JP2017057284A - Fine fibrous cellulose-containing composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a composition containing fine fibrous cellulose excellent in flowability and re-dispersibility into a solvent such as water.SOLUTION: The invention relates to a composition containing (A) a granular article containing fine fibrous cellulose and moisture and (B) a non-cellulose granular article and having moisture content in the composition of 2 to 94 mass% based on the total mass of the composition and content of the (B) non-cellulose granular article of 0.1 to 12 mass% based on the total mass of the composition.SELECTED DRAWING: None

Description

  The present invention relates to a composition containing fine fibrous cellulose. Specifically, the present invention relates to a composition comprising fine fibrous cellulose and non-cellulose powder and having excellent fluidity and redispersibility.

  In recent years, materials that use reproducible natural fibers have attracted attention due to the substitution of petroleum resources and the growing environmental awareness. Among natural fibers, fibrous cellulose having a fiber diameter of 10 to 50 μm, particularly fibrous cellulose (pulp) derived from wood has been widely used mainly as a paper product so far.

  As the fibrous cellulose, fine fibrous cellulose having a fiber diameter of 1 μm or less is also known. Sheets and composites containing fine fibrous cellulose significantly increase the tensile strength because the contact points between fibers are remarkably increased. Moreover, transparency is greatly improved because the fiber width is shorter than the wavelength of visible light. For example, Patent Document 1 discloses a fiber-reinforced composite material in which high transparency is maintained without being affected by temperature conditions, wavelengths, and the like, and various functions are imparted by combining fibers and a matrix material. Has been. It is also known that fine fibrous cellulose can be used for applications such as thickeners.

  In the case of using fine fibrous cellulose as a thickener, for example, a liquid in which fine fibrous cellulose is dispersed is transported to a processing factory or the like. However, since 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 is high. 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.

  As one of concentrated forms, a powder form is known. Also in the field of pulp materials, a technique for making cellulose into powder is conventionally known. For example, Patent Documents 2 and 3 disclose techniques for producing powdery cellulose using a wood pulp sheet as a raw material and using a roller mill, a cutter mill, or the like. Patent Document 4 discloses a cellulose powder suitable for an excipient for compression molding. Here, it is said that cellulose powder excellent in compression moldability can be obtained by spray drying the cellulose dispersion.

JP 2008-24788 A JP 2014-88538 A JP 2012-207056 A International Publication WO02 / 02643

It is said that the cellulose powder preferably has higher fluidity from the viewpoint of ease of filling at the time of packaging and ease of mixing with other components. In the cellulose powder obtained from cellulose having a conventional fiber diameter of about 10 to 50 μm, attempts have been made to improve fluidity and the like.
However, the powder containing fine fibrous cellulose has a problem that the fluidity is remarkably inferior compared with the conventional cellulose powder. This is because fine fibrous cellulose is a fiber whose fiber diameter is refined to the nano order and has different physical properties from normal cellulose fibers such as high water retention. For this reason, improvement of the fluidity | liquidity of the powder containing a fine fibrous cellulose is desired.

  Moreover, the powder containing fine fibrous cellulose tends to be difficult to disperse again in a solvent such as water. Since the powder containing fine fibrous cellulose can exhibit its effect by being dispersed in a solvent in water or the like, it is also required to have excellent redispersibility.

  Therefore, in order to solve such problems of the prior art, the inventors have obtained a powder (composition) containing fine fibrous cellulose having excellent fluidity and excellent redispersibility in a solvent such as water. We proceeded with the study for the purpose of providing.

As a result of diligent studies to solve the above problems, the present inventors have made it possible to contain fine granular cellulose and moisture-containing powder and non-cellulosic powder at a predetermined ratio. It has been found that a composition having excellent properties and redispersibility can be obtained.
Specifically, the present invention has the following configuration.

[1] A composition containing (A) fine fibrous cellulose and water and (B) non-cellulose powder, and the water content in the composition is the total mass of the composition. On the other hand, it is 2-94 mass%, (B) Content of a non-cellulose granular material is 0.1-12 mass% with respect to the total mass of a composition.
[2] The composition according to [1], wherein the content of the fine fibrous cellulose is more than 5% by mass with respect to the total mass of the composition.
[3] The composition according to [1] or [2], wherein the water content in the composition is 15 to 80% by mass relative to the total mass of the composition.
[4] The composition according to any one of [1] to [3], wherein the (B) non-cellulose powder is an inorganic fine particle.
[5] The composition according to any one of [1] to [4], wherein the (B) non-cellulose powder particles are hydrophobic inorganic fine particles.
[6] The composition according to any one of [1] to [4], wherein the (B) non-cellulose powder particles are silica fine particles.
[7] The composition according to any one of [1] to [6], wherein the (B) non-cellulose powder particles are hydrophobic silica fine particles.
[8] The composition according to any one of [1] to [7], wherein the cumulative median diameter of the composition is 100 to 1350 μm.
[9] The composition according to any one of [1] to [8], wherein the angle of repose of the composition is 4 to 50 °.
[10] The composition according to any one of [1] to [9], wherein the bulk density of the composition is 0.1 to 0.7 g / ml.
[11] The composition according to any one of [1] to [10], wherein the fine fibrous cellulose is a fine fibrous cellulose having an ionic substituent.
[12] The composition according to [11], wherein the ionic substituent is an anionic group.
[13] The composition according to [12], wherein the anionic group is at least one selected from a phosphate group, a carboxyl group, and a sulfone group.
[14] The composition according to any one of [11] to [13], wherein the fine fibrous cellulose has an ionic substituent of 0.1 to 3.5 mmol / g.
[15] Concentrate the slurry containing fine fibrous cellulose to obtain (A) a fine particle containing fine fibrous cellulose and moisture, (A) a fine granular material containing fine fibrous cellulose and moisture, and (B And a step of mixing the non-cellulose granules.

  According to the present invention, a composition excellent in fluidity and redispersibility can be obtained. Thus, since the composition of this invention is excellent in fluidity | liquidity, it is excellent in handling property, such as being easy to fill. Moreover, since the composition of this invention is excellent in redispersibility, it is preferably used for various uses including uses, such as a thickener.

FIG. 1 is a graph showing the relationship between the amount of NaOH dripped with respect to the fiber material and the electrical conductivity.

Hereinafter, the present invention will be described in detail. The description of the constituent elements described below may be made based on representative embodiments and specific examples, but the present invention is not limited to such embodiments. In the present specification, a numerical range expressed using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
Moreover, the value regarding the mass of fibers, such as a cellulose, is based on the absolute dry mass (solid content) except the case where it describes especially. “A and / or B” means at least one of A and B unless otherwise specified, and may be A alone, B alone, or both A and B. Means it may be.

(Fine fibrous cellulose-containing composition)
The composition of the present invention comprises (A) a granular material containing fine fibrous cellulose and moisture, and (B) a non-cellulose granular material. The water content in this composition is 2 to 94% by mass relative to the total mass of the composition, and the content of (B) non-cellulose granules is 0.1% relative to the total mass of the composition. ˜12% by mass. In addition, in this-application specification, said composition may be called a fine fibrous cellulose containing composition.

  The composition of the present invention comprises (A) a granular material containing fine fibrous cellulose and moisture, and (B) a non-cellulose granular material, and by setting the content of each element within a predetermined range, Excellent fluidity. Furthermore, the composition of the present invention is excellent in redispersibility in a dispersion medium in water or the like. Such an effect is due to the presence of (B) non-cellulose granular material around (A) fine fibrous cellulose and water-containing powder, and (A) fine fibrous cellulose and water-containing powder. This is considered to be obtained by improving the fluidity of the granules themselves. In addition, the composition contains a certain amount of water, and (A) a fine granular material containing fine fibrous cellulose and water is finely divided, and therefore has excellent redispersibility. it is conceivable that.

The composition of the present invention is a granular material. That is, the composition of the present invention comprises a powdery and / or granular material. Here, the powdery substance is smaller than the granular substance. In general, the powdery substance refers to fine particles having a particle diameter of 1 nm or more and less than 0.1 mm, and the granular substance refers to particles having a particle diameter of 0.1 to 10 mm, but is not particularly limited.
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 content of fine fibrous cellulose in the composition of the present invention is preferably more than 5% by mass relative to the total mass of the composition. The content of fine fibrous cellulose is preferably 10% by mass or more, more preferably 15% by mass or more, and further preferably 20% by mass or more. By making content of a fine fibrous cellulose into the said range, the fluidity | liquidity and redispersibility of a composition can be improved more effectively. Moreover, the characteristic which a fine fibrous cellulose has is easily exhibited by making content of a fine fibrous cellulose into the said range.

