Classifications

• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K8/00—Cosmetics or similar toiletry preparations
  • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
  • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
  • A61K8/73—Polysaccharides
  • A61K8/731—Cellulose; Quaternized cellulose derivatives
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
  • C08B1/00—Preparatory treatment of cellulose for making derivatives thereof, e.g. pre-treatment, pre-soaking, activation
  • C08B1/06—Rendering cellulose suitable for etherification
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K8/00—Cosmetics or similar toiletry preparations
  • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
  • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
  • A61K8/73—Polysaccharides
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
  • A61Q19/00—Preparations for care of the skin
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
  • C08B1/00—Preparatory treatment of cellulose for making derivatives thereof, e.g. pre-treatment, pre-soaking, activation
• • 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
  • C08B15/08—Fractionation of cellulose, e.g. separation of cellulose crystallites

Definitions

• the present invention relates to a method for producing amorphous cellulose.
• Patent Document 1 discloses a wood pretreatment method that breaks cellulose microfibrils in wood by pulverizing with a vibration ball mill after adjusting the moisture content of the wood to 3 to 6%.
• the wood material is first roughly pulverized, and then the wood material obtained by the vibration ball mill is further finely pulverized while adjusting the moisture content of the obtained wood material to 2 to 7%.
• a multi-stage pulverization method is disclosed.
• Examples 1 and 4 of Patent Document 3 include a method of treating sheet pulp with a vibrating ball mill or a twin screw extruder
• Examples 1 to 3 of Patent Document 4 include a method of treating pulp with a ball mill
• Patent Documents Examples 1 and 2 of No. 5 disclose a method of treating cellulose powder obtained by chemical treatment such as hydrolysis of pulp with a ball mill or an airflow type pulverizer. However, these methods are not satisfactory in efficiency and productivity in reducing the crystallinity of cellulose.
• Patent Documents 6 and 7 a cellulose-containing raw material having a bulk density of 100 to 500 kg / m 3 is treated with a pulverizer filled with balls or rods, and a cellulose I type crystallinity of 33% or less is obtained.
• a method for producing crystallized cellulose is disclosed. However, development of a method for more efficiently reducing the crystallinity of cellulose is desired.
• the cellulose content in the remaining components excluding water from the cellulose-containing raw material is 20% by mass or more, and the cellulose I type crystallinity of the cellulose represented by the following formula (1) exceeds 33%.
• the present invention relates to a method for producing amorphous cellulose, in which a cellulose-containing raw material having a water content of 1.8% by mass or less is treated with a pulverizer to reduce the cellulose I-type crystallinity to 33% or less.
• Cellulose type I crystallinity (%) [(I 22.6 -I 18.5 ) / I 22.6 ] ⁇ 100 (1)
• the present invention relates to a production method excellent in productivity, capable of efficiently obtaining non-crystalline cellulose having a reduced cellulose I-type crystallinity from a cellulose-containing raw material.
• the present inventors have found that the above problem can be solved by treating a cellulose-containing raw material having a moisture content of 1.8% by mass or less with a pulverizer. That is, in the present invention, the cellulose content in the remaining components excluding water from the cellulose-containing raw material is 20% by mass or more, and the cellulose I-type crystallinity of the cellulose represented by the following formula (1) is 33%.
• a cellulose-containing raw material having a water content of 1.8% by mass or less is processed by a pulverizer to reduce the cellulose I-type crystallinity to 33% or less.
• Cellulose type I crystallinity (%) [(I 22.6 -I 18.5 ) / I 22.6 ] ⁇ 100 (1)
• the cellulose type I crystallinity of cellulose is sometimes simply referred to as “crystallinity”.
• the cellulose-containing raw material used in the present invention has a cellulose content in the remaining components excluding water from the raw material of 20% by mass or more, preferably 40% by mass or more, more preferably 60% by mass or more.
• the cellulose content in the present invention means the total amount of cellulose and hemicellulose.
• the cellulose-containing raw material is not particularly limited, and various wood chips, various tree pruned branches, thinned wood, branch timber, building waste, factory waste, etc .; wood pulp produced from wood, cotton seeds Pulp such as cotton linter pulp obtained from surrounding fibers; Paper such as newspaper, cardboard, magazine, and fine paper; Plant stems and leaves such as rice straw and corn stalk; Plants such as rice husk, palm husk and coconut husk Shells and the like. Of these, pulps and woods are preferable.
