[go: up one dir, main page]

WO2010116826A1 - Procédé pour la production de nanofibres de cellulose - Google Patents

Procédé pour la production de nanofibres de cellulose Download PDF

Info

Publication number
WO2010116826A1
WO2010116826A1 PCT/JP2010/053570 JP2010053570W WO2010116826A1 WO 2010116826 A1 WO2010116826 A1 WO 2010116826A1 JP 2010053570 W JP2010053570 W JP 2010053570W WO 2010116826 A1 WO2010116826 A1 WO 2010116826A1
Authority
WO
WIPO (PCT)
Prior art keywords
cellulose
raw material
treatment
cellulosic
dispersion
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2010/053570
Other languages
English (en)
Japanese (ja)
Inventor
正一 宮脇
志穂 勝川
裕 阿部
夕子 飯嶋
明 磯貝
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nippon Paper Industries Co Ltd
Jujo Paper Co Ltd
Original Assignee
Nippon Paper Industries Co Ltd
Jujo Paper Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from JP2009082651A external-priority patent/JP5329279B2/ja
Priority claimed from JP2009082604A external-priority patent/JP2010235679A/ja
Priority claimed from JP2009082520A external-priority patent/JP5404131B2/ja
Priority claimed from JP2009082377A external-priority patent/JP5426209B2/ja
Priority claimed from JP2009129297A external-priority patent/JP5381338B2/ja
Application filed by Nippon Paper Industries Co Ltd, Jujo Paper Co Ltd filed Critical Nippon Paper Industries Co Ltd
Publication of WO2010116826A1 publication Critical patent/WO2010116826A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H19/00—Coated paper; Coating material
    • D21H19/10—Coatings without pigments
    • D21H19/14—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12
    • D21H19/34—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12 comprising cellulose or derivatives thereof
    • 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
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
    • C12P19/00—Preparation of compounds containing saccharide radicals
    • C12P19/04—Polysaccharides, i.e. compounds containing more than five saccharide radicals attached to each other by glycosidic bonds

