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WO2020050347A1 - Corps solide et procédé de fabrication de corps solide - Google Patents

Corps solide et procédé de fabrication de corps solide Download PDF

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Publication number
WO2020050347A1
WO2020050347A1 PCT/JP2019/034905 JP2019034905W WO2020050347A1 WO 2020050347 A1 WO2020050347 A1 WO 2020050347A1 JP 2019034905 W JP2019034905 W JP 2019034905W WO 2020050347 A1 WO2020050347 A1 WO 2020050347A1
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Prior art keywords
fibrous cellulose
fine fibrous
phosphate group
group
ion
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Ceased
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PCT/JP2019/034905
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English (en)
Japanese (ja)
Inventor
孟晨 趙
雄右 轟
裕一 野口
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Oji Holdings Corp
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Oji Holdings Corp
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Priority to JP2020541288A priority Critical patent/JPWO2020050347A1/ja
Publication of WO2020050347A1 publication Critical patent/WO2020050347A1/fr
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B15/00—Preparation of other cellulose derivatives or modified cellulose, e.g. complexes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B5/00—Preparation of cellulose esters of inorganic acids, e.g. phosphates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
    • C08L1/08—Cellulose derivatives
    • 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
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F2/00—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H11/00—Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only
    • D21H11/16—Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only modified by a particular after-treatment
    • D21H11/20—Chemically or biochemically modified fibres

Definitions

  • the present invention relates to a solid body and a method for producing the solid body.
  • cellulose fibers have been widely used in clothing, absorbent articles, paper products, and the like.
  • a fine fibrous cellulose having a fiber diameter of 1 ⁇ m or less is known in addition to a fibrous cellulose having a fiber diameter of 10 ⁇ m or more and 50 ⁇ m or less.
  • Fine fibrous cellulose is attracting attention as a new material, and its use is diversified. For example, development of sheets, resin composites, and thickeners containing fine fibrous cellulose has been promoted.
  • fine fibrous cellulose is stably dispersed in an aqueous solvent, it is provided in the form of an aqueous dispersion and is often used for various purposes.
  • a composite or the like is produced by mixing fine fibrous cellulose with a resin, there is a demand that the fine fibrous cellulose be mixed with an organic solvent and used.
  • a technique for producing a fine fibrous cellulose-containing dispersion in which fine fibrous cellulose is dispersed in a dispersion medium containing an organic solvent has been studied.
  • Patent Document 1 discloses a fine fibrous cellulose composite in which a surfactant is adsorbed to fine fibrous cellulose having a carboxy group.
  • a method of agglomerating and dispersing the fine fibrous cellulose in an organic solvent or a method of obtaining fine fibrous cellulose by refining the cellulose fibers in an organic solvent is used. It has been disclosed.
  • Patent Document 2 discloses a process of preparing an aqueous dispersion of fine fibrous cellulose having a carboxylate type group, and converting the carboxylate type group to a carboxylic acid amine salt type of an amine having an organic group.
  • a method for producing a fine fibrous cellulose dispersion which comprises a step of substituting with a group and a step of dispersing the fine fibrous cellulose having a carboxylic acid amine salt type group in an organic solvent.
  • a melt kneading method and a casting method are known.
  • a method for producing a solid containing fine fibrous cellulose a method of obtaining a solid by injecting an aqueous dispersion into a large amount of an organic solvent is also known.
  • the fine fibrous cellulose as described above is used, the water absorption and yellowness of the solid body may be increased.
  • the present inventors have studied to provide a solid having a low water absorption and a low yellowness.
  • the present inventors have found that a fibrous cellulose having a phosphate group or a substituent derived from a phosphate group, It has been found that by containing an organic onium ion having a predetermined structure as a counter ion of a substituent derived from a group, a solid having low water absorption and low yellowness can be obtained.
  • the present invention has the following configuration.
  • a fibrous cellulose having a fiber width of 1000 nm or less and having a phosphate group or a substituent derived from a phosphate group, and containing an organic onium ion as a counter ion of the phosphate group or the substituent derived from the phosphate group.
  • a solid body, The organic onium ion is a solid that satisfies at least one condition selected from the following (a) and (b): (A) containing a hydrocarbon group having 5 or more carbon atoms; (B) The total number of carbon atoms is 17 or more.
  • a composition comprising water and a first solvent with a second solvent having a hydrogen bond term ( ⁇ h) of Hansen solubility parameter of 12.0 MPa 1/2 or more
  • ⁇ h hydrogen bond term
  • a solid having low water absorption and low yellowness can be provided.
  • FIG. 1 is a graph showing the relationship between the amount of NaOH added to fibrous cellulose having a phosphate group and the electrical conductivity.
  • FIG. 2 is a graph showing the relationship between the amount of NaOH added to fibrous cellulose having a carboxy group and the electrical conductivity.
  • the present invention relates to a solid body containing fibrous cellulose having a fiber width of 1000 nm or less. Specifically, the present invention provides a fibrous cellulose having a fiber width of 1,000 nm or less and having a phosphate group or a phosphate group-derived substituent, and a counter ion of the phosphate group or the phosphate group-derived substituent.
  • the present invention relates to a solid containing organic onium ions.
  • the organic onium ion satisfies at least one condition selected from the following (a) and (b).
  • B) The total number of carbon atoms is 17 or more.
  • the water absorption of the solid body is preferably 200% or less, more preferably 100% or less, and even more preferably 70% or less.
  • the lower limit of the water absorption of the solid body may be 0%.
  • the water resistance of the solid body can be increased by setting the water absorption of the solid body within the above range. Further, by setting the water absorption of the solid body within the above range, the surface smoothness of the solid body can be more effectively improved.
  • the yellowness of the solid body is a yellowness measured according to ASTM E313 of the pellet produced under the following condition a.
  • the powder is press-molded at a surface pressure of 600 MPa for 1 minute so that the basis weight becomes 3000 g / m 2 to obtain a pellet for measuring yellowness.
  • the pellets produced in this way under the condition a are used as the pellets for measuring the yellowness.
  • the yellowness of the yellowness measurement pellet is measured by reflected light measurement according to ASTM E313.
  • the yellowness is measured using a spectrophotometer.
  • a spectrophotometer manufactured by Spectroeye; Gretag Macbeth can be used.
  • the yellowness (YI 0 ) of the solid body measured according to ASTM E313 is preferably 30 or less, more preferably 27 or less, and even more preferably 25 or less.
  • the lower limit of the yellowness (YI 0 ) of the solid is not particularly limited, but is preferably, for example, 0.1 or more.
  • the yellowness of the solid body of the present invention is kept low.
  • the surface smoothness of the solid body can be more effectively improved by setting the yellowness of the solid body within the above range.
  • the yellowness (YI 100 ) of the sheet in terms of the film thickness of 100 ⁇ m calculated by the following equation b is 32 or less.
  • Sheet yellowness (YI 100 ) in terms of film thickness 100 ⁇ m sheet yellowness (YI) ⁇ 100 ( ⁇ m) / sheet film thickness ( ⁇ m)
  • the yellowness (YI 100 ) of the sheet is the yellowness of the sheet measured by transmitted light measurement according to JIS K 7373.
  • a device for measuring the yellowness (YI) of the sheet for example, Color Cut i manufactured by Suga Test Instruments Co., Ltd. can be mentioned.
  • the yellowness (YI 100 ) of the sheet is preferably 32 or less, more preferably 28 or less, and even more preferably 24 or less.
  • the lower limit (YI 100 ) of the yellowness of the sheet is not particularly limited, but is preferably, for example, 0.1 or more.
  • the present invention relates to fibrous cellulose having a fiber width of 1000 nm or less and having a phosphate group or a phosphate-derived substituent, and an organic onium ion as a counter ion of the phosphate group or the phosphate-derived substituent. It may be related to a solid body consisting of In the present invention, the fine fibrous cellulose has a phosphate group or a substituent derived from a phosphate group, and contains an organic onium ion having a predetermined structure, so that the solid body contains a hydrophobic resin or the like. Even in the absence, a low water absorption and a low yellowness are achieved.
  • the form of the solid body of the present invention is not particularly limited, and is preferably, for example, sheet-like, powder-like, or thread-like.
  • the solid body may be a gel body.
  • the solid body is preferably in the form of a sheet, beads (granules), or filaments (filaments), and particularly preferably in the form of sheets.
  • the particle diameter of the beads is preferably 0.1 mm or more and 10 mm or less.
  • the width of the filament is preferably 0.1 mm or more and 10 mm or less, and the length of the filament is preferably 1 mm or more and 10000 mm or less.
  • the solid content concentration of the solid body is preferably 80% by mass or more, more preferably 84% by mass or more, even more preferably 88% by mass or more based on the total mass of the solid body. .
  • the solid content concentration of the solid body may be 100% by mass.
  • the solid body may contain water, and when the solid body contains water, the water content is preferably 20% by mass or less based on the total mass of the solid body, and is preferably 15% by mass or less. %, More preferably 10% by mass or less.
  • the water content in the solid body can be measured by placing 200 mg of the solid body on a moisture meter (MS-70, manufactured by A & D Corporation) and heating at 140 ° C. The water content in the solid body can be calculated from the measured water content.
  • the solid body of the present invention is preferably a molded body.
  • a molded body is a solid body molded into a desired shape.
  • the molded body include sheets, beads, and filaments.
  • the molded article is preferably a sheet, beads or filament, and particularly preferably a sheet.
  • the solid body of the present invention contains fibrous cellulose having a fiber width of 1,000 nm or less and having a phosphate group or a substituent derived from a phosphate group.
  • the fiber width of the fibrous cellulose having a phosphate group or a substituent derived from a phosphate group is preferably 100 nm or less, more preferably 8 nm or less.
  • the fiber width of the fibrous cellulose can be measured by, for example, observation with an electron microscope.
  • fibrous cellulose having a fiber width of 1000 nm or less may be referred to as fine fibrous cellulose.
  • the fiber width of fibrous cellulose can be measured by, for example, observation with an electron microscope.
  • the average fiber width of the fibrous cellulose is, for example, 1000 nm or less.
  • the average fiber width of the fibrous cellulose is, for example, preferably from 2 nm to 1000 nm, more preferably from 2 nm to 100 nm, further preferably from 2 nm to 50 nm, and more preferably from 2 nm to 10 nm. Particularly preferred.
  • the fibrous cellulose is, for example, a monofibrous cellulose.
