US20100151527A1 - Fine fibrous cellulosic material and process for producing the same - Google Patents

Fine fibrous cellulosic material and process for producing the same Download PDF

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US20100151527A1
US20100151527A1 US12/450,570 US45057008A US2010151527A1 US 20100151527 A1 US20100151527 A1 US 20100151527A1 US 45057008 A US45057008 A US 45057008A US 2010151527 A1 US2010151527 A1 US 2010151527A1
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cellulosic material
fine fibrous
fibrillation
fibrous cellulosic
sample
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Takashi Endo
Seung-Hwan Lee
Yoshikuni Teramoto
Noriko Tanaka
Manami Sakai
Naomi Kadotani
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National Institute of Advanced Industrial Science and Technology AIST
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National Institute of Advanced Industrial Science and Technology AIST
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    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
    • C12P19/00—Preparation of compounds containing saccharide radicals
    • C12P19/14—Preparation of compounds containing saccharide radicals produced by the action of a carbohydrase (EC 3.2.x), e.g. by alpha-amylase, e.g. by cellulase, hemicellulase
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L97/00—Compositions of lignin-containing materials
    • C08L97/02—Lignocellulosic material, e.g. wood, straw or bagasse
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
    • C12P19/00—Preparation of compounds containing saccharide radicals
    • C12P19/02—Monosaccharides
    • C—CHEMISTRY; METALLURGY
    • C13—SUGAR INDUSTRY
    • C13K—SACCHARIDES OBTAINED FROM NATURAL SOURCES OR BY HYDROLYSIS OF NATURALLY OCCURRING DISACCHARIDES, OLIGOSACCHARIDES OR POLYSACCHARIDES
    • C13K1/00—Glucose; Glucose-containing syrups
    • C13K1/02—Glucose; Glucose-containing syrups obtained by saccharification of cellulosic materials
    • C—CHEMISTRY; METALLURGY
    • C13—SUGAR INDUSTRY
    • C13K—SACCHARIDES OBTAINED FROM NATURAL SOURCES OR BY HYDROLYSIS OF NATURALLY OCCURRING DISACCHARIDES, OLIGOSACCHARIDES OR POLYSACCHARIDES
    • C13K13/00—Sugars not otherwise provided for in this class
    • C13K13/002—Xylose
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2913—Rod, strand, filament or fiber
    • Y10T428/298—Physical dimension

Definitions

  • the present invention relates to: fine fibrous cellulosic materials; processes for producing fine fibrous cellulosic materials; and processes for producing saccharides.
  • cellulosic materials such as cellulose, hemicellulose and lignin.
  • cellulose and hemicellulose are high-molecular materials in which saccharides are bound in a straight- or branched-chain shape.
  • Such cellulosic materials are known to be converted into saccharides by hydrolysis.
  • Such hydrolysis methods include an acid hydrolysis method and an enzymatic hydrolysis method.
  • reaction control is difficult due to occurrence of heat generation. Even if the reaction control is enabled, constituents in a cellulosic material are prone to be excessively decomposed and carbonized, and therefore a saccharide cannot be obtained in a sufficient yield.
  • a method in which wood is finely pulverized and then the enzymatic hydrolysis of the pulverized wood is performed for example, see Patent Document 1 or 2
  • a method in which acid is added to a plant body containing lignocellulose and the mixture is heated by microwaves and subjected to acid hydrolysis for example, see Patent Document 3
  • a method in which a cellulose-containing material is treated with a dimethylformamide solution containing nitrogen oxides and thereafter subjected to enzymatic hydrolysis for example, see Patent Document 4
  • lignocellulose-based biomass is treated with pressurized hot water and subjected to mechanical pulverization and then to enzymatic hydrolysis
  • Patent Document 1 Japanese Patent Application Laid-Open Publication No. 55-9758
  • Patent Document 2 Japanese Patent Application Laid-Open Publication No. 63-137690
  • Patent Document 3 Japanese Patent Application Laid-Open Publication No. 59-146594
  • Patent Document 4 Japanese Patent Application Laid-Open Publication No. 61-242591
  • Patent Document 5 Japanese Unexamined Patent Application Publication No. 2006-136263
  • the present invention is desired with respect to the above-mentioned circumstances and is directed at providing: a fine fibrous cellulosic material capable of producing a saccharide in a high yield by hydrolysis; a process for producing the fine fibrous cellulosic material from a cellulosic material; and a process for producing the saccharide using the fine fibrous cellulosic material.
  • the present inventors undertook thorough research in order to solve the above-mentioned problem and thus found that the respective aggregation units of cellulose, hemicellulose and lignin form blocks, which are mixed to form a rigid network structure, in a cellulosic material.
  • the molecular chains of cellulose regularly self-assemble just after in vivo biosynthesis to form crystalline microfibrils having a width of several nanometers and assemble, together with amorphous hemicellulose and lignin, to be fibrous.
  • microfibrils of cellulose regularly line in a specific direction to form a cell wall; and hemicellulose and lignin cover the periphery of the microfibrils of the cellulose or fill between the microfibrils of the cellulose and function as an adhesive.
  • the present invention is (1) a fine fibrous cellulosic material containing cellulose, hemicellulose and lignin, which fine fibrous cellulosic material has a width of 1 ⁇ m or less and a length of 5,000 ⁇ m or less and is used for glycation reaction by hydrolysis.
  • the present invention is (2) the fine fibrous cellulosic material according to the above-mentioned (1), wherein the hydrolysis is enzymatic hydrolysis.
  • the present invention is (3) a process for producing a fine fibrous cellulosic material used for glycation reaction by hydrolysis, including: carrying out mechanical pulverization of a mixture prepared by mixing a cellulosic material containing cellulose, hemicellulose and lignin with a fibrillation material for fibrillating the cellulosic material; and making a fine fibrous cellulosic material having a width of 1 ⁇ m or less and a length of 5,000 ⁇ m or less from the cellulosic material.
  • the present invention is (4) the process for producing a fine fibrous cellulosic material according to the above-mentioned (3), wherein the mechanical pulverization is performed by a ball mill, a rod mill, a bead mill, a disk mill or a mixer.
  • the present invention is (5) the process for producing a fine fibrous cellulosic material according to the above-mentioned (3), wherein the mechanical pulverization pulverization is performed by a batch-type or continuous-type extruder.
  • the present invention is (6) the process for producing a fine fibrous cellulosic material according to the above-mentioned (3), wherein the mechanical pulverization is performed under a temperature condition of 20-350° C. and/or a pressure condition of 0.1-20 MPa.
  • the present invention is (7) the process for producing a fine fibrous cellulosic material according to the above-mentioned (3), comprising: preliminarily pulverizing the cellulosic material to make a chip-like, fibrous or powdered fine cellulosic material; thereafter mixing the fine cellulosic material with the fibrillation material; and performing the mechanical pulverization.
  • the present invention is (8) the process for producing a fine fibrous cellulosic material according to the above-mentioned (3), wherein a mixing rate of the fibrillation material is 0.01-200 parts by mass with respect to 1 part by mass of cellulosic material.
  • the present invention is (9) the process for producing a fine fibrous cellulosic material according to the above-mentioned (3), wherein the fibrillation material is water.
  • the present invention is (10) the process for producing a fine fibrous cellulosic material according to the above-mentioned (3), wherein the fibrillation material is a low-molecular compound.
  • the present invention is (11) the process for producing a fine fibrous cellulosic material according to the above-mentioned (3), wherein the fibrillation material is a high-molecular compound.
  • the present invention is (12) the process for producing a fine fibrous cellulosic material according to the above-mentioned (3), wherein the fibrillation material is a fatty acid.
  • the present invention is (13) the process for producing a fine fibrous cellulosic material according to the above-mentioned (3), wherein the fibrillation material is constituted of water and a low-molecular compound; and a mixing rate of the low-molecular compound is 0.1-99.9 mass % with respect to a total weight of the fibrillation material.
  • the present invention is (14) the process for producing a fine fibrous cellulosic material according to the above-mentioned (3), wherein the fibrillation material is constituted of water and a high-molecular compound; and a mixing rate of the high-molecular compound is 0.1-99.9 mass % with respect to a total weight of the fibrillation material.
  • the present invention is (15) the process for producing a fine fibrous cellulosic material according to the above-mentioned (3), wherein the fibrillation material is constituted of water and a fatty acid; and a mixing rate of the fatty acid is 0.1-99.9 mass % with respect to a total weight of the fibrillation material.
  • the present invention is (16) the process for producing a fine fibrous cellulosic material according to the above-mentioned (3), wherein the fibrillation material is constituted of water and an inorganic alkali; and a mixing rate of the inorganic alkali is 0.1-99.9 mass % with respect to a total weight of the fibrillation material.
  • the present invention is (17) a process for producing a saccharide, including: carrying out mechanical pulverization of a mixed liquid prepared by mixing a cellulosic material containing cellulose, hemicellulose and lignin as well as a fibrillation material for fibrillating the cellulosic material with an enzyme; and, concurrently with making a fine fibrous cellulosic material from the cellulosic material, carrying out enzymatic hydrolysis of the fine fibrous cellulosic material with the enzyme to make a saccharide.
  • the present invention is (18) a process for producing a saccharide, including: providing a saccharide by performing acid hydrolysis or enzymatic hydrolysis of a fine fibrous cellulosic material provided by the process for producing a fine fibrous cellulosic material according to any one of the above-mentioned (3) to (16).
  • a cellulosic material made to have a width of 1 ⁇ m or less and a length of 5,000 ⁇ m or less results in improvement in hydrolysis (glycation reaction) rate and improvement in yield of a saccharine to be obtained.
