JP6540925B1 - Fibrous cellulose-containing composition and paint - Google Patents

Abstract

An object of the present invention is to provide a fibrous cellulose-containing composition and a paint having improved coatability. A fibrous cellulose-containing composition comprising 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 pigment dispersant having an ionic group. Cellulose fibrous composition, wherein the pigment dispersant has an acid value of 5 mg KOH / g to 200 mg KOH / g, or the pigment dispersant has an amine value of 5 mg KOH / g to 200 mg KOH / g object. 【Selection chart】 None

Description

  The present invention relates to fibrous cellulose-containing compositions and paints.

  BACKGROUND ART In recent years, materials using renewable natural fibers have attracted attention due to substitution of petroleum resources and heightened environmental awareness. Among natural fibers, fibrous cellulose with a fiber diameter of 10 to 50 μm, particularly fibrous cellulose (pulp) derived from wood, has been widely used mainly as a paper product.

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

  In addition, application of fibrous cellulose to a paint has been studied. Patent Document 1 describes a water-based paint composition containing cellulose fibers having a number average fiber diameter of 2 nm to 500 nm, a water-based resin, and a colorant.

JP, 2016-69618, A

  The present inventors have investigated using fine fibrous cellulose as a thickener for paints. However, it was found that when the fine fibrous cellulose is contained in the paint, there is room for improvement in the coating properties of the paint. An object of the present invention is to provide a fibrous cellulose-containing composition and a paint having improved coatability.

MEANS TO SOLVE THE PROBLEM As a result of conducting earnest examination, in order to solve the said subject, the present inventors have an ionic group, and add the pigment dispersing agent which has a predetermined acid value or an amine value, and a fibrous cellulose containing composition. Was found to be able to improve the coatability of The present invention has been completed based on these findings.
The present invention has the following configuration.

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

  According to the present invention, a fibrous cellulose-containing composition and a paint having improved coatability can be provided.

FIG. 1 is a graph showing the relationship between the amount of NaOH added and the pH with respect to a fibrous cellulose-containing slurry having a phosphorus oxo group. FIG. 2 is a graph showing the relationship between the dropping amount of NaOH and the pH for the fibrous cellulose-containing slurry having a carboxy group.

  Hereinafter, the present invention will be described in detail. The description of the configuration requirements described below may be made based on typical embodiments and 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 is a fibrous cellulose having a phosphorous acid group or a substituent derived from a phosphorous acid group (sometimes referred to as "fine fibrous cellulose") And a pigment dispersant having an ionic group (sometimes referred to as "specific component").

(Fibrous cellulose)
The fibrous cellulose-containing composition of the present invention contains fine fibrous cellulose. The fine fibrous cellulose has a phosphorous acid group or a substituent derived from the phosphorous acid group (hereinafter, also simply referred to as a phosphorous acid group).

  The fibrous cellulose raw material for obtaining the fine fibrous cellulose is not particularly limited, but it is preferable to use pulp in terms of availability and low cost. The pulp may include wood pulp, non-wood pulp and deinked pulp. As wood pulp, for example, hardwood kraft pulp (LBKP), softwood kraft pulp (NBKP), sulfite pulp (SP), dissolving pulp (DP), soda pulp (AP), unbleached kraft pulp (UKP), oxygen bleached kraft Chemical pulp, such as pulp (OKP), etc. are mentioned. In addition, semichemical pulp such as semichemical pulp (SCP), chemiground wood pulp (CGP), mechanical pulp such as ground pulp (GP), thermomechanical pulp (TMP, BCTMP), etc. may be mentioned, but it is not particularly limited. Non-wood pulps include cotton-based pulps such as cotton linters and cotton lint, non-wood-based pulps such as hemp, straw and bagasse, celluloses isolated from ascidians and seaweeds, chitin, chitosan and the like, but are not particularly limited . Examples of the deinked pulp include, but not particularly limited to, deinked pulp made from waste paper. The pulp of this embodiment may be used singly or in combination of two or more. Among the above-mentioned pulps, wood pulps containing cellulose and deinked pulps are preferable in terms of availability. Among wood pulps, chemical pulp has a large cellulose ratio, so the yield of fine fibrous cellulose is high at the time of fiber refining (fibrillation), and decomposition of cellulose in the pulp is small, and fine fibers of long fibers having a large axial ratio It is preferable at the point from which fibrous cellulose is obtained. Among them, kraft pulp and sulfite pulp are most preferably selected. A sheet containing fine fibrous cellulose of long fibers with a large axial ratio tends to obtain high strength.

  The average fiber width of the fine fibrous cellulose is 1000 nm or less as observed by an electron microscope. The average fiber width is preferably 2 nm to 1000 nm, more preferably 2 nm to less than 1000 nm, more preferably 2 nm to 100 nm, more preferably 2 nm to 50 nm, and still more preferably 2 nm to 10 nm. There is no particular limitation. If the average fiber width of the fine fibrous cellulose is less than 2 nm, it dissolves in water as cellulose molecules, so the physical properties (strength, rigidity, and dimensional stability) as the fine fibrous cellulose tend to be difficult to express . The fine fibrous cellulose is, for example, monofibrillar cellulose having a fiber width of 1000 nm or less.

  The measurement of the fiber width by electron microscopic observation of fine fibrous cellulose is performed as follows. Prepare an aqueous suspension of fine fibrous cellulose with a concentration of 0.05% by mass or more and 0.1% by mass or less, cast this suspension on a hydrophilized carbon film-coated grid, and prepare a sample for TEM observation Do. If wide fibers are 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 fiber to be constructed. However, the sample, observation conditions and magnification are adjusted to satisfy the following conditions.

(1) One straight line X is drawn at an arbitrary position in the observation image, and 20 or more fibers cross the straight line X.
(2) Draw a straight line Y intersecting perpendicularly with the straight line in the same image, and 20 or more fibers cross the straight line Y.

  With respect to the observation image satisfying the above conditions, the width of the fiber intersecting with the straight line X and the straight line Y is visually read. Thus, three or more sets of images of at least non-overlapping surface portions are observed, and for each image, the width of the fiber intersecting the straight line X and the straight line Y is read. Thus, a fiber width of at least 20 x 2 x 3 = 120 is read. The average fiber width (sometimes simply referred to as "fiber width") of fine fibrous cellulose is the average value of the fiber widths read in this manner.

The fiber length of the fine fibrous cellulose is not particularly limited, but is preferably 0.1 μm to 1000 μm, more preferably 0.1 μm to 800 μm, and particularly preferably 0.1 μm to 600 μm. 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 to make the slurry viscosity of the fine fibrous cellulose into an appropriate range. In addition, the fiber length of fine fibrous cellulose can be calculated | required from the image analysis by TEM, SEM, and 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 value or more, it is easy to form a fine fiber-containing sheet, and sufficient viscosity can be easily obtained when a solvent dispersion is prepared. By setting the axial ratio to the upper limit value or less, for example, when treating fibrous cellulose as an aqueous dispersion, it is preferable in that handling such as dilution is facilitated.

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

  The proportion of crystal form I in fine fibrous cellulose is preferably 30% or more, more preferably 40% or more, and still more preferably 50% or more. In this case, further excellent performance can be expected in terms of heat resistance and low linear thermal expansion. With regard to the degree of crystallinity, the X-ray diffraction profile is measured, and the pattern is determined by a conventional method (Seagal et al., Textile Research Journal, 29: 786, 1959).

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 Formula (2), b is a natural number, m is an arbitrary number, and b × m = 1. α represents a hydrogen atom, a saturated-linear hydrocarbon group, a saturated-branched hydrocarbon group, a saturated-cyclic hydrocarbon group, an unsaturated-linear hydrocarbon group, an unsaturated-branched hydrocarbon group And unsaturated-cyclic hydrocarbon groups, aromatic groups, or derivatives thereof. Among them, α is particularly preferably a hydrogen atom. In addition, the group derived from a cellulose molecular chain is not contained in (alpha) in Formula (2).

  Examples of the saturated-linear hydrocarbon group represented by α of the formula (2) include, but not particularly limited to, a methyl group, an ethyl group, an n-propyl group, and an n-butyl group. Examples of the saturated-branched hydrocarbon group include i-propyl group and t-butyl group, but are not particularly limited. Although a cyclopentyl group, a cyclohexyl group, etc. are mentioned as a saturated cyclic hydrocarbon group, It does not specifically limit. Examples of the unsaturated-linear hydrocarbon group include, but are not particularly limited to, a vinyl group, an allyl group and the like. Examples of unsaturated-branched hydrocarbon groups include i-propenyl group and 3-butenyl group, but are not particularly limited. Although a cyclopentenyl group, a cyclohexenyl group, etc. are mentioned as unsaturated-cyclic hydrocarbon group, It does not specifically limit. As an aromatic group, although a phenyl group or a naphthyl group etc. are mentioned, it does not specifically limit.

  In addition, as a derivative group in α, at least one of functional groups such as carboxy group, hydroxy group or amino group is added or substituted to the main chain or side chain of the above various hydrocarbon groups. Although a group is mentioned, it is not limited in particular. Further, 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 setting the number of carbon atoms constituting the main chain of R in the above range, the molecular weight of the phosphorous acid group can be made in an appropriate range, facilitating penetration into the fiber material, and the yield of fine cellulose fibers It can also be enhanced.

(Beta) ^{b +} in Formula (2) is the monovalent | monohydric or more cation which consists of organic substance or an inorganic substance. The monovalent or more monovalent cations of organic substances include aliphatic ammonium or aromatic ammonium, and the monovalent or more monovalent cations of inorganic substances include ions of alkali metals such as sodium, potassium or lithium, Examples thereof include cations of divalent metals such as calcium or magnesium, or hydrogen ions, but not particularly limited. These can also be applied combining 1 type or 2 or more types. The monovalent or more monovalent cation composed of an organic substance or an inorganic substance is preferably an ion of sodium or potassium which is not easily yellowed when the fiber material containing β is heated and which is industrially easy to use, but is not particularly limited.