  • the average fiber width of the fibrous cellulose is measured, for example, using an electron microscope as follows. First, an aqueous suspension of fibrous cellulose having a concentration of 0.05% by mass or more and 0.1% by mass or less was prepared, and this suspension was cast on a carbon film-coated grid that had been subjected to a hydrophilization treatment, and a TEM observation sample was prepared. And In the case of including a wide fiber, an SEM image of a surface cast on glass may be observed. Next, observation with an electron microscope image is performed at a magnification of 1,000 times, 5000 times, 10,000 times, or 50,000 times depending on the width of the fiber to be observed. However, the sample, observation conditions and magnification are adjusted so as to satisfy the following conditions.
  • One straight line X is drawn at an arbitrary position in the observation image, and 20 or more fibers intersect the straight line X.
  • a straight line Y perpendicular to the straight line is drawn in the same image, and 20 or more fibers intersect the straight line Y.
  • the width of the fiber that intersects the straight line X and the straight line Y is visually read for an observation image satisfying the above conditions. In this way, at least three or more sets of observation images of the surface portions that do not overlap each other are obtained.
  • the average value of the read fiber width is defined as the average fiber width of the fibrous cellulose.
  • the fiber length of the fibrous cellulose is not particularly limited, but is preferably, for example, 0.1 ⁇ m or more and 1000 ⁇ m or less, more preferably 0.1 ⁇ m or more and 800 ⁇ m or less, and further preferably 0.1 ⁇ m or more and 600 ⁇ m or less. preferable.
  • the fiber length of the fibrous cellulose can be determined by, for example, image analysis using TEM, SEM, or AFM.
  • the fibrous cellulose preferably has an I-type crystal structure.
  • the proportion of the type I crystal structure in the fine fibrous cellulose is, for example, preferably 30% or more, more preferably 40% or more, and even more preferably 50% or more. Thereby, further excellent performance can be expected in terms of heat resistance and low linear thermal expansion coefficient.
  • the crystallinity can be determined by measuring the X-ray diffraction profile and using the pattern by a conventional method (Seagal et al., Textile Research Journal, Vol. 29, p. 786, 1959).
  • the axial ratio (fiber length / fiber width) of the fibrous cellulose is not particularly limited, but is preferably, for example, 20 or more and 10,000 or less, and more preferably 50 or more and 1000 or less.
  • the axial ratio is equal to or more than the lower limit, a sheet containing fine fibrous cellulose is easily formed. It is preferable that the axial ratio be equal to or less than the above upper limit, for example, when handling fibrous cellulose as an aqueous dispersion, handling such as dilution becomes easy.
  • the fibrous cellulose in the present embodiment has, for example, both a crystalline region and an amorphous region.
  • the fine fibrous cellulose having both the crystalline region and the non-crystalline region and having a high axial ratio is realized by the method for producing fine fibrous cellulose described below.
  • Fibrous cellulose has a phosphate group or a substituent derived from a phosphate group (sometimes simply referred to as a phosphate group).
  • the phosphate group has, for example, a larger number of anionic groups per molecule than a carboxy group or the like, and thus may have more organic onium ions as counterions. Thereby, it is considered that the water absorption and the yellowness of the solid body can be more effectively increased.
  • the phosphate group or a substituent derived from a phosphate group is, for example, a substituent represented by the following formula (1), and is generalized as a phosphorus oxo acid group or a substituent derived from a phosphorus oxo acid.
  • the phosphate group is a divalent functional group corresponding to, for example, phosphoric acid obtained by removing a hydroxy group. Specifically, it is a group represented by —PO 3 H 2 .
  • the substituent derived from the phosphate group includes substituents such as a salt of the phosphate group and a phosphate group.
  • the substituent derived from the phosphate group may be contained in the fibrous cellulose as a group in which the phosphate group is condensed (for example, a pyrophosphate group).
  • the phosphate group may be, for example, a phosphite group (phosphonate group), and the substituent derived from the phosphate group may be a salt of a phosphite group, a phosphite ester group, or the like. Is also good.
  • R represents a hydrogen atom, a saturated-straight hydrocarbon group, a saturated-branched hydrocarbon group, a saturated-cyclic hydrocarbon group, an unsaturated-straight hydrocarbon group, or an unsaturated-branched hydrocarbon group, respectively.
  • Examples of the saturated-linear hydrocarbon group include a methyl group, an ethyl group, an n-propyl group, and an n-butyl group, but are not particularly limited.
  • Examples of the saturated-branched hydrocarbon group include an i-propyl group and a t-butyl group, but are not particularly limited.
  • Examples of the saturated-cyclic hydrocarbon group include a cyclopentyl group and a cyclohexyl group, but are not particularly limited.
  • Examples of the unsaturated-linear hydrocarbon group include a vinyl group and an allyl group, but are not particularly limited.
  • Examples of the unsaturated-branched hydrocarbon group include an i-propenyl group and a 3-butenyl group, but are not particularly limited.
  • Examples of the unsaturated-cyclic hydrocarbon group include a cyclopentenyl group and a cyclohexenyl group, but are not particularly limited.
  • Examples of the aromatic group include a phenyl group and a naphthyl group, but are not particularly limited.
  • a group is mentioned, it is not particularly limited.
  • the number of carbon atoms constituting the main chain of R is not particularly limited, but is preferably 20 or less, more preferably 10 or less.
  • ⁇ b + is a monovalent or higher cation composed of an organic or inorganic substance.
  • the monovalent or higher cation composed of an organic substance include aliphatic ammonium and aromatic ammonium, and at least a part of ⁇ b + is an organic onium ion described later.
  • the monovalent or higher cation composed of an inorganic substance include ions of alkali metals such as sodium, potassium, and lithium, and cations of divalent metals such as calcium and magnesium, and hydrogen ions. There is no particular limitation. These can be applied alone or in combination of two or more.
  • the monovalent or higher cation composed of an organic or inorganic substance is preferably, but not particularly limited to, sodium or potassium ions that are less likely to yellow when a ⁇ -containing fiber material is heated and are easily industrially used.
  • the amount of the phosphate group or the substituent derived from the phosphate group (the amount of the phosphate group) introduced into the fibrous cellulose is preferably, for example, 0.10 mmol / g or more per 1 g (mass) of the fibrous cellulose, and 0.20 mmol / g. / G or more, more preferably 0.50 mmol / g or more, and particularly preferably 1.00 mmol / g or more.
  • the amount of phosphate groups introduced into fibrous cellulose is, for example, preferably 5.20 mmol / g or less, more preferably 3.65 mmol / g or less, per 1 g (mass) of fibrous cellulose.
  • the unit mmol / g indicates the amount of the substituent per 1 g of the mass of fibrous cellulose when the counter ion of the phosphate group is a hydrogen ion (H + ).
  • H + hydrogen ion
  • the amount of phosphate groups introduced into fibrous cellulose can be measured, for example, by conductivity titration.
  • the amount of introduction is measured by determining the change in conductivity while adding an alkali such as an aqueous sodium hydroxide solution to the obtained slurry containing fibrous cellulose.
  • FIG. 1 is a graph showing the relationship between the amount of NaOH added to fibrous cellulose having a phosphate group and the electrical conductivity.
  • the amount of phosphate groups introduced into fibrous cellulose is measured, for example, as follows. First, a slurry containing fibrous cellulose is treated with a strongly acidic ion exchange resin. If necessary, before the treatment with the strongly acidic ion exchange resin, a fibrillation treatment similar to the fibrillation treatment step described later may be performed on the measurement target. Next, a change in electric conductivity is observed while adding an aqueous solution of sodium hydroxide, and a titration curve as shown in FIG. 1 is obtained. As shown in FIG.
  • first region the electrical conductivity sharply decreases at first
  • second region the conductivity starts to slightly increase
  • third region the increment of the conductivity increases
  • boundary point between the second region and the third region is defined as the point at which the amount of change in the conductivity twice (ie, the increment (slope) of the conductivity) becomes maximum.
  • the amount of alkali required in the first region is equal to the amount of strongly acidic groups in the slurry used for titration
  • the amount of alkali required in the second region is equal to the amount of weakly acidic groups in the slurry used for titration.
  • the amount of the strongly acidic group matches the amount of the phosphorus atom regardless of the presence or absence of condensation.
  • the value obtained by dividing the alkali amount (mmol) required in the first region of the titration curve obtained above by the solid content (g) in the slurry to be titrated is the phosphate group introduction amount (mmol / mmol). g).
  • the amount of the substituent may be lower than it should be. It is desirable to titrate the aqueous sodium solution by 50 ⁇ L every 30 seconds.
  • Fine fibrous cellulose is produced from a fiber raw material containing cellulose.
  • the fiber material containing cellulose is not particularly limited, but pulp is preferably used because it is easily available and inexpensive.
  • Pulp includes, for example, wood pulp, non-wood pulp, and deinked pulp. Examples of the wood pulp include, but are not particularly limited to, hardwood kraft pulp (LBKP), softwood kraft pulp (NBKP), sulfite pulp (SP), dissolved pulp (DP), soda pulp (AP), and unbleached kraft pulp (UKP).
  • Non-wood pulp includes, but is not limited to, cotton pulp such as cotton linter and cotton lint, and non-wood pulp such as hemp, straw and bagasse.
  • Examples of the deinked pulp include, but are not particularly limited to, deinked pulp made from waste paper.
  • one of the above-mentioned types may be used alone, or two or more types may be used in combination.
  • wood pulp and deinked pulp are preferable from the viewpoint of availability.
  • cellulose ratio is large and the yield of fine fibrous cellulose at the time of defibration treatment is high, and the decomposition of cellulose in pulp is small, and fine fibrous cellulose of long fibers having a large axial ratio can be obtained.
  • chemical pulp is more preferable, and kraft pulp and sulfite pulp are more preferable.
  • fine fibrous cellulose of long fibers having a large axial ratio is used, the viscosity tends to increase.
  • cellulose raw material containing cellulose for example, cellulose contained in ascidians or bacterial cellulose produced by acetic acid bacteria can be used.
  • a fiber formed by a linear nitrogen-containing polysaccharide polymer such as chitin or chitosan can be used in place of the fiber material containing cellulose.
  • the step of producing fine fibrous cellulose includes a step of introducing a phosphate group.
  • a phosphate group introduction step at least one compound selected from compounds capable of introducing a phosphate group by reacting with a hydroxyl group of a cellulose-containing fiber material (hereinafter, also referred to as “compound A”) is converted into cellulose.