Definitions

  • the present invention relates to a method for producing a cellulose nanofiber dispersion liquid having a lower energy and a higher concentration than conventional materials from a cellulose raw material oxidized with an N-oxyl compound.
  • Non-Patent Document 1 Cellulose-based raw materials in the presence of a catalytic amount of 2,2,6,6-tetramethyl-1-piperidine-N-oxy radical (hereinafter referred to as TEMPO) and an inexpensive oxidizing agent sodium hypochlorite When treated, carboxyl groups can be efficiently introduced onto the surface of cellulose microfibrils.
  • Cellulosic raw materials into which these carboxyl groups have been introduced are highly viscous and transparent by performing a simple mechanical treatment with a mixer in water. It is known that it can be prepared into an aqueous cellulose nanofiber dispersion (Non-Patent Document 1).
  • Cellulose nanofiber is a new biodegradable water-dispersible material. Since the carboxyl group is introduced into the surface of the cellulose nanofiber by an oxidation reaction, the cellulose nanofiber can be freely modified with the carboxyl group as a base point. In addition, since the cellulose nanofibers obtained by the above method are in the form of a dispersion, the quality can be modified by blending with various water-soluble polymers or by combining with organic / inorganic pigments. it can. Furthermore, cellulose nanofibers can be made into sheets or fibers. Taking advantage of such characteristics of cellulose nanofibers, it is envisaged to be applied to highly functional packaging materials, transparent organic substrate members, highly functional fibers, separation membranes, regenerative medical materials, and the like. In the future, it is expected to develop new high-functional products that are essential for the formation of a recycling-type safety and security society by making the best use of the characteristics of cellulose nanofibers.
  • the cellulose nanofiber dispersion obtained by oxidizing the above-described method that is, oxidizing the cellulosic raw material with TEMPO and defibrating with a mixer is 0.3 to 0.5% (w / v).
  • the B-type viscosity 60 rpm, 20 ° C.
  • the B-type viscosity has a very high viscosity such as 800 to 4000 mPa ⁇ s, it is not easy to handle, and its application range is actually limited. It was.
  • the dispersion when a cellulose nanofiber dispersion is applied to a substrate to form a film on the substrate, the dispersion cannot be uniformly applied if the viscosity of the dispersion is too high, so the B-type viscosity of the dispersion (60 rpm, 20 ° C.) must be adjusted to about 500 to 3000 mPa ⁇ s, and for this purpose, the concentration of cellulose nanofibers in the dispersion is reduced to a low concentration of about 0.2 to 0.4% (w / v). I had to set it.
  • a low-concentration dispersion when such a low-concentration dispersion is used, there is a problem that the application and drying must be repeated many times until the desired film thickness is achieved, resulting in poor efficiency.
  • the dispersion when the cellulose nanofiber dispersion is mixed with a paint containing a pigment and a binder and applied to paper or the like, the dispersion cannot be uniformly mixed if the viscosity of the dispersion is too high. However, if such a low-concentration dispersion liquid is used, the concentration of the paint becomes dilute, making it difficult to apply the sufficient viscosity necessary for application and increasing the drying load. In addition, there is also a problem that the desired function expected for the coating film such as gloss development, surface strength, and suppression of printing unevenness does not appear because the effective coating film becomes thin by the penetration of the paint into the base paper. .
  • the viscosity of the obtained dispersion becomes very high, causing various problems.
  • the viscosity is too high, the dispersion proceeds only around the stirring blade, so that the dispersion becomes non-uniform and the dispersion becomes low in transparency.
  • the oxidized cellulosic material is defibrated using a homogenizer with higher defibration / dispersion power than the mixer, the cellulosic material will thicken significantly in the initial stage of dispersion and fluidity will deteriorate.
  • the amount of power consumption required sometimes increases significantly, the cellulose nanofiber dispersion liquid adheres to the inside of the apparatus and the dispersion is not sufficiently performed, and operations such as taking out the dispersion liquid from the apparatus are performed.
  • the yield of the dispersion is lowered due to difficulty.
  • an object of the present invention is to provide a method capable of efficiently producing a high-concentration cellulose nanofiber dispersion excellent in fluidity and transparency with low energy.
  • the present inventors have used an oxidizing agent in the presence of (1) N-oxyl compound and (2) bromide, iodide or a mixture thereof.
  • an oxidizing agent in the presence of (1) N-oxyl compound and (2) bromide, iodide or a mixture thereof.
  • the viscosity reduction treatment is a treatment for appropriately cutting the cellulose chain of the oxidized cellulose raw material (shortening fiber) and lowering the viscosity of the raw material, and specifically, an ultraviolet irradiation treatment.
  • hydrolytic treatment with enzymes oxidative degradation treatment with hydrogen peroxide and ozone, and hydrolysis treatment with acid.
  • the cellulose raw material is oxidized in the presence of the N-oxyl compound and bromide, iodide, or a mixture thereof, and the resulting oxidized cellulose raw material is reduced in viscosity and then defibrated. ⁇
  • cellulose nanofiber dispersions that are excellent in fluidity, easy to handle and excellent in transparency even at high concentrations can be efficiently produced with low power consumption. Can do.
  • the cellulose nanofiber dispersion obtained by the present invention is excellent in fluidity even at a high concentration.
  • a paint containing cellulose nanofibers at a high concentration of 1 to 3% (w / v) can be prepared at a low viscosity of 500 to 3000 mPa ⁇ s (B type viscosity, 60 rpm, 20 ° C.).
  • B type viscosity, 60 rpm, 20 ° C. There is an advantage that a film having a thickness of about 5 to 30 ⁇ m can be formed only by coating.
  • the concentration of cellulose nanofiber is 0.2 to 0.4% (w / v).
  • the concentration of cellulose nanofiber is very excellent.
  • a cellulose raw material oxidized by oxidizing a cellulosic raw material in water using an oxidizing agent in the presence of (1) an N-oxyl compound and (2) bromide, iodide or a mixture thereof. It is prepared and subjected to a viscosity reduction treatment before defibration and dispersion treatment.
  • a viscosity reduction treatment before defibration / dispersion treatment power consumption in the defibration / dispersion treatment can be reduced, and cellulose nanofibers can be produced efficiently with low energy. can do.
  • N-oxyl compounds As the N-oxyl compound used in the present invention, any compound can be used as long as it promotes the target oxidation reaction.
  • examples of the N-oxyl compound used in the present invention include substances represented by the following general formula (Formula 1).
  • R 1 to R 4 are the same or different alkyl groups having about 1 to 4 carbon atoms.
  • TEMPO 2,2,6,6-tetramethyl-1-piperidine-oxy radical
  • 4-hydroxy-2,2,6,6-tetramethyl-1 A -piperidine-oxy radical hereinafter referred to as 4-hydroxy TEMPO
  • N-oxyl compound represented by any one of the following formulas 2 to 4 that is, the hydroxyl group of 4-hydroxy TEMPO was etherified with alcohol or esterified with carboxylic acid or sulfonic acid to impart moderate hydrophobicity.
  • a 4-hydroxy TEMPO derivative is particularly preferable because it is inexpensive and can provide uniform oxidized cellulose.
  • R is a linear or branched carbon chain having 4 or less carbon atoms.
  • an N-oxyl compound represented by the following formula 5, that is, an azaadamantane type nitroxy radical is particularly preferable because it can produce uniform cellulose nanofibers in a short time.
  • R 5 and R 6 represent the same or different hydrogen or a C 1 -C 6 linear or branched alkyl group.
  • the amount of the N-oxyl compound used is not particularly limited as long as it is a catalyst amount capable of converting the cellulose raw material into nanofibers.
  • 0.01 to 10 mmol, preferably 0.01 to 1 mmol, and more preferably about 0.05 to 0.5 mmol can be used with respect to 1 g of cellulosic raw material.
  • bromide or iodide As the bromide or iodide used in oxidizing the cellulosic raw material, a compound that can be dissociated and ionized in water, such as an alkali metal bromide or an alkali metal iodide, can be used.
  • the amount of bromide or iodide used can be selected as long as the oxidation reaction can be promoted. For example, 0.1 to 100 mmol, preferably 0.1 to 10 mmol, and more preferably about 0.5 to 5 mmol can be used for 1 g of cellulosic raw material.
