WO2020050348A1 - 繊維状セルロース含有物、フラッフ化セルロース及び組成物 - Google Patents
繊維状セルロース含有物、フラッフ化セルロース及び組成物 Download PDFInfo
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- WO2020050348A1 WO2020050348A1 PCT/JP2019/034906 JP2019034906W WO2020050348A1 WO 2020050348 A1 WO2020050348 A1 WO 2020050348A1 JP 2019034906 W JP2019034906 W JP 2019034906W WO 2020050348 A1 WO2020050348 A1 WO 2020050348A1
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
- D21C9/00—After-treatment of cellulose pulp, e.g. of wood pulp, or cotton linters ; Treatment of dilute or dewatered pulp or process improvement taking place after obtaining the raw cellulosic material and not provided for elsewhere
- D21C9/001—Modification of pulp properties
- D21C9/002—Modification of pulp properties by chemical means; preparation of dewatered pulp, e.g. in sheet or bulk form, containing special additives
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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
- C08B15/05—Derivatives containing elements other than carbon, hydrogen, oxygen, halogens or sulfur
- C08B15/06—Derivatives containing elements other than carbon, hydrogen, oxygen, halogens or sulfur containing nitrogen, e.g. carbamates
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
- B01J20/261—Synthetic macromolecular compounds obtained by reactions only involving carbon to carbon unsaturated bonds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28023—Fibres or filaments
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/2803—Sorbents comprising a binder, e.g. for forming aggregated, agglomerated or granulated products
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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
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- 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
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- 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
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
- D21C9/00—After-treatment of cellulose pulp, e.g. of wood pulp, or cotton linters ; Treatment of dilute or dewatered pulp or process improvement taking place after obtaining the raw cellulosic material and not provided for elsewhere
- D21C9/001—Modification of pulp properties
- D21C9/002—Modification of pulp properties by chemical means; preparation of dewatered pulp, e.g. in sheet or bulk form, containing special additives
- D21C9/005—Modification of pulp properties by chemical means; preparation of dewatered pulp, e.g. in sheet or bulk form, containing special additives organic compounds
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- 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
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- 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
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/20—Macromolecular organic compounds
- D21H17/33—Synthetic macromolecular compounds
- D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D21H17/35—Polyalkenes, e.g. polystyrene
Definitions
- the present invention relates to a fibrous cellulose-containing material, a fluffed cellulose and a composition.
- fibrous cellulose (pulp) derived from wood has been widely used mainly for absorbent articles and paper products.
- Patent Document 1 discloses an absorbent article including a liquid-permeable top sheet, a liquid-impermeable back sheet, an absorber, and a nonwoven sheet for the absorber, and a nonwoven sheet for the absorber. Contains pulp and hydrophilic fibers.
- Patent Literature 1 discloses an embodiment in which fluff pulp, which is considered to have a higher ability to absorb bodily fluids and the like, is contained in an absorber.
- Patent Document 2 discloses a coating comprising a porous cellulose layer containing at least one kind of cellulose selected from the group consisting of lightly beaten cellulose pulp, mercerized cellulose and fluffed cellulose, and internally added with a porous filler.
- a recording medium is disclosed.
- fluffed cellulose also called fluff pulp
- the fluffed cellulose is obtained by fluffing a cellulose fiber, and is a fluffy or fluffy cellulose fiber.
- Fluffed cellulose can quickly absorb and diffuse liquids by capillary action.
- fluffed cellulose has been mainly used for the purpose of promoting the absorption of aqueous liquids, and at present, it has not been studied to modify the surface properties of fluffed cellulose.
- the present inventors have studied the purpose of modifying the surface of fluffed cellulose to provide a fluffed cellulose having a completely new property and a fibrous cellulose-containing material capable of realizing the same.
- the present inventors introduce an anionic group into fibrous cellulose, and further introduce an organic onium ion having a predetermined structure as a counter ion of the anionic group.
- an organic onium ion having a predetermined structure as a counter ion of the anionic group.
- fluffed cellulose having good fluffing properties and hydrophobicity and a fibrous cellulose-containing material capable of realizing the fluffed cellulose can be obtained.
- the present invention has the following configuration.
- a fibrous cellulose-containing material containing a fibrous cellulose having an anionic group The yield of the fibrous cellulose-containing material measured by the following measurement method is 50% by mass or more,
- the fibrous cellulose-containing material has an organic onium ion as a counter ion of the anionic group, The organic onium ion satisfies at least one condition selected from the following (a) and (b): a fibrous cellulose-containing material; (A) containing a hydrocarbon group having 5 or more carbon atoms; (B) total carbon number is 17 or more; (Measuring method) After immersing the fibrous cellulose-containing material in ion-exchanged water for 24 hours, the solid content is adjusted to 20% by mass, and a dispersion treatment is performed for 15 minutes with a high-speed rotating disperser having a peripheral speed of 10 m / s; The liquid is subjected to wet classification on a JIS test sieve having an aperture of 150 ⁇ m, and the yield
- Retention [mass%] absolute dry mass of fibrous cellulose-containing material remaining on test sieve / absolute dry mass of tested fibrous cellulose-containing material ⁇ 100
- a fluffed cellulose obtained by fluffing the fibrous cellulose-containing material according to any one of [1] to [4].
- a fluffed cellulose having a novel property can be provided. Specifically, it is possible to provide a fluffed cellulose having a good fluffing property and a hydrophobic property and a fibrous cellulose-containing material capable of realizing the same.
- 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 fibrous cellulose-containing material containing a fibrous cellulose having an anionic group.
- the fibrous cellulose-containing material has an organic onium ion as a counter ion of the anionic group, and the organic onium ion satisfies at least one condition selected from the following (a) and (b).
- the yield of the fibrous cellulose-containing material measured by the following method is 50% by mass or more.
- the yield of the fibrous cellulose-containing material measured by the above-described measurement method may be 50% by mass or more, preferably 70% by mass or more, more preferably 80% by mass or more, and 90% by mass or more. More preferably, it is not less than mass%.
- the upper limit of the yield of the fibrous cellulose-containing material is not particularly limited, and may be 100% by mass.
- TK Robomix manufactured by Primix using a stirring blade having a radius of 15 mm
- the obtained dispersion is subjected to wet classification on a JIS test sieve having an aperture of 150 ⁇ m.
- a shower of ion-exchanged water having a flow rate of 150 mL / sec may be allowed to flow from above the test sieve so that the fibrous cellulose sufficiently spreads on the test sieve.
- the fibrous cellulose-containing material of the present invention becomes fluffed cellulose having good fluffing properties.
- the fluffing property can be evaluated by the fluffing recovery rate and the bulk of the fluffed cellulose when the fibrous cellulose-containing material is made into fluffed cellulose.
- the fluffing property is good when the fluffing recovery rate when fluffing the fibrous cellulose-containing material is high and the bulk of the fluffed cellulose is large.
- the fluffing recovery rate is a value calculated by the following method.
- the fibrous cellulose-containing material was diluted to a concentration of 1% by mass with ion-exchanged water, adjusted to have a basis weight of 200 g / m 2 in terms of absolute dry mass, and again filtered under reduced pressure to form a sheet.
- the sheet is dried under a condition of 30 ° C. and a relative humidity of 40% until a constant weight is obtained to obtain a fibrous cellulose-containing sheet.
- 1 g (0.005 m 2 ) of the obtained fibrous cellulose-containing sheet is cut off in absolutely dry mass, and fluffing is performed by performing treatment at 20,000 rpm for 20 seconds with a crusher (Labo Mill Surplus) having a capacity of 75 mL.
- the fibrous cellulose (fluffed cellulose) after the fluff treatment is spread on a test sieve having an aperture of 2 mm ⁇ , gently shaken, and the mass of the fibrous cellulose-containing material that has passed through the mesh is measured. And the fluffing recovery rate is calculated.
- Fluffization recovery rate [mass%] absolute dry mass of fibrous cellulose-containing material passed through test sieve / absolute dry mass of tested fibrous cellulose-containing material ⁇ 100
- the fluffing recovery calculated by the above method is preferably 30% by mass or more, more preferably 50% by mass or more, and even more preferably 60% by mass or more. Note that the fluffing recovery rate may be 100% by mass.
- the bulk of the fluffed cellulose is measured by the following method.
- the fibrous cellulose-containing material was diluted to a concentration of 1% by mass with ion-exchanged water, adjusted to have a basis weight of 200 g / m 2 in terms of absolute dry mass, and again filtered under reduced pressure to form a sheet.
- the sheet is dried under a condition of 30 ° C. and a relative humidity of 40% until a constant weight is obtained to obtain a fibrous cellulose-containing sheet.
- 1 g (0.005 m 2 ) of the obtained fibrous cellulose-containing sheet is cut off in absolutely dry mass, and fluffing is performed by performing treatment at 20,000 rpm for 20 seconds with a crusher (Labo Mill Surplus) having a capacity of 75 mL.
- the fibrous cellulose (fluffed cellulose) after the fluff treatment is spread on a test sieve having an opening of 2 mm ⁇ , gently shaken, and the fibrous cellulose that has passed through the mesh is placed in a measuring cylinder arranged immediately below the test sieve. After dropping and accumulating a certain volume, the absolute dry mass of the fibrous cellulose occupying the volume is measured to calculate the bulk (mL / g).
- the bulk of the fluffed cellulose measured by the above method is preferably 5 mL / g or more, more preferably 10 mL / g or more, and even more preferably 20 mL / g or more.
- the upper limit of the bulk of the fluffed cellulose is not particularly limited, but is preferably 100 mL / g or less.
- the fibrous cellulose-containing material of the present invention since it has the above-mentioned constitution, it becomes a fluffed cellulose having hydrophobicity.
- the hydrophobicity of the fluffed cellulose can be evaluated by the degree of sedimentation when water is poured into the fluffed cellulose. Specifically, hydrophobicity can be evaluated by the rate of sedimentation from the water surface after water is poured into the fluffed cellulose by the following method. First, the fibrous cellulose-containing material was diluted to a concentration of 1% by mass with ion-exchanged water, adjusted to have a basis weight of 200 g / m 2 in terms of absolute dry mass, and again filtered under reduced pressure to form a sheet.
- the sheet is dried under a condition of 30 ° C. and a relative humidity of 40% until a constant weight is obtained to obtain a fibrous cellulose-containing sheet.
- 1 g (0.005 m 2 ) of the obtained fibrous cellulose-containing sheet is cut off in absolutely dry mass, and fluffing is performed by performing treatment at 20,000 rpm for 20 seconds with a crusher (Labo Mill Surplus) having a capacity of 75 mL. .
- the fibrous cellulose (fluffed cellulose) after the fluff treatment was spread on a test sieve having a mesh size of 2 mm ⁇ , gently shaken, and the fibrous cellulose passed through the mesh was placed at a position 50 mm immediately below the test sieve. Drop into a container having a diameter of 40 mm ⁇ .
