WO2013176102A1 - Cellulose sous forme de fibres fines ainsi que procédé de fabrication de celle-ci, liquide de dispersion de cellulose sous forme de fibres fines, et tissu non tissé - Google Patents

Cellulose sous forme de fibres fines ainsi que procédé de fabrication de celle-ci, liquide de dispersion de cellulose sous forme de fibres fines, et tissu non tissé Download PDF

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Publication number
WO2013176102A1
WO2013176102A1 PCT/JP2013/064007 JP2013064007W WO2013176102A1 WO 2013176102 A1 WO2013176102 A1 WO 2013176102A1 JP 2013064007 W JP2013064007 W JP 2013064007W WO 2013176102 A1 WO2013176102 A1 WO 2013176102A1
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Prior art keywords
fine fibrous
fibrous cellulose
cellulose
group
alkali
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PCT/JP2013/064007
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English (en)
Japanese (ja)
Inventor
豪 盤指
裕一 野口
泰友 野一色
宏幸 永谷
Original Assignee
王子ホールディングス株式会社
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Priority claimed from JP2012118510A external-priority patent/JP5857881B2/ja
Priority claimed from JP2012130886A external-priority patent/JP5857885B2/ja
Application filed by 王子ホールディングス株式会社 filed Critical 王子ホールディングス株式会社
Publication of WO2013176102A1 publication Critical patent/WO2013176102A1/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
    • C08B15/02—Oxycellulose; Hydrocellulose; Cellulosehydrate, e.g. microcrystalline cellulose
    • C08B15/04—Carboxycellulose, e.g. prepared by oxidation with nitrogen dioxide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C08J5/045—Reinforcing macromolecular compounds with loose or coherent fibrous material with vegetable or animal fibrous material
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
    • D04H1/425—Cellulose series
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/32—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
    • D06M11/34—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxygen, ozone or ozonides
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/68—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with phosphorus or compounds thereof, e.g. with chlorophosphonic acid or salts thereof
    • D06M11/70—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with phosphorus or compounds thereof, e.g. with chlorophosphonic acid or salts thereof with oxides of phosphorus; with hypophosphorous, phosphorous or phosphoric acids or their salts
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/68—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with phosphorus or compounds thereof, e.g. with chlorophosphonic acid or salts thereof
    • D06M11/72—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with phosphorus or compounds thereof, e.g. with chlorophosphonic acid or salts thereof with metaphosphoric acids or their salts; with polyphosphoric acids or their salts; with perphosphoric acids or their salts
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/02—Natural fibres, other than mineral fibres
    • D06M2101/04—Vegetal fibres
    • D06M2101/06—Vegetal fibres cellulosic

Definitions

  • the present invention relates to fine fibrous cellulose and a method for producing the same, a fine fibrous cellulose dispersion, and a nonwoven fabric.
  • This application claims priority based on Japanese Patent Application No. 2012-118510 filed in Japan on May 24, 2012 and Japanese Patent Application No. 2012-130886 filed in Japan on June 8, 2012. The contents are incorporated herein.
  • cellulose fibers having a fiber diameter of 10 to 50 ⁇ m, especially wood-derived cellulose fibers (pulp) have been widely used as paper products so far.
  • cellulose fibers fine fibrous cellulose having a fiber diameter of 1000 nm or less is also known.
  • Various applications have been studied for the use of fine fibrous cellulose. For example, it is said that when fine fibrous cellulose is added to a resin or rubber as a reinforcing agent, the effect of improving mechanical properties is increased.
  • a fiber raw material containing cellulose is treated with ozone and then fibrillated and refined (Patent Document 1), and the fiber raw material containing cellulose is oxidized with an N-oxyl compound.
  • Patent Document 3 a method of performing distributed processing
  • a method for producing fine fibrous cellulose a method in which a fiber raw material containing cellulose is treated with a co-oxidant such as N-oxyl and sodium hypochlorite, then treated with an alkaline solution, fibrillated and refined.
  • Patent Document 2 and Non-Patent Document 1 and a method (Patent Document 4) of treating with phosphoric acid or sulfonic acid after defibration and refinement of a fiber raw material are known.
  • Patent Documents 1 and 3 have insufficient yields of fine fibrous cellulose. Moreover, since the dispersion stability in the acidic side of the dispersion liquid which slurried the fine fibrous cellulose was inadequate, it was difficult to use for the use which makes a slurry acidic. In the methods described in Patent Document 2 and Non-Patent Document 1, the degree of polymerization of the obtained fine fibrous cellulose tends to increase. In general, when the degree of polymerization of fine fibrous cellulose increases, the fiber length increases and the dispersibility when blended with a resin or rubber tends to decrease.
  • An object of the present invention is to provide fine fibrous cellulose that is produced from a fiber raw material in a high yield and has high dispersibility when blended with a resin or rubber. Moreover, it aims at providing the manufacturing method of the fine fibrous cellulose which can manufacture the fine fibrous cellulose with high dispersibility at the time of mix
  • Another object of the present invention is to provide a fine fibrous cellulose that can be produced in a high yield, can ensure the stability of the slurry dispersion in the acidic side, and can reduce the viscosity of the dispersion.
  • Another object of the present invention is to provide a method for producing fine fibrous cellulose that can ensure the stability of the slurry dispersion in the acidic side and can produce fine fibrous cellulose that can reduce the viscosity of the dispersion with high yield. .
  • the present invention has, for example, the following aspects.
  • It has a functional group represented by the following formula (1), has a (—COO ⁇ ) content of 0.06 to 1.2 mmol / g, and a polymerization degree of 50 to 500.
  • Fine fibrous cellulose (1) (—COO ⁇ ) n ⁇ X n + (where n is a natural number of 1 to 3.
  • a fine fibrous cellulose having a functional group represented by the following formula (3) and a functional group represented by the following formula (4).
  • Q is 1 or 2.
  • a fine fibrous cellulose having a functional group represented by the following formula (3) and a functional group represented by the following formula (5). (3) (—COO ⁇ ) p ⁇ X p + (5) (—SO 3 ⁇ ) r ⁇ Z r + (where p and r are each independently a natural number of 1 to 3.
  • an acid group forming step of obtaining acid group-containing cellulose is obtained from an oxo acid containing a sulfur atom or a salt thereof.
  • a fine fibrous cellulose dispersion wherein the cellulose fibers according to [7] or [8] are dispersed in a dispersion medium.
  • a nonwoven fabric comprising the fine fibrous cellulose according to [7] or [8].
  • at least one cation selected from the group consisting of alkaline earth metal ions and polyvalent metal ions when n 2 or 3.
  • a method for producing fine fibrous cellulose comprising adjusting the ozone treatment conditions and the alkali compound concentration of the alkaline solution, (1) (—COO ⁇ ) n ⁇ X n + (2) X n + ⁇ (OH ⁇ ) n (Where n is a natural number of 1 to 3.
  • n 2 or 3, it is at least one cation selected from the group consisting of alkaline earth metal ions and polyvalent metal ions.
  • Fine fibrous cellulose having a functional group represented by the following formula (3) and a functional group represented by the following formula (5); (3) (—COO ⁇ ) p ⁇ X p + (5) (—SO 3 ⁇ ) r ⁇ Z r + (Here, p and r are each independently a natural number of 1 to 3.
  • An oxidation process in which a fiber raw material containing cellulose is oxidized to form a carboxy group, and after the oxidation step, the fiber raw material is treated with an oxo acid containing a sulfur atom or a salt thereof to treat a sulfonic acid group.
  • An acid group forming step of forming an acid group-containing cellulose to form a fine fibrous cellulose [13] The method for producing fine fibrous cellulose according to [11] or [12], wherein the oxidation step is a step of forming a carboxy group by performing at least ozone treatment on the fiber raw material, [14] The method according to any one of [11] to [13], comprising an alkali treatment step of obtaining a cellulose salt by alkali treatment of the acid group-containing cellulose after the acid group formation step, and a defibration step of defibrating the cellulose salt
  • the fine fibrous cellulose of the present invention is produced from a fiber raw material in a high yield, has a small degree of polymerization, and has a high dispersibility when blended with a resin or rubber. According to the method for producing fine fibrous cellulose of the present invention, fine fibrous cellulose having a small degree of polymerization and high dispersibility when blended with a resin or rubber can be produced from a fiber raw material in a high yield.
  • the nonwoven fabric of the present invention is suitable as a reinforcing agent or the like.
  • the fine fibrous cellulose of the present invention can be produced in a high yield, can ensure the stability of the slurry dispersion in the acidic side, and can lower the viscosity of the dispersion. According to the method for producing fine fibrous cellulose of the present invention, the stability of the slurry dispersion can be ensured even on the acidic side, and the fine fibrous cellulose capable of reducing the viscosity of the dispersion can be produced in a high yield.
  • the fine fibrous cellulose of one aspect of the present invention is a cellulose fiber having a functional group represented by the above formula (1) (hereinafter referred to as “functional group (1)”).
  • the content of (—COO ⁇ ) in the fine fibrous cellulose is 0.06 to 1.2 mmol / g, preferably 0.1 to 0.9 mmol / g, and preferably 0.2 to 0.8 mmol / g. More preferably, it is g.
  • the content of (—COO ⁇ ) is less than 0.06 mmol / g, it becomes difficult to produce in a high yield, and the dispersion stability when fine fibrous cellulose is slurried becomes low. .
  • (-COO -) content is, per cellulose 1 g - a content of (-COO).
  • the content of (—COO ⁇ ) is measured in a state where X + of the functional group (1) is H + . That is, the content of (—COO ⁇ ) measures the content of carboxy groups.
  • the content of the carboxy group can be measured by the following method.
  • the absolutely dry cellulose fiber used as a measurement sample is one obtained by freeze-drying in order to avoid alteration of cellulose that may occur due to heating during heat drying.
  • an alkali metal for example, sodium, potassium, lithium, etc.
