Hydrophobic cellulose nanofiber, hydrophobic cellulose nanofiber dispersion, and cosmetic

Abstract

To provide a hydrophobic cellulose nanofiber capable of being dispersed in an oil solution which is liquid at room temperature, especially a silicone oil and to provide a dispersion of the same.SOLUTION: There is provided a hydrophobic cellulose nanofiber which contains (A) a cellulose nanofiber and (B) an isocyanate group-containing organopolysiloxane, wherein the isocyanate group-containing organopolysiloxane is bonded to the hydroxy group of the cellulose nanofiber via a urethane bond.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to hydrophobic cellulose nanofibers, a dispersion of the hydrophobic cellulose nanofibers, and a cosmetic. [Background technology]

[0002] Water-soluble polymers are used in cosmetic formulations to thicken water to alter the feel of the product or to prevent powder settling, thereby improving formulation stability. Water-soluble polymers can be broadly classified into natural polymers such as xanthan gum and tamarind gum, semi-synthetic polymers such as hydroxyethyl cellulose, and synthetic polymers such as polyacrylic acid. The use of water-soluble polymers presents challenges, including stickiness after application, which can impair the feel of the product, and the inability to achieve sufficient thickening effects depending on the presence of salts and the formulation's pH. In recent years, cellulose nanofibers have attracted attention as one type of water-soluble polymer. They offer a non-sticky feel and a refreshing, thixotropic feel, potentially addressing these challenges (Patent Document 1). Furthermore, due to their excellent properties, such as high strength, high elastic modulus, and low thermal expansion coefficient, they have been used in applications other than cosmetics, such as gas barrier materials and reinforcing materials for polymeric materials (Patent Document 2).

[0003] To maximize the above-mentioned properties, cellulose fibers must be finely defibrated to nano-size. One way to achieve this is to introduce anionic functional groups onto the surface of cellulose fibers. This allows the preparation of a uniform and transparent aqueous dispersion of cellulose nanofibers due to the charge repulsion between the nanofibers and the osmotic pressure effect of water. Examples of such anionic functional groups include carboxyl groups, carboxymethyl groups, sulfate ester groups, phosphate ester groups, phosphite ester groups, and xanthate ester groups, and various studies have been conducted to date (Patent Documents 3, 4, and 5).

[0004] On the other hand, because cellulose nanofibers have many hydrophilic groups on their surface, their dispersing medium is limited to water. Therefore, when cellulose nanofibers are heated and melted with resins with low polarity and poor compatibility, they aggregate in the resin, resulting in a lower strength than the original resin. Furthermore, they have poor viscosity-enhancing properties in dispersing media other than water, making it difficult to improve the texture or emulsion stability of formulations, such as water-in-oil emulsions. Therefore, dispersing cellulose nanofibers in various organic solvents other than water is a challenge. However, in organic solvents, the anionic functional groups present on the cellulose nanofiber surface have a low degree of ionization, weakening charge repulsion, leading to preferential hydrogen bonding between hydroxyl groups, making them prone to aggregation.

[0005] Patent Document 6 describes that neutralizing carboxyl group-containing cellulose nanofibers with a long-chain monoalkylamine enables dispersion in a 1:1 acetone:water mixed solvent or isopropanol. However, dispersion in low-polarity solvents, particularly silicone oil, has not been achieved. Patent Document 7 describes that neutralizing carboxyl group-containing cellulose nanofibers with a polyetheramine enables thickening and dispersion in toluene, methylene chloride, and ethylene glycol used as a dispersion medium. However, dispersion in silicone oil has not been achieved. Patent Document 8 describes that using an aqueous dispersion of carboxyl group-containing cellulose nanofibers neutralized with a monoamine improves emulsion stability when an oily ingredient is incorporated into a formulation. However, the dispersion medium is water, and dispersion in other dispersion media has not been achieved.

[0006] Cellulose nanofibers treated with silane or silicone are also known. Patent Document 9 describes improving the emulsion stability of oil-in-water emulsions by mixing an aqueous dispersion of carboxyl-containing cellulose nanofibers with low-viscosity dimethylsilicone oil and amino-modified silicone, and using cellulose nanofibers hydrophobized with silicone in the formulation. However, there is no mention of using hydrophobic cellulose nanofibers in water-in-oil emulsions. Patent Document 10 describes hydrophobizing some of the hydroxyl groups on the surface of carboxyl-containing cellulose nanofibers with alkoxysilane or silazane, enabling uniform dispersion in resins or rubbers. However, dispersion in organic solvents or silicone oils has not been achieved. Patent Document 11 describes treating carboxyl-containing cellulose nanofibers substituted with polar organic solvents with amino-modified silicones, enabling dispersion in toluene or tetrahydrofuran, but has not achieved dispersion in silicone oils.

[0007] As mentioned above, there are examples of dispersing cellulose nanofibers in dispersants other than water using various approaches, but dispersibility in low-polarity oils such as silicone oil remains an issue. Furthermore, when replacing the water dispersant with an organic solvent to simplify hydrophobization, charge repulsion weakens, making aggregation more likely. Once aggregated, cellulose nanofibers are difficult to defibrate, and there are still challenges in approaches to hydrophobizing without forming aggregates. Furthermore, while there are examples of using cellulose nanofibers in oil-in-water emulsions, there are no examples of their application to water-in-oil emulsions, making it unclear whether they contribute to emulsion stability. [Prior art documents] [Patent documents]

[0008] [Patent Document 1] Japanese Patent Application Laid-Open No. 2014-141675 [Patent Document 2] Japanese Patent Application Laid-Open No. 2009-057552 [Patent Document 3] JP 2017-071700 A [Patent Document 4] Japanese Patent Application Laid-Open No. 2013-127141 [Patent Document 5] Japanese Patent Application Publication No. 2018-141249 [Patent Document 6] Japanese Patent Application Publication No. 2012-021081 [Patent Document 7] Japanese Patent Application Publication No. 2017-019896 [Patent Document 8] Japanese Patent Application Laid-Open No. 2012-126786 [Patent Document 9] Patent Publication No. 2021-095557 [Patent Document 10] Japanese Patent Application Publication No. 2020-128476 [Patent Document 11] Japanese Patent Application Publication No. 2020-164670 Summary of the Invention [Problem to be solved by the invention]

[0009] The present invention has been made in view of the above circumstances, and aims to provide hydrophobic cellulose nanofibers that are dispersible in oils that are liquid at room temperature, particularly silicone oil, and a dispersion thereof. Another aim is to provide a cosmetic preparation that has excellent application properties, a refreshing feel when used, and good stability over time. [Means for solving the problem]

[0010] In order to solve the above problems, the present invention provides a hydrophobic cellulose nanofiber, (A) Cellulose nanofibers, and (B) Isocyanate group-containing organopolysiloxane The present invention provides hydrophobic cellulose nanofibers, which comprise the above-mentioned cellulose nanofibers, and in which the isocyanate group-containing organopolysiloxane is bonded to the hydroxy groups of the cellulose nanofibers via urethane bonds.

[0011] Such hydrophobic cellulose nanofibers can be dispersed in oils that are liquid at room temperature, particularly silicone oils.

[0012] In the present invention, it is also preferable that the (A) cellulose nanofibers further have anionic functional groups.

[0013] Such hydrophobic cellulose nanofibers are preferred because they exhibit high dispersibility.

[0014] In this case, it is preferable that a 0.2 mass% aqueous dispersion of the cellulose nanofibers having anionic functional groups has a light transmittance of 80% or more at 600 nm, and that the fiber width of the cellulose nanofibers having anionic functional groups in the aqueous dispersion is 300 nm or less.

[0015] Such hydrophobic cellulose nanofibers are preferred because they do not reduce the light transmittance of the dispersion and maintain the transparency of the film.

[0016] In the present invention, the anionic functional group is preferably selected from a carboxyl group, a carboxymethyl group, a sulfate ester group, a phosphate ester group, a phosphite ester group, and a xanthate ester group.

[0017] Such hydrophobic cellulose nanofibers are preferred because they are easily defibrated, a dispersion having high light transmittance is easily obtained, and solubility in water is reduced.

