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WO2018143149A1 - Procédé de production de nanofibres de cellulose séchées - Google Patents

Procédé de production de nanofibres de cellulose séchées Download PDF

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Publication number
WO2018143149A1
WO2018143149A1 PCT/JP2018/002846 JP2018002846W WO2018143149A1 WO 2018143149 A1 WO2018143149 A1 WO 2018143149A1 JP 2018002846 W JP2018002846 W JP 2018002846W WO 2018143149 A1 WO2018143149 A1 WO 2018143149A1
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WO
WIPO (PCT)
Prior art keywords
cnf
molecular weight
redispersibility
anion
dry
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PCT/JP2018/002846
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English (en)
Japanese (ja)
Inventor
藤槻薫麗
半埜賢治
Original Assignee
株式会社片山化学工業研究所
日本製紙株式会社
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Application filed by 株式会社片山化学工業研究所, 日本製紙株式会社 filed Critical 株式会社片山化学工業研究所
Priority to JP2018565537A priority Critical patent/JP6931837B2/ja
Publication of WO2018143149A1 publication Critical patent/WO2018143149A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B11/00—Preparation of cellulose ethers
    • C08B11/02—Alkyl or cycloalkyl ethers
    • C08B11/04—Alkyl or cycloalkyl ethers with substituted hydrocarbon radicals
    • C08B11/10—Alkyl or cycloalkyl ethers with substituted hydrocarbon radicals substituted with acid radicals
    • C08B11/12—Alkyl or cycloalkyl ethers with substituted hydrocarbon radicals substituted with acid radicals substituted with carboxylic radicals, e.g. carboxymethylcellulose [CMC]
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B5/00—Preparation of cellulose esters of inorganic acids, e.g. phosphates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
    • C08L1/02—Cellulose; Modified cellulose
    • C08L1/04—Oxycellulose; Hydrocellulose, e.g. microcrystalline cellulose
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
    • C08L1/08—Cellulose derivatives
    • C08L1/16—Esters of inorganic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
    • C08L1/08—Cellulose derivatives
    • C08L1/26—Cellulose ethers

Definitions

  • the present disclosure relates to a method for producing dry cellulose nanofibers and a method for improving the redispersibility of dry cellulose nanofibers.
  • CNF Cellulose nanofiber
  • CNF is a plant-derived fiber refined to a fiber diameter of about several nm to several hundred nm.
  • CNF has a small environmental load and has various characteristics such as light weight, high strength, high gas barrier property, small dimensional deformation due to heat, high specific surface area, high transparency, and high viscosity in water. For this reason, CNF is expected to be used not only in automobile parts and food packaging materials but also in a wide range of fields such as foods, pharmaceuticals and cosmetics.
  • CNF is usually produced as a low concentration aqueous dispersion (wet state).
  • aqueous dispersion there are problems such as high transportation and storage costs and contamination with bacteria. For this reason, a method of drying CNF has been proposed (for example, Patent Document 1).
  • the dried CNF is usually used after being redispersed in a dispersion medium such as water.
  • a dispersion medium such as water.
  • CNF is not sufficiently redispersed.
  • CNF obtained by drying a transparent CNF solution, especially dried anion-modified CNF, particularly 2,6,6-tetramethylpiperidine-1-oxy radical (TEMPO) oxidized CNF has low redispersibility and transparency. There is a problem of not recovering. For this reason, a new method capable of drying CNF while maintaining sufficient redispersibility is demanded.
  • TEMPO 2,6,6-tetramethylpiperidine-1-oxy radical
  • the present disclosure provides a method for producing dry CNF with improved redispersibility, particularly a method for producing dry CNF with improved transparent dispersibility during redispersion.
  • the present disclosure provides a method that can improve the redispersibility of CNF.
  • this indication provides the method of making it possible to improve the transparent dispersibility at the time of re-dispersion of dry TEMPO oxidation CNF in one aspect
  • transparent dispersibility at the time of redispersion means that, in one or a plurality of embodiments, CNF is dispersed in a dispersion medium at a level close to microfibril units or microfibril units, and is dispersed in a highly transparent state. That means.
  • the present disclosure provides an aqueous suspension of anion-modified cellulose nanofibers by mixing an anion-modified cellulose nanofiber and a redispersibility improver, and drying the aqueous suspension to dry cellulose.
  • a dry cellulose nanofiber comprising: obtaining a nanofiber, wherein the redispersibility improving agent is selected from the group consisting of a saccharide having a molecular weight of 50,000 or less, a low molecular weight polypeptide, an amino acid, and a low molecular weight polyvinyl alcohol. It relates to the manufacturing method.
  • the present disclosure includes mixing an anion-modified cellulose nanofiber and a redispersibility improver to obtain an aqueous suspension of the anion-modified cellulose nanofiber, and drying the aqueous suspension.
  • the redispersibility improving agent relates to a method for improving redispersibility of cellulose nanofibers selected from the group consisting of sugars having a molecular weight of 50,000 or less, low molecular weight polypeptides, amino acids, and low molecular weight polyvinyl alcohol.
  • the present disclosure provides an agent for improving or improving the redispersibility of dry cellulose nanofibers in a dispersion medium, in particular, redispersibility, a saccharide having a molecular weight of 50,000 or less, a low molecular weight poly
  • a redispersibility improving agent comprising at least one selected from the group consisting of peptides, amino acids, and low molecular weight polyvinyl alcohol.
  • the present disclosure is a dry composition containing anion-modified cellulose nanofibers and a redispersibility improver, wherein the redispersibility improver is a saccharide having a molecular weight of 50,000 or less, a low molecular weight polypeptide,
  • the present invention relates to a dry composition comprising at least one selected from the group consisting of amino acids and low molecular weight polyvinyl alcohol.
  • a method for producing dry CNF with improved redispersibility particularly a method for producing dry CNF with improved transparent dispersibility during redispersion can be provided. Further, according to the present disclosure, it is possible to provide a method capable of improving or improving the redispersibility of CNF, particularly a method capable of improving or improving the transparent dispersibility during redispersion. According to the present disclosure, it is preferable to provide a method for producing dry TEMPO-oxidized CNF having improved transparent dispersibility during redispersion and a method capable of improving the transparent dispersibility during redispersion of dry TEMPO-oxidized CNF.
  • CM carboxymethyl
  • a method for producing dry carboxymethyl (CM) -modified CNF having improved dispersibility during re-dispersion and a method capable of improving the dispersibility during re-dispersion of dry C-methyl CNF.
  • a method for producing dry phosphate esterified CNF with improved dispersibility during redispersion and a method capable of improving the transparent dispersibility during redispersion of dry phosphate esterified CNF.
  • the present disclosure improves the redispersibility of dry CNF obtained by drying an aqueous suspension in which anion-modified CNF is mixed with a low molecular weight saccharide such as cyclodextrin or low molecular weight polycarboxymethylcellulose (CMC). Based on the knowledge that can be done. In addition, when the anion-modified CNF is TEMPO-oxidized CNF, mixing with the above low molecular weight saccharide and drying improves the transparent dispersibility during redispersion of the dry CNF, and the resulting dry CNF is dispersed in water or the like. It is based on the knowledge that a highly transparent dry CNF redispersion liquid can be obtained by contacting with a medium.
  • a low molecular weight saccharide such as cyclodextrin or low molecular weight polycarboxymethylcellulose (CMC).
