WO2024057830A1 - Procédé de broyage de polymère de cellulose - Google Patents

Procédé de broyage de polymère de cellulose Download PDF

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WO2024057830A1
WO2024057830A1 PCT/JP2023/029955 JP2023029955W WO2024057830A1 WO 2024057830 A1 WO2024057830 A1 WO 2024057830A1 JP 2023029955 W JP2023029955 W JP 2023029955W WO 2024057830 A1 WO2024057830 A1 WO 2024057830A1
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cellulose
bead mill
pulp
beads
treatment
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PCT/JP2023/029955
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English (en)
Japanese (ja)
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一彦 井上
貴之 阪後
昂輝 柴田
佑馬 金子
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日本製紙株式会社
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B02—CRUSHING, PULVERISING, OR DISINTEGRATING; PREPARATORY TREATMENT OF GRAIN FOR MILLING
    • B02C—CRUSHING, PULVERISING, OR DISINTEGRATING IN GENERAL; MILLING GRAIN
    • B02C17/00—Disintegrating by tumbling mills, i.e. mills having a container charged with the material to be disintegrated with or without special disintegrating members such as pebbles or balls
    • B02C17/16—Mills in which a fixed container houses stirring means tumbling the charge
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B02—CRUSHING, PULVERISING, OR DISINTEGRATING; PREPARATORY TREATMENT OF GRAIN FOR MILLING
    • B02C—CRUSHING, PULVERISING, OR DISINTEGRATING IN GENERAL; MILLING GRAIN
    • B02C17/00—Disintegrating by tumbling mills, i.e. mills having a container charged with the material to be disintegrated with or without special disintegrating members such as pebbles or balls
    • B02C17/18—Details
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B02—CRUSHING, PULVERISING, OR DISINTEGRATING; PREPARATORY TREATMENT OF GRAIN FOR MILLING
    • B02C—CRUSHING, PULVERISING, OR DISINTEGRATING IN GENERAL; MILLING GRAIN
    • B02C17/00—Disintegrating by tumbling mills, i.e. mills having a container charged with the material to be disintegrated with or without special disintegrating members such as pebbles or balls
    • B02C17/18—Details
    • B02C17/20—Disintegrating members
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/12—Powdering or granulating

Definitions

  • the present invention relates to a method for pulverizing cellulose polymers.
  • cellulose-based polymers such as carboxymethylcellulose are used in various fields for reasons such as high safety, and their use is being considered.
  • carboxymethylcellulose or a salt thereof is a product in which a carboxymethyl group is bonded to a part of the hydroxyl group of a glucopyranose monomer that constitutes the cellulose skeleton, or a carboxymethyl group is salt.
  • the quality of CMC can be adjusted by adjusting the degree of substitution of carboxymethyl groups, the length of the cellulose skeleton, etc. It is used as a binding agent, binder, water absorbing material, water retaining agent, emulsion stabilizer, etc.
  • it since it is derived from natural cellulose, it is an extremely environmentally friendly material that has gradual biodegradability and can be disposed of by incineration, and it is predicted that the applications of CMC will expand in the future.
  • Patent Document 1 describes that cellulose fiber is better than carboxymethyl cellulose when used as a binder for adhering the electrode active material of a non-aqueous secondary battery to a current collector, for example.
  • the applications of cellulose-based polymers have been limited due to
  • An object of the present invention is to provide a method for pulverizing cellulose polymers that can stably produce cellulose polymers having a particle size of less than 50 ⁇ m.
  • a method of pulverizing a cellulose polymer using a bead mill wherein the average diameter of the beads used in the bead mill is 0.1 to 10 mm, the peripheral speed of the agitator of the bead mill is 2 to 15 m/sec, and the bead filling rate of the bead mill is A method for pulverizing a cellulose-based polymer in which the amount is 50 to 90 vol%, (2) The method for pulverizing a cellulose polymer according to (1), wherein the beads have an average diameter of 3 to 8 mm; (3) The method for producing a cellulose polymer according to (1) or (2), wherein the bead mill is a dry bead mill; (4) The material of the agitator and/or vessel of the bead mill is at least one selected from zirconia, zircon, stabilized zirconia, partially stabilized zirconia, alumina, or silicon nitride (1) or (2) The method for pulverizing
  • the present invention it is possible to provide a method for pulverizing a cellulose-based polymer that can stably produce a cellulose-based polymer having a particle size of less than 50 ⁇ m.
  • FIG. 1 is a schematic diagram showing an example of a crushing device including a bead mill used in the present invention.
  • the method for pulverizing cellulose polymers of the present invention is a method for pulverizing cellulose polymers using a bead mill, wherein the beads used in the bead mill have an average diameter of 0.1 to 10 mm, and the peripheral speed of the agitator of the bead mill is 2 to 15 m/min. sec, the bead filling rate of the bead mill is 50 to 90 vol%.
  • cellulose polymer In the present invention, as the cellulose-based polymer to be pulverized, any compound derived from cellulose can be used without particular limitation, but it is preferable to use a chemically modified cellulose-based polymer or unmodified pulp.
  • Cellulose-based polymers can be obtained using cellulose as a raw material. That is, cellulose that can be used as a cellulose raw material in the present invention is a polysaccharide with a structure in which D-glucopyranose (simply referred to as "glucose residue” or “anhydroglucose”) is linked by ⁇ , 1-4 bonds. means. Cellulose is generally classified into natural cellulose, regenerated cellulose, fine cellulose, microcrystalline cellulose excluding non-crystalline regions, etc. based on its origin, manufacturing method, etc.
  • Examples of natural cellulose include bleached pulp or unbleached pulp (bleached wood pulp or unbleached wood pulp); linters, purified linters; cellulose produced by microorganisms such as acetic acid bacteria, and the like.
  • the raw material for bleached pulp or unbleached pulp is not particularly limited, and examples thereof include wood, cotton, straw, bamboo, and the like.
  • the method for producing bleached pulp or unbleached pulp is not particularly limited, and may be a mechanical method, a chemical method, or a combination of the two in between.
  • Examples of bleached pulp or unbleached pulp classified by manufacturing method include mechanical pulp, chemical pulp, groundwood pulp, sulfite pulp, and kraft pulp.
  • dissolving pulp may be used in addition to papermaking pulp. Dissolving pulp is a chemically refined pulp that is mainly used after being dissolved in chemicals, and is the main raw material for artificial fibers, cellophane, etc.
