WO2023171748A1 - Matériau à base de cellulose - Google Patents

Matériau à base de cellulose Download PDF

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Publication number
WO2023171748A1
WO2023171748A1 PCT/JP2023/009057 JP2023009057W WO2023171748A1 WO 2023171748 A1 WO2023171748 A1 WO 2023171748A1 JP 2023009057 W JP2023009057 W JP 2023009057W WO 2023171748 A1 WO2023171748 A1 WO 2023171748A1
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Prior art keywords
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cellulose
usually
ppm
cellulose material
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PCT/JP2023/009057
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English (en)
Japanese (ja)
Inventor
薫 佐治
敦 小野
Original Assignee
日本製紙株式会社
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Priority claimed from JP2022037771A external-priority patent/JP2023132440A/ja
Priority claimed from JP2022037772A external-priority patent/JP2023132441A/ja
Application filed by 日本製紙株式会社 filed Critical 日本製紙株式会社
Publication of WO2023171748A1 publication Critical patent/WO2023171748A1/fr

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Classifications

    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K47/00—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient
    • A61K47/30—Macromolecular organic or inorganic compounds, e.g. inorganic polyphosphates
    • A61K47/36—Polysaccharides; Derivatives thereof, e.g. gums, starch, alginate, dextrin, hyaluronic acid, chitosan, inulin, agar or pectin
    • A61K47/38—Cellulose; Derivatives thereof
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
    • C08L1/02—Cellulose; Modified cellulose
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L21/00—Compositions of unspecified rubbers

Definitions

  • the present invention relates to cellulose materials.
  • Cellulose materials such as powdered cellulose are used as reinforcing agents for resin materials such as rubber and plastics (for example, Patent Document 1).
  • the present invention has been made in view of the above, and provides a cellulose material that has good recyclability even when used as an additive for a resin component, and a cellulose material that has excellent recyclability and tabletability.
  • the purpose is to
  • the present invention provides [1] to [17].
  • a cellulose material in which the amount of iron component detected by a triple quadrupole-inductively coupled plasma mass spectrometer is 1 to 50 ppm.
  • the cellulose material according to [1], wherein the amount of iron component detected by a triple quadrupole-inductively coupled plasma mass spectrometer is more than 10 ppm and less than 50 ppm.
  • the cellulose material according to [1] or [2], wherein the ash content after heating at 800° C. for 2 hours is 0.13% by weight or more based on 100% by weight of the cellulose material before heating.
  • a rubber composition comprising the cellulose material according to any one of [1] to [11].
  • a molded article comprising the cellulose material according to any one of [1] to [11].
  • the molded article according to [16] which has a hardness of 30 to 100 MPa.
  • the present invention also provides the following [1-1] to [1-10].
  • [1-1] A cellulose material in which the amount of iron component detected by a triple quadrupole-inductively coupled plasma mass spectrometer is more than 10 ppm and less than 50 ppm.
  • [1-2] The cellulose material according to [1-1], wherein the ash content after heating at 800° C. for 2 hours is 0.13% by weight or more based on 100% by weight of the cellulose material before heating.
  • the cellulose material according to [1-1] or [1-2] which has a thermogravimetric residual rate at 500° C. of 10% or more.
  • [1-5] The cellulose material according to any one of [1-1] to [1-4], which is powdered cellulose.
  • [1-6] The cellulose material according to [1-5], wherein the powdered cellulose has an average particle diameter of 5.0 to 150.0 ⁇ m.
  • [1-8] A resin composition containing the cellulose material according to any one of [1-1] to [1-6].
  • [1-9] A rubber composition comprising the cellulose material according to any one of [1-1] to [1-6].
  • [1-10] A molded article comprising the cellulose material according to any one of [1-1] to [1-6].
  • the present invention further provides the following [2-1] to [2-10].
  • [2-1] Powdered cellulose having an average particle diameter of 5.0 to 150.0 ⁇ m and an amount of iron component detected by a triple quadrupole-inductively coupled plasma mass spectrometer of 1 to 10 ppm.
  • [2-2] The powdered cellulose according to [2-1], wherein the ash content after heating at 800° C. for 2 hours is 1.0% by weight or less based on 100% by weight of the powdered cellulose before heating.
  • [2-3] The powdered cellulose according to [2-1] or [2-2], which has a thermogravimetric residual rate at 400°C of 10 to 20%.
  • thermogravimetric residual rate a cellulose material that can exhibit a high thermogravimetric residual rate and has good recyclability as a biomass material when mixed with a resin.
  • powdered cellulose that can exhibit a high thermogravimetric residual rate, has excellent recyclability as a biomass material when mixed with resin, and has excellent tabletability.
  • a cellulose material is a material whose main component is cellulose and contains an iron component.
  • Iron component Cellulosic materials contain iron components.
  • the iron component may be bound to the cellulose molecules of the cellulose material, or may be present separately without being bound (it can also be said to be a composition containing the cellulose material).
  • Iron components usually exist as iron atoms, compounds and derivatives containing iron atoms.
  • iron atoms Fe
  • oxides Fe 2 O 3 , Fe 3 O 4
  • hydroxides Fe(OH) 2 , Fe(OH) 3
  • oxyhydroxides FeO( OH)
  • chlorides FeCl 2 , FeCl 3
  • nitrates Fe(NO) 3
  • sulfates FeSO 4 , Fe 2 (SO 4 ) 3
  • halides Br, I
  • complex compounds The main component is usually an oxide.
  • the iron component content is a value detected by a triple quadrupole-inductively coupled plasma (ICP) mass spectrometer. Specifically, it can be measured under the following conditions, and the values in Examples are also the values measured by the following method. Note that when the iron component is other than iron atoms, the amount of iron component represents the amount of iron atoms.
  • the amount of iron component in the cellulose material is usually 1 ppm or more, preferably 1.3 ppm or more or 1.5 ppm or more, more preferably 1.6 ppm or more or 1.7 ppm or more. Thereby, the effect of containing the iron component can be efficiently exhibited.
  • the upper limit is usually 50 ppm or less, preferably 40 ppm or less, more preferably 29 ppm or less, 28 ppm or less, 27 ppm or less, or 26 ppm or less. Thereby, it is possible to suppress the contamination of foreign matter into the resin during recycling. Therefore, the amount of iron component is usually 1 to 50 ppm, preferably 1.3 to 40 ppm, more preferably 1.5 to 29 ppm, 1.5 to 28 ppm, 1.6 to 27 ppm, or 1.7 to 26 ppm. be.
  • the amount of iron component in the cellulose material is usually more than 10 ppm, preferably 10.5 ppm or more, more preferably 11 ppm or more, so that the thermogravimetric residual rate is high and the recyclability of the biomass material when mixed with resin is improved. An excellent cellulose material can be obtained.
  • the upper limit is usually 50 ppm or less, preferably 40 ppm or less, more preferably 30 ppm or less, still more preferably 29 ppm or less, 28 ppm or less, 27 ppm or less, or 26 ppm or less. Thereby, it is possible to suppress the contamination of foreign matter into the resin during recycling.
  • the iron component content of the cellulose material is usually more than 10 ppm and less than 50 ppm, more preferably more than 10 ppm and less than 40 ppm, still more preferably 10.5 to 30 ppm, even more preferably 11 to 29 ppm, 11 to 28 ppm. , 11 to 27 ppm, or 11 to 26 ppm.
  • the amount of iron component in the cellulose material is usually 1 ppm or more, preferably 1.3 ppm or more, more preferably 1.5 ppm or more, 1.6 ppm or more, or 1.7 ppm or more, so that the thermogravimetric residual rate is high, It can improve the recyclability of biomass materials when mixed with resin, and prevents the frictional force on the tablet surface from becoming excessively strong when tabletting cellulose materials (e.g., powdered cellulose), making them less likely to break. You can get tablets.
  • the upper limit is usually 10 ppm or less, preferably 7 ppm or less, more preferably 5 ppm or less, still more preferably 4 ppm or less, 3.8 ppm or less, 3.6 ppm or less, or 3.5 ppm or less.
  • the powdered cellulose can be made into tablets. Therefore, the iron content of the powdered cellulose is preferably 1 to 10 ppm, more preferably 1 to 7 ppm, even more preferably 1.3 to 5 ppm, even more preferably 1.5 to 4 ppm, and 1.6 to 3 ppm. .8 ppm, 1.7 to 3.6 ppm, or 1.7 to 3.5 ppm.
  • the amount of iron component can be adjusted by the amount of iron component contained in the raw material and the amount of iron component mixed during manufacturing.
  • the cellulosic material contains ash after heating at 800°C for 2 hours.
  • Ash is usually a component other than organic matter that remains after the raw material is ashed.
  • the ash content after heating is usually 0.05% by weight or more, preferably 0.07% by weight or more, based on 100% by weight of the cellulose material before heating. This makes it possible to obtain a cellulose material with a high thermogravimetric residual rate and excellent recyclability of the biomass material when mixed with resin.