  • the present disclosure is based on the finding that the redispersibility of the obtained dry CNF can be improved by drying an aqueous suspension in which anion-modified CNF and a low molecular weight polypeptide or amino acid are mixed.
  • the anion-modified CNF is TEMPO-oxidized CNF
  • the transparent dispersibility at the time of redispersion of the dry CNF is improved, and the obtained dry CNF is converted into water or the like. It is based on the knowledge that a highly transparent dry CNF redispersion liquid can be obtained when brought into contact with a dispersion medium.
  • the present disclosure is based on the finding that the redispersibility of the obtained dry CNF can be improved by drying an aqueous suspension obtained by mixing anion-modified CNF and low molecular weight polyvinyl alcohol (PVA). Further, when the anion-modified CNF is TEMPO-oxidized CNF, when mixed with a low molecular weight PVA and dried, the transparent dispersibility during re-dispersion of the dried CNF is improved, and the resulting dried CNF is mixed with a dispersion medium such as water. This is based on the knowledge that a highly transparent dry CNF redispersion liquid can be obtained by contact.
  • PVA polyvinyl alcohol
  • the present disclosure shows that low molecular weight sugars such as cyclodextrin and low molecular weight CMC, low molecular weight polypeptides, amino acids, and low molecular weight PVA can be used as a dispersibility improving agent when redispersing dry CNF. based on.
  • “molecular weight of the redispersibility improver” refers to an average molecular weight, preferably a weight average molecular weight, when the redispersibility improver is a polymer.
  • the redispersibility improving agent may be used alone or in combination of two or more.
  • “Improvement or improvement of redispersibility” in the present disclosure is obtained by mixing dry CNF obtained by the dry CNF production method of the present disclosure with a dispersion medium such as water in one or a plurality of embodiments.
  • a liquid (or CNF suspension) it means that the turbidity is low or the amount of undispersed CNF pieces or gelled products is small.
  • “improvement or improvement of transparent dispersibility during redispersion” means that in one or a plurality of embodiments, CNF is dispersed in a dispersion medium at a level close to microfibril units or microfibril units, and is in an undispersed state. It means that transparency is higher than CNF pieces or gelled products are hardly observed.
  • the dry CNF obtained by the dry CNF production method of the present disclosure is mixed with a dispersion medium such as water and stirred, and the CNF is separated at a level close to a microfibril unit or a microfibril unit.
  • dry CNF can be dispersed in the dispersion medium in a highly transparent state.
  • a highly transparent dry CNF re-dispersion liquid can be obtained in one or a plurality of embodiments.
  • “High transparency” in the present disclosure includes high light transmittance in one or more embodiments.
  • Japanese Patent Application Laid-Open No. 9-165402 discloses a method of adding a third component (components other than BC and water) to an aqueous suspension of bacterial cellulose (BC), followed by drying, thereby condensing BC after drying. It is disclosed that various properties such as dispersibility and sedimentation degree are restored to the state before drying.
  • bacterial cellulose is a naturally occurring cellulose fiber produced from bacteria and has no charge.
  • the anion-modified CNF of the present disclosure is a cellulose nanofiber obtained by chemical treatment as described later, and has a charge on the surface of the cellulose fiber by the chemical treatment. For this reason, the anion-modified CNF and bacterial cellulose of the present disclosure are completely different.
  • this document restores the original disaggregated state, specifically, a state in which a large amount of liquid component is included in the surface of the fine fibers or the voids of the network structure constituted by the fine fibers. It is intended.
  • the regenerated product obtained by the method of the same literature (the product obtained by adding water to the dried product of bacterial cellulose to restore the wet state) is a white turbid body.
  • the dry CNF redispersed liquid obtained by the present disclosure separates and disperses the fibers (CNF) separately, and thus a highly transparent CNF redispersed liquid is obtained. Therefore, the method disclosed in Japanese Patent Laid-Open No. 9-165402 is a method that is completely different from the method of the present disclosure in terms of not only the object to be processed but also the technical idea.
  • anion-modified CNF refers to cellulose nanofibers obtained by chemically treating cellulose, and more specifically, nanofibers are obtained by fibrillating cellulose fibers whose fiber surfaces are chemically treated. It refers to fine fibers (nanofibers).
  • the anion-modified CNF in the present disclosure has a charge on the surface of the cellulose fiber by chemical treatment.
  • the anion-modified CNF in the present disclosure does not include naturally-derived cellulose nanofibers such as bacterial cellulose produced from bacteria.
  • Examples of the chemical treatment include carboxymethyl (CM) treatment, carboxylation (oxidation) treatment, phosphate esterification treatment and the like in one or a plurality of embodiments.
  • Examples of the method for carboxymethylation of the cellulose raw material or the defibrated cellulose fiber include a method in which cellulose as a bottoming raw material is mercerized and then etherified.
  • a solvent is usually used.
  • the solvent include water, alcohol (eg, lower alcohol), and mixed solvents thereof.
  • Specific examples of the lower alcohol include methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n-butanol, isobutanol, and tertiary butanol.
  • the lower limit is usually 60% by weight or more
  • the upper limit is usually 95% by weight or less, preferably 60% by weight to 95% by weight.
  • the amount of the solvent is usually 3 times or more by weight based on the cellulose raw material or defibrated cellulose fiber.
  • the upper limit of the quantity of a solvent is not specifically limited, Usually, it is 20 weight times or less with respect to a cellulose raw material or a defibrated cellulose fiber. Therefore, the amount of the solvent is preferably 3 to 20 times by weight with respect to the cellulose raw material or defibrated cellulose fiber.
  • Mercerization is usually performed by mixing a cellulose raw material or defibrated cellulose fiber and a mercerizing agent.
  • mercerizing agents include alkali metal hydroxides (eg, sodium hydroxide, potassium hydroxide).
  • the lower limit of the amount of the mercerizing agent used is usually 0.5 times mol or more per anhydroglucose residue of cellulose raw material or defibrated cellulose fiber. Moreover, an upper limit is 20 times mole or less normally. Therefore, the amount of the mercerizing agent used is preferably 0.5 to 20 times mol per anhydroglucose residue of the cellulose raw material or defibrated cellulose fiber.
  • the lower limit of the mercerization reaction temperature is usually 0 ° C or higher, preferably 10 ° C or higher.
  • the upper limit is usually 70 ° C. or lower, preferably 60 ° C. or lower. Therefore, the reaction temperature for mercerization is usually 0 ° C. to 70 ° C., preferably 10 ° C. to 60 ° C.
  • the lower limit of the mercerization reaction time is usually 15 minutes or longer, preferably 30 minutes or longer.
  • the lower limit is usually 8 hours or less, preferably 7 hours or less. Therefore, the reaction time for mercerization is usually 15 minutes to 8 hours, preferably 30 minutes to 7 hours.
  • the etherification reaction is usually performed by adding a carboxymethylating agent to the reaction system after mercerization.
  • a carboxymethylating agent include sodium monochloroacetate.
  • the lower limit of the addition amount of the carboxymethylating agent is usually 0.05 times mole or more per glucose residue of the cellulose raw material or defibrated cellulose fiber.
  • the upper limit is usually 10.0 times mol or less. Accordingly, the addition amount of the carboxymethylating agent is usually 0.05 times to 10.0 times moles per glucose residue of the cellulose raw material or defibrated cellulose fiber.
  • the lower limit of the etherification reaction temperature is usually 30 ° C or higher, preferably 40 ° C or higher.