  • regenerated cellulose examples include those obtained by dissolving cellulose in some kind of solvent such as a cupric ammonia solution, a cellulose xanthate solution, or a morpholine derivative, and respinning the resulting cellulose.
  • solvent such as a cupric ammonia solution, a cellulose xanthate solution, or a morpholine derivative
  • Fine cellulose is obtained by depolymerizing cellulose materials such as the above-mentioned natural cellulose and regenerated cellulose (for example, acid hydrolysis, alkaline hydrolysis, enzymatic decomposition, blasting treatment, vibrating ball mill treatment, etc.) Examples include those obtained by mechanically processing the above-mentioned cellulose-based materials.
  • ⁇ Chemically modified cellulose polymer for example, a cellulose polymer obtained by anion modification or a cellulose polymer obtained by cation modification may be used.
  • cellulose-based polymers obtained by anionic modification include carboxylated cellulose (also called oxidized cellulose), carboxymethyl cellulose, hydroxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, and phosphate-esterified cellulose. may be in the form of a salt. Although the type of salt does not matter, it is preferable to select a suitable salt, such as a metal salt such as a sodium salt or an ammonium salt, depending on the use and purpose. Although there are no particular limitations on the cellulose-based polymer used in the present invention, it is preferable to use carboxymethylcellulose and/or a salt thereof.
  • carboxylated cellulose (oxidized cellulose)
  • carboxylated cellulose (oxidized cellulose)
  • carboxylated cellulose oxidized cellulose
  • it can be obtained by carboxylating (oxidizing) a cellulose raw material by a known method.
  • the amount of carboxyl groups is 2.4 to 9.3 mmol/g, preferably 3.1 to 8.0 mmol/g, more preferably 3. It is preferable to adjust it to 7 to 6.8 mmol/g.
  • a cellulosic raw material is oxidized in water with an oxidizing agent in the presence of an N-oxyl compound and a compound selected from the group consisting of bromides, iodides or mixtures thereof.
  • an oxidizing agent in the presence of an N-oxyl compound and a compound selected from the group consisting of bromides, iodides or mixtures thereof.
  • the primary hydroxyl group at the C6 position of the glucopyranose ring on the cellulose surface is selectively oxidized, resulting in cellulose fibers having an aldehyde group and a carboxy 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.
  • the N-oxyl compound refers to a compound that can generate nitroxy radicals.
  • any compound can be used as long as it promotes the desired oxidation reaction. Examples include 2,2,6,6-tetramethylpiperidine-1-oxyradical (TEMPO) and its derivatives (eg, 4-hydroxyTEMPO).
  • TEMPO 2,2,6,6-tetramethylpiperidine-1-oxyradical
  • 4-hydroxyTEMPO 4-hydroxyTEMPO
  • the amount of the N-oxyl compound used is not particularly limited as long as it is a catalytic amount that can oxidize cellulose as a raw material.
  • it is preferably 0.01 to 10 mmol, more preferably 0.01 to 1 mmol, and even more preferably 0.05 to 0.5 mmol, per 1 g of bone dry cellulose. Further, it is preferably about 0.1 to 4 mmol/L to the reaction system.
  • a bromide is a compound containing bromine, and examples thereof include alkali metal bromides that can be dissociated and ionized in water.
  • iodide is a compound containing iodine, and examples thereof include alkali metal iodide.
  • the amount of bromide or iodide to be used can be selected within a range that can promote the oxidation reaction.
  • the total amount of bromide and iodide is, for example, preferably 0.1 to 100 mmol, more preferably 0.1 to 10 mmol, and even more preferably 0.5 to 5 mmol, per 1 g of bone dry cellulose.
  • the oxidizing agent known ones can be used, such as halogen, hypohalous acid, halous acid, perhalogenic acid, or salts thereof, halogen oxides, peroxides, etc.
  • sodium hypochlorite is preferred because it is inexpensive and has a low environmental impact.
  • the amount of the oxidizing agent used is, for example, preferably 0.5 to 500 mmol, more preferably 0.5 to 50 mmol, even more preferably 1 to 25 mmol, and most preferably 3 to 10 mmol, per 1 g of bone dry cellulose. Further, for example, it is preferably 1 to 40 mol per 1 mol of the N-oxyl compound.
  • the reaction temperature is preferably 4 to 40°C, and may be room temperature of about 15 to 30°C.
  • carboxy groups are generated in the cellulose, so a decrease in the pH of the reaction solution is observed.
  • an alkaline solution such as an aqueous sodium hydroxide solution to maintain the pH of the reaction solution at about 8 to 12, preferably about 10 to 11. Water is preferable as the reaction medium because of its ease of handling and the fact that side reactions are less likely to occur.
  • the reaction time in the oxidation reaction can be appropriately set according to the degree of progress of oxidation, and is usually about 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 can be improved without being inhibited by the salt produced 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 a cellulose raw material by bringing it into contact with a gas containing ozone. This oxidation reaction oxidizes the hydroxyl groups at at least the 2- and 6-positions of the glucopyranose ring and causes decomposition of the cellulose chain.
  • the ozone concentration in the ozone-containing gas is preferably 50 to 250 g/m 3 , more preferably 50 to 220 g/m 3 .
  • the amount of ozone added to the cellulose raw material is preferably 0.1 to 30 parts by mass, more preferably 5 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 to 50°C, more preferably 20 to 50°C.
  • the ozone treatment time is not particularly limited, but is about 1 to 360 minutes, preferably about 30 to 360 minutes. When the ozone treatment conditions are within these ranges, excessive oxidation and decomposition of cellulose can be prevented, resulting in a good yield of oxidized cellulose.
  • additional oxidation treatment may be performed using an oxidizing agent.
  • the oxidizing agent used in the additional oxidation treatment is not particularly limited, but examples thereof include chlorine-based compounds such as chlorine dioxide and sodium chlorite, oxygen, hydrogen peroxide, persulfuric acid, and peracetic acid.
  • the additional oxidation treatment can be performed by dissolving these oxidizing agents in water or a polar organic solvent such as alcohol to prepare an oxidizing agent solution, and immersing the cellulose raw material in the solution.
  • the amount of carboxy groups in the oxidized cellulose can be adjusted by controlling the reaction conditions such as the amount of the oxidizing agent added and the reaction time.
