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WO2017141800A1 - Substance contenant une cellulose fibreuse et procédé de production de substance contenant de la cellulose fibreuse - Google Patents

Substance contenant une cellulose fibreuse et procédé de production de substance contenant de la cellulose fibreuse Download PDF

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Publication number
WO2017141800A1
WO2017141800A1 PCT/JP2017/004664 JP2017004664W WO2017141800A1 WO 2017141800 A1 WO2017141800 A1 WO 2017141800A1 JP 2017004664 W JP2017004664 W JP 2017004664W WO 2017141800 A1 WO2017141800 A1 WO 2017141800A1
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WIPO (PCT)
Prior art keywords
fibrous cellulose
containing material
mass
cellulose
water
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PCT/JP2017/004664
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English (en)
Japanese (ja)
Inventor
拓里 尾崎
郁絵 本間
絵美 相澤
萌 水上
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王子ホールディングス株式会社
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Priority to JP2018500067A priority Critical patent/JP7095595B2/ja
Publication of WO2017141800A1 publication Critical patent/WO2017141800A1/fr

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    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/73—Polysaccharides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B15/00—Preparation of other cellulose derivatives or modified cellulose, e.g. complexes
    • C08B15/02—Oxycellulose; Hydrocellulose; Cellulosehydrate, e.g. microcrystalline cellulose
    • C08B15/04—Carboxycellulose, e.g. prepared by oxidation with nitrogen dioxide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B16/00—Regeneration of cellulose
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B5/00—Preparation of cellulose esters of inorganic acids, e.g. phosphates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • 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

Definitions

  • the present invention relates to a fibrous cellulose-containing material and a method for producing a fibrous cellulose-containing material.
  • fibrous cellulose having a fiber diameter of 10 ⁇ m or more and 50 ⁇ m or less, in particular, fibrous cellulose (pulp) derived from wood has been widely used mainly as a paper product so far.
  • fibrous cellulose fine fibrous cellulose having a fiber diameter of 1 ⁇ m or less is also known.
  • the fine fibrous cellulose can be used as a constituent material of a sheet or a composite. It is known that when fine fibrous cellulose is used, the contact point between the fibers is remarkably increased, so that the tensile strength and the like are greatly improved. In addition, the use of fine fibrous cellulose for applications such as thickeners is also being studied.
  • fine fibrous cellulose When fine fibrous cellulose is used as a thickener, for example, a liquid in which fine fibrous cellulose is dispersed is transported to a processing factory or the like.
  • the liquid in which fine fibrous cellulose is dispersed contains a large amount of dispersion medium, there is a problem that the cost for transportation increases. For this reason, in order to reduce transportation cost, it is desired to make the liquid in which fine fibrous cellulose is dispersed as concentrated as possible.
  • Patent Document 1 discloses a step of mixing a carboxyl group-containing fine fibrous cellulose fiber and a redispersion accelerator to obtain a gel-like body.
  • a water-soluble organic liquid is used as the redispersion accelerator, and examples of the water-soluble organic liquid include glycerin and dimethyl sulfoxide (DMSO).
  • Patent Document 2 discloses a method for producing a dry solid of cellulose nanofibers by adjusting the pH of an aqueous suspension of fine fibrous cellulose to 9 to 11 and then dehydrating and drying.
  • Patent Document 3 discloses a method for producing a dry product of fine fibrous cellulose by freeze-drying an aqueous suspension of fine fibrous cellulose.
  • a disaggregation product of bacterial cellulose is used as the fine fibrous cellulose, and components such as trehalose are added when freeze-drying.
  • a dry solid (powder) is known as a concentrate of fine fibrous cellulose.
  • a dry solid (powder) When making fine fibrous cellulose into a dry solid (powder), higher fluidity is preferable from the viewpoint of easy filling when packing and ease of mixing with other components.
  • the fine fibrous cellulose concentrate is dispersed again in the dispersion medium, the fine fibrous cellulose concentrate is uniformly dispersed and can exhibit the same quality as the fine fibrous cellulose before concentration. It has been demanded.
  • fine fibrous cellulose is used as a thickener, the redispersed liquid of the fine fibrous cellulose concentrate is required to exhibit a high viscosity.
  • the fine fibrous cellulose concentrate (dried solid) obtained in the prior art is not sufficient in fluidity, and problems remain in redispersibility.
  • the present inventors provide a fine fibrous cellulose concentrate (fine fibrous cellulose-containing material) excellent in fluidity and redispersibility in order to solve such problems of the prior art. We proceeded with a study for this purpose.
  • the present inventors have made the fibrous cellulose-containing material containing fibrous cellulose having a fiber width of 1000 nm or less contain a predetermined water-soluble organic compound, and The inventors have found that the fluidity of the fibrous cellulose-containing material can be enhanced and the redispersibility can be enhanced by setting the moisture content to a certain amount or more.
  • the present invention has the following configuration.
  • the water content is 1% by mass or more based on the total mass of the fibrous cellulose-containing material, and the water-soluble organic compound is solid at 20 ° C. and has a number average molecular weight.
  • a fibrous cellulose-containing material having a value of 2000 or less.
  • a method for producing a fibrous cellulose-containing material comprising a step of obtaining a slurry containing fibrous cellulose having a fiber width of 1000 nm or less and a water-soluble organic compound, and a step of drying the slurry.
  • the organic compound is solid at 20 ° C.
  • the content of fibrous cellulose is 5% by mass with respect to the total mass of the fibrous cellulose-containing material.
  • the method for producing a fibrous cellulose-containing material which is a step of drying so that the moisture content is 1% by mass or more based on the total mass of the fibrous cellulose-containing material.
  • a fine fibrous cellulose-containing material having excellent fluidity and excellent redispersibility can be provided.
  • Such a fine fibrous cellulose-containing material can be applied to various uses such as thickeners for cosmetics and foods, composites with resins, and fluids for underground layer treatment.
  • FIG. 1 is a graph showing the relationship between the amount of dropped NaOH and electrical conductivity for a fiber material having a phosphate group.
  • FIG. 2 is a graph showing the relationship between the amount of dropped NaOH and electrical conductivity for a fiber material having a carboxyl group.
  • the present invention relates to a fibrous cellulose-containing material containing fibrous cellulose having a fiber width of 1000 nm or less (hereinafter sometimes referred to as fine fibrous cellulose), moisture, and a water-soluble organic compound.
  • the content of fibrous cellulose in the fibrous cellulose-containing material is 5% by mass or more with respect to the total mass of the fibrous cellulose-containing material.
  • the water content in the fibrous cellulose-containing material is 1% by mass or more with respect to the total mass of the fibrous cellulose-containing material.
  • the water-soluble organic compound contained in the fibrous cellulose-containing material is solid at 20 ° C. and has a number average molecular weight of 2000 or less.
  • the fibrous cellulose-containing material of the present invention can also be referred to as a fine fibrous cellulose-containing material.
  • the fibrous cellulose-containing material contains a water-soluble organic compound that is solid at 20 ° C. and has a number average molecular weight of 2000 or less, and the moisture content in the fibrous cellulose-containing material is a certain amount or more.
  • a high redispersibility of the fibrous cellulose-containing material means that the uniform dispersibility of the fibrous cellulose-containing material is high.
  • the uniform dispersibility of the fibrous cellulose-containing material can be determined by whether or not the fibrous cellulose-containing material can restore the properties of the fine fibrous cellulose before concentration. For example, it can be confirmed by measuring the viscosity and haze of the re-dispersion of the fibrous cellulose-containing material.
