becomes an appropriate quantity, and is efficient.
  • the upper limit is usually 10% by mass or less, preferably 6% by mass or less. Thereby, fluidity
  • the order of the defibrating process and the dispersing process is not particularly limited, and either may be performed first or simultaneously, but it is preferable to perform the defibrating process after the dispersing process.
  • the combination of each process should just be performed at least once and may be repeated twice or more.
  • preliminary treatment may be performed as necessary.
  • the pretreatment may be performed using a mixing, stirring, emulsifying, and dispersing device such as a high-speed shear mixer.
  • the average fiber diameter of the oxidized CNF of the present invention is preferably 3 nm or more or 500 nm or less.
  • the average fiber diameter and average fiber length of cellulose nanofibers are measured by, for example, preparing a 0.001% by mass aqueous dispersion of oxidized CNF, extending the diluted dispersion thinly on a mica sample stage, and drying by heating at 50 ° C. Then, an observation sample is prepared, and by measuring the cross-sectional height of the shape image observed with an atomic force microscope (AFM), the number average fiber diameter or fiber length can be calculated.
  • AFM atomic force microscope
  • the average aspect ratio of oxidized CNF is usually 50 or more. Although an upper limit is not specifically limited, Usually, it is 1000 or less.
  • oxidized CNF of the present invention (Specific example 1 of oxidized CNF of the present invention)
  • the oxidized CNF aqueous dispersion adjusted to 0.5% by mass was adjusted to 0.5% by mass with respect to the viscosity at a shear rate of 0.1 / s measured by leaving the oxidized CNF aqueous dispersion adjusted to 0.5% by mass for 6 hours.
  • the amount of carboxyl groups was determined to be 50% or less at a shear rate of 0.1 / s measured by standing for 6 hours. Mention may be made of oxidized CNF at 0.4 to 0.8 mmol / g with respect to the dry mass.
  • Oxidized CNF having a carboxyl group content of 0.4 to 0.8 mmol / g can be prepared by controlling the reaction conditions such as the amount of oxidant added and the reaction time in the above-described method for producing oxidized cellulose. .
  • An oxidized CNF in which the ratio of carboxyl groups in the oxidized CNF determined by the following formula (1) is 50% or more is 2 to 2.0 mmol / g.
  • Ratio of carboxyl group (%) (total amount of carboxyl group amount / carboxyl group amount and carboxylate group amount) ⁇ 100
  • required by the said Formula (1) can be adjusted by desalting oxidized CNF with a cation exchange resin, or adding an acid.
  • a cation salt (Na salt) is replaced with a proton by contacting with the cation exchange resin. Since a cation exchange resin is used, unnecessary by-products such as sodium chloride are not generated. After acid treatment using a cation exchange resin, the cation exchange resin is simply removed by filtration with a metal mesh or the like. Thus, an aqueous dispersion of oxidized CNF having an acid type / salt type adjusted as a filtrate can be obtained.
  • the target to be removed as a filtrate by a metal mesh or the like is a cation exchange resin, and the oxidized CNF is hardly removed by the diameter of the metal mesh or the like, and almost the entire amount is contained in the filtrate.
  • the filtrate contains a large amount of oxidized CNF having a very short fiber length.
  • oxidized CNF is hard to aggregate. Accordingly, an aqueous dispersion of oxidized CNF having a high light transmittance can be obtained.
  • both strong acid ion exchange resins and weak acid ion exchange resins can be used as long as the counter ion is a proton.
  • the strong acid ion exchange resin and the weak acid ion exchange resin include those obtained by introducing a sulfonic acid group or a carboxy group into a styrene resin or an acrylic resin.
  • the shape of the cation exchange resin is not particularly limited, and various shapes such as fine particles (particles), membranes, and fibers can be used. Among these, granular is preferable from the viewpoint of efficiently treating oxidized CNF and facilitating separation after the treatment.
  • a commercial item can be used as such a cation exchange resin.