  • compound A a compound selected from compounds capable of introducing a phosphate group by reacting with a hydroxyl group of a cellulose-containing fiber material (hereinafter, also referred to as “compound A”) is converted into cellulose.
  • This is a step of acting on a fiber raw material containing.
  • a phosphate group-introduced fiber is obtained.
  • the reaction between the fiber material containing cellulose and the compound A is performed in the presence of at least one selected from urea and its derivatives (hereinafter, also referred to as “compound B”). You may.
  • the reaction between the fiber raw material containing cellulose and the compound A may be performed in a state where the compound B is not present.
  • a method of mixing compound A and compound B with a dry, wet, or slurry fiber raw material may be mentioned.
  • a fiber material in a dry state or a wet state it is preferable to use a fiber material in a dry state, because of high uniformity of the reaction.
  • the form of the fiber raw material is not particularly limited, but is preferably, for example, cotton or a thin sheet.
  • the compound A and the compound B may be added to the fiber material in the form of a powder, a solution dissolved in a solvent, or a state in which the compound A and the compound B are heated to a melting point or higher and melted.
  • the compound A and the compound B may be added simultaneously to the fiber raw material, may be added separately, or may be added as a mixture.
  • the method of adding the compound A and the compound B is not particularly limited, but when the compound A and the compound B are in a solution state, the fiber raw material may be immersed in the solution, absorbed and then taken out. May be added dropwise to the solution.
  • the necessary amount of compound A and compound B may be added to the fiber raw material, or the excessive amount of compound A and compound B may be added to the fiber raw material, respectively, and then the excess compound A and compound B may be squeezed or filtered. It may be removed.
  • Examples of the compound A used in the present embodiment include a compound having a phosphorus atom and capable of forming an ester bond with cellulose, and specifically, phosphoric acid or a salt thereof, phosphorous acid or a salt thereof, dehydration condensation Examples thereof include phosphoric acid or a salt thereof, phosphoric anhydride (diphosphorus pentoxide), and the like, but are not particularly limited.
  • phosphoric acid those having various purities can be used. For example, 100% phosphoric acid (normal phosphoric acid) and 85% phosphoric acid can be used.
  • Examples of the phosphorous acid include 99% phosphorous acid (phosphonic acid).
  • the dehydrated condensed phosphoric acid is obtained by condensing two or more molecules of phosphoric acid by a dehydration reaction, and examples thereof include pyrophosphoric acid and polyphosphoric acid.
  • examples of the phosphate, phosphite, and dehydrated condensed phosphate include phosphoric acid, lithium salt, sodium salt, potassium salt, and ammonium salt of phosphoric acid or dehydrated condensed phosphoric acid. It can be the sum.
  • phosphoric acid, phosphoric acid, phosphoric acid from the viewpoint of high efficiency of introduction of the phosphate group, easier to improve the defibration efficiency in the defibration step described later, low cost, and industrially applicable
  • a sodium salt, a potassium salt of phosphoric acid, or an ammonium salt of phosphoric acid is preferable, and phosphoric acid, sodium dihydrogen phosphate, disodium hydrogen phosphate, or ammonium dihydrogen phosphate is more preferable.
  • the amount of the compound A added to the fiber raw material is not particularly limited.
  • the amount of the phosphorus atom added to the fiber raw material (absolute dry mass) is 0.5% by mass or more. It is preferably 100% by mass or less, more preferably 1% by mass or more and 50% by mass or less, further preferably 2% by mass or more and 30% by mass or less.
  • the amount of the phosphorus atom added to the fiber raw material within the above range, the yield of fine fibrous cellulose can be further improved.
  • the amount of phosphorus atoms added to the fiber raw material to be equal to or less than the above upper limit, the effect of improving the yield and the cost can be balanced.
  • the compound B used in this embodiment is at least one selected from urea and its derivatives as described above.
  • Compound B includes, for example, urea, biuret, 1-phenylurea, 1-benzylurea, 1-methylurea, 1-ethylurea and the like.
  • the compound B is preferably used as an aqueous solution.
  • the amount of the compound B to be added to the fiber raw material is not particularly limited, but is, for example, preferably 1% by mass or more and 500% by mass or less, more preferably 10% by mass or more and 400% by mass or less, More preferably, it is 100% by mass or more and 350% by mass or less.
  • amides or amines may be included in the reaction system.
  • the amide include formamide, dimethylformamide, acetamide, dimethylacetamide and the like.
  • amines include methylamine, ethylamine, trimethylamine, triethylamine, monoethanolamine, diethanolamine, triethanolamine, pyridine, ethylenediamine, hexamethylenediamine, and the like. Among these, it is known that triethylamine particularly works as a good reaction catalyst.
  • the phosphoric acid group introduction step it is preferable to add or mix the compound A or the like to the fiber raw material and then perform a heat treatment on the fiber raw material.
  • the heat treatment temperature it is preferable to select a temperature at which a phosphate group can be efficiently introduced while suppressing the thermal decomposition and hydrolysis of the fiber.
  • the heat treatment temperature is, for example, preferably from 50 ° C. to 300 ° C., more preferably from 100 ° C. to 250 ° C., and even more preferably from 130 ° C. to 200 ° C.
  • equipment having various heat media can be used for the heat treatment, for example, a stirring drying apparatus, a rotary drying apparatus, a disk drying apparatus, a roll heating apparatus, a plate heating apparatus, a fluidized bed drying apparatus, an air current A drying device, a reduced-pressure drying device, an infrared heating device, a far-infrared heating device, and a microwave heating device can be used.
  • the compound A is added to a thin sheet-form fiber material by impregnation or the like, and then the fiber material and the compound A are heated while kneading or stirring with a kneader or the like.
  • the concentration unevenness of the compound A in the fiber raw material and more uniformly introduce the phosphate group to the surface of the cellulose fiber contained in the fiber raw material.
  • the dissolved compound A is attracted to the water molecules by the surface tension and moves to the fiber material surface similarly (that is, the concentration unevenness of the compound A decreases). It can be considered that this is caused by the fact that it can be suppressed.
  • the heating device used for the heat treatment always generates, for example, the water retained by the slurry and the water generated by the dehydration condensation (phosphate esterification) reaction between compound A and the hydroxyl group contained in cellulose or the like in the fiber material. It is preferable that the device can be discharged outside the device system. As such a heating device, for example, an air-blowing oven or the like can be mentioned. By constantly discharging the water in the system, it is possible to suppress the hydrolysis reaction of the phosphate ester bond, which is the reverse reaction of the phosphorylation, and also to suppress the acid hydrolysis of the sugar chains in the fiber. it can. For this reason, it becomes possible to obtain fine fibrous cellulose having a high axial ratio.
  • the time of the heat treatment is, for example, preferably from 1 second to 300 minutes after water is substantially removed from the fiber raw material, more preferably from 1 second to 1000 seconds, and more preferably from 10 seconds to 800 seconds. Is more preferable.
  • the amount of the phosphate group introduced can be set in a preferable range.
  • the phosphate group introduction step may be performed at least once, but may be repeated twice or more. By performing the phosphate group introduction step twice or more, a large number of phosphate groups can be introduced into the fiber raw material.
  • a case where the phosphate group introduction step is performed twice is exemplified.
  • a washing step can be performed on the phosphate group-introduced fiber as necessary.
  • the washing step is performed, for example, by washing the phosphate group-introduced fiber with water or an organic solvent. Further, the cleaning step may be performed after each step described later, and the number of times of cleaning performed in each cleaning step is not particularly limited.
  • the fiber raw material may be subjected to an alkali treatment between the phosphate group introduction step and the defibration treatment step described below.
  • the method of the alkali treatment is not particularly limited, and includes, for example, a method of immersing the phosphate group-introduced fiber in an alkaline solution.
  • the alkali compound contained in the alkali solution is not particularly limited, and may be an inorganic alkali compound or an organic alkali compound. In the present embodiment, it is preferable to use, for example, sodium hydroxide or potassium hydroxide as the alkali compound because of high versatility.
  • the solvent contained in the alkaline solution may be either water or an organic solvent. Among them, the solvent contained in the alkaline solution is preferably a polar solvent containing water or a polar organic solvent exemplified by alcohol, and more preferably an aqueous solvent containing at least water.
  • an aqueous solution of sodium hydroxide or an aqueous solution of potassium hydroxide is preferable because of high versatility.
  • the temperature of the alkali solution in the alkali treatment step is not particularly limited, but is preferably, for example, 5 ° C or more and 80 ° C or less, more preferably 10 ° C or more and 60 ° C or less.
  • the immersion time of the phosphate group-introduced fiber in the alkali solution in the alkali treatment step is not particularly limited, but is preferably, for example, 5 minutes or more and 30 minutes or less, and more preferably 10 minutes or more and 20 minutes or less.
  • the amount of the alkali solution used in the alkali treatment is not particularly limited. For example, it is preferably from 100% by mass to 100,000% by mass, and preferably from 1,000% by mass to 10,000% by mass, based on the absolute dry mass of the phosphate group-introduced fiber. Is more preferable.
  • the phosphate group-introduced fiber may be washed with water or an organic solvent after the phosphate group introduction step and before the alkali treatment step. After the alkali treatment step and before the fibrillation treatment step, it is preferable to wash the alkali-treated phosphate group-introduced fiber with water or an organic solvent from the viewpoint of improving the handleability.
  • an acid treatment may be performed on the fiber raw material between the step of introducing a phosphate group and the defibration treatment step described below.
  • a phosphoric acid group introduction step, an acid treatment, an alkali treatment, and a fibrillation treatment may be performed in this order.
  • the method of the acid treatment is not particularly limited, and examples thereof include a method of immersing the fiber raw material in an acid-containing acid solution.
  • the concentration of the acidic liquid used is not particularly limited, but is preferably, for example, 10% by mass or less, and more preferably 5% by mass or less.
  • the pH of the acidic liquid used is not particularly limited, but is preferably, for example, 0 or more and 4 or less, and more preferably 1 or more and 3 or less.
  • As the acid contained in the acidic liquid for example, an inorganic acid, a sulfonic acid, a carboxylic acid and the like can be used.
  • Examples of the inorganic acid include sulfuric acid, nitric acid, hydrochloric acid, hydrobromic acid, hydroiodic acid, hypochlorous acid, chlorous acid, chloric acid, perchloric acid, phosphoric acid, boric acid and the like.
