JP6696600B1 - Fibrous cellulose-containing composition and paint - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a fibrous cellulose-containing composition and coating material having improved coatability. SOLUTION: (a) A fibrous cellulose having a fiber width of 1000 nm or less and having a phosphite group or a substituent derived from a phosphite group, and (b) a molecular weight having a functional group capable of forming a hydrogen bond. A fibrous cellulose-containing composition comprising 200 or less water-soluble compound or saccharide. [Selection diagram] None

Description

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

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

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

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

JP, 2016-69618, A

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

As a result of intensive studies to solve the above problems, the present inventors have found that by adding a water-soluble compound or a saccharide having a specific functional group, the coatability of the fibrous cellulose-containing composition can be improved. I found it. The present invention has been completed based on these findings.
The present invention has the following configurations.

[1] (a) Fiber width is 1000 nm or less and fibrous cellulose having a phosphorous acid group or a substituent derived from a phosphorous acid group, and (b) a molecular weight of 200 having a functional group capable of forming a hydrogen bond. A fibrous cellulose-containing composition comprising the following water-soluble compound or sugar.
[2] The content of a water-soluble compound having a functional group capable of forming a hydrogen bond and having a molecular weight of 200 or less, or a saccharide content is 1 part by mass or more based on 100 parts by mass of fibrous cellulose, [1] Fibrous cellulose-containing composition.
[3] The fibrous cellulose-containing composition according to [1] or [2], wherein the functional group is a carbonyl group or an amino group.
[4] The fibrous cellulose-containing composition according to any one of [1] to [3], wherein the water-soluble compound is a urea derivative.
[5] The fibrous cellulose-containing composition according to [1] or [2], wherein the saccharide is a trehalose derivative.
[6] The fibrous cellulose-containing composition according to any one of [1] to [5], 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 solution is coated on a smooth polyethylene terephthalate plate using an applicator so as to have a thickness of 30 μm, and immediately after coating, it is dried at 80 ° C. for 30 minutes.
[7] The fibrous material according to any one of [1] to [6], wherein the total amount of the fibrous cellulose, the saccharide or the water-soluble compound, and water is 90% by mass or more based on the entire composition. Cellulose-containing composition.
[8] The fibrous cellulose-containing composition according to any one of [1] to [7], wherein the content of the saccharide or the water-soluble compound is 10 parts by mass or more based on 100 parts by mass of fibrous cellulose.
[9] Any one of [1] to [8], which has a viscosity of 40,000 mPa · s or less measured at 23 ° C. and a rotation speed of 3 rpm with the solid content concentration of the fibrous cellulose being 0.4% by mass. The fibrous cellulose-containing composition according to.
[10] The fibrous cellulose is used as a dispersion liquid, and the supernatant yield when the supernatant liquid separated from the dispersion liquid under the following conditions is collected is 80% by mass or more. [1] to [9] Fibrous cellulose-containing composition.
(conditions)
The dispersion liquid of fibrous cellulose is adjusted to a solid content concentration of 0.2% by mass, and centrifuged using a cooling high-speed centrifuge under the conditions of 12000 G and 10 minutes. The obtained supernatant was collected and the solid content concentration of the supernatant was measured. The yield of fibrous cellulose is calculated based on the following formula.
Supernatant yield (%) = supernatant solid content concentration (%) / 0.2 × 100
[11] The fibrous cellulose-containing composition according to any one of [1] to [10], wherein the coating film obtained under the following conditions has a Young's modulus of 0.7 GPa or more.
(conditions)
Application obtained by mixing the fibrous cellulose-containing composition, 156 parts by mass of an acrylic resin with respect to 1 part by mass of the fibrous cellulose, and 44 parts by mass of polyisocyanate with respect to 1 part by mass of the fibrous cellulose. The solution is coated on a smooth polypropylene plate with an applicator so as to have a thickness of 30 μm, and immediately after coating, it is dried at 80 ° C. for 30 minutes.
[12] The fibrous cellulose-containing composition according to any one of [1] to [11], which further contains an enzyme.
[13] The fibrous cellulose-containing composition according to any one of [1] to [12], which is used in a paint.
[14] The fibrous cellulose-containing composition according to any one of [1] to [12] for use in a thickener.
[15] A coating material containing the fibrous cellulose-containing composition according to any one of [1] to [14].
[16] A fibrous cellulose having a fiber width of 1000 nm or less and having a phosphite group or a substituent derived from a phosphite group, and a water-soluble compound having a functional group capable of forming a hydrogen bond and having a molecular weight of 200 or less, Alternatively, a kit for a composition containing fibrous cellulose, which is combined with a saccharide.

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

FIG. 1 is a graph showing the relationship between the dropping amount of NaOH and the pH of a slurry containing fibrous cellulose having a phosphorous acid group. FIG. 2 is a graph showing the relationship between the amount of NaOH dropped and the pH for a fibrous cellulose-containing slurry having a carboxy group.

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

  The fibrous cellulose-containing composition of the present invention has a fiber width of 1000 nm or less and a fibrous cellulose having a phosphorous acid group or a substituent derived from a phosphorous acid group (may be referred to as “fine fibrous cellulose”). And a water-soluble compound having a functional group capable of forming a hydrogen bond and having a molecular weight of 200 or less, or a saccharide (these may be referred to as a “specific component”).

(Fibrous cellulose)
The fibrous cellulose-containing composition of the present invention contains fine fibrous cellulose. The fine fibrous cellulose is a fiber having a phosphite group or a substituent derived from the phosphite group (sometimes referred to simply as a phosphite group).

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

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

  The measurement of the fiber width of the fine fibrous cellulose by observation with an electron microscope is performed as follows. An aqueous suspension of fine fibrous cellulose having a concentration of 0.05% by mass or more and 0.1% by mass or less was prepared, and this suspension was cast on a hydrophilized carbon film-covered grid to obtain 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 so as to satisfy the following conditions.

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

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

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

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

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

  The fine fibrous cellulose has a phosphite group or a substituent derived from the phosphite group. The substituent derived from the phosphorous acid group may be a salt of the phosphorous acid group.

In the present invention, the phosphorous acid group or the substituent derived from the phosphorous acid group is, for example, a substituent represented by the following formula (2).

  In the formula (2), b is a natural number, m is an arbitrary number, and b × m = 1. α is a hydrogen atom, a saturated-linear hydrocarbon group, a saturated-branched hydrocarbon group, a saturated-cyclic hydrocarbon group, an unsaturated-linear hydrocarbon group, an unsaturated-branched hydrocarbon group , Unsaturated-cyclic hydrocarbon groups, aromatic groups, or derivatives thereof. Of these, α is particularly preferably a hydrogen atom. Note that α in the formula (2) does not include a group derived from a cellulose molecular chain.

