WO2015087868A1 - Fibres de cellulose et leur procédé de production, dispersion de fibres de cellulose ultrafine et son procédé de production, et procédé de production de fibres de cellulose ultrafine - Google Patents

Fibres de cellulose et leur procédé de production, dispersion de fibres de cellulose ultrafine et son procédé de production, et procédé de production de fibres de cellulose ultrafine Download PDF

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WO2015087868A1
WO2015087868A1 PCT/JP2014/082533 JP2014082533W WO2015087868A1 WO 2015087868 A1 WO2015087868 A1 WO 2015087868A1 JP 2014082533 W JP2014082533 W JP 2014082533W WO 2015087868 A1 WO2015087868 A1 WO 2015087868A1
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cellulose fiber
dispersion
drying
cellulose
cast film
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PCT/JP2014/082533
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English (en)
Japanese (ja)
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明 磯貝
賢志 高市
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国立大学法人東京大学
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    • 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
    • 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

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  • the present invention relates to a cellulose fiber that can be finely dispersed in a solvent even after being dried, a fine cellulose fiber dispersion using the cellulose fiber as a raw material, a fine cellulose fiber thereof, a molded article comprising the fine cellulose fiber, and these It relates to a manufacturing method.
  • Fine cellulose fibers (hereinafter sometimes referred to as “cellulose nanofibers”), which are nano-sized materials, use cellulose, an abundantly existing biomass, as an oxidation catalyst using N-oxyl compounds as an oxidation catalyst. And then finely dispersed (hereinafter referred to as “nanodispersion”) by mechanical fibrillation treatment that imparts a shearing force in water to the oxidized cellulose (hereinafter sometimes referred to as “oxidized cellulose fiber”). Sometimes obtained).
  • the oxidized cellulose nanofiber dispersion in which the oxidized cellulose fibers are nano-dispersed can be used as a thickening agent as it is or in the form of a gel combined with other materials.
  • a material such as a sheet, a film, a foam, and an airgel can be produced by drying the oxidized cellulose nanofiber dispersion as it is or by combining it with another material (for example, Patent Documents). 1).
  • the oxidized cellulose nanofiber is a bio-based nanofiber with a uniform width and a high aspect ratio, and has an excellent nanodispersibility in water due to a large specific surface area, high strength, and introduced carboxyl groups. There are features. Therefore, it is expected to be used in various fields such as an oxygen barrier film, a general-purpose plastic reinforcing material, a medical material, a cell culture substrate, a catalyst carrier, an adsorbent, and a separating material.
  • oxidized cellulose nanofiber dispersion has a solid content concentration of 0.1% by mass to 5%. Mass% is very low. Therefore, when transporting the oxidized cellulose nanofiber dispersion used for producing a product using the oxidized cellulose nanofiber, there is a problem that a large amount of water is transported and the cost for transport is high. In addition, when the oxidized cellulose nanofiber dispersion is stored, there is a problem that it must be refrigerated or treated with a preservative as a countermeasure against microorganisms.
  • fibrous oxidized cellulose before defibration and nano-dispersion treatment (width 0.01 mm to 0.06 mm, length 0.1 mm to 5 mm, wood cellulose fiber before oxidation treatment) Squeezed in the washing and filtration process, and the solid concentration was raised to about 10% to 40% (that is, containing 90% to 60% water) in an undried state. It is conceivable to carry. If it is the said undried oxycellulose, a cellulose nanofiber dispersion can always be manufactured by the fibrillation process in water. However, there is still a problem that the amount of water is still large even in an undried state, and the cost for transportation is high, and that preservative measures during storage are necessary.
  • the present invention is a cellulose that can be finely dispersed in a solvent, even when it is once dried, as in the case of being prepared from an undried state, can reduce transportation costs, and has excellent storage stability.
  • Means for solving the problems are as follows. That is, ⁇ 1> An oxidation step in which an oxidized cellulose fiber is obtained by oxidizing a cellulosic raw material in a reaction solution containing an N-oxyl compound and a co-oxidant; A reduction step of reducing the oxidized cellulose fibers in a reaction solution containing a reducing agent to obtain reduced oxidized cellulose fibers; A drying step of drying the reduced oxidized cellulose fiber, The cellulose fiber obtained by drying the reduced oxidized cellulose fiber can be finely dispersed in a solvent.
  • Cellulose fibers that can be finely dispersed in a solvent after drying, After drying the cellulose fiber at 105 ° C. for 3 hours, the cellulose fiber is diluted with water to a concentration of 0.1% by mass to obtain a 40 mL dispersion, and the dispersion is placed in a 50 mL container. After defibrating for 2 minutes at 7,500 rpm using a cylindrical homogenizer, when the fiber is defibrated for 8 minutes with an ultrasonic homogenizer while cooling around the vessel with ice water, the light transmittance at a wavelength of 600 nm of the dispersion is It is a cellulose fiber characterized by having a birefringence of 80% or more.
  • ⁇ 5> A fine cellulose fiber dispersion in which cellulose fibers are finely dispersed in a solvent, The cellulose fiber is a cellulose fiber that can be finely dispersed in a solvent after drying, After drying the cellulose fiber at 105 ° C.
  • the cellulose fiber is diluted with water to a concentration of 0.1% by mass to obtain a 40 mL dispersion, and the dispersion is placed in a 50 mL container.