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

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

In Formula (3), a and b are natural numbers, m is an arbitrary number, and n is a natural number of 2 or more (where a = b × m). ^{α 1, α 2, ···,} a number of alpha ⁿ and alpha 'is O ^- a and the remainder is either R or OR. Here, R represents a hydrogen atom, a saturated-linear hydrocarbon group, a saturated-branched hydrocarbon group, a saturated-cyclic hydrocarbon group, an unsaturated-linear hydrocarbon group, an unsaturated-branched group It is a hydrocarbon group, an unsaturated-cyclic hydrocarbon group, an aromatic group, or a derivative thereof. In the formula (3), α may be a group derived from a cellulose molecular chain.

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

The fact that the fine fibrous cellulose has a phosphite group as a substituent means that the infrared absorption spectrum of the dispersion containing the fine fibrous cellulose is measured, and the tautomer of the phosphite group is around 1210 cm ^-1. This can be confirmed by observing the P = O-based absorption of a certain phosphonic acid group. Moreover, that fibrous cellulose has a phosphoric acid group as a substituent means that the infrared absorption spectrum of the dispersion containing fibrous cellulose is measured, and the absorption based on P = O of the phosphoric acid group is made in the vicinity of 1230 cm ^-1. It can confirm by observing. Further, the fact that fibrous cellulose has a phosphorous acid group or a phosphoric acid 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 phosphorous group>
The introduction of the phosphorous acid group is performed on at least one selected from a compound having a phosphorous acid group and a salt thereof (hereinafter referred to as “phosphorous acid oxidizing reagent” or “compound A”) with respect to a fiber raw material containing cellulose. It can be carried out by reaction. Such a phosphorous oxidizing reagent may be mixed with the dry or wet fiber raw material in the form of powder or an aqueous solution. As another example, a powder or an aqueous solution of a phosphorous oxidation reagent may be added to the fiber material slurry.

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

  As an example of the method of allowing compound A to act on the fiber raw material in the coexistence of compound B, a method of mixing powder or an aqueous solution of compound A and compound B with a dry or wet fiber raw material can be mentioned. Moreover, the method of adding the powder and aqueous solution of the compound A and the compound B to the slurry of a fiber raw material as another example is mentioned. Among them, the method of adding the aqueous solution of compound A and compound B to the fibrous material in the dry state or adding the powder or the aqueous solution of compound A and compound B to the fibrous material in the wet state is preferable because the reaction uniformity is high. The method is preferred. Compound A and Compound B may be added simultaneously or separately. Alternatively, the compound A and the compound B to be tested first may be added as an aqueous solution, and excess chemical solution may be removed by pressing. The form of the fiber material is preferably cotton-like or thin sheet, but is not particularly limited.

The compound A used in the present embodiment is at least one selected from a compound having a phosphorous acid group and a salt thereof.
Examples of the compound having a phosphite group include phosphorous acid, and examples of phosphorous acid include 99% phosphorous acid (phosphonic acid). Examples of salts of compounds having a phosphorous acid group include lithium salts, sodium salts, potassium salts and ammonium salts of phosphorous acid. Among these, from the viewpoint of high efficiency of introduction of a phosphorus oxo group, easy improvement of the fibrillation efficiency in the fibrillation step to be described later, low cost, and easy industrial application, phosphorous acid and phosphorous Sodium salts of acids, potassium salts of phosphorous acid, or ammonium salts of phosphorous acid are preferably used.

  Further, Compound A is preferably used as an aqueous solution because the uniformity of the reaction is enhanced and the efficiency of phosphorous acid group introduction is enhanced. The pH of the aqueous solution of compound A is not particularly limited, but is preferably 7 or less because the efficiency of the introduction of the phosphorous acid group is high, and more preferably pH 3 or more and pH 7 or less from the viewpoint of suppressing hydrolysis of pulp fibers. The pH of the aqueous solution of the compound A may be adjusted, for example, by using a combination of a compound having a phosphorous acid group and one exhibiting acidity and one exhibiting alkalinity, and changing the ratio of the amounts. 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 that exhibits acidity.

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

  As compound B used in this embodiment, urea, biuret, 1-phenylurea, 1-benzylurea, 1-methylurea, 1-ethylurea and the like can be mentioned.

  The compound B is preferably used as an aqueous solution like the compound A. 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. It is preferable that the addition amount of the compound B with respect to a fiber raw material (absolute dry mass) is 1 mass% or more and 500 mass% or less, more preferably 10 mass% or more and 400 mass% or less, 100 mass% or more and 350 mass% It is more preferable that it is the following, and it is especially preferable that it is 150 to 300 mass%.

  In addition to the compound A and the compound 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, hexamethylenediamine and the like. Among these, triethylamine is known to work as a good reaction catalyst.

  It is preferable to heat-process in introduction of a phosphorous acid 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 the thermal decomposition or hydrolysis reaction of the fiber. Specifically, the temperature is preferably 50 ° C. or more and 300 ° C. or less, more preferably 100 ° C. or more and 250 ° C. or less, and still more preferably 130 ° C. or more and 200 ° C. or less. For the heat treatment, equipment having various heat media can be used. For example, stirring and drying apparatus, rotary drying apparatus, disk drying apparatus, roll type heating apparatus, plate type heating apparatus, fluidized bed drying apparatus, air flow A drying device, a reduced pressure drying device, an infrared heating device, a far infrared heating device, a microwave heating device, or a high frequency drying device can be used.

  During the heat treatment, while the fiber material slurry to which Compound A is added contains water, if the time for which the fiber material is allowed to stand becomes long, Compound A, which is dissolved with water molecules, moves to the surface of the fiber material as it dries. Do. Therefore, unevenness may occur in the concentration of the compound A in the fiber raw material, and there is a possibility that the introduction of the phosphorous acid group to the fiber surface does not proceed uniformly. In order to suppress the occurrence of concentration unevenness of the compound A in the fiber material due to drying, a very thin sheet-like fiber material is used, or the fiber material and the compound A are heated or dried under reduced pressure while kneading or stirring with a kneader. You should take the method.

  The heating device used for the heat treatment is preferably a device capable of always discharging the water held by the slurry and the water produced by the addition reaction to the hydroxyl groups of the fibers such as phosphorous acid groups out of the device system. An oven or the like is preferred. In addition to the fact that hydrolysis of the phosphate ester bond, which is the reverse reaction of phosphorylation, can be suppressed by constantly draining the water in the system, acid hydrolysis of sugar chains in fibers can also be suppressed. And fine fibers with high axial ratio can be obtained.

  The heat treatment time is also affected by the heating temperature, but it is preferably 1 second or more and 300 minutes or less after water is substantially removed from the fiber material slurry, and more preferably 1 second or more and 1000 seconds or less Preferably, it is 10 seconds or more and 800 seconds or less. In the present invention, by setting the heating temperature and the heating time to an appropriate range, the introduction amount of the phosphorous acid group can be set to a preferable range.

  The amount of introduced phosphorous acid group is preferably 5.20 mmol / g or less per 1 g (mass) of fine fibrous cellulose, and more preferably 0.1 mmol / g or more and 3.65 mmol / g or less. 0.14 mmol / g or more and 3.5 mmol / g or less is still more preferable, 0.2 mmol / g or more and 3.2 mmol / g or less is more preferable, 0.4 mmol / g or more and 3.0 mmol / g or less is particularly preferable, the most Preferably they are 0.6 mmol / g or more and 2.5 mmol / g or less. By making the introduction amount of the phosphorous acid group within the above range, it is possible to facilitate the miniaturization of the fiber raw material and to enhance the stability of the fine fibrous cellulose. Further, by setting the introduction amount of the phosphorous acid group within the above range, it is possible to easily leave the hydrogen bond between the fine fibrous celluloses while being easily refined, and it is preferable in the case of a sheet. Strong expression can be expected.

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

FIG. 1 is a graph showing the relationship between the amount of NaOH added and the pH with respect to a fibrous cellulose-containing slurry having a phosphorus oxo group. The amount of phosphorus oxo group introduced into fibrous cellulose is measured, for example, as follows.
First, a slurry containing fibrous cellulose is treated with a strongly acidic ion exchange resin. In addition, you may implement the disintegration processing similar to the below-mentioned disintegration processing process with respect to a measuring object before the processing by strongly acidic ion exchange resin as needed.
Then, while the aqueous sodium hydroxide solution is added, the change in pH is observed to obtain a titration curve as shown in the upper part of FIG. 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. 1 shows the pH relative to the amount of alkali added. Increments (differential values) (1 / mmol) are plotted. In this neutralization titration, in the curve obtained by plotting the measured pH against the amount of addition of alkali, two points at which the increment (the differential value of the pH with respect to the amount dropped by the alkali) becomes maximum are confirmed. Among 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. The amount of alkali required from the start of titration to the first end point becomes equal to the amount of first dissociable acid of fibrous cellulose contained in the slurry used for titration, and the alkali required from the first end point to the second end point The amount is equal to the second dissociated acid amount of fibrous cellulose contained in the slurry used for titration, and the fibrous amount contained in the slurry used for titration the alkali amount required from the start of titration to the second end point It becomes equal to the total amount of dissociated acid. Then, 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 becomes the introduced amount of phosphorus oxo group (mmol / g). In addition, when it only says the phosphorus oxo acid group introduction amount (or phosphorus oxo acid group amount), it represents the amount of 1st dissociated acid.
In addition, in FIG. 1, the area | region from the titration start to a 1st end point is called a 1st area | region, and the area | region from a 1st end point to a 2nd end point is called a 2nd area | region. For example, in the case where the phosphorus oxo group is a phosphate group and the phosphate group causes condensation, the amount of weakly acidic group in the phosphorus oxo group (also referred to as the second dissociated acid amount in this specification) is apparently As a result, the amount of alkali required for the second region is reduced compared to the amount of alkali required for the first region. On the other hand, the amount of strongly acidic group in the phosphorus oxo group (also referred to herein as the amount of the first dissociating acid) matches the amount of phosphorus atom regardless of the presence or absence of condensation. In addition, when the phosphorous oxo group is a phosphorous acid group, since a weak acidic group is not present in the phosphorous oxo group, the amount of alkali required for the second region is reduced or the amount of alkali needed for the second region May be zero. In this case, in the titration curve, the point at which the increment of pH becomes maximum is one.