  • Commercially available products include, for example, Amberjet 1020, 1024, 1060, 1220 (above, Organo), Amberlite IR-200C, IR-120B (above, Tokyo Organic Chemical Co., Ltd.), Lebatit SP 112 S100 (manufactured by Bayer), GEL CK08P (manufactured by Mitsubishi Chemical), Dowex 50W-X8 (manufactured by Dow Chemical) and the like.
  • the contact between the oxidized CNF and the cation exchange resin is, for example, mixing the granular cation exchange resin and the aqueous dispersion of the oxidized CNF, and stirring and shaking as necessary to keep the oxidized CNF and the cation exchange resin constant. After the contact for a period of time, the cation exchange resin and the aqueous dispersion can be separated.
  • the concentration of the oxidized CNF in the aqueous dispersion and the ratio with the cation exchange resin are not particularly limited, and those skilled in the art can appropriately set them from the viewpoint of efficiently performing proton substitution.
  • the concentration of the aqueous dispersion of oxidized CNF is preferably 0.05 to 10% by mass. If the concentration of the aqueous dispersion is less than 0.05% by mass, it may take too much time for proton substitution. If the concentration of the aqueous dispersion is more than 10% by mass, sufficient proton substitution effect may not be obtained.
  • the contact time is also not particularly limited, and can be appropriately set by those skilled in the art from the viewpoint of efficiently performing proton substitution. For example, the contact can be performed for 0.25 to 4 hours.
  • H form an acid form
  • the acid addition treatment is a treatment for adding an acid to the dispersion of oxidized CNF.
  • the acid may be an inorganic acid or an organic acid.
  • the inorganic acid include mineral acids such as sulfuric acid, hydrochloric acid, nitric acid, sulfurous acid, nitrous acid, phosphoric acid, and residual acid of chlorine dioxide generator, and hydrochloric acid is preferable.
  • the organic acid include acetic acid, lactic acid, succinic acid, citric acid, formic acid and the like.
  • the pH during the acid treatment is usually 2 or more, preferably 3 or more.
  • the upper limit is preferably 6 or less, and preferably 5 or less.
  • the pH is preferably 2 to 6, more preferably 2 to 5, and still more preferably 3 to 5.
  • the addition amount of an acid What is necessary is just to complete
  • a washing treatment is preferably performed after the acid addition. Thereby, a dispersion of oxidized CNF can be obtained.
  • the washing treatment is preferably performed to the extent that free acid is removed from the gel substance. Thereby, the storage stability and dispersibility of oxidized CNF can be improved.
  • the amount of free acid contained in the washing solution after the washing is not particularly limited, but is preferably 0.05% by mass or less, more preferably the detection limit or less.
  • the method of the washing treatment is not particularly limited.
  • the gel-like substance obtained after acidification is preliminarily dehydrated, washed, dispersed and pulverized as necessary, and such a series of processes is repeated twice or more.
  • a method is mentioned.
  • Any solvent can be used as long as the oxidized CNF can be sufficiently dispersed in the solvent. Examples thereof include water, an organic solvent, and a mixed solvent of two or more solvents selected from these.
  • the organic solvent is preferably a hydrophilic solvent such as methanol.
  • the mixed solvent preferably contains at least water. Since the cellulose raw material is hydrophilic, the solvent is preferably water, a hydrophilic organic solvent, or a hydrophilic mixed solvent, and more preferably water.
  • the amount of the solvent added is usually an amount that gives a solid content of about 1 to 2% of the gel substance.
  • Dispersion may be performed using a slurrying device such as a mixer.
  • the dispersion is preferably performed until the particle size is reduced (slurry) until the gel material has a particle size that does not settle in a short time.
  • the pulverizer examples include a pulverizer that does not use media, such as a pulverizer that uses media such as a bead mill, a high-speed rotary type, a colloid mill type, a high-pressure type, a roll mill type, and an ultrasonic disperser.
  • a pulverizer that does not use media is preferable, a high-pressure disperser is more preferable, a wet high-pressure disperser is further preferable, and a wet high-pressure or ultrahigh-pressure homogenizer is even more preferable.