  • the light transmittance at a wavelength of 600 nm of the dispersion is It is a fine cellulose fiber dispersion characterized by having a birefringence of 80% or more.
  • the conventional problems can be solved and the object can be achieved, and even if it is once dried, it can be finely dispersed in a solvent in the same manner as when prepared from an undried state.
  • Cellulose fibers that can be reduced in transportation costs and have excellent storage stability, a cellulose fiber production method that can easily produce the cellulose fibers with a low environmental load, and fine cellulose using the cellulose fibers
  • a fiber dispersion and a method for producing the same, and a method for producing fine cellulose fibers using the fine cellulose fiber dispersion can be provided.
  • FIG. 1 is a graph showing the results of measuring the light transmittance of the dispersions of Examples 1 and 2 and Comparative Example 1.
  • FIG. 2 is a photograph confirming the state of light transmission of the dispersions of Example 1 and Comparative Example 1.
  • FIG. 3 is a photograph observing the birefringence of the dispersions of Example 1 and Comparative Example 1.
  • FIG. 4 is a graph showing the results of measuring the ultraviolet absorption spectrum of Test Example 1.
  • FIG. 5 is a graph showing the results of measuring the light transmittance of the dispersion in Test Example 2-1.
  • FIG. 6 is a graph showing the results of measuring the ultraviolet absorption spectrum of Test Example 2-2.
  • the cellulose fiber of this invention can be suitably manufactured with the manufacturing method of the cellulose fiber of this invention.
  • the cellulose fiber of this invention is demonstrated with description of the manufacturing method of the cellulose fiber of this invention.
  • the method for producing a cellulose fiber of the present invention includes at least an oxidation step, a reduction step, and a drying step, and further includes other steps such as a further oxidation step as necessary.
  • the oxidation step is a step of obtaining oxidized cellulose fibers by oxidizing a cellulosic material in a reaction solution containing an N-oxyl compound and a co-oxidant.
  • the cellulose-based raw material is not particularly limited and may be appropriately selected depending on the intended purpose.
  • the cellulosic material may be subjected to a treatment for increasing the surface area such as beating.
  • N-oxyl compound is not particularly limited and may be appropriately selected depending on the intended purpose.
  • ““ Cellulose ”Vol. 10, 2003, pages 335-341. Shibata and A.I. Examples include the compounds described in “The Catalytic Oxidation of Cellulose Using TEMPO Derivatives: HPSEC and NMR Analysis of Oxidation Products” by Isogai. These may be used individually by 1 type and may use 2 or more types together.
  • N-oxyl compound examples include 2,2,6,6-tetramethylpiperidine-N-oxyl (hereinafter sometimes referred to as “TEMPO”), 4-acetamido TEMPO, 4-carboxy-TEMPO, 4-phosphonooxy-TEMPO and the like can be mentioned.
  • the content of the N-oxyl compound in the reaction solution is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include a catalyst amount.
  • the co-oxidant is not particularly limited and may be appropriately selected depending on the intended purpose.
  • hypohalous acid or a salt thereof hypohalous acid or a salt thereof, perhalogen acid or a salt thereof, hydrogen peroxide And perorganic acids.
  • hypohalous acid or a salt thereof hypohalous acid or a salt thereof, perhalogen acid or a salt thereof, hydrogen peroxide And perorganic acids.
  • these may be used individually by 1 type and may use 2 or more types together.
  • Specific examples of the co-oxidant include sodium hypochlorite and sodium hypobromite.
  • the reaction liquid may contain other components other than the above-described cellulose-based material, N-oxyl compound, and co-oxidant.
  • bromide and iodide there is no restriction
  • the conditions such as pH of the reaction solution, reaction temperature, pressure, and reaction time in the oxidation step are not particularly limited and can be appropriately selected depending on the purpose.
  • the oxidized cellulose fiber obtained by the oxidation step has a carboxyl group content of 0.8 mmol / g to 2.2 mmol / g and an aldehyde group content of 0.8 mmol / g or less.
  • the amount of carboxyl group and aldehyde group in the oxidized cellulose fiber is determined according to “T. Saito and A. Isogai”, “TEMPO-mediated oxidation of native cellulose. The effect of oxidative conditions in chemistry and chemistry. Biomacromolecules, Vol. 5, pp. 1983 to 1989, 2004 ”, and can be measured by an additional oxidation treatment with sodium chlorite and conductivity titration.
  • an oxidized cellulose fiber that does not contain an aldehyde group can be obtained without performing a later-described additional oxidation step.
  • the conditions for the oxidation step not containing the aldehyde group are not particularly limited. For example, “S. Saito, M. Hirota, N. Tamura, S. Kimura, H. Fukuzumi, L. Heux, A. Isogai,“ Individualization. of nano-sized plant cells fibers by direct surface carboxylating using TEMPO catalyst unneutral conditions, Biomacromolecules, Vol. 10, pp. 1992-1996, 2009 ”can be appropriately selected.
  • a further oxidation step may be included between the oxidation step and a reduction step described later.
  • the additional oxidation step is a step of further oxidizing the oxidized cellulose fiber obtained in the oxidation step with sodium chlorite.
  • the conditions for the additional oxidation process are not particularly limited. For example, “T. Saito and A. Isogai”, “TEMPO-mediated oxidation of native cellulose chemistry and the conditions of oxidative conditions for chemistry. ", Biomacromolecules, Vol. 5, pp. 1983 to 1989, 2004 ”can be appropriately selected. Oxidized cellulose fibers not containing an aldehyde group can be obtained by oxidizing the aldehyde group generated in a small amount at the C6 position to a carboxyl group by the additional oxidation step.