[0018] In the present invention, the (B) isocyanate group-containing organopolysiloxane is preferably one represented by the following general formula (1) or (2). [ka] (In the formula, R 1 is a monovalent alkyl group having 1 to 6 carbon atoms, and R 2are independently an alkyl group having 1 to 6 carbon atoms, a phenyl group, or -OSiR 3 3(R 3 are independently a monovalent organic group having 1 to 6 carbon atoms.) is a triorganosiloxy group represented by the formula: m is an integer of 1 to 10, and a is an integer of 0 to 1. [ka] (In the formula, R 2 is the same as above, m is an integer of 1 to 10, and n is an integer of 1 to 500.

[0019] Such hydrophobic cellulose nanofibers can further improve the effects of the present invention.

[0020] In this case, the isocyanate group-containing organopolysiloxane represented by the general formula (1) is preferably tristrimethylsiloxysilylpropylisocyanate.

[0021] Such hydrophobic cellulose nanofibers can further improve the effects of the present invention.

[0022] The present invention also provides a hydrophobic cellulose nanofiber dispersion in which the above-described hydrophobic cellulose nanofibers are dispersed in an oil agent (C).

[0023] Such a hydrophobic cellulose nanofiber dispersion can be made dispersible in an oil agent that is liquid at room temperature, particularly in silicone oil.

[0024] In this case, the (C) oil agent is preferably one or more selected from the group consisting of aliphatic alcohols, silicone oils, and hydrocarbon oils.

[0025] In the present invention, a hydrophobic cellulose nanofiber dispersion can be prepared by dispersing the cellulose nanofiber in such an oil agent.

[0026] In the present invention, the mass ratio of the (C) oil agent to the hydrophobic cellulose nanofibers is preferably 1:0.0001 to 1:0.5.

[0027] Such a hydrophobic cellulose nanofiber dispersion is preferable from the viewpoint of usability because the cellulose nanofiber concentration is not too high and the viscosity is not too high.

[0028] In the present invention, it is also preferable that the 0.2 mass % silicone oil dispersion of the hydrophobic cellulose nanofiber dispersion has a light transmittance of 70% or more at 600 nm.

[0029] Such a hydrophobic cellulose nanofiber dispersion is preferable because it has sufficient transparency, does not contain many aggregates, and does not reduce reactivity.

[0030] The present invention also provides a cosmetic preparation containing the above-described hydrophobic cellulose nanofiber dispersion.

[0031] Such a cosmetic preparation has excellent application properties, a refreshing feel when used, and good stability over time of the preparation.

[0032] In this case, it is preferable that the hydrophobic cellulose nanofiber dispersion is used as an emulsion composition.

[0033] Such a cosmetic product can further improve the effects of the present invention. [Effects of the Invention]

[0034] The hydrophobic cellulose nanofibers of the present invention can be easily dispersed in a specific dispersion medium, and when the dispersion medium evaporates, they can form a highly transparent and flexible film. Cosmetics containing this hydrophobic cellulose nanofiber dispersion have a good feel in use, long-lasting makeup, and good spreadability and finish.

[0035] In particular, using cellulose nanofibers containing anionic functional groups as a raw material makes it possible to obtain dispersions with few aggregates, enabling high thickening properties for oily solutions. Furthermore, by changing the bonding ratio of the isocyanate-containing organopolysiloxane to the hydroxyl groups of the cellulose nanofibers, it is possible to control the thickening properties for oily solutions. Therefore, by incorporating the hydrophobic cellulose nanofiber dispersion of the present invention into cosmetics as a feel-improving agent, cosmetics with excellent feel and stability over time can be produced. Furthermore, the low level of aggregates allows the dispersion medium to volatilize, forming a highly transparent film. When incorporated into cosmetics, the resulting film is not sticky upon application, has a good feel in use, is water-resistant and durable, and adheres well to the skin. Furthermore, this cosmetic has good long-lasting properties and a good spreadability and finish. Furthermore, it exhibits excellent functionality as a viscosity imparting agent and dispersion stabilizer in various applications, such as pharmaceuticals, agricultural chemicals, toiletries, spray products, and paints. DETAILED DESCRIPTION OF THE INVENTION

[0036] As described above, there has been a need for the development of hydrophobic cellulose nanofibers that are dispersible in oils that are liquid at room temperature, particularly silicone oil, and a dispersion medium for such nanofibers.

[0037] The present inventors have discovered that by hydrophobizing cellulose nanofibers with an isocyanate group-containing organopolysiloxane, they can be dispersed in a dispersion medium other than water. They also discovered that these hydrophobic cellulose nanofibers form a film when the dispersion medium is volatilized. They also discovered that the hydrophobic cellulose nanofibers thicken the dispersion medium, allowing the dispersion medium to function as a feel improver or stabilizer.

[0038] Furthermore, when modifying cellulose nanofibers with an isocyanate group-containing compound, it is preferable to avoid water in the reaction system, as this can cause side reactions. However, cellulose nanofibers are highly hydrophilic and are usually in the form of an aqueous dispersion. Therefore, if the water in the dispersion medium is replaced with an organic solvent, the charge repulsion weakens, making the nanofibers more susceptible to aggregation. However, by replacing the water with a water-soluble organic compound with a boiling point of 100°C or higher at 25°C and 1 atmosphere, it is possible to obtain a cellulose nanofiber dispersion without forming aggregates. This method makes it possible to remove water while suppressing aggregation, resulting in a highly transparent organic solvent dispersion of cellulose nanofibers. Therefore, the hydroxyl groups of the cellulose nanofibers can react with the isocyanate groups without side reactions. The researchers discovered that the resulting hydrophobic cellulose nanofiber dispersion can solve the above-mentioned problems, leading to the present invention.

[0039] That is, the present invention provides a hydrophobic cellulose nanofiber, (A) Cellulose nanofibers, and (B) Isocyanate group-containing organopolysiloxane The hydrophobic cellulose nanofibers comprise the cellulose nanofibers, and the isocyanate group-containing organopolysiloxane is bonded to the hydroxy groups of the cellulose nanofibers via urethane bonds.

[0040] The present invention will be described in detail below, but the present invention is not limited thereto.

[0041] The present invention provides hydrophobic cellulose nanofibers in which (A) hydroxy groups of cellulose nanofibers are bonded to (B) an isocyanate group-containing organopolysiloxane via urethane bonds. Each of these is described in detail below.

[0042] (A) Cellulose nanofiber Cellulose nanofibers are fine cellulose fibers obtained by defibrating plant raw materials such as pulp fibers. They consist of cellulose microfibrils alone or aggregates thereof, and have a fiber width of 3 to 100 nm, an aspect ratio of 10 or more, and a length of 100 μm or less. Cellulose raw materials for producing cellulose nanofibers include the following: chemical pulps such as hardwood kraft pulp and softwood kraft pulp; mechanical pulps such as stoneground pulp and thermoground pulp; and waste paper pulp such as used tea leaves, newspapers, and flyers. These raw materials can be used alone or in combination depending on the purpose of the present invention.

[0043] The cellulose fibers can be defibrated by any known method, which can be broadly divided into two types: mechanical treatment and chemical treatment, and the method is not limited.

[0044] Examples of mechanical defibration methods include the grinder method, which grinds materials between grinding stones; the microfluidizer method, which defibrates materials by colliding pressurized materials with each other at high speed using the impact force, pressure difference, and microcavitation; pulverization methods using ball mills or bead mills; and the two-screw kneading method, which kneads materials into resin.

[0045] In recent years, chemical treatment-based fiber defibration technologies have been developed to reduce the energy required for production. Chemical treatment-based fiber defibration methods involve chemical reactions with the raw cellulose fibers, which can introduce anionic functional groups, for example. The introduction of these functional groups creates charge repulsion between the nanofibers and an osmotic pressure effect in water, making it possible to prepare a uniform and transparent aqueous dispersion of cellulose nanofibers with low energy consumption.

[0046] The cellulose nanofibers used as the raw material in the present invention are preferably those with a smaller fiber diameter (fiber width) because highly dispersed cellulose nanofibers have better reactivity with isocyanate group-containing organopolysiloxanes. In particular, defibration by chemical treatment is preferred because it allows for high dispersion with low energy.

[0047] The cellulose nanofibers (A) used in the present invention preferably further have anionic functional groups, which can be introduced by chemically reacting the raw cellulose fibers.