  Examples of the saturated-linear hydrocarbon group represented by α in formula (2) include a methyl group, an ethyl group, an n-propyl group, and an n-butyl group, but are not particularly limited. Examples of the saturated-branched hydrocarbon group include i-propyl group and t-butyl group, but are not particularly limited. Examples of the saturated-cyclic hydrocarbon group include a cyclopentyl group and a cyclohexyl group, but are not particularly limited. Examples of the unsaturated-straight chain hydrocarbon group include a vinyl group and an allyl group, but are not particularly limited. Examples of the unsaturated-branched hydrocarbon group include i-propenyl group and 3-butenyl group, but are not particularly limited. Examples of the unsaturated-cyclic hydrocarbon group include a cyclopentenyl group and a cyclohexenyl group, but are not particularly limited. Examples of the aromatic group include a phenyl group and a naphthyl group, but are not particularly limited.

  Further, the derivative group in α is a functional group in which at least one of functional groups such as a carboxy group, a hydroxy group, or an amino group is added to or substituted with respect to the main chain or side chain of each of the above hydrocarbon groups. Examples thereof include groups, but are not particularly limited. The number of carbon atoms constituting the main chain of R is not particularly limited, but is preferably 20 or less, more preferably 10 or less. By adjusting the number of carbon atoms constituting the main chain of R to the above range, the molecular weight of the phosphite group can be adjusted to an appropriate range, facilitating the penetration into the fiber raw material, and increasing the yield of fine cellulose fibers. It can also be increased.

Β ^{b +} in the formula (2) is a monovalent or higher cation composed of an organic substance or an inorganic substance. Examples of monovalent or more cations composed of organic substances include aliphatic ammonium and aromatic ammonium, and examples of monovalent or more cations composed of inorganic substances include alkali metal ions such as sodium, potassium, or lithium, Examples thereof include cations of divalent metals such as calcium and magnesium, hydrogen ions and the like, but are not particularly limited. These may be applied alone or in combination of two or more. As the cation having a valence of 1 or more consisting of an organic substance or an inorganic substance, sodium or potassium ions which are less likely to yellow when the fiber raw material containing β is heated and which are industrially usable are preferable, but are not particularly limited.

  The fine fibrous cellulose may further have a phosphoric acid group or a group derived from a phosphoric acid group, in addition to the phosphorous acid group or the substituent derived from the phosphorous acid group. The group derived from a phosphoric acid group or a phosphoric acid group is, for example, a substituent represented by the following formula (1) or (3). The phosphoric acid group or the group derived from the phosphoric acid group may be a condensed phosphorous oxo acid group represented by the following formula (3).

In the formula (1), a and b are natural numbers and m is an arbitrary number (however, a = b × m). a of α and α ′ are O ⁻ , and the rest are OR. Here, R is a hydrogen atom, a saturated-linear hydrocarbon group, a saturated-branched hydrocarbon group, a saturated-cyclic hydrocarbon group, an unsaturated-linear hydrocarbon group, an unsaturated-branched hydrocarbon group. It is a hydrocarbon group, an unsaturated-cyclic hydrocarbon group, an aromatic group, or a derivative group thereof. Note that α in the formula (1) may be a group derived from a cellulose molecular chain.

In the formula (3), a and b are natural numbers, m is an arbitrary number, and n is a natural number of 2 or more (however, a = b × m). Of α ¹ , α ² , ..., α ⁿ and α ′, a is O ⁻ , and the rest is either R or OR. Here, R is a hydrogen atom, a saturated-linear hydrocarbon group, a saturated-branched hydrocarbon group, a saturated-cyclic hydrocarbon group, an unsaturated-linear hydrocarbon group, an unsaturated-branched hydrocarbon group. It is a hydrocarbon group, an unsaturated-cyclic hydrocarbon group, an aromatic group, or a derivative group thereof. In addition, α in the formula (3) may be a group derived from a cellulose molecular chain.

Specific examples of each group in formulas (1) and (3) are the same as the specific examples of each group in formula (2). Further, specific examples of β ^{b +} in formulas (1) and (3) are the same as the specific examples of β ^{b +} in formula (2).

The fact that the fine fibrous cellulose has a phosphite group as a substituent means that the infrared absorption spectrum of the dispersion liquid containing the fine fibrous cellulose is measured, and it is a tautomer of the phosphite group at around 1210 cm ^-1. This can be confirmed by observing the absorption based on P = O of a phosphonic acid group. In addition, the fact that the fibrous cellulose has a phosphate group as a substituent means that the dispersion containing the fibrous cellulose was subjected to infrared absorption spectrum measurement, and the absorption based on P = O of the phosphate group at 1230 cm ^-1 was measured. It can be confirmed by observing. The fact that the fibrous cellulose has a phosphite group or a phosphate group as a substituent can also be confirmed by a method of confirming a chemical shift using NMR, a method of combining titration with elemental analysis, or the like.

<Introduction of phosphite group>
The introduction of the phosphite group is carried out by introducing at least one kind selected from a compound having a phosphite group and a salt thereof into the fiber raw material containing cellulose (hereinafter, referred to as “phosphite oxidation reagent” or “compound A”). It can be carried out by reacting. Such a phosphorylation reagent may be mixed with a fiber raw material in a dry state or a wet state in a powder or aqueous solution state. As another example, a powder or an aqueous solution of a phosphorous oxidant may be added to the slurry of the fiber raw material.

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

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

  The compound A used in this embodiment is at least one selected from compounds having a phosphorous acid group and salts thereof. Examples of the compound having a phosphorous acid group include phosphorous acid, and examples of the phosphorous acid include 99% phosphorous acid (phosphonic acid). Examples of the salt of the compound having a phosphorous acid group include lithium salt, sodium salt, potassium salt, and ammonium salt of phosphorous acid, and these can have various degrees of neutralization. Among these, from the viewpoint of high efficiency of introduction of phosphorus oxo acid group, easier improvement of defibration efficiency in the defibration step described later, low cost, and easy industrial application, phosphorous acid, phosphorus A sodium salt of an acid, a potassium salt of phosphorous acid, or an ammonium salt of phosphorous acid is preferably used.

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

  The addition amount of the compound A to the fiber raw material is not particularly limited, but when the addition amount of the compound A is converted into the phosphorus atom amount, the addition amount of the phosphorus atom to the fiber raw material (absolute dry mass) is 0.5% by mass or more and 100% by mass. The following is preferable, 1 mass% or more and 50 mass% or less is more preferable, and 2 mass% or more and 30 mass% or less is most preferable. When the amount of phosphorus atoms added to the fiber raw material is within the above range, the yield of fine fibrous cellulose can be further improved. Further, by setting the amount of phosphorus atoms added to the fiber raw material to 100% by mass or less, the cost of the compound A to be used can be suppressed while improving the phosphorous oxidation efficiency.