  • the viscosity of the re-dispersion of the fibrous cellulose-containing material is high, and the viscosity recovery rate of the re-dispersion is high.
  • the viscosity restoration rate is the ratio of the viscosity of the re-dispersed liquid after increasing the concentration to the viscosity that can be expressed by the fine fibrous cellulose before increasing the concentration. It means that the fibrous cellulose-containing material can exhibit the same properties as the fine fibrous cellulose before high concentration.
  • the haze value of the re-dispersion liquid of a fibrous cellulose containing material is small, and the transparency of a re-dispersion liquid is high. This means that the uniform dispersibility of the fibrous cellulose-containing material is high and no aggregation or the like occurs.
  • the fibrous cellulose-containing material of the present invention is also characterized by high fluidity.
  • a fibrous cellulose-containing material having high fluidity has good handling properties, and is excellent in terms of ease of filling during packaging and ease of mixing with other components.
  • the high fluidity of the fibrous cellulose-containing material is particularly useful when the fine fibrous cellulose concentrate is a granular product, as will be described later.
  • the fibrous cellulose containing material of this invention is a concentrate of a fine fibrous cellulose, It is preferable that it is a dry solid substance, and it is more preferable that it is a granular material.
  • the granular material is a powdery and / or granular substance.
  • the powdery substance is smaller than the granular substance.
  • the powdery substance refers to fine particles having a particle diameter of 1 nm or more and less than 0.1 mm
  • the granular substance refers to particles having a particle diameter of 0.1 to 10 mm, but is not particularly limited.
  • a granular material may be called powder.
  • the particle diameter of the granular material in the present specification can be measured and calculated using a laser diffraction method. Specifically, the value is measured using a laser diffraction / scattering particle size distribution measuring device (Microtrac 3300 EXII, Nikkiso Co., Ltd.).
  • the moisture content in the fibrous cellulose-containing material may be 1% by mass or more with respect to the total mass of the fibrous cellulose-containing material, preferably 5% by mass or more, and preferably 10% by mass or more. More preferred. Moreover, it is preferable that it is 20 mass% or less with respect to the total mass of a fibrous cellulose containing material, and, as for the water content in a fibrous cellulose containing material, it is more preferable that it is 18 mass% or less.
  • the water content in the fibrous cellulose-containing material is dared to be constant. By controlling so that it may become more than quantity, the outstanding fluidity
  • the water content in the fibrous cellulose-containing material can be measured by placing 200 mg of the fibrous cellulose-containing material on a moisture meter (MS-70, manufactured by A & D) and heating at 140 ° C.
  • the water content in the fibrous cellulose-containing material can be calculated from the measured water content.
  • the repose angle of the fibrous cellulose-containing material is preferably 2 ° or more, more preferably 3 ° or more, and further preferably 4 ° or more. Further, the repose angle of the fibrous cellulose-containing material is preferably less than 30 °, more preferably 25 ° or less, further preferably 20 ° or less, and even more preferably 10 ° or less. preferable.
  • the angle of repose is a parameter related to the fluidity of the fibrous cellulose-containing material. A smaller angle of repose tends to increase the fluidity of the fibrous cellulose-containing material. However, if it is less than the above lower limit value, powder flow may occur and fluidity may deteriorate. That is, the angle of repose of the fibrous cellulose-containing material is preferably within the above range, whereby the fluidity of the fibrous cellulose-containing material can be made good.
  • the angle of repose of the fibrous cellulose-containing material is measured using an angle of repose measuring instrument (As One). Specifically, 100 ml of fibrous cellulose-containing material is charged into a chute of an angle of repose measuring instrument, and the chute mouth is opened to drop the fibrous cellulose-containing material downward. And the angle which the slope of the fibrous cellulose containing material after fall and the horizontal plane make is measured, and it is set as the repose angle of the fibrous cellulose containing material.
  • As One an angle of repose measuring instrument
  • the viscosity of the dispersion is preferably 1000 mPa ⁇ s or more, and preferably 5000 mPa ⁇ s. It is more preferably s or more, more preferably 10,000 mPa ⁇ s or more, and particularly preferably 12000 mPa ⁇ s or more.
  • the upper limit of the viscosity of the dispersion is not particularly limited, but can be set to, for example, 40000 mPa ⁇ s.
  • the viscosity of the dispersion of fibrous cellulose-containing material (fine fibrous cellulose concentration: 0.4% by mass) can be measured using a B-type viscometer (manufactured by BLOOKFIELD, analog viscometer T-LVT). The measurement conditions are 25 ° C., and the measurement is performed by rotating at 3 rpm for 3 minutes.
  • BLOOKFIELD analog viscometer T-LVT.
  • the measurement conditions are 25 ° C., and the measurement is performed by rotating at 3 rpm for 3 minutes.
  • the viscosity restoration rate in the re-dispersion of the fibrous cellulose-containing material is preferably 30% or more, more preferably 50% or more, further preferably 60% or more, and 70% or more. Is more preferable, and 80% or more is particularly preferable.
  • the viscosity recovery rate is the ratio of the viscosity of the re-dispersed liquid after increasing the concentration to the viscosity that can be expressed by the fine fibrous cellulose before increasing the concentration, and is specifically calculated by the following equation.
  • Viscosity restoration rate (%) (redispersion liquid viscosity / viscosity of fine fibrous cellulose dispersion as raw material) ⁇ 100
  • the redispersion viscosity is the viscosity of the dispersion of the fibrous cellulose-containing material (fine fibrous cellulose concentration 0.4% by mass), and the viscosity of the fine fibrous cellulose dispersion that is the raw material is fibrous cellulose-containing Viscosity of the dispersion obtained by dispersing fine fibrous cellulose, which is a raw material before obtaining a product, in ion-exchanged water so that the concentration is 0.4% by mass and stirring at 1500 rpm for 5 minutes using a disperser It is.
  • the haze of the dispersion of fibrous cellulose-containing material is preferably 5% or less, more preferably 4% or less, and more preferably 3% or less. More preferably, it is particularly preferably 2% or less.
  • the haze of the dispersion of the fibrous cellulose-containing material (fine fibrous cellulose concentration 0.2% by mass) in the above range indicates that the redispersibility of the fibrous cellulose-containing material is high, and the fibrous cellulose Even after the concentration is increased, the inclusions can exhibit the characteristics of the fine fibrous cellulose before the concentration increase.
  • the haze of the dispersion of the fibrous cellulose-containing material (fine fibrous cellulose concentration 0.2% by mass) is obtained by dispersing the fibrous cellulose-containing material in a glass cell (MG-40, manufactured by Fujiwara Seisakusho) having an optical path length of 1 cm. It is a value measured using a haze meter (manufactured by Murakami Color Research Laboratory Co., Ltd., HM-150) in accordance with JIS K 7136.
  • the mass ratio of the fine fibrous cellulose and the water-soluble organic compound (P: Q ) Is preferably from 2: 8 to 9.9: 0.1, and more preferably from 4: 6 to 8: 2.
  • the fibrous cellulose-containing material of the present invention contains a water-soluble organic compound.
  • the water-soluble organic compound in the present specification is a compound having a solubility in ion exchange water of 1 L at 20 ° C. of 2 g / L or more.