  • the upper limit is usually 2.0% by weight or less, preferably 1.6% by weight. Thereby, it is possible to suppress the contamination of foreign matter into the resin during recycling. Therefore, the ash content is usually 0.05 to 2.0% by weight, preferably 0.07 to 1.6% by weight.
  • the ash content after heating is preferably 0.13% by weight or more or 0.14% by weight based on 100% by weight of the cellulose material before heating.
  • the content is more preferably 0.15% by weight or more.
  • the upper limit is preferably 2.0% by weight or less, more preferably 1.6% by weight or less.
  • the ash content is preferably 0.13 to 2.0% by weight or 0.14 to 2.0% by weight, more preferably 0.15 to 1.6% by weight.
  • the ash content after heating is preferably 1.0% by weight or less or 0.5% by weight based on 100% by weight of the powdered cellulose before heating. It is 5% by weight or less, more preferably 0.3% by weight or less or 0.15% by weight or less. Thereby, the powdered cellulose can be made into tablets.
  • the lower limit is preferably 0.05% by weight or more or 0.07% by weight or more, more preferably 0.09% by weight or more.
  • the ash content is preferably 0.05 to 1.0% by weight or 0.07 to 0.5% by weight, more preferably 0.09 to 0.3% by weight or 0.09 to 0.15% by weight. It is.
  • the amount of ash after heating at 800 ° C. for 2 hours can be determined by, for example, carbonizing a sample (measure the sample weight in advance), heating it at 800 ° C. for 2 hours to incinerate it, and measuring the weight of the residue after ashing. It can be measured by calculating the ratio (%) of the ash residue to the sample weight.
  • thermogravimetric residual rate Cellulose materials can exhibit a high thermogravimetric survival rate.
  • the thermogravimetric residual rate after heating at 500°C is usually 6% or more, 7% or more, or 10% or more, preferably 10.5% or more, more preferably 11% or more.
  • the upper limit is preferably 35% or less, more preferably 30% or less.
  • the thermogravimetric residual rate after heating at 400° C. is usually 8% or more, 9% or more, or 10% or more.
  • the upper limit is usually 20% or less, or 18% or less, preferably 16% or less, or 15% or less, more preferably 13% or less.
  • thermogravimetric residual rate after heating at 500° C. satisfies the above range.
  • the amount of iron component in the cellulose material is 10 ppm or less, it is preferable that the thermogravimetric residual rate after heating at 400°C satisfies the above range, and when the cellulose material is powdered cellulose, the thermogravimetric residual rate after heating at 400°C It is more preferable that the residual rate satisfies the above range.
  • the thermogravimetric residual rate after heating at 500°C or 400°C can be confirmed using a thermal analyzer as the ratio (%) of the weight after heating at 500°C or 400°C to the weight before the start of heating.
  • Form of cellulose material examples include powder and fibrous forms (microfibrils and nanofibers), with powdered cellulose being preferred.
  • the particle size distribution of powdered cellulose is the particle size distribution when the integrated value of the volume accumulation distribution is 10%, 50%, and 90% (10% diameter, 50% diameter, 90% diameter, respectively, D.10, D.50, D.90).
  • the particle size distribution is a value obtained by wet measurement (with ultrasonic irradiation), wet measurement (without ultrasonic irradiation), or dry measurement using a laser scattering method as the measurement principle.
  • the span of the particle size distribution is determined by the D. 10,D. 50, D. It is calculated by substituting 90 into the following formula (1).
  • Formula (1): Span of particle size distribution ((D.90)-(D.10))/(D.50)
  • wet conditions refer to conditions in which the particle diameter is directly measured without ultrasonic irradiation after adding water to the sample.
  • D under wet conditions no ultrasonic irradiation.
  • 10,D. 50, D. 90 the preferred range of span is as follows. Generally, the larger the particle size, the more entangled the fibers tend to be. Further, within the following range, when added to resins, rubbers, etc., the strength can be appropriately improved without impairing their properties. Further, when the amount of iron component is 1 to 10 ppm, in addition to the above properties, it can exhibit good tabletability.
  • D. 10 is usually 5.0 ⁇ m or more, preferably 9.0 ⁇ m or more, more preferably 10.0 ⁇ m or more, even more preferably 11.0 ⁇ m or more.
  • the upper limit is usually 40.0 ⁇ m or less, preferably 25.0 ⁇ m or less, more preferably 23.0 ⁇ m or less, even more preferably 22.0 ⁇ m or less. Therefore, it is usually 5.0 to 40.0 ⁇ m, preferably 9.0 to 25.0 ⁇ m, more preferably 10.0 to 23.0 ⁇ m, and still more preferably 11.0 to 22.0 ⁇ m.
  • the amount of iron component in powdered cellulose exceeds 10 ppm and is 50 ppm, D. 10 is usually 5.0 ⁇ m or more, 9.0 ⁇ m or more, or 10.0 ⁇ m or more, preferably 11.0 ⁇ m or more, more preferably 11.5 ⁇ m or more, preferably 12.0 ⁇ m or more, more preferably 13.0 ⁇ m or more.
  • the upper limit is usually 40.0 ⁇ m or less or 25.0 ⁇ m or less, preferably 23.0 ⁇ m or less or 22.0 ⁇ m or less, preferably 14.0 ⁇ m or less, more preferably 13.0 ⁇ m or less.
  • D. 10 is usually 5.0 ⁇ m or more, 9.0 ⁇ m or more, or 10.0 ⁇ m or more, preferably 12.0 ⁇ m or more, more preferably 13.0 ⁇ m or more.
  • the upper limit is usually 40.0 ⁇ m or less or 25.0 ⁇ m or less, preferably 23.0 ⁇ m or less, and more preferably 22.0 ⁇ m or less. Therefore, it is usually 5.0 to 40.0 ⁇ m, 9.0 to 40.0 ⁇ m, or 10.0 to 25.0 ⁇ m, preferably 12.0 to 23.0 ⁇ m, more preferably 13.0 to 22.0 ⁇ m. be.
  • D. 50 (average particle diameter) is usually 5.0 ⁇ m or more, 10.0 ⁇ m or more, preferably 20.0 ⁇ m or more, or 25.0 ⁇ m or more, more preferably 30.0 ⁇ m or more, or 34.0 ⁇ m or more, even more preferably It is 36.0 ⁇ m or more, or 38.0 ⁇ m or more (however, it is a value larger than D.10).
  • the upper limit is usually 150.0 ⁇ m or less, 140.0 ⁇ m or less, or 130.0 ⁇ m or less, preferably 120.0 ⁇ m or less, or 110.0 ⁇ m or less, more preferably 100.0 ⁇ m or less, or 90.0 ⁇ m or less, even more preferably is 80.0 ⁇ m or less, 75.0 ⁇ m or less, or 70.0 ⁇ m or less.
  • 50 (average particle diameter) is usually 5.0 to 150.0 ⁇ m, 5.0 to 140.0 ⁇ m, 10.0 to 130.0 ⁇ m, 10.0 to 120.0 ⁇ m, 20.0 to 110.0 ⁇ m, 20.0 to 100.0 ⁇ m, 25.0 to 90.0 ⁇ m, 30.0 to 80.0 ⁇ m, 34.0 to 80.0 ⁇ m, 36.0 to 75.0 ⁇ m, and 38.0 to 70.0 ⁇ m.
  • D. 50 (average particle diameter) is usually 5.0 ⁇ m or more, 10.0 ⁇ m or more, 20.0 ⁇ m or more, or 25.0 ⁇ m or more, preferably 30.0 ⁇ m or more or 34.0 ⁇ m or more, more preferably 36.0 ⁇ m or more, More preferably, it is 38.0 ⁇ m or more (however, it is a value larger than D.10).
  • the upper limit is usually 150.0 ⁇ m or less, 100.0 ⁇ m or less, 90.0 ⁇ m or less, 70.0 ⁇ m or less, or 50.0 ⁇ m or less, preferably 45.0 ⁇ m or less, 44.0 ⁇ m or less, or 43.0 ⁇ m or less, more preferably It is 42.0 ⁇ m or less, more preferably 40.0 ⁇ m or less.
  • 50 (average particle diameter) is usually 5.0 to 150.0 ⁇ m, 5.0 to 100.0 ⁇ m, 10.0 to 90.0 ⁇ m, 20.0 to 70.0 ⁇ m or 25.0 to 50.0 ⁇ m, Preferably it is 30.0 to 45.0 ⁇ m, 30.0 to 44.0 ⁇ m or 34.0 to 43.0 ⁇ m, more preferably 36.0 to 42.0 ⁇ m, still more preferably 38.0 to 40.0 ⁇ m.
