JP7088273B2 - Manufacturing method of fine fibrous cellulose redispersion slurry and fine fibrous cellulose redispersion slurry - Google Patents

Description

The present invention relates to a method for producing a fine fibrous cellulose redispersed slurry dispersed in a high concentration. The present invention further relates to a highly concentrated finely dispersed fine fibrous cellulose redispersed slurry.

In recent years, due to the substitution of petroleum resources and the growing environmental awareness, materials using reproducible natural fibers have been attracting attention. 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 paper products.

Further, as the fibrous cellulose, fine fibrous cellulose having a fiber diameter of 1 μm or less is also known. In the sheet or complex containing fine fibrous cellulose, the contact points between the fibers are significantly increased, so that the tensile strength is greatly improved. Further, since the fiber width is shorter than the wavelength of visible light, the transparency is greatly improved. For example, Patent Document 1 discloses a fiber-reinforced composite material in which high transparency is maintained without being affected by temperature conditions, wavelength, etc., and various functions are imparted by compounding a fiber and a matrix material. Has been done.

It is well known that it is effective to perform pretreatment by chemical treatment and biological treatment in addition to mechanical treatment in order to produce fine fibrous cellulose. In particular, when a hydrophilic functional group (for example, a carboxy group, a cationic group, a phosphoric acid group, etc.) is introduced into a hydroxy group on the surface of cellulose by chemical treatment, the electrical repulsive force between the ions and the hydration of the ion occur. In particular, the dispersibility in an aqueous solvent is significantly improved. It is important that the electrical repulsive force between the ions of the hydrophilic functional group-introduced cellulose is reduced so that nanodispersion can be performed even in a solvent having a low relative permittivity. As a technique for this purpose, Non-Patent Document 1 and Patent Document 2 describe that TEMPO-oxidized fine fibrous cellulose is subjected to a micronization treatment into fibrous cellulose in which bulky quaternary ammonium ion is introduced.

On the other hand, there is known a method of adding an organic solvent to a fine fibrous cellulose slurry already nano-dispersed, instead of directly nano-dispersing in a solvent having a low relative permittivity (for example, Patent Document 3). Another idea is to remove (ie, concentrate) the solvent from the already nano-dispersed fine fibrous cellulose slurry and redisperse it into a solvent with a low relative permittivity. As a method for concentrating the fine fibrous cellulose slurry, for example, a method of aggregating the fine fibrous cellulose by adding an acid, a base, a salt, a polyvalent ion, a flocculant, and a surfactant to obtain a concentrate is used. Are known. A method of redispersing the concentrate in pH-adjusted water is also known.

For example, Patent Document 4 describes a fine fibrous cellulose aggregate containing fine fibrous cellulose having an average fiber width of 2 nm to 50 nm and a liquid compound consisting of at least one of water and an organic solvent. In this fine fibrous cellulose aggregate, the content of the fine fibrous cellulose is 6 to 80% by mass with respect to the total mass of the fine fibrous cellulose aggregate, and the content of the liquid compound is the fine fibrous cellulose aggregate. It is 15% by mass or more with respect to the total mass. In Patent Document 4, in the production of agglomerates, salts of polyvalent metals, acids / alkalis, surfactants, and polymer flocculants are used in order to obtain the agglomerates. Further, Patent Documents 5 and 6 relate to 2,2,6,6-tetramethylpiperidinooxy radical (TEMPO) oxidized cellulose fine fibers, and concentrate fine fibrous cellulose using an organic solvent or an acid. It is stated that it should be done. Patent Document 7 describes that an aqueous suspension of bacterial cellulose is once concentrated to a predetermined concentration in order to improve the dispersibility and suspension stability of the bacterial cellulose. Further, Patent Document 8 describes that an anionic polymer or a surfactant is added to a cationic cellulose nanofiber, filtered water (concentrated), and then redispersed in a resin. Further, Non-Patent Document 2 describes that fine fibrous cellulose is treated with an acid and then solvent substitution is repeated.

Japanese Unexamined Patent Publication No. 2008-24788 Japanese Unexamined Patent Publication No. 2015-101649 WO2011 / 111612 WO2014 / 024876 WO2012 / 107642 WO2013 / 121086 Japanese Patent Application Laid-Open No. 9-316102 WO2012 / 124652 (Patent No. 5150792)

Biomacromolecules 2014, 15, 1904-1090 Biomacromolecules 2013, 14, 1541-1546

However, when the method of using an organic ammonium salt as a counterion as described in Non-Patent Documents 1 and 2 is used, although nanodispersion occurs in a solvent having a low relative permittivity, the mechanical treatment required for it is performed. There was a problem that the number of times (that is, energy) increased. In addition, since the efficiency of miniaturization is lowered by the treatment at a high concentration, there is substantially no fine fibrous cellulose slurry having a high concentration and highly dispersed in a solvent having a low non-dielectric constant. Similarly, in the method of Patent Document 3 in which an organic solvent is added after miniaturization, there is a problem that the fine fibrous cellulose slurry is diluted and a high concentration and highly dispersed fine fibrous cellulose slurry cannot be obtained in the solvent. rice field. Further, regarding the method of removing the solvent from the already nano-dispersed one and redispersing it in a solvent having a low relative permittivity, Patent Documents 4 to 7 are all carried out by redispersing in water and have a low relative permittivity. The dispersibility in the solvent and its efficiency are not described. However, as a result of the study by the present inventors, when the solvent is removed from the already nano-dispersed material and redispersed, the redispersibility to the solvent having a low relative permittivity is poor. The method described in Patent Document 8 is limited to cationic cellulose nanofibers, and compounds containing at least one selected from alkali-soluble metals and polyvalent metal ions, which will be described later, cannot be used. Further, as described later, when the present inventors tried to redisperse by adding a cationic polymer or a surfactant to the anionic cellulose nanofiber, the redispersibility to a solvent having a low relative permittivity was poor. rice field. Further, from the description of Non-Patent Document 2, it is possible to consider repeatedly performing solvent substitution using a solvent having a low relative permittivity, but there is a problem that the amount of the solvent used becomes extremely large.

The present invention has been made in view of the above problems. An object to be solved by the present invention is to provide a method for producing a fine fibrous cellulose redispersed slurry nano-dispersed in a solvent having an energy efficiency and a low relative permittivity. Yet another problem to be solved by the present invention is to provide a method for producing a fine fibrous cellulose redispersion slurry in which the dispersion concentration can be set to a high concentration. Further, another problem to be solved by the present invention is to provide a fine fibrous cellulose redispersed slurry nano-dispersed in a solvent having an energy efficiency and a low relative permittivity.

The present inventors have diligently studied to solve the above problems, and added a compound containing at least one selected from an alkali-soluble metal and a polyvalent metal ion to the fine fibrous cellulose slurry to obtain the fine fibrous cellulose. Attempts were made to add at least one selected from tetraalkylonium hydroxide and alkylamines to the concentrate. As a result, it has been found that the above method can provide a method for producing a fine fibrous cellulose redispersed slurry that solves the above problems. The present invention has been completed based on these findings.

That is, according to the present invention, the following invention is provided.
(1) The first step of adding a compound containing at least one selected from an alkali-soluble metal and a polyvalent metal ion to a fine fibrous cellulose slurry to obtain a fine fibrous cellulose concentrate; and the above-mentioned fine fibrous cellulose concentration. Second step of adding at least one selected from tetraalkylonium hydroxide and alkylamine to the product:
A method for producing a fine fibrous cellulose redispersed slurry.
(2) Prior to the first step, a step of micronizing fibrous cellulose having an anionic substituent in a first solvent having a relative permittivity of more than 70 at 25 ° C. to obtain a fine fibrous cellulose slurry is performed. The production method according to (1), which includes.
(3) The anionic substituent is one or more selected from the group consisting of a phosphate group or a substituent derived from a phosphate group, a group derived from a carboxylic acid, and a group derived from sulfuric acid (2). ).
(4) The present invention comprises a step of resuspending the fine fibrous cellulose obtained in the second step in a second solvent having a relative permittivity of 70 or less at 25 ° C. to obtain a fine fibrous cellulose redispersed slurry. The manufacturing method according to any one of (1) to (3).
(5) The production method according to any one of (1) to (4), further comprising a step of treating the fine fibrous cellulose concentrate with an acid between the first step and the second step.
(6) The production method according to any one of (1) to (5), further comprising a step of washing the fine fibrous cellulose concentrate between the first step and the second step.
(7) The above-mentioned one of (1) to (6), wherein the alkali-soluble metal or polyvalent metal is one or more selected from the group consisting of aluminum, zinc, iron and calcium. Manufacturing method.
(8) The production method according to any one of (1) to (7), wherein the tetraalkylonium hydroxide is tetraalkylammonium hydroxide.