  The water content in the composition may be 2 to 94% by mass relative to the total mass of the composition. The water content is preferably 5 to 92% by mass, more preferably 10 to 90% by mass, still more preferably 15 to 80% by mass, and particularly preferably 20 to 80% by mass. preferable. By setting the water content within the above range, the fluidity and redispersibility of the composition can be improved more effectively.

  Content of (B) non-cellulose granular material in a composition should just be 0.1-12 mass% with respect to the total mass of a composition. (B) It is preferable that content of a non-cellulose granular material is 0.4-12 mass%, It is more preferable that it is 1-12 mass%, It is further more preferable that it is 3-10 mass%. (B) By making content of a non-cellulose granular material into the said range, the magnitude | size (cumulative median diameter) of the particle | grains in a composition can be controlled to a desired range, generation | occurrence | production of static electricity, etc. Can be suppressed. Thereby, the fluidity | liquidity of a composition can be improved effectively. Moreover, (B) By making content of a non-cellulose granular material into the said range, since the dry state of a composition can be controlled to a desired state, redispersibility can be improved effectively. .

  It is preferable that the compounding ratio (mass ratio) of the fine fibrous cellulose and the non-cellulose granular material in the composition is 1: 1 to 200: 1. By setting the blending ratio (mass ratio) of fine fibrous cellulose and non-cellulose powder within the above range, the fluidity and redispersibility of the composition can be more effectively enhanced.

The cumulative median diameter of the composition is preferably 100 to 1350 μm, more preferably 200 to 1300 μm, and even more preferably 500 to 1200 μm.
In the composition, (A) there is one or more particles of (B) non-cellulose granules around one or more particles of granules containing fine fibrous cellulose and moisture, and There is a granular body (powder body). Further, in the composition, (A) one particle or a plurality of particles of a granular material containing fine fibrous cellulose and moisture, and (B) one particle or a plurality of particles of a non-cellulose particle are present alone. That is, the cumulative median diameter of the composition is the total cumulative median diameter of all types of particles (powder particles) present in the composition.
By making the cumulative median diameter of the composition not more than the above upper limit value, the surface area of the particles contained in the composition can be in an appropriate range, the contact area with a dispersion medium such as water can be increased, and redispersion Can increase the sex. By setting the cumulative median diameter of the composition to be equal to or greater than the above lower limit value, dusting can be suppressed and fluidity can be improved. In addition, by setting the cumulative median diameter of the composition to the above lower limit value or more, it is possible to suppress unintended aggregation of particles in the composition, and to improve fluidity and redispersibility. .

The cumulative median diameter of the composition can be measured and calculated using a laser diffraction method. Specifically, the particle size is measured using a laser diffraction scattering type particle size distribution measuring device (Microtrac 3300 EXII, Nikkiso Co., Ltd.). Next, a cumulative curve is obtained by setting the total volume of the composition group as 100%, and the particle diameter at the point where the cumulative curve becomes 50% is calculated.

  The angle of repose of the composition is preferably 4 to 50 °, more preferably 5 to 45 °, still more preferably 5 to 40 °, and particularly preferably 10 to 40 °. The angle of repose is a parameter involved in the fluidity of the composition. The smaller the angle of repose tends to increase the fluidity (feedability) of the composition, but even if the angle of repose is small, if a large amount of fine particles are present in the composition, powdering occurs. The fluidity (feed property) deteriorates. That is, it is preferable that the angle of repose of the composition is within the above range, and thereby the fluidity of the composition can be effectively increased.

  The angle of repose of the composition is measured using an angle of repose measuring instrument (As One). Specifically, 100 ml of the composition is charged into a chute of an angle of repose measuring instrument, and the chute is opened to drop the composition downward. Then, the angle formed by the slope of the composition after falling and the horizontal plane is measured to obtain the angle of repose of the composition.

  The bulk density of the composition is preferably 0.1 to 0.7 g / ml, more preferably 0.2 to 0.7 g / ml, and 0.2 to 0.5 g / ml. Is more preferable. The larger the bulk density, the smaller the particle size of the particles constituting the composition. For this reason, a contact area with dispersion media, such as water, can be enlarged, and redispersibility improves. On the other hand, if the bulk density is too large, particles in the composition may cause unintended aggregation, which is not preferable. On the other hand, if the bulk density is too small, the shape of the particles becomes non-uniform and the particle size tends to increase, so that the fluidity (feedability) is deteriorated. That is, the bulk density of the composition is preferably within the above range, whereby the fluidity of the composition can be effectively increased.

The bulk density of the composition is measured using an angle of repose measuring instrument (As One). Specifically, 100 ml of the composition is charged into the chute of the angle of repose measuring instrument, the chute is opened, the composition is dropped to the lower part, and the container placed below (full volume ∨ = 50 ml) is filled and filled. . Next, the raised portion of the raised composition is cut horizontally to fill the volume. The mass of the composition remaining in the container is weighed, and the bulk density (g / ml) is calculated from the following formula.
Bulk density (g / ml) = Mass of powder (g) / Volume of powder (ml)

In order to reduce the angle of repose or increase the bulk density, it is conceivable to further reduce the water content in the composition. However, if the water content in the composition is too low, the redispersibility of the composition tends to deteriorate, such being undesirable.
Further, in order to reduce the angle of repose or increase the bulk density, it is also conceivable to increase the amount of (B) non-cellulose powder particles in the composition. However, when there is too much addition amount of a non-cellulose granular material, since the powder of (B) non-cellulose granular material occurs, it exists in the tendency for fluidity | liquidity (feed property) to deteriorate, and is unpreferable. Moreover, when the addition amount of (B) non-cellulose powder granules is increased, the viscosity of the re-dispersed liquid is increased by a large amount of non-cellulose powder granules, and re-dispersion becomes difficult.
That is, in the present invention, it is important that the blending ratio of each element such as the angle of repose, the cumulative median diameter, the bulk density and the water content, and the balance of all of these are good.

((A) Fine granules containing fine fibrous cellulose and moisture)
The composition of the present invention includes (A) a granular material containing fine fibrous cellulose and moisture.

  (A) The concentration of the fine fibrous cellulose contained in the fine fibrous cellulose and the granular material containing moisture is preferably 5% by mass or more based on the total mass of the (A) granular material, and is 10 masses. % Or more is more preferable, and 20% by mass or more is further preferable. Moreover, it is preferable that the water | moisture content contained in the granular material containing (A) fine fibrous cellulose and a water | moisture content is 2-94 mass% with respect to the total mass of (A) granular material. More preferably, it is 90 mass%, It is more preferable that it is 15-80 mass%, It is especially preferable that it is 20-80 mass%.

<Fine fibrous cellulose>
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. Examples of the pulp include wood pulp, non-wood pulp, and deinked pulp. Examples of 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. Further, semi-chemical pulps such as semi-chemical pulp (SCP) and chemiground wood pulp (CGP), mechanical pulps such as ground wood pulp (GP), and thermomechanical pulp (TMP, BCTMP) are exemplified, but not limited thereto. 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. Among the above pulps, wood pulp containing cellulose and deinked pulp are preferable in terms of availability. Among wood pulps, chemical pulp has a large cellulose ratio, so the yield of fine fibrous cellulose is high at the time of fiber refinement (defibration), and the cellulose in 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. Of these, kraft pulp and sulfite pulp are most preferably selected. Sheets containing long fibrous fine fibrous cellulose having a large axial ratio tend to provide high strength.

  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 to 1000 nm, more preferably 2 to 100 nm, more preferably 2 to 50 nm, and still more preferably 2 to 10 nm, but is not particularly limited. When 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. .

  Measurement of the average fiber width of the fine fibrous cellulose by observation with an electron microscope is performed as follows. An aqueous suspension of fine fibrous cellulose having a concentration of 0.05 to 0.1% by mass is prepared, and this suspension is cast on a carbon film-coated grid subjected to a hydrophilic treatment to obtain a sample for TEM observation. 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.