  • Examples of the sulfonic acid include methanesulfonic acid, ethanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, trifluoromethanesulfonic acid and the like.
  • Examples of the carboxylic acid include formic acid, acetic acid, citric acid, gluconic acid, lactic acid, oxalic acid, tartaric acid and the like. Among these, it is particularly preferable to use hydrochloric acid or sulfuric acid.
  • the temperature of the acid solution in the acid treatment is not particularly limited, but is preferably, for example, 5 ° C or more and 100 ° C or less, and more preferably 20 ° C or more and 90 ° C or less.
  • the immersion time in the acid solution in the acid treatment is not particularly limited, but is preferably, for example, 5 minutes or more and 120 minutes or less, and more preferably 10 minutes or more and 60 minutes or less.
  • the amount of the acid solution used in the acid treatment is not particularly limited, but is preferably, for example, 100% by mass to 100,000% by mass, and more preferably 1,000% by mass to 10,000% by mass, based on the absolute dry mass of the fiber raw material. Is more preferred.
  • ⁇ Fibrillation processing> By subjecting the phosphate group-introduced fibers to defibration in the defibration step, fine fibrous cellulose is obtained.
  • a defibrating device can be used.
  • the defibrating apparatus is not particularly limited, but includes, for example, a high-speed defibrating machine, a grinder (stone mill-type crusher), a high-pressure homogenizer or an ultra-high-pressure homogenizer, a high-pressure collision-type crusher, a ball mill, a bead mill, a disc refiner, a conical refiner, and a twin-screw.
  • a kneader, a vibration mill, a homomixer under high-speed rotation, an ultrasonic disperser, a beater, or the like can be used.
  • the fibrillation treatment step for example, it is preferable to dilute the phosphate group-introduced fiber with a dispersion medium to form a slurry.
  • a dispersion medium one or more kinds selected from water and an organic solvent such as a polar organic solvent can be used.
  • the polar organic solvent is not particularly limited, but, for example, alcohols, polyhydric alcohols, ketones, ethers, esters, aprotic polar solvents, and the like are preferable.
  • the alcohols include methanol, ethanol, isopropanol, n-butanol, isobutyl alcohol and the like.
  • polyhydric alcohols include ethylene glycol, propylene glycol, glycerin and the like.
  • ketones include acetone and methyl ethyl ketone (MEK).
  • the ethers include diethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono n-butyl ether, and propylene glycol monomethyl ether.
  • the esters include ethyl acetate, butyl acetate and the like.
  • the aprotic polar solvent include dimethyl sulfoxide (DMSO), dimethylformamide (DMF), dimethylacetamide (DMAc), N-methyl-2-pyrrolidinone (NMP) and the like.
  • the solid content concentration of the fine fibrous cellulose during the defibration treatment can be set as appropriate.
  • the slurry obtained by dispersing the phosphate group-introduced fibers in a dispersion medium may contain a solid content other than the phosphate group-introduced fibers such as urea having hydrogen bonding properties.
  • the solid of the present invention contains an organic onium ion as a counter ion of a phosphate group or a substituent derived from a phosphate group of fibrous cellulose.
  • an organic onium ion is present as a counter ion of fibrous cellulose, but a free organic onium ion may be present in the solid. Note that the organic onium ion does not form a covalent bond with the fibrous cellulose.
  • the organic onium ion satisfies at least one condition selected from the following (a) and (b).
  • (A) It contains a hydrocarbon group having 5 or more carbon atoms.
  • (B) The total number of carbon atoms is 17 or more. That is, the fibrous cellulose has at least one selected from an organic onium ion having a hydrocarbon group having 5 or more carbon atoms and an organic onium ion having a total carbon number of 17 or more, and is derived from a phosphate group or a phosphate group. Includes as a counter ion of the substituent.
  • the hydrocarbon group having 5 or more carbon atoms is preferably an alkyl group having 5 or more carbon atoms or an alkylene group having 5 or more carbon atoms, and an alkyl group having 6 or more carbon atoms or an alkylene having 6 or more carbon atoms.
  • the organic onium ion is preferably an organic onium ion having an alkyl group having 5 or more carbon atoms, more preferably an organic onium ion having an alkyl group having 5 or more carbon atoms and having a total carbon number of 17 or more. preferable.
  • the organic onium ion is preferably an organic onium ion represented by the following general formula (A).
  • M is preferably a nitrogen atom or a phosphorus atom
  • R 1 to R 4 each independently represent a hydrogen atom or an organic group.
  • at least one of R 1 to R 4 is preferably an organic group having 5 or more carbon atoms, or the total number of carbon atoms of R 1 to R 4 is preferably 17 or more.
  • M is preferably a nitrogen atom. That is, the organic onium ion is preferably an organic ammonium ion.
  • at least one of R 1 to R 4 is preferably an alkyl group having 5 or more carbon atoms, and the total number of carbon atoms of R 1 to R 4 is preferably 17 or more.
  • Such organic onium ions include, for example, lauryl trimethyl ammonium, cetyl trimethyl ammonium, stearyl trimethyl ammonium, octyl dimethyl ethyl ammonium, lauryl dimethyl ethyl ammonium, didecyl dimethyl ammonium, lauryl dimethyl benzyl ammonium, tributyl benzyl ammonium, methyl tri-n -Octyl ammonium, hexyl ammonium, n-octyl ammonium, dodecyl ammonium, tetradecyl ammonium, hexadecyl ammonium, stearyl ammonium, N, N-dimethyldodecyl ammonium, N, N-dimethyltetradecyl ammonium, N, N-dimethylhexadecyl Ammonium, N, N-dimethyl-n-octadecyl
  • the central element of the organic onium ion is bonded to a total of four groups or hydrogen.
  • the number of bonding groups is less than four, the remaining hydrogen atoms are bonded to form an organic onium ion.
  • N N-didodecylmethylammonium
  • hydrogen is bonded to the other one to form an organic onium ion.
  • the mass ratio of C atoms to O atoms is preferably as large as possible.
  • C / O ratio it is preferable that C / O> 5.
  • the molecular weight of the organic onium ion is preferably 2000 or less, more preferably 1800 or less.
  • the molecular weight of the organic onium ion is preferably 2000 or less, more preferably 1800 or less.
  • the content of the organic onium ion is preferably 1.0% by mass or more, more preferably 1.5% by mass or more, and more preferably 2.0% by mass or more based on the total mass of the solid. Is more preferable. Further, the content of the organic onium ion is preferably 90% by mass or less, more preferably 80% by mass or less based on the total mass of the solid.
  • the content of the organic onium ion in the solid body is preferably 0.5 to 2 times the molar amount of the phosphate group contained in the fibrous cellulose, but is not particularly limited. .
  • the content of the organic onium ion can be measured by tracking atoms typically contained in the organic onium ion. Specifically, the nitrogen atom is measured when the organic onium ion is an ammonium ion, and the phosphorus atom is measured when the organic onium ion is a phosphonium ion.
  • the fibrous cellulose contains a nitrogen atom or a phosphorus atom in addition to the organic onium ion
  • a method of extracting only the organic onium ion for example, performing an extraction operation with an acid, and then measuring the amount of the target atom just do it.
  • the organic onium ion is preferably an ion exhibiting hydrophobicity. That is, the fibrous cellulose in the present invention exhibits hydrophobicity by having an organic onium ion, and as a result, it becomes easy to lower the water absorption of the solid.
  • the solid body of the present invention may further contain a resin.
  • the type of the resin is not particularly limited, and examples thereof include a thermoplastic resin and a thermosetting resin.
  • the resin examples include polyolefin resin, acrylic resin, polycarbonate resin, polyester resin, polyamide resin, silicone resin, fluorine resin, chlorine resin, epoxy resin, melamine resin, phenol resin, and polyurethane resin.
  • Resins, diallyl phthalate resins, alcohol resins, cellulose derivatives, and precursors of these resins can be mentioned.
  • a cellulose derivative carboxymethylcellulose, methylcellulose, hydroxyethylcellulose, etc. can be mentioned, for example.
  • the solid body of the present invention may contain a resin precursor as the resin.
  • the type of the resin precursor is not particularly limited, and examples thereof include a thermoplastic resin and a thermosetting resin precursor.
  • the precursor of the thermoplastic resin means a monomer or an oligomer having a relatively low molecular weight used for producing the thermoplastic resin.
  • the precursor of the thermosetting resin means a monomer or an oligomer having a relatively low molecular weight that can form a thermosetting resin by causing a polymerization reaction or a cross-linking reaction by the action of light, heat, and a curing agent.
  • the solid body of the present invention may further contain a water-soluble polymer as a resin in addition to the above-mentioned resin species.
  • the water-soluble polymer include synthetic water-soluble polymers (eg, carboxyvinyl polymer, polyvinyl alcohol, alkyl methacrylate / acrylic acid copolymer, polyvinylpyrrolidone, sodium polyacrylate, polyethylene glycol, diethylene glycol, triethylene glycol, propylene) Glycol, dipropylene glycol, polypropylene glycol, isoprene glycol, hexylene glycol, 1,3-butylene glycol, polyacrylamide, etc.), thickening polysaccharides (eg, xanthan gum, guar gum, tamarind gum, carrageenan, locust bean gum, quince seed) , Alginic acid, pullulan, carrageenan, pectin, etc.), cationized starch, raw starch, oxidized starch
  • the content of the resin contained in the solid body is preferably 40% by mass or less, more preferably 30% by mass or less, based on the total mass of the solid matter contained in the solid body. More preferably, it is 20% by mass or less. Further, the content of the resin contained in the solid body may be 1% by mass or more based on the total mass of the solid matter contained in the solid body. The resin does not have to be substantially contained in the solid body. The state in which the resin is not substantially contained means that the content of the resin is less than 1% by mass relative to the total mass of the solid contained in the solid.
  • the solid body may further contain other optional components.
  • the optional component include a moisture absorbent.
  • the moisture absorbent include silica gel, zeolite, alumina, carboxymethyl cellulose, polyvinyl alcohol-soluble cellulose acetate, polyethylene glycol, sepiolite, calcium oxide, diatomaceous earth, activated carbon, activated clay, white carbon, calcium chloride, magnesium chloride, and potassium acetate.
  • surfactants organic ions, coupling agents, inorganic layered compounds, inorganic compounds, leveling agents, preservatives, defoamers, organic particles, lubricants, antistatic agents, ultraviolet protection agents, Dyes, pigments, stabilizers, magnetic powders, alignment promoters, plasticizers, dispersants, crosslinking agents, and the like can be given.