  • the reason why the yield of a saccharine is improved as described above is unclear but is likely to be that the fine fibrous cellulosic material made to have a predetermined width, length or aspect ratio (hereinafter generally referred to as “size”) results in the increase in surface area and the facilitation of adhesion of an acid or an enzyme to the fine fibrous cellulosic material as well as in the increase in the number of reaction points of an enzyme or an acid which can be hydrolyzed.
  • size results in the increase in surface area and the facilitation of adhesion of an acid or an enzyme to the fine fibrous cellulosic material as well as in the increase in the number of reaction points of an enzyme or an acid which can be hydrolyzed.
  • size results in the increase in surface area and the facilitation of adhesion of an acid or an enzyme to the fine fibrous cellulosic material as well as in the increase in the number of reaction points of an enzyme or an acid which can be hydrolyzed.
  • size results in the increase in surface area and the facilitation of
  • An aspect ratio as described herein refers to a ration between a long side (length) and a short side (width).
  • the fine fibrous cellulosic material having the aforementioned size allows the sufficient undoing of the entanglement of lignin with cellulose and hemicellulose.
  • the above-mentioned hydrolysis is preferably enzymatic hydrolysis.
  • a saccharide can be inexpensively obtained since a cellulosic material can be sufficiently hydrolyzed even with a comparatively small amount of enzyme.
  • a process for producing a fine fibrous cellulosic material the mechanical pulverization of a mixture prepared by mixing a cellulosic material with a fibrillation material is carried out to obtain a fine fibrous cellulosic material having a width of 1 ⁇ m or less and a length of 5,000 ⁇ m or less as described above.
  • the mechanical pulverization of the mixture prepared by mixing the cellulosic material with the fibrillation material is carried out, whereby the fibrillation material enters between cellulose microfibrils to widen these gaps and concurrently damage a texture, and the hemicellulose and the lignin which are adhered to the cellulose microfibrils are removed.
  • the cellulosic material will be undone to a microfibril which is a minimum aggregation unit of a cellulose molecular chain.
  • the process for producing a fine fibrous cellulosic material provides the fine fibrous cellulosic material which is fibrillated into a cellulose microfibril in the pure form that is most efficient for a hydrolysis reaction while a cellulosic material is in a solid state without inhibiting the hydrolysis reaction.
  • the unique crystallinity of a cellulosic material is maintained in the obtained fine fibrous cellulosic material since the bundle of the cellulosic material formed by assembling cellulose microfibrils is undone to form the individual cellulose microfibrils.
  • surface or internal cellulose molecules provide the cellulose microfibrils having crystallinity which are scarcely subjected to the disorder of the sequence and orientation of molecular chains or chemical modification.
  • the process for producing a fine fibrous cellulosic material provides the fine fibrous cellulosic material, of which the hydrolysis reaction easily proceeds, even in case of cellulose having a high crystallinity.
  • the hydrolysis is enzymatic hydrolysis, the surface of cellulose microfibrils is not subjected to strong modification, and therefore the hydrolysis easily proceeds without inhibiting the substrate specificity of an enzyme.
  • an obtained fine fibrous cellulosic material need not be hydrolyzed under severe conditions such as strong chemical agents such as sulfuric acid and high-pressure and high-temperature water since a cellulosic material is a fibrillated cellulose microfibril.
  • reaction control is easy, and a saccharide can be efficiently produced from the fine fibrous cellulosic material without generating an excessively decomposed product and without applying great pulverization energy.
  • a cellulosic material is derived from a plant (including algae) and has a chip-like, fibrous or powdered shape, a plant tissue is partially damaged prior to mechanical pulverization, and therefore a fine fibrous cellulosic material can be efficiently produced in a comparatively short time.
  • a fine fibrous cellulosic material can be comparatively easily produced by performing the mechanical pulverization by a ball mill, a rod mill, a bead mill, a disk mill or a mixer.
  • a fine fibrous cellulosic material can be efficiently produced in a shorter time by performing the mechanical pulverization by a batch-type or continuous-type extruder.
  • a fine fibrous cellulosic material can be efficiently produced in a shorter time by the mechanical pulverization under a temperature condition of 20-350° C. and/or a pressure condition of 0.1-20 MPa.
  • a cellulosic material is preliminarily pulverized to make a fine cellulosic material, followed by mixing the fine cellulosic material with a fibrillation material and performing mechanical pulverization, and the slurry fine fibrous cellulosic material having a low aspect ratio is thus obtained.
  • Such a fine fibrous cellulosic material has a high flowability, is easy to, e.g., transport with a pump, and is thus excellent in handleability.
  • a mixing rate of a fibrillation material is 0.01-200 parts by mass with respect to 1 part by mass of cellulosic material, the cellulosic material is surely mechanically pulverized, and a fine fibrous cellulosic material having a predetermined shape can be produced.
  • an enzyme is mixed with a cellulosic material containing cellulose, hemicellulose and lignin and a fibrillation material for fibrillating the cellulosic material, and a saccharide can be obtained from a cellulosic material in a high yield at a time by mechanical pulverization.
  • hemicellulose and lignin are removed by the fine fiberization of the cellulosic material, cellulose microfibrils appear on a surface, and the enzyme approaches and is adsorbed to the cellulose microfibrils to hydrolyze the fine fibrous cellulosic material.
  • a fine fibrous cellulosic material according to the present embodiment is constituted of cellulose materials including cellulose, hemicellulose and lignin and has fine fibrous form.
  • a cellulosic material in accordance with the present embodiment refers to a mixture including cellulose, hemicellulose and lignin.
  • Such cellulosic materials are obtained from, e.g., plants such as wood, vegetation, agricultural products and raw cotton.
  • a fine fibrous cellulosic material has a width of 1 ⁇ m or less, preferably 0.1 ⁇ m or less, further preferably 3-5 nm, and a length of 5,000 ⁇ m or less, preferably 50 ⁇ m or less.
  • the fine fibrous cellulosic material made to have the sizes in the above-mentioned ranges allows sufficient undoing of entanglement of lignin with cellulose and hemicellulose.
  • the hydrolysis be enzymatic hydrolysis.
  • the fine fibrous cellulosic material has many exposed surfaces, which is approached by an enzyme and to which the enzyme is adsorbed, to facilitate hydrolysis, and a space, into which the enzyme easily moves, is formed around the fine fibrous cellulosic material.
  • hydrolysis of the cellulosic material is sufficiently performed with a comparatively small amount of enzyme, and a saccharide can be inexpensively provided. Details of hydrolysis will be described below.
  • the fine fibrous cellulosic material is produced by mixing cellulosic materials with fibrillation materials for fibrillating the cellulosic materials and performing mechanical pulverization. Specifically, the cellulosic materials are mixed with the fibrillation materials and the mixture is mechanically pulverized; therefore the cellulosic materials enter between the microfibrils of cellulose to widen these gaps and concurrently damage a texture; and the fine fibrous cellulosic material having the above-mentioned predetermined sizes is provided.
  • the cellulosic material is preferably derived from a plant.
  • Cellulosic materials derived from plants self-assemble just after biosynthesis to form microfibrils of cellulose and therefore has an extremely large surface area without change in the orientation of cellulose molecular chains by being fibrillated into microfibrils.
  • the fibrillation material functions as a medium for fibrillating a cellulosic material.
  • a fibrillation material which is not limited in particular, water, a low-molecular compound, a high-molecular compound, a fatty acid or inorganic alkali is preferably used.
  • a low-molecular compound a high-molecular compound, a fatty acid or inorganic alkali is preferably used.
  • One of these may be singly used or two or more of these may be mixedly used.
  • the inorganic alkali is used together with water.
  • the fibrillation material is water
  • water molecules are small, therefore the water easily enters into the fine pores and gaps of a tissue and further easily enters between cell walls containing a large amount of ingredient having a high affinity for water, such as cellulose or hemicellulose, and therefore the tissue can be swollen.
  • the fibrillation material is a low-molecular compound
  • the low-molecular compound enters between tissues or cell walls and acts like a wedge to facilitate the proceeding of fibrillation.
  • the fibrillation material is a high-molecular compound
  • a tissue is partially melted and flowability is enhanced by pressure, shearing force or heat during mechanical pulverization.
  • the fibrillation material is a fatty acid
  • the fatty acid exhibits an affinity for hemicellulose, in which the side chain of a constituent saccharide has an acetyl group, and easily enters between tissues or cell walls.
  • water is preferably mixedly used with a low-molecular compound, a high-molecular compound, a fatty acid or inorganic alkali.
  • the low-molecular compound, the high-molecular compound and the fatty acid are preferably water-soluble.
  • the low-molecular compound is preferably at least one selected from the group consisting of alcohols, ethers, ketones, sulfoxides, amides, amines, aromatics and morpholines.
  • the alcohols include methanol, ethanol, 1-propanolol, 2-propanolol, 1-butanol, t-butanol, alkylene glycols such as ethylene glycol, trimethylene propanolol, butanediol, glycerin, etc. One of these may be singly used or two or more of these may be mixedly used.
  • the ethers include 1,4-dioxane, etc. One of these may be singly used or two or more of these may be mixedly used.
  • the ketones include acetone, methyl ethyl ketone, diethyl ketone, methyl propyl ketone, stearyl ketene dimers, etc. One of these may be singly used or two or more of these may be mixedly used.
  • the sulfoxides include dimethylsulfoxide, bisphenyl sulfoxides, bishydroxyphenyl sulfoxides such as bis(4-hydroxyphenyl)sulfoxide, bis(3,5-dimethyl-4-hydroxyphenyl)sulfoxide, bis(2,3-dihydroxyphenyl)sulfoxide, bis(5-chloro-2,3-dihydroxyphenyl)sulfoxide, bis(2,4-dihydroxyphenyl)sulfoxide, bis(2,4-dihydroxy-6-methylphenyl)sulfoxide, bis(5-chloro-2,4-dihydroxyphenyl)sulfoxide, bis(2,5-dihydroxyphenyl)sulfoxide and bis(3,4-dihydroxyphenyl)sulfoxide, etc.