  • the target oxidation reaction such as halogen, hypohalous acid, halous acid, perhalogen acid or salts thereof, halogen oxide, peroxide
  • Any oxidizing agent can be used as long as it is an oxidizing agent.
  • sodium hypochlorite which is currently most widely used in industrial processes and has low environmental impact, is particularly suitable.
  • the amount of the oxidizing agent used can be selected within a range that can promote the oxidation reaction. For example, about 0.5 to 500 mmol, preferably 0.5 to 50 mmol, and more preferably about 2.5 to 25 mmol can be used for 1 g of cellulosic raw material.
  • the cellulose-based raw material used in the present invention is not particularly limited, and kraft pulp or sulfite pulp derived from various woods, powdered cellulose obtained by pulverizing them with a high-pressure homogenizer or a mill, or chemical treatment such as acid hydrolysis.
  • plants such as kenaf, hemp, rice, bacus, and bamboo can also be used.
  • bleached kraft pulp, bleached sulfite pulp, powdered cellulose, or microcrystalline cellulose powder is preferably used from the viewpoint of mass production and cost.
  • it is particularly preferable to use powdered cellulose and microcrystalline cellulose powder because a cellulose nanofiber dispersion having a lower viscosity can be produced even at a high concentration.
  • Powdered cellulose is rod-like particles made of microcrystalline cellulose obtained by removing the non-crystalline part of wood pulp by acid hydrolysis and then pulverizing and sieving.
  • the degree of polymerization of cellulose in powdered cellulose is about 100 to 500
  • the degree of crystallinity of powdered cellulose by X-ray diffraction is 70 to 90%
  • the volume average particle size by a laser diffraction type particle size distribution analyzer is preferably 100 ⁇ m. Or less, more preferably 50 ⁇ m or less.
  • the volume average particle diameter is 100 ⁇ m or less, a cellulose nanofiber dispersion excellent in fluidity can be obtained.
  • the powdered cellulose used in the present invention for example, a fixed particle size in the form of a rod shaft produced by a method of purifying and drying an undegraded residue obtained after acid hydrolysis of a selected pulp, pulverizing and sieving.
  • Crystalline cellulose powder having a distribution may be used, KC Flock (registered trademark) (manufactured by Nippon Paper Chemical Co., Ltd.), Theolas (trademark) (manufactured by Asahi Kasei Chemicals), Avicel (registered trademark) (manufactured by FMC), etc.
  • Commercial products may be used.
  • the method of the present invention is characterized in that the oxidation reaction can proceed smoothly even under mild conditions. Therefore, the reaction temperature may be a room temperature of about 15 to 30 ° C. In addition, since a carboxyl group produces
  • the reaction time in the oxidation reaction can be appropriately set and is not particularly limited, but is, for example, about 0.5 to 4 hours.
  • the viscosity-reducing treatment is performed on the oxidized cellulose raw material obtained by the above oxidation reaction.
  • the viscosity reduction treatment refers to a treatment that moderately cuts the cellulose chain of the oxidized cellulose raw material (shortens the cellulose chain) and lowers the viscosity of the raw material. Any treatment can be used as long as the viscosity of the cellulosic raw material is lowered.
  • the treatment of irradiating the oxidized cellulosic raw material with ultraviolet rays examples include a process of oxidizing and decomposing the cellulose-based raw material with hydrogen peroxide and ozone, a process of hydrolyzing the oxidized cellulose-based raw material with an acid, and combinations thereof.
  • the wavelength of the ultraviolet rays is preferably 100 to 400 nm, more preferably 100 to 300 nm.
  • ultraviolet rays having a wavelength of 135 to 260 nm are particularly preferable because they can directly act on cellulose and hemicellulose to cause low molecular weight and shorten the fiber.
  • a light source for irradiating ultraviolet rays a light source having a wavelength of 100 to 400 nm can be used.
  • a xenon short arc lamp, an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, A hydrogen lamp, a metal halide lamp, etc. are mentioned as an example, These 1 type (s) or 2 or more types can be used in arbitrary combinations.
  • a container for storing the oxidized cellulosic raw material when performing ultraviolet irradiation for example, when ultraviolet rays having a wavelength longer than 300 nm are used, those made of hard glass can be used, but ultraviolet rays having a shorter wavelength than that can be used. In the case of using, it is better to use a quartz glass that transmits ultraviolet rays more.
  • a suitable thing can be selected from the materials with little deterioration with respect to the wavelength of the ultraviolet-ray used.
  • the concentration of the oxidized cellulose raw material when irradiated with ultraviolet rays is preferably 0.1% by mass or more because energy efficiency is increased, and if it is 12% by mass or less, the concentration of cellulose raw materials in the ultraviolet irradiation device is preferable. It is preferable because the fluidity is good and the reaction efficiency is increased. Therefore, the range of 0.1 to 12% by mass is preferable. More preferably, it is 0.5 to 5% by mass, and still more preferably 1 to 3% by mass.
  • the temperature of the cellulosic raw material when irradiated with ultraviolet rays is preferably 20 ° C. or higher because the efficiency of the photooxidation reaction is increased. This is preferable because there is no fear and there is no possibility that the pressure in the reactor exceeds atmospheric pressure. Therefore, the range of 20 to 95 ° C. is preferable. Within this range, there is also an advantage that there is no need to design a device in consideration of pressure resistance. More preferably, it is 20 to 80 ° C., and further preferably 20 to 50 ° C.
  • the pH at the time of irradiation with ultraviolet rays is not particularly limited. However, in view of simplification of the process, it is preferable to perform the treatment in a neutral region, for example, pH 6.0 to 8.0.
  • the degree of irradiation received by the cellulosic raw material in the ultraviolet irradiation reaction can be arbitrarily set by adjusting the residence time of the cellulosic raw material in the irradiation reaction apparatus, adjusting the amount of energy of the irradiation light source, or the like. Also, for example, by adjusting the concentration of the cellulosic material in the irradiation device by diluting with water, or by adjusting the concentration of the cellulosic material by blowing an inert gas such as air or nitrogen into the cellulosic material.
  • the irradiation amount of ultraviolet rays received by the cellulosic material in the irradiation reaction apparatus can be arbitrarily controlled. These conditions such as residence time and concentration can be appropriately set in accordance with the quality (fiber length, cellulose polymerization degree, etc.) of the oxidized cellulose raw material after the target ultraviolet irradiation reaction.
  • the ultraviolet irradiation treatment in the present invention is performed in the presence of an auxiliary such as oxygen, ozone, or peroxide (hydrogen peroxide, peracetic acid, sodium percarbonate, sodium perborate, etc.), photooxidation is performed. Since the efficiency of reaction can be improved more, it is preferable.
  • an auxiliary such as oxygen, ozone, or peroxide (hydrogen peroxide, peracetic acid, sodium percarbonate, sodium perborate, etc.)
  • ozone is generated because air is usually present in the gas phase around the light source.
  • the generated ozone is continuously extracted, and this extracted ozone is injected into the oxidized cellulosic raw material, so that the outside of the system is removed.
  • ozone can be used as an auxiliary for the photo-oxidation reaction.
  • oxygen supplied to the gas phase around the light source, a larger amount of ozone can be generated in the system, and the generated ozone can be used as an auxiliary agent for the photooxidation reaction.
  • the ultraviolet irradiation treatment can be repeated a plurality of times.
  • the number of repetitions can be appropriately set according to the relationship with the target quality of the oxidized cellulosic raw material and the post-treatment such as bleaching.
  • ultraviolet rays of 100 to 400 nm, preferably 135 to 260 nm are irradiated for 1 to 10 times, preferably about 2 to 5 times, for a length of about 0.5 to 3 hours per time. be able to.
  • the reason why the oxidized cellulose raw material can be efficiently reduced in viscosity by irradiation with ultraviolet rays is presumed as follows.
  • a carboxyl group is localized on the surface of the cellulosic raw material oxidized with the N-oxyl compound, and a hydrated layer is formed. Therefore, it is considered that there is a microscopic gap between the raw materials which is not found in ordinary pulp due to the action of the charge repulsive force between the carboxyl groups.