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

  Like the compound A, the compound B is preferably used as an aqueous solution. Further, it is preferable to use an aqueous solution in which both the compound A and the compound B are dissolved because the uniformity of the reaction is enhanced. The addition amount of the compound B to the fiber raw material (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. It is more preferable that the amount is 150% by mass or more and 300% by mass or less.

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

  A heat treatment is preferably applied to introduce the phosphite group. As the heat treatment temperature, it is preferable to select a temperature at which the phosphorous acid group can be efficiently introduced while suppressing thermal decomposition or hydrolysis reaction of the fiber. Specifically, it is preferably 50 ° C. or higher and 300 ° C. or lower, more preferably 100 ° C. or higher and 250 ° C. or lower, and further preferably 130 ° C. or higher and 200 ° C. or lower. Further, for the heat treatment, equipment having various heat mediums can be used, and for example, a stirring dryer, a rotary dryer, a disk dryer, a roll type heater, a plate type heater, a fluidized bed dryer, an air stream. A drying device, a reduced pressure drying device, an infrared heating device, a far infrared heating device, a microwave heating device, and a high frequency drying device can be used.

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

  The heating device used for the heat treatment is preferably a device that can always discharge the water held by the slurry and the water generated by the addition reaction of the fibers such as phosphite groups to the hydroxyl groups of the slurry, to the outside of the apparatus system, for example, a blowing method. An oven or the like is preferable. If water in the device system is constantly discharged, in addition to suppressing the hydrolysis reaction of the phosphoric acid ester bond, which is the reverse reaction of phosphoric acid esterification, it is also possible to suppress the acid hydrolysis of sugar chains in the fiber. It is possible to obtain fine fibers having a high axial ratio.

  Although the time of the heat treatment is influenced by the heating temperature, it is preferably 1 second or more and 300 minutes or less, more preferably 1 second or more and 1000 seconds or less after the water is substantially removed from the fiber raw material slurry. It is more preferably 10 seconds or more and 800 seconds or less. In the present invention, the introduction amount of the phosphite group can be set within a preferable range by setting the heating temperature and the heating time within appropriate ranges.

  The introduction amount of the phosphite group 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. More preferably, 0.14 mmol / g or more and 3.5 mmol / g or less, further 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 It is preferably 0.6 mmol / g or more and 2.5 mmol / g or less. By controlling the amount of the phosphite group introduced to be within the above range, it is possible to facilitate the miniaturization of the fiber raw material and enhance the stability of the fine fibrous cellulose. Further, by setting the introduction amount of the phosphite group within the above range, it is possible to leave hydrogen bonds between the fine fibrous celluloses even though it is easy to miniaturize, which is good when formed into a sheet. Strength development can be expected.

  The amount of phosphorus oxo acid group (including phosphite group) introduced into the fine fibrous cellulose can be measured, for example, by the neutralization titration method. In the measurement by the neutralization titration method, the introduced amount is measured by determining the pH change while adding an alkali such as an aqueous sodium hydroxide solution to the obtained slurry containing fine fibrous cellulose.

FIG. 1 is a graph showing the relationship between the dropping amount of NaOH and the pH of a slurry containing fibrous cellulose having a phosphorous acid group. The amount of phosphorus oxo acid group introduced into the fibrous cellulose is measured, for example, as follows.
First, a slurry containing fibrous cellulose is treated with a strongly acidic ion exchange resin. If necessary, a defibration process similar to the defibration process step described below may be performed on the measurement target before the treatment with the strongly acidic ion exchange resin.
Then, the pH change is observed while adding the aqueous sodium hydroxide solution, and a titration curve as shown in the upper part of FIG. 1 is obtained. The titration curve shown in the upper part of FIG. 1 plots the measured pH against the amount of alkali added, and the titration curve shown in the lower part of FIG. The increment (differential value) (1 / mmol) is plotted. In this neutralization titration, two points at which the increment (the differential value of pH with respect to the amount of alkali added) is maximized are confirmed in the curve plotting the pH measured against the amount of alkali added. Of these, the maximum point of the increment obtained first after adding alkali is referred to as the first end point, and the maximum point of the increment obtained next is referred to as the second end point. The amount of alkali required from the start of titration to the first end point becomes equal to the amount of the first dissociated acid of fibrous cellulose contained in the slurry used for the titration, and the alkali amount required from the first end point to the second end point. The amount of the second dissociated acid of the fibrous cellulose contained in the slurry used for the titration is equal to that of the fibrous cellulose contained in the slurry used for the titration, and the amount of alkali required from the start of the titration to the second end point is contained. Is equal to the total dissociated acid amount of. The value obtained by dividing the amount of alkali required from the start of titration to the first end point by the solid content (g) in the slurry to be titrated is the phosphorus oxo acid group introduction amount (mmol / g). In addition, when simply saying the phosphorus oxo acid group introduction amount (or phosphorus oxo acid group amount), it means the first dissociated acid amount.
In FIG. 1, the region from the start of titration to the first end point is called the first region, and the region from the first end point to the second end point is called the second region. For example, when the phosphorous acid group is a phosphoric acid group and the phosphoric acid group causes condensation, the amount of the weakly acidic group in the phosphorous acid group (also referred to as the amount of the second dissociated acid in the present specification) is apparent. As a result, the amount of alkali required for the second region decreases compared to the amount of alkali required for the first region. On the other hand, the amount of the strongly acidic group in the phosphorus oxo acid group (also referred to as the amount of the first dissociated acid in the present specification) matches the amount of the phosphorus atom regardless of the presence or absence of condensation. When the phosphorus oxo acid group is a phosphite group, the weak acidic group does not exist in the phosphorus oxo acid group, so that the alkali amount required for the second region is reduced or the alkali amount required for the second region is reduced. May be zero. In this case, there is only one point in the titration curve where the pH increment becomes maximum.

In addition, since the denominator indicates the mass of the acid-type fibrous cellulose, the above-mentioned phosphorus-oxo acid group introduction amount (mmol / g) indicates the amount of the phosphorus-oxo acid group contained in the acid-type fibrous cellulose (hereinafter, the phosphorus-oxo acid group amount). (Called acid type)). On the other hand, when the counterion of the phosphorus oxo acid group is substituted with an arbitrary cation C so as to have a charge equivalent, the denominator is converted into the mass of the fibrous cellulose when the cation C is the counterion. Thus, the amount of phosphorus oxo acid group contained in the fibrous cellulose having the cation C as a counter ion (hereinafter, amount of phosphorus oxo acid group (C type)) can be obtained.
That is, it is calculated by the following calculation formula.
Phosphorus oxo acid group amount (C type) = phosphorus oxo acid group amount (acid type) / {1+ (W-1) × A / 1000}
A [mmol / g]: Total amount of anions derived from phosphorus oxo acid group of fibrous cellulose (total amount of dissociated acid of phosphorus oxo acid group)
W: Formula weight per valence of cation C (for example, 23 for Na and 9 for Al)

  In the measurement of the amount of phosphorus oxo acid group by the titration method, an accurate value such as a lower amount of phosphorus oxo acid group than originally should be obtained when the amount of one drop of the aqueous sodium hydroxide solution is too large or the titration interval is too short. Sometimes you can't get it. As an appropriate dropping amount and titration interval, for example, it is desirable to titrate an aqueous 0.1N sodium hydroxide solution in an amount of 10 to 50 μL in 5 to 30 seconds. In order to eliminate the influence of carbon dioxide dissolved in the fibrous cellulose-containing slurry, for example, it is desirable to measure while blowing an inert gas such as nitrogen gas into the slurry from 15 minutes before the start of titration to the end of titration.