  • D. 50 (average particle diameter) is usually 5.0 ⁇ m or more, 10.0 ⁇ m or more, 20.0 ⁇ m or more, or 25.0 ⁇ m or more, preferably 30.0 ⁇ m or more or 34.0 ⁇ m or more, more preferably 38.0 ⁇ m or more, More preferably, it is 40.0 ⁇ m or more (however, it is a value larger than D.10).
  • the upper limit is usually 150.0 ⁇ m or less, 140.0 ⁇ m or less, 130.0 ⁇ m or less, 120.0 ⁇ m or less, or 110.0 ⁇ m or less, preferably 100.0 ⁇ m or less, 90.0 ⁇ m or less, or 80.0 ⁇ m or less, more preferably It is 75.0 ⁇ m or less, more preferably 70.0 ⁇ m or less.
  • 50 (average particle diameter) is usually 5.0 to 150.0 ⁇ m, 5.0 to 140.0 ⁇ m, 10.0 to 130.0 ⁇ m, 20.0 to 120.0 ⁇ m or 25.0 to 110.0 ⁇ m, Preferably 30.0 to 100.0 ⁇ m, 30.0 to 90.0 ⁇ m or 34.0 to 80.0 ⁇ m, more preferably 38.0 to 75.0 ⁇ m, still more preferably 40.0 to 70.0 ⁇ m.
  • D. 90 is usually 70.0 ⁇ m or more or 75.0 ⁇ m or more, preferably 80.0 ⁇ m or more, 85.0 ⁇ m or more, or 90.0 ⁇ m or more, more preferably 95.0 ⁇ m or more, still more preferably 100.0 ⁇ m or more, 105. It is 0 ⁇ m or more, or 110.0 ⁇ m or more (however, it is a value larger than D.50).
  • the upper limit is usually 250.0 ⁇ m or less, or 240.0 ⁇ m or less, preferably 230.0 ⁇ m or less, or 225.0 ⁇ m or less, more preferably 220.0 ⁇ m or less, or 215.0 ⁇ m or less, even more preferably 210.0 ⁇ m or less. It is.
  • D. 90 is usually 70.0 ⁇ m or more or 75.0 ⁇ m or more, preferably 80.0 ⁇ m or more, 85.0 ⁇ m or more, or 90.0 ⁇ m or more, more preferably 95.0 ⁇ m or more, and still more preferably 100.0 ⁇ m or more ( However, the value is larger than D.50).
  • the upper limit is usually 250.0 ⁇ m or less, 230.0 ⁇ m or less, or 220.0 ⁇ m or less, preferably 210.0 ⁇ m or less or 200.0 ⁇ m or less, more preferably 195.0 ⁇ m or less, and even more preferably 190.0 ⁇ m or less. .
  • D. 90 is usually 70.0 ⁇ m or more or 80.0 ⁇ m or more, preferably 90.0 ⁇ m or more, 95.0 ⁇ m or more, or 100.0 ⁇ m or more, more preferably 105.0 ⁇ m or more, and still more preferably 110.0 ⁇ m or more ( However, the value is larger than D.50).
  • the upper limit is usually 250.0 ⁇ m or less, 240.0 ⁇ m or less, or 230.0 ⁇ m or less, preferably 225.0 ⁇ m or less or 220.0 ⁇ m or less, more preferably 215.0 ⁇ m or less, and still more preferably 210.0 ⁇ m or less. .
  • the span of the particle size distribution is usually 1.5 or more, preferably 1.7 or more, more preferably 1.9 or more, and still more preferably 2.0 or more.
  • the upper limit is usually 6.0 or less, preferably 5.5 or less, more preferably 5.0 or less, still more preferably 4.5 or less. Therefore, usually 1.5 to 6.0, or 1.7 to 6.0, preferably 1.9 to 5.5, more preferably 1.9 to 5.0, or 2.0 to 5.0 , more preferably from 2.0 to 4.5.
  • the span of the particle size distribution is usually 1.5 or more, preferably 1.7 or more, more preferably 1.9 or more, and even more preferably 2. .0 or more.
  • the upper limit is usually 6.0 or less, preferably 5.5 or less, more preferably 5.0 or less, still more preferably 4.5 or less. Therefore, it is usually 1.5 to 6.0, preferably 1.7 to 5.5, more preferably 1.9 to 5.0, and even more preferably 2.0 to 4.5.
  • the span of the particle size distribution is usually 2.1 or more, preferably 2.2 or more, more preferably 2.3 or more, and still more preferably 2.4. That's all.
  • the upper limit is usually 6.0 or less, preferably 5.0 or less, more preferably 4.0 or less, and even more preferably 3.0 or less. Therefore, it is usually 2.1 to 6.0, preferably 2.2 to 5.0, more preferably 2.3 to 4.0, and even more preferably 2.4 to 3.0.
  • wet conditions refer to conditions in which a sample is subjected to ultrasonic irradiation after being hydrated, and then the particle diameter is measured.
  • D. for wet type (with ultrasonic waves) 10,D. 50, D. 90 the preferred range of span is as follows. Generally, the larger the particle size, the more entangled the fibers tend to be. Further, within the following range, when added to resins, rubbers, etc., the strength can be appropriately improved without impairing their properties. Further, when the amount of iron component is 1 to 10 ppm, in addition to the above properties, it can exhibit good tabletability.
  • D. 10 is usually 1.0 ⁇ m or more, or 3.0 ⁇ m or more, preferably 5.0 ⁇ m or more, or 9.0 ⁇ m or more, more preferably 9.5 ⁇ m or more, or 10.0 ⁇ m or more, and even more preferably 10.5 ⁇ m. That's all.
  • the upper limit is usually 24.0 ⁇ m or less, preferably 23.0 ⁇ m or less, more preferably 22.5 ⁇ m or less, still more preferably 22.0 ⁇ m or less.
  • the amount of iron component in powdered cellulose exceeds 10 ppm and is 50 ppm, D. 10 is usually 1.0 ⁇ m or more, 3.0 ⁇ m or more, or 5.0 ⁇ m or more, preferably 9.0 ⁇ m or more or 10.0 ⁇ m or more, more preferably 10.5 ⁇ m or more, and still more preferably 11.0 ⁇ m or more.
  • the upper limit is usually 20.0 ⁇ m or less or 16.0 ⁇ m or less, preferably 13.0 ⁇ m or less, and more preferably 12.5 ⁇ m or less.
  • D. 10 is usually 1.0 ⁇ m or more, 3.0 ⁇ m or more, or 5.0 ⁇ m or more, preferably 9.0 ⁇ m or more or 9.5 ⁇ m or more, more preferably 10.0 ⁇ m or more, still more preferably 10.5 ⁇ m or more.
  • the upper limit is usually 24.0 ⁇ m or less or 23.0 ⁇ m or less, preferably 22.5 ⁇ m or less, and more preferably 22.0 ⁇ m or less.
  • D. 50 is usually 5.0 ⁇ m or more, or 10.0 ⁇ m or more, preferably 20.0 ⁇ m or more, or 23.0 ⁇ m or more, more preferably 25.0 ⁇ m or more, or 26.0 ⁇ m or more, still more preferably 27 .0 ⁇ m or more, 27.5 ⁇ m or more, or 28.0 ⁇ m or more (however, the value is larger than D.10).
  • the upper limit is usually 150.0 ⁇ m or less, preferably 120.0 ⁇ m or less, more preferably 100.0 ⁇ m or less, still more preferably 80.0 ⁇ m or less, or 70.0 ⁇ m or less.
  • D. 50 is usually 5.0 ⁇ m or more, 10.0 ⁇ m or more, or 20.0 ⁇ m or more, preferably 25.0 ⁇ m or more, 30.0 ⁇ m or more, or 32.0 ⁇ m or more, more preferably 34.0 ⁇ m or more or 36.0 ⁇ m or more, More preferably, it is 36.5 ⁇ m or more (however, the value is larger than D.10).
  • the upper limit is usually 70.0 ⁇ m or less, 60.0 ⁇ m or less, or 50.0 ⁇ m or less, preferably 45.0 ⁇ m or less or 40.0 ⁇ m or less, more preferably 39.5 ⁇ m or less, still more preferably 39.0 ⁇ m or less. Therefore, usually 5.0 to 70.0 ⁇ m, 10.0 to 60.0 ⁇ m or 20.0 to 50.0 ⁇ m, preferably 25.0 to 45.0 ⁇ m, 30.0 to 40.0 ⁇ m or 32.0 to 40.0 ⁇ m, more preferably 34.0 to 39.5 ⁇ m, still more preferably 36.0 to 39.0 ⁇ m or 36.5 to 39.0 ⁇ m.
  • D. 50 is usually 5.0 ⁇ m or more, 10.0 ⁇ m or more, or 20.0 ⁇ m or more, preferably 23.0 ⁇ m or more, 25.0 ⁇ m or more, or 26.0 ⁇ m or more, more preferably 27.0 ⁇ m or more or 27.5 ⁇ m or more, More preferably, it is 28.0 ⁇ m or more (however, the value is larger than D.10).
