JP2019038980A - Fibrous cellulose-containing composition and coating - Google Patents

Abstract

To provide a fibrous cellulose-containing composition having improved coatability and a coating.SOLUTION: A fibrous cellulose-containing composition contains fibrous cellulose with a fiber width of 1000 nm or less, and a pigment dispersant having an ionic group, where the pigment dispersant has an acid value of 5 mgKOH/g or more and 200 mgKOH/g or less, or the pigment dispersant has an amine value of 5 mgKOH/g or more and 200 mgKOH/g or less.SELECTED DRAWING: None

Description

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

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

  As the fibrous cellulose, fine fibrous cellulose having a fiber diameter of 1 μm or less is also known. Fine fibrous cellulose is 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.

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

Japanese Patent Laid-Open No. 2006-69618

  The inventors have studied the use of fine fibrous cellulose as a thickener for paints. However, it has been found that when fine fibrous cellulose is contained in the paint, there is room for improvement in the coatability of the paint. This invention makes it the problem which should be solved to provide the fibrous cellulose containing composition and coating material by which coating property was improved.

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

[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 acid value of the pigment dispersant is 5 mgKOH / g or more and 200 mgKOH Or a fibrous cellulose-containing composition, wherein the pigment dispersant has an amine value of 5 mgKOH / g or more and 200 mgKOH / g or less.
[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 coated on a smooth polyethylene terephthalate plate so as to have a thickness of 30 μm using an applicator, and dried at 80 ° C. for 30 minutes immediately after coating.
[5] The fibrous cellulose content 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 with respect to 100 parts by mass of the fibrous cellulose.
[7] Any one of [1] to [6], wherein a viscosity measured at 23 ° C. and a rotation speed of 3 rpm with a solid content concentration of the fibrous cellulose of 0.4 mass% is 40,000 mPa · s or less. The fibrous cellulose containing composition as described in any one of.
[8] The method according to any one of [1] to [7], wherein a fibrous cellulose is used as a dispersion, and a supernatant yielded when the supernatant separated under the following conditions is recovered is 80% by mass or more. Fibrous cellulose-containing composition.
(conditions)
The dispersion of fibrous cellulose is adjusted to a solid content concentration of 0.2% by mass, and centrifuged at 12000 G for 10 minutes using a cooling high-speed centrifuge. The obtained supernatant was collected, and the solid content concentration of the supernatant was measured. Based on the following formula, the yield of fibrous cellulose is determined.
Supernatant yield (%) = Supernatant solids 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 of 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 liquid is coated on a smooth polypropylene plate so as to have a thickness of 30 μm using an applicator, and dried at 80 ° C. for 30 minutes immediately after coating.
[10] The fibrous cellulose-containing composition according to any one of [1] to [9], further comprising 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 paint comprising the fibrous cellulose-containing composition according to any one of [1] to [12].
[14] A fibrous cellulose-containing composition kit comprising a combination of fibrous cellulose having a fiber width of 1000 nm or less and a pigment dispersant having an ionic group.

  ADVANTAGE OF THE INVENTION According to this invention, the fibrous cellulose containing composition and coating material with which coating property was improved can be provided.

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

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

  The fibrous cellulose-containing composition of the present invention comprises 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”). Contain).

(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 anionic group). Examples of the anionic group include a phosphate group or a substituent derived from a phosphate group (sometimes simply referred to as a phosphate group), a carboxyl group or a substituent derived from a carboxyl group (sometimes simply referred to as a carboxyl group), In addition, it is preferably at least one selected from a sulfone group or a substituent derived from a sulfone group (sometimes simply referred to as a sulfone group), and at least one selected from a phosphate group and a carboxyl group Is more preferable, and a phosphate group is particularly preferable.

  Although it does not specifically limit as a fibrous cellulose raw material for obtaining a fine fibrous cellulose, It is preferable to use a pulp from the point of being easy to acquire and cheap. Examples of the pulp include wood pulp, non-wood pulp, and deinked pulp. Examples of wood pulp include hardwood kraft pulp (LBKP), softwood kraft pulp (NBKP), sulfite pulp (SP), dissolved pulp (DP), soda pulp (AP), unbleached kraft pulp (UKP), oxygen bleached craft Chemical pulps such as pulp (OKP) are listed. Moreover, semi-chemical pulps such as semi-chemical pulp (SCP) and chemi-ground wood pulp (CGP), mechanical pulps such as ground wood pulp (GP), thermomechanical pulp (TMP, BCTMP) and the like can be mentioned, but are not particularly limited. Non-wood pulp includes cotton pulp such as cotton linter and cotton lint, non-wood pulp such as hemp, straw and bagasse, cellulose isolated from sea squirts and seaweed, chitin, chitosan, etc., but is not particularly limited. . The deinking pulp includes deinking pulp made from waste paper, but is not particularly limited. The pulp of this embodiment may be used alone or in combination of two or more. Among the above pulps, wood pulp containing cellulose and deinked pulp are preferable in terms of availability. Among wood pulps, chemical pulp has a large cellulose ratio, so the yield of fine fibrous cellulose during fiber refinement (defibration) is high, and the degradation of cellulose in the pulp is small, and the fineness of long fibers with a large axial ratio is high. It is preferable at the point from which fibrous cellulose is obtained. Of these, kraft pulp and sulfite pulp are most preferably selected. Sheets containing long fibrous fine fibrous cellulose having a large axial ratio tend to provide high strength.

  The average fiber width of the fine fibrous cellulose is 1000 nm or less as observed with an electron microscope. The average fiber width is preferably 2 nm to 1000 nm, more preferably 2 nm to less than 1000 nm, more preferably 2 nm to 100 nm, more preferably 2 nm to 50 nm, and even more preferably 2 nm to 10 nm. There is no particular limitation. When the average fiber width of the fine fibrous cellulose is less than 2 nm, the physical properties (strength, rigidity, dimensional stability) as the fine fibrous cellulose tend to be difficult to be expressed because the cellulose molecules are dissolved in water. . The fine fibrous cellulose is monofilamentous cellulose having a fiber width of 1000 nm or less, for example.

  Measurement of the fiber width of the fine fibrous cellulose by electron microscope observation is performed as follows. An aqueous suspension of fine fibrous cellulose having a concentration of 0.05% by mass or more and 0.1% by mass or less is prepared, and the suspension is cast on a carbon film-coated grid subjected to a hydrophilic treatment to prepare a sample for TEM observation. To do. When a wide fiber is included, an SEM image of the surface cast on glass may be observed. Observation with an electron microscope image is performed at a magnification of 1000 times, 5000 times, 10000 times, or 50000 times depending on the width of the constituent fibers. However, the sample, observation conditions, and magnification are adjusted to satisfy the following conditions.

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

  The width of the fiber that intersects with the straight line X and the straight line Y is visually read from the observation image that satisfies the above conditions. In this way, at least three sets of images of the surface portion that do not overlap each other are observed, and the width of the fiber intersecting with the straight line X and the straight line Y is read for each image. Thus, at least 20 × 2 × 3 = 120 fiber widths are read. The average fiber width (sometimes simply referred to as “fiber width”) of fine fibrous cellulose is an average value of the fiber widths read in this way.

The fiber length of the fine fibrous cellulose is not particularly limited, but is preferably 0.1 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 making the fiber length within the above range, the destruction of the crystalline region of the fine fibrous cellulose can be suppressed, and the slurry viscosity of the fine fibrous cellulose can be made an appropriate range. Note that the fiber length of the fine fibrous cellulose can be determined by image analysis using TEM, SEM, or AFM.
The axial ratio (fiber length / fiber width) of 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 be equal to or higher than the above lower limit value, it is easy to form a fine fiber-containing sheet, and it is easy to obtain sufficient thickening when a solvent dispersion is produced. By setting the axial ratio to be equal to or less than the above upper limit value, for example, when handling fibrous cellulose as an aqueous dispersion, it is preferable in terms of easy handling such as dilution.

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

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

The fine fibrous cellulose preferably has a phosphate group or a substituent derived from a phosphate group. The phosphoric acid group is a divalent functional group equivalent to the phosphoric acid obtained by removing the hydroxyl group. Specifically, it is a group represented by —PO ₃ H ₂ . Substituents derived from phosphoric acid groups include substituents such as groups obtained by polycondensation of phosphoric acid groups, salts of phosphoric acid groups, and phosphoric acid ester groups. It may be a group.