  • the content of the optional components contained in the solid is preferably 40% by mass or less, more preferably 30% by mass or less, based on the total mass of the solids contained in the solid. , 20% by mass or less.
  • the solid body may contain an organic solvent as an optional component.
  • the organic solvent is not particularly limited, for example, methanol, ethanol, n-propyl alcohol, isopropyl alcohol (IPA), 1-butanol, m-cresol, glycerin, acetic acid, pyridine, tetrahydrofuran (THF), acetone , Methyl ethyl ketone (MEK), ethyl acetate, aniline, N-methyl-2-pyrrolidone (NMP), dimethyl sulfoxide (DMSO), N, N-dimethylformamide (DMF), hexane, cyclohexane, benzene, toluene, p-xylene, Examples thereof include diethyl ether chloroform.
  • the content of the organic solvent in the solid is preferably 10% by mass or less, more preferably 5% by mass or less, and more preferably 1% by mass or less, based on the total mass of the
  • a fibrous cellulose having a fiber width of 1000 nm or less and having a phosphate group or a substituent derived from a phosphate group, and an organic counter ion of a phosphate group or a substituent derived from a phosphate group are used.
  • the method preferably includes a step of obtaining a composition containing onium ions and a non-aqueous first solvent, and a step of forming a solid from the composition.
  • the organic onium ion satisfies at least one condition selected from the following (a) and (b).
  • (A) It contains a hydrocarbon group having 5 or more carbon atoms.
  • B) The total number of carbon atoms is 17 or more.
  • the solvent-containing composition is obtained by adding an organic onium ion or a compound capable of forming an organic onium ion by neutralization to a fine fibrous cellulose-containing slurry to obtain a fine fibrous cellulose concentrate; Dispersing the fibrous cellulose concentrate in the non-aqueous first solvent to obtain a composition.
  • the organic onium ion is preferably added as a solution containing the organic onium ion, and more preferably as an aqueous solution containing the organic onium ion.
  • the aqueous solution containing an organic onium ion usually contains an organic onium ion and a counter ion (anion).
  • a counter ion anion
  • the organic onium ion may be dissolved in water as it is.
  • Organic onium ions may be generated only after neutralization with an acid, for example, dodecylamine.
  • the organic onium ion is obtained by reacting a compound that forms an organic onium ion by neutralization with an acid.
  • the acid used for neutralization include inorganic acids such as hydrochloric acid, sulfuric acid, and nitric acid, and organic acids such as lactic acid, acetic acid, formic acid, and oxalic acid.
  • a compound that forms an organic onium by neutralization may be directly added to the fibrous cellulose-containing slurry, and the phosphate group contained in the fibrous cellulose may be used as a counter ion to form the organic onium ion.
  • the addition amount of the organic onium ion in the step of obtaining the concentrate is preferably 2% by mass or more, more preferably 10% by mass or more, and more preferably 50% by mass or more based on the total mass of the fibrous cellulose. More preferably, it is particularly preferably 100% by mass or more. In addition, it is preferable that the addition amount of an organic onium ion is 1000 mass% or less with respect to the total mass of fibrous cellulose.
  • the number of moles of the organic onium ion to be added is preferably at least 0.2 times, more preferably at least 0.5 times the value obtained by multiplying the amount (mole number) of the phosphate group contained in the fibrous cellulose by the valence.
  • the number of moles of the organic onium ion to be added is preferably 10 times or less the value obtained by multiplying the amount (mol number) of the phosphate group contained in the fibrous cellulose by the valence.
  • the fibrous cellulose concentrate can be recovered by filtering the slurry containing the fibrous cellulose in which the aggregates are generated under reduced pressure.
  • the obtained fibrous cellulose concentrate may be washed with ion-exchanged water. By repeatedly washing the fibrous cellulose concentrate with ion-exchanged water, excess organic onium ions and the like contained in the fibrous cellulose concentrate can be removed.
  • the ratio of the N atom content to the P atom content (the value of N / P) in the obtained fibrous cellulose concentrate is preferably larger than 1.2, more preferably larger than 2.0. preferable. Further, the ratio of the N atom content to the P atom content (the value of N / P) in the obtained fibrous cellulose concentrate is preferably 5.0 or less.
  • the content of P atoms and the content of N atoms in the fibrous cellulose concentrate can be appropriately calculated by elemental analysis. As the elemental analysis, for example, a trace nitrogen analysis or a molybdenum blue method can be performed after an appropriate pretreatment. When the composition other than the fibrous cellulose concentrate contains P atoms and N atoms, the composition may be separated from the fibrous cellulose concentrate by an appropriate method, followed by elemental analysis.
  • the solid content concentration of the obtained fibrous cellulose concentrate is preferably 5% by mass or more, more preferably 10% by mass or more, and even more preferably 20% by mass or more. Further, the solid content concentration of the fibrous cellulose concentrate is preferably 99.5% by mass or less. Note that a step of drying the fibrous cellulose concentrate may be provided so that the solid content concentration of the fibrous cellulose concentrate is in a desired range.
  • the step of dispersing the obtained fine fibrous cellulose concentrate in the non-aqueous first solvent to obtain a composition is a step of redispersing the fine fibrous cellulose concentrate.
  • the non-aqueous first solvent is preferably a solvent other than water.
  • the non-aqueous first solvent is preferably an organic solvent.
  • organic solvent examples include methanol, ethanol, n-propyl alcohol, isopropyl alcohol (IPA), 1-butanol, and m- Cresol, glycerin, acetic acid, pyridine, tetrahydrofuran (THF), acetone, methyl ethyl ketone (MEK), ethyl acetate, aniline, N-methyl-2-pyrrolidone (NMP), dimethyl sulfoxide (DMSO), N, N-dimethylformamide (DMF) ), Hexane, cyclohexane, benzene, toluene, p-xylene, diethyl ether chloroform and the like.
  • NMP N-methyl-2-pyrrolidone
  • DMSO dimethyl sulfoxide
  • DMF N-dimethylformamide
  • a mixed solvent obtained by mixing two or more of these organic solvents may be used.
  • NMP N-methyl-2-pyrrolidone
  • DMSO dimethyl sulfoxide
  • MEK methyl ethyl ketone
  • toluene and methanol are preferably used.
  • the relative dielectric constant of the non-aqueous first solvent at 25 ° C. is preferably 60 or less, and more preferably 50 or less. Since the fine fibrous cellulose used in the present invention can exhibit excellent dispersibility even in a non-aqueous first solvent having a low relative dielectric constant, the relative dielectric constant of the non-aqueous first solvent at 25 ° C. It may be 40 or less, 30 or less, or 20 or less.
  • ⁇ p of Hansen solubility parameters of the non-aqueous first solvent it is preferably, 10 MPa 1/2 or more 19 MPa 1/2 or less is 5 MPa 1/2 or more 20 MPa 1/2 or less Is more preferable, and it is more preferable that it is 12 MPa1 / 2 or more and 18 MPa1 / 2 or less.
  • .delta.h a hydrogen bond of the HSP value is preferably 5 MPa 1/2 or more 40 MPa 1/2 or less, more preferably 5 MPa 1/2 or more 30 MPa 1/2 or less, 5 MPa 1/2 More preferably, it is not less than 20 MPa 1/2 .
  • ⁇ p is in the range of 0 MPa 1/2 to 4 MPa 1/2 and ⁇ h is in the range of 0 MPa 1/2 to 6 MPa 1/2 at the same time.
  • a dispersing device used for dispersing the fine fibrous cellulose concentrate in the non-aqueous first solvent for example, the same dispersing device as described in the above-described fibrillation treatment can be used.
  • the fine fibrous cellulose concentrate may be dispersed in an organic solvent by performing ultrasonic treatment.
  • the step of forming a solid from the composition obtained in the above-described step may be a step of molding the composition using a melt-kneading method or a casting method.
  • the fibrous cellulose having a fiber width of 1,000 nm or less and having a phosphate group or a substituent derived from a phosphate group is substituted with a fibrous cellulose having a phosphate group or a phosphate group.
  • a composition comprising an organic onium ion as a counter ion of a group and a non-aqueous first solvent with a second solvent having a hydrogen bond term ( ⁇ h) of Hansen solubility parameter of 12.0 MPa 1/2 or more.
  • the method for producing a solid body of the present invention preferably includes a second solvent contacting step, whereby the water absorption and the yellowness of the solid body can be more effectively reduced.
  • the composition obtained in the step of obtaining the composition is brought into contact with a second solvent having a hydrogen bond term ( ⁇ h) of the Hansen solubility parameter of 12.0 MPa 1/2 or more.
  • a second solvent having a hydrogen bond term ( ⁇ h) of the Hansen solubility parameter of 12.0 MPa 1/2 or more include, for example, water, methanol, ethanol, n-propyl alcohol, isopropyl alcohol (IPA), 1-butanol, m -Cresol, glycerin, acetic acid and the like.
  • IPA isopropyl alcohol
  • 1-butanol 1-butanol
  • m -Cresol 1-butanol
  • glycerin glycerin
  • acetic acid acetic acid
  • a mixed solvent obtained by mixing two or more of these solvents may be used.
  • the second solvent is preferably at least one selected from water and methanol, and more preferably water.
  • the first non-aqueous solvent and the second solvent used in the method for producing a solid are preferably compatible with each other.
  • the difference in the hydrogen bond term ( ⁇ h) of the Hansen solubility parameter between the nonaqueous first solvent and the second solvent is preferably 15 MPa 1/2 or more, more preferably 20 MPa 1/2 or more, and 25 MPa More preferably, it is 1/2 or more.
  • the relative permittivity of the second solvent at 25 ° C. is preferably 18 or more, more preferably 30 or more, and further preferably 60 or more.
  • ⁇ p of the Hansen solubility parameter (HSP value) of the second solvent is preferably 5 MPa 1/2 or more and 20 MPa 1/2 or less, and is preferably 10 MPa 1/2 or more and 20 MPa 1/2 or less. Is more preferred.
  • .delta.h a hydrogen bond of the HSP value is preferably 12 MPa 1/2 or more, more preferably 20 MPa 1/2 or more, more preferably 40 MPa 1/2 or more.
  • the second solvent contacting step is preferably a step of immersing the composition in the second solvent.
  • the composition may be immersed in the second solvent by injecting or dropping the composition into the second solvent.