  • a cation or polyvalent metal for example, iron, or an alkaline earth metal (for example, magnesium, calcium, or barium)
  • magnesium is also included in the alkaline earth metal.
  • the fine fibrous cellulose of another aspect of the present invention has a functional group represented by the above formula (3) (hereinafter referred to as “functional group (3)”) and a functional group represented by the above formula (4) ( Hereinafter, it is a cellulose fiber having “functional group (4)”.
  • the content of (—COO ⁇ ) of the functional group (3) in the fine fibrous cellulose of this embodiment is preferably 0.06 to 1.2 mmol / g, and preferably 0.1 to 0.9 mmol / g. It is more preferable.
  • (-COO -) When the content of 0.06 mmol / g or more, can be manufactured at high yield, whereas, (- COO -) content is at most 1.2 mmol / g, the cellulose molecules Therefore, the characteristics (high strength, high rigidity, or high dimensional stability) as fine fibrous cellulose can be easily obtained.
  • the content of (—O—PO 3 2 ⁇ ) in the functional group (4) in the fine fibrous cellulose is preferably 0.1 to 2.0 mmol / g, and preferably 0.2 to 1.5 mmol / g. It is more preferable.
  • the content of (—O—PO 3 2 ⁇ ) is 0.1 mmol / g or more, it can be produced with higher yield.
  • the content of (—O—PO 3 2 ⁇ ) exceeds 2.0 mmol / g, fine fibrous cellulose is dissolved, and the yield may be lowered.
  • the content of (—PO 3 2 ⁇ ) in the functional group (4) is the content of (—PO 3 2 ⁇ ) per 1 g of cellulose, and was measured by applying TAPPI T237 cm-08 (2008).
  • sodium bicarbonate (NaHCO 3 ) / sodium chloride (NaCl) A test solution obtained by dissolving 0.84 g / 5.85 g in 1000 ml with distilled water was changed to a test solution obtained by dissolving 1.60 g of sodium hydroxide in 1000 ml with distilled water, and further (-O-PO 3 2- ) Measured according to TAPPI T237 cm-08 (2008), except that the difference in the measured values of cellulose fibers before and after introduction was changed to a substantial (—O—PO 3 2 ⁇ ) content.
  • the acidic group content measurement method is basically a method for measuring the introduction amount of a monovalent acidic group (carboxy group)
  • the introduction amount of a phosphate group which is a polyvalent acidic group is as described above.
  • the ( ⁇ O—PO 3 2 ⁇ ) content obtained as the content of monovalent acidic groups was divided by the (—O—PO 3 2 ⁇ ) acid number 2.
  • the total content of (—COO ⁇ ) and (—O—PO 3 2 ⁇ ) in the fine fibrous cellulose of the present embodiment is 0.2 to 3.0 mmol / g. Preferably, it is 0.5 to 2.5 mmol / g. If the total content of (—COO ⁇ ) and (—O—PO 3 2 ⁇ ) is 0.2 mmol / g or more, it can be produced with higher yield. Further, when the total content of (—COO ⁇ ) and (—O—PO 3 2 ⁇ ) is within the above range, the dispersion stability when the fine fibrous cellulose is slurried becomes higher.
  • p is a natural number of 1 to 3.
  • q is 1 or 2.
  • the fine fibrous cellulose is a cellulose fiber or cellulose rod-like particle having an I-type crystal structure that is much finer and shorter than pulp fibers usually used in papermaking applications.
  • the degree of crystallinity of the fine fibrous cellulose determined by the X-ray diffraction method is preferably 60% or more and 99% or less, more preferably 65% or more and 99% or less, and further preferably 70% or more and 99% or less. If the degree of crystallinity is 60% or more, further excellent performance can be expected in terms of heat resistance and low linear thermal expansion.
  • the degree of crystallinity can be obtained by measuring an X-ray diffraction profile and determining the crystallinity by a conventional method (Segal et al., Textile Research Journal, 29, 786, 1959).
  • the fine fibrous cellulose is a cellulose having an average fiber width of 1000 nm or less determined by observation with an electron microscope when the minor axis of the fine fibrous cellulose is defined as the width.
  • the average fiber width of the fine fibrous cellulose is preferably 200 nm or less, and more preferably 100 nm or less.
  • the average fiber width of the fine fibrous cellulose is 1000 nm or less, the characteristics (high strength, high rigidity, or high dimensional stability) as the fine fibrous cellulose can be easily obtained.
  • the average fiber width of the fine fibrous cellulose is preferably 1 nm or more, and more preferably 2 nm or more.
  • the range of the average fiber width of the fine fibrous cellulose is preferably 1 nm to 1000 nm, more preferably 2 nm to 500 nm, further preferably 2 nm to 200 nm, and particularly preferably 2 nm to 100 nm.
  • the average fiber width exceeds 30 nm, it approaches 1/10 of the wavelength of visible light, and when combined with a matrix material, refraction and scattering of visible light at the interface
  • the average fiber width is preferably 2 nm to 30 nm, and more preferably 2 to 20 nm.
  • Measurement of the average fiber width of the fine fibrous cellulose by observation with an electron microscope is performed as follows. A slurry containing fine fibrous cellulose having a concentration of 0.05 to 0.1% by mass is prepared, and the slurry is cast on a carbon film-coated grid subjected to a hydrophilic treatment to prepare a sample for TEM observation. When wide fibers are included, an SEM image of the surface cast on glass may be observed. Observation by an electron microscope image is performed at a magnification of 1000 times, 5000 times, 10000 times, 20000 times, 50000 times, or 100000 times depending on the width of the constituting fiber. However, the sample, observation conditions, and magnification are adjusted to satisfy the following conditions (1) and (2).
  • 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 perpendicularly intersecting the straight line X is drawn in the same image, and 20 or more fibers intersect the straight line Y.
  • the width is at least 20 (that is, the total is at least 40). read. In this way, at least three sets of the electron microscope images as described above are observed, and the fiber width of at least 40 ⁇ 3 sets (that is, at least 120 sets) is read. The average fiber width is obtained by dividing the fiber width read in this way by the number of read fibers.
  • the degree of polymerization of the fine fibrous cellulose is preferably 50 to 500, more preferably 100 to 400, and even more preferably 150 to 300.
  • the degree of polymerization of fine fibrous cellulose means the number of glucose molecules contained in one cellulose molecule. If the degree of polymerization of the fine fibrous cellulose is less than 50, it cannot be said to be “fibrous”, and it becomes difficult to use as a reinforcing agent. If it exceeds 500, dispersibility when blended with a resin or rubber Further, the slurry viscosity becomes too high when the fine fibrous cellulose is slurried, and the dispersion stability is lowered.
  • the degree of polymerization of fine fibrous cellulose is measured by the following method.
  • Fine fibrous cellulose (supernatant liquid after centrifugation, concentration of about 0.5% by mass) is reduced in pressure on a 500 mesh polyester mesh to prepare a wet sheet, and dried at 105 ° C. to obtain a dry sheet. .
  • the pulp viscosity is measured according to Tappi T230 using the obtained dry sheet.
  • a blank test is performed without using a cellulose sample by the same method, and a blank viscosity is measured. By subtracting 1 from the value obtained by dividing the pulp viscosity by the blank viscosity to obtain the specific viscosity ( ⁇ sp), the intrinsic viscosity ([ ⁇ ]) is calculated using the following formula.
  • the average fiber length is preferably 0.1 to 5 ⁇ m.
  • the fiber length can be determined by TEM, SEM, or AFM image analysis. That is, with respect to the electron microscope observation image as described above used for measuring the average fiber width, at least 20 fibers (that is, the total of the fibers intersecting with the straight line X and the fibers intersecting with the straight line Y). Read at least 40 fibers).
  • the fiber length of at least 40 ⁇ 3 sets (that is, at least 120 sets) is read.
  • the average fiber length is determined by dividing the fiber length read in this way by the number of read fibers.
  • the axial ratio of fine fibrous cellulose (that is, expressed by fiber length / average fiber width) is preferably in the range of 10 to 1,000. If the axial ratio is 10 or more, it is more suitable as a reinforcing agent for resin or rubber. When the axial ratio is 1000 or less, the viscosity when slurried becomes lower and the dispersion stability becomes higher. That is, the fine fibrous cellulose of one aspect of the present invention has an average fiber width of 1 nm to 200 nm when the short diameter of the fine fibrous cellulose is taken as the width, and the long diameter of the fine fibrous cellulose is taken as the length. Cellulose fibers or cellulose rod-like particles of type I crystal structure having a length of 0.1 to 5 ⁇ m and an axial ratio represented by fiber length / average fiber width of 10 to 1000.
  • the axial ratio (fiber length / average fiber width) of the fine fibrous cellulose is preferably in the range of 100 to 10,000. If the axial ratio is 100 or more, it is more suitable as a reinforcing agent for resin or rubber. If the axial ratio is 10,000 or less, the viscosity when slurried becomes low, and the dispersion stability becomes higher. That is, the fine fibrous cellulose according to another aspect of the present invention has an average fiber width of 1 nm to 200 nm when the short diameter of the fine fibrous cellulose is taken as the width and the long diameter of the fine fibrous cellulose is taken as the length. Cellulose fibers or cellulose rod-like particles of type I crystal structure having a length of 0.1 to 5 ⁇ m and an axial ratio of fiber length / average fiber width of 100 to 10,000.
  • the fine fibrous cellulose of the present invention has a high hydrophilicity (—COO ⁇ ) content of 0.06 mmol / g or more and a degree of polymerization of 500 or less.
  • a high hydrophilicity (—COO ⁇ ) content of 0.06 mmol / g or more and a degree of polymerization of 500 or less.
  • the fine fibrous cellulose of the present invention can be prevented from being dissolved in water when the content of (—COO ⁇ ) is 1.2 mmol / g or less.
  • Cellulose that dissolves in water is not suitable for use in resins and rubbers that are too hydrophilic and have low hydrophilicity.