In the present invention, the phosphate group or the substituent derived from the phosphate 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 (where a = b × m); α and α ′ each independently represent R or OR. R represents a hydrogen atom, a saturated-linear hydrocarbon group, a saturated-branched hydrocarbon group, a saturated-cyclic hydrocarbon group, an unsaturated-linear hydrocarbon group, an unsaturated-branched hydrocarbon group. , 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 introduction of phosphoric acid groups involves reacting 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”) with a fiber raw material containing cellulose. Can be performed. Such a phosphorylating reagent may be mixed in a powder or aqueous solution with a dry or wet fiber raw material. As another example, a phosphorylating reagent powder or an aqueous solution may be added to the fiber raw material slurry.

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

  As an example of a method for causing Compound A to act on a fiber raw material in the presence of Compound B, a method of mixing a powder or an aqueous solution of Compound A and Compound B with a dry or wet fiber raw material can be mentioned. Another example is a method in which powders and aqueous solutions of Compound A and Compound B are added to the fiber raw material slurry. Of these, since the uniformity of the reaction is high, a method of adding an aqueous solution of Compound A and Compound B to a dry fiber material, or a powder or an aqueous solution of Compound A and Compound B to a wet fiber material The method is preferred. Moreover, the compound A and the compound B may be added simultaneously, or may be added separately. Moreover, you may add the compound A and the compound B first used for reaction as aqueous solution, and remove an excess chemical | medical solution by pressing. The form of the fiber raw material is preferably cotton or thin sheet, but is not particularly limited.

Compound A used in this embodiment is at least one selected from a compound having a phosphate group and a salt thereof.
Examples of the compound having a phosphate group include, but are not limited to, phosphoric acid, lithium salt of phosphoric acid, sodium salt of phosphoric acid, potassium salt of phosphoric acid, ammonium salt of phosphoric acid, and the like. Examples of the lithium salt of phosphoric acid include lithium dihydrogen phosphate, dilithium hydrogen phosphate, trilithium phosphate, lithium pyrophosphate, and lithium polyphosphate. Examples of the sodium salt of phosphoric acid include sodium dihydrogen phosphate, disodium hydrogen phosphate, trisodium phosphate, sodium pyrophosphate, and sodium polyphosphate. Examples of the potassium salt of phosphoric acid include potassium dihydrogen phosphate, dipotassium hydrogen phosphate, tripotassium phosphate, potassium pyrophosphate, and potassium polyphosphate. Examples of the ammonium salt of phosphoric acid include ammonium dihydrogen phosphate, diammonium hydrogen phosphate, triammonium phosphate, ammonium pyrophosphate, and ammonium polyphosphate.

  Among these, phosphoric acid and phosphoric acid are introduced efficiently from the viewpoint that the introduction efficiency of phosphate groups is high, the fibrillation efficiency is easily improved in the fibrillation process described later, the cost is low, and the industrial application is easy. Sodium salt, potassium salt of phosphoric acid, and ammonium salt of phosphoric acid are preferable. Sodium dihydrogen phosphate or disodium hydrogen phosphate is more preferable.

  In addition, compound A is preferably used as an aqueous solution because the uniformity of the reaction is increased and the efficiency of introduction of phosphate groups is increased. The pH of the aqueous solution of Compound A is not particularly limited, but is preferably 7 or less because the efficiency of introduction of phosphate groups is increased, and more preferably pH 3 or more and pH 7 or less from the viewpoint of suppressing the hydrolysis of pulp fibers. The pH of the aqueous solution of Compound A may be adjusted by, for example, using a phosphoric acid group-containing compound that exhibits acidity and an alkalinity, and changing the amount ratio thereof. You may adjust pH of the aqueous solution of the compound A by adding an inorganic alkali or an organic alkali to the thing which shows acidity among the compounds which have a phosphoric acid group.

  The amount of compound A added to the fiber raw material is not particularly limited, but when the amount of compound A added is converted to phosphorus atomic weight, the amount of phosphorus atom added to the fiber raw material (absolute dry mass) is 0.5 mass% to 100 mass%. Or less, more preferably 1% by mass or more and 50% by mass or less, and most preferably 2% by mass or more and 30% by mass or less. If the amount of phosphorus atoms added to the fiber raw material is within the above range, the yield of fine fibrous cellulose can be further improved. Moreover, the cost of the compound A to be used can be suppressed while improving phosphorylation efficiency by making the addition amount of the phosphorus atom with respect to a fiber raw material into 100 mass% or less.

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

  Compound B is preferably used as an aqueous solution in the same manner as Compound A. Moreover, since the uniformity of reaction increases, it is preferable to use the aqueous solution in which both compound A and compound B are dissolved. The amount of Compound B added to the fiber raw material (absolute 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 or less. More preferably, it is more preferably 150% by mass or more and 300% by mass or less.

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

  In introducing the phosphate group, it is preferable to perform a heat treatment. As the heat treatment temperature, it is preferable to select a temperature at which a phosphate group can be efficiently introduced while suppressing thermal decomposition and hydrolysis reaction of the fiber. Specifically, it is preferably 50 ° C. or higher and 300 ° C. or lower, more preferably 100 ° C. or higher and 250 ° C. or lower, and further preferably 130 ° C. or higher and 200 ° C. or lower. Moreover, you may use a vacuum dryer, an infrared heating apparatus, and a microwave heating apparatus for a heating.

  During the heat treatment, while water is contained in the fiber raw material slurry to which compound A is added, if the time for allowing the fiber raw material to stand still becomes long, the compound A dissolved with water molecules moves to the fiber raw material surface with drying. To do. Therefore, the concentration of the compound A in the fiber raw material may be uneven, and the introduction of phosphate groups on the fiber surface may not proceed uniformly. In order to suppress the occurrence of unevenness in concentration of Compound A in the fiber material due to drying, a very thin sheet-like fiber material is used, or the fiber material and Compound A are kneaded or stirred with a kneader or the like and dried by heating or reduced pressure. The method should be taken.

  The heating device used for the heat treatment is preferably a device that can always discharge the moisture retained by the slurry and the moisture generated by the addition reaction of the fibers such as phosphate groups to the hydroxyl group of the fiber, such as a blower oven. Etc. are preferred. If water in the system is always discharged, the hydrolysis reaction of the phosphate ester bond, which is the reverse reaction of the esterification, can be suppressed, and the acid hydrolysis of the sugar chain in the fiber can also be suppressed. A fine fiber having a high axial ratio can be obtained.

  The heat treatment time is also affected by the heating temperature, but it is preferably 1 second or more and 300 minutes or less, preferably 1 second or more and 1000 seconds or less after moisture is substantially removed from the fiber raw material slurry. Preferably, it is 10 seconds or more and 800 seconds or less. In the present invention, the amount of phosphate groups introduced can be within a preferred range by setting the heating temperature and the heating time to appropriate ranges.

  The amount of phosphate groups introduced is preferably 5.20 mmol / g or less, more preferably 0.1 mmol / g or more and 3.65 mmol / g or less per 1 g (mass) of 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 more 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. By making the introduction amount of the phosphoric acid group within the above range, the fiber raw material can be easily refined, and the stability of the fine fibrous cellulose can be enhanced. In addition, by making the introduction amount of phosphoric acid groups within the above range, it is possible to leave hydrogen bonds between fine fibrous celluloses while being easy to make fine, and when used as a sheet, it has good strength Expression can be expected.

  The amount of phosphate group introduced into the fiber material can be measured by a conductivity titration method. Specifically, by performing the defibration process step, after treating the resulting fine fibrous cellulose-containing slurry with an ion exchange resin, by determining the change in electrical conductivity while adding an aqueous sodium hydroxide solution, The amount introduced can be measured.

  In conductivity titration, when alkali is added, the curve shown in FIG. 1 is given. Initially, the electrical conductivity rapidly decreases (hereinafter referred to as “first region”). Thereafter, the conductivity starts to increase slightly (hereinafter referred to as “second region”). Thereafter, the conductivity increment increases (hereinafter referred to as “third region”). That is, three areas appear. The boundary point between the second region and the third region is defined as a point at which the amount of change in conductivity twice, that is, the increase (inclination) in conductivity is maximized. Among these, the amount of alkali required in the first region is equal to the amount of strongly acidic groups in the slurry used for titration, and the amount of alkali required in the second region is the amount of weakly acidic groups in the slurry used for titration. Will be equal. When the phosphoric acid group undergoes condensation, apparently weakly acidic groups are lost, and the amount of alkali required in the second region is reduced compared to the amount of alkali required in the first region. On the other hand, the amount of strongly acidic groups coincides with the amount of phosphorus atoms regardless of the presence or absence of condensation, so that the amount of phosphate groups introduced (or the amount of phosphate groups) or the amount of substituent introduced (or the amount of substituents) is simply When said, it represents the amount of strongly acidic group. That is, the alkali amount (mmol) required in the first region of the curve shown in FIG. 1 is divided by the solid content (g) in the titration target slurry to obtain the substituent introduction amount (mmol / g).

