JP6686989B2 - Fibrous cellulose-containing composition and paint - Google Patents

Description

  The present invention relates to a fibrous cellulose-containing composition and a paint.

  In recent years, materials that use reproducible natural fibers have been attracting attention due to the substitution of petroleum resources and increasing environmental awareness. Among natural fibers, fibrous cellulose having a fiber diameter of 10 to 50 μm, in particular, fibrous cellulose (pulp) derived from wood has been widely used as paper products until now.

  As the fibrous cellulose, fine fibrous cellulose having a fiber diameter of 1 μm or less is also known. Fine fibrous cellulose has been attracting attention as a new material, and its uses are diverse. For example, the development of sheets, resin composites, and thickeners containing fine fibrous cellulose is in progress.

  Also, application of fibrous cellulose to paints has been studied. Patent Document 1 describes an aqueous coating composition containing a cellulose fiber having a number average fiber diameter of 2 nm or more and 500 nm or less, an aqueous resin, and a colorant.

JP, 2016-69618, A

  The inventors have investigated the use of fine fibrous cellulose as a thickening agent for paints. However, it has been found that when the fine fibrous cellulose is contained in the paint, there is room for improvement in the coatability of the paint. It is an object of the present invention to provide a fibrous cellulose-containing composition and a paint having improved coatability.

As a result of intensive studies to solve the above-mentioned problems, the present inventors have a fibrous cellulose-containing composition having an ionic group and adding a pigment dispersant having a predetermined acid value or amine value. It has been found that the coating properties of can be improved. The present invention has been completed based on these findings.
The present invention has the following configurations.

[1] A fibrous cellulose-containing composition comprising fibrous cellulose having a fiber width of 1000 nm or less and a pigment dispersant having an ionic group, wherein the pigment dispersant has an acid value of 5 mgKOH / g or more and 200 mgKOH. / G or less, or the amine value of the pigment dispersant is 5 mgKOH / g or more and 200 mgKOH / g or less, a fibrous cellulose-containing composition.
[2] The fibrous cellulose-containing composition according to [1], wherein the pigment dispersant is an alkylol ammonium salt or a (meth) acrylate resin / potassium salt.
[3] The fibrous cellulose-containing composition according to [1] or [2], wherein the pigment dispersant has a weight average molecular weight of 1,000 or more and 100,000 or less.
[4] The fibrous cellulose-containing composition according to any one of [1] to [3], wherein the coating film obtained under the following conditions has a surface roughness Ra of 0.20 μm or less.
(conditions)
Application obtained by mixing the fibrous cellulose-containing composition, 156 parts by mass of an acrylic resin with respect to 1 part by mass of the fibrous cellulose, and 44 parts by mass of polyisocyanate with respect to 1 part by mass of the fibrous cellulose. The liquid is applied onto a smooth polyethylene terephthalate plate using an applicator so as to have a thickness of 30 μm, and immediately after application, it is dried at 80 ° C. for 30 minutes.
[5] The fibrous cellulose according to any one of [1] to [4], wherein the total amount of the fibrous cellulose, the pigment dispersant, and water is 90% by mass or more based on the entire composition. Composition.
[6] The fibrous cellulose-containing composition according to any one of [1] to [5], wherein the content of the pigment dispersant is 10 parts by mass or more based on 100 parts by mass of fibrous cellulose.
[7] Any one of [1] to [6] having a viscosity of 40,000 mPa · s or less measured at 23 ° C. and a rotation speed of 3 rpm with the solid content concentration of the fibrous cellulose being 0.4% by mass. The fibrous cellulose-containing composition according to.
[8] The fibrous cellulose is used as a dispersion liquid, and the supernatant yield when the supernatant liquid separated from the dispersion liquid under the following conditions is collected is 80% by mass or more. [1] to [7] Fibrous cellulose-containing composition.
(conditions)
The dispersion liquid of fibrous cellulose is adjusted to a solid content concentration of 0.2% by mass, and centrifuged using a cooling high-speed centrifuge under the conditions of 12000 G and 10 minutes. The obtained supernatant was collected and the solid content concentration of the supernatant was measured. The yield of fibrous cellulose is calculated based on the following formula.
Supernatant yield (%) = supernatant solid content concentration (%) / 0.2 × 100
[9] The Young's modulus of the coating film obtained under the following conditions is 0.7 GPa or more [1]
~ The fibrous cellulose-containing composition according to any one of [8].
(conditions)
Application obtained by mixing the fibrous cellulose-containing composition, 156 parts by mass of an acrylic resin with respect to 1 part by mass of the fibrous cellulose, and 44 parts by mass of polyisocyanate with respect to 1 part by mass of the fibrous cellulose. The solution is coated on a smooth polypropylene plate with an applicator so as to have a thickness of 30 μm, and immediately after coating, it is dried at 80 ° C. for 30 minutes.
[10] The fibrous cellulose-containing composition according to any one of [1] to [9], which further contains an enzyme.
[11] The fibrous cellulose-containing composition according to any one of [1] to [10] for use in a paint.
[12] The fibrous cellulose-containing composition according to any one of [1] to [10] for use in a thickener.
[13] A coating material containing the fibrous cellulose-containing composition according to any one of [1] to [12].
[14] A kit for a composition containing a fibrous cellulose, which is a combination of a fibrous cellulose having a fiber width of 1000 nm or less and a pigment dispersant having an ionic group.

  According to the present invention, it is possible to provide a fibrous cellulose-containing composition and a paint having improved coatability.

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

  Hereinafter, the present invention will be described in detail. The description of the constituent elements described below may be made based on typical embodiments or specific examples, but the present invention is not limited to such embodiments.

  The fibrous cellulose-containing composition of the present invention comprises a fibrous cellulose having a fiber width of 1000 nm or less (sometimes referred to as “fine fibrous cellulose”) and a pigment dispersant having an ionic group (referred to as “specific component”). There are) and.

(Fibrous cellulose)
The fibrous cellulose-containing composition of the present invention contains fine fibrous cellulose. The fine fibrous cellulose is preferably a fiber having an ionic substituent, and in this case, the ionic substituent is preferably an anionic substituent (hereinafter, also referred to as an anion group). As the anion group, for example, a phosphoric acid group or a substituent derived from a phosphoric acid group (sometimes simply referred to as a phosphoric acid group), a carboxyl group or a substituent derived from a carboxyl group (may be simply referred to as a carboxyl group), And at least one selected from a sulfone group or a substituent derived from a sulfone group (sometimes simply referred to as a sulfone group), and at least one selected from a phosphoric acid group and a carboxyl group Is more preferable, and a phosphoric acid group is particularly preferable.

  The fibrous cellulose raw material for obtaining the fine fibrous cellulose is not particularly limited, but pulp is preferably used because it is easily available and inexpensive. Examples of pulp include wood pulp, non-wood pulp, and deinked pulp. Examples of the wood pulp include hardwood kraft pulp (LBKP), softwood kraft pulp (NBKP), sulfite pulp (SP), dissolving pulp (DP), soda pulp (AP), unbleached kraft pulp (UKP), oxygen bleaching kraft. Examples include chemical pulp such as pulp (OKP). In addition, semi-chemical pulp such as semi-chemical pulp (SCP) and chemi-ground wood pulp (CGP), mechanical pulp such as ground wood pulp (GP), thermomechanical pulp (TMP, BCTMP), etc. are mentioned, but not particularly limited. Examples of the non-wood pulp include cotton-based pulp such as cotton linter and cotton lint, non-wood-based pulp such as hemp, straw and bagasse, cellulose isolated from ascidian and seaweed, chitin, chitosan and the like, but are not particularly limited. . Examples of the deinked pulp include deinked pulp made from waste paper, but are not particularly limited. The pulp of this embodiment may be used alone or as a mixture of two or more kinds. Among the above pulps, wood pulp containing cellulose and deinked pulp are preferable from the viewpoint of easy availability. Among the wood pulp, the chemical pulp has a high cellulose ratio, so the yield of fine fibrous cellulose at the time of fiber refining (defibration) is high, and the decomposition of cellulose in the pulp is small, and the fine fiber of long fibers with a large axial ratio is used. It is preferable in that fibrous cellulose can be obtained. Among these, kraft pulp and sulfite pulp are most preferably selected. A sheet containing long-fiber fine fibrous cellulose having a large axial ratio tends to have high strength.

  The average fiber width of the fine fibrous cellulose is 1000 nm or less as observed by an electron microscope. The average fiber width is preferably 2 nm or more and 1000 nm or less, more preferably 2 nm or more and less than 1000 nm, more preferably 2 nm or more and 100 nm or less, more preferably 2 nm or more and 50 nm or less, and further preferably 2 nm or more and 10 nm or less. It is not particularly limited. If the average fiber width of the fine fibrous cellulose is less than 2 nm, the fine fibrous cellulose is dissolved in water as a cellulose molecule, so that the physical properties (strength, rigidity, dimensional stability) of the fine fibrous cellulose tend to be difficult to develop. . The fine fibrous cellulose is, for example, a single fibrous cellulose having a fiber width of 1000 nm or less.

  The measurement of the 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% by mass or more and 0.1% by mass or less was prepared, and the suspension was cast on a hydrophilized carbon film-covered grid to obtain a TEM observation sample. To do. When a wide fiber is included, an SEM image of the surface cast on glass may be observed. Observation with an electron microscope image is performed at a magnification of 1000 times, 5000 times, 10,000 times, or 50,000 times depending on the width of the constituent fibers. However, the sample, observation conditions and magnification are adjusted so as to satisfy the following conditions.

(1) One straight line X is drawn at an arbitrary position in the observed 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 intersecting the straight line X and the straight line Y is visually read from the observed image satisfying the above conditions. In this way, three or more sets of images of the surface portion that do not at least overlap are observed, and the width of the fiber intersecting the straight line X and the straight line Y is read for each image. In this way, the fiber width of at least 20 fibers × 2 × 3 = 120 fibers is read. The average fiber width of the fine fibrous cellulose (simply referred to as “fiber width”) is the average value of the fiber width read in this way.

The fiber length of the fine fibrous cellulose is not particularly limited, but is preferably 0.1 μm or more and 1000 μm or less, more preferably 0.1 μm or more and 800 μm or less, and particularly preferably 0.1 μm or more and 600 μm or less. By setting the fiber length within the above range, it is possible to suppress the destruction of the crystalline region of the fine fibrous cellulose, and the slurry viscosity of the fine fibrous cellulose can be set to an appropriate range. The fiber length of the fine fibrous cellulose can be determined by image analysis using TEM, SEM, or AFM.
The axial ratio (fiber length / fiber width) of the fibrous cellulose is not particularly limited, but is preferably 20 or more and 10000 or less, and more preferably 50 or more and 1000 or less. By setting the axial ratio to the above lower limit or more, it is easy to form a fine fiber-containing sheet, and it is easy to obtain sufficient viscosity increase when a solvent dispersion is prepared. It is preferable that the axial ratio is not more than the above upper limit because handling such as dilution becomes easy when handling fibrous cellulose as an aqueous dispersion.

  The fine fibrous cellulose preferably has a type I crystal structure. Here, the fact that the fine fibrous cellulose has the I-type crystal structure can be identified in the diffraction profile obtained from the wide-angle X-ray diffraction photograph using CuKα (λ = 1.5418Å) monochromated with graphite. Specifically, it can be identified by having typical peaks at two positions near 2θ = 14 ° or more and 17 ° or less and around 2θ = 22 ° or more and 23 ° or less.

  The proportion of the I-type crystal structure in the fine fibrous cellulose is preferably 30% or more, more preferably 40% or more, still more preferably 50% or more. In this case, more excellent performance can be expected in terms of heat resistance and low linear thermal expansion coefficient. The crystallinity is determined by measuring the X-ray diffraction profile and using the pattern in a conventional manner (Seagal et al., Textile Research Journal, Vol. 29, page 786, 1959).

The fine fibrous cellulose preferably has a phosphoric acid group or a substituent derived from a phosphoric acid group. The phosphoric acid group is a divalent functional group corresponding to phosphoric acid from which a hydroxyl group has been removed. Specifically, it is a group represented by —PO ₃ H ₂ . Substituents derived from phosphoric acid groups include substituents such as groups in which a phosphoric acid group has been polycondensed, salts of phosphoric acid groups, and phosphoric acid ester groups. It may be a group.