- Sedimentation rate from water surface [mass%] absolute dry mass of sedimented fibrous cellulose-containing material / (absolute dry mass of sedimented fibrous cellulose-containing material + absolute dry mass of fibrous cellulose-containing material floating on water surface) ⁇ 100
- the sedimentation rate of the fluffed cellulose calculated by the above method is preferably 50% by mass or less, more preferably 40% by mass or less, and even more preferably 30% by mass or less.
- the sedimentation rate of the fluffed cellulose is particularly preferably 10% by mass or less.
- the yield when wet classification is performed on a JIS test sieve with a mesh size of 150 ⁇ m may be 50% by mass or more, but the wet classification is performed on a JIS test sieve with a mesh size of 300 ⁇ m.
- the yield at the time of mixing is preferably 30% by mass or more, more preferably 60% by mass or more, and even more preferably 80% by mass or more.
- the upper limit of the yield when wet classification is performed on a JIS test sieve having a mesh size of 300 ⁇ m is not particularly limited, but may be 100% by mass.
- the above-described method was used except that a JIS test sieve with a mesh size of 300 ⁇ m was used instead of the JIS test sieve with a mesh size of 150 ⁇ m. It can be calculated by the same method as the method for measuring the yield when performing wet classification on a JIS test sieve having an opening of 150 ⁇ m.
- the fact that the yield when performing wet classification on a JIS test sieve having an opening of 150 ⁇ m within the above range means that the fiber width of the fibrous cellulose is equal to or more than a certain value. It means that In addition, the fact that the yield when performing wet classification on a JIS test sieve having an aperture of 300 ⁇ m within the above range means that the fibrous cellulose is a coarser fiber.
- the fibrous cellulose-containing material of the present invention may be composed of fibrous cellulose or may contain water and the like in addition to fibrous cellulose.
- the fibrous cellulose-containing material is preferably a solid.
- the form of the solid body is not particularly limited, and may be, for example, a sheet or a powder.
- the fibrous cellulose-containing material may be in the form of a paste or tatter containing a solvent such as water.
- the fibrous cellulose-containing material is preferably in the form of powder.
- the granular material is a powdery and / or granular substance. Note that the powdery substance is smaller than the granular substance.
- a powdery substance refers to fine particles having a particle diameter of 1 nm or more and less than 0.1 mm
- a granular substance refers to particles having a particle diameter of 0.1 mm to 10 mm, but is not particularly limited.
- a granular material may be called a powder.
- the particle diameter of the granular material in the present specification can be measured and calculated using a laser diffraction method. Specifically, it is a value measured using a laser diffraction / scattering type particle size distribution analyzer (Microtrac 3300EXII, Nikkiso Co., Ltd.).
- the solid content concentration of the fibrous cellulose-containing material is preferably 40% by mass or more, more preferably 60% by mass or more, and preferably 80% by mass or more based on the total mass of the fibrous cellulose-containing material. Is more preferable.
- the solid content of the fibrous cellulose-containing material may be 100% by mass.
- the fibrous cellulose-containing material of the present invention contains fibrous cellulose having an anionic group.
- the fiber width of the fibrous cellulose is preferably larger than 1000 nm.
- the fibrous cellulose-containing material may contain fine fibrous cellulose having a fiber width of 1000 nm or less.
- the weight ratio of the fibrous cellulose having a fiber width larger than 1000 nm is determined by the fiber width. Is preferably larger than the weight ratio of the fibrous cellulose having a thickness of 1000 nm or less.
- the proportion of the weight occupied by the fibrous cellulose having a fiber width of more than 1000 nm is greater than the proportion of the weight occupied by the fibrous cellulose having a fiber width of 1000 nm or less.
- a fibrous cellulose having substantially no fibrous cellulose of 1000 nm or less before micronization was tested, and a fibrous cellulose suspension having a constant concentration C was observed with an optical microscope.
- the area S occupied by cellulose fibers having a fiber width larger than 1000 nm observed in a certain area S 0 in the visual field is measured. At this time, the next value R 0 is calculated.
- R 0 S / S 0 / C
- R 0 at this time is defined as R.
- C at the time of measurement has the same concentration.
- the meaning of “at least” is derived from the fact that “thickness” of the fiber is not considered in “area” observed with an optical microscope. That is, if the thickness of the fiber can be ideally converted into an area, R 0 and R take larger values (hereinafter, these are expressed as true R 0 and true R).
- the fiber width of the fibrous cellulose can be measured using, for example, a Kayani fiber length measuring instrument (model FS-200) manufactured by Kayani Automation or an optical microscope. It can be measured using a scanning microscope (SEM), a transmission electron microscope (TEM), an atomic force microscope (AFM) or the like according to the width of the fiber.
- SEM scanning microscope
- TEM transmission electron microscope
- AFM atomic force microscope
- a pulp aqueous suspension having a concentration of 0.05% by mass or more and 0.1% by mass or less is prepared, and the suspension is cast on a carbon film-coated grid that has been subjected to a hydrophilic treatment to prepare a TEM observation sample.
- an SEM image of the surface cast on the glass may be observed.
- 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 constituent fibers.
- 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 intersecting with the straight lines X and Y is visually read. In this way, at least three or more sets of images of the non-overlapping surface portion are observed, and the width of the fiber intersecting the straight line X and the straight line Y is read for each image.
- the fiber length of the fibrous cellulose contained in the fibrous cellulose-containing material of the present invention is not particularly limited, but is preferably 10 ⁇ m or more, more preferably 100 ⁇ m or more, and even more preferably 500 ⁇ m or more. Further, the fiber length of the fibrous cellulose is preferably 10000 ⁇ m or less, more preferably 5000 ⁇ m or less, and still more preferably 3000 ⁇ m or less. By setting the fiber length within the above range, a fibrous cellulose-containing material having excellent fluffing properties can be easily obtained.
- the fiber length of the fibrous cellulose is measured using, for example, a Kayani fiber length measuring instrument (model FS-200) manufactured by Kayani Automation or an optical microscope. In addition, it can also be measured using a scanning microscope (SEM), a transmission electron microscope (TEM), an atomic force microscope (AFM) or the like according to the length of the fiber.
- the fibrous cellulose preferably has an I-type crystal structure.
- the proportion of the type I crystal structure in the fibrous cellulose is, for example, preferably 30% or more, more preferably 40% or more, still more preferably 50% or more, and preferably 70% or more. Most preferred.
- 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 fibrous cellulose is not particularly limited, but is, for example, preferably 5 or more and 5000 or less, and more preferably 10 or more and 1000 or less.
- the axial ratio is equal to or more than the lower limit, a sheet containing fibrous cellulose can be 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 supernatant yield of fibrous cellulose measured by the following measurement method is preferably 50% by mass or less, more preferably 40% by mass or less, and even more preferably 20% by mass or less.
- the supernatant yield of fibrous cellulose may be 0% by mass.
- fibrous cellulose is dispersed in ion-exchanged water so as to have a solid content concentration of 0.1% by mass to obtain a dispersion. This dispersion is centrifuged at 12000 G for 10 minutes using a cooling high-speed centrifuge (H-2000B, manufactured by Kokusan).
- the obtained supernatant is collected, the solid content concentration of the supernatant is measured, and the supernatant yield of the cellulose fiber is calculated based on the following formula.
- Supernatant yield (mass%) of fibrous cellulose solid content of supernatant (mass%) / 0.1 ⁇ 100
- the supernatant yield after centrifugation is an index of the degree of fineness of the fibrous cellulose, and that the supernatant yield of the fibrous cellulose is within the above range indicates that the fiber width of the fibrous cellulose is within the above range. Within the above preferred range, meaning that the fibrous cellulose is a so-called coarse fiber.
- Fibrous cellulose has an anionic group.
- the anionic group include a phosphate group or a substituent derived from a phosphate group (sometimes simply referred to as a phosphate group), a carboxy group or a substituent derived from a carboxy group (sometimes referred to simply as a carboxy group), And at least one selected from a sulfone group or a substituent derived from a sulfone group (which may be simply referred to as a sulfone group), and preferably at least one selected from a phosphate group and a carboxy group. More preferably, it is particularly preferably a phosphate group.
- a phosphate group has 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, the hydrophobicity of the fluffed cellulose obtained by fluffing the fibrous cellulose-containing material 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 functional group in which at least one of functional groups such as a carboxy group, a hydroxy group, or an amino group is added or substituted to a main chain or a side chain of the above various hydrocarbon groups 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 anionic group introduced into the fibrous cellulose is, for example, preferably 0.10 mmol / g or more per 1 g (mass) of the fibrous cellulose, more preferably 0.20 mmol / g or more. It is more preferably at least 0.50 mmol / g, particularly preferably at least 1.00 mmol / g.
- the amount of the anionic group introduced into the 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 the fibrous cellulose. More preferably, it is not more than 00 mmol / g.
- 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 anionic group is a hydrogen ion (H + ).
- the amount of anionic group introduced into fibrous cellulose can be measured, for example, by conductivity titration.
- the amount of introduction is measured by determining a change in conductivity while adding an alkali such as an aqueous sodium hydroxide solution to a slurry containing fine fibrous cellulose.
- fibrous cellulose is refined prior to the measurement by the conductivity titration method. The fibrous cellulose is refined by treating a 2% by mass fibrous cellulose dispersion with a high-pressure homogenizer at a pressure of 200 MPa six times.
- FIG. 1 is a graph showing the relationship between the amount of NaOH dropped and the electrical conductivity of fibrous cellulose having finely divided phosphate groups.
- the amount of phosphate groups introduced into fibrous cellulose is measured, for example, as follows. First, a slurry containing fine fibrous cellulose is treated with a strongly acidic ion exchange resin. 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. 1, the electrical conductivity sharply decreases at first (hereinafter, referred to as “first region”). Thereafter, the conductivity starts to slightly increase (hereinafter, referred to as “second region”).
- the increment of the conductivity increases (hereinafter, referred to as “third region”).
- the 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.
- three regions appear in the titration curve.
- 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. Become equal.
- the phosphate group introduction amount (or phosphate group amount) or the substituent group introduction amount (or substituent amount) indicates a strongly acidic group amount. Therefore, 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).
- FIG. 2 is a graph showing the relationship between the amount of NaOH dropped and the electrical conductivity of fibrous cellulose having a finely divided carboxy group.
- the amount of carboxy groups introduced into fibrous cellulose is measured, for example, as follows. First, a slurry containing fine fibrous cellulose is treated with a strongly acidic ion exchange resin. Next, a change in electric conductivity is observed while adding an aqueous solution of sodium hydroxide, and a titration curve as shown in FIG. 2 is obtained. As shown in FIG. 2, the titration curve shows a first region where the increment (slope) of the conductivity becomes substantially constant after the decrease in the electric conductivity, and thereafter, the increment (slope) of the conductivity increases. It is divided into a second area.