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

<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 oxidation treatment such as TEMPO (2,2,6,6-tetramethylpiperidine-1-oxyl) oxidation treatment. Alternatively, a carboxyl group can be introduced by treatment with a compound having a group derived from a carboxylic acid, a derivative thereof, or an acid anhydride or derivative thereof.

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

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

  Although it does not specifically limit as a derivative of the compound which has a carboxyl group, The derivative of the acid anhydride of the compound which has a carboxyl group and the acid anhydride imidation of a compound which has a carboxyl group are mentioned. Although it does not specifically limit as an acid anhydride imidation thing of a compound which has a carboxyl group, Imidation thing of dicarboxylic acid compounds, such as maleimide, succinic acid imide, and phthalic acid imide, is mentioned.

  The acid anhydride derivative of the compound having a carboxyl group is not particularly limited. For example, at least some of the hydrogen atoms of the acid anhydride of the compound having a carboxyl group, such as dimethylmaleic anhydride, diethylmaleic anhydride, diphenylmaleic anhydride, etc. are substituted (for example, alkyl group, phenyl group, etc. ) Are substituted.

The amount of carboxyl group introduced is preferably 0.1 mmol / g or more and 3.65 mmol / g or less, more preferably 0.14 mmol / g or more and 3.5 mmol / g or less, per 1 g (mass) of fine fibrous cellulose. 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 group introduced into the fiber material can be measured by a conductivity titration method. In conductivity titration, when an alkali is added, the curve shown in FIG. 2 is given. 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 the substituent introduction amount (mmol / g).

<Alkali treatment process>
When manufacturing a fine fibrous cellulose, you may perform an alkali treatment with respect to a fiber raw material between a substituent introduction | transduction process and the fibrillation process mentioned later. Although it does not specifically limit as a method of an alkali treatment, For example, the method of immersing a substituent introduction | transduction fiber in an alkaline solution is mentioned.

  The alkali compound contained in the alkali solution is not particularly limited, and may be an inorganic alkali compound or an organic alkali compound. In this embodiment, since versatility is high, it is preferable to use sodium hydroxide or potassium hydroxide as an alkali compound, for example. Further, 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 exemplified by alcohol, and more preferably an aqueous solvent containing at least water. As an alkaline solution, since versatility is high, sodium hydroxide aqueous solution or potassium hydroxide aqueous solution is preferable, for example.

  Although the temperature of the alkali solution in an alkali treatment process is not specifically limited, For example, it is preferable that it is 5 to 80 degreeC, and it is more preferable that it is 10 to 60 degreeC. Although the immersion time of the substituent-introduced fiber in the alkali solution in the alkali treatment step is not particularly limited, for example, it is preferably 5 minutes or longer and 30 minutes or shorter, and more preferably 10 minutes or longer and 20 minutes or shorter. Although the usage-amount of the alkaline solution in an alkali treatment is not specifically limited, For example, it is preferable that it is 100 mass% or more and 100,000 mass% or less with respect to the absolute dry mass of a substituent introduction | transduction fiber, and is 1000 mass% or more and 10000 mass% or less. More preferably.

  In order to reduce the amount of the alkali solution used in the alkali treatment step, the substituent introduction 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 substituent-introduced fiber subjected to the alkali treatment with water or an organic solvent from the viewpoint of improving the handleability.

<Acid treatment process>
When manufacturing fine fibrous cellulose, you may acid-treat with respect to a fiber raw material between the process of introduce | transducing a substituent, and the fibrillation process mentioned later. As an example of this embodiment, the case where a substituent introduction process, an acid treatment, an alkali treatment, and a fibrillation treatment are performed in this order can be mentioned.

  Although the temperature of the acid solution in an acid treatment is not specifically limited, For example, 5 to 100 degreeC is preferable and 20 to 90 degreeC is more preferable. Although the immersion time in the acid solution in acid treatment is not specifically limited, For example, 5 minutes or more and 120 minutes or less are preferable, and 10 minutes or more and 60 minutes or less are more preferable. Although the usage-amount of the acid solution in an acid treatment is not specifically limited, For example, it is preferable that it is 100 mass% or more and 100,000 mass% or less with respect to the absolute dry mass of a fiber raw material, and it is 1000 mass% or more and 10000 mass% or less. Is more preferable.

  Although it does not specifically limit as a method of an acid treatment, For example, the method of immersing a fiber raw material in the acidic liquid containing an acid is mentioned. Although the density | concentration of the acidic liquid to be used is not specifically limited, For example, 10 mass% or less is preferable and it is more preferable that it is 5 mass% or less. Further, the pH of the acidic liquid to be used is not particularly limited, but is preferably 0 to 4, for example, and more preferably 1 to 3. 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, boric acid and the like. Examples of the sulfonic acid include methanesulfonic acid, ethanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, trifluoromethanesulfonic acid and the like. Examples of the carboxylic acid include formic acid, acetic acid, citric acid, gluconic acid, lactic acid, oxalic acid, and tartaric acid. Among these, it is particularly preferable to use hydrochloric acid or sulfuric acid.

<Defibration processing (miniaturization)>
Substituent-introduced fibers are fibrillated in the defibrating process, whereby fine fibrous cellulose is obtained. In the defibrating process, for example, a defibrating apparatus can be used. The defibrating apparatus is not particularly limited. For example, a wet atomizer, a high-speed defibrator, a grinder (stone mortar pulverizer), a high-pressure homogenizer or an ultra-high pressure homogenizer, a high-pressure collision pulverizer, a ball mill, a bead mill, a disk type refiner, A conical refiner, a twin-screw kneader, a vibration mill, a homomixer under high-speed rotation, an ultrasonic disperser, or a beater can be used, and the solid content concentration of fine fibrous cellulose during defibrating is set as appropriate. it can. Among the above-described defibrating apparatuses, it is more preferable to use a wet atomizer, a high-speed defibrator, a high-pressure homogenizer, or an ultra-high pressure homogenizer that is less affected by the pulverization media and has less risk of contamination. The number of times of defibrating treatment (miniaturization) is not particularly limited, but it is preferable to perform the number of times in order to promote sufficient miniaturization. Although an upper limit is not specifically limited, It is practical that it is 10 times or less.

  In the defibrating process, for example, the substituent-introduced fiber is preferably diluted with a dispersion medium to form a slurry. As a dispersion medium, 1 type, or 2 or more types selected from water and organic solvents, such as a polar organic solvent, 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 the 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, propylene glycol monomethyl ether, and the like. Examples of the esters include ethyl acetate and butyl acetate. 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, an enzyme treatment may be performed. That is, the cellulose-containing composition of the present invention may contain an enzyme. Moreover, the cellulose-containing composition of the present invention may contain a protein formed by inactivating an enzyme.
Enzymes that can be used in the present invention are cellulase enzymes, and are classified into the carbohydrate hydrolase family based on the higher-order structure of the catalytic domain having a cellulose hydrolysis reaction function. Cellulase enzymes are classified into endo-glucanase and cellobiohydrolase according to their cellulolytic properties. Endo-type glucanase is highly hydrolyzable to an amorphous part of cellulose, a soluble cellooligosaccharide, or a cellulose derivative such as carboxymethyl cellulose, and randomly cleaves the molecular chain from the inside to reduce the degree of polymerization. However, endo-type glucanase has low hydrolysis reactivity to cellulose microfibrils having crystallinity. In contrast, cellobiohydrolase decomposes the crystalline 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 endo-type glucanase.

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

  Hemicellulose is a polysaccharide excluding pectins between cellulose microfibrils in the plant cell wall. Hemicelluloses are diverse and differ between plant types and cell wall layers. In wood, glucomannan is the main component in the secondary wall of conifers, and 4-O-methylglucuronoxylan is the main component in the secondary walls of hardwood. Therefore, in order to obtain fine fibers from coniferous trees, it is preferable to use mannase, and in the case of hardwoods, it is preferable to use xylanase.

According to this invention, the manufacturing method of a cellulose containing composition including the process of adding an enzyme is provided. By adding an enzyme to the fine fibrous cellulose, the fine fibrous cellulose and the enzyme can be reacted. In this invention, the form which does not perform the washing | cleaning process of a fine fibrous cellulose after an enzyme process is employable.
In the present invention, the enzyme may be deactivated after the enzyme treatment. As a method for inactivating the enzyme, the mixture of the fine fibrous cellulose and the enzyme is heated to 100 ° C. and allowed to stand for 30 minutes to 1 hour while maintaining the temperature, or the mixture of the fine fibrous cellulose and the enzyme. On the other hand, it is possible to adjust the pH to 10 or more by adding a strong base, but it is not particularly limited.
The cellulose-containing composition of the present invention can be produced by the above-described method for producing 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. × 10 ⁻⁵ parts by mass or less is more preferable, and 5.0 × 10 ⁻⁶ parts by mass or less is particularly preferable. The amount of the 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 with respect to 1 part by mass of fibrous cellulose. preferable.
By setting the addition amount of the enzyme within the above range, particles (aggregates) in the coated product can be suppressed.