  In addition, in addition to the phosphite group, whether the phosphorous acid detected in the case of containing one or both of the phosphoric acid group and the condensed phosphoric acid group is derived from phosphorous acid, phosphoric acid, and condensed phosphoric acid As a method of distinguishing, for example, a method of performing the titration operation described above after performing a treatment of cutting the condensed structure such as acid hydrolysis, or a treatment of converting a phosphite group into a phosphate group such as an oxidation treatment. Examples include a method of performing the above-mentioned titration operation after the operation.

  The phosphite group introduction step may be performed at least once, but may be repeated multiple times. In this case, more phosphite groups are introduced, which is preferable.

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

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

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

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

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

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

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

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

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

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

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

  Hemicellulose is a polysaccharide excluding pectins between cellulose microfibrils of plant cell walls. Hemicellulose has a wide variety, and it is different in 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 secondary walls of hardwoods. Therefore, it is preferable to use mannase for obtaining fine fibers from conifers, and it is preferable to use xylanase for hardwoods.

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

The amount of enzyme added to 1 part by mass of fibrous cellulose having a fiber width of 1000 nm or less is not particularly limited, but is preferably 1 × 10 ⁻³ parts by mass or less, more preferably 1 × 10 ⁻⁴ parts by mass or less, and 1 It is more preferably not more than × 10 ^-5 parts by mass, particularly preferably not more than 5.0 × 10 ^-6 parts by mass. The amount of enzyme added is preferably 1 × 10 ⁻⁷ parts by mass or more, more preferably 3 × 10 ⁻⁷ parts by mass or more, and further preferably 1 × 10 ⁻⁶ parts by mass or more, relative to 1 part by mass of fibrous cellulose. preferable.
By setting the amount of enzyme added 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 1 minute to 24 hours, more preferably 1 minute to 1 hour.
The reaction temperature and the reaction pH of the fine fibrous cellulose and the enzyme are preferably maintained at the optimum temperature and the optimum pH of the enzyme to be used, and are generally 20 ° C to 80 ° C and pH 4.5 to 9.5. It is preferable to keep.
By setting the reaction conditions within the above range, particles (aggregates) in the coated product can be suppressed.

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

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

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

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

The fine fibrous cellulose dispersion was 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 (H-2000B, manufactured by Kokusan Co., Ltd.). The obtained supernatant was collected and the solid content concentration of the supernatant was measured. The yield of fine fibrous cellulose was calculated based on the following formula.
Yield (%) of fine fibrous cellulose = solid content concentration (%) of supernatant / 0.2 × 100

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

(Specific component)
<Sugar>
Examples of the specific component used in the present invention include sugars. The saccharides include monosaccharides and polysaccharides, of which monosaccharides or disaccharides are preferable, and disaccharides are more preferable. Preferred saccharides include those having a glucose unit or fructose unit, and those having a glucose unit are more preferred. Specific examples include trehalose, maltose, sucrose, lactulose, lactose, cellobiose, glucose, fructose, mannose, galactose, arabinose, xylose, or derivatives thereof, and among them, trehalose derivatives are preferable. When referred to as a “derivative” in the present specification, in addition to the compound, a compound in which an arbitrary substituent is introduced or a part of the compound may be eliminated or cyclized as long as the effect of the present invention is not impaired. And a compound having an acidic group or a basic group introduced therein, or a salt thereof. Examples of the optional substituent include the examples of the substituent Z described later. Examples of the derivative having a substituent introduced into trehalose include an ester (acyl compound), a sulfate ester or a salt thereof, a quaternary cation compound or a salt thereof, and the like. When the acyl group of the acylated product is represented by R ^Y CO-, examples of R ^Y include an alkyl group, a hydroxyalkyl group, an aryl group, an aralkyl group and the like which are mentioned as the substituent Z described later.
Although the reason why the saccharides have an effect in the present invention is not clear, the glucose units possessed by the cellulose and the glucose possessed by the saccharides, and the structure of the saccharide units such as fructose, interact with each other particularly through hydrogen bonds, and the fine fibrous cellulose is obtained. It is estimated to suppress the aggregation of

<Water-soluble compound>
A second example of the specific component used in the present invention is a water-soluble compound. The water-soluble compound used in the present invention is a compound having a functional group capable of forming a hydrogen bond and having a molecular weight of 200 or less. The functional group is preferably a carbonyl group or an amino group. The water-soluble compound is preferably a urea derivative. Specifically, the urea derivative is preferably a compound represented by the following formula (A) or a salt thereof.

R ^{1 to} R ⁴ each independently represent a hydrogen atom or a monovalent organic group. As the monovalent organic group, an alkyl group (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, further preferably 1 to 3 carbon atoms, may be linear or cyclic, may be linear or branched), or is alkenyl group. (C2-C12 is preferable, 2-6 is more preferable, 2-3 is more preferable. It may be linear or cyclic, and may be linear or branched.), Aryl group (C6-C22 is preferable, 6 To 18 are more preferable, 6 to 10 are more preferable, and an aralkyl group (having 7 to 23 carbon atoms is preferable, 7 to 19 is more preferable, 7 to 11 is more preferable.) The alkylene moiety may be linear or cyclic. Linear or branched), carbamoyl group (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and further preferably 1 to 3 carbon atoms), acyl group (preferably having 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms). The alkyl moiety may be linear or cyclic, may be linear or branched, and an aryloyl group (preferably having 7 to 23 carbon atoms, more preferably has 7 to 19 carbon atoms, and has 7 to 11 carbon atoms). (More preferable). Among them, R ^{1 to} R ⁴ are preferably a hydrogen atom, a methyl group, an ethyl group, a phenyl group, a benzyl group, a hydroxymethyl group, a hydroxyethyl group or a carbamoyl group, and more preferably a hydrogen atom. Two or more of R ^{1 to} R ⁴ are preferably hydrogen atoms, three or more of R ^{1 to} R ⁴ are more preferably hydrogen atoms, and all of R ^{1 to} R ⁴ are hydrogen atoms. Is particularly preferable.