  • the degree of polymerization of cellulose is 50 or more, characteristics (high strength, high rigidity, or high dimensional stability) as fine fibrous cellulose can be easily obtained, and it is suitable as a reinforcing agent for resins and rubbers.
  • the fine fibrous cellulose of the present invention has a slightly lower degree of polymerization, that is, a slightly shorter fiber length. Theoretically, when the fiber length is shortened, the reinforcing effect when blended with a resin or rubber is reduced, but the fine fibrous cellulose of the present invention is excellent in dispersibility when blended with a resin or rubber. The fiber length reflecting the degree of polymerization is not too short. Therefore, a sufficient reinforcing effect can be ensured.
  • the fine fibrous cellulose of another aspect of the present invention has the functional group (3) and the functional group (4), it is produced in a high yield. That is, electrical repulsion does not occur between mere celluloses, so the defibration property is not high.
  • the fine fibrous cellulose having the functional group (3) and the functional group (4) can be obtained with a high yield.
  • the fine fibrous cellulose of another aspect of the present invention is excellent in dispersion stability regardless of whether the dispersion is alkaline or acidic.
  • the dispersion containing the fine fibrous cellulose is excellent in dispersion stability even on the acidic side.
  • Acid dissociation constant pK a of the carboxylic acid is relatively large (about 4-5), are easily dissociated hydrogen ions in an alkaline under -COO - but is formed, the hydrogen ions is less likely to dissociate under acidic conditions, -COO - it is unlikely to be formed. Therefore, sufficient dispersion stability under acidic conditions cannot be obtained with the functional group (3) alone.
  • the phosphoric acid group has a small acid dissociation constant pKa (about 1 to 2)
  • pKa about 1 to 2
  • the fine fibrous cellulose according to another aspect of the present invention has a slightly lower degree of polymerization, and therefore can reduce the viscosity when used as a dispersion. In particular, a low viscosity can be maintained even when the concentration of the dispersion is increased.
  • the manufacturing method of the fine fibrous cellulose of another side surface of this invention is demonstrated.
  • the manufacturing method of the fine fibrous cellulose of this embodiment has an oxidation process, an alkali treatment process, and a defibration process. Hereinafter, each step will be described in detail.
  • the fiber raw material containing cellulose which is a raw material for the fine fibrous cellulose, includes pulp for papermaking, cotton pulp such as cotton linter and cotton lint, non-wood pulp such as hemp, straw or bagasse, or Examples include cellulose isolated from squirts and seaweeds. Among these, paper pulp is preferable in terms of availability.
  • Paper pulp includes hardwood kraft pulp (bleached kraft pulp (LBKP), unbleached kraft pulp (LUKP), oxygen bleached kraft pulp (LOKP), etc.), softwood kraft pulp (bleached kraft pulp (NBKP), unbleached kraft pulp) (NUCKP, oxygen bleached kraft pulp (NOKP), etc.), sulfite pulp (SP), chemical pulp such as soda pulp (AP), semi-chemical pulp (SCP), semi-chemical pulp (CGP), etc.
  • Mechanical pulp such as chemical pulp, groundwood pulp (GP), or thermomechanical pulp (TMP, or BCTMP), non-wood pulp made from straw, sardine, hemp, or kenaf, or deinked pulp made from waste paper Is mentioned.
  • kraft pulp, deinked pulp, or sulfite pulp is preferable because it is more easily available.
  • a fiber raw material may be used individually by 1 type, and may be used in mixture of 2 or more types.
  • the oxidation step is a step of obtaining oxidized fibers by performing at least ozone treatment on the fiber raw material. Specifically, as shown in the following reaction formula, it is a step of oxidizing at least the 2- and 6-position hydroxy groups of the glucopyranose ring constituting cellulose and decomposing cellulose to lower the molecular weight. In the oxidation step, the glucopyranose ring other than the 2nd and 6th positions may be oxidized.
  • Oxidation treatment can be performed only by ozone treatment. However, since the yield of fine fibrous cellulose can be further increased, the ozone-treated fiber raw material is further oxidized by an oxidizing agent other than ozone (hereinafter, “ It is preferably referred to as “additional oxidation treatment”.
  • the ozone treatment is a treatment in which the fiber raw material is brought into contact with ozone.
  • a specific ozone treatment method a method of leaving a fiber raw material in a gas containing ozone for a predetermined time, a method of passing a fiber raw material in a gas containing ozone, a method of applying a gas containing ozone to a fiber raw material, etc. Can be applied.
  • the gas containing ozone can be generated using a known ozone generator using an oxygen-containing gas such as air, oxygen gas, or oxygen-added air as an ozone raw material.
  • the fine fibrous cellulose obtained (-COO -) content and as the degree of polymerization is within the above range, the ozone concentration in the gas containing ozone treatment conditions (ozone, ozone amount for textile raw materials, The ozone treatment time or the ozone treatment temperature is adjusted.
  • the higher the concentration of ozone in the gas containing ozone the greater the amount of ozone added to the fiber raw material, or the longer the ozone treatment time, the greater the oxidation and the greater the content of (—COO ⁇ ).
  • the degree of polymerization decreases as the molecular weight of cellulose advances.
  • the ozone concentration in the gas containing ozone is preferably 50 to 1000 g / m 3 , more preferably 100 to 500 g / m 3 with respect to the volume of the gas. If the ozone concentration is 50 g / m 3 or more, the cellulose can be sufficiently oxidized, and further, the cellulose fibers can be sufficiently decomposed or cut, so that the yield of the fine fibrous cellulose is further increased. The dispersion stability when slurryed can be further improved.
  • the ozone concentration is 1000 g / m 3 or less, excessive oxidation and decomposition of cellulose fibers can be prevented, and the characteristics (high strength, high rigidity, or high dimensional stability) as fine fibrous cellulose are easy. Can get to.
  • the mass of ozone with respect to the total mass of the fiber raw material is preferably 0.1 to 80% by mass, and more preferably 5 to 60% by mass. If the ozone addition rate is 0.1% by mass or more, the cellulose can be sufficiently oxidized, and further, the cellulose fibers can be sufficiently decomposed or cut, so that the yield of fine fibrous cellulose is further increased, and the fine fibrous form The dispersion stability when cellulose is slurried can be further improved.
  • the ozone addition rate is 80% by mass or less, excessive oxidation and decomposition of cellulose fibers can be prevented, and the characteristics (high strength, high rigidity, or high dimensional stability) as fine fibrous cellulose are easy. Can get to.
  • the ozone treatment time is preferably 1 minute or longer, and more preferably 30 minutes or longer. If the ozone treatment time is 1 minute or longer, the cellulose can be sufficiently oxidized, and further, the cellulose fibers can be sufficiently decomposed or cut. Therefore, the yield of the fine fibrous cellulose is further increased, and the fine fibrous cellulose is slurried. The dispersion stability can be further improved.
  • the ozone treatment time is preferably 600 minutes or less, and more preferably 360 minutes or less. If the ozone treatment time is 600 minutes or less, excessive oxidation and decomposition of the cellulose fibers can be prevented, and characteristics (high strength, high rigidity, or high dimensional stability) as fine fibrous cellulose can be easily obtained. Can do.
  • the range of the ozone treatment time is preferably 1 minute to 600 minutes, more preferably 30 minutes to 360 minutes.
  • the ozone treatment temperature is preferably 0 to 100 ° C., more preferably 20 to 50 ° C. If the ozone treatment temperature is 0 ° C. or higher, the apparatus for ozone treatment can be simplified, and if it is 100 ° C. or lower, decomposition of ozone can be suppressed and the fiber raw material can be efficiently ozone treated.
  • Additional oxidation treatment Although it does not specifically limit as a method of an additional oxidation process, for example, the method of immersing the fiber raw material which carried out ozone treatment in the oxidizing agent solution is mentioned.
  • a known oxidizing agent for example, chlorine dioxide or a chlorine-based compound such as sodium chlorite
  • the oxidizing agent may be used alone or in combination of two or more.
  • the solvent in the oxidant solution may be either water or an organic solvent, but a polar solvent (polar organic solvent such as water or alcohol) is preferable, and an aqueous solvent containing at least water is more preferable.
  • the mass of the oxidant with respect to the total mass of the fiber raw material is preferably 0.1 to 100% by mass, and more preferably 1 to 30% by mass. If the oxidant addition rate is 0.1% by mass or more, cellulose can be further oxidized, and further, cellulose fibers can be further decomposed or cut. Therefore, the yield of fine fibrous cellulose is further increased, and fine fibrous cellulose The dispersion stability when the slurry is made into a slurry can be further improved. On the other hand, if the oxidizing agent addition rate is 100% by mass or less, excessive oxidation and decomposition of the cellulose fibers can be prevented, and the characteristics as fine fibrous cellulose can be easily obtained.
  • the oxidizing agent treatment time is preferably 10 to 360 minutes, and more preferably 60 to 180 minutes. If the oxidizing agent treatment time is 10 minutes or longer, cellulose can be oxidized more, and further, the cellulose fibers can be further decomposed or cut, so the yield of fine fibrous cellulose is further increased, and the fine fibrous cellulose is slurried. The dispersion stability can be further improved. On the other hand, if the oxidizing agent treatment time is 360 minutes or less, excessive oxidation and decomposition of the cellulose fibers can be prevented, and the characteristics as fine fibrous cellulose can be easily obtained.
  • the oxidant treatment temperature is preferably 5 to 90 ° C, more preferably 10 to 70 ° C. If the oxidizing agent treatment temperature is 5 ° C. or higher, the oxidizing treatment can be promoted, and if it is 90 ° C. or lower, the decomposition of the oxidizing agent can be suppressed and the fiber raw material can be efficiently treated with the oxidizing agent.
  • the alkali treatment step is a step of treating the oxidized fiber with an alkali solution containing an alkali compound represented by (2) X n + ⁇ (OH ⁇ ) n .
  • an alkali solution containing an alkali compound represented by (2) X n + ⁇ (OH ⁇ ) n .