  • One of these may be singly used or two or more of these may be mixedly used.
  • the amides include N,N-dimethylformamide, N,N-dimethylacetamide, oleic amide, stearic acid amide, etc. One of these may be singly used or two or more of these may be mixedly used.
  • the amines include ammonia, aniline, dimethylamine, triethylamine, ethanolamine, diethylethanolamine, etc. One of these may be singly used or two or more of these may be mixedly used.
  • the aromatic compounds include benzene, toluene, xylene, phenol, p-cresol, o-cresol, catechins, terpenes, etc. One of these may be singly used or two or more of these may be mixedly used.
  • the morpholines include N-methylmorpholine, N-methylmorpholine-N-oxide, etc. One of these may be singly used or two or more of these may be mixedly used.
  • the low-molecular compounds include an ionic liquid.
  • an ionic liquid refers to a salt which is present in liquid even at room temperature.
  • Such ionic liquids as described above include 1-butyl-3-methylimidazolium chloride, 1-butyl-3-methylimidazolium, 1-ethyl-3-(hydroxymethyl)pyridinium ethyl sulfate, 1-ethyl-3-methylpyridinium ethyl sulfate, 1,3-dimethyl imidazolium dimethyl phosphate, etc.
  • One of these may be singly used or two or more of these may be mixedly used.
  • the high-molecular compound is at least one selected from the group consisting of alcoholic polymers, ether polymers, amide polymers, amine polymers and aromatic polymers.
  • the alcoholic polymers include polyethylene glycol, polyetherpolyol, polyesterpolyol, polyvinyl alcohol, amylose, amylopectin, sorbitol, polycaprolactone, polyvalerolactone, polybutyrolactone, polyglycol, polylactic acid, etc. One of these may be singly used or two or more of these may be mixedly used.
  • the ether polymers include crown ether, polyethylene glycol, polypropylene glycol, etc. One of these may be singly used or two or more of these may be mixedly used.
  • the amide polymers include polyacrylamide, chitin, chitosan, polyvinylpyrrolidone, polycaprolactam, etc. One of these may be singly used or two or more of these may be mixedly used.
  • the amine polymers include polyallylamine, polylysine, various amine-modified acrylic copolymers, etc. One of these may be singly used or two or more of these may be mixedly used.
  • the aromatic polymers include polyphenylene oxide, catechin, tannin, terpene, etc. One of these may be singly used or two or more of these may be mixedly used.
  • the fatty acid is preferably at least one selected from the group consisting of saturated fatty acids, unsaturated fatty acids and salts thereof.
  • the saturated fat acids include formic acid, acetic acid, oxalic acid, citric acid, malonic acid, succinic acid, propionic acid, butyric acid, palmitic acid, stearic acid, etc. One of these may be singly used or two or more of these may be mixedly used.
  • the unsaturated fatty acids include benzoic acid, oleic acid, linoleic acid, linolenic acid, etc. One of these may be singly used or two or more of these may be mixedly used.
  • the inorganic alkalis include lithium hydroxide, sodium hydroxide, potassium hydroxide, etc. One of these may be singly used or two or more of these may be mixedly used.
  • the above-mentioned fibrillation material may be a solid or a liquid at room temperature.
  • the fibrillation material When being a solid at room temperature, the fibrillation material preferably becomes a liquid under a temperature condition during mechanical pulverization described below.
  • the fibrillation material preferably has a lower melting point than temperature during the mechanical pulverization described below.
  • the fibrillation material enters between the microfibrils of cellulose of a cellulosic material, and therefore the entanglement of lignin with cellulose and hemicellulose can be sufficiently undone.
  • the fibrillation material is preferably 0.01-200 parts by mass, more preferably 0.01-100 parts by mass, further more preferably 0.1-20 parts by mass, with respect to 1 part by mass of the cellulosic material.
  • the mixing rate of the fibrillation material When the mixing rate of the fibrillation material is less than 0.01 parts by mass, the cellulosic material tends not to be sufficiently fibrillated in comparison with the case in which the mixing rate is within the above-mentioned range; and when the mixing rate is more than 200 parts by mass, most of pulverization energy is absorbed in a fibrillation material, the rate of the pulverization energy used in the fibrillation of the cellulosic material is decreased, and the fibrillation tends to be inhibited from efficiently proceeding, in comparison with the case in which the mixing rate is within the above-mentioned range.
  • a mixing rate of the medium is preferably 0.1-99.9 mass %, more preferably 0.1-50 mass %, with respect to the total weight of the fibrillation material.
  • a mixing rate of the low-molecular compound of 0.1-99.9 mass % with respect to the total weight of the fibrillation material results in entering of a low-molecular compound as well as water molecules between tissues or cell walls to swell the tissues.
  • a fibrillation material is constituted of water and a high-molecular compound
  • a mixing rate of the high-molecular compound of 0.1-99.9 mass % with respect to the total weight of the fibrillation material results in increase of the flexibility of high-molecular compound molecules which is enhanced by a swelling effect and a fibrillation effect by water molecules as well as dissolution in water
  • the high-molecular compound having a hydration structure results in facilitation of entering between the gaps of cellulose and hemicellulose having a high affinity for water, and therefore the proceeding of fibrillation is facilitated by synergistic effect.
  • a mixing rate of fatty acid of 0.1-99.9 mass % with respect to the total weight of the fibrillation material results in a swelling effect and a fibrillation effect by water molecules, lower fatty acid enters between tissues or cell walls like water, and the proceeding of fibrillation is facilitated by synergistic effect.
  • higher fatty acid has such an advantage that the proceeding of fibrillation is facilitated by synergistic effect since the dissolution of the higher fatty acid in water results in the adhesion of water molecules to the periphery of its molecules to become in a hydration state and it is easy to enter between the gaps of cellulose or hemicellulose having a affinity for water.
  • a fibrillation material is constituted of water and inorganic alkali
  • an added medium is alkaline
  • cellulose and hemicellulose in a cellulosic material are hydrolyzed partially, rigid cell walls are embrittled, and a tissue is easily damaged by pulverization energy to facilitate the proceeding of fibrillation.
  • alkali ions have a hydration structure and therefore have such an advantage that they enter between tissues and cell walls to widen the network of cellulose and hemicellulose and the proceeding of fibrillation is facilitated by synergistic effect.
  • the crystal structure of cellulose is known to be converted from a cellulose I type crystal to a cellulose II type crystal in a natural type alkali medium.
  • Such alkali treatment is referred to as mercerization treatment.
  • the cellulose II type crystal has high chemical and biological reactivity and facilitates the proceeding of hydrolysis.
  • Methods of the mechanical pulverization are not limited in particular, but a method capable of coexistence with a medium to apply shearing force to a cellulosic material is preferred.
  • the methods include, for example, methods by a ball mill, a rod mill, a hammer mill, an impeller mil, a high-speed mixer, a disk mill (batch-type or continuous-type), a mixer, a high-pressure homogenizer, a mechanical homogenizer or an ultrasonic wave homogenizer, etc.
  • the mechanical pulverization method is carried out preferably by the ball mill, the rod mill, a bead mill, the disk mill or the mixer, more preferably by the ball mill, the disk mill or the mixer.
  • a fine fibrous cellulosic material can be comparatively easily produced.
  • variations in the size of the obtained fine fibrous cellulosic material are reduced.
  • the mechanical pulverization method is carried out by the disk mill.
  • the thick bundle of a cellulosic material in which cellulose microfibrils are assembled may be undone to a thinner cellulosic material by applying pressure or shearing force and this treatment may be continuously carried out.
  • Pulverization treatment may be also carried out while heating, and a throughput may be also increased by increasing the diameter of the disk.
  • Mechanical pulverization is performed preferably by a batch-type or continuous-type extruder.
  • a fine fibrous cellulosic material can be efficiently produced in a shorter time.
  • the twin-screw extruder extrudes a material between screws while applying shearing force or pressure thereto, allowing continuous treatment. Therefore, the homogeneous dispersion and penetration of a fibrillation material in an overall cellulosic material is facilitated, and consequently a cellulosic material can be sufficiently fibrillated even with a small amount of fibrillation material.
  • twin-screw extruder enables treatment while heating and therefore comparatively easily uses a molten thermoplastic polymer or the like as a fibrillation material.
  • viscosity after melting becomes high, strong pressure or shearing force can be propagated and applied to an overall cellulosic material, and the cellulosic material can be fibrillated even with a small amount of fibrillation material.
  • Mechanical pulverization is preferably performed under a temperature condition of 20-350° C.
  • Mechanical pulverization is preferably carried out under a pressure condition of 0.1-20 MPa.
  • a fibrillation material When pressure is less than 1 MPa, in case of adding a low-boiling fibrillation material, a fibrillation material is partially vaporized to inhibit pulverization energy transfer, and therefore a cellulosic material tends not to be fully fibrillated, in comparison with the case in which pressure is within the above-mentioned range; and when pressure is more than 20 MPa, a cellulosic material or a fibrillation material may be decomposed or modified in comparison with the case in which pressure is within the above-mentioned range.
  • Mechanical pulverization is more preferably carried out under a temperature condition of 20-350° C. and/or a pressure condition of 0.1-20 MPa.
  • a fine fibrous cellulosic material can be efficiently produced in a shorter time.
  • pulverization of a cellulosic material with a fibrillation material by mechanically applying shearing force or pressure results in fibrillation of the cellulosic material into cellulose microfibrils.
  • preliminarily pulverize a cellulosic material to make a chip-like, fibrous or powdered fine cellulosic material.