• the cellulose content in the remaining components excluding water is usually 75 to 99% by mass, and other components include lignin and the like.
• the cellulose I type crystallinity of commercially available pulp is usually 60% or more.
• the non-crystalline cellulose produced by the present invention has a cellulose I type crystallinity reduced to 33% or less.
• the degree of crystallinity is calculated by the Segal method from the diffraction intensity value by the X-ray diffraction method, and is defined by the following calculation formula (1).
• Cellulose type I crystallinity (%) [(I 22.6 -I 18.5 ) / I 22.6 ] ⁇ 100 (1)
• the degree of crystallinity is 33% or less, the chemical reactivity of cellulose is improved.
• the degree of crystallinity is preferably 20% or less, more preferably 15% or less, still more preferably 10% or less, and particularly preferably 0% in which no type I crystal is detected by analysis.
• the cellulose I-type crystallinity is the ratio of the amount of crystal region of cellulose to the total amount.
• Cellulose type I is a crystalline form of natural cellulose.
• the degree of crystallinity is also related to the physical and chemical properties of cellulose, and the larger the value, the higher the crystallinity of cellulose and the less non-crystalline parts, so the hardness, density, etc. increase, but elongation, flexibility, Solubility and chemical reactivity in water and solvent decrease.
• amorphous cellulose the cellulose-containing raw material having a water content of 1.8% by mass or less is treated with a pulverizer, and the cellulose I type crystallinity in the cellulose is reduced to 33% or less to obtain amorphous cellulose.
• this treatment is referred to as “amorphization treatment”.
• the water content in the cellulose-containing raw material used for the amorphization treatment in the present invention is 1.8% by mass or less, preferably 1.7% by mass or less, preferably 1.5% by mass or less, and 1.2% by mass or less. Is more preferable, and 1.0% by mass or less is particularly preferable.
• the water content is 1.8% by mass or less, it can be easily pulverized, the non-crystallization speed by the pulverization treatment can be improved, and the crystallinity can be efficiently reduced in a short time.
• the lower limit of the water content is preferably 0.2% by mass or more, more preferably 0.3% by mass or more, and still more preferably 0.4% by mass or more from the viewpoint of productivity and drying efficiency.
• the water content in the cellulose-containing raw material used for the amorphization treatment is preferably 0.2 to 1.8% by mass, more preferably 0.3 to 1.7% by mass, and 0.4 to 1 0.5% by mass is more preferable, and 0.4 to 1.0% by mass is particularly preferable.
• the cellulose-containing raw material used for the amorphization treatment in the present invention preferably has a bulk density of 50 to 600 kg / m 3 and a specific surface area of preferably 0.2 to 750 m 2 / kg.
• the bulk density of the cellulose-containing raw material used for the amorphization treatment in the present invention is preferably 50 kg / m 3 or more, more preferably 65 kg / m 3 or more, and still more preferably, from the viewpoint of more efficiently performing pulverization and amorphization. Is 100 kg / m 3 or more.
• the bulk density is 50 kg / m 3 or more, the cellulose-containing raw material has an appropriate volume, and thus handleability is improved.
• the upper limit of the bulk density is preferably 600 kg / m 3 or less, more preferably 500 kg / m 3 or less, and still more preferably 400 kg / m 3 or less, from the viewpoints of handleability and productivity. From these viewpoints, the bulk density is preferably 50 to 600 kg / m 3 , more preferably 65 to 500 kg / m 3 , and still more preferably 100 to 400 kg / m 3 . In addition, said bulk density can be measured by the method as described in an Example.
• the cellulose-containing raw material supplied to the pulverizer is preferably one having a specific surface area of 0.2 to 750 m 2 / kg from the viewpoint of efficiently dispersing the pulverized raw material in the pulverizer. If this specific surface area is 0.2 m 2 / kg or more, when supplying into the pulverizer, the pulverized raw material can be efficiently dispersed in the pulverizer, and a predetermined crystallization can be achieved without taking a long time. Degrees and particle sizes can be reached. On the other hand, the upper limit of the specific surface area is preferably 750 m 2 / kg or less from the viewpoint of productivity.
• the specific surface area is more preferably 0.65 to 200 m 2 / kg, still more preferably 0.8 to 50 m 2 / kg.
• said specific surface area can be measured by the method as described in an Example.