[0048] Cellulose nanofibers having anionic functional groups can be highly dispersed due to the repulsion between the anionic groups. In a 0.2% by mass aqueous dispersion, the light transmittance at 600 nm is preferably 80% or higher. More preferably, it is 85% or higher, and even more preferably, it is 90% or higher. At 80% or higher, sufficient transparency is achieved, there are few aggregates, and reactivity is not reduced. Furthermore, the average fiber diameter (fiber width) is preferably 300 nm or less. More preferably, it is 100 nm or less, and even more preferably, it is 80 nm or less. At 300 nm or less, the light transmittance of the dispersion is not reduced, and the transparency of the coating is maintained. Furthermore, the average fiber length is preferably 0.1 μm or more and 1,000 μm or less, more preferably 0.1 μm or more and 800 μm or less, and even more preferably 0.1 μm or more and 600 μm or less. Within this range, the thickening effect is not impaired, and strength is likely to increase when composited with a resin.

[0049] In the present invention, the light transmittance is the transmittance obtained by measuring directly transmitted light at a wavelength of 600 nm using an ultraviolet-visible spectrophotometer.

[0050] A cellulose nanofiber dispersion with a solids concentration of 0.01% by mass is prepared, dropped onto a copper grid, and dried to form an observation sample, which is then observed under a transmission electron microscope. Three or more images in which the fibers do not overlap are observed, and the diameter and length of 20 fibers per image are calculated. The average values are taken as the average fiber diameter and length.

[0051] The average aspect ratio (axial ratio, fiber length / fiber width) of cellulose nanofibers is preferably 50 or more, and although there is no particular upper limit, it is preferably 20,000 or less. When the aspect ratio is 50 or more, the cellulose nanofibers are fibrous, and the viscosity of the dispersion is sufficient and stable. When the aspect ratio is 20,000 or less, the viscosity of the dispersion does not become too high, making it easy to handle. The average aspect ratio can also be calculated by the formula: average fiber length / average fiber diameter = average aspect ratio.

[0052] Hydrophobic cellulose nanofibers, which are made from natural cellulose as their raw material, desirably have a cellulose type I crystal structure. From the viewpoint of film-forming properties or strength, the degree of crystallinity is 65% or more, preferably 70% or more. The presence of type I crystal structure can be identified from the peaks around 2θ = 14 to 17° and 22 to 23° in the profile obtained by wide-angle X-ray diffraction.

[0053] The degree of crystallinity of cellulose nanofibers is a value measured by X-ray diffraction in accordance with JIS K0131:1996 "General rules for X-ray diffraction analysis." Cellulose nanofibers have both amorphous and crystalline parts, and the proportion of crystalline parts is expressed as the degree of crystallinity.

[0054] The anionic functional group to be introduced may be selected from the group consisting of a carboxy group, a carboxymethyl group, a sulfate ester group, a phosphate ester group, a phosphite ester group, and a xanthate ester group. These functional groups can be introduced into cellulose nanofibers by known methods. Alternatively, commercially available modified cellulose nanofibers to which an anionic functional group has already been introduced may be used.

[0055] The amount of anionic functional group introduced is optimized depending on the type of functional group. Specifically, it is preferable that the amount is within the following range. If the amount is within the following range, the cellulose nanofibers are easily defibrated, a dispersion with high light transmittance is easily obtained, and solubility in water is also suppressed.

[0056] For example, in the case of carboxy groups, the amount is preferably 0.6 to 2.0 mmol / g, more preferably 1.0 to 2.0 mmol / g, relative to the weight of the carboxylated cellulose nanofibers. Furthermore, in the case of carboxymethyl groups, the amount is preferably 0.6 to 2.0 mmol / g, more preferably 1.0 to 2.0 mmol / g, relative to the weight of the carboxylated cellulose nanofibers. Furthermore, in the case of sulfate ester groups, the amount is preferably 0.4 to 3.0 mmol / g, more preferably 0.5 to 3.0 mmol / g, and particularly preferably 0.5 to 2.0 mmol / g, relative to the weight of the sulfate ester cellulose nanofibers. Furthermore, in the case of phosphate ester groups, the amount is preferably 0.1 to 2.0 mmol / g, more preferably 0.2 to 1.5 mmol / g, relative to the weight of the phosphate ester group-containing cellulose nanofibers. In the case of phosphite ester groups, the concentration is preferably 0.1 to 3.5 mmol / g, more preferably 0.6 to 1.8 mmol / g, and particularly preferably 0.9 to 1.5 mmol / g, relative to the weight of the phosphite cellulose nanofibers. In the case of xanthate ester groups, the concentration is preferably 0.3 to 1.2, more preferably 0.3 to 1.0, per glucose unit.

[0057] The amount of anionic functional groups introduced into cellulose nanofibers can be measured, for example, by conductometric titration. This method involves dropping an alkaline solution, such as an aqueous sodium hydroxide solution or an aqueous potassium hydroxide solution, into a slurry or dispersion containing cellulose nanofibers to measure the amount introduced. For example, if the anionic functional group is a carboxyl group and the alkaline solution is an aqueous sodium hydroxide solution, the amount of carboxyl groups can be calculated from the amount of sodium hydroxide required for neutralization.

[0058] Counter ions of the introduced anionic functional groups include alkali metal ions such as lithium, sodium, and potassium, alkaline earth metal ions such as calcium and magnesium, hydrogen ions, aliphatic ammonium, and aromatic ammonium. These can be used alone or in combination of two or more. Sodium and potassium cations are preferred.

[0059] For cellulose nanofibers containing anionic functional groups, it is preferable to use a water-soluble organic compound or water as a dispersion medium. Examples of the water-soluble organic compound include methanol and ethanol.

[0060] From the viewpoints of the efficiency of introducing modifying groups into cellulose nanofibers and efficient dispersion in silicone, the anionic functional group is preferably a carboxyl group, a phosphate ester group, or a phosphite ester group, and more preferably a phosphate ester group or a phosphite ester group. Phosphate groups and phosphite groups are bonded to hydroxyl groups and oxo groups, and have a high negative charge, which leads to strong charge repulsion between cellulose nanofibers and facilitates defibration. Furthermore, from the viewpoint of suppressing yellowing of cellulose nanofibers, phosphite ester groups are even more preferable. Phosphate groups dissociate more hydrogen ions than phosphite groups, resulting in a lower pH. It is thought that a lower pH makes it easier for double bonds to form in cellulose through Maillard reactions and reduction reactions, making yellowing more likely.

[0061] In the present invention, the binding mode of the organopolysiloxane to the cellulose nanofiber is a urethane bond, which is formed by the reaction between the hydroxyl groups of the cellulose nanofiber and the isocyanate groups of the organopolysiloxane in the presence of a catalyst.

[0062] (B) Isocyanate group-containing organopolysiloxane (B) The isocyanate group-containing organopolysiloxane is preferably an organopolysiloxane represented by the following general formula (1) or (2). [ka] (In the formula, R 1 is a monovalent alkyl group having 1 to 6 carbon atoms, and R 2 are independently an alkyl group having 1 to 6 carbon atoms, a phenyl group, or -OSiR 3 3(R 3 are independently a monovalent organic group having 1 to 6 carbon atoms.) is a triorganosiloxy group represented by the formula: m is an integer of 1 to 10, and a is an integer of 0 to 1. [ka] (In the formula, R 2 is the same as above, m is an integer of 1 to 10, and n is an integer of 1 to 500.

[0063] In the above formula (1), R 1 is a monovalent alkyl group having 1 to 6 carbon atoms, and specific examples thereof include alkyl groups such as a methyl group, an ethyl group, a propyl group, and a butyl group, and cycloalkyl groups such as a cyclopentyl group and a cyclohexyl group. 2 are independently an alkyl group having 1 to 6 carbon atoms, a phenyl group, or -OSiR 3 3 (R 3 are independently monovalent organic groups having 1 to 6 carbon atoms. The alkyl group having 1 to 6 carbon atoms is 1 The same examples as those given above can be used. 3 Examples of the group represented by 3 include a trimethylsiloxy group, an ethyldimethylsiloxy group, a phenyldimethylsiloxy group, a vinyldimethylsiloxy group, a chloromethyldimethylsiloxy group, and a 3,3,3-trifluoropropyldimethylsiloxy group.

[0064] In the above general formula (1), a is an integer of 0 to 1, and m is an integer of 1 to 10. In a preferred embodiment of the above general formula (1), m is 3, and R 1 , R 2 are all preferably methyl groups and a is preferably 0.

[0065] In the general formula (2), n is an integer of 1 to 500, preferably 1 to 100, and more preferably 1 to 50. Within this range, the weight ratio of organopolysiloxane does not become too high, and the properties derived from the cellulose nanofibers do not deteriorate.