  • the dispersion liquid in which the acid-type cellulose nanofibers are sufficiently dispersed can be efficiently obtained.
  • the pulverization conditions are preferably 50 MPa or more, more preferably 100 MPa or more, and still more preferably 140 MPa or more.
  • the crusher preferably has the ability to disperse under these conditions.
  • the number of treatments (passes) in the pulverizer may be one or two or more.
  • dehydration may be performed as necessary.
  • dehydration include dehydration by centrifugation.
  • the dehydration is preferably performed until the solid content in the solvent reaches about 3 to 20%.
  • the temperature of the cleaning treatment is preferably 10 ° C or higher, more preferably 20 ° C or higher.
  • the upper limit is preferably 50 ° C. or lower, and more preferably 40 ° C. or lower. Accordingly, 10 to 50 ° C. is preferable, and 20 to 40 ° C. is more preferable.
  • the ratio of a carboxyl group can be calculated by the following method.
  • a 0.1% by mass slurry of oxidized (carboxylated) cellulose nanofiber salt is prepared.
  • 0.1 M hydrochloric acid aqueous solution is added to the prepared slurry to adjust the pH to 2.5, and then 0.1 N sodium hydroxide aqueous solution is added to measure the electric conductivity until the pH becomes 11.
  • the amount of carboxyl groups is calculated from the amount of sodium hydroxide consumed in the neutralization step of the weak acid with a gradual change in electrical conductivity (b) using the following formula (3):
  • Formula (3): Amount of carboxyl group (mmol / g oxidized cellulose nanofiber) b (mL) ⁇ 0.1 / mass of oxidized cellulose nanofiber (g)
  • the proportion of carboxyl groups can be calculated using the following formula (1):
  • Ratio of carboxyl group (%) (total amount of carboxyl group amount / carboxyl group amount and carboxylate group amount) ⁇ 100
  • oxidized CNF of the present invention (Specific example 3 of oxidized CNF of the present invention)
  • the oxidized CNF aqueous dispersion adjusted to 0.5% by mass was adjusted to 0.5% by mass with respect to the viscosity at a shear rate of 0.1 / s measured by leaving the oxidized CNF aqueous dispersion adjusted to 0.5% by mass for 6 hours.
  • the amount of carboxyl groups of the oxidized CNF was 0. 0 as the CNF having a viscosity reduction rate of 50% or less at a shear rate of 0.1 / s measured by standing for 6 hours.
  • examples thereof include oxidized CNF containing 2 to 2.0 mmol / g and 40 to 100 mol% of a polyvalent metal with respect to the amount of carboxyl groups of oxidized CNF.
  • Examples of the method for producing an oxidized CNF dispersion containing a polyvalent metal of the present invention include the following methods.
  • an aqueous dispersion of oxidized CNF having a carboxyl group content adjusted to 0.2 to 2.0 mmol / g is prepared.
  • 40 to 100 mol% of a polyvalent metal is added to the aqueous dispersion of oxidized CNF with respect to the amount of carboxyl groups contained in the oxidized CNF and mixed.
  • an oxidized cellulose nanofiber dispersion containing 40 to 100 mol% of a polyvalent metal with respect to the carboxyl group amount of oxidized CNF can be obtained.
  • the concentration of the oxidized CNF dispersion, the temperature and the pressure when adding the polyvalent metal to the oxidized CNF dispersion are not particularly limited, but the concentration of the dispersion is usually 0.5 to 1.2% by mass, the temperature
  • the pressure is usually 18 to 35 ° C. and preferably at normal pressure.
  • the number of rotations, mixing time, and the like when adding and mixing the polyvalent metal to the oxidized CNF dispersion are particularly limited as long as the polyvalent metal can be uniformly mixed with the oxidized CNF dispersion. Although it is not a thing, it is preferable to set it as the rotation speed 1000-3000 rpm and the mixing time 5-30 minutes.