  • functional groups (1) are formed at least at the 2-position and the 6-position of cellulose.
  • the functional group (1) is also formed in the portions other than the 2-position and the 6-position.
  • the alkali compound contained in the alkali solution may be an inorganic alkali compound or an organic alkali compound.
  • X n + is an alkali metal cation, ammonium ion, alkaline earth metal ion or polyvalent metal ion, it is an inorganic alkali compound, and an aliphatic ammonium ion or aromatic ammonium ion is an organic alkali compound.
  • alkali compound containing an alkali metal cation include lithium hydroxide, sodium hydroxide, or potassium hydroxide, and sodium hydroxide is preferred.
  • Examples of the alkali compound containing an alkaline earth metal cation include magnesium hydroxide, calcium hydroxide, and barium hydroxide, and magnesium hydroxide and calcium hydroxide are preferred.
  • alkali compound containing a polyvalent metal cation examples include an aqueous solution of aluminum hydroxide / sodium hydroxide.
  • Aqueous ammonia is mentioned as an alkaline compound containing an ammonium ion.
  • alkali compound containing an aliphatic ammonium ion examples include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, and tetrabutylammonium hydroxide. Tetramethylammonium hydroxide, tetraethylammonium hydroxide, or Tetrapropylammonium hydroxide is preferred.
  • alkali compound containing an aromatic ammonium ion examples include aqueous solutions of phenylamine (aniline), diphenylamine, and triphenylamine, and phenylamine (aniline) or diphenylamine is preferable.
  • the solvent in the alkaline solution may be either water or an organic solvent, but a polar solvent (polar organic solvent such as water or alcohol) is preferred, and an aqueous solvent containing at least water is more preferred.
  • a polar solvent polar organic solvent such as water or alcohol
  • an aqueous solvent containing at least water is more preferred.
  • alkaline solutions a sodium hydroxide aqueous solution, a potassium hydroxide aqueous solution and an ammonia aqueous solution are particularly preferred because of their high versatility.
  • the alkali compound concentration of the alkali solution is adjusted so as to neutralize all carboxy groups formed by the oxidation treatment.
  • the concentration of the inorganic alkali compound in the alkali solution is preferably 0.01 to 5% by mass, and 0.05 to 3% by mass with respect to the total mass of the alkali solution. More preferably. If the concentration of the inorganic alkali compound is 0.01% by mass or more, the yield of fine fibrous cellulose can be further improved, and if it is 5% by mass or less, the pH can be suppressed from becoming excessively high. Handleability is improved.
  • the concentration of the organic alkali compound in the alkali solution is preferably 0.01 to 5% by mass with respect to the total mass of the alkali solution, and 0.05 to 3% by mass More preferably. If the concentration of the organic alkali compound is 0.01% by mass or more, the yield of fine fibrous cellulose can be further improved, and if it is 5% by mass or less, the pH can be suppressed from becoming excessively high. Handleability is improved.
  • the pH of the alkaline solution at 25 ° C. is preferably 9 to 14, more preferably 10 to 14, and still more preferably 11 to 14. If the pH of the alkaline solution is 9 or more, the yield of fine fibrous cellulose will be higher, and if the pH is 14 or less, the handleability of the alkaline solution will be good.
  • the “alkaline solution having a pH of 9 to 14 at 25 ° C.” in the present invention means that the pH of the alkaline solution is within the above range when the temperature at 25 ° C. is used as a reference. That is, when the alkaline solution is prepared at a temperature other than 25 ° C., the pH range is corrected according to the temperature. It is also included in the scope of the present invention to prepare an alkaline solution in the pH range thus corrected. In other words, even if the pH at a certain temperature is not in the range of 9 to 14, it is possible to prepare an alkaline solution whose pH is corrected to the range of 9 to 14 when 25 ° C. is used as a reference. Included in the range.
  • the range of the alkali treatment step is preferably 1 to 180 minutes.
  • the temperature range of the alkali treatment step is preferably 20 to 100 ° C.
  • the defibrating step is a step of defibrating an alkali-treated fiber obtained by alkali-treating oxidized fiber or oxidized cellulose after the alkali treatment step.
  • the defibrating process means that the alkali-treated fiber is dispersed in a solvent by a defibrating apparatus described later. In the defibrating process, a defibrating apparatus is usually used.
  • Defibration treatment equipment includes high-speed defibrator, grinder (stone mortar grinder), high-pressure homogenizer and ultra-high pressure homogenizer, high-pressure collision grinder, ball mill, bead mill, disk refiner, conical refiner, twin-screw kneader, vibration mill
  • grinder stone mortar grinder
  • high-pressure homogenizer and ultra-high pressure homogenizer high-pressure collision grinder
  • ball mill ball mill
  • bead mill disk refiner
  • conical refiner conical refiner
  • twin-screw kneader vibration mill
  • An apparatus for wet pulverization such as a homomixer under high-speed rotation, an ultrasonic disperser, or a beater, can be used as appropriate.
  • the alkali-treated fiber In the defibrating process, it is preferable to dilute the alkali-treated fiber with water and an organic solvent alone or in combination to form a slurry.
  • the solid content concentration of the alkali-treated fiber after dilution is preferably 0.1 to 20% by mass, and more preferably 0.5 to 10% by mass. If the solid content concentration of the alkali-treated fiber after dilution is 0.1% by mass or more, the efficiency of the defibrating process is improved, and if it is 20% by mass or less, blockage in the defibrating apparatus can be prevented.
  • the functional group (1) is formed in the cellulose by the oxidation step and the alkali treatment step, and the ozone treatment conditions and the alkali compound concentration in the alkaline solution are set to (-COO ⁇ ). Since the content and the degree of polymerization are adjusted to be in the above ranges, fine fibrous cellulose can be produced from the fiber raw material in a high yield. Moreover, the degree of polymerization of the obtained fine fibrous cellulose is slightly smaller, and the dispersibility when blended with a resin or rubber is excellent. Furthermore, fine fibrous cellulose excellent in dispersion stability when slurried can be easily produced.
  • the manufacturing method of the fine fibrous cellulose of another side surface of this invention has an oxidation process, an acid group formation process, an alkali treatment process, and a defibration process.
  • an oxidation process an acid group formation process
  • an alkali treatment process an alkali treatment process
  • a defibration process a defibration process
  • the same fiber raw material as described above can be used as a fiber raw material containing cellulose, which is a raw material for fine fibrous cellulose.
  • the oxidation step is a step of forming a carboxy group by oxidizing a fiber raw material containing cellulose. Specifically, as shown in the following reaction formula (A), it is a step of forming a carboxy group by oxidizing at least the 6-position hydroxy group of the glucopyranose ring constituting cellulose. In this step, not all of the 6-position hydroxy groups are oxidized, but only some of them are oxidized. Some hydroxy groups are not oxidized to carboxy groups but become carbonyl groups.
  • the oxidation step examples include ozone treatment in which the fiber raw material is brought into contact with ozone, or oxyl treatment in which the fiber raw material is brought into contact with the N-oxyl compound, but ozone treatment is preferable in that the viscosity of the dispersion can be lowered.
  • the oxidation step can be performed only with ozone treatment or oxyl treatment, but since the yield of fine fibrous cellulose can be increased by oxidizing the carbonyl group to form a carboxy group, the ozone treatment or oxyl treatment can be performed.
  • the fiber raw material that has been subjected to ozone treatment or oxyl treatment may be further oxidized (hereinafter referred to as “additional oxidation treatment”) with an oxidizing agent other than ozone and N-oxyl compounds.
  • the gas containing ozone can be generated using a known ozone generator using an oxygen-containing gas such as air, oxygen gas, or oxygen-added air as an ozone raw material.
  • an oxygen-containing gas such as air, oxygen gas, or oxygen-added air as an ozone raw material.
  • the ozone treatment conditions (the ozone concentration in the gas containing ozone, the amount of ozone added to the fiber raw material, the ozone treatment time, the ozone treatment temperature, etc.) are adjusted as appropriate.
  • the higher the ozone concentration in the gas containing ozone the greater the amount of ozone added to the fiber material, the longer the ozone treatment time, or the higher the ozone treatment temperature, the more the hydroxyl group oxidation proceeds and the functional group.
  • the content of (3) increases, and the degree of polymerization decreases as the molecular weight of cellulose progresses.
  • the mass of ozone with respect to the total mass of the fiber raw material is preferably 0.1 to 80% by mass, and more preferably 1 to 60% by mass. If the ozone addition rate is 0.1% by mass or more, the cellulose can be sufficiently oxidized, and further, the cellulose fibers can be sufficiently decomposed or cut, so that the yield of fine fibrous cellulose is further increased, and the fine fibrous form The dispersion stability when cellulose is slurried can be further improved.
  • the ozone addition rate is 80% by mass or less, excessive oxidation and decomposition of cellulose fibers can be prevented, and the characteristics (high strength, high rigidity, or high dimensional stability) as fine fibrous cellulose are easy. Can get to.
  • the ozone concentration in the gas containing ozone, the ozone treatment time, and the ozone treatment temperature are the same as described above.
  • the N-oxyl compound used in the oxyl treatment generates 2,2,6,6-tetramethylpiperidinooxy radical (hereinafter referred to as “TEMPO”). Therefore, in the oxyl treatment, the fiber raw material is treated by TEMPO. That is, oxyl treatment means contacting the fiber raw material with TEMPO.
  • the amount of the N-oxyl compound used is not particularly limited, and is preferably 1 to 80 parts by mass with respect to 100 parts by mass of the fiber raw material.
  • a co-oxidant is usually reacted with a fiber raw material together with an N-oxyl compound.
  • the co-oxidant include sodium hypochlorite, sodium chlorite, sodium hypobromite, or sodium bromite.
  • Sodium hypochlorite, sodium chlorite, or sodium hypobromite Is preferred.
  • the amount of the co-oxidant used is not particularly limited, and is preferably 1 to 80 parts by mass with respect to 100 parts by mass of the fiber raw material.