  • the oxidized cellulose fiber obtained in the oxidation step or the oxidized cellulose fiber obtained in the additional oxidation step may be used in a reduction step described later after suction filtration washing with water. Since the oxidized cellulose fibers are not dispersed evenly to the nanofiber unit at this stage, they can be washed by a normal water washing-suction filtration washing method. Specific examples of the washing method include a method of washing and washing with at least one of suction filtration and centrifugation. The number of times of washing may be one time or a plurality of times. The unreacted cooxidant and various byproducts can be removed by the washing.
  • the reduction step is a step of reducing the oxidized cellulose fibers in a reaction solution containing a reducing agent to obtain reduced oxidized cellulose fibers.
  • a ketone group is generated at the C2 position and the C3 position in the oxidized cellulose fiber as a side reaction.
  • a small amount of an aldehyde group is generated at the C6 position in addition to the above-described ketone group.
  • the oxidation step is performed using TEMPO, NaClO, and NaClO 2 that are weakly acidic to neutral, there is no aldehyde at the C6 position of the oxidized cellulose fiber.
  • the oxidation step is performed using TEMPO, NaBr, and NaClO with weak alkalinity, and then the additional oxidation step is performed, the aldehyde group at the C6 position of the oxidized cellulose fiber does not exist.
  • the reduction step at least a part of the ketone group and / or aldehyde group is converted to an alcoholic hydroxyl group. That is, in the reduced oxidized cellulose fiber obtained in the reduction step, the amount of the ketone group or the amount of both the ketone group and the aldehyde group is less than the amount in the oxidized cellulose fiber.
  • the oxidized cellulose fiber is an oxidized cellulose fiber obtained by the oxidation process described above. There is no restriction
  • the reducing agent is not particularly limited and may be appropriately selected depending on the intended purpose.
  • sodium borohydride, thiourea, hydrosulfite, sodium bisulfite, sodium cyanoborohydride, lithium borohydride Etc may be used individually by 1 type and may use 2 or more types together.
  • sodium borohydride is preferable because of excellent selective reactivity.
  • the solvent in the reaction solution is preferably water.
  • the said reaction liquid may contain other components other than the oxidized cellulose fiber mentioned above and a reducing agent.
  • the other components are not particularly limited as long as the effects of the present invention are not impaired, and can be appropriately selected according to the purpose.
  • the pH of the reaction solution is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 7 to 11, more preferably 9 to 10, and particularly preferably 10.
  • the pH is in a more preferable range, the amount of ketone groups or the amount of ketone groups and aldehyde groups in the reduced oxidized cellulose fiber can be reduced, and when the pH is in a particularly preferable range, Even when the amount of reducing agent used is reduced, it is advantageous in that the amount of ketone groups or the amount of ketone groups and aldehyde groups in the reduced oxidized cellulose fiber can be further reduced.
  • restoration process there is no restriction
  • restoration process According to the objective, it can select suitably, For example, it can be set as a normal pressure.
  • restoration process Although it can select suitably according to the objective, 1 hour or more is preferable and 5 hours or more are more preferable.
  • the reduction step is preferably performed while stirring the reaction solution.
  • the reduced-type oxidized cellulose fiber obtained in the reduction step is preferably used in a drying step described later after washing.
  • the reduced oxidized cellulose fibers are not dispersed evenly to the nanofiber unit at this stage, and can be washed by a normal washing method.
  • Specific examples of the cleaning method include the same methods as those described in the above oxidation step.
  • the drying step is a step of drying the reduced oxidized cellulose fiber.
  • drying method using an oven dryer, the freeze-drying method, the spray-drying method etc. are mentioned.
  • the drying conditions are not particularly limited and may be appropriately selected depending on the purpose.
  • the cellulose fiber of the present invention can be suitably produced by the above-described method for producing a cellulose fiber of the present invention, and can be finely dispersed in a solvent even after drying.
  • the cellulose fibers can be finely dispersed in water at a solid content of 0.01% by mass to 5% by mass after drying at 105 ° C. for 3 hours.
  • the drying conditions at 105 ° C. for 3 hours are generally the absolutely dry conditions for cellulose fibers.
  • Whether or not the cellulose fiber can be finely dispersed in a solvent can be confirmed, for example, as follows.
  • the cellulose fiber (reduced oxidized cellulose fiber obtained in the drying step) is dried at 105 ° C. for 3 hours. After the drying, the cellulose fiber is diluted with water to a concentration of 0.1% by mass to obtain a 40 mL dispersion. The dispersion was placed in a 50 mL centrifuge tube (polypropylene; manufactured by Corning) and used as it was by using a double-cylindrical homogenizer (blade diameter 1.5 cm, Microtech Nichion NS-56). Defibration treatment is performed at 500 rpm for 2 minutes.
  • the surroundings of the container are immediately cooled with ice water as they are, and the ultrasonic homogenizer (US-300T, manufactured by Nippon Seiki Co., Ltd., probe tip 7 mm, output 300 W, 19.5 kHz) is used for 8 minutes.
