Cellulose-containing composition, method for producing same, and method for adjusting viscosity

Abstract

A composition containing cellulose and a thickener, wherein the cellulose contains oxidized cellulose that is an oxide of a cellulosic raw material oxidized using hypochlorous acid or a salt thereof, and / or nanocellulose that is a defibrated material of the oxidized cellulose, and the cellulose is substantially free of N-oxyl compounds.

Description

Cellulose-containing composition, method for producing same, and method for adjusting viscosity

[0001] The present invention relates to a cellulose-containing composition, a method for producing the same, and a method for adjusting viscosity.

[0002] Various techniques have been proposed for producing nanocellulose materials by oxidizing various cellulosic raw materials with an oxidizing agent and then micronizing the resulting oxidized cellulose.

[0003] For example, Patent Document 1 discloses a method for producing cellulose nanofibers, which includes a step of oxidizing a cellulosic raw material using hypochlorous acid or a salt thereof having an available chlorine concentration of 14 to 43% by mass to produce oxidized cellulose, and a step of defibrating the oxidized cellulose to nanosize it. Patent Document 2 also discloses a method for producing oxidized cellulose, which involves oxidizing a cellulosic raw material using hypochlorous acid or a salt thereof having an available chlorine concentration of 6 to 14% by mass while adjusting the pH to a range of 5.0 to 14.0. These methods perform the oxidation treatment without using N-oxyl compounds such as 2,2,6,6-tetramethyl-1-piperidine-N-oxy radical (TEMPO), so no N-oxyl compounds remain in the cellulose fibers, thereby reducing their impact on the environment, etc.

[0004] Patent Document 3 discloses oxidized cellulose, which is an oxidation product of a cellulosic raw material with hypochlorous acid or a salt thereof, which is substantially free of N-oxyl compounds and has a degree of polymerization of 600 or less. Patent Document 4 discloses nanocellulose, which is an oxidation product of a cellulosic raw material with hypochlorous acid or a salt thereof, which has an average fiber width of 1 nm or more and 200 nm or less, which is substantially free of N-oxyl compounds, and has a zeta potential of -30 mV or less.

[0005] International Publication No. WO 2018 / 230354 International Publication No. WO 2020 / 027307 International Publication No. WO 2022 / 009979 International Publication No. WO 2022 / 009980

[0006] An object of the present invention is to provide a composition that contains oxidized cellulose, which is an oxidation product of a cellulosic raw material with hypochlorous acid or a salt thereof, and / or nanocellulose, which is a defibrated product of the oxidized cellulose, and that has a suitably adjustable (or adjusted) viscosity.

[0007] The present inventors have found that when a dispersion containing oxidized cellulose, which is an oxidation product of a cellulose-based raw material using hypochlorous acid or its salt, and / or nanocellulose, which is a defibrated product of the oxidized cellulose, is mixed with a thickener, the viscosity increases significantly.

[0008] The present invention includes the following embodiments. [1] A composition comprising cellulose and a thickener, wherein the cellulose comprises oxidized cellulose, which is an oxidation product of a cellulose-based raw material with hypochlorous acid or a salt thereof, and / or nanocellulose, which is a defibrated product of the oxidized cellulose, and the composition is substantially free of N-oxyl compounds. [2] A composition comprising cellulose and a thickener, wherein the cellulose comprises oxidized cellulose having a structure in which dicarboxy groups have been introduced by oxidizing the second and third hydroxyl groups of the glucopyranose ring, and / or nanocellulose, which is a defibrated product of the oxidized cellulose. [3] The composition of claim [1] or [2], wherein the thickener is a thickening polysaccharide. [4] The composition of any of claims [1] to [3], wherein the thickener has a hydrophobic region capable of hydrophobic interaction with the oxidized cellulose. [5] The composition of any of claims [1] to [4], wherein the amount of the thickener is 0.1 to 40% by mass relative to the mass (solid content) of the oxidized cellulose. [6] The composition according to any one of claims [1] to [5], further comprising a salt. [7] The composition according to [6], wherein the amount of the salt is 0.01 to 10% by mass relative to the composition. [8] The composition according to any one of claims [1] to [7], further comprising a pH adjuster. [9] The composition according to [8], wherein the pH of the composition is in the range of 0 to 14.0.

[10] The composition according to [8] or [9], wherein the pH adjuster comprises an acid or a base.

[11] The composition according to any one of claims [1] to

[10] , wherein the cellulose comprises nanocellulose.

[12] The composition according to any one of claims [1] to

[11] , wherein the composition is an aqueous composition.

[13] The composition according to

[12] , wherein the viscosity of the aqueous composition is 0.01 to 1,000 Pa s.

[14] The viscosity of the aqueous composition is 10 to 1 x 10 higher than the viscosity of a control composition obtained by omitting the thickener from the aqueous composition. ６% higher.

[15] A composition comprising cellulose and a thickener, wherein the cellulose comprises oxidized cellulose, which is an oxidation product of a cellulose-based raw material with hypochlorous acid or a salt thereof, and / or nanocellulose, which is a defibrated product of the oxidized cellulose, and is substantially free of N-oxyl compounds, and the pH of the composition is within the range of 0 to 14.0.

[16] A composition comprising cellulose and a thickener, wherein the cellulose comprises oxidized cellulose having a structure in which the second and third hydroxyl groups of the glucopyranose ring are oxidized to introduce dicarboxy groups, and / or nanocellulose, which is a defibrated product of the oxidized cellulose, and the pH of the composition is within the range of 0 to 14.0.

[17] The composition according to any of claims [1] to

[16] , wherein the composition is a cosmetic.

[18] A method for producing a composition, comprising the step of mixing cellulose with a thickener, wherein the cellulose comprises oxidized cellulose, which is an oxidation product of a cellulosic raw material with hypochlorous acid or a salt thereof, and / or nanocellulose, which is a defibrated product of the oxidized cellulose, and the method is substantially free of N-oxyl compounds.

[19] A method for producing a composition, comprising the step of mixing cellulose with a thickener, wherein the cellulose comprises oxidized cellulose having a structure in which dicarboxy groups have been introduced by oxidation of the second and third hydroxyl groups of the glucopyranose ring, and / or nanocellulose, which is a defibrated product of the oxidized cellulose.

[20] A method for adjusting the viscosity of an aqueous composition containing cellulose, comprising the step of mixing the aqueous composition with a thickener, wherein the cellulose comprises oxidized cellulose, which is an oxidation product of a cellulosic raw material with hypochlorous acid or a salt thereof, and / or nanocellulose, which is a defibrated product of the oxidized cellulose, and the method is substantially free of N-oxyl compounds.

[21] A method for adjusting the viscosity of an aqueous composition containing cellulose, comprising the step of mixing the aqueous composition with a thickener, wherein the cellulose comprises oxidized cellulose having a structure in which the second and third hydroxyl groups of the glucopyranose ring are oxidized to introduce dicarboxy groups, and / or nanocellulose, which is a defibrated product of the oxidized cellulose.

[22] By mixing the aqueous composition with the thickener, the viscosity of the aqueous composition is adjusted to 10 to 1 x 10. ６ The method according to

[20] or

[21] , wherein the concentration of hydroxybenzoates in the blood is increased by %.

[0009] The present invention can provide a composition that contains oxidized cellulose, which is an oxidation product of a cellulosic raw material using hypochlorous acid or a salt thereof, and / or nanocellulose, which is a defibrated product of the oxidized cellulose, and that has a suitably adjustable (or adjusted) viscosity.

[0010]

[0023] Figure 1 shows the viscosities of various CNFs and mixtures of the CNFs and methyl cellulose (10% by mass relative to the CNF mass).

[0024] Figure 1 shows the viscosities of various CNFs and mixtures of the CNFs and methyl cellulose (2% by mass relative to the CNF mass).