In the present invention, the phosphoric acid group or the substituent derived from the phosphoric acid group may be a substituent represented by the following formula (1).

  In the formula (1), a, b, m and n each independently represent an integer (provided that a = b × m); α and α ′ each independently represent R or OR. R is 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 , An aromatic group, or a derivative group thereof; β is a monovalent or higher cation composed of an organic substance or an inorganic substance.

<Introduction of phosphate group>
The phosphoric acid group is introduced by reacting a cellulose-containing fiber raw material with at least one selected from a compound having a phosphoric acid group and a salt thereof (hereinafter, referred to as "phosphorylation reagent" or "compound A"). Can be done by. Such a phosphorylating reagent may be mixed with the fiber raw material in a dry state or a wet state in the state of powder or aqueous solution. As another example, powder of phosphorylation reagent or aqueous solution may be added to the slurry of fiber raw material.

  The introduction of the phosphoric acid group can be carried out by reacting the cellulose-containing fiber raw material with at least one compound (phosphorylation reagent or compound A) selected from a compound having a phosphoric acid group and a salt thereof. This reaction may be carried out in the presence of at least one kind selected from urea and its derivatives (hereinafter referred to as “compound B”).

  As an example of a method of allowing the compound A to act on the fiber raw material in the coexistence of the compound B, there is a method of mixing the powder or the aqueous solution of the compound A and the compound B with the fiber raw material in a dry state or a wet state. Another example is a method of adding powders or aqueous solutions of compound A and compound B to a slurry of fiber raw material. Among these, since the reaction is highly uniform, a method of adding an aqueous solution of compound A and compound B to a fiber material in a dry state, or a powder or an aqueous solution of compound A and compound B to a fiber material in a wet state is added. The method is preferred. Further, the compound A and the compound B may be added simultaneously or separately. Alternatively, the compound A and the compound B to be tested in the reaction may be added as an aqueous solution first, and the excess chemical solution may be removed by pressing. The form of the fiber raw material is preferably cotton or a thin sheet, but is not particularly limited.

The compound A used in this embodiment is at least one selected from a compound having a phosphoric acid group and a salt thereof.
Examples of the compound having a phosphoric acid group include phosphoric acid, a lithium salt of phosphoric acid, a sodium salt of phosphoric acid, a potassium salt of phosphoric acid, and an ammonium salt of phosphoric acid, but are not particularly limited. 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 ammonium salts of phosphoric acid include ammonium dihydrogen phosphate, diammonium hydrogen phosphate, triammonium phosphate, ammonium pyrophosphate, and ammonium polyphosphate.

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

  Further, the compound A is preferably used as an aqueous solution because the uniformity of the reaction is enhanced and the efficiency of introducing the phosphate group is enhanced. The pH of the aqueous solution of the compound A is not particularly limited, but is preferably 7 or less because the efficiency of introducing the phosphate group is high, and more preferably 3 or more and 7 or less from the viewpoint of suppressing hydrolysis of pulp fiber. The pH of the aqueous solution of the compound A may be adjusted by, for example, using a compound having an acid group and a compound having an alkalinity among the compounds having a phosphoric acid group and changing the amount ratio. The pH of the aqueous solution of the compound A may be adjusted by adding an inorganic alkali or an organic alkali to a compound having a phosphoric acid group and showing an acidity.

  The addition amount of the compound A to the fiber raw material is not particularly limited, but when the addition amount of the compound A is converted into the phosphorus atom amount, the addition amount of the phosphorus atom to the fiber raw material (absolute dry mass) is 0.5% by mass or more and 100% by mass. The following is preferable, 1 mass% or more and 50 mass% or less is more preferable, and 2 mass% or more and 30 mass% or less is most preferable. When 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. Further, by setting the amount of phosphorus atoms added to the fiber raw material to 100% by mass or less, it is possible to suppress the cost of the compound A to be used while improving the phosphorylation efficiency.

  Examples of the compound B used in this embodiment include urea, biuret, 1-phenylurea, 1-benzylurea, 1-methylurea and 1-ethylurea.

  Like the compound A, the compound B is preferably used as an aqueous solution. Further, it is preferable to use an aqueous solution in which both the compound A and the compound B are dissolved because the uniformity of the reaction is enhanced. The addition amount of the compound B to the fiber raw material (absolutely dry mass) is preferably 1% by mass or more and 500% by mass or less, more preferably 10% by mass or more and 400% by mass or less, and 100% by mass or more and 350% by mass. The amount is more preferably the following or less, and particularly preferably 150% by mass or more and 300% by mass or less.

  In addition to the compounds A and B, amides or amines may be included in the reaction system. Examples of the amides include formamide, dimethylformamide, acetamide, dimethylacetamide and the like. Examples of amines include methylamine, ethylamine, trimethylamine, triethylamine, monoethanolamine, diethanolamine, triethanolamine, pyridine, ethylenediamine, and hexamethylenediamine. Of these, triethylamine is known to work particularly as a good reaction catalyst.

  A heat treatment is preferably applied to introduce the phosphate group. As the heat treatment temperature, it is preferable to select a temperature at which the phosphoric acid group can be efficiently introduced while suppressing thermal decomposition or hydrolysis reaction of the fiber. Specifically, it is preferably 50 ° C or higher and 300 ° C or lower, more preferably 100 ° C or higher and 250 ° C or lower, and further preferably 130 ° C or higher and 200 ° C or lower. Further, a vacuum dryer, an infrared heating device, or a microwave heating device may be used for heating.

  During the heat treatment, while the fiber raw material slurry containing the compound A contains water, if the fiber raw material is allowed to stand for a long time, the compound A dissolved in water molecules moves to the surface of the fiber raw material with drying. To do. Therefore, the concentration of the compound A in the fiber raw material may be uneven, and the introduction of the phosphate group to the fiber surface may not proceed uniformly. In order to suppress the occurrence of uneven concentration of the compound A in the fiber raw material due to drying, an extremely thin sheet-shaped fiber raw material is used, or the fiber raw material and the compound A are heated or dried under reduced pressure while kneading or stirring the fiber raw material and the compound A. Just take the method.

  The heating device used for the heat treatment is preferably a device that can always discharge the water held in the slurry and the water generated by the addition reaction of the fibers such as phosphate groups to the hydroxyl groups of the fiber, to the outside of the apparatus system, for example, a blower type oven. Etc. are preferred. If water in the device system is constantly discharged, not only the hydrolysis reaction of the phosphate ester bond, which is the reverse reaction of phosphate esterification, can be suppressed, but also the acid hydrolysis of sugar chains in the fiber can be suppressed. It is possible to obtain fine fibers having a high axial ratio.

  Although the time of the heat treatment is influenced by the heating temperature, it is preferably 1 second or more and 300 minutes or less, more preferably 1 second or more and 1000 seconds or less after the water is substantially removed from the fiber raw material slurry. It is preferably 10 seconds or more and 800 seconds or less. In the present invention, by introducing the heating temperature and the heating time in appropriate ranges, the amount of phosphate groups introduced can be kept within the preferred range.

  The introduction amount of the phosphate group is preferably 5.20 mmol / g or less, more preferably 0.1 mmol / g or more and 3.65 mmol / g or less, and 0 per 1 g (mass) of the fine fibrous cellulose. .14 mmol / g or more and 3.5 mmol / g or less is more preferable, 0.2 mmol / g or more and 3.2 mmol / g or less is further preferable, 0.4 mmol / g or more and 3.0 mmol / g or less is particularly preferable, and most preferable. Is 0.6 mmol / g or more and 2.5 mmol / g or less. When the amount of the phosphate group introduced is within the above range, the fiber raw material can be easily made finer and the stability of the fine fibrous cellulose can be increased. Further, by setting the amount of the phosphate group introduced within the above range, it is easy to miniaturize, but it is also possible to leave hydrogen bonds between the fine fibrous celluloses, and good strength when formed into a sheet. Expression can be expected.

  The amount of the phosphate group introduced into the fiber raw material can be measured by a conductivity titration method. Specifically, it is refined by 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, the addition of alkali gives the curve shown in FIG. At first, the electrical conductivity sharply decreases (hereinafter referred to as "first region"). After that, the conductivity starts to slightly increase (hereinafter, referred to as “second region”). After that, the increment of conductivity increases (hereinafter, referred to as “third region”). That is, three areas appear. The boundary point between the second region and the third region is defined as the point where the second derivative of the conductivity, that is, the amount of change in the conductivity increment (slope) is maximum. Of these, the amount of alkali required in the first region is equal to the amount of strong acidic groups in the slurry used for titration, and the amount of alkali required in the second region is the amount of weak acidic groups in the slurry used for titration. Will be equal. When the phosphoric acid groups undergo condensation, apparently weak acidic groups are lost, and the amount of alkali required in the second region is smaller than the amount of alkali required in the first region. On the other hand, since the amount of strong acidic group is the same as the amount of phosphorus atom regardless of the presence or absence of condensation, simply the amount of introduced phosphate group (or the amount of phosphate group) or the introduced amount of substituent (or the amount of substituent) When said, it means the amount of strongly acidic groups. That is, the amount of alkali (mmol) required in the first region of the curve shown in FIG. 1 is divided by the solid content (g) in the slurry to be titrated to obtain the amount of introduced substituent (mmol / g).

  The phosphate group introducing step may be performed at least once, but may be repeated a plurality of times. In this case, more phosphate groups are introduced, which is preferable.

<Introduction of carboxyl group>
In the present invention, when the fine fibrous cellulose has a carboxyl group, for example, the fiber raw material is subjected to an oxidation treatment such as TEMPO (2,2,6,6-tetramethylpiperidine-1-oxyl) oxidation treatment. Alternatively, a carboxyl group can be introduced by treating with a compound having a group derived from a carboxylic acid, a derivative thereof, or an acid anhydride thereof or a derivative thereof.

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

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

  The derivative of the compound having a carboxyl group is not particularly limited, and examples thereof include an imidized product of an acid anhydride of a compound having a carboxyl group and a derivative of an acid anhydride of a compound having a carboxyl group. The imidized product of an acid anhydride of a compound having a carboxyl group is not particularly limited, and examples thereof include imidized products of dicarboxylic acid compounds such as maleimide, succinimide, and phthalimide.

  The derivative of the acid anhydride of the compound having a carboxyl group is not particularly limited. For example, at least a part of hydrogen atoms of an acid anhydride of a compound having a carboxyl group such as dimethyl maleic anhydride, diethyl maleic anhydride, and diphenyl maleic anhydride is a substituent (for example, an alkyl group, a phenyl group, etc.). ).

The introduction amount of the carboxyl group is preferably 0.1 mmol / g or more and 3.65 mmol / g or less, more preferably 0.14 mmol / g or more and 3.5 mmol / g or less, per 1 g (mass) of fine fibrous cellulose. It is more preferably 0.2 mmol / g or more and 3.2 mmol / g or less, particularly preferably 0.4 mmol / g or more and 3.0 mmol / g or less, and most preferably 0.6 mmol / g or more and 2.5 mmol / g or less.
The amount of carboxyl groups introduced into the fiber raw material can be measured by a conductivity titration method. In conductivity titration, the addition of alkali gives the curve shown in FIG. The alkali amount (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 a substituent introduction amount (mmol / g).

<Alkali treatment process>
When producing fine fibrous cellulose, an alkali treatment may be performed on the fiber raw material between the substituent introduction step and the defibration treatment step described later. The method of alkali treatment is not particularly limited, and examples thereof include a method of immersing the substituent-introduced fiber in an alkali solution.

  The alkaline compound contained in the alkaline solution is not particularly limited, and may be an inorganic alkaline compound or an organic alkaline compound. In this embodiment, for example, sodium hydroxide or potassium hydroxide is preferably used as the alkali compound because of its high versatility. The solvent contained in the alkaline solution may be either water or an organic solvent. The solvent contained in the alkaline solution is preferably a polar solvent containing water or a polar organic solvent such as an alcohol, and more preferably an aqueous solvent containing at least water. As the alkaline solution, for example, an aqueous solution of sodium hydroxide or an aqueous solution of potassium hydroxide is preferable because it has high versatility.