The reaction time between the fine fibrous cellulose and the enzyme is not particularly limited, but is generally preferably 1 minute to 24 hours, and more preferably 1 minute to 1 hour.
The reaction temperature and reaction pH of the fine fibrous cellulose and the enzyme are preferably kept at the optimum temperature and pH of the enzyme used. In general, the reaction temperature is 20 to 80 ° C. and the pH is 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 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 refined, but a part thereof may remain without being refined. 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 is prepared by adjusting the cellulose dispersion to a solid content concentration of 0.2% by mass, and using a cooling high-speed centrifuge (Kokusan, H-2000B). It is a fibrous cellulose that settles when centrifuged at 12000G for 10 minutes.

  That there are few sedimentation components means that the yield of the supernatant liquid after centrifugation is high. 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.

In addition, the supernatant yield after centrifugation of said fine fibrous cellulose dispersion can be measured by the following method in this specification.
The supernatant yield after centrifuging the fine fibrous cellulose dispersion was measured by the method described below. The supernatant yield after centrifugation is an indicator 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 was adjusted to a solid content concentration of 0.2% by mass and centrifuged using a cooling high-speed centrifuge (Kokusan Co., Ltd., H-2000B) under the conditions of 12000G for 10 minutes. The obtained supernatant was collected, and the solid content concentration of the supernatant was measured. Based on the following formula, the yield of fine fibrous cellulose was determined.
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, it is characterized in that the content of coarse fibers is small in the fibrous cellulose-containing composition, and the fine fibrous cellulose dispersion By setting the yield of the supernatant after centrifugation in the above range, good coating properties can be obtained when blended into the paint.

(Specific ingredients)
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 preparing a stable dispersion by uniformly dispersing a pigment (fine solid) in a dispersion medium.

The pigment dispersant is, for example, structurally a kind of surfactant, and in particular, a pigment dispersant having a function for adsorbing to a solid surface such as a pigment as well as affinity for the dispersion medium is preferable. Furthermore, in addition to the pigment adsorbing action and the dispersion medium affinity, there are those having both electrostatic repulsion or steric repulsion (giving repulsive force during dispersion) for preventing reaggregation of pigment and suppressing sedimentation. In the present invention, those having both the pigment adsorption action, the dispersion medium affinity action, and the repulsive force imparting action at the time of dispersion are effective in preventing aggregation of fine fibrous cellulose.
As a pigment dispersant having both of these three functions, a resin-type pigment dispersant can be mentioned.

  Examples of resin-type pigment dispersants include polyester resins, polyolefin resins, polyurethane resins, and polymers composed of (meth) acrylic acid resins, with amino groups, hydroxyl groups, carboxyl groups, carboxylic acids in the side chains. Those having a functional group such as an ester group, an amide group, an ammonium group, a sulfo group, a sulfuric ester group, a phosphoryl group, a phosphoric acid group, a carbamoyl group, and a sulfamoyl group are preferred.

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

Solvent: tetrahydrofuran (THF)
Column: Shodex K806, K805, K803G
(Used by connecting three Showa Denko Co., Ltd.)
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 rate): 1.0 ml / min
Injection volume: 10 μL
Calibration curve: Standard polystyrene STK standard polystyrene (manufactured by Tosoh Co., Ltd.) Mw = 500 to 2,800,000 was used for 13 calibration curves. Thirteen samples are used at approximately 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, and further 25 mgKOH / g or more. 30 mgKOH / g or more is particularly preferable. As an upper limit of an acid value, 200 mgKOH / g or less is preferable, 180 mgKOH / g or less is more preferable, 150 mgKOH / g or less is more preferable, 120 mgKOH / g or less is more preferable, 100 mgKOH / g or less is especially preferable.

  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, and 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.

  If the acid value or amine value of the pigment dispersant having an ionic group is less than the above lower limit value, the interaction with the fine fibrous cellulose tends to be insufficient, and a sufficient anti-aggregation effect cannot be obtained, resulting in poor coatability. In some cases, a smooth surface cannot be obtained. On the other hand, when the acid value or the amine value exceeds the upper limit, the steric hindrance layer may be less than the affinity part for fine fibrous cellulose, and the aggregation preventing effect may be insufficient.

  The ionic group of the pigment dispersant having an ionic group is not particularly limited, but may be a cationic group, an anionic group, or a dissociable group by an acid or a base. Examples of the cationic group include an amino group and a quaternary ammonium group. Examples of the anionic group include a sulfo group, a carboxyl group, a sulfate group, and a phosphate group. An example of the dissociable group is an amide group. The ionic group may form a salt having a counter ion. The pigment dispersant having an ionic group may have the above cationic group, anionic group, and dissociable group in the molecule at the same time.

  Various pigment dispersants having an ionic group can be mentioned. Examples of polymer dispersants include styrene / maleic anhydride copolymers, naphthalene sulfonate formalin conjugates, poly (meth) acrylates, 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 And polymer dispersants such as Satokinsan, resin (polymer) having a (meth) acrylate alkali metal salt moiety, resin having a (meth) acrylic acid moiety, and resin having an alkylol ammonium salt moiety. For these polymer dispersants, see, for example, Mito Kuji “Dispersant” J. Org. Jpn. Soc. Color Mater. 78 [3] (2005) pp. 41-48 can be referred to.

  In particular, 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 acid groups, alkylol ammonium salts such as polyfunctional polymer alkylol ammonium salts, (meth) acrylate resins and potassium salts, etc. Is particularly preferred. In the present specification, the term “(meth) acrylate” means a general term for acrylate and methacrylate.

The alkylol ammonium salt site is preferably a reaction site between an acidic group (for example, a sulfo group, a carboxyl group, a sulfate group, a phosphoryl group, or phosphoric acid) and an alkylol ammonium. The alkylol ammonium salt moiety preferably has the following partial structure.
—C (═O) —N (—R ¹ ) (— R ² —OH) Formula (2)
Wherein, R ¹ represents a hydrogen atom or an alkyl group (preferably having 1 to 12 carbon atoms, more preferably 1-6, more preferably 1 to 3), R ² is preferably an alkylene group (having 1 to 12 carbon atoms, 1 -6 is more preferable, and 1-3 are more preferable. R ¹ and R ² may further have a substituent Z as long as the effects of the present invention are exhibited.

The pigment dispersant having an anionic group is preferably a polymer having a partial structure represented by 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.

The pigment dispersant having an anionic group is also preferably a polymer having a partial structure of the following formula (4).
-C (= O) -O-L 1 -A formula (4)
A is an acidic group, and is preferably a sulfo group, a carboxyl group, a sulfuric 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 (C1-12 is preferable, 1-6 is more preferable, and 2 or 3 is more preferable) is preferable.

As a pigment dispersant having an alkylol ammonium salt moiety,
DISPERBYK,
DISPERBYK-180,
DISPERBYK-181,
DISPERBYK-187,
DISPERBYK-140,
DISPERBYK-250,
BYK-9076,
BYK-W969
(Both 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 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 (C1-C24 is preferable, C1-C12 is more preferable, C1-C6 is more preferable), an aralkyl group (C7-C21 is preferable, C7 is preferable). -15 is more preferable, C7-11 is more preferable, a hydroxyl group, an amino group or a salt thereof (C0-24 is preferable, C0-12 is more preferable, and C0-6 is more 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, and further preferably 1 to 6 carbon atoms), a sulfamoyl group or a salt thereof ( C0-24 is preferable, C0-12 is more preferable, C0-6 is more preferable, and an aryl group (C6-22 is preferable). C6-C18 is more preferable, C6-C10 is still more preferable), an acyl group (C2-C12 is preferable, C2-C6 is more preferable, C2-C3 is further more preferable), Acyloxy Group (C2-C12 is preferable, C2-C6 is more preferable, C2-C3 is more preferable), and heterocyclic group (C2-C8 is more preferable, C2-C5 is more preferable) ), A halogen atom, a quaternary ammonium group or a salt thereof (C3-C23 is preferable, C3-C19 is more preferable, and C3-C11 is more preferable).

Examples of the linking group Y include 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 according 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, 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, still more preferably 300 parts by mass or less, relative to 100 parts by mass of fibrous cellulose. It is particularly preferable that the amount is not more than part by mass. Further, 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. By setting it as more than said lower limit, the coating property of a fibrous cellulose containing composition and the smoothness of a coating film can be achieved at a high level as needed, and it is preferable. By setting it as the above upper limit value or less, it is preferable because the desired effect can be exhibited without impairing the properties and manufacturing suitability required for the fibrous cellulose-containing composition.