(1) One straight line X is drawn at an arbitrary location in the observation image, and 20 or more fibers intersect the straight line X.
(2) A straight line Y perpendicular to the straight line is drawn in the same image, and 20 or more fibers intersect the straight line Y.

  The width of the fiber that intersects with the straight line X and the straight line Y is visually read from the observation image that satisfies the above conditions. In this way, at least three sets of images of the surface portion that do not overlap each other are observed, and the width of the fiber intersecting with the straight line X and the straight line Y is read for each image. Thus, at least 20 × 2 × 3 = 120 fiber widths are read. 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 to 1000 μm, more preferably 0.1 to 800 μm, and particularly preferably 0.1 to 600 μm. By making the fiber length within the above range, the destruction of the crystalline region of the fine fibrous cellulose can be suppressed, and the slurry viscosity of the fine fibrous cellulose can be made an appropriate range. Note that 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. Here, the fact that the fine fibrous cellulose has a type I crystal structure can be identified in a diffraction profile obtained from a wide-angle X-ray diffraction photograph using CuKα (λ = 1.5418Å) monochromatized with graphite. Specifically, it can be identified by having typical peaks at two positions near 2θ = 14-17 ° and 2θ = 22-23 °.
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 part 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 an X-ray diffraction method 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 a conventional method (Seagal et al., Textile Research Journal, 29, 786, 1959).

<Chemical treatment>
Fine fibrous cellulose can be obtained by defibrating a cellulose raw material. Moreover, in this invention, it is preferable to perform a chemical process to a cellulose raw material and to add an ionic substituent to a fine fibrous cellulose before a fibrillation process. The ionic substituent is preferably an anionic group, and examples of the anionic group include at least one substituent selected from a phosphate group, a carboxyl group, and a sulfone group. Among them, the fine fibrous cellulose preferably has a phosphate group.

  The fine fibrous cellulose used in the present invention preferably has an ionic substituent of 0.1 to 3.5 mmol / g. The fine fibrous cellulose having the above-described ionic substituents in the above ratio is preferable in that it can be ultrafine due to the electrostatic repulsion effect. Moreover, the fine fibrous cellulose having an ionic substituent is preferable in that it does not aggregate in water due to the electrostatic repulsion effect and is stable.

<General chemical treatment>
The method of chemical treatment of the cellulose raw material is not particularly limited as long as it is a method capable of obtaining fine fibers. Examples of chemical treatment include acid treatment, ozone treatment, TEMPO (2,2,6,6-tetramethylpiperidine-1-oxyl radical) oxidation treatment, enzyme treatment, or sharing with functional groups in cellulose or fiber raw materials. And treatment with a compound capable of forming a bond. In addition, it is preferable that the fine fibrous cellulose used by this invention has a phosphoric acid group or a carboxyl group. For this reason, as a chemical treatment method, treatment with a compound having a phosphate group or a carboxyl group and / or a salt thereof is preferably performed.

Examples of acid treatment include Otto van den Berg; Jeffrey R. Capadona; Christoph Weder;
The method described in Biomacromolecules 2007, 8, 1353-1357. Can be mentioned. Specifically, the fine fibrous cellulose is hydrolyzed with sulfuric acid, hydrochloric acid, or the like. Those produced by high-concentration acid treatment are almost decomposed in non-crystalline regions and have short fibers (also called cellulose nanocrystals), which are also included in fine fibrous cellulose.

  As an example of the ozone treatment, a method described in JP 2010-254726 A can be exemplified, but it is not particularly limited. Specifically, after the fiber is treated with ozone, it is dispersed in water, and the resulting aqueous suspension of the fiber is pulverized.

  An example of TEMPO oxidation includes the method described in Saito T & al. Homogeneous suspensions of individualized microfibrils from TEMPO-catalyzed oxidation of native cellulose. Biomacromolecules 2006, 7 (6), 1687-91. Specifically, after the fiber is subjected to TEMPO oxidation treatment, it is dispersed in water, and the aqueous suspension of the obtained fiber is pulverized.

  As an example of the enzyme treatment, the method described in WO2013 / 176033 (all contents described in WO2013 / 176033 shall be cited in the present specification) can be mentioned, but is not particularly limited. . Specifically, the fiber raw material is treated with an enzyme at least under a condition where the ratio of the enzyme EG activity to the CBHI activity is 0.06 or more.

  The treatment with a compound capable of forming a covalent bond with a functional group in cellulose or a fiber raw material is described in International Publication WO2013 / 073652 (PCT / JP2012 / 079743) “an oxo acid containing a phosphorus atom in its structure, And a method using at least one compound selected from polyoxoacids or salts thereof.

<Introduction of anionic substituent>
The fine fibrous cellulose preferably has an anionic group. Among these, the anionic group is preferably at least one selected from a phosphate group (sometimes referred to as a phosphate ester group), a carboxyl group, and a sulfone group, and at least selected from a phosphate group and a carboxyl group. One type is more preferable, and a phosphate group is particularly preferable.

<Introduced amount of substituent>
The amount of ionic substituent introduced is not particularly limited, but is preferably 0.1 to 3.5 mmol / g, more preferably 0.14 to 2.5 mmol / g, per 1 g (mass) of fine fibrous cellulose. 0.2 to 2.0 mmol / g is more preferable, and 0.2 to 1.8 mmol / g is particularly preferable. By making the introduction amount of the ionic substituent within the above range, the fiber raw material can be easily refined, and the stability of the fine fibrous cellulose can be enhanced. Moreover, the viscosity of the slurry of fine fibrous cellulose can be adjusted to an appropriate range by setting the introduction amount of the ionic substituent within the above range.

<Introduction of phosphate group>
In the present invention, the fine fibrous cellulose preferably has a substituent derived from phosphoric acid such as a phosphate group (sometimes simply referred to as a phosphate group).

<Phosphate group introduction process>
The phosphoric acid group introduction step can be performed by reacting a fiber material containing cellulose with a compound having a phosphoric acid group and / or a salt thereof (hereinafter referred to as “compound A”). This reaction may be performed in the presence of urea and / or a derivative thereof (hereinafter referred to as “compound B”), whereby a phosphate group can be introduced into the hydroxyl group of the fine fibrous cellulose. .

  The phosphate group introduction step necessarily includes a step of introducing a phosphate group into cellulose, and may include an alkali treatment step described later, a step of washing excess reagent, and the like as desired.

  As an example of a method for causing compound A to act on a fiber raw material in the presence of compound B, a method of mixing powder or an aqueous solution of compound A and compound B with a dry or wet fiber raw material can be mentioned. 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. Among these, since the uniformity of the reaction is high, 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 The method is preferred. Moreover, the compound A and the compound B may be added simultaneously, or may be added separately. Moreover, you may add the compound A and the compound B first used for reaction as aqueous solution, and remove an excess chemical | medical solution by pressing. 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 a compound having a phosphate group and / or a salt thereof.
Examples of 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. Examples of 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.

  Among these, phosphoric acid, sodium phosphate, from the viewpoint of high phosphate group introduction efficiency, easy defibration efficiency in the defibration process described later, low cost, and easy industrial application. A salt, or a potassium salt of phosphoric acid or an ammonium salt of phosphoric acid is preferable. Sodium dihydrogen phosphate or disodium hydrogen phosphate is more preferable.

  In addition, compound A is preferably used as an aqueous solution because the uniformity of the reaction is increased and the efficiency of introduction of phosphate groups 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 phosphoric acid groups is high, and more preferably 3 to 7 from the viewpoint of suppressing 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 a phosphorus atomic weight, the amount of phosphorus atom added to the fiber raw material is preferably 0.5 to 100% by weight, and 1 to 50% by weight. % Is more preferable, and 2 to 30% by mass is most preferable. 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 following lower limit.

  Examples of the compound B used in this embodiment include urea, thiourea, biuret, phenylurea, benzylurea, dimethylurea, diethylurea, tetramethylurea, benzoleinurea, and hydantoin. Among these, urea is preferable because it is easy to handle at low cost and easily forms a hydrogen bond with a fiber raw material having a hydroxyl group.

  Compound B is preferably used as an aqueous solution in the same manner as 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 to 300% by mass.