  • the polyvalent metal added to the oxidized CNF is not particularly limited, but a divalent or trivalent metal hydroxide, carbonate, or organic acid salt is preferably used, and calcium, zinc, aluminum, More preferably, cobalt, nickel, copper hydroxide, carbonate, and organic acid salt are used, and calcium, aluminum hydroxide, carbonate, and organic acid salt are more preferably used, and calcium hydroxide, It is particularly preferable to use a carbonate or an organic acid salt.
  • calcium acetate etc. are mentioned as an organic acid salt of calcium.
  • the content of the polyvalent metal in the oxidized CNF dispersion can be qualitatively and quantitatively confirmed from elemental analysis such as ICP emission spectroscopic analysis and fluorescent X-ray.
  • the remaining 300 g of the oxidized CNF aqueous dispersion was transferred to a 500 mL beaker and stirred with a stirrer for 1 day (float stirrer 3 cm, 1000 rpm, 23 ° C.). Note that the mouth of the beaker was sealed with parafilm to prevent water evaporation during stirring. After leaving the oxidized CNF aqueous dispersion stirred for one day for 6 hours, the viscosity at a shear rate of 0.1 / s was measured by a rheometer (viscosity after stirring).
  • Viscosity reduction rate (%) at a shear rate of 0.1 / s ((viscosity before stirring ⁇ viscosity after stirring) / viscosity before stirring) ⁇ 100
  • Example 1-1 Bleached unbeaten kraft pulp derived from conifers (whiteness 85%) 5.00 g (absolutely dry), 20 mg of TEMPO (Sigma Aldrich), 0.025 mmol per 1 g of absolute dry cellulose and 514 mg of sodium bromide The solution was added to 500 mL of an aqueous solution in which 1.0 mmol) was dissolved in 1 g of cellulose, and stirred until the pulp was uniformly dispersed. An aqueous sodium hypochlorite solution was added to the reaction system so that sodium hypochlorite was 1.4 mmol / g, and the oxidation reaction was started.
  • Example 1-2 Bleached unbeaten kraft pulp derived from conifers (whiteness 85%), 5.00 g (absolutely dry), 39 mg of TEMPO (Sigma Aldrich) and 0.05 mmol of sodium bromide (absolutely dry) The solution was added to 500 mL of an aqueous solution in which 1.0 mmol) was dissolved in 1 g of cellulose, and stirred until the pulp was uniformly dispersed. An aqueous sodium hypochlorite solution was added to the reaction system so that sodium hypochlorite was 6.0 mmol / g, and the oxidation reaction was started.
  • ⁇ Comparative Example 1-1 Bleached unbeaten kraft pulp derived from conifers (whiteness 85%), 5.00 g (absolutely dry), 39 mg of TEMPO (Sigma Aldrich) and 0.05 mmol of sodium bromide (absolutely dry) The solution was added to 500 mL of an aqueous solution in which 1.0 mmol) was dissolved in 1 g of cellulose, and stirred until the pulp was uniformly dispersed. An aqueous sodium hypochlorite solution was added to the reaction system so that sodium hypochlorite was 6.0 mmol / g, and the oxidation reaction was started.
  • Example 2-1 Bleached unbeaten kraft pulp derived from conifers (whiteness 85%), 5.00 g (absolutely dry), 39 mg of TEMPO (Sigma Aldrich) and 0.05 mmol of sodium bromide (absolutely dry) The solution was added to 500 mL of an aqueous solution in which 1.0 mmol) was dissolved in 1 g of cellulose, and stirred until the pulp was uniformly dispersed. An aqueous sodium hypochlorite solution was added to the reaction system so that sodium hypochlorite was 6.0 mmol / g, and the oxidation reaction was started.