(9) A compound and / or a salt thereof containing at least one selected from fine fibrous cellulose, an alkali-soluble metal and a polyvalent metal ion, and at least one or / and a salt thereof selected from tetraalkylonium hydroxide and an alkylamine. Alkaline additives for fine fibrous cellulose concentrates, including.
(10) The content of the compound or / or a salt thereof containing at least one selected from an alkali-soluble metal and a polyvalent metal ion satisfies the following (formula 1), and at least selected from tetraalkylonium hydroxide and an alkylamine. The alkaline additive of the fine fibrous cellulose concentrate according to (9), wherein the content of one or / or a salt thereof satisfies the following (formula 2).
0.1 × A × B × C / D ≦ E ≦ 10 × A × B × C / D (Equation 1)
During the ceremony
A: Amount of functional group introduced into cellulose [mmol / g]
B: Functional group valence [-]
C: Amount of cellulose tested [g]
D: Alkali-soluble metal ion valence [-]
E: Amount of compound or / or salt thereof containing an alkali-soluble metal [mmol]
Is.
0.01 × E ≦ F ≦ 100 × E (Equation 2)
During the ceremony
Amount of compound or / or salt thereof containing an alkali-soluble metal E [mmol]
Amount of tetraalkylonium hydroxide and / or a salt thereof F [mmol]
Is.
(11) A fine fibrous cellulose redispersed slurry containing fine fibrous cellulose and a solvent having a specific dielectric constant of 70 or less at 25 ° C., in which the fine fibrous cellulose is dispersed in the solvent. A fine fibrous cellulose redispersed slurry having a solution haze of 30% or less when the content of the fine fibrous cellulose with respect to the entire fine cellulose redispersed slurry is 0.5% by mass.
(12) A fine fibrous cellulose redispersed slurry containing fine fibrous cellulose and a solvent having a specific dielectric constant of 70 or less at 25 ° C., in which the fine fibrous cellulose is dispersed in the solvent. A fine fibrous cellulose redispersed slurry in which the content of the fine fibrous cellulose with respect to the entire fine cellulose redispersed slurry is 3% by mass or more.

According to the method for producing a fine fibrous cellulose redispersion slurry according to the present invention, the fine fibrous cellulose can be nano-dispersed in a solvent having high energy efficiency and a low relative permittivity. In the method for producing a fine fibrous cellulose redispersion slurry according to the present invention, the dispersion concentration can be set to a high concentration. Further, in the fine fibrous cellulose redispersion slurry according to the present invention, the fine fibrous cellulose is nano-dispersed in a solvent having high energy efficiency and a low relative permittivity.

FIG. 1 shows the relationship between the amount of NaOH dropped and the electrical conductivity with respect to the fiber raw material. FIG. 2 is a graph showing the relationship between the amount of NaOH dropped and the electrical conductivity with respect to the fiber raw material having a carboxyl group.

“Parts” and “%” represent proportions based on mass (parts by mass,% by mass) unless otherwise specified. The value regarding the mass of fibers such as cellulose is based on the absolute dry mass (solid content) unless otherwise specified. Further, the numerical range "XY" includes the values at both ends unless otherwise specified. "A or / and B" refers to at least one of A and B, unless otherwise stated, and may be A alone, B alone, or both A and B. It means that it may be.

The method for producing a fine fibrous cellulose redispersed slurry according to the present invention is a method including the following first and second steps.
The first step of adding a compound containing at least one selected from an alkali-soluble metal and a polyvalent metal ion to a fine fibrous cellulose slurry to obtain a fine fibrous cellulose concentrate; and to the above-mentioned fine fibrous cellulose concentrate. Second step of adding at least one selected from tetraalkylonium hydroxide and alkylamines:

<Raw material for fibrous cellulose>
The raw material for fibrous cellulose for obtaining fibrous cellulose is not particularly limited, but pulp is preferably used because it is easily available and inexpensive. The pulp is selected from wood pulp, non-wood pulp, and deinked pulp. Examples of wood pulp include broadleaf kraft pulp (LBKP), coniferous kraft pulp (NBKP), sulfite pulp (SP), dissolved pulp (DP), soda pulp (AP), unbleached kraft pulp (UKP), and oxygen bleached craft. Examples thereof include chemical pulp such as pulp (OKP). Examples thereof include semi-chemical pulp such as semi-chemical pulp (SCP) and chemiground wood pulp (CGP), mechanical pulp such as crushed wood pulp (GP) and thermomechanical pulp (TMP, BCTMP), but are not particularly limited. .. Examples of the non-wood pulp include 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 and the like, but are not particularly limited. .. Examples of the deinked pulp include deinked pulp made from recycled paper, but the pulp is not particularly limited. As the pulp of this embodiment, one of the above may be used alone, or two or more of them may be mixed and used. 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 during fiber finening (defibration) is high, the decomposition of cellulose in the pulp is small, and the fineness of long fibers with a large axial ratio It is preferable in that fibrous cellulose can be obtained, but it is not particularly limited. Of these, kraft pulp and sulfite pulp are most preferably selected, but are not particularly limited. A sheet containing fine fibrous cellulose of long fibers having a large axial ratio can obtain high strength.

<Introduction of anionic substituent>
In the method of the present invention, prior to the first step, fibrous cellulose having an anionic substituent is refined in a first solvent having a relative permittivity of more than 70 at 25 ° C. to obtain a fine fibrous cellulose slurry. A method including a step of obtaining may be used. The fibrous cellulose having an anionic substituent can be produced by introducing an anionic substituent into the fibrous cellulose. The method for introducing an anionic substituent into the fibrous cellulose is not particularly limited, and examples thereof include an oxidation treatment and a treatment with a compound capable of forming a covalent bond with a functional group in the cellulose.

The oxidation treatment is a treatment for converting a hydroxy group in cellulose into an aldehyde group or a carboxy group. Examples of the oxidation treatment include TEMPO (2,2,6,6-tetramethylpiperidine-1-oxyl radical) oxidation treatment and treatment using various oxidizing agents (sodium chlorite, ozone, etc.). As an example of the oxidation treatment, the method described in Biomacromolecules 8, 2485-2491, 2007 (Saito et al.) Can be mentioned, but is not particularly limited.

The treatment with the compound can be carried out by introducing the above-mentioned substituent into the fiber raw material by mixing the fiber raw material in a dry state or a wet state with a compound that reacts with the fiber raw material. The heating method is particularly effective because it promotes the reaction at the time of introduction. The heat treatment temperature for introducing the substituent is not particularly limited, but it is preferably in a temperature range in which thermal decomposition or hydrolysis of the fiber raw material is unlikely to occur. For example, from the viewpoint of the thermal decomposition temperature of cellulose, it is preferably 250 ° C. or lower, and from the viewpoint of suppressing the hydrolysis of cellulose, heat treatment at 100 to 170 ° C. is preferable.

The compound that reacts with the fiber raw material is not particularly limited as long as fine fibers can be obtained and an anionic substituent is introduced.
When an anionic substituent is introduced, examples of the compound that reacts with the fiber raw material include a phosphoric acid group or a compound having a substituent derived from a phosphoric acid group, a compound having a group derived from a carboxylic acid group, and a group derived from sulfuric acid. Examples thereof include compounds and compounds having a group derived from sulfonic acid. From the viewpoint of ease of handling and reactivity with fibers, a compound having at least one selected from the group consisting of a phosphate group or a substituent derived from a phosphate group, a group derived from a carboxylic acid and a group derived from sulfuric acid is preferable. It is more preferred, but not particularly limited, for these compounds to form esters or / and ethers with the fibers.

The amount of the substituent introduced in the anionic substituent-introduced fiber (by the titration method) is not particularly limited, but is preferably 0.005α to 0.11α, more preferably 0.01α to 0.08α per 1 g (mass) of the fiber. When the introduction amount of the substituent is 0.005α or more, the fiber raw material can be easily refined (defibration), and when the introduction amount of the substituent is 0.11α or less, the dissolution of the fiber can be suppressed. However, α is an amount (unit: mmol / g) in which a functional group that can react with a compound that reacts with the fiber material, for example, a hydroxyl group or an amino group is contained in 1 g of the fiber material.

Unless otherwise specified, the amount of substituents introduced on the fiber surface (titration method) can be measured by the following method:
A fine fiber-containing slurry containing a solid content of about 0.04 g by absolute dry mass is separated and diluted to about 50 g using ion-exchanged water. While stirring this solution, measure the change in the value of electrical conductivity when a 0.01 N sodium hydroxide aqueous solution is dropped, and determine the amount of the 0.01 N sodium hydroxide aqueous solution dropped when the value becomes the minimum. , The amount of dropping at the end point of titration. The amount of substituent X on the surface of cellulose is represented by X (mmol / g) = 0.01 (mol / l) × V (ml) / W (g). Here, V: 0.01N aqueous sodium hydroxide solution (ml), W: solid content (g) contained in the fine fibrous cellulose-containing slurry.

As described above, the amount of the phosphoric acid group introduced into the fiber raw material can be measured by the conductivity titration method. In the conductivity titration, the addition of alkali gives the curve shown in FIG. Initially, the electrical conductivity drops sharply (hereinafter referred to as the "first region"). After that, the conductivity begins to increase slightly (hereinafter referred to as "second region"). After that, the increment of conductivity increases (hereinafter referred to as "third region"). The boundary point between the second region and the third region is defined by the point where the second derivative value of the conductivity, that is, the amount of change in the increment (slope) of the conductivity is maximized. That is, three regions appear. Of 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 equal to the amount of weakly acidic groups in the slurry used for titration. Will be equal. When the phosphoric acid group causes condensation, the weakly acidic group is apparently lost, and the amount of alkali required for the second region is smaller than the amount of alkali required for the first region. On the other hand, since the amount of strongly acidic group is the same as the amount of phosphorus atom regardless of the presence or absence of condensation, it is simply referred to as the amount of phosphoric acid group introduced (or the amount of phosphoric acid group) or the amount of substituent introduced (or the amount of substituent). When it is said, it means the amount of strongly acidic groups.

Further, the amount of the carboxyl group introduced into the fiber raw material can also be measured by the conductivity titration method. In the conductivity titration, the addition of alkali gives the curve shown in FIG. This curve is divided into a first region after the electrical conductivity decreases until the increase (slope) of the conductivity becomes almost constant, and then a second region where the increase (slope) of the conductivity increases. The boundary points of the first and second regions are defined by the point where the second derivative value of the conductivity, that is, the amount of change in the increment (slope) of the conductivity is maximized. The amount of alkali (mmol) required in the first region of the curve shown in FIG. 2 is divided by the solid content (g) in the slurry to be titrated to obtain the amount of substituent introduced (mmol / g).