  • An upper limit is 90 degrees C or less normally, Preferably it is 80 degrees C or less. Accordingly, the reaction temperature for etherification is usually 30 ° C. to 90 ° C., preferably 40 ° C. to 80 ° C.
  • the lower limit of the etherification reaction time is usually 30 minutes or longer, preferably 1 hour or longer.
  • the upper limit is usually 10 hours or less, preferably 4 hours or less. Therefore, the reaction time for etherification is usually 30 minutes to 10 hours, preferably 1 hour to 4 hours.
  • the carboxymethyl substitution degree per glucose unit of carboxymethylated cellulose fiber or carboxymethylated cellulose nanofiber for example, it can be obtained by the following method. That is, 1) About 2.0 g of carboxymethylated cellulose fiber or carboxymethylated cellulose nanofiber (absolutely dried) is precisely weighed and placed in a 300 mL conical stoppered Erlenmeyer flask. 2) Add 100 mL of special concentrated nitric acid solution to 1000 mL of methanol, add 100 mL of methanol solution of nitric acid, and shake for 3 hours to convert carboxymethyl cellulose salt (CM-modified cellulose salt: eg Na-CMC) into H-CM-converted cellulose. (H-CMC).
  • CM-modified cellulose salt eg Na-CMC
  • carboxymethyl cellulose which is a kind of modified cellulose used for the preparation of modified CNF, means that at least a part of the fibrous shape is maintained even when dispersed in water. Therefore, it is distinguished from carboxymethyl cellulose (CMC) which is a kind of water-soluble polymer described later.
  • CMC carboxymethyl cellulose
  • a fibrous substance can be observed.
  • carboxymethyl cellulose which is a kind of water-soluble polymer
  • a fibrous substance is not observed.
  • “carboxymethylated cellulose” can observe the peak of cellulose I-type crystals when measured by X-ray diffraction, but cellulose I-type crystals are not observed in the water-soluble polymer carboxymethylcellulose.
  • carboxylated (oxidized) cellulose when carboxylated (oxidized) cellulose is used as the modified cellulose, carboxylated cellulose (also referred to as oxidized cellulose) can be obtained by carboxylating (oxidizing) the above cellulose raw material by a known method. .
  • the amount of carboxyl groups should be adjusted to 0.6 mmol / g to 2.0 mmol / g with respect to the absolute dry mass of anion-modified CNF. It is preferable to adjust the concentration to 1.0 mmol / g to 2.0 mmol / g.
  • a cellulose raw material is oxidized in water using an oxidizing agent in the presence of an N-oxyl compound and a compound selected from the group consisting of bromide, iodide, or a mixture thereof.
  • a method can be mentioned.
  • the primary hydroxyl group at the C6 position of the glucopyranose ring on the cellulose surface is selectively oxidized, and the cellulose fiber having an aldehyde group and a carboxyl group (—COOH) or carboxylate group (—COO—) on the surface.
  • the concentration of cellulose during the reaction is not particularly limited, but is preferably 5% by mass or less.
  • N-oxyl compound refers to a compound capable of generating a nitroxy radical.
  • any compound can be used as long as it promotes the target oxidation reaction. Examples include 2,2,6,6-tetramethylpiperidine-1-oxy radical (TEMPO) and its derivatives (eg, 4-hydroxy TEMPO).
  • TEMPO 2,2,6,6-tetramethylpiperidine-1-oxy radical
  • its derivatives eg, 4-hydroxy TEMPO
  • the amount of N-oxyl compound used is not particularly limited as long as it is a catalytic amount capable of oxidizing cellulose as a raw material.
  • a catalytic amount capable of oxidizing cellulose as a raw material For example, with respect to 1 g of absolutely dry cellulose, 0.01 mmol to 10 mmol is preferable, 0.01 mmol to 1 mmol is more preferable, and 0.05 mmol to 0.5 mmol is more preferable. Further, it is preferably about 0.1 mmol / L to 4 mmol / L with respect to the reaction system.
  • Bromide is a compound containing bromine, and examples thereof include alkali metal bromide that can be dissociated and ionized in water.
  • an iodide is a compound containing iodine, and examples thereof include alkali metal iodide.
  • the amount of bromide or iodide used can be selected as long as the oxidation reaction can be promoted.
  • the total amount of bromide and iodide is, for example, preferably from 0.1 mmol to 100 mmol, more preferably from 0.1 mmol to 10 mmol, and even more preferably from 0.5 mmol to 5 mmol with respect to 1 g of absolutely dry cellulose.
  • oxidizing agent known ones can be used, and for example, halogen, hypohalous acid, halous acid, perhalogen acid or salts thereof, halogen oxide, peroxide and the like can be used.
  • sodium hypochlorite is preferable because it is inexpensive and has a low environmental impact.
  • the amount of the oxidizing agent used is, for example, preferably 0.5 mmol to 500 mmol, more preferably 0.5 mmol to 50 mmol, further preferably 1 mmol to 25 mmol, and most preferably 3 mmol to 10 mmol with respect to 1 g of absolutely dry cellulose. Further, for example, 1 to 40 mol is preferable with respect to 1 mol of the N-oxyl compound.
  • the carboxylation (oxidation) of cellulose allows the reaction to proceed efficiently even under relatively mild conditions. Therefore, the reaction temperature is preferably 4 ° C. to 40 ° C., and may be room temperature of about 15 ° C. to 30 ° C. As the reaction proceeds, a carboxyl group is generated in the cellulose, so that the pH of the reaction solution is reduced.
  • an alkaline solution such as an aqueous sodium hydroxide solution is added to maintain the pH of the reaction solution at about 8 to 12, preferably about 10 to 11.
  • the reaction medium is preferably water because it is easy to handle and hardly causes side reactions.
  • the reaction time in the oxidation reaction can be appropriately set according to the progress of oxidation, and is usually 0.5 to 6 hours, for example, about 0.5 to 4 hours.
  • the oxidation reaction may be carried out in two stages. For example, by oxidizing the oxidized cellulose obtained by filtration after the completion of the first-stage reaction again under the same or different reaction conditions, the efficiency is not affected by the reaction inhibition by the salt generated as a by-product in the first-stage reaction. Can be oxidized well.
  • Another example of the carboxylation (oxidation) method is a method of oxidizing by contacting a gas containing ozone and a cellulose raw material. By this oxidation reaction, at least the 2-position and 6-position hydroxyl groups of the glucopyranose ring are oxidized and the cellulose chain is decomposed.
  • the ozone concentration in the gas containing ozone is preferably 50 g / m 3 to 250 g / m 3 , and more preferably 50 g / m 3 to 220 g / m 3 .
  • the amount of ozone added to the cellulose raw material is preferably 0.1 parts by mass to 30 parts by mass, and more preferably 5 parts by mass to 30 parts by mass when the solid content of the cellulose raw material is 100 parts by mass. .
  • the ozone treatment temperature is preferably 0 ° C. to 50 ° C., more preferably 20 ° C. to 50 ° C.
  • the ozone treatment time is not particularly limited, but is about 1 minute to 360 minutes, preferably about 30 minutes to 360 minutes. When the conditions for the ozone treatment are within these ranges, the cellulose can be prevented from being excessively oxidized and decomposed, and the yield of oxidized cellulose is improved.
  • an additional oxidation treatment may be performed using an oxidizing agent.