  • Carboxymethyl cellulose, hydroxymethyl cellulose, hydroxyethyl cellulose, or hydroxypropyl cellulose which are exemplified above as cellulose-based polymers obtained by anion modification, may be obtained by etherifying cellulose raw materials by a known method, or commercially available products. May be used.
  • Carboxymethyl cellulose or its salt For example, when obtaining carboxymethylcellulose or a salt thereof (hereinafter sometimes referred to as "CMC"), the method for producing carboxymethylcellulose or a salt thereof is not limited, and any known method for producing carboxymethylcellulose or a salt thereof may be applied. can. That is, after treating cellulose, which is a raw material, with a mercerizing agent (alkali) to prepare mercerized cellulose (alkali cellulose), an etherifying agent is added to cause an etherification reaction to produce carboxymethylcellulose or its salt in the present invention. can be manufactured.
  • a mercerizing agent alkali
  • any of the above-mentioned celluloses can be used without particular limitation, but those with high cellulose purity are preferred, and it is particularly preferred to use dissolving pulp and linters. By using these, highly pure carboxymethyl cellulose or a salt thereof can be obtained.
  • alkali metal hydroxide salts such as sodium hydroxide and potassium hydroxide can be used.
  • etherification agent monochloroacetic acid, monochloroacetic acid soda, etc. can be used.
  • the molar ratio of the mercerizing agent to the etherifying agent in the general production method of water-soluble carboxymethylcellulose is generally 2.00 to 2.45 when monochloroacetic acid is used as the etherifying agent. .
  • the reason for this is that if it is less than 2.00, the etherification reaction may not be carried out sufficiently, resulting in unreacted monochloroacetic acid remaining and being wasted; This is because there is a possibility that a side reaction between an excess of the mercerizing agent and monochloroacetic acid may proceed to produce an alkali metal salt of glycolic acid, which may be uneconomical.
  • carboxymethylcellulose or its salt may be used as it is, or after treatment if necessary.
  • Commercially available products include, for example, the trade name "Sunrose” (sodium salt of carboxymethyl cellulose) manufactured by Nippon Paper Industries, Ltd.
  • carboxymethylcellulose or salt thereof of the present invention has a degree of carboxymethyl substitution per anhydroglucose unit of 0.5 or more, more preferably 0.6 or more. If the degree of carboxymethyl substitution is less than 0.5, the solubility in water may be insufficient.
  • anhydroglucose units refer to individual anhydroglucoses (glucose residues) that constitute cellulose.
  • the degree of carboxymethyl substitution also referred to as the degree of etherification refers to the proportion of hydroxyl groups (-OH) in glucose residues constituting cellulose that are substituted with carboxymethyl ether groups (-OCH 2 COOH). show. Note that the degree of carboxymethyl substitution may be abbreviated as DS or CM-DS.
  • the upper limit of the degree of carboxymethyl substitution per anhydroglucose unit of carboxymethyl cellulose or its salt is preferably 1.2 or less, more preferably 1.0 or less.
  • the method for measuring the degree of substitution of carboxymethyl groups is as follows: Weigh approximately 2.0 g of the sample accurately and place it in a 300 mL Erlenmeyer flask with a stopper. Add 100 mL of a solution prepared by adding 100 mL of special grade concentrated nitric acid to 1000 mL of methanol, and shake for 3 hours to convert carboxymethyl cellulose salt (CMC) to H-CMC (hydrogen form carboxymethyl cellulose). Accurately weigh 1.5 to 2.0 g of the bone-dried H-CMC and place it in a 300 mL Erlenmeyer flask with a stopper.
  • CMC carboxymethyl cellulose salt
  • the CMC used in the present invention may be one type, or a combination of two or more types of CMC with different degrees of etherification, CM-DS, viscosity, molecular weight, etc. Viscosity will be described later.
  • the cellulose When using phosphoric acid esterified cellulose as a cellulose-based polymer obtained by anion modification, the cellulose can be prepared by mixing the powder or aqueous solution of phosphoric acid compound A with the cellulose raw material described above, or by adding phosphoric acid to a slurry of the cellulose raw material. It can be obtained by adding an aqueous solution of Compound A.
  • Examples of the phosphoric acid compound A include phosphoric acid, polyphosphoric acid, phosphorous acid, phosphonic acid, polyphosphonic acid, or esters thereof. These may be in the form of salts. Among these, compounds having a phosphoric acid group are preferred because they are low cost and easy to handle. Examples of compounds having a phosphoric acid group include phosphoric acid, sodium dihydrogen phosphate, disodium hydrogen phosphate, trisodium phosphate, sodium pyrophosphate, sodium metaphosphate, potassium dihydrogen phosphate, dipotassium hydrogen phosphate, and phosphoric acid.
  • Examples include tripotassium acid, potassium pyrophosphate, potassium metaphosphate, ammonium dihydrogen phosphate, diammonium hydrogen phosphate, triammonium phosphate, ammonium pyrophosphate, and ammonium metaphosphate. These can be used alone or in combination of two or more.
  • phosphoric acid, a sodium salt of phosphoric acid, a potassium salt of phosphoric acid, and an ammonium salt of phosphoric acid are more preferable from the viewpoint of high efficiency of introducing a phosphoric acid group and easy industrial application.
  • Particularly preferred are sodium dihydrogen phosphate and disodium hydrogen phosphate.
  • the phosphoric acid compound A in the form of an aqueous solution, since the uniformity of the reaction and the efficiency of introducing phosphoric acid groups are increased.
  • the pH of the aqueous solution of the phosphoric acid compound A is preferably 7 or less since this increases the efficiency of introducing phosphoric acid groups, but the pH is preferably 3 to 7 from the viewpoint of suppressing hydrolysis of pulp fibers.
  • a phosphoric acid compound A is added to a dispersion of a cellulose raw material having a solid content concentration of 0.1 to 10% by mass while stirring to introduce phosphoric acid groups into the cellulose.
  • the amount of phosphoric acid compound A added is preferably 0.2 to 500 parts by mass, more preferably 1 to 400 parts by mass as the amount of phosphorus element. If the proportion of phosphoric acid compound A is equal to or higher than the lower limit, the yield of fine fibrous cellulose can be further improved. However, if the above upper limit is exceeded, the effect of improving the yield reaches a ceiling, which is not preferable from a cost standpoint.
  • compound B is not particularly limited, but is preferably a nitrogen-containing compound that exhibits basicity.