When the substituent to be introduced is at least one selected from the group consisting of a phosphate group or a substituent derived from a phosphate group, a group derived from a carboxylic acid and a group derived from sulfuric acid, the amount of the substituent introduced is particularly high. It can be, but is not limited to, 0.001 to 5.0 mmol / g. It may be 0.005 to 4.0 mmol / g, or 0.01 to 2.0 mmol / g.

When a compound having a phosphoric acid group or a substituent derived from a phosphoric acid group is used as the compound that reacts with the fiber raw material, the present invention is not particularly limited, but is limited to phosphoric acid, polyphosphoric acid, phosphoric acid, phosphonic acid, polyphosphonic acid or these. At least one selected from the group consisting of salts or esters of. Among these, compounds having a phosphoric acid group are preferable, but are not particularly limited because they are low in cost, easy to handle, and can further improve the miniaturization (defibration) efficiency by introducing a phosphoric acid group into the fiber raw material. ..

The compound having a phosphoric acid group is not particularly limited, and examples thereof include phosphoric acid, lithium dihydrogen phosphate which is a lithium salt of phosphoric acid, dilithium hydrogen phosphate, trilithium phosphate, lithium pyrophosphate, and lithium polyphosphate. .. Further, examples thereof include sodium dihydrogen phosphate, disodium hydrogen phosphate, trisodium phosphate, sodium pyrophosphate, and sodium polyphosphate, which are sodium salts of phosphoric acid. Further, potassium dihydrogen phosphate, which is a potassium salt of phosphoric acid, dipotassium hydrogen phosphate, tripotassium phosphate, potassium pyrophosphate, and potassium polyphosphate can be mentioned. Further, ammonium dihydrogen phosphate, diammonium hydrogen phosphate, triammonium phosphate, ammonium pyrophosphate, ammonium polyphosphate and the like, which are ammonium salts of phosphoric acid, can be mentioned.

Of these, phosphoric acid, a sodium salt of phosphoric acid, a potassium salt of phosphoric acid, and an ammonium salt of phosphoric acid are preferable, and sodium dihydrogen phosphate is preferable from the viewpoint of high efficiency of introducing a phosphoric acid group and easy industrial application. , Disodium hydrogen phosphate is more preferred, but is not particularly limited.

Further, the compound is preferably used as an aqueous solution because of the uniformity of the reaction and the high efficiency of introducing the phosphate group or the substituent derived from the phosphate group, but the compound is not particularly limited. The pH of the aqueous solution of the compound is not particularly limited, but is preferably 7 or less because of the high efficiency of introducing a phosphate group. From the viewpoint of suppressing the hydrolysis of fibers, pH 3 to 7 is particularly preferable, but is not particularly limited.

When a compound having a group derived from a carboxylic acid is used as the compound that reacts with the fiber raw material, it is not particularly limited, but is composed of a group consisting of a compound having a carboxy group, an acid anhydride of a compound having a carboxy group, and a derivative thereof. At least one of the choices.

The compound having a carboxy group is not particularly limited, and examples thereof include dicarboxylic acid compounds such as maleic acid, succinic acid, phthalic acid, fumaric acid, glutaric acid, adipic acid and itaconic acid, and tricarboxylic acid compounds such as citric acid and aconitic acid. ..

The acid anhydride of the compound having a carboxy group is not particularly limited, and examples thereof include acid anhydrides of dicarboxylic acid compounds such as maleic anhydride, succinic anhydride, phthalic anhydride, glutaric anhydride, adipic acid anhydride, and itaconic acid anhydride. Be done.

The derivative of the compound having a carboxy group is not particularly limited, and examples thereof include an imide of an acid anhydride of a compound having a carboxy group and a derivative of an acid anhydride of a compound having a carboxy group. The imide of the acid anhydride of the compound having a carboxy group is not particularly limited, and examples thereof include an imide of a dicarboxylic acid compound such as maleimide, succinic acidimide, and phthalateimide.

The derivative of the acid anhydride of the compound having a carboxy group is not particularly limited. For example, at least a part of the hydrogen atom of the acid anhydride of a compound having a carboxy group, such as dimethylmaleic anhydride, diethylmaleic anhydride, diphenylmaleic anhydride, etc., is a substituent (for example, an alkyl group, a phenyl group, etc.). ) Is substituted.

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

When a compound having a group derived from sulfuric acid is used as the compound that reacts with the fiber raw material, it is not particularly limited, but is at least one selected from the group consisting of anhydrous sulfuric acid, sulfuric acid, and salts and esters thereof. Among these, sulfuric acid is preferable, but is not particularly limited, because it is low in cost and can further improve the miniaturization (defibration) efficiency by introducing a sulfuric acid group into the fiber raw material.

<Miniaturization treatment of fibrous cellulose>
The fine fibrous cellulose slurry can be produced by subjecting the fibrous cellulose to a micronization (defibration) treatment.

During the miniaturization treatment, the fibrous cellulose is dispersed in a solvent. The type of solvent used here is not particularly limited, but a solvent having a relative permittivity at 25 ° C. of preferably 50 or more, more preferably 60 or more, still more preferably 70 or more, and particularly preferably 75 or more is used. be able to. The upper limit of the relative permittivity of the solvent is not particularly limited, but for example, 150 or less can be used. When the value of the relative permittivity is shown, it is a value at 25 ° C. unless otherwise specified. The relative permittivity is the ratio of the permittivity to the electric constant (vacuum permittivity). The permittivity and relative permittivity of pure solvents are well known. The dielectric constant of the mixed solvent can be measured by a known method such as a dielectric constant meter for liquids. As the approximate permittivity and relative permittivity of the mixed solvent, the values obtained by the proportional calculation based on the mixing ratio may be referred to.

Specific examples of the solvent include water (relative permittivity 78 at 25 ° C.), an organic solvent alone, and a mixture of water and an organic solvent. The organic solvent is not particularly limited as long as the intended relative permittivity can be secured. For example, alcohols, polyhydric alcohols, ketones, ethers, dimethyl sulfoxide (DMSO), dimethylformamide (DMF), dimethylacetamide (DMAc) and the like can be mentioned. Examples of alcohols include methanol, ethanol, n-propanol, isopropanol, n-butanol, t-butyl alcohol and the like. Examples of polyhydric alcohols include ethylene glycol and glycerin. Examples of the ketone include acetone, methyl ethyl ketone and the like. Examples of ethers include diethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono n-butyl ether, ethylene glycol mono t-butyl ether and the like. Only one kind of organic solvent may be used, or two or more kinds may be used. Of the above, the solvent is preferably water.

The dispersion concentration of the fibrous cellulose in the solvent is preferably 0.1 to 20% by mass, more preferably 0.5 to 10% by mass, but is not particularly limited. This is because if the dispersion concentration is 0.1% by mass or more, the efficiency of the defibration treatment is improved, and if it is 20% by mass or less, blockage in the defibration treatment apparatus can be prevented.

The defibrating processing device is not particularly limited. Examples thereof include a high-speed defibrator, a grinder (stone mill type crusher), a high-pressure homogenizer, an ultra-high pressure homogenizer, a clear mix, a high-pressure collision type crusher, a ball mill, a bead mill, a disc type refiner, and a conical refiner. Further, a twin-screw kneader, a vibration mill, a homomixer under high-speed rotation, an ultrasonic disperser, a beater, etc., a wet pulverizing device and the like can be appropriately used.

By the micronization treatment, a fine fibrous cellulose slurry is obtained. The average fiber width of the obtained fine fibrous cellulose is not particularly limited, but can be, for example, 1 to 1000 nm, preferably 2 to 1000 nm, more preferably 2 to 500 nm, and further preferably 3 to 100 nm. When the average fiber width of the fine fibers is 1 nm or more, the dissolution of the molecules in water is suppressed, so that the physical characteristics (strength, rigidity, dimensional stability) of the fine fibers are sufficiently expressed. On the other hand, when the average fiber width is 1000 nm or less, the features (high transparency, high elastic modulus, low linear expansion coefficient, flexibility) as fine fibers are easily exhibited. The obtained fine fibrous cellulose dispersion may contain fibrous cellulose having a fiber width of more than 1000 nm, but preferably does not contain fibrous cellulose having a fiber width of more than 1000 nm.

In applications where transparency is required for fine fibers, if the average fiber width is 30 nm or less, it approaches 1/10 of the wavelength of visible light, and when combined with a matrix material, refraction and scattering of visible light occur at the interface. It tends to be difficult to occur and highly transparent. Therefore, the average fiber width is not particularly limited, but is preferably 2 nm to 30 nm, more preferably 2 to 20 nm. The complex obtained from the fine fibers as described above generally has a high strength because it has a dense structure, and high transparency can be obtained because it scatters less visible light.

The average fiber width is measured as follows. A fine fiber-containing slurry having a concentration of 0.05 to 0.1% by mass is prepared, and the slurry is cast onto a hydrophilized carbon film-coated grid to prepare a sample for TEM observation. If it contains wide fibers, an SEM image of the surface cast on the glass may be observed. Observation with an electron microscope image is performed at a magnification of 1000 times, 5000 times, 10000 times, 20000 times, or 50,000 times depending on the width of the constituent fibers. However, the sample, observation conditions and magnification should be adjusted so as to satisfy the following conditions.
(1) A straight line X is drawn at an arbitrary position in the observation image, and 20 or more fibers intersect the straight line X.
(2) A straight line Y that intersects the straight line perpendicularly is drawn in the same image, and 20 or more fibers intersect the straight line Y.
The width of the fiber intersecting the straight line X and the straight line Y is visually read with respect to the observation image satisfying the above conditions. In this way, at least three sets of images of the non-overlapping surface portions are observed, and the widths of the fibers intersecting the straight lines X and Y are read for each image. In this way, at least 20 fibers × 2 × 3 = 120 fibers are read. The average fiber width is the average value of the fiber width read in this way.