  The temperature of the alkali solution in the alkali treatment step is not particularly limited, but is preferably 5 ° C. or higher and 80 ° C. or lower, and more preferably 10 ° C. or higher and 60 ° C. or lower. The time for immersing the substituent-introduced fiber in the alkali solution in the alkali treatment step is not particularly limited, but is preferably 5 minutes or more and 30 minutes or less, and more preferably 10 minutes or more and 20 minutes or less. The amount of the alkaline solution used in the alkaline treatment is not particularly limited, but is preferably 100% by mass or more and 100000% by mass or less and 1000% by mass or more and 10000% by mass or less based on the absolute dry mass of the substituent-introduced fiber. More preferably.

  In order to reduce the amount of alkali solution used in the alkali treatment step, the substituent-introduced fiber may be washed with water or an organic solvent after the substituent introduction step and before the alkali treatment step. After the alkali treatment step and before the defibration treatment step, it is preferable to wash the alkali-treated substituent-introduced fiber with water or an organic solvent from the viewpoint of improving handleability.

<Acid treatment step>
In the case of producing fine fibrous cellulose, the fiber raw material may be subjected to an acid treatment between the step of introducing a substituent and the defibration treatment step described later. An example of the present embodiment is a case where the substituent introduction step, the acid treatment, the alkali treatment, and the defibration treatment are performed in this order.

  The temperature of the acid solution in the acid treatment is not particularly limited, but is preferably 5 ° C. or higher and 100 ° C. or lower, and more preferably 20 ° C. or higher and 90 ° C. or lower. The immersion time in the acid solution in the acid treatment is not particularly limited, but is preferably 5 minutes or more and 120 minutes or less, more preferably 10 minutes or more and 60 minutes or less. The amount of the acid solution used in the acid treatment is not particularly limited, but for example, is preferably 100% by mass or more and 100000% by mass or less, and 1000% by mass or more and 10000% by mass or less based on the absolute dry mass of the fiber raw material. Is more preferable.

  The method of acid treatment is not particularly limited, and examples thereof include a method of immersing the fiber raw material in an acid solution containing an acid. The concentration of the acidic liquid used is not particularly limited, but is preferably 10% by mass or less, and more preferably 5% by mass or less. The pH of the acidic liquid used is not particularly limited, but is preferably 0 to 4 and more preferably 1 to 3, for example. As the acid contained in the acidic liquid, for example, an inorganic acid, a sulfonic acid, a carboxylic acid or the like can be used. Examples of the inorganic acid include sulfuric acid, nitric acid, hydrochloric acid, hydrobromic acid, hydroiodic acid, hypochlorous acid, chlorous acid, chloric acid, perchloric acid, phosphoric acid and boric acid. Examples of the sulfonic acid include methanesulfonic acid, ethanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, trifluoromethanesulfonic acid and the like. Examples of the carboxylic acid include formic acid, acetic acid, citric acid, gluconic acid, lactic acid, oxalic acid, tartaric acid and the like. Among these, it is particularly preferable to use hydrochloric acid or sulfuric acid.

<Disentanglement treatment (miniaturization)>
Fine fiber cellulose is obtained by defibrating the substituent-introduced fiber in the defibrating process. In the defibration processing step, for example, a defibration processing device can be used. The defibration treatment device is not particularly limited, but includes, for example, a wet atomization device, a high-speed defibration device, a grinder (stone mill type crusher), a high pressure homogenizer or an ultrahigh pressure homogenizer, a high pressure collision type crusher, a ball mill, a bead mill, a disc type refiner, A conical refiner, a twin-screw kneader, a vibration mill, a homomixer under high-speed rotation, an ultrasonic disperser, or a beater can be used, and the solid content concentration of fine fibrous cellulose at the time of defibration treatment is appropriately set. it can. Among the above-mentioned defibration treatment devices, it is more preferable to use a wet atomization device, a high-speed defibration device, a high-pressure homogenizer, and an ultrahigh-pressure homogenizer, which are less affected by the grinding media and less likely to cause contamination. The number of defibration treatments (miniaturization) is not particularly limited, but it is preferably performed multiple times in order to promote sufficient miniaturization. The upper limit is not particularly limited, but it is practical that it is 10 times or less.

  In the defibration process step, for example, the substituent-introduced fibers are preferably diluted with a dispersion medium to form a slurry. As the dispersion medium, one or more selected from water and organic solvents such as polar organic solvents can be used. The polar organic solvent is not particularly limited, but alcohols, polyhydric alcohols, ketones, ethers, esters, aprotic polar solvents and the like are preferable. Examples of alcohols include methanol, ethanol, isopropanol, n-butanol, and isobutyl alcohol. Examples of polyhydric alcohols include ethylene glycol, propylene glycol, glycerin and the like. Examples of ketones include acetone and methyl ethyl ketone (MEK). Examples of ethers include diethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono n-butyl ether, and propylene glycol monomethyl ether. Examples of the esters include ethyl acetate, butyl acetate and the like. Examples of the aprotic polar solvent include dimethyl sulfoxide (DMSO), dimethylformamide (DMF), dimethylacetamide (DMAc), N-methyl-2-pyrrolidinone (NMP) and the like.

<Enzyme treatment>
In the present invention, enzyme treatment may be performed. That is, the cellulose-containing composition of the present invention may contain an enzyme. Further, the cellulose-containing composition of the present invention may contain a protein obtained by deactivating an enzyme.
The enzyme that can be used in the present invention is a cellulase-based enzyme, and is classified into the sugar hydrolase family based on the higher-order structure of the catalytic domain having the hydrolysis reaction function of cellulose. Cellulase-based enzymes are classified into endo-glucanases and cellobiohydrolases according to their cellulolytic properties. Endo-glucanase has a high hydrolyzability with respect to an amorphous portion of cellulose, soluble cellooligosaccharides, or a cellulose derivative such as carboxymethyl cellulose, and randomly cleaves their molecular chains from the inside to reduce the degree of polymerization. However, endo-glucanase has low hydrolytic reactivity to crystalline cellulose microfibrils. On the other hand, cellobiohydrolase decomposes the crystal part of cellulose to give cellobiose. Cellobiohydrolase hydrolyzes from the end of the cellulose molecule and is also called an exo-type or processive enzyme. In the present invention, it is preferable to use an endo-type glucanase.

  As the enzyme used in the present invention, a hemicellulase enzyme may be used in addition to the endo-glucanase and cellobiohydrolase. Among hemicellulase-based enzymes, xylanase, which is an enzyme that decomposes xylan, mannase, which is an enzyme that decomposes mannan, or arabanase, which is an enzyme that decomposes araban, can be mentioned. Pectinase, which is an enzyme that decomposes pectin, can also be used as a hemicellulase enzyme. Microorganisms that produce hemicellulase enzymes often produce cellulase enzymes.

  Hemicellulose is a polysaccharide excluding pectins between cellulose microfibrils of plant cell walls. Hemicellulose is a wide variety, and it is different in the type of plant and the wall layer of the cell wall. In wood, glucomannan is the main component in the secondary wall of conifers, and 4-O-methylglucuronoxylan is the main component in secondary walls of hardwoods. Therefore, it is preferable to use mannase for obtaining fine fibers from conifers, and it is preferable to use xylanase for hardwoods.

According to the present invention, there is provided a method for producing a cellulose-containing composition, which comprises the step of adding an enzyme. The enzyme can be reacted with the fine fibrous cellulose by adding the enzyme to the fine fibrous cellulose. In the present invention, it is possible to adopt a form in which the washing step of the fine fibrous cellulose is not performed after the enzyme treatment.
In the present invention, the enzyme may be deactivated after the enzyme treatment. As a method for deactivating the enzyme, a mixture of fine fibrous cellulose and enzyme is heated to 100 ° C. and left standing for 30 minutes to 1 hour while maintaining the temperature, or a mixture of fine fibrous cellulose and enzyme. On the other hand, it is possible to add a strong base to adjust the pH to 10 or more, but it is not particularly limited.
The cellulose-containing composition of the present invention can be manufactured by the above-described method for manufacturing a cellulose-containing composition.

The amount of enzyme added to 1 part by mass of fibrous cellulose having a fiber width of 1000 nm or less is not particularly limited, but is preferably 1 × 10 ⁻³ parts by mass or less, more preferably 1 × 10 ⁻⁴ parts by mass or less, and 1 It is more preferably not more than × 10 ^-5 parts by mass, particularly preferably not more than 5.0 × 10 ^-6 parts by mass. The amount of enzyme added is preferably 1 × 10 ^-7 parts by mass or more, more preferably 3 × 10 ^-7 parts by mass or more, and further preferably 1 × 10 ^-6 parts by mass or more, relative to 1 part by mass of fibrous cellulose. preferable.
By setting the addition amount of the enzyme within the above range, it is possible to suppress the particles (aggregates) in the coated product.

The reaction time between the fine fibrous cellulose and the enzyme is not particularly limited, but is generally 1 minute to 24 hours, more preferably 1 minute to 1 hour.
The reaction temperature and the reaction pH of the fine fibrous cellulose and the enzyme are preferably maintained at the optimum temperature and the optimum pH of the enzyme to be used, and are generally 20 ° C to 80 ° C and pH 4.5 to 9.5. It is preferable to keep.
By setting the reaction conditions within the above range, particles (aggregates) in the coated product can be suppressed.

<Coarse fibrous cellulose>
As described above, the step of obtaining the fine fibrous cellulose preferably includes a step of refining the fiber raw material (coarse fibrous cellulose). At this time, most of the coarse fibrous cellulose is pulverized, but a part thereof may remain without being pulverized. In such a case, the fibrous cellulose-containing composition of the present invention contains coarse fibrous cellulose.

  The coarse fibrous cellulose contained in the fibrous cellulose-containing composition of the present invention means that the cellulose dispersion is adjusted to a solid concentration of 0.2% by mass, and a cooling high-speed centrifuge (Kokusan Co., Ltd., H-2000B) is used. It is a fibrous cellulose that precipitates when it is used and centrifuged at 12000 G for 10 minutes.

  Less sedimentation component means higher yield of supernatant after centrifugation. The supernatant yield after this centrifugation is preferably 80% by mass or more based on the total mass of the fibrous cellulose. The supernatant yield after centrifugation is more preferably 90% by mass or more, further preferably 95% by mass or more, and particularly preferably 99% by mass or more.

The supernatant yield of the above-mentioned fine fibrous cellulose dispersion after centrifugation can be measured by the following method in this specification.
The supernatant yield after centrifugation of the fine fibrous cellulose dispersion was measured by the method described below. The supernatant yield after centrifugation is an index of the yield of fine fibrous cellulose, and the higher the supernatant yield, the higher the yield of fine fibrous cellulose.

The fine fibrous cellulose dispersion liquid was adjusted to a solid content concentration of 0.2% by mass, and centrifuged using a cooling high-speed centrifuge (H-2000B, manufactured by Kokusan Co., Ltd.) under the conditions of 12000 G and 10 minutes. The obtained supernatant was collected and the solid content concentration of the supernatant was measured. The yield of fine fibrous cellulose was calculated based on the following formula.
Yield (%) of fine fibrous cellulose = solid content concentration (%) of supernatant / 0.2 × 100

  In the present embodiment, the supernatant yield after centrifugation of the fine fibrous cellulose dispersion is high, that is, the fibrous cellulose-containing composition is characterized in that the content of coarse fibers is small, the fine fibrous cellulose dispersion By setting the supernatant yield after centrifugation in the above range, good coatability can be obtained when blended in a coating material.

(Specific component)
In the present invention, a pigment dispersant having an ionic group (also referred to as "specific component") is used. The pigment dispersant used in the present invention has an acid value of 5 mgKOH / g or more and 200 mgKOH / g or less, or an amine value of 5 mgKOH / g or more and 200 mgKOH / g or less. The pigment dispersant is a component used for uniformly dispersing a pigment (fine solid) in a dispersion medium to prepare a stable dispersion.