  In addition to Compound A and Compound B, amides or amines may be included in the reaction system. Examples of amides include formamide, dimethylformamide, acetamide, dimethylacetamide and the like. Examples of 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.

<Introduction amount of phosphate group>
The amount of phosphate groups introduced is preferably 0.1 to 3.5 mmol / g, more preferably 0.14 to 2.5 mmol / g, and more preferably 0.2 to 2 per 1 g (mass) of fine fibrous cellulose. 0.0 mmol / g is more preferable, 0.2 to 1.8 mmol / g is more preferable, 0.4 to 1.8 mmol / g is particularly preferable, and 0.6 to 1.8 mmol / g is most preferable. By making the introduction amount of the phosphoric acid group within the above range, the fiber raw material can be easily refined, and the stability of the fine fibrous cellulose can be enhanced. Moreover, the viscosity of the slurry of a fine fibrous cellulose can be adjusted to an appropriate range by making the introduction amount of phosphoric acid groups within the above range.

  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.

  In conductivity titration, when alkali is added, the curve shown in FIG. 1 is given. Initially, the electrical conductivity rapidly decreases (hereinafter referred to as “first region”). Thereafter, the conductivity starts to increase slightly (hereinafter referred to as “second region”). Thereafter, the conductivity increment increases (hereinafter referred to as “third region”). That is, three areas appear. Among these, the amount of alkali required in the first region is equal to the amount of strongly acidic groups in the slurry used for titration, and 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. When the phosphoric acid group undergoes condensation, apparently weakly acidic groups are lost, and the amount of alkali required in the second region is reduced compared to the amount of alkali required in the first region. On the other hand, 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.

<Introduction of carboxyl group>
In the present invention, when the fine fibrous cellulose has a carboxyl group, it is possible to introduce a carboxyl group by using a compound having a group derived from a carboxylic acid in the above-described <phosphate group introduction step>. it can.

  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. It is done.

  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.

  Although it does not specifically limit as a derivative of the compound which has a carboxyl group, The derivative of the acid anhydride of the compound which has a carboxyl group and the acid anhydride imidation of a compound which has a carboxyl group are mentioned. 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. For example, 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.

  Among the compounds having a group derived from a carboxylic acid, maleic anhydride, succinic anhydride, and phthalic anhydride are preferred because they are easily applied industrially and easily gasified, but are not particularly limited.

<Cationic substituent introduction>
In this embodiment, a cationic substituent may be introduced into the fine fibrous cellulose as an ionic substituent. For example, 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 causing the fiber raw material to react.
As the cationizing agent, one having a quaternary ammonium group and a group that reacts with a hydroxyl group of cellulose can be used. Examples of 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. Specific examples of 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>
In the case of producing fine fibrous cellulose, alkali treatment can be performed between the substituent introduction step and the defibration treatment step described later. Although it does not specifically limit as a method of an alkali treatment, For example, the method of immersing a phosphate group introduction | transduction fiber in an alkaline solution is mentioned.
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.
Of the alkaline solutions, a sodium hydroxide aqueous solution or a potassium hydroxide aqueous solution is particularly preferred because of its high versatility.

Although the temperature of the alkali solution in an alkali treatment process is not specifically limited, 5-80 degreeC is preferable and 10-60 degreeC is more preferable.
Although the immersion time in the alkaline solution in the alkali treatment step is not particularly limited, it is preferably 5 to 30 minutes, and more preferably 10 to 20 minutes.
Although the usage-amount of the alkaline solution in an alkali treatment is not specifically limited, It is preferable that it is 100-100000 mass% with respect to the absolute dry mass of a phosphate group introduction | transduction fiber, and it is more preferable that it is 1000-10000 mass%.

  In order to reduce the amount of alkaline solution used in the alkali treatment step, the phosphate group-introduced fiber may be washed with water or an organic solvent before the alkali treatment step. After 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.

<Defibration processing>
The ionic substituent-introduced fiber is defibrated in the defibrating process. 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.
As the 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. Alternatively, as a defibrating apparatus, 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 worried about contamination.

  In the defibrating process, it is preferable to dilute the fiber raw material with water and an organic solvent alone or in combination to form a slurry, but there is no particular limitation. As the dispersion medium, in addition to water, a polar organic solvent can be used. Preferable polar organic solvents include alcohols, ketones, ethers, dimethyl sulfoxide (DMSO), dimethylformamide (DMF), dimethylacetamide (DMAc), and the like, but are not particularly limited. Examples of alcohols include methanol, ethanol, n-propanol, isopropanol, n-butanol, and t-butyl alcohol. Examples of ketones include acetone and methyl ethyl ketone (MEK). Examples of ethers include diethyl ether and tetrahydrofuran (THF). 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.

  In the present invention, the fibrillation treatment may be performed after the fine fibrous cellulose is concentrated and dried. In this case, 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. Moreover, a well-known method, for example, the method described in WO2014 / 024876, WO2012 / 107642, and WO2013 / 121086 can be used. Further, the concentrated fine fibrous cellulose may be formed into a sheet. The sheet can be pulverized to perform a defibrating process.

  The equipment used for pulverization of fine fibrous cellulose includes high-speed defibrator, grinder (stone mill type pulverizer), high-pressure homogenizer, ultra-high pressure homogenizer, high-pressure collision type pulverizer, ball mill, bead mill, disk type refiner, conical An apparatus for wet pulverization such as a refiner, a twin-screw kneader, a vibration mill, a homomixer under high-speed rotation, an ultrasonic disperser, a beater, and the like can be used, but is not particularly limited.

<Other ingredients>
(A) The granular material containing fine fibrous cellulose and moisture may contain other components in addition to the fine fibrous cellulose and moisture. Examples of other components include water-soluble polymers and surfactants. Examples of 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) Hydroxyethyl cellulose, etc.), cationized starch, raw starch, oxidized starch, etherified starch, esterified starch, starch such as amylose, glycerins such as glycerin, diglycerin, polyglycerin, etc., hyaluronic acid, hyaluronic acid A metal salt etc. can be mentioned. Moreover, as a surfactant, a nonionic surfactant, an anionic surfactant, and a cationic surfactant can be used.

((B) non-cellulose powder)
The composition of the present invention comprises (B) a non-cellulose powder. The non-cellulose granular material is a granular material containing 1% by mass or less of cellulose with respect to the total mass of the non-cellulose granular material, and is preferably a granular material having a cellulose content of 0% by mass.
Non-cellulose granules consist of powdered and / or granular materials. Here, the powdery substance is smaller than the granular substance, and is a fine particle having a particle diameter of 1 nm or more and less than 0.1 mm. Moreover, a granular material means a particle | grain with a particle diameter of 0.1-10 mm. The particle diameter can be calculated by a method similar to the method described in the item “(A) Fine granular material containing fine fibrous cellulose and moisture”.

Especially, it is preferable that (B) non-cellulose granular material is a powdery substance. Examples of (B) non-cellulose powders include inorganic fine particles and organic fine particles.
Examples of the inorganic fine particles include, but are not limited to, fine particles composed of metals, glass fibers, rock components, inorganic compounds, components produced by chemical synthesis, and the like. For example, zeolite, light calcium carbonate, heavy calcium carbonate, magnesium carbonate, kaolin, talc, calcium sulfate, barium sulfate, titanium oxide, zinc oxide, zinc sulfide, zinc carbonate, satin white, carbon black, aluminum silicate, diatomaceous earth , Calcium silicate, magnesium silicate, silica, aluminum hydroxide, alumina, alumina hydrate, aluminosilicate, boehmite, pseudoboehmite, iron oxide and the like.
Examples of the organic fine particles include, but are not limited to, fine particles composed of a resin, a component derived from a natural product, a saccharide, a component produced by chemical synthesis, and the like. For example, acrylic resin, polystyrene, polysiloxane, melamine resin, benzoguanamine resin, polytetrafluoroethylene, polycarbonate, polyamide, chitin, chitosan, dextrin, oligosaccharide, wheat starch, rice starch, corn starch, potato starch, dextrin, cyclodextrin And microparticles such as lactose, glucose, sugar, reduced maltose, sorbitol, erythritol, xylitol, lactitol, mannitol, lactic acid bacteria, and casein.
The above-mentioned fine particles are preferably used alone, but a plurality of them may be used in combination.