  • the oxyl treatment is usually performed in the presence of an alkali halide.
  • the alkali halide include alkali iodide, alkali bromide, alkali chloride, and alkali fluoride, and alkali iodide, alkali bromide, and alkali chloride are preferable.
  • the amount of alkali halide used is not particularly limited, and is preferably 0.1 to 15 parts by mass with respect to 100 parts by mass of the fiber raw material.
  • the treatment temperature during the oxyl treatment is preferably in the range of 20 to 100 ° C., and the treatment time is preferably 0.5 to 4 hours. Moreover, in order to perform an oxyl process uniformly, it is preferable to process, stirring with various stirring apparatuses.
  • the fiber raw material is treated with an oxo acid containing a phosphorus atom (hereinafter referred to as “phosphoro oxo acid”) or a salt thereof, whereby the acid group-containing cellulose is treated. It is a process to obtain. Treating the fiber raw material with phosphorus oxo acid or a salt thereof means adding a solvent containing phosphorus oxo acid or a salt thereof to the fine fiber raw material containing cellulose after the oxidation step and heating.
  • phosphoro oxo acid an oxo acid containing a phosphorus atom
  • the acid group formation step for example, when a hydroxy group remaining in the cellulose molecule after the oxidation step and a phosphorus oxoacid having at least (HPO 4 ) 2- or a salt thereof undergo a dehydration reaction, the following reaction formula (B) Thus, the phosphate group of the functional group (4) is formed.
  • Examples of the phosphorus oxo acid include phosphoric acid, metaphosphoric acid, and polyphosphoric acid, and phosphoric acid or metaphosphoric acid is preferable.
  • Examples of the salt of phosphorus oxo acid include lithium salt, sodium salt, potassium salt, calcium salt, ammonium salt, or organic alkali salt of phosphoric acid, metaphosphoric acid, or polyphosphoric acid.
  • Phosphoric acid, lithium salt of metaphosphoric acid Sodium salt, potassium salt, calcium salt, ammonium salt, organic alkali salt, etc. are preferable.
  • Phosphooxo acids or salts thereof may be used alone or in combination of two or more. Among them, at least one of phosphoric acid and sodium salt of phosphoric acid, or potassium salt is preferable because it is easy to handle at low cost and increases the introduction efficiency of phosphoric acid groups.
  • the mass ratio of the phosphorus oxoacid or salt thereof to the fiber raw material is preferably 0.2 to 500 parts by mass, more preferably 1 to 400 parts by mass as the amount of phosphorus element with respect to 100 parts by mass of the fiber raw material. Most preferred is 2 to 200 parts by weight. If the ratio of a phosphorus oxo acid or its salt is 0.2 mass part or more, the yield of a fine fibrous cellulose can be improved more. However, even if the amount exceeds 500 parts by mass, the effect of improving the yield reaches a peak, and only the use of phosphorus oxoacid or a salt thereof is wasted.
  • the heat processing temperature in an acid group formation process is 30 degreeC or more and 250 degrees C or less from the point of the thermal decomposition temperature of a cellulose.
  • the heat treatment temperature is preferably 100 to 170 ° C.
  • the heat treatment temperature while water is contained in the system to which the phosphorus oxo acid or salt thereof is added during the heat treatment is preferably 30 ° C. or higher and 130 ° C. or lower, more preferably 30 ° C. or higher and 110 ° C. or lower.
  • the slurry is sufficiently dried to remove moisture from the slurry. Thereafter, heat treatment is preferably performed at 100 to 170 ° C.
  • an organic compound that melts at a high temperature such as urea can coexist in the system.
  • the cellulose swells, and the organic compound melts to provide a solid-liquid reaction field, thereby improving the efficiency of acid group formation.
  • the heat treatment time in the acid group forming step is preferably 1 to 300 minutes.
  • the alkali treatment step is a step of treating the acid group-containing cellulose with an alkali solution containing an alkali compound represented by X p + ⁇ (OH ⁇ ) p or Y q + ⁇ (OH ⁇ ) q .
  • an alkali compound represented by X p + ⁇ (OH ⁇ ) p or Y q + ⁇ (OH ⁇ ) q By the alkali treatment, a functional group (3) and a functional group (4) are formed in the cellulose.
  • X p + ⁇ (OH ⁇ ) p and Y q + ⁇ (OH ⁇ ) q may be the same or different.
  • it does not specifically limit as a method of an alkali treatment For example, the method of immersing an acid group containing cellulose in an alkaline solution is mentioned.
  • the alkali compound contained in the alkali solution may be an inorganic alkali compound or an organic alkali compound.
  • X p + is an alkali metal cation, ammonium ion, alkaline earth metal cation or polyvalent metal cation is an inorganic alkali compound, and an aliphatic ammonium ion or aromatic ammonium ion is organic. It is an alkali compound.
  • the solvent in the alkaline solution may be either water or an organic solvent, but a polar solvent (polar organic solvent such as water or alcohol) is preferred, and an aqueous solvent containing at least water is more preferred.
  • a polar solvent polar organic solvent such as water or alcohol
  • an aqueous solvent containing at least water is more preferred.
  • alkaline solutions a sodium hydroxide aqueous solution, a potassium hydroxide aqueous solution and an ammonia aqueous solution are particularly preferred because of their high versatility.
  • the alkali compound concentration in the alkali solution is adjusted so as to neutralize all carboxy groups formed in the oxidation step and all phosphate groups formed in the acid group formation step.
  • the concentration of the inorganic alkali compound in the alkali solution is preferably 0.01 to 5% by mass, and 0.05 to 3% by mass with respect to the total mass of the alkali solution. More preferably. If the concentration of the inorganic alkali compound is 0.01% by mass or more, the yield of fine fibrous cellulose can be further improved, and if it is 5% by mass or less, the pH can be suppressed from becoming excessively high. Handleability is improved.
  • the concentration of the organic alkali compound in the alkali solution is preferably 0.01 to 5% by mass with respect to the total mass of the alkali solution, and 0.05 to 3% by mass More preferably. If the concentration of the organic alkali compound is 0.01% by mass or more, the yield of fine fibrous cellulose can be further improved, and if it is 5% by mass or less, the pH can be suppressed from becoming excessively high. Handleability is improved.
  • the pH of the alkaline solution at 25 ° C. is the same as described above.
  • the defibrating step is a step of defibrating an alkali-treated fiber obtained by alkali-treating oxidized cellulose after the alkali treatment step, and is the same as described above.
  • the fine fibrous cellulose of the said embodiment since the electrical repulsion between cellulose becomes large by forming a functional group (3) and a functional group (4) in a cellulose, defibration property becomes high. From the fiber raw material, fine fibrous cellulose can be produced in a high yield. Further, the fine fibrous cellulose obtained by the production method of the present embodiment has a functional group (4) having a small pK a , and hydrogen ions are easily dissociated not only under alkaline but also under acidic conditions, so that —PO 3 H Since it forms - and -PO 3 2- , it can be stabilized in a dispersion medium.
  • the dispersion of fine fibrous cellulose is excellent in dispersion stability regardless of whether it is alkaline or acidic.
  • the fine fibrous cellulose obtained by the manufacturing method of this embodiment since a polymerization degree becomes a little small by an oxidation process, the viscosity at the time of setting it as a dispersion liquid can be made low.
  • the said manufacturing method has an alkali treatment process, the fibrillation property of a cellulose becomes higher and can manufacture a fine fibrous cellulose from a fiber raw material with a higher yield.
  • the said manufacturing method has a fibrillation process, the acid group containing cellulose which carried out the alkali treatment can be refined
  • the fine fibrous cellulose of the present embodiment is a cellulose fiber having a functional group (3) and a functional group represented by the above formula (5) (hereinafter referred to as “functional group (5)”).
  • the polymerization degree, average fiber width, fiber length, and axial ratio of the fine fibrous cellulose of this embodiment are the same as those of the fine fibrous cellulose of the above-described embodiment.
  • the content of (—COO ⁇ ) of the functional group (3) in the fine fibrous cellulose of this embodiment is preferably 0.06 to 1.2 mmol / g, and preferably 0.1 to 0.9 mmol / g. It is more preferable.
  • (-COO -) When the content of 0.06 mmol / g or more, can be manufactured at high yield, whereas, (- COO -) content is at most 1.2 mmol / g, the cellulose molecules Therefore, the characteristics (high strength, high rigidity, or high dimensional stability) as fine fibrous cellulose can be easily obtained.
  • the (—SO 3 ⁇ ) content of the functional group (5) in the fine fibrous cellulose is preferably 0.01 to 2.0 mmol / g, more preferably 0.05 to 1.5 mmol / g. preferable.
  • the content of (—SO 3 ⁇ ) in the functional group (5) is the content of (—SO 3 ⁇ ) per gram of cellulose, and was measured by applying TAPPI T237 cm-08 (2008).
  • sodium bicarbonate (NaHCO 3 ) / sodium chloride (NaCl) 0.84 g / test solutions prepared by dissolving diluted 1000ml with distilled water 5.85 g, change in the test solution prepared by dissolving diluted 1000ml with distilled water and sodium hydroxide 1.60 g, further (-SO 3 -) before and after the introduction of substantially the difference between the measured value in the cellulose fibers (-SO 3 -) except for using content was measured according to TAPPI T237 cm-08 (2008) .
  • the acidic group content measurement method is basically a method for measuring the introduction amount of a monovalent acidic group (carboxy group)
  • the introduction amount of a sulfonic acid group that is a polyvalent acidic group is The (—SO 3 ⁇ ) content obtained as the monovalent acidic group content was divided by the (—SO 3 ⁇ ) acid number 2.