• the specific surface area is in the range of 0.2 to 4 m 2 / kg from the viewpoint of efficiently dispersing the pulverized raw material in the pulverizer. Is preferable, 0.65 to 3.5 m 2 / kg is more preferable, and 0.8 to 3 m 2 / kg is still more preferable.
• the specific surface area is in the range of 3 to 750 m 2 / kg from the viewpoint of productivity and efficient dispersion of the pulverized raw material in the pulverizer. Is preferable, 4.5 to 200 m 2 / kg is more preferable, and 7.5 to 50 m 2 / kg is still more preferable.
• Pre-treatment of amorphous treatment When a cellulose-containing raw material having a bulk density of less than 50 kg / m 3 is used, pretreatment is performed so that the bulk density ranges from 50 to 600 kg / m 3 or the specific surface area ranges from 0.2 to 750 m 2 / kg. preferable.
• the bulk density and the specific surface area of the cellulose-containing raw material can be set to the above-described preferable ranges by performing a cutting treatment and / or a crushing treatment. From the viewpoint of producing amorphous cellulose with a small number of steps, it is preferable to perform a cutting treatment as a pretreatment of the cellulose-containing raw material.
• the method for cutting the cellulose-containing raw material can be selected as appropriate depending on the type and shape of the cellulose-containing raw material. For example, a method using one or more cutting machines selected from a shredder, a slitter cutter, and a rotary cutter. Is mentioned. When using a sheet-like cellulose-containing raw material, it is preferable to use a shredder or a slitter cutter as a cutter, and it is more preferable to use a slitter cutter from the viewpoint of productivity.
• the slitter cutter is vertically cut along the longitudinal direction of the sheet with a roll cutter to make a long and narrow strip, and then cut shortly along the width direction of the sheet with a fixed blade and a rotary blade, A cellulose-containing raw material having a shape can be easily obtained.
• a sheet pelletizer manufactured by Horai Co., Ltd. can be preferably used. When this apparatus is used, a sheet-like cellulose-containing raw material can be cut into about 1 to 20 mm square.
• a rotary cutter when cutting wood such as thinned wood, pruned branches, construction waste, etc., or cellulose-containing raw materials other than sheets.
• the rotary cutter is composed of a rotary blade and a screen, and can easily obtain a cellulose-containing raw material that is cut by the rotary blade below the opening of the screen.
• a fixed blade may be provided and cutting may be performed with a rotary blade and a fixed blade.
• the screen opening is preferably 1 to 70 mm, more preferably 2 to 50 mm, and even more preferably 3 to 40 mm.
• the opening of the screen is 1 mm or more, a coarsely pulverized product having an appropriate bulkiness is obtained, and the handleability is improved. If the opening of the screen is 70 mm or less, the subsequent pulverization process has an appropriate size as a pulverization raw material, and thus the load can be reduced.
• the size of the cellulose-containing raw material obtained after the cutting treatment is preferably 1 to 70 mm square, more preferably 2 to 50 mm square.
• the cellulose-containing raw material preferably the cellulose-containing raw material obtained by the above-described cutting treatment
• an extruder treatment is preferable.
• a compressive shear force can be applied, the crystal structure of cellulose can be destroyed, the cellulose-containing raw material can be pulverized, and the bulk density can be further increased.
• conventionally used impact type pulverizers such as a cutter mill, a hammer mill, a pin mill, etc., make the pulverized material fluffy and bulky. And the mass-based throughput is reduced.
• an extruder a pulverized raw material having a desired bulk density can be obtained, and handleability can be improved.
• the extruder may be either a single-screw type or a twin-screw type, but a twin-screw extruder is preferable from the viewpoint of increasing the conveyance capability.
• the twin screw extruder is an extruder in which two screws are rotatably inserted into a cylinder, and conventionally known ones can be used.
• the rotation directions of the two screws may be the same or opposite directions, but the rotation in the same direction is preferable from the viewpoint of increasing the conveyance capability.
• the screw engagement conditions may be any of full-engagement, partial meshing, and non-meshing extruders. However, from the viewpoint of improving the processing capability, the complete meshing type and the partial meshing type are preferable.
• a kneading disk part in any part of a screw from a viewpoint of applying a strong compressive shear force.
• the kneading disc part is composed of a plurality of kneading discs, which are continuously combined at a constant phase, for example, 90 °, and are kneaded as the screw rotates.
• a constant phase for example, 90 °
• an extremely strong shearing force can be applied.
• the kneading disk portion and the plurality of screw segments are alternately arranged. In the case of a twin screw extruder, it is preferable that the two screws have the same configuration.