  • the oxidizing agent used for the additional oxidation treatment is not particularly limited, and examples thereof include chlorine compounds such as chlorine dioxide and sodium chlorite, oxygen, hydrogen peroxide, persulfuric acid, and peracetic acid.
  • these oxidizing agents can be dissolved in a polar organic solvent such as water or alcohol to prepare an oxidizing agent solution, and a cellulose raw material can be immersed in the solution for additional oxidation treatment.
  • the amount of carboxyl groups in the oxidized cellulose can be adjusted by controlling the reaction conditions such as the amount of the oxidant added and the reaction time.
  • phosphorylated cellulose can be used as the modified cellulose.
  • the said cellulose is obtained by the method of mixing the powder and aqueous solution of phosphoric acid type compound A with a cellulose raw material, and the method of adding the aqueous solution of phosphoric acid type compound A to the slurry of a cellulose raw material.
  • Examples of the phosphoric acid compound A include phosphoric acid, polyphosphoric acid, phosphorous acid, phosphonic acid, polyphosphonic acid, and esters thereof. These may be in the form of salts.
  • a compound having a phosphate group is preferable because it is low in cost, easy to handle, and can improve the fibrillation efficiency by introducing a phosphate group into cellulose of the pulp fiber.
  • Compounds having a phosphate group include phosphoric acid, sodium dihydrogen phosphate, disodium hydrogen phosphate, trisodium phosphate, sodium pyrophosphate, sodium metaphosphate, potassium dihydrogen phosphate, dipotassium hydrogen phosphate, phosphorus
  • Examples include tripotassium acid, potassium pyrophosphate, potassium metaphosphate, ammonium dihydrogen phosphate, diammonium hydrogen phosphate, triammonium phosphate, ammonium pyrophosphate, ammonium metaphosphate, and the like. These can be used alone or in combination of two or more.
  • phosphoric acid phosphoric acid sodium salt, phosphoric acid potassium salt, phosphoric acid
  • the ammonium salt is more preferred.
  • sodium dihydrogen phosphate and disodium hydrogen phosphate are preferred.
  • the phosphoric acid compound A is preferably used as an aqueous solution because the uniformity of the reaction is enhanced and the efficiency of introduction of phosphate groups is increased.
  • the pH of the aqueous solution of the phosphoric acid compound A is preferably 7 or less because of the high efficiency of introducing phosphate groups, but is preferably pH 3 to 7 from the viewpoint of suppressing hydrolysis of pulp fibers.
  • Phosphoric acid compound A is added to a cellulose raw material dispersion having a solid content concentration of 0.1% by mass to 10% by mass with stirring to introduce phosphate groups into the cellulose.
  • the addition amount of the phosphoric acid compound A is preferably 0.2 to 500 parts by mass, preferably 1 to 400 parts by mass as the amount of phosphorus element. Is more preferable. If the ratio of the phosphoric acid type compound A is more than the said lower limit, the yield of a fine fibrous cellulose can be improved more. However, if the upper limit is exceeded, the effect of improving the yield reaches its peak, which is not preferable from the viewpoint of cost.
  • Compound B is not particularly limited, but a nitrogen-containing compound showing basicity is preferable.
  • “Basic” as used herein is defined as an aqueous solution exhibiting a pink to red color in the presence of a phenolphthalein indicator, or an aqueous solution having a pH greater than 7.
  • the basic nitrogen-containing compound used in the present disclosure is not particularly limited as long as the effect of the present disclosure is exhibited, but a compound having an amino group is preferable.
  • urea methylamine, ethylamine, trimethylamine, triethylamine, monoethanolamine, diethanolamine, triethanolamine, pyridine, ethylenediamine, hexamethylenediamine and the like can be mentioned, but not particularly limited. Among these, urea which is easy to handle at low cost is preferable.
  • the amount of compound B added is preferably 2 parts by mass to 1000 parts by mass, and more preferably 100 parts by mass to 700 parts by mass with respect to 100 parts by mass of the solid content of the cellulose raw material.
  • the reaction temperature is preferably 0 ° C. to 95 ° C., more preferably 30 ° C. to 90 ° C.
  • the reaction time is not particularly limited, but is about 1 to 600 minutes, more preferably 30 to 480 minutes.
  • the conditions of the phosphoric esterification reaction are within these ranges, it is possible to prevent the cellulose from being excessively phosphorylated and easily dissolved, and the yield of phosphorylated esterified cellulose is improved.
  • water is contained in the heat treatment, it is preferably heated at 130 ° C. or lower, preferably 110 ° C. or lower, after removing water, it is preferably heat treated at 100 ° C. to 170 ° C.
  • the phosphate group substitution degree per glucose unit of the phosphorylated cellulose is preferably 0.001 to 0.40.
  • the phosphate group substitution degree per glucose unit of the phosphorylated cellulose is preferably 0.001 to 0.40.
  • the celluloses are electrically repelled. For this reason, the cellulose which introduce
  • the degree of phosphate group substitution per glucose unit is greater than 0.40, it may swell or dissolve, and may not be obtained as a nanofiber.
  • it is preferable that the phosphoric esterified cellulose raw material obtained above is boiled and then washed with cold water.
  • an apparatus for defibrating is not particularly limited, but a strong shearing force is applied to the aqueous dispersion of the modified cellulose by using an apparatus such as a high-speed rotation type, a colloid mill type, a high-pressure type, a roll mill type, or an ultrasonic type. It is preferable to apply.
  • a wet high-pressure or ultrahigh-pressure homogenizer that can apply a pressure of 50 MPa or more to the aqueous dispersion and can apply a strong shearing force.
  • the pressure is more preferably 100 MPa or more, and further preferably 140 MPa or more.
  • the modified cellulose may be pretreated using a known mixing, stirring, emulsifying, and dispersing device such as a high-speed shear mixer. Is possible.
  • the number of treatments (passes) in the defibrating device may be one time, two times or more, and preferably two times or more.
  • the modified cellulose is usually dispersed in a solvent.
  • a solvent will not be specifically limited if a modified cellulose can be disperse
  • distributed For example, water, organic solvents (for example, hydrophilic organic solvents, such as methanol), and those mixed solvents are mentioned. Since it uses for foodstuffs, it is preferred that a solvent is water.
  • the solid content concentration of the modified cellulose in the dispersion is usually 0.1% by weight or more, preferably 0.2% by weight or more, more preferably 0.3% by weight or more. Thereby, the liquid quantity with respect to the quantity of a cellulose fiber raw material becomes an appropriate quantity, and is efficient.
  • the upper limit is usually 10% by weight or less, preferably 6% by weight or less. Thereby, fluidity
  • the fiber width of the anion-modified CNF is, in one or more embodiments, about 1 nm to 500 nm or 2 nm to 100 nm, preferably 1 nm to less than 20 nm, 2 nm to 15 nm, or 3 nm to 5 nm. .
  • the average aspect ratio of anion-modified CNF is usually 100 or more.
  • the upper limit of the average aspect ratio is not particularly limited, but is usually 1000 or less.
  • Examples of the cellulose raw material include plant materials, animal materials, and algae in one or more embodiments.
  • examples of the plant material include wood, bamboo, hemp, jute, kenaf, cloth, pulp, recycled pulp, and waste paper.
  • examples of the pulp include kraft pulp (KP), sulfate pulp (SP), dissolved sulfite pulp (DSP), dissolved kraft pulp (DKP), powdered cellulose, and microcrystalline cellulose powder in one or more embodiments.