  • the upper limit is usually 150.0 ⁇ m or less, 120.0 ⁇ m or less, or 100.0 ⁇ m or less, preferably 80.0 ⁇ m or less or 70.0 ⁇ m or less, more preferably 69.5 ⁇ m or less, still more preferably 69.0 ⁇ m or less. Therefore, usually 5.0 to 150.0 ⁇ m, 10.0 to 120.0 ⁇ m or 20.0 to 100.0 ⁇ m, preferably 23.0 to 80.0 ⁇ m, 25.0 to 70.0 ⁇ m or 26.0 to 70.0 ⁇ m, more preferably 27.0 to 69.5 ⁇ m, even more preferably 27.5 to 69.0 ⁇ m or 28.0 to 69.0 ⁇ m.
  • D. 90 is usually 50.0 ⁇ m or more, 55.0 ⁇ m or more, 60.0 ⁇ m or more, 65.0 ⁇ m or more, 70.0 ⁇ m or more, 75.0 ⁇ m or more (however, it is a value larger than D.50).
  • the upper limit is usually 230.0 ⁇ m or less, 225.0 ⁇ m or less, or 220.0 ⁇ m or less, preferably 215.0 ⁇ m or less, 210.0 ⁇ m or less. Therefore, D.
  • 90 is usually 50.0 to 230.0 ⁇ m, 55.0 to 225.0 ⁇ m, 60.0 to 220.0 ⁇ m, 65.0 to 215.0 ⁇ m or 70.0 to 210.0 ⁇ m, preferably 75.0 ⁇ 200.0 ⁇ m, 80.0 to 215.0 ⁇ m, more preferably 90.0 to 215.0 ⁇ m, even more preferably 100.0 to 210.0 ⁇ m.
  • D. 90 is usually 50.0 ⁇ m or more, 60.0 ⁇ m or more, 70.0 ⁇ m or more, or 90.0 ⁇ m or more, preferably 98.0 ⁇ m or more, more preferably 100.0 ⁇ m or more, even more preferably 101.5 ⁇ m or more ( However, the value is larger than D.50).
  • the upper limit is usually 210.0 ⁇ m or less or 200.0 ⁇ m or less, preferably 200.0 ⁇ m or less, more preferably 195.0 ⁇ m or less, even more preferably 190.0 ⁇ m or less. Therefore, D.
  • 90 is usually 50.0 to 210.0 ⁇ m, 60.0 to 200.0 ⁇ m or 70.0 to 200.0 ⁇ m, preferably 80.0 to 195.0 ⁇ m, more preferably 90.0 to 190.0 ⁇ m, More preferably, it is 100.0 to 190.0 ⁇ m.
  • D. 90 is usually 50.0 ⁇ m or more, 55.0 ⁇ m or more, or 60.0 ⁇ m or more, preferably 65.0 ⁇ m or more, more preferably 70.0 ⁇ m or more, even more preferably 75.0 ⁇ m or more (however, D.50 ).
  • the upper limit is usually 230.0 ⁇ m or less or 225.0 ⁇ m or less, preferably 220.0 ⁇ m or less, more preferably 215.0 ⁇ m or less, even more preferably 210.0 ⁇ m or less. Therefore, D.
  • 90 is usually 50.0 to 230.0 ⁇ m, 55.0 to 225.0 ⁇ m or 60.0 to 225.0 ⁇ m, preferably 65.0 to 220.0 ⁇ m, more preferably 70.0 to 215.0 ⁇ m, More preferably, it is 75.0 to 210.0 ⁇ m.
  • the span of the particle size distribution is usually 1.5 or more, preferably 1.7 or more, more preferably 1.9 or more, and still more preferably 2.0 or more.
  • the upper limit is usually 5.0 or less, preferably 4.5 or less. Therefore, it is usually 1.5 to 5.0, preferably 1.7 to 5.0, more preferably 1.9 to 5.0, or 2.0 to 4.5.
  • the span of the particle size distribution is usually 1.5 or more, preferably 1.7 or more, more preferably 1.9 or more, and even more preferably 2. .0 or more.
  • the upper limit is usually 5.0 or less, preferably 4.5 or less. Therefore, it is usually 1.5 to 5.0, preferably 1.7 to 4.5, more preferably 1.9 to 4.5, or 2.0 to 4.5.
  • the span of the particle size distribution is usually 1.5 or more, preferably 1.7 or more, more preferably 2.0 or more, and even more preferably 2.2. That's all.
  • the upper limit is usually 5.0 or less, preferably 3.5 or less, more preferably 2.9 or less. Therefore, it is usually 1.5 to 5.0, preferably 2.0 to 3.5, and more preferably 2.2 to 2.9.
  • dry measurement refers to conditions in which the particle diameter is directly measured without adding water to the sample.
  • D. for dry measurement. 10,D. 50, D. 90 the preferred range of span is as follows. Generally, the larger the particle size, the more entangled the fibers tend to be. Further, within the following range, when added to resins, rubbers, etc., the strength can be appropriately improved without impairing their properties. Further, when the amount of iron component is 1 to 10 ppm, in addition to the above properties, it can exhibit good tabletability.
  • D. 10 is usually 1.0 ⁇ m or more, 3.0 ⁇ m or more, or 5.0 ⁇ m or more, preferably 7.0 ⁇ m or more or 8.0 ⁇ m or more, more preferably 9.0 ⁇ m or more, or 9.5 ⁇ m or more.
  • the upper limit is usually 40.0 ⁇ m or less, 35.0 ⁇ m or less, or 30.0 ⁇ m or less, preferably 27.0 ⁇ m or less, 26.0 ⁇ m or less. Therefore, usually 1.0 to 40.0 ⁇ m, 3.0 to 40.0 ⁇ m or 5.0 to 35.0 ⁇ m, preferably 7.0 to 35.0 ⁇ m, 8.0 to 30.0 ⁇ m, or 9.0 ⁇ m -27.0 ⁇ m, more preferably 9.5-26.0 ⁇ m.
  • the amount of iron component in powdered cellulose exceeds 10 ppm and is 50 ppm, D. 10 is usually 1.0 ⁇ m or more, 3.0 ⁇ m or more, or 5.0 ⁇ m or more, preferably 7.0 ⁇ m or more or 8.0 ⁇ m or more, more preferably 9.0 ⁇ m or more, and still more preferably 9.5 ⁇ m or more.
  • the upper limit is usually 40.0 ⁇ m or less or 20.0 ⁇ m or less, preferably 15.0 ⁇ m or less, more preferably 14.0 ⁇ m or less, even more preferably 13.0 ⁇ m or less.
  • D. 10 is usually 1.0 ⁇ m or more, 3.0 ⁇ m or more, or 5.0 ⁇ m or more, preferably 7.0 ⁇ m or more or 10.0 ⁇ m or more, more preferably 13.0 ⁇ m or more, and still more preferably 13.5 ⁇ m or more.
  • the upper limit is usually 40.0 ⁇ m or less or 35.0 ⁇ m or less, preferably 30.0 ⁇ m or less, more preferably 27.0 ⁇ m or less, even more preferably 26.0 ⁇ m or less.
  • D. 50 is usually 5.0 ⁇ m or more, 10.0 ⁇ m or more, or 15.0 ⁇ m or more, preferably 20.0 ⁇ m or more, 25.0 ⁇ m or more, or 30.0 ⁇ m or more, more preferably 33.0 ⁇ m or more, 34.0 ⁇ m or more, or 35.0 ⁇ m or more (however, the value is larger than D.10).
  • the upper limit is usually 150.0 ⁇ m or less, or 100.0 ⁇ m or less, preferably 90.0 ⁇ m or less, more preferably 88.0 ⁇ m or less, even more preferably 87.0 ⁇ m or less. Therefore, D.
  • 50 is usually 5.0 to 150.0 ⁇ m, 10.0 to 150.0 ⁇ m or 15.0 to 100.0 ⁇ m, preferably 20.0 to 100.0 ⁇ m, 25.0 to 90.0 ⁇ m or 30.0 ⁇ m. -90.0 ⁇ m, more preferably 33.0-88.0 ⁇ m or 34.0-88.0 ⁇ m, even more preferably 35.0-87.0 ⁇ m.
  • D. 50 is usually 5.0 ⁇ m or more, 10.0 ⁇ m or more, or 15.0 ⁇ m or more, preferably 20.0 ⁇ m or more, 25.0 ⁇ m or more, or 30.0 ⁇ m or more, more preferably 33.0 ⁇ m or more, 34.0 ⁇ m or more, More preferably, it is 35.0 ⁇ m or more (however, the value is larger than D.10).
  • the upper limit is usually 100.0 ⁇ m or less or 60.0 ⁇ m or less, preferably 52.5 ⁇ m or less or 52.0 ⁇ m or less, more preferably 51.5 ⁇ m or less. Therefore, D.