  • the total content of (—COO ⁇ ) and (—SO 3 ⁇ ) in the fine fibrous cellulose is preferably 0.1 to 3.0 mmol / g, preferably 0.5 to 2 More preferably, it is 5 mmol / g. If the total content of (—COO ⁇ ) and (—SO 3 ⁇ ) is 0.1 mmol / g or more, it can be produced in a higher yield. Further, when the total content of (—COO ⁇ ) and (—SO 3 ⁇ ) is within the above range, the dispersion stability when the fine fibrous cellulose is slurried becomes higher.
  • r is a natural number of 1 to 3.
  • the fine fibrous cellulose of this embodiment Since the fine fibrous cellulose of this embodiment has a functional group (3) and a functional group (5), it is manufactured with a high yield. That is, electrical repulsion does not occur between mere celluloses, so that the defibration property is not high. However, between celluloses having a functional group (3) and a functional group (4), (—COO ⁇ ) and (—SO 3 - ) It is easy to cause electric repulsion due to (), so the defibration property is high. Therefore, the fine fibrous cellulose having the functional group (3) and the functional group (5) can be obtained with a high yield. Moreover, the fine fibrous cellulose of this embodiment is excellent in dispersion stability regardless of whether the dispersion is alkaline or acidic.
  • the dispersion containing the fine fibrous cellulose is excellent in dispersion stability even on the acidic side.
  • Acid dissociation constant pK a of the carboxylic acid is relatively large (about 4-5), are easily dissociated hydrogen ions in an alkaline under -COO - but is formed, the hydrogen ions is less likely to dissociate under acidic conditions, -COO - it is unlikely to be formed. Therefore, sufficient dispersion stability under acidic conditions cannot be obtained with the functional group (3) alone.
  • the sulfonic acid group has a small acid dissociation constant pKa (about 1 to 2), in the fine fibrous cellulose of this embodiment having the functional group (5), —SO 3 — is formed under acidity.
  • the degree of polymerization is slightly small, the viscosity when used as a dispersion can be lowered. In particular, a low viscosity can be maintained even when the concentration of the dispersion is increased.
  • the manufacturing method of this embodiment which manufactures the said fine fibrous cellulose has an oxidation process, an acid group formation process, an alkali treatment process, and a defibration process.
  • the manufacturing method of this embodiment differs in the acid group formation process from the manufacturing method of above-mentioned embodiment.
  • the oxidation process, the alkali treatment process, and the defibration process in the present embodiment are the same as the oxidation process, the alkali treatment process, and the defibration process in the above-described embodiment, and a description thereof is omitted.
  • the fiber raw material is treated with an oxo acid containing a sulfur atom (hereinafter referred to as “sulfur oxo acid”) or a salt thereof to form a sulfonic acid group.
  • sulfur oxo acid an oxo acid containing a sulfur atom
  • acid group-containing cellulose is obtained.
  • the acid group formation step for example, when a carbonyl group remaining in the cellulose molecule after the oxidation step reacts with a sulfur oxo acid having at least (HSO 3 ) ⁇ or a salt thereof, the following reaction formula (C)
  • the sulfonic acid group of the functional group (5) is formed.
  • sulfur oxo acid examples include sulfurous acid and dithionic acid.
  • salt of sulfur oxo acid examples include sulfurous acid, lithium salt of dithionite, sodium salt, potassium salt, calcium salt, ammonium salt, and organic alkali salt.
  • Sulfur oxo acid or a salt thereof may be used alone or in combination of two or more. Among these, a sodium salt or potassium salt of sulfite is preferable because it is easy to handle at low cost and increases the introduction efficiency.
  • the amount of sulfur oxo acid or salt thereof added to 100 parts by mass of the fiber raw material is preferably 1 to 500 parts by mass, more preferably 5 to 100 parts by mass, and even more preferably 10 to 40 parts by mass.
  • the addition amount of sulfur oxo acid or a salt thereof is 1 part by mass or more, the yield of fine fibrous cellulose can be further improved. However, even if the addition amount exceeds 500 parts by mass, the effect of improving the yield reaches its peak, and the sulfur oxo acid is merely used in vain.
  • the treatment temperature in the acid group formation step is preferably 10 to 90 ° C, more preferably 20 to 70 ° C. If processing temperature is 10 degreeC or more, a sulfonic acid group can be formed easily, and if it is 90 degrees C or less, thermal decomposition of a cellulose can be suppressed.
  • a phosphoric acid group may be formed by treatment with a phosphorus oxoacid or a salt thereof.
  • the phosphorus oxo acid or salt thereof is added to treat the fiber raw material with the sulfur oxo acid or salt thereof to form a sulfonic acid group. Treatment with a salt may form a phosphate group.
  • the fine fibrous cellulose of the said embodiment since the electrical repulsion between cellulose becomes large by forming a functional group (3) and a functional group (5) in a cellulose, defibration property becomes high. From the fiber raw material, fine fibrous cellulose can be produced in a high yield. Further, the fine fibrous cellulose obtained by the production method of this embodiment has a pK a less functional group (5), -SO 3 are easily dissociated hydrogen ions under acidic conditions not only alkaline under - Can be stabilized in the dispersion medium. Therefore, the dispersion of fine fibrous cellulose is excellent in dispersion stability regardless of whether it is alkaline or acidic.
  • the fine fibrous cellulose obtained by the manufacturing method of this embodiment since a polymerization degree becomes a little small by an oxidation process, the viscosity at the time of setting it as a dispersion liquid can be made low. Moreover, since the said manufacturing method has an alkali treatment process, the fibrillation property of a cellulose becomes higher and can manufacture a fine fibrous cellulose from a fiber raw material with a higher yield. Moreover, since the said manufacturing method has a fibrillation process, the acid group containing cellulose which carried out the alkali treatment can be refined
  • the fine fibrous cellulose dispersion according to another aspect of the present invention is obtained by dispersing fine fibrous cellulose in a dispersion medium.
  • a dispersion medium water or a polar organic solvent can be used.
  • Preferred polar organic solvents include alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, or t-butyl alcohol, ketones such as acetone or methyl ethyl ketone (MEK), diethyl ether, or tetrahydrofuran (THF).
  • MEK methyl ethyl ketone
  • THF tetrahydrofuran
  • a nonpolar organic solvent can be used as long as the dispersion stability of the fine fibrous cellulose dispersion is not hindered.
  • the content of the fine fibrous cellulose contained in the fine fibrous cellulose dispersion is preferably 0.05 to 20% by mass, more preferably 0.1 to 10% by mass with respect to the fine fibrous cellulose. If the content of fine fibrous cellulose is 0.05% by mass or more, it is excellent in production efficiency when producing a nonwoven fabric using fine fibrous cellulose or a composite material containing fine fibrous cellulose in a resin or the like. . On the other hand, if the content of fine fibrous cellulose is 20% by mass or less, the dispersion stability of the dispersion is excellent.
  • the viscosity of the fine fibrous cellulose dispersion is preferably 400 mPa ⁇ s or less, and more preferably 200 mPa ⁇ s or less, because the handleability of the dispersion becomes high.
  • the viscosity of the fine fibrous cellulose dispersion is preferably 1 mPa ⁇ s or more, and more preferably 5 mPa ⁇ s or more, from the viewpoint of ease of preparation.
  • the viscosity range of the fine fibrous cellulose dispersion is preferably 1 to 400 mPa ⁇ s, more preferably 5 to 200 mPa ⁇ s.
  • the viscosity is a value measured at 25 ° C. using a B-type viscometer using a dispersion containing 0.5% by mass of fine fibrous cellulose as a measurement sample.
  • Nonwoven fabric contains the fine fibrous cellulose.
  • the thickness of the nonwoven fabric of the present invention is not particularly limited, but is preferably 10 ⁇ m or more, more preferably 50 ⁇ m or more, particularly preferably 80 ⁇ m or more, preferably 10 cm or less, more preferably 1 cm or less, more preferably 1 mm. Hereinafter, it is particularly preferably 250 ⁇ m or less.
  • the thickness of the nonwoven fabric is preferably 10 ⁇ m or more from the viewpoint of production stability or strength, and is preferably 10 cm or less and from the viewpoint of productivity, uniformity, or resin impregnation.
  • the thickness range of the nonwoven fabric is preferably 10 ⁇ m to 10 cm, more preferably 10 ⁇ m to 1 cm, still more preferably 10 ⁇ m to 1 mm, and particularly preferably 10 ⁇ m to 250 ⁇ m.
  • the nonwoven fabric of the present invention preferably has a porosity of 35% by volume or more, more preferably 35 to 60% by volume. If the porosity of the nonwoven fabric is small, the resin is difficult to impregnate when a matrix material such as a resin is blended to obtain a composite material, and the unimpregnated portion remains, so scattering may occur at the interface and haze may increase. Moreover, when the porosity of a nonwoven fabric is high, in the composite material which mix
  • the porosity here refers to the volume ratio of the voids in the nonwoven fabric, and the porosity can be determined from the area, thickness, and mass of the nonwoven fabric according to the following formula.
  • Porosity (volume%) ⁇ 1-B / (M ⁇ A ⁇ t) ⁇ ⁇ 100
  • A is the area (cm 2 ) of the nonwoven fabric
  • t (cm) is the thickness
  • B is the mass (g) of the nonwoven fabric
  • M 1.5 g / cm 3 is assumed in the present invention.
  • the film thickness of the nonwoven fabric is measured at 10 points at various positions of the nonwoven fabric using a film thickness meter (PDN-20 manufactured by PEACOK), and the average value is adopted.
  • the porosity when obtaining the porosity of the nonwoven fabric in the composite material, the porosity can also be obtained by image analysis of spectroscopic analysis or SEM observation of the cross section of the composite material.
  • Air permeability of the nonwoven fabric of the present invention is not particularly limited since it depends on the basis weight, for example, when a basis weight of the sheet 50 g / m 2 is preferably 100 to 20,000 sec / 100 cc.
  • the present invention is not limited to the above embodiment.
  • the alkali treatment step may be omitted, and the fibrillation step may be performed after the acid group formation step.