[0025] Figure 1 shows the viscosities of various CNFs and mixtures of the CNFs and methyl cellulose (10% by mass relative to the CNF mass).

[0026] Figure 1 shows the viscosities of various CNFs and mixtures of the CNFs and methyl cellulose (2% by mass relative to the CNF mass).

[0027] Figure 1 shows the viscosities of emulsions containing acrylic resins and mixtures of the emulsions with CNF and / or methyl cellulose.

[0028] Figure 1 shows the viscosities of CNFs, mixtures of CNFs and methyl cellulose (1.4%, 7.1%, and 14% by mass relative to the CNF mass), and mixtures of CNFs and guar gum (1.4%, 7.1%, and 14% by mass relative to the CNF mass).

[0033] Figure 1 shows the viscosity of compositions with different salt concentrations (Example 5 and Comparative Example 4). Figure 2 shows the viscosity of compositions with different salt concentrations (Example 5 and Comparative Example 5). Figure 3 shows the viscosity of compositions with different salt concentrations (Example 5 and Comparative Example 6). Figure 4 shows the viscosity of compositions with different salt concentrations (Example 5 and Comparative Example 7). Figure 5 shows the relationship between pH and viscosity for each of the compositions of Example 6 and Comparative Examples 8 and 9.

[0011] Hereinafter, embodiments of the present invention will be described in detail, but the present invention is not limited to these and various modifications are possible without departing from the gist of the present invention.

[0012] <Composition> One embodiment of the present invention relates to a composition comprising oxidized cellulose, which is an oxidation product of a cellulosic raw material with hypochlorous acid or a salt thereof, and / or nanocellulose, which is a defibrated product of the oxidized cellulose, and a thickener.

[0013] Dispersions containing oxidized cellulose and / or nanocellulose in this embodiment tend to have lower viscosities than dispersions containing oxidized cellulose and / or nanocellulose (hereinafter also referred to as "comparative cellulose") obtained by other methods (e.g., TEMPO oxidation or mechanical fiberization). Surprisingly, dispersions containing comparative cellulose are less likely to increase in viscosity when mixed with a thickener, whereas dispersions containing oxidized cellulose and / or nanocellulose in this embodiment increase in viscosity significantly when mixed with a thickener. Therefore, viscosity can be increased with a small amount of thickener, making viscosity adjustment easy.

[0014] Furthermore, the dispersion containing oxidized cellulose and / or nanocellulose in this embodiment preferably exhibits thixotropy, and therefore the viscosity can be temporarily reduced by applying force. As a result, for example, when the dispersion containing oxidized cellulose and / or nanocellulose in this embodiment is used as a paint, cosmetic, etc., the viscosity is reduced during application, making it easier to use, and the viscosity increases and is easily maintained after application.

[0015] The reason why the viscosity increases significantly when the oxidized cellulose and / or nanocellulose is mixed with the thickener in this embodiment is presumed to be due to an interaction (preferably a hydrophobic interaction) between the oxidized cellulose and / or nanocellulose and the thickener, but the present invention is not limited by this presumption.

[0016] The pH of the composition according to this embodiment is not particularly limited, but is preferably in the range of 0 to 14.0 from the viewpoint of suppressing a decrease in viscosity.

[0017] The lower limit of the pH of the composition according to this embodiment is preferably 2.0, more preferably 2.5, from the viewpoint of maintaining viscosity. The upper limit of the pH of the composition according to this embodiment is preferably 13.0, more preferably 12.0, from the viewpoint of maintaining viscosity. The pH of the composition according to this embodiment is preferably 2.0 or more and 13.0 or less, more preferably 2.5 or more and 12.0 or less.

[0018] The pH of the composition of this embodiment may be in the range of 0 or more and less than 7.0, 0 or more and 6.9 or less, 0 or more and 6.8 or less, 0 or more and 6.7 or less, 0 or more and 6.6 or less, 0 or more and 6.5 or less, more than 7.0 and 14.0 or less, 7.1 or more and 14.0 or less, 7.2 or more and 14.0 or less, 7.3 or more and 14.0 or less, 7.4 or more and 14.0 or less, or 7.5 or more and 14.0 or less.

[0019] The pH range of the composition according to this embodiment may be a range that is a combination of the above ranges, such as a range of 0 or more and less than 7.0, and more than 7.0 and 14.0 or less; or a range of 0 or more and less than 7.0, and 7.5 or more and 14.0 or less.

[0020] The pH of the composition can be adjusted, for example, by adding a pH adjuster described below.

[0021] The pH of the composition of this embodiment can be measured using a pH meter.

[0022] The amount of oxidized cellulose and / or nanocellulose in this embodiment is not particularly limited, but is preferably 0.01 to 50% by mass, more preferably 0.1 to 30% by mass, even more preferably 0.1 to 20% by mass, and particularly preferably 0.1 to 15% by mass, relative to the mass of the composition. When both oxidized cellulose and nanocellulose are contained in the composition, the above amount refers to the total amount of oxidized cellulose and nanocellulose.

[0023] The composition according to this embodiment may not contain a dispersion medium. In other words, the composition according to this embodiment may be in a dry state. The dry composition can be mixed with a dispersion medium as needed to adjust the viscosity to an appropriate level.

[0024] The composition according to the present embodiment preferably contains a dispersion medium. The dispersion medium preferably contains water, and from the viewpoint of safety, more preferably contains only water. In this specification, a composition containing water as a dispersion medium is referred to as an "aqueous composition."

[0025] The viscosity of the aqueous composition according to this embodiment may be adjusted appropriately depending on the intended use, and may be, for example, 0.01 to 1000 Pa·s, 0.1 to 100 Pa·s, or 0.1 to 10 Pa·s.

[0026] In this specification, unless otherwise specified, the "viscosity" is measured using a shear type rheometer at 25°C and 0.01 to 100 s －１ When the measurement was performed at a shear rate of 0.1 s －１ The viscosity is measured at a shear rate of 100 MPa. A specific method for measuring the viscosity is as described in the Examples below.

[0027] The viscosity of the aqueous composition according to this embodiment is 10 s －１ In the measurement of the shear rate, the viscosity of the aqueous composition is 10 to 1 × 10 higher than that of a control composition obtained by removing the thickener from the aqueous composition. ６ % higher, preferably 100 to 1×10 ５ % higher, more preferably 1×10 ３ ~1 x 10 ５The viscosity increase rate is calculated by the following formula: Viscosity increase rate (%) = [(viscosity of aqueous composition - viscosity of control composition) / (viscosity of control composition)] x 100

[0028] [Oxidized Cellulose] In the present embodiment, oxidized cellulose refers to an oxide of a cellulose-based raw material with hypochlorous acid or a salt thereof before defibration.

[0029] Examples of hypochlorous acid or salts thereof include hypochlorous acid water, sodium hypochlorite, potassium hypochlorite, calcium hypochlorite, and ammonium hypochlorite.

[0030] Although the amount of hypochlorous acid or its salt to be used is not particularly limited, it is preferable to use it so that the effective chlorine concentration in the reaction system is 6 to 43 mass%. The effective chlorine concentration may be a low concentration of 6 to 14 mass% or a high concentration of 14 to 43 mass%.

[0031] The definition of the effective chlorine concentration of hypochlorous acid or a salt thereof is as described in WO 2022 / 009979.

[0032] The cellulosic raw material is not particularly limited as long as it is a material primarily composed of cellulose, and examples thereof include pulp, natural cellulose, and fine cellulose obtained by depolymerizing cellulose through mechanical processing. The cellulosic raw material preferably has a type I crystal structure. Commercially available cellulose-based raw materials, such as crystalline cellulose derived from pulp, can be used as is. Alternatively, unused biomass containing a large amount of cellulose, such as soybean hulls or soybean pulp, may also be used as the raw material. Furthermore, the cellulosic raw material may be pre-treated with an appropriate concentration of alkali to facilitate the penetration of the oxidizing agent into the raw pulp. Cellulose is the main component of plants, and bundles of cellulose molecules are called cellulose microfibrils. The cellulose in the cellulosic raw material is also present in the form of cellulose microfibrils.