  • the solid body is a filament
  • the step of performing When the solid is in the form of a sheet, the composition may be injected into the second solvent in the form of a sheet, or the sheet precursor formed in the sheet mold may be immersed in the second solvent.
  • the sheet precursor When the sheet precursor is immersed in the second solvent, the sheet precursor may be immersed in the second solvent together with the sheet mold.
  • the step of bringing the composition into contact with the second solvent it is preferable to bring the composition into contact with the second solvent in an amount of at least 40 times the total volume of the composition. That is, it is preferable that the composition be present in a second solvent atmosphere. Further, the second solvent may be exchanged or circulated as necessary.
  • the non-aqueous first solvent is removed to form a solid.
  • the step of producing the solid it is preferable to include, after the step of bringing the composition into contact with the second solvent, a step of further immersing the solid obtained in the step in the second solvent for a predetermined time or more.
  • the solid is preferably immersed in the second solvent for 1 hour or more, more preferably for 5 hours or more, and even more preferably for 8 hours or more.
  • the upper limit of the immersion time is not particularly limited, but is preferably, for example, 100 hours or less.
  • the drying temperature is preferably at least 30 ° C, more preferably at least 40 ° C, even more preferably at least 50 ° C. Further, the drying temperature is preferably 200 ° C. or less.
  • the drying time is preferably 1 minute or more and 100 hours or less.
  • the present invention may relate to a fibrous cellulose-containing composition obtained by dispersing the solid obtained through the above-described steps again in an organic solvent.
  • the fibrous cellulose-containing composition may further contain a resin. Since the solid body of the present invention uses fibrous cellulose having excellent compatibility with the organic solvent and the resin, the resin composite formed from the fibrous cellulose-containing composition has excellent strength, Furthermore, it has excellent dimensional stability. In addition, the resin composite formed from the fibrous cellulose-containing composition has excellent transparency.
  • the resin composite formed from the fibrous cellulose-containing composition may be in the form of a sheet.
  • the method for forming the sheet includes a step of applying the above-described fibrous cellulose-containing composition onto a substrate.
  • the material of the base material used in the coating step is not particularly limited, but those having high wettability to the composition may be able to suppress shrinkage of the sheet during drying, etc. It is preferable to select one that can be easily peeled off. Above all, a resin film or plate or a metal film or plate is preferable, but not particularly limited.
  • a stainless steel film or plate, a brass film or plate, or the like can be used.
  • the composition has low viscosity and spreads on the substrate, use a fixed damming frame on the substrate to obtain a sheet of a predetermined thickness and basis weight. May be.
  • the damming frame is not particularly limited. For example, it is preferable to select a frame that can easily peel off the end of the sheet that adheres after drying. From such a viewpoint, a resin plate or a metal plate is more preferable.
  • a resin plate such as an acrylic plate, a polyethylene terephthalate plate, a vinyl chloride plate, a polystyrene plate, a polypropylene plate, a polycarbonate plate, a polyvinylidene chloride plate, and a metal plate such as an aluminum plate, a zinc plate, a copper plate, and an iron plate And those obtained by oxidizing the surface thereof, and forming a stainless steel plate, a brass plate, or the like.
  • a resin plate such as an acrylic plate, a polyethylene terephthalate plate, a vinyl chloride plate, a polystyrene plate, a polypropylene plate, a polycarbonate plate, a polyvinylidene chloride plate, and a metal plate such as an aluminum plate, a zinc plate, a copper plate, and an iron plate And those obtained by oxidizing the surface thereof, and forming a stainless steel plate, a brass plate, or the like.
  • a coating machine for coating the composition on the base material is not particularly limited, and for example, a roll coater, a gravure coater, a die coater, a curtain coater, an air doctor coater, or the like can be used. Die coaters, curtain coaters, and spray coaters are particularly preferred because the thickness of the coating (sheet) can be made more uniform.
  • the temperature and the ambient temperature of the liquid composition when applying the composition to the substrate are not particularly limited, but are preferably, for example, 5 ° C or more and 80 ° C or less, more preferably 10 ° C or more and 60 ° C or less.
  • the temperature is more preferably from 15 ° C to 50 ° C, and particularly preferably from 20 ° C to 40 ° C.
  • the composition is prepared such that the finished basis weight of the sheet is preferably 10 g / m 2 or more and 100 g / m 2 or less, more preferably 20 g / m 2 or more and 60 g / m 2 or less. It is preferable to apply to the substrate. By coating so that the grammage is in the above range, a sheet having more excellent strength can be obtained.
  • the coating step includes a step of drying the composition applied on the substrate.
  • the step of drying the composition is not particularly limited, and is performed, for example, by a non-contact drying method, a method of drying while restraining a sheet, or a combination thereof.
  • the non-contact drying method is not particularly limited. For example, a method of drying by heating with hot air, infrared rays, far infrared rays or near infrared rays (heating drying method), or a method of drying by vacuum (vacuum drying method) is applied. can do.
  • the heat drying method and the vacuum drying method may be combined, but usually, the heat drying method is applied.
  • Drying with infrared, far-infrared, or near-infrared light can be performed using, for example, but not limited to, an infrared device, a far-infrared device, or a near-infrared device.
  • the heating temperature in the heating and drying method is not particularly limited, but is, for example, preferably from 20 ° C to 150 ° C, more preferably from 25 ° C to 105 ° C.
  • the heating temperature is equal to or higher than the lower limit, the dispersion medium can be quickly volatilized.
  • the heating temperature is equal to or lower than the upper limit, the cost required for heating and the discoloration of fibrous cellulose due to heat can be suppressed.
  • the use of the solid body of the present invention is not particularly limited, but a reinforcing material, an interior material, an exterior material, a packaging material, an electronic material, an optical material, an acoustic material, a process material, a transport equipment member, an electronic equipment member, It is suitable for applications such as members of electrochemical devices.
  • the solid of the present invention is a filament
  • it can be used for ropes, fishing lines, medical sutures and the like. Further, it can be used as a reinforcing material by being added to resin, rubber, cement and the like.
  • a nonwoven fabric may be formed by randomly laminating filaments. Nonwoven fabrics using filaments are suitable for applications such as filters, battery separators, nets, interior materials, exterior materials, packaging materials, clothing materials, and medical materials.
  • the solid body of the present invention is a bead, it can be used as an ink, a paint, a molded article, a film, a coating agent, etc. by adding it to a resin or a solvent in addition to an adsorbent and an abrasive.
  • the solid body of the present invention is a sheet
  • it is suitable for use in light-transmitting substrates such as various display devices and various solar cells.
  • it is also suitable for use as substrates for electronic devices, separators for electrochemical devices, members for home appliances, window materials for various vehicles and buildings, interior materials, exterior materials, packaging materials, and the like.
  • it is also suitable for applications in which the sheet itself is used as a reinforcing material.
  • the raw material pulp was phosphorylated as follows. First, a mixed aqueous solution of ammonium dihydrogen phosphate and urea is added to 100 parts by mass (absolute dry mass) of the raw material pulp to obtain 45 parts by mass of ammonium dihydrogen phosphate, 120 parts by mass of urea, and 150 parts by mass of water. To obtain a chemical-impregnated pulp. Next, the obtained chemical-impregnated pulp was heated with a hot air drier at 165 ° C. for 200 seconds to introduce a phosphate group into cellulose in the pulp, thereby obtaining phosphorylated pulp 1.
  • the obtained phosphorylated pulp 1 was subjected to a washing treatment.
  • a pulp dispersion obtained by pouring 10 L of ion-exchanged water into 100 g (absolute dry mass) of the phosphorylated pulp 1 is stirred so that the pulp is uniformly dispersed, and then filtered and dehydrated repeatedly. It was done by doing.
  • the electric conductivity of the filtrate became 100 ⁇ S / cm or less, it was regarded as the washing end point.
  • the phosphorylated pulp 1 after the washing was subjected to a neutralization treatment as follows. First, the phosphorylated pulp slurry 1 having a pH of 12 or more and 13 or less is diluted by diluting the washed phosphorylated pulp 1 with 10 L of ion-exchanged water, and gradually adding a 1N aqueous sodium hydroxide solution with stirring. Obtained. Next, the phosphorylated pulp slurry was dehydrated to obtain a phosphorylated pulp 1 subjected to a neutralization treatment. Next, the above-mentioned washing treatment was performed on the phosphorylated pulp after the neutralization treatment.
  • ⁇ ⁇ ⁇ Ion-exchanged water was added to the obtained phosphorylated pulp 1 to prepare a slurry having a solid concentration of 2% by mass. This slurry was treated six times at a pressure of 200 MPa with a wet atomizer (manufactured by Sugino Machine Co., Ltd., Starburst) to obtain a fine fibrous cellulose dispersion A containing fine fibrous cellulose.
  • the fiber width of the fine fibrous cellulose was measured using a transmission electron microscope and found to be 3 to 5 nm.
  • the amount of phosphate groups (the amount of strongly acidic groups) measured by a measurement method described later was 2.0 mmol / g.
  • the washing treatment is performed by dehydrating the pulp slurry after TEMPO oxidation, obtaining a dehydrated sheet, pouring 5,000 parts by mass of ion-exchanged water, stirring and uniformly dispersing, and then repeating filtration and dehydration.
  • the washing treatment is performed by dehydrating the pulp slurry after TEMPO oxidation, obtaining a dehydrated sheet, pouring 5,000 parts by mass of ion-exchanged water, stirring and uniformly dispersing, and then repeating filtration and dehydration.
  • the electric conductivity of the filtrate became 100 ⁇ S / cm or less, it was regarded as the washing end point.
  • ⁇ ⁇ ⁇ Ion-exchanged water was added to the obtained TEMPO oxidized pulp to prepare a slurry having a solid content of 2% by mass.
  • This slurry was treated with a wet atomizer (Starburst, manufactured by Sugino Machine Co., Ltd.) at a pressure of 200 MPa six times to obtain a fine fibrous cellulose dispersion B containing fine fibrous cellulose.
  • the fiber width of the fine fibrous cellulose was measured using a transmission electron microscope and found to be 3 to 5 nm.
  • the amount of carboxy groups measured by the measurement method described later was 1.80 mmol / g.
  • the washing treatment is performed by repeating the operation of pulverizing a pulp dispersion obtained by pouring 10 L of ion-exchanged water into 100 g of phosphorylated pulp (absolute dry mass) so that the pulp is uniformly dispersed, and then filtering and dewatering. went.