  • Such a fine fibrous cellulosic material has a high flowability, is easy to transport with a pump, and is thus excellent in handleability.
  • a fine fibrous cellulosic material having a width of 1 ⁇ m or less and a length of 5,000 ⁇ m or less.
  • a fine fibrous cellulosic material can be efficiently produced in a shorter time.
  • the process for producing a fine fibrous cellulosic material provides the fine fibrous cellulosic material which is fibrillated into a cellulose microfibril in the pure form that is most efficient for a hydrolysis reaction while a cellulosic material is in a solid state without inhibiting the hydrolysis reaction.
  • the unique crystallinity of a cellulosic material is maintained in the obtained fine fibrous cellulosic material since the bundle of the cellulosic material formed by assembling cellulose microfibrils is undone to form the individual cellulose microfibrils.
  • surface or internal cellulose molecules provide the cellulose microfibrils having crystallinity which are scarcely subjected to the disorder of the sequence and orientation of molecular chains or chemical modification.
  • the process for producing a fine fibrous cellulosic material provides the fine fibrous cellulosic material, of which the hydrolysis reaction easily proceeds, even in case of cellulose having a high crystallinity.
  • the hydrolysis is enzymatic hydrolysis, the surface of cellulose microfibrils is not subjected to strong modification, and therefore the hydrolysis easily proceeds without inhibiting the substrate specificity of an enzyme.
  • an obtained fine fibrous cellulosic material need not be hydrolyzed under severe conditions such as strong chemical agents such as sulfuric acid and high-pressure and high-temperature water since a cellulosic material is a fibrillated cellulose microfibril.
  • reaction control is easy, and a saccharide can be efficiently produced from the fine fibrous cellulosic material without generating an excessively decomposed product and without applying great pulverization energy.
  • Fine fibrous cellulose obtained in such a manner can be used not only in the production of a saccharide or ethanol from the saccharide but also as a high-strength material by conjugated as a filler to a resin or the like because of having extremely high strength in terms of a molecular structure.
  • the fine fibrous cellulose can be also converted into a high-strength material without being processed, without any operation such as the use of an adhesive or the chemical denaturalization of the fine fibrous cellulose, because of having strong self-cohesive power.
  • the fine fibrous cellulose is a natural product, has neither taste nor odor, is atoxic, has fine fibers and therefore offers no foreign body feeling on the tongue, the fine fibrous cellulose can be added to a food product to be imparted with water retentivity, oil retentivity, texture, morphological stability or dietetic properties.
  • a saccharide is obtained by hydrolyzing the fine fibrous cellulose.
  • Hydrolysis methods include acid hydrolysis using acids such as sulfuric acid, hydrochloric acid and fluorinated acid and enzymatic hydrolysis using enzymes such as cellulases.
  • the hydrolysis is preferably enzymatic hydrolysis.
  • a cellulosic material can be sufficiently hydrolyzed with a comparatively small amount of enzyme, and therefore a saccharide can be inexpensively obtained.
  • the cellulases are classified roughly into endo-type and exo-type cellulases.
  • the endo-type cellulases well hydrolyze amorphous cellulose, whereas the exo-type cellulases well hydrolyze crystalline cellulose.
  • the mixture may be mixed with an enzyme without being processed to perform hydrolysis.
  • the mixture when a material which inhibits an enzyme reaction or deactivates an enzyme is contained in the mixture, the mixture may be diluted till the effect of the material is deteriorated, followed by the enzymatic hydrolysis.
  • the (inhibition) material may be also removed by washing, solvent substitution, decompression or the like, followed by the enzymatic hydrolysis.
  • Saccharides are obtained in such a manner. Further, glucose is obtained from cellulose; and xylose, mannose, arabinose, galactose and the like are obtained from hemicellulose.
  • Saccharified solutions from these saccharides can be converted into ethanol by fermentation.
  • the ethanol is used in raw materials for chemical products, solvents, automotive fuels, etc.
  • An aqueous solution containing the ethanol may be also made to be an alcoholic beverage.
  • the saccharified solutions are also used as medium materials or carbon sources for biologically producing useful resources.
  • the saccharified solutions are also used in useful materials such as chemical products, polymer raw materials and physiologically active materials by chemically converting the saccharides.
  • the fine fibrous cellulosic material according to the present embodiment need not be derived from a plant.
  • it may be a fine fibrous cellulosic material derived from ascidian, acetic acid bacteria and the like.
  • a cellulosic material In the production process of a fine fibrous cellulosic material, it is preferable to immerse a cellulosic material in an aqueous inorganic alkaline solution for several hours to several days prior to mechanical pulverization.
  • the cellulosic material is prone to be undone by swelling, and cellulose and hemicellulose are hydrolyzed to decrease a molecular weight.
  • the cellulosic material is embrittled.
  • cellulose microfibrils are partially cut or prone to be cut by external force.
  • inorganic alkalis as described above include lithium hydroxide, sodium hydroxide, potassium hydroxide and the like.
  • the cellulosic material is prone to be undone by swelling, and cellulose and hemicellulose are hydrolyzed to decrease a molecular weight.
  • the cellulosic material is embrittled.
  • cellulose microfibrils are partially cut or prone to be cut by external force.
  • hydrolyzability is significantly improved by the partial dissolution and desorption of hemicellulose and lignin.
  • the fine fibrous cellulosic material may be hydrolyzed concurrently with being produced.
  • an enzyme is mixed with a cellulosic material containing cellulose, hemicellulose and lignin and a fibrillation material for fibrillating the cellulosic material, and a saccharide can be obtained from a cellulosic material in a high yield at a time by mechanical pulverization.
  • hemicellulose and lignin are removed by the fine fiberization of the cellulosic material, cellulose microfibrils appear on a surface, and the enzyme approaches and is adsorbed to the cellulose microfibrils to hydrolyze the fine fibrous cellulosic material.
  • the rough pulverization of eucalyptus chips for making paper used as the eucalyptus was performed to make 0.2 mm-pass eucalyptus wood flour by a cutter mill.
  • the resultant eucalyptus wood flour (20 g) was charged into a planetary ball mill pot made of zirconia (internal capacity: 500 ml; P-5 type; manufactured by Fritsch Corporation (Germany)), and 25 zirconia balls having a diameter of 20 mm were filled thereinto.
  • a cycle of treatment at an autorotation speed of 120 rpm for 20 minutes and stop for 10 minutes was repeated 100 times, and mechanical pulverization (hereinafter also referred to as “fibrillation treatment”) was performed for total treatment time of 33 hours to obtain a brown, creamy mixture.
  • temperature and pulverization energy which can be applied to the ball in the container of the ball mill were set at 40° C. and 1.8 G at 120 rpm, respectively.
  • the water in the mixture was substituted with t-butylalcohol, and a dried sample 1 (fine fibrous cellulosic material; average width of 0.07 ⁇ m and average length of 4 ⁇ m) was obtained by drying under reduced pressure.
  • the aspect ratio of the sample 1 was measured from an SEM observation image.
  • a sample 2 (fine fibrous cellulosic material; average width of 0.04 ⁇ m and average length of 7 ⁇ m) was obtained by the same method as in Example 1 except that eucalyptus wood flour was 13.5 g. The amount of water was 15 times that of the eucalyptus wood flour. As a result of fibrillation treatment, the obtained mixture had low viscosity and was brown and slurry.
  • the rough pulverization of eucalyptus chips for making paper used as the eucalyptus was performed to make 0.2 mm-pass eucalyptus wood flour by the cutter mill, and a sample A (cellulosic material; average width of 50 ⁇ m and average length of 250 ⁇ m) was obtained. No fibrillation treatment was carried out.
  • the samples 1 and 2 were dispersed in 30 ml of water, respectively, followed by measuring a particle size distribution by an aqueous medium circulation cell in a laser diffraction type particle size distribution measuring apparatus (Model LMS-24; manufactured by Seishin Corporation).
  • the obtained measurement results are listed in Table 1.
  • the values listed in Table 1 exhibit the sizes of the light aggregates of the fine fibrous cellulosic materials.
  • sample 2 was put on the sample table of the scanning electron microscope made of aluminum using a double-stick tape, and surface electroconductive treatment was performed by platinum vapor deposition, followed by observation by a scanning electron microscope (S-3400 Model; manufactured by Hitachi High-Technologies Corporation) at an acceleration voltage of 25 kV.
  • S-3400 Model manufactured by Hitachi High-Technologies Corporation
  • the electron microscope photograph of the observation result of the obtained sample 2 is shown in FIG. 1 .
  • Example 1 As shown in FIG. 1 , the fibrous cellulose of from around 100 nm to around 10 nm in the fine part was able to be observed. Further, the observation result of the sample 1 obtained in Example 1 was also similar (not shown).
  • sample 2 and the sample A were evaluated by powder X-ray diffractometry. Specifically, 100 mg of sample 2 and sample A were formed as discoid pellets in a die having a diameter of 13 mm, respectively, and the diffraction patterns were measured with CuK ⁇ radiation at 50 kV-300 mA using a RINT-TTR3 type powder X-ray diffraction apparatus (manufactured by Rigaku Corporation).
  • the enzymatic hydrolysis was carried out using the samples 1, 2 and A. Specifically, the samples 1, 2 and A (50 mg) were suspended in 15 ml of acetate buffer (pH 5.0, 50 mM), respectively. To the suspension was added 2 ml of enzyme solution (enzyme level: 2 mg) prepared by dissolving 50 mg of meicelase (enzyme; manufactured by Meiji Seika Kaisha, Ltd.) in 50 ml of acetate buffer (pH 5.0) to make enzymatic hydrolysis test liquids 1, 2 and A, of which the total amount was 17 ml. Further, the test liquids were set in a dry incubator at 45° C. just after the addition of the enzyme liquid, and the enzymatic hydrolysis was made to proceed at 120 rpm.