• a method of continuously processing the cellulose-containing raw material preferably the cellulose-containing raw material obtained by the cutting treatment is put into an extruder.
• the shear rate is preferably 10 sec -1 or more, more preferably 20 ⁇ 30000 sec -1, more preferably 50 ⁇ 3000 sec -1, particularly preferably 500 ⁇ 3000 sec -1. If the shear rate is 10 sec ⁇ 1 or more, pulverization proceeds effectively.
• Other treatment conditions are not particularly limited, but the treatment temperature is preferably 5 to 200 ° C.
• the extruder As the number of passes by the extruder, a sufficient effect can be obtained even with one pass, but from the viewpoint of reducing the crystallinity and the degree of polymerization of cellulose, if one pass is insufficient, perform two or more passes. Is preferred. From the viewpoint of productivity, 1 to 10 passes are preferable. By repeating the pass, coarse particles are pulverized and a powdery cellulose-containing raw material with little variation in particle size can be obtained. When performing two or more passes, in consideration of production capacity, a plurality of extruders may be arranged in series for processing.
• the average particle size of the cellulose-containing raw material obtained after the coarse pulverization treatment is preferably in the range of 0.01 to 1 mm from the viewpoint of efficiently dispersing the pulverized raw material in the pulverizer in the amorphization treatment. If this average particle size is 1 mm or less, the pulverized raw material can be efficiently dispersed in the pulverizer during the amorphization treatment, and the predetermined particle size can be reached without taking a long time. it can.
• the lower limit of the average particle diameter is preferably 0.01 mm or more from the viewpoint of productivity. From these viewpoints, the average particle diameter is more preferably 0.01 to 0.7 mm, and further preferably 0.05 to 0.5 mm. In addition, said average particle diameter can be measured by the method as described in an Example.
• the cellulose-containing raw material preferably the cellulose-containing raw material obtained by the above-described cutting treatment and / or crushing treatment, is preferably dried before the amorphous treatment.
• commercially available pulps, papers used as biomass resources, woods, plant stems / leaves, plant shells and other generally available cellulose-containing raw materials contain more than 5% by weight of moisture. Usually, it contains about 5 to 30% by mass of water. Therefore, in this invention, it is preferable to adjust the moisture content of a cellulose containing raw material to 1.8 mass% or less by performing a drying process.
• a known drying means may be appropriately selected.
• hot air heat receiving drying method hot air heat receiving drying method, conductive heat receiving drying method, dehumidified air drying method, cold air drying method, microwave drying method, infrared drying method, sun drying method , Vacuum drying method, freeze drying method and the like.
• a known dryer can be appropriately selected and used.
• “Introduction to Powder Engineering” Edited by Japan Powder Industry Technology Association, Powder Technology Information Center 1995) page 176 And the like.
• These drying methods and dryers may be used alone or in combination of two or more.
• the drying process can be either a batch process or a continuous process, but a continuous process is desirable from the viewpoint of productivity.
• a conductive heat receiving horizontal stirring dryer is preferable from the viewpoint of heat transfer efficiency.
• a biaxial horizontal stirrer is preferable from the viewpoint of the stability of continuous discharge because fine powder is hardly generated.
• a biaxial horizontal stirrer / dryer a biaxial paddle dryer manufactured by Nara Machinery Co., Ltd. can be preferably used.
• the temperature in the drying treatment cannot be generally determined depending on the drying means, drying time, etc., but is preferably 10 to 250 ° C., more preferably 25 to 180 ° C., and further preferably 50 to 150 ° C.
• the treatment time is preferably 0.01 to 2 hr, more preferably 0.02 to 1 hr.
• the drying treatment may be performed under reduced pressure.
• the pressure is preferably 1 to 120 kPa, more preferably 50 to 105 kPa.
• a medium pulverizer As a pulverizer used for the amorphization treatment, a medium pulverizer can be preferably used.
• the medium type pulverizer includes a container driven pulverizer and a medium stirring pulverizer.
• the container-driven crusher include a rolling mill, a vibration mill, a planetary mill, and a centrifugal fluid mill. Among these, a vibration mill is preferable from the viewpoint of high grinding efficiency and productivity.
• a tower-type pulverizer such as a tower mill
• an agitator-type pulverizer such as an attritor, an aquamizer, and a sand grinder
• a distribution tank-type pulverizer such as a visco mill and a pearl mill
• a stirring tank type pulverizer is preferable from the viewpoint of high pulverization efficiency and productivity.