  • active oxygen species having excellent oxidizing power such as ozone are generated from oxygen dissolved in the hydrated layer on the surface of the raw material or pore water of the raw material, and the cellulose chain is efficiently formed. It is considered that the oxidative decomposition eventually promotes shortening of the fiber of the cellulosic material and lowers the viscosity of the cellulosic material.
  • cellulase that is a cellulose degrading enzyme or hemicellulase that is a degrading enzyme of hemicellulose is added to the oxidized cellulose raw material to hydrolyze the cellulose chain.
  • hemicellulase for example, xylanase or mannase
  • Cellulase or hemicellulase-producing filamentous fungi, bacteria, actinomycetes, basidiomycetes, or genetic engineering such as genetic recombination or cell fusion were used.
  • a thing can be used individually or in mixture of 2 or more types.
  • Commercial products can also be used.
  • Examples of commercially available cellulases include Novozymes 476 from Novozymes Japan, Cellulase AP3 from Amano Enzyme, Cellulase Onozuka RS from Yakult Pharmaceutical Co., Ltd., Optimase CX40L from Genencor Kyowa Co., Ltd. Cellulase XL-522 manufactured by Chemtex, Enchiron CM manufactured by Nitto Kasei Kogyo Co., Ltd., etc. can be used.
  • hemicellulases for example, Pulpzyme manufactured by Novozymes Japan, Hemicellulase Amano 90 manufactured by Amano Enzyme, and Sumiteam X manufactured by Shin Nippon Chemical Industry Co., Ltd. can be used.
  • the amount of the enzyme added is 0.001% by mass or more with respect to the absolutely dry cellulosic raw material, it is sufficient to cause the desired enzyme reaction from the viewpoint of treatment time and efficiency, and 10% by mass.
  • the following is preferable because excessive hydrolysis of cellulose can be suppressed and a decrease in the yield of cellulose nanofibers can be prevented. Therefore, the addition amount of the enzyme is preferably 0.001 to 10% by mass with respect to the absolutely dry cellulosic material. More preferably, the content is 0.01 to 5% by mass, and still more preferably 0.05 to 2% by mass.
  • the “enzyme amount” here refers to the dry solid content of the enzyme aqueous solution.
  • the hydrolysis treatment with an enzyme is performed at pH 4 to 10, preferably pH 5 to 9, more preferably pH 6 to 8, temperature 40 to 70 ° C., preferably 45 to 65 ° C., more preferably 50 to 60 ° C.
  • the reaction time is preferably 0.5 to 24 hours, preferably 1 to 10 hours, and more preferably 2 to 6 hours from the viewpoint of enzyme reaction efficiency.
  • the reason why the oxidized cellulose raw material can be efficiently reduced in viscosity by enzyme treatment is presumed as follows.
  • a carboxyl group is localized on the surface of the cellulosic raw material oxidized with the N-oxyl compound, and a hydrated layer is formed. Therefore, it is considered that there is a microscopic gap between the raw materials which is not found in ordinary pulp due to the action of the charge repulsive force between the carboxyl groups.
  • an enzyme is added to the raw material for hydrolysis, a strong network of cellulose molecules is broken, the specific surface area of the raw material is increased, the shortening of the cellulose-based raw material is promoted, and the cellulose-based raw material is It is thought that the viscosity is lowered.
  • ozone can be generated by a known method using an ozone generator using air or oxygen as a raw material.
  • the addition amount (mass) of ozone in the present invention is preferably 0.1 to 3 times the absolute dry mass of the cellulosic material. If the amount of ozone added is at least 0.1 times the absolute dry mass of the cellulosic material, the amorphous part of the cellulose can be sufficiently decomposed, greatly increasing the energy required for the defibration / dispersion treatment in the next step.
  • the amount of ozone added is more preferably 0.3 to 2.5 times, more preferably 0.5 to 1.5 times the absolute dry mass of the cellulosic material.
  • the addition amount (mass) of hydrogen peroxide is preferably 0.001 to 1.5 times the absolute dry mass of the cellulosic material.
  • hydrogen peroxide is used in an amount of 0.001 times or more of the addition amount of the cellulosic material, a synergistic effect between ozone and hydrogen peroxide is exhibited.
  • the amount of hydrogen peroxide added is more preferably 0.1 to 1.0 times the absolute dry mass of the cellulosic material.
  • the oxidative decomposition treatment with ozone and hydrogen peroxide is pH 2 to 12, preferably pH 4 to 10, more preferably pH 6 to 8, and temperature is 10 to 90 ° C., preferably 20 to 70 ° C., more preferably 30. From the viewpoint of oxidative decomposition reaction efficiency, it is preferable to carry out the reaction at -50 ° C. for 1-20 hours, preferably 2-10 hours, more preferably 3-6 hours.
  • a device for performing treatment with ozone and hydrogen peroxide a device commonly used by those skilled in the art can be used.
  • a reactor can be used.
  • ozone and hydrogen peroxide remaining in the aqueous solution can effectively work in the defibration / dispersion treatment in the next step, and can further promote the lowering of the viscosity of the cellulose nanofiber dispersion. .
  • the acid used is sulfuric acid, hydrochloric acid, nitric acid, or phosphorus. It is preferred to use a mineral acid such as an acid.
  • the conditions for the acid hydrolysis treatment can be set as appropriate as long as the acid acts on the amorphous part of the cellulose, and are not particularly limited.
  • the amount of acid added is preferably 0.01 to 0.5% by mass, more preferably 0.1 to 0.5% by mass, based on the absolute dry mass of the cellulosic material.
  • the amount of acid added is 0.01% by mass or more, hydrolysis of cellulose proceeds and the fibrillation / dispersion efficiency of the cellulose-based raw material in the next step is improved, and preferably 0.5% by mass or less.
  • the pH of the reaction solution during acid hydrolysis is 2.0 to 4.0, preferably 2.0 or more and less than 3.0.
  • the acid hydrolysis treatment is preferably performed at a temperature of 70 to 120 ° C. for 1 to 10 hours from the viewpoint of acid hydrolysis efficiency.
  • an alkali such as sodium hydroxide from the viewpoint of the efficiency of the subsequent defibration / dispersion treatment.
  • the reason why the oxidized cellulose raw material can be efficiently reduced in viscosity by the acid hydrolysis treatment is presumed as follows. A carboxyl group is localized on the surface of the cellulosic raw material oxidized with the N-oxyl compound, and a hydrated layer is formed. For this reason, it is considered that there is a microscopic gap between the raw materials which is not found in ordinary pulp due to the action of the electric repulsion between carboxyl groups. Then, when an acid is added to the raw material for hydrolysis, a strong network of cellulose molecules is broken, the specific surface area of the raw material is increased, shortening of the cellulose-based raw material is promoted, and the cellulose-based raw material is It is thought that the viscosity is lowered.
  • N-oxyl compound removal treatment In the present invention, if necessary, from an oxidized cellulose raw material between the oxidation treatment and the viscosity reduction treatment of the cellulose raw material, or between the viscosity reduction treatment and the defibration / dispersion treatment, A treatment for removing the N-oxyl compound used for the oxidation of the acid may be performed. Any method may be used for the removal treatment of the N-oxyl compound.
  • the oxidized cellulose raw material is heated to a temperature of 50 to 120 ° C. or less under the condition of pH 3 to 10, it is washed with cellulose. This is preferable because the N-oxyl compound can be efficiently removed without reducing the yield of the system raw material.
  • a cellulosic raw material in the form of an aqueous dispersion having a pulp concentration of 0.1 to 50% by mass, more preferably The pulp concentration is 1 to 30% by mass, more preferably 2 to 20% by mass.
  • the pH of the aqueous dispersion of the oxidized cellulose raw material is adjusted to pH 3 to 10, preferably pH 3 to 9, and most preferably pH 3 to 8.
  • the kind of acid or alkali used for adjusting the pH is not particularly limited, and may be an inorganic compound or an organic compound.
  • hydrochloric acid or sulfuric acid can be used as the acid, and an aqueous sodium hydroxide solution can be used as the alkali.
  • the oxidized cellulose raw material is at a temperature of 50 ° C. to 120 ° C., preferably 70 ° C. to less than 100 ° C., more preferably 70 ° C. to 90 ° C. It is preferable to heat it.
  • the heating temperature is less than 50 ° C.
  • the removal rate of the N-oxyl compound is remarkably reduced, and when heated to a temperature higher than 120 ° C., the cellulose is significantly decomposed and solubilized. Since the yield is significantly reduced, it is not preferable.