- the boundary point between the first region and the second region is defined as a point at which the amount of change in the conductivity twice (in other words, the increment (slope) of the conductivity becomes maximum).
- the value obtained by dividing the amount of alkali (mmol) required in the first region of the titration curve by the solid content (g) in the slurry containing fine fibrous cellulose to be titrated is the amount of carboxy group introduced ( mmol / g).
- the amounts of the phosphate groups and carboxy groups are values when the counter ion is a hydrogen ion (H + ).
- the counter ion is a hydrogen ion (H + ).
- acid treatment or the like is performed a sufficient number of times to convert the other counter ion to hydrogen ion. The measurement may be performed later.
- 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.
- the denominator is converted into the mass of fibrous cellulose when the cation C is a counter ion.
- the amount of carboxy groups of the fibrous cellulose having the cation C as a counter ion (hereinafter, the amount of carboxy groups (C type)) can be determined. That is, the carboxy group introduction amount is calculated by the following formula.
- Carboxy group introduction amount (C type) carboxy group amount (acid type) / [1+ (W-1) ⁇ (carboxy group amount (acid type)) / 1000]
- W Formula weight per valence of cation C (eg, 23 for Na, 9 for Al)
- 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.
- chemical pulp is more preferable
- kraft pulp and sulfite pulp are more preferable, from the viewpoint of decomposing cellulose in the pulp and obtaining fibrous cellulose of long fiber having a large axial ratio.
- 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 the fibrous cellulose includes a step of introducing a phosphate group.
- the 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. This is a step of acting on a fiber raw material containing. By this step, 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 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 is possible to obtain 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.
- the amount of phosphate groups introduced into the fiber raw material is, for example, preferably 0.10 mmol / g or more, more preferably 0.20 mmol / g or more, and more preferably 0.50 mmol / g per 1 g (mass) of fibrous cellulose. More preferably, it is more preferably 1.00 mmol / g or more.
- the amount of the phosphate group introduced into the fiber raw material is, for example, preferably 5.20 mmol / g or less, more preferably 3.65 mmol / g or less, and more preferably 3.00 mmol / g per 1 g (mass) of fibrous cellulose. / G or less.
- the content of the organic onium ion that can be included in the fibrous cellulose can be set to an appropriate range, thereby fluffing the fibrous cellulose-containing material. Can increase the hydrophobicity of the fluffed cellulose obtained more effectively.
- the step of producing the fibrous cellulose includes a step of introducing a carboxy group.
- the carboxy group introduction step has a compound having a carboxylic acid-derived group or a derivative thereof, or a carboxylic acid-derived group, or a carboxylic acid-derived compound or a carboxylic acid-derived group, for a fiber raw material containing cellulose, such as ozone oxidation or oxidation by the Fenton method, or TEMPO oxidation treatment. It is carried out by treating with an acid anhydride of a compound or a derivative thereof.
- Examples of the compound having a group derived from a carboxylic acid include, but are not particularly limited to, dicarboxylic acid compounds such as maleic acid, succinic acid, phthalic acid, fumaric acid, glutaric acid, adipic acid, and itaconic acid, and citric acid and aconitic acid. Tricarboxylic acid compounds.
- the derivative of the compound having a group derived from a carboxylic acid is not particularly limited, and examples thereof include an imidized product of an acid anhydride of a compound having a carboxy group and a derivative of an acid anhydride of a compound having a carboxy group.
- the imidized product of the acid anhydride of the compound having a carboxy group is not particularly limited, and examples thereof include imidized products of dicarboxylic acid compounds such as maleimide, succinimide and phthalic imide.
- Examples of the acid anhydride of the compound having a group derived from a carboxylic acid include, but are not particularly limited to, maleic anhydride, succinic anhydride, phthalic anhydride, glutaric anhydride, adipic anhydride, and dicarboxylic acid compounds such as itaconic anhydride. Acid anhydrides.
- the derivative of the acid anhydride of the compound having a group derived from a carboxylic acid is not particularly limited. For example, dimethylmaleic anhydride, diethylmaleic anhydride, and a compound having a carboxy group such as diphenylmaleic anhydride can be used.
- An acid anhydride in which at least a part of hydrogen atoms are substituted with a substituent such as an alkyl group or a phenyl group is exemplified.
- the treatment be performed, for example, at a pH of 6 to 8.
- a neutral TEMPO oxidation process is also called a neutral TEMPO oxidation process.
- the TEMPO oxidation treatment may be performed at a pH of 10 or more and 11 or less. Such a treatment is also called an alkaline TEMPO oxidation treatment.
- the alkali TEMPO oxidation treatment can be performed, for example, by adding a nitroxy radical such as TEMPO as a catalyst, sodium bromide as a cocatalyst, and sodium hypochlorite as an oxidizing agent to pulp as a fiber raw material. .
- the amount of the carboxy group introduced into the fiber raw material varies depending on the type of the substituent.
- the amount is preferably 0.10 mmol / g or more per 1 g (mass) of fibrous cellulose, It is more preferably at least 0.20 mmol / g, even more preferably at least 0.50 mmol / g, particularly preferably at least 0.90 mmol / g. Further, it is preferably at most 2.5 mmol / g, more preferably at most 2.20 mmol / g, even more preferably at most 2.00 mmol / g.
- the substituent when it is a carboxymethyl group, it may be 5.8 mmol / g or less per 1 g (mass) of fibrous cellulose.
- the amount of the carboxy group By setting the amount of the carboxy group to be in the above range, the content of the organic onium ion that can be included in the fibrous cellulose can be set to an appropriate range, thereby fluffing the fibrous cellulose-containing material. The hydrophobicity of the obtained fluffed cellulose can be more effectively increased.
- a washing step can be performed on the anionic group-introduced fiber as necessary.
- the washing step is performed, for example, by washing the anionic 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 (neutralization treatment) after the anionic group introduction step.
- the method of the alkali treatment is not particularly limited, and includes, for example, a method of dipping the anionic 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 anionic 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, but is, for example, preferably from 100% by mass to 100,000% by mass, and more preferably from 1,000% by mass to 10,000% by mass, based on the absolute dry mass of the anionic group-introduced fiber. Is more preferable.
- the anionic group-introduced fiber may be washed with water or an organic solvent after the anionic group introduction step and before the alkali treatment step. It is also preferable to provide a washing step after the alkali treatment step.
- the fibrous raw material may be subjected to an acid treatment after the anionic group introduction step.
- an anionic group introduction step, an acid treatment and an alkali 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.
- the anionic group-introduced fiber may be subjected to a fibrillation treatment as necessary.
- the yield of the fibrous cellulose-containing material does not fall below 50% by mass by appropriately selecting the defibration treatment method and defibration treatment conditions.
- a mode in which the anionic group-introduced fiber is not subjected to defibration is also a preferable mode.
- a defibration 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 anionic 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 fibrous cellulose at the time of defibration can be set as appropriate. Further, the slurry obtained by dispersing the anionic group-introduced fiber in the dispersion medium may contain a solid content other than the anionic group-introduced fiber such as urea having hydrogen bonding properties.
- the fibrous cellulose-containing material of the present invention contains an organic onium ion as a counter ion of the anionic group of the fibrous cellulose.
- an organic onium ion exists as a counter ion of the fibrous cellulose, but a free organic onium ion may be present in the fibrous cellulose-containing material.
- the organic onium ion satisfies at least one condition selected from the following (a) and (b).
- 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 at least 1.0% by mass, more preferably at least 1.5% by mass, and preferably at least 2.0% by mass based on the total mass of the fibrous cellulose-containing material. Is more preferable. Further, the content of the organic onium ion is preferably at most 90% by mass, more preferably at most 80% by mass, based on the total mass of the fibrous cellulose-containing material.
- the content of the organic onium ion in the fibrous cellulose-containing material is preferably from 0.5 to 2 times the molar amount of the anionic group contained in the fibrous cellulose, Not 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 do it.
- the organic onium ion is preferably an ion exhibiting hydrophobicity. That is, the fluffed cellulose obtained by fluffing the fibrous cellulose-containing material in the present invention can exhibit hydrophobicity by having an organic onium ion. Further, as a result, the affinity of the fluffed cellulose for an organic solvent and a resin can be increased.
- the fibrous cellulose-containing material may be composed of fibrous cellulose having an anionic group and an organic onium ion, but may further contain an optional component.
- Optional components include, for example, 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, binders and the like can be mentioned.
- the content of the optional component contained in the fibrous cellulose-containing material is preferably 40% by mass or less, and more preferably 30% by mass or less, based on the total mass of the solid content contained in the fibrous cellulose-containing material. Is more preferable, and it is further preferable that it is 20 mass% or less.
- the present invention also relates to fluffed cellulose obtained by fluffing the above-mentioned fibrous cellulose-containing material.
- the fluffed cellulose is obtained by fluffing a cellulose fiber, and is a fluffy or fluffy cellulose fiber.
- the fluffed cellulose of the present invention has good fluffing properties and has hydrophobicity.
- the fluffing recovery rate of the fluffed cellulose is preferably 50% by mass or more, more preferably 60% by mass or more, and even more preferably 70% by mass or more. Note that the fluffing recovery rate may be 100% by mass.
- the bulk of the fluffed cellulose is preferably at least 5 mL / g, more preferably at least 10 mL / g, even more preferably at least 20 mL / g.
- the upper limit of the bulk of the fluffed cellulose is not particularly limited, but is preferably 100 mL / g or less.
- the hydrophobicity of fluffed cellulose can be evaluated by the degree of sedimentation after pouring ion-exchanged water into fluffed cellulose as described above.
- the sedimentation rate of the fluffed cellulose is preferably 50% by mass or less, more preferably 40% by mass or less, and even more preferably 30% by mass or less.
- the sedimentation rate of the fluffed cellulose is particularly preferably 10% by mass or less.
- the fluffed cellulose is compressible, that is, bulky in a stationary state, but it is also preferable that the volume is reduced by physical compressive force.
- V i the volume of the fluffed cellulose in a stationary state
- V f the volume of the fluffed cellulose after compression
- V i / V f the compression ratio
- Compressibility of fluffed cellulose is preferably 5 or more, more preferably 10 or more, still more preferably 20 or more, further not less than 50 preferable.
- the step of producing a fibrous cellulose-containing material includes a step of adding an organic onium ion or a compound that forms an organic onium ion by neutralization to a slurry containing fibrous cellulose having an anionic group.
- the above-mentioned organic onium ion or a compound that forms an organic onium ion by neutralization is added to the fibrous cellulose-containing slurry obtained in the above-described step.
- 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 anionic group contained in the fibrous cellulose may be used as a counter ion to cause organic onium ionization.