• the peripheral speed at the tip of the stirring blade is preferably 0.5 to 20 m / s, more preferably 1 to 15 m / s.
• the type of pulverizer can be referred to “Chemical Engineering Advances 30th Particulate Control” (Chemical Engineering Society, Tokai Branch, issued October 10, 1996, Sakai Shoten).
• the processing method may be either batch processing or continuous processing, but continuous processing is preferable from the viewpoint of productivity.
• Examples of the pulverizer medium include balls, rods, and tubes. Of these, balls and rods are preferable and rods are more preferable from the viewpoint of high grinding efficiency and productivity.
• a material of the medium of a grinder For example, iron, stainless steel, an alumina, a zirconia, silicon carbide, a silicon nitride, glass etc. are mentioned.
• the outer diameter of the ball is preferably 0.1 to 100 mm, more preferably 0.5 to 50 mm. If the size of the balls is in the above range, the desired pulverization force can be obtained, and the cellulose can be efficiently amorphized without contaminating the cellulose-containing raw material by mixing pieces of balls and the like. .
• the cellulose in the raw material can be efficiently amorphousized by pulverizing with a vibration mill filled with a rod.
• a vibration mill Vibro Mill manufactured by Eurus Techno Co., Ltd., vibration mill manufactured by Chuo Kako Co., Ltd., small vibration rod mill 1045 type manufactured by Yoshida Seisakusho Co., Ltd., vibration cup mill P-9 type manufactured by Fritsch, Germany, Nissho A small vibration mill NB-O type manufactured by Kagaku Corporation can be used.
• the rod used as the medium of the pulverizer is a rod-shaped medium, and a rod having a cross section of a polygon such as a quadrangle or a hexagon, a circle, or an ellipse can be used.
• the outer diameter of the rod is preferably in the range of 0.5 to 200 mm, more preferably 1 to 100 mm, and still more preferably 5 to 50 mm.
• the length of the rod is not particularly limited as long as it is shorter than the length of the pulverizer container. If the size of the rod is in the above range, the desired crushing force can be obtained, and the cellulose can be efficiently amorphized without contamination of the cellulose-containing raw material by mixing fragments of the rod and the like. .
• the filling ratio of the medium such as balls and rods varies depending on the type of pulverizer, but is preferably 10 to 97%, more preferably 15 to 95%. If the filling rate is within this range, the contact frequency between the cellulose-containing raw material and the medium is improved, and the grinding efficiency can be improved without hindering the movement of the medium.
• the filling rate refers to the apparent volume of the medium relative to the volume of the stirring unit of the pulverizer.
• the processing time of the pulverizer cannot be determined unconditionally depending on the type of pulverizer, the type of medium such as balls and rods, the size and the filling rate, etc., but preferably from the viewpoint of efficiently reducing the crystallinity.
• the treatment temperature is not particularly limited, but is preferably 5 to 250 ° C., more preferably 10 to 200 ° C. from the viewpoint of preventing cellulose from being deteriorated by heat.
• amorphous cellulose having a cellulose I-type crystallinity of 33% or less can be efficiently obtained from the cellulose-containing raw material. Can be processed dry without sticking.
• the average particle size of the obtained amorphous cellulose is preferably from 1 to 150 ⁇ m, more preferably from 5 to 100 ⁇ m, still more preferably from the viewpoint of chemical reactivity and handleability when the amorphous cellulose is used as an industrial raw material. 7 to 100 ⁇ m. In particular, when the average particle size is 7 ⁇ m or more, it is possible to suppress “mamasko” (dama) when the amorphous cellulose is brought into contact with a liquid such as water.
• the non-crystalline cellulose obtained by the non-crystallizing treatment can be further reduced in particle size as necessary.
• a known pulverizer can be appropriately selected and used. For example, “Revised Sixth Edition, Chemical Engineering Handbook” (edited by Chemical Society of Japan, published by Maruzen Co., Ltd. 1999), page 843 And the pulverizer described. These pulverizers may be used alone or in combination of two or more.
• the particle size reduction treatment can be either batch processing or continuous processing, but continuous processing is desirable from the viewpoint of productivity.
• a high-speed rotary mill is preferable, and a turbo type and an annular type mill are more preferable from the viewpoint of high pulverization efficiency and a small particle size.
• a turbo mill manufactured by Turbo Industry Co., Ltd. can be preferably used.