[0033] (N-oxyl compounds) The oxidized cellulose of the present embodiment is substantially free of N-oxyl compounds. By being substantially free of N-oxyl compounds, its impact on the environment and human body is sufficiently reduced, resulting in a high level of safety. An example of an N-oxyl compound is 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO).

[0034] As used herein, "substantially free of N-oxyl compounds" means that no N-oxyl compounds are used in producing the oxidized cellulose, that the oxidized cellulose contains no N-oxyl compounds, or that the content of N-oxyl compounds is 2.0 ppm by mass or less, preferably 1.0 ppm by mass or less, relative to the total amount of oxidized cellulose. Furthermore, when the content of N-oxyl compounds, as an increase from the cellulosic raw material, is preferably 2.0 ppm by mass or less, more preferably 1.0 ppm by mass or less, it is also considered to be "substantially free of N-oxyl compounds."

[0035] The content of N-oxyl compounds can be measured by known means, such as a method using a trace total nitrogen analyzer (for example, TN-2100H manufactured by Nitto Seiko Analytech Co., Ltd.).

[0036] (Carboxy group amount) The carboxy group amount of the oxidized cellulose in this embodiment is preferably 0.1 to 3.0 mmol / g, more preferably 0.2 to 2.0 mmol / g, even more preferably 0.3 to 1.5 mmol / g, particularly preferably 0.4 to 1.2 mmol / g, and most preferably 0.5 to 0.9 mmol / g.

[0037] The amount of carboxy groups in oxidized cellulose can be measured by the method described in WO 2022 / 009979.

[0038] The oxidized cellulose in this embodiment preferably has a structure in which at least two of the hydroxyl groups on the glucopyranose ring that constitutes the cellulose are oxidized, and more specifically, preferably has a structure in which the hydroxyl groups at the second and third positions on the glucopyranose ring are oxidized and dicarboxyl groups are introduced. Furthermore, it is preferable that the hydroxyl group at the sixth position on the glucopyranose ring is not oxidized and remains as a hydroxyl group. The position of the carboxyl group on the glucopyranose ring is determined by the solid １３ It can be analyzed by C-NMR spectrum.

[0039] Rayon has the same chemical structure as cellulose, and its oxide (rayon oxide) is water-soluble. １３ By performing C-NMR measurement, a carbon peak attributable to a carboxy group is observed at 165 to 185 ppm. In one embodiment of the oxidation of a cellulosic raw material with hypochlorous acid or its salt, two signals appear in this chemical shift range. Furthermore, by solution two-dimensional NMR measurement, it can be determined that the carboxy groups are introduced at the 2- and 3-positions.

[0040] Solid oxide of cellulosic raw materials with hypochlorous acid or its salts １３ In C-NMR, when the amount of carboxyl groups introduced is large, two signals appear at 165 to 185 ppm, and when the amount of carboxyl groups introduced is small, a very broad signal may appear. As can be seen from the results for oxidized rayon, the signals of the carboxyl group carbons introduced at the 2nd and 3rd positions are close to each other, and the signals are not clearly visible in solid state analysis with low resolution. １３ In C-NMR, the separation of the two signals is insufficient. Therefore, when the amount of carboxyl group introduced is small, a broad signal is observed. １３ In the C-NMR spectrum, the introduction of carboxy groups at the 2- and 3-positions can be confirmed by evaluating the broadening of the peak appearing at 165 to 185 ppm.

[0041] That is, solid １３A baseline is drawn around the peak in the range of 165 ppm to 185 ppm in a C-NMR spectrum to determine the overall area value, and then the area value is vertically divided at the peak top to determine the ratio of the two peak area values ​​(larger area value / smaller area value). If this peak area value ratio is 1.2 or greater, the peak is considered to be broad. The presence or absence of a broad peak can be determined by the ratio of the length L of the baseline in the range of 165 ppm to 185 ppm to the length L' of the perpendicular line from the peak top to the baseline. That is, if the ratio L' / L is 0.1 or greater, it can be determined that a broad peak is present. The ratio L' / L may be 0.2 or greater, 0.3 or greater, 0.4 or greater, or 0.5 or greater. The upper limit of the ratio L' / L is not particularly limited, but it is usually 3.0 or less, or may be 2.0 or less, or 1.0 or less.

[0042] The structure of the glucopyranose ring can also be determined by analysis according to the method described in Sustainable Chem. Eng. 2020, 8, 48, 17800-17806.

[0043] (Viscosity-average degree of polymerization) The viscosity-average degree of polymerization of the oxidized cellulose in this embodiment is preferably 30-500, more preferably 60-300, even more preferably 70-150, and particularly preferably 80-130.

[0044] The viscosity average degree of polymerization is the average degree of polymerization measured by a viscosity method. The viscosity average degree of polymerization can be measured by the method described in WO 2022 / 009979.

[0045] [Method for producing oxidized cellulose] The oxidized cellulose in this embodiment can be produced by oxidizing a cellulosic raw material with hypochlorous acid or a salt thereof. Specific production methods include those described in WO 2022 / 009979 and WO 2022 / 009980. Oxidized cellulose is also available as a commercially available product, such as Aronfibro (registered trademark) manufactured by Toagosei Co., Ltd.

[0046] [Nanocellulose] Nanocellulose in this embodiment refers to an oxide of a cellulose-based raw material with hypochlorous acid or a salt thereof, after defibration.

[0047] Nanocellulose is a general term for micronized cellulose, and includes micronized cellulose fibers and cellulose nanocrystals (CNC). Micronized cellulose fibers are also called cellulose nanofibers (CNF). From the viewpoint of increasing viscosity, nanocellulose is preferably CNF. Nanocellulose preferably has an amorphous portion. CNF has an amorphous portion, whereas CNC does not have an amorphous portion.

[0048] The nanocellulose in this embodiment contains a carboxyl group. The carboxyl group may be in the H type (—COOH) or in the salt type. The type of salt is not particularly limited, but examples include alkali metal salts such as lithium salts, sodium salts, and potassium salts; alkaline earth metal salts such as calcium salts and barium salts; other metal salts such as magnesium salts and aluminum salts; ammonium salts, and organic amine salts.

[0049] Nanocellulose is a collection of individual fibers. When nanocellulose contains carboxylated nanocellulose, it is sufficient that it contains at least one carboxylated nanocellulose, and it is preferable that carboxylated nanocellulose is the main component. Here, carboxylated nanocellulose being the main component means that the proportion of carboxylated nanocellulose in the total amount of nanocellulose exceeds 50% by mass, preferably exceeds 70% by mass, and more preferably exceeds 80% by mass. The upper limit of the above proportion is 100% by mass, but it may also be 98% by mass or 95% by mass.

[0050] (N-oxyl compounds) The nanocellulose in this embodiment is substantially free of N-oxyl compounds. The meaning of "nanocelulose is substantially free of N-oxyl compounds" and the method for measuring the content of N-oxyl compounds are as described in the (N-oxyl compounds) section of [Oxidized Cellulose] above.

[0051] (Carboxy group amount) The carboxy group amount of nanocellulose in this embodiment and the method for measuring it shall follow the description in the (Carboxy group amount) section of [Oxidized cellulose] above.

[0052] (Average fiber length) The average fiber length of the nanocellulose in this embodiment is preferably 50 to 700 nm, more preferably 50 to 500 nm, even more preferably 50 to 300 nm, still more preferably 60 to 300 nm, and particularly preferably 70 to 200 nm.