The fiber length is not particularly limited, but is preferably 0.1 μm or more. When the fiber length is 0.1 μm or more, it is preferable that the tear strength of the sheet is sufficient when the sheet described later is manufactured. The fiber length can be obtained by image analysis of TEM, SEM, and AFM. The fiber length is a fiber length that occupies 30% by mass or more of the fine fibers.

The axial ratio (fiber length / fiber width) of the fiber is not particularly limited, but is preferably in the range of 20 to 10,000. When the axial ratio is 20 or more, it is preferable in that a fine fiber-containing sheet can be easily formed. When the axial ratio is 10,000 or less, the slurry viscosity is preferable.

By the micronization treatment, a fine fibrous cellulose slurry is obtained. The concentration of the fine fibrous cellulose here is, for example, 0.1 to 20% by mass, and may be 0.5 to 10% by mass.

<Fine fibrous cellulose concentrate>
In the first step of the present invention, a compound containing at least one selected from an alkali-soluble metal and a polyvalent metal ion is added to the fine fibrous cellulose slurry to obtain a fine fibrous cellulose concentrate.

Examples of the alkali-soluble metal include, but are not limited to, iron, aluminum, zinc, tin, lead and the like. Aluminum, zinc, tin, or lead is a metal called an amphoteric metal. As the alkali-soluble metal, it is preferable to use one or more selected from the group consisting of aluminum, zinc and iron.

The compound containing the alkali-soluble metal is not particularly limited, and examples thereof include salts of the alkali-soluble metal and an acid, and examples thereof include iron (II) sulfate (FeSO ₄ ) and iron (III) sulfate (Fe ₂ (Fe 2). SO ₄ ) ₃ ), Iron (II) Chloride (FeCl ₂ ), Iron (III) (FeCl ₃ ), Aluminum Sulfate (Al ₂ (SO ₄ ) ₂ ), Aluminum Chloride (AlCl ₃ ), Zinc Sulfate (ZnSO ₄ ) ), Zinc chloride (ZnCl ₂ ), polyaluminum chloride and the like.

Examples of the polyvalent metal include, but are not limited to, aluminum, calcium, magnesium and the like. Compounds containing polyvalent metal ions can be used as salts of polyvalent metals. Examples of the salt of the polyvalent metal include aluminum sulfate (sulfate band), polyaluminum chloride, calcium chloride, aluminum chloride, magnesium chloride, calcium sulfate, magnesium sulfate and the like, but are not particularly limited.

The addition amount E of the compound containing at least one selected from the alkali-soluble metal and the polyvalent metal ion is preferably within the range specified by (formula 1), and more preferably within the range specified by (formula 1A). Yes, more preferably within the range specified by (Equation 1B), but not particularly limited.
0.1 × A × B × C / D ≦ E ≦ 10 × A × B × C / D (Equation 1)
0.2 × A × B × C / D ≦ E ≦ 5 × A × B × C / D (Equation 1A)
0.5 × A × B × C / D ≦ E ≦ 2 × A × B × C / D (Equation 1B)
During the ceremony
A: Amount of functional group introduced into modified cellulose [mmol / g]
B: Functional group valence [-]
C: Amount of modified cellulose tested [g]
D: Alkali-soluble metal ion or multivalent metal ion valence [-]
E: Amount of alkali-soluble metal ion or polyvalent metal ion contained in a compound containing at least one selected from an alkali-soluble metal and a polyvalent metal ion and / or a salt thereof [mmol]
Is.

The addition of the compound containing at least one selected from the alkali-soluble metal and the polyvalent metal ion can be carried out by a conventional method, and the compound is selected from the alkali-soluble metal and the polyvalent metal ion while stirring the fine fibrous cellulose slurry. By adding a compound containing at least one of the above and continuing stirring, an aggregated fine fibrous cellulose concentrate can be obtained. The form for adding the compound containing at least one selected from the alkali-soluble metal and the polyvalent metal ion can be appropriately selected from the state of a solid or / and a solution. The stirring time is not particularly limited, but for example, the fine fibrous cellulose concentrate can be obtained by stirring for 1 minute to 120 minutes, preferably 10 minutes to 90 minutes.

The aggregated fine fibrous cellulose concentrate obtained above can be recovered by a conventional method. For example, the fine fibrous cellulose concentrate can be recovered by pouring the fine fibrous cellulose concentrate onto a filter paper and performing vacuum sorting with an aspirator or the like.

<Acid treatment of fine fibrous cellulose concentrate>
The fine fibrous cellulose concentrate obtained in the above first step may be used as it is in the second step, but between the first step and the second step, the fine fibrous cellulose concentrate obtained in the first step may be used. A step of treating the substance with an acid may be included.

By performing the above-mentioned step of treating with an acid, a metal component such as an alkali-soluble metal or a polyvalent metal can be washed. That is, the acid treatment step may be an acid cleaning step for removing the metal component (concentrator).

In the acid treatment step, for example, inorganic acids (sulfuric acid, hydrochloric acid, nitrate, 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) , Tartrate acid, fumaric acid, gluconic acid, etc.). Specifically, it is preferable to immerse the concentrate obtained in the above-mentioned step in the above-mentioned acidic liquid. The concentration of the acidic liquid used is not particularly limited, but is preferably 10% or less, more preferably 5% or less, 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.

Further, it is preferable to perform filtration after the acid treatment step. In this filtration treatment step, a liquid removal step such as a compression step may be further performed.

<Washing of fine fibrous cellulose concentrate>
The fine fibrous cellulose concentrate obtained in the above first step may be used as it is in the second step, but between the first step and the second step, the fine fibrous cellulose concentrate obtained in the first step may be used. It may include a step of cleaning the object.

The washing can be performed using, for example, water (ion-exchanged water or the like). Specifically, the fine fibrous cellulose concentrate obtained in the first step is resuspended in ion-exchanged water, and then the operation of vacuum filtration is performed once or twice or more to perform washing. Can be done.

<Drying process>
The fine fibrous cellulose concentrate obtained in the above first step may be used as it is in the second step, but between the first step and the second step, the fine fibrous cellulose obtained in the first step A step of drying the concentrate may be provided. When the drying step is provided, it is preferable to provide it after the acid treatment step. The drying step is preferably an oven drying step, and for example, it is preferable to perform drying in an oven set at 30 to 70 ° C. for 1 to 60 minutes.

<Alkaline additive of fine fibrous cellulose concentrate>
In the second step of the present invention, at least one selected from tetraalkylonium hydroxide and alkylamine is added to the fine fibrous cellulose concentrate. This gives an alkaline additive of the fine fibrous cellulose concentrate.

Examples of the tetraalkylonium hydroxide include tetraalkylammonium hydroxide and tetraalkylphosphonium hydroxide. Among the above, tetraalkylammonium hydroxide is preferable. Examples of the tetraalkylammonium hydroxide include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, and triethylmethylammonium hydroxide. Examples of the tetraalkylphosphonium hydroxide include tetramethylphosphonium hydroxide, tetraethylphosphonium hydroxide, tetrapropylphosphonium hydroxide, tetrabutylphosphonium hydroxide, and triethylmethylphosphonium hydroxide.

As an alkylamine,
Methylamine, ethylamine, propylamine, butylamine, amylamine (pentylamine), hexylamine, heptylamine, n-octylamine, nonylamine, aminodecane, aminoundecane, dodecylamine, aminotridecane, tetratecilamine, aminopentadecane, hexadecyl Monoalkylamines such as amines, aminoheptadecanes, stearylamines, aminononadecans, cyclohexylamines, aniline;
Dialkylamines such as dimethylamine, diethylamine, dipropylamine, dibutylamine, diamilamine, dihexylamine, diheptylamine, di (2-ethylhexyl) amine, di-n-octylamine, didecylamine, didodecylamine;
Trialkylamines such as trimethylamine, diethylmethylamine, diethyldi-n-octylamine, didecylmethylamine, N, N-didodecylmethylamine:
Etc., but are not particularly limited.

The addition amount F of tetraalkylonium hydroxide or alkylamine is preferably within the range specified by the formula (formula 2), more preferably within the range specified by the formula (formula 2A), and further preferably within the range specified by the formula (formula 2A). ), But is not particularly limited.
0.01 × E ≦ F ≦ 100 × E (Equation 2)
0.1 × E ≦ F ≦ 50 × E (Equation 2A)
1 × E ≦ F ≦ 10 × E (Equation 2B)
During the ceremony
Amount of alkali-soluble metal ion or polyvalent metal ion contained in a compound containing at least one selected from alkali-soluble metal and polyvalent metal ion and / or a salt thereof E [mmol]
Addition amount of tetraalkylonium hydroxide or alkylamine F [mmol]
Is.

However, when polyvalent metal ions are used and washed with an acid, the amount F of tetraalkylonium hydroxide or alkylamine added is preferably within the range specified by the formula (formula 3), and more preferably. It is within the range specified by (Equation 3A), more preferably within the range specified by (Equation 3B), but is not particularly limited.
0.01 × A × B × C ≦ F ≦ 100 × A × B × C (Equation 3)
0.1 × A × B × C ≦ F ≦ 50 × A × B × C (Equation 3A)
0.5 × A × B × C ≦ F ≦ 5 × A × B × C (Equation 3B)
The definitions of A, B, C and F are as described above in this document.

The addition of the tetraalkylonium hydroxide or the alkylamine can be carried out by a conventional method, and by adding the solution of the tetraalkylonium hydroxide or the alkylamine while stirring the fine fibrous cellulose concentrate, the fine fibrous is formed. Alkaline additives of cellulose concentrate can be obtained.