The monovalent organic group may have a substituent Z described below. For example, the above alkyl group may be a hydroxyalkyl group together with a hydroxy group.
R ^{1 to} R ⁴ may combine with each other to form a ring. When forming a ring, a linking group Y described later may be interposed.

  X represents an oxygen atom or a sulfur atom, and an oxygen atom is preferable. However, a compound represented by the formula (A) by substituting an oxygen atom or a sulfur atom with a hydrogen atom or an alkyl group (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 and further preferably 1 to 3) is used. It may have an isourea structure.

  When the compound represented by the formula (A) forms a salt, the salt is not particularly limited, and examples thereof include hydrochloride, sulfate, phosphate, nitrate and the like.

  The molecular weight of the water-soluble compound is 200 or less, preferably 150 or less, more preferably 100 or less, particularly preferably 80 or less. The lower limit value is practically 40 or more. The molecular weight of the water-soluble compound can be confirmed by mass spectroscopy.

  Specific examples of the water-soluble compound include urea, thiourea, biuret, phenylurea, benzylurea, dimethylurea, diethylurea, tetramethylurea, benzoleinurea, hydantoin, and salts thereof. preferable.

  The reason why a water-soluble compound having a functional group capable of forming a hydrogen bond and having a molecular weight of 200 or less is effective is not clear, but the glucose unit of cellulose and the water-soluble compound interact with each other particularly through a hydrogen bond. It is presumed that the aggregation of fine fibrous cellulose is suppressed.

  The water-soluble compound is not particularly limited as long as it is a compound soluble in water, but it can be defined as a compound that is soluble in ion-exchanged water at 25 ° C. in an amount of 0.5% by mass or more, and is soluble in 1% by mass or more. It is preferable that 10% by mass or more is dissolved.

  As the substituent Z, an alkyl group (preferably having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, further preferably 1 to 6 carbon atoms), an aralkyl group (preferably having 7 to 21 carbon atoms, and 7 carbon atoms) To 15 are more preferable, and those having 7 to 11 carbons are more preferable, a hydroxy group, an amino group or a salt thereof (0 to 24 carbon atoms are preferable, 0 to 12 carbon atoms are more preferable, and 0 to 6 carbon atoms are further preferable). ), A thiol group, a carboxy group or a salt thereof, a carbamoyl group or a salt thereof (preferably having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, further preferably 1 to 6 carbon atoms), a sulfamoyl group or salt thereof ( 0 to 24 carbon atoms are preferable, 0 to 12 carbon atoms are more preferable, 0 to 6 carbon atoms are further preferable, and aryl groups (6 to 22 carbon atoms are preferable, 6 to 18 carbon atoms are more preferable, and 6 carbon atoms are included. 10 is more preferable), an acyl group (having 2 to 12 carbon atoms is preferable, having 2 to 6 carbon atoms is more preferable, having 2 or 3 carbon atoms is more preferable), an acyloxy group (having 2 to 12 carbon atoms is preferable, and carbon number is 2 to 6 is more preferable, 2 or 3 carbon atoms is more preferable), a heterocyclic group (2 to 8 carbon atoms is more preferable, 2 to 5 carbon atoms is further preferable), a halogen atom, a quaternary ammonium group or the same. Examples thereof include salts (preferably having 3 to 23 carbon atoms, more preferably having 3 to 19 carbon atoms, and further preferably having 3 to 11 carbon atoms).

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

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

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

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

  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 the fibrous cellulose when it is used as a paint. Is particularly preferable. Further, the content of the resin is preferably 500 parts by mass or less, more preferably 300 parts by mass or less, and particularly preferably 200 parts by mass or less, relative to 1 part by mass of the fibrous cellulose. By containing the resin so as to have the above content, the effects of the specific component can be suitably exerted, and the coatability, the smoothness of the coating film, the optimization of the elastic modulus and the strength can be realized.

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

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

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

(Fibrous cellulose-containing composition)
When the fibrous cellulose-containing composition is a coating material, the content of the fibrous cellulose is preferably 0.05% by mass or more based on the solid content in the fibrous cellulose-containing composition, and is 0. It is more preferably 1% by mass or more, and further preferably 0.3% by mass or more. Further, 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 thickener, the content of the fibrous cellulose is preferably 0.1% by mass or more based on the total amount of the fibrous cellulose-containing composition, and 1% by mass. % Or more, 5 mass% or more, 10 mass% or more, 20 mass% or more, 30 mass% or more, 40 mass% or more, 50 mass% or more, or 55 mass% or more. The content of fibrous cellulose is preferably 95% by mass or less, more preferably 90% by mass or less.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

<Papermaking process>
When producing a sheet, the step of producing the sheet may include a step of papermaking a composition containing fine fibrous cellulose and a specific component (which may be the above-mentioned paint or thickener). Examples of paper machines used in the paper making step include a fourdrinier type, a cylinder type, an inclined type and the like, and a multi-layered paper machine which is a combination thereof. In the papermaking process, known papermaking such as handmaking may be performed.

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

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

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

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

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

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

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

  The synthetic resin is preferably at least one selected from polycarbonate resin, polyethylene terephthalate resin, polyethylene naphthalate resin, polyethylene resin, polypropylene resin, polyimide resin, polystyrene resin, polyurethane resin and acrylic resin. Among them, 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 forming the resin layer include aromatic polycarbonate-based resins and aliphatic polycarbonate-based resins. These specific polycarbonate-based resins are known, and examples thereof include the polycarbonate-based resins described in JP 2010-023275A.

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

  An adhesive layer may be provided between the coating film or sheet and the resin layer, or no adhesive layer may be provided and the coating film or sheet and the resin layer may be in direct contact with each other. When an adhesive layer is provided between the coating film or sheet and the resin layer, the adhesive forming the adhesive layer may be, for example, an acrylic resin. Examples of adhesives other than acrylic resins include vinyl chloride resins, (meth) acrylic acid ester resins, styrene / acrylic acid ester copolymer resins, vinyl acetate resins, vinyl acetate / (meth) acrylic acid ester copolymers. Polymer resins, urethane resins, silicone resins, epoxy resins, ethylene / vinyl acetate copolymer resins, polyester resins, polyvinyl alcohol resins, ethylene vinyl alcohol copolymer resins and rubber emulsions such as SBR and NBR. Be 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 aid, and the surface of the resin layer may be subjected to surface treatment such as hydrophilic treatment. Good.
Examples of the adhesion aid include a compound containing at least one selected from an isocyanate group, a carbodiimide group, an epoxy group, an oxazoline group, an amino group and a silanol group, and an organic silicon compound. Among them, the adhesion aid is preferably at least one selected from a compound containing an isocyanate group (isocyanate compound) and an organic silicon compound. Examples of the organosilicon compound include a silane coupling agent condensate and a silane coupling agent.
Examples of surface treatment methods other than the hydrophilic treatment include corona treatment, plasma discharge treatment, UV irradiation treatment, electron beam irradiation treatment, and flame treatment.