[0053] (Average fiber width) The average fiber width of the nanocellulose in this embodiment is preferably 1 to 200 nm, more preferably 1 to 15 nm, even more preferably 1 to 10 nm, and particularly preferably 1 to 5 nm.

[0054] The average fiber width and average fiber length of nanocellulose can be measured by the method described in WO 2022 / 009980.

[0055] (Aspect Ratio) The aspect ratio (average fiber length / average fiber width) of the nanocellulose in this embodiment is preferably 20 to 200, more preferably 30 to 190, and even more preferably 40 to 180.

[0056] (Zeta potential) The zeta potential of the nanocellulose in this embodiment is preferably −30 mV or less, more preferably −90 mV or more and −30 mV or less, even more preferably −80 mV or more and −30 mV or less, still more preferably −70 mV or more and −30 mV or less, and particularly preferably −65 mV or more and −35 mV or less.

[0057] The zeta potential can be measured by the method described in WO 2022 / 009980.

[0058] (Light transmittance) The nanocellulose dispersion in this embodiment, in which nanocellulose is dispersed in a dispersion medium, has little light scattering by cellulose fibers and can exhibit high light transmittance. Specifically, the light transmittance of a mixed solution in which nanocellulose is mixed with water to a solids concentration of 0.1% by mass is preferably 95% or more, more preferably 96% or more, even more preferably 97% or more, and particularly preferably 99% or more. The light transmittance is the value at a wavelength of 660 nm measured using a spectrophotometer.

[0059] The light transmittance can be measured by the method described in WO 2022 / 009979.

[0060] [Method for producing nanocellulose] The nanocellulose in this embodiment can be produced by defibrating the above-mentioned oxidized cellulose. Specific production methods include those described in WO 2022 / 009979 and WO 2022 / 009980. Nanocellulose can also be obtained by defibrating commercially available oxidized cellulose (for example, Aronfibro (registered trademark) manufactured by Toagosei Co., Ltd.).

[0061] [Thickener] The composition according to this embodiment contains a thickener. By combining the oxidized cellulose and / or nanocellulose according to this embodiment with a thickener, it is possible to significantly increase the viscosity. One type of thickener may be used alone, or two or more types may be used in combination.

[0062] The thickener is preferably a thickening polysaccharide. The thickening polysaccharide is preferably water-soluble. In this specification, "water-soluble" means that the amount that dissolves in 100 g of water at 20°C is 1 g or more. The amount that dissolves is preferably 3 g or more, more preferably 10 g or more, and even more preferably 20 g or more.

[0063] Examples of thickening polysaccharides include methylcellulose, carboxymethylcellulose, guar gum, xanthan gum, locust bean gum, cassia gum, gellan gum, psyllium seed gum, tragacanth gum, karaya gum, gum arabic, gum ghatti, tara gum, tamarind seed gum, carrageenan, pectin, pullulan, curdlan, starch, gelatin, agar, alginic acid, and soybean polysaccharides.

[0064] The thickener may be a thickener having a hydrophobic region capable of hydrophobic interaction with the oxidized cellulose and / or nanocellulose in this embodiment (hereinafter referred to as a "hydrophobic thickener").

[0065] Examples of the hydrophobic region of the hydrophobic thickener include a continuous cyclic structure and a linear or branched hydrocarbon chain structure.

[0066] A hydrophobic thickener having a continuous cyclic structure can be obtained, for example, by polymerizing a monomer having a cyclic structure. Examples of the cyclic structure include an aromatic hydrocarbon structure and an alicyclic hydrocarbon structure. The cyclic structure is preferably a cycloalkane structure, more preferably a cyclohexane structure. The thickening polysaccharides generally have a continuous cyclohexane structure, and therefore are included in the hydrophobic thickeners.

[0067] The amount of thickener can be adjusted appropriately depending on the desired viscosity, but in this embodiment, it is preferably 0.1 to 40% by mass, more preferably 0.3 to 35% by mass, even more preferably 0.5 to 30% by mass, and particularly preferably 0.5 to 20% by mass, relative to the mass (solid content) of oxidized cellulose and / or nanocellulose. When both oxidized cellulose and nanocellulose are contained in the composition, the "mass (solid content) of oxidized cellulose and / or nanocellulose" refers to the "total mass (solid content) of oxidized cellulose and nanocellulose." The viscosity of the dispersion containing oxidized cellulose and nanocellulose in this embodiment can be significantly increased with a small amount of thickener.

[0068] [Salt] The composition according to this embodiment may further contain a salt. As used herein, a salt is a compound consisting of a positive ion (hereinafter also referred to as a "cation") and a negative ion (hereinafter also referred to as an "anion"). The viscosity increased by combining the oxidized cellulose and / or nanocellulose with a thickener according to this embodiment can be maintained without decrease even when a salt is contained.

[0069] As mentioned above, the mechanism of the viscosity increase is presumed to be due to the interaction (preferably hydrophobic interaction) between the oxidized cellulose and / or nanocellulose and the thickener, and since this interaction is not easily affected by salt, it is presumed that the decrease in viscosity is suppressed even in the presence of salt.

[0070] The salts may be used alone or in combination of two or more.

[0071] The salt may be an inorganic salt, an organic salt, or a mixture thereof.

[0072] Examples of cations constituting inorganic salts or organic salts include lithium ions (Li + ), sodium ions (Na + ), potassium ions (K + ions of alkali metals such as magnesium ions (Mg 2+ ), calcium ions (Ca 2+ ions of alkaline earth metals such as iron ions (Fe 3+ , Fe 2+ ), copper ions (Cu 2+ , Cu + ) and zinc ions (Zn 2+ ), aluminum ions (Al 3+ Among these cations, it is preferable to use a monovalent cation from the viewpoint of maintaining viscosity.

[0073] Examples of anions constituting inorganic salts or organic salts include chloride ions (Cl - ), bromide ion (Br - ), iodide ion (I -) and other halogen ions; sulfate ions (SO4 2- ), nitrate ion (NO - ); carbonate ion (CO 2- ); hydrogen carbonate ion (HCO - ); hydrogen sulfate ion (HSO4 - ); phosphate ion (PO 3- ); hydrogen phosphate ion (HPO 2- ); dihydrogen phosphate ion (H2PO4 - ); sulfite ion (SO 2- ); thiosulfate ion (SO 2- chlorate ion (ClO - ); perchlorate ion (ClO - ), and acid groups such as carboxyl groups (-C(=O)-OH) and sulfo groups (-S(=O)-OH) to hydrogen ions (H + ) is removed.

[0074] Examples of inorganic salts include chlorides of alkali metals such as sodium chloride (NaCl) and potassium chloride (KCl); hydrochlorides such as ammonium chloride (NH4Cl); sulfates such as sodium sulfate (Na2SO4), potassium sulfate (K2SO4), ammonium sulfate ((NH4)2SO4), magnesium sulfate (MgSO4), aluminum sulfate (Al2(SO4)3), nickel sulfate (NiSO4), alum (AlK(SO4)2), and ammonium alum (Al(NH4)(SO4)2); nitrates such as sodium nitrate (NaNO3), potassium nitrate (KNO3), ammonium nitrate (NH4NO3), calcium nitrate tetrahydrate (Ca(NO3)2.4H2O), and calcium nitrate (Ca(NO3)); carbonates such as potassium carbonate (K2CO3); hydrogen carbonates such as potassium hydrogen carbonate (KHCO3) and sodium hydrogen carbonate (NaHCO3); calcium chloride (CaCl2), Examples of suitable alkali metal salts include alkaline earth metal chlorides such as magnesium chloride (MgCl); hydrogen phosphates such as sodium dihydrogen phosphate (NaHPO), disodium hydrogen phosphate (NaHPO), potassium dihydrogen phosphate (KHPO), dipotassium hydrogen phosphate (KHPO), ammonium dihydrogen phosphate (NHHPO), and diammonium hydrogen phosphate ((NH)HPO); phosphates such as trisodium phosphate (NaPO); sulfites such as sodium sulfite (NaSO); chlorates such as potassium chlorate (KClO); perchlorates such as sodium perchlorate (NaClO); thiosulfates such as sodium thiosulfate (NaSO); alkali metal bromides such as potassium bromide (KBr) and sodium bromide (NaBr); alkali metal iodides such as potassium iodide (KI) and sodium iodide (NaI); and borates such as borax (NaBO). These inorganic salts may be used alone or in combination of two or more. Among these cations, it is preferable to use an inorganic salt having a monovalent cation from the viewpoint of maintaining viscosity.