  • Examples of the animal material include squirts in one or a plurality of embodiments.
  • the present disclosure includes mixing an anion-modified CNF and a redispersibility improver to obtain an aqueous suspension of the anion-modified CNF, and drying the aqueous suspension to obtain a dry CNF.
  • the present invention relates to a method for producing dry CNF (a method for producing dry CNF of the present disclosure).
  • a method for producing dry CNF of the present disclosure in one or a plurality of embodiments, film-like dry CNF and / or powder-like dry CNF having sufficient transparent dispersibility upon redispersion can be obtained.
  • the method for producing dry CNF of the present disclosure can be preferably used for TEMPO-oxidized CNF among anion-modified CNFs.
  • the redispersibility of a dried product of TEMPO-oxidized CNF dry CNF
  • Dispersibility can be improved or improved.
  • the manufacturing method of the dry CNF of this indication can be utilized for CCM CNF in one or some embodiment.
  • the dispersibility at the time of redispersion of the dried product of CCM CNF can be improved or improved.
  • the manufacturing method of the dry CNF of this indication can be preferably utilized for phosphate ester CNF in anion modified CNF in one or some embodiment.
  • the redispersibility of a dried product of phosphoesterified CNF can be improved or improved.
  • the transparent dispersibility of can be improved or improved.
  • dry CNF having improved redispersibility can be obtained, and in particular, dry CNF having improved transparent dispersibility during redispersion can be obtained.
  • the obtained dry CNF may have sufficient transparent dispersibility when redispersed. “Having sufficient transparent dispersibility when redispersed” means that, in one or more embodiments, the transparency and re-dispersion to the dispersion medium at the same or comparable level as the anion-modified CNF suspension before drying. It has dispersibility.
  • the obtained dry CNF is used in various chemical products, foods, cosmetics, pharmaceuticals, beverages, reinforcing materials (including paper), absorbent products such as diapers, heat insulating materials, automobile members, paints, and the like. It can be used for agricultural chemicals, construction, batteries, household goods, water treatment, or cleaning agents.
  • the redispersibility improving agent in the present disclosure includes, in one or more embodiments, low molecular weight saccharides, low molecular weight polypeptides, amino acids, and low molecular weight PVA.
  • the method for producing dry CNF of the present disclosure includes mixing an anion-modified CNF and a low molecular weight saccharide to obtain an aqueous suspension of the anion-modified CNF, and the obtained aqueous suspension. Including drying the liquid.
  • low molecular weight saccharide refers to a saccharide having a molecular weight of 50,000 or less.
  • the saccharide include monosaccharides, disaccharides, oligosaccharides, and polysaccharides in one or more embodiments.
  • the molecular weight of the low molecular weight saccharide is 50,000 or less, 20,000 or less, 15,000 or less, 10,000 or less, 5000 or less, 3000 or less, 2000 or less, or 200 or less, Or 150 or more.
  • Examples of monosaccharides include glucose and the like in one or more embodiments.
  • the molecular weight of the monosaccharide is 150 or more or 200 or less in one or more embodiments.
  • disaccharides examples include maltose and lactose in one or more embodiments.
  • the molecular weight of the disaccharide is 200 or more, or 400 or less, 380 or less, 360 or less, or 350 or less.
  • Oligosaccharides include cyclodextrin in one or more embodiments.
  • the molecular weight (weight average molecular weight) of the oligosaccharide is 400 or more, 600 or more, 800 or more, or 900 or more, or 5000 or less, 4000 or less, 3000 or less, or 2000 or less.
  • Examples of cyclodextrins include ⁇ -cyclodextrin (natural molecular weight: 973), ⁇ -cyclodextrin (natural molecular weight: 1135), and ⁇ -cyclodextrin (natural molecular weight: 1297).
  • the cyclodextrin may be a natural cyclodextrin or a chemically modified cyclodextrin (cyclodextrin derivative).
  • cyclodextrin derivative in one or more embodiments, hydroxypropylated cyclodextrin, acetylated cyclodextrin, triacetylated cyclodextrin, methylated cyclodextrin, monochlorotriazinated cyclodextrin, amino Cyclodextrin, ethylene diaminated cyclodextrin and the like.
  • ⁇ -cyclodextrin and ⁇ -cyclodextrin derivatives having a molecular weight of 3000 or less or 2000 or less from the viewpoint of obtaining good redispersibility, in particular, good transparent redispersibility upon redispersion.
  • ⁇ -cyclodextrin or glucose is preferable.
  • ⁇ -cyclodextrin, ⁇ -cyclodextrin derivative, or ⁇ -cyclodextrin is more preferable because it does not inhibit the properties (thixotropic properties, viscosity, etc.) of anion-modified CNF.
  • polysaccharides examples include dextrin and low molecular weight CMC in one or more embodiments.
  • the molecular weight of dextrin is 50,000 or less, 20,000 or less, 17,000 or less, 15,000 or less, 13,000 or less, 120,000 or less, 11,000 or less, or 10,000. 000 or less, or 200 or more, 500 or more, 1,000 or more, 2,000 or more, 3,000 or more, 4,000 or more, 5,000 or more, or 6,000 or more.
  • Examples of the low molecular weight CMC include CMC having a molecular weight of 20,000 or less.
  • the molecular weight of the low molecular weight CMC is 20,000 or less, 15,000 or less, or 200 or more in one or more embodiments.
  • the degree of etherification (carboxymethyl group substitution) of CMC is not particularly limited, and may be 0.55 to 1.6 or 0.65 to 1.1 in one or more embodiments.
  • the method for producing dry CNF according to the present disclosure includes mixing an anion-modified CNF in a wet state (dispersed in water) and a low molecular weight saccharide. Thereby, an aqueous suspension containing anion-modified CNF and a low molecular weight saccharide can be obtained.
  • the blending ratio of the low molecular weight saccharide to the anion-modified CNF is 5 parts by mass or more, 5 parts by mass to 500 parts by mass, 5 parts by mass to 400 parts by mass in one or more embodiments. Part by mass, 5 parts by mass to 300 parts by mass or 10 parts by mass to 200 parts by mass, and preferably 30 parts by mass to 350 parts by mass or 30 parts by mass to 150 parts by mass.
  • the blending ratio of the low molecular weight saccharide to the anion-modified CNF is 5 parts by mass in one or a plurality of embodiments. 5 parts by weight to 500 parts by weight, 5 parts by weight to 400 parts by weight, 5 parts by weight to 300 parts by weight or 10 parts by weight to 200 parts by weight, preferably 30 parts by weight to 250 parts by weight or 45 parts by weight. 150 parts by mass.
  • the blending ratio of the low molecular weight saccharide to the anion-modified CNF is 5 parts by mass or more and 10 parts by mass in one or more embodiments. From 500 parts by weight or from 30 parts by weight to 400 parts by weight, preferably from 50 parts by weight to 350 parts by weight or from 75 parts by weight to 350 parts by weight.
  • the blending ratio of the low molecular weight saccharide to the anion-modified CNF is 5 parts by mass or more in one or more embodiments, Parts by weight to 500 parts by weight, 5 parts by weight to 400 parts by weight, 5 parts by weight to 300 parts by weight or 10 parts by weight to 200 parts by weight, preferably 30 parts by weight to 250 parts by weight or 45 parts by weight to 150 parts by weight. It is.