  • the solubility in 1 L of ion-exchanged water at 20 ° C. is preferably 5 g / L or more, more preferably 15 g / L or more, further preferably 100 g / L or more, and 200 g / L or more. Is still more preferable, and it is especially preferable that it is 500 g / L or more.
  • the water-soluble organic compound used in the present invention is solid at 20 ° C.
  • the fluidity of the fibrous cellulose-containing material is further improved, and the handling property can be enhanced.
  • the water-soluble organic compound used in the present invention has a number average molecular weight of 2000 or less.
  • the number average molecular weight of the water-soluble organic compound is preferably 1500 or less, more preferably 1000 or less, further preferably 800 or less, and particularly preferably 500 or less.
  • the number average molecular weight of the water-soluble organic compound is preferably 50 or more. That is, the water-soluble organic compound is preferably a low molecular compound.
  • water-soluble organic compound examples include glucose, sucrose, trehalose, lactose, cellobiose, fructose, maltose, galactose, fructooligosaccharide, saccharide such as galactooligosaccharide, dairy oligosaccharide, cyclodextrin; Arginine, methionine, glycine, alanine, tryptophan, asparagine, cysteine, tyrosine, lysine, leucine, isoleucine, proline, threonine, valine, glutamine, aspartic acid, etc .; adenosine, guanosine, 5-methyluridine, uridine, cytidine, etc.
  • Nucleosides; urea and phenylurea, benzylurea, N-ethyl-N′-phenylurea, thiourea, biuret, dimethylurea, diethylurea Tetramethylurea, urea derivatives such as hydantoin; can be exemplified anhydrous betaine.
  • the water-soluble organic compound is preferably at least one selected from saccharides, amino acids, and urea, more preferably at least one selected from saccharides and urea, and more preferably a saccharide. preferable.
  • the saccharide it is more preferable to use at least one selected from glucose, sucrose and trehalose, and it is particularly preferable to use trehalose.
  • the compound mentioned above as a water-soluble organic compound may be used individually by 1 type, and may use 2 or more types together.
  • the content of the water-soluble organic compound is preferably 0.75% by mass or more, more preferably 3.5% by mass or more, and more preferably 7% by mass or more with respect to the total mass of the fibrous cellulose-containing material. More preferably it is.
  • the content of the water-soluble organic compound is preferably 80% by mass or less, more preferably 66% by mass or less, and 50% by mass or less with respect to the total mass of the fibrous cellulose-containing material. Is more preferable.
  • content of a water-soluble organic compound is 1 mass part or more with respect to 100 mass parts of fibrous cellulose whose fiber width contained in a fibrous cellulose containing material is 1000 nm or less, and 5 mass parts or more.
  • the content of the water-soluble organic compound is preferably 400 parts by mass or less, and 200 parts by mass or less with respect to 100 parts by mass of the fibrous cellulose having a fiber width of 1000 nm or less contained in the fibrous cellulose-containing material. It is more preferable that it is 100 parts by mass or less.
  • the total atomic weight of nitrogen, oxygen, sulfur and phosphorus with respect to the total molecular weight of the water-soluble organic compound is preferably 25% or more, more preferably 30% or more, and further preferably 40% or more, It is especially preferable that it is 50% or more.
  • the fibrous cellulose-containing material of the present invention contains fibrous cellulose (fine fibrous cellulose) having a fiber width of 1000 nm or less.
  • the content of fibrous cellulose may be 5% by mass or more with respect to the total mass of the fibrous cellulose-containing material, preferably 10% by mass or more, more preferably 20% by mass or more, and 30 The content is more preferably at least 50% by mass, and particularly preferably at least 50% by mass.
  • pulp Although it does not specifically limit as a fibrous cellulose raw material for obtaining a fine fibrous cellulose, It is preferable to use a pulp from the point of being easy to acquire and cheap.
  • the pulp include wood pulp, non-wood pulp, and deinked pulp.
  • wood pulp include hardwood kraft pulp (LBKP), softwood kraft pulp (NBKP), sulfite pulp (SP), dissolved pulp (DP), soda pulp (AP), unbleached kraft pulp (UKP), oxygen bleached craft Chemical pulps such as pulp (OKP) are listed.
  • semi-chemical pulps such as semi-chemical pulp (SCP) and chemi-ground wood pulp (CGP), mechanical pulps such as ground wood pulp (GP) and thermomechanical pulp (TMP, BCTMP), and the like are exemplified, but not particularly limited.
  • Non-wood pulp includes cotton pulp such as cotton linter and cotton lint, non-wood pulp such as hemp, straw and bagasse, cellulose isolated from sea squirts and seaweed, chitin, chitosan, etc., but is not particularly limited.
  • the deinking pulp includes deinking pulp made from waste paper, but is not particularly limited. The pulp of this embodiment may be used alone or in combination of two or more.
  • wood pulp containing cellulose and deinked pulp are preferable in terms of availability.
  • chemical pulp has a large cellulose ratio, so the yield of fine fibrous cellulose during fiber refinement (defibration) is high, and the degradation of cellulose in the pulp is small, and the fineness of long fibers with a large axial ratio is high. It is preferable at the point from which fibrous cellulose is obtained.
  • kraft pulp and sulfite pulp are most preferably selected.
  • the average fiber width of the fine fibrous cellulose is 1000 nm or less as observed with an electron microscope.
  • the average fiber width is preferably 2 nm or more and 1000 nm or less, more preferably 2 nm or more and 100 nm or less, more preferably 2 nm or more and 50 nm or less, and further preferably 2 nm or more and 10 nm or less, but is not particularly limited.
  • the average fiber width of the fine fibrous cellulose is less than 2 nm, the physical properties (strength, rigidity, dimensional stability) as the fine fibrous cellulose tend to be difficult to be expressed because the cellulose molecules are dissolved in water. .
  • the fine fibrous cellulose is monofilamentous cellulose having a fiber width of 1000 nm or less, for example.
  • Measurement of the fiber width of the fine fibrous cellulose by electron microscope observation is performed as follows. An aqueous suspension of fine fibrous cellulose 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 subjected to a hydrophilic treatment to prepare a sample for TEM observation. To do. When a wide fiber is included, an SEM image of the surface cast on glass may be observed. Observation with an electron microscope image is performed at a magnification of 1000 times, 5000 times, 10000 times, or 50000 times depending on the width of the constituent fibers. However, the sample, observation conditions, and magnification are adjusted to satisfy the following conditions.
  • One straight line X is drawn at an arbitrary location 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 average fiber width (sometimes simply referred to as “fiber width”) of fine fibrous cellulose is an average value of the fiber widths read in this way.
  • the fiber length of the fine fibrous cellulose is not particularly limited, but is preferably 0.1 ⁇ m or more and 1000 ⁇ m or less, more preferably 0.1 ⁇ m or more and 800 ⁇ m or less, and particularly preferably 0.1 ⁇ m or more and 600 ⁇ m or less.
  • the fiber length of the fine fibrous cellulose can be determined by image analysis using TEM, SEM, or AFM.
  • the fine fibrous cellulose preferably has an I-type crystal structure.
  • the proportion of the I-type crystal structure in the fine fibrous cellulose is preferably 30% or more, more preferably 50% or more, and further preferably 70% or more.
  • the ratio of the crystal parts contained in the fine fibrous cellulose is not particularly limited in the present invention, but it is preferable to use cellulose having a crystallinity obtained by X-ray diffraction of 60% or more.