The above-mentioned phosphorus oxo group introduction amount (mmol / g) is the amount of phosphorus oxo acid group possessed by acid type fibrous cellulose since the denominator indicates the mass of acid type fibrous cellulose (hereinafter, phosphorus oxo acid group amount (Referred to as acid type)). On the other hand, when the counter ion of the phosphorus oxo group is substituted by an arbitrary cation C so as to be charge equivalent, the denominator is converted to the mass of fibrous cellulose when the cation C is a counter ion Thus, it is possible to determine the amount of phosphorus oxo acid groups (hereinafter, the amount of phosphorus oxo acid groups (C type)) possessed by the fibrous cellulose in which the cation C is a counter ion.
That is, it calculates with the following formula.
Phosphorus oxo acid group content (C type) = Phosphorus oxo acid group content (acid type) / {1 + (W-1) x A / 1000}
A [mmol / g]: total amount of anions derived from phosphorus oxo group possessed by fibrous cellulose (total amount of dissociable acid of phosphorus oxo group)
W: Formula weight per monovalent C cation (for example, 23 for Na, 9 for Al)

  In addition, in the measurement of the amount of phosphorus oxo acid groups by the titration method, when the dropping amount of 1 drop of sodium hydroxide aqueous solution is too large, or when the titration interval is too short, an accurate value such as becoming the phosphorus oxo acid group amount lower than originally becomes accurate It can not be obtained. As a suitable dripping amount and titration interval, for example, it is desirable to titrate 10 N aqueous solution of 0.1 N sodium hydroxide every 10 to 50 in 5 to 30 seconds. Further, 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 until the end of titration.

  Also, which of phosphorous acid, phosphoric acid and condensed phosphoric acid is derived from phosphorous oxo acid which is detected when phosphoric acid group or condensed phosphate group or both is contained in addition to phosphorous acid group As a method of distinguishing between, for example, a method of performing a treatment of cutting a condensed structure such as acid hydrolysis and then performing the above-mentioned titration operation, and a treatment of converting a phosphite group into a phosphate group such as oxidation treatment There is a method of performing the above-mentioned titration operation after the reaction.

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

<Alkali treatment process>
In the case of producing fine fibrous cellulose, an alkali treatment may be performed on the fiber material between the phosphorous acid group introducing step and the defibrating treatment step described later. Although it does not specifically limit as the method of an alkali treatment, For example, the method of immersing a phosphite group-introduced fiber in an alkali solution is mentioned.

  The alkali compound contained in the alkali solution is not particularly limited, and may be an inorganic alkali compound or an organic alkali compound. In the present embodiment, it is preferable to use, for example, sodium hydroxide or potassium hydroxide as an alkali compound because of its high versatility. Also, the solvent contained in the alkaline solution may be either water or an organic solvent. The solvent contained in the alkaline solution is preferably a polar solvent containing water or a polar organic solvent exemplified by alcohols, 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 high versatility.

  The temperature of the alkali solution in the alkali treatment step is not particularly limited, but is preferably 5 ° C. or more and 80 ° C. or less, and more preferably 10 ° C. or more and 60 ° C. or less. The immersion time of the phosphite group-introduced fiber into the alkali solution in the alkali treatment step is not particularly limited, but is preferably 5 minutes to 30 minutes, and more preferably 10 minutes to 20 minutes. The use amount of the alkali solution in the alkali treatment is not particularly limited, but is preferably 100% by mass or more and 100000% by mass or less, for example, 1000% by mass or more and 10000% by mass with respect to the dry mass of the phosphorous acid group-introduced fiber. It is more preferable that

  In order to reduce the amount of alkali 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 phosphorous acid group-introduced fiber with water or an organic solvent, from the viewpoint of improving the handleability.

<Acid treatment process>
In the case of producing the fine fibrous cellulose, the fiber material may be subjected to an acid treatment between the step of introducing the phosphorous acid group and the defibration treatment step described later. As an example of this embodiment, the case where a phosphorous acid group introduction process, acid treatment, alkali treatment and defibration treatment are performed in this order can be mentioned.

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

  Although it does not specifically limit as the method of an acid treatment, For example, the method of immersing a fiber raw material in the acidic liquid containing an acid is mentioned. The concentration of the acidic solution to be used is not particularly limited, but for example, 10% by mass or less is preferable, and 5% by mass or less is more preferable. Further, the pH of the acidic solution to be used is not particularly limited, but it is preferably, for example, 0 to 4, and more preferably 1 to 3. As an acid contained in an acidic liquid, an inorganic acid, sulfonic acid, carboxylic acid etc. can be used, for example. Examples of the inorganic acid include sulfuric acid, nitric acid, hydrochloric acid, hydrobromic acid, hydroiodic acid, hypochlorous acid, chlorous acid, chloric acid, perchloric acid, phosphoric acid, boric acid and the like. As a sulfonic acid, methanesulfonic acid, ethanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, trifluoromethanesulfonic acid etc. are mentioned, for example. Examples of carboxylic acids 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.

<Disintegration process (refining)>
The phosphite group-introduced fiber is subjected to a defibration treatment in a defibration treatment step to obtain a fine fibrous cellulose. In the defibration treatment step, for example, a defibration treatment device can be used. The defibration processing apparatus is not particularly limited, but, for example, a wet atomization apparatus, a high speed defibrator, 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, Conical refiner, twin screw kneader, vibration mill, homomixer under high speed rotation, ultrasonic disperser, beater, etc. can be used, and solid content concentration of fine fibrous cellulose at the time of defibration treatment is set appropriately it can. It is more preferable to use a wet atomization device, a high-speed fibrillation machine, a high pressure homogenizer, and an ultrahigh pressure homogenizer which are less affected by the grinding media and less likely to contaminate among the above-mentioned fibrillation treatment devices. There are no particular limitations on the number of times of defibration treatment (micronization), but in order to promote sufficient miniaturization, it is preferable to carry out multiple times. Although the upper limit is not particularly limited, it is practical that it is 10 times or less.

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

<Enzyme treatment>
In the present invention, an enzyme treatment may be performed. That is, the cellulose-containing composition of the present invention may contain an enzyme. In addition, the cellulose-containing composition of the present invention may contain a protein in which the enzyme is inactivated.
Enzymes that can be used in the present invention are cellulase enzymes, and are classified into a carbohydrate hydrolase family based on the higher order structure of a catalytic domain having a hydrolysis reaction function of cellulose. Cellulase enzymes are classified into endo-glucanase and cellobiohydrolase according to their cellulolytic properties. Endo-type glucanase is highly hydrolyzable to the amorphous part of cellulose, soluble cellooligosaccharides, or cellulose derivatives such as carboxymethyl cellulose, and these molecular chains are randomly cut from the inside to lower the degree of polymerization. However, endo-type glucanase has low hydrolysis reactivity to crystalline cellulose microfibrils. In contrast, cellobiohydrolase decomposes the crystalline part of cellulose to give cellobiose. In addition, cellobiohydrolase hydrolyzes from the end of cellulose molecule and is also called 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, hemicellulase enzymes may be used in addition to endo type glucanase and cellobiohydrolase. Among hemicellulase enzymes, xylanase which is an enzyme which degrades xylan, mannase which is an enzyme which degrades mannan (mannase) or arabanase which is an enzyme which degrades araban may be mentioned. Pectinase, which is an enzyme that degrades pectin, can also be used as a hemicellulase enzyme. Microorganisms producing hemicellulase enzymes often produce cellulase enzymes.

  Hemicellulose is a polysaccharide from which pectins are removed between cellulose microfibrils of plant cell walls. Hemicelluloses are diverse and vary with plant types and cell wall layers. In wood, glucomannan is the main component in the secondary wall of softwood and 4-O-methylglucuronoxylan is the main component in the secondary wall of hardwood. Therefore, in order to obtain fine fiber from softwood, it is preferable to use mannase, and in the case of hardwood, it is preferable to use xylanase.

According to the present invention, there is provided a method of producing a cellulose-containing composition comprising the step of adding an enzyme. By adding an enzyme to the fine fibrous cellulose, the fine fibrous cellulose can be reacted with the enzyme. In the present invention, it is possible to adopt a mode in which the step of washing the fine fibrous cellulose is not performed after the enzyme treatment.
In the present invention, the enzyme may be inactivated after the enzyme treatment. As a method for inactivating 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, although adding a strong base and adjusting pH to 10 or more etc. is mentioned, it does not specifically limit.
The cellulose-containing composition of the present invention can be produced by the method for producing a cellulose-containing composition described above.

The amount of enzyme added to 1 part by mass of fibrous cellulose having a fiber width of 1000 nm or less and having a phosphite group or a substituent derived from a phosphite group is not particularly limited, but 1 × 10 ⁻³ mass Or less is preferable, 1 × 10 ⁻⁴ parts by mass or less is more preferable, 1 × 10 ⁻⁵ parts by mass or less is more preferable, and 5.0 × 10 ⁻⁶ parts by mass or less is particularly preferable. The amount of enzyme added is preferably 1 × 10 ⁻⁷ parts by mass or more, more preferably 3 × 10 ⁻⁷ parts by mass or more, and 1 × 10 ⁻⁶ parts by mass or more with respect to 1 part by mass of fibrous cellulose. preferable.
By making the addition amount of an enzyme into said range, the particle | grains (aggregates) in a coated material can be suppressed.

The reaction time of the fine fibrous cellulose and the enzyme is not particularly limited, but generally, 1 minute to 24 hours is preferable, and 1 minute to 1 hour is more preferable.
It is preferable to keep the reaction temperature and reaction pH of the fine fibrous cellulose and the enzyme at the optimum temperature and pH of the enzyme used, generally, 20 ° C. to 80 ° C., 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, in the step of obtaining the fine fibrous cellulose, it is preferable to include the step of refining the fiber raw material (coarse fibrous cellulose). At this time, most of the coarse fibrous cellulose is refined, but a part of the coarse fibrous cellulose may remain without being refined. In such a case, coarse fibrous cellulose is contained in the fibrous cellulose-containing composition of the present invention.