  • the ultrasonic homogenizer US-300T, manufactured by Nippon Seiki Co., Ltd., probe tip 7 mm, output 300 W, 19.5 kHz
  • the ultrasonic homogenizer US-300T, manufactured by Nippon Seiki Co., Ltd., probe tip 7 mm, output 300 W, 19.5 kHz
  • the whole dispersion having a cellulose fiber concentration of 0.1% by mass obtained as described above (a dispersion without removing any defibrated material. There is no defibrated material after complete nano-dispersion.
  • Light transmittance at a wavelength of 600 nm (hereinafter sometimes referred to as “transmittance”) is measured, and if the light transmittance is 80% or more, it is finely dispersed (nanodispersed). I can judge. When the light transmittance does not reach 80%, it can be determined that the fiber contains undefibrated components that are not finely dispersed.
  • cellulose fibers can be finely dispersed in a solvent can also be confirmed by confirming whether or not the cellulose fiber dispersion exhibits birefringence.
  • the dispersion prepared by the measurement of the “light transmittance” if there is undefibrated residue, removed by centrifugation
  • the dispersion prepared by the measurement of the “light transmittance” is placed between orthogonal polarizing plates. It can be confirmed by observing the birefringence.
  • the cellulose fiber of the present invention is a reduced oxidation in which the amount of the ketone group or the amount of the ketone group and the aldehyde group is reduced by the reduction step compared to the amount in the oxidized cellulose fiber after the oxidation step or the additional oxidation step.
  • the reduced oxidized cellulose fiber can be refined in water (nanodispersion) even after the drying step.
  • the method for confirming that the amount of the ketone group or the amount of the ketone group and the aldehyde group is reduced is not particularly limited and can be appropriately selected according to the purpose. For example, it can be confirmed by measuring an ultraviolet absorption spectrum according to the following procedure.
  • cellulose fiber is dried at 105 ° C. for 3 hours. After the drying, the cellulose fiber is diluted with water to a concentration of 0.1% by mass to obtain a 40 mL dispersion.
  • the dispersion was placed in a 50 mL centrifuge tube (polypropylene; manufactured by Corning) and used as it was by using a double-cylindrical homogenizer (blade diameter 1.5 cm, Microtech Nichion NS-56). Defibration treatment is performed at 500 rpm for 2 minutes.
  • the surroundings of the container are immediately cooled with ice water as they are, and the ultrasonic homogenizer (US-300T, manufactured by Nippon Seiki Co., Ltd., probe tip 7 mm, output 300 W, 19.5 kHz) is used for 8 minutes.
  • a defibrating treatment is performed to prepare a dispersion having a cellulose fiber concentration of 0.1% by mass.
  • a cycle of ultrasonic treatment for 2 minutes and standing and cooling for 1 minute is repeated, and the total ultrasonic treatment time is reached. For 8 minutes.
  • the concentration of the cellulose fiber in the dispersion can be appropriately selected within the range of 0.05% by mass to 0.5% by mass.
  • the undissolved cellulose fibers are removed by centrifuging with a centrifuge at 12,000 G for 10 minutes while leaving the container. A supernatant containing no cellulose fibers is obtained.
  • the absorbance at a wavelength of 600 nm of the dispersion subjected to the defibration treatment in water is less than 80%, and the weight ratio of the undefibrated portion removed by centrifuging and removing the dispersion is 10% or more.
  • the cellulose fiber contained in the dispersion is judged as “cannot be nanodispersed in water”.
  • the supernatant is poured into a petri dish, dried in a drier, and peeled from the petri dish to obtain a fine cellulose fiber film (hereinafter sometimes referred to as “cast film”).
  • the injection amount of the supernatant is adjusted so that the thickness of the cast film is 5 ⁇ m to 50 ⁇ m.
  • the cast film has a density of 1 g / cm 3 to 1.6 g / cm 3 .
  • the film thickness of the cast film may be adjusted by adjusting the size of the petri dish.
  • the temperature of the dryer is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably room temperature to 50 ° C., more preferably 40 ° C.
  • the drying period is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 3 days to 6 days, and more preferably 5 days.
  • the amount of aldehyde group and ketone group in the original cellulose fiber can be measured from the absorbance value of the ultraviolet absorption spectrum. Specifically, when the C2-position and C3-position ketone groups are present in the original cellulose fiber, the absorbance at 290 nm of the ultraviolet absorption spectrum increases. Further, when an aldehyde group is present in the original cellulose fiber, the absorbance at 260 nm of the ultraviolet absorption spectrum increases.
  • the amount of sodium borohydride added to the oxidized cellulose fiber is sufficient in the reduction step (for example, when 0.01 g of sodium borohydride is added to 1 g of oxidized cellulose fiber)
  • There are no ketone groups or aldehyde groups in the cellulose fiber and no peak is observed at 290 nm and 260 nm when the ultraviolet absorption spectrum is measured.
  • the ultraviolet absorbance of the cast film affects the thickness of the film (the greater the thickness of the film, the greater the absorbance and the smaller the thickness). Therefore, by dividing the absorbance by the thickness of the film, it is possible to evaluate and compare with the normalized absorbance (standardized conditions).
  • the absorbance at 290 nm and 260 nm is corrected to the absorbance per 1 ⁇ m thickness of the cast film, and evaluated and compared.
  • absorption is observed at 235 nm.
  • the absorbance at 260 nm is overestimated, the value obtained by correcting the absorbance at 260 nm to the absorbance per 1 ⁇ m thickness of the dry cast film is corrected by multiplying by 0.7.