  • the degree of crystallinity is preferably 65% or more, more preferably 70% or more. In this case, further excellent performance can be expected in terms of heat resistance and low linear thermal expansion.
  • the degree of crystallinity is obtained by measuring an X-ray diffraction profile and determining the crystallinity by an ordinary method (Seagal et al., Textile Research Journal, 29, 786, 1959).
  • the fine fibrous cellulose is preferably a fiber having an ionic functional group.
  • the ionic functional group is preferably an anionic functional group (hereinafter also referred to as 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 carboxyl group or a substituent derived from a carboxyl group (sometimes simply referred to as a carboxyl group), And at least one selected from a sulfone group or a substituent derived from a sulfone group (sometimes simply referred to as a sulfone group), and at least one selected from a phosphate group and a carboxyl group It is more preferable that it is a phosphate group.
  • the fine fibrous cellulose is preferably one having a phosphate group or a substituent derived from a phosphate group.
  • the phosphoric acid group is a divalent functional group equivalent to the phosphoric acid obtained by removing the hydroxyl group. Specifically, it is a group represented by —PO 3 H 2 .
  • Substituents derived from phosphoric acid groups include substituents such as groups obtained by polycondensation of phosphoric acid groups, salts of phosphoric acid groups, and phosphoric acid ester groups. It may be a group.
  • the phosphate group or the substituent derived from the phosphate group may be a substituent represented by the following formula (1).
  • R represents a hydrogen atom, a saturated-linear hydrocarbon group, a saturated-branched hydrocarbon group, a saturated-cyclic hydrocarbon group, an unsaturated-linear hydrocarbon group, an unsaturated-branched hydrocarbon group.
  • ⁇ is a monovalent or higher cation composed of an organic substance or an inorganic substance.
  • the fiber raw material containing cellulose is reacted with at least one selected from a compound having a phosphate group and a salt thereof (hereinafter referred to as “phosphorylation reagent” or “compound A”).
  • a phosphorylating reagent may be mixed in a powder or aqueous solution with a dry or wet fiber raw material.
  • a phosphorylating reagent powder or an aqueous solution may be added to the fiber raw material slurry.
  • the phosphoric acid group introduction step can be performed by reacting a fiber raw material containing cellulose with at least one selected from a phosphoric acid group-containing compound and a salt thereof (phosphorylation reagent or compound A). This reaction may be carried out in the presence of at least one selected from urea and derivatives thereof (hereinafter referred to as “compound B”).
  • An example of a method for causing compound A to act on the fiber raw material in the presence of compound B is a method of mixing powder or an aqueous solution of compound A and compound B with a dry or wet fiber raw material.
  • Another example is a method in which powders and aqueous solutions of Compound A and Compound B are added to the fiber raw material slurry.
  • a method of adding an aqueous solution of Compound A and Compound B to a dry fiber material, or a powder or an aqueous solution of Compound A and Compound B to a wet fiber material is preferred.
  • the compound A and the compound B may be added simultaneously, or may be added separately.
  • the form of the fiber raw material is preferably cotton or thin sheet, but is not particularly limited.
  • Compound A used in this embodiment is at least one selected from a compound having a phosphate group and a salt thereof.
  • the compound having a phosphate group include, but are not limited to, phosphoric acid, lithium salt of phosphoric acid, sodium salt of phosphoric acid, potassium salt of phosphoric acid, ammonium salt of phosphoric acid, and the like.
  • the lithium salt of phosphoric acid include lithium dihydrogen phosphate, dilithium hydrogen phosphate, trilithium phosphate, lithium pyrophosphate, and lithium polyphosphate.
  • Examples of the sodium salt of phosphoric acid include sodium dihydrogen phosphate, disodium hydrogen phosphate, trisodium phosphate, sodium pyrophosphate, and sodium polyphosphate.
  • Examples of the potassium salt of phosphoric acid include potassium dihydrogen phosphate, dipotassium hydrogen phosphate, tripotassium phosphate, potassium pyrophosphate, and potassium polyphosphate.
  • Examples of the ammonium salt of phosphoric acid include ammonium dihydrogen phosphate, diammonium hydrogen phosphate, triammonium phosphate, ammonium pyrophosphate, and ammonium polyphosphate.
  • phosphoric acid and phosphoric acid are introduced efficiently from the viewpoint that the introduction efficiency of phosphate groups is high, the fibrillation efficiency is easily improved in the fibrillation process described later, the cost is low, and the industrial application is easy.
  • Sodium salt, potassium salt of phosphoric acid, and ammonium salt of phosphoric acid are preferable.
  • Sodium dihydrogen phosphate or disodium hydrogen phosphate is more preferable.
  • the compound A is preferably used as an aqueous solution because the uniformity of the reaction is increased and the efficiency of introducing a phosphate group is increased.
  • the pH of the aqueous solution of Compound A is not particularly limited, but is preferably 7 or less because the efficiency of introduction of phosphate groups is increased, and more preferably pH 3 or more and pH 7 or less from the viewpoint of suppressing the hydrolysis of pulp fibers.
  • the pH of the aqueous solution of Compound A may be adjusted by, for example, using a phosphoric acid group-containing compound that exhibits acidity and an alkalinity, and changing the amount ratio thereof. You may adjust pH of the aqueous solution of the compound A by adding an inorganic alkali or an organic alkali to the thing which shows acidity among the compounds which have a phosphoric acid group.
  • the amount of compound A added to the fiber raw material is not particularly limited, but when the amount of compound A added is converted to phosphorus atomic weight, the amount of phosphorus atom added to the fiber raw material (absolute dry mass) is 0.5 mass% to 100 mass%. Or less, more preferably 1% by mass or more and 50% by mass or less, and most preferably 2% by mass or more and 30% by mass or less. If the amount of phosphorus atoms added to the fiber raw material is within the above range, the yield of fine fibrous cellulose can be further improved. When the addition amount of phosphorus atoms with respect to the fiber raw material exceeds 100% by mass, the effect of improving the yield reaches a peak and the cost of the compound A to be used increases. On the other hand, a yield can be raised by making the addition amount of the phosphorus atom with respect to a fiber raw material more than the said lower limit.
  • Compound B used in this embodiment includes urea, biuret, 1-phenylurea, 1-benzylurea, 1-methylurea, 1-ethylurea and the like.
  • Compound B is preferably used as an aqueous solution like Compound A. Moreover, since the uniformity of reaction increases, it is preferable to use the aqueous solution in which both compound A and compound B are dissolved.
  • the amount of Compound B added to the fiber raw material is 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, and 100% by mass or more and 350% by mass or less. More preferably, it is more preferably 150% by mass or more and 300% by mass or less.
  • amides or amines may be included in the reaction system.
  • amides 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, triethylamine is known to work as a good reaction catalyst.
  • the heat treatment temperature it is preferable to select a temperature at which a phosphate group can be efficiently introduced while suppressing thermal decomposition and hydrolysis reaction of the fiber. Specifically, it is preferably 50 ° C. or higher and 300 ° C. or lower, more preferably 100 ° C. or higher and 250 ° C. or lower, and further preferably 130 ° C. or higher and 200 ° C. or lower. Moreover, you may use a vacuum dryer, an infrared heating apparatus, and a microwave heating apparatus for a heating.
  • the concentration of the compound A in the fiber raw material may be uneven, and the introduction of phosphate groups on the fiber surface may not proceed uniformly.