  • the temperature during heating is less than 100 ° C., it is not necessary to use a pressure-resistant container during the heat treatment, which is advantageous from the viewpoint of equipment cost.
  • the pressure at the time of heating is not particularly limited, and it may be under atmospheric pressure or under pressure.
  • the heating time can be appropriately set in the range of about 10 minutes to 10 hours, preferably about 30 minutes to 6 hours, and most preferably about 1 to 5 hours, depending on the pH and temperature.
  • the N-oxyl compound remaining in the raw material can be sufficiently removed by thoroughly washing the oxidized cellulose raw material treated at the above specific pH and temperature.
  • the cellulose nanofiber dispersion or a film prepared therefrom is used for the purpose of a cosmetic thickener or food packaging, TEMPO and its derivatives whose toxicity to the environment and human body has not yet been clarified. It is highly preferable to sufficiently remove
  • the oxidized cellulose raw material is subjected to a viscosity reduction treatment (and N-oxyl compound removal treatment as necessary), and then subjected to a fibrillation / dispersion treatment.
  • a viscosity reduction treatment and N-oxyl compound removal treatment as necessary
  • fibrillation / dispersion treatment examples include high-speed rotary type, colloid mill type, high pressure type, roll mill type, ultrasonic type, etc., but cellulose nanofiber dispersion with excellent transparency and fluidity
  • the cellulose nanofibers produced by the present invention are cellulose single microfibrils having a width of 2 to 5 nm and a length of about 1 to 5 ⁇ m.
  • “to form a nanofiber” means that a cellulosic raw material is processed into cellulose nanofiber which is a single microfibril of cellulose having a width of about 2 to 5 nm and a length of about 1 to 5 ⁇ m.
  • the cellulose nanofiber dispersion obtained by the present invention has a B-type viscosity (60 rpm, 20 ° C.) at a concentration of 1.0% by mass (w / v) of 1000 mPa ⁇ s or less, preferably 800 mPa ⁇ s or less, more preferably It is 500 mPa ⁇ s or less, and the light transmittance (660 nm) at a concentration of 0.1% by mass (w / v) is 90% or more, preferably 95% or more.
  • Cellulose nanofibers produced according to the present invention are excellent in fluidity and transparency, and are also excellent in barrier properties and heat resistance, and thus can be used for various applications such as packaging materials.
  • the B-type viscosity of the cellulose nanofiber dispersion can be measured using a normal B-type viscometer commonly used by those skilled in the art, for example, TV-10 type viscosity of Toki Sangyo Co., Ltd. Using a meter, it can be measured at 20 ° C. and 60 rpm.
  • the light transmittance of the cellulose nanofiber dispersion can be measured with an ultraviolet / visible spectrophotometer.
  • the B-type viscosity of the dispersion in the defibration / dispersion treatment in the next step is significantly reduced by shortening the fiber of the cellulose-based raw material oxidized using the N-oxyl compound to reduce the viscosity.
  • the fluidity of the dispersion can be significantly improved.
  • distribution can be reduced significantly.
  • the cellulose nanofiber dispersion liquid excellent in transparency can be prepared by shortening a cellulose raw material.
  • the B-type viscosity (60 rpm, 20 ° C.) of the obtained 1% (w / v) cellulose nanofiber dispersion was measured using a TV-10 viscometer (Toki Sangyo Co., Ltd.) and 0.1% ( The w / v) cellulose nanofiber dispersion transparency (660 nm fluorescence transmittance) was measured using a UV-VIS spectrophotometer UV-265FS (Shimadzu Corporation), and the power consumption required for defibration / dispersion treatment was determined by (power during processing) ⁇ (processing time) / (sample amount processed). The results are shown in Table 1.
  • a nanofiber dispersion was obtained in the same manner as in Example 1 except that ultraviolet rays having a wavelength range of 260 to 400 nm and having a main peak at 310 nm were irradiated using a 20 W low-pressure mercury lamp. The results are shown in Table 1.
  • a nanofiber dispersion was obtained in the same manner as in Example 1 except that ultraviolet rays having a wavelength range of 340 to 400 nm and having a main peak at 360 nm were irradiated using a 20 W low-pressure mercury lamp. The results are shown in Table 1.
  • a nanofiber dispersion was obtained in the same manner as in Example 1 except that the treatment pressure of the ultrahigh pressure homogenizer was 100 MPa. The results are shown in Table 1.
  • a nanofiber dispersion was obtained in the same manner as in Example 1 except that the treatment pressure of the ultrahigh pressure homogenizer was 50 MPa. The results are shown in Table 1.
  • a nanofiber dispersion was obtained in the same manner as in Example 1 except that the treatment pressure of the ultrahigh pressure homogenizer was changed to 30 MPa. The results are shown in Table 1.
  • a nanofiber dispersion was obtained in the same manner as in Example 1 except that powdered cellulose (Nippon Paper Chemical Co., Ltd., particle size 75 ⁇ m) was used as the cellulose-based material. The results are shown in Table 1.
  • a nanofiber dispersion was obtained in the same manner as in Example 5 except that powdered cellulose (Nippon Paper Chemical Co., Ltd., particle size 75 ⁇ m) was used as the cellulose-based material. The results are shown in Table 1.
  • a nanofiber dispersion was obtained in the same manner as in Example 6 except that powdered cellulose (Nippon Paper Chemical Co., Ltd., particle size 75 ⁇ m) was used as the cellulose-based material. The results are shown in Table 1.
  • a nanofiber dispersion was obtained in the same manner as in Example 1 except that a high shear mixer (circumferential speed 37 m / s, Nippon Seiki Seisakusho) equipped with a rotating blade as a dispersing device was used instead of the ultrahigh pressure homogenizer.
  • the results are shown in Table 1.
  • a nanofiber dispersion was obtained in the same manner as in Example 1 except that 1% (w / v) of hydrogen peroxide was added to the oxidized pulp during UV irradiation. The results are shown in Table 1.
  • a nanofiber dispersion was obtained in the same manner as in Example 1 except that a 20 W low-pressure ultraviolet lamp that simultaneously irradiates ultraviolet rays of 254 nm and 185 nm was used. The results are shown in Table 1.
  • Example 1 A nanofiber dispersion was obtained in the same manner as in Example 1 except that ultraviolet rays were not irradiated (that is, the viscosity was not reduced). The results are shown in Table 1.
  • Example 2 Nanofibers as in Example 1 except that a high shear mixer (circumferential speed 37 m / s, Nippon Seiki Seisakusho) equipped with a rotating blade as a dispersing device without using a low viscosity treatment was used instead of the ultra-high pressure homogenizer. A dispersion was obtained. The results are shown in Table 1.
  • a nanofiber dispersion was obtained in the same manner as in Example 13 except that the treatment pressure of the ultrahigh pressure homogenizer was 100 MPa. The results are shown in Table 2.
  • a nanofiber dispersion was obtained in the same manner as in Example 13 except that the treatment pressure of the ultrahigh pressure homogenizer was 50 MPa. The results are shown in Table 2.
  • a nanofiber dispersion was obtained in the same manner as in Example 13 except that the treatment pressure of the ultrahigh pressure homogenizer was changed to 30 MPa. The results are shown in Table 2.
  • a nanofiber dispersion was obtained in the same manner as in Example 13 except that powdered cellulose (Nippon Paper Chemical Co., Ltd., particle size 75 ⁇ m) was used as the cellulose-based material. The results are shown in Table 2.
  • a nanofiber dispersion was obtained in the same manner as in Example 15 except that powdered cellulose (Nippon Paper Chemical Co., Ltd., particle size 75 ⁇ m) was used as the cellulose-based material. The results are shown in Table 2.
  • a nanofiber dispersion was obtained in the same manner as in Example 16 except that powdered cellulose (Nippon Paper Chemical Co., Ltd., particle size 75 ⁇ m) was used as the cellulose-based material. The results are shown in Table 2.
  • a nanofiber dispersion was obtained in the same manner as in Example 13 except that a high shear mixer (circumferential speed: 37 m / s, Nippon Seiki Seisakusho) equipped with a rotating blade as a dispersing device was used instead of the ultrahigh pressure homogenizer.
  • the results are shown in Table 2.
  • a nanofiber dispersion was obtained in the same manner as in Example 13 except that cellulase AP3 (manufactured by Amano Enzyme) was used as the cellulolytic enzyme. The results are shown in Table 2.
  • a nanofiber dispersion was obtained in the same manner as in Example 22 except that the treatment pressure of the ultrahigh pressure homogenizer was 100 MPa. The results are shown in Table 3.