  • 50 is usually 5.0 to 100.0 ⁇ m, 10.0 to 60.0 ⁇ m or 15.0 to 60.0 ⁇ m, preferably 20.0 to 52.5 ⁇ m, 25.0 to 52.5 ⁇ m or 30.0 ⁇ 52.5 ⁇ m, more preferably 33.0 ⁇ 52.0 ⁇ m or 34.0 ⁇ 52.0 ⁇ m, still more preferably 35.0 ⁇ 51.5 ⁇ m.
  • D. 50 is usually 5.0 ⁇ m or more, 10.0 ⁇ m or more, or 15.0 ⁇ m or more, preferably 25.0 ⁇ m or more, 30.0 ⁇ m or more, or 35.0 ⁇ m or more, more preferably 40.0 ⁇ m or more or 41.0 ⁇ m or more, More preferably, it is 41.5 ⁇ m or more (however, it is a value larger than D.10).
  • the upper limit is usually 150.0 ⁇ m or less or 100.0 ⁇ m or less, preferably 90.0 ⁇ m or less or 88.0 ⁇ m or less, more preferably 87.0 ⁇ m or less. Therefore, D.
  • 50 is usually 5.0 to 150.0 ⁇ m, 10.0 to 100.0 ⁇ m or 15.0 to 100.0 ⁇ m, preferably 25.0 to 90.0 ⁇ m, 30.0 to 90.0 ⁇ m or 35.0 -90.0 ⁇ m, more preferably 40.0-88.0 ⁇ m or 41.0-88.0 ⁇ m, even more preferably 41.5-87.0 ⁇ m.
  • D. 90 is usually 80.0 ⁇ m or more, preferably 90.0 ⁇ m or more, more preferably 93.0 ⁇ m or more, even more preferably 94.0 ⁇ m or more (however, it is a value larger than D.50) .
  • the upper limit is usually 330.0 ⁇ m or less, preferably 320.0 ⁇ m or less, more preferably 315.0 ⁇ m or less, or 310.0 ⁇ m or less, still more preferably 305.0 ⁇ m or less. Therefore, D. 90 is usually 80.0 to 330.0 ⁇ m, preferably 80.0 to 320.0 ⁇ m, more preferably 90.0 to 315.0 ⁇ m, or 93.0 to 310.0 ⁇ m, still more preferably 94 .0 to 305.0 ⁇ m.
  • D. 90 is usually 80.0 ⁇ m or more, or 90.0 ⁇ m or more, preferably 93.0 ⁇ m or more, more preferably 94.0 ⁇ m or more (however, it is a value larger than D.50).
  • the upper limit is usually 310.0 ⁇ m or less or 280.0 ⁇ m or less, preferably 260.0 ⁇ m or less or 255.0 ⁇ m, more preferably 251.0 ⁇ m or less. Therefore, D. 90 is usually 80.0 to 310.0 ⁇ m or 90.0 to 280.0 ⁇ m, preferably 93.0 to 260.0 ⁇ m or 93.0 to 255.0 ⁇ m, more preferably 94.0 to 251.0 ⁇ m. be.
  • D. 90 is usually 90.0 ⁇ m or more or 110.0 ⁇ m or more, preferably 120.0 ⁇ m or more, more preferably 130.0 ⁇ m or more (however, it is a value larger than D.50).
  • the upper limit is usually 330.0 ⁇ m or less or 320.0 ⁇ m or less, preferably 315.0 ⁇ m or less or 310.0 ⁇ m or less, more preferably 305.0 ⁇ m or less. Therefore, D. 90 is usually 90.0 to 330.0 ⁇ m or 110.0 to 320.0 ⁇ m, preferably 120.0 to 315.0 ⁇ m or 120.0 to 310.0 ⁇ m, more preferably 130.0 to 305.0 ⁇ m. be.
  • the span of the particle size distribution is usually 1.5 or more, preferably 1.7 or more, more preferably 1.8 or more, still more preferably 2.0 or more.
  • the upper limit is usually 9.0 or less, preferably 7.0 or less, more preferably 6.0 or less, even more preferably 5.0 or less. Therefore, the span of the particle size distribution is usually 1.5 to 9.0, preferably 1.7 to 7.0, more preferably 1.8 to 6.0, even more preferably 2.0 to 5.0. It is.
  • the span of the particle size distribution is usually 1.5 or more, preferably 1.7 or more, more preferably 1.8 or more, and still more preferably 2. .0 or more.
  • the upper limit is usually 9.0 or less, preferably 7.0 or less, more preferably 6.0 or less, still more preferably 5.0 or less. Therefore, the span of the particle size distribution is usually 1.5 to 9.0, preferably 1.7 to 7.0, more preferably 1.8 to 6.0, even more preferably 2.0 to 5.0. It is.
  • the span of the particle size distribution is usually 2.5 or more, preferably 2.6 or more, more preferably 2.7 or more, and still more preferably 2.8. That's all.
  • the upper limit is usually 7.0 or less, preferably 6.0 or less, more preferably 5.0 or less, still more preferably 4.0 or less. Therefore, the span of the particle size distribution is usually 2.5 to 7.0, preferably 2.6 to 6.0, more preferably 2.7 to 5.0, even more preferably 2.8 to 4.0. It is.
  • the average fiber width ( ⁇ m), average fiber length (mm), average fiber length/average fiber width
  • the average fiber width (minor axis) refers to the average value of the minimum value orthogonal to the major axis of the fiber width of powdered cellulose.
  • the average fiber length (length axis) refers to the average value of the maximum length of the fiber width of powdered cellulose.
  • the average fiber width is usually 10 ⁇ m or more, preferably 15 ⁇ m or more, and more preferably 20 ⁇ m or more.
  • the upper limit is usually 40 ⁇ m or less, preferably 35 ⁇ m or less, more preferably 33 ⁇ m or less, still more preferably 32 ⁇ m or less. Therefore, the average fiber width is usually 10 to 40 ⁇ m, preferably 10 to 35 ⁇ m or 10 to 24 ⁇ m, more preferably 15 to 33 ⁇ m, and still more preferably 20 to 32 ⁇ m.
  • the average fiber width is preferably 10 ⁇ m or more, more preferably 15 ⁇ m or more, and still more preferably 20 ⁇ m or more.
  • the upper limit is preferably 35 ⁇ m or less, more preferably 30 ⁇ m or less, even more preferably 24 ⁇ m or less. Therefore, the average fiber width is preferably 10 to 35 ⁇ m or 10 to 24 ⁇ m, more preferably 15 to 30 ⁇ m, even more preferably 20 to 24 ⁇ m.
  • the average fiber width is usually 10 ⁇ m or more, preferably 20 ⁇ m or more, more preferably 24 ⁇ m or more, and still more preferably 24.5 ⁇ m or more.
  • the upper limit is usually 40 ⁇ m or less, preferably 35 ⁇ m or less, more preferably 33 ⁇ m or less, even more preferably 32 ⁇ m or less. Therefore, the average fiber width is usually 10 to 40 ⁇ m, preferably 20 to 35 ⁇ m, more preferably 24 to 33 ⁇ m, and still more preferably 24.5 to 32 ⁇ m.
  • the average fiber length is usually 0.03 mm or more, preferably 0.05 mm or more.
  • the upper limit is usually 0.3 mm or less, preferably 0.25 mm or less, more preferably 0.2 mm or less. Therefore, the average fiber length is usually 0.03 to 0.3 mm, preferably 0.05 to 0.25, and more preferably 0.05 to 0.2 mm.
  • the average fiber length is preferably 0.05 mm or more, more preferably 0.06 mm or more.
  • the upper limit is preferably 0.3 mm or less, more preferably 0.25 mm or less. Therefore, the average fiber length is preferably 0.05 to 0.3 mm, more preferably 0.06 to 0.25 mm.
  • the average fiber length is preferably 0.03 mm or more, more preferably 0.05 mm or more.
  • the upper limit is preferably 0.3 mm or less, more preferably 0.2 mm or less. Therefore, the average fiber length is preferably 0.03 to 0.3 mm, more preferably 0.05 to 0.2 mm.
  • the average fiber length/average fiber width (L/D) of powdered cellulose is usually 2.0 or more, preferably 3.0 or more.
  • the upper limit is usually 12.0 or less, preferably 11.5 or less. Therefore, L/D is usually 2.0 to 12.0, preferably 3.0 to 11.5.
  • L/D is preferably 2.5 to 12.0, more preferably 3.0 to 11.5.
  • the larger the L/D the more entangled the fibers tend to be.
  • the strength can be appropriately improved without impairing their properties.
  • L/D is preferably 3.0 to 8.0, more preferably 3.0 to 7.0, and still more preferably 3.0 to 8.0. It is 0 to 6.0. Generally, the larger the L/D, the more entangled the fibers tend to be. Further, within the above range, when added to resins, rubbers, etc., the strength can be appropriately improved without impairing their properties, and good suitability for tabletting can be exhibited.