  • a very thin sheet-like fiber material is used, or the fiber material and Compound A are kneaded or stirred with a kneader or the like and dried by heating or reduced pressure. The method should be taken.
  • the heating device used for the heat treatment is preferably a device that can always discharge the moisture retained by the slurry and the moisture generated by the addition reaction of the fibers such as phosphate groups to the hydroxyl group of the fiber, such as a blower oven. Etc. are preferred. If water in the system is always discharged, the hydrolysis reaction of the phosphate ester bond, which is the reverse reaction of the esterification, can be suppressed, and the acid hydrolysis of the sugar chain in the fiber can also be suppressed. A fine fiber having a high axial ratio can be obtained.
  • the heat treatment time is also affected by the heating temperature, but it is preferably 1 second or more and 300 minutes or less, preferably 1 second or more and 1000 seconds or less after moisture is substantially removed from the fiber raw material slurry. Preferably, it is 10 seconds or more and 800 seconds or less.
  • the amount of phosphate groups introduced can be within a preferred range by setting the heating temperature and the heating time to appropriate ranges.
  • the amount of phosphate group introduced is preferably 0.1 mmol / g or more and 3.65 mmol / g or less, more preferably 0.14 mmol / g or more and 3.5 mmol / g or less per 1 g (mass) of fine fibrous cellulose.
  • 0.2 mmol / g or more and 3.2 mmol / g or less is more preferable, 0.4 mmol / g or more and 3.0 mmol / g or less is particularly preferable, and most preferably 0.6 mmol / g or more and 2.5 mmol / g or less.
  • the fiber raw material can be easily refined, and the stability of the fine fibrous cellulose can be enhanced.
  • the introduction amount of phosphoric acid groups within the above-mentioned range it is possible to leave hydrogen bonds between fine fibrous celluloses while being easily miniaturized, and good strength can be expected.
  • the amount of phosphate group introduced into the fiber material can be measured by a conductivity titration method. Specifically, by performing the defibration process step, after treating the resulting fine fibrous cellulose-containing slurry with an ion exchange resin, by determining the change in electrical conductivity while adding an aqueous sodium hydroxide solution, The amount introduced can be measured.
  • first region the electrical conductivity rapidly decreases
  • second region the conductivity starts to increase slightly
  • third region the conductivity increment increases (hereinafter referred to as “third region”). That is, three areas appear.
  • the boundary point between the second region and the third region is defined as a point at which the amount of change in conductivity twice, that is, the increase (inclination) in conductivity is maximized.
  • 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 the amount of weakly acidic groups in the slurry used for titration. Will be equal.
  • the amount of alkali required in the second region is reduced compared to the amount of alkali required in the first region.
  • the amount of strongly acidic groups coincides with the amount of phosphorus atoms regardless of the presence or absence of condensation, so that the amount of phosphate groups introduced (or the amount of phosphate groups) or the amount of substituent introduced (or the amount of substituents) is simply When said, it represents the amount of strongly acidic group. That is, the alkali amount (mmol) required in the first region of the curve shown in FIG. 1 is divided by the solid content (g) in the titration target slurry to obtain the substituent introduction amount (mmol / g).
  • the phosphate group introduction step may be performed at least once, but may be repeated a plurality of times. In this case, more phosphoric acid groups are introduced, which is preferable.
  • the fine fibrous cellulose when it has a carboxyl group, it is treated with an oxidation treatment such as a TEMPO oxidation treatment or a compound having a carboxylic acid-derived group, a derivative thereof, or an acid anhydride or a derivative thereof. By doing so, a carboxyl group can be introduced.
  • an oxidation treatment such as a TEMPO oxidation treatment or a compound having a carboxylic acid-derived group, a derivative thereof, or an acid anhydride or a derivative thereof.
  • the compound having a carboxyl group is not particularly limited, and examples thereof include dicarboxylic acid compounds such as maleic acid, succinic acid, phthalic acid, fumaric acid, glutaric acid, adipic acid and itaconic acid, and tricarboxylic acid compounds such as citric acid and aconitic acid. .
  • the acid anhydride of the compound having a carboxyl group is not particularly limited, but examples thereof include acid anhydrides of dicarboxylic acid compounds such as maleic anhydride, succinic anhydride, phthalic anhydride, glutaric anhydride, adipic anhydride, and itaconic anhydride. It is done.
  • the derivative of the compound having a carboxyl group is not particularly limited, and examples thereof include an acid anhydride imidized compound having a carboxyl group and an acid anhydride derivative of a compound having a carboxyl group. Although it does not specifically limit as an acid anhydride imidation thing of a compound which has a carboxyl group, Imidation thing of dicarboxylic acid compounds, such as maleimide, succinic acid imide, and phthalic acid imide, is mentioned.
  • the acid anhydride derivative of the compound having a carboxyl group is not particularly limited.
  • at least some of the hydrogen atoms of the acid anhydride of the compound having a carboxyl group such as dimethylmaleic anhydride, diethylmaleic anhydride, diphenylmaleic anhydride, etc. are substituted (for example, alkyl group, phenyl group, etc. ) Are substituted.
  • the amount of carboxyl groups introduced is preferably 0.1 mmol / g or more, more preferably 0.2 mmol / g or more, and 0.3 mmol / g or more per 1 g (mass) of fine fibrous cellulose. Is more preferably 0.5 mmol / g or more.
  • the amount of carboxyl group introduced is preferably 3.5 mmol / g or less, more preferably 3.0 mmol / g or less, further preferably 2.5 mmol / g or less, and 2.0 mmol / g. It is particularly preferred that it is g or less.
  • a cationic substituent may be introduced into the fine fibrous cellulose as an ionic functional group.
  • a cationic substituent can be introduced into the fiber raw material by adding a cationizing agent and an alkali compound to the fiber raw material and reacting them.
  • the cationizing agent one having a quaternary ammonium group and a group that reacts with a hydroxyl group of cellulose can be used.
  • the group that reacts with the hydroxyl group of cellulose include an epoxy group, a functional group having a halohydrin structure, a vinyl group, and a halogen group.
  • the cationizing agent include glycidyltrialkylammonium halides such as glycidyltrimethylammonium chloride and 3-chloro-2-hydroxypropyltrimethylammonium chloride or halohydrin type compounds thereof.
  • the alkali compound contributes to the promotion of the cationization reaction.
  • Alkali compounds include alkali metal hydroxides or alkaline earth metal hydroxides, alkali metal carbonates or alkaline earth metal carbonates, alkali metal phosphates or alkaline earth metal phosphates, etc.
  • Organic alkali compounds such as ammonia, aliphatic amines, aromatic amines, aliphatic ammoniums, aromatic ammoniums, heterocyclic compounds and their hydroxides, carbonates, phosphates, etc. It may be.
  • the introduction amount of the cationic substituent can be measured using, for example, elemental analysis.
  • alkali treatment When manufacturing a fine fibrous cellulose, you may perform an alkali treatment between an ionic functional group introduction
  • the alkali compound contained in the alkali solution is not particularly limited, but may be an inorganic alkali compound or an organic alkali compound.
  • the solvent in the alkaline solution may be either water or an organic solvent.
  • the solvent is preferably a polar solvent (polar organic solvent such as water or alcohol), and more preferably an aqueous solvent containing at least water.
  • a sodium hydroxide aqueous solution or a potassium hydroxide aqueous solution is particularly preferred because of its high versatility.