  The specific component may be used alone or in combination of two or more. When using 2 or more types, it is preferable that the total amount is said range.

(resin)
When the fibrous cellulose-containing composition of the present invention is, for example, a paint, it may further contain a resin such as a thermoplastic resin, a thermosetting resin, or a photocurable resin. Examples of the resin include styrene resins, acrylic resins, aromatic polycarbonate resins, aliphatic polycarbonate resins, aromatic polyester resins, aliphatic polyester resins, aliphatic polyolefin resins, cyclic olefin resins, polyamides. 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, A phenol resin, an epoxy resin, etc. are mentioned, However, It is not restrict | limited to these.

  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 paint. It is particularly preferred. Moreover, it is preferable that it is 500 mass parts or less with respect to 1 mass part of fibrous cellulose, as for content of resin, it is more preferable that it is 300 mass parts or less, and it is especially preferable that it is 200 mass parts or less. By containing resin so that it may become the said content, the effect of the said specific component can be exhibited suitably, and applicability | paintability, the smoothness of a coating film, the optimization of an elasticity modulus, intensity | strength, etc. can be implement | achieved.

(Curing agent)
When the fibrous cellulose-containing composition of the present invention is used as a paint, it is preferable to contain a curing agent. Known curing agents can be appropriately used as the curing agent, and examples thereof include isocyanate curing agents (polyisocyanate, etc.), epoxy (oxirane) curing agents, oxetane curing agents, and the like. In the present invention, among them, an isocyanate curing agent is preferable.

  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 when the coating material is used. It is particularly preferred. 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 fibrous cellulose. . By containing the curing agent so as to have the above content, the effect of the specific component can be suitably exhibited, and coating properties, smoothness of the coating film, optimization of the elastic modulus, and the like can be realized.

(Optional component)
The fibrous cellulose-containing composition of the present invention may contain optional components other than the components described above. 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, and 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 fibrous cellulose is preferably 0.05% by mass or more with respect to 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 a thickening agent, the fibrous cellulose content 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. Moreover, it is preferable that content of fibrous cellulose is 95 mass% or less, and it is more preferable that it is 90 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 a solid content concentration of fibrous cellulose of 0.4 mass%. Preferably, it is 35,000 mPa · s or less, 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 It is particularly preferable that the slurry be 1,000 mPa · s or more. It is preferable that the viscosity is not more than the above upper limit value because good coatability is exhibited. By setting it as more than said lower limit, the Young's modulus and intensity | strength when it is set as a coating film can be optimized, and it 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 is 0.4% by mass, and then stirred at 1500 rpm for 5 minutes with a disperser. Next, the viscosity of the resulting dispersion 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. In addition, the dispersion liquid to be measured is allowed to stand for 24 hours in an environment of 23 ° C. and 50% relative humidity before measurement. The measurement temperature of the viscosity is 23 ° C. Other detailed measurement conditions and the like are based on JISZ8803: 2011. Five samples are prepared for each level, a total of 10 measurements are made twice, and the arithmetic average 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 in combination with other components as necessary. In this case, the combination amount and ratio of the fine fibrous cellulose and the specific component are the same as the blending amount and the like in the fibrous cellulose-containing composition.

(Coating)
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 use form as a paint, it is preferably 1000 μm or less, more preferably 500 μm or less, further preferably 300 μm or less, and 100 μm or less. More preferably, it is particularly preferably 80 μm or less. The lower limit is preferably 1 μm or more, more preferably 5 μm or more, and particularly preferably 10 μm or more.

  The surface roughness of the coating film (in this specification, unless otherwise specified, the surface roughness refers to the arithmetic average roughness: Ra specified in JIS B0601: 2013) is not particularly limited. For example, it is preferable to have better smoothness. According to the present invention, the arithmetic average 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. It is particularly preferable that Although a lower limit is not specifically limited, It is practical that it is 0.001 micrometer or more.

  The surface roughness is measured using a light interference type non-contact surface shape measuring instrument (manufactured by Ryoka System Co., Ltd., non-contact surface / layer cross-sectional shape measurement system VertScan 2.0, model: R5500 GML), and a measurement range of 470. The arithmetic average roughness (Ra) of 92 μm × 353.16 μm is measured. The measurement is performed 5 times per level, and the arithmetic average roughness is obtained from the average value. Details such as the definition of arithmetic mean roughness (Ra), measurement conditions, and calculation method are based on JIS B0601: 2013.

  The Young's modulus of the coating 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. More preferably, it is 0.8 GPa or more. The upper limit is practically 8 GPa or less. According to the present invention, such a high Young's modulus can be achieved, so that it can be suitably used in applications 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 Co., Ltd.) is used and the length of the test piece between the grips is 50 mm and the tensile speed is 5 mm / min. Measure in compliance. When measuring the Young's modulus, a specimen 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 per level, and the average value is adopted.

(Membrane production method)
The production process of the thickener, paint, film, etc. is not particularly limited.
The thickener mixes a dispersion (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 other components (for example, water) as necessary. Can be manufactured.
The paint includes fine fibrous cellulose (which may be a dispersion), a specific component (which may be a solution), a resin (for example, an acrylic resin), a curing agent (for example, a polyisocyanate), and others as necessary. It can manufacture by mixing the component (for example, organic solvent).
A film | membrane can be manufactured by apply | coating the composition (For example, above-described coating material or thickener etc.) containing a fine fibrous cellulose and a specific component, and forming a coating film. Specifically, for example, the coating film can be formed by applying a composition containing fine fibrous cellulose and a specific component onto a substrate and drying the composition.
The coating film formed above may be peeled off from the substrate to form a sheet.
Further, the sheet may be produced by paper making a composition containing fine fibrous cellulose and a specific component (which may be the above-described paint or thickener).

<Coating process>
A coating process is a process of coating the composition (it may be an above-described coating material or a thickener) containing a fine fibrous cellulose and a specific component on a base material.
When manufacturing a sheet | seat, a sheet | seat can be continuously manufactured by using a coating device and a elongate base material.

  The material of the base material used in the coating process is not particularly limited, but the one with higher wettability 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. Among them, a resin film or plate or a metal film or plate is preferable, but is 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, and iron plates, and their surfaces oxidized, stainless steel Or a brass film or plate can be used.

  In the coating process, when the composition to be coated is low in viscosity and spreads on the base material, a damming frame is fixed on the base material in order to obtain a sheet having a predetermined thickness and basis weight. May be used. The quality of the damming frame is not particularly limited, but it is preferable to select one that can easily peel off the edge of the sheet attached after drying. Of these, a molded resin plate or metal plate is preferable, but is not particularly limited. For example, resin plates such as acrylic plates, polyethylene terephthalate plates, vinyl chloride plates, polystyrene plates, polypropylene plates, polyvinylidene chloride plates, metal plates such as aluminum plates, zinc plates, copper plates, iron plates, and the surfaces thereof were oxidized. What formed the thing, a stainless plate, a brass plate, etc. can be used.

  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. An applicator, a die coater, a curtain coater, and a spray coater 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. If the coating temperature is at least the above lower limit, the composition can be applied easily, and if it is at most the above upper limit, volatilization of the dispersion medium during coating can be suppressed.

In the coating step, the composition is preferably applied so that the finished basis weight of the sheet is 10 g / m ² or more and 100 g / m ² or less, 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.

  It is preferable that a coating process includes the process of drying the composition coated on the base material. Although it does not specifically limit as a drying method, Either a non-contact drying method or the method of drying while restraining a sheet | seat may be sufficient, and these may be combined.

  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) or a method of drying in vacuum (vacuum drying method) is applied. Can do. Although the heat drying method and the vacuum drying method may be combined, the heat drying method is usually applied. Although drying by 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, it is not particularly limited. The heating temperature in the heat 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 not less than the above lower limit value, the dispersion medium can be volatilized quickly, and if it is not more than the above upper limit value, it is possible to suppress the cost required for heating and to prevent the fine fibrous cellulose from being discolored by heat. .

<Paper making process>
When manufacturing a sheet | seat, the manufacturing process of a sheet | seat may include the process of paper-making the composition (it may be the above-mentioned coating material or thickener) containing a fine fibrous cellulose and a specific component. Examples of the paper machine in the paper making process include a continuous paper machine such as a long-mesh type, a circular net type, and an inclined type, and a multi-layered paper machine combining these. In the paper making process, known paper making such as hand making may be performed.