  • a nanofiber dispersion was obtained in the same manner as in Example 22 except that the treatment pressure of the ultrahigh pressure homogenizer was 50 MPa. The results are shown in Table 3.
  • a nanofiber dispersion was obtained in the same manner as in Example 22 except that the treatment pressure of the ultrahigh pressure homogenizer was 30 MPa. The results are shown in Table 3.
  • a nanofiber dispersion was obtained in the same manner as in Example 22 except that powdered cellulose (Nippon Paper Chemical Co., Ltd., particle size 75 ⁇ m) was used as the cellulose-based material. The results are shown in Table 3.
  • a nanofiber dispersion was obtained in the same manner as in Example 24 except that powdered cellulose (Nippon Paper Chemical Co., Ltd., particle size 75 ⁇ m) was used as the cellulose-based material. The results are shown in Table 3.
  • a nanofiber dispersion was obtained in the same manner as in Example 25 except that powdered cellulose (Nippon Paper Chemical Co., Ltd., particle size 75 ⁇ m) was used as the cellulose-based material. The results are shown in Table 3.
  • a nanofiber dispersion was obtained in the same manner as in Example 22 except that a high shear mixer (circumferential speed 37 m / s, Nippon Seiki Seisakusho) equipped with a rotary blade was used as a dispersing device. The results are shown in Table 3.
  • the ozone concentration is 10 g / L (corresponding to 1.0 times the absolute dry mass of the cellulosic material), and the hydrogen peroxide concentration is 3 g / L (corresponding to 0.3 times the absolute dry mass of the cellulosic material).
  • the nanofiber dispersion was obtained in the same manner as in Example 22 except that it was added so that The results are shown in Table 3.
  • Example 3 A nanofiber dispersion was obtained in the same manner as in Example 22 except that treatment with hydrogen peroxide alone was performed. The results are shown in Table 3.
  • Example 4 A nanofiber dispersion was obtained in the same manner as in Example 22 except that treatment with ozone alone was performed. The results are shown in Table 3.
  • a nanofiber dispersion was obtained in the same manner as in Example 31 except that the amount of hydrochloric acid added was 0.3% by mass with respect to the absolute dry mass of the pulp, and acid hydrolysis treatment was performed at pH 2.4. The results are shown in Table 4.
  • Comparative Example 5 The concentration of the 1% (w / v) cellulose nanofiber dispersion produced in Comparative Example 1 was adjusted to have a B-type viscosity of 600 mPa ⁇ s (60 rpm, 20 ° C.). The cellulose nanofiber concentration at this time was 0.4% (w / v).
  • This dispersion was applied to one side of a polyethylene terephthalate film (thickness 20 ⁇ m) with a bar for hand coating (bar No. 16) and dried at 50 ° C. to form a film. The film thickness was about 2.0 ⁇ m. In order to form a 5.9 ⁇ m film having the same thickness as the film obtained using the cellulose nanofiber dispersion liquid of Example 1, it was necessary to repeat coating and drying at least twice.
  • the difference between the nitrogen content of the oxidized cellulosic raw material and the nitrogen content of the bleached unbeaten sulfite pulp that is the raw pulp is considered to be based on the nitrogen content of the N-oxyl compound (TEMPO) used in the oxidation reaction
  • TEMPO N-oxyl compound
  • 0.2 g (absolutely dry) of the oxidized cellulose raw material was dispersed in 25 ml of ultrapure water, and the pH was adjusted to 3.5 with a 0.5N hydrochloric acid aqueous solution. After heating this at 85 ° C. for 2 hours, the cellulosic material was filtered off with a glass filter and washed thoroughly with water to remove residual N-oxyl compound (TEMPO) in the cellulosic material. After the obtained cellulose raw material was dried at 70 ° C., the amount of nitrogen in the cellulose raw material was measured and found to be 23 ppm.
  • TEMPO N-oxyl compound
  • the amount of nitrogen derived from TEMPO that existed before the removal treatment of the N-oxyl compound was 11 ppm. Therefore, the above treatment can remove 82% of TEMPO remaining in the oxidized cellulose raw material. I understand that.
  • the total organic carbon content in the filtrate obtained by filtering the pulp after the heating was measured using a total organic carbon meter (Shimadzu Corporation, TOC-V). .
  • Table 6 shows the results of the residual TEMPO-derived nitrogen amount (ppm), the residual TEMPO removal rate (%), and the total organic carbon amount (ppm) in the filtrate.
  • Example 6 shows the results of the residual TEMPO-derived nitrogen amount (ppm), the residual TEMPO removal rate (%), and the total organic carbon amount (ppm) in the filtrate, measured in the same manner as in Example 34.
  • Heating was performed in the same manner as in Example 34 except that the pH was adjusted to 11.9 using a 0.5N aqueous sodium hydroxide solution. The results are shown in Table 6.
  • Heating was performed in the same manner as in Example 34 except that the temperature was 50 ° C. and the time was 4 hours. The results are shown in Table 6.
  • Heating was performed in the same manner as in Example 34 except that the temperature was 120 ° C. and the time was 30 minutes. The results are shown in Table 6.
  • Heating was performed in the same manner as in Example 34 except that the temperature was 40 ° C. and the time was 6 hours. The results are shown in Table 6.
  • Heating was performed in the same manner as in Example 34 except that the temperature was 130 ° C. and the time was 10 minutes. The results are shown in Table 6.
  • Example 34 Heating was carried out in the same manner as in Example 34, except that an oxidized cellulose material obtained by ultraviolet treatment obtained by the method described in Example 1 was used.
  • the amount of nitrogen in the cellulosic material after the heat treatment (after removal of TEMPO) was 21 ppm.
  • TEMPO removal treatment TEMPO remaining in the oxidized cellulosic material could be removed 100%. The results are shown in Table 6.
  • Heating was performed in the same manner as in Example 34 except that the cellulase-treated oxidized cellulose material obtained by the method described in Example 13 was used.
  • the amount of nitrogen in the cellulosic material after the heat treatment was 23 ppm.
  • Example 44 Heating was performed in the same manner as in Example 34 except that the oxidized cellulose raw material treated with ozone and hydrogen peroxide obtained by the method described in Example 22 was used. The results obtained by the method described in Example 44 are shown in Table 6.
  • Example 44 Heating was performed in the same manner as in Example 34 except that the acid-hydrolyzed oxidized cellulose material obtained by the method described in Example 31 was used. The results obtained by the method described in Example 44 are shown in Table 6.
  • Example 43 After neutralizing the TEMPO-removed low-viscosity oxidized cellulose-based material obtained in Example 43 with alkali, it was treated 10 times at a pressure of 140 MPa using an ultra-high pressure homogenizer, and a transparent gel dispersion was used. A cellulose nanofiber dispersion was obtained. The transparency of the obtained cellulose nanofiber dispersion, the B-type viscosity, and the power consumption required for the fibrillation / dispersion treatment were determined by the method described in Example 1. The results are shown in Table 7.
  • a dispersion of cellulose nanofibers which is a transparent gel-like dispersion, was obtained in the same manner as in Example 43, except that the low-viscosity oxidized cellulose-based raw material obtained by removing TEMPO obtained in Example 44 was used. The results are shown in Table 7.
  • a dispersion of cellulose nanofibers which is a transparent gel-like dispersion, was obtained in the same manner as in Example 43 except that the low-viscosity oxidized cellulose-based raw material obtained by removing TEMPO obtained in Example 45 was used. The results are shown in Table 7.
  • a dispersion of cellulose nanofibers which is a transparent gel-like dispersion, was obtained in the same manner as in Example 43 except that the low-viscosity oxidized cellulose-based raw material obtained by removing TEMPO obtained in Example 46 was used. The results are shown in Table 7.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Biochemistry (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Nanotechnology (AREA)
  • Zoology (AREA)
  • Wood Science & Technology (AREA)
  • Microbiology (AREA)
  • Genetics & Genomics (AREA)
  • Biotechnology (AREA)
  • Polymers & Plastics (AREA)
  • Bioinformatics & Cheminformatics (AREA)
  • General Engineering & Computer Science (AREA)
  • General Health & Medical Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Composite Materials (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Medicinal Chemistry (AREA)
  • Polysaccharides And Polysaccharide Derivatives (AREA)
  • Chemical Or Physical Treatment Of Fibers (AREA)