• the annular mill a kryptron series manufactured by Earth Technica Co., Ltd. can be preferably used.
• a method for reducing the particle size a method in which the amorphous cellulose obtained by the amorphous treatment is put into a pulverizer and continuously treated is preferable.
• the peripheral speed of the rotor of the high-speed rotary mill is preferably 50 m / s or more, and more preferably 100 m / s or more.
• Other treatment conditions are not particularly limited, but the treatment temperature is preferably 5 to 200 ° C.
• the non-crystalline cellulose obtained by the non-crystallizing treatment can be further classified as required.
• amorphous cellulose having a desired particle size can be obtained.
• a known dry classification means may be appropriately selected, and examples thereof include sieving and air classification. The coarse powder after the classification treatment is again put into a vibration mill together with the cellulose-containing raw material and subjected to an amorphization treatment, whereby an amorphous cellulose having a small particle diameter can be obtained efficiently.
• the bulk density, specific surface area, average particle size, crystallinity, water content, and cellulose content of the cellulose-containing raw material and non-crystalline cellulose were measured by the methods described below.
• (1) Measurement of bulk density The bulk density was measured using "Powder Tester” manufactured by Hosokawa Micron Corporation. The measurement was calculated by vibrating the sieve, dropping the sample through a chute, receiving it in a specified container (capacity 100 mL), and measuring the mass of the sample in the container. However, the cotton-like sample was calculated by dropping through a chute without passing through a sieve, receiving it in a specified container (capacity 100 mL), and measuring the mass of the sample in the container.
• the equivalent circle diameter per cellulose-containing raw material is obtained from an electronic image, and the surface area A 1 (m 2 ) and volume V 1 (m 3 ) are obtained from the equivalent circle diameter. , A 1 / (V 1 ⁇ ⁇ ).
• the cellulose I type crystallinity is calculated by measuring the X-ray diffraction intensity of a sample using the “Rigaku RINT 2500VC X-RAY diffractometer” manufactured by Rigaku Corporation under the following conditions. Calculated based on the formula.
• the measurement sample was prepared by compressing a pellet having an area of 320 mm 2 ⁇ thickness of 1 mm.
• Example 1 As a cellulose-containing raw material, a sheet-like wood pulp (“HV-10” manufactured by Tenbeck, 800 mm ⁇ 600 mm ⁇ 1.0 mm, crystallinity 81.5%, cellulose content (residual components obtained by removing water from the cellulose-containing raw material) 96 mass%, moisture content 8.5 mass%] is applied to a sheet pelletizer (“SG (E) -220” manufactured by Horai Co., Ltd.), and about 4 mm ⁇ 4 mm ⁇ 1.0 mm (Specific surface area 1.8 m 2 / kg).
• HV-10 sheet-like wood pulp
• SG (E) -220 manufactured by Horai Co., Ltd.
• [Amorphization treatment] 100 g of the pulp obtained by the drying treatment is put into a batch type vibration mill (Chuo Kako Co., Ltd., “MB-1”, total container capacity: 3.5 L), and the rod is 30 mm in diameter, 218 mm in length, material
• Thirteen stainless steel rods with a circular cross-sectional shape were filled into a vibration mill (filling rate 57%) and treated for 30 minutes under conditions of an amplitude of 8 mm and a circular rotation of 1200 cpm. After completion of the treatment, no pulp sticking matter was found on the wall or bottom of the vibration mill.
• the amorphous cellulose was taken out from the vibration mill, the median diameter of the obtained amorphous cellulose was measured, and the crystallinity was calculated from the X-ray diffraction intensity. The results are shown in Table 1.
• Example 2 In the drying process, the pulp obtained by the cutting process was dried so that the moisture content of the pulp after drying was 0.4% by mass, the cellulose-containing raw material having a crystallinity of 79% was used, Amorphized cellulose was obtained in the same manner as in Example 1 except that the amorphous treatment was performed for 15 minutes. The median diameter of the obtained amorphous cellulose was measured, and the crystallinity was calculated from the X-ray diffraction intensity. The results are shown in Table 1.
• Example 3 In the drying process, the pulp obtained by the cutting process was dried so that the moisture content of the pulp after drying was 0.6% by mass, and QAD (hot air receiving dryer) as a dryer: Mitsubishi Materials Amorphized cellulose was obtained in the same manner as in Example 1 except that Techno Co., Ltd. was used. The median diameter of the obtained amorphous cellulose was measured, and the crystallinity was calculated from the X-ray diffraction intensity. The results are shown in Table 1.