  • “Basic” herein is defined as the aqueous solution exhibiting a pink to red color in the presence of the phenolphthalein indicator, or the pH of the aqueous solution being greater than 7.
  • the basic nitrogen-containing compound used in the present invention is not particularly limited as long as it exhibits the effects of the present invention, but compounds having an amino group are preferred.
  • Examples include, but are not limited to, urea, methylamine, ethylamine, trimethylamine, triethylamine, monoethanolamine, diethanolamine, triethanolamine, pyridine, ethylenediamine, and hexamethylenediamine.
  • urea is preferred because it is low cost and easy to handle.
  • the amount of compound B added is preferably 2 to 1000 parts by weight, more preferably 100 to 700 parts by weight, based on 100 parts by weight of the solid content of the cellulose raw material.
  • the reaction temperature is preferably 0 to 95°C, more preferably 30 to 90°C.
  • the reaction time is not particularly limited, but is approximately 1 to 600 minutes, more preferably 30 to 480 minutes.
  • cellulose can be prevented from being excessively esterified and easily dissolved, and the yield of phosphoric acid esterified cellulose can be improved.
  • After dehydrating the obtained phosphoric acid esterified cellulose suspension it is preferably heat-treated at 100 to 170° C. from the viewpoint of suppressing hydrolysis of cellulose. Further, during heat treatment, it is preferable to heat at 130° C. or lower, preferably 110° C. or lower while water is contained, and after removing water, heat treatment at 100 to 170° C.
  • the degree of phosphoric acid group substitution per glucose unit of the phosphoric acid esterified cellulose is preferably 0.001 to 0.40.
  • a cationically modified cellulose polymer As the chemically modified cellulose polymer, cellulose obtained by further cationizing the carboxylated cellulose can be used.
  • the cationically modified cellulose is produced by adding a cationizing agent such as glycidyltrimethylammonium chloride, 3-chloro-2-hydroxypropyltrialkylammonium halide or its halohydrin type to the carboxylated cellulose raw material, and an alkali metal hydroxide as a catalyst. (sodium hydroxide, potassium hydroxide, etc.) in the presence of water or an alcohol having 1 to 4 carbon atoms.
  • the degree of cation substitution per glucose unit is preferably 0.02 to 0.50.
  • the degree of cation substitution can be adjusted by adjusting the amount of the cationizing agent to be reacted and the composition ratio of water or alcohol having 1 to 4 carbon atoms.
  • the viscosity of a 1% by mass aqueous solution of the chemically modified cellulose polymer to be pulverized at 25°C as measured by a B-type viscometer (30 rpm) is preferably 1,000 to 20,000 mPa ⁇ s, or more. It is preferably 1,500 to 15,000 mPa ⁇ s, more preferably 1,500 to 10,000 mPa ⁇ s.
  • the viscosity measurement method is as follows: A chemically modified cellulose polymer to be crushed is measured into a 1000 mL glass beaker and dispersed in 900 mL of distilled water to prepare an aqueous dispersion with a solid content of 1% (w/v). The aqueous dispersion is stirred at 25° C. using a stirrer at 600 rpm for 3 hours. Thereafter, according to the method of JIS-Z-8803, using a B-type viscometer (manufactured by Toki Sangyo Co., Ltd.), No. Measure the viscosity after 3 minutes with 4 rotors/30 rpm.
  • the unmodified pulp is not particularly limited, but it is preferable to use powdered cellulose using unmodified pulp.
  • powdered cellulose using unmodified pulp include those obtained by mechanically crushing pulp or acid hydrolyzing it to powder.
  • the method for producing powdered cellulose is not particularly limited as long as it is a method for obtaining powdered cellulose from a cellulose raw material, but examples include a method that includes at least a pulverization process, and it is easy to obtain powdered cellulose with few impurities. A method in which an acid hydrolysis treatment is further performed is preferred.
  • the cellulose raw materials include those mentioned above, but it is preferable to use pulp, and pulp derived from wood is more preferable.
  • pulp derived from wood include pulp derived from broad-leaved trees and pulp derived from coniferous trees.
  • Examples of the method for preparing wood-derived pulp include a method including a treatment using a pulping method (cooking method).
  • the pulping method dissolves and removes the colored substance lignin, making it possible to obtain pulp with a high degree of whiteness.
  • the pulping method (cooking method) include sulfite cooking, kraft cooking, soda quinone cooking, and organosolve cooking, with kraft pulp being preferred from an environmental standpoint.
  • Bleaching treatment methods include, for example, chlorine treatment (C), chlorine dioxide bleaching (D), alkali extraction (E), hypochlorite bleaching (H), Hydrogen peroxide bleaching (P), alkaline hydrogen peroxide treatment stage (Ep), alkaline hydrogen peroxide/oxygen treatment stage (Eop), ozone treatment (Z), chelation treatment (Q), and two or more of these treatments.
  • chlorine treatment C
  • chlorine dioxide bleaching D
  • alkali extraction E
  • hypochlorite bleaching H
  • Hydrogen peroxide bleaching P
  • alkaline hydrogen peroxide treatment stage Ep
  • alkaline hydrogen peroxide/oxygen treatment stage Eop
  • Z ozone treatment
  • Q chelation treatment
  • Examples of combinations (sequences) of two or more processes include D-E/P-D, C/D-E-HD, Z-E-D-PZ/D-Ep-D, and Z/D- Ep-DP, D-Ep-D, D-Ep-DP, D-Ep-PD, Z-Eop-DD, Z/D-Eop-D, Z/D-Eop-D- ED (the "/" in the sequence means that the processes before and after the "/" are performed consecutively without washing).
  • Bleaching treatment is not limited to the above example, and may be any commonly used method. Pulp that has undergone bleaching treatment is usually in a fluid state (fluid pulp). The whiteness of the pulp is preferably 80% or more based on ISO 2470.
  • acids used in the acid hydrolysis treatment include mineral acids such as hydrochloric acid, sulfuric acid, and nitric acid.
  • the acid concentration is not particularly limited, but from the viewpoint of maintaining the degree of polymerization and whiteness, it is preferably lower than the acid concentration in the conventional acid hydrolysis treatment for producing powdered cellulose, and is preferably 0.4 to 2.0N. More preferably, 0.5 to 1.5N is more preferable.