  • It has a functional group represented by the following formula (1), and the content of —COO 2 — is 0.06 to 1.2 mmol / g, The degree of polymerization is 50-500, The average fiber width is 1 nm to 200 nm, The average fiber length is 0.1-5 ⁇ m, Fine fibrous cellulose having an axial ratio expressed by fiber length / average fiber width of 10 to 1000 is preferred.
  • a method for producing fine fibrous cellulose comprising producing a fine fibrous cellulose having a functional group represented by the following formula (1): In the oxidation step and the alkali treatment step, the content of —COO ⁇ with respect to the mass of the obtained fine fibrous cellulose is 0.06 to 1.2 mmol / g, and the degree of polymerization is 50 to 500.
  • the oxidation step further includes a post-oxidation step of further oxidizing the ozone-treated fiber raw material with an oxidizing agent other than ozone after the ozone treatment, After the alkali treatment step, further comprising a defibration step of defibrating the alkali-treated oxidized fiber,
  • the fiber raw material is at least one pulp selected from the group consisting of kraft pulp, deinked pulp, and sulfite pulp;
  • the ozone concentration in the ozone treatment is such that the mass of ozone with respect to the volume of gas is 50 to 1000 g / m 3 ,
  • the ozone addition rate with respect to the fiber raw material in the ozone treatment is such that the mass of ozone with respect to the total mass of the fiber raw material is 0.1 to 80% by mass,
  • the ozone treatment time in the ozone treatment is 1 minute to 600 minutes,
  • the ozone treatment temperature in the ozone treatment is 1 minute to 600 minutes,
  • the alkaline solution is at least one aqueous solution selected from the group consisting of an aqueous sodium hydroxide solution, an aqueous potassium hydroxide solution and an aqueous ammonia solution;
  • the concentration of the alkali compound in the alkali solution is 0.01 to 5% by mass relative to the total mass of the alkali solution;
  • the time of the alkali treatment step is 1 to 180 minutes,
  • the temperature of the alkali treatment step is 20 to 100 ° C .
  • the oxidizing agent in the additional oxidation treatment step is at least one oxidizing agent selected from the group consisting of chlorine dioxide and sodium chlorite,
  • the addition ratio of the oxidant to the fiber material is such that the mass of the oxidant is 0.1 to 100% by mass with respect to the total mass of the fiber material
  • the treatment time of the oxidizing agent in the additional oxidation treatment step is 10 to 360 minutes, A method for producing fine fibrous cellulose is preferred in which the treatment temperature of the oxidizing agent in the
  • the degree of polymerization is 50-500,
  • the average fiber width is 1 nm to 200 nm,
  • the average fiber length is 0.1-5 ⁇ m,
  • Fine fibrous cellulose having an axial ratio represented by fiber length / average fiber width of 100 to 10,000 is preferable.
  • p and r are each independently a natural number of 1 to 3.
  • An oxidation process of oxidizing a fiber raw material containing cellulose to form a carboxy group and a method of producing fine fibrous cellulose having an acid group formation process after the oxidation process,
  • the fiber raw material is treated with an oxo acid containing a phosphorus atom or a salt thereof to form a phosphate group to obtain an acid group-forming cellulose, or the fiber raw material is converted to a sulfur atom.
  • a step of forming a sulfonic acid group by treatment with an oxo acid or a salt thereof to obtain an acid group-containing cellulose is a step of forming a carboxy group by performing at least ozone treatment on the fiber raw material, After the acid group formation step, an alkali treatment step for obtaining a cellulose salt by alkali treatment of the acid group-containing cellulose, and a defibration step for defibrating the cellulose salt, After the acid group formation step, it has a defibration step of defibrating the acid group-containing cellulose,
  • the fiber raw material is at least one pulp selected from the group consisting of kraft pulp, deinked pulp, and sulfite pulp;
  • the ozone concentration in the ozone treatment is such that the mass of ozone with respect to the volume of gas is 50 to 1000 g / m 3 ,
  • the oxo acid containing a phosphorus atom is at least one oxo acid selected from
  • the salt of The ozone addition rate with respect to the fiber raw material in the ozone treatment is such that the mass of ozone with respect to the total mass of the fiber raw material is 0.1 to 80% by mass,
  • the ozone treatment time in the ozone treatment is 1 minute to 600 minutes,
  • the ozone treatment temperature in the ozone treatment is preferably 0 to 100 ° C.
  • Example 1 As a fiber raw material containing cellulose, a hardwood bleached kraft pulp (LBKP) having a carboxyl group content of 0.06 mmol / g, a solid content concentration of 30% by mass (water content of 70% by mass), and an absolute dry mass conversion was prepared.
  • the LBKP was placed in a container, and 5 L of a mixed gas of ozone and oxygen having an ozone concentration of 200 g / m 3 was introduced into the container and shaken at 25 ° C. for 2 minutes. The ozone addition rate at this time was 5 mass% with respect to the pulp dry mass. After standing for 6 hours, ozone and air in the container were removed, and the ozone oxidation treatment was completed.
  • LLKP hardwood bleached kraft pulp
  • the suspension was washed with ion-exchanged water, and the washing was repeated until the pH of the washing water reached 6 or higher. Then, it filtered under reduced pressure using the filter paper, and obtained the oxidation process pulp with a solid content concentration of 20 mass%.
  • Ion exchange water was added to the oxidized pulp (20 g in terms of absolute dry mass) to prepare a slurry having a solid content concentration of 2% by mass.
  • Sodium hydroxide was added to the slurry so that the sodium hydroxide concentration was 0.3% by mass, and the mixture was stirred for 5 minutes and then allowed to stand at room temperature for 30 minutes.
  • a cellulose fiber aqueous dispersion having a cellulose fiber concentration of 0.5% by mass.
  • the cellulose fiber aqueous dispersion was defibrated for 30 minutes at 21500 rpm using a defibrating apparatus (Cleamix-2.2S, manufactured by MTechnic Co., Ltd.).
  • Example 2 An aqueous dispersion of fine fibrous cellulose was obtained in the same manner as in Example 1 except that the amount of the mixed gas of ozone and oxygen was 15 L (ozone addition rate: 15% by mass).
  • Example 3 An aqueous dispersion of fine fibrous cellulose was obtained in the same manner as in Example 1 except that the amount of the mixed gas of ozone and oxygen was 30 L (ozone addition rate: 30% by mass).
  • Example 4 An aqueous dispersion of fine fibrous cellulose was obtained in the same manner as in Example 1 except that the amount of the mixed gas of ozone and oxygen was 60 L (ozone addition rate 60 mass%).
  • Example 5 Example except that tetramethylammonium hydroxide (TMAH) was added to the slurry containing the oxidized pulp so that the TMAH concentration was 1.0% by mass and subjected to alkali treatment instead of adding sodium hydroxide. In the same manner as in Example 1, an aqueous dispersion of fine fibrous cellulose was obtained.
  • TMAH tetramethylammonium hydroxide
  • Example 6 LBKP similar to Example 1 was accommodated in a container, 15 L of a mixed gas of ozone and oxygen having an ozone concentration of 200 g / m 3 was introduced into the container, and shaken at 25 ° C. for 2 minutes. The ozone addition rate at this time was 15 mass% with respect to the pulp dry mass. After standing for 6 hours, ozone and air in the container were removed, and the ozone oxidation treatment was completed. After the treatment, the suspension was washed with ion-exchanged water, and the washing was repeated until the pH of the washing water reached 6 or higher. Then, it filtered under reduced pressure using the filter paper, and obtained the ozone oxidation process pulp with a solid content concentration of 20 mass%.
  • ozone-oxidized pulp 20 g in terms of absolute dry mass
  • 200 g of 0.3% by mass aqueous sodium chlorite solution adjusted to pH 4 to 5 with hydrochloric acid (relative to the absolute dry mass of cellulose fibers, 3% by weight as sodium chlorite) was added and reacted at 70 ° C. for 3 hours for additional oxidation.
  • the suspension was washed with ion-exchanged water, and washing was repeated until the pH of the washing water became 6 or more to obtain an oxidized treated pulp.
  • Example 2 In the same manner as in Example 1, the oxidized pulp (20 g in terms of absolute dry mass) was subjected to alkali treatment, defibration treatment, and centrifugal separation treatment with sodium hydroxide to obtain an aqueous dispersion of fine fibrous cellulose. .
  • Example 7 An aqueous dispersion of fine fibrous cellulose was obtained in the same manner as in Example 6 except that the amount of the mixed gas of ozone and oxygen was 30 L.
  • Example 8 Example except that tetramethylammonium hydroxide (TMAH) was added to the slurry containing the oxidized pulp so that the TMAH concentration was 1.0% by mass and subjected to alkali treatment instead of adding sodium hydroxide. In the same manner as in Example 6, an aqueous dispersion of fine fibrous cellulose was obtained.
  • TMAH tetramethylammonium hydroxide
  • Example 2 Ozone treatment in Example 1 was omitted, and LBKP was subjected to alkali treatment, defibration treatment, and centrifugal separation treatment as in Example 1 to obtain fine fibrous cellulose.
  • Example 4 Ozone treatment in Example 6 was omitted, and LBKP was subjected to alkali treatment, fibrillation treatment, and centrifugal separation treatment as in Example 6 to obtain fine fibrous cellulose.
  • TEMPO oxidation pulp with a solid content concentration of 20 mass%. 100 g of TEMPO oxidized pulp (20 g in terms of dry mass) was sampled, 18 g of sodium chlorite, 60 g of acetic acid and 700 ml of ion-exchanged water were added, and the pH was adjusted to 4.5 with a 20 g / L sodium hydroxide aqueous solution. did. The reaction was continued for 48 hours at room temperature to carry out additional oxidation treatment.
  • Example 1 to 8 and Comparative Examples 1 to 6 the defibration yield was measured using an aqueous dispersion containing fine fibrous cellulose. That is, the centrifugal recovery rate of the aqueous dispersion containing fine fibrous cellulose was determined from the following formula, and the centrifugal recovery rate was defined as the fibrillation yield. The results of the defibration yield are shown in Table 1.