The alkali additives of the above-mentioned fine fibrous cellulose concentrate include fine fibrous cellulose, a compound containing at least one selected from alkali-soluble metals and polyvalent metal ions and / or salts thereof, and tetraalkylonium hydroxide and alkyl. Includes at least one selected from amines and / and salts thereof.
Whether or not the alkali additive of the above fine fibrous cellulose concentrate contains a compound containing an alkali-soluble metal or / or a salt thereof is subjected to appropriate pretreatment such as ashing and acid extraction as necessary. After that, it can be measured by ion chromatography, ICP mass analysis method, ICP-issued spectroscopic analysis method, atomic absorption spectroscopy, or the like.
Whether or not the alkaline additive of the above fine fibrous cellulose concentrate contains tetraalkylonium hydroxide or / or a salt thereof is measured by ion chromatography, and in the case of tetraalkylammonium hydroxide, a trace amount of nitrogen is used. In the case of an analytical method, tetraalkylphosphonium hydroxide, it can be measured by the molybdenum blue method or the like.

<Fine fibrous cellulose redispersion slurry>
In the present invention, the fine fibrous cellulose redispersed slurry can be obtained by resuspending the fine fibrous cellulose obtained in the second step in a solvent. In the step of obtaining the redispersed slurry, the fine fibrous cellulose obtained in the second step is resuspended in a solvent having a relative permittivity of 70 or less at 25 ° C. to obtain a fine fibrous cellulose redispersed slurry. It may be a process.

The type of solvent used to obtain the redispersed slurry is not particularly limited, but the relative permittivity at 25 ° C. is preferably 70 or less, more preferably 60 or less, still more preferably 50 or less, and particularly preferably 40 or less. Certain solvents can be used. Specific examples of the solvent include water (relative permittivity 78 at 25 ° C.), an organic solvent alone, and a mixture of water and an organic solvent. The organic solvent is not particularly limited as long as the intended relative permittivity can be secured. For example, alcohols, polyhydric alcohols, ketones, ethers, dimethyl sulfoxide (DMSO), dimethylformamide (DMF), dimethylacetamide (DMAc) and the like can be mentioned. Examples of alcohols include methanol, ethanol, n-propanol, isopropanol, n-butanol, t-butyl alcohol and the like. Examples of polyhydric alcohols include ethylene glycol and glycerin. Examples of the ketone include acetone, methyl ethyl ketone and the like. Examples of ethers include diethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono n-butyl ether, ethylene glycol mono t-butyl ether and the like. Only one kind of organic solvent may be used, or two or more kinds may be used. Among the above, the solvent is preferably a mixture of alcohols and water, a mixture of ethers and water, or a mixture of DMSO and water.

The mixing ratio of the mixture of alcohols and water is preferably a ratio that can achieve the above-mentioned relative permittivity, for example, alcohol: water = 40 to 80:20 to 60.
The mixing ratio of the mixture of ethers and water is preferably a ratio that can achieve the above-mentioned relative permittivity, for example, ethers: water = 40 to 80:20 to 60.
The mixing ratio of the mixture of DMSO and water is preferably a ratio that can achieve the above-mentioned relative permittivity, for example, DMSO: water = 80 to 95: 20 to 5.

The redispersion of the fine fibrous cellulose can be carried out by a conventional method. For example, a step of adding the above-mentioned solvent to an alkaline additive of a fine fibrous cellulose concentrate to prepare a fine fibrous cellulose-containing liquid, and a step of dispersing the fine fibrous cellulose in the fine fibrous cellulose-containing liquid. Allows redispersion.

When a solvent is added to the alkaline additive of the fine fibrous cellulose concentrate to prepare a fine fibrous cellulose-containing liquid, the fine fibrous cellulose content of the fine fibrous cellulose-containing liquid is adjusted with respect to the fine fibrous cellulose-containing liquid. It is preferably 0.1% by mass to 10% by mass. It is more preferable that the content of the fine fibrous cellulose in the fine fibrous cellulose-containing liquid is 0.2% by mass to 3% by mass with respect to the fine fibrous cellulose-containing liquid. When the content is 0.1% by mass or more, the dispersion stability of the fine fibrous cellulose is high, and when the content is 10% by mass or less, the viscosity of the fine fibrous cellulose is not too high and the handling is easy. It will be relatively easy.
The fine fibrous cellulose content of the fine fibrous cellulose-containing liquid can be adjusted by the amount of the solvent added, and the larger the amount of the solvent added, the lower the fine fibrous cellulose content.

As the dispersion device used in the step of dispersing the fine fibrous cellulose in the fine fibrous cellulose-containing liquid, the same disperser as the defibrillation treatment device described in the above <Fiberous cellulose miniaturization treatment> may be used. can.

In the fine fibrous cellulose redispersion slurry obtained as described above, the content of the fine fibrous cellulose in the entire fine fibrous cellulose redispersion slurry is preferably 0.1% by mass or more, more preferably 0.5. It is 1% by mass or more, more preferably 1% by mass or more, and further preferably 3% by mass or more. The upper limit of the content of the fine fibrous cellulose is not particularly limited, but is generally 50% by mass or less. By keeping the content of the fine fibrous cellulose within the above range, the relative permittivity of the fine fibrous cellulose redispersed slurry can be set low.
Dispersibility can be evaluated by subjecting the dispersion treatment with a homodisper or the like and visually observing the liquid immediately after that to see if precipitation or coarse agglomerates are observed.

The fine fibrous cellulose redispersed slurry obtained as described above has a fine fibrous cellulose content of 0.5% by mass with respect to the entire fine fibrous cellulose redispersed slurry in a solvent having a relative permittivity of 70 or less at 25 ° C. At that time, the solution haze is preferably 30% or less. The above solution haze is more preferably 25% or less, more preferably 20% or less, still more preferably 15% or less, and particularly preferably 10% or less.

<Other processes>
In the present invention, the fine fibrous cellulose redispersed slurry obtained as described above may be further subjected to a treatment with an ion exchange resin (for example, a treatment with an anion exchange resin and / or a treatment with a cation exchange resin). .. By the above treatment, the purity of the fine fibrous cellulose in the fine fibrous cellulose redispersion slurry can be further increased.

Examples of the anion exchange resin include a strong basic anion exchange resin and a weakly basic anion exchange resin. For example, a styrene-divinylbenzene crosslinked polymer containing a dimethylamino group or a monomethyl group as an ion exchange group. Can be mentioned.
Examples of the cation exchange resin include a strongly acidic cation exchange resin and a weakly acidic cation exchange resin, and examples thereof include a styrene-divinylbenzene crosslinked polymer containing a sulfonic acid group or a carboxyl group as an ion exchange group. Be done.

The ion exchange resin can be used alone or in combination of two or more. Further, a biion exchange resin having both a cation moiety and an anion moiety in one resin can also be used. The shape of the ion exchange resin is not particularly limited, and examples thereof include a gel type and a porous type.

Examples of commercially available ion exchange resins include, but are not limited to, the following.
Gel-type strong acid cation exchange resin such as Diaion (registered trademark, the same applies hereinafter) SK104, SK110, SK112;
Porous strong acid cation exchange resin such as diamonds PK208, PK212, PK216, PK218, PK220, PK228;
Gel-type uniform particle size strongly acidic cation exchange resin such as Diaion UBK08, UBK10, UBK12;
Gel type I strong basic anion exchange resin such as Diaion SA10A, SA12, NSA100;
Gel type II strong basic anion exchange resin such as Diaion SA20A, SA21A;
Porous type I strong basic anion exchange resin such as Diaion PA306S, PA308, PA312, PA316, PA318L;
Acrylic weak basic anion exchange resin such as Diaion WA10;
Styrene-based polyamine-type weakly basic anion exchange resin such as Diaion WA20 and WA21J;
Styrene-based dimethylamine type weakly basic anion exchange resin such as Diaion WA30;
Amphoteric ion exchange resin such as Diaion AMP03 (above, manufactured by Mitsubishi Chemical Corporation);
Strong acid cation exchange resin such as Dowex (registered trademark, the same applies hereinafter) 50W × 8;
Strongly basic anion exchange resin such as Dowex 1x2, 1x4, 1x8 (manufactured by Dow Chemical Co., Ltd.);
Strong acid cation exchange resin such as Amberlite (registered trademark, the same applies hereinafter) IR120B, IR124, etc.;
Strongly basic anion exchange resins such as Amberlite IRA400J and IRA411 (all manufactured by Organo Corporation):

<Other ingredients>
The fine fibrous cellulose concentrate, the alkaline additive of the fine fibrous cellulose concentrate, or the fine fibrous cellulose redispersion slurry may contain a surfactant. By including the surfactant, the surface tension is lowered, the wettability to the process substrate can be enhanced, and the fine fibrous cellulose-containing sheet can be formed more easily.

As the surfactant, a nonionic surfactant, an anionic surfactant, and a cationic surfactant can be used. When cellulose is anionic, nonionic surfactants and anionic surfactants are preferable, and when cellulose is cationic, nonionic surfactants and cationic surfactants are preferable.