The pigment dispersant is, for example, structurally one kind of a surfactant, and in particular, one having an affinity for a dispersion medium and a function for adsorbing it on a solid surface such as a pigment is preferable. Further, in addition to the pigment adsorbing action and the affinity for the dispersion medium, there is one that also has electrostatic repulsion or steric repulsion (giving repulsive force at the time of dispersion) in order to prevent reaggregation of the pigment and prevent sedimentation. In the present invention, it is preferable that the pigment adsorption action, the dispersion medium affinity action, and the repulsive force imparting action at the time of dispersion are effective in preventing the aggregation of the fine fibrous cellulose.
Examples of the pigment dispersant having these three functions include resin-type pigment dispersants.

  Examples of the resin-type pigment dispersant include a polymer composed of polyester resin, polyolefin resin, polyurethane resin, (meth) acrylic acid resin, and an amino group, a hydroxyl group, a carboxyl group, a carboxylic acid in a side chain. Those having a functional group such as an ester group, an amide group, an ammonium group, a sulfo group, a sulfate ester group, a phosphoryl group, a phosphoric acid group, a carbamoyl group and a sulfamoyl group are preferable.

  The molecular weight of the pigment dispersant having an ionic group is not particularly limited, but a high molecular weight compound is preferable, a weight average molecular weight of 1,000 or more is preferable, and 2,000 or more is more preferable. The upper limit is preferably 100,000 or less, more preferably 60,000 or less. If the weight average molecular weight of the pigment dispersant is less than the above lower limit value, sufficient steric hindrance cannot be obtained, and the dispersing effect may decrease. When the weight average molecular weight is larger than the above upper limit, conversely, an aggregation action may occur. Unless otherwise specified, the weight average molecular weight (Mw) of the pigment dispersant is a value measured by gel permeation chromatography (GPC) under the following conditions.

Solvent: Tetrahydrofuran (THF)
Column: Shodex K806, K805, K803G
(Use 3 by connecting Showa Denko KK)
Column temperature: 40 ° C
Sample concentration: 0.1% by mass
Detector: RI Model 504 (GL Science Co., Ltd.)
Pump: L6000 (manufactured by Hitachi, Ltd.)
Flow rate (flow velocity): 1.0 ml / min
Injection volume: 10 μL
Calibration curve: Standard polystyrene STK standard polystyrene (manufactured by Tosoh Corp.) A calibration curve of 13 samples from Mw = 500 to 2.8 million was used. The 13 samples are used at substantially equal intervals.

The pigment dispersant having an ionic group has an acid value of 5 mgKOH / g or more and 200 mgKOH / g or less, or an amine value of 5 mgKOH / g or more and 200 mgKOH / g or less.
The acid value of the pigment dispersant having an ionic group is preferably 5 mgKOH / g or more, more preferably 10 mgKOH / g or more, further preferably 15 mgKOH / g or more, further preferably 20 mgKOH / g or more, further preferably 25 mgKOH / g or more. 30 mgKOH / g or more is particularly preferable. The upper limit of the acid value is preferably 200 mgKOH / g or less, more preferably 180 mgKOH / g or less, further preferably 150 mgKOH / g or less, further preferably 120 mgKOH / g or less, and particularly preferably 100 mgKOH / g or less.

  The amine value of the pigment dispersant having an ionic group is preferably 5 mgKOH / g or more, more preferably 10 mgKOH / g or more, further preferably 15 mgKOH / g or more, further preferably 20 mgKOH / g or more, further 25 mgKOH / g or more. 30 mgKOH / g or more is particularly preferable. The upper limit of the amine value is preferably 200 mgKOH / g or less, more preferably 180 mgKOH / g or less, further preferably 150 mgKOH / g or less, further preferably 120 mgKOH / g or less, and particularly preferably 100 mgKOH / g or less.

  When the acid value or amine value of the pigment dispersant having an ionic group is less than the above lower limit, the interaction with the fine fibrous cellulose is likely to be insufficient, a sufficient aggregation preventing effect cannot be obtained, and the coatability is poor. However, a smooth surface may not be obtained. On the other hand, when the acid value or amine value exceeds the upper limit, the steric hindrance layer becomes smaller than that in the affinity portion for fine fibrous cellulose, and the effect of preventing aggregation may be insufficient.

  The ionic group of the pigment dispersant having an ionic group is not particularly limited, and may be a cation group, an anion group, or an acid or base dissociable group. Examples of the cationic group include an amino group and a quaternary ammonium group. Examples of the anion group include a sulfo group, a carboxyl group, a sulfuric acid ester group, and a phosphoric acid group. Examples of the dissociative group include an amide group. The ionic group may form a salt with a counterion. The pigment dispersant having an ionic group may have the above-mentioned cation group, anion group and dissociative group in the molecule at the same time.

  Examples of the pigment dispersant having an ionic group include various ones, and as the polymer dispersant, a styrene / maleic anhydride copolymer, a formalin bond of naphthalene sulfonate, a poly (meth) acrylate, Carboxymethyl cellulose, olefin / maleic anhydride copolymer, polystyrene sulfonate, acrylamide / acrylic acid copolymer, anionic polymer dispersant such as sodium alginate, polyethyleneimine, aminoalkyl (meth) acrylate copolymer, polyvinylimidazoline , Satkin sun, a resin (polymer) having a (meth) acrylate alkali metal salt moiety, a resin having a (meth) acrylic acid moiety, a resin having an alkylol ammonium salt moiety, and the like. For these polymer dispersants, see, for example, Mito Kushi “Dispersant” J. Jpn. Soc. Color Mater. , 78 [3] (2005) pp. 41-48 can be referred to.

  Among them, in the present invention, the pigment dispersant having an ionic group is a resin having an alkylol ammonium salt moiety, a resin having a (meth) acrylic acid moiety, or a resin having a (meth) acrylate alkali metal salt moiety. Preferred are alkylol ammonium salts of polycarboxylic acids, alkylol ammonium salts of copolymers containing an acid group, alkylol ammonium salts such as alkylol ammonium salts of polyfunctional polymers, (meth) acrylate resins, potassium salts, etc. Is particularly preferable. In addition, in this specification, the term (meth) acrylate means a generic term for acrylate and methacrylate.

The alkylol ammonium salt site is preferably a reactive site between an acidic group (for example, a sulfo group, a carboxyl group, a sulfate ester group, a phosphoryl group, phosphoric acid, etc.) and an alkylol ammonium salt. The alkylol ammonium salt moiety preferably has the following partial structure.
-C (= O) -N (-R 1) (- R 2 -OH) formula (2)
Here, R ¹ is a hydrogen atom or an alkyl group (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 and further preferably 1 to 3), and R ² is an alkylene group (preferably having 1 to 12 carbon atoms, 1 ~ 6 are more preferred, and 1-3 are still more preferred). R ¹ and R ² may further have a substituent Z within the range that the effect of the present invention is exhibited.

The pigment dispersant having an anion group is preferably a polymer having a partial structure of the following formula (3).
-C (= O) -OM formula (3)
Here, M is a hydrogen atom or an alkali metal. The alkali metal is preferably sodium or potassium. In the formula, O may be an anion and M may be a cation to form a salt.

As the pigment dispersant having an anion group, a polymer having a partial structure of the following formula (4) is also preferable.
-C (= O) -O-L 1 -A formula (4)
A is an acidic group, preferably a sulfo group, a carboxyl group, a sulfate ester group, a phosphoryl group, or a phosphoric acid group. This acidic group may form a salt. Preferred salts are alkali metal salts, with sodium or potassium salts being preferred. L ¹ is a linking group Y described later, and among them, an alkylene group (C 1-12 is preferable, 1-6 is more preferable, 2 or 3 is more preferable).

As the pigment dispersant having an alkylol ammonium salt moiety,
DISPERBYK,
DISPERBYK-180,
DISPERBYK-181,
DISPERBYK-187,
DISPERBYK-140,
DISPERBYK-250,
BYK-9076,
BYK-W969
(All are trade names, manufactured by BIC-Chemie) and the like can be used.
As the pigment dispersant having a (meth) acrylate potassium salt moiety, a polymer (including a copolymer) synthesized by using potassium sulfopropyl (meth) acrylate as a monomer can be used.
As the (meth) acrylate resin / potassium salt, for example, DISPER-AW300P (manufactured by Otsuka Chemical Co., Ltd.) can be used.

  As the substituent Z, an alkyl group (preferably having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, further preferably 1 to 6 carbon atoms), an aralkyl group (preferably having 7 to 21 carbon atoms, and 7 carbon atoms) To 15 are more preferable, and those having 7 to 11 carbon atoms are more preferable), hydroxyl group, amino group or salts thereof (0 to 24 carbon atoms are preferable, 0 to 12 carbon atoms are more preferable, and 0 to 6 carbon atoms are further preferable). ), A thiol group, a carboxyl group or a salt thereof, a carbamoyl group or a salt thereof (preferably having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, further preferably 1 to 6 carbon atoms), a sulfamoyl group or a salt thereof ( It preferably has 0 to 24 carbon atoms, more preferably 0 to 12 carbon atoms, further preferably 0 to 6 carbon atoms, and an aryl group (preferably 6 to 22 carbon atoms). C6-18 is more preferable, C6-10 is more preferable), acyl group (C2-12 is preferable, C2-6 is more preferable, C2 or C3 is more preferable), acyloxy. Group (C2-12 is preferable, C2-6 is more preferable, C2 or C3 is more preferable), heterocyclic group (C2-8 is more preferable, C2-5 is further preferable. ), A halogen atom, a quaternary ammonium group or a salt thereof (preferably having 3 to 23 carbon atoms, more preferably 3 to 19 carbon atoms, and further preferably 3 to 11 carbon atoms).

As the linking group Y, an alkylene group (methylene group, ethylene group, propylene group, etc.), an oxygen atom, a sulfur atom, a carbonyl group, a sulfonyl group, a sulfinyl group, an imino group (NR ^L ), and a linking group related to a combination thereof. Is mentioned. R ^L is a hydrogen atom, a methyl group, an ethyl group, or a propyl group. The number of atoms contained in the linking group Y is preferably 1 or more and 12 or less, and more preferably 1 or more and 6 or less.

  The content of the specific component is preferably 600 parts by mass or less, more preferably 400 parts by mass or less, further preferably 300 parts by mass or less, and 200 with respect to 100 parts by mass of the fibrous cellulose. It is particularly preferable that the amount is less than or equal to parts by mass. In addition, the content of the specific component is preferably 1 part by mass or more, more preferably 5 parts by mass or more, and further preferably 10 parts by mass or more with respect to 100 parts by mass of the fibrous cellulose. , 15 parts by mass or more is particularly preferable. When the content is at least the above lower limit, the coatability of the fibrous cellulose-containing composition and, if necessary, the smoothness of the coating film can be achieved at a high level, which is preferable. When the content is not more than the above upper limit, the desired effect can be exhibited without impairing the properties required for the fibrous cellulose-containing composition and the manufacturing suitability, which is preferable.

  Only one specific component may be used, or two or more specific components may be used in combination. When two or more kinds are used, the total amount is preferably within the above range.

(resin)
The fibrous cellulose-containing composition of the present invention may further contain a resin such as a thermoplastic resin, a thermosetting resin, or a photocurable resin when it is used as a paint. Examples of the resin include styrene resin, acrylic resin, aromatic polycarbonate resin, aliphatic polycarbonate resin, aromatic polyester resin, aliphatic polyester resin, aliphatic polyolefin resin, cyclic olefin resin, polyamide Resin, polyphenylene ether resin, thermoplastic polyimide resin, polyacetal resin, polysulfone resin, amorphous fluorine resin, rosin resin, nitrocellulose, vinyl chloride resin, chlorinated rubber resin, vinyl acetate resin, Examples include, but are not limited to, phenol resins and epoxy resins.

  The content of the resin is preferably 30 parts by mass or more, more preferably 70 parts by mass or more, and 100 parts by mass or more with respect to 1 part by mass of fibrous cellulose in the case of a coating material. Is particularly preferred. Further, the content of the resin is preferably 500 parts by mass or less, more preferably 300 parts by mass or less, and particularly preferably 200 parts by mass or less, relative to 1 part by mass of the fibrous cellulose. By containing the resin so as to have the above content, the effects of the specific component can be suitably exhibited, and the coatability, the smoothness of the coating film, and the optimization of the elastic modulus and the strength can be realized.