(B) It is preferable that the primary average particle diameter of a non-cellulose granular material is 3-2000 nm, It is more preferable that it is 5-500 nm, It is further more preferable that it is 5-50 nm. Also, (B) a specific surface area by the BET method of the non-cellulosic granular material is preferably 20 to 500 m ² / g, more preferably 30 to 400 m ² / g, with 50 to 300 m ² / g More preferably it is. (B) The fluidity | liquidity of a composition can be improved more effectively by making the primary average particle diameter and specific surface area of a non-cellulose granular material into the said range.

In the present invention, inorganic fine particles are preferably used as the non-cellulose powder (B), and hydrophobic inorganic fine particles are more preferably used. In the present invention, the hydrophobic inorganic fine particles are preferably fine particles having a carbon atom content of 1.0% by mass or more, and more preferably inorganic fine particles having a hydrophobic group. The carbon atom content in the hydrophobic inorganic fine particles is preferably 1.5 to 10% by mass or more, and more preferably 1.5 to 7% by mass or more.
Examples of the hydrophobic group include a group having a hydrocarbon group that does not have a polar group. Examples of the group having a hydrocarbon group include an alkyl group and a phenyl group. Examples of the group having a hydrocarbon group include an alkylsilyl group and a group having a siloxane bond. Examples of the alkylsilyl group include a trimethylsilyl group, a triethylsilyl group, and a triisopropylsilyl group. Examples of the group having a siloxane bond include a dimethylpolysiloxane group.

  Among these, (B) the non-cellulose powder is preferably silica fine particles, and more preferably hydrophobic silica fine particles. The hydrophobic silica fine particles are preferably silica fine particles having a hydrophobic group, and examples of the hydrophobic group include the groups described above. Among these, it is preferable to use silica fine particles having a trimethylsilyl group or silica fine particles having a dimethylpolysiloxane group.

  Hydrophobicity may be imparted by performing a surface treatment on the inorganic fine particles using a surface treatment agent. Preferred surface treatment agents include, for example, silane coupling agents, silylating agents, silane coupling agents having an alkyl fluoride group, organic titanate coupling agents, aluminum coupling agents, silicone oils, modified silicone oils, and the like. Can be mentioned.

(Other ingredients)
The composition of the present invention may further contain a hygroscopic agent. Examples of the moisture absorbent 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, acetic acid. Examples include potassium, dibasic sodium phosphate, sodium citrate, and a water-absorbing polymer.

  The composition of the present invention may further contain other components. Examples of other components include water-soluble polymers and surfactants. Examples of 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, oxidized starch, etherified starch, esterified starch, starch such as amylose, glycerol such as glycerin, diglycerin, polyglycerin, etc., hyaluronic acid, hyaluronic acid A metal salt etc. can be mentioned. Moreover, as a surfactant, a nonionic surfactant, an anionic surfactant, and a cationic surfactant can be used.

(Method for producing composition)
The present invention includes a step of obtaining a slurry of fine fibrous cellulose, a step of concentrating the slurry containing fine fibrous cellulose, and (A) obtaining a granular material (concentrate) containing fine fibrous cellulose and moisture; The present invention relates to a method for producing a composition comprising: A) a granular material (concentrate) containing fine fibrous cellulose and moisture, and (B) a step of mixing non-cellulose granular material.

  The step of obtaining a fine fibrous cellulose slurry preferably includes a chemical treatment step and a defibration treatment step as described above. If necessary, other steps such as an alkali treatment step may be provided between the chemical treatment and the defibration treatment step.

  The step of concentrating the slurry containing fine fibrous cellulose and (A) obtaining a granular material (concentrate) containing fine fibrous cellulose and moisture (hereinafter also referred to as the concentration step) is performed in the slurry of fine fibrous cellulose. In this step, a part of the water is removed to obtain a concentrate. In this step, since a part of the water remains in the concentrate, the concentrate contains water and fine fibrous cellulose.

  In the concentration step, it is preferable to add a concentration agent to the slurry of fine fibrous cellulose to perform gelation. Examples of the thickener include acids, alkalis, polyvalent metal salts, cationic surfactants, anionic surfactants, cationic polymer flocculants, anionic polymer flocculants and the like. Among these, the concentration agent is preferably a polyvalent metal salt. Examples of the polyvalent metal salt include aluminum sulfate (sulfuric acid band), polyaluminum chloride, calcium chloride, aluminum chloride, magnesium chloride, calcium sulfate, magnesium sulfate and the like.

  In the concentration step, it is preferable to perform filtration after adding the concentration agent. The filtration treatment step preferably includes a compression step. By providing such a compression step, the water content in the concentrate can be adjusted to a preferred range.

The filter medium used in the filtration process is not particularly limited, and filter media such as stainless steel, filter paper, polypropylene, nylon, polyethylene, and polyester can be used. Since an acid may be used, a polypropylene filter medium is preferable. The lower the air permeability of the filter medium, the higher the yield. Therefore, it is 30 cm ³ / cm ² · sec or less, more preferably 10 cm ³ / cm ² · sec or less, and further preferably 1 cm ³ / cm ² · sec or less.
In the compression step, a squeezing device may be used. As such an apparatus, a general press apparatus such as a belt press, a screw press, or a filter press can be used, and the apparatus is not particularly limited.
The concentration of the slurry used for the compression step is preferably 0.5% by mass or more, more preferably 1% by mass or more, and further preferably 2% by mass or more. By making the density | concentration of the slurry used for a compression process in the said range, the increase in a dehydration filtrate can be suppressed and a dehydration process can be performed efficiently. The pressure during compression is preferably 0.2 MPa or more, and more preferably 0.4 MPa or more.

The concentration step may further include an acid treatment step. The acid treatment step is preferably provided before and after the filtration treatment step and the like, and is preferably provided after the filtration treatment step. When the acid treatment step is provided after the filtration treatment step, the acid treatment step may be an acid washing step for removing the concentration agent.
In the acid treatment step, for example, inorganic acids (sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, etc.), organic acids (formic acid, acetic acid, citric acid, malic acid, lactic acid, adipic acid, sebacic acid, stearic acid, maleic acid, succinic acid , Tartaric acid, fumaric acid, gluconic acid and the like). Specifically, it is preferable to immerse the concentrate obtained in the above-described step in the acidic solution. The concentration of the acidic solution to be used is not particularly limited, but is preferably 10% or less, more preferably 5% or less, and still more preferably 1% or less. By setting the concentration of the acidic liquid in the above range, deterioration due to decomposition of cellulose can be suppressed.

  Furthermore, it is preferable to perform filtration after the acid treatment step. In this filtration treatment step, a compression step may be further performed.

  In the concentration step, a drying step may be further provided. When providing a drying process, it is preferable to provide after an acid treatment process. The drying step is preferably an oven drying step, and for example, drying is preferably performed for 1 to 60 minutes in an oven set to 30 to 70 ° C.

  The solid concentration of the concentrate obtained in the concentration step is preferably 5% by mass or more, more preferably 10% by mass or more, and further preferably 20% by mass or more.

  In the concentration step, dehydration with an organic solvent may be used as a concentration method. After concentration using an organic solvent, a drying step may be provided. By drying after treating with an organic solvent, hydrogen bonding of fine fibrous cellulose can be suppressed, which is preferable from the viewpoint of redispersibility.