  • the glucose concentrations obtained from the samples 1, 2 and A are listed in Table 2.
  • the amounts of glucoses dissolved when suspending the samples in the acetate buffer prior to the charge of the enzyme are shown at enzyme reaction time of 0 hour.
  • the total saccharide concentrations of the samples 1, 2 and A, determined by a phenol-sulfuric acid method, are listed in Table 3.
  • Example 2 Example 1 time (hr) (Sample 1) (Sample 2) (Sample A) 0 6.9 4.9 8.5 1 258.8 211.4 45.8 3 402.4 337.1 48.7 6 444.6 399.2 52.7 12 512.4 425.1 54.4 18 481.5 455.6 58.8 24 466.9 466.5 59.6 36 485.6 454.8 60.0 48 501.8 472.2 60.9
  • the rough pulverization of the Oregon pine chips for making paper was performed to make 0.2 mm-pass Oregon pine wood flour by a cutter mill.
  • the resultant Oregon pine wood flour (2.3 g) was charged into a planetary ball mill pot made of zirconia (internal capacity: 45 ml; P-7 type; manufactured by Fritsch Corporation (Germany)), and seven zirconia balls having a diameter of 10 mm were filled thereinto.
  • the water in the mixture was substituted with t-butylalcohol, and a dried sample 3 (fine fibrous cellulosic material; average width of 0.05 ⁇ m and average length of 15 ⁇ m) was obtained by drying under reduced pressure.
  • a sample 4 (fine fibrous cellulosic material; average width of 0.07 ⁇ m and average length of 10 ⁇ m) was obtained by the same method as in Example 3 except that Oregon pine wood flour was 3.3 g. The amount of water was 7 times that of the Oregon pine wood flour. As a result of fibrillation treatment, the obtained mixture was milky-white and creamy.
  • the rough pulverization of Oregon pine chips for making paper was performed to make 0.2 mm-pass Oregon pine wood flour by the cutter mill, and a sample B (cellulosic material; average width of 50 ⁇ m and average length of 250 ⁇ m) was obtained. No fibrillation treatment was carried out.
  • Particle size distributions were measured by the same method as in Evaluation 1 except that the samples 3 and 4 were used instead of the samples 1 and 2.
  • the electron microscope photograph of the observation result of the obtained sample 4 is shown in FIG. 3 .
  • Example 3 As shown in FIG. 3 , the fibrous cellulose of from around 100 nm to around 10 nm in the fine part was able to be observed. Further, the observation result of the sample 3 obtained in Example 3 was also similar (not shown).
  • Glucose concentrations were calculated by the same method as in Evaluation 4 except that the samples 3, 4 and B were used instead of the samples 1, 2 and A.
  • the amounts of glucoses dissolved when suspending the samples in the acetate buffer prior to the charge of the enzyme are shown at enzyme reaction time of 0 hour.
  • the total saccharide concentrations of the samples 3, 4 and B, determined by a phenol-sulfuric acid method, are listed in Table 6.
  • the rough pulverization of the Oregon pine chips for making paper was performed to make 2 mm-pass Oregon pine wood flour by a cutter mill.
  • the resultant Oregon pine wood flour (13.5 g) was charged into a planetary ball mill pot made of zirconia (internal capacity: 500 ml; manufactured by Fritsch Corporation (Germany)), and 25 zirconia balls having a diameter of 20 mm were filled thereinto.
  • the water in the mixture was substituted with t-butylalcohol, and a dried sample 5 (fine fibrous cellulosic material; average width of 0.08 ⁇ m and average length of 10 ⁇ m) was obtained by drying under reduced pressure.
  • the rough pulverization using Oregon pine chips for making paper was performed to make 2 mm-pass Oregon pine wood flour by the cutter mill, and a sample C (cellulosic material; average width of 1,500 ⁇ m and average length of 3,500 ⁇ m) was obtained. No fibrillation treatment was carried out.
  • Glucose concentrations were calculated by the same method as in Evaluation 4 except that the samples 5 and C were used instead of the samples 1, 2 and A.
  • the glucose concentrations obtained from the samples 5 and C are listed in Table 7.
  • the amounts of glucoses dissolved when suspending the samples in the acetate buffer prior to the charge of the enzyme are shown at enzyme reaction time of 0 hour.
  • the rough pulverization of the Oregon pine chips for making paper was performed to make 0.2 mm-pass Oregon pine wood flour by a cutter mill.
  • the resultant Oregon pine wood flour (2.0 g) was charged into a planetary ball mill pot made of zirconia (internal capacity: 45 ml; manufactured by Fritsch Corporation (Germany)), and seven zirconia balls having a diameter of 10 mm were filled thereinto.
  • water fibrillation material
  • a lid was put on the planetary ball mill pot made of zirconia.
  • ball mill treatment a cycle of treatment at an autorotation speed of 400 rpm for 20 minutes and stop for 10 minutes was repeated six times, and fibrillation treatment was performed for total treatment time of 2 hours to obtain a pale yellow powdered mixture.
  • temperature and pulverization energy which can be applied to the ball in the container of the ball mill were set at 40° C. and 7.8 G at 400 rpm, respectively.
  • the water in the mixture was substituted with t-butylalcohol, and a dried sample 6 having a low aspect ratio (fine fibrous cellulosic material; average width of 0.9 ⁇ m and average length of 3 ⁇ m) was obtained by drying under reduced pressure.
  • a sample 7 (fine fibrous cellulosic material; average width of 0.8 ⁇ m and average length of 5 ⁇ m) was obtained by the same method as in Example 6 except that acetic acid (fibrillation material) was used instead of water.
  • a sample 8 having a low aspect ratio (fine fibrous cellulosic material; average width of 0.9 ⁇ m and average length of 5 ⁇ m) was obtained by the same method as in Example 6 except that polyethylene glycol 400 (molecular weight: 400; PEG 400) (fibrillation material) was used instead of water.
  • a sample 9 having a low aspect ratio (fine fibrous cellulosic material; average width of 1 ⁇ m and average length of 10 ⁇ m) was obtained by the same method as in Example 6 except that 1,4-dioxane (fibrillation material) was used instead of water.
  • a sample 10 having a low aspect ratio (fine fibrous cellulosic material; average width of 1 ⁇ m and average length of 3 ⁇ m) was obtained by the same method as in Example 6 except that dimethyl sulfoxide (DMSO) (fibrillation material) was used instead of water.
  • DMSO dimethyl sulfoxide
  • a sample 11 (fine fibrous cellulosic material; average width of 1 ⁇ m and average length of 3 ⁇ m) was obtained by the same method as in Example 6 except that dimethylacetamide (DMAc) (fibrillation material) was used instead of water.
  • DMAc dimethylacetamide
  • a sample 12 (fine fibrous cellulosic material; average width of 0.9 ⁇ m and average length of 3 ⁇ m) was obtained by the same method as in Example 6 except that ethanol (EtOH) (fibrillation material) was used instead of water.
  • EtOH ethanol
  • Glucose concentrations were calculated by the same method as in Evaluation 4 except that the samples 6 to 12 were used instead of the samples 1, 2 and A.
  • the glucose concentrations obtained from the samples 6 to 12 are listed in Table 8.
  • the amounts of glucoses dissolved when suspending the samples in the acetate buffer prior to the charge of the enzyme are shown at enzyme reaction time of 0 hour.
  • Example 7 Example 8
  • Example 9 time (hr) (Sample 6) (Sample 7) (Sample 8) (Sample 9) 0 5.7 6.5 3.2 3.2 48 1043.8 966.7 614.2 639.3
  • Example 10 Example 11
  • Example 12 time (hr) (Sample 10) (Sample 11) (Sample 12) 0 2.4 4.1 7.7 48 770.7 676.7 655.2
  • a sample 13 (fine fibrous cellulosic material; average width of 0.9 ⁇ m and average length of 3 ⁇ m) was obtained by the same method as in Example 6 except that added water was 30 mass %.
  • a sample 14 (fine fibrous cellulosic material; average width of 1 ⁇ m and average length of 2 ⁇ m) was obtained by the same method as in Example 6 except 30 mass % of glycerin was used instead of water.
  • a sample 15 (fine fibrous cellulosic material; average width of 0.9 ⁇ m and average length of 3 ⁇ m) was obtained by the same method as in Example 6 except 30 mass % of ethylene glycol was used instead of water.
  • Glucose concentrations were calculated by the same method as in Evaluation 4 except that the samples 13 to 15 were used instead of the samples 1, 2 and A.
  • the glucose concentrations obtained from the samples 13 to 15 are listed in Table 9.
  • the amounts of glucoses dissolved when suspending the samples in the acetate buffer prior to the charge of the enzyme are shown at enzyme reaction time of 0 hour.
  • the rough pulverization of the Oregon pine chips for making paper was performed to make 0.2 mm-pass Oregon pine wood flour by a cutter mill.
  • the resultant Oregon pine wood flour (1.5 g) was charged into a planetary ball mill pot made of zirconia (internal capacity: 45 ml; manufactured by Fritsch Corporation (Germany)), and seven zirconia balls having a diameter of 10 mm were filled thereinto.
  • the water in the mixture was substituted with t-butylalcohol, and a dried sample 16 (fine fibrous cellulosic material; average width of 0.05 ⁇ m and average length of 7 ⁇ m) was obtained by drying under reduced pressure.
  • a sample 17 (fine fibrous cellulosic material; average width of 0.07 ⁇ m and average length of 5 ⁇ m) was obtained by the same method as in Example 16 except that methanol (MeOH) (fibrillation material) was used instead of water.