(Curing agent)
The fibrous cellulose-containing composition of the present invention preferably contains a curing agent when it is used as a coating material. As the curing agent, known ones can be appropriately used, and examples thereof include an isocyanate curing agent (polyisocyanate and the like), an epoxy (oxirane) curing agent, an oxetane curing agent, and the like. In the present invention, the isocyanate curing agent is particularly preferable.

  When used as a coating material, the content of the curing agent is preferably 10 parts by mass or more, more preferably 20 parts by mass or more, and 30 parts by mass or more with respect to 1 part by mass of fibrous cellulose. It is particularly preferable that Further, the content of the curing agent is preferably 100 parts by mass or less, more preferably 80 parts by mass or less, and particularly preferably 60 parts by mass or less, with respect to 1 part by mass of the fibrous cellulose. . By containing the curing agent so as to have the above content, the effects of the above-mentioned specific components can be suitably exerted, and the coatability, the smoothness of the coating film, and the optimization of the elastic modulus can be realized.

(Arbitrary component)
The fibrous cellulose-containing composition of the present invention may contain optional components other than the above-mentioned components. Examples of optional components include antifoaming agents, lubricants, ultraviolet absorbers, dyes, pigments, stabilizers, surfactants, coupling agents, inorganic layered compounds, inorganic compounds, leveling agents, organic particles, antistatic agents. , Magnetic powder, orientation promoter, plasticizer, preservative, cross-linking agent and the like. Moreover, you may add an organic ion as an arbitrary component.

(Fibrous cellulose-containing composition)
When the fibrous cellulose-containing composition is a paint, the content of the fibrous cellulose is preferably 0.05% by mass or more based on the solid content in the fibrous cellulose-containing composition, It is more preferably 1% by mass or more, and further preferably 0.3% by mass or more. The content of fibrous cellulose is preferably 10% by mass or less, more preferably 5% by mass or less, and further preferably 2% by mass or less.

  When the fibrous cellulose-containing composition is used as the thickener, the content of the fibrous cellulose is preferably 0.1% by mass or more based on the total amount of the fibrous cellulose-containing composition, It may be 4% by mass or more, 1% by mass or more, 5% by mass or more, 10% by mass or more, 20% by mass or more, 30% by mass or more, 40% by mass or more, 50% by mass or more, or 55% by mass or more. The content of fibrous cellulose is preferably 95% by mass or less, and more preferably 90% by mass or less.

  In the use of the thickener, the total amount of the fibrous cellulose, the specific component and water is preferably 80% by mass or more, and 90% by mass or more with respect to the entire fibrous cellulose-containing composition. It is more preferable that the content is 95% by mass or more.

  The form of the fibrous cellulose-containing composition of the present invention is not particularly limited and can be present in various forms such as powder, slurry and solid. Among them, the fibrous cellulose-containing composition is preferably a slurry, and more preferably a high viscosity slurry. Specifically, the fibrous cellulose-containing composition has a viscosity of 40,000 mPa · s or less measured at 23 ° C. and a rotation speed of 3 rpm with the solid content concentration of the fibrous cellulose being 0.4% by mass. It is more preferably 35,000 mPa · s or less, still more preferably 30,000 mPa · s or less, and particularly preferably 25,000 mPa · s or less. The lower limit is preferably a slurry of 3,000 mPa · s or more, more preferably a slurry of 5,000 mPa · s or more, further preferably a slurry of 6,000 mPa · s or more, 7 A slurry of 1,000 mPa · s or more is particularly preferable. When the viscosity is not more than the above upper limit, good coatability is exhibited, which is preferable. By setting the above lower limit value or more, the Young's modulus and strength of the coating film can be optimized, which is preferable.

  The viscosity of the fibrous cellulose-containing composition is measured as follows. The fibrous cellulose-containing composition is diluted with ion-exchanged water so that the solid content concentration becomes 0.4% by mass, and then stirred with a disperser at 1500 rpm for 5 minutes. Next, the viscosity of the dispersion liquid thus obtained is measured using a B-type viscometer (manufactured by BLOOKFIELD, analog viscometer T-LVT). The measurement conditions are a rotation speed of 3 rpm, and the viscosity value 3 minutes after the start of measurement is the viscosity of the dispersion liquid. Further, the dispersion liquid to be measured is allowed to stand overnight for 24 hours in an environment of 23 ° C. and relative humidity of 50% before measurement. The viscosity measurement temperature is 23 ° C. Other detailed measurement conditions and the like comply with JIS Z8803: 2011. Five samples are prepared for each level, each measurement is performed twice, a total of 10 times, and the arithmetic mean value is adopted.

  The fibrous cellulose-containing composition of the present invention may be a kit in which fine fibrous cellulose and a specific component are combined. For example, both can be provided separately and, if necessary, combined with other components. In this case, the combination amount and ratio of the fine fibrous cellulose and the specific component are the same as the compounding amount and the like in the fibrous cellulose-containing composition.

(Coating film)
The fibrous cellulose-containing composition of the present invention is preferably applied to form a coating film. The thickness of the coating film is not particularly limited, but when considering the usage as a coating material, it is preferably 1000 μm or less, more preferably 500 μm or less, further preferably 300 μm or less, and 100 μm or less. It is more preferable that it is, and it is particularly preferable that it is 80 μm or less. The lower limit value is preferably 1 μm or more, more preferably 5 μm or more, particularly preferably 10 μm or more.

  The surface roughness of the coating film (in the present specification, unless otherwise specified, the surface roughness means the arithmetic average roughness: Ra defined in JIS B0601: 2013) is not particularly limited, In consideration of such uses, it is preferable that the smoothness is excellent. According to the present invention, the arithmetic mean roughness (Ra) can be improved if necessary, and Ra is preferably 0.2 μm or less, more preferably 0.17 μm or less, and 0.15 μm or less. Is particularly preferable. The lower limit value is not particularly limited, but it is practically 0.001 μm or more.

  The surface roughness is measured with an optical interference type non-contact surface shape measuring instrument (Ryoka System Co., Ltd., non-contact surface / layer cross-sectional shape measuring system VertScan 2.0, model: R5500GML) and a measuring range of 470. The arithmetic mean roughness (Ra) of 92 μm × 353.16 μm is measured. The measurement is performed 5 times for each level, and the arithmetic mean roughness is calculated from the average value. The details of the definition of the arithmetic mean roughness (Ra), the measurement conditions, the calculation method and the like are based on JISB0601: 2013.

  The Young's modulus of the coating film is not particularly limited, but when considering a higher Young's modulus, for example, it is preferably 0.3 GPa or more, more preferably 0.5 GPa or more, and 0.7 GPa or more. Is more preferable, and 0.8 GPa or more is particularly preferable. It is practical that the upper limit value is 8 GPa or less. According to the present invention, since such a high Young's modulus can be achieved, it is possible to favorably cope with the application requiring a high elastic modulus.

  The Young's modulus of the coating film is JIS P 8113: 2006, except that the tensile tester Tensilon (manufactured by A & D Company) is used, and the length of the test piece between the grips is 50 mm and the pulling speed is 5 mm / min. Measure in compliance. When measuring the Young's modulus, a sample that has been conditioned at 23 ° C. and a relative humidity of 50% for 24 hours is used as a test piece. The measurement is performed 5 times for each level, and the average value is adopted.

(Membrane manufacturing method)
The manufacturing process of the thickener, paint, film, etc. is not particularly limited.
The thickener mixes a dispersion liquid (which may be in the form of a slurry) containing fibrous cellulose having a fiber width of 1000 nm or less, a specific component or a solution containing this, and optionally other components (for example, water). It can be manufactured.
The coating material includes fine fibrous cellulose (which may be a dispersion liquid), a specific component (which may be a solution), a resin (for example, an acrylic resin), a curing agent (for example, polyisocyanate), and optionally other components. It can be produced by mixing with the component (for example, an organic solvent).
The film can be produced by applying a composition containing fine fibrous cellulose and a specific component (for example, the above-mentioned coating material or thickener) to form a coating film. Specifically, for example, a coating film can be formed by a step of applying a composition containing fine fibrous cellulose and a specific component on a substrate and a step of drying the composition.
The coating film formed above may be peeled from the base material to form a sheet.
Further, the sheet may be produced by making a paper containing a composition containing fine fibrous cellulose and a specific component (which may be the above-mentioned coating material or thickener).

<Coating process>
The coating step is a step of coating a composition containing fine fibrous cellulose and a specific component (which may be the above-mentioned coating material or thickener) on a substrate.
When manufacturing a sheet, a sheet can be continuously manufactured by using a coating device and a long base material.

  The material of the base material used in the coating step is not particularly limited, but the one having higher wettability with respect to the composition may be able to suppress the shrinkage of the sheet during drying, but the sheet formed after drying is It is preferable to select one that can be easily peeled off. Of these, a resin film or plate or a metal film or plate is preferable, but not particularly limited. For example, resin films and plates of acrylic, polyethylene terephthalate, vinyl chloride, polystyrene, polypropylene, polyvinylidene chloride, etc., metal films and plates of aluminum, zinc, copper, iron plates, and those whose surfaces are oxidized, stainless steel Films and plates of, and brass films and plates can be used.

  In the coating process, if the composition to be coated has a low viscosity and spreads on the substrate, fix the damming frame on the substrate to obtain a sheet with a predetermined thickness and basis weight. You may use it. The quality of the damming frame is not particularly limited, but it is preferable to select one that allows the edges of the sheet attached after drying to be easily peeled off. Of these, a resin plate or a metal plate is preferable, but not particularly limited. For example, a resin plate such as an acrylic plate, a polyethylene terephthalate plate, a vinyl chloride plate, a polystyrene plate, a polypropylene plate, or a polyvinylidene chloride plate, a metal plate such as an aluminum plate, a zinc plate, a copper plate, or an iron plate, and their surfaces are oxidized. It is possible to use a molded product such as a product, a stainless plate or a brass plate.

  As a coating machine for coating the composition, for example, an applicator, a roll coater, a gravure coater, a die coater, a curtain coater, an air doctor coater or the like can be used. Applicators, die coaters, curtain coaters, and spray coaters are preferable because the thickness can be made more uniform.

  The coating temperature is not particularly limited, but is preferably 20 ° C. or higher and 45 ° C. or lower, more preferably 25 ° C. or higher and 40 ° C. or lower, and further preferably 27 ° C. or higher and 35 ° C. or lower. When the coating temperature is at least the above lower limit, the composition can be easily coated, and when it is at most the above upper limit, volatilization of the dispersion medium during coating can be suppressed.

In the coating step, it is preferable to coat the composition so that the finished basis weight of the sheet is 10 g / m ² or more and 100 g / m ² or less, and preferably 20 g / m ² or more and 60 g / m ² or less. By coating so that the basis weight is within the above range, a sheet having excellent strength can be obtained.

  The coating step preferably includes a step of drying the composition coated on the base material. The drying method is not particularly limited, and may be either a non-contact drying method or a method of drying while restraining the sheet, or a combination thereof.

  The non-contact drying method is not particularly limited, but a method of drying by heating with hot air, infrared rays, far infrared rays or near infrared rays (heating drying method), and a method of drying in vacuum (vacuum drying method) are applied. You can The heat drying method and the vacuum drying method may be combined, but the heat drying method is usually applied. Drying with infrared rays, far infrared rays, or near infrared rays can be performed using an infrared device, a far infrared device, or a near infrared device, but is not particularly limited. The heating temperature in the heating and drying method is not particularly limited, but is preferably 20 ° C. or higher and 150 ° C. or lower, and more preferably 25 ° C. or higher and 105 ° C. or lower. If the heating temperature is equal to or higher than the lower limit value, the dispersion medium can be quickly volatilized, and if the heating temperature is equal to or lower than the upper limit value, it is possible to suppress cost required for heating and prevent fine fibrous cellulose from being discolored by heat. .

<Papermaking process>
In the case of producing a sheet, the step of producing the sheet may include a step of making a composition containing fine fibrous cellulose and a specific component (which may be the above-mentioned coating material or thickener). Examples of paper machines used in the papermaking process include a fourdrinier, cylinder, and inclined continuous paper machines, and a multi-layered paper machine that combines these machines. In the papermaking process, known papermaking such as handmaking may be performed.