- the addition amount of the organic onium ion is preferably 2% by mass or more, more preferably 10% by mass or more, even more preferably 50% by mass or more, based on the total mass of the fibrous cellulose. It is particularly preferred that the amount is at least mass%. 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. Further, the number of moles of the organic onium ion to be added is preferably 0.2 times or more, more preferably 0.5 times or more of the value obtained by multiplying the amount (mol number) of the anionic group contained in the fibrous cellulose by the valence. Is more preferable, and it is still more preferable that it is 1.0 times or more. 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 anionic group contained in the fibrous cellulose by the valence.
- the fibrous cellulose-containing slurry (concentrate) can be recovered by vacuum filtration of the fibrous cellulose-containing slurry in which the aggregate is generated.
- the obtained fibrous cellulose aggregate may be washed with ion-exchanged water. By repeatedly washing the fibrous cellulose aggregate with ion-exchanged water, excess organic onium ions and the like contained in the fibrous cellulose aggregate 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 aggregate is preferably larger than 1.2, and more preferably larger than 2.0. preferable.
- the ratio of the content of N atoms to the content of P atoms in the obtained fibrous cellulose aggregate (value of N / P) is preferably 5.0 or less.
- the content of P atoms and the content of N atoms in the fibrous cellulose aggregate can be appropriately calculated by elemental analysis.
- the elemental analysis for example, a trace nitrogen analysis or a molybdenum blue method can be performed after an appropriate pretreatment.
- the composition other than the fibrous cellulose aggregate contains P atoms and N atoms
- the composition may be separated from the fibrous cellulose aggregate by an appropriate method, followed by elemental analysis.
- the solid content concentration of the obtained fibrous cellulose aggregate is preferably 40% by mass or more, more preferably 60% by mass or more, even more preferably 80% by mass or more.
- the solid content concentration of the fibrous cellulose aggregate may be 100% by mass.
- the obtained fibrous cellulose aggregate (concentrate) is the fibrous cellulose-containing material in the present invention, and may be further provided with the following post-treatment step.
- the post-treatment step for example, a drying step, an aging step, a spray drying step, a granulation step, a sheeting step, a heating step, a wetting step, a pulverizing step, a spraying step, a dipping step, a filtration step, a freezing step, a sublimation step, A water squeezing step, a pressure dehydration step, a centrifugal dehydration step, a surface treatment step, and the like can be given.
- a drying step as a post-treatment step is preferably provided, and the drying step is preferably performed under a constant temperature and humidity condition.
- the temperature at which the fibrous cellulose aggregate (concentrate) is dried under a constant temperature and humidity condition is preferably 10 ° C or more, more preferably 20 ° C or more.
- the temperature under constant temperature and humidity conditions is preferably 100 ° C. or lower, more preferably 80 ° C. or lower, and further preferably 60 ° C. or lower.
- the relative humidity under the condition of constant temperature and constant humidity is preferably 20% or more, and more preferably 30% or more.
- the relative humidity under constant temperature and humidity conditions is preferably 70% or less.
- the drying time for drying under constant temperature and humidity conditions is preferably 10 minutes or more, more preferably 20 minutes or more, and further preferably 30 minutes or more.
- the drying time when drying under constant temperature and humidity conditions is preferably 100 hours or less, and more preferably 80 hours or less.
- the fluffed cellulose is obtained, for example, by subjecting the above-mentioned fibrous cellulose-containing substance to a crushing treatment. Specifically, it is preferable to obtain a fluffed cellulose by performing a crushing treatment at a rotation speed of 1000 rpm or more and 100000 rpm or less for 0.01 seconds or more and 1000 seconds or less.
- a laboratory mill surplus manufactured by Osaka Chemical Co., Ltd. can be mentioned.
- the fibrous cellulose-containing material to be subjected to the crushing treatment is preferably a predetermined sheet material.
- the fibrous cellulose-containing material is diluted with ion-exchanged water to a concentration of 1% by mass, the basis weight in terms of absolute dry mass is adjusted to 200 g / m 2, and the sheet is again formed under reduced pressure filtration. It is preferable to subject the fibrous cellulose-containing sheet obtained by drying under a condition of 30 ° C. and a relative humidity of 40% to a constant weight to a crushing treatment.
- fluffing of the fibrous cellulose-containing material may be performed in a dry or semi-dry state using various refiners, or may be performed using a device such as a pin mill or a hammer mill.
- composition may relate to a composition containing the above-mentioned fibrous cellulose-containing material or the above-mentioned fluffed cellulose and an organic solvent.
- 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. Among them, N-methyl-2-pyrrolidone (NMP), dimethyl sulfoxide (DMSO), methyl ethyl ketone (MEK), toluene and methanol are preferably used.
- NMP N-methyl
- the relative dielectric constant of the organic solvent at 25 ° C. is preferably 60 or less, more preferably 50 or less. Since the fibrous cellulose used in the present invention can exhibit excellent dispersibility even in an organic solvent having a low relative dielectric constant, the relative dielectric constant of the organic solvent at 25 ° C. may be 40 or less. , 30 or less, or 20 or less.
- the organic solvent of Hansen Solubility Parameter (Hansen solubility parameter, HSP value) .delta.p of, is preferably 5 MPa 1/2 or more 20 MPa 1/2 or less, more preferably 10 MPa 1/2 or more 19 MPa 1/2 or less , further preferably 12 MPa 1/2 or more 18 MPa 1/2 or less.
- .delta.h a hydrogen bond of the HSP value is preferably 20 MPa 1/2 or less, more preferably 15 MPa 1/2 or less, more preferably 7.5 MPa 1/2 or less.
- ⁇ h is preferably 1.0 MPa 1/2 or more.
- the fibrous cellulose-containing material of the present invention is well dispersed in an organic solvent having a hydrogen bond term of the HSP value that is somewhat low.
- the content of the organic solvent contained in the composition is preferably at least 10% by mass, more preferably at least 50% by mass, based on the total mass of the solid content contained in the composition. Further, the content of the organic solvent is preferably at most 99.9% by mass, more preferably at most 99.0% by mass, based on the total mass of the solid content contained in the composition. More preferably, it is not more than 0.0% by mass.
- the dispersion medium of the composition is preferably an organic solvent, but may further contain water in addition to the organic solvent.
- the water content is preferably 10% by mass or less, more preferably 5% by mass or less, even more preferably 1% by mass or less based on the total mass of the composition.
- the present invention may also relate to a composition containing the above-mentioned fibrous cellulose-containing material or the above-mentioned fluffed cellulose and 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 fibrous cellulose-containing material or the fluffed cellulose may contain a resin precursor as a 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 fibrous cellulose-containing material or the fluffed cellulose may further contain a water-soluble polymer as a resin in addition to the above-mentioned resin species.
- a 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
- the content of the resin contained in the composition is preferably 10% by mass or more, more preferably 50% by mass or more, based on the total mass of the solid content contained in the composition. Further, the content of the resin is preferably 99.9% by mass or less, more preferably 99.0% by mass or less, and more preferably 99.0% by mass or less, based on the total mass of the solid content contained in the composition. More preferably, it is 0% by mass or less.
- the fibrous cellulose-containing material of the present invention is preferably used for producing fluffed cellulose.
- the obtained fluffed cellulose is preferably used for mixing an organic solvent or a resin. Particularly, it can be preferably used for mixing with an organic solvent containing a resin component.
- a molded article or sheet can be produced by removing the organic solvent from the resin composition comprising the fluffed cellulose, the organic solvent and the resin and molding.
- a resin composition comprising fluffed cellulose, an organic solvent and a resin can also be used as a coating material.
- the fluffed cellulose may be directly mixed with the resin component by a melt-kneading method or the like. At the time of melt-kneading, the kneaded product may contain water or an organic solvent.
- the fibrous cellulose-containing material of the present invention may not be used for producing fluffed cellulose.
- the fibrous cellulose-containing material of the present invention may be used for producing a molded article or sheet without fluffing.
- a molded article or sheet obtained by molding a fluffed cellulose, a resin composition comprising an organic solvent and a resin, or a fibrous cellulose-containing material, a resin composition comprising an organic solvent and a resin is a reinforcing material, an interior material. It is also suitable for applications such as exterior materials, packaging materials, electronic materials, optical materials, acoustic materials, process materials, transportation equipment members, electronic equipment members, and electrochemical element members.
- 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, a phosphorylated pulp slurry having a pH of 12 or more and 13 or less is obtained by diluting the washed phosphorylated pulp 1 with 10 L of ion-exchanged water and then gradually adding a 1N aqueous sodium hydroxide solution with stirring. Was. 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.
- the following table shows the fiber width of the obtained phosphorylated pulp 1 (fibrous cellulose) and the supernatant yield measured by the method described below.
- the amount of a phosphate group (the amount of a strongly acidic group) measured by a measuring method described later was 1.45 mmol / g.
- a fibrous cellulose-containing material was obtained in the same manner as in Production Example 1, except that the aqueous solution of polyoxyethylene dodecylamine lactate was added with 0.44 parts by mass of lactic acid.
- 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 was finished.
- the obtained TEMPO oxidized pulp was used in place of the phosphorylated pulp 1 immediately before the addition of the organic onium salt aqueous solution, and 3.86% by mass of di-n-alkyldimethylammonium chloride (the alkyl chain had 16 carbon atoms) Or 18)
- a fibrous cellulose-containing material was obtained in the same manner as in Production Example 1 except that the number of added portions of the aqueous solution was changed to 39 parts by mass.
- Phosphorylated pulp 2 was obtained in the same manner as in Production Example 1, except that 33 parts by mass of phosphorous acid (phosphonic acid) was used instead of 45 parts by mass of ammonium dihydrogen phosphate.
- An infrared absorption spectrum of the phosphorylated pulp 2 was measured 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 phosphorous acid
- ammonium dihydrogen phosphate ammonium dihydrogen phosphate
- the fiber width of the obtained phosphorylated pulp 2 (fibrous cellulose) and the supernatant yield by centrifugation described later are shown in the table below.
- the phosphite group amount (strongly acidic group amount) measured by the measurement method described in [Measurement of Phosphate Group Amount] described later was 1.50 mmol / g.
- the amount of the weak acidic group was 0.13 mmol / g.
- Phosphorylated pulp 2 is used in place of phosphorylated pulp 1 immediately before adding an aqueous solution of an organic onium salt, and 3.86% by mass of di-n-alkyldimethylammonium chloride (the alkyl chain has 16 or 18 carbon atoms) )
- a fibrous cellulose-containing material was obtained in the same manner as in Production Example 1 except that the number of added parts of the aqueous solution was changed to 49 parts by mass.
- the following table shows the fiber width of the obtained phosphorylated pulp 3 (fibrous cellulose) and the supernatant yield measured by the method described below.
- the amount of phosphate groups (the amount of strongly acidic groups) measured by the measurement method described later was 2.00 mmol / g.