  • the electric conductivity of the filtrate became 100 ⁇ S / cm or less, it was regarded as the washing end point.
  • the phosphorylated pulp 2 after the washing was subjected to a neutralization treatment as follows.
  • the phosphorylated pulp slurry having a pH of 12 or more and 13 or less is obtained by diluting the washed phosphorylated pulp 2 with 10 L of ion-exchanged water and then adding a 1N aqueous sodium hydroxide solution little by little with stirring.
  • the phosphorylated pulp slurry was dehydrated to obtain a phosphorylated pulp 2 subjected to a neutralization treatment.
  • the above-described washing treatment was performed on the phosphorylated pulp 2 after the neutralization treatment.
  • the phosphorylated pulp 2 thus obtained was measured for infrared absorption spectrum using FT-IR.
  • absorption based on P O of the phosphonic acid group, which is a tautomer of the phosphite group, was observed at around 1210 cm ⁇ 1 , and the phosphite group (phosphonate group) was added to the pulp.
  • P O of the phosphonic acid group, which is a tautomer of the phosphite group
  • ⁇ ⁇ ⁇ Ion-exchanged water was added to the obtained phosphorylated pulp 2 to prepare a slurry having a solid concentration of 2% by mass.
  • This slurry was treated six times with a wet atomizer (Starburst, manufactured by Sugino Machine Co., Ltd.) at a pressure of 200 MPa to obtain a fine fibrous cellulose dispersion C containing fine fibrous cellulose.
  • the amount of the phosphite group (the amount of the strongly acidic group) of the obtained phosphorylated pulp 2 measured by the measuring method described later was 1.50 mmol / g.
  • the amount of the weak acidic group was 0.13 mmol / g.
  • Example 1 (Production of fine fibrous cellulose concentrate) 0.60 g of lactic acid was added to 100 g of a 2.43 mass% N, N-didodecylmethylamine aqueous solution to neutralize it in advance, and then added to 100 g of the fine fibrous cellulose dispersion A obtained in Production Example 1. After stirring for 5 minutes, aggregates were formed in the fine fibrous cellulose dispersion. The fine fibrous cellulose dispersion in which the aggregate was generated was filtered under reduced pressure to obtain a fine fibrous cellulose aggregate.
  • the resulting fine fibrous cellulose aggregates were repeatedly washed with ion-exchanged water to remove excess N, N-didodecylmethylamine, lactic acid, and eluted ions contained in the fine fibrous cellulose aggregates.
  • the obtained fine fibrous cellulose aggregate was dried at 30 ° C. and a relative humidity of 40% to obtain a fine fibrous cellulose concentrate.
  • the counter ion of the phosphate group contained in the fine fibrous cellulose concentrate was N, N-didodecylmethylammonium (DDMA + ).
  • the solid content concentration of the obtained fine fibrous cellulose concentrate was 95% by mass.
  • NMP N-methyl-2-pyrrolidone
  • the fine fibrous cellulose injection product after immersion is taken out of the coagulation bath, dried on a hot plate at 70 ° C. for 30 minutes, then heated to 120 ° C. and further dried for 2 hours to obtain a fine fibrous cellulose-containing filament.
  • the water absorption and the yellowness (YI 0 ) of the obtained fine fibrous cellulose-containing filament were measured and evaluated by the methods described below.
  • Example 2 The fine fibrous cellulose dispersion C obtained in Production Example 3 was used in place of the fine fibrous cellulose dispersion A. The procedure of Example 1 was repeated, except that 0.30 g of lactic acid was added to 100 g of an aqueous solution of N, N-didodecylmethylamine at a concentration of 1.20% by mass to neutralize the solution, and then added to the fine fibrous cellulose dispersion C. , A fine fibrous cellulose concentrate, a fine fibrous cellulose re-dispersed slurry, and a fine fibrous cellulose-containing filament were obtained.
  • the counter ion of the phosphate group contained in the fine fibrous cellulose concentrate was polyoxyethylene dodecyl ammonium ion (POEDA + ).
  • the solid content concentration of the obtained fine fibrous cellulose concentrate was 92% by mass.
  • the water absorption and the yellowness (YI 0 ) of the obtained fine fibrous cellulose-containing filament were measured and evaluated by the methods described below.
  • Example 3 100 g of a 1.83% by mass aqueous solution of polyoxyethylene dodecylamine (the number of oxyethylene residues is 2) was used in place of the aqueous solution of N, N-didodecylmethylamine, and dimethyl sulfoxide (DMSO) was used as the first solvent in N-
  • DMSO dimethyl sulfoxide
  • the counter ion of the phosphate group contained in the fine fibrous cellulose concentrate was polyoxyethylene dodecyl ammonium ion (POEDA + ).
  • the solid content concentration of the obtained fine fibrous cellulose concentrate was 92% by mass.
  • the water absorption and the yellowness (YI 0 ) of the obtained fine fibrous cellulose-containing filament were measured and evaluated by the methods described below.
  • Example 4 100 g of a 2.33 mass% aqueous solution of alkyldimethylbenzylammonium chloride (alkyl chain having 8 to 18 carbon atoms) was used in place of the aqueous solution of N, N-didodecylmethylamine neutralized with lactic acid, and the first solvent was used.
  • methanol was used in place of N-methyl-2-pyrrolidone (NMP)
  • NMP N-methyl-2-pyrrolidone
  • the counter ion of the phosphate group contained in the fine fibrous cellulose concentrate was alkyldimethylbenzylammonium (ADMBA + ).
  • the solid content concentration of the obtained fine fibrous cellulose concentrate was 84% by mass.
  • the water absorption and the yellowness (YI 0 ) of the obtained fine fibrous cellulose-containing filament were measured and evaluated by the methods described below.
  • Example 5 100 g of a 3.86% by mass aqueous di-n-alkyldimethylammonium chloride solution (having 16 or 18 carbon atoms in the alkyl chain) was used in place of the aqueous alkyldimethylbenzylammonium chloride solution, and toluene was used as the first solvent. And the fine fibrous cellulose concentrate, the fine fibrous cellulose redispersed slurry, and the fine fibrous cellulose were prepared in the same manner as in Example 4 except that methanol was used instead of ion-exchanged water as the second solvent. A containing filament was obtained.
  • the counter ion of the phosphate group contained in the fine fibrous cellulose concentrate was di-n-alkyldimethylammonium (DADMA + ).
  • the solid content concentration of the obtained fine fibrous cellulose concentrate was 91% by mass.
  • the water absorption and the yellowness (YI 0 ) of the obtained fine fibrous cellulose-containing filament were measured and evaluated by the methods described below.
  • the fine fibrous cellulose dispersion B obtained in Production Example 2 was used in place of the fine fibrous cellulose dispersion A.
  • a fine fibrous cellulose concentrate, a fine fibrous cellulose re-dispersed slurry, and a fine fibrous cellulose concentrate were prepared in the same manner as in Example 4 except that 100 g of an aqueous 1.27% by mass alkyldimethylbenzylammonium solution was added to the fine fibrous cellulose dispersion B.
  • a fine fibrous cellulose-containing filament was obtained.
  • the counter ion of the carboxy group contained in the fine fibrous cellulose concentrate was alkyldimethylbenzylammonium (ADMBA + ).
  • the solid content concentration of the obtained fine fibrous cellulose concentrate was 81% by mass.
  • the water absorption and the yellowness (YI 0 ) of the obtained fine fibrous cellulose-containing filament were measured and evaluated by the methods described below.
  • the fine fibrous cellulose dispersion B obtained in Production Example 2 was used in place of the fine fibrous cellulose dispersion A. 2.
  • a fine fibrous cellulose concentrate and a fine fibrous cellulose concentrate were prepared in the same manner as in Example 5 except that 100 g of a 10% by mass aqueous di-n-alkyldimethylammonium chloride solution was added to the fine fibrous cellulose dispersion B.
  • a dispersed slurry and a fine fibrous cellulose-containing filament were obtained.
  • the counter ion of the carboxy group contained in the fine fibrous cellulose concentrate was di-n-alkyldimethylammonium (DADMA + ).
  • the solid content concentration of the obtained fine fibrous cellulose concentrate was 89% by mass.
  • the water absorption and the yellowness (YI 0 ) of the obtained fine fibrous cellulose-containing filament were measured and evaluated by the methods described below.
  • Example 5 The same procedure as in Example 1 was carried out except that the fine fibrous cellulose dispersion A obtained in Production Example 1 was used instead of the fine fibrous cellulose re-dispersed slurry, and ethanol was used instead of ion-exchanged water as the second solvent. Thus, a fine fibrous cellulose-containing filament was obtained. The water absorption and the yellowness (YI 0 ) of the obtained fine fibrous cellulose-containing filament were measured and evaluated by the methods described below.
  • Example 6 After filling the re-dispersed slurry of fine fibrous cellulose obtained in the same manner as in Example 1 into a syringe (needle diameter: ⁇ 1.5 mm), it was dropped at 2 g / min into a coagulation tank filled with ion-exchanged water (second solvent). Then, a fine fibrous cellulose injection product was formed in the coagulation bath. After repeating the operation of replacing the ion-exchanged water in the coagulation tank every 30 minutes three times, the fine fibrous cellulose injection product was immersed in the ion-exchanged water for further 12 hours.
  • the fine fibrous cellulose injection product after immersion is taken out of the coagulation bath, dried on a hot plate at 70 ° C. for 30 minutes, then heated to 120 ° C. and further dried for 2 hours to obtain beads containing fine fibrous cellulose.
  • the water absorption and the yellowness (YI 0 ) of the obtained microfibrous cellulose-containing beads were measured and evaluated by the methods described below.
  • Example 7 Except that the fine fibrous cellulose re-dispersed slurry obtained in Example 2 was used in place of the fine fibrous cellulose re-dispersed slurry obtained in Example 1, the same procedure as in Example 6 was carried out. Beads were obtained. The water absorption and the yellowness (YI 0 ) of the obtained microfibrous cellulose-containing beads were measured and evaluated by the methods described below.
  • Example 8 Except that the fine fibrous cellulose re-dispersed slurry obtained in Example 3 was used instead of the fine fibrous cellulose re-dispersed slurry obtained in Example 1, the same procedure as in Example 6 was carried out. Beads were obtained. The water absorption and the yellowness (YI 0 ) of the obtained microfibrous cellulose-containing beads were measured and evaluated by the methods described below.