  • the temperature of the alkali solution in an alkali treatment process is not specifically limited, 5 to 80 degreeC is preferable and 10 to 60 degreeC is more preferable.
  • the immersion time in the alkaline solution in the alkali treatment step is not particularly limited, but is preferably 5 minutes or longer and 30 minutes or shorter, and more preferably 10 minutes or longer and 20 minutes or shorter.
  • the usage-amount of the alkaline solution in an alkali treatment is not specifically limited, It is preferable that it is 100 mass% or more and 100,000 mass% or less with respect to the absolute dry mass of a phosphate group introduction
  • the phosphate group-introduced fiber may be washed with water or an organic solvent before the alkali treatment step.
  • the alkali treatment in order to improve the handleability, it is preferable to wash the alkali-treated phosphate group-introduced fiber with water or an organic solvent before the defibrating treatment step.
  • the phosphate group-introduced fiber is defibrated in the defibrating process.
  • the fiber is usually defibrated using a defibrating apparatus to obtain a fine fibrous cellulose-containing slurry, but the processing apparatus and the processing method are not particularly limited.
  • a defibrating apparatus a high-speed defibrator, a grinder (stone mill type pulverizer), a high-pressure homogenizer, an ultra-high pressure homogenizer, a high-pressure collision type pulverizer, a ball mill, a bead mill, or the like can be used.
  • a device for wet grinding such as a disk type refiner, a conical refiner, a twin-screw kneader, a vibration mill, a homomixer under high-speed rotation, an ultrasonic disperser, or a beater should be used. You can also.
  • the defibrating apparatus is not limited to the above.
  • Preferable defibrating treatment methods include a high-speed defibrator, a high-pressure homogenizer, and an ultra-high pressure homogenizer that are less affected by the grinding media and less concerned about contamination.
  • polar organic solvent in addition to water, a polar organic solvent can be used.
  • polar organic solvents include alcohols, ketones, ethers, dimethyl sulfoxide (DMSO), dimethylformamide (DMF), dimethylacetamide (DMAc), and the like, but are not particularly limited.
  • alcohols include methanol, ethanol, n-propanol, isopropanol, n-butanol, and t-butyl alcohol.
  • ketones include acetone and methyl ethyl ketone (MEK).
  • ethers include diethyl ether and tetrahydrofuran (THF).
  • THF tetrahydrofuran
  • the dispersion medium may be one type or two or more types. Further, the dispersion medium may contain a solid content other than the fiber raw material, such as urea having hydrogen bonding property.
  • the fine fibrous cellulose-containing slurry of the present invention may be obtained by once concentrating and / or drying the fine fibrous cellulose-containing slurry obtained by the defibrating treatment and then performing the defibrating treatment again.
  • the concentration and drying methods are not particularly limited, and examples thereof include a method of adding a concentrating agent to a slurry containing fine fibrous cellulose, a generally used dehydrator, a press, and a method using a dryer.
  • a well-known method for example, the method described in WO2014 / 024876, WO2012 / 107642, and WO2013 / 121086 can be used.
  • it can concentrate and dry by making a fine fibrous cellulose containing slurry into a sheet
  • a high-speed defibrator As a device used when the fine fibrous cellulose slurry is concentrated and / or dried and then defibrated (pulverized) again, a high-speed defibrator, a grinder (stone mill pulverizer), a high-pressure homogenizer, an ultra-high pressure homogenizer, Use wet grinding equipment such as high-pressure collision type pulverizer, ball mill, bead mill, disk type refiner, conical refiner, twin-screw kneader, vibration mill, homomixer under high-speed rotation, ultrasonic disperser, beater, etc. However, it is not particularly limited.
  • the fibrous cellulose-containing product having a phosphate group obtained by the above-described method is a fine fibrous cellulose-containing slurry, and may be diluted with water so as to have a desired concentration.
  • the fibrous cellulose-containing material may further contain other components.
  • the other components may be added to and mixed with the fibrous cellulose-containing material obtained after concentration, or may be contained in the slurry before concentration.
  • a hygroscopic agent can be mentioned.
  • the hygroscopic agent include silica gel, zeolite, alumina, carboxymethyl cellulose, polyvinyl alcohol water-soluble cellulose acetate, polyethylene glycol, sepiolite, calcium oxide, diatomaceous earth, activated carbon, activated clay, white carbon, calcium chloride, magnesium chloride, potassium acetate.
  • examples of other components include water-soluble polymers and surfactants.
  • water-soluble polymers include synthetic water-soluble polymers (for example, carboxyvinyl polymer, polyvinyl alcohol, alkyl methacrylate / acrylic acid copolymer, polyvinyl pyrrolidone, 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.), cellulose derivatives (eg, carboxymethylcellulose, methylcellulose) Such as hydroxyethyl cellulose), cationized starch, raw starch,
  • the organic solvent is not contained in the fibrous cellulose containing material of this invention.
  • content of the organic solvent in a fibrous cellulose containing material is 1 mass% or less, it can be said that the organic solvent is not contained in the fibrous cellulose containing material.
  • the fibrous cellulose-containing material does not contain an organic solvent, the ease of handling of the fibrous cellulose-containing material can be enhanced, and the handling property can be enhanced. Also, redispersibility and fluidity can be improved.
  • the fibrous cellulose-containing material of the present invention is preferably used by being redispersed in a solvent such as water.
  • a solvent such as water.
  • the kind of solvent used in order to obtain such a redispersion slurry is not specifically limited, Water, an organic solvent, and the mixture of water and an organic solvent can be mentioned.
  • the organic solvent include alcohols, polyhydric alcohols, ketones, ethers, dimethyl sulfoxide (DMSO), dimethylformamide (DMF), dimethylacetamide (DMAc), and the like.
  • examples of alcohols include methanol, ethanol, n-propanol, isopropanol, n-butanol, and t-butyl alcohol.
  • Examples of polyhydric alcohols include ethylene glycol and glycerin.
  • Examples of ketones include acetone and methyl ethyl ketone.
  • Examples of ethers include diethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono n-butyl ether, ethylene glycol mono t-butyl ether and the like.
  • the same device as the defibrating device described in the above-mentioned ⁇ defibrating treatment> may be used.
  • the present invention also relates to a method for producing a fibrous cellulose-containing material.
  • the manufacturing process of the fibrous cellulose-containing material of the present invention includes a step of obtaining a slurry containing fibrous cellulose having a fiber width of 1000 nm or less and a water-soluble organic compound, and a step of obtaining a fibrous cellulose-containing material from the slurry.
  • the step of obtaining the fibrous cellulose-containing material from the slurry is preferably a step of concentrating the slurry, and the concentration step is preferably a step of drying the slurry.
  • the content of fibrous cellulose is 5% by mass or more with respect to the total mass of the fibrous cellulose-containing material, and the moisture content is 1 with respect to the total mass of the fibrous cellulose-containing material. It is preferable that it is the process of drying so that it may become mass% or more.
  • the water-soluble organic compound used in the production process of the fibrous cellulose-containing product of the present invention is solid at 20 ° C. and has a number average molecular weight of 2000 or less.
  • fibrous cellulose having a fiber width of 1000 nm or less fine fibrous cellulose
  • a water-soluble organic compound are added to water.
  • the concentration of the fine fibrous cellulose is 0.1% by mass or more and 10% by mass or less.
  • concentration of a water-soluble organic compound may be 0.01 to 1 mass% in the process of obtaining a slurry.