  Coarse fibrous cellulose contained in the fibrous cellulose-containing composition of the present invention is a high-speed centrifugal centrifuge (Kokusan Co., Ltd., H-2000B) by adjusting the cellulose dispersion to a solid content concentration of 0.2% by mass. It is a fibrillar cellulose which is precipitated when it is centrifuged at 12000 G for 10 minutes.

  The less precipitated component means that the yield of supernatant after centrifugation is high. It is preferable that the supernatant yield after this centrifugation is 80 mass% or more with respect to the total mass of fibrous cellulose. The supernatant yield after centrifugation is more preferably 90% by mass or more, still more preferably 95% by mass or more, and particularly preferably 99% by mass or more.

In addition, the supernatant yield after centrifugation of said fine fibrous cellulose dispersion liquid can be measured by the following method in this specification.
The supernatant yield after centrifuging the fine fibrous cellulose dispersion was measured by the method described below. The supernatant yield after centrifugation is an 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 concentration of 0.2% by mass, and centrifuged at 12000 G for 10 minutes using a cooling high-speed centrifuge (Kokusan Co., Ltd., H-2000B). The obtained supernatant was collected, and the solid concentration of the supernatant was measured. The yield of fine fibrous cellulose was determined based on the following formula.
Fine fibrous cellulose yield (%) = supernatant solid concentration (%) / 0.2 × 100

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

(Specific component)
In the present invention, a pigment dispersant having an ionic group (also referred to as “specific component”) is used. The pigment dispersant used in the present invention has an acid value of 5 mg KOH / g to 200 mg KOH / g, or an amine value of 5 mg KOH / g to 200 mg KOH / g. The pigment dispersant is a component used to uniformly disperse a pigment (fine solid) in a dispersion medium to prepare a stable dispersion.

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

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

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

Solvent: Tetrahydrofuran (THF)
Column: Shodex K806, K805, K803G
(Connected with three made by Showa Denko KK)
Column temperature: 40 ° C
Sample concentration: 0.1% by mass
Detector: RI Model 504 (manufactured by GL Science)
Pump: L6000 (manufactured by Hitachi, Ltd.)
Flow rate (flow rate): 1.0 ml / min
Injection volume: 10 μL
Calibration curve: Standard polystyrene STK standard A calibration curve with 13 samples of polystyrene (manufactured by Tosoh Corp.) Mw = 500 or more and 2,800,000 or less was used. Thirteen samples are used at approximately equal intervals.

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

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

  When the acid value or the amine value of the pigment dispersant having an ionic group is less than the above lower limit, the interaction with the fine fibrous cellulose tends to be insufficient, and a sufficient aggregation preventing effect can not be obtained, and the coatability is inferior. , Smooth surface may not be obtained. On the other hand, when the acid value or the amine value exceeds the above upper limit value, the steric hindrance layer may be smaller than the affinity to the fine fibrous cellulose, and the aggregation preventing effect may be insufficient.

  The ionic group of the pigment dispersant having an ionic group is not particularly limited, but may be a cationic group, an anionic group or a dissociative group by an acid or a base. The cationic group includes an amino group and a quaternary ammonium group. As an anion group, a sulfo group, a carboxy group, a sulfuric acid ester group, and a phosphoric acid group are mentioned. An amide group is mentioned as a dissociative group. The ionic group may form a salt having a counter ion. The pigment dispersant having an ionic group may simultaneously have the above-mentioned cationic group, anionic group and dissociative group in the molecule.

  As the pigment dispersant having an ionic group, various ones can be mentioned, and as the polymer dispersant, styrene / maleic anhydride copolymer, formalin conjugate of naphthalene sulfonate, poly (meth) acrylate, Carboxymethyl cellulose, Olefin / maleic anhydride copolymer, polystyrene sulfonate, acrylamide / acrylic acid copolymer, anionic polymer dispersant such as sodium alginate, polyethylene imine, aminoalkyl (meth) acrylate copolymer, polyvinyl imidazoline And polymer dispersants such as a resin having a (meth) acrylate alkali metal salt moiety, a resin having a (meth) acrylic acid moiety, and a resin having an alkylol ammonium salt moiety. As for these polymer dispersants, for example, M. Kushi "Dispersant" J. Mol. Jpn. Soc. Color Mater. , 78 [3] (2005) pp. 41-48.

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

The alkylol ammonium salt site is preferably a reaction site of an acidic group (eg, a sulfo group, a carboxy group, a sulfuric acid ester group, a phosphoryl group, or a phosphoric acid) with an alkylol ammonium. The alkylol ammonium salt moiety preferably has the following partial structure.
-C (= O) -N (-R 1) (- R 2 -OH) formula (A)
Here, R ¹ is a hydrogen atom or an alkyl group (preferably having a carbon number of 1 to 12, more preferably 1 to 6, still more preferably 1 to 3), and R ² is an alkylene group (having a carbon number of 1 to 12 is preferred, 1 To 6 is more preferable, and 1 to 3 is further preferable). R ¹ and R ² may further have a substituent Z within the scope of achieving the effects of the present invention.

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

The pigment dispersant having an anionic group is also preferably a polymer having a partial structure of the following formula (C).
-C (= O) -O-L 1 -A formula (C)
A is an acidic group and is preferably a sulfo group, a carboxy group, a sulfuric acid ester group, a phosphoryl group or a phosphoric acid group. The acidic group may form a salt. Preferred salts are alkali metal salts, preferably sodium or potassium salts. L ¹ is a post-linking linking group Y, and among them, an alkylene group (C 1-12 is preferable, 1 to 6 is more preferable, and 2 or 3 is more preferable) is preferable.

As a pigment dispersant having an alkylol ammonium salt site,
DISPERBYK,
DISPERBYK-180,
DISPERBYK-181,
DISPERBYK-187,
DISPERBYK-140,
DISPERBYK-250,
BYK-9076,
BYK-W969
(Any brand name, made by Big-Chemie) or the like can be used.
As a pigment dispersant having a (meth) acrylate potassium salt site, a polymer (including a copolymer) synthesized using potassium sulfopropyl (meth) acrylate as a monomer can be used.
As (meth) acrylate resin and potassium salt, DISPER-AW300P (made by Otsuka Chemical Co., Ltd.) etc. can be used, for example.

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

As the linking group Y, a linking group related to 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 combination thereof Can be 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, still more preferably 300 parts by mass or less, with respect to 100 parts by mass of fibrous cellulose. It is particularly preferred that the amount is at most parts by mass. In addition, the content of the specific component is preferably 1 part by mass or more, more preferably 5 parts by mass or more, and still more preferably 10 parts by mass or more with respect to 100 parts by mass of fibrous cellulose. And particularly preferably 15 parts by mass or more. By setting the content to the above lower limit value or more, the coatability of the fibrous cellulose-containing composition and the smoothness of the coating film can be achieved at a high level by necessity, which is preferable. By setting the content to the above upper limit value or less, desired properties can be exhibited without impairing the properties and production suitability required for the fibrous cellulose-containing composition, which is preferable.

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

(resin)
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, for example. 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, Although a phenol resin, an epoxy resin, etc. are mentioned, it is not restrict | limited to these.

  The content of the resin is preferably 30 parts by mass or more, more preferably 70 parts by mass or more, and more preferably 100 parts by mass or more based on 1 part by mass of fibrous cellulose, when used as a paint. Is particularly preferred. In addition, 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 with respect to 1 part by mass of fibrous cellulose. By containing the resin in the above content, the effects of the above specific components can be suitably exhibited, and the coating property, the smoothness of the coating film, and the optimization of the elastic modulus and the strength can be realized.

(Hardening agent)
When the fibrous cellulose-containing composition of the present invention is used as a paint, it is preferable to contain a curing agent. As a curing agent, although a well-known thing can be used suitably, For example, an isocyanate type curing agent (polyisocyanate etc.), an epoxy (oxirane) type curing agent, an oxetane type curing agent, etc. are mentioned. Among these, in the present invention, isocyanate-based curing agents are preferred.

  The content of the curing agent is preferably 10 parts by mass or more, more preferably 20 parts by mass or more, and more preferably 30 parts by mass or more with respect to 1 part by mass of fibrous cellulose, when used as a paint. Being particularly preferred. In addition, the content of the curing agent is preferably 100 parts by mass or less, more preferably 80 parts by mass or less, and particularly preferably 60 parts by mass or less with respect to 1 part by mass of fibrous cellulose. . By incorporating the curing agent to the content described above, the effects of the specific component can be suitably exhibited, and the coating property, the smoothness of the coating film, the optimization of the elastic modulus, and the like can be realized.

(Optional ingredient)
The fibrous cellulose-containing composition of the present invention may contain optional components other than the components described above. As an optional component, for example, an antifoamer, a lubricant, an ultraviolet light absorber, a dye, a pigment, a stabilizer, a surfactant, a coupling agent, an inorganic layered compound, an inorganic compound, a leveling agent, organic particles, an antistatic agent And magnetic powders, orientation accelerators, plasticizers, preservatives, crosslinking agents and the like. Moreover, you may add an organic ion as an arbitrary component.

(Fibrous cellulose-containing composition)
When the fibrous cellulose-containing composition is a paint, the content of fibrous cellulose is preferably 0.05% by mass or more based on the solid content in the fibrous cellulose-containing composition, and the content of the fibrous cellulose is preferably 0. It is more preferably 1% by mass or more, and still more preferably 0.3% by mass or more. The content of fibrous cellulose is preferably 10% by mass or less, more preferably 5% by mass or less, and still more 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 with respect to the total amount of the fibrous cellulose-containing composition, and it is preferably 0. 4 mass% or more, 1 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 may be sufficient. Moreover, it is preferable that it is 95 mass% or less, and, as for content of fibrous cellulose, it is more preferable that it is 90 mass% or less.

  In the application of a thickener, it is preferable that the total amount of the said fibrous cellulose, the said specific component, and water is 80 mass% or more with respect to the whole fibrous cellulose containing composition, and is 90 mass% or more Is more preferable, and 95% by mass or more is particularly preferable.