  • the acid concentration is less than 0.4N, depolymerization of cellulose due to acid is suppressed and a decrease in the degree of polymerization of cellulose can be reduced, but it may be difficult to refine the cellulose.
  • reaction conditions for the acid hydrolysis treatment are not particularly limited, but the reaction temperature is usually 80 to 100°C, and the reaction time is usually 30 minutes to 3 hours.
  • the cellulose raw material Prior to the acid hydrolysis treatment, the cellulose raw material may be pretreated. Examples include slurrying the cellulose raw material (preparation of a dispersion) and adjusting the concentration of the cellulose raw material. The concentration of the cellulose raw material is usually 3 to 10% by weight (based on solid content) based on the dispersion.
  • a treatment to increase the pulp density is usually performed before hydrolysis.
  • a dehydrator such as a screw press or a belt filter may be used to adjust (concentrate) the cellulose raw material concentration.
  • the acid hydrolysis treatment may be performed on a slurry of cellulose raw material, or may be performed on a sheet-shaped cellulose raw material. When the cellulose raw material is a dry sheet of pulp, the acid hydrolysis treatment is usually performed after the pulp is loosened. When loosening the pulp, a crusher such as a roll crusher may be used.
  • the neutralization treatment may be performed by adding an alkaline agent.
  • the deliquid treatment is usually a solid-liquid separation treatment, and waste acid can be separated from the hydrolyzed product.
  • the hydrolyzate may undergo a drying (dehydration) treatment.
  • the solid content concentration can be adjusted and the physical properties of the powdered cellulose can be easily controlled.
  • the solid content concentration is usually adjusted to 15% or more, preferably 20% or more.
  • a flash dryer For drying, it is preferable to use a flash dryer. As a result, regardless of whether the processed material after hydrolysis is a cake-like solid, slurry, solution, etc., it is possible to apply high-speed hot air to the product while dispersing it in the air stream, and also to utilize the depressurizing effect inside the dryer. It can be dried instantly. In addition, since the exposure time to hot air is extremely short, the product temperature can be kept low, making it ideal for drying products that are sensitive to heat or products with low melting points.
  • the conditions for drying using a flash dryer are not particularly limited and can be set as appropriate, but an example is as follows.
  • the outlet drying temperature is usually 80 to 180°C, preferably 90 to 160°C.
  • the amount of air supplied is usually 150 to 350 m 3 /h, preferably 160 to 320 m 3 /h.
  • the product is sprayed and instantly dried with hot air to produce granules. Therefore, it is often not suitable for drying solid or semi-solid objects with low moisture content, and the particles are more likely to be exposed to high heat instantaneously than when drying with a flash dryer, which may affect the product. be done.
  • the unmodified pulp may be pulverized by mechanically pulverizing the processed material that has undergone the previous step.
  • a classification process may be performed simultaneously with the pulverization or after the pulverization.
  • the crusher used for the powdering treatment of unmodified pulp can be used without any particular restrictions, but examples include a jaw crusher (manufactured by Makino Co., Ltd.), a pulverizer (manufactured by Hosokawa Micron Co., Ltd.), a super micron mill (manufactured by Hosokawa Micron Co., Ltd.), Tornado mill (manufactured by Nikkiso Co., Ltd.), Jiyu crusher (manufactured by Nara Kikai Seisakusho Co., Ltd.), Turbo mill (manufactured by Freund Sangyo Co., Ltd.), Spar powder mill (manufactured by Nishimura Kikai Seisakusho Co., Ltd.), Blade mill (Nissin Engineering Co., Ltd.) It is preferable to use a supersonic jet mill (manufactured by Nippon Pneumatic Industries Co., Ltd.), or a current jet (manufactured by Nisshin Engineering Co.,
  • the conditions for the powdering treatment of the unmodified pulp or the classification treatment performed as necessary can be appropriately set so as to obtain the desired powdered cellose.
  • the processing conditions can be adjusted with reference to a calibration curve created from the pulverization conditions (eg, processing time, input amount) and desired physical properties of the powdered cellulose.
  • At least one other component for example, an organic component, an inorganic component
  • the pulverization treatment together with the acid-hydrolyzed product, if necessary.
  • functionality can be imparted to the powdered cellulose or the functionality can be improved.
  • the amounts of other components to be blended may be appropriately selected.
  • chemical treatment may be performed as necessary.
  • any treatment that does not pose a risk of significantly impairing the degree of polymerization of the cellulose raw material can be selected as appropriate.
  • the timing of the chemical treatment includes, for example, before the acid hydrolysis treatment and at the same time as the pulverization treatment, but is not particularly limited.
  • a bead mill usually has a grinding container called a vessel, a large number of beads as grinding media filled in the vessel, and an agitator that stirs the beads by high-speed rotation.
  • the material to be pulverized is placed in a vessel, and the agitator rotates at high speed to agitate the beads, causing the beads to collide with each other, the beads and the inner wall of the vessel, and the beads and the agitator, respectively.
  • the agitator rotates at high speed to agitate the beads, causing the beads to collide with each other, the beads and the inner wall of the vessel, and the beads and the agitator, respectively.
  • objects to be crushed existing in the gaps between the beads, the gaps between the beads and the inner wall of the vessel, and the gaps between the beads and the agitator are crushed by shearing force, impact force, frictional force, etc.
  • the type of agitator is not particularly limited, and a disk type, pin type, annular gap type, etc. can be adopted. Further, there is no particular restriction on the orientation of the vessel, and a vertical or horizontal type can be adopted.
  • the material of the beads and/or vessels can be used without any particular restriction as long as it has high hardness and is resistant to wear.
  • examples of the stabilized zirconia include yttria-stabilized zirconia, magnesia-stabilized zirconia, calcia-stabilized zirconia, ceria-stabilized zirconia, and examples of the partially-stabilized zirconia include yttria-stabilized zirconia and magnesia-stabilized zirconia. Examples include zirconia, calcia partially stabilized zirconia, and ceria partially stabilized zirconia.
  • a wet bead mill or a dry bead mill can be used without any particular restriction, but it is preferable to use a dry bead mill.
  • examples of the dry bead mill include Dynamic Mill (manufactured by Nippon Coke Industry Co., Ltd.), Dry Star (manufactured by Ashizawa Finetech Co., Ltd.), and the like.
  • the classification method is not particularly limited, but a method using a dry classifier is preferred.
  • a method using a dry classifier is preferred.