- the phosphorylated pulp 3 was used in place of the phosphorylated pulp 1 immediately before the addition of the organic onium salt aqueous solution, and 3.86% by mass of di-n-alkyldimethylammonium chloride (the alkyl chain has 16 or 18 carbon atoms)
- Example 2 A fibrous cellulose-containing material was obtained in the same manner as in Production Example 1 except that the number of added parts of the aqueous solution was changed to 100 parts by mass.
- the infrared absorption spectrum of the obtained unbleached phosphorylated pulp was measured using FT-IR. As a result, absorption based on a phosphate group was observed at around 1230 cm ⁇ 1 , confirming that a phosphate group was added to the pulp.
- the following table shows the fiber width of the obtained unbleached phosphorylated pulp (fibrous cellulose) and the supernatant yield measured by the method described below.
- the amount of a phosphate group (the amount of a strongly acidic group) measured by a measuring method described later was 1.45 mmol / g.
- a fibrous cellulose-containing material was obtained in the same manner as in Production Example 1 except that the unbleached phosphorylated pulp was used in place of the phosphorylated pulp 1 immediately before the addition of the organic onium salt aqueous solution.
- a fibrous cellulose-containing material was obtained in the same manner as in Production Example 1, except that the obtained mechanically treated fibrous cellulose was used instead of the phosphorylated pulp 1 immediately before adding the organic onium salt aqueous solution.
- a mechanically treated fibrous cellulose was obtained in the same manner as in Production Example 13 except that the TEMPO oxidized pulp obtained in Production Example 5 was used instead of the phosphorylated pulp 1 obtained in Production Example 1.
- the fiber width of the mechanically treated fibrous cellulose and the supernatant yield measured by the method described below are shown in the table below. X-ray diffraction confirmed that the mechanically treated fibrous cellulose also maintained cellulose type I crystals.
- a fibrous cellulose-containing material was obtained in the same manner as in Production Example 5, except that the obtained mechanically treated fibrous cellulose was used instead of the TEMPO oxidized pulp immediately before adding the organic onium salt aqueous solution.
- Examples 1 to 10 and Comparative Examples 1 to 10 Regarding the fibrous cellulose-containing material obtained in Production Examples 1 to 20, [1] yield after wet classification, [2] fluffing recovery rate, [3] bulk, [4] sedimentation from the water surface, by the method described below. The rate was measured. The results are shown in the table below. In addition, about the fibrous cellulose content (production example) used in each Example and each Comparative Example, it described in the following table.
- the fibrous cellulose-containing material was diluted with ion-exchanged water to a concentration of 1% by mass, adjusted to have a basis weight of 200 g / m 2 in terms of absolute dry mass, and again subjected to filtration under reduced pressure to form a sheet. And dried under a condition of a relative humidity of 40% to a constant weight to obtain a fibrous cellulose-containing sheet.
- 1 g (0.005 m 2 ) of the obtained fibrous cellulose-containing sheet was cut off in absolutely dry mass and fluffed by performing treatment at 20,000 rpm for 20 seconds in a 75-mL capacity pulverizer (Labo Mill Surplus). Was.
- the fibrous cellulose-containing material after fluff treatment (including both fluffed cellulose and non-fluffed cellulose) is spread on a test sieve having an aperture of 2 mm ⁇ , gently shaken, and the fiber that has passed through the test sieve
- the absolute dry mass of the cellulose-containing material (fluffed cellulose) was measured, and the fluffing recovery rate was calculated according to the following equation.
- Fluffization recovery rate [mass%] absolute dry mass of fibrous cellulose-containing material passed through test sieve / absolute dry mass of fibrous cellulose-containing sheet before fluffing ⁇ 100
- Sedimentation rate from water surface [mass%] absolute dry mass of sedimented fibrous cellulose-containing material / (absolute dry mass of sedimented fibrous cellulose-containing material + absolute dry mass of fibrous cellulose-containing material floating on water surface) ⁇ 100
- the phosphate group content of the fibrous cellulose was measured by treating the fine fibrous cellulose-containing slurry obtained as described below with an ion exchange resin, and then performing titration with an alkali.
- the fine fibrous cellulose-containing slurry is obtained by sufficiently pulverizing the target fibrous cellulose (2% by mass of the fibrous cellulose dispersion is treated with a high-pressure homogenizer at a pressure of 200 MPa six times). It was prepared by diluting with ion-exchanged water so that the content became 0.2% by mass.
- 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 fibrous cellulose was measured by treating the slurry containing fine fibrous cellulose obtained as described below with an ion exchange resin, and then performing titration with an alkali.
- the fine fibrous cellulose-containing slurry is obtained by sufficiently pulverizing the target fibrous cellulose (treating a 2% by mass fibrous cellulose dispersion with a high-pressure homogenizer at a pressure of 200 MPa six times), and then removing the fine fibrous cellulose.
- the fibrous cellulose dispersion was diluted with ion-exchanged water so as to have a content of 0.2% by mass.
- 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 supernatant yield of fibrous cellulose was calculated by centrifuging the fibrous cellulose dispersion.
- the supernatant yield after centrifugation is an index of the degree of micronization, and becomes higher as finer cellulose fibers are included.
- a fibrous cellulose dispersion was adjusted to a solid concentration of 0.1% by mass, and centrifuged at 12,000 G for 10 minutes using a cooling high-speed centrifuge (H-2000B, manufactured by Kokusan). The obtained supernatant was collected and the solid content concentration of the supernatant was measured. Based on the following equation, the supernatant yield of the cellulose fiber was determined.
- Supernatant yield (mass%) of fibrous cellulose solid content of supernatant (mass%) / 0.1 ⁇ 100
- Fiber width For the fibrous celluloses of Production Examples 1 to 8 and 18 to 20, the average length of the fiber width was measured using a Kayani fiber length measuring instrument (model FS-200) manufactured by Kayani Automation. For Production Examples 13 to 17, the fiber width was measured by observation with a transmission electron microscope. For Production Examples 9-12 are not present in substantially the following fibrous cellulose width 1000 nm, based on the cellulose fibers tried subjected to Production Example 1 (R 0), by light microscopy as described above, at least there fiber The ratio of the weight of the cellulose fiber having a width of 1000 nm or less was calculated. The fibrous cellulose concentration (C) at the time of observation was 0.2% by mass, and the area S 0 of the visual field to be observed was 20 mm 2 in total (20 images of 1 mm 2 in different areas).
- C fibrous cellulose concentration
- DADMA di-n-alkyldimethylammonium
- DDMA didodecylmethylammonium
- POEDA polyoxyethylenedodecylammonium
- ADMBA alkyldimethylbenzylammonium
- TBA tetrabutylammonium Na: sodium * 1 Average value measured by Kayani Fiber Lab * 2 Optical Measurement result by microscope observation * 3 Observation result by TEM
- the fiber diameter was measured, and this fiber diameter was equivalent to the fiber width of the fibrous cellulose constituting the fibrous cellulose-containing material obtained by adding an organic onium salt described later.
- this fiber diameter was equivalent to the fiber width of the fibrous cellulose constituting the fibrous cellulose-containing material obtained by adding an organic onium salt described later.
- the fibrous cellulose-containing material of the example had a high fluffing recovery rate, and the fluffed cellulose was bulky. Moreover, the fluffed cellulose obtained from the fibrous cellulose-containing material of the example had a low sedimentation rate from the water surface and was excellent in hydrophobicity. From this, in the examples, fluffed cellulose having good fluffing properties and excellent hydrophobicity after fluffing was obtained.
- ⁇ Evaluation 2> The fluffed cellulose recovered under a test sieve having an aperture of 2 mm ⁇ by the method described in ⁇ Fluffing recovery rate> (using the fibrous cellulose-containing materials of Examples 1, 5, 8, and Comparative Examples 4, 7) was subjected to [1] solvent wetting test and [2] resin composite test by the following methods.