[0075] Organic salts include, for example, acetate, lactate, maleate, fumarate, tartrate, methanesulfonate, p-toluenesulfonate, triethanolamine salts, and amino acid salts.

[0076] The amount of the salt is preferably 0.01 to 10% by mass, more preferably 0.01 to 5% by mass, and even more preferably 0.05 to 5% by mass, based on the mass of the composition.

[0077] The amount of salt is preferably 1 to 1000% by mass, more preferably 1 to 500% by mass, and even more preferably 5 to 500% by mass, relative to the mass (solid content) of oxidized cellulose and / or nanocellulose in this embodiment. When both oxidized cellulose and nanocellulose are contained in the composition, the "mass (solid content) of oxidized cellulose and / or nanocellulose" refers to the "total mass (solid content) of oxidized cellulose and nanocellulose."

[0078] [pH Adjusting Agent] The composition according to this embodiment may further contain a pH adjusting agent. As used herein, a pH adjusting agent is an agent that adjusts the pH to a predetermined range. The viscosity increased by the combination of oxidized cellulose and / or nanocellulose with a thickener according to this embodiment can be maintained without decrease even when a pH adjusting agent is included.

[0079] As described above, the mechanism of the viscosity increase is presumed to be due to an interaction (preferably hydrophobic interaction) between the oxidized cellulose and / or nanocellulose and the thickener, and since this interaction is not easily affected by pH, it is presumed that a decrease in viscosity is suppressed even if the pH changes.

[0080] The pH adjusters may be used alone or in combination of two or more.

[0081] The pH adjuster may be any of an acid, a base, or a neutralizing agent, but preferably contains an acid or a base. Furthermore, as the pH adjuster, a combination of an acid and a neutralizing agent may be used, or a combination of a base and a neutralizing agent may be used.

[0082] The acid may be an organic acid, an inorganic acid, or a mixture thereof.

[0083] Organic acids include, for example, citric acid, tartaric acid, fumaric acid, malic acid, maleic acid, gluconic acid, succinic acid, ascorbic acid, glycolic acid, and salicylic acid.

[0084] Inorganic acids include, for example, hydrochloric acid, sulfuric acid, phosphoric acid, and sulfamic acid.

[0085] The base may be an organic base, an inorganic base, or a mixture thereof.

[0086] Organic bases include, for example, triethanolamine, carbamide peroxide, and cement phosphate.

[0087] Inorganic bases include, for example, ammonia, ammonium hydroxide, and alkali metal salts such as lithium, sodium, and potassium.

[0088] The neutralizing agent is not particularly limited as long as it has the effect of adjusting the pH to the desired level. The neutralizing agent can be used to adjust or maintain the acidity or basicity level. The neutralizing agent can also be described as a buffering agent. Examples of the neutralizing agent include citric acid, sodium carbonate, phosphoric acid, ammonium hydroxide, and glycolic acid.

[0089] The amount of the pH adjuster may be appropriately changed depending on the target pH. The pH of the composition according to this embodiment is as described above.

[0090] [Optional Components] The composition according to the present embodiment may contain further components (optional components). Even if the composition contains optional components, it can still exhibit a thickening effect.

[0091] The optional components may be selected appropriately depending on the intended use, and examples thereof include resins, pigments, surfactants, antifoaming agents, preservatives, plasticizers, stabilizers, and antioxidants.

[0092] [Cosmetics] Examples of the composition of the present embodiment include paints and cosmetics, and cosmetics are preferred.

[0093] Examples of cosmetics include makeup cosmetics, hair cosmetics, skin cosmetics, perfumes, colognes, bath cosmetics, nail cosmetics, lip care cosmetics, and body powders.

[0094] Examples of makeup cosmetics include lip cosmetics such as lipstick and lip gloss; point makeup cosmetics such as eye shadow, eye liner, blush and mascara; and base makeup cosmetics such as foundation, concealer and powder.

[0095] Examples of hair cosmetics include hair styling products, hair coloring agents (hair dyes), hair washes, and rinses.

[0096] Examples of skin cosmetics include lotions, lotions, creams, emulsions, sunscreen cosmetics, sunscreen cosmetics, aftercare lotions, cleansers, and packs.

[0097] Nail cosmetics include, for example, manicures, pedicures, and nail polish removers.

[0098] Cosmetics as used herein also include quasi-drugs, i.e., cosmetics containing active ingredients for purposes such as prevention and hygiene are also included in the cosmetics of this specification.

[0099] For example, hair colorants (hair dyes) fall under both the category of cosmetics and quasi-drugs. Examples of hair colorants (hair dyes) include permanent hair dyes such as hair color and gray hair dye; bleaching agents such as hair bleach; semi-permanent hair dyes such as hair manicure, color treatment, and color rinse; and temporary hair dyes such as hair mascara, hair color spray, hair marker, and hair foundation, and the term "hair colorant (hair dye)" in this specification includes these embodiments.

[0100] Another embodiment of the present invention relates to a composition comprising cellulose and a thickener, wherein the cellulose comprises oxidized cellulose having a structure in which the second and third hydroxyl groups of the glucopyranose ring are oxidized to introduce dicarboxy groups, and / or nanocellulose, which is a defibrated product of the oxidized cellulose. For details of the composition according to this embodiment (such as preferred properties and ingredients), the description of the composition according to the above embodiment is cited as appropriate.

[0101] <Method for Producing Composition> One embodiment of the present invention relates to a method for producing a composition, comprising a step of mixing cellulose, a thickener, and, if necessary, a salt and / or a pH adjuster, wherein the cellulose comprises oxidized cellulose, which is an oxidation product of a cellulose-based raw material with hypochlorous acid or a salt thereof, and / or nanocellulose, which is a defibrated product of the oxidized cellulose, and which is substantially free of N-oxyl compounds.

[0102] Details of the production method according to this embodiment (for example, details of the composition and its materials) are to be in accordance with the description in the <Composition> section above.

[0103] Oxidized cellulose obtained by an oxidation reaction using hypochlorous acid or its salt is easily defibrated, so even when mixed gently with a thickener, at least a portion of the oxidized cellulose is defibrated into nanocellulose.

[0104] Another embodiment of the present invention relates to a method for producing a composition, comprising the step of mixing cellulose with a thickener, wherein the cellulose comprises oxidized cellulose having a structure in which the second and third hydroxyl groups of the glucopyranose ring have been oxidized to introduce dicarboxy groups, and / or nanocellulose, which is a defibrated product of the oxidized cellulose. For details of the production method according to this embodiment, the description of the production method according to the above embodiment is cited as appropriate.

[0105] <Method for adjusting viscosity of a composition> One embodiment of the present invention relates to a method for adjusting the viscosity of an aqueous composition containing cellulose, the method comprising the step of mixing the aqueous composition with a thickener, and, as needed, a salt and / or a pH adjuster, wherein the cellulose comprises oxidized cellulose, which is an oxidation product of a cellulose-based raw material with hypochlorous acid or a salt thereof, and / or nanocellulose, which is a defibrated product of the oxidized cellulose, and is substantially free of N-oxyl compounds.