  • the method for producing dry CNF of the present disclosure includes drying an aqueous suspension containing an anion-modified CNF and a low molecular weight saccharide.
  • the aqueous suspension may be dried by forming a thin film, or may be spray-dried. Thereby, a dry film and / or a dry powder containing an anion-modified CNF and a low molecular weight saccharide can be obtained.
  • the method for producing dry CNF according to the present disclosure is obtained by mixing an anion-modified CNF and a low molecular weight polypeptide or amino acid to obtain an aqueous suspension of the anion-modified CNF. Drying the aqueous suspension.
  • low molecular weight polypeptide refers to a polypeptide having a molecular weight of 10,000 or less.
  • the molecular weight of the low molecular weight polypeptide is 1000 or less, 500 or less, or 150 or more in one or more embodiments.
  • the amino acid include neutral amino acids such as glycine and glutamine in one or more embodiments.
  • the method for producing dry CNF according to the present disclosure includes mixing an anion-modified CNF in a wet state (dispersed in water) with a low molecular weight polypeptide or amino acid. Thereby, an aqueous suspension containing anion-modified CNF and a low molecular weight polypeptide or amino acid can be obtained.
  • the blending ratio of the low molecular weight polypeptide or amino acid to anion-modified CNF is 5 parts by mass or more, 5 parts by mass to 500 parts by mass, and 5 parts by mass in one or more embodiments. 400 parts by weight, 5 parts by weight to 300 parts by weight or 10 parts by weight to 200 parts by weight, preferably 30 parts by weight to 350 parts by weight or 30 parts by weight to 150 parts by weight.
  • the method for producing dry CNF of the present disclosure includes drying an aqueous suspension containing an anion-modified CNF and a low molecular weight polypeptide or amino acid.
  • the aqueous suspension may be dried by forming a thin film, or may be spray-dried. Thereby, a dry film and / or a dry powder containing an anion-modified CNF and a low molecular weight polypeptide or amino acid can be obtained.
  • the method for producing dry CNF of the present disclosure includes mixing an anion-modified CNF and a low molecular weight PVA to obtain an aqueous suspension of the anion-modified CNF, and the obtained aqueous suspension. Including drying the liquid.
  • low molecular weight PVA refers to PVA having a molecular weight of 3000 or less. In one or more embodiments, the molecular weight of the low molecular weight PVA is 2500 or less, 2000 or less, 1500 or less, or 100 or more.
  • the method for producing dry CNF according to the present disclosure includes mixing an anion-modified CNF in a wet state (dispersed in water) and a low molecular weight PVA. Thereby, an aqueous suspension containing anion-modified CNF and low molecular weight PVA can be obtained.
  • the blending ratio of the low molecular weight PVA to the anion-modified CNF is 5 parts by mass or more, 5 parts by mass to 500 parts by mass, and 5 parts by mass to 400 parts by mass in one or more embodiments.
  • the method for producing dry CNF according to the present disclosure includes drying an aqueous suspension containing an anion-modified CNF and a low molecular weight PVA.
  • the aqueous suspension may be dried by forming a thin film, or may be spray-dried. Thereby, a dry film and / or dry powder containing anion-modified CNF and low molecular weight PVA can be obtained.
  • the drying method of the aqueous suspension is not particularly limited, and in one or a plurality of embodiments, spray drying, air drying, hot air drying, vacuum drying, pressing, and the like can be given.
  • dry CNF obtained by the dry CNF production method of the present disclosure is added to 5 g of distilled CNF refined to about 1 mm to 2 mm to 5 g of distilled water, and then for about 1 minute with a point mixer. After stirring, when left standing at room temperature for about 24 hours and then again stirred for about 1 minute with a point mixer, it has a transparent dispersibility at least at the same level or comparable to that of the CNF dispersion before drying.
  • the dry CNF obtained by the dry CNF manufacturing method of the present disclosure is obtained by pulverizing a dry CNF in a film shape to about 3 ⁇ 3 mm in a 200 mL beaker.
  • distilled water is added to 7% and then stirred with a three-one motor at 600 rpm and a blade diameter of 3.5 cm for 1 to 3 hours, it is at least as high as the CNF dispersion before drying. Or, it has a transparent dispersibility at a comparable level.
  • the dry CNF obtained by the dry CNF production method of the present disclosure may be a dry product, and in one or more embodiments, in the form of a film, from the viewpoint of further improving the transparent dispersibility in the dispersion medium to be redispersed. It may be in powder form.
  • the present disclosure relates to dry CNF comprising a redispersibility improver and an anion-modified CNF (dry CNF of the present disclosure).
  • dry CNF of this indication can be obtained by the manufacturing method of dry CNF of this indication in one or some embodiment.
  • the dry CNF of the present disclosure is mainly composed of an anion-modified CNF that is not particularly limited.
  • the dry CNF of the present disclosure may be in the form of a film or powder.
  • the present disclosure relates to a method for producing a transparent redispersion of CNF (a method for producing a transparent redispersion of the present disclosure).
  • the method for producing a transparent redispersion of the present disclosure includes obtaining an aqueous suspension containing an anion-modified CNF and a redispersibility improving agent, drying the aqueous suspension, And redispersing the obtained dried product in a dispersion medium.
  • the method for producing a transparent redispersion of CNF according to the present disclosure includes redispersing the dry CNF obtained by the method for producing dry CNF according to the present disclosure in a dispersion medium.
  • a transparent redispersion of can be obtained.
  • a transparent redispersion of dry CNF having high transparency in which dry TEMPO-oxidized CNF is redispersed can be obtained.
  • the redispersion may be a liquid or a gel.
  • the dispersion medium examples include an aqueous dispersion medium such as water in one or a plurality of embodiments.
  • the dispersion medium may contain various polymers other than CNF.
  • the method for producing a transparent redispersion of the present disclosure may further include removing the redispersibility improver from the obtained transparent redispersion.
  • the redispersibility improver is a cyclodextrin
  • the removal of the redispersibility improver is performed in one or more embodiments by mixing a linear aliphatic alcohol such as 1-decanol and a transparent redispersion, This can then be done by separating the cyclodextrin from the transparent redispersion by applying physical stress.
  • the addition amount of the linear aliphatic alcohol is not particularly limited, and in one or a plurality of embodiments, it may be a molar equivalent with respect to the cyclodextrin contained in the transparent redispersion. Examples of the physical stress include centrifugation in one or more embodiments.
  • the dispersion medium examples include an aqueous dispersion medium such as water in one or a plurality of embodiments.
  • the dispersion medium may contain various polymers other than CNF.
  • the present disclosure relates to a method for producing a redispersion of CNF (a method for producing a redispersion of the present disclosure).
  • the method for producing a redispersion of the present disclosure includes obtaining an aqueous suspension containing CCM CNF and a redispersibility improving agent, drying the aqueous suspension, and Re-dispersing the obtained dried product in a dispersion medium.
  • the method for producing a CNF redispersion of the present disclosure includes redispersing the dry CNF obtained by the method for producing a dry CNF of the present disclosure in a dispersion medium.
  • the dispersibility is the same as or comparable to that of a CCM CNF aqueous suspension or aqueous dispersion that is not dried.
  • a re-dispersion of dry CMized CNF can be obtained.
  • the redispersion may be a liquid or a gel.
  • the method for removing the dispersion medium and the redispersibility improver is the same as the method for producing the transparent redispersion of the present disclosure.