[0066] In the present invention, the (B) isocyanate group-containing organopolysiloxane may be a commercially available product or may be synthesized according to a known method. One type may be used alone, or two or more types may be used in combination.

[0067] (B) The isocyanate group-containing organopolysiloxane has a kinematic viscosity of 1 mm at 25°C measured using a Canon-Fenske viscometer according to JIS Z8803:2011. 2 / s or more 500mm 2 / s or less is preferable, and 1mm 2 / s or more 100mm 2 / s or less is preferable. Within this range, it is preferable in terms of usability and reactivity.

[0068] In particular, the (B) isocyanate group-containing organopolysiloxane is tristrimethylsiloxysilylpropyl isocyanate (in the above general formula (1), m=3, R 2 is a methyl group and a is 0. It is preferable to use the following formula (3). When tristrimethylsiloxysilylpropyl isocyanate is reacted with cellulose nanofibers, the hydroxy groups in the cellulose nanofibers react, resulting in hydrophobic cellulose nanofibers represented by the following general formula (4). [ka] [ka]

[0069] For example, when the cellulose nanofiber is a phosphite-containing cellulose nanofiber, the hydroxy group at any of the C2, C3, and C6 positions is modified via a urethane bond.

[0070] (C) Oil The hydrophobic cellulose nanofibers are preferably dispersed in an oil agent (C) to form a hydrophobic cellulose nanofiber dispersion, and the oil agent (C) preferably contains one or more oils selected from the group consisting of aliphatic alcohols, silicone oils, and hydrocarbon oils.

[0071] Examples of the aliphatic alcohol include monohydric aliphatic alcohols such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-methyl-1-propanol, 2-butanol, 2-methyl-2-propanol, 1-pentanol, 2-methylbutanol, 2-pentanol, 1-hexanol, 2-methylpentanol, 1-heptanol, 1-octanol, 1-nonanol, and 1-decanol; and dihydric aliphatic alcohols such as ethylene glycol and 1,2-propylene glycol. Examples of the hydrocarbon oil include aromatic hydrocarbons such as toluene and xylene, aliphatic ketones such as acetone, methyl ethyl ketone, diethyl ketone and methyl isobutyl ketone, and aliphatic hydrocarbons such as hexane, heptane, octane, cyclohexane, isooctane, isododecane and isohexadecane. Examples of the silicone oil include dimethylpolysiloxane (KF-96L-1cs, KF-96L-1.5cs, KF-96L-2cs, etc., manufactured by Shin-Etsu Chemical Co., Ltd.), octamethyltetrasiloxane (D4), decamethylpentasiloxane (D5) (KF-995, manufactured by Shin-Etsu Chemical Co., Ltd.), dodecamethylhexasiloxane (D6), tristrimethylsiloxymethylsilane (TMF-1.5, manufactured by Shin-Etsu Chemical Co., Ltd.), caprylylmethylsilane (D7), and the like. Examples of silicone oils include low- to high-viscosity linear or branched organopolysiloxanes such as thiazolinone, phenyl trimethicone, methylphenyl polysiloxane (Shin-Etsu Chemical Co., Ltd.: KF-54, KF-54HV), diphenylsiloxyphenyl trimethicone (Shin-Etsu Chemical Co., Ltd.: KF-56A), methylhexyl polysiloxane, and dimethylsiloxane-methylphenyl siloxane copolymers. Among the above oils, it is preferable to use silicone oil.

[0072] The mass ratio of (C) oil to hydrophobic cellulose nanofibers is preferably 1:0.0001 to 1:0.5, which is preferable from the standpoint of usability because within this range the cellulose nanofiber concentration does not become too high and the viscosity does not become too high.

[0073] The light transmittance at a wavelength of 600 nm of a 0.2% by mass silicone oil dispersion of a hydrophobic cellulose nanofiber dispersion is preferably 70% or more, more preferably 80% or more, and even more preferably 90% or more. If it is 70% or more, transparency is sufficient, there are few aggregates, and reactivity is not reduced.

[0074] The average fiber diameter is preferably 300 nm or less. It is more preferably 100 nm or less, and even more preferably 80 nm or less. If it is 300 nm or less, the light transmittance of the dispersion does not decrease, and the transparency of the film is maintained. The average fiber length is preferably 0.1 μm or more and 1,000 μm or less, more preferably 0.1 μm or more and 800 μm or less, and even more preferably 0.1 μm or more and 600 μm or less. Within this range, the thickening effect is not impaired, and strength is likely to increase when compounded with a resin.

[0075] [Manufacturing method] Because cellulose nanofibers are hydrophilic, they use water-soluble polar solvents, typically water or alcohol, as their dispersion medium. When producing hydrophobic cellulose nanofibers of the present invention, substitution of the dispersion medium is necessary because water and alcohol are reactive with isocyanate groups and are not suitable as reaction solvents. Therefore, it is preferable to first substitute the dispersion medium with a hydrophilic dispersion medium with a low water or alcohol content, then perform a hydrophobic treatment, and then further substitute the dispersion medium with the desired oil.

[0076] Regarding the above-described embodiment, a method for producing a hydrophobic cellulose nanofiber dispersion including the following steps 1 to 3 will be described. Step 1: (A) A step of replacing the water, which is the dispersion medium in an aqueous dispersion of cellulose nanofibers, with (D) an organic solvent to obtain a cellulose nanofiber dispersion. Step 2: Adding (B) an isocyanate group-containing organopolysiloxane to the dispersion obtained in Step 1 to hydrophobize (A) the cellulose nanofibers in the dispersion. Step 3: A step of replacing the organic solvent in the hydrophobic cellulose nanofiber dispersion obtained in Step 2 with (C) an oil agent

[0077] In step 1, the (D) organic solvent is an organic compound that is a water-soluble liquid with a boiling point of 100°C or higher and is not reactive with isocyanate groups. The boiling point is the boiling point under 1 atmosphere, and is preferably 100°C or higher, more preferably 110°C or higher, and even more preferably 150°C or higher. A temperature of 100°C or higher is preferred because there is no risk of component (D) volatilizing when removing water, which does not cause the cellulose nanofibers to aggregate.

[0078] The solubility of the component (D) in water is preferably 30 g or more, and more preferably 50 g or more, per 100 g of water at 25° C. A solubility of 30 g or more is preferable because there is no risk of precipitation of cellulose nanofibers in the dispersion.

[0079] Specific examples of the component (D) include amides such as N,N-dimethylacetamide, N,N-dimethylformamide, and N-methyl-2-pyrrolidone, heterocyclic compounds such as pyridine, and sulfoxides such as dimethyl sulfoxide. These may be used alone or in combination. Of these, N-methyl-2-pyrrolidone is particularly preferred.

[0080] Any of the following devices can be used as the defibration device used in the dispersion step of step 1. For example, a household mixer, a homomixer under high-speed rotation, a disperser, a low-pressure homogenizer, a high-pressure homogenizer, a ball mill, a jet mill, a twin-screw extruder, an ultrasonic dispersion treatment, a grinder, etc. can be used. Regardless of the above devices, any defibration device that is generally used for household or industrial production can be used. Of the above defibration devices, it is preferable to use a low-pressure homogenizer or a high-pressure homogenizer.

[0081] When reacting the hydroxy groups of the cellulose nanofibers with the isocyanate group-containing organopolysiloxane in step 2, it is undesirable to leave behind any solvent reactive with the isocyanate groups. Therefore, remaining water or alcohol in the reaction system is undesirable and must be thoroughly removed. In particular, since water, which is a dispersant, also has the effect of stably dispersing cellulose nanofibers, it is undesirable to remove water in the absence of other dispersants. Therefore, a method for selectively removing water and replacing it with (D) the organic solvent is preferably to distill off the water under reduced pressure. The pressure is 100 mmHg or less, and more preferably 50 mmHg or less.

[0082] The amount of water / alcohol contained in the dispersion of cellulose nanofibers substituted with component (D) is preferably 1% by mass or less, and more preferably 0.1% by mass or less. A content of 1% by mass or less is preferable because it prevents the isocyanate groups of component (B), the isocyanate group-containing organopolysiloxane, from being deactivated and causing the generation of by-products.