- styrene polymer (degree of polymerization: about 2,000) is dissolved in toluene to a concentration of 10% by mass, and fluffed cellulose is added to the solution at a concentration of 5% by mass with respect to the total mass of the styrene polymer. Gently stirred. The resulting styrene polymer / fluffed cellulose dispersion was cast-dried to a basis weight of 2000 g / m 2 , and the composite properties of fibrous cellulose and styrene resin were visually observed. :: fibrous cellulose is distributed over almost the entire area in the thickness direction x: fibrous cellulose is localized at the bottom in the thickness direction
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Abstract
Description
具体的に、本発明は、以下の構成を有する。
繊維状セルロース含有物の下記測定方法で測定される歩留りが50質量%以上であり、
繊維状セルロース含有物は、アニオン性基の対イオンとして有機オニウムイオンを有し、
有機オニウムイオンは、下記(a)及び(b)から選択される少なくとも一方の条件を満たす、繊維状セルロース含有物;
(a)炭素数が5以上の炭化水素基を含む;
(b)総炭素数が17以上である;
(測定方法)
繊維状セルロース含有物を24時間、イオン交換水に浸漬した後、固形分濃度を20質量%に調製し、周速10m/sの高速回転ディスパーザーで15分間分散処理を行う;得られた分散液について、目開き150μmのJIS試験篩上で湿式分級を行い、下記式によって歩留りを算出する。
歩留り[質量%]=試験篩上に残った繊維状セルロース含有物の絶乾質量/供試した繊維状セルロース含有物の絶乾質量×100
[2] 有機オニウムイオンは、有機アンモニウムイオンである[1]に記載の繊維状セルロース含有物。
[3] 繊維状セルロースの繊維幅は、1000nmより大きい、[1]又は[2]に記載の繊維状セルロース含有物。
[4] アニオン性基量が、0.50mmol/g以上である[1]~[3]のいずれかに記載の繊維状セルロース含有物。
[5] [1]~[4]のいずれかに記載の繊維状セルロース含有物をフラッフ化してなるフラッフ化セルロース。
[6] [1]~[4]のいずれかに記載の繊維状セルロース含有物、もしくは、[5]に記載のフラッフ化セルロースと、
有機溶剤とを含む組成物。
[7] [1]~[4]のいずれかに記載の繊維状セルロース含有物、もしくは、[5]に記載のフラッフ化セルロースと、
樹脂とを含む組成物。
本発明は、アニオン性基を有する繊維状セルロースを含む繊維状セルロース含有物に関する。繊維状セルロース含有物は、アニオン性基の対イオンとして有機オニウムイオンを有し、有機オニウムイオンは、下記(a)及び(b)から選択される少なくとも一方の条件を満たす。
(a)炭素数が5以上の炭化水素基を含む。
(b)総炭素数が17以上である。
また、繊維状セルロース含有物の下記測定方法で測定される歩留りは50質量%以上である。
(測定方法)
繊維状セルロース含有物を24時間、イオン交換水に浸漬した後、固形分濃度を20質量%に調製し、周速10m/sの高速回転ディスパーザーで15分間分散処理を行う。得られた分散液について、目開き150μmのJIS試験篩上で湿式分級を行い、下記式によって歩留りを算出する。
歩留り[質量%]=試験篩上に残った繊維状セルロース含有物の絶乾質量/供試した繊維状セルロース含有物の絶乾質量×100
繊維状セルロース含有物の歩留りを測定する際には、まず、繊維状セルロース含有物を24時間、イオン交換水に浸漬した後、固形分濃度を20質量%に調製し、周速10m/sの高速回転ディスパーザーで15分間分散処理を行う。高速回転ディスパーザーとしては、例えば、プライミクス社製のTKロボミックス(半径15mmの撹拌羽根を使用)を用いることができる。次いで、得られた分散液を、目開き150μmのJIS試験篩上で湿式分級を行う。この際、流量150mL/secのイオン交換水のシャワーを試験篩上部から流し、十分に繊維状セルロースが試験篩上に広がるようにしてもよい。
フラッフ化回収率[質量%]=試験篩を通過した繊維状セルロース含有物の絶乾質量/供試した繊維状セルロース含有物の絶乾質量×100
上記方法で算出されるフラッフ化回収率は、30質量%以上であることが好ましく、50質量%以上であることがより好ましく、60質量%以上であることがさらに好ましい。なお、フラッフ化回収率は100質量%であってもよい。
上記方法で測定されるフラッフ化セルロースの嵩は、5mL/g以上であることが好ましく、10mL/g以上であることがより好ましく、20mL/g以上であることがさらに好ましい。なお、フラッフ化セルロースの嵩の上限値は特に限定されるものではないが、100mL/g以下であることが好ましい。
水面からの沈降率[質量%]=沈降した繊維状セルロース含有物の絶乾質量/(沈降した繊維状セルロース含有物の絶乾質量+水面に浮上した繊維状セルロース含有物の絶乾質量)×100
上記方法で算出されるフラッフ化セルロースの沈降率は、50質量%以下であることが好ましく、40質量%以下であることがより好ましく、30質量%以下であることがさらに好ましい。なお、フラッフ化セルロースの沈降率は、10質量%以下質量%であることが特に好ましい。
目開き300μmのJIS試験篩上で湿式分級を行った際の歩留りを算出する際には、開き150μmのJIS試験篩に代えて、目開き300μmのJIS試験篩を用いること以外は、上述した目開き150μmのJIS試験篩上で湿式分級を行った際の歩留りの測定方法と同様の方法で算出することができる。
なお、目開き150μmのJIS試験篩上で湿式分級を行った際の歩留りが上記範囲内であることは、繊維状セルロースの繊維幅が一定以上であることを意味し、繊維状セルロースが粗大繊維であることを意味している。また、目開き300μmのJIS試験篩上で湿式分級を行った際の歩留りが上記範囲内であることは、繊維状セルロースがより粗大繊維であることを意味している。
本発明の繊維状セルロース含有物は、アニオン性基を有する繊維状セルロースを含有する。ここで、繊維状セルロースの繊維幅は、1000nmよりも大きいものであることが好ましい。なお、繊維状セルロース含有物には、繊維幅が1000nm以下の微細繊維状セルロースが含まれていてもよいが、この場合、繊維幅が1000nmより大きい繊維状セルロースの占める重量の割合が、繊維幅が1000nm以下の繊維状セルロースが占める重量の割合よりも大きいものとなることが好ましい。
R0=S/S0/C
次に、この繊維状セルロースに対して微細化を行なった後の繊維状セルロースについて同様に測定を行い、この時のR0をRとする。なお、測定する際のCは同じ濃度とする。ここで、Q=1-R/R0の値が、少なくとも存在する繊維幅が1000nm以下のセルロース繊維の重量の割合を示す。
なお、「少なくとも」の意味は、光学顕微鏡で観察される「面積」に、繊維の厚さが勘案されていないことに起因する。すなわち、理想的に、繊維の厚さも面積に変換できたとすれば、R0、Rは、より大きな値を取ることになる(以降、これらを真のR0、真のRと表現する)。繊維厚さを面積に変換した際に増加する面積は、R0の方がRよりも大きい。すなわち、(真のR0/R0)>(真のR/R)となる。
これより、1-(真のR/新のR0)>1-R/R0が成り立つから、Q=1-R/R0の値が、少なくとも存在する繊維幅が1000nm以下のセルロース繊維の重量の割合を示すことになる。
(2)同じ画像内で該直線と垂直に交差する直線Yを引き、該直線Yに対し、20本以上の繊維が交差する。
上記条件を満足する観察画像に対し、直線X、直線Yと交錯する繊維の幅を目視で読み取る。こうして少なくとも重なっていない表面部分の画像を3組以上観察し、各々の画像に対して、直線X、直線Yと交錯する繊維の幅を読み取る。このように少なくとも20本×2×3=120本の繊維幅を読み取る。
繊維状セルロースの上澄み収率(質量%)=上澄みの固形分濃度(質量%)/0.1×100
なお、遠心分離後の上澄み収率は、繊維状セルロースの微細化度の指標となるものであり、繊維状セルロースの上澄み収率が上記範囲内であることは、繊維状セルロースの繊維幅が上述した好ましい範囲内にあり、繊維状セルロースがいわゆる粗大繊維であることを意味する。
リン酸基は、たとえばリン酸からヒドロキシ基を取り除いたものにあたる、2価の官能基である。具体的には-PO3H2で表される基である。リン酸基に由来する置換基には、リン酸基の塩、リン酸エステル基などの置換基が含まれる。なお、リン酸基に由来する置換基は、リン酸基が縮合した基(たとえばピロリン酸基)として繊維状セルロースに含まれていてもよい。また、リン酸基は、たとえば、亜リン酸基(ホスホン酸基)であってもよく、リン酸基に由来する置換基は、亜リン酸基の塩、亜リン酸エステル基などであってもよい。
すなわち、下記計算式によってカルボキシ基導入量を算出する。
カルボキシ基導入量(C型)=カルボキシ基量(酸型)/[1+(W-1)×(カルボキシ基量(酸型))/1000]
W:陽イオンCの1価あたりの式量(例えば、Naは23、Alは9)
<繊維原料>
繊維状セルロースは、セルロースを含む繊維原料から製造される。セルロースを含む繊維原料としては、とくに限定されないが、入手しやすく安価である点からパルプを用いることが好ましい。パルプとしては、たとえば木材パルプ、非木材パルプ、および脱墨パルプが挙げられる。木材パルプとしては、とくに限定されないが、たとえば広葉樹クラフトパルプ(LBKP)、針葉樹クラフトパルプ(NBKP)、サルファイトパルプ(SP)、溶解パルプ(DP)、ソーダパルプ(AP)、未晒しクラフトパルプ(UKP)および酸素漂白クラフトパルプ(OKP)等の化学パルプ、セミケミカルパルプ(SCP)およびケミグラウンドウッドパルプ(CGP)等の半化学パルプ、砕木パルプ(GP)およびサーモメカニカルパルプ(TMP、BCTMP)等の機械パルプ等が挙げられる。非木材パルプとしては、とくに限定されないが、たとえばコットンリンターおよびコットンリント等の綿系パルプ、麻、麦わらおよびバガス等の非木材系パルプが挙げられる。脱墨パルプとしては、とくに限定されないが、たとえば古紙を原料とする脱墨パルプが挙げられる。本実施態様のパルプは上記の1種を単独で用いてもよいし、2種以上混合して用いてもよい。
上記パルプの中でも、入手のしやすさという観点からは、たとえば木材パルプおよび脱墨パルプが好ましい。また、木材パルプの中でも、パルプ中のセルロースの分解が小さく軸比の大きい長繊維の繊維状セルロースが得られる観点から、たとえば化学パルプがより好ましく、クラフトパルプ、サルファイトパルプがさらに好ましい。
繊維状セルロースがリン酸基を有する場合、繊維状セルロースの製造工程は、リン酸基導入工程を含む。リン酸基導入工程は、セルロースを含む繊維原料が有する水酸基と反応することで、リン酸基を導入できる化合物から選択される少なくとも1種の化合物(以下、「化合物A」ともいう)を、セルロースを含む繊維原料に作用させる工程である。この工程により、リン酸基導入繊維が得られることとなる。