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

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

  Further, as a method of forming the inorganic layer, an atomic layer deposition method (Atomic Layer Deposition, ALD) can also be adopted. The ALD method is a method of forming a thin film in atomic layer units by alternately supplying source gases of the respective elements forming the film to be formed to the surface forming the layer. Although it has a drawback that the film forming speed is slow, it has an advantage over the plasma CVD method that it can cover even a surface having a complicated shape cleanly and can form a thin film with few defects. Further, the ALD method has advantages that the film thickness can be controlled on the nano-order, and that it is relatively easy to cover a wide surface. Further, in the ALD method, it is expected that the reaction rate can be improved, the process can be performed at a low temperature, and unreacted gas can be reduced by using plasma.

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

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

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

<Production of fine fibrous cellulose dispersion (1)>
(Phosphorylation step)
As a raw material pulp, a softwood kraft pulp made by Oji Paper Co., Ltd. (solid content 93 mass%, basis weight 245 g / m ² sheet, disaggregated and measured according to JIS P 8121, Canadian Standard Freeness (CSF) is 700 ml) It was used.

  This raw material pulp was subjected to phosphorus oxo oxidation treatment as follows. First, a mixed aqueous solution of phosphorous acid (phosphonic acid) and urea is added to 100 parts by mass of the raw material pulp (absolute dry mass) to form 33 parts by mass of phosphorous acid (phosphonic acid), 120 parts by mass of urea, and 150 parts of water. The pulp was prepared so as to be part by mass to obtain a chemical solution-impregnated pulp. Next, the obtained chemical liquid-impregnated pulp was heated with a hot air dryer at 165 ° C. for 250 seconds to introduce a phosphite group into the cellulose in the pulp to obtain a phosphorous acid pulp.

  Then, the obtained phosphorous-oxidized pulp was washed. The washing treatment is performed by pouring 10 L of ion-exchanged water with respect to 100 g of phosphorous pulp (absolute dry mass), stirring the pulp dispersion liquid so that the pulp is uniformly dispersed, and then repeating the operation of filtering and dehydrating. Went by. When the electric conductivity of the filtrate became 100 μS / cm or less, the washing end point was set.

  Then, the washed phosphorous acid pulp was neutralized as follows. First, after diluting the washed phosphite pulp with 10 L of ion-exchanged water, a 1N sodium hydroxide aqueous solution is added little by little while stirring to give a phosphite pulp slurry having a pH of 12 or more and 13 or less. Obtained. Then, the phosphorous oxide pulp slurry was dehydrated to obtain a phosphorous acid pulp subjected to neutralization treatment. Next, the washing treatment was performed on the phosphorous acid pulp after the neutralization treatment.

The infrared absorption spectrum of the phosphorous-oxidized pulp thus obtained was measured using FT-IR. As a result, the absorption based on P = O of the phosphonic acid group, which is a tautomer of the phosphorous acid group, was observed near 1210 cm ^-1 , and the phosphorous acid group (phosphonic acid group) was added to the pulp. Was confirmed. Moreover, when the obtained phosphorous phosphite pulp was tested and analyzed by an X-ray diffractometer, two positions of 2θ = 14 ° or more and 17 ° or less and 2θ = 22 ° or more and 23 ° or less were determined. Was confirmed to have a typical peak, and it was confirmed to have a cellulose type I crystal. The amount of phosphite group (first amount of dissociated acid) measured by the measuring method described in <Measurement of amount of phosphite group> to be described later is 1.51 mmol / g for the obtained phosphorous phosphite pulp. It was The total amount of dissociated acid was 1.54 mmol / g.

(Disentanglement processing)
Ion-exchanged water was added to the obtained phosphorous oxide pulp to prepare a slurry having a solid content concentration of 2% by mass. This slurry was treated with a wet atomization device (Starburst manufactured by Sugino Machine Ltd.) at a pressure of 200 MPa three times to obtain a fine fibrous cellulose dispersion liquid (1) containing fine fibrous cellulose. It was confirmed by X-ray diffraction that the fine fibrous cellulose maintained the cellulose type I crystal. Further, the fiber width of the fine fibrous cellulose was measured by a transmission electron microscope according to the following measuring method, and it was 3 to 5 nm.
The 0.4% by mass viscosity of the fine fibrous cellulose was measured and found to be 22,400 [mPa · s].

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

<Production of fine fibrous cellulose dispersion (2)>
To the fine fibrous cellulose dispersion liquid (1), 3.0 × 10 ^{− of} an enzyme-containing liquid (manufactured by AB Enzymes, ECOPULP R, enzyme content is about 5% by mass) per 1 part by mass of the fine fibrous cellulose. ⁶ parts by mass was added, and the mixture was stirred at 18,500 rpm for 2 minutes. This was recovered to obtain a fine fibrous cellulose dispersion liquid (2). The fine fibrous cellulose dispersion liquid (2) contains an enzyme.
The 0.4% by mass viscosity of the fine fibrous cellulose was measured and found to be 9,200 [mPa · s].

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

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

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

Regarding the TEMPO oxidized pulp thus obtained, the amount of carboxy groups measured by the measuring method described later was 1.30 mmol / g.
Further, the obtained TEMPO oxidized pulp was tested and analyzed by an X-ray diffractometer. At 2 positions of 2θ = 14 ° or more and 17 ° or less and 2θ = 22 ° or more and 23 ° or less. A typical peak was confirmed and it was confirmed to have a cellulose type I crystal.

(Disentanglement processing)
Ion-exchanged water was added to the obtained phosphorylated pulp to prepare a slurry having a solid content concentration of 2% by mass. This slurry was treated with a wet atomizer (Starburst manufactured by Sugino Machine Ltd.) three times at a pressure of 200 MPa to obtain a fine fibrous cellulose dispersion liquid (A) containing fine fibrous cellulose. It was confirmed by X-ray diffraction that the fine fibrous cellulose maintained the cellulose type I crystal. The fiber width of the fine fibrous cellulose was measured with a transmission electron microscope and found to be 3 to 5 nm.
The 0.4% by mass viscosity of the fine fibrous cellulose was measured and found to be 20400 [mPa · s].