  Examples of the organic solvent are not particularly limited and can include the following: methanol, ethanol, 1-propanol (n-propanol), 1-butanol (n-butanol), 2-butanol, isobutyl alcohol, isopropyl alcohol (Isopropanol, 2-propanol), isopentyl alcohol (isoamyl alcohol), t-butyl alcohol (2-methyl-2-propanol), 1,2-dioxane, 1,3-dioxane, 1,4-dioxane, tetrahydrofuran ( THF), acetone, methyl isobutyl ketone, methyl ethyl ketone (MEK)), methyl cyclohexanol, methyl cyclohexanone, methyl normal-butyl ketone, ethyl ether (diethyl ether), ethylene glycol monoethyl ether (Cellosolve), ethylene glycol monoethyl ether acetate (cellosolve acetate), ethylene glycol mono-normal-butyl ether (butyl cellosolve), ethylene glycol monomethyl ether (methyl cellosolve), dimethyl sulfoxide (DMSO), dimethylformamide (DMF, N, N- Dimethylformamide), dimethylacetamide (DMAc, DMA, N, N-dimethylacetamide), ortho-dichlorobenzene, xylene, cresol, chlorobenzene, isobutyl acetate, isopropyl acetate, isopentyl acetate (isoamyl acetate), ethyl acetate, normal acetate -Butyl, normal-propyl acetate, normal-pentyl acetate (normal-amyl acetate), methyl acetate, cyclohexanol, cyclohexane Sanone, dichloromethane (methylene dichloride), styrene, tetrachloroethylene (perchlorethylene), 1,1,1-trichloroethane, toluene, normal hexane, chloroform, carbon tetrachloride, 1,2-dichloroethane (ethylene dichloride) 1,2-dichloroethylene (acetylene dichloride), 1,1,2,2-tetrachloroethane (acetylene tetrachloride), trichloroethylene, carbon disulfide, gasoline, coal tar naphtha (including solvent naphtha). , Petroleum ether, petroleum naphtha, petroleum benzine, turpentine, mineral spirits (including mineral thinners, petroleum spirits, white spirits and mineral terpenes).

  Further, examples of the organic solvent are not particularly limited, but those having miscibility with water are preferable, and those having polarity are more preferable. Preferable examples of the organic solvent having polarity include alcohols, dioxanes (1,2-dioxane, 1,3-dioxane, 1,4-dioxane), tetrahydrofuran (THF) and the like, but are not particularly limited. Specific examples of alcohols are methanol, ethanol, n-propanol, isopropanol, n-butanol, t-butyl alcohol, and the like. Preferable examples of organic solvents having other polarities include ketones, ethers, dimethyl sulfoxide (DMSO), dimethylformamide (DMF), dimethylacetamide (DMAc), and the like. Examples of ketones include acetone and methyl ethyl ketone (MEK). Examples of ethers include diethyl ether and tetrahydrofuran (THF). When selecting the organic solvent, the solubility parameter value (SP value) may be taken into consideration. It is empirically known that the smaller the difference between the SP values of the two components, the greater the solubility. Therefore, from the viewpoint of good miscibility with water, an organic solvent having an SP value close to water is selected. can do.

  Concentration or drying may be performed by combining a thickener and an organic solvent. Although the process order is not particularly limited, it is preferable to perform treatment with an organic solvent after concentration with a concentrating agent because the amount of the organic solvent used can be reduced.

  When concentration or drying is performed by combining a concentration agent and an organic solvent, it is preferable to use a concentration agent to increase the concentration of fine fibrous cellulose to 5% by mass or more prior to the addition of the organic solvent. More preferably, it is more preferably 20% by mass or more. By setting the fine fibrous cellulose concentration within the above range, the necessary amount of the organic solvent is suppressed, which is preferable.

An alkaline or acidic solution may be added before or after the treatment with the organic solvent, or during the treatment. When the concentrate is redispersed by adding an alkaline solution, the fine fibrous cellulose is increased in charge and easily redispersed. It is preferable to add the concentrate in the presence of an organic solvent because the concentrate swells by adding an alkaline solution and the concentration degree may deteriorate. An organic solvent can suppress swelling.
Acidic solutions are used to remove the concentrate from the fine fibrous cellulose concentrate or dried product, but the presence of the organic solvent causes the fine fibrous cellulose concentrate or dried product to swell in the presence of the organic solvent. Can be suppressed.

  The amount of the organic solvent used when the concentrating agent and the organic solvent are used is not particularly limited, but is preferably 100 to 100,000% by mass, more preferably 100 to 10000% by mass with respect to the absolutely dry mass of the fine fibrous cellulose. Is more preferable, and it is further more preferable that it is 100-1000 mass%. By setting the amount of the organic solvent used within the above range, it is preferable because the swelling suppression effect can be sufficiently obtained while suppressing the amount of the organic solvent used.

  One type of these thickeners may be used, or two or more types may be used in combination. Examples of the drying method include a method using a commonly used dryer.

(A) The granular material containing fine fibrous cellulose and moisture, and (B) the step of mixing non-cellulose granular material (hereinafter, also referred to as mixing step) is (A) the granular material containing fine fibrous cellulose and moisture. In this step, (B) non-cellulose powder is added to the product, followed by stirring and mixing. In the mixing step, it is preferable to perform stirring and mixing using a stirrer.
In the mixing step, it is also possible to employ a method in which (A) a granular material containing fine fibrous cellulose and moisture is dispersed again in the solution and then the non-cellulose granular material is added. In the mixing step, it is preferable to employ a method in which (A) the flowability of the fine granular cellulose and water-containing granular material is ensured, and the non-cellulose granular material can be stirred uniformly.

  A fine fibrous cellulose containing composition is obtained by passing through said process. The storage temperature of this composition is preferably 4 to 40 ° C, more preferably 4 to 30 ° C. The pressure is preferably stored at normal pressure. The humidity is preferably 70% or less, and more preferably 60% or less.

  When the fine fibrous cellulose-containing composition is stored, it is preferably added to a bag such as an aluminum pouch or a container that can be sealed, and stored after sealing. Aluminum pouches and sealed containers can be transported as they are.

<Redispersion>
The fine fibrous cellulose-containing composition obtained in the steps described above is preferably used by being redispersed in a solvent such as water. Although 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. Examples of 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, and ethylene glycol mono t-butyl ether.

  Redispersion of the fine fibrous cellulose-containing composition can be performed by a conventional method. For example, a step of adding a solvent to the fine fibrous cellulose-containing composition to prepare a liquid containing the fine fibrous cellulose-containing composition, and a fine fibrous form in the liquid containing the fine fibrous cellulose-containing composition Redispersion can be performed by the step of dispersing cellulose.

  As the dispersing device used in the step of dispersing the fine fibrous cellulose in the liquid containing the fine fibrous cellulose-containing composition, the same device as the defibrating treatment device described in the above <defibrating treatment> may be used. Good.

(Use)
The use of the fine fibrous cellulose-containing composition of the present invention is not particularly limited. The fine fibrous cellulose-containing composition is preferably used as a thickener, for example. In this case, the re-dispersed slurry of the fine fibrous cellulose-containing composition can be used as a thickener for various uses (for example, additives to food, cosmetics, cement, paint, ink, etc.). Moreover, it can also mix with resin and emulsion and can also be used for the use as a reinforcing material. Furthermore, it can form into a film using fine fibrous cellulose redispersion slurry, and can also be used as various films.

  The features of the present invention will be described more specifically with reference to examples and comparative examples. The materials, amounts used, ratios, processing details, processing procedures, and the like shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be construed as being limited by the specific examples shown below.

[Production Example 1]
Production of Fine Fibrous Cellulose 1 (CNF1) 100 g of urea, 55.3 g of sodium dihydrogen phosphate dihydrate, and 41.3 g of disodium hydrogen phosphate were dissolved in 109 g of water to prepare a phosphorylating reagent.
The dried softwood bleached kraft pulp paper was processed with a cutter mill and a pin mill to form cotton-like fibers. 100 g of this cotton-like fiber was taken in absolute dry mass, and the phosphorylating reagent was sprayed evenly with a spray, and then kneaded by hand to obtain a chemical-impregnated pulp.
The obtained chemical-impregnated pulp was heat-treated for 160 minutes in a blower dryer with a damper heated to 140 ° C. to obtain phosphorylated pulp.

The obtained phosphorylated pulp was fractionated by 100 g, and 10 L of ion-exchanged water was poured, stirred and dispersed uniformly, and then subjected to filtration and dehydration to obtain a dehydrated sheet, which was repeated twice. Next, 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 to 13. 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. An infrared absorption spectrum of the obtained dehydrated sheet was measured by FT-IR. As a result, absorption based on phosphate groups was observed at 1320 to 1290 cm ⁻¹ , confirming the addition of phosphate groups. Therefore, the obtained dehydrated sheet (phosphoric acid oxyacid-introduced cellulose) was one in which a part of the hydroxyl group of cellulose was substituted with the functional group of the following structural formula (1).

In the formula, a, b, m and n each independently represent a natural number (where a = b × m). α ¹ , α ² ,..., α ⁿ and α ′ each independently represent R or OR. 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. , Aromatic groups, and any of these derived groups. β is a monovalent or higher cation composed of an organic substance or an inorganic substance.