  In the papermaking step, the composition is filtered on a wire and dehydrated to obtain a wet paper sheet, which is then pressed and dried to obtain the sheet. When the above composition is filtered and dehydrated, the filter cloth at the time of filtration is not particularly limited, but it is important that the fine fibrous cellulose and the preservative do not pass through and the filtration rate does not become too slow. The filter cloth is not particularly limited, but a sheet, a woven fabric, and a porous membrane made of an organic polymer are preferable. The organic polymer is not particularly limited, but non-cellulosic organic polymers such as polyethylene terephthalate, polyethylene, polypropylene, and polytetrafluoroethylene (PTFE) are preferable. Specific examples thereof include a porous film of polytetrafluoroethylene having a pore diameter of 0.1 μm or more and 20 μm or less, for example, 1 μm, and a polyethylene terephthalate or polyethylene woven fabric having a pore diameter of 0.1 μm or more and 20 μm or less, for example, but are not particularly limited.

  The method for producing a sheet from the above composition is not particularly limited, and examples thereof include a method using a production apparatus described in WO2011 / 013567. This manufacturing apparatus discharges a composition containing fine fibrous cellulose onto the upper surface of an endless belt, squeezes a dispersion medium from the discharged composition to squeeze a web, and a squeezing section for drying the web to produce fibers. And a drying section for producing a sheet. An endless belt is arranged from the water squeezing section to the drying section, and the web generated in the water squeezing section is conveyed to the drying section while being placed on the endless belt.

  The dehydration method that can be employed is not particularly limited, and examples thereof include the dehydration methods that are commonly used in the production of paper, and a method of dehydrating with a Fourdrinier, a cylinder, an inclined wire or the like and then a roll press is preferable. The drying method is not particularly limited, and examples thereof include methods used in the production of paper, and for example, methods such as a cylinder dryer, a Yankee dryer, hot air drying, a near infrared heater, and an infrared heater are preferable.

(Laminate)
You may form a laminated body by laminating | stacking another layer further on the coating film or sheet obtained by the process mentioned above. Such other layer may be provided on both surfaces of the coating film or sheet, or may be provided only on one surface of the coating film or sheet. Examples of the other layer laminated on at least one surface of the coating film or sheet include a resin layer and an inorganic layer.

  Specific examples of the laminate include, for example, a laminate in which a resin layer is directly laminated on at least one surface of a coating film or a sheet, or an inorganic layer is directly laminated on at least one surface of a coating film or a sheet. Laminate, resin layer, coating film or sheet, laminate in which an inorganic layer is laminated in this order, coating film or sheet, resin layer, laminate in which inorganic layer is laminated in this order, coating film or inorganic layer A laminated body in which the resin layers are laminated in this order can be mentioned. The layer structure of the laminate is not limited to the above, and various modes can be adopted according to the application.

<Resin layer>
The resin layer is a layer containing a natural resin or a synthetic resin as a main component. Here, the main component means a component contained in an amount of 50% by mass or more based on the total mass of the resin layer. The content of the resin is preferably 60% by mass or more, more preferably 70% by mass or more, further preferably 80% by mass or more, and 90% by mass with respect to the total mass of the resin layer. The above is particularly preferable. The resin content may be 100% by mass or may be 95% by mass or less.

  Examples of the natural resin include rosin-based resins such as rosin, rosin ester, and hydrogenated rosin ester.

  The synthetic resin is preferably at least one selected from polycarbonate resin, polyethylene terephthalate resin, polyethylene naphthalate resin, polyethylene resin, polypropylene resin, polyimide resin, polystyrene resin, polyurethane resin and acrylic resin. Above all, the synthetic resin is preferably at least one selected from a polycarbonate resin and an acrylic resin, and more preferably a polycarbonate resin. The acrylic resin is preferably at least one selected from polyacrylonitrile and poly (meth) acrylate.

  Examples of the polycarbonate resin forming the resin layer include aromatic polycarbonate-based resins and aliphatic polycarbonate-based resins. These specific polycarbonate-based resins are known, and examples thereof include the polycarbonate-based resins described in JP 2010-023275A.

  The resin constituting the resin layer may be used alone, or a copolymer obtained by copolymerizing or graft-polymerizing a plurality of resin components may be used. Moreover, you may use as a blend material which mixed the several resin component by a physical process.

  An adhesive layer may be provided between the coating film or sheet and the resin layer, or no adhesive layer may be provided and the coating film or sheet and the resin layer may be in direct contact with each other. When an adhesive layer is provided between the coating film or sheet and the resin layer, an acrylic resin can be used as the adhesive forming the adhesive layer. Examples of adhesives other than acrylic resins include vinyl chloride resins, (meth) acrylic acid ester resins, styrene / acrylic acid ester copolymer resins, vinyl acetate resins, vinyl acetate / (meth) acrylic acid ester copolymers. Polymer resins, urethane resins, silicone resins, epoxy resins, ethylene / vinyl acetate copolymer resins, polyester resins, polyvinyl alcohol resins, ethylene vinyl alcohol copolymer resins and rubber emulsions such as SBR and NBR. To be

When the adhesive layer is not provided between the coating film or sheet and the resin layer, the resin layer may have an adhesion aid, and the surface of the resin layer may be subjected to surface treatment such as hydrophilic treatment. Good.
Examples of the adhesion aid include a compound containing at least one selected from an isocyanate group, a carbodiimide group, an epoxy group, an oxazoline group, an amino group and a silanol group, and an organic silicon compound. Among them, the adhesion aid is preferably at least one selected from a compound containing an isocyanate group (isocyanate compound) and an organic silicon compound. Examples of the organosilicon compound include a silane coupling agent condensate and a silane coupling agent.
Examples of surface treatment methods other than hydrophilic treatment include corona treatment, plasma discharge treatment, UV irradiation treatment, electron beam irradiation treatment, and flame treatment.

<Inorganic layer>
The substance constituting the inorganic layer is not particularly limited, but includes, for example, aluminum, silicon, magnesium, zinc, tin, nickel, titanium; oxides, carbides, nitrides, oxycarbides, oxynitrides, or oxycarbonitrides of these. Or a mixture thereof. From the viewpoint that high moisture resistance can be stably maintained, silicon oxide, silicon nitride, silicon oxycarbide, silicon oxynitride, silicon oxycarbonitride, aluminum oxide, aluminum nitride, aluminum oxycarbide, aluminum oxynitride, or these Mixtures are preferred.

  The method for forming the inorganic layer is not particularly limited. Generally, a method for forming a thin film is roughly classified into a chemical vapor deposition method (Chemical Vapor Deposition, CVD) and a physical film forming method (Physical Vapor Deposition, PVD), but any method may be adopted. . Specific examples of the CVD method include plasma CVD using plasma, a catalytic chemical vapor deposition method (Cat-CVD) in which a material gas is catalytically pyrolyzed using a heating catalyst, and the like. Specific examples of the PVD method include vacuum deposition, ion plating, and sputtering.

  Further, as a method for forming the inorganic layer, an atomic layer deposition method (Atomic Layer Deposition, ALD) can also be adopted. The ALD method is a method of forming a thin film in atomic layer units by alternately supplying source gases of the respective elements forming the film to be formed to the surface on which the layer is formed. Although it has a drawback that the film formation rate is slow, it has an advantage over the plasma CVD method that it can cover even a complicated surface cleanly and can form a thin film with few defects. In addition, the ALD method has advantages that the film thickness can be controlled on the order of nanometers, and it is relatively easy to cover a wide surface. Further, in the ALD method, the use of plasma can be expected to improve the reaction rate, realize a low temperature process, and reduce unreacted gas.

(Use)
The cellulose-containing composition of the present invention can be used in various applications as a thickener.
In addition, the fibrous cellulose-containing composition of the present invention may be used as a reinforcing material by mixing with, for example, a coating material, a resin, an emulsion, a hydraulic material (cement), or rubber.
Various coatings or sheets may be produced using the cellulose-containing composition of the present invention.

  The sheet is suitable for use in light-transmissive substrates such as various display devices and various solar cells. Further, it is also suitable for use as substrates for electronic devices, members for home appliances, window materials for various vehicles and buildings, interior materials, exterior materials, packaging materials, and the like. Furthermore, in addition to threads, filters, fabrics, cushioning materials, sponges, abrasives, etc., it is also suitable for the use of the sheet itself as a reinforcing material.

  The features of the present invention will be described more specifically below with reference to Examples and Comparative Examples. The materials, usage amounts, ratios, processing contents, processing procedures, and the like shown in the following examples can be appropriately changed without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be limitedly interpreted by the following specific examples. In the following examples, for convenience of description, a slurry obtained by treating fine fibrous cellulose is referred to as a dispersion, and a composition containing this and a specific component is referred to as a fibrous cellulose-containing composition. A mixture of the fibrous cellulose-containing composition, a resin, a curing agent and the like is called a paint. However, this should not be construed as limiting the scope of the present invention. For example, those containing fine fibrous cellulose such as paint, a specific component and other components are also included in the range of the fibrous cellulose-containing composition of the present invention.

<Production of fine fibrous cellulose dispersion (1)>
(Phosphorylation process)
As a raw material pulp, a softwood kraft pulp made by Oji Paper Co., Ltd. (solid content 93 mass%, basis weight 208 g / m ² sheet, disaggregated and measured according to JIS P 8121-2: 2012 Canadian standard freeness (CSF ) Used 700 ml). This raw material pulp was subjected to phosphorylation treatment as follows. First, a mixed aqueous solution of ammonium dihydrogen phosphate and urea is added to 100 parts by mass of the raw material pulp (absolute dry mass) to obtain 45 parts by mass of ammonium dihydrogen phosphate, 120 parts by mass of urea, and 150 parts by mass of water. Was adjusted as described above to obtain a chemical solution-impregnated pulp. Next, the obtained chemical liquid-impregnated pulp was heated for 200 seconds with a hot air dryer at 165 ° C. to introduce phosphoric acid groups into the cellulose in the pulp to obtain phosphorylated pulp. Then, the obtained phosphorylated pulp was subjected to a washing treatment. The washing treatment is carried out by repeating the operation of pouring the pulp dispersion obtained by pouring 10 L of ion-exchanged water to 100 g of phosphorylated pulp (absolute dry mass) so that the pulp is uniformly dispersed, and then filtering and dehydrating. went. When the electric conductivity of the filtrate became 100 μS / cm or less, the washing end point was set.

  Then, the phosphorylated pulp after washing was subjected to alkali treatment as follows. First, the washed phosphorylated pulp was diluted with 10 L of ion-exchanged water, and a 1N sodium hydroxide aqueous solution was added little by little with stirring to obtain a phosphorylated pulp slurry having a pH of 12 or more and 13 or less. . Then, the phosphorylated pulp slurry was dehydrated to obtain alkali treated phosphorylated pulp.

Next, the above-mentioned washing treatment was performed on the phosphorylated pulp after the alkali treatment.
The infrared absorption spectrum of the phosphorylated pulp thus obtained was measured using FT-IR. As a result, absorption based on a phosphate group was observed around 1230 cm ^-1 , and it was confirmed that the phosphate group was added to the pulp. The amount of phosphoric acid groups (the amount of strong acidic groups) measured by the measuring method described later was 1.45 mmol / g.
Also, the phosphorylated pulp obtained was tested and analyzed by an X-ray diffractometer. At two positions, 2θ = 14 ° or more and 17 ° or less and 2θ = 22 ° or more and 23 ° or less. A typical peak was confirmed and it was confirmed to have a cellulose type I crystal.

(Disentanglement processing)
Ion-exchanged water was added to the obtained phosphorylated pulp to prepare a slurry having a solid content concentration of 2% by mass. This slurry was treated with a wet atomizer (Starburst manufactured by Sugino Machine Ltd.) three times at a pressure of 200 MPa to obtain a fine fibrous cellulose dispersion liquid (1) containing fine fibrous cellulose. It was confirmed by X-ray diffraction that the fine fibrous cellulose maintained the cellulose type I crystal. Further, the fiber width of the fine fibrous cellulose was measured by a transmission electron microscope according to the following measuring method, and it was 3 to 5 nm.
The 0.4% by mass viscosity of the fine fibrous cellulose was measured and found to be 22400 [mPa · s].