[0083] The amount of (D) organic solvent used is preferably 10 to 90% by mass of the total reaction solution (system), more preferably 20 to 90% by mass. Within this range, the reaction system is maintained uniformly, and the reaction proceeds efficiently. If the concentration is 10% by mass or more, the cellulose nanofibers do not thicken component (D), so the viscosity does not increase and reactivity does not decrease. If the concentration is 90% by mass or less, the concentration does not become too low, and work efficiency does not decrease.

[0084] In step 2, the amount of (B) isocyanate group-containing organopolysiloxane mixed relative to the cellulose nanofibers contained in (A) cellulose nanofibers substituted with (D) is preferably in the range of 2 to 60 mass% (weight of isocyanate group-containing organopolysiloxane / weight of cellulose nanofibers), and more preferably 5 to 40 mass%. If it is 2 mass% or more, there is sufficient isocyanate group-containing organopolysiloxane reacted with the hydroxy groups of the cellulose nanofibers, so dispersibility in (C) oil is not reduced. If it is 60 mass% or less, the amount of hydroxy groups necessary for thickening (C) oil that are blocked is not too large, so thickening properties are not reduced.

[0085] In step 2, it is preferable to add component (E), a urethanization catalyst.

[0086] Specific examples of component (E) include known catalysts used in forming urethane bonds, such as amines such as triethylamine, triethylenediamine, and N-methylmorpholine, and organometallic compounds such as di-n-butyltin dilaurate and stannous oleate. The amount added may be an appropriate amount depending on the type and amount of component (B) and the reaction temperature.

[0087] The conditions for the urethane bond-forming reaction are not particularly limited, but the reaction temperature under reflux is preferably 25 to 100°C, more preferably 30 to 90°C. If the reaction temperature is 100°C or lower, yellowing of the cellulose and a decrease in the degree of polymerization do not occur, and if it is 25°C or higher, there is no concern about a decrease in the reaction rate. The reaction time is preferably 1 to 10 hours of heating. A reaction time within this range is preferable because there is no risk of yellowing of the cellulose nanofibers.

[0088] After the urethane bond-forming reaction, it is desirable to add a lower alcohol such as methanol or ethanol or water to deactivate the unreacted isocyanate group-containing organopolysiloxane (B). Methanol, ethanol, and 2-propanol are particularly preferred because they are easy to remove. The amount added is preferably 1% to 10% by weight, and more preferably 1% to 8% by weight, of component (B).

[0089] In the present invention, in step 3, it is preferable to add a step of washing the cellulose nanofiber dispersion containing component (D) as a dispersion medium with component (F) a liquid organic compound at 25°C and 1 atmosphere before replacing component (D) with component (C).

[0090] A cellulose nanofiber dispersion using component (D) as a dispersion medium is washed with component (F), a liquid organic compound, at 25°C and 1 atmosphere, and filtered repeatedly to obtain a swollen gel in which the hydrophobic cellulose nanofibers are swollen by component (F).

[0091] Specific examples of component (F) include alcohols having 1 to 4 carbon atoms, such as methanol, ethanol, n-propyl alcohol, 2-propanol, n-butyl alcohol, and isobutyl alcohol; ketones, such as acetone, diethyl ketone, and methyl ethyl ketone; esters, such as methyl acetate, ethyl acetate, and butyl acetate; aromatic hydrocarbons, such as toluene and xylene; and ethers, such as diethyl ether and tetrahydrofuran. From the viewpoint of ease of removal, the use of methanol, ethanol, and 2-propanol is particularly preferred.

[0092] Washing with component (F) makes it possible to remove unreacted (B) isocyanate group-containing organopolysiloxane, by-products derived from (B), (D) organic solvent, and (E) urethane catalyst.

[0093] In particular, the unreacted (B) isocyanate group-containing organopolysiloxane used as a raw material and by-products derived from (B) are unstable raw materials and therefore undesirable to remain. By washing with component (F), it is preferable to reduce their total amount relative to the hydrophobic cellulose nanofibers to 1% by mass or less. This is preferably 0.1% by mass or less, and more preferably 0.01% by mass or less.

[0094] In the present invention, by adding component (C) oil solution and removing component (F), a dispersion of hydrophobic cellulose nanofibers substituted with component (C) can be obtained.

[0095] A preferred method for selectively removing component (F) is distillation under reduced pressure. The pressure is preferably 100 mmHg or less, and more preferably 50 mmHg or less. Furthermore, when an oil solution (C) with a boiling point lower than that of component (F) is used, distillation under reduced pressure also removes component (C), which is undesirable because it can cause the hydrophobic cellulose nanofibers to aggregate. Even if component (C) is added to a dried product or gel of hydrophobic cellulose nanofibers from which all or part of the liquid components have been removed from a dispersion of component (F), it is difficult to defibrate the aggregates and to uniformly disperse the hydrophobic cellulose nanofibers in component (C), which is undesirable.

[0096] [Physical properties of hydrophobic cellulose nanofibers] The hydrophobic cellulose nanofibers of the present invention are solid and have film-forming properties. Since the transparency and continuity of the formed film decrease depending on the amount of aggregates contained in the dispersion, the light transmittance of the dispersion is preferably 70% or higher, more preferably 80% or higher, and even more preferably 90% or higher. When the light transmittance is within the above range, the dispersion can be suitably used as a film-forming agent.

[0097] Whether the hydrophobic cellulose nanofibers of the present invention exhibit film-forming properties can be determined by dropping 1.5 g of the above hydrophobic cellulose nanofiber dispersion diluted with (C) oil onto a polytetrafluoroethylene (PTFE) resin plate, drying at 105°C for 3 hours, and determining whether a film forms. If a film is not formed, the appearance will be powdery rather than transparent. Therefore, when incorporated into cosmetics, the nanofibers have poor skin conformability, resulting in an unnatural finish.

[0098] When blended into cosmetics as a film-forming agent, it produces cosmetics that are not sticky when applied and have a pleasant feel when used. The film formed also has excellent water resistance and durability, and adheres well to the skin, resulting in long-lasting makeup and excellent spreadability and finish.

[0099] Furthermore, the hydrophobic cellulose nanofibers of the present invention have the effect of thickening the dispersion medium by entangling the nanofibers with each other through interactions within the dispersion medium. This thickening effect is particularly pronounced when the dispersion medium is silicone. Therefore, when a hydrophobic cellulose nanofiber dispersion is used as an emulsion composition, it is possible to thicken the oil phase, thereby providing cosmetics with excellent texture and stability over time. Therefore, when used in a water-in-oil emulsion composition in particular, it is possible to thicken the outer phase, thereby contributing to improved texture and stabilization.

[0100] [Cosmetics] The hydrophobic cellulose nanofibers and hydrophobic cellulose nanofiber dispersions of the present invention can be used in a variety of applications, particularly as raw materials for all cosmetics applied externally to skin and hair. In such cases, they are preferably applied in the form of a dispersion. That is, cosmetics containing the hydrophobic cellulose nanofiber dispersion described above can be produced. The blending amount of hydrophobic cellulose nanofibers is preferably in the range of 0.1 to 40% by mass of the total cosmetic, more preferably 0.1 to 20% by mass. A blending amount of 0.1% by mass or more provides a satisfactory feel to the touch, while a blending amount of 40% by mass or less does not adversely affect the feel during use.

[0101] The hydrophobic cellulose nanofibers, hydrophobic cellulose nanofiber dispersions, and cosmetics containing them of the present invention can contain various other components commonly used in cosmetics. These other components may include, for example, (G) oils other than component (C), (H) powders, (I) surfactants, (J) crosslinked organopolysiloxanes, (K) film-forming agents, and (L) other additives. These can be used alone or in appropriate combinations of two or more. These components are selected and used appropriately depending on the type of cosmetic, and their amounts can be known amounts depending on the type of cosmetic.

[0102] (G) Component: Oil other than (C) The cosmetic of the present invention can contain, as component (G), one or more oils selected from oils other than component (C), depending on the purpose. Any solid, semi-solid, or liquid oil used in conventional cosmetics can be used, including natural animal and vegetable oils and semi-synthetic oils and fats, hydrocarbon oils, silicone oils, higher alcohols, ester oils, fluorine-based oils, and ultraviolet absorbers. When an oil other than component (C) is contained, the amount of the oil other than component (C) is not particularly limited, but is preferably 1 to 95% by mass, and more preferably 1 to 30% by mass, of the total cosmetic.