[0106] Details of the method according to this embodiment (for example, details of the aqueous composition and its materials) are as described in the above <Composition> section.

[0107] By mixing the water-based composition with the thickener, －１ In the measurement of the shear rate, the viscosity of the aqueous composition is 10 to 1 × 10 ６ %, and preferably 100 to 1×10 ５ %, and more preferably 1×10 ３ ~1 x 10 ５ It is more preferable to increase the temperature by 100°C.

[0108] Another embodiment of the present invention relates to a method for adjusting the viscosity of an aqueous composition containing cellulose, the method comprising the step of mixing the aqueous composition with a thickener, wherein the cellulose comprises oxidized cellulose having a structure in which the second and third hydroxyl groups of the glucopyranose ring are oxidized to introduce dicarboxy groups, and / or nanocellulose, which is a defibrated product of the oxidized cellulose. For details of the adjustment method according to this embodiment, the description of the adjustment method according to the above embodiment is cited as appropriate.

[0109] The present invention will be described in more detail below using examples and comparative examples, but the technical scope of the present invention is not limited thereto. Various values ​​in the examples may be used as preferred lower or upper limits in the embodiments of the present invention. Furthermore, two values ​​of the same type in the examples may be appropriately combined to form a preferred numerical range.

[0110] [Production Example 1] Commercially available powdered cellulose was used as the cellulose-based raw material. 350 g of sodium hypochlorite pentahydrate crystals with an effective chlorine concentration of 42% by mass were placed in a beaker, and pure water was added and stirred to obtain a sodium hypochlorite aqueous solution with an effective chlorine concentration of 21% by mass. 35% by mass of hydrochloric acid was added thereto and stirred to obtain an aqueous solution with a pH of 11.0. This sodium hypochlorite aqueous solution was heated to 30 ° C. in a constant temperature water bath while stirring at 200 rpm using a propeller-type stirring blade in a Shinto Scientific agitator (Three-One Motor, BL600), and then 50 g of the powdered cellulose was added. After supplying the cellulose-based raw material, the pH during the reaction was adjusted to 11.0 while adding 48% by mass of sodium hydroxide while maintaining the temperature at 30 ° C. in the same constant temperature water bath. The mixture was then stirred at 200 rpm using a propeller-type stirring blade in the agitator for 30 minutes, and the oxidation reaction was carried out. After completion of the reaction, the product was subjected to solid-liquid separation by suction filtration using a PTFE membrane filter with 0.1 μm openings, yielding oxidized cellulose. The resulting oxidized cellulose was washed with pure water, and the carboxyl group content of the filtered residue (oxidized cellulose) after washing was measured, yielding a value of 0.70 mmol / g. Furthermore, the nitrogen content derived from N-oxyl compounds in the oxidized cellulose was measured as the nitrogen content using a trace total nitrogen analyzer (manufactured by Nitto Seiko Analytech Co., Ltd., device name: TN-2100H), and the increase from the raw pulp was calculated, resulting in a value of 1 ppm or less.

[0111] The effective chlorine concentration in the sodium hypochlorite aqueous solution was measured by the following method. (Measurement of effective chlorine concentration in sodium hypochlorite aqueous solution) 0.582 g of an aqueous solution prepared by adding sodium hypochlorite pentahydrate crystals to pure water was precisely weighed, 50 ml of pure water was added, 2 g of potassium iodide and 10 ml of acetic acid were added, and the container was immediately sealed and left in the dark for 15 minutes. After leaving the container for 15 minutes, the liberated iodine was titrated with 0.1 mol / L sodium thiosulfate solution (indicator: starch test solution), and the titration amount was 34.55 ml. A blank test was separately performed to correct for this, and 1 ml of 0.1 mol / L sodium thiosulfate solution corresponded to 3.545 mg Cl, so the effective chlorine concentration in the sodium hypochlorite aqueous solution was 21% by mass.

[0112] The amount of carboxy groups in oxidized cellulose was measured by the following method. (Measurement of carboxy group amount) 60 ml of an oxidized cellulose aqueous dispersion, in which the oxidized cellulose concentration had been adjusted to 0.5% by mass, was added with 0.1 M aqueous hydrochloric acid to adjust the pH to 2.5, and then 0.05 N aqueous sodium hydroxide solution was added dropwise, and the electrical conductivity was measured until the pH reached 11.0. The amount of carboxy groups (mmol / g) was calculated using the following formula from the amount of sodium hydroxide (a) consumed in the neutralization stage of the weak acid, in which the change in electrical conductivity was gradual: Amount of carboxy groups = a (ml) × 0.05 / mass of oxidized cellulose (g).

[0113] The oxidized cellulose obtained in Production Example 1 was freeze-dried, and then the solid of the sample was left at 23°C and 50% RH for 24 hours or more. １３ As a result of measuring C-NMR, it was confirmed that both compounds had a structure in which the hydroxyl groups at the second and third positions of the glucopyranose ring were oxidized to introduce carboxyl groups. １３ The C-NMR measurement conditions are as follows: (1) Sample tube: Zirconia tube (4 mm diameter) (2) Magnetic field strength: 9.4 T (1H resonance frequency: 400 MHz) (3) MAS rotation speed: 15 kHz (4) Pulse sequence: CPMAS method (5) Contact time: 3 ms (6) Waiting time: 5 seconds (7) Number of accumulations: 10,000 to 15,000 (8) Measurement equipment: JNM ECA-400 (manufactured by JEOL Ltd.) The fact that the obtained oxidized cellulose has a structure in which the hydroxyl groups at the second and third positions of the glucopyranose ring have been oxidized and carboxyl groups have been introduced was also confirmed by the results of two-dimensional NMR measurement using a model molecule of the oxidized cellulose as a sample. In addition, the solid state of the cellulose-based raw material related to item 6 was １３ C-NMR and solid oxidized cellulose １３ Since no change in the spectral data was observed with C-NMR, it was determined that the hydroxyl group at position 6 was not oxidized and remained as a hydroxyl group in the oxidized cellulose.

[0114] Comparative Production Example 1 Nanocellulose obtained by TEMPO oxidation was obtained by production in accordance with Angew. Chem. Int. Ed. 2021, 60, 24630-24636. That is, it was produced by the following method. 0.016 g of TEMPO and 0.1 g of sodium bromide were placed in a beaker, pure water was added and stirred to obtain an aqueous solution, and 1.0 g of powdered pulp (KC Flock W-100GK) from Nippon Paper Industries Co., Ltd. was added as a cellulose-based raw material. The above aqueous solution was heated to 25 ° C. in a constant temperature water bath while stirring with a stirrer, and then 0.1 mol / L sodium hydroxide was added and stirred to obtain an aqueous solution with a pH of 10.0. To this was added 2.58 g of an aqueous sodium hypochlorite solution with an effective chlorine concentration of 13.2% by mass. The mixture was then kept at 25°C in the same thermostatic water bath. During the reaction, 0.1 mol / L sodium hydroxide was added to adjust the pH to 10.0, and the mixture was stirred with a stirrer for 120 minutes. After completion of the reaction, the product was subjected to solid-liquid separation by suction filtration using a PTFE membrane filter with a mesh size of 0.1 μm to obtain oxidized cellulose. The resulting filtered material was washed with pure water and then the amount of carboxy groups was measured. The amount of carboxy groups was 1.55 mmol / g, and the amount of filtered material was approximately 1.0 g. Furthermore, the nitrogen component derived from N-oxyl compounds in the oxidized cellulose was measured as the amount of nitrogen using a trace total nitrogen analyzer (manufactured by Nitto Seiko Analytech Co., Ltd., instrument name: TN-2100H). The increase from the raw pulp was calculated to be 5 ppm. This oxidized cellulose was mechanically defibrated to obtain an aqueous nanocellulose dispersion (solid content 2.0% by mass) obtained by TEMPO oxidation.