  • the dry classification it is preferable to perform airflow classification.
  • the coarse powder that has been subjected to the classification treatment is pulverized again using a bead mill.
  • FIG. 1 is a schematic diagram showing an example of a crushing device including a bead mill used in the present invention.
  • the pulverizing device 2 includes a bead mill 4 for pulverizing a cellulose polymer as a raw material (material to be pulverized), and a classifier 6 for classifying the cellulose polymer pulverized by the bead mill 4.
  • the bead mill 4 and the classifier 6 are connected by a connecting part 8.
  • the cellulose-based polymer (fine powder) having a particle size less than a predetermined value, which has been crushed by the bead mill 4 and classified by the classifier 6, is collected in a product collection section 10 that includes a bag filter or the like.
  • a blower 11 is provided downstream of the product recovery section 10.
  • the arrows in FIG. 1 indicate the direction of movement of the cellulosic polymer and/or air.
  • the bead mill 4 is equipped with a vessel 12 which is a crushing container, and inside the vessel 12 is equipped with an agitator 14 which is arranged horizontally and is configured to be rotatable by a drive device (not shown), and a large number of beads 16 as crushing media. Further, a raw material supply section 18 is provided in the vessel 12 for supplying a cellulose-based polymer as a raw material to be crushed. In addition, what is illustrated by a circle in the vessel 12 indicates a bead even if no code is attached thereto. Note that the crushing device 2 is configured so that the beads 16 do not flow into the classifier 6 through the connection portion 8 or the coarse powder recovery port 22, nor flow into the raw material supply portion 18.
  • the classifier 6 has a product recovery port 20 for sending the classified cellulose polymer (fine powder) to the product recovery section 10, and a product recovery port 20 for sending the cellulose polymer (coarse powder) having a particle size of a predetermined value or more to the vessel 12.
  • a coarse powder collection port 22 is provided.
  • the process of pulverizing cellulose polymer will be explained.
  • the bead mill 4 starts rotating the agitator 14 by a drive device (not shown). Further, the blower 11 is also activated. As the agitator 14 rotates, the beads 16 are agitated.
  • the cellulose-based polymer as a material to be crushed When the cellulose-based polymer as a material to be crushed is supplied from the raw material supply section 18 into the vessel 12, it is crushed by the beads 16 that are being stirred in the vessel 12. That is, by stirring the beads 16, collisions occur between the beads 16, collisions between the beads 16 and the inner wall of the vessel 12, and collisions between the beads 16 and the agitator 14. As a result of this collision, the cellulose-based polymer that is the object to be crushed, which exists in the gaps between the beads, the gaps between the beads and the inner wall of the vessel, and the gaps between the beads and the agitator, is crushed by shear force, impact force, frictional force, etc. Ru.
  • the cellulose-based polymer pulverized in the vessel 12 is sent to the classifier 6 via the connection part 8. Then, classification is performed by the classifier 6, and the cellulose polymer (fine powder) having a particle size smaller than a predetermined value is sent to the product recovery section 10 via the product recovery port 20. Further, the cellulose-based polymer (coarse powder) having a particle diameter of a predetermined value or more is supplied to the vessel 12 of the bead mill 4 through the coarse powder collection port 22 and subjected to a pulverization process by the bead mill 4 .
  • the average diameter (bead diameter) of the beads used in the bead mill is 0.1 to 10 mm, preferably 3 to 8 mm. If the particle size of the beads is too large, a problem arises in that the particle size of the obtained sample becomes large. Furthermore, if the particle size of the beads is too small, a problem arises in that the viscosity of the sample obtained becomes low.
  • the filling rate of beads filled in the vessel is 50 to 90 vol%, preferably 70 to 90 vol%. If the filling rate of beads is too large, a problem arises in that contamination is likely to occur. Moreover, if the filling rate of beads is too small, there will be a problem that productivity will be low.
  • the peripheral speed of the agitator is 2 to 15 m/sec, preferably 6 to 15 m/sec. If the circumferential speed of the agitator is too high, a problem arises in that the viscosity of the sample obtained becomes low. Further, if the circumferential speed of the agitator is too slow, a problem arises in that the particle size of the sample obtained becomes large.
  • the amount of cellulose polymer supplied from the raw material supply section 18 is preferably 30 to 150 kg/h, more preferably 40 to 120 kg/h. If the supply amount is too large, a problem arises in that the particle size of the obtained sample becomes large. Furthermore, if the supply amount is too small, a problem arises in that the viscosity of the sample obtained becomes low.
  • the particle diameter indicates the maximum particle diameter (D max ) determined by a grain gauge (grind gauge). Specifically, it is the maximum particle diameter (D max ) determined from the dispersity of the linear method measured with a grind gauge in accordance with JIS K5600 and JIS K5400 (1990).
  • a chemically modified cellulose polymer when used as the cellulose polymer, a 1% by mass aqueous solution of the cellulose polymer after pulverization with a bead mill at 25°C measured with a B-type viscometer (30 rpm)
  • the viscosity is preferably 500 to 15,000 mPa ⁇ s, more preferably 800 to 13,000 mPa ⁇ s, and still more preferably 1,000 to 10,000 mPa ⁇ s. Note that the viscosity of the cellulose polymer after being pulverized by a bead mill can be measured in the same manner as the method for measuring the viscosity of the cellulose polymer to be pulverized described above.
  • the ratio of mass M to mass m is preferably less than 50 ppm. If it is 50 ppm or more, when a film is formed using a cellulose polymer, appearance defects such as streaks and pinholes may occur in the film, and the quality of products using the film may deteriorate.
  • the lower limit of the ratio of the mass M to the mass m is not particularly limited, and the smaller the ratio, the better.
  • the cellulose-based polymer to be pulverized may be pre-pulverized.
  • an impact mill can be used, although it is not particularly limited.
  • Impact mills include Pulperizer (manufactured by Hosokawa Micron Co., Ltd.), Fine Impact Mill (manufactured by Hosokawa Micron Co., Ltd.), Super Micron Mill (manufactured by Hosokawa Micron Co., Ltd.), Sample Mill (manufactured by Seishin Co., Ltd.), and Bantam Mill (manufactured by Seishin Co., Ltd.).
  • Examples include Seishin Co., Ltd.), an atomizer (Seishin Co., Ltd.), a tornado mill (Nikkiso Co., Ltd.), a turbo mill (Turbo Kogyo Co., Ltd.), and a bevel impactor (Aikawa Tekko Co., Ltd.).