[0103] Natural animal and vegetable oils and semi-synthetic oils As natural animal and plant oils and semi-synthetic oils, there are avocado oil (display name (INCI: Persea Gratissima (Avocado) Oil)), linseed oil (display name (INCI: Linum Usitatissimum (Linseed) Seed Oil)), almond oil (display name (INCI: Prunus Amygdalus Dulcis (Sweet Almond) Oil)), perilla oil, olive oil (display name (INCI: Olea Europaea (Olive) Fruit Oil)), torreya nucifera oil (display name (INCI: Torreya Californica (California Nutmeg) Oil)), citronella oil (display name (INCI: Cymbopogon Nardus (Citronella) Oil)), kyounin oil (display name (INCI: Kyounin Yu)), wheat germ oil (display name (INCI: Triticum Vulgare (Wheat) Germ Oil)), sesame oil (display name (INCI: Sesamum Indicum (Sesame) Seed Oil)), rice germ oil (display name (INCI: Oryza Sativa (Rice) Germ Oil)), rice bran oil (display name (INCI: Oryza Sativa (Rice) Bran Oil)), camellia kissi seed oil (display name (INCI: Camellia Kissi Seed Oil)), safflower oil (display name (INCI: Carthamus Tinctorius (Safflower) Seed Oil)), sinagiri oil, cinnamon oil, squalane, squalene, soybean oil, tea seed oil, camellia japonica seed oil (display name (INCI: Camellia Japonica Seed Oil)), evening primrose oil (display name (INCI: Oenothera Biennis (Evening Primrose) Oil)), corn oil (INCI: Zea Mays (Corn) Oil), rapeseed oil (display name (INCI: RAPE SHUSHI YU)), Japanese cypress oil, corn germ oil (display name (INCI: Zea Mays (Corn) Germ Oil)), persic oil (display name), palm oil (display name (INCI: ElaeisGuineensis (Palm) Oil)), palm kernel oil (INCI:Elaeis Guineensis (Palm) Kernel Oil)), castor oil (INCI:Ricinus Communis (Castor) Seed Oil)), sunflower oil (INCI:Helianthus Annuus (Sunflower) Seed Oil)), grape seed oil (INCI:Vitis Vinifera (Grape) Seed Oil)), jojoba oil (INCI:Simmondsia Chinensis (Jojoba) Seed Oil)), macadamia nut oil (INCI:Macadamia Ternifolia Seed Oil)), meadowfoam oil (INCI:Limnanthes Alba (Meadowfoam) Seed Oil)), cottonseed oil (INCI:Gossypium Herbaceum (Cotton) Natural vegetable oils such as coconut oil (INCI: Cocos Nucifera (Coconut) Oil), peanut oil (INCI: Arachis Hypogaea (Peanut) Oil), natural animal oils such as shark liver oil (INCI: Shark Liver Oil), cod liver oil (INCI: Cod Liver Oil), fish liver oil (INCI: Fish Liver Oil), turtle oil (INCI: Turtle Oil), mink oil (INCI: Mink Oil), egg yolk oil (INCI: Egg Oil), hydrogenated coconut oil (INCI: Hydrogenated Coconut Oil), hardened castor oil, castor oil fatty acid methyl ester, liquid lanolin (INCI: Lanolin) Semi-synthetic oils and fats such as synthetic oils and fats.

[0104] Hydrocarbon oil The hydrocarbon oil may be a linear or branched hydrocarbon oil, and may be either a volatile or non-volatile hydrocarbon oil. Specific examples include olefin oligomer, dodecane (INCI), undecane (INCI), squalane (INCI), squalene (INCI), mineral oil (INCI), polyisobutylene (display name), hydrogenated polyisobutene (display name (INCI: Hydrogenated Polyisobutene)), (C13-15) alkane (INCI), etc.

[0105] Silicone oil Examples of silicone oils include amino-modified organopolysiloxanes, pyrrolidone-modified organopolysiloxanes, pyrrolidonecarboxylic acid-modified organopolysiloxanes, silicone rubbers such as high-polymerization gummy dimethicone (INCI), gummy amino-modified organopolysiloxanes, and gummy dimethylsiloxane-methylphenylsiloxane copolymers, as well as cyclic organopolysiloxane solutions of silicone gums and rubbers, amino acid-modified silicones, fluorine-modified silicones, silicone resins, and silicone resin solutions.

[0106] Higher alcohol Preferred examples of higher alcohols include alcohols having 6 or more carbon atoms. Specific examples include lauryl alcohol, myristyl alcohol, palmityl alcohol, stearyl alcohol, behenyl alcohol, hexadecyl alcohol, oleyl alcohol, isostearyl alcohol, hexyldodecanol, octyldodecanol, cetostearyl alcohol, 2-decyltetradecynol, cholesterol, phytosterol, POE cholesterol ether, monostearyl glycerin ether (batyl alcohol), and monooleyl glyceryl ether (selachyl alcohol).

[0107] Ester oil Ester oils are liquid oils formed by condensing fatty acids having 1 to 20 carbon atoms with alcohols having 1 to 20 carbon atoms, and examples of such ester oils include polyesters such as monoesters, diesters, and triesters. Specifically, n-alkyl glycol monoisostearates such as diisobutyl adipate (label name (INCI: Diisobutyl Adipate)), dihexyldecyl adipate (label name (INCI: Diheptylundecyl Adipate)), and isostearyl isostearate (label name (INCI: Isostearyl Isostearate)), isocetyl isostearate (label name (INCI: Isocetyl Isostearate)), trimethylolpropane triisostearate (label name (INCI: Trimethylolpropane Triisostearate)), glycol diethylhexanoate (label name (INCI: Glycol Diethylhexanoate)), and cetyl ethylhexanoate (label name (INCI: Cetyl Octyldodecyl esters such as triethylhexanoin (labeled as (INCI: Triethylhexanoin)), trimethylolpropane triethylhexanoate (labeled as (INCI: Trimethylolpropane Triethylhexanoate)), pentaerythrityl tetraethylhexanoate (labeled as (INCI: Pentaerythrityl Tetraethylhexanoate)), cetyl octanoate (labeled as (INCI: Cetyl Ethylhexanoate)), octyldodecyl stearoyloxystearate (labeled as (INCI: Octyldodecyl Stearoyl Stearate)), oleyl oleate (labeled as (INCI: Oleyl Oleate)), octyldodecyl oleate (labeled as (INCI: Octyldodecyl Oleate)), decyl oleate (labeled as (INCI: Decyl Oleate), Neopentyl Glycol Dioctanoate (Indication Name (INCI: Neopentyl GlycolDiethylhexanoate), neopentyl glycol dicaprate (: Display name (INCI: Neopentyl Glycol Dicaprate)), triethyl citrate (: Display name (INCI: Triethyl Citrate)), diethylhexyl succinate (: Display name (INCI: Diethylhexyl Succinate)), amyl acetate (: Display name (INCI: Amyl Acetate)), ethyl acetate (: Display name (INCI: Et h Butyl Acetate), Butyl Acetate (Indication Name (INCI: Butyl Ac Andate), Isocetyl stearate (InCI: Isocetyl Stearate), Butyl stearate (InCI: Butyl Stearate), Diisopropyl sebacate (InCI: Diisopropyl Sebacate), Diethylhexyl sebacate (InCI: Diethylhexyl Sebacate), Cetyl lactate (InCI: Cetyl Lactate), Myristyl lactate (InCI: Myristyl Lactate), Isononyl isononanoate (InCI: Isononyl Isononanoate), Isotridecyl isononanoate (InCI: Isotridecyl Isononanoate), Isopropyl palmitate (InCI: Isopropyl Palmitate), Ethylhexyl palmitate (InCI: Ethylhexyl Palmitic acid esters such as hexyldecyl palmitate (label name (INCI: Isocetyl Palmitate, Hexyldecyl Palmitate)), cholesteryl hydroxystearate (label name (INCI: Cholesteryl Hydroxystearate)), isopropyl myristate (label name (INCI: Isopropyl Myristate)), octyldodecyl myristate (label name (INCI: Octyldodecyl Myristate)), myristyl myristate (label name (INCI: Myristyl Myristate)), ethylhexyl laurate (label name (INCI: Ethylhexyl Laurate)), hexyl laurate (label name (INCI: Hexyl Laurate)), dioctyldodecyl lauroyl glutamate (label name (INCI: Dioctyldodecyl Lauroyl Glutamate), Lauroyl Sarcosine Isopropyl Ester (Indication Name (INCI: Isopropyl Lauroyl Sarcosinate)), Diisostearyl Malate (Indication Name (INCI: DiisostearylExamples of glyceride oils include glyceryl malate, glyceryl acetate (INCI: Glyceryl Acetate), and glyceryl stearate (INCI: Glyceryl Stearate).