  In the paper making process, the composition is filtered and dehydrated on a wire to obtain a wet paper sheet, and then the sheet is obtained by pressing and drying. 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 fine fibrous cellulose and preservatives do not pass through and the filtration rate is not too slow. Although it does not specifically limit as such a filter cloth, The sheet | seat, fabric, and porous film which consist of organic polymers are preferable. The organic polymer is not particularly limited, but non-cellulosic organic polymers such as polyethylene terephthalate, polyethylene, polypropylene, polytetrafluoroethylene (PTFE) and the like are preferable. Specific examples include a porous film of polytetrafluoroethylene having a pore size of 0.1 μm to 20 μm, for example, 1 μm, polyethylene terephthalate or polyethylene woven fabric having a pore size of 0.1 μm to 20 μm, for example, 1 μm, but is not particularly limited.

  Although it does not specifically limit as a method of manufacturing a sheet | seat from the said composition, For example, the method of using the manufacturing apparatus of WO2011 / 013567, etc. are mentioned. This manufacturing apparatus is configured to discharge a composition containing fine fibrous cellulose onto the upper surface of an endless belt, squeeze a dispersion medium from the discharged composition to generate a web, and dry the web to produce a fiber. And a drying section for producing a sheet. An endless belt is disposed from the squeezing section to the drying section, and the web generated in the 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 a dehydration method that is usually used in paper production. A method of dehydrating with a long net, a circular net, an inclined wire, etc., and then dehydrating with a roll press is preferable. The drying method is not particularly limited, and examples thereof include methods used in paper production. 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 laminate | stack another layer on the coating film or sheet | seat obtained at the process mentioned above, and may form a laminated body. Such other layers may be provided on both surfaces of the coating film or sheet, but may be provided only on one surface of the coating film or sheet. As another layer laminated | stacked on the at least one surface of a coating film or a sheet | seat, a resin layer and an inorganic layer can be mentioned, for example.

  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, and an inorganic layer directly laminated on at least one surface of a coating film or a sheet. Laminated body, resin layer, coating film or sheet, laminated body in which inorganic layers are laminated in this order, coated film or sheet, resin layer, laminated body in which inorganic layers are laminated in this order, coating film or sheet, inorganic layer And a laminate in which the resin layers are laminated in this order. The layer structure of the laminate is not limited to the above, and various forms can be used depending on the application.

<Resin layer>
The resin layer is a layer mainly composed of natural resin or synthetic resin. Here, a main component refers to the component contained 50 mass% or more with respect to the total mass of a 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. In addition, content of resin can also be 100 mass%, and may be 95 mass% or less.

  Examples of natural resins include rosin resins such as rosin, rosin ester, and hydrogenated rosin ester.

  The synthetic resin is preferably at least one selected from, for example, polycarbonate resin, polyethylene terephthalate resin, polyethylene naphthalate resin, polyethylene resin, polypropylene resin, polyimide resin, polystyrene resin, polyurethane resin, and acrylic resin. Among these, the synthetic resin is preferably at least one selected from polycarbonate resin and acrylic resin, and more preferably polycarbonate resin. The acrylic resin is preferably at least one selected from polyacrylonitrile and poly (meth) acrylate.

  Examples of the polycarbonate resin constituting the resin layer include an aromatic polycarbonate resin and an aliphatic polycarbonate resin. These specific polycarbonate resins are known, and examples thereof include polycarbonate resins described in JP2010-023275A.

  As the resin constituting the resin layer, one kind may be used alone, or a copolymer obtained by copolymerization or graft polymerization of a plurality of resin components may be used. Moreover, you may use as a blend material which mixed the some resin component with the 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. When an adhesive layer is provided between the coating film or sheet and the resin layer, for example, an acrylic resin can be used as an adhesive constituting the adhesive layer. Examples of adhesives other than acrylic resins include vinyl chloride resin, (meth) acrylate resin, styrene / acrylate copolymer resin, vinyl acetate resin, vinyl acetate / (meth) acrylate ester. Examples include 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. It is done.

When the adhesive layer is not provided between the coating film or sheet and the resin layer, the resin layer may have an adhesion assistant, and the surface of the resin layer is subjected to a surface treatment such as a hydrophilic treatment. Also good.
Examples of the adhesion assistant 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 organosilicon compound. Among these, the adhesion assistant is preferably at least one selected from a compound containing an isocyanate group (isocyanate compound) and an organosilicon compound. Examples of organosilicon compounds include silane coupling agent condensates and silane coupling agents.
Examples of surface treatment methods other than hydrophilization treatment include corona treatment, plasma discharge treatment, UV irradiation treatment, electron beam irradiation treatment, and flame treatment.

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

  The formation method of an inorganic layer is not specifically limited. In general, a method for forming a thin film is roughly classified into a chemical vapor deposition method (CVD) and a physical film deposition method (Physical Vapor Deposition, PVD), and either method may be adopted. . Specific examples of the CVD method include plasma CVD using plasma and catalytic chemical vapor deposition (Cat-CVD) in which a material gas is contact pyrolyzed using a heated catalyst body. Specific examples of the PVD method include vacuum deposition, ion plating, and sputtering.

  In addition, as an inorganic layer forming method, an atomic layer deposition (ALD) can be employed. The ALD method is a method of forming a thin film in units of atomic layers by alternately supplying source gases of respective elements constituting a film to be formed to a surface on which a layer is formed. Although there is a drawback that the film forming speed is slow, there is an advantage that it is possible to form a thin film with few defects because it can cleanly cover even a complicated surface more than the plasma CVD method. In addition, the ALD method has an advantage that the film thickness can be controlled on the nano order and it is relatively easy to cover a wide surface. Furthermore, the ALD method can be expected to improve the reaction rate, lower the temperature, and reduce the unreacted gas by using plasma.

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

  A sheet | seat is suitable for the use of light transmissive substrates, such as various display apparatuses and various solar cells. It is also suitable for applications such as substrates for electronic devices, members of household appliances, various vehicles and building windows, interior materials, exterior materials, packaging materials, and the like. Furthermore, it is also suitable for applications in which the sheet itself is used as a reinforcing material in addition to threads, filters, fabrics, cushioning materials, sponges, abrasives, and the like.

  The features of the present invention will be described more specifically with reference to examples and comparative examples. The materials, amounts used, ratios, processing details, processing procedures, and the like shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be construed as being limited by the specific examples shown below. In the following examples, for convenience of explanation, a slurry obtained by treating fine fibrous cellulose is referred to as a dispersion, and a slurry containing this and a specific component is referred to as a fibrous cellulose-containing composition. And what mix | blended fibrous cellulose containing composition, resin, the hardening | curing agent, etc. is called a coating material. However, this does not limit the scope of the present invention. For example, what contains fine fibrous cellulose, a specific component, and other components, such as a coating material, is also included in the scope of the fibrous cellulose-containing composition of the present invention.

<Production of fine fibrous cellulose dispersion (1)>
(Phosphorylation process)
Oji Paper's softwood kraft pulp (solid content 93% by mass, basis weight 208 g / m ² sheet, disaggregated and measured according to JIS P 8121-2: 2012) ) Was 700 ml). The raw material pulp was phosphorylated as follows. First, a mixed aqueous solution of ammonium dihydrogen phosphate and urea is added to 100 parts by mass (absolutely dry mass) of the above raw pulp to obtain 45 parts by mass of ammonium dihydrogen phosphate, 120 parts by mass of urea, and 150 parts by mass of water. Thus, a chemical solution-impregnated pulp was obtained. Next, the obtained chemical solution-impregnated pulp was heated with a hot air dryer at 165 ° C. for 200 seconds to introduce phosphate groups into cellulose in the pulp to obtain phosphorylated pulp. Subsequently, the obtained phosphorylated pulp was washed. The washing treatment is performed by repeating the operation of filtering and dewatering after stirring the pulp dispersion obtained by pouring 10 L of ion-exchanged water into 100 g of phosphorylated pulp (absolute dry mass) so that the pulp is uniformly dispersed. went. When the electrical conductivity of the filtrate reached 100 μS / cm or less, the end point of washing was determined.

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

Next, the washing treatment was performed on the phosphorylated pulp after the alkali treatment.
The infrared absorption spectrum was measured using FT-IR with respect to the phosphorylated pulp obtained by this. As a result, absorption based on phosphate groups was observed in the vicinity of 1230 cm ⁻¹ , confirming that phosphate groups were added to the pulp. Moreover, the amount of phosphate groups (strongly acidic group amount) measured by the measurement method described later was 1.45 mmol / g.
Moreover, when the obtained phosphorylated pulp was tested and analyzed with an X-ray diffractometer, it was found at two positions of 2θ = 14 ° to 17 ° and 2θ = 22 ° to 23 °. A typical peak was confirmed and confirmed to have cellulose type I crystals.