<Measurement of fiber width>
The fiber width of the fine fibrous cellulose was measured by the following method.
The supernatant liquid of the fine fibrous cellulose dispersion obtained by treatment with a wet atomization device is treated with water so that the concentration of the fine fibrous cellulose becomes 0.01% by mass or more and 0.1% by mass or less. It was diluted and added dropwise to the hydrophilized carbon grid film. After drying this, it was dyed with uranyl acetate and observed with a transmission electron microscope (JEOL-2000EX, manufactured by JEOL Ltd.).

<Production of fine fibrous cellulose dispersion (2)>
(TEMPO oxidation process)
Softwood kraft pulp (undried) made by Oji Paper Co., Ltd. was used as the raw material pulp. This raw material pulp was subjected to alkali TEMPO oxidation treatment as follows. First, the raw material pulp equivalent to 100 parts by mass of dry mass, TEMPO (2,2,6,6-tetramethylpiperidine-1-oxyl) 1.6 parts by mass, 10 parts by mass of sodium bromide, and 10000 parts by mass of water. Dispersed in parts. Then, a 13 mass% sodium hypochlorite aqueous solution was added so as to be 3.8 mmol with respect to 1.0 g of pulp to start the reaction. During the reaction, a 0.5 M sodium hydroxide aqueous solution was added dropwise to maintain the pH at 10 or more and 10.5 or less, and the reaction was considered to be completed when no change in the pH was observed.

  Then, a cleaning process was performed on the obtained TEMPO oxidized pulp. The washing treatment is carried out by dewatering the pulp slurry after TEMPO oxidation to obtain a dewatering sheet, then pouring 5000 parts by mass of ion-exchanged water, stirring and uniformly dispersing, and then repeating the operation of filtering and dewatering. It was When the electric conductivity of the filtrate became 100 μS / cm or less, the washing end point was set.

This dehydrated sheet was subjected to additional oxidation treatment of the remaining aldehyde group as follows. The above dehydrated sheet corresponding to 100 parts by mass of dry mass was dispersed in 10000 parts by mass of 0.1 mol / L acetate buffer solution (pH 4.8). Then, 113 parts by mass of 80% sodium chlorite was added, and the mixture was immediately sealed and then allowed to react at room temperature for 48 hours while stirring at 500 rpm using a magnetic stirrer to obtain a pulp slurry.
Then, a washing treatment was performed on the obtained TEMPO-oxidized pulp having undergone additional oxidation. The washing treatment is performed by dewatering the pulp slurry after additional oxidation to obtain a dewatering sheet, pouring 5000 parts by mass of ion-exchanged water, stirring and uniformly dispersing, and then repeating the operation of filtering and dewatering. It was When the electric conductivity of the filtrate became 100 μS / cm or less, the washing end point was set.

The TEMPO oxidized pulp thus obtained had a carboxyl group content of 1.30 mmol / g as measured by the measurement method described below.
Moreover, when the obtained TEMPO oxidized pulp was tested and analyzed by an X-ray diffractometer, it was found to be at two positions of 2θ = 14 ° or more and 17 ° or less and 2θ = 22 ° or more and 23 ° or less. A typical peak was confirmed and it was confirmed to have a cellulose type I crystal.

(Disentanglement processing)
Ion-exchanged water was added to the obtained phosphorylated pulp to prepare a slurry having a solid content concentration of 2% by mass. This slurry was treated 6 times with a wet atomizer (Starburst, manufactured by Sugino Machine Ltd.) at a pressure of 200 MPa to obtain a fine fibrous cellulose dispersion liquid (2) containing fine fibrous cellulose. It was confirmed by X-ray diffraction that the fine fibrous cellulose maintained the cellulose type I crystal. The fiber width of the fine fibrous cellulose was measured with a transmission electron microscope, and it was 3 to 5 nm.
The 0.4% by mass viscosity of the fine fibrous cellulose was measured and found to be 11000 [mPa · s].

<Production of fine fibrous cellulose dispersion (3)>
In the fine fibrous cellulose dispersion liquid (1), 3.0 × 10 ^{− of} an enzyme-containing liquid (manufactured by AB Enzymes, ECOPULP R, the enzyme content is about 5% by mass) with respect to 1 part by mass of the fine fibrous cellulose. ⁶ parts by mass was added, and the mixture was stirred at 18,500 rpm for 2 minutes. This was recovered to obtain a fine fibrous cellulose dispersion liquid (3). The fine fibrous cellulose dispersion liquid (3) contains an enzyme.
The 0.4% by mass viscosity of the fine fibrous cellulose was measured and found to be 9000 [mPa · s].

<Production of fine fibrous cellulose dispersion A>
Fine fibrous cellulose dispersion liquid was obtained in the same manner as the fine fibrous cellulose dispersion liquid (2) except that the number of treatments using a wet atomization device (Starburst manufactured by Sugino Machine Ltd.) at a pressure of 200 MPa was set to 3. I got A.
The 0.4% by mass viscosity of the fine fibrous cellulose was measured and found to be 20400 [mPa · s].

  The physical properties of each fine fibrous cellulose were measured according to the following procedures. The results are shown in Table 1 above.

<Measurement of phosphate group amount>
The phosphate group amount of the fine fibrous cellulose is a fibrous substance prepared by diluting a fine fibrous cellulose dispersion liquid containing the target fine fibrous cellulose with ion-exchanged water to a content of 0.2% by mass. The cellulose-containing slurry was treated with an ion exchange resin and then titrated with an alkali for measurement.
The treatment with an ion exchange resin was carried out by adding 1/10 by volume of a strongly acidic ion exchange resin (Amber Jet 1024; Organo Co., Ltd., already conditioned) to the above-mentioned fibrous cellulose-containing slurry and performing a shaking treatment for 1 hour. , And the resin and the slurry were separated by pouring onto a mesh having an opening of 90 μm.
In addition, titration with an alkali was performed by adding 50 μL of a 0.1N sodium hydroxide aqueous solution to the fibrous cellulose-containing slurry after the treatment with the ion exchange resin once every 30 seconds while the electrical conductivity of the slurry was shown. It was carried out by measuring the change in the value of. The phosphate group amount (mmol / g) was obtained by dividing the amount of alkali (mmol) required in the region corresponding to the first region shown in FIG. 1 in the measurement result by the solid content (g) in the titration target slurry. Calculated.

<Measurement of carboxyl group amount>
The amount of carboxyl groups in the fine fibrous cellulose is a fibrous cellulose prepared by diluting a fine fibrous cellulose dispersion liquid containing the target fine fibrous cellulose with ion-exchanged water to a content of 0.2% by mass. The contained slurry was treated with an ion exchange resin and then titrated with an alkali for measurement.
The treatment with an ion exchange resin was carried out by adding 1/10 by volume of a strongly acidic ion exchange resin (Amber Jet 1024; Organo Co., Ltd., already conditioned) to the above-mentioned fibrous cellulose-containing slurry and performing a shaking treatment for 1 hour. , And the resin and the slurry were separated by pouring onto a mesh having an opening of 90 μm.
In addition, titration with an alkali was performed by adding 50 μL of a 0.1 N sodium hydroxide aqueous solution once every 30 seconds to the fibrous cellulose-containing slurry after the treatment with the ion exchange resin, while measuring the electric conductivity of the slurry. This was done by measuring the change in value. The carboxyl group amount (mmol / g) is obtained by dividing the amount of alkali (mmol) required in the region corresponding to the first region shown in FIG. 2 in the measurement result by the solid content (g) in the titration target slurry. It was calculated.

<Measurement of viscosity of fine fibrous cellulose dispersion>
The viscosity of the fine fibrous cellulose dispersion was measured as follows. First, the fine fibrous cellulose dispersion was diluted with ion-exchanged water so that the solid content concentration was 0.4% by mass, and then stirred with a disperser at 1500 rpm for 5 minutes. Then, the viscosity of the dispersion liquid thus obtained was measured using a B-type viscometer (manufactured by BLOOKFIELD, analog viscometer T-LVT). The measurement conditions were a rotation speed of 3 rpm, and the viscosity value 3 minutes after the start of measurement was taken as the viscosity of the dispersion liquid. Further, the dispersion liquid to be measured was allowed to stand overnight for 24 hours in an environment of 23 ° C. and 50% relative humidity before measurement. The viscosity measurement temperature was 23 ° C. Other detailed measurement conditions and the like are based on JISZ8803: 2011. Five samples were prepared for each level, each measurement was performed twice, a total of 10 times, and the arithmetic mean value was adopted.

<Measurement of supernatant after centrifugation of fine fibrous cellulose dispersion>
The supernatant yield after centrifugation of the fine fibrous cellulose dispersion was measured by the method described below. The supernatant yield after centrifugation is an index of the yield of fine fibrous cellulose, and the higher the supernatant yield, the higher the yield of fine fibrous cellulose.
The fine fibrous cellulose dispersion liquid was adjusted to a solid content concentration of 0.2% by mass, and centrifuged using a cooling high-speed centrifuge (H-2000B, manufactured by Kokusan Co., Ltd.) under the conditions of 12000 G and 10 minutes. The obtained supernatant was collected and the solid content concentration of the supernatant was measured. The yield of fine fibrous cellulose was calculated based on the following formula.
Supernatant yield (%) = supernatant solid content concentration (%) / 0.2 × 100
Five samples were prepared for each level, each measurement was performed twice, a total of 10 times, and the arithmetic mean value was adopted.

<Example 1>
(Preparation of composition containing fibrous cellulose)
Ion-exchanged water was added to the pigment dispersant DISPERBYK-187 (manufactured by BYK-Chemie, alkylol ammonium salt / acid value: 35 mgKOH / g amine value: 35 mgKOH / g) to give an aqueous solution having a solid content concentration of 2% by mass.
100 g of a fine fibrous cellulose dispersion liquid (1) having a solid content concentration of 2% by mass was placed in a beaker, and 360 g of ion-exchanged water and 40 g of a 2% by mass DISPERBYK-187 aqueous solution were added thereto. The addition is T. K. The mixture was stirred with a homodisper (manufactured by Tokushu Kika Kogyo) at 1500 rpm, stirred for 5 minutes after the addition of DISPERBYK-187, and then with a defoaming device (Synky, rotation / revolution mixer AR-250). Defoaming treatment was performed.
Thereby, the solid content concentration of fine fibrous cellulose is 0.4% by mass, the solid content concentration of DISPERBYK-187 is 0.016, and the fibrous form of fine fibrous cellulose to DISPERBYK-187 = 100: 40 (mass ratio). A cellulose-containing composition was obtained.

(Measurement of viscosity of fibrous cellulose-containing composition)
The viscosity of the obtained fibrous cellulose-containing composition is measured by using a B-type viscometer (manufactured by BLOOKFIELD, analog viscometer T-LVT) after allowing it to stand overnight under an environment of 23 ° C. and a relative humidity of 50%. did. The measurement conditions were a rotation speed of 3 rpm, and the viscosity value 3 minutes after the start of measurement was taken as the viscosity of the dispersion liquid. The viscosity measurement temperature was 23 ° C. Other detailed measurement conditions and the like are based on JISZ8803: 2011. Five samples were prepared for each level, each measurement was performed twice, a total of 10 times, and the arithmetic mean value was adopted.

(Preparation of paint)
24.8 g of the obtained fibrous cellulose-containing composition was weighed in a beaker, 34.6 g of ion-exchanged water, 35.1 g of acrylic resin (DIC Co., product name: Barnock WD-551, solid content concentration 44.1%), A curing agent (manufactured by DIC, product name: Bernock DNW-5500, polyisocyanate, solid content concentration 79.8%) (5.5 g) was added in that order. The addition is T. K. Homodispers (manufactured by Tokushu Kika Kogyo Co., Ltd.) are stirred at 1500 rpm, stirred for 5 minutes after all the additions, and then defoamed by a defoaming device (Synky, rotation / revolution mixer AR-250). Processed.
In this way, the solid content ratio is acrylic resin: 78, curing agent 22, fine fibrous cellulose: 0.5, DISPERBYK-187: 0.2 (mass ratio), and the total solid content concentration is 20 mass%. A paint for evaluation was obtained.

<Example 2>
In the same manner as in Example 1 except that 2% by mass aqueous solution of DISPERBYK-180 (manufactured by BYK-Chemie, alkylol ammonium salt / acid value: 94 mgKOH / g amine value: 94 mgKOH / g) was used instead of DISPERBYK-187. Thus, a coating material for evaluation was obtained.