  • the cellulose fiber of the present invention is a value obtained by correcting the absorbance of the dry cast film at wavelengths of 290 nm and 260 nm to the absorbance per 1 ⁇ m thickness of the dry cast film (however, in the measurement of the ultraviolet absorption spectrum, it is derived from hexene uronic acid groups).
  • the value obtained by correcting the absorbance at 260 nm to the absorbance per 1 ⁇ m thickness of the dry cast film is a value obtained by multiplying the corrected value by 0.7).
  • Both are preferably 0.020 or less.
  • the amount of aldehyde groups and ketone groups in cellulose fibers by the above method can be applied to undried cellulose fibers. Since the aldehyde group amount and the ketone group amount in the undried cellulose fiber and the dried cellulose fiber can be measured by the above method, whether or not the reduction step has been performed on the unknown cellulose fiber sample. Can be determined.
  • the cellulose fiber of the present invention can be finely dispersed in a solvent in the same manner as when prepared from an undried state, so that the cost for transportation can be reduced. Excellent storage stability.
  • the fine cellulose fiber dispersion of the present invention can be suitably produced by the method for producing a fine cellulose fiber dispersion of the present invention.
  • the fine cellulose fiber dispersion of the present invention will be described together with the description of the method for producing the fine cellulose fiber dispersion of the present invention.
  • the method for producing a fine cellulose fiber dispersion of the present invention includes at least a dispersion step, and further includes other steps as necessary.
  • distribution process is a process of disperse
  • the cellulose fiber can be finely dispersed by the dispersing step.
  • the solvent is not particularly limited and may be appropriately selected depending on the intended purpose. Water, alcohols, ethers, ketones, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide Etc. These may be used individually by 1 type and may use 2 or more types together. Specific examples of the alcohols include methanol, ethanol, isopropanol, isobutanol, sec-butanol, tert-butanol, methyl cellosolve, ethyl cellosolve, ethylene glycol, glycerin and the like.
  • ethers include ethylene glycol dimethyl ether, 1,4-dioxane, tetrahydrofuran and the like.
  • ketones include acetone and methyl ethyl ketone.
  • solvents water is preferable.
  • the dispersion means used in the dispersion step (hereinafter also referred to as “defibration means”) is not particularly limited and may be appropriately selected depending on the intended purpose.
  • the conditions for the dispersion step are not particularly limited and may be appropriately selected depending on the purpose.
  • the above-mentioned “light transmittance” column and “fine amount of ketone group, amount of aldehyde group” “fine” Examples of the conditions for the preparation of the dispersion described in the column “Preparation of dispersion”.
  • the above-described cellulose fiber of the present invention is finely dispersed, and a fine cellulose fiber dispersion in which the fine cellulose fiber is dispersed is obtained.
  • the fine cellulose fibers are cellulose single microfibrils having a width of about 2 nm to 5 nm and a length of about 0.2 ⁇ m to 5 ⁇ m.
  • the fine cellulose fiber of this invention can be suitably manufactured with the manufacturing method of the fine cellulose fiber of this invention.
  • the fine cellulose fiber of this invention is demonstrated with description of the manufacturing method of the fine cellulose fiber of this invention.
  • the manufacturing method of the fine cellulose fiber of this invention includes a drying process at least, and also includes another process as needed.
  • the drying step is a step of drying the fine cellulose fiber dispersion of the present invention described above.
  • the drying method can carry out similarly to the drying process in the manufacturing method of the cellulose fiber of this invention mentioned above. Fine cellulose fibers can be obtained by the drying step.
  • the fine cellulose fiber can be suitably used in various fields such as an oxygen-preventing membrane, a general-purpose plastic reinforcing material, a medical material, a cell culture substrate, a catalyst carrier, an adsorbent, and a separating material.
  • the said fine cellulose fiber molded object can be suitably manufactured with the manufacturing method of the following fine cellulose fiber molded objects.
  • the said fine cellulose fiber molded object is demonstrated with description of the manufacturing method of a fine cellulose fiber molded object.
  • the manufacturing method of the said fine cellulose fiber molded object includes at least the process of removing a liquid component, hold
  • the method for removing the liquid component while holding the fine cellulose fiber dispersion in a predetermined shape is not particularly limited and may be appropriately selected depending on the purpose.
  • the fine cellulose fiber dispersion may be selected on a substrate such as a glass plate.
  • Examples include a method of forming a film by removing the liquid component of the dispersion by a drying method such as natural drying, air blowing drying, or vacuum drying after casting the cellulose fiber dispersion.
  • a fine cellulose fiber molded body can be obtained by peeling the film from the substrate.
  • a fine cellulose fiber molded object by forming a fine cellulose fiber layer on the molded object using the said fine cellulose fiber dispersion.
  • foil-like articles such as a film, a sheet
  • a material of the said molded object According to the objective, it can select suitably, For example, paper, paperboard, a plastics, a metal, these composites etc. are mentioned.
  • the structure of the molded product may be a single layer or multiple layers.
  • the said fine cellulose fiber composite body can be suitably manufactured with the manufacturing method of the following fine cellulose fiber composite bodies.
  • the said fine cellulose fiber composite is demonstrated with description of the manufacturing method of a fine cellulose fiber composite.
  • the method for producing the fine cellulose fiber composite includes at least a step of preparing a dispersion liquid obtained by mixing the above-described fine cellulose fiber dispersion of the present invention and a liquid material containing the composite material. And other steps.
  • the material of the composite is not particularly limited and may be appropriately selected depending on the intended purpose.