  • the use of the pulverized cellulose-based polymer obtained by the cellulose-based polymer pulverization method of the present invention is not particularly limited, and can be applied to various uses.
  • thickeners thickeners, gelling agents, sizing agents, food additives, excipients, paint additives, adhesive additives, paper manufacturing additives, abrasives, compounded materials for rubber and plastics, water retention agents, It can be used as a filler, mud water conditioner, filter aid, mud flooding prevention agent, etc.
  • the pulverized cellulose polymer obtained by the cellulose polymer pulverization method of the present invention can be used as a binder for the positive electrode and/or negative electrode of a nonaqueous electrolyte secondary battery such as a lithium ion secondary battery.
  • the above-mentioned positive electrode and/or negative electrode can be formed by laminating an electrode composition on a current collector by blade coating, bar coating, die coating, etc., and then heating, drying, pressurizing, etc.
  • the electrode composition contains an electrode active material, a binder, and other components such as a conductive material as necessary, and as a binder, a pulverized cellulose polymer obtained by the cellulose polymer pulverization method of the present invention is used. Can be used.
  • the manufacturing conditions for the electrode composition are not particularly limited, but for example, other components constituting the electrode composition are added to the above-mentioned aqueous solution or dispersion of the pulverized cellulose-based polymer, and if necessary, while stirring. Obtained by mixing.
  • the properties of the electrode composition are not particularly limited, and may be any of liquid, paste, and slurry forms.
  • the electrode active material in the electrode composition includes a positive electrode active material or a negative electrode active material.
  • the positive electrode active material is preferably a LiMe x O y (Me means a transition metal containing at least one of Ni, Co, and Mn. x and y represent arbitrary numbers) type positive electrode active material, LiCoO 2 or the like can be preferably used.
  • Examples of negative electrode active materials include graphite materials such as graphite (natural graphite, artificial graphite), coke, and carbon fiber; elements that can form an alloy with lithium (for example, Al, Si, Sn, Ag, Bi , Mg, Zn, In, Ge, Pb, Ti, etc.); a composite of an element capable of forming an alloy with lithium and the compound, and carbon and/or the graphitic material; Nitrides containing nitrides, etc. can be used.
  • graphite materials and/or silicon-based compounds are preferable, it is more preferable that graphite and/or silicon-based compounds are included, and it is preferable that at least a silicon-based compound is included.
  • a pulverized cellulose polymer obtained by the cellulose polymer pulverization method of the present invention and a rubber binder such as styrene butadiene rubber (SBR) may be used in combination, if necessary.
  • the conductive material one that can ensure electrical conductivity of the positive electrode and/or negative electrode can be used.
  • the conductive material include one or a mixture of two or more carbon substances such as carbon black, acetylene black, and graphite.
  • any electrical conductor that does not cause a fatal chemical change in the constructed battery can be used.
  • the current collector for the negative electrode active material stainless steel, nickel, copper, titanium, carbon, copper, or stainless steel whose surface is coated with carbon, nickel, titanium, or silver can be used. Among these, copper or copper alloy is preferred, and copper is more preferred.
  • the material for the current collector for the positive electrode include metals such as aluminum and stainless steel, with aluminum being preferred.
  • As the shape of the current collector a net, punched metal, foam metal, foil processed into a plate shape, etc. can be used, and foil processed into a plate shape is preferable.
  • a non-aqueous electrolyte secondary battery such as a lithium ion secondary battery has a structure in which positive electrodes and negative electrodes are alternately stacked with separators interposed therebetween and wound many times.
  • An electrode containing as a binder a pulverized cellulose-based polymer obtained by the cellulose-based polymer pulverization method described above can be used.
  • the separator is usually impregnated with a nonaqueous electrolyte.
  • each index for carboxymethylcellulose or its salt as a cellulose-based polymer was measured by the following method.
  • CM-DS degree of carboxymethyl substitution
  • CM-DS was calculated by the following formula 1.
  • ⁇ Viscosity> A cellulose-based polymer was measured into a 1000 mL glass beaker and dispersed in 900 mL of distilled water to prepare an aqueous dispersion with a solid content of 1% (w/v). The aqueous dispersion was stirred at 25° C. using a stirrer at 600 rpm for 3 hours. Thereafter, according to the method of JIS-Z-8803, using a B-type viscometer (manufactured by Toki Sangyo Co., Ltd.), No. The viscosity was measured after 3 minutes using 4 rotors/30 rpm.
  • ⁇ Particle size (grain gauge)> The particle size was measured using a grain gauge (grind gauge). Specifically, the maximum particle diameter (D max ) was determined by the dispersity of the linear method measured using a grind gauge in accordance with JIS K5600 and JIS K5400 (1990).
  • Example 1 1161 g of isopropyl alcohol and 121 g of sodium hydroxide dissolved in 231 g of water were added to a twin-screw kneader whose rotational speed was adjusted to 100 rpm, and the dry mass of linter pulp (160 g when dried at 100° C. for 60 minutes) was charged. After stirring and mixing at 30°C for 90 minutes to prepare mercerized cellulose, a solution of 124 g of monochloroacetic acid in 142 g of isopropyl alcohol was added, and the mixture was heated to 70°C to carry out a carboxymethylation reaction for 90 minutes.
  • CMC1 carboxymethyl cellulose
  • the obtained CMC1 was pulverized using a pulverizer including a bead mill shown in FIG.
  • a pulverizer including a bead mill shown in FIG.
  • zirconia beads with a bead diameter of 5 mm were used at a filling rate of 80 vol%, and the peripheral speed of the agitator 14 was set to 10 m/sec.
  • the amount of CMC1 supplied into the vessel 12 of the bead mill 4 was 120 kg/h.
  • the viscosity of the 1 mass % aqueous solution of CMC1 after pulverization was 3,300 mPa ⁇ s, and the maximum particle diameter (D max ) determined by a particle gauge was 43 ⁇ m.
  • Example 2 Same as Example 1 except that the bead diameter was changed to 8 mm, the peripheral speed of the agitator 14 was changed to 8 m/sec, and the amount of CMC 1 supplied into the vessel 12 of the bead mill 4 was changed to 40 kg/h. CMC1 was pulverized.