Ion exchange water was added to the obtained phosphorylated cellulose to prepare a 0.5 mass% slurry. This slurry was defibrated for 30 minutes under a condition of 21500 rotations / minute using a defibrating apparatus (Cleamix-2.2S, manufactured by M Technique Co., Ltd.) to obtain a cellulose 1 suspension.
This cellulose 1 suspension was further treated once with a wet atomizer ("Ultimizer" manufactured by Sugino Machine Co., Ltd.) at a pressure of 245 MPa to obtain fine fibrous cellulose 1 (CNF1). By X-ray diffraction, fine fibrous cellulose 1 (CNF1) maintained a cellulose type I crystal.

(Measurement of phosphate group introduction amount (substituent amount))
The amount of substituent introduction is the amount of phosphate groups introduced into the fiber material, and the larger this value, the more phosphate 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. Thereafter, the mixture was poured onto a mesh having an opening of 90 μm to separate the resin and the slurry. In titration using an alkali, a change in the value of electrical conductivity exhibited by the slurry was measured while adding a 0.1N sodium hydroxide aqueous solution to the fibrous cellulose-containing slurry after ion exchange. That is, the alkali amount (mmol) required in the first region of the curve shown in FIG. 1 was divided by the solid content (g) in the titration target slurry to obtain the substituent introduction amount (mmol / g).

[Production Example 2]
Production of fine fibrous cellulose 2 (CNF2) Undried softwood bleached kraft pulp equivalent to a dry mass of 200 g, TEMPO 2.5 g, and sodium bromide 25 g were dispersed in 1500 ml of water. Then, 13 mass% sodium hypochlorite aqueous solution was added so that the quantity of sodium hypochlorite might be set to 5.0 mmol with respect to 1.0 g of pulp, and reaction was started. During the reaction, a 0.5 M aqueous sodium hydroxide solution was added dropwise to maintain the pH at 10 to 11, and the reaction was terminated when no change in pH was observed.
Thereafter, the pulp slurry was dehydrated to obtain a dehydrated sheet, and then 10 L of ion exchange water was added. Next, after stirring and uniformly dispersing, the process of dewatering by filtration to obtain a dehydrated sheet was repeated twice. An infrared absorption spectrum of the obtained dehydrated sheet was measured by FT-IR. As a result, absorption based on a carboxyl group was observed at 1730 cm ⁻¹ , confirming the addition of a carboxyl group. Using this dehydrated sheet (TEMPO oxidized cellulose), fine fibrous cellulose was prepared.

Ion exchange water was added to the TEMPO-oxidized cellulose to which the carboxyl group was added as described above to prepare a slurry of 0.5% by mass. This slurry was defibrated for 30 minutes at 21500 rpm using a defibrating apparatus (Cleamix-2.2S, manufactured by MTechnic Co., Ltd.) to obtain a cellulose 2 suspension.
This cellulose 2 suspension was further treated 10 times at a pressure of 245 MPa with a wet atomizer (“Ultimizer” manufactured by Sugino Machine Co., Ltd.) to obtain fine fibrous cellulose 2 (CNF2). By X-ray diffraction, fine fibrous cellulose 2 (CNF2) maintained the cellulose I type crystal.

<Measurement of fiber width>
The fiber width of the fine fibrous cellulose 1 and 2 was measured by the following method.
The supernatant liquid of the defibrated pulp slurry was diluted with water to a concentration of 0.01 to 0.1% by mass and dropped onto a hydrophilic carbon grid membrane. After drying, it was stained with uranyl acetate and observed with a transmission electron microscope (JEOL-2000EX, manufactured by JEOL Ltd.). In Production Examples 1 and 2, it was confirmed that the fine fibrous cellulose had a width of about 4 nm.

  About the crystallinity degree of the fine fibrous cellulose 1 and 2, it measured using the X-ray-diffraction apparatus and calculated | required from the following formula. The “crystallization index” in the formula below is also referred to as “crystallinity”.

Cellulose type I crystallization index (%) = [(I22.6-I18.5) /I22.6] × 100 (1)
[I22.6 is the diffraction intensity of the grating plane (002 plane) (diffraction angle 2θ = 22.6 °) in X-ray diffraction, and I18.5 is the diffraction of the amorphous part (diffraction angle 2θ = 18.5 °). Indicates strength. ]
0.45 ≦ αω (m · rad / sec) (2)
[Α represents a half amplitude (m), and ω represents an angular velocity (rad / sec). ].

  The amount of substituents and crystallinity of the fine fibrous celluloses 1 and 2 are shown in Table 1.

<Example 1>
The solution was diluted in water so that the solid content concentration of CNF1 was 0.4% by mass. 1 g of calcium chloride was added as a concentrating agent to 100 ml of this diluted solution to cause gelation. The gel was filtered and then compressed with filter paper for 2 minutes to obtain a concentrate having a solid content concentration of 21.4% by mass. This concentrate was immersed in 100 ml of 0.1N hydrochloric acid aqueous solution for 30 minutes and then filtered to obtain a concentrate having a solid content concentration of 21.2% by mass. The balance other than the solid content of the concentrate is moisture.
3.8 parts by mass of silica (AEROSIL (registered trademark) R 812 S (Nippon Aerosil), hereinafter referred to as "silica A")) was added to 96.2 parts by mass of the concentrate, and the mixture was stirred with a mixer. Thus, the fine fibrous cellulose containing composition of Example 1 was obtained.

<Example 2>
In Example 1, a concentrate was obtained in the same manner as in Example 1 except that the compression time on the filter paper was changed to 30 seconds. The solid content concentration of the concentrate was 4.1% by mass. This concentrate was immersed in 100 mL of a 0.1N hydrochloric acid aqueous solution for 30 minutes and then filtered to obtain a concentrate having a solid content concentration of 5.6% by mass. The subsequent treatment was the same as in Example 1, and the fine fibrous cellulose-containing composition of Example 1 was obtained.

<Example 3>
In Example 1, a concentrate was obtained in the same manner as in Example 1 except that the compression time on the filter paper was changed to 60 seconds. The solid content concentration of the concentrate was 8.1% by mass. This concentrate was immersed in 100 mL of a 0.1N hydrochloric acid aqueous solution for 30 minutes and then filtered to obtain a concentrate having a solid content concentration of 10.5% by mass. The subsequent treatment was the same as in Example 1, and the fine fibrous cellulose-containing composition of Example 3 was obtained.

<Example 4>
A concentrate was obtained in the same manner as in Example 1. The solid content concentration of the concentrate was 21.4% by mass. This concentrate was immersed in 100 mL of a 0.1N hydrochloric acid aqueous solution for 30 minutes and then filtered to obtain a concentrate having a solid content concentration of 21.2% by mass. This concentrate was heat-treated in an oven at 60 ° C. for 15 minutes to obtain a concentrate having a solid content concentration of 31.2% by mass. 3.8 parts by mass of silica (AEROSIL (registered trademark) R 812 S, manufactured by Nippon Aerosil Co., Ltd., hereinafter referred to as “silica A”) was added to 96.2 parts by mass of the concentrate, and the mixture was stirred with a mixer. . Thus, the fine fibrous cellulose containing composition of Example 4 was obtained.

<Example 5>
The fine fibrous cellulose-containing composition of Example 5 was obtained in the same manner as in Example 4 except that the heating time in an oven at 60 ° C. was 25 minutes and a concentrate having a solid content concentration of 42.2% by mass was obtained. It was.

<Example 6>
The fine fibrous cellulose-containing composition of Example 6 was obtained in the same manner as in Example 4 except that the heating time in an oven at 60 ° C. was 35 minutes and a concentrate with a solid content concentration of 50.3% by mass was obtained. It was.

<Example 7>
The fine fibrous cellulose-containing composition of Example 7 was obtained in the same manner as in Example 4 except that the heating time in an oven at 60 ° C. was 45 minutes and a concentrate having a solid content concentration of 63.5% by mass was obtained. It was.

<Example 8>
The fine fibrous cellulose-containing composition of Example 8 was obtained in the same manner as in Example 4 except that the heating time in an oven at 60 ° C. was 50 minutes and a concentrate having a solid content concentration of 94.1% by mass was obtained. It was.