  • Example 9 Except that the fine fibrous cellulose re-dispersed slurry obtained in Example 4 was used instead of the fine fibrous cellulose re-dispersed slurry obtained in Example 1, the same procedure as in Example 6 was carried out. Beads were obtained. The water absorption and the yellowness (YI 0 ) of the obtained microfibrous cellulose-containing beads were measured and evaluated by the methods described below.
  • Example 10 Except that the fine fibrous cellulose redispersed slurry obtained in Example 5 was used instead of the fine fibrous cellulose redispersed slurry obtained in Example 1, and methanol was used as the second solvent instead of ion-exchanged water. In the same manner as in Example 6, fine fibrous cellulose-containing beads were obtained. The water absorption and the yellowness (YI 0 ) of the obtained microfibrous cellulose-containing beads were measured and evaluated by the methods described below.
  • Example 11 Except that the fine fibrous cellulose re-dispersed slurry obtained in Comparative Example 4 was used instead of the fine fibrous cellulose re-dispersed slurry obtained in Example 5, the same procedure as in Example 10 was carried out. Beads were obtained. The water absorption and the yellowness (YI 0 ) of the obtained microfibrous cellulose-containing beads were measured and evaluated by the methods described below.
  • Comparative Example 13 Comparative Example 4 was repeated except that the fine fibrous cellulose dispersion D obtained in Production Example 4 was used instead of the fine fibrous cellulose dispersion A obtained in Production Example 1, and tetrahydrofuran was used as the second solvent instead of ethanol. In the same manner as in Example 12, fine fibrous cellulose-containing beads were obtained. The water absorption and the yellowness (YI 0 ) of the obtained microfibrous cellulose-containing beads were measured and evaluated by the methods described below.
  • Fine fibrous cellulose dispersion containing fine fibrous cellulose was prepared in the same manner as in Comparative Example 12, except that the fine fibrous cellulose dispersion B obtained in Production Example 2 was used instead of the fine fibrous cellulose dispersion A obtained in Production Example 1. Beads were obtained. The water absorption and the yellowness (YI 0 ) of the obtained microfibrous cellulose-containing beads were measured and evaluated by the methods described below.
  • Example 11 The re-dispersed slurry of fine fibrous cellulose obtained in the same manner as in Example 1 was dripped into a glass Petri dish so as to have a basis weight of 80 g / m 2, and was placed in a coagulation tank filled with ion-exchanged water (second solvent) together with the glass Petri dish. It was immersed gently. The operation of exchanging the ion-exchanged water in the coagulation tank every 30 minutes was repeated three times, and then immersed in the ion-exchanged water for further 12 hours, to obtain a hydrous fine fibrous cellulose-containing sheet. The hydrous fine fibrous cellulose was taken out of the coagulation bath, dried on a hot plate at 70 ° C.
  • Example 12 Except that the fine fibrous cellulose re-dispersed slurry obtained in Example 2 was used in place of the fine fibrous cellulose re-dispersed slurry obtained in Example 1, the same procedure as in Example 11 was carried out. I got a sheet. The water absorption, yellowness (YI 0 ), and yellowness (YI 100 ) of the obtained fine fibrous cellulose-containing sheet were measured and evaluated by the methods described below.
  • Example 13 Except that the fine fibrous cellulose re-dispersed slurry obtained in Example 3 was used instead of the fine fibrous cellulose re-dispersed slurry obtained in Example 1, the same procedure as in Example 11 was carried out. I got a sheet. The water absorption, yellowness (YI 0 ), and yellowness (YI 100 ) of the obtained fine fibrous cellulose-containing sheet were measured and evaluated by the methods described below.
  • Example 14 Except that the fine fibrous cellulose re-dispersed slurry obtained in Example 4 was used instead of the fine fibrous cellulose re-dispersed slurry obtained in Example 1, the same procedure as in Example 11 was carried out. I got a sheet. The water absorption, yellowness (YI 0 ), and yellowness (YI 100 ) of the obtained fine fibrous cellulose-containing sheet were measured and evaluated by the methods described below.
  • Example 15 Except that the fine fibrous cellulose redispersed slurry obtained in Example 5 was used instead of the fine fibrous cellulose redispersed slurry obtained in Example 1, and methanol was used as the second solvent instead of ion-exchanged water. In the same manner as in Example 11, a fine fibrous cellulose-containing sheet was obtained. The water absorption, yellowness (YI 0 ), and yellowness (YI 100 ) of the obtained fine fibrous cellulose-containing sheet were measured and evaluated by the methods described below.
  • Comparative Example 20 Comparative Example 4 was repeated except that the fine fibrous cellulose dispersion D obtained in Production Example 4 was used instead of the fine fibrous cellulose dispersion A obtained in Production Example 1, and tetrahydrofuran was used as the second solvent instead of ethanol. In the same manner as in Example 19, a fine fibrous cellulose-containing sheet was obtained. The water absorption, yellowness (YI 0 ), and yellowness (YI 100 ) of the obtained fine fibrous cellulose-containing sheet were measured and evaluated by the methods described below.
  • Fine fibrous cellulose dispersion containing fine fibrous cellulose was prepared in the same manner as in Comparative Example 19 except that the fine fibrous cellulose dispersion B obtained in Production Example 2 was used instead of the fine fibrous cellulose dispersion A obtained in Production Example 1. I got a sheet. The water absorption, yellowness (YI 0 ), and yellowness (YI 100 ) of the obtained fine fibrous cellulose-containing sheet were measured and evaluated by the methods described below.
  • the phosphate group content of the fine fibrous cellulose is a fibrous shape prepared by diluting a fine fibrous cellulose dispersion containing the target fine fibrous cellulose with ion-exchanged water so that the content becomes 0.2% by mass.
  • the measurement was performed by performing titration using an alkali.
  • the treatment with the ion-exchange resin is performed by adding 1/10 by volume of a strongly acidic ion-exchange resin (Amberjet 1024; Organo, Inc., conditioned) to the fibrous cellulose-containing slurry and shaking for 1 hour.
  • the resin and the slurry were separated by pouring on a mesh having a mesh size of 90 ⁇ m.
  • titration using an alkali is performed by adding an aqueous 0.1 N sodium hydroxide solution to a fibrous cellulose-containing slurry after treatment with an ion-exchange resin at a rate of 50 ⁇ L once every 30 seconds while maintaining the electrical conductivity of the slurry. The measurement was performed by measuring the change in the value.
  • the amount of phosphoric acid groups (mmol / g) is obtained by dividing the amount of alkali (mmol) required in the region corresponding to the first region shown in FIG. 1 by the solid content (g) in the slurry to be titrated. Was calculated.
  • the carboxy group content of the fine fibrous cellulose is a fibrous cellulose prepared by diluting the fine fibrous cellulose dispersion containing the target fine fibrous cellulose with ion-exchanged water so that the content becomes 0.2% by mass.
  • the content of the slurry was measured by performing a treatment with an ion-exchange resin and then performing a titration using an alkali.
  • the treatment with the ion-exchange resin is performed by adding 1/10 by volume of a strongly acidic ion-exchange resin (Amberjet 1024; Organo, Inc., conditioned) to the fibrous cellulose-containing slurry and shaking for 1 hour.
  • the resin and the slurry were separated by pouring on a mesh having a mesh size of 90 ⁇ m.
  • titration using an alkali is performed by adding 50 ⁇ L of a 0.1N aqueous sodium hydroxide solution once every 30 seconds to a fibrous cellulose-containing slurry after treatment with an ion-exchange resin while maintaining the electric conductivity of the slurry. This was done by measuring the change in value.
  • the amount of carboxy groups (mmol / g) is obtained by dividing the amount of alkali (mmol) required in a region corresponding to the first region shown in FIG. 2 in the measurement results by the solid content (g) in the slurry to be titrated. Calculated.
  • the solid material (filament, bead, sheet) was conditioned for 24 hours at 23 ° C. and 50% relative humidity, and the conditioned weight was measured. Next, the solid after measuring the humidity control weight was immersed in ion-exchanged water for 24 hours to wipe off excess water remaining on the surface, and then the wet weight was measured.
  • Sheet yellowness (YI 100 ) in terms of film thickness of 100 ⁇ m yellowness of sheet (YI) ⁇ (100 ( ⁇ m)) / (sheet thickness ( ⁇ m))
  • the thickness of the sheet was measured using a constant-pressure thickness meter (PG-02; Teklock) in accordance with JIS K6783.

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Abstract

L'invention concerne un corps solide pour lequel le coefficient d'absorption d'eau ainsi que le degré de jaune sont faibles. Plus spécifiquement, l'invention concerne un corps solide contenant des fibres de cellulose dont la largeur de fibre est inférieure ou égale à 1000 nm et possédant un groupe phosphate ou un groupe substitué dérivé d'un groupe phosphate, et contenant un ion onium organique en tant que contre-ion du groupe substitué dérivé d'un groupe phosphate ou du groupe phosphate. Le ion onium organique satisfait au moins une conditions choisie parmi les conditions (a) et (b) ci-dessous. (a) le corps solide contient un groupe hydrocarboné dont le nombre d'atomes de carbone est supérieur ou égal à 5. (b) le nombre total d'atomes de carbone est supérieur ou égal à 17.
PCT/JP2019/034905 2018-09-06 2019-09-05 Corps solide et procédé de fabrication de corps solide Ceased WO2020050347A1 (fr)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2014144998A (ja) * 2013-01-25 2014-08-14 Daicel Corp 固体状セルロースの製造方法及びセルロースエステルの製造方法
JP2017065109A (ja) * 2015-09-30 2017-04-06 王子ホールディングス株式会社 シートおよび積層体
WO2017111016A1 (fr) * 2015-12-25 2017-06-29 日本製紙株式会社 Procédé de production de solide sec de nanofibres de cellulose
JP2018104502A (ja) * 2016-12-22 2018-07-05 日本製紙株式会社 エステル化セルロースナノファイバー分散液の製造方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2014144998A (ja) * 2013-01-25 2014-08-14 Daicel Corp 固体状セルロースの製造方法及びセルロースエステルの製造方法
JP2017065109A (ja) * 2015-09-30 2017-04-06 王子ホールディングス株式会社 シートおよび積層体
WO2017111016A1 (fr) * 2015-12-25 2017-06-29 日本製紙株式会社 Procédé de production de solide sec de nanofibres de cellulose
JP2018104502A (ja) * 2016-12-22 2018-07-05 日本製紙株式会社 エステル化セルロースナノファイバー分散液の製造方法

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