The fine fibrous cellulose concentrate, the alkaline additive of the fine fibrous cellulose concentrate, or the fine fibrous cellulose redispersion slurry is a mixture of at least one fiber other than the fine fibrous cellulose (hereinafter referred to as "additional fiber"). It can also be prepared by Examples of the additional fiber include, but are not limited to, semi-synthetic fiber and regenerated fiber such as inorganic fiber, organic fiber, and synthetic fiber. Examples of the inorganic fiber include, but are not limited to, glass fiber, rock fiber, metal fiber and the like. Examples of the organic fiber include, but are not limited to, fibers derived from natural substances such as cellulose, carbon fiber, pulp, chitin, and chitosan. Examples of the synthetic fiber include, but are not limited to, nylon, vinylon, vinylidene, polyester, polyolefin (for example, polyethylene, polypropylene, etc.), polyurethane, acrylic, polyvinyl chloride, aramid, and the like. Examples of the semi-synthetic fiber include, but are not limited to, acetate, triacetate, promix and the like. Examples of the recycled fiber include, but are not limited to, rayon, cupra, polynosic rayon, lyocell, and tencel. The additional fiber can be subjected to a treatment such as a chemical treatment or a defibration treatment, if necessary. When the additional fiber is subjected to a treatment such as a chemical treatment or a defibration treatment, the additional fiber may be mixed with the fine fiber and then subjected to a chemical treatment or a defibration treatment, or the additional fiber may be chemically treated or defibrated. It can also be mixed with fine fibers after being subjected to a treatment such as treatment. When the additional fibers are mixed, the amount of the additional fibers added in the total amount of the fine fibers and the additional fibers is not particularly limited, but is preferably 50% by mass or less, more preferably 40% by mass or less, still more preferably 30. It is less than mass%. Particularly preferably, it is 20% by mass or less.

A hydrophilic polymer may be added to the fine fibrous cellulose concentrate, the alkaline additive of the fine fibrous cellulose concentrate, or the fine fibrous cellulose redispersion slurry. The hydrophilic polymer is not particularly limited. Examples thereof include polyethylene glycol, cellulose derivatives (hydroxyethyl cellulose, carboxyethyl cellulose, carboxymethyl cellulose, etc.), casein, dextrin, starch, modified starch and the like. In addition, polyvinyl alcohol, modified polyvinyl alcohol (acetoacetylated polyvinyl alcohol, etc.) can be mentioned. Further, polyethylene oxide, polyvinylpyrrolidone, polyvinylmethyl ether, polyacrylic acid salts, polyacrylamide, acrylic acid alkyl ester copolymer, urethane-based copolymer and the like can be mentioned.

Further, a hydrophilic low molecular weight compound can be used instead of the hydrophilic polymer. The hydrophilic low molecular weight compound is not particularly limited. For example, glycerin, erythritol, xylitol, sorbitol, galactitol, mannitol, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, butylene glycol and the like can be mentioned. When a hydrophilic polymer or a hydrophilic low molecular compound is added, the amount added is not particularly limited. For example, it is 1 to 200 parts by mass, preferably 1 to 150 parts by mass, more preferably 2 to 120 parts by mass, and further preferably 3 to 100 parts by mass with respect to 100 parts by mass of the solid content of the fine fiber.

<Use>
The use of the alkaline additive and / and the fine fibrous cellulose redispersion slurry of the fine fibrous cellulose concentrate according to the present invention is not particularly limited. As an example, a fine fibrous cellulose redispersed slurry can be used to form a film and used as various films. As another example, the fine fibrous cellulose redispersed slurry can be used for various purposes as a thickener. Further, it can be mixed with a resin or an emulsion and used as a reinforcing material.
The present invention will be described in more detail with reference to the following examples, but the scope of the present invention is not limited to the following examples.

(Production Example 1) Production of phosphorylated pulp (H type) and introduction of phosphoric acid group As coniferous kraft pulp, pulp made by Oji Paper (solid content 93%, paper density 208 g / m ² sheet-like disintegration, conforming to JIS P8121 The Canadian standard drainage degree (CSF) 700 ml) measured in the above was used. 100 parts by mass of the above coniferous kraft pulp is impregnated with a mixed aqueous solution of ammonium dihydrogen phosphate and urea, squeezed to 49 parts by mass of ammonium dihydrogen phosphate and 130 parts by mass of urea, and impregnated with a chemical solution. Obtained pulp. The obtained chemical-impregnated pulp was dried in a dryer at 105 ° C. to evaporate the water content and pre-dried. Then, it was heated for 10 minutes with a blower dryer set at 140 ° C., and a phosphoric acid group was introduced into the cellulose in the pulp to obtain phosphorylated pulp.

-Cleaning of phosphorylated pulp 10,000 parts by mass of ion-exchanged water was poured with respect to 100 parts by mass as the absolute dry mass of the obtained phosphorylated pulp, and after stirring and uniformly dispersing, the dehydrated sheet was dehydrated by filtration. Was repeated twice to obtain a dehydrated sheet A of phosphorylated pulp.

-Phosphorylation multiple times Using the obtained phosphorylated pulp dehydration sheet A as a raw material, the steps of introducing a phosphate group and filtering and dehydrating are repeated twice more (phosphorylation and filtration dehydration). The total number of times was 3), and a dehydrated sheet B of phosphorylated pulp was obtained.

-Amount of substituents introduced In the dehydrated sheet B of the phosphorylated pulp, the amount of phosphate groups introduced by the titration method described later was 1.435 mmol / g.

-Salt type conversion of phosphorylated pulp 5000 parts by mass of ion-exchanged water was added to 100 parts by mass as the absolute dry mass of the dehydrated sheet B of H-type phosphorylated pulp to dilute it. Then, while stirring, 1N hydrochloric acid was added little by little to obtain a pulp slurry having a pH of 2 to 3. Then, this pulp slurry was dehydrated to obtain a dehydrated sheet, and then ion-exchanged water was poured again and stirred to uniformly disperse the pulp slurry. Then, by repeating the operation of filtering and dehydrating to obtain a dehydrated sheet, excess hydrochloric acid was sufficiently washed away to obtain phosphorylated pulp (H type).

(Production Example 2) Production of Phosphorylated Pulp (TBA Type) The phosphorylated pulp (H type) obtained in Production Example 1 was diluted by adding 5000 parts by mass of ion-exchanged water to 100 parts by mass as an absolute dry mass. Then, while stirring, a 10% aqueous solution of tetrabutylammonium hydroxide was added little by little to obtain a pulp slurry having a pH of 10 to 12. Then, this pulp slurry was dehydrated to obtain a dehydrated sheet, and then ion-exchanged water was poured again and stirred to uniformly disperse the pulp slurry. Then, by repeating the operation of filtering and dehydrating to obtain a dehydrated sheet, the excess tetrabutylammonium hydroxide aqueous solution was sufficiently washed away to obtain a phosphorylated pulp (TBA type) (counterion carbon number 16).

(Production Example 3) Production of Phosphorylated Pulp (Na Type) Phosphorylated Pulp (Na Type) (Na type) in the same manner as in Production Example 2 except that a 1N NaOH aqueous solution was used instead of the 10% tetrabutylammonium hydroxide aqueous solution. The carbon number of the counter ion was 0).

(Production Example 4) Production of phosphorylated pulp (TPA type) Phosphorylated pulp in the same manner as in Production Example 2 except that a 10% tetrapropylammonium hydroxide aqueous solution was used instead of the 10% tetrabutylammonium hydroxide aqueous solution. (TPA type) (12 carbon atoms of the counter ion) was obtained.

(Production Example 5) Production of Phosphorylated Pulp (TEA Type) Phosphorylated pulp (Production Example 5) in the same manner as in Production Example 2 except that a 10% tetraethylammonium hydroxide aqueous solution was used instead of the 10% tetrabutylammonium hydroxide aqueous solution. TEA type) (counterion carbon number 8) was obtained.

(Production Example 6) Production of TEMPO Oxidized Pulp (H-type) -TEMPO Oxidation Reaction An undried coniferous bleached kraft pulp equivalent to 100 parts by mass of dry mass, 1.25 parts by mass of TEMPO, and 12.5 parts by mass of sodium bromide were added. It was dispersed in 10000 parts by mass of water. Then, a 13 mass% sodium hypochlorite aqueous solution was added to 1.0 g of pulp so that the amount of sodium hypochlorite was 8.0 mmol, and the reaction was started. During the reaction, a 0.5 M aqueous sodium hydroxide solution was added dropwise to keep the pH at 10 to 11, and when no change was observed in the pH, the reaction was considered to be completed.

-Washing of TEMPO oxidized pulp After that, this pulp slurry is dehydrated to obtain a dehydrated sheet, and then 5000 parts by mass of ion-exchanged water is poured, stirred and uniformly dispersed, and then filtered and dehydrated to form a dehydrated sheet. The obtaining process was repeated twice.

-Amount of substituents introduced The amount of substituents (carboxy groups) introduced by the titration method was 1.502 mmol / g.

Further, 5000 parts by mass of ion-exchanged water was added to the obtained dehydrated sheet for dilution. Then, while stirring, 1N hydrochloric acid was added little by little to obtain a pulp slurry having a pH of 2 to 3. Then, this pulp slurry was dehydrated to obtain a dehydrated sheet, and then ion-exchanged water was poured again and stirred to uniformly disperse the pulp slurry. Then, by repeating the operation of filtering and dehydrating to obtain a dehydrated sheet, excess hydrochloric acid was sufficiently washed away to obtain TEMPO oxide pulp (H type).

(Production Example 7) Production of TEMPO Oxidized Pulp (Na Type) 5000 parts by mass of ion-exchanged water was added to 100 parts by mass as an absolute dry mass of the obtained TEMPO Oxidized Pulp (H type) to dilute it. Then, while stirring, a 1N NaOH aqueous solution was added little by little to obtain a pulp slurry having a pH of 10 to 12. Then, this pulp slurry was dehydrated to obtain a dehydrated sheet, and then ion-exchanged water was poured again and stirred to uniformly disperse the pulp slurry. Then, by repeating the operation of filtering and dehydrating to obtain a dehydrated sheet, the excess NaOH aqueous solution was sufficiently washed away to obtain TEMPO oxide pulp (Na type) (counterion carbon number 0).