  • ⁇ Comparative Example 2-2 Bleached unbeaten kraft pulp derived from conifers (whiteness 85%), 5.00 g (absolutely dry), 39 mg of TEMPO (Sigma Aldrich) and 0.05 mmol of sodium bromide (absolutely dry) The solution was added to 500 mL of an aqueous solution in which 1.0 mmol) was dissolved in 1 g of cellulose, and stirred until the pulp was uniformly dispersed. An aqueous sodium hypochlorite solution was added to the reaction system so that sodium hypochlorite was 6.0 mmol / g, and the oxidation reaction was started.
  • ⁇ Comparative Example 2-3 Bleached unbeaten kraft pulp derived from conifers (whiteness 85%), 5.00 g (absolutely dry), 39 mg of TEMPO (Sigma Aldrich) and 0.05 mmol of sodium bromide (absolutely dry) The solution was added to 500 mL of an aqueous solution in which 1.0 mmol) was dissolved in 1 g of cellulose, and stirred until the pulp was uniformly dispersed. An aqueous sodium hypochlorite solution was added to the reaction system so that sodium hypochlorite was 6.0 mmol / g, and the oxidation reaction was started.
  • Viscosity-shear rate relationship of oxidized CNF before stirring in Example 1-1 11 Viscosity-shear rate relationship of oxidized CNF after stirring in Example 1-1 20 Oxidized CNF before stirring in Example 1-2 Viscosity-Shear Rate Relationship 21 Viscosity-shear rate relationship of oxidized CNF after stirring in Example 1-2 30 Viscosity-shear rate relationship of oxidized CNF before stirring in Comparative Example 1-1 Comparative Example 1 100 Viscosity-shear rate relationship of oxidized CNF after stirring 100 Viscosity-shear rate relationship of oxidized CNF before stirring in Example 2-1 110 Viscosity-shear rate of oxidized CNF after stirring in Example 2-1 Relationship 200 Viscosity-shear rate relationship of oxidized CNF before stirring in Comparative Example 2-1 Relationship 210 viscosity / shear rate of oxidized CNF after stirring in Comparative Example 2-1 300 Before stirring in Comparative Example 2-2 Viscosity of oxid

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Abstract

L'invention concerne des nanofibres de cellulose oxydée caractérisées en ce qu'une dispersion aqueuse des nanofibres de cellulose oxydée présentant une concentration ajustée à 0,5 % en masse possède une viscosité mesurée à une vitesse de cisaillement de 0,1 /s après avoir été agitée avec un agitateur à une vitesse de rotation de 1 000 tr/min pendant 24 heures, puis laissée reposer pendant 6 heures, ladite viscosité présentant une diminution inférieure ou égale à 50 % à partir d'une viscosité mesurée à une vitesse de cisaillement de 0,1 /s de la dispersion aqueuse des nanofibres de cellulose oxydée, qui présente une concentration ajustée à 0,5 % en masse, qui a été laissée reposer pendant 6 heures.
PCT/JP2018/018029 2017-05-24 2018-05-10 Nanofibres de cellulose oxydée, dispersion de nanofibres de cellulose oxydée, et procédé de production de dispersion de nanofibres de cellulose oxydée WO2018216474A1 (fr)

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JP2020105429A (ja) * 2018-12-28 2020-07-09 日本製紙株式会社 変性セルロース繊維、その分散液及びその製造方法
WO2020220300A1 (fr) * 2019-04-30 2020-11-05 钟春燕 Fibre de biocellulose, pansement hémostatique comprenant ladite fibre et application associée
US20220002442A1 (en) * 2018-10-16 2022-01-06 Oji Holdings Corporation Fibrous cellulose, fibrous cellulose dispersion, and production method for fibrous cellulose
WO2024203024A1 (fr) * 2023-03-27 2024-10-03 日本製紙株式会社 Procédé de production d'une dispersion de nanofibres de cellulose oxydée

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WO2020220300A1 (fr) * 2019-04-30 2020-11-05 钟春燕 Fibre de biocellulose, pansement hémostatique comprenant ladite fibre et application associée
WO2024203024A1 (fr) * 2023-03-27 2024-10-03 日本製紙株式会社 Procédé de production d'une dispersion de nanofibres de cellulose oxydée

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