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

<Measurement of phosphorous acid group amount>
The phosphite group content of the fine fibrous cellulose is a fiber prepared by diluting a fine fibrous cellulose dispersion liquid containing the target fine fibrous cellulose with ion-exchanged water to a content of 0.2% by mass. The granular cellulose-containing slurry was treated with an ion exchange resin, and then titrated with an alkali for measurement.
The treatment with the ion-exchange resin was performed by adding 1/10 by volume of a strongly acidic ion-exchange resin (Amber Jet 1024; Organo Co., Ltd., already conditioned) to the fibrous cellulose-containing slurry, and performing a shaking treatment for 1 hour. , And the resin and the slurry were separated by pouring onto a mesh having an opening of 90 μm.
In addition, titration using an alkali measures the change in the pH value of the slurry while adding 10 μL of 0.1 N sodium hydroxide aqueous solution to the slurry containing fibrous cellulose after the treatment with the ion exchange resin every 5 seconds. It was done by doing. The titration was performed 15 minutes before the start of titration while blowing nitrogen gas into the slurry. In this neutralization titration, two points at which the increment (the differential value of pH with respect to the amount of alkali added) is maximized are observed in the curve plotting the pH measured with respect to the amount of alkali added. Of these, the maximum point of the increment obtained first after adding alkali is called the first end point, and the maximum point of the increment obtained next is called the second end point (FIG. 1). The amount of alkali required from the start of titration to the first end point becomes equal to the amount of first dissociated acid in the slurry used for titration. Also, the amount of alkali required from the start of titration to the second end point becomes equal to the total amount of dissociated acid in the slurry used for titration. A value obtained by dividing the amount of alkali (mmol) required from the start of titration to the first end point by the solid content (g) in the slurry to be titrated was defined as the amount of phosphite group (mmol / g).

<Measurement of the amount of carboxy group>
The amount of carboxy groups in the fine fibrous cellulose was determined by adding ion-exchanged water to the fine fibrous cellulose-containing slurry containing the target fine fibrous cellulose to bring the content to 0.2% by mass, and treating with an ion-exchange resin. After that, it was measured by performing titration with alkali.
The treatment with the ion-exchange resin is performed by adding 1/10 by volume of a strongly acidic ion-exchange resin (Amber Jet 1024; manufactured by Organo Co., already conditioned) to a slurry containing 0.2% by mass of fine fibrous cellulose for 1 hour. After the shaking treatment, it was poured onto a mesh having an opening of 90 μm to separate the resin and the slurry.
In addition, titration using an alkali measures the change in the pH value of the slurry while adding 10 μL of 0.1 N sodium hydroxide aqueous solution to the slurry containing fibrous cellulose after the treatment with the ion exchange resin every 5 seconds. It was done by doing. When the change in pH is observed while adding the aqueous sodium hydroxide solution, a titration curve as shown in FIG. 2 is obtained. As shown in FIG. 2, in this neutralization titration, there is one point where the increment (differential value of pH with respect to the amount of alkali added) becomes maximum in the curve in which the pH measured against the amount of added alkali is plotted. To be observed. The maximum point of this increment is called the first end point. Here, the region from the start of titration to the first end point in FIG. 2 is called the first region. The amount of alkali required in the first region becomes equal to the amount of carboxy groups in the slurry used for titration. Then, by dividing the alkali amount (mmol) required in the first region of the titration curve by the solid content (g) in the fine fibrous cellulose-containing slurry to be titrated, the introduction amount of the carboxy group (mmol / g) ) Was calculated.
The amount of introduced carboxy groups (mmol / g) is the amount of substituents per 1 g of the mass of fibrous cellulose when the counter ion of the carboxy group is a hydrogen ion (H ⁺ ) (hereinafter, the amount of carboxy groups (acid. Type))).

<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 at 1500 rpm for 5 minutes with a disperser. Then, the viscosity of the dispersion liquid thus obtained was measured using a B-type viscometer (manufactured by BLOOKFIELD, analog viscometer T-LVT). The measurement conditions were a rotation speed of 3 rpm, and the viscosity value 3 minutes after the start of measurement was taken as the viscosity of the dispersion liquid. In addition, the dispersion liquid to be measured was allowed to stand still overnight under an environment of 23 ° C. and a relative humidity of 50% before the measurement. The viscosity measurement temperature was 23 ° C. Other detailed measurement conditions and the like are based on JISZ8803: 2011. Five samples were prepared for each level, each measurement was performed twice, a total of 10 times, and the arithmetic mean value was adopted.

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

<Example 1>
(Preparation of composition containing fibrous cellulose)
Ion-exchanged water was added to trehalose (manufactured by Wako Pure Chemical Industries, Ltd.) to obtain an aqueous solution having a solid content concentration of 2 mass%.
100 g of a fine fibrous cellulose dispersion liquid (1) having a solid content concentration of 2% by mass was placed in a beaker, and 360 g of ion-exchanged water and 40 g of a 2% by mass aqueous trehalose solution were added thereto. The addition is T. K. It is stirred with a homodisper (manufactured by Tokushu Kika Kogyo Co., Ltd.) at 1500 rpm, stirred for 5 minutes after the addition of trehalose, and then defoamed with a defoaming device (Synky, rotation / revolution mixer AR-250). Processed.
Thereby, the fibrous cellulose-containing composition in which the solid content concentration of the fine fibrous cellulose is 0.4% by mass, the solid content concentration of trehalose is 0.16%, and the fine fibrous cellulose to trehalose is 100: 40 (mass ratio). Got

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

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

<Example 2>
A coating material for evaluation was obtained in the same manner as in Example 1 except that a 2 mass% aqueous solution of urea (manufactured by Wako Pure Chemical Industries, Ltd.) was used instead of trehalose.

<Example 3>
A coating material for evaluation was obtained in the same manner as in Example 1 except that the fine fibrous cellulose dispersion liquid (2) was used. The fibrous cellulose-containing composition of Example 4 contains an enzyme.

<Example 4>
The solid content ratio of fine fibrous cellulose to trehalose in the fibrous cellulose-containing composition was 100: 20 (mass ratio), and the amount of the paint prepared was 24.9 g of the fibrous cellulose-containing composition and 34. A coating material for evaluation was obtained in the same manner as in Example 1 except that 5 g and the acrylic resin were 35.2 g.
(The solid content ratio of the obtained coating material for evaluation is acrylic resin: 78, curing agent: 22, fine fibrous cellulose: 0.5, trehalose: 0.1 (mass ratio).)

<Example 5>
The solid content ratio of fine fibrous cellulose to trehalose in the fibrous cellulose-containing composition was 100 to 160 (mass ratio), and the amount taken in the paint preparation was 24.7 g of the water dispersion, 35 g of ion-exchanged water, and acrylic resin. A coating material for evaluation was obtained in the same manner as in Example 1 except that 34.9 g and a curing agent were 5.4 g.
(The solid content ratio of the obtained coating amount for evaluation is acrylic resin: 78, curing agent: 22, fine fibrous cellulose: 0.5, trehalose: 0.8 (mass ratio).)

<Example 6>
A coating material for evaluation was obtained in the same manner as in Example 4 except that a 2% by mass aqueous solution of urea (manufactured by Wako Pure Chemical Industries, Ltd.) was used instead of trehalose.
((The solid content ratio of the obtained coating composition for evaluation is acrylic resin: 78, curing agent: 22, fine fibrous cellulose: 0.5, urea: 0.1 (mass ratio).)