In the following examples, the concentration (step B) corresponds to the first step of adding a compound containing an alkali-soluble metal to the fine fibrous cellulose slurry to obtain a fine fibrous cellulose concentrate. Further, the addition of alkali (step C) corresponds to the second step of adding tetraalkylonium hydroxide to the fine fibrous cellulose concentrate.

(Example 1)
-Dilution before miniaturization (step A)
The obtained phosphorylated pulp (Na type) was diluted with ion-exchanged water so that the content was 2.0% by mass to obtain a pre-miniaturized slurry A. Further, it was confirmed that the relative permittivity of the solvent contained in the pre-miniaturized slurry A at 25 ° C. was 70 or more.

-Miniaturization The obtained pre-miniaturized slurry A was subjected to 2-pass treatment at an operating pressure of 1500 MPa using an explosion-proof high-pressure homogenizer to obtain a fine fibrous cellulose slurry A.

・ Concentration (step B)
100 g of the obtained fine fibrous cellulose slurry A was fractionated, and 0.39 g of aluminum sulfate was added with stirring. When stirring was continued for another 30 minutes, aggregates of fine fibrous cellulose were observed.

The amount of aluminum ions E ¹ [mmol] contained in the added aluminum sulfate was 1.2 × A ¹ × B ¹ × C ¹ / D ¹ .
Here, A ¹ : The amount of phosphate groups introduced into the modified cellulose [mmol / g]
B ¹ : Phosphate group valence [-]
C ¹ : Amount of modified cellulose tested [g]
D ¹ : Aluminum ion valence [-]
Is. The same applies to the other examples and comparative examples. When a modified cellulose having a functional group other than the phosphoric acid group is used as a trial, the valence of the phosphoric acid group shall be read as the valence of the functional group. When a metal other than aluminum is used, the amount of aluminum and the valence of aluminum ions shall be read as the amount of metal and the valence of the metal ions.

-Recovery of Concentrate The fine fibrous cellulose slurry in which aggregates are generated is poured onto a qualitative filter paper (ADVANTEC, φ90 mm, No. 2) mounted on a filter holder, and vacuum-separated with an aspirator to aggregate the fine fibrous cellulose. The thing (before cleaning) was collected.

-Washing of concentrate The obtained fine fibrous cellulose aggregate (before washing) was resuspended with ion-exchanged water so that the content of fine fibrous cellulose was 2.0% by mass. Then, the operation of vacuum filtering was repeated three times to obtain a fine fibrous cellulose concentrate (the content of the fine fibrous cellulose in the whole concentrate was 5.2% by mass).

-Addition of alkali (process C)
To the obtained fine fibrous cellulose concentrate, 21.8 g of a 10% tetrabutylammonium hydroxide (TBA) aqueous solution was added with stirring to obtain an alkaline additive of the fine fibrous cellulose concentrate.

The amount of tetrabutylammonium added, F ¹ [mmol], was 4.0 × E ¹ .
Here, E ¹ : The amount of aluminum contained in the added aluminum sulfate [mmol]
Is.

-Redispersion (process D)
To the alkaline additive of the obtained fine fibrous cellulose concentrate, isopropanol and ion-exchanged water so that the isopropanol (IPA) / water mass ratio is 60/40 and the fine fibrous cellulose content is 0.5 mass%. Was added. Then, a fine fibrous cellulose redispersed slurry was obtained by a homodisper (8000 rpm 1 minute manufactured by Tokushu Kagaku Kogyo Co., Ltd.) treatment. Further, it was confirmed that the relative permittivity of the solvent contained in the fine fibrous cellulose redispersion slurry at 25 ° C. was 70 or less.

-Evaluation The table below describes the relative permittivity of the solvent during miniaturization, the relative permittivity of the solvent during redispersion, the redispersibility, and the haze of the slurry after redispersion. The haze and redispersibility were evaluated by the method described later.

(Example 2)
A fine fibrous cellulose concentrate was obtained in the same manner as in Example 1 except that 0.47 g of zinc chloride was added instead of 0.39 g of aluminum sulfate. Furthermore, the haze was measured and the redispersibility was evaluated. The results are listed in the table.

(Example 3)
A fine fibrous cellulose concentrate was obtained in the same manner as in Example 1 except that 0.46 g of iron (III) sulfate was added instead of 0.39 g of aluminum sulfate. Furthermore, the haze was measured and the redispersibility was evaluated. The results are listed in the table.

(Example 4)
A fine fibrous cellulose concentrate was obtained in the same manner as in Example 1 except that 17.1 g of a 10% tetrapropylammonium hydroxide (TPA) aqueous solution was added instead of 21.8 g of the 10% tetrabutylammonium hydroxide aqueous solution. rice field. Furthermore, the haze was measured and the redispersibility was evaluated. The results are listed in the table.

(Example 5)
A fine fibrous cellulose concentrate was obtained in the same manner as in Example 1 except that 12.4 g of a 10% tetraethylammonium hydroxide (TEA) aqueous solution was added instead of the 10% tetrabutylammonium hydroxide aqueous solution. Furthermore, the haze was measured and the redispersibility was evaluated. The results are listed in the table.

(Example 6)
A fine fibrous cellulose redispersed slurry was obtained in the same manner as in Example 1 except that the isopropanol (IPA) / water mass ratio was set to 70/30 when the solvent was added before the redispersion. It was confirmed that the relative permittivity of the solvent contained in the fine fibrous cellulose redispersion slurry at 25 ° C. was 70 or less. Furthermore, the haze was measured and the redispersibility was evaluated. The results are listed in the table.

(Example 7)
A fine fibrous cellulose redispersed slurry was obtained in the same manner as in Example 1 except that the dimethyl sulfoxide (DMSO) / water mass ratio was 90/10 when the solvent was added before the redispersion. It was confirmed that the relative permittivity of the solvent contained in the fine fibrous cellulose redispersion slurry at 25 ° C. was 70 or less. Furthermore, the haze was measured and the redispersibility was evaluated. The results are listed in the table.

(Example 8)
When the solvent was added before the redispersion, the fine fibrous cellulose redispersed slurry was prepared in the same manner as in Example 1 except that the ethylene glycol monotarsial butyl ether (EG-tBE) / water mass ratio was set to 60/40. Obtained. It was confirmed that the relative permittivity of the solvent contained in the fine fibrous cellulose redispersion slurry at 25 ° C. was 70 or less. Furthermore, the haze was measured and the redispersibility was evaluated. The results are listed in the table.

(Example 9)
A fine fibrous cellulose concentrate was obtained in the same manner as in Example 1 except that TEMPO oxidized pulp (Na type) was used instead of phosphorylated pulp (Na type). Furthermore, the haze was measured and the redispersibility was evaluated. The results are listed in the table.

(Example 10)
-Recovery of high-concentration concentrate After recovering the concentrate in the same manner as in Example 1, the concentrate is applied to a square press to further concentrate, and the high-concentration concentrate of fine fibrous cellulose (for the entire concentrate). The content of fine fibrous cellulose was 30% by mass).

-Addition of alkali (process C)
To the obtained high-concentration concentrate of fine fibrous cellulose, 5.45 g of a 40% tetrabutylammonium hydroxide (TBA) aqueous solution was added with stirring to obtain an alkaline additive of the fine fibrous cellulose concentrate.

-Redispersion (process D)
Isopropanol and ion-exchanged water were added to the alkaline additive of the obtained fine fibrous cellulose concentrate so that the isopropanol (IPA) / water mass ratio was 60/40 and the fine fibrous cellulose content was 5% by mass. did. Then, the mixture was stirred with a vertical kneader (Inoue Seisakusho, Trimix) for 5 minutes and redispersed to obtain a fine fibrous cellulose redispersed slurry. The obtained fine fibrous cellulose redispersed slurry had good redispersability without discharging the solvent and no visual agglomeration was observed.

(Example 11)
A fine fibrous cellulose redispersed slurry was obtained in the same manner as in Example 10 except that isopropanol and ion-exchanged water were added so that the content of the fine fibrous cellulose was 7% by mass. The obtained fine fibrous cellulose redispersed slurry had good redispersability without discharging the solvent and no visual agglomeration was observed.

(Example 12)
Except for the fact that the <acid treatment step> described later was performed between <recovery of concentrate> and <washing of concentrate>, and the amount of 10% tetrabutylammonium hydroxide (TBA) aqueous solution added was 17.9 g. A fine fibrous cellulose concentrate was obtained in the same manner as in Example 1. Furthermore, the haze was measured and the redispersibility was evaluated. The results are listed in the table.

The fine fibrous cellulose concentrate obtained in the acid treatment step <recovery of concentrate> was immersed in 0.1N hydrochloric acid for 30 minutes, filtered, and the fine fibrous cellulose concentrate was recovered again.

(Example 13)
A fine fibrous cellulose concentrate was obtained in the same manner as in Example 12 except that 0.47 g of zinc chloride was added instead of 0.39 g of aluminum sulfate. Furthermore, the haze was measured and the redispersibility was evaluated. The results are listed in the table.

(Example 14)
A fine fibrous cellulose concentrate was obtained in the same manner as in Example 12 except that 0.38 g of calcium chloride was added instead of 0.39 g of aluminum sulfate. Furthermore, the haze was measured and the redispersibility was evaluated. The results are listed in the table.

(Example 15)
A fine fibrous cellulose concentrate was obtained in the same manner as in Example 12 except that 14.0 g of a 10% tetrapropylammonium hydroxide (TPA) aqueous solution was added instead of the 10% tetrabutylammonium hydroxide (TBA) aqueous solution. .. Furthermore, the haze was measured and the redispersibility was evaluated. The results are listed in the table.