  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 3 rpm with a solid content concentration of fibrous cellulose of 0.4 mass%. The viscosity is preferably 35,000 mPa · s or less, more preferably 30,000 mPa · s or less, and particularly preferably 25,000 mPa · s or less. As a lower limit, 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 more preferable, 7 It is particularly preferable that the slurry has a viscosity of 1,000 mPa · s or more. Favorable coating property is exhibited by making this viscosity below the said upper limit, and it is preferable. By setting it as the above-mentioned lower limit or more, Young's modulus and strength when forming a 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 exchange water so that the solid content concentration becomes 0.4% by mass, and then stirred for 5 minutes at 1500 rpm with a disperser. Subsequently, the viscosity of the dispersion liquid obtained by this is measured using a Brookfield viscometer (made by BLOOKFIELD, analog viscometer T-LVT). The measurement conditions are a rotational speed of 3 rpm, and the viscosity value 3 minutes after the start of the measurement is the viscosity of the dispersion. In addition, the dispersion to be measured is allowed to stand overnight under an environment of 23 ° C. and 50% relative humidity before measurement. The measurement temperature of viscosity is 23 ° C. Other detailed measurement conditions, etc. conform to JIS Z 8803: 2011. Prepare 5 samples per level, make 2 measurements each 10 times in total, and adopt the arithmetic mean value.

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

(Coating)
The fibrous cellulose-containing composition of the present invention is preferably coated to form a coating. The thickness of the coating film is not particularly limited, but when considering the application form as a paint, it is preferably 1000 μm or less, more preferably 500 μm or less, still more preferably 300 μm or less, and 100 μm or less. It is more preferable that the thickness be 80 μm or less. As a lower limit, 1 micrometer or more is preferable, 5 micrometers or more are more preferable, and 10 micrometers or more are especially preferable.

  The surface roughness of the coating (in the present specification, unless otherwise specified, the surface roughness refers to the arithmetic average roughness: Ra defined in JIS B 0601: 2013) is not particularly limited, but the coating is When considering applications such as, it is preferable that the smoothness be better. 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 It is particularly preferable to Although the lower limit value is not particularly limited, it is practical that it is 0.001 μm or more.

  The surface roughness is measured using an optical interference type non-contact surface profilometer (non-contact surface / layer cross-section profile measuring system VertScan 2.0, model: R5500 GML, manufactured by Lyso system Co., Ltd.), and a measurement range of 470 with an × 10 objective lens. The arithmetic mean roughness (Ra) of 92 μm × 353.16 μm is measured. The measurement is performed 5 times per level, and the arithmetic average roughness is determined from the average value. Details of the definition of arithmetic mean roughness (Ra), measurement conditions, calculation method and the like conform to JIS B 0601: 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 preferably, and particularly preferably 0.8 GPa or more. The upper limit is practically 8 GPa or less. According to the present invention, since such a high Young's modulus can be achieved, it can be suitably coped with in applications where a high elastic modulus is required.

  The Young's modulus of the coating is JIS P 8113: 2006 except that the length of the test piece between the jaws is 50 mm and the tensile speed is 5 mm / min using a tensile tester Tensilon (manufactured by A & D Co.). Measure in compliance. When measuring Young's modulus, what was conditioned for 24 hours at 23 degreeC and 50% of relative humidity is used as a test piece. The measurement is performed 5 times per level, and the average value is adopted.

(Method of manufacturing membrane)
The manufacturing process of the thickener, the paint, the film and the like is not particularly limited.
The thickener includes a dispersion (which may be in the form of a slurry) containing 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 specific component or a dispersion thereof It can be produced by mixing a solution containing and optionally other components (for example, water).
The coating material may, if necessary, other fine fibrous cellulose (which may be a dispersion), a specific component (which may be a solution), a resin (such as an acrylic resin), a curing agent (such as a polyisocyanate), and the like. It can be produced by mixing with a component (for example, an organic solvent) of
The film can be produced by applying a composition containing fine fibrous cellulose and a specific component (for example, the above-mentioned paint, thickener, etc.) to form a coating film. Specifically, for example, a coated 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 same.
The coating film formed above may be peeled off from the substrate to form a sheet.
Alternatively, the sheet may be produced by papermaking of a composition (which may be the above-mentioned paint 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-described paint or thickener) containing fine fibrous cellulose and a specific component on a substrate.
In the case of producing a sheet, the sheet can be produced continuously by using a coating apparatus and a long base material.

  The material of the substrate used in the coating step is not particularly limited, but a material having high wettability to the composition may be able to suppress shrinkage and the like of the sheet at the time of drying, but the sheet formed after drying is It is preferable to select one that can be easily peeled off. Among them, a resin film or plate or a metal film or plate is preferable, but is not particularly limited. For example, films or plates of resins such as acrylic, polyethylene terephthalate, vinyl chloride, polystyrene, polypropylene, polyvinylidene chloride, aluminum, zinc, copper, metal films or plates of iron plate, and those surfaces of which are oxidized, stainless steel Films and boards, brass films and boards, etc. can be used.

  In the coating process, when the viscosity of the composition to be coated is low and it develops on a substrate, a frame for haze prevention is fixed on the substrate to obtain a sheet of a predetermined thickness and basis weight. You may use it. The quality of the frame for blocking is not particularly limited, but it is preferable to select one that can be easily peeled off the end of the sheet adhering after drying. Among them, one obtained by molding a resin plate or a metal plate is preferable, but it is not particularly limited. For example, resin plates such as acrylic plates, polyethylene terephthalate plates, vinyl chloride plates, polystyrene plates, polypropylene plates, polyvinylidene chloride plates, etc., metal plates such as aluminum plates, zinc plates, copper plates, iron plates, etc. and their surfaces oxidized The thing which shape | molded the thing, a stainless steel plate, a brass plate etc. can be used.

  As a coating machine which coats a composition, an applicator, a roll coater, a gravure coater, a die coater, a curtain coater, an air doctor coater etc. can be used, for example. An applicator, a die coater, a curtain coater, and a spray coater are preferable because the thickness can be made more uniform.

  The coating temperature is not particularly limited, but is preferably 20 ° C. or more and 45 ° C. or less, more preferably 25 ° C. or more and 40 ° C. or less, and still more preferably 27 ° C. or more and 35 ° C. or less. If the coating temperature is equal to or higher than the above lower limit, the composition can be easily coated, and if it is equal to or lower than the above upper limit, volatilization of the dispersion medium during coating can be suppressed.

In the coating step, the composition is preferably coated such 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 a basis weight may become in the said range, the sheet | seat excellent in intensity | strength is obtained.

  The coating step preferably includes the step of drying the composition coated on the substrate. The drying method is not particularly limited, but it 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 heating and drying with hot air, infrared rays, far infrared rays or near infrared rays (heat drying method), a method of vacuum drying (vacuum drying method) may be applied. Can. Although the heat drying method and the vacuum drying method may be combined, the heat drying method is usually applied. Drying by infrared light, far infrared light or near infrared light can be performed using an infrared light device, a far infrared light device or a near infrared light 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 more and 150 ° C. or less, and more preferably 25 ° C. or more and 105 ° C. or less. The dispersion medium can be volatilized quickly if the heating temperature is at least the lower limit, and the cost required for heating can be suppressed and the fine fibrous cellulose can be prevented from being discolored by heat if the heating temperature is at least the upper limit. .

<Paper-making process>
In the case of producing a sheet, the step of producing the sheet may include the step of producing a composition containing the fine fibrous cellulose and the specific component (which may be the above-mentioned paint or thickener). Examples of the paper making machine in the paper making process include continuous paper machines such as long mesh type, circular net type and inclined type, and a multilayer paper making machine combining these. In the paper making process, known paper making such as hand paper making may be performed.

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

  Although it does not specifically limit as a method to manufacture a sheet | seat from the said composition, For example, the method of using the manufacturing apparatus as described in WO2011 / 2013567, etc. are mentioned. This manufacturing apparatus discharges a composition containing fine fibrous cellulose onto the top surface of an endless belt, squeezes the dispersion medium from the discharged composition to form a web, and the web is dried to form fibers. And a drying section for producing a sheet. An endless belt is disposed from the water squeezing section to the drying section, and the web generated in the water squeezing section is conveyed to the drying section while being placed on the endless belt.

  The dehydrating method that can be adopted is not particularly limited, but the dehydrating method usually used in the production of paper may be mentioned, and a method of dehydrating with a long mesh, circular net, inclined wire or the like and then dehydrating with a roll press is preferable. Further, the drying method is not particularly limited, and examples thereof include methods used in the production of paper. For example, methods such as a cylinder drier, a Yankee drier, hot air drying, a near infrared heater, and an infrared heater are preferable.

(Laminate)
Another layer may be further laminated on the coating film or sheet obtained in the above-described process to form a laminate. Such other layers may be provided on both surfaces of the coating or sheet, but may be provided only on one side of the coating or sheet. As another layer laminated | stacked on at least one surface of a coating film or a sheet | seat, a resin layer and an inorganic layer can be mentioned, for example.

  Specific examples of the laminate include, for example, a laminate in which a resin layer is directly laminated on at least one surface of a coating film or a sheet, 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 obtained by laminating inorganic layer in this order, coating film or sheet, resin layer, laminate obtained by laminating inorganic layer in this order, coating film or sheet, inorganic layer And a laminated body in which resin layers are laminated in this order. The layer configuration of the laminate is not limited to the above, and various embodiments can be made depending on the application.

<Resin layer>
The resin layer is a layer mainly composed of a natural resin or a synthetic resin. Here, the main component refers to a component contained at 50% by mass or more with respect to 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, and still more preferably 80% by mass or more, based on the total mass of the resin layer. It is particularly preferable to be the above. In addition, content of resin can also be 100 mass%, and may be 95 mass% or less.

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

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

  As polycarbonate resin which comprises a resin layer, aromatic polycarbonate-type resin and aliphatic polycarbonate-type resin are mentioned, for example. These specific polycarbonate resins are known, and examples thereof include polycarbonate resins described in JP-A-2010-023275.