  • examples thereof include synthetic polymers such as polyvinyl alcohol, nylon (registered trademark), polypropylene, polyethylene terephthalate, and polyester. .
  • the synthetic polymer can be dissolved in an organic solvent and spun (solution spinning) or shaped into a film. Therefore, by using a dispersion obtained by mixing the fine cellulose fiber dispersion and a liquid material containing the synthetic polymer, a fibrous molded article or a film-like molded article that is the fine cellulose fiber composite is obtained. be able to.
  • a monomer and the fine cellulose fiber dispersion are mixed in an organic solvent, and the monomer is polymerized to synthesize a polymer, thereby forming a composite of the fine cellulose fiber and the synthetic polymer. You can also.
  • Example 1 After dispersing softwood bleached kraft pulp (corresponding to 4 g in dry mass), 62.4 mg of TEMPO, and 0.4 g of sodium bromide in 400 mL of distilled water, 13 g of aqueous sodium hypochlorite solution was added to 1 g of The reaction was started by adding sodium hypochlorite to the pulp in an amount of 5 mmol. During the reaction, a 0.5 M aqueous sodium hydroxide solution was added dropwise to keep the pH at 10, and the reaction was carried out with stirring at room temperature (20 ° C. to 25 ° C.).
  • the reaction product is filtered through a glass filter, washed with a sufficient amount of water and filtered five times, and the solid content is 9.3% by mass.
  • Some oxidized cellulose fibers were obtained (yield> 90%).
  • the amount of carboxyl groups of the oxidized cellulose fiber was 1.43 mmol / g, and the amount of aldehyde groups was 0.04 mmol / g.
  • the amount of carboxyl group and aldehyde group per gram of the oxidized cellulose is determined according to “T. Saito and A. Isogai”, “TEMPO-mediated oxidation of native cell oxidization and qualitative chemistry and chemistry”. Biomacromolecules, Vol. 5, pp. 1983 to 1989, 2004 ”, and was measured by an additional oxidation treatment with sodium chlorite and conductivity titration.
  • the reduced oxidized cellulose fiber obtained in the reduction step was dried at 105 ° C. for 3 hours or more using an oven to obtain reduced oxidized cellulose fiber having a solid content of 100% by mass.
  • ⁇ Dispersing process> Water was added to the reduced oxidized cellulose fiber obtained in the drying step, and 40 mL of a dispersion diluted to have a cellulose concentration of 0.1% by mass was centrifuged in a 50 mL container (made of polypropylene; manufactured by Corning). Then, using a double cylindrical homogenizer (blade diameter 1.5 cm, NS-56 manufactured by Microtech Nichion Co., Ltd.) for 2 minutes at 7,500 rpm. After the defibrating process with the double cylindrical homogenizer, it is defibrated with an ultrasonic homogenizer (Nippon Seiki US-300T, probe tip 7 mm, output 300 W, 19.5 kHz) for 8 minutes while immediately cooling the surroundings with ice water.
  • an ultrasonic homogenizer Nippon Seiki US-300T, probe tip 7 mm, output 300 W, 19.5 kHz
  • the light transmittance of the dispersion liquid (a dispersion liquid that remains unremoved even if there is undefibrated material, which may be completely nanodispersed and may have no undefibrated material) is measured by an ultraviolet-visible near infrared spectrophotometer
  • the results of measurement using V-670 manufactured by JASCO Corporation are shown in FIG. 1 (“NaBH 4 addition amount: 1/64 of the weight of pulp” in FIG. 1).
  • the light transmittance of the dispersion at a wavelength of 600 nm was 90.9%.
  • the state of light transmission of the dispersion is shown in FIG.
  • Example 1 In Example 1, except that the reduction step was not performed, a dispersion having a cellulose concentration of 0.1% by mass (a dispersion without being removed even if undefibrated material was present) in the same manner as in Example 1. ) The results of measuring the dispersion in the same manner as in Example 1 are shown in FIG. 1 (“untreated” in FIG. 1). The light transmittance of the dispersion at a wavelength of 600 nm was 39.4%. The state of light transmission of the dispersion is shown in FIG.
  • Example 1 and Comparative Example 1 From the results of Example 1 and Comparative Example 1, it was not possible to finely disperse the cellulose fibers after the drying process in the dispersion liquid of Comparative Example 1 in which the reduction process of the present invention was not performed. On the other hand, since the dispersion of Example 1 has a light transmittance of 600% or more at a wavelength of 600 nm and birefringence was observed, the reduction step of the present invention is performed, and then the drying step is performed. Even so, it has been shown that cellulose fibers can be finely dispersed.
  • Example 2 In the reduction step of Example 1, the cellulose concentration was 0.1 mass in the same manner as in Example 1 except that the amount of sodium borohydride used was 1/32 g with respect to 1 g of the oxidized cellulose fiber. % Dispersion (dispersion that remains unremoved even if undefibrated material is present). The results obtained by measuring the dispersion in the same manner as in Example 1 are shown in FIG. 1 (“NaBH 4 addition amount: 1/32 of the weight of the pulp” in FIG. 1). The light transmittance of the dispersion at a wavelength of 600 nm was 91.5%. Further, when it was confirmed whether or not birefringence was observed in the same manner as in Example 1, the birefringence was confirmed. Therefore, also in Example 2, it was shown that it is possible to finely disperse the cellulose fibers after the drying process.