  • Example 1 to 8 and Comparative Examples 1 to 6 the oxidized pulp after completion of all oxidation treatments was subjected to the carboxy group by the method described in “Method for measuring the content of carboxy group in cellulose fiber” above. The content of was measured. Table 1 shows the results of the content of carboxy groups.
  • the polymerization degree of the obtained fine fibrous cellulose was measured. In the measurement of the degree of polymerization, first, a fine fibrous cellulose (concentration of about 0.5% by mass) was reduced in pressure on a 500 mesh polyester mesh to prepare a wet sheet, dried at 105 ° C., and a dry sheet was obtained. Obtained. Next, the obtained dry sheet was dissolved in a 0.5 M copper ethylenediamine solution, and the degree of polymerization was determined by a viscosity method. Table 1 shows the measurement results of the degree of polymerization.
  • Comparative Examples 2 and 4 that were not subjected to oxidation treatment had a high degree of polymerization. Moreover, although the TEMPO oxidation process and the additional oxidation process were performed, the comparative examples 5 and 6 which did not perform the alkali treatment also had a large degree of polymerization. These are considered to have low dispersibility when blended with resin or rubber.
  • Example 9 As a fiber raw material containing cellulose, a hardwood bleached kraft pulp (LBKP) having a carboxyl group content of 0.05 mmol / g, a solid content concentration of 30% by mass (water content of 70% by mass), and an absolute dry mass conversion of 20 g was prepared.
  • the LBKP was housed in a container, and 2 L of a mixed gas of ozone and oxygen having an ozone concentration of 200 g / m 3 was introduced into the container and shaken at 25 ° C. for 2 minutes. The ozone addition rate at this time was 2 mass% with respect to the pulp dry mass. After standing for 6 hours, ozone and air in the container were removed, and the ozone oxidation treatment was completed.
  • LLKP hardwood bleached kraft pulp
  • the suspension was washed with ion-exchanged water, and the washing was repeated until the pH of the washing water reached 6 or higher. Then, it filtered under reduced pressure using the filter paper, and obtained the oxidation process pulp with a solid content concentration of 20 mass%. Next, 11.27 g of sodium dihydrogen phosphate dihydrate and 8.07 g of disodium hydrogen phosphate are dissolved in 22.60 g of water, and an aqueous solution of a phosphate compound (hereinafter referred to as “phosphorylation reagent”). Got. The pH of this phosphorylating reagent was 6.0 at 25 ° C.
  • Sodium hydroxide was added to the slurry so that the sodium hydroxide concentration was 0.3% by mass, and the mixture was stirred for 5 minutes and then allowed to stand at room temperature for 30 minutes. Subsequently, the suspension was washed with ion-exchanged water, and washing was repeated until the pH of the washing water became 8 or less to obtain a slurry containing alkali-treated pulp. Next, ion-exchanged water was added to the slurry to prepare a cellulose fiber aqueous dispersion having a cellulose fiber concentration of 0.5% by mass.
  • the cellulose fiber aqueous dispersion was defibrated for 30 minutes at 21500 rpm using a defibrating apparatus (Cleamix-2.2S, manufactured by MTechnic Co., Ltd.). Thereafter, using a centrifuge (“H-200NR” manufactured by Kokusan Co., Ltd.), the mixture was treated at about 12000 G for 10 minutes, and the separated supernatant was recovered as an aqueous dispersion of fine fibrous cellulose.
  • Example 10 An aqueous dispersion of fine fibrous cellulose was obtained in the same manner as in Example 9 except that the amount of the mixed gas of ozone and oxygen was changed to 5 L (ozone addition rate 5 mass%).
  • Example 11 An aqueous dispersion of fine fibrous cellulose was obtained in the same manner as in Example 9 except that the amount of the mixed gas of ozone and oxygen was 10 L (ozone addition rate: 10% by mass).
  • Example 12 An aqueous dispersion of fine fibrous cellulose was obtained in the same manner as in Example 9 except that the amount of the mixed gas of ozone and oxygen was 20 L (ozone addition rate: 20% by mass).
  • Example 13 An aqueous dispersion of fine fibrous cellulose was obtained in the same manner as in Example 9 except that the amount of the mixed gas of ozone and oxygen was 30 L (ozone addition rate: 30% by mass).
  • Example 14 LBKP similar to Example 13 was accommodated in a container, and 30 L of a mixed gas of ozone and oxygen having an ozone concentration of 200 g / m 3 was introduced into the container and shaken at 25 ° C. for 2 minutes. The ozone addition rate at this time was 30 mass% with respect to the pulp dry mass. After standing for 6 hours, ozone and air in the container were removed, and the ozone oxidation treatment was completed. After the treatment, the suspension was washed with ion-exchanged water, and the washing was repeated until the pH of the washing water reached 6 or higher. Then, it filtered under reduced pressure using the filter paper, and obtained the ozone oxidation process pulp with a solid content concentration of 20 mass%.
  • Example 9 In the same manner as in Example 9, the above oxidized pulp (20 g in terms of absolute dry mass) was subjected to alkali treatment, fibrillation treatment, and centrifugal separation treatment with sodium hydroxide to obtain an aqueous dispersion of fine fibrous cellulose. .
  • Example 7 An aqueous dispersion of fine fibrous cellulose was prepared in the same manner as in Example 9 except that the amount of the mixed gas of ozone and oxygen was 30 L (ozone addition rate: 30% by mass) and the formation of phosphate groups was omitted. Obtained.
  • Example 9 An aqueous dispersion of fine fibrous cellulose was obtained in the same manner as in Example 9 except that sulfonic acid groups were formed without subjecting LBKP to ozone oxidation treatment.
  • Example 10 An aqueous dispersion of fine fibrous cellulose was prepared in the same manner as in Example 9 except that the amount of the mixed gas of ozone and oxygen was 60 L (ozone addition rate 60 mass%), and the formation of phosphate groups was omitted. Obtained.
  • the defibration yield was measured using an aqueous dispersion containing fine fibrous cellulose. That is, the centrifugal recovery rate of the aqueous dispersion containing fine fibrous cellulose was determined from the following formula, and the centrifugal recovery rate was defined as the fibrillation yield. The results of the defibration yield are shown in Table 2.
  • the oxidized pulp after the oxidation treatment was completed, the content of carboxy groups was determined by the method described in the above “Method for measuring the content of carboxy groups in cellulose fibers”. The amount was measured. Table 2 shows the results of the content of carboxy groups. Further, the phosphoric acid group or sulfonic acid group content of the obtained fine fibrous cellulose is determined based on the above-mentioned “content of (—PO 3 2 ⁇ ) in the functional group (4)” or “( -SO 3 -) was measured by the method described in content ". The measurement results are shown in Table 2. Moreover, the polymerization degree of the obtained fine fibrous cellulose was measured.
  • the viscosity and dispersion stability of the aqueous dispersion containing each fine fibrous cellulose were measured.
  • the viscosity was measured at 25 ° C. using a dispersion containing 0.5% by mass of fine fibrous cellulose as a measurement sample and using a B-type viscometer (manufactured by BROOKFIELD).
  • B-type viscometer manufactured by BROOKFIELD.
  • the aqueous dispersion of fine fibrous cellulose is alkaline, this dispersion stability is evaluated on the alkaline side.
  • dispersible unstable state indicated as “B” in the table
  • dispersion stable state indicated as “A” in the table
  • This evaluation of dispersion stability is an evaluation on the acidic side.
  • the fine fibrous cellulose of the present invention can be used for nonwoven fabrics, foods, medicines, various reinforcing materials, and the like.
  • the nonwoven fabric of this invention can be utilized for a composite with a filter or a matrix material.

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Abstract

L'invention concerne une cellulose sous forme de fibres fines qui est caractéristique en ce qu'elle possède un groupe fonctionnel représenté par la formule (1), que la teneur en (-COO-) est comprise entre 0,06 et 1,2mmol/g, et que son degré de polymérisation est compris entre 50 et 500. (1) (-COO-)n.Xn+ (n est un entier de 1 à 3. Xn+ représente au moins une sorte de cation choisie dans un groupe constitué d'un cation de métal alcalin, d'un ion ammonium, d'un ion ammonium aliphatique, et d'un ion ammonium aromatique, lorsque n=1, et représente au moins une sorte de cation choisie dans un groupe constitué d'un ion de métal alcalino-terreux et d'un ion de métal polyvalent, lorsque n=2 ou 3.) Ainsi, l'invention permet de fournir une cellulose sous forme de fibres fines qui est fabriquée à haut rendement à partir d'une matière première de fibres, et qui présente un indice d'égouttage élevé, et des propriétés de dispersion élevées lors du mélange d'une résine ou d'un caoutchouc.
PCT/JP2013/064007 2012-05-24 2013-05-21 Cellulose sous forme de fibres fines ainsi que procédé de fabrication de celle-ci, liquide de dispersion de cellulose sous forme de fibres fines, et tissu non tissé WO2013176102A1 (fr)

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CN107326533A (zh) * 2017-07-26 2017-11-07 奥美医疗用品股份有限公司 原棉冷堆脱脂的水刺无纺布生产工艺
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CN115038837A (zh) * 2020-01-31 2022-09-09 尤妮佳股份有限公司 制造羧基化纤维素纳米纤维化用浆粕纤维的方法以及羧基化纤维素纳米纤维化用浆粕纤维
CN115038837B (zh) * 2020-01-31 2023-11-10 尤妮佳股份有限公司 制造羧基化纤维素纳米纤维化用浆粕纤维的方法以及羧基化纤维素纳米纤维化用浆粕纤维
JP7458802B2 (ja) 2020-01-31 2024-04-01 ユニ・チャーム株式会社 カルボキシル化セルロースナノファイバー化用パルプ繊維を製造する方法、及びカルボキシル化セルロースナノファイバー化用パルプ繊維

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