(Defibration processing)
Ion exchange water was added to the resulting phosphorylated pulp to prepare a slurry having a solid content concentration of 2% by mass. This slurry was treated three times at a pressure of 200 MPa with a wet atomizer (Sugino Machine, Starburst) to obtain a fine fibrous cellulose dispersion (1) containing fine fibrous cellulose. X-ray diffraction confirmed that the fine fibrous cellulose maintained the cellulose I-type crystals. Moreover, it was 3-5 nm when the fiber width of the fine fibrous cellulose was measured using the transmission electron microscope according to the following measuring method.
In addition, it was 22400 [mPa * s] when the 0.4 mass% viscosity of the said fine fibrous cellulose was measured.

<Measurement of fiber width>
The fiber width of the fine fibrous cellulose was measured by the following method.
The supernatant of the fine fibrous cellulose dispersion obtained by treatment with a wet atomizer is water so that the concentration of fine fibrous cellulose is 0.01% by mass or more and 0.1% by mass or less. It diluted and dripped at the carbon grid membrane hydrophilized. After drying, this was stained 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)
As the raw material pulp, Oji Paper's softwood kraft pulp (undried) was used. The raw material pulp was subjected to alkali TEMPO oxidation treatment as follows. First, the above raw material pulp equivalent to 100 parts by mass of dry mass, 1.6 parts by mass of TEMPO (2,2,6,6-tetramethylpiperidine-1-oxyl), 10 parts by mass of sodium bromide, 10000 parts by mass of water It was dispersed in the part. Subsequently, 13 mass% sodium hypochlorite aqueous solution was added so that it might become 3.8 mmol with respect to 1.0 g of pulp, and reaction was started. During the reaction, a 0.5 M aqueous sodium hydroxide solution was added dropwise to keep the pH at 10 or more and 10.5 or less, and the reaction was regarded as completed when no change in pH was observed.

  Next, the obtained TEMPO oxidized pulp was washed. The washing treatment is performed by dehydrating the pulp slurry after TEMPO oxidation to obtain a dehydrated sheet, then pouring 5000 parts by mass of ion exchange water, stirring and dispersing uniformly, and then repeating the operation of filtration and dehydration. It was. When the electrical conductivity of the filtrate reached 100 μS / cm or less, the end point of washing was determined.

The dehydration sheet was subjected to a post-oxidation treatment of remaining aldehyde groups as follows. The dehydration sheet corresponding to a dry mass of 100 parts by mass was dispersed in 10000 parts by mass of a 0.1 mol / L acetate buffer solution (pH 4.8). Next, 113 parts by mass of 80% sodium chlorite was added and immediately sealed, followed by reaction at room temperature for 48 hours while stirring at 500 rpm using a magnetic stirrer to obtain a pulp slurry.
Next, the obtained post-oxidized TEMPO oxidized pulp was washed. The washing treatment is performed by dehydrating the post-oxidation pulp slurry to obtain a dehydrated sheet, pouring 5000 parts by mass of ion exchange water, stirring and dispersing uniformly, and then repeating the operation of filtration and dehydration. It was. When the electrical conductivity of the filtrate reached 100 μS / cm or less, the end point of washing was determined.

About the TEMPO oxidation pulp obtained by this, the amount of carboxyl groups measured with the measuring method mentioned later was 1.30 mmol / g.
Moreover, when the obtained TEMPO oxidized pulp was tested and analyzed with an X-ray diffractometer, it was found at two positions of 2θ = 14 ° to 17 ° and 2θ = 22 ° to 23 °. A typical peak was confirmed and confirmed to have cellulose type I crystals.

(Defibration processing)
Ion exchange water was added to the resulting phosphorylated pulp to prepare a slurry having a solid content concentration of 2% by mass. This slurry was treated 6 times at a pressure of 200 MPa with a wet atomizer (Sugino Machine, Starburst) to obtain a fine fibrous cellulose dispersion (2) containing fine fibrous cellulose. X-ray diffraction confirmed that the fine fibrous cellulose maintained the cellulose I-type crystals. Moreover, it was 3-5 nm when the fiber width of the fine fibrous cellulose was measured using the transmission electron microscope.
It was 11000 [mPa * s] when the 0.4 mass% viscosity of the said fine fibrous cellulose was measured.

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

<Production of fine fibrous cellulose dispersion A>
The fine fibrous cellulose dispersion liquid is the same as the fine fibrous cellulose dispersion liquid (2) except that the number of treatments at a pressure of 200 MPa using a wet atomizer (Sugino Machine, Starburst) is three. A was obtained.
In addition, it was 20400 [mPa * s] when the 0.4 mass% viscosity of the said fine fibrous cellulose was measured.

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

<Measurement of phosphate group amount>
The amount of phosphoric acid group of fine fibrous cellulose is a fibrous form prepared by diluting a fine fibrous cellulose dispersion containing fine fibrous cellulose of interest with ion exchange water so that the content becomes 0.2% by mass. It measured by performing the titration using an alkali, after processing a cellulose containing slurry with an ion exchange resin.
In the treatment with the ion exchange resin, 1/10 by volume of the strongly acidic ion exchange resin (Amberjet 1024; Organo Corporation, conditioned) is added to the fibrous cellulose-containing slurry, and the mixture is shaken for 1 hour. The mixture was poured onto a mesh having an opening of 90 μm to separate the resin and the slurry.
In addition, titration using an alkali is performed by adding 50 μL of a 0.1 N aqueous sodium hydroxide solution to a fibrous cellulose-containing slurry after treatment with an ion exchange resin once every 30 seconds. This was done by measuring the change in the value of. The phosphate group amount (mmol / g) is obtained by dividing the alkali amount (mmol) required in the region corresponding to the first region shown in FIG. 1 by the solid content (g) in the slurry to be titrated. Calculated.

<Measurement of carboxyl group content>
The amount of carboxyl groups of the fine fibrous cellulose is fibrous cellulose prepared by diluting the fine fibrous cellulose dispersion containing the fine fibrous cellulose of interest with ion exchange water so that the content becomes 0.2% by mass. It measured by performing the titration using an alkali, after processing with an ion exchange resin with respect to the containing slurry.
In the treatment with the ion exchange resin, 1/10 by volume of the strongly acidic ion exchange resin (Amberjet 1024; Organo Corporation, conditioned) is added to the fibrous cellulose-containing slurry, and the mixture is shaken for 1 hour. The mixture was poured onto a mesh having an opening of 90 μm to separate the resin and the slurry.
In addition, titration with an alkali was performed by adding 50 μL of a 0.1 N aqueous sodium hydroxide solution to a fibrous cellulose-containing slurry after treatment with an ion exchange resin once every 30 seconds. This was done by measuring the change in value. The carboxyl group amount (mmol / g) is obtained by dividing the alkali amount (mmol) required in the region corresponding to the first region shown in FIG. 2 by the solid content (g) in the slurry to be titrated. 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. Subsequently, the viscosity of the obtained dispersion was measured using a B-type viscometer (manufactured by BLOOKFIELD, analog viscometer T-LVT). The measurement conditions were a rotational speed of 3 rpm, and the viscosity value 3 minutes after the start of measurement was taken as the viscosity of the dispersion. Moreover, the dispersion liquid to be measured was left overnight in an environment of 23 ° C. and 50% relative humidity before measurement. The measurement temperature of the viscosity was 23 ° C. Other detailed measurement conditions and the like were based on JISZ8803: 2011. Five samples were prepared for each level, a total of 10 measurements were made twice, and the arithmetic average value was adopted.

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

<Example 1>
(Adjustment of fibrous cellulose-containing composition)
Ion-exchanged water was added to a pigment dispersant DISPERBYK-187 (manufactured by BYK-Chemie Corporation, alkylol ammonium salt / acid value: 35 mgKOH / g, amine value: 35 mgKOH / g) to obtain an aqueous solution having a solid content concentration of 2% by mass.
100 g of a fine fibrous cellulose dispersion (1) having a solid 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.W. K. Stirring with a homodisper (made by Koki Kogyo Co., Ltd.) at 1500 rpm. After adding DISPERBYK-187, stirring was further performed for 5 minutes, followed by a defoaming device (Sinky Corp., rotation / revolution mixer AR-250). Defoaming treatment was performed.
Thereby, the solid content concentration of the fine fibrous cellulose is 0.4 mass%, the solid content concentration of DISPERBYK-187 is 0.016, and the fibrous shape is fine fibrous cellulose to DISPERBYK-187 = 100 to 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 was measured using a B-type viscometer (manufactured by BLOOKFIELD, analog viscometer T-LVT) after being left overnight in an environment of 23 ° C. and 50% relative humidity. did. The measurement conditions were a rotational speed of 3 rpm, and the viscosity value 3 minutes after the start of measurement was taken as the viscosity of the dispersion. The measurement temperature of the viscosity was 23 ° C. Other detailed measurement conditions and the like were based on JISZ8803: 2011. Five samples were prepared for each level, a total of 10 measurements were made twice, and the arithmetic average value was adopted.