  • the concentration of the organic solvent in the slurry is 1% by mass or less, it can be said that the organic solvent is not added.
  • the safety of the manufacturing process can be further improved.
  • the step of obtaining the fibrous cellulose-containing material from the slurry is preferably a step of concentrating the slurry.
  • a concentration process a thickener addition, filtration, pressing, drying, a membrane process etc. can be mentioned, for example.
  • a concentration process is a drying process, and it is preferable to obtain a fibrous cellulose containing material by drying the slurry obtained at the process of obtaining a slurry.
  • the slurry is preferably dried in an environment of 30 ° C. or higher and 100 ° C. or lower for 5 hours or more and 100 hours or less, and the drying may be performed in a blowing environment.
  • the drying step is also preferably performed in a reduced pressure environment.
  • the fibrous cellulose-containing material obtained in the drying process is preferably pulverized.
  • a pulverizer for example, a mixer, a grinder (stone mortar pulverizer), a high-pressure collision pulverizer, a ball mill, a bead mill, a vibration mill, or the like can be used.
  • the step of obtaining the fibrous cellulose-containing material from the slurry may be a spray drying step.
  • a spray drying process a slurry containing fine fibrous cellulose and a water-soluble organic compound is spray dried using a spray dryer or the like.
  • a spray dryer is a device that dries a solution such as a slurry in a short time by atomizing the solution with a sprayer such as a disk atomizer or a nozzle to increase the surface area and bringing it into contact with hot air.
  • a spray dryer generally available equipment can be used.
  • the ODA-25 type manufactured by Okawara Chemical Industries Co., Ltd. can be used.
  • the moisture content in the fibrous cellulose-containing material can be easily controlled by adopting the concentration step described above. That is, it becomes easy to make the water content in the fibrous cellulose-containing material 1% by mass or more. Thereby, the redispersibility of a fibrous cellulose containing material can be improved more effectively.
  • the use of the fibrous cellulose-containing material of the present invention is not particularly limited.
  • the fibrous cellulose-containing material is preferably used as a thickener, for example.
  • the re-dispersed slurry of fibrous cellulose-containing material can be used as a thickener for various purposes (for example, additives for food, cosmetics, cement, paint, ink, etc.).
  • it can also mix with resin and emulsion and can also be used for the use as a reinforcing material.
  • it can form into a film using fine fibrous cellulose redispersion slurry, and can also be used as various films.
  • Oji Paper's pulp solid content 93% basis weight 208 g /
  • the step of obtaining 100 g of the obtained phosphorylated pulp by pulp mass, pouring 10 L of ion exchange water, stirring and dispersing uniformly, and then performing filtration and dehydration to obtain a dehydrated sheet was repeated twice.
  • the obtained dehydrated sheet was diluted with 10 L of ion-exchanged water, and a 1N sodium hydroxide aqueous solution was added little by little while stirring to obtain a pulp slurry having a pH of 12 or more and 13 or less. Thereafter, the pulp slurry was dehydrated to obtain a dehydrated sheet, and then 10 L of ion exchange water was added.
  • the step of stirring and dispersing uniformly, followed by filtration and dehydration to obtain a dehydrated sheet was repeated twice.
  • the step of introducing phosphate groups and the step of filtration and dehydration were repeated on the obtained dehydrated sheet to obtain a dehydrated sheet of phosphorylated cellulose.
  • the obtained dehydrated sheet was measured for infrared absorption spectrum by FT-IR. As a result, absorption based on phosphate groups was observed at 1230 cm ⁇ 1 or more and 1290 cm ⁇ 1 or less, and addition of phosphate groups was confirmed. Therefore, in the obtained dehydrated sheet (phosphorylated cellulose), a part of the hydroxyl group of cellulose was substituted with the functional group of the following structural formula (1).
  • R represents a hydrogen atom, a saturated-linear hydrocarbon group, a saturated-branched hydrocarbon group, a saturated-cyclic hydrocarbon group, an unsaturated-linear hydrocarbon group, an unsaturated-branched hydrocarbon group.
  • ⁇ is a monovalent or higher cation composed of an organic substance or an inorganic substance.
  • Ion exchange water was added to the obtained twice phosphorylated cellulose to prepare a slurry having a solid content concentration of 2% by mass.
  • This slurry was further processed using a wet atomizer (manufactured by Sugino Machine Co., Ltd., an optimizer) to obtain fine fibrous cellulose 1.
  • the treatment chamber was passed three times at a pressure of 245 MPa. It was confirmed by X-ray diffraction that the fine fibrous cellulose 1 maintained a cellulose I type crystal.
  • Ion exchange water was added to the obtained TEMPO oxidized cellulose to prepare a slurry having a solid content concentration of 2% by mass.
  • This slurry was further processed using a wet atomizer (manufactured by Sugino Machine Co., Ltd., an optimizer) to obtain fine fibrous cellulose 2.
  • the treatment chamber was passed three times at a pressure of 245 MPa. It was confirmed by X-ray diffraction that the fine fibrous cellulose 2 maintained cellulose I type crystals.
  • the introduction amount of the substituent is the introduction amount of the phosphoric acid group or carboxylic acid group to the fiber raw material. The larger this value, the more phosphoric acid groups or carboxylic acid groups are introduced.
  • the amount of substituent introduced was measured by diluting the target fine fibrous cellulose with ion-exchanged water so that the content was 0.2% by mass, and then treating with ion-exchange resin and titration with alkali. In the treatment with an ion exchange resin, 1/10 by volume of a strongly acidic ion exchange resin (Amberjet 1024; Organo Co., Ltd., conditioned) is added to the 0.2 mass% fibrous cellulose-containing slurry and shaken for 1 hour. Went.
  • a strongly acidic ion exchange resin Amberjet 1024; Organo Co., Ltd., conditioned
  • the obtained fine fibrous cellulose was diluted to 0.4 mass%, and the viscosity of the diluted dispersion was measured using a B-type viscometer (analog viscometer T-LVT manufactured by BLOOKFIELD). The measurement was performed by rotating at 25 ° C. and 3 rpm for 3 minutes.
  • the fiber width of the fine fibrous cellulose was measured by the following method.
  • the supernatant liquid of the defibrated pulp slurry was diluted with water to a concentration of 0.01% by mass or more and 0.1% by mass or less and dropped onto a carbon grid membrane subjected to a hydrophilic treatment. After drying, it was stained with uranyl acetate and observed with a transmission electron microscope (JEOL-2000EX, manufactured by JEOL Ltd.). It was confirmed that the fine fibrous celluloses 1 and 2 were fine fibrous cellulose having a fiber width of about 4 nm.
  • Example 1 It added to ion-exchange water so that the density
  • Teflon registered trademark
  • Example 2 In Example 1, sucrose was used instead of glucose. Except that, fibrous cellulose-containing materials were obtained in the same manner as in Example 1.
  • Example 3 In Example 1, trehalose was used instead of glucose. Except that, fibrous cellulose-containing materials were obtained in the same manner as in Example 1.
  • Example 4 In Example 1, urea was used instead of glucose. Except that, fibrous cellulose-containing materials were obtained in the same manner as in Example 1.
  • Example 5 In Example 1, anhydrous betaine was used instead of glucose. Except that, fibrous cellulose-containing materials were obtained in the same manner as in Example 1.
  • Example 6 In Example 1, serine was used instead of glucose. Except that, fibrous cellulose-containing materials were obtained in the same manner as in Example 1.