  • MeOH methanol
  • a sample 18 (fine fibrous cellulosic material; average width of 0.07 ⁇ m and average length of 5 ⁇ m) was obtained by the same method as in Example 16 except that ethanol (EtOH) (fibrillation material) was used instead of water.
  • EtOH ethanol
  • a sample 19 (fine fibrous cellulosic material; average width of 0.12 ⁇ m and average length of 5 ⁇ m) was obtained by the same method as in Example 16 except that 1-propanol (1-PrOH) (fibrillation material) was used instead of water.
  • a sample 20 (fine fibrous cellulosic material; average width of 0.3 ⁇ m and average length of 5 ⁇ m) was obtained by the same method as in Example 16 except that 2-propanol (2-PrOH) (fibrillation material) was used instead of water.
  • a sample 21 (fine fibrous cellulosic material; average width of 0.3 ⁇ m and average length of 2 ⁇ m) was obtained by the same method as in Example 16 except that toluene (fibrillation material) was used instead of water.
  • Glucose concentrations were calculated by the same method as in Evaluation 4 except that the samples 16 to 21 were used instead of the samples 1, 2 and A.
  • the glucose concentrations obtained from the samples 16 to 21 are listed in Table 10.
  • the amounts of glucoses dissolved when suspending the samples in the acetate buffer prior to the charge of the enzyme are shown at enzyme reaction time of 0 hour.
  • Example 17 Example 18 time (hr) (Sample 16) (Sample 17) (Sample 18) 0 0.0 8.1 2.0 48 958.2 1071.4 919.3 Enzyme Glucose concentration (mg/L) reaction Example 19
  • Example 20 Example 21 time (hr) (Sample 19) (Sample 20) (Sample 21) 0 2.8 3.2 6.1 48 604.4 468.5 997.9
  • a sample 22 (fine fibrous cellulosic material; average width of 0.15 ⁇ m and average length of 10 ⁇ m) was obtained by the same method as in Example 16 except that 23 ml of aqueous solution of 20 wt % polyethylene glycol 400 (molecular weight: 400; PEG 400) was used instead of water.
  • a sample 23 (fine fibrous cellulosic material; average width of 0.05 ⁇ m and average length of 10 ⁇ m) was obtained by the same method as in Example 16 except that 23 ml of aqueous solution of 20 wt % acetic acid was used instead of water.
  • a sample 24 (fine fibrous cellulosic material; average width of 0.2 ⁇ m and average length of 20 ⁇ m) was obtained by the same method as in Example 16 except that 23 ml of aqueous solution of 20 wt % 1,4-dioxane was used instead of water.
  • a sample 25 (fine fibrous cellulosic material; average width of 0.1 ⁇ m and average length of 10 ⁇ m) was obtained by the same method as in Example 16 except that 23 ml of aqueous solution of 20 wt % dimethyl sulfoxide (DMSO) was used instead of water.
  • DMSO dimethyl sulfoxide
  • Glucose concentrations were calculated by the same method as in Evaluation 4 except that the samples 22 to 25 were used instead of the samples 1, 2 and A.
  • a cellulosic material 1.5 g of purified wood pulp W-100 (manufactured by Nippon Paper Chemicals Co., Ltd.) was charged into a planetary ball mill pot made of zirconia (internal capacity: 45 ml; manufactured by Fritsch Corporation (Germany)), and seven zirconia balls having a diameter of 10 mm were filled thereinto.
  • the water in the mixture was substituted with t-butylalcohol, and a dried sample 26 (fine fibrous cellulosic material; average width of 0.05 ⁇ m and average length of 10 ⁇ m) was obtained by drying under reduced pressure.
  • the above-mentioned purified pulp (W-100) was subjected to various types of chemical treatment and pulverization treatment in a production step and therefore fibrillated to some extent.
  • a sample 27 (fine fibrous cellulosic material; average width of 0.1 ⁇ m and average length of 7 ⁇ m) was obtained by the same method as in Example 26 except that ethanol (EtOH) was used instead of water.
  • a sample 28 (fine fibrous cellulosic material; average width of 0.05 ⁇ m and average length of 15 ⁇ m) was obtained by the same method as in Example 26 except that CF 11 (manufactured by Whatman) was used instead of W-100.
  • a sample 29 (fine fibrous cellulosic material; average width of 0.1 ⁇ m and average length of 10 ⁇ m) was obtained by the same method as in Example 28 except that ethanol (EtOH) was used instead of water.
  • Glucose concentrations were calculated by the same method as in Evaluation 4 except that the samples 26 to 29 were used instead of the samples 1, 2 and A.
  • the glucose concentrations obtained from the samples 26 to 29 are listed in Table 12.
  • the amounts of glucoses dissolved when suspending the samples in the acetate buffer prior to the charge of the enzyme are shown at enzyme reaction time of 0 hour.
  • the rough pulverization of eucalyptus chips for making paper used as cellulosic materials was performed to make 0.2 mm-pass eucalyptus wood flour by a cutter mill.
  • the resultant eucalyptus wood flour (1.5 g) was charged into a planetary ball mill pot made of zirconia (internal capacity: 45 ml; manufactured by Fritsch Corporation (Germany)), and seven zirconia balls having a diameter of 10 mm were filled thereinto.
  • a sample D was obtained by the same method as in Example 30 except that no meicelase (enzyme) was used.
  • a sample 31 was obtained by the same method as in Example 30 except that Oregon pine wood flour was used instead of the eucalyptus chips for making paper.
  • a sample E was obtained by the same method as in Example 31 except that no meicelase (enzyme) was used.
  • the glucose concentration of each of the samples 30, 31, D and E was measured after 33 hours. Specifically, 200 ⁇ L was taken out of each of the samples 30, 31, D and E (which were slurry or creamy), the supernatants after centrifugation were colored by Glucose Test Wako (manufactured by Wako Pure Chemical Industries, Ltd.), and the absorbances were measured using a spectrophotometer. Glucose concentrations were calculated, based on a previously prepared calibration curve, from the obtained absorbances.
  • the glucose concentrations obtained from the samples 30, 31, D and E are listed in Table 13.
  • the rough pulverization was performed to make 0.2 mm-pass eucalyptus wood flour by a cutter mill. Furthermore, the preliminary dry pulverization of the eucalyptus wood flour was carried out for 20 minutes to make the powdered fine cellulosic material.
  • the water in the mixture was substituted with t-butylalcohol, and a dried sample 32 (fine fibrous cellulosic material; width of 0.05 ⁇ m and length of 5 ⁇ m) was obtained by drying under reduced pressure.
  • a sample 33 (fine fibrous cellulosic material; average width of 0.03 ⁇ m and average length of 5 ⁇ m) was obtained by the same method as in Example 32 except that Oregon pine wood flour was used instead of the eucalyptus chips for making paper.
  • Glucose concentrations were calculated by the same method as in Evaluation 4 except that the samples 32 and 33 were used instead of the samples 1, 2 and A.
  • the glucose concentrations obtained from the samples 32 and 33 are listed in Table 14.
  • the amounts of glucoses dissolved when suspending the samples in the acetate buffer prior to the charge of the enzyme are shown at enzyme reaction time of 0 hour.
  • the rough pulverization of the Oregon pine chips for making paper as cellulosic materials was performed to make 3 mm-pass Oregon pine wood flour by a cutter mill.
  • the resultant Oregon pine wood flour 500 g was dispersed in 10 L of water, the dispersed substance was charged into Super Masscolloider (disk mill; disk material: silicon carbide; disk diameter: 10 inches; disk rotation number: 1,800 rpm; disk spacing: 200 ⁇ m; manufactured by Masuko Sangyo Co., Ltd.), and the fibrillation treatment was carried out for two minutes. Such fibrillation treatment was repeated five times (accumulated total treatment time: 10 minutes) to obtain a brown slurry mixture.
  • temperature was set at 45° C.
  • the water in the mixture was substituted with t-butylalcohol, and a dried sample 34 (fine fibrous cellulosic material; average width of 0.15 ⁇ m and average length of 15 ⁇ m) was obtained by drying under reduced pressure.
  • a sample 35 (fine fibrous cellulosic material; average width of 0.1 ⁇ m and average length of 10 ⁇ m) was obtained by the same method as in Example 34 except that the fibrillation treatment was carried out ten times (accumulated total treatment time: 20 minutes).
  • the rough pulverization using Oregon pine chips for making paper was performed to make 3 mm-pass Oregon pine wood flour by a cutter mill, and a sample F (fine fibrous cellulosic material; average width of 3,200 ⁇ m and average length of 3,200 ⁇ m) was obtained. No fibrillation treatment was carried out.
  • the electron microscope photograph of the observation result of the obtained sample 35 is shown in FIG. 4 .
  • Example 34 As shown in FIG. 4 , the fibrous cellulose of from around 100 nm to around 10 nm in the fine part was able to be observed. Further, the observation result of the sample 34 obtained in Example 34 was also similar (not shown).
  • Glucose concentrations were calculated by the same method as in Evaluation 4 except that the samples 34, 35 and F were used instead of the samples 1, 2 and A.
  • the glucose concentrations obtained from the samples 34, and F are listed in Table 15.
  • the amounts of glucoses dissolved when suspending the samples in the acetate buffer prior to the charge of the enzyme are shown at enzyme reaction time of 0 hour.
  • the rough pulverization of the Oregon pine chips for making paper as cellulosic materials was performed to make 2 mm-pass Oregon pine wood flour by a cutter mill.
  • the resultant Oregon pine wood flour (100 g) was mixed with ethylene glycol (200 g), and the mixture was charged into a twin-screw extruder (Labo-Prastomill; manufactured by Toyo Seiki Seisaku-Sho, Ltd.), where a twin-screw multiple-thread flight type 2D20S was used as the screw.
  • the fibrillation treatment was carried out by continuous extrusion at a speed of 30 rpm, and about 20 g of mixture was thus obtained for 10 minutes.