[0115] Comparative Production Example 2 Commercially available powdered cellulose was defibrated using a Starburst to obtain a nanocellulose aqueous dispersion (solid content 2.0% by mass) obtained by mechanical defibration.

[0116] Example 1 The oxidized cellulose obtained in Production Example 1 was prepared as an aqueous dispersion (solids content: approximately 10% by mass), and distilled water was added to dilute it to a solids content of 5% by mass. In this state, the mixture was stirred at 10,000 rpm for 60 minutes using a homomixer (Tokushu Kika Robo Mics) to defibrate the oxidized cellulose into CNF. Separately, an aqueous solution of methylcellulose (MC) with a concentration of 1% by mass and distilled water were prepared. A CNF aqueous dispersion with a solids content of 5% by mass, a 1% by mass aqueous solution of methylcellulose, and distilled water were mixed to prepare samples with the specified CNF / methylcellulose / water ratio (see Results for specific ratios).

[0117] The viscosity of each sample was measured as follows: A shear rheometer (Anton Paar, Physica MCR301) was used for viscosity measurement, and a parallel disk jig with a diameter of 50 mm was used. The shear rate was 0.01 to 100 s －１ The temperature was set to 25°C. Measurements were performed twice for each sample (0.01 to 100 s). －１ The measurement was performed once, and the sample was left to stand for 20 seconds after the measurement. After that, a second measurement was performed in the same shear rate range. The data from the second measurement was used.

[0118] [Comparative Example 1] The nanocellulose aqueous dispersion (solid content 2.0% by mass) obtained by TEMPO oxidation produced in Comparative Production Example 1, a 1% by mass aqueous methylcellulose solution, and distilled water were mixed to prepare a sample having a predetermined CNF / methylcellulose / water ratio.

[0119] [Comparative Example 2] The nanocellulose aqueous dispersion (solid content 2.0% by mass) obtained by mechanical defibration produced in Comparative Production Example 2, a 1% by mass aqueous methylcellulose solution, and distilled water were mixed to prepare a sample having a predetermined CNF / methylcellulose / water ratio.

[0120] The measurement results of various samples in Example 1, Comparative Example 1, and Comparative Example 2 are shown in Figures 1 to 4. Note that the percentage of each component in the figures represents the mass % of each component relative to the total amount of each component in each sample.

[0121] Example 2 The oxidized cellulose obtained in Production Example 1 was prepared as an aqueous dispersion (solids content approximately 10% by mass), and distilled water was added to dilute it to a solids content of 5% by mass. This dispersion was stirred at 10,000 rpm for 60 minutes using a homomixer (Tokushu Kika Robo Mics) to defibrate the oxidized cellulose into CNF (pre-defibration). Separately, an acrylic emulsion with a solids content of 18% by mass and a 1% by mass aqueous solution of methylcellulose were prepared. A 5% by mass aqueous dispersion of CNF, the acrylic emulsion, a 1% by mass aqueous solution of methylcellulose, and distilled water were mixed to prepare Sample 1 with the specified CNF / emulsion / methylcellulose ratio. Viscosity measurements were performed using the same method as in Example 1.

[0122] Comparative Example 3 Sample 2 was prepared by removing CNF from the sample of Example 2, Sample 3 was prepared by removing methylcellulose from the sample of Example 2, and Sample 4 was prepared by removing CNF and methylcellulose from the sample of Example 2. Viscosity measurements were carried out using the same viscosity measurement method as in Example 1.

[0123] The compositions of the various samples in Example 2 and Comparative Example 3 are shown in Table 1, and the measurement results are shown in FIG.

[0124] Example 3 The oxidized cellulose obtained in Production Example 1 was prepared as an aqueous dispersion (solid content approximately 10% by mass), and distilled water was added to dilute it to a solid content of 5% by mass. In this state, the mixture was stirred at 10,000 rpm for 60 minutes using a homomixer (Tokushu Kika Robo Mics) to defibrate the oxidized cellulose into CNF. A sample was prepared by mixing CNF, methyl cellulose, and water in a specified ratio. Viscosity was measured using the same viscosity measurement method as in Example 1.

[0125] Example 4 A sample was prepared using guar gum (GG) instead of the methyl cellulose used in Example 3. The viscosity was measured using the same viscosity measurement method as in Example 1.

[0126] The measurement results of the various samples in Examples 3 and 4 are shown in Figure 6. Note that the percentage of each component in the figure represents the mass % of each component relative to the total amount of each component in each sample.

[0127] Example 5 The oxidized cellulose obtained in Production Example 1 was prepared as an aqueous dispersion (solids content approximately 10% by mass), and distilled water was added to dilute it to a solids content of 7.5% by mass. This dispersion was stirred at 10,000 rpm for 60 minutes using a homomixer (Tokushu Kika Robo Mics) to defibrate the oxidized cellulose into CNF. Separately, a 1% by mass aqueous solution of methylcellulose (MC) was prepared. A 12.5% ​​by mass aqueous solution of sodium chloride (NaCl) and distilled water were also prepared. A 7.5% by mass CNF aqueous dispersion, a 1% by mass aqueous solution of methylcellulose, a 12.5% ​​by mass aqueous solution of sodium chloride, and distilled water were mixed to prepare samples with CNF / methylcellulose / sodium chloride ratios of 1.0% by mass, 0.1% by mass, and 0-1.0% by mass relative to the total composition. The viscosity of each sample was measured using the same viscosity measurement method as in Example 1.

[0128] Comparative Example 4: Carbopol (registered trademark) 980 was used, and a 12.5% ​​by mass aqueous solution of sodium chloride and distilled water were mixed to prepare samples in which the ratio of Carbopol (registered trademark) to sodium chloride relative to the total composition amount was 0.075% by mass and 0 to 1.0% by mass. The viscosity of each sample was measured using the same viscosity measurement method as in Example 1.

[0129] Comparative Example 5: Carbopol (registered trademark) 980 was used, and a 12.5% ​​by mass aqueous solution of sodium chloride and distilled water were mixed to prepare samples in which the ratio of Carbopol (registered trademark) to the total composition was 1.0% by mass / 0 to 1.0% by mass. The viscosity of each sample was measured using the same viscosity measurement method as in Example 1.

[0130] The results of viscosity measurements for Example 5 (CNF and MC) and Comparative Example 4 (Carbopol® 980) are shown in Figure 7. The salt-free sample in Example 5 and the salt-free sample in Comparative Example 4 had similar viscosities. In Comparative Example 4, the addition of salt significantly reduced the viscosity, but in Example 5, the addition of salt only limited the viscosity reduction.

[0131] The results of viscosity measurements for Example 5 (CNF and MC) and Comparative Example 5 (Carbopol® 980) are shown in Figure 8. The amount of CNF in Example 5 was the same as the amount of Carbopol® in Comparative Example 5. In Comparative Example 5, the addition of salt reduced the viscosity, but in Example 5, the reduction in viscosity was suppressed even when salt was added.

[0132] Comparative Example 6 Carbopol (registered trademark) Ultrez 30 (hereinafter also simply referred to as Ultrez 30) was mixed with a 12.5% ​​by mass aqueous solution of sodium chloride and distilled water to prepare samples in which the ratio of Ultrez 30 to sodium chloride relative to the total composition amount was 0.075% by mass and 0 to 1.0% by mass. The viscosity of each sample was measured using the same viscosity measurement method as in Example 1.

[0133] Comparative Example 7: Samples were prepared by mixing Ultrez 30 with a 12.5% ​​by mass aqueous solution of sodium chloride and distilled water, with the ratio of Ultrez 30 / sodium chloride being 1.0% by mass / 0 to 1.0% by mass relative to the total composition amount. The viscosity of each sample was measured using the same viscosity measurement method as in Example 1.