  • “NaBH 4 addition amount: 1/64 of the weight of the pulp” uses the dispersion liquid of Example 1
  • “NaBH 4 addition amount: 1/32 of the weight of the pulp” uses the dispersion liquid of Example 2.
  • Used, “untreated” indicates the ultraviolet absorption spectrum of the cast film obtained using the dispersion of Comparative Example 1.
  • absorption at 235 nm derived from hexeneuronic acid groups was observed, so the absorbance per 1 ⁇ m thickness of the cast film was The value obtained by correcting and further multiplying the absorbance by 0.7 was defined as a “value corrected to the absorbance per 1 ⁇ m thickness of the cast film”.
  • the absorbance at 260 nm corresponds to the amount of aldehyde groups
  • the absorbance at 290 nm corresponds to the amount of ketone groups.
  • Table 1 in Comparative Example 1 in which the reduction process was not performed, the absorbance at 260 nm and the absorbance at 290 nm were 0.050 or more, whereas Example 1 in which the reduction process was performed and 2, the absorbance at 260 nm and the absorbance at 290 nm were both 0.020 or less. Therefore, it was shown that in order to finely disperse the cellulose fibers after the drying step, the absorbance at 260 nm and the absorbance at 290 nm must both be 0.020 or less.
  • Example 3 Undried TEMPO oxidized cellulose (manufactured by Nippon Paper Industries Co., Ltd., carboxyl group amount; 1.45 mmol / g, aldehyde group amount; 0.05 mmol / g, solid content rate: 15.95%) was measured for an absolute dry weight of 2 g. And dispersed in 200 mL of distilled water. The pH of this dispersion was adjusted to 10 with a 0.05 M aqueous sodium hydroxide solution, and 0.5 g of sodium borohydride was added to initiate the reaction. The reaction was carried out for 24 hours with stirring at room temperature.
  • the reduced oxidized cellulose fibers were dried at 105 ° C. for 3 hours or more using an oven to obtain reduced oxidized cellulose fibers having a solid content of 100% by mass.
  • Example 2-1 Light transmission and birefringence
  • 40 mL of a dispersion diluted with water so that the cellulose concentration was 0.1% by mass was centrifuged in a 50 mL container (made of polypropylene; Corning Then, the fiber was defibrated for 2 minutes at 7,500 rpm using a double cylinder type homogenizer (blade diameter 1.5 cm, NS-56 manufactured by Microtech Nichion Co., Ltd.).
  • the defibrating process with the double cylindrical homogenizer After the defibrating process with the double cylindrical homogenizer, it is defibrated with an ultrasonic homogenizer (Nippon Seiki US-300T, probe tip 7 mm, output 300 W, 19.5 kHz) for 8 minutes while immediately cooling the surroundings with ice water. Processed. In the sonication, in order to avoid the temperature rise of the dispersion, a cycle of sonicating for 2 minutes and allowing to cool for 1 minute is repeated so that the total sonication time becomes 8 minutes. went. With the above treatment, a dispersion liquid (including undefibrated parts) having a cellulose concentration of 0.1% by mass was obtained.
  • an ultrasonic homogenizer Natural Seiki US-300T, probe tip 7 mm, output 300 W, 19.5 kHz
  • FIG. 5 shows the results of measuring the light transmittance of each dispersion in the same manner as in Example 1.
  • the light transmittance at a wavelength of 600 nm of each of the dispersions was 91.1% for the dispersion of Example 3, whereas it was 68.7% for the dispersion of Comparative Example 2.
  • each said dispersion liquid an undisentangled part is removed by centrifugation, the dispersion liquid of supernatant is poured into a petri dish, dried for 5 days in a dryer at 40 ° C., and peeled from the petri dish to thereby remove the cellulose nanofiber film. Obtained (film thickness: 5 to 10 ⁇ m).
  • the obtained film was heat-treated with a dryer at 105 ° C. for 3 hours. Thereafter, an ultraviolet absorption spectrum (range of 190 nm to 400 nm) of the heat-treated film was measured. The results are shown in Table 2 and FIG.
  • Examples of the aspect of the present invention include the following. ⁇ 1> An oxidation step in which an oxidized cellulose fiber is obtained by oxidizing a cellulosic raw material in a reaction solution containing an N-oxyl compound and a co-oxidant; A reduction step of reducing the oxidized cellulose fibers in a reaction solution containing a reducing agent to obtain reduced oxidized cellulose fibers; A drying step of drying the reduced oxidized cellulose fiber, The cellulose fiber obtained by drying the reduced oxidized cellulose fiber can be finely dispersed in a solvent.
  • ⁇ 2> The method for producing a cellulose fiber according to ⁇ 1>, further including a further oxidation step of further oxidizing the oxidized cellulose fiber obtained in the oxidation step with sodium chlorite between the oxidation step and the reduction step. .
  • ⁇ 3> The method for producing a cellulose fiber according to any one of ⁇ 1> to ⁇ 2>, wherein the pH of the reaction solution in the reduction step is 9 to 10.
  • ⁇ 5> Cellulose fibers that can be finely dispersed in a solvent after drying, After drying the cellulose fiber at 105 ° C.
  • the cellulose fiber is diluted with water to a concentration of 0.1% by mass to obtain a 40 mL dispersion, and the dispersion is placed in a 50 mL container.
  • the light transmittance at a wavelength of 600 nm of the dispersion is It is a cellulose fiber characterized by having a birefringence of 80% or more. ⁇ 6> After drying the cellulose fiber at 105 ° C.