  • the water in the mixture was substituted with t-butylalcohol, and a dried sample 36 (fine fibrous cellulosic material; average width of 0.08 ⁇ m and average length of 10 ⁇ m) was obtained by drying under reduced pressure.
  • a sample 37 (fine fibrous cellulosic material) was obtained by the same method as in Example 36 except that W-100 was used instead of the Oregon pine wood flour.
  • a sample G (fine fibrous cellulosic material) was obtained by the same method as in Example 36 except that no fibrillation treatment was carried out.
  • a sample H fine fibrous cellulosic material was obtained by the same method as in Example 37 except that no fibrillation treatment was carried out.
  • the electron microscope photograph of the observation result of the obtained sample 36 is shown in FIG. 5 .
  • the fibrous cellulose of from around 100 nm to around 10 nm in the fine part was able to be observed.
  • Glucose concentrations were calculated by the same method as in Evaluation 4 except that the samples 36, 37, G and H were used instead of the samples 1, 2 and A.
  • the glucose concentrations obtained from the samples 36, 37, G and H are listed in Table 16.
  • Example 36 The comparison between Example 36 and Reference Example 3 reveals that the enzymatic hydrolysis hardly proceeded in the sample G of Reference Example 3 whereas the amount of generated glucose was increased and the effect of improvement in enzymatic hydrolyzability was observed in the sample 36 of Example 36.
  • Example 37 Similarly, the comparison between Example 37 and Reference Example 4 reveals that the enzymatic hydrolysis proceeded to some extent in the sample H of Reference Example 4 whereas the amount of generated glucose was further increased and the effect of improvement in enzymatic hydrolyzability was observed in the sample 37 of Example 37.
  • the rough pulverization of the Oregon pine chips for making paper as cellulosic materials was performed to make 2 mm-pass Oregon pine wood flour by a cutter mill.
  • the resultant Oregon pine wood flour (100 g) was mixed with polyethylene glycol (5 g; molecular weight: 20,000), and the mixture was charged into a twin-screw extruder (Labo-Prastomill), where a twin-screw multiple-thread flight type 2D20S was used as the screw.
  • the fibrillation treatment was carried out once at a temperature increased to 120° C. by continuous extrusion at a speed of 50 rpm, and about 30 g of mixture was thus obtained for 10 minutes.
  • the water in the mixture was substituted with t-butylalcohol, and a dried sample 38 (fine fibrous cellulosic material; average width of 0.3 ⁇ m and average length of 15 ⁇ m) was obtained by drying under reduced pressure.
  • a sample 39 (fine fibrous cellulosic material; average width of 0.2 ⁇ m and average length of 15 ⁇ m) was obtained by the same method as in Example 38 except that the fibrillation treatment was carried out twice.
  • Glucose concentrations were calculated by the same method as in Evaluation 4 except that the samples 38 and 39 were used instead of the samples 1, 2 and A.
  • the glucose concentrations obtained from the samples 38 and 39 are listed in Table 17.
  • the rough pulverization of eucalyptus chips for making paper used as cellulosic materials was performed to make 0.2 mm-pass eucalyptus wood flour by a cutter mill.
  • the resultant eucalyptus wood flour (1.5 g) was charged into a planetary ball mill pot made of zirconia (internal capacity: 45 ml), and seven zirconia balls having a diameter of 10 mm were filled thereinto.
  • aqueous solution of sodium hydroxide (2 wt %) was added as a medium, and a lid was put on the planetary ball mill pot made of zirconia.
  • ball mill treatment a cycle of treatment at an autorotation speed of 200 rpm for 20 minutes and stop for 10 minutes was repeated 100 times, and fibrillation treatment was performed for total treatment time of 33 hours to obtain a brown, creamy mixture.
  • temperature and pulverization energy which can be applied to the ball in the container of the ball mill were set at 40° C. and 1.8 G, respectively.
  • the water in the mixture was substituted with t-butylalcohol, and a dried sample 40 (fine fibrous cellulosic material; average width of 0.06 ⁇ m and average length of 10 ⁇ m) was obtained by drying under reduced pressure.
  • a sample 41 (fine fibrous cellulosic material; average width of 0.07 ⁇ m and average length of 10 ⁇ m) was obtained by the same method as in Example 40 except that an aqueous solution of lithium hydroxide was used instead of the aqueous solution of sodium hydroxide.
  • a sample 42 (fine fibrous cellulosic material; average width of 0.04 ⁇ m and average length of 15 ⁇ m) was obtained by the same method as in Example 40 except that Oregon pine wood flour was used instead of the eucalyptus wood flour.
  • a sample 43 (fine fibrous cellulosic material; average width of 0.05 ⁇ m and average length of 15 ⁇ m) was obtained by the same method as in Example 42 except that an aqueous solution of lithium hydroxide was used instead of the aqueous solution of sodium hydroxide.
  • Glucose concentrations were calculated by the same method as in Evaluation 4 except that the samples 40 to 43 were used instead of the samples 1, 2 and A.
  • the glucose concentrations obtained from the samples 40 to 43 are listed in Table 18.
  • the amounts of glucoses dissolved when suspending the samples in the acetate buffer prior to the charge of the enzyme are shown at enzyme reaction time of 0 hour.
  • Example 41 Example 42
  • Example 43 time(hr) (Sample 40) (Sample 41) (Sample 42) (Sample 43) 0 8.9 0.8 0.4 2.0 48 953.3 946.0 1130.6 1118.0
  • the rough pulverization of eucalyptus chips for making paper used as cellulosic materials was performed to make 0.2 mm-pass eucalyptus wood flour by a cutter mill.
  • the resultant eucalyptus wood flour (13.5 g) was charged into a planetary ball mill pot made of zirconia (internal capacity: 500 ml), and 25 zirconia balls having a diameter of 20 mm were filled thereinto.
  • the water in the mixture was substituted with t-butylalcohol, and a dried sample 44 (fine fibrous cellulosic material; average width of 0.04 ⁇ m and average length of 7 ⁇ m) was obtained by drying under reduced pressure.
  • Example 44 The mixture obtained in Example 44 was used as a sample 45 (fine fibrous cellulosic material; average width of 0.04 ⁇ m and average length of 7 ⁇ m) without being processed, without being washed or dried.
  • a sample 46 (fine fibrous cellulosic material; average width of 0.05 ⁇ m and average length of 15 ⁇ m) was obtained by the same method as in Example 44 except that Oregon pine wood flour was used instead of the eucalyptus wood flour.
  • Example 46 The mixture obtained in Example 46 was used as a sample 47 (fine fibrous cellulosic material; average width of 0.05 ⁇ m and average length of 15 ⁇ m) without being processed, without being washed or dried.
  • Glucose concentrations were calculated by the same method as in Evaluation 4 except that the samples 44 to 47 were used instead of the samples 1, 2 and A.
  • the glucose concentrations obtained from the samples 44 to 47 are listed in Table 19.
  • the amounts of glucoses dissolved when suspending the samples in the acetate buffer prior to the charge of the enzyme are shown at enzyme reaction time of 0 hour.
  • FIGS. 6 ( a ) and ( b ) are cross-sectional pictures for explaining the kneading portions of the small segment mixer.
  • the small segment mixer 10 has the system of applying high shearing force and pressure to contents to open by the rotation of segment-type screws 2 in the same direction in the kneading portion 1 .
  • the cellulosic material can be fibrillated to a nano-scale in water.
  • FIG. 7 ( a ) shows a front view of the segment-type screw and FIG. 7 ( b ) shows a side view of the segment-type screw.
  • the segment-type screw 2 is capable of applying high shearing force by combining six segment blades overlapped by 22.5 degrees each. There are such combinations of various angles and shapes, which combinations are not limited to the combination shown in the figure.
  • the mixture obtained by the fibrillation treatment was not washed or dried but was used as a sample 48 without being processed.
  • Glucose concentrations were calculated by the same method as in Evaluation 4 except that the samples 48 and I were used instead of the samples 1, 2 and A.
  • the glucose concentrations obtained from the samples 48 and I are listed in Table 20.
  • the electron microscope photograph of the observation result of the obtained sample 48 is shown in FIG. 8 .
  • the rough pulverization of eucalyptus chips for making paper used as a cellulosic material was performed to make 0.2 mm-pass eucalyptus wood flour by a cutter mill.
  • the resultant eucalyptus wood flour (1.5 g) was immersed in 23 ml of water, left to stand for 24 hours, and then treated using an autoclave for sterilization at 121° C. for 60 minutes.
  • This treated product was left to stand to room temperature, the total amount thereof was then charged into a planetary ball mill pot made of zirconia (internal capacity: 45 ml; manufactured by Fritsch Corporation (Germany)), seven zirconia balls having a diameter of 10 mm were filled thereinto, and a lid was put on the planetary ball mill pot.
  • a cycle of treatment at an autorotation speed of 400 rpm for 20 minutes and stop for 10 minutes was repeated six times, and fibrillation treatment was performed for total treatment time of 2 hours to obtain a brown, creamy mixture having a comparatively high flowability.
  • temperature and pulverization energy which can be applied to the ball in the container of the ball mill were set at 40° C. and 7.8 G at 400 rpm, respectively.
  • the water in the mixture was substituted with t-butylalcohol, and a dried sample 49 (fine fibrous cellulosic material; average width of 0.04-0.09 ⁇ m and average length of 3-7 ⁇ m) was obtained by drying under reduced pressure.
  • a sample 50 (fine fibrous cellulosic material; average width of 0.04-0.09 ⁇ m and average length of 3-7 ⁇ m) was obtained by the same method as in Example 49 except that treatment time with the autoclave for sterilization was set at 240 minutes.