(Example 16)
A fine fibrous cellulose concentrate was obtained in the same manner as in Example 12 except that 10.1 g of a 10% tetraethylammonium hydroxide (TEA) aqueous solution was added instead of the 10% tetrabutylammonium hydroxide (TBA) aqueous solution. Furthermore, the haze was measured and the redispersibility was evaluated. The results are listed in the table.

(Example 17)
Fine fibrous cellulose concentration in the same manner as in Example 12 except that a mixture of 12.8 g of a 10% dodecylamine-isopropyl alcohol solution and 0.1 g of ween60 was added instead of the 10% tetrabutylammonium hydroxide (TBA) aqueous solution. I got something. Furthermore, the haze was measured and the redispersibility was evaluated. The results are listed in the table.

(Example 18)
Fine fibrous cellulose concentrate in the same manner as in Example 12 except that 24.4 g of a 10% didodecylamine-isopropyl alcohol solution and 0.1 g of ween60 were added instead of the 10% tetrabutylammonium hydroxide (TBA) aqueous solution. Got Furthermore, the haze was measured and the redispersibility was evaluated. The results are listed in the table.

(Example 19)
Fine fibrous cellulose concentration in the same manner as in Example 12 except that 25.3 g of a 10% didodecylmethylamine-isopropyl alcohol solution and 0.1 g of ween60 were added instead of the 10% tetrabutylammonium hydroxide (TBA) aqueous solution. I got something. Furthermore, the haze was measured and the redispersibility was evaluated. The results are listed in the table.

(Comparative Example 1)
A fine fibrous cellulose redispersed slurry was obtained in the same manner as in Example 1 except that the homodisper treatment at the time of redispersion was 8000 rpm for 30 minutes by concentrating with sulfuric acid instead of aluminum sulfate. It was confirmed that the relative permittivity of the solvent contained in the fine fibrous cellulose redispersion slurry at 25 ° C. was 70 or less. Furthermore, the haze was measured and the redispersibility was evaluated. The results are listed in the table.

(Comparative Example 2)
A fine fibrous cellulose redispersed slurry was obtained in the same manner as in Example 1 except that the homodisper treatment at the time of redispersion was 8000 rpm for 30 minutes by concentrating with didecyldimethylammonium chloride instead of aluminum sulfate. .. It was confirmed that the relative permittivity of the solvent contained in the fine fibrous cellulose redispersion slurry at 25 ° C. was 70 or less. Furthermore, the haze was measured and the redispersibility was evaluated. The results are listed in the table.

(Comparative Example 3)
It was concentrated using polyacrylamide (PAM; FS-614 manufactured by Arakawa Chemical Co., Ltd.) instead of aluminum sulfate, and was in the form of fine fibers in the same manner as in Example 1 except that the homodisper treatment at the time of redispersion was 8000 rpm for 30 minutes. A cellulose redispersed slurry was obtained. It was confirmed that the relative permittivity of the solvent contained in the fine fibrous cellulose redispersion slurry at 25 ° C. was 70 or less. Furthermore, the haze was measured and the redispersibility was evaluated. The results are listed in the table.

(Comparative Example 4)
Fine fibers in the same manner as in Example 1 except that in step C, 3.4 g of 10% NaOH was added instead of 21.8 g of 10% tetrabutylammonium hydroxide and the homodisper treatment at the time of redispersion was 8000 rpm for 30 minutes. A cellulose redispersed slurry was obtained. It was confirmed that the relative permittivity of the solvent contained in the fine fibrous cellulose redispersion slurry at 25 ° C. was 70 or less. Furthermore, the haze was measured and the redispersibility was evaluated. The results are listed in the table.

(Reference example 1)
Phosphorylated pulp (TBA type) is used as the phosphorylated pulp, the solvent in the pre-dilution dilution is isopropanol (IPA) / water mass ratio of 60/40, and the content of phosphorylated pulp (TBA type) is 2.0. Diluted to the percentage of% to obtain pre-miniaturized slurry B. The obtained pre-miniaturized slurry B was subjected to 9-pass treatment at an operating pressure of 150 MPa using an explosion-proof high-pressure homogenizer to obtain a fine fibrous cellulose slurry B. Further, it was confirmed that the relative permittivity of the solvent contained in the fine fibrous cellulose slurry B at 25 ° C. was 70 or less. Furthermore, the haze was measured and the redispersibility was evaluated. The results are listed in the table.

(Reference example 2)
When the same procedure as in Reference Example 1 was carried out except that phosphorylated pulp (TPA type) was used instead of phosphorylated pulp (TBA type), a fine fibrous cellulose slurry C was obtained. Further, it was confirmed that the relative permittivity of the solvent contained in the fine fibrous cellulose slurry C at 25 ° C. was 70 or less. Furthermore, the haze was measured and the redispersibility was evaluated. The results are listed in the table.

(Reference example 3)
When the same procedure as in Reference Example 1 was carried out except that phosphorylated pulp (TEA type) was used instead of phosphorylated pulp (TBA type), a fine fibrous cellulose slurry D was obtained. Further, it was confirmed that the relative permittivity of the solvent contained in the fine fibrous cellulose slurry D at 25 ° C. was 70 or less. Furthermore, the haze was measured and the redispersibility was evaluated. The results are listed in the table.

〔evaluation〕
[Measurement of substituent introduction amount (phosphate group introduction amount, carboxyl group introduction amount)]
The amount of phosphoric acid group introduced is the amount of phosphoric acid group introduced into the fiber raw material, and the larger this value is, the more phosphoric acid groups are introduced. The amount of the substituent introduced was measured by diluting the target fine fibrous cellulose with ion-exchanged water so that the content was 0.2% by mass, treating with an ion-exchange resin, and titrating with an alkali. In the treatment with an ion exchange resin, a strongly acidic ion exchange resin (Amberjet 1024; Organo Corporation, conditioned) with a volume of 1/10 is added to a slurry containing 0.2% by mass fibrous cellulose and shaken for 1 hour. Was done. Then, it was poured onto a mesh having an opening of 90 μm, and the resin and the slurry were separated. In the titration using alkali, the change in the electric conductivity value shown by the slurry was measured while adding a 0.1 N sodium hydroxide aqueous solution to the fibrous cellulose-containing slurry after ion exchange. That is, the amount of alkali (mmol) required in the first region of the curve shown in FIG. 1 was divided by the solid content (g) in the slurry to be titrated to obtain the amount of substituent introduced (mmol / g).
The amount of carboxyl group introduced is the amount of substituent introduced by dividing the amount of alkali (mmol) required in the first region of the curve shown in FIG. 2 (carboxyl group) by the solid content (g) in the slurry to be titrated. It was set to (mmol / g).

[Measurement of haze]
The solid content concentration of the slurry to be measured is set to 0.5% by mass, and the glass cell for liquid (manufactured by Fujiwara Seisakusho, MG-40, backlit path) having an optical path length of 1 cm is filled. Measurements were made in accordance with JIS K 7136, except that the glass cell filled with this slurry was used as a test piece. The zero point measurement was performed with ion-exchanged water contained in the same glass cell.

[Evaluation of redispersibility]
As described above, the liquid immediately after the redispersion treatment by the homodisper (8000 rpm 1 minute manufactured by Tokushu Kagaku Kogyo Co., Ltd.) treatment was visually evaluated.
-Good when the redispersion concentration is 0.5%: No precipitation is observed.
Defective: Precipitation is observed.
-Good when the redispersion concentration is 3% or more: No solvent is discharged and no visual agglomerates are observed.
Defective: Solvent runs out. Visual agglomerates are observed.

Claims (4)

Fine, containing at least one selected from fine fibrous cellulose, alkali-soluble metals and polyvalent metal ions and / and salts thereof, and at least one selected from tetraalkylonium hydroxide and alkylamines and / or salts thereof. The content of a compound or / or a salt thereof, which is an alkali additive of a fibrous cellulose concentrate and contains at least one selected from an alkali-soluble metal and a polyvalent metal ion, satisfies the following (formula 1) and is hydroxylated. An alkaline additive of a fine fibrous cellulose concentrate, wherein the content of at least one selected from tetraalkylonium and alkylamine and / or a salt thereof satisfies the following (formula 2).
0.1 × A × B × C / D ≦ E ≦ 10 × A × B × C / D (Equation 1)
During the ceremony
A: Amount of functional group introduced into cellulose [mmol / g]
B: Functional group valence [-]
C: Amount of cellulose tested [g]
D: Alkali-soluble metal ion or multivalent metal ion valence [-]
E: The amount [mmol] of the alkali-soluble metal ion or polyvalent metal ion contained in the compound containing at least one selected from the alkali-soluble metal and the polyvalent metal ion and / or a salt thereof .
0.01 × E ≦ F ≦ 100 × E (Equation 2)
During the ceremony
Amount of alkali-soluble metal ion or polyvalent metal ion contained in a compound containing at least one selected from alkali-soluble metal and polyvalent metal ion and / or a salt thereof E [mmol]
Amount of tetraalkylonium hydroxide and / or a salt thereof F [mmol]
Is. The alkaline additive of the fine fibrous cellulose concentrate according to claim 1, wherein the alkali-soluble metal or polyvalent metal is one or more selected from the group consisting of aluminum, zinc, iron and calcium. .. The alkaline additive of the fine fibrous cellulose concentrate according to claim 1 or 2, wherein the tetraalkylonium hydroxide is tetraalkylammonium hydroxide. Claims 1 to 3 wherein the fine fibrous cellulose has one or more selected from the group consisting of a phosphate group or a substituent derived from a phosphate group, a group derived from a carboxylic acid and a group derived from sulfuric acid. The alkaline additive of the fine fibrous cellulose concentrate according to any one item.

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