[0134] The results of viscosity measurements for Example 5 (CNF and MC) and Comparative Example 6 (Ultrez 30) are shown in Figure 9. The sample containing no salt in Example 5 and the sample containing no salt in Comparative Example 6 had similar viscosities. In Comparative Example 6, the addition of salt significantly reduced the viscosity, but in Example 5, the reduction in viscosity was suppressed even when salt was added.

[0135] The results of viscosity measurements for Example 5 (CNF and MC) and Comparative Example 7 (Ultrez 30) are shown in Figure 10. The amount of CNF in Example 5 was the same as the amount of Ultrez 30 in Comparative Example 7. In Comparative Example 7, the addition of salt reduced the viscosity, but in Example 5, the reduction in viscosity was suppressed even when salt was added.

[0136] Example 6: The oxidized cellulose obtained in Production Example 1 was prepared as an aqueous dispersion (solids content approximately 10% by mass), and distilled water was added to dilute it to a solids content of 7.5% by mass. This dispersion was stirred at 10,000 rpm for 60 minutes using a homomixer (Tokushu Kika Robo Mics) to defibrate the oxidized cellulose into CNF. Separately, a 1% by mass aqueous solution of methylcellulose (MC) and distilled water were prepared. A 7.5% by mass CNF aqueous dispersion, a 1% by mass aqueous solution of methylcellulose, and distilled water were mixed to prepare a sample with a CNF / methylcellulose ratio of 1% by mass to 0.1% by mass relative to the total composition. The pH of the sample was adjusted using 0.5 M hydrochloric acid or 0.5 M aqueous sodium hydroxide solution. When adjusting to the acidic side, 0.5 M hydrochloric acid was used, and when adjusting to the alkaline side, 0.5 M aqueous sodium hydroxide solution was used. The electrode of a pH meter (HORIBA D-51 pH METER) was immersed in the screw tube containing the sample, and the above reagent was added dropwise while checking the value. Viscosity measurements were performed using the same viscosity measurement method as in Example 1, with shear rates of 1 [1 / s] and 10 [1 / s]. The results are shown in Figure 11.

[0137] Comparative Example 8: Carbopol® 980 and distilled water were mixed to prepare a sample containing 0.1% by mass of Carbopol® based on the total mass of the composition. Viscosity measurements were carried out in the same manner as in Example 6, except that this sample was used. The results are shown in Figure 11.

[0138] Comparative Example 9 Carbopol (registered trademark) Ultrez 30 and distilled water were mixed to prepare a sample containing 0.1% by mass of Ultrez 30 relative to the total mass of the composition. Viscosity measurements were carried out in the same manner as in Example 6, except that this sample was used. The results are shown in Figure 11.

[0139] 11 , the composition of Example 6 (CNF and MC) tends to be able to suppress a decrease in viscosity even when the pH is changed from 7. On the other hand, the composition of Comparative Example 8 (Carbopol (registered trademark) 980) or the composition of Comparative Example 9 (Ultrez 30) tends to show a decrease in viscosity when the pH is changed from 7. Therefore, a dispersion containing oxidized cellulose, which is an oxide of a cellulose-based raw material using hypochlorous acid or a salt thereof, and / or nanocellulose, which is a defibrated product of the oxidized cellulose, and a thickener can increase viscosity and suppress a decrease in viscosity due to a change in pH.

Claims

1. A composition comprising cellulose and a thickener, wherein the cellulose comprises oxidized cellulose, which is an oxidation product of a cellulose-based raw material with hypochlorous acid or a salt thereof, and / or nanocellulose, which is a defibrated product of the oxidized cellulose, and the composition is substantially free of N-oxyl compounds.

2. A composition comprising cellulose and a thickener, wherein the cellulose comprises oxidized cellulose having a structure in which the second and third hydroxyl groups of the glucopyranose ring have been oxidized to introduce dicarboxy groups, and / or nanocellulose, which is a defibrated product of the oxidized cellulose.

3. The composition according to claim 1 or 2, wherein the thickening agent is a thickening polysaccharide.

4. The composition according to claim 1 or 2, wherein the thickener has hydrophobic regions capable of hydrophobic interaction with the oxidized cellulose and / or the nanocellulose.

5. The composition according to claim 1 or 2, wherein the amount of the thickener is 0.1 to 40% by mass relative to the mass (solid content) of the oxidized cellulose and / or the nanocellulose.

6. The composition according to claim 1 or 2, further comprising a salt.

7. The composition according to claim 6, wherein the amount of said salt is 0.01 to 10% by weight based on the weight of said composition.

8. The composition according to claim 1 or 2, further comprising a pH adjuster.

9. The composition according to claim 8, wherein the pH of the composition is in the range of from 0 to 14.

0.

10. The composition of claim 8, wherein the pH adjuster comprises an acid or a base.

11. The composition according to claim 1 or 2, wherein the cellulose comprises nanocellulose.

12. The composition according to claim 1 or 2, wherein the composition is a water-based composition.

13. The composition according to claim 12, wherein the viscosity of the aqueous composition is 0.01 to 1000 Pa·s.

14. The viscosity of the aqueous composition is 10 to 1 x 10 lower than the viscosity of a control composition obtained by removing the thickener from the aqueous composition. ６ % higher. The composition of claim 12 .

15. A composition comprising cellulose and a thickener, wherein the cellulose comprises oxidized cellulose, which is an oxidation product of a cellulose-based raw material with hypochlorous acid or a salt thereof, and / or nanocellulose, which is a defibrated product of the oxidized cellulose, and the composition is substantially free of N-oxyl compounds, and the pH of the composition is within the range of 0 to 14.

0.

16. A composition comprising cellulose and a thickener, wherein the cellulose comprises oxidized cellulose having a structure in which the second and third hydroxyl groups of the glucopyranose ring are oxidized to introduce dicarboxy groups, and / or nanocellulose, which is a defibrated product of the oxidized cellulose, and the pH of the composition is within the range of 0 to 14.

0.

17. The composition according to any one of claims 1, 2, 15 and 16, wherein the composition is a cosmetic product.

18. A method for producing a composition, comprising the step of mixing cellulose with a thickener, wherein the cellulose comprises oxidized cellulose, which is an oxidation product of a cellulose-based raw material with hypochlorous acid or a salt thereof, and / or nanocellulose, which is a defibrated product of the oxidized cellulose, and the composition is substantially free of N-oxyl compounds.

19. A method for producing a composition, comprising the step of mixing cellulose with a thickener, wherein the cellulose comprises oxidized cellulose having a structure in which the second and third hydroxyl groups of the glucopyranose ring have been oxidized to introduce dicarboxy groups, and / or nanocellulose, which is a defibrated product of the oxidized cellulose.

20. A method for adjusting the viscosity of an aqueous composition containing cellulose, comprising a step of mixing the aqueous composition with a thickener, wherein the cellulose comprises oxidized cellulose, which is an oxidation product of a cellulose-based raw material with hypochlorous acid or a salt thereof, and / or nanocellulose, which is a defibrated product of the oxidized cellulose, and is substantially free of N-oxyl compounds.

21. A method for adjusting the viscosity of an aqueous composition containing cellulose, comprising a step of mixing the aqueous composition with a thickener, wherein the cellulose comprises oxidized cellulose having a structure in which the second and third hydroxyl groups of the glucopyranose ring have been oxidized to introduce dicarboxy groups, and / or nanocellulose, which is a defibrated product of the oxidized cellulose.

22. The viscosity of the aqueous composition is increased to 10 to 1×10 by mixing the aqueous composition with the thickener. ６ 22. The method of claim 20 or 21, wherein the concentration of the ion exchange resin is increased by 100%.

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