  • the present disclosure includes mixing an anion-modified CNF and a redispersibility improver to obtain an aqueous suspension of anion-modified cellulose nanofibers, and drying the aqueous suspension.
  • the present invention relates to a method for improving redispersibility of contained CNF, in particular, transparent dispersibility during redispersion.
  • the transparent dispersibility at the time of redispersion of a dried product of TEMPO-oxidized CNF among anion-modified CNFs can be further improved or improved.
  • dispersibility during redispersion of a dry product of C-modified CNF among anion-modified CNFs can be further improved or improved.
  • the redispersibility improving method of the present disclosure in one or a plurality of embodiments, it is possible to further improve or improve the transparent dispersibility during redispersion of the dried product of phosphate esterified CNF among anion-modified CNFs. .
  • the redispersibility improving agent and the blending ratio are the same as in the method for producing dry CNF of the present disclosure.
  • the aqueous suspension may contain a third component other than the anion-modified CNF and the redispersibility improving agent during redispersion.
  • the third component include a water-soluble polymer in one or a plurality of embodiments.
  • the aqueous suspension can be dried in the same manner as the dry CNF production method of the present disclosure.
  • the present disclosure provides a redispersibility improving agent for improving or improving redispersibility of dry cellulose nanofibers in an aqueous dispersion medium, in particular, transparent dispersibility during redispersion (redispersion of the present disclosure).
  • Property improver includes one or more selected from the group consisting of low molecular weight saccharides, low molecular weight polypeptides, amino acids, and low molecular weight PVC.
  • the redispersibility improver of the present disclosure is used in one or a plurality of embodiments in the production of dry cellulose nanofibers having improved or improved redispersibility in a dispersion medium, in particular, transparent dispersibility during redispersion. can do.
  • Low molecular weight saccharides, low molecular weight polypeptides, amino acids, and low molecular weight PVC are as described above.
  • the present disclosure is a dry composition containing anion-modified cellulose nanofibers and a redispersibility improver, wherein the redispersibility improver is a saccharide having a molecular weight of 50,000 or less, a low molecular weight polypeptide,
  • the present invention relates to a dry composition (dry composition of the present disclosure) comprising at least one selected from the group consisting of amino acids and low molecular weight PVC.
  • the proportion of the redispersibility improver in the dry composition of the present disclosure is 5% by mass or more and 5% by mass to 500% by mass with respect to the anion-modified CNF (absolutely dry solid content). 5% by mass to 400% by mass, 5% by mass to 300% by mass, 10% by mass to 200% by mass, or 20% by mass to 300% by mass, and preferably 30% by mass to 350% by mass or 30% by mass to 150% by mass.
  • the proportion of the redispersibility improver in the dry composition of the present disclosure is, in one or more embodiments, 5 masses relative to TEMPO-oxidized CNF (absolutely dry solids). % Or more, 5 mass% to 500 mass%, 5 mass% to 400 mass%, 5 mass% to 300 mass%, or 10 mass% to 200 mass%, preferably 30 mass% to 250 mass% or 45 mass%. ⁇ 150% by weight.
  • the proportion of the redispersibility improver in the dry composition of the present disclosure is, in one or more embodiments, 5 masses with respect to TEMPO oxidized CNF (absolutely dry solids). % Or more, 10 mass% to 500 mass%, or 30 mass% to 400 mass%, preferably 50 mass% to 350 mass%, or 75 mass% to 350 mass%.
  • the proportion of the redispersibility improver in the dry composition of the present disclosure is, in one or more embodiments, based on phosphate esterified CNF (absolutely dry solids). 5 mass% or more, 5 mass% to 500 mass%, 5 mass% to 400 mass%, 5 mass% to 300 mass%, or 10 mass% to 200 mass%, preferably 30 mass% to 250 mass%. Or 45 mass% to 150 mass%.
  • the dry composition of the present disclosure may include a third component other than the anion-modified CNF and the redispersibility improving agent.
  • the third component include a water-soluble polymer in one or a plurality of embodiments.
  • the dry composition of the present disclosure may be a film, a solid, or a powder.
  • the film thickness of the dry composition of this indication is 50 micrometers or more or 100 micrometers or more, or 1000 micrometers or less or 300 micrometers or less in one or some embodiment.
  • the dry composition of the present disclosure may be produced by mixing an anion-modified CNF and a redispersibility improver, and, if necessary, the third component and drying it.
  • the dry CNF of the present disclosure and the third component may be mixed and dried.
  • the present disclosure further relates to one or more of the following embodiments.
  • An anion-modified CNF and a redispersibility improver are mixed to obtain an aqueous suspension of the anion-modified CNF, and the aqueous suspension is dried to obtain a dry CNF.
  • the method for producing dry CNF wherein the redispersibility improving agent is selected from the group consisting of sugars having a molecular weight of 50,000 or less, low molecular weight polypeptides, amino acids, and low molecular weight polyvinyl alcohol.
  • the redispersibility improving agent is carboxymethylcellulose having a molecular weight of 20,000 or less.
  • [10] comprising mixing an anion-modified CNF and a redispersibility improver to obtain an aqueous suspension of the anion-modified CNF, and drying the aqueous suspension;
  • the method for improving redispersibility of CNF wherein the redispersibility improving agent is selected from the group consisting of sugars having a molecular weight of 50,000 or less, low molecular weight polypeptides, amino acids, and low molecular weight polyvinyl alcohol.
  • a method for improving the redispersibility of CNF comprising mixing an anion-modified CNF and a low molecular weight saccharide to obtain an aqueous suspension of the anion-modified CNF, and drying the aqueous suspension.
  • a method for improving the redispersibility of CNF comprising mixing an anion-modified CNF and a low molecular weight CMC to obtain an aqueous suspension of the anion-modified CNF, and drying the aqueous suspension.
  • Redispersion of CNF comprising mixing an anion-modified CNF with at least one of a low molecular weight polypeptide and an amino acid to obtain an aqueous suspension of the anion-modified CNF, and drying the aqueous suspension Improvement method.
  • a method for improving the redispersibility of CNF comprising mixing an anion-modified CNF and a low molecular weight PVA to obtain an aqueous suspension of the anion-modified CNF, and drying the aqueous suspension.
  • the method for improving redispersibility of CNF according to any one of [10] to [14], wherein the anion-modified CNF is carboxylated CNF, CCM CNF, or phosphate ester CNF.
  • a drug for improving or improving the redispersibility of dry CNF in an aqueous dispersion medium selected from the group consisting of low molecular weight saccharides, low molecular weight polypeptides, amino acids, and low molecular weight polyvinyl alcohol
  • a redispersibility improving agent containing one or more of the above [17] A redispersibility improving agent for improving or improving the redispersibility of dry CNF in an aqueous dispersion medium, comprising a low molecular weight CMC.
  • a redispersibility improver for use in the production of dry CNF comprising at least one selected from the group consisting of low molecular weight sugars, low molecular weight polypeptides, amino acids, and low molecular weight polyvinyl alcohol. Redispersibility improving agent containing.
  • a redispersibility improving agent for use in the production of dry CNF comprising a low molecular weight CMC.
  • a redispersibility improver for use in the method for producing dry CNF according to any one of [1] to [9] or the redispersibility improving method according to any one of [10] to [15] A redispersibility improving agent comprising at least one selected from the group consisting of a low molecular weight saccharide, a low molecular weight polypeptide, an amino acid, and a low molecular weight polyvinyl alcohol.