Abstract

Une matière première cellulosique est oxydée avec un agent oxydant dans de l'eau en présence de (1) un composé N-oxyle et (2) un bromure, un iodure ou un mélange de ceux-ci pour préparer une matière première cellulosique oxydée et la matière oxydée est soumise à un traitement de réduction de viscosité puis à un traitement de fibrillation/dispersion, ce qui produit de cette manière de façon efficace, avec une faible énergie, une dispersion de nanofibres de cellulose de concentration élevée ayant d'excellentes aptitude à l'écoulement et transparence. Les exemples du traitement de réduction de viscosité comprennent l'irradiation par des ultraviolets, l'hydrolyse avec une cellulase et/ou une hémicellulase, la décomposition par oxydation avec de l'ozone et du peroxyde d'hydrogène, l'hydrolyse avec un acide et des combinaisons de celles-ci. On préfère enlever le composé N-oxyle de la matière première cellulosique oxydée par chauffage de la matière première cellulosique oxydée à 50-120°C à un pH de 3-10 et lavage de la matière ainsi obtenue avec de l'eau.
PCT/JP2010/053570 2009-03-30 2010-03-04 Procédé pour la production de nanofibres de cellulose Ceased WO2010116826A1 (fr)

Applications Claiming Priority (10)

Application Number Priority Date Filing Date Title
JP2009082651A JP5329279B2 (ja) 2009-03-30 2009-03-30 セルロースナノファイバーの製造方法
JP2009-082651 2009-03-30
JP2009-082604 2009-03-30
JP2009-082520 2009-03-30
JP2009-082377 2009-03-30
JP2009082604A JP2010235679A (ja) 2009-03-30 2009-03-30 セルロースナノファイバーの製造方法
JP2009082520A JP5404131B2 (ja) 2009-03-30 2009-03-30 セルロースナノファイバーの製造方法
JP2009082377A JP5426209B2 (ja) 2009-03-30 2009-03-30 酸化パルプ中に残留する有機系酸化触媒の除去方法
JP2009129297A JP5381338B2 (ja) 2009-05-28 2009-05-28 セルロースナノファイバーの製造方法
JP2009-129297 2009-05-28

Publications (1)

Publication Number Publication Date
WO2010116826A1 true WO2010116826A1 (fr) 2010-10-14

Family

ID=42936114

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2010/053570 Ceased WO2010116826A1 (fr) 2009-03-30 2010-03-04 Procédé pour la production de nanofibres de cellulose

Country Status (1)

Country Link
WO (1) WO2010116826A1 (fr)

Cited By (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20100282422A1 (en) * 2007-12-28 2010-11-11 Shoichi Miyawaki Processes for producing cellulose nanofibers, cellulose oxidation catalysts and methods for oxidizing cellulose
WO2011118746A1 (fr) * 2010-03-26 2011-09-29 日本製紙株式会社 Procédé de fabrication de nanofibres cellulosiques
WO2012043103A1 (fr) * 2010-09-28 2012-04-05 日本製紙株式会社 Nanofibre cellulosique
WO2012132903A1 (fr) * 2011-03-30 2012-10-04 日本製紙株式会社 Procédé de production de nanofibres en cellulose
JP2012207135A (ja) * 2011-03-30 2012-10-25 Nippon Paper Industries Co Ltd セルロースナノファイバーの製造方法
JP2012214717A (ja) * 2011-03-30 2012-11-08 Nippon Paper Industries Co Ltd セルロースナノファイバーの製造方法
JPWO2011040547A1 (ja) * 2009-09-30 2013-02-28 日本製紙株式会社 紙製バリア材料
WO2013047218A1 (fr) * 2011-09-30 2013-04-04 日本製紙株式会社 Procédé de fabrication de nanofibres de cellulose
JP2013163773A (ja) * 2012-02-13 2013-08-22 Oji Holdings Corp 微細繊維状セルロースの製造方法
WO2013137140A1 (fr) * 2012-03-14 2013-09-19 日本製紙株式会社 Procédé de production d'un liquide de dispersion de nanofibres de cellulose modifiées par un anion
WO2013188657A1 (fr) * 2012-06-13 2013-12-19 University Of Maine System Board Of Trustees Procédé écoénergétique pour la préparation de fibres de nanocellulose
WO2014029909A1 (fr) * 2012-08-20 2014-02-27 Stora Enso Oyj Procédé et intermédiaire pour la production de cellulose hautement raffinée ou microfibrillée
US8710213B2 (en) 2012-05-14 2014-04-29 The United States Of America As Represented By The Secretary Of Agriculture Methods for integrating the production of cellulose nanofibrils with the production of cellulose nanocrystals
CN104387478A (zh) * 2014-12-17 2015-03-04 菏泽市产品质量监督检验所 一种油用牡丹茎纳米纤维素的制备方法
JP2016501926A (ja) * 2012-11-03 2016-01-21 ウーペーエム−キュンメネ コーポレイションＵＰＭ−Ｋｙｍｍｅｎｅ Ｃｏｒｐｏｒａｔｉｏｎ ナノフィブリル化セルロースの製造方法
JP2016030809A (ja) * 2014-07-30 2016-03-07 ハイモ株式会社 セルロースナノファイバーの製造方法
CN106192040A (zh) * 2016-08-08 2016-12-07 四川大学 一种高长径比纤维素纳米纤维的制备方法
WO2020085479A1 (fr) * 2018-10-26 2020-04-30 王子ホールディングス株式会社 Composition contenant de la cellulose fibreuse fine et procédé de fabrication correspondant
US10968283B2 (en) 2014-07-28 2021-04-06 Anomera Inc. Method for producing functionalized nanocrystalline cellulose and functionalized nanocrystalline cellulose thereby produced
CN112867738A (zh) * 2018-10-16 2021-05-28 王子控股株式会社 纤维状纤维素、纤维状纤维素分散液和纤维状纤维素的制造方法
US20210301034A1 (en) * 2018-08-03 2021-09-30 Toagosei Co., Ltd. Oxidized Cellulose, Method of Producing Oxidized Cellulose and Nanocellulose, and Nanocellulose Dispersion
JP2022165987A (ja) * 2020-07-09 2022-11-01 東亞合成株式会社 酸化セルロース、ナノセルロース及びそれらの分散液

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003026701A (ja) * 2001-03-28 2003-01-29 Natl Starch & Chem Investment Holding Corp 改質毛羽立ちパルプ、毛羽立ちパルプ製品及びその使用法
JP2003512540A (ja) * 1999-10-15 2003-04-02 ウェヤーハウザー・カンパニー カルボキシル化セルロース繊維を製造する方法及び該方法の製品
JP2003516939A (ja) * 1999-11-08 2003-05-20 エスシーエイ・ハイジーン・プロダクツ・ゼイスト・ベー・ブイ 第一級アルコールを酸化する方法
JP2008001728A (ja) * 2006-06-20 2008-01-10 Asahi Kasei Corp 微細セルロース繊維
JP2008169497A (ja) * 2007-01-10 2008-07-24 Kimura Chem Plants Co Ltd ナノファイバーの製造方法およびナノファイバー

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003512540A (ja) * 1999-10-15 2003-04-02 ウェヤーハウザー・カンパニー カルボキシル化セルロース繊維を製造する方法及び該方法の製品
JP2003516939A (ja) * 1999-11-08 2003-05-20 エスシーエイ・ハイジーン・プロダクツ・ゼイスト・ベー・ブイ 第一級アルコールを酸化する方法
JP2003026701A (ja) * 2001-03-28 2003-01-29 Natl Starch & Chem Investment Holding Corp 改質毛羽立ちパルプ、毛羽立ちパルプ製品及びその使用法
JP2008001728A (ja) * 2006-06-20 2008-01-10 Asahi Kasei Corp 微細セルロース繊維
JP2008169497A (ja) * 2007-01-10 2008-07-24 Kimura Chem Plants Co Ltd ナノファイバーの製造方法およびナノファイバー