  • the average fiber length and average fiber width can be measured using Fiber Tester Plus manufactured by ABB, and L/D is a value calculated from these measured values.
  • Fibrous cellulose refers to cellulose fibers prepared through a micronization process and having a fiber diameter on the nano-order or micro-order. In this specification, they are respectively referred to as cellulose nanofibers (CNF) and cellulose microfibrils (MFC).
  • CNF cellulose nanofibers
  • MFC cellulose microfibrils
  • the average fiber diameter (length-weighted average fiber diameter) of CNF is 500 nm or less, preferably 300 nm or less, more preferably 100 nm or less, even more preferably 50 nm or less.
  • the lower limit is not particularly limited, it is usually 1 nm or more, preferably 2 nm or more. Therefore, the average fiber diameter (length-weighted average fiber diameter) of CNF is usually 1 to 500 nm or 2 to 500 nm, preferably 2 to 300 nm or 2 to 100 nm, more preferably 2 to 50 nm or 3 to 30 nm.
  • the average fiber length (length-weighted average fiber length) is usually 50 to 2000 nm, preferably 100 to 1000 nm.
  • the aspect ratio of CNF is usually 10 or more, preferably 50 or more.
  • the upper limit is not particularly limited, but is usually 1000 or less.
  • the average fiber diameter of MFC is usually 500 nm or more, preferably 1 ⁇ m or more, and more preferably 3 ⁇ m or more. As a result, it can exhibit higher water retention than undefibrated cellulose fibers, and even in a small amount, a high strength imparting effect and yield improvement effect can be obtained compared to finely defibrated CNF.
  • the upper limit of the average fiber diameter is preferably 60 ⁇ m or less, more preferably 40 ⁇ m or less, even more preferably 30 ⁇ m or less, and even more preferably 20 ⁇ m or less, but there is no particular restriction.
  • the average fiber length is usually 10 ⁇ m or more, 20 ⁇ m or more, or 40 ⁇ m or more, preferably 200 ⁇ m or more, 300 ⁇ m or more, or 400 ⁇ m or more, more preferably 500 ⁇ m or more or 550 ⁇ m or more, even more preferably 600 ⁇ m or more, 700 ⁇ m or more, or 800 ⁇ m. That's all.
  • the upper limit is not particularly limited, but is usually 3,000 ⁇ m or less, preferably 2,500 ⁇ m or less, more preferably 2,000 ⁇ m or less, still more preferably 1,500 ⁇ m or less, 1,400 ⁇ m or less, or 1,300 ⁇ m.
  • the aspect ratio of MFC is preferably 3 or more, more preferably 5 or more, even more preferably 7 or more, and may be 10 or more, 20 or more, or 30 or more.
  • the upper limit of the aspect ratio is not particularly limited, but is preferably 1000 or less, more preferably 100 or less, and even more preferably 80 or less.
  • the average fiber diameter and average fiber length of fibrous cellulose can be determined using a fractionator manufactured by Valmet Corporation. When using a fractionator, it can be determined as length-weighted fiber width and length-weighted average fiber length, respectively.
  • the fibrous cellulose may be modified or unmodified.
  • Modified fibrous cellulose refers to fine cellulose fibers (e.g., cellulose nanofibers, cellulose microfibrils) in which at least one of the three hydroxyl groups contained in the glucose unit has been chemically modified (hereinafter simply referred to as "modified"). ) means.
  • modified cellulose fibers are sufficiently refined, and cellulose nanofibers having a uniform average fiber length and average fiber diameter can be obtained by defibration. Therefore, when compounded with a rubber component, it can exhibit a sufficient reinforcing effect. From this point of view, modified cellulose fibers are preferred.
  • modification examples include oxidation, etherification, esterification such as phosphoric acid esterification, silane coupling, fluorination, cationization, and the like. Among these, oxidation (carboxylation), etherification, cationization, and esterification are preferred, and oxidation (carboxylation) is more preferred.
  • the cellulose material is not particularly limited as long as it is obtained by a method of obtaining a cellulose material from a cellulose raw material.
  • a method including at least a pulverization treatment may be mentioned, and a method including a mechanical pulverization treatment is preferred.
  • a method including defibration treatment can be mentioned.
  • the cellulose raw material is usually naturally derived cellulose, preferably pulp, and more preferably pulp derived from wood.
  • pulp derived from wood include pulp derived from broad-leaved trees and pulp derived from coniferous trees.
  • methods for preparing wood-derived pulp include methods that include bleaching treatment.
  • Bleaching treatment methods include, for example, chlorine treatment (C), chlorine dioxide bleaching (D), alkaline extraction (E), hypochlorite bleaching (H), Hydrogen peroxide bleaching (P), alkaline hydrogen peroxide treatment stage (Ep), alkaline hydrogen peroxide/oxygen treatment stage (Eop), ozone treatment (Z), chelation treatment (Q), and two or more of these treatments
  • chlorine treatment C
  • chlorine dioxide bleaching D
  • alkaline extraction E
  • hypochlorite bleaching H
  • Hydrogen peroxide bleaching P
  • alkaline hydrogen peroxide treatment stage Ep
  • alkaline hydrogen peroxide/oxygen treatment stage Eop
  • Z ozone treatment
  • chelation treatment Q
  • Examples of combinations (sequences) of two or more processes include D-E/P-D, C/D-E-HD, Z-E-D-PZ/D-Ep-D, and Z/D- Ep-DP, D-Ep-D, D-Ep-DP, D-Ep-PD, Z-Eop-DD, Z/D-Eop-D, Z/D-Eop- An example is DE (the "/" in the sequence means that the processes before and after the "/" are performed consecutively without washing).
  • Bleaching treatment is not limited to the above example, and may be any commonly used method. Pulp that has undergone bleaching treatment is usually in a fluid state (fluid pulp). The whiteness of the pulp is preferably 80% or more based on ISO 2470.
  • An example of a method for preparing pulp is a pulping method (cooking method).
  • the pulping method dissolves and removes the colored substance lignin, making it possible to obtain pulp with a high degree of whiteness.
  • Examples of the pulping method (cooking method) include sulfite cooking, kraft cooking, soda quinone cooking, and organosolve cooking, with kraft pulp being preferred from an environmental standpoint.
  • Mechanical pulps such as ground wood pulp (GP), refined ground wood pulp (RGP), thermomechanical pulp (TMP), and chemi-thermomechanical pulp (CTMP) can also be used.
  • the moisture content of the cellulose raw material is usually preferably 5 to 30%, preferably 6 to 20%, based on 100% of the cellulose raw material.
  • the moisture content may be adjusted by dehydration/drying treatment described below.
  • the pulverization process is a process of mechanically pulverizing the cellulose raw material. Prior to the pulverization treatment, pretreatment such as dehydration/drying treatment, acid hydrolysis treatment, etc. may be performed, and dehydration/drying treatment is preferred. A classification process may be performed simultaneously with the pulverization process or after the pulverization process.
  • Examples of the crusher include a cutting type mill, an impact type mill, an air flow type mill, a hammer type mill, a roll mill, a roller mill, a media mill, a media stirring mill, a vibration mill, and a freeze crusher. Two or more types may be used in combination.
  • cutting-type mills examples include cutting mills (manufactured by Horai Co., Ltd.), mesh mills (manufactured by Horai Co., Ltd.), Atoms (manufactured by Yamamoto Hyakuma Seisakusho Co., Ltd.), knife mills (manufactured by Palman Co., Ltd.), and cutter mills (manufactured by Tokyo Atomizer Co., Ltd.).
  • Examples of the hammer type mill include a hammer mill (manufactured by Hosokawa Micron Co., Ltd.), a jaw crusher (manufactured by Makino Co., Ltd.), and a hammer crusher (manufactured by Makino Sangyo Co., Ltd.).
  • impact mills examples include Pulverizer (manufactured by Hosokawa Micron Corporation), Fine Impact Mill (manufactured by Hosokawa Micron Corporation), Super Micron Mill (registered trademark, manufactured by Hosokawa Micron Corporation), Innomizer (registered trademark, manufactured by Hosokawa Micron Corporation), Fine Mill (manufactured by Japan Pneumatic Industries Co., Ltd.), CUM centrifugal mill (manufactured by Mitsui Mining Co., Ltd.), Exceed Mill (manufactured by Makino Sangyo Co., Ltd.), Ultraplex (manufactured by Makino Sangyo Co., Ltd.), Contraplex (manufactured by Makino Sangyo Co., Ltd.) Coloplex (manufactured by Makino Sangyo Co., Ltd.), Atomizer (manufactured by Seishin Kogyo Co., Ltd.), Tornado Mill (manufactured by Nikkiso Co.,
  • airflow mills examples include CGS type jet mill (manufactured by Mitsui Mining Co., Ltd.), Micron Jet (registered trademark, manufactured by Hosokawa Micron Co., Ltd.), Counter Jet Mill (registered trademark, manufactured by Hosokawa Micron Co., Ltd.), and Cross Jet Mill (trademark manufactured by Hosokawa Micron Co., Ltd.).