反応の均一性を向上させる観点から、化合物Bは水溶液として用いることが好ましい。また、反応の均一性をさらに向上させる観点からは、化合物Aと化合物Bの両方が溶解した水溶液を用いることが好ましい。
繊維状セルロースがカルボキシ基を有する場合、繊維状セルロースの製造工程は、カルボキシ基導入工程を含む。カルボキシ基導入工程は、セルロースを含む繊維原料に対し、オゾン酸化やフェントン法による酸化、TEMPO酸化処理などの酸化処理やカルボン酸由来の基を有する化合物もしくはその誘導体、またはカルボン酸由来の基を有する化合物の酸無水物もしくはその誘導体によって処理することにより行われる。
本実施形態における繊維状セルロースの製造方法においては、必要に応じてアニオン性基導入繊維に対して洗浄工程を行うことができる。洗浄工程は、たとえば水や有機溶媒によりアニオン性基導入繊維を洗浄することにより行われる。また、洗浄工程は後述する各工程の後に行われてもよく、各洗浄工程において実施される洗浄回数は、とくに限定されない。
繊維状セルロースを製造する場合、アニオン性基導入工程の後に、繊維原料に対してアルカリ処理(中和処理)を行ってもよい。アルカリ処理の方法としては、特に限定されないが、例えばアルカリ溶液中に、アニオン性基導入繊維を浸漬する方法が挙げられる。
繊維状セルロースを製造する場合、アニオン性基導入工程の後に、繊維原料に対して酸処理を行ってもよい。例えば、アニオン性基導入工程、酸処理及びアルカリ処理をこの順で行ってもよい。
アニオン性基導入繊維には、必要に応じて解繊処理を施してもよい。但し、本発明においては、上述した方法で測定される繊維状セルロース含有物の歩留りが、50質量%を下回らない程度に解繊処理を施す必要がある。例えば、解繊処理方法や解繊処理条件を適宜選択することにより、繊維状セルロース含有物の歩留りが50質量%を下回らないようにすることが好ましい。なお、本発明においては、アニオン性基導入繊維に解繊処理を施さない態様も好ましい態様である。
本発明の繊維状セルロース含有物は、繊維状セルロースが有するアニオン性基の対イオンとして、有機オニウムイオンを含む。本発明においては、少なくとも一部の有機オニウムイオンは、繊維状セルロースの対イオンとして存在しているが、繊維状セルロース含有物中には、遊離した有機オニウムイオンが存在していてもよい。
(a)炭素数が5以上の炭化水素基を含む。
(b)総炭素数が17以上である。
すなわち、繊維状セルロースは、炭素数が5以上の炭化水素基を含む有機オニウムイオン、及び総炭素数が17以上の有機オニウムイオンから選択される少なくとも一方を、アニオン性基の対イオンとして含む。有機オニウムイオンを、上記(a)及び(b)から選択される少なくとも一方の条件を満たすものとすることにより、繊維状セルロース含有物をフラッフ化することで得られるフラッフ化セルロースの疎水性を高めることができる。
中でも、Mは、窒素原子であることが好ましい。すなわち、有機オニウムイオンは有機アンモニウムイオンであることが好ましい。また、R1~R4の少なくとも1つは、炭素数が5以上のアルキル基であり、かつR1~R4の炭素数の合計が17以上であることが好ましい。
繊維状セルロース含有物は、アニオン性基を有する繊維状セルロースと有機オニウムイオンからなるものであってもよいが、さらに任意成分を含有していてもよい。
本発明は、上述した繊維状セルロース含有物をフラッフ化してなるフラッフ化セルロースに関するものでもある。フラッフ化セルロースは、セルロース繊維を毛羽立たせたものであり、毛羽状もしくは軟毛状のセルロース繊維である。本発明のフラッフ化セルロースは、フラッフ性が良好であり、かつ疎水性を有している。
繊維状セルロース含有物の製造工程は、アニオン性基を有する繊維状セルロースを含有するスラリーに、有機オニウムイオン、または、中和により有機オニウムイオンを形成する化合物を添加する工程を含む。具体的には、上述した工程で得られた繊維状セルロース含有スラリーに、上述したような有機オニウムイオンまたは、中和により有機オニウムイオンを形成する化合物を添加する。この際、有機オニウムイオンは、有機オニウムイオンを含有した溶液として添加することが好ましく、有機オニウムイオンを含有した水溶液として添加することがより好ましい。
また、添加する有機オニウムイオンのモル数は、繊維状セルロースが含むアニオン性基の量(モル数)に価数を乗じた値の0.2倍以上であることが好ましく、0.5倍以上であることがより好ましく、1.0倍以上であることがさらに好ましい。なお、添加する有機オニウムイオンのモル数は、繊維状セルロースが含むアニオン性基の量(モル数)に価数を乗じた値の10倍以下であることが好ましい。
フラッフ化セルロースは、例えば、上述した繊維状セルロース含有物を解砕処理することで得られる。具体的には、1000rpm以上100000rpm以下の回転数で0.01秒以上1000秒以下解砕処理することでフラッフ化セルロースを得ることが好ましい。この際に用いる装置としては、例えば、大阪ケミカル社製のラボミルサープラス等を挙げることができる。
本発明は、上述した繊維状セルロース含有物、もしくは、上述したフラッフ化セルロースと、有機溶剤とを含む組成物に関するものであってもよい。
本発明の繊維状セルロース含有物は、フラッフ化セルロース製造用であることが好ましい。そして、得られるフラッフ化セルロースは、有機溶媒混合用や樹脂混合用として好ましく用いられる。特に樹脂成分を含む有機溶媒との混合に好ましく用いることができる。例えば、フラッフ化セルロース、有機溶媒及び樹脂からなる樹脂組成物から有機溶媒を除き、成形することで成形体やシートを製造することができる。また、フラッフ化セルロース、有機溶媒および樹脂からなる樹脂組成物を塗料として用いることも出来る。さらに、フラッフ化セルロースを溶融混練法などにより、樹脂成分に直接混合させてもよい。なお、溶融混練の際には、混練物に水や有機溶媒が含まれていてもよい。
原料パルプとして、王子製紙製の針葉樹クラフトパルプ(固形分93質量%、坪量208g/m2シート状、離解してJIS P 8121に準じて測定されるカナダ標準濾水度(CSF)が700ml)を使用した。
製造例1における3.86質量%のジ-n-アルキルジメチルアンモニウムクロリド水溶液74質量部を、2.43質量%のN,N-ジドデシルメチルアミン水溶液74質量部に0.44質量部の乳酸を添加してなるN,N-ジドデシルメチルアミン乳酸塩水溶液に変更した以外は、製造例1と同様にして、繊維状セルロース含有物を得た。
製造例1における3.86質量%のジ-n-アルキルジメチルアンモニウムクロリド水溶液74質量部を、1.83質量%のポリオキシエチレンドデシルアミン(オキシエチレン残基の個数は2)水溶液74質量部に0.44質量部の乳酸を添加してなるポリオキシエチレンドデシルアミン乳酸塩水溶液に変更した以外は、製造例1と同様にして、繊維状セルロース含有物を得た。
製造例1における3.86質量%のジ-n-アルキルジメチルアンモニウムクロリド水溶液74質量部を、2.33質量%のアルキルジメチルベンジルアンモニウムクロリド水溶液74質量部に変更した以外は、製造例1と同様にして、繊維状セルロース含有物を得た。
原料パルプとして、王子製紙製の針葉樹クラフトパルプ(固形分93質量%、坪量208g/m2シート状、離解してJIS P 8121に準じて測定されるカナダ標準濾水度(CSF)が700ml)を使用した。この原料パルプに対してTEMPO酸化処理を次のようにして行った。
リン酸二水素アンモニウム45質量部の代わりに、亜リン酸(ホスホン酸)33質量部を用いた以外は製造例1と同様に操作を行い、リン酸化パルプ2を得た。
得られたリン酸化パルプ2に対しFT-IRを用いて赤外線吸収スペクトルの測定を行った。その結果、1210cm-1付近に亜リン酸基の互変異性体であるホスホン酸基のP=Oに基づく吸収が観察され、パルプに亜リン酸基(ホスホン酸基)が付加されていることが確認された。
製造例1における洗浄後のリン酸化パルプ1に対して、さらに製造例1におけるリン酸化処理、洗浄処理をこの順に1回ずつ行い、リン酸化パルプ3を得た。
原料パルプとして、王子製紙製の未漂白針葉樹クラフトパルプ(固形分93質量%、坪量208g/m2シート状、離解してJIS P 8121に準じて測定されるカナダ標準濾水度(CSF)が700ml、カッパー価45)を使用した以外は製造例1と同様にし、未漂白リン酸化パルプを得た。
製造例1で得られたリン酸化パルプ1にイオン交換水を添加し、固形分濃度が2質量%のスラリーを調製した。このスラリーを、直径12インチのシングルディスクリファイナー(熊谷理機工業社製)を用いて、クリアランス50μm、回転数3000rpmに設定して3回(製造例9)、8回(製造例10)、35回(製造例11)通液処理し、機械処理された繊維状セルロースを得た。これら機械処理された繊維状セルロースの繊維幅と、後述する方法で測定した上澄み収率を下表に示した。いずれの条件で機械処理された繊維状セルロースもX線回折により、セルロースI型結晶を維持していることが確認された。得られた機械処理された繊維状セルロースを、有機オニウム塩水溶液を加える直前のリン酸化パルプ1の代わりに用いた以外は、製造例1と同様にして、繊維状セルロース含有物を得た。
製造例1で得られたリン酸化パルプ1にイオン交換水を添加し、固形分濃度が2質量%のスラリーを調製した。このスラリーを、湿式微粒化装置(スギノマシン社製、スターバースト)で200MPaの圧力にて1回(製造例12)、6回(製造例13)処理し、機械処理された繊維状セルロースを得た。これら機械処理された繊維状セルロースの繊維幅と、後述する方法で測定した上澄み収率を下表に示した。いずれの条件で機械処理された繊維状セルロースもX線回折により、セルロースI型結晶を維持していることが確認された。得られた機械処理された繊維状セルロースを、有機オニウム塩水溶液を加える直前のリン酸化パルプ1の代わりに用いた以外は、製造例1と同様にして、繊維状セルロース含有物を得た。
製造例13における、3.86質量%のジ-n-アルキルジメチルアンモニウムクロリド水溶液74質量部を、2.43質量%のN,N-ジドデシルメチルアミン水溶液74質量部に0.44質量部の乳酸を添加してなるN,N-ジドデシルメチルアミン乳酸塩水溶液に変えた以外は製造例13と同様にして、繊維状セルロース含有物を得た。
製造例13における、3.86質量%のジ-n-アルキルジメチルアンモニウムクロリド水溶液74質量部を、1.83質量%のポリオキシエチレンドデシルアミン(オキシエチレン残基の個数は2)水溶液74質量部に0.44質量部の乳酸を添加してなるポリオキシエチレンドデシルアミン乳酸塩水溶液に変えた以外は製造例13と同様にして、繊維状セルロース含有物を得た。
製造例13における、3.86質量%のジ-n-アルキルジメチルアンモニウムクロリド水溶液74質量部を、2.33質量%のアルキルジメチルベンジルアンモニウムクロリド水溶液74質量部に変えた以外は製造例13と同様にして、繊維状セルロース含有物を得た。
製造例1で得られたリン酸化パルプ1の代わりに、製造例5で得られたTEMPO酸化パルプを用いた以外は、製造例13と同様にして、機械処理された繊維状セルロースを得た。この機械処理された繊維状セルロースの繊維幅と、後述する方法で測定した上澄み収率を下表に示した。機械処理された繊維状セルロースもX線回折により、セルロースI型結晶を維持していることが確認された。得られた機械処理された繊維状セルロースを、有機オニウム塩水溶液を加える直前のTEMPO酸化パルプの代わりに用いた以外は、製造例5と同様にして、繊維状セルロース含有物を得た。
王子製紙製の針葉樹クラフトパルプ(固形分93質量%、坪量208g/m2シート状、離解してJIS P 8121に準じて測定されるカナダ標準濾水度(CSF)が700ml)を離解した後、減圧濾過によって脱水し、ケーキ状の繊維状セルロース含有物を得た。