  • a sample 51 (fine fibrous cellulosic material; average width of 0.04-0.09 ⁇ m and average length of 3-7 ⁇ m) was obtained by the same method as in Example 49 except that treatment temperature with the autoclave for sterilization was set at 135° C.
  • a sample 52 (fine fibrous cellulosic material; average width of 0.04-0.09 ⁇ m and average length of 3-7 ⁇ m) was obtained by the same method as in Example 51 except that treatment time with the autoclave for sterilization was set at 240 minutes.
  • a sample J was obtained by the same method as in Example 49 except that treatment with the autoclave for sterilization was carried out, followed by performing no fibrillation treatment.
  • a sample K was obtained by the same method as in Example 50 except that treatment with the autoclave for sterilization was carried out, followed by performing no fibrillation treatment.
  • a sample L was obtained by the same method as in Example 51 except that treatment with the autoclave for sterilization was carried out, followed by performing no fibrillation treatment.
  • a sample M was obtained by the same method as in Example 52 except that treatment with the autoclave for sterilization was carried out, followed by performing no fibrillation treatment.
  • Glucose concentrations were calculated by the same method as in Evaluation 4 except that the samples 49-52 and J-M were used instead of the samples 1, 2 and A.
  • Enzyme reaction time 0 hour indicates the amount of glucose dissolved when suspending a sample in an acetate buffer prior to charging an enzyme.
  • Example 50 Example 52 time(hr) (Sample 49) (Sample 50) (Sample 51) (Sample 52) 0 31.4 19.9 3.6 5.3 48 540.6 605.7 1020.7 1301.2
  • the rough pulverization of straw as a cellulosic material was performed to make 3 mm-pass by a cutter mill.
  • the resultant pulverized crude straw product (1.5 g) together with 23 ml of water was charged into a planetary ball mill pot made of zirconia (internal capacity: 45 ml; manufactured by Fritsch Corporation (Germany)), seven zirconia balls having a diameter of 10 mm were filled thereinto, and a lid was put on the planetary ball mill pot.
  • a cycle of treatment at an autorotation speed of 400 rpm for 20 minutes and stop for 10 minutes was repeated six times, and fibrillation treatment was performed for total treatment time of 2 hours to obtain a brown, creamy mixture having a comparatively high flowability.
  • temperature and pulverization energy which can be applied to the ball in the container of the ball mill were set at 40° C. and 7.8 G at 400 rpm, respectively.
  • the water in the mixture was substituted with t-butylalcohol, and a dried sample 53 (fine fibrous cellulosic material; average width of 0.05 ⁇ m and average length of 6 ⁇ m) was obtained by drying under reduced pressure.
  • a sample 54 (fine fibrous cellulosic material; average width of 0.04 ⁇ m and average length of 4 ⁇ m) was obtained by the same method as in Example 53 except that straw subjected to rough pulverization to 0.2 mm-pass by a cutter mill was used.
  • Glucose concentrations were calculated by the same method as in Evaluation 4 except that the samples 53 and 54 were used instead of the samples 1, 2 and A.
  • Enzyme reaction time 0 hour indicates the amount of glucose dissolved when suspending a sample in an acetate buffer prior to charging an enzyme.
  • the rough pulverization of eucalyptus chips for making paper used as a cellulosic material was performed to make 3 mm-pass eucalyptus wood flour by a cutter mill.
  • the resultant eucalyptus wood flour (about 1 kg) was immersed in 10 L of water, left to stand for 24 hours, and then treated using an autoclave for sterilization at 135° C. for 240 minutes.
  • This treated product was left to stand to room temperature, water was added so that a solid content concentration of the eucalyptus wood flour was 5 mass %, 20 L of resultant dispersion was charged into Super Masscolloider (disk mill; disk material: silicon carbide; disk diameter: 10 inches; disk rotation number: 1,800 rpm; disk spacing: 200 ⁇ m; manufactured by Masuko Sangyo Co., Ltd.), and the fibrillation treatment was carried out for 4 minutes to obtain a brown slurry mixture. As the condition of the fibrillation treatment, temperature was set at 45° C.
  • the water in the mixture was substituted with t-butylalcohol, and a dried sample 55 (fine fibrous cellulosic material; average width of 0.1 ⁇ m and average length of 10 ⁇ m) was obtained by drying under reduced pressure.
  • a sample 56 (fine fibrous cellulosic material; average width of 0.1 ⁇ m and average length of 10 ⁇ m) was obtained by the same method as in Example 55 except that fibrillation treatment was repeated ten times (accumulated total treatment time: 40 minutes).
  • a sample 57 (fine fibrous cellulosic material; average width of 0.15 ⁇ m and average length of 15 ⁇ m) was obtained by the same method as in Example 55 except that the rough pulverization of eucalyptus chips for making paper was performed to make 0.2 mm-pass eucalyptus wood flour by a cutter mill and no treatment using the autoclave for sterilization was carried out.
  • a sample 58 (fine fibrous cellulosic material; average width of 0.15 ⁇ m and average length of 15 ⁇ m) was obtained by the same method as in Example 57 except that fibrillation treatment was repeated ten times (accumulated total treatment time: 40 minutes).
  • Glucose concentrations were calculated by the same method as in Evaluation 4 except that the samples 55-58 were used instead of the samples 1, 2 and A.
  • Enzyme reaction time 0 hour indicates the amount of glucose dissolved when suspending a sample in an acetate buffer prior to charging an enzyme.
  • the rough pulverization of straw as a cellulosic material was performed to make 3 mm-pass by a cutter mill.
  • the resultant pulverized crude straw product (1.5 g) together with 23 ml of water was charged into a planetary ball mill pot made of zirconia (internal capacity: 45 ml; manufactured by Fritsch Corporation (Germany)), and 25 zirconia balls having a diameter of 20 mm were filled thereinto.
  • a sample 60 was obtained by the same method as in Example 59 except that the heat treatment with the heater was performed for 60 minutes.
  • Glucose concentrations were calculated by the same method as in Evaluation 4 except that the samples 59 and 60 were used instead of the samples 1, 2 and A.
  • Enzyme reaction time 0 hour indicates the amount of glucose dissolved when suspending a sample in an acetate buffer prior to charging an enzyme.
  • twin-screw extruder (Labo-Prastomill; manufactured by Toyo Seiki Seisaku-Sho, Ltd.), where a twin-screw multiple-thread flight type 2D20S was used as the screw.
  • the twin-screw extruder was continuously operated at the rate of 30 rpm at room temperature.
  • the mixture was then taken out of the twin-screw extruder and 50 mg on a solid content basis was put in 15 ml of acetate buffer solution, and a solution in which 2 mg of cellulase (trade name: meicelase; manufactured by Meiji Seika Kaisha, Ltd.) was dissolved in 2 ml of acetate buffer solution was further added, and enzymatic hydrolysis (saccharification) was performed at 45° C. for 48 hours to obtain a sample 61.
  • cellulase trade name: meicelase; manufactured by Meiji Seika Kaisha, Ltd.
  • Switchgrass subjected to rough pulverization to 0.2 mm-pass was used as a sample O.
  • saccharides were identified using high performance liquid chromatograph (LC-2000 Puls HPLC System made by JASCO Corporation; sample injection rate: 20 ⁇ l; detection: refractive index detector; column: Aminex HPX-87P (Bio-Rad); column temperature: 80° C.; flow rate: 1.0 ml/min), and the concentrations of the respective saccharides were quantified from calibration curves made using preparations.
  • LC-2000 Puls HPLC System made by JASCO Corporation
  • sample injection rate 20 ⁇ l
  • detection refractive index detector
  • column Aminex HPX-87P (Bio-Rad)
  • column temperature 80° C.
  • flow rate 1.0 ml/min
  • Glucose concentrations were calculated by the same method as in Evaluation 4 except that the samples 61 and O were used instead of the samples 1, 2 and A.
  • the glucose concentrations obtained from the samples 61 and O are listed in Table 27.
  • the xylose concentrations obtained from the samples 61 and O are listed in Table 28.
  • the fine fibrous cellulosic material of the present invention was confirmed to allow the production of a saccharide in a high yield by hydrolysis.
  • the fine fibrous cellulose of the present invention can be used not only in the production of a saccharide or ethanol from the saccharide but also as a high-strength material by conjugated as a filler to a resin or the like because of having extremely high strength in terms of a molecular structure.
  • the fine fibrous cellulose can be also converted into a high-strength material without being processed, without any operation such as the use of an adhesive or the chemical denaturalization of the fine fibrous cellulose, because of having strong self-cohesive power.
  • the fine fibrous cellulose is a natural product, has neither taste nor odor, is atoxic, has fine fibers and therefore offers no foreign body feeling on the tongue, the fine fibrous cellulose can be added to a food product to be imparted with water retentivity, oil retentivity, texture, morphological stability or dietetic properties.
  • FIG. 1 is a scanning electron micrograph of a sample 2 obtained in Example 2.
  • FIG. 2 is a graph illustrating diffraction patterns prepared by measuring the crystallinities of the sample 2 obtained in Example 2 and the sample A obtained in Comparative Example 1 by powder X-ray diffractometry.
  • FIG. 3 is a scanning electron micrograph of a sample 4 obtained in Example 4.
  • FIG. 4 is a scanning electron micrograph of a sample 35 obtained in Example 35.
  • FIG. 5 is a scanning electron micrograph of a sample 36 obtained in Example 36.
  • FIGS. 6 ( a ) and ( b ) are cross-sectional pictures for explaining the kneading portions of the small segment mixer used in Example 48.
  • FIG. 7 ( a ) is a front view illustrating the segment-type screw used in Example 48; and FIG. 7 ( b ) is a side view of the segment-type screw.
  • FIG. 8 is a scanning electron micrograph of the sample 48 obtained in Example 48.

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