• Example 4 In the drying process, the amorphous cellulose was obtained by the same method as in Example 1 except that the pulp obtained by the cutting process was dried so that the moisture content of the pulp after drying was 1.7% by mass. Obtained. The median diameter of the obtained amorphous cellulose was measured, and the crystallinity was calculated from the X-ray diffraction intensity. The results are shown in Table 1.
• Example 5 A plastic grinder (Morita Seiki Kogyo Co., Ltd.) was used as a cellulose-containing raw material using a pruned branch of Satsuma mandarin orange ( ⁇ 10 mm ⁇ 500 mm, cellulose content 64 mass%, crystallinity 46%, moisture content 22 mass%). (Made by JC-2 type) and cut into a chip shape (specific surface area 2.2 m 2 / kg) of about 2 mm ⁇ 3 mm ⁇ 1 mm. [Drying process] Using the obtained chip-like cellulose-containing raw material, the moisture content of the pulp after drying becomes 1.7% by mass using a shelf dryer (manufactured by ADVANTEC, vacuum constant temperature dryer “DRV320DA”). So as to dry.
• a shelf dryer manufactured by ADVANTEC, vacuum constant temperature dryer “DRV320DA”. So as to dry.
• Comparative Examples 1 and 2 In the drying process, the pulp obtained by cutting was dried so that the moisture content of the pulp after drying was 4.9% by mass (Comparative Example 1) and 5.9% by mass (Comparative Example 2). Except for the above, cutting, drying, and amorphous treatment were performed in the same manner as in Example 1. The median diameter of the obtained cellulose was measured, and the crystallinity was calculated from the X-ray diffraction intensity. The results are shown in Table 2.
• Comparative Examples 3 and 4 [Cutting] As a cellulose-containing raw material, a pruned branch of a stick-shaped street tree (a mixture of Yoshino cherry tree, Ubamegashi, camphor tree, Kunugi and Nozenkazura) (Comparative Example 3: ⁇ 10 mm ⁇ 300 mm, cellulose content 67 mass%, crystallinity 51%, moisture content) 12% by weight), and pruned branches of Wenzhou mandarin orange (Comparative Example 4: ⁇ 10 mm ⁇ 500 mm, cellulose content 64% by mass, crystallinity 46%, water content 22% by mass) and Example 5 Cutting was performed in the same manner.
• a pruned branch of a stick-shaped street tree a mixture of Yoshino cherry tree, Ubamegashi, camphor tree, Kunugi and Nozenkazura
• the chip-shaped cellulose-containing raw material thus obtained was subjected to an amorphous treatment by the same method as in Example 5 without performing a drying treatment to obtain amorphous cellulose.
• the median diameter of the obtained cellulose was measured, and the crystallinity was calculated from the X-ray diffraction intensity. The results are shown in Table 2.
• the method for producing non-crystalline cellulose of Examples 1 to 5 is more efficient than the comparative examples 1 to 4 in that non-crystalline cellulose having a reduced cellulose crystallinity is efficiently obtained in a short time. It can be obtained and the productivity is excellent.
• Comparative Example 5 In the drying process, the amorphous cellulose was obtained in the same manner as in Example 1 except that the pulp obtained by the cutting process was dried so that the moisture content of the pulp after drying was 2.0% by mass. Obtained. The median diameter of the obtained amorphous cellulose was measured, and the crystallinity was calculated from the X-ray diffraction intensity. The results are shown in Table 3.
• Comparative Example 6 In the drying process, the amorphous cellulose was obtained by the same method as in Example 1 except that the pulp obtained by the cutting process was dried so that the moisture content of the pulp after drying was 3.2% by mass. Obtained. The median diameter of the obtained amorphous cellulose was measured, and the crystallinity was calculated from the X-ray diffraction intensity. The results are shown in Table 3.
• Comparative Example 7 In the drying process, the amorphous cellulose was obtained by the same method as in Example 1 except that the pulp obtained by the cutting process was dried so that the moisture content of the pulp after drying was 3.9% by mass. Obtained. The median diameter of the obtained amorphous cellulose was measured, and the crystallinity was calculated from the X-ray diffraction intensity. The results are shown in Table 3.