製造例1で得られたリン酸化パルプ1(ジ-n-アルキルジメチルアンモニウムクロリド水溶液を加える前)を減圧濾過によって脱水し、ケーキ状の繊維状セルロース含有物を得た。
製造例1の中和処理の際に用いるアルカリを、1N水酸化ナトリウムから1Nテトラブチルアンモニウムヒドロキシドに変えることで、対イオンがテトラブチルアンモニウムとなったリン酸化パルプ4を得た。このリン酸化パルプ4を減圧濾過によって脱水し、ケーキ状の繊維状セルロース含有物を得た。
製造例1~20で得られた繊維状セルロース含有物について、後述する方法により、[1]湿式分級後の歩留り、[2]フラッフ化回収率、[3]嵩、[4]水面からの沈降率を測定した。結果を下表に示した。なお、各実施例及び各比較例において用いた繊維状セルロース含有物(製造例)については、下表に記載した。
得られた繊維状セルロース含有物を24時間、イオン交換水に浸漬した後、固形分濃度が20質量%となるように調製し、周速10m/sの高速回転ディスパーザーで15分間分散処理を行った。得られた分散液について、目開き150μmのJIS試験篩上で湿式分級を行い、下記式によって歩留りを算出した。なお、湿式分級時には、流量150mL/secのイオン交換水のシャワーを試験篩上部から流し、十分に繊維状セルロースが試験篩上に広がるようにした。
また、目開き300μmのJIS試験篩上でも同様に湿式分級を行い、下記式によって歩留りを算出した。
歩留り[質量%]=試験篩上に残った繊維状セルロース含有物の絶乾質量/供試した繊維状セルロース含有物の絶乾質量×100
繊維状セルロース含有物をイオン交換水で1質量%濃度に希釈し、絶乾質量換算での坪量が200g/m2となるよう調整して再度減圧濾過にてシート状態とした後、30℃、相対湿度40%の条件下で恒量となるまで乾燥し、繊維状セルロース含有シートを得た。得られた繊維状セルロース含有シートを絶乾質量で1g(0.005m2)切り取り、容量75mLの粉砕機(ラボミルサープラス)にて、20,000rpmで20秒間処理を行うことでフラッフ化を行った。フラッフ処理後の繊維状セルロース含有物(フラッフ化セルロースとフラッフ化されなかったセルロースの両方を含む)を目開き2mmφの試験篩上に展開し、緩やかに振とうして、試験篩を通過した繊維状セルロース含有物(フラッフ化セルロース)の絶乾質量を測定し、下記式にしたがって、フラッフ化回収率を算出した。
フラッフ化回収率[質量%]=試験篩を通過した繊維状セルロース含有物の絶乾質量/フラッフ化前の繊維状セルロース含有シートの絶乾質量×100
フラッフ化回収率の算出時に、目開き2mmφの試験篩を通過した繊維状セルロースを、試験篩の直下に配備したメスシリンダーに落とし込み、一定体積溜まった後に、当該体積を占める繊維状セルロースの絶乾質量を測定することで、嵩(mL/g)を算出した。
フラッフ化回収率の算出時に、目開き2mmφの試験篩を通過した繊維状セルロースを、試験篩の直下50mmの位置に配備した40mmφの直径を有する容器に落下させた。この容器の壁面を伝わせながら、イオン交換水を20g/minの速度で、50g静かに注ぎ入れた直後に、撥水して水面に浮き上がった繊維状セルロースと、底部に沈降した繊維状セルロースとを別々に回収し、下記式にしたがって、水面からの沈降率を算出した。
水面からの沈降率[質量%]=沈降した繊維状セルロース含有物の絶乾質量/(沈降した繊維状セルロース含有物の絶乾質量+水面に浮上した繊維状セルロース含有物の絶乾質量)×100
〔リン酸基量の測定〕
繊維状セルロースのリン酸基量は、以下のようにして得た微細繊維状セルロース含有スラリーに対し、イオン交換樹脂による処理を行った後、アルカリを用いた滴定を行うことにより測定した。微細繊維状セルロース含有スラリーは、対象となる繊維状セルロースを十分に微細化(2質量%の繊維状セルロース分散液を圧力200MPaの高圧ホモジナイザーで6回処理)した後に、微細繊維状セルロース分散液をイオン交換水で含有量が0.2質量%となるように希釈して作製した。
イオン交換樹脂による処理は、上記繊維状セルロース含有スラリーに体積で1/10の強酸性イオン交換樹脂(アンバージェット1024;オルガノ株式会社、コンディショング済)を加え、1時間振とう処理を行った後、目開き90μmのメッシュ上に注いで樹脂とスラリーを分離することにより行った。
また、アルカリを用いた滴定は、イオン交換樹脂による処理後の繊維状セルロース含有スラリーに、0.1Nの水酸化ナトリウム水溶液を、30秒に1回、50μLずつ加えながら、スラリーが示す電気伝導度の値の変化を計測することにより行った。リン酸基量(mmol/g)は、計測結果のうち図1に示す第1領域に相当する領域において必要としたアルカリ量(mmol)を、滴定対象スラリー中の固形分(g)で除して算出した。
繊維状セルロースのカルボキシ基量は、以下のようにして得た微細繊維状セルロース含有スラリーに対し、イオン交換樹脂による処理を行った後、アルカリを用いた滴定を行うことにより測定した。微細繊維状セルロース含有スラリーは、対象となる繊維状セルロースを十分に微細化(2質量%の繊維状セルロース分散液を圧力200MPaの高圧ホモジナイザーで6回処理)した後に、微細繊維状セルロースを含む微細繊維状セルロース分散液をイオン交換水で含有量が0.2質量%となるように希釈して作製した。
イオン交換樹脂による処理は、上記繊維状セルロース含有スラリーに体積で1/10の強酸性イオン交換樹脂(アンバージェット1024;オルガノ株式会社、コンディショング済)を加え、1時間振とう処理を行った後、目開き90μmのメッシュ上に注いで樹脂とスラリーを分離することにより行った。
また、アルカリを用いた滴定は、イオン交換樹脂による処理後の繊維状セルロース含有スラリーに、0.1Nの水酸化ナトリウム水溶液を30秒に1回、50μLずつ加えながら、スラリーが示す電気伝導度の値の変化を計測することにより行った。カルボキシ基量(mmol/g)は、計測結果のうち図2に示す第1領域に相当する領域において必要としたアルカリ量(mmol)を、滴定対象スラリー中の固形分(g)で除して算出した。
繊維状セルロースの上澄み収率は、繊維状セルロース分散液を遠心分離することで算出した。遠心分離後の上澄み収率は、微細化度の指標となり、微細なセルロース繊維が含まれるほど高い値となる。まず、繊維状セルロース分散液を固形分濃度0.1質量%に調製し、冷却高速遠心分離機(コクサン社製、H-2000B)を用い、12000G、10分の条件で遠心分離した。得られた上澄み液を回収し、上澄み液の固形分濃度を測定した。下記式に基づいて、セルロース繊維の上澄み収率を求めた。
繊維状セルロースの上澄み収率(質量%)=上澄みの固形分濃度(質量%)/0.1×100
製造例1~8および18~20の繊維状セルロースについては、カヤーニオートメーション社のカヤーニ繊維長測定器(FS-200形)を用いて長さ平均繊維幅を測定した。製造例13~17については、透過電子顕微鏡による観察により、繊維幅を測定した。製造例9~12については、幅1000nm以下の繊維状セルロースが実質的に存在しない、製造例1に供試したセルロース繊維を基準(R0)として、前述した光学顕微鏡観察による、少なくとも存在する繊維幅が1000nm以下のセルロース繊維の重量の割合の算出を行った。なお、観察時の繊維状セルロース濃度(C)は0.2質量%とし、観察する視野の面積S0は合計20mm2(1mm2の範囲を異なる画像で20枚)とした。
DADMA:ジ-n-アルキルジメチルアンモニウム
DDMA:ジドデシルメチルアンモニウム
POEDA:ポリオキシエチレンドデシルアンモニウム
ADMBA:アルキルジメチルベンジルアンモニウム
TBA:テトラブチルアンモニウム
Na:ナトリウム
*1 カヤーニファイバーラボで測定された平均値
*2 光学顕微鏡観察での測定結果
*3 TEMでの観察結果
<フラッフ化回収率>に記載の方法で、目開き2mmφの試験篩の下に回収されたフラッフ化セルロース(実施例1、5、8、比較例4、7の繊維状セルロース含有物を使用)を分取し、[1]溶剤濡れテスト、[2]樹脂複合テストを下記の方法で行った。
フラッフ化された繊維状セルロースに固液比6mL/g(mLはトルエンの体積、gは繊維状セルロースの絶乾質量)になるようにトルエンを加え、常温で緩やかに撹拌した際の、液層の流動性を目視で観察した。
○:目視で液の流動性が下がる(湿潤したひと塊の状態になる)
×:目視で液の流動性が下がらない(自由に流動するトルエンが多い)
トルエンにスチレンポリマー(重合度 約2000)を10質量%の濃度となるように溶解させ、この溶液にフラッフ化セルロースを、スチレンポリマーの全質量に対して、5質量%になるよう加え、常温で緩やかに撹拌した。得られたスチレンポリマー・フラッフ化セルロース分散液を、坪量2000g/m2になるように、キャスト乾燥させた後、繊維状セルロースとスチレン樹脂との複合性を目視で観察した。
○:厚さ方向で、ほぼ全域に繊維状セルロースが分布している
×:厚さ方向で、底部に繊維状セルロースが局在している
Claims (7)
- アニオン性基を有する繊維状セルロースを含む繊維状セルロース含有物であって、
前記繊維状セルロース含有物の下記測定方法で測定される歩留りが50質量%以上であり、
前記繊維状セルロース含有物は、前記アニオン性基の対イオンとして有機オニウムイオンを有し、
前記有機オニウムイオンは、下記(a)及び(b)から選択される少なくとも一方の条件を満たす、繊維状セルロース含有物;
(a)炭素数が5以上の炭化水素基を含む;
(b)総炭素数が17以上である;
(測定方法)
繊維状セルロース含有物を24時間、イオン交換水に浸漬した後、固形分濃度を20質量%に調製し、周速10m/sの高速回転ディスパーザーで15分間分散処理を行う;得られた分散液について、目開き150μmのJIS試験篩上で湿式分級を行い、下記式によって歩留りを算出する。
歩留り[質量%]=試験篩上に残った繊維状セルロース含有物の絶乾質量/供試した繊維状セルロース含有物の絶乾質量×100 - 前記有機オニウムイオンは、有機アンモニウムイオンである請求項1に記載の繊維状セルロース含有物。
- 前記繊維状セルロースの繊維幅は、1000nmより大きい、請求項1又は2に記載の繊維状セルロース含有物。
- 前記アニオン性基量が、0.50mmol/g以上である請求項1~3のいずれか1項に記載の繊維状セルロース含有物。
- 請求項1~4のいずれか1項に記載の繊維状セルロース含有物をフラッフ化してなるフラッフ化セルロース。
- 請求項1~4のいずれか1項に記載の繊維状セルロース含有物、もしくは、請求項5に記載のフラッフ化セルロースと、
有機溶剤とを含む組成物。 - 請求項1~4のいずれか1項に記載の繊維状セルロース含有物、もしくは、請求項5に記載のフラッフ化セルロースと、
樹脂とを含む組成物。
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JPWO2020050348A1 (ja) | 2021-09-16 |
JP7255598B2 (ja) | 2023-04-11 |
EP3848504C0 (en) | 2023-11-08 |
CN112654746A (zh) | 2021-04-13 |
KR20210039466A (ko) | 2021-04-09 |
EP3848504B1 (en) | 2023-11-08 |
CN112654746B (zh) | 2022-04-29 |
US20210253744A1 (en) | 2021-08-19 |
EP3848504A4 (en) | 2022-05-25 |
EP3848504A1 (en) | 2021-07-14 |
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