Cited By (37)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20100282422A1 (en) * 2007-12-28 2010-11-11 Shoichi Miyawaki Processes for producing cellulose nanofibers, cellulose oxidation catalysts and methods for oxidizing cellulose
US8287692B2 (en) * 2007-12-28 2012-10-16 Nippon Paper Industries Co., Ltd. Processes for producing cellulose nanofibers
JPWO2011040547A1 (ja) * 2009-09-30 2013-02-28 日本製紙株式会社 紙製バリア材料
WO2011118746A1 (fr) * 2010-03-26 2011-09-29 日本製紙株式会社 Procédé de fabrication de nanofibres cellulosiques
WO2012043103A1 (fr) * 2010-09-28 2012-04-05 日本製紙株式会社 Nanofibre cellulosique
JP2012214717A (ja) * 2011-03-30 2012-11-08 Nippon Paper Industries Co Ltd セルロースナノファイバーの製造方法
JP2012207135A (ja) * 2011-03-30 2012-10-25 Nippon Paper Industries Co Ltd セルロースナノファイバーの製造方法
WO2012132903A1 (fr) * 2011-03-30 2012-10-04 日本製紙株式会社 Procédé de production de nanofibres en cellulose
US9139662B2 (en) 2011-03-30 2015-09-22 Nippon Paper Industries Co., Ltd. Method for producing cellulose nanofibers
WO2013047218A1 (fr) * 2011-09-30 2013-04-04 日本製紙株式会社 Procédé de fabrication de nanofibres de cellulose
JP5285197B1 (ja) * 2011-09-30 2013-09-11 日本製紙株式会社 セルロースナノファイバーの製造方法
US9365973B2 (en) 2011-09-30 2016-06-14 Nippon Paper Industries Co., Ltd. Method for producing cellulose nanofibers
JP2013163773A (ja) * 2012-02-13 2013-08-22 Oji Holdings Corp 微細繊維状セルロースの製造方法
JPWO2013137140A1 (ja) * 2012-03-14 2015-08-03 日本製紙株式会社 アニオン変性セルロースナノファイバー分散液の製造方法
WO2013137140A1 (fr) * 2012-03-14 2013-09-19 日本製紙株式会社 Procédé de production d'un liquide de dispersion de nanofibres de cellulose modifiées par un anion
CN104169306A (zh) * 2012-03-14 2014-11-26 日本制纸株式会社 阴离子改性纤维素纳米纤维分散液的制造方法
US8710213B2 (en) 2012-05-14 2014-04-29 The United States Of America As Represented By The Secretary Of Agriculture Methods for integrating the production of cellulose nanofibrils with the production of cellulose nanocrystals
WO2013188657A1 (fr) * 2012-06-13 2013-12-19 University Of Maine System Board Of Trustees Procédé écoénergétique pour la préparation de fibres de nanocellulose
US10563352B2 (en) 2012-06-13 2020-02-18 University Of Maine System Board Of Trustees Energy efficient process for preparing nanocellulose fibers
US10900169B2 (en) 2012-08-20 2021-01-26 Stora Enso Oyj Method and intermediate for the production of highly refined or microfibrillated cellulose
CN104619913A (zh) * 2012-08-20 2015-05-13 斯塔诺阿埃索澳吉有限公司 用于制备高度精制的或微纤维化的纤维素的方法和中间产物
WO2014029909A1 (fr) * 2012-08-20 2014-02-27 Stora Enso Oyj Procédé et intermédiaire pour la production de cellulose hautement raffinée ou microfibrillée
US9797093B2 (en) 2012-11-03 2017-10-24 Upm-Kymmene Corporation Method for producing nanofibrillar cellulose
JP2016501926A (ja) * 2012-11-03 2016-01-21 ウーペーエム−キュンメネ コーポレイションＵＰＭ−Ｋｙｍｍｅｎｅ Ｃｏｒｐｏｒａｔｉｏｎ ナノフィブリル化セルロースの製造方法
US10968283B2 (en) 2014-07-28 2021-04-06 Anomera Inc. Method for producing functionalized nanocrystalline cellulose and functionalized nanocrystalline cellulose thereby produced
JP2016030809A (ja) * 2014-07-30 2016-03-07 ハイモ株式会社 セルロースナノファイバーの製造方法
CN104387478A (zh) * 2014-12-17 2015-03-04 菏泽市产品质量监督检验所 一种油用牡丹茎纳米纤维素的制备方法
CN106192040A (zh) * 2016-08-08 2016-12-07 四川大学 一种高长径比纤维素纳米纤维的制备方法
US11919974B2 (en) * 2018-08-03 2024-03-05 Toagosei Co., Ltd. Oxidized cellulose, method of producing oxidized cellulose and nanocellulose, and nanocellulose dispersion
US20210301034A1 (en) * 2018-08-03 2021-09-30 Toagosei Co., Ltd. Oxidized Cellulose, Method of Producing Oxidized Cellulose and Nanocellulose, and Nanocellulose Dispersion
CN112867738A (zh) * 2018-10-16 2021-05-28 王子控股株式会社 纤维状纤维素、纤维状纤维素分散液和纤维状纤维素的制造方法
US11945884B2 (en) 2018-10-16 2024-04-02 Oji Holdings Corporation Fibrous cellulose, fibrous cellulose dispersion, and production method for fibrous cellulose
WO2020085479A1 (fr) * 2018-10-26 2020-04-30 王子ホールディングス株式会社 Composition contenant de la cellulose fibreuse fine et procédé de fabrication correspondant
JP7355028B2 (ja) 2018-10-26 2023-10-03 王子ホールディングス株式会社 微細繊維状セルロース含有組成物およびその製造方法
JPWO2020085479A1 (ja) * 2018-10-26 2021-10-07 王子ホールディングス株式会社 微細繊維状セルロース含有組成物およびその製造方法
JP2022165987A (ja) * 2020-07-09 2022-11-01 東亞合成株式会社 酸化セルロース、ナノセルロース及びそれらの分散液
JP7636723B2 (ja) 2020-07-09 2025-02-27 東亞合成株式会社 酸化セルロース、ナノセルロース及びそれらの分散液

Similar Documents

Publication Publication Date Title
WO2010116826A1 (fr) Procédé pour la production de nanofibres de cellulose
JP5330882B2 (ja) セルロースゲル分散液の製造方法
JP5178931B2 (ja) セルロースナノファイバーの製造方法
WO2011118748A1 (fr) Procédé de production de nanofibres cellulosiques
WO2012132903A1 (fr) Procédé de production de nanofibres en cellulose
JP5381338B2 (ja) セルロースナノファイバーの製造方法
JP5285197B1 (ja) セルロースナノファイバーの製造方法
JP5329279B2 (ja) セルロースナノファイバーの製造方法
WO2011118746A1 (fr) Procédé de fabrication de nanofibres cellulosiques
JP5731253B2 (ja) セルロースナノファイバーの製造方法
JP2010235679A (ja) セルロースナノファイバーの製造方法
WO2013137140A1 (fr) Procédé de production d'un liquide de dispersion de nanofibres de cellulose modifiées par un anion
JP2009263652A (ja) セルロースナノファイバーの製造方法
JP2009243014A (ja) セルロースナノファイバーの製造方法
JP5179616B2 (ja) セルロースナノファイバーの製造方法
JP6877136B2 (ja) カルボキシル化セルロースナノファイバーの製造方法
JP5404131B2 (ja) セルロースナノファイバーの製造方法
JP6405751B2 (ja) 微小セルロースの製造方法
WO2012132663A1 (fr) Procédé de production de nanofibres en cellulose

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 10761528

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 10761528

Country of ref document: EP

Kind code of ref document: A1