[0108] Fluorine-based oils Examples of fluorine-based oils include perfluoropolyethers such as polyperfluoromethylisopropyl ether (INCI: Polyperfluoromethylisopropyl Ether), and perfluorocarbons such as perfluorodecalin (INCI: Perfluorodecalin) and perfluorohexane (INCI: Perfluorohexane).

[0109] UV absorber UV absorbers include homosalate (INCI), octocrylene (INCI), t-butyl methoxydibenzoylmethane (INCI: Butyl Methoxydibenzoylmethane), ethylhexyl salicylate (INCI: Ethylhexyl Salicylate), diethylamino hydroxybenzoyl hexyl benzoate (INCI: Diethylamino Hydroxybenzoyl Hexyl Benzoate), oxybenzone-6 (INCI: Benzophenone-6), oxybenzone-9 (INCI: Benzophenone-9), oxybenzone-1 (INCI: Benzophenone-1), polysilicone-15 (INCI), and dimethoxybenzylidene dioxoimidazolidine octyl propionate (INCI: Ethylhexyl Dimethoxybenzylidene Dioxoimidazolidine Propionate), Oxybenzone-2 (Inc. Name: Benzophenone-2), Terephthalylidene Dicamphor Sulfonic Acid (Inc. Name: Terephthalylidene Dicamphor Sulfonic Acid), Ethylhexyl Triazone (Inc.), Bis(trimethylsiloxy)silylisopentyl Methyl Trimethoxycinnamate (Inc. Name: Isopentyl Trimethoxycinnamate Trisiloxane), Drometrizole Trisiloxane (Inc.), Ethylhexyl Dimethyl PABA (Inc. Name: Ethylhexyl Dimethyl PABA), Isopropyl Methoxycinnamate (Inc. Name: Isopropyl Methoxycinnamate), Ethylhexyl Methoxycinnamate (Inc. Name: Ethylhexyl Methoxycinnamate), Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine (Inc. Name: Bis-Ethylhexyloxyphenol) MethoxyphenylTriazine), Oxybenzone-3 (Indication Name (INCI: Benzophenone-3)), Oxybenzone-4 (Indication Name (INCI: Benzophenone-4)), Oxybenzone-5 (Indication Name (INCI: Benzophenone-5)), Phenylbenzimidazole Sulfonic Acid (Indication Name (INCI: Phenylbenzimidazole Sulfonic Acid)), Methylene Bis-Benzotriazolyl Tetramethylbutylphenol (Indication Name (INCI: Methylene Bis-Benzotriazolyl Tetramethylbutylphenol)), Glyceryl Dimethoxycinnamate Ethylhexanoate (Indication Name (INCI: Glyceryl Ethylhexanoate Dimethoxycinnamate)), Glyceryl PABA (Indication Name (INCI: Glyceryl PABA)), Diisopropyl Methyl Cinnamate (Indication Name (INCI: Diisopropyl Methyl Examples of such UV absorbers include diethylamino hydroxybenzoyl hexyl benzoate (INCI: Diethylamino Hydroxybenzoyl Hexyl Benzoate), cinoxate (INCI), and ethylhexyl dimethoxybenzylidene dioxoimidazolidine propionate (INCI: Ethylhexyl Dimethoxybenzylidene Dioxoimidazolidine Propionate). In addition, UVA absorbers (e.g., diethylamino hydroxybenzoyl hexyl benzoate (INCI: Diethylamino Hydroxybenzoyl Hexyl Benzoate)) and UVB absorbers (e.g., ethylhexyl methoxycinnamate (INCI: Ethylhexyl Methoxycinnamate)) can be used in combination, and they can also be combined in any desired manner.

[0110] (H) Component: Powder The powder is not particularly limited as long as it is a raw material that can normally be blended into cosmetics, and examples include pigments, silicone spherical powders, etc. When blending powder, the blending amount of the powder is not particularly limited, but it is desirable for the blending amount to be 0.1 to 90% by mass, and more preferably 1 to 35% by mass, of the total cosmetic.

[0111] The pigment is not particularly limited as long as it is one generally used in makeup cosmetics. Examples include inorganic pigments such as talc, mica, sericite, synthetic phlogopite, barium sulfate, aluminum oxide, kaolin, silica, calcium carbonate, zinc oxide, titanium oxide, red iron oxide, yellow iron oxide, black iron oxide, ultramarine, Prussian blue, carbon black, low-order titanium oxide, cobalt violet, chromium oxide, chromium hydroxide, cobalt titanate, bismuth oxychloride, and titanium-mica pearl pigments; organic pigments such as zirconium, barium, or aluminum lakes, such as Red No. 201, Red No. 202, Red No. 204, Red No. 205, Red No. 220, Red No. 226, Red No. 228, Red No. 405, Orange No. 203, Yellow No. 205, Yellow No. 4, Yellow No. 5, Blue No. 1, Blue No. 404, and Green No. 3; natural pigments such as chlorophyll and β-carotene; and dyes.

[0112] The above-mentioned powders may also be surface-treated. The surface treatment agent is preferably one that can impart hydrophobicity from the viewpoint of water resistance of the preparation, and is not particularly limited as long as it can impart hydrophobicity, and examples thereof include silicone treatment agents, waxes, paraffins, organic fluorine compounds such as perfluoroalkyl phosphates, surfactants, amino acids such as N-acyl glutamic acid, and metal soaps such as aluminum stearate and magnesium myristate. More preferred are silicone treatment agents, including silanes or silylating agents such as caprylsilane (AES-3083, manufactured by Shin-Etsu Chemical Co., Ltd.) or trimethoxysilyldimethicone, silicone oils such as dimethylsilicone (KF-96A series, manufactured by Shin-Etsu Chemical Co., Ltd.), methylhydrogen polysiloxane (KF-99P, KF-9901, etc., manufactured by Shin-Etsu Chemical Co., Ltd.), and branched silicone treatment agents (KF-9908, KF-9909, etc., manufactured by Shin-Etsu Chemical Co., Ltd.), and acrylic silicones (KP-574, KP-541, manufactured by Shin-Etsu Chemical Co., Ltd.). The above surface hydrophobic treatment agents may be used alone or in combination of two or more. Specific examples of surface-treated color pigments include the KTP-09 series, particularly KTP-09W, 09R, 09Y, and 09B, manufactured by Shin-Etsu Chemical Co., Ltd. Specific examples of dispersions containing hydrophobized titanium oxide fine particles or hydrophobized zinc oxide fine particles include SPD-T5, T6, T7, T5L, Z5, Z6, and Z5L, manufactured by Shin-Etsu Chemical Co., Ltd. When these components are incorporated, the amount is preferably 0.01 to 95% by mass of the cosmetic.

[0113] Examples of silicone spherical powders include crosslinked silicone powders (i.e., so-called silicone rubber powders composed of organopolysiloxanes having a structure in which repeating chains of diorganosiloxane units are crosslinked), silicone resin particles (polyorganosilsesquioxane resin particles having a three-dimensional network structure), and silicone resin-coated silicone rubber powders. Specific examples of crosslinked silicone powders and silicone resin particles are known as (dimethicone / vinyldimethicone) crosspolymers and polymethylsilsesquioxanes. These are commercially available as powders or as swollen products containing silicone oil, such as KMP-598, KMP-590, KMP-591, and KSG-016F (all manufactured by Shin-Etsu Chemical Co., Ltd.). These powders impart slipperiness to cosmetics and improve their feel due to the rolling effect unique to spherical powders. These powders may be used alone or in combination.

[0114] Silicone resin-coated silicone rubber powder is particularly preferred for its improved feel, such as preventing stickiness, and its ability to correct unevenness such as wrinkles and pores. Specific examples of silicone resin-coated silicone rubber powder are known under the names defined in the cosmetic labeling system, such as (vinyl dimethicone / methicone silsesquioxane) crosspolymer, (diphenyl dimethicone / vinyl diphenyl dimethicone / silsesquioxane) crosspolymer, polysilicone-22, and polysilicone-1 crosspolymer. These are commercially available under the trade names KSP-100, KSP-101, KSP-102, KSP-105, KSP-300, KSP-411, and KSP-441 (all manufactured by Shin-Etsu Chemical Co., Ltd.). These powders can be used alone or in combination with one another. When this component is incorporated, it is preferably present in an amount of 0.01 to 95% by mass of the cosmetic.