  The resin constituting the resin layer may be used alone, or a copolymer obtained by copolymerization or graft polymerization of a plurality of resin components may be used. Also, a plurality of resin components may be used as a blend material mixed in a physical process.

  An adhesive layer may be provided between the coating film or sheet and the resin layer, or the adhesive layer may not be provided, and the coating film or sheet may be in direct contact with the resin layer. When an adhesive layer is provided between a coating film or a sheet and a resin layer, an acrylic resin can be mentioned as an adhesive agent which comprises an adhesive layer, for example. Moreover, as adhesives other than acrylic resin, for example, vinyl chloride resin, (meth) acrylic acid ester resin, styrene / acrylic acid ester copolymer resin, vinyl acetate resin, vinyl acetate / (meth) acrylic acid ester copolymer Polymer resin, urethane resin, silicone resin, epoxy resin, ethylene / vinyl acetate copolymer resin, polyester resin, polyvinyl alcohol resin, ethylene vinyl alcohol copolymer resin, and rubber-based emulsions such as SBR and NBR. Be

When the adhesive layer is not provided between the coating film or the sheet and the resin layer, the resin layer may have a cohesion aid, and the surface of the resin layer is subjected to surface treatment such as hydrophilization treatment. It is also good.
Examples of the adhesion assistant include compounds 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 assistant is preferably at least one selected from a compound containing an isocyanate group (isocyanate compound) and an organic silicon compound. As an organosilicon compound, a silane coupling agent condensate and a silane coupling agent can be mentioned, for example.
As surface treatment methods other than the hydrophilization treatment, corona treatment, plasma discharge treatment, UV irradiation treatment, electron beam irradiation treatment, flame treatment and the like can be mentioned.

<Inorganic layer>
The material constituting the inorganic layer is not particularly limited, but, for example, aluminum, silicon, magnesium, zinc, tin, nickel, titanium; their oxides, carbides, nitrides, oxidized carbides, oxynitrides, or oxycarbonitriding Or mixtures thereof. Silicon oxide, silicon nitride, silicon oxycarbide, silicon oxynitride, silicon oxynitride carbonitride, aluminum oxide, aluminum nitride, aluminum oxycarbide, aluminum oxynitride, or these from the viewpoint of high stability of maintaining high moisture resistance. Mixtures are preferred.

  The method of forming the inorganic layer is not particularly limited. Generally, methods for forming thin films are roughly classified into chemical vapor deposition (CVD) and physical vapor deposition (PVD), but any method may be adopted. . Specific examples of the CVD method include plasma CVD using plasma, and catalytic chemical vapor deposition (Cat-CVD) which catalytically decomposes a material gas using a heating catalyst. Specifically as a PVD method, vacuum evaporation, ion plating, sputtering etc. are mentioned.

  In addition, as a method of forming the inorganic layer, 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 constituting the film to be formed to the surface on which the layer is formed. Although there is a disadvantage that the deposition rate is slow, there is an advantage over the plasma CVD method that it can cleanly cover even complex shapes and can deposit a thin film with few defects. In addition, the ALD method has an advantage that the film thickness can be controlled in nano order, and covering a wide surface is relatively easy. Furthermore, the ALD method can be expected to improve the reaction rate, reduce the temperature to a low temperature, and reduce the unreacted gas by using plasma.

(Use)
The cellulose-containing composition of the present invention can be used as a thickener in various applications.
In addition, 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 a rubber and used as a reinforcing material.
Various films or sheets may be produced using the cellulose-containing composition of the present invention.

  The sheet is suitable for use as a light transmitting substrate such as various display devices and various solar cells. In addition, it is suitable for applications such as substrates of electronic devices, members of household appliances, window materials of various vehicles and buildings, interior materials, exterior materials, packaging materials, and the like. Furthermore, in addition to yarns, filters, fabrics, cushioning materials, sponges, abrasives and the like, the sheet itself is suitable for use as a reinforcing material.

  The features of the present invention will be more specifically described below with reference to examples and comparative examples. The materials, amounts used, proportions, treatment contents, treatment procedures, etc. 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 construed as limited by the specific examples shown below. In addition, in consideration of the convenience of description in the following examples, 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. And what mix | blended fibrous cellulose containing composition, resin, a hardening agent etc. is called a coating material. However, this should not be construed as limiting the scope of the present invention. For example, one containing fine fibrous cellulose such as a paint, a specific component and other components is also included in the scope of the fibrous cellulose-containing composition of the present invention.

<Production of Fine Fibrous Cellulose Dispersion (1)>
(Phosphorus oxidation process)
Softwood kraft pulp manufactured by Oji Paper Co., Ltd. (solid content 93% by mass, basis weight 245 g / m ^{2 in} sheet form, Canadian standard freeness (CSF) of 700 ml determined according to JIS P 8121) 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 (raw dry mass) of the above-mentioned raw material pulp, 33 parts by mass of phosphorous acid (phosphonic acid), 120 parts by mass of urea, water 150 It prepared so that it might become a mass part and the chemical | medical solution impregnated pulp was obtained. Next, the chemical-impregnated pulp obtained was heated for 250 seconds with a hot-air drier at 165 ° C. to introduce a phosphorous group to cellulose in the pulp to obtain a phosphorous-oxidized pulp.

  Then, the resulting phosphorous oxide pulp was washed. After washing the pulp dispersion obtained by pouring 10 L of ion-exchanged water per 100 g (absolute dry mass) of phosphorous oxide pulp, the washing treatment is repeated so as to uniformly disperse the pulp, and then the filtration dewatering operation is repeated. Went by. When the electric conductivity of the filtrate became 100 μS / cm or less, it was regarded as the washing end point.

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

The infrared absorption spectrum of the phosphorous oxide pulp thus obtained was measured using FT-IR. As a result, P = O-based absorption of the phosphonic acid group, which is a tautomer of the phosphite group, was observed around 1210 cm ^-1 , and the phosphite group (phosphonic acid group) was added to the pulp. Was confirmed. In addition, when the obtained phosphorous oxide pulp is 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 are detected. A typical peak was confirmed, and it was confirmed to have cellulose type I crystals. In addition, about the obtained phosphorous oxide pulp, the amount of phosphorous acid groups (the amount of 1st dissociating acid) measured by the measuring method as described in the measurement of the amount of phosphorous acid groups mentioned later is 1.51 mmol / g. The The total amount of dissociated acid was 1.54 mmol / g.

(Disintegration process)
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 three times at a pressure of 200 MPa with a wet atomization apparatus (starburst, manufactured by Sugino Machine Co., Ltd.) to obtain a fine fibrous cellulose dispersion (1) containing fine fibrous cellulose. It was confirmed by X-ray diffraction that this fine fibrous cellulose maintained cellulose type I crystals. Moreover, it was 3-5 nm when the fiber width of fine fibrous cellulose was measured using the transmission electron microscope according to the following measuring method.
In addition, when the 0.4 mass% viscosity of the said fine fibrous cellulose was measured, it was 22400 [mPa * s].

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

<Production of Fine Fibrous Cellulose Dispersion (2)>
In the fine fibrous cellulose dispersion (1), an enzyme-containing solution (manufactured by AB Enzymes Co., Ltd., ECOPULP R, with an enzyme content of about 5% by mass) relative to 1 part by mass of the fine fibrous cellulose is 3.0 × 10 ^{− 6} parts by mass were added and stirred at 18,500 rpm for 2 minutes. This was collected to obtain a fine fibrous cellulose dispersion (2). The fine fibrous cellulose dispersion (2) contains an enzyme.
In addition, when the 0.4 mass% viscosity of the said fine fibrous cellulose was measured, it was 9200 [mPa * s].

<Production of Fine Fibrous Cellulose Dispersion A>
(TEMPO oxidation process)
As raw material pulp, softwood kraft pulp (undried) made by Oji Paper Co., Ltd. was used. The raw material pulp was subjected to alkaline TEMPO oxidation treatment as follows. First, the above raw material pulp equivalent to a dry mass of 100 parts by mass, 1.6 parts by mass of TEMPO (2,2,6,6-tetramethylpiperidine-1-oxyl), 10 parts by mass of sodium bromide, 10000 parts of water It was dispersed in the department. Then, 13 mass% sodium hypochlorite aqueous solution was added so that it might become 3.8 mmol with respect to 1.0 g of pulp, and reaction was started. During the reaction, a 0.5 M aqueous solution of sodium hydroxide was added dropwise to maintain the pH at 10 or more and 10.5 or less, and when no change was observed in the pH, the reaction was regarded as complete.

  Next, the obtained TEMPO oxidized pulp was washed. Washing is performed by dewatering the pulp slurry after TEMPO oxidation to obtain a dewatered sheet, pouring 5000 parts by mass of ion-exchanged water, stirring and uniformly dispersing, and then repeating the operation of filtering and dewatering. The When the electric conductivity of the filtrate became 100 μS / cm or less, it was regarded as the washing end point.

On this dehydrated sheet, additional oxidation treatment of the remaining aldehyde group was performed as follows. The dehydrated sheet equivalent to 100 parts by mass of dry mass was dispersed in 10000 parts by mass of 0.1 mol / L acetate buffer (pH 4.8). Next, 113 parts by mass of 80% sodium chlorite was added and immediately sealed, and then reacted at room temperature for 48 hours while stirring at 500 rpm using a magnetic stirrer to obtain a pulp slurry.
Next, the obtained post-oxidized TEMPO oxidized pulp was washed. The washing treatment is performed by dewatering the pulp slurry after the additional oxidation to obtain a dewatered sheet, pouring 5000 parts by mass of ion exchanged water, stirring and uniformly dispersing, and then repeating the operation of filtering and dewatering. The When the electric conductivity of the filtrate became 100 μS / cm or less, it was regarded as the washing end point.

The amount of carboxy groups measured by the measurement method described later was 1.30 mmol / g for the TEMPO oxidized pulp thus obtained.
In addition, when the obtained TEMPO oxidized pulp is tested and analyzed by an X-ray diffractometer, it is found at two positions of 2θ = 14 ° or more and 17 ° or less and 2θ = 22 or more and 23 ° or less A typical peak was confirmed and confirmed to have cellulose type I crystals.