<Example 7>
A coating material for evaluation was obtained in the same manner as in Example 5 except that a 2 mass% aqueous solution of urea (manufactured by Wako Pure Chemical Industries, Ltd.) was used instead of trehalose.
(The solid content ratio of the obtained coating amount for evaluation is acrylic resin: 78, curing agent: 22, fine fibrous cellulose: 0.5, urea: 0.8 (mass ratio).)

<Comparative Example 1>
24.9 g of the fine fibrous cellulose dispersion liquid (1) having a solid content concentration of 0.4% by mass was placed in a beaker, and 34.4 g of ion-exchanged water, 35.2 g of an acrylic resin, and 5.5 g of a curing agent were added in that order. The addition is T. K. Homodispers (manufactured by Tokushu Kika Kogyo Co., Ltd.) was carried out while stirring at 1500 rpm, and after all were added, stirring was further carried out for 5 minutes, followed by defoaming with a defoaming device (Shinky Co., rotation / revolution mixer AR-250). A foam treatment was performed.
In this way, an evaluation paint having a solid content ratio of acrylic resin: 78, a curing agent: 22, and a fine fibrous cellulose: 0.5 (mass ratio) was obtained.

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

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

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

  From the above results, it can be seen that the fibrous cellulose-containing composition of the present invention has excellent coatability when it is used as a paint (Examples 1 to 7), and there are few foreign matters in the film after coating. Further, it is understood that the use of the fibrous cellulose-containing composition of the present invention can make the surface of the coating film smooth, if necessary, and realize the Young's modulus and strength of the coating film which are practically suitable. On the other hand, in the fibrous cellulose-containing composition containing no specific component according to the present invention (Comparative Examples 1 and 2), the coatability was poor and the coating film surface was rough.

(Creation of coating film for appearance evaluation)
Using the obtained paint, a PET (polyethylene terephthalate) film (manufactured by Toray Industries, Inc., product name: Lumirror T60, thickness 75 μm) is used as a base material, and is applied at room temperature using an applicator so that the coating film thickness after drying is 30 μm. did. Immediately after coating, it was heated for 30 minutes in a dryer at a temperature of 80 ° C. to obtain a coated coating film having a PET film as a base material. The thickness of the coating film was measured with a stylus thickness meter (Millitron 1202D manufactured by Marl Co., Ltd.), and an arithmetic average value of 20 points was adopted. Details of other measurement conditions, calculation methods, etc. were based on JISP8118: 2014.

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

(Evaluation of coatability)
Performs observation of the coating prepared by the base PET film using an optical microscope (manufactured by Nikon Corporation), confirmed over 5μm during 1 mm ² in size of the aggregates number N (the number / mm ²⁾ at 20 sites Then, the arithmetic mean value (N / 20) was determined. The measurement was performed 5 times per level and the average value was adopted. The numerical values (pieces / mm ² ) are shown in the table, and the results were evaluated as follows.
There are 3 particles / mm ² or more with a size of 5 μm or more: ×
Presence or absence of particles with a size of 5 μm or more less than 3 / mm ² : ○
The size of the particles is equivalent to a circle, and the details of measurement conditions, calculation methods, etc. are based on JIS Z8827-1: 2008.

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

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

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

Claims (12)

A coating containing a fibrous cellulose-containing composition, a resin, and an isocyanate curing agent,
The fibrous cellulose-containing composition,
(A) a fibrous cellulose having a fiber width of 1000 nm or less and having a phosphite group or a substituent derived from a phosphite group;
(B) a water-soluble compound having a functional group capable of forming a hydrogen bond and having a molecular weight of 200 or less, or a saccharide,
Viewing including the door,
The water-soluble compound is urea, thiourea, biuret, phenylurea, benzylurea, dimethylurea, diethylurea, tetramethylurea, benzoleinurea, hydantoin or a salt thereof,
The saccharide is trehalose, maltose, sucrose, lactulose, lactose, cellobiose, glucose, fructose, mannose, galactose, arabinose, xylose or a derivative thereof .   The coating material according to claim 1, wherein the content of the water-soluble compound having a functional group capable of forming a hydrogen bond and having a molecular weight of 200 or less, or saccharide is 1 part by mass or more based on 100 parts by mass of fibrous cellulose.   The coating material according to claim 1 or 2, wherein the functional group is a carbonyl group or an amino group.   The paint according to any one of claims 1 to 3, wherein the water-soluble compound is a urea derivative.   The paint according to claim 1, wherein the saccharide is a trehalose derivative. The coating material according to claim 1, wherein when the coating film is formed under the following conditions, the surface roughness Ra of the coating film 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 solution is coated on a smooth polyethylene terephthalate plate using an applicator so as to have a thickness of 30 μm, and immediately after coating, it is dried at 80 ° C. for 30 minutes.   The total amount of the fibrous cellulose, the saccharide or the water-soluble compound, and water in the fibrous cellulose-containing composition is 90% by mass or more based on the total mass of the fibrous cellulose-containing composition. The paint according to any one of 1 to 6.   The coating material according to any one of claims 1 to 7, wherein the content of the saccharide or the water-soluble compound is 10 parts by mass or more based on 100 parts by mass of fibrous cellulose. The viscosity of the above case where the fibrous cellulose-containing composition was 0.4 wt% solids concentration by diluting with water, the fibrous cellulose-containing composition was measured under conditions of 23 ° C. and the rotational speed 3rpm 40 The coating material according to any one of claims 1 to 8, which has a viscosity of 1,000 mPa · s or less. The coating material according to any one of claims 1 to 9, wherein the fibrous cellulose is used as a dispersion liquid, and a supernatant yield when the supernatant liquid separated from the dispersion liquid under the following conditions is recovered is 80% by mass or more.
(conditions)
The dispersion liquid of fibrous cellulose is adjusted to a solid content concentration of 0.2% by mass, and centrifuged using a cooling high-speed centrifuge under the conditions of 12000 G and 10 minutes. The obtained supernatant was collected and the solid content concentration of the supernatant was measured. The yield of fibrous cellulose is calculated based on the following formula.
Supernatant yield (%) = supernatant solid content concentration (%) / 0.2 × 100 When the coating film is formed under the following conditions, the coating film has a Young's modulus of 0.7 GPa or more.
(conditions)
Application obtained by mixing the fibrous cellulose-containing composition, 156 parts by mass of an acrylic resin with respect to 1 part by mass of the fibrous cellulose, and 44 parts by mass of polyisocyanate with respect to 1 part by mass of the fibrous cellulose. The solution is coated on a smooth polypropylene plate with an applicator so as to have a thickness of 30 μm, and immediately after coating, it is dried at 80 ° C. for 30 minutes.   The paint according to any one of claims 1 to 11, further comprising an enzyme.

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