<Example 9>
The solution was diluted in water so that the solid content concentration of CNF2 was 0.4% by mass. 1 g of calcium chloride was added as a concentrating agent to 100 ml of this diluted solution to cause gelation. The gel was filtered and then compressed with filter paper for 2 minutes to obtain a concentrate having a solid content concentration of 19.8% by mass. This concentrate was immersed in 100 ml of 0.1N aqueous hydrochloric acid for 30 minutes and then filtered to obtain a concentrate having a solid content concentration of 20.2% by mass. The subsequent treatment was the same as in Example 1, and the fine fibrous cellulose-containing composition of Example 9 was obtained.

<Example 10>
Except having changed the silica A into the silica B (AEROSIL (trademark) 200, Nippon Aerosil Co., Ltd. make), it was all the same as that of Example 1, and the fine fibrous cellulose containing composition of Example 10 was obtained.

<Example 11>
A fine fibrous cellulose-containing composition of Example 11 was obtained in the same manner as in Example 1 except that silica A was changed to hydrophobic titanium oxide (STV-455, manufactured by Titanium Industry Co., Ltd.).

<Example 12>
A fine fibrous cellulose-containing composition of Example 12 was obtained in the same manner as in Example 1 except that the amount of silica A added was 0.5 parts by mass with respect to 99.5 parts by mass of the concentrate.

<Example 13>
A fine fibrous cellulose-containing composition of Example 13 was obtained in the same manner as in Example 1 except that the amount of silica A added was 4.8 parts by mass with respect to 95.2 parts by mass of the concentrate.

<Example 14>
A fine fibrous cellulose-containing composition of Example 14 was obtained in the same manner as in Example 1 except that the amount of silica A added was 9.1 parts by mass with respect to 90.9 parts by mass of the concentrate.

<Comparative Example 1>
In Example 1, except that silica A was not added, everything was the same as Example 1, and the fine fibrous cellulose-containing composition of Comparative Example 1 was obtained.

<Comparative example 2>
The fine fibrous cellulose-containing composition of Comparative Example 2 was obtained in the same manner as in Example 4 except that the heating time in an oven at 60 ° C. was 90 minutes and a 98.3% by mass concentrate was obtained.

<Comparative Example 3>
A fine fibrous cellulose-containing composition of Comparative Example 3 was obtained in the same manner as in Example 1 except that the amount of silica A added was 0.05 parts by mass with respect to 99.95 parts by mass of the concentrate.

<Comparative example 4>
A fine fibrous cellulose-containing composition of Comparative Example 4 was obtained in the same manner as in Example 1 except that the amount of silica A added was 13 parts by mass with respect to 87 parts by mass of the concentrate.

  The physical properties of the non-cellulose silica used in Examples and Comparative Examples are as follows.

(Measurement of repose angle)
The angle of repose of the fine fibrous cellulose-containing compositions obtained in Examples and Comparative Examples was measured using an angle of repose measuring instrument (As One). A fine fibrous cellulose-containing composition for 100 ml was charged into a chute of an angle of repose measuring instrument, the chute was opened, and the fine fibrous cellulose-containing composition was dropped to the lower part. The angle formed by the slope of the fine fibrous cellulose-containing composition after dropping and the horizontal plane was measured and defined as the angle of repose.

(Measurement of cumulative median diameter)
The cumulative median diameter of the fine fibrous cellulose-containing compositions obtained in Examples and Comparative Examples is a laser diffraction scattering type particle size distribution measuring device (Microtrac 3300 EXII, Nikkiso Co., Ltd.).
It measured using.

(Measurement of bulk density)
The bulk density of the fine fibrous cellulose-containing compositions obtained in Examples and Comparative Examples was measured using an angle of repose measuring instrument (As One). A fine fibrous cellulose-containing composition for 100 ml is charged into a shoot of an angle of repose measuring instrument, a chute is opened, the fine fibrous cellulose-containing composition is dropped to the lower part, and a container placed underneath (full capacity ∨ = 50 ml) Filled up and down. Next, the raised portion of the swelled fine fibrous cellulose-containing composition was horizontally cut to fill the volume. The mass of the fine fibrous cellulose-containing composition remaining in the container was weighed, and the bulk density (g / ml) was calculated from the following formula.
Bulk density (g / ml) = Mass of powder (g) / Volume of powder (ml)

(Evaluation)
(Evaluation of feed properties)
The fine fibrous cellulose-containing compositions obtained in the examples and comparative examples were charged into a beaker (volume: 100 ml), and the mass W1 (g) was weighed. The beaker was gently rotated 180 ° C. downward to drop the powder. The mass W2 (g) of the dropped fine fibrous cellulose-containing composition was weighed. The ratio of the mass of the fallen fine fibrous cellulose containing composition with respect to the mass of the prepared fine fibrous cellulose containing composition was computed with the following formula, and feed property was evaluated with the following evaluation criteria. In addition, in this-application specification, that feed property is favorable means that it is excellent in the fluidity | liquidity of a composition.
Feedability (%) = W2 / W1 × 100
<Feeding evaluation criteria>
◎: 95% or more ○: 80% or more, less than 95% ×: less than 80%

(Evaluation of redispersibility)
The fine fibrous cellulose-containing composition obtained in Examples and Comparative Examples was added to 100 ml of ion exchange water and neutralized with sodium hydroxide. This aqueous solution was stirred at 1500 rpm for 5 minutes to prepare a solution containing 0.4% by mass of fine fibrous cellulose. The solution was allowed to stand for 30 minutes, the presence or absence of separation was observed, and redispersibility was evaluated according to the following criteria.
<Evaluation criteria for redispersibility>
(Double-circle): It disperse | distributes uniformly, without isolate | separating with water.
○: Some turbidity is observed, but dispersed without being separated from water.
X: Separated from water.

  The fine fibrous cellulose-containing composition obtained in the examples was excellent in feedability and redispersibility. On the other hand, it turns out that the fine fibrous cellulose containing composition obtained by the comparative example is inferior in feed property and redispersibility, or both, and does not have a preferable property.

  The present invention can provide a fine fibrous cellulose-containing composition excellent in fluidity (feedability) and redispersibility.

Claims (15)

(A) A composition containing fine fibrous cellulose and moisture, and (B) a composition containing non-cellulose granules,
The water content in the composition is 2 to 94% by mass with respect to the total mass of the composition,
Content of the said (B) non-cellulose powder granular material is 0.1-12 mass% with respect to the total mass of the said composition.   The composition according to claim 1, wherein the content of the fine fibrous cellulose is more than 5% by mass with respect to the total mass of the composition.   The composition according to claim 1 or 2, wherein the water content in the composition is 15 to 80% by mass relative to the total mass of the composition.   The composition according to any one of claims 1 to 3, wherein the (B) non-cellulose granular material is an inorganic fine particle.   The composition according to any one of claims 1 to 4, wherein the non-cellulose powder (B) is hydrophobic inorganic fine particles.   The composition according to any one of claims 1 to 4, wherein the non-cellulose powder (B) is silica fine particles.   The composition according to any one of claims 1 to 6, wherein the non-cellulose powder (B) is hydrophobic silica fine particles.   The composition according to any one of claims 1 to 7, wherein the cumulative median diameter of the composition is 100 to 1350 µm.   The composition according to any one of claims 1 to 8, wherein an angle of repose of the composition is 4 to 50 °.   The bulk density of the said composition is 0.1-0.7 g / ml, The composition of any one of Claims 1-9.   The composition according to claim 1, wherein the fine fibrous cellulose is a fine fibrous cellulose having an ionic substituent.   The composition according to claim 11, wherein the ionic substituent is an anionic group.   The composition according to claim 12, wherein the anionic group is at least one selected from a phosphate group, a carboxyl group, and a sulfone group.   The composition according to any one of claims 11 to 13, wherein the fine fibrous cellulose has an ionic substituent of 0.1 to 3.5 mmol / g. Concentrating the slurry containing fine fibrous cellulose, (A) obtaining a granular material containing fine fibrous cellulose and moisture,
(A) The process of mixing the granular material containing a fine fibrous cellulose and a water | moisture content, and the (B) non-cellulose granular material, The manufacturing method of the composition containing.

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