(Disintegration process)
Ion-exchanged water was added to the obtained TEMPO oxidized pulp to prepare a slurry having a solid content concentration of 2% by mass. This slurry was treated three times at a pressure of 200 MPa with a wet atomization apparatus (starburst, manufactured by Sugino Machine Co., Ltd.) to obtain a fine fibrous cellulose dispersion A containing fine fibrous cellulose. It was confirmed by X-ray diffraction that this fine fibrous cellulose maintained cellulose type I crystals. Moreover, it was 3-5 nm when the fiber width of fine fibrous cellulose was measured using the transmission electron microscope.
In addition, when the 0.4 mass% viscosity of the said fine fibrous cellulose was measured, it was 20400 [mPa * s].

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

<Measurement of phosphorous acid content>
The phosphite group content of the fine fibrous cellulose was prepared by diluting the fine fibrous cellulose dispersion containing the fine fibrous cellulose to be treated with ion-exchanged water to a content of 0.2% by mass. The cellulose-containing slurry was treated with an ion exchange resin and then measured by titration with an alkali.
The treatment with ion exchange resin is carried out by adding 1/10 strongly acidic ion exchange resin (Amberjet 1024; Organo Corporation, conditioned) to the above fibrous cellulose-containing slurry and shaking it for 1 hour It was carried out by pouring on a mesh of 90 μm mesh to separate resin and slurry.
Moreover, the titration using an alkali measures the change of the pH value which a slurry shows, adding 10 microliters of 0.1 N sodium hydroxide aqueous solution for 5 seconds to the fibrous cellulose containing slurry after the process by an ion exchange resin. It did by doing. The titration was performed while blowing nitrogen gas into the slurry 15 minutes before the start of the titration. In this neutralization titration, in the curve obtained by plotting the measured pH against the amount of addition of alkali, two points at which the increment (the differential value of the pH with respect to the amount dropped by the alkali) becomes maximum are observed. Among 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 the titration to the first end point is equal to the amount of the first dissociated acid in the slurry used for the 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 the titration. In addition, the value which remove | divided the amount of alkalis (mmol) required from the titration start to the 1st end point with solid content (g) in the slurry for titration is made the amount of phosphorous acid groups (mmol / g).

<Measurement of amount of carboxy group>
The amount of carboxy groups of the fine fibrous cellulose is obtained by adding ion exchange water to the fine fibrous cellulose-containing slurry containing the fine fibrous cellulose to be treated to have a content of 0.2 mass%, and treating with an ion exchange resin After the measurement, measurement was performed by titration with an alkali.
The treatment with the ion exchange resin is carried out by adding 1/10 by volume of a strongly acidic ion exchange resin (Amberjet 1024; manufactured by Organo Corporation, conditioned) to 0.2% by mass of a fine fibrous cellulose-containing slurry, and one hour After shaking, it was poured onto a mesh of 90 μm mesh to separate resin and slurry.
Moreover, the titration using an alkali measures the change of the pH value which a slurry shows, adding 10 microliters of 0.1 N sodium hydroxide aqueous solution for 5 seconds to the fibrous cellulose containing slurry after the process by an ion exchange resin. It did by doing. When a change in pH is observed while adding an aqueous sodium hydroxide solution, a titration curve as shown in FIG. 2 is obtained. As shown in FIG. 2, in this neutralization titration, in the curve in which the measured pH is plotted against the amount of added alkali, the point at which the increment (the differential value of the pH with respect to the amount dropped by the alkali) becomes maximum is one It is 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 referred to as a first region. The amount of alkali required in the first region is equal to the amount of carboxy groups in the slurry used for titration. And the amount of carboxyl groups introduced (mmol / g) is obtained by dividing the amount of alkali (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. ) Was calculated.
The above-mentioned carboxy group introduction amount (mmol / g) is the amount of substituent per 1 g of fibrous cellulose when the counter ion of the carboxy group is a hydrogen ion (H ⁺ ) (hereinafter, the carboxy group amount (acid Show the 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 mass%, and then stirred with a disperser at 1500 rpm for 5 minutes. Subsequently, the viscosity of the dispersion obtained thereby was measured using a B-type viscometer (analog viscometer T-LVT, manufactured by BLOOKFIELD). The measurement conditions were a rotational speed of 3 rpm, and a viscosity value 3 minutes after the start of measurement was taken as the viscosity of the dispersion. Further, the dispersion to be measured was allowed to stand overnight under an environment of 23 ° C. and a relative humidity of 50% before the measurement. The measurement temperature of viscosity was 23 ° C. Other detailed measurement conditions etc. followed JISZ8803: 2011. Five samples were prepared for one level, and two measurements each were taken for a total of 10 measurements, and the arithmetic mean value was adopted.

<Measurement of supernatant yield after centrifugal separation of fine fibrous cellulose dispersion>
The supernatant yield after centrifuging the fine fibrous cellulose dispersion was measured by the method described below. The supernatant yield after centrifugation is an 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 concentration of 0.2% by mass, and centrifuged at 12000 G for 10 minutes using a cooling high-speed centrifuge (Kokusan Co., Ltd., H-2000B). The obtained supernatant was collected, and the solid concentration of the supernatant was measured. The yield of fine fibrous cellulose was determined based on the following formula.
Supernatant yield (%) = solid concentration of supernatant (%) / 0.2 x 100
Five samples were prepared for one level, and two measurements each were taken for a total of 10 measurements, and the arithmetic mean value was adopted.

Example 1
(Preparation of Fibrous Cellulose-Containing Composition)
A pigment dispersant, DISPERBYK-187 (manufactured by Bick-Chemie, alkylol ammonium salt / acid value: 35 mg KOH / g, amine value: 35 mg KOH / g) was added to ion exchanged water to form an aqueous solution having a solid content concentration of 2% by mass.
100 g of a fine fibrous cellulose dispersion (1) having a solid content concentration of 2% by mass was taken in a beaker, and 360 g of ion exchanged water and 40 g of a 2% by mass aqueous solution of DISPERBYK-187 were added thereto. Addition is T. K. After stirring with a homodisper (manufactured by Tokushu Kika Kogyo Co., Ltd.) at 1500 rpm and stirring for a further 5 minutes after addition of DISPERBYK-187, it is stirred by a degassing apparatus (Shinky Co., autorotation / revolution mixer AR-250). Defoaming treatment was performed.
Thereby, the fibrous form in which the solid content concentration of the fine fibrous cellulose is 0.4% by mass, the solid content concentration of DISPERBYK-187 is 0.016, and the fine fibrous cellulose to DISPERBYK-187 = 100 to 40 (mass ratio) A cellulose-containing composition was obtained.

(Measurement of viscosity of fibrous cellulose-containing composition)
The viscosity of the obtained fibrous cellulose-containing composition is measured by using a B-type viscometer (analog viscometer T-LVT manufactured by BLOOKFIELD, Inc.) after standing overnight under an environment of 23 ° C. and a relative humidity of 50%. did. The measurement conditions were a rotational speed of 3 rpm, and a viscosity value 3 minutes after the start of measurement was taken as the viscosity of the dispersion. The measurement temperature of viscosity was 23 ° C. Other detailed measurement conditions etc. followed JISZ8803: 2011. Five samples were prepared for one level, and two measurements each were taken for a total of 10 measurements, and the arithmetic mean value was adopted.

(Preparation of paint)
24.8 g of the obtained fibrous cellulose-containing composition is weighed in a beaker, and 34.6 g of ion-exchanged water, 35.1 g of an acrylic resin (DIC, product name: Burnock WD-551, solid content concentration 44.1%), A curing agent (manufactured by DIC, product name: Burnock DNW-5500, polyisocyanate, solid concentration 79.8%) was added in the order of 5.5 g. Addition is T. K. After stirring with a homodisper (manufactured by Tokushu Kika Kogyo Co., Ltd.) at 1500 rpm and stirring for a further 5 minutes after all addition, defoaming is carried out using a degassing apparatus (made by Shinky, rotation / revolution mixer AR-250) I did the processing.
Thus, the solid content ratio acrylic resin: 78, curing agent 22, fine fibrous cellulose: 0.5, DISPERBYK-187: 0.2 (mass ratio), and the concentration of total solids is 20% by mass An evaluation paint was obtained.

Example 2
Same as Example 1 except that 2% by mass aqueous solution of DISPERBYK-180 (manufactured by Bick-Chemie, alkylol ammonium salt / acid number: 94 mg KOH / g amine number: 94 mg KOH / g) was used instead of DISPERBYK-187. The paint for evaluation was obtained.

Example 3
In the same manner as in Example 1 except that a 2% by mass aqueous solution of DISPERBYK (Bikk-Chemie, alkylol ammonium salt / acid value: 85 mg KOH / g amine value: 85 mg KOH / g) was used instead of DISPERBYK-187, The paint for evaluation was obtained.

Example 4
The paint for evaluation was obtained like Example 1 except having used 2 mass% aqueous solution of DISPER-AW300P (Otsuka Chemical Co., Ltd. make, methacrylate resin * potassium salt) instead of DISPERBYK-187.

Example 5
A paint for evaluation was obtained in the same manner as in Example 1 except that the fine fibrous cellulose dispersion (2) was used. The fibrous cellulose-containing composition of Example 5 contains an enzyme.

Example 6
The solid content ratio of fine fibrous cellulose to DISPERBYK-187 in the fibrous cellulose-containing composition is 100 to 20 (mass ratio), and the amount taken in preparation of the coating is 24.9 g of fibrous cellulose-containing composition, ion exchanged water A paint for evaluation was obtained in the same manner as in Example 1 except that 34.5 g and 35.2 g of an acrylic resin were used.
(The solid content ratio of the obtained paint for evaluation is acrylic resin: 78, curing agent: 22, fine fibrous cellulose: 0.5, DISPERBYK-187: 0.1 (mass ratio).)