  • the viscosity of a 1% by mass aqueous solution of CMC1 after pulverization at 25° C. measured with a B-type viscometer was 3,300 mPa ⁇ s, and the maximum particle diameter (D max ) determined by a particle gauge was 45 ⁇ m.
  • Example 3 1201 g of isopropyl alcohol and 101 g of sodium hydroxide dissolved in 255 g of water were added to a twin-screw kneader whose rotation speed was adjusted to 100 rpm, and the dry mass of linter pulp (160 g when dried at 100° C. for 60 minutes) was charged. After stirring and mixing at 30°C for 90 minutes to prepare mercerized cellulose, a solution of 104 g of monochloroacetic acid in 118 g of isopropyl alcohol was added, and the mixture was heated to 70°C to carry out a carboxymethylation reaction for 90 minutes.
  • CMC2 carboxymethyl cellulose
  • the obtained CMC2 was pulverized using a pulverizer including a bead mill shown in FIG.
  • a pulverizer including a bead mill shown in FIG.
  • zirconia beads with a bead diameter of 3 mm were used at a filling rate of 85 vol%, and the peripheral speed of the agitator 14 was set to 10 m/sec.
  • the amount of CMC1 supplied into the vessel 12 of the bead mill 4 was 60 kg/h.
  • the viscosity of the 1 mass % aqueous solution of CMC2 after pulverization was 8,420 mPa ⁇ s, and the maximum particle diameter (D max ) determined by a particle gauge was 37 ⁇ m.
  • Example 4 1201 g of isopropyl alcohol and 101 g of sodium hydroxide dissolved in 255 g of water were added to a twin-screw kneader whose rotation speed was adjusted to 100 rpm, and the dry mass of linter pulp (160 g when dried at 100° C. for 60 minutes) was charged. After stirring and mixing at 40° C. for 120 minutes to prepare mercerized cellulose, a solution of 104 g of monochloroacetic acid dissolved in 118 g of isopropyl alcohol was added, and the mixture was heated to 70° C. to carry out a carboxymethylation reaction for 90 minutes.
  • CMC3 carboxymethyl cellulose having a maximum particle diameter (D max ) determined by a gauge of more than 100 ⁇ m was obtained.
  • the obtained CMC3 was pulverized using a pulverizer including a bead mill shown in FIG.
  • a pulverizer including a bead mill shown in FIG.
  • zirconia beads with a bead diameter of 5 mm were used at a filling rate of 75 vol%, and the peripheral speed of the agitator 14 was set to 12 m/sec.
  • the amount of CMC1 supplied into the vessel 12 of the bead mill 4 was 85 kg/h.
  • the viscosity of a 1% by mass aqueous solution of CMC3 after pulverization at 25° C. measured with a B-type viscometer was 8,800 mPa ⁇ s, and the maximum particle diameter (D max ) determined by a particle gauge was 45 ⁇ m.
  • Example 1 CMC1 was pulverized in the same manner as in Example 1, except that the bead diameter was changed to 12 mm, the filling rate was changed to 60 vol%, and the peripheral speed of the agitator 14 was changed to 5 m/sec.
  • a method for pulverizing cellulose-based polymers using a bead mill wherein the beads used in the bead mill have an average diameter of 0.1 to 10 mm, the peripheral speed of the agitator of the bead mill is 2 to 15 m/sec, and the bead mill
  • the beads used in the bead mill have an average diameter of 0.1 to 10 mm
  • the peripheral speed of the agitator of the bead mill is 2 to 15 m/sec
  • the bead mill When a cellulose-based polymer was pulverized using a cellulose-based polymer pulverization method with a bead filling rate of 50 to 90 vol%, it was possible to stably produce a cellulose-based polymer with a particle size of less than 50 ⁇ m.

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Abstract

Le problème à la base de la présente invention concerne un procédé de broyage d'un polymère de cellulose, le procédé étant apte à produire de manière stable un polymère de cellulose qui présente un diamètre de particule inférieur à 50 µm. La solution porte sur un procédé de broyage d'un polymère de cellulose au moyen d'un broyeur à billes 4, dans lequel : le diamètre moyen des billes 16 qui sont utilisées pour le broyeur à billes est de 0,1 mm à 10 mm ; la vitesse périphérique d'un agitateur 14 du broyeur à billes est de 2 m/sec à 15 m/s ; et le taux de remplissage de billes du broyeur à billes est de 50 % en volume à 90 % en volume.
PCT/JP2023/029955 2022-09-15 2023-08-21 Procédé de broyage de polymère de cellulose WO2024057830A1 (fr)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2014000574A (ja) * 2009-11-13 2014-01-09 Moriroku Chemicals Co Ltd 微粉末の製造方法および同方法で製造された微粉末
WO2017047755A1 (fr) * 2015-09-16 2017-03-23 宇部興産株式会社 Poudre d'oxyde composite de lithium-titane contenant du carbone fibreux, feuille d'électrode utilisant celle-ci et dispositif de stockage d'énergie utilisant celle-ci
WO2019167961A1 (fr) * 2018-02-28 2019-09-06 株式会社Ｍｉｚｋａｎ Ｈｏｌｄｉｎｇｓ Composition contenant de l'huile et des corps gras solides, son procédé de production, procédé d'ajustement des propriétés physiques de celle-ci, et agent de durcissement de l'huile et des corps gras
WO2020179701A1 (fr) * 2019-03-01 2020-09-10 塩野義製薬株式会社 Composition de nanoparticule appauvrie en contaminants et son procédé de production

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2014000574A (ja) * 2009-11-13 2014-01-09 Moriroku Chemicals Co Ltd 微粉末の製造方法および同方法で製造された微粉末
WO2017047755A1 (fr) * 2015-09-16 2017-03-23 宇部興産株式会社 Poudre d'oxyde composite de lithium-titane contenant du carbone fibreux, feuille d'électrode utilisant celle-ci et dispositif de stockage d'énergie utilisant celle-ci
WO2019167961A1 (fr) * 2018-02-28 2019-09-06 株式会社Ｍｉｚｋａｎ Ｈｏｌｄｉｎｇｓ Composition contenant de l'huile et des corps gras solides, son procédé de production, procédé d'ajustement des propriétés physiques de celle-ci, et agent de durcissement de l'huile et des corps gras
WO2020179701A1 (fr) * 2019-03-01 2020-09-10 塩野義製薬株式会社 Composition de nanoparticule appauvrie en contaminants et son procédé de production

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