<Example 3>
In the same manner as in Example 1 except that 2% by mass aqueous solution of DISPERBYK (manufactured by BYK-Chemie, alkylol ammonium salt / acid value: 85 mgKOH / g amine value: 85 mgKOH / g) was used instead of DISPERBYK-187. An evaluation paint was obtained.

<Example 4>
A coating material for evaluation was obtained in the same manner as in Example 1 except that a 2 mass% aqueous solution of DISPER-AW300P (manufactured by Otsuka Chemical Co., Ltd., methacrylate resin / potassium salt) was used instead of DISPERBYK-187.

<Example 5>
A coating material for evaluation was obtained in the same manner as in Example 1 except that the fine fibrous cellulose dispersion liquid (2) was used.

<Example 6>
A coating material for evaluation was obtained in the same manner as in Example 1 except that the fine fibrous cellulose dispersion liquid (3) was used. The fibrous cellulose-containing composition of Example 6 contains an enzyme.

<Example 7>
The solid content ratio of fine fibrous cellulose to DISPERBYK-187 in the fibrous cellulose-containing composition was 100: 20 (mass ratio), and the amount taken in the paint preparation was 24.9 g of the fibrous cellulose-containing composition and ion-exchanged water. A coating material for evaluation was obtained in the same manner as in Example 1 except that 34.5 g and 35.2 g of acrylic resin were used.
(The solid content ratio of the obtained coating material for evaluation is acrylic resin: 78, curing agent: 22, fine fibrous cellulose: 0.5, DISPERBYK-187: 0.1 (mass ratio).)

<Example 8>
The solid content ratio of fine fibrous cellulose to DISPERBYK-187 in the fibrous cellulose-containing composition was 100 to 160 (mass ratio), and the amount taken in the paint preparation was 24.7 g of an aqueous dispersion, 35 g of ion-exchanged water, and acrylic. A coating material for evaluation was obtained in the same manner as in Example 1 except that 34.9 g of the resin and 5.4 g of the curing agent were used.
(The solid content ratio of the obtained coating amount for evaluation is acrylic resin 78, curing agent 22, fine fibrous cellulose 0.5, DISPERBYK-187: 0.8 (mass ratio).)

<Example 9>
Evaluation was performed in the same manner as in Example 7 except that a 2 mass% aqueous solution of the pigment dispersant DISPER-AW300P (manufactured by Otsuka Chemical Co., Ltd., methacrylate resin / potassium salt / acid value: 120 mgKOH / g) was used instead of DISPERBYK-187. Got the paint for. (The solid content ratio of the obtained coating material for evaluation is acrylic resin: 78, curing agent: 22, fine fibrous cellulose: 0.5, DISPWER-AW300P: 0.1 (mass ratio).)

<Example 10>
A coating material for evaluation was obtained in the same manner as in Example 8 except that a 2 mass% aqueous solution of the pigment dispersant DISPER-AW300P (manufactured by Otsuka Chemical Co., Ltd., methacrylate resin / potassium salt) was used in place of DISPERBYK-187. (The solid content ratio of the obtained coating amount for evaluation is acrylic resin 78, curing agent 22, fine fibrous cellulose 0.5, DISPWER-AW300P: 0.8 (mass ratio).)

<Comparative Example 1>
24.9 g of the fine fibrous cellulose dispersion liquid (1) having a solid content concentration of 0.4% by mass was placed in a beaker, and 34.4 g of deionized water, 35.2 g of an acrylic resin, and 5.49 g of a curing agent were added in that order. The addition is T. K. Homodispers (manufactured by Tokushu Kika Kogyo Co., Ltd.) were stirred at 1500 rpm, and after all the additions, stirring was continued for 5 minutes, and then defoaming was performed with a defoaming device (Synky, rotation / revolution mixer AR-250). A foam treatment was performed.
In this way, an evaluation coating material having a solid content ratio acrylic resin 78, a curing agent 22, and a fine fibrous cellulose 0.5 (mass ratio) was obtained.

<Comparative example 2>
A coating material for evaluation was obtained in the same manner as in Comparative Example 1 except that the fine fibrous cellulose dispersion A was used.

<Comparative example 3>
A coating material for evaluation was obtained in the same manner as in Example 1 except that a 2 mass% aqueous solution of the pigment dispersant DISPERBYK-193 (manufactured by BYK-Chemie, nonionic dispersant) was used in place of DISPERBYK-187.

<Reference example>
Example 1 except that the fine fibrous cellulose dispersion liquid was not added, and the amounts taken in the paint preparation were 35.2 g of acrylic resin, 34.4 g of ion-exchanged water, and 5.5 g of curing agent, and they were added in this order. Similarly, a coating material for evaluation was obtained.
(The solid content ratio of the obtained coating material for evaluation is acrylic resin 78 and curing agent 22 (mass ratio).)

  The physical properties of each coating material prepared above and its cured coating film were evaluated. The evaluation results are shown in Table 2 below. The measurement conditions for each evaluation item will be described later.

  From the above results, it can be seen that the fibrous cellulose-containing composition of the present invention has excellent coatability when it is used as a paint (Examples 1 to 10), and there are few foreign matters in the film after coating. Further, it is understood that the use of the fibrous cellulose-containing composition of the present invention makes it possible to smooth the surface of the coating film and realize the Young's modulus and strength of the coating film which are practically suitable, if necessary. On the other hand, the fibrous cellulose-containing composition containing no specific component according to the present invention (Comparative Examples 1 and 2) or the one using a nonionic dispersant (Comparative Example 3) has poor coatability, and The surface of the coating film has become rough.

(Creation of coating film for appearance evaluation)
Using the obtained coating material, a PET (polyethylene terephthalate) film (manufactured by Toray Industries, Inc., product name: Lumirror T60, thickness 75 μm) was used as a base material, and an applicator was used to apply a coating film thickness after drying of 30 μm. Immediately after coating, it was heated in a dryer at a temperature of 80 ° C. for 30 minutes to obtain a coated coating film having a PET film as a base material. The thickness of the coating film was measured with a stylus thickness meter (Millitron 1202D manufactured by Marl Co., Ltd.), and an arithmetic average value of 20 points was adopted. Details of other measurement conditions, calculation methods and the like were performed according to JIS P8118: 2014.

(Surface roughness)
Using a light interference type non-contact surface shape measuring instrument (Ryoka System Co., Ltd., non-contact surface / layer cross-section shape measuring system VertScan 2.0, model: R5500GML), a measuring range of 470.92 μm × 353.16 μm with a × 10 objective lens. The arithmetic mean roughness (Ra) of was measured. The measurement was performed 5 times per level, and the arithmetic mean roughness was determined from the average value. The details of the definition of the arithmetic mean roughness (Ra), the measurement conditions, the calculation method, etc. were performed according to JISB0601: 2013.

(Evaluation of coatability)
Performs observation of the coating prepared by the base PET film using an optical microscope (manufactured by Nikon Corporation), confirmed over 5μm during 1 mm ² in size of the aggregates number N (the number / mm ²⁾ at 20 sites Then, the arithmetic average value (N / 20) was calculated from the average value of. The measurement was performed 5 times per level and the average value was adopted. The numerical values (pieces / mm ² ) are shown in the table, and the results were evaluated as follows.
There are 3 particles / mm ² or more with size 5 μm or more: ×
Presence or absence of particles of size 5 μm or more less than 3 / mm ² : ○
The size of the particles was equivalent to a circle, and the details of measurement conditions, calculation methods, etc. were based on JISZ8827-1: 2008.

(Preparation of coating film for evaluation of strength and Young's modulus)
The test piece was prepared in the same manner as the test piece prepared in "Appearance evaluation coating film preparation" except that a PP (polypropylene) film (manufactured by Toray, product name: Trefan BO, thickness 60 μm) was used as the base material.
The prepared coating film was peeled off from the PP film and used as a sample for evaluating strength and Young's modulus.

(Young's modulus of the coating film)
Young's modulus was calculated using a tensile tester Tensilon (manufactured by A & D Company) in accordance with JIS P 8113: 2006 except that the length of the test piece was 80 mm and the distance between chucks was 50 mm. In addition, when measuring Young's modulus, what was conditioned for 24 hours at 23 degreeC and 50% of relative humidity was used as a test piece. The measurement was performed 5 times per level, and the average value was adopted.

(Strength of coating film)
The strength (tensile strength) of the coating film prepared using the fibrous cellulose-containing composition of Reference Example was taken as the base strength. At this time, the tester, the test conditions, and the compliance standard were the same as those used for measuring the Young's modulus. The same test was performed on each test piece of the example and the comparative example, and a test piece whose strength (tensile strength) was increased by 20% or more from the base strength was evaluated as “◯”. Those with 10% or more and less than 20% were marked with “Δ” and those with less than 10% were marked with “x”. The measurement was performed 5 times per level, and the average value was adopted.

Claims (11)

Fiber width is Ri der less 1000 nm, and comprises a fibrous cellulose having an anionic substituent, and a pigment dispersant having an ionic group, a fibrous cellulose-containing composition,
The acid value of the pigment dispersant is 5 mgKOH / g or more and 200 mgKOH / g or less, or the amine value of the pigment dispersant is 5 mgKOH / g or more and 200 mgKOH / g or less,
The pigment dispersant has a weight average molecular weight of 1,000 or more and 100,000 or less,
A fibrous cellulose-containing composition in which the surface roughness Ra of the coating film obtained under the following conditions is 0.20 μm or less;
(conditions)
Application obtained by mixing the fibrous cellulose-containing composition, 156 parts by mass of an acrylic resin with respect to 1 part by mass of the fibrous cellulose, and 44 parts by mass of polyisocyanate with respect to 1 part by mass of the fibrous cellulose. The liquid is applied onto a smooth polyethylene terephthalate plate using an applicator so as to have a thickness of 30 μm, and immediately after application, it is dried at 80 ° C. for 30 minutes.   The fibrous cellulose-containing composition according to claim 1, wherein the pigment dispersant is an alkylol ammonium salt or a (meth) acrylate resin / potassium salt.   The fibrous cellulose-containing composition according to claim 1 or 2, wherein the total amount of the fibrous cellulose, the pigment dispersant, and water is 90% by mass or more based on the entire composition.   The fibrous cellulose-containing composition according to any one of claims 1 to 3, wherein the content of the pigment dispersant is 10 parts by mass or more based on 100 parts by mass of fibrous cellulose.   The fiber according to any one of claims 1 to 4, which has a viscosity of 40,000 mPa · s or less measured at 23 ° C and a rotation speed of 3 rpm when the solid content concentration of the fibrous cellulose is 0.4% by mass. Cellulose-containing composition. The fibrous cellulose is used as a dispersion liquid, and the supernatant yield when the supernatant separated from the dispersion liquid under the following conditions is recovered is 80% by mass or more. Composition.
(conditions)
The dispersion liquid of fibrous cellulose is adjusted to a solid content concentration of 0.2% by mass, and centrifuged using a cooling high-speed centrifuge under the conditions of 12000 G and 10 minutes. The obtained supernatant was collected and the solid content concentration of the supernatant was measured. The yield of fibrous cellulose is calculated based on the following formula.
Supernatant yield (%) = supernatant solid content concentration (%) / 0.2 × 100 The fibrous cellulose-containing composition according to any one of claims 1 to 6, wherein the coating film obtained under the following conditions has a Young's modulus of 0.7 GPa or more:
(conditions)
Application obtained by mixing the fibrous cellulose-containing composition, 156 parts by mass of an acrylic resin with respect to 1 part by mass of the fibrous cellulose, and 44 parts by mass of polyisocyanate with respect to 1 part by mass of the fibrous cellulose. The solution is coated on a smooth polypropylene plate with an applicator so as to have a thickness of 30 μm, and immediately after coating, it is dried at 80 ° C. for 30 minutes.   The fibrous cellulose-containing composition according to any one of claims 1 to 7, further comprising an enzyme.   A fibrous cellulose-containing composition according to any one of claims 1 to 8 for use in paints.   The fibrous cellulose-containing composition according to any one of claims 1 to 8 for use in a thickener. A paint comprising the fibrous cellulose-containing composition according to any one of claims 1 to 10.

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