  • Example 7 phenylalanine was used instead of glucose. Except that, fibrous cellulose-containing materials were obtained in the same manner as in Example 1.
  • Example 8 In Example 1, glutamic acid was used instead of glucose. Except that, fibrous cellulose-containing materials were obtained in the same manner as in Example 1.
  • Example 9 In Example 1, histidine was used instead of glucose. Except that, fibrous cellulose-containing materials were obtained in the same manner as in Example 1.
  • Example 10 ⁇ Example 10> In Example 1, adenosine was used instead of glucose. Except that, fibrous cellulose-containing materials were obtained in the same manner as in Example 1.
  • Example 11 In Example 3, trehalose was added to 3% by mass to prepare a dispersion. In all other cases, fibrous cellulose-containing material was obtained in the same manner as in Example 3.
  • Example 12 trehalose was added to 1% by mass to prepare a dispersion. In all other cases, fibrous cellulose-containing material was obtained in the same manner as in Example 3.
  • Example 13 trehalose was added to 0.11% by mass to prepare a dispersion. In all other cases, fibrous cellulose-containing material was obtained in the same manner as in Example 3.
  • Example 14 trehalose was added to a concentration of 0.052% by mass to prepare a dispersion. In all other cases, fibrous cellulose-containing material was obtained in the same manner as in Example 3.
  • Example 15 trehalose was added to 0.01% by mass to prepare a dispersion. In all other cases, fibrous cellulose-containing material was obtained in the same manner as in Example 3.
  • Example 16 In Example 3, fine fibrous cellulose 2 was used instead of fine fibrous cellulose 1. In all other cases, fibrous cellulose-containing material was obtained in the same manner as in Example 3.
  • Example 17 In Example 13, instead of the fine fibrous cellulose 1, fine fibrous cellulose 2 was used. In all other cases, a fibrous cellulose-containing material was obtained in the same manner as in Example 13.
  • Example 1 ⁇ Comparative Example 1> In Example 1, the test which does not add glucose was implemented. Except that, fibrous cellulose-containing materials were obtained in the same manner as in Example 1.
  • Example 3 a test was conducted at a drying process temperature of 105 ° C. In all other cases, fibrous cellulose-containing material was obtained in the same manner as in Example 3.
  • Example 3 liquid paraffin was used instead of glucose. Except that, fibrous cellulose-containing materials were obtained in the same manner as in Example 1.
  • Example 4 glycerin was used instead of glucose. Except that, fibrous cellulose-containing materials were obtained in the same manner as in Example 1.
  • Example 16 a test in which glucose was not added was performed. In all other cases, a fibrous cellulose-containing material was obtained in the same manner as in Example 16.
  • Example 16 a test was conducted at a drying process temperature of 105 ° C. In all other cases, a fibrous cellulose-containing material was obtained in the same manner as in Example 16.
  • Example 7 ⁇ Comparative Example 7>
  • liquid paraffin was used instead of glucose.
  • a fibrous cellulose-containing material was obtained in the same manner as in Example 16.
  • the fine fibrous cellulose (fine fibrous cellulose 1 or fine fibrous cellulose 2) used in Examples and Comparative Examples, which is a raw material before obtaining the fibrous cellulose-containing material, has a concentration of 0.4% by mass.
  • the fine fibrous cellulose was added to ion exchange water.
  • the mixture was stirred at 1500 rpm for 5 minutes to prepare 100 g of a dispersion.
  • the viscosity of this dispersion was measured by the same method as described above, and was defined as “viscosity of fine fibrous cellulose dispersion as a raw material”.
  • Viscosity restoration rate (%) (redispersion liquid viscosity / viscosity of fine fibrous cellulose dispersion as raw material) ⁇ 100
  • the angle of repose of the fibrous cellulose-containing material was measured using an angle of repose measuring instrument (As One). 100 ml of fibrous cellulose-containing material was charged into a chute of an angle of repose measuring instrument, and the chute mouth was opened to drop the fibrous cellulose-containing material downward. The angle formed by the slope of the fibrous cellulose-containing material after dropping and the horizontal plane was measured and defined as the angle of repose.
  • the fibrous cellulose-containing material obtained in the examples exhibited high viscosity even after redispersion, and the viscosity recovery rate was also a high value. Moreover, the haze value of the re-dispersion liquid of fibrous cellulose containing material was small, and it turned out that the re-dispersibility of fibrous cellulose containing material is favorable. Furthermore, the repose angle of the fibrous cellulose-containing material obtained in the examples was small, and the handling property as a powder was excellent. In Examples 1 to 10 and 16, it was possible to show that water-soluble organic compounds such as saccharides, urea and amino acids are effective.
  • Examples 11 to 15 and 17 were prepared by changing the ratio of the fine fibrous cellulose and the water-soluble organic compound, but it was shown that the present invention can be used in a wide range.
  • Comparative Examples 1 and 5 did not contain a water-soluble organic compound, and the redispersibility was insufficient.
  • Comparative Examples 2 and 6 were dried under strong conditions, and the moisture content of the fibrous cellulose-containing material was low. Under these conditions, redispersibility was insufficient even when an additive was added.
  • Comparative Examples 3 and 7 those which were not water-soluble organic compounds were used as additives, but did not have a favorable effect on redispersibility.
  • glycerin which is a water-soluble liquid, was used as an additive, but the fibrous cellulose-containing material (powder) was sticky and the angle of repose increased.

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Abstract

La présente invention concerne la préparation d'une substance contenant de la cellulose microfibreuse qui est excellente en termes de fluidité et de redispersibilité. La présente invention concerne une substance contenant de la cellulose fibreuse qui comprend de la cellulose fibreuse présentant une largeur de fibre de 1 000 nm ou moins, de l'eau, et un composé organique soluble dans l'eau, la teneur de la cellulose fibreuse étant de 5 % en masse ou plus par rapport à la masse totale de la substance contenant de la cellulose fibreuse, la teneur de l'eau étant de 1 % en masse ou plus par rapport à la masse totale de la substance contenant de la cellulose fibreuse, et le composé organique soluble dans l'eau étant solide à 20 °C et présentant un poids moléculaire moyen en nombre de 2 000 ou moins.
PCT/JP2017/004664 2016-02-19 2017-02-09 Substance contenant une cellulose fibreuse et procédé de production de substance contenant de la cellulose fibreuse WO2017141800A1 (fr)

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Cited By (15)

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JPWO2019059079A1 (ja) * 2017-09-20 2020-09-03 日本製紙株式会社 アニオン変性セルロースナノファイバーの製造方法
JP2019089870A (ja) * 2017-11-10 2019-06-13 国立研究開発法人産業技術総合研究所 セルロースナノファイバー乾燥紛体の製造方法
CN111836930A (zh) * 2018-01-10 2020-10-27 王子控股株式会社 片
CN112262175A (zh) * 2018-07-13 2021-01-22 大王制纸株式会社 纤维状纤维素含有物及其制造方法、纤维状纤维素干燥体及其制造方法、以及纤维状纤维素复合树脂及其制造方法
CN112867738A (zh) * 2018-10-16 2021-05-28 王子控股株式会社 纤维状纤维素、纤维状纤维素分散液和纤维状纤维素的制造方法
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US11945884B2 (en) 2018-10-16 2024-04-02 Oji Holdings Corporation Fibrous cellulose, fibrous cellulose dispersion, and production method for fibrous cellulose
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