  • Kurimoto Iron Works Co., Ltd. Kurimoto Iron Works Co., Ltd.
  • supersonic jet mill Japan Pneumatic Industry Co., Ltd.
  • current jet Nesin Engineering Co., Ltd.
  • jet mill Selenium mirror (Masuko Sangyo Co., Ltd.) company
  • New Microsictomat manufactured by Masuno Seisakusho Co., Ltd.
  • Kryptron manufactured by Earth Technica Co., Ltd.
  • Nano Jet Miser manufactured by Aisin Nano Technologies Co., Ltd.
  • roller mill examples include a vertical roller mill (manufactured by Seishin Co., Ltd.), a vertical roller mill (manufactured by Shinion Co., Ltd.), a roller mill (manufactured by Kotobuki Giken Kogyo Co., Ltd.), and a VX mill (manufactured by Kurimoto Iron Works Co., Ltd.). ), KVM type vertical roller mill (manufactured by Earth Technica Co., Ltd.), and IS mill (manufactured by IHI Plant Engineering Co., Ltd.).
  • vibration mill examples include a batch type vibration mill (manufactured by Chuo Kakoki Co., Ltd.). Among these, cutting type mills, roller mills, and vibration mills are preferred.
  • the conditions for the pulverization treatment can be appropriately set so as to obtain the desired powdered cellulose.
  • the processing conditions can be adjusted with reference to a calibration curve created from the pulverization conditions (eg, processing time, input amount) and desired physical properties of the powdered cellulose.
  • pretreatment When producing powdered cellulose from cellulose raw materials, appropriate pretreatment is performed before pulverization. Examples of pretreatment include neutralization, washing, deliquification, and drying treatment, and it is preferable to perform dehydration and drying treatment in this order.
  • the solid content concentration of the cellulose raw material can be adjusted by drying (dehydration) treatment, and the physical properties of the powdered cellulose can be easily controlled.
  • the solid content concentration is usually adjusted to 15% or more, preferably 20% or more. For drying, it is preferable to use a flash dryer.
  • the processed cellulose raw material is in the form of a cake-like solid, slurry, solution, etc.
  • it is possible to apply high-speed hot air while dispersing it in the air stream, and also to utilize the depressurizing effect inside the dryer. can be dried instantly.
  • the product temperature can be kept low, making it ideal for drying products that are sensitive to heat or products with low melting points.
  • the conditions for drying using the flash dryer are not particularly limited and can be set as appropriate, but an example is as follows.
  • the outlet drying temperature is usually 80 to 180°C, preferably 90 to 160°C.
  • the amount of air supplied is usually 150 to 350 m 3 /h, preferably 160 to 320 m 3 /h.
  • the product when using a spray dryer, the product is sprayed and instantly dried with hot air to produce granules. Therefore, it may not be suitable for drying solid or semi-solid objects with a small moisture content. Furthermore, the particles are more easily exposed to high heat instantaneously than when drying with a flash dryer, and there may be concerns about the effect on the product.
  • acids used in the acid hydrolysis treatment include mineral acids such as hydrochloric acid, sulfuric acid, and nitric acid.
  • the acid concentration is not particularly limited, but from the viewpoint of maintaining the degree of polymerization and whiteness, it is preferably lower than the acid concentration in the conventional acid hydrolysis treatment for producing powdered cellulose, and is preferably 0.4 to 2.0N. More preferably, 0.5 to 1.5N is more preferable.
  • the acid concentration is less than 0.4N, depolymerization of cellulose due to acid is suppressed and a decrease in the degree of polymerization of cellulose can be reduced, but it may be difficult to refine the cellulose.
  • reaction conditions for the acid hydrolysis treatment are not particularly limited, but the reaction temperature is usually 80 to 100°C and the reaction time is usually 30 minutes to 3 hours.
  • the cellulose raw material Prior to the acid hydrolysis treatment, the cellulose raw material may be pretreated. Examples include slurrying the cellulose raw material (preparation of a dispersion) and adjusting the concentration of the cellulose raw material. The concentration of the cellulose raw material is usually 3 to 10% by weight (based on solid content) based on the dispersion.
  • a treatment to increase the pulp density is usually performed before hydrolysis.
  • a dehydrator such as a screw press or a belt filter may be used to adjust (concentrate) the cellulose raw material concentration.
  • the acid hydrolysis treatment may be performed on a slurry of cellulose raw material, or may be performed on a sheet-shaped cellulose raw material. When the cellulose raw material is a dry sheet of pulp, the acid hydrolysis treatment is usually performed after the pulp is loosened. When loosening the pulp, a crusher such as a roll crusher may be used.
  • At least one other component for example, an organic component, an inorganic component
  • the acid-hydrolyzed product may be further subjected to the above-mentioned neutralization, washing, dehydration, and drying treatments.
  • the cellulose material may be chemically treated as necessary.
  • the chemical treatment is preferably a treatment that does not significantly impair the degree of polymerization of the cellulose raw material.
  • the chemical treatment may be performed on the cellulose raw material during the pulverization treatment, or may be performed before the pretreatment of the pulverization treatment.
  • Fibrous cellulose can be produced by a method including defibration treatment.
  • Defibration is usually obtained by mechanical treatment, and the mechanical treatment is preferably defibration or beating treatment.
  • the mechanical treatment preferably beating or disintegration treatment
  • Examples of devices used for mechanical processing include refining devices (refiners; e.g., disk type, conical type, cylinder type), high-speed fibrillators, shear type stirrers, colloid mills, high-pressure injection dispersers, beaters, PFI mills, Kneader, disperser, high-speed disintegrator (top finer), high-pressure or ultra-high-pressure homogenizer, grinder (stone mill type crusher), ball mill, vibration mill, bead mill, single-shaft, double-shaft or multi-shaft kneading machine or high-speed extruder homomixers under rotation, refiners, defibrators, friction grinders, high-share defibrators, dispergers, homogenizers (e.g., microfluidizers)
  • a device that can apply a mechanical defibrating force such as a microfluidizer (microfluidizer) can be mentioned, and a device that can apply a defibrating force in a
  • the fibrous cellulose is modified fibrous cellulose
  • chemical modification treatment is performed before or after (usually before) defibration.
  • the modification treatment include oxidation, etherification, esterification such as phosphoric acid esterification, silane coupling, fluorination, and cationization.
  • oxidation (carboxylation), etherification (for example, carboxyalkylation), cationization, and esterification are preferred, and oxidation (carboxylation) and carboxyalkylation are more preferred.
  • cellulose materials include, for example, industrial additives (for example, for resins such as polypropylene, phenol resin, melamine resin, and various rubbers), and for tablets and other preparations (foods, pharmaceuticals, quasi-drugs, cosmetics). It can be used as an excipient.
  • resin compositions e.g., polyolefin resins, modified polyolefin resins, rubber
  • rubber compositions e.g., automobiles, personal computers, building materials, containers
  • food additives e.g., shredded cheese, fried products, bread crumbs, ham, sausage casings, their pickle liquid
  • hygiene products/cosmetics e.g.
  • Powdered cellulose can be used as an excipient for molded bodies (for example, preparations for foods, medicines, quasi-drugs, cosmetics, manufacturing industry, construction industry, etc.). Thereby, the molded product can exhibit good hardness.
  • Examples of the dosage form of the molded product include tablets.
  • the molded body has a moderate (practical) hardness, for example, usually 30 MPa or more, more preferably 40 MPa or more, still more preferably 50 MPa or more.
  • the upper limit is preferably 100 MPa or less, more preferably 80 MPa or less, still more preferably 60 MPa or less. Therefore, the hardness of the powdered cellulose is preferably 30 to 100 MPa, more preferably 40 to 80 MPa, and still more preferably 50 to 60 MPa. Tablet hardness can be measured, for example, using a tablet hardness meter under the conditions shown in Examples.
  • a sample was prepared by weighing 0.5 g of powdered cellulose into a microwave digestion container and adding 2 ml of pure water and 5 ml of nitric acid. After the sample was subjected to microwave digestion, it was transferred to a constant volume polypropylene container. After adding 2 ml of the internal standard solution to the sample, the volume was fixed (50 ml), and the iron component content was measured using a triple quadrupole ICP mass spectrometer.