  • a redispersibility improver for use in the method for producing dry CNF according to any one of [1] to [9] or the redispersibility improving method according to any one of [10] to [15] A redispersibility improver comprising low molecular weight CMC.
  • a dry composition comprising an anion-modified CNF and a redispersibility improver
  • a composition comprising the redispersibility improving agent comprising at least one selected from the group consisting of sugars having a molecular weight of 50,000 or less, low molecular weight polypeptides, amino acids, and low molecular weight polyvinyl alcohol.
  • the anion-modified CNF is carboxylated CNF, CCM CNF, or phosphate ester CNF.
  • the reaction product was taken out, neutralized and washed to obtain a carboxymethylated pulp having a carboxymethyl substitution degree of 0.25 per glucose unit.
  • the pulp solid content is 1.2% (w / v) with water, and the fiber is fibrillated by treating with a high-pressure homogenizer five times at 20 ° C. and a pressure of 150 MPa.
  • the carboxymethylated cellulose nanofiber (hereinafter referred to as CM-CNF) )
  • the average fiber diameter was 12 nm and the aspect ratio was 130.
  • This pulp sheet was immersed in 31.2 g of the phosphorylating reagent (80 parts by mass as the amount of phosphorus element with respect to 100 parts by mass of the dried pulp), and heated for 1 hour with an air dryer at 105 ° C. (Yamato Scientific Co., Ltd. DKM400) Further, heat treatment was performed at 150 ° C. for 1 hour to introduce phosphate groups into the cellulose fibers. Subsequently, 500 ml of ion-exchanged water was added to the pulp sheet in which the phosphate group was introduced into the cellulose fiber, and the mixture was dehydrated after washing with stirring.
  • the phosphorylating reagent 80 parts by mass as the amount of phosphorus element with respect to 100 parts by mass of the dried pulp
  • the dehydrated sheet was diluted with 300 ml of ion-exchanged water, and 5 ml of 1N aqueous sodium hydroxide solution was added little by little with stirring to obtain a cellulose suspension having a pH of 12 to 13. Thereafter, the cellulose suspension was dehydrated and washed by adding 500 ml of ion exchange water. This dehydration washing was repeated two more times. Ion exchange water was added to the sheet obtained after washing and dehydration, and the mixture was stirred to obtain a 0.5 mass% cellulose suspension.
  • This cellulose suspension was defibrated for 30 minutes using a defibrating apparatus (Cleamix-2.2S, manufactured by M Technique Co., Ltd.) at 21500 rpm, and defibrated cellulose (phosphate ester) Cellulose nanofiber) suspension was obtained.
  • a defibrating apparatus Cleamix-2.2S, manufactured by M Technique Co., Ltd.
  • defibrated cellulose (phosphate ester) Cellulose nanofiber) suspension was obtained.
  • fine fibrous cellulose having a width of 4 nm was contained.
  • Example 1 Using the chemicals shown in Table 1, production of dry anion-modified CNF (dry CNF) and redispersibility of dry CNF were evaluated.
  • dry CNF dry anion-modified CNF
  • anion-modified CNF1 T-CNF, average fiber width: 3 nm, aspect ratio: 250
  • the obtained liquid was applied on a Teflon (trademark) plate or a Teflon (trademark) dish, and dried with hot air of 60 ° C. to 105 ° C. to obtain a film-like dry CNF.
  • the blank was the same as above except that no drug was added.
  • Example 2 Using CMC (manufactured by Nippon Paper Industries Co., Ltd.) shown in Table 2 below, the redispersibility of anion-modified CNF was evaluated.
  • anion-modified CNF anion-modified CNF1 (T-CNF, average fiber diameter: 3 nm, aspect ratio: 250) was used.
  • “Sunrose” is a registered trademark of Nippon Paper Industries Co., Ltd.
  • a film-like dry CNF was obtained in the same procedure as in Experimental Example 1, except that the CMC shown in Table 2 below was used instead of the drugs in Table 1.
  • Film-like dry CNF is pulverized to about 3 x 3 mm, adjusted in distilled water to a solid content of 0.7% (w / v) in a 200 mL beaker, and a stirrer with a three-one motor of 600 rpm and a blade diameter of 3.5 cm The mixture was stirred for 1 to 3 hours to obtain an aqueous redispersion or aqueous suspension.
  • the blank was the same as above except that no drug was added.
  • the redispersibility of dry CNF could be improved by using CMC having a molecular weight of 20,000 or less.
  • CMC having a molecular weight of 20,000 or less was added and the stirring time was 2 hours or more, no precipitate or undispersed gel was confirmed, and anion-modified CNF dispersion before drying was confirmed.
  • a highly transparent CNF redispersion liquid equivalent to the liquid could be obtained. It was also confirmed that the time required for redispersion of dry CNF could be shortened by using CMC having a molecular weight of 20,000 or less.
  • CM-CNF anion-modified CNF2
  • average fiber width 12 nm, aspect ratio: 130 or more
  • the temperature of the hot air during the production of the dried film was 60 ° C.
  • dry CNF was produced and dry CNF was redispersed in the same manner as in Experimental Example 1 to obtain an aqueous dispersion or suspension in which dry CM CNF was redispersed.
  • the obtained dried CNF could be dispersed in distilled water for C-converted CNF. Moreover, it has confirmed that the redispersibility was improved compared with the conventional chemical

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Abstract

L'invention concerne un procédé de production de nanofibres de cellulose séchées (CNF) présentant une redispersibilité suffisante, et un procédé apte à améliorer la redispersibilité des CNF. L'invention concerne : un procédé de production de CNF séchées qui comprend le mélange de CNF modifiées par des anions et d'un agent d'amélioration de la redispersibilité pour obtenir une suspension aqueuse de CNF modifiées par des anions, et le séchage de la suspension aqueuse pour obtenir des CNF séchées, l'agent d'amélioration de la redispersibilité étant choisi dans le groupe constitué par les sucres ayant un poids moléculaire inférieur ou égal à 50 000, des polypeptides de bas poids moléculaire, des acides aminés et un alcool polyvinylique de faible poids moléculaire ; et un procédé d'amélioration de la redispersibilité de CNF qui implique le mélange de CNF modifiées par un anion et d'un agent d'amélioration de la redispersibilité pour obtenir une suspension aqueuse de CNF modifiées par des anions, et le séchage de la suspension aqueuse, l'agent d'amélioration de la redispersibilité étant choisi dans le groupe constitué par les sucres ayant un poids moléculaire inférieur ou égal à 50 000, des polypeptides de bas poids moléculaire, des acides aminés et un alcool polyvinylique de faible poids moléculaire.
PCT/JP2018/002846 2017-02-03 2018-01-30 Procédé de production de nanofibres de cellulose séchées WO2018143149A1 (fr)

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JP2020050804A (ja) * 2018-09-28 2020-04-02 大王製紙株式会社 ゲル状洗浄剤組成物及び洗浄剤製品
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JP2021138875A (ja) * 2020-03-06 2021-09-16 ユニチカ株式会社 ポリプロピレン樹脂組成物およびそれを用いた樹脂組成物
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JP7232072B2 (ja) * 2019-02-15 2023-03-02 第一工業製薬株式会社 変性セルロースナノファイバー、ガスバリア用材料及びガスバリア性成形体
CN115651086B (zh) * 2022-11-07 2024-01-30 宁波大学 一种多肽改性纤维素的绿色制备方法

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