  • the cellulose fiber is diluted with water to a concentration of 0.1% by mass to obtain a 40 mL dispersion, and the dispersion is placed in a 50 mL container.
  • defibrating for 2 minutes at 7,500 rpm using a double cylindrical homogenizer defibrating for 8 minutes with an ultrasonic homogenizer while cooling around the vessel with ice water, and then undefibrated cellulose fibers in the dispersion
  • a cast film is prepared using the dispersion obtained by removing, and the cast film is dried at 105 ° C. for 3 hours to obtain a dry cast film.
  • ⁇ 7> At least one of the cellulose fiber produced by the method for producing a cellulose fiber according to any one of ⁇ 1> to ⁇ 3> and the cellulose fiber according to any one of ⁇ 4> to ⁇ 6>. It is a manufacturing method of the fine cellulose fiber dispersion characterized by including the dispersion
  • ⁇ 8> A fine cellulose fiber dispersion produced by the production method according to ⁇ 7>.
  • ⁇ 9> A fine cellulose fiber dispersion in which cellulose fibers are finely dispersed in a solvent, The cellulose fiber is a cellulose fiber that can be finely dispersed in a solvent after drying, After drying the cellulose fiber at 105 ° C.
  • the cellulose fiber is diluted with water to a concentration of 0.1% by mass to obtain a 40 mL dispersion, and the dispersion is placed in a 50 mL container.
  • the light transmittance at a wavelength of 600 nm of the dispersion is It is a fine cellulose fiber dispersion characterized by having a birefringence of 80% or more. ⁇ 10> After drying the cellulose fiber at 105 ° C.
  • the cellulose fiber is diluted with water to a concentration of 0.1% by mass to form a 40 mL dispersion, and the dispersion is placed in a 50 mL container.
  • defibrating for 2 minutes at 7,500 rpm using a double cylindrical homogenizer defibrating for 8 minutes with an ultrasonic homogenizer while cooling around the vessel with ice water, and then undefibrated cellulose fibers in the dispersion
  • a cast film is prepared using the dispersion obtained by removing, and the cast film is dried at 105 ° C. for 3 hours to obtain a dry cast film.
  • ⁇ 11> Dry to dry at least one of the fine cellulose fiber dispersion produced by the production method according to ⁇ 7> and the fine cellulose fiber dispersion according to any one of ⁇ 8> to ⁇ 10>. It is a manufacturing method of the fine cellulose fiber characterized by including a process. ⁇ 12> A fine cellulose fiber produced by the production method according to ⁇ 11>. ⁇ 13> At least one of the fine cellulose fiber dispersion produced by the production method according to ⁇ 7> and the fine cellulose fiber dispersion according to any one of ⁇ 8> to ⁇ 10> is formed into a predetermined shape. It is a manufacturing method of the fine cellulose fiber molded object characterized by removing a liquid component, hold
  • ⁇ 14> A fine cellulose fiber molded article produced by the production method according to ⁇ 13>.
  • ⁇ 15> A fine cellulose fiber dispersion produced by the production method according to ⁇ 7>, and at least one of the fine cellulose fiber dispersion according to any one of ⁇ 8> to ⁇ 10>, and a composite
  • a method for producing a fine cellulose fiber composite comprising using a dispersion obtained by mixing a liquid material containing a material.
  • ⁇ 16> A fine cellulose fiber composite produced by the production method according to ⁇ 15>.

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Abstract

La présente invention concerne, par exemple, un procédé de production de fibres de cellulose, qui comprend : une étape d'oxydation permettant d'obtenir des fibres d'oxyde de cellulose par l'oxydation d'une matière première cellulosique dans un liquide de réaction qui contient un composé N-oxyle et un agent co-oxydant ; une étape de réduction permettant d'obtenir des fibres d'oxyde de cellulose réduite par la réduction de fibres d'oxyde de cellulose dans un liquide de réaction qui contient un agent réducteur ; et une étape de séchage permettant de sécher les fibres d'oxyde de cellulose réduite. Les fibres de cellulose obtenues par le séchage des fibres d'oxyde de cellulose réduite peuvent être dispersées finement dans un solvant.
PCT/JP2014/082533 2013-12-10 2014-12-09 Fibres de cellulose et leur procédé de production, dispersion de fibres de cellulose ultrafine et son procédé de production, et procédé de production de fibres de cellulose ultrafine WO2015087868A1 (fr)

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WO2019061817A1 (fr) * 2017-09-26 2019-04-04 南通强生石墨烯科技有限公司 Fibre composite de cellulose régénérée par oxyde de graphène modifié et son procédé de préparation
CN113198427A (zh) * 2021-04-30 2021-08-03 深圳信息职业技术学院 玉米髓三维类气凝胶吸附材料的制备方法及其应用

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WO2017131084A1 (fr) * 2016-01-26 2017-08-03 日本製紙株式会社 Liquide de dispersion de nanofibres de cellulose à modification anionique et son procédé de production
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WO2019061817A1 (fr) * 2017-09-26 2019-04-04 南通强生石墨烯科技有限公司 Fibre composite de cellulose régénérée par oxyde de graphène modifié et son procédé de préparation
CN113198427A (zh) * 2021-04-30 2021-08-03 深圳信息职业技术学院 玉米髓三维类气凝胶吸附材料的制备方法及其应用

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