  • the measurement conditions of the ICP mass spectrometer are as follows. ⁇ Model: Agilent 8800 (manufactured by Agilent Technologies Co., Ltd.) ⁇ Collision and reaction cell introduction gas: Helium and hydrogen ⁇ Measurement m/z: Iron; 56 ⁇ Internal standard element m/z: Rhodium; 103
  • ⁇ Particle size distribution, average particle size, span of particle size distribution> A laser diffraction particle size distribution analyzer (Mastersizer 3000, Spectris Malvern Panalytical Division) was used. Using a laser scattering method as the measurement principle, particle size distribution was measured by dry measurement, wet measurement (with ultrasonic irradiation), and wet measurement (without ultrasonic irradiation). When the particle size distribution is expressed as a volume accumulation distribution, the values at which the integrated value of the volume accumulation distribution is 10%, 50%, and 90% are respectively defined as the particle size distribution D. 10,D. 50, D. It was set at 90. Wet type (no ultrasonic irradiation) D. 50 was taken as the average particle diameter. Furthermore, the span of the particle size distribution was calculated using the above equation (1).
  • the dry measurement was carried out under the following conditions by adding a sample into the supply port so that the scattering intensity was less than 1%.
  • ⁇ Distributed unit Aero5 ⁇ Air pressure: 2 bar ⁇ Feed rate: 25
  • thermogravimetric residual rate 500°C% or thermogravimetric residual rate (400°C)%>
  • the thermogravimetric residual rate was measured using a thermal analyzer. That is, heat the powdered cellulose to 600°C (in an oxygen-free, nitrogen atmosphere), read the weight at 500°C or 400°C, and calculate the ratio (%) to the weight before the start of heating as the thermogravimetric residual rate (500°C). It was calculated as % (°C)% or thermogravimetric residual rate (400°C)%.
  • a cylindrical molded body or tablet made of 100% cellulose powder was produced as follows. 0.3 g of the sample was placed in a mortar (manufactured by Ichihashi Seiki Co., Ltd., 8 mm in diameter) and compressed with a pestle (manufactured by Ichihashi Seiki Co., Ltd.) with a diameter of 8 mm. 100% cellulose powder was compressed at 10 MPa and the stress was maintained for 10 seconds to produce a cylindrical molded body or tablet (the compressor used was HANDTAB-100 manufactured by Enerpac).
  • the load when the produced cylindrical molded body or tablet was broken was measured using a Schleungel hardness meter (manufactured by Freund Sangyo Co., Ltd., model MT50). The load was applied in the diametrical direction of the cylindrical molded body or tablet. Calculated using the average value of 5 samples.
  • Example 1 A pulverized product obtained by cutting a bleached wood pulp sheet (LBKP dry sheet, manufactured by Nippon Paper Industries Co., Ltd., moisture 20%) with a cutting mill (PIH3-20210YRFS, manufactured by Horai Co., Ltd., using a 3 mm diameter punching plate) as a raw material. was pulverized with a vertical roller mill (STR-20, manufactured by Seishin Enterprise Co., Ltd., feed rate 600 g/min, pulverizing rotor 40 Hz, classification rotor 50 Hz, blower 50 Hz), and the obtained pulverized product was used as the powdered cellulose of Example 1. It was used as Various physical property values are shown in Table 1.
  • Example 2 The process was carried out in the same manner as in Example 1, except that a cutting mill (HA8-2542, manufactured by Horai Co., Ltd., main mesh #250, auxiliary mesh #20) was used as the second-stage crusher, and the obtained pulverized product was It was used as the powdered cellulose in Example 2.
  • a cutting mill H8-2542, manufactured by Horai Co., Ltd., main mesh #250, auxiliary mesh #20
  • Example 3 Wood pulp (thermomechanical pulp, manufactured by Nippon Paper Industries Co., Ltd., moisture 60%) is dehydrated, loosened and dried, and then processed into a cutting mill (HA8-2542, manufactured by Horai Co., Ltd., main mesh #). 250, auxiliary mesh #50), and the resulting pulverized product was used as powdered cellulose in Example 3.
  • Various physical property values are listed in Table 1.
  • Example 4 Using a bleached wood pulp sheet (NDPT dry sheet, manufactured by Nippon Paper Industries Co., Ltd., moisture 7%) as a raw material, a raw material charge amount of 100 kg and a feed rate of 5. It was pulverized under the conditions of 0 kg/min and 10 rpm. The obtained pulverized product was processed using a batch type vibration mill (MB3 type, manufactured by Chuo Kakoki Co., Ltd.) with a raw material charge amount of 45 g (0.25 L), a vibration frequency of 1000 cpm, an amplitude of 8 mm, a ball diameter of 30 mm, and a ball filling rate of 80. % for 30 minutes, and the resulting pulverized product was used as the powdered cellulose of Example 4. Various physical property values are listed in Table 1.
  • Example 5 The same operation as in Example 4 was carried out, except that a bleached wood pulp sheet (LDPT dry sheet, manufactured by Nippon Paper Industries, Ltd., water content: 7%) was used, and the obtained pulverized material was mixed with the powdered cellulose of Example 5. It was used as Various physical property values are shown in Table 1.
  • LDPT dry sheet manufactured by Nippon Paper Industries, Ltd., water content: 7%
  • Example 6 A bleached wood pulp sheet (NDPT dry sheet, manufactured by Nippon Paper Industries Co., Ltd., moisture 7%) was used as a raw material, and a raw material amount of 40 g (pulp slurry concentration 5%) was acid-hydrolyzed with 0.5N hydrochloric acid at 90°C for 40 minutes. The obtained powdered cellulose was used as the powdered cellulose of Example 6.
  • NDPT dry sheet manufactured by Nippon Paper Industries Co., Ltd., moisture 7%
  • the obtained powdered cellulose was used as the powdered cellulose of Example 6.
  • Various physical property values are listed in Table 1.
  • Comparative example 1 Commercially available powdered cellulose ST-02 (manufactured by Asahi Kasei Corporation) was used as the powdered cellulose in Comparative Example 1. Various physical property values are listed in Table 1.
  • Example 3 it was difficult to make tablets, whereas in Examples 4 to 6, it was possible to make tablets.
  • the tablets obtained from Examples 4 to 6 had appropriate hardness. It is presumed that in Comparative Example 1, as a result of no inorganic substance being contained, the frictional force on the tablet surface was strong, making it easier to break, whereas in Example 3, the tablet was not formed as a result of the high inorganic substance content.

Abstract

Le but de la présente invention est de fournir : un matériau à base de cellulose qui présente une excellente efficacité de recyclage même lorsqu'il est utilisé en tant qu'additif pour un constituant de résine ; et un matériau à base de cellulose qui présente une excellente efficacité de recyclage et une excellente aptitude à la formation de comprimés. La présente invention concerne un matériau à base de cellulose d'une poudre de cellulose ou similaire contenant un constituant fer en une quantité de 1 à 50 ppm telle que détectée par un spectromètre de masse à plasma couplé par induction à triple quadripôle. Le matériau à base de cellulose peut être utilisé en tant que matériau pour un corps moulé tel qu'un comprimé, un excipient, une composition de caoutchouc, une composition de résine et un additif industriel.
PCT/JP2023/009057 2022-03-11 2023-03-09 Matériau à base de cellulose WO2023171748A1 (fr)

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JP2002020402A (ja) * 2000-05-12 2002-01-23 Johnson & Johnson Medical Ltd 溶解鉄への選択的結合性を示す固体組成物
JP2004115700A (ja) * 2002-09-27 2004-04-15 Nippon Paper Industries Co Ltd 粉末状セルロースおよびその製造法
JP2011093990A (ja) * 2009-10-28 2011-05-12 Mitsubishi Paper Mills Ltd セルロース含有熱可塑性樹脂の製造方法、セルロース含有熱可塑性樹脂およびその成形体
JP2012528256A (ja) * 2009-05-28 2012-11-12 ゲーペー ツェルローゼ ゲーエムベーハー 化学的クラフト繊維由来の修飾セルロース、ならびにそれを作製および使用する方法
JP2013139540A (ja) * 2011-12-08 2013-07-18 Nippon Paper Industries Co Ltd 粉末状セルロース
WO2016125497A1 (fr) * 2015-02-04 2016-08-11 日本ゼオン株式会社 Dispersion de nanofibres de cellulose oxydée contenant un métal et procédé de préparation associé

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JP2002020402A (ja) * 2000-05-12 2002-01-23 Johnson & Johnson Medical Ltd 溶解鉄への選択的結合性を示す固体組成物
JP2004115700A (ja) * 2002-09-27 2004-04-15 Nippon Paper Industries Co Ltd 粉末状セルロースおよびその製造法
JP2012528256A (ja) * 2009-05-28 2012-11-12 ゲーペー ツェルローゼ ゲーエムベーハー 化学的クラフト繊維由来の修飾セルロース、ならびにそれを作製および使用する方法
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JP2013139540A (ja) * 2011-12-08 2013-07-18 Nippon Paper Industries Co Ltd 粉末状セルロース
WO2016125497A1 (fr) * 2015-02-04 2016-08-11 日本ゼオン株式会社 Dispersion de nanofibres de cellulose oxydée contenant un métal et procédé de préparation associé

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