[0115] (I) Component: Surfactant Surfactants include nonionic, anionic, cationic, and amphoteric surfactants. Surfactants commonly used in cosmetics can be used depending on the objectives of the present invention. Among these surfactants, partially crosslinked polyether-modified silicones, partially crosslinked polyglycerin-modified silicones, linear or branched polyoxyethylene-modified organopolysiloxanes, linear or branched polyoxyethylene-polyoxypropylene-modified organopolysiloxanes, linear or branched polyoxyethylene-alkyl-co-modified organopolysiloxanes, linear or branched polyoxyethylene-polyoxypropylene-alkyl-co-modified organopolysiloxanes, linear or branched polyglycerin-modified organopolysiloxanes, linear or branched polyglycerin-alkyl-co-modified organopolysiloxanes, and linear or branched pyrrolidone-modified organopolysiloxanes are preferred. In these surfactants, the content of hydrophilic polyoxyethylene groups, polyoxyethylene-polyoxypropylene groups, or polyglycerin residues preferably accounts for 10 to 70% by mass of the molecule. Furthermore, when a partially crosslinked polyether-modified silicone or a partially crosslinked polyglycerin-modified silicone is used, in a composition comprising the crosslinked organopolysiloxane and an oil that is liquid at room temperature, the crosslinked organopolysiloxane preferably swells with the liquid oil in an amount equal to or greater than its own weight. The liquid oil may be a liquid silicone, hydrocarbon oil, ester oil, natural animal or vegetable oil, semi-synthetic oil, or fluorine-based oil, among the optional oil components. For example, a liquid silicone having a kinematic viscosity at 25°C of 0.65 to 100 mm 2Examples of crosslinked organopolysiloxanes include low-viscosity silicones (1 / s), liquid paraffin, hydrocarbon oils such as squalane, isododecane, and isohexadecane, glyceride oils such as triethylhexanoin, ester oils such as isotridecyl isononanoate, and natural animal and vegetable oils such as jojoba oil. Specific examples of crosslinked organopolysiloxanes include KSG-210, KSG-240, KSG-310, KSG-320, KSG-330, KSG-340, KSG-320Z, KSG-350Z, KSG-710, KSG-810, KSG-820, KSG-830, KSG-840, KSG-820Z, and KSG-850Z, all manufactured by Shin-Etsu Chemical Co., Ltd. Specific examples of non-crosslinked organopolysiloxanes include KF-6011, KF-6013, KF-6043, KF-6017, KF-6028, KF-6038, KF-6048, KF-6100, KF-6104, KF-6105, and KF-6106 manufactured by Shin-Etsu Chemical Co., Ltd. In any case, the amount of surfactant blended is preferably 0.1 to 20 mass% of the entire cosmetic, and one or more types of crosslinked organopolysiloxane, non-crosslinked organopolysiloxane, or both can be appropriately selected depending on the object of the present invention.

[0116] When component (I) is blended, the blending amount is preferably 0.01 to 15% by mass in the cosmetic.

[0117] Component (J): Crosslinked organopolysiloxane The crosslinked organopolysiloxane is not particularly limited as long as it is one that is normally used in cosmetics, and one type may be used alone or two or more types may be used in appropriate combination.

[0118] Unlike the silicone spherical powder described above in connection with component (H), this crosslinked organopolysiloxane does not have a spherical shape.

[0119] Unlike the surfactant of component (I), component (J) is preferably a compound that does not have a polyether or polyglycerin structure in its molecular structure. It is also preferably an elastomer that exhibits structural viscosity when swollen with an oil. Specific examples include (dimethicone / vinyl dimethicone) crosspolymer, (dimethicone / phenyl vinyl dimethicone) crosspolymer, (vinyl dimethicone / lauryl dimethicone) crosspolymer, and (lauryl polydimethylsiloxyethyl dimethicone / bis vinyl dimethicone) crosspolymer, as defined by the cosmetic labeling name. These are commercially available as swelling products containing oil that is liquid at room temperature, and specific examples include KSG-15, KSG-1510, KSG-16, KSG-1610, KSG-18A, KSG-19, KSG-41A, KSG-42A, KSG-43, KSG-44, KSG-042Z, KSG-045Z, and KSG-048Z manufactured by Shin-Etsu Chemical Co., Ltd.

[0120] When component (J) is blended, the blending amount is preferably 0.01 to 30 mass % in the cosmetic as solid content.

[0121] (K) Ingredient: Film-forming agent The film-forming agent can be used in combination with an existing film-forming agent. The existing film-forming agent is not particularly limited as long as it is a raw material that can be incorporated into ordinary cosmetics, but specific examples include latexes such as polyvinyl alcohol, polyvinylpyrrolidone, polyvinyl acetate, and alkyl polyacrylates, dextrin, cellulose derivatives such as alkyl cellulose and nitrocellulose, siliconized polysaccharide compounds such as tri(trimethylsiloxy)silylpropylcarbamate pullulan, acrylic-silicone graft copolymers such as (alkyl acrylate / dimethicone) copolymers, silicone resins such as trimethylsiloxysilicate, silicone-based resins such as silicone-modified polynorbornene and fluorine-modified silicone resins, fluororesins, aromatic hydrocarbon resins, polymer emulsion resins, terpene resins, polybutene, polyisoprene, alkyd resins, polyvinylpyrrolidone-modified polymers, rosin-modified resins, and polyurethanes.

[0122] Among these, silicone-based coating agents are particularly preferred, and examples thereof that can be used include, but are not limited to, tri(trimethylsiloxy)silylpropylcarbamate pullulan (commercially available products dissolved in solvents include TSPL-30-D5 and ID manufactured by Shin-Etsu Chemical Co., Ltd.), (alkyl acrylate / dimethicone) copolymers (commercially available products dissolved in solvents include KP-543, KP-545, KP-549, KP-550, and KP-545L manufactured by Shin-Etsu Chemical Co., Ltd.), trimethylsiloxysilicate (commercially available products dissolved in solvents include KF-7312J and X-21-5250 manufactured by Shin-Etsu Chemical Co., Ltd.), silicone-modified polynorbornene (commercially available products dissolved in solvents include NBN-30-ID manufactured by Shin-Etsu Chemical Co., Ltd.), and organosiloxane-grafted polyvinyl alcohol polymers.

[0123] When component (K) is blended, the blending amount is preferably 0.1 to 20% by mass in the cosmetic.

[0124] (L) Ingredients: Other additives Other additives include oil-soluble gelling agents, water-soluble thickeners, antiperspirants, preservatives and disinfectants, fragrances, salts, antioxidants, pH adjusters, chelating agents, cooling agents, anti-inflammatory agents, skin-beautifying ingredients (whitening agents, cell activators, skin roughness improving agents, blood circulation promoters, skin astringents, antiseborrheic agents, etc.), vitamins, amino acids, nucleic acids, hormones, and inclusion compounds. These (L) components can be used alone or in appropriate combinations of two or more. When the (L) component is incorporated, the amount incorporated is preferably 0.1 to 20% by mass of the cosmetic.

[0125] Oil-soluble gelling agent Examples of oil-soluble gelling agents include metal soaps such as aluminum stearate, magnesium stearate, and zinc myristate; amino acid derivatives such as N-lauroyl-L-glutamic acid and α,γ-di-n-butylamine; dextrin fatty acid esters such as dextrin palmitate, dextrin stearate, and dextrin 2-ethylhexanoate palmitate; sucrose fatty acid esters such as sucrose palmitate and sucrose stearate; fructooligosaccharide fatty acid esters such as fructooligosaccharide stearate and fructooligosaccharide 2-ethylhexanoate; benzylidene derivatives of sorbitol such as monobenzylidene sorbitol and dibenzylidene sorbitol; and organically modified clay minerals such as disteardimonium hectorite, stearalkonium hectorite, and hectorite.

[0126] Water-soluble thickener Examples of water-soluble thickeners include gum arabic, tragacanth, galactan, carob gum, guar gum, karaya gum, carrageenan, pectin, agar, quince seed, starch (rice, corn, potato, wheat, etc.), algae colloid, tolant gum, and plant-based polymers such as locust bean gum; microbial polymers such as xanthan gum, dextran, succinoglucan, and pullulan; animal polymers such as collagen, casein, albumin, and gelatin