Example 7
The solid content ratio of fine fibrous cellulose to DISPERBYK-187 in the fibrous cellulose-containing composition is 100 to 160 (mass ratio), the amount taken in preparation of paint is 24.7 g of aqueous dispersion, 35 g of ion exchanged water, acrylic A paint for evaluation was obtained in the same manner as in Example 1 except that 34.9 g of a resin and 5.4 g of a curing agent were used.
(The solid content ratio of the obtained coating amount for evaluation is acrylic resin 78, curing agent 22, fine fibrous cellulose 0.5, DISPERBYK-187: 0.8 (mass ratio).)

Example 8
Evaluation was carried out in the same manner as in Example 7 except that a 2% by mass aqueous solution of pigment dispersant DISPER-AW300P (manufactured by Otsuka Chemical Co., Ltd., methacrylate resin / potassium salt / acid number: 120 mg KOH / g) was used instead of DISPERBYK-187. I got the paint for. (The solid content ratio of the obtained paint for evaluation is acrylic resin: 78, curing agent: 22, fine fibrous cellulose: 0.5, DISPWER-AW 300 P: 0.1 (mass ratio).)

Example 9
A paint for evaluation was obtained in the same manner as in Example 8 except that a 2 mass% aqueous solution of pigment dispersant DISPER-AW300P (methacrylate resin, potassium salt, manufactured by Otsuka Chemical Co., Ltd.) was used instead of DISPERBYK-187. (The solid content ratio of the obtained coating amount for evaluation is acrylic resin 78, curing agent 22, fine fibrous cellulose 0.5, DISPWER-AW300P: 0.8 (mass ratio).)

Comparative Example 1
24.9 g of a fine fibrous cellulose dispersion (1) having a solid content concentration of 0.4% by mass was placed in a beaker, and 34.4 g of ion exchanged water, 35.2 g of an acrylic resin, and 5.49 g of a curing agent were added in this order. Addition is T. K. The mixture is stirred with a homodisper (manufactured by Tokushu Kika Kogyo) at 1500 rpm, and after all addition, stirring is performed for 5 minutes, and then defoaming is performed by a degassing apparatus (made by Shinky, rotation / revolution mixer AR-250). Foam treatment was performed.
Thus, a paint for evaluation of the solid content ratio acrylic resin 78, the curing agent 22, and the fine fibrous cellulose 0.5 (mass ratio) was obtained.

Comparative Example 2
A paint for evaluation was obtained in the same manner as in Comparative Example 1 except that the fine fibrous cellulose dispersion A was used.

Comparative Example 3
A paint for evaluation was obtained in the same manner as in Example 1 except that a 2% by mass aqueous solution of a pigment dispersant DISPERBYK-193 (manufactured by Bick-Chemie, non-ionic dispersant) was used instead of DISPERBYK-187.

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

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

  From the above results, it can be seen that the fibrous cellulose-containing composition of the present invention is excellent in coatability when used as a paint (Examples 1 to 9), and the amount of foreign matter in the film after application is small. In addition, it can be seen that by using the fibrous cellulose-containing composition of the present invention, the surface of the coating film can be made smooth if necessary, and the Young's modulus and strength of the coating film practically suitable can be realized. On the other hand, in the case of using the fibrous cellulose-containing composition (Comparative Examples 1 and 2) not containing the specific component according to the present invention (Comparative Examples 1 and 2) or the nonionic dispersant (Comparative Example 3), the coatability is inferior and The coating surface has become rough.

(Creating a coating for appearance evaluation)
Using the obtained paint, a PET (polyethylene terephthalate) film (manufactured by Toray Industries, product name: Lumirror T60, thickness 75 μm) was used as a substrate, and coated using an applicator so that the thickness of the coated film after drying was 30 μm. Immediately after coating, the coated film was heated for 30 minutes with a dryer at a temperature of 80 ° C. to obtain a coated film of a cured coating film using a PET film as a substrate. In addition, the thickness of the coating film was measured by a stylus thickness gauge (Miritron 1202D, manufactured by Marle), and an arithmetic average value of 20 points was adopted. Details of other measurement conditions, calculation methods and the like were performed according to JIS P 8118: 2014.

(Surface roughness)
Measurement range 470.92 μm × 353.16 μm with an × 10 objective lens using a non-contact optical surface profilometer (non-contact surface / layer cross-section profile measurement system VertScan 2.0, model: R5500 GML, manufactured by Ryoka Systems Co., Ltd.) Arithmetic mean roughness (Ra) was measured. The measurement was performed 5 times per level, and the arithmetic average roughness was determined from the average value. Details of the definition of arithmetic mean roughness (Ra), measurement conditions, calculation method and the like were performed according to JIS B 0601: 2013.

(Evaluation of coatability)
It performs observation of the coating prepared by the base PET film using an optical microscope (manufactured by Nikon Corporation), confirmed over 5μm during 1 mm ² in size of the aggregates number N (the number / mm ²⁾ at 20 sites The arithmetic mean value (N / 20) was obtained from the mean value. The measurement was performed 5 times per level and the average value was adopted. The numerical values (pieces / mm ² ) are shown in the table, and the results are evaluated as follows.
There are 3 particles / mm ² or more with size 5μm or more: ×
Less than 3 particles / mm ² with or without size 5 μm or more: ○
In addition, the magnitude | size of particle | grains was made into a circle equivalent diameter, and the details of measurement conditions, a calculation method, etc. were performed according to JISZ8827-1: 2008.

(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 “coating film preparation for appearance evaluation” except that a PP (polypropylene) film (manufactured by Toray Industries, product name: Trefan BO, thickness 60 μm) was used as a substrate.
The coated film was peeled off from the PP film and used as a sample for evaluation of strength and Young's modulus.

(Young's modulus of the coating)
The Young's modulus was calculated using a tensile tester Tensilon (manufactured by A & D Co., Ltd.) 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 a Young's modulus, what was humidity-controlled by 23 degreeC and 50% of relative humidity for 24 hours was used as a test piece. The measurement was performed 5 times per level, and the average value was adopted.

(Strength of coating film)
The strength (tensile strength) of the coating film prepared using the fibrous cellulose-containing composition of the reference example was taken as the base strength. At this time, the test machine, the test conditions and the compliance standard were the same as the measurement of the above Young's modulus. A test was similarly performed about each test piece of an Example and a comparative example, and what 20% or more of strength (tensile strength) increased from base strength was made into "(circle)". The thing of 10% or more and less than 20% was made into "(triangle | delta)", and the thing of less than 10% was made into "x". The measurement was performed 5 times per level, and the average value was adopted.

Claims (14)

  A fibrous cellulose-containing composition comprising a fibrous cellulose having a fiber width of 1,000 nm or less and having a phosphite group or a substituent derived from a phosphite group, and a pigment dispersant having an ionic group, The fibrous cellulose-containing composition, wherein the acid value of the pigment dispersant is 5 mg KOH / g to 200 mg KOH / g, or the amine value of the pigment dispersant is 5 mg KOH / g to 200 mg KOH / g.   The fibrous cellulose-containing composition according to claim 1, wherein the pigment dispersant is an alkylol ammonium salt or a (meth) acrylate resin / potassium salt.   The fibrous cellulose-containing composition according to claim 1 or 2, wherein the weight average molecular weight of the pigment dispersant is 1,000 or more and 100,000 or less. The surface roughness Ra of the coating film obtained by the following conditions is 0.20 micrometer or less, The fibrous cellulose containing composition of any one of Claims 1-3.
(conditions)
Coating obtained by mixing the fibrous cellulose-containing composition, 156 parts by mass of an acrylic resin to 1 part by mass of the fibrous cellulose, and 44 parts by mass of polyisocyanate to 1 part by mass of the fibrous cellulose The solution is coated on a smooth polyethylene terephthalate plate to a thickness of 30 μm using an applicator and immediately after coating, it is dried at 80 ° C. for 30 minutes.   The total amount of the said fibrous cellulose, the said pigment dispersant, and water is 90 mass% or more with respect to the whole composition, The fibrous cellulose containing composition of any one of Claims 1-4.   Content of the said pigment dispersant is 10 mass parts or more with respect to 100 mass parts of fibrous cellulose, The fibrous cellulose containing composition of any one of Claims 1-5.   The fiber according to any one of claims 1 to 6, which has a viscosity of 40,000 mPa · s or less when measured at 23 ° C and a rotational speed of 3 rpm with a solid content concentration of the fibrous cellulose of 0.4% by mass. Cellulose-containing composition. The fibrous cellulose content according to any one of claims 1 to 7, wherein when the fibrous cellulose is used as a dispersion and the supernatant separated from the dispersion under the following conditions is recovered, the supernatant yield is 80% by mass or more. Composition.
(conditions)
The dispersion of fibrous cellulose is adjusted to a solid concentration of 0.2% by mass, and centrifuged at 12000 G for 10 minutes using a cooling high-speed centrifuge. The obtained supernatant was collected, and the solid concentration of the supernatant was measured. The yield of fibrous cellulose is determined based on the following formula.
Supernatant yield (%) = solid concentration of supernatant (%) / 0.2 x 100 The Young's modulus of the coating film obtained according to the following conditions is 0.7 GPa or more, The fibrous cellulose containing composition of any one of Claims 1-8.
(conditions)
Coating obtained by mixing the fibrous cellulose-containing composition, 156 parts by mass of an acrylic resin to 1 part by mass of the fibrous cellulose, and 44 parts by mass of polyisocyanate to 1 part by mass of the fibrous cellulose The solution is coated on a smooth polypropylene plate to a thickness of 30 μm using an applicator and immediately after coating, it is dried at 80 ° C. for 30 minutes.   The fibrous cellulose-containing composition according to any one of claims 1 to 9, further comprising an enzyme.   The fibrous cellulose-containing composition according to any one of claims 1 to 10 for use in paints.   11. A fibrous cellulose-containing composition according to any one of claims 1 to 10 for use in thickeners.   The coating material containing the fibrous cellulose containing composition of any one of Claims 1-12.   A kit for a fibrous cellulose-containing composition, which comprises a fibrous cellulose having a fiber width of 1,000 nm or less and having a phosphite group or a substituent derived from a phosphite group, and a pigment dispersant having an ionic group. .

Images