• Comparative Examples 8 and 9 As a cellulose-containing raw material, the same bar-shaped pruned branch of the roadside tree used in Comparative Example 3 (Comparative Example 8: water content 12% by mass), the same bar-shaped pruned branch of Wenzhou mandarin tree used in Comparative Example 4 Using (Comparative Example 9: moisture content 22% by mass), cutting was performed in the same manner as in Example 5. Next, a shelf dryer (manufactured by ADVANTEC Co., Ltd., vacuum constant temperature dryer) until the water content of the pruned branches of the obtained chip-shaped street trees and mandarin orange trees becomes 2.3 mass% and 3.5 mass%, respectively.
• a shelf dryer manufactured by ADVANTEC Co., Ltd., vacuum constant temperature dryer
• the amorphous cellulose obtained from Comparative Examples 5 to 9 has a relatively large median diameter and a relatively high degree of crystallinity due to the large amount of water in the raw material before the amorphization treatment. I understand that. In Example 1 above, it can be seen that the median diameter and crystallinity can be reduced in a more balanced manner as compared with Comparative Examples 5 to 9.
• Reference example 1 [Drying with a biaxial horizontal stir dryer] A biaxial paddle dryer ("NPD-1.6W-1 / 2L" manufactured by Nara Machinery Co., Ltd.) in which the pulp obtained by the cutting treatment of Example 1 was heated with steam of 0.18 MPa (130 degrees) as a heating medium. , Volume 47 L, heat transfer area 1.445 m 2 ] continuously at 21 kg / h and dried for 47 minutes. The dried product was always discharged at 21 kg / h from the discharge port. The moisture content of the dried pulp was 0.7% by mass. The amount of fine powder recovered from the inner wall of the dryer and the bag filter after drying was 0.6% by mass with respect to the input amount of the raw material.
• NPD-1.6W-1 / 2L manufactured by Nara Machinery Co., Ltd.
• Reference example 2 [Drying with a single-axis disk dryer] A uniaxial disk dryer ("FDK-60LDK” manufactured by Mitsubishi Materials Techno Co., Ltd., volume 60 L, heat transfer) in which the pulp obtained by the cutting treatment of Example 1 was heated with 0.18 MPa (130 degrees) steam as a heating medium. An area of 1.4 m 2 ] was continuously fed at 21 kg / h and dried for 90 minutes. The discharge flow rate of the dried product gradually increased from the start of drying and reached 21 kg / h after 60 minutes. The moisture content of the dried pulp was 1.1% by mass. The amount of fine powder recovered from the inner wall of the dryer and the bag filter after drying was 1.1% by mass with respect to the input amount of the raw material.
• FDK-60LDK uniaxial disk dryer
• Example 3 [Amorphization treatment] In the drying treatment, Example 1 except that the pulp obtained by the cutting treatment was dried so that the moisture content of the dried pulp was 0.8% by mass, and the amorphization treatment was performed for 13 minutes. Amorphized cellulose was obtained in the same manner as above. The amorphous cellulose had a median diameter of 59 ⁇ m and a crystallinity of 15%.
• Amorphized cellulose having a median diameter of 59 ⁇ m obtained by the above-described amorphization treatment was continuously applied to a kryptron (“KTM-0 type” manufactured by Earth Technica Co., Ltd.) with a rotor peripheral speed of 135 m / s at a rate of 18 kg / h.
• the particle size reduction process was performed by supplying.
• the median diameter after the treatment was 25 ⁇ m.
• Reference example 4 [Reducing particle size by turbo type mill] Amorphous cellulose having a median diameter of 64 ⁇ m obtained by the amorphization treatment of Reference Example 3 was continuously added to a turbo mill (“T400-RS type” manufactured by Turbo Kogyo Co., Ltd.) with a rotor peripheral speed of 157 m / s. The particle size was reduced by supplying at h. The median diameter after the treatment was 23 ⁇ m.
• Reference Example 1 using a biaxial horizontal stirring dryer can further reduce the amount of fine powder and can more efficiently reduce the amount of water.
• the amorphous cellulose obtained by the method of the present invention can be further refined by a mill. This refined non-crystalline cellulose can be suitably used, for example, as a resin reinforcing agent.
• the method for producing amorphous cellulose of the present invention is excellent in productivity, can efficiently obtain amorphous cellulose having a cellulose I-type crystallinity reduced to 33% or less, and is useful as an industrial production method. is there.
• the obtained amorphous cellulose is particularly useful for industrial raw materials such as cellulose ether raw materials, cosmetics, foods, biomass materials, resin reinforcing agents and the like.

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