(Preparation of paint)
24.8 g of the obtained fibrous cellulose-containing composition was weighed into a beaker, 34.6 g of ion-exchanged water, 35.1 g of an acrylic resin (DIC, product name: Burnock WD-551, solid content concentration 44.1%), Curing agents (manufactured by DIC, product name: Bernock DNW-5500, polyisocyanate, solid concentration 79.8%) were added in the order of 5.5 g. The addition is T.W. K. Stirring at 1500 rpm with a homodisper (manufactured by Koki Kogyo Co., Ltd.), stirring for 5 minutes after all addition, then defoaming with a defoaming device (Sinky Corp., rotation / revolution mixer AR-250) Processing was performed.
Thus, it is solid content ratio acrylic resin: 78, hardening | curing agent 22, fine fibrous cellulose: 0.5, DISPERBYK-187: 0.2 (mass ratio), and the density | concentration of total solid content is 20 mass%. An evaluation paint was obtained.

<Example 2>
Instead of DISPERBYK-187, the same procedure as in Example 1 was used except that a 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. Thus, a paint for evaluation was obtained.

<Example 3>
In the same manner as in Example 1 except that a 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 paint for evaluation was obtained in the same manner as in Example 1 except that a 2% by 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 paint for evaluation was obtained in the same manner as in Example 1 except that the fine fibrous cellulose dispersion (2) was used.

<Example 6>
A paint for evaluation was obtained in the same manner as in Example 1 except that the fine fibrous cellulose dispersion (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 is 100: 20 (mass ratio), and the amount taken in the preparation of the coating is 24.9 g of the fibrous cellulose-containing composition, ion-exchanged water. A paint for evaluation was obtained in the same manner as in Example 1 except that 34.5 g and 35.2 g of the 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 is 100 to 160 (mass ratio), and the amount taken up in coating preparation is 24.7 g of water dispersion, 35 g of ion-exchanged water, acrylic A paint 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 carried out in the same manner as in Example 7 except that a 2% by mass aqueous solution of a 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. A paint was obtained. (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 paint 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 instead 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 fine fibrous cellulose dispersion (1) having a solid content concentration of 0.4% by mass was placed in a beaker, and 34.4 g of ion-exchanged water, 35.2 g of acrylic resin, and 5.49 g of curing agent were added in this order. The addition is T.W. K. Stirring is performed at 1,500 rpm with a homodisper (manufactured by Tokushu Kika Kogyo Co., Ltd.). After all addition, stirring is further performed for 5 minutes, followed by degassing with a defoaming device (Sinky Corp., rotation / revolution mixer AR-250). Foam treatment was performed.
Thus, the coating material for evaluation of the solid content ratio acrylic resin 78, the hardening | curing agent 22, and the fine fibrous cellulose 0.5 (mass ratio) was obtained.

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

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

  The physical properties of each paint 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 is excellent in coating properties when used as a paint (Examples 1 to 10) and has few foreign substances on the film after coating. It can also be seen that by using the fibrous cellulose-containing composition of the present invention, the surface of the coating film can be smoothed if necessary, and the Young's modulus and strength of the coating film suitable for practical use can be realized. 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, The coating surface has become rough.

(Creation of appearance evaluation film)
Using the obtained paint, a PET (polyethylene terephthalate) film (manufactured by Toray Industries, Inc., product name: Lumirror T60, thickness 75 μm) was used as a base material, and coating was performed using an applicator so that the coating thickness after drying was 30 μm. Immediately after coating, the coating was heated for 30 minutes with a drier at a temperature of 80 ° C. to obtain a cured coating film coated with a PET film. In addition, the thickness of the coating film was measured with a stylus type thickness meter (manufactured by Marl, Millitron 1202D), and an arithmetic average value of 20 points was adopted. Details of other measurement conditions, calculation methods, and the like were performed in accordance with JISP 8118: 2014.

(Surface roughness)
Using an optical interference type non-contact surface shape measuring instrument (manufactured by Ryoka System Co., Ltd., non-contact surface / layer cross-sectional shape measurement system VertScan 2.0, model: R5500 GML), a measuring range of 470.92 μm × 353.16 μm with a × 10 objective lens The arithmetic average roughness (Ra) was measured. The measurement was performed 5 times per level, and the arithmetic average roughness was determined from the average value. Details such as the definition of arithmetic average roughness (Ra), measurement conditions, and calculation method were performed in accordance with JIS B0601: 2013.

(Evaluation of coatability)
It 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 The arithmetic average value (N / 20) was obtained from the average value. 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 distinguished as follows.
There are 3 particles / mm ² or more with a size of 5 μm or more: ×
With or without 3 / mm ² grains with a size of 5 μm or more: ○
In addition, the size of the particles was set to the equivalent circle diameter, and the details of the measurement conditions, the calculation method, and the like were performed according to JISZ8827-1: 2008.

(Create coating film for strength and Young's modulus evaluation)
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 Industries, Inc., product name: Trephan 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 strength and Young's modulus evaluation.

(Young's modulus of the coating film)
The Young's modulus was calculated using a tensile tester Tensilon (manufactured by A & D) 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. When measuring the Young's modulus, a specimen conditioned at 23 ° C. and a relative humidity of 50% for 24 hours was used as a test piece. The measurement was performed 5 times per level, and the average value was adopted.

(Strength of coating)
The strength (tensile strength) of the coating film prepared using the fibrous cellulose-containing composition of Reference Example was defined as the base strength. The testing machine, test conditions, and compliance standards at this time were the same as those for measuring the Young's modulus. Each test piece of the example and the comparative example was tested in the same manner, and “◯” was given when the strength (tensile strength) increased by 20% or more from the base strength. 10% or more and less than 20% was designated as “Δ”, and less than 10% was designated as “x”. The measurement was performed 5 times per level, and the average value was adopted.

Claims (14)

  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 acid value of the pigment dispersant is 5 mgKOH / g or more and 200 mgKOH / g or less Or a fibrous cellulose-containing composition wherein the amine value of the pigment dispersant is 5 mgKOH / g or more and 200 mgKOH / g or less.   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 pigment dispersant has a weight average molecular weight of 1,000 or more and 100,000 or less. The fibrous cellulose-containing composition according to any one of claims 1 to 3, wherein 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 coated on a smooth polyethylene terephthalate plate so as to have a thickness of 30 μm using an applicator, and dried at 80 ° C. for 30 minutes immediately after coating.   The total amount of the said fibrous cellulose, the said pigment dispersant, and water is 90 mass% or more with respect to the whole composition, The fibrous cellulose containing composition of any one of Claims 1-4.   The fibrous cellulose-containing composition according to any one of claims 1 to 5, wherein a content of the pigment dispersant is 10 parts by mass or more with respect to 100 parts by mass of the fibrous cellulose.   The fiber according to any one of claims 1 to 6, wherein the fiber has a viscosity of 40,000 mPa · s or less measured at 23 ° C and a rotation speed of 3 rpm with a solid content concentration of 0.4% by mass. -Like cellulose-containing composition. The fibrous cellulose content according to any one of claims 1 to 7, wherein fibrous cellulose is used as a dispersion, and the supernatant yield when the supernatant separated under the following conditions is collected is 80% by mass or more. Composition.
(conditions)
The dispersion of fibrous cellulose is adjusted to a solid content concentration of 0.2% by mass, and centrifuged at 12000 G for 10 minutes using a cooling high-speed centrifuge. The obtained supernatant was collected, and the solid content concentration of the supernatant was measured. Based on the following formula, the yield of fibrous cellulose is determined.
Supernatant yield (%) = Supernatant solids concentration (%) / 0.2 × 100 The fibrous cellulose-containing composition according to any one of claims 1 to 8, wherein the Young's modulus of the coating film obtained under the following conditions is 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 liquid is coated on a smooth polypropylene plate so as to have a thickness of 30 μm using an applicator, and dried at 80 ° C. for 30 minutes immediately after coating. The fibrous cellulose-containing composition according to any one of claims 1 to 9, further comprising an enzyme.   The fibrous cellulose containing composition of any one of Claims 1-10 for using in a coating material.   The fibrous cellulose-containing composition according to any one of claims 1 to 10, for use in a thickener.   The coating material containing the fibrous cellulose containing composition of any one of Claims 1-12.   A kit for fibrous cellulose-containing composition comprising a combination of fibrous cellulose having a fiber width of 1000 nm or less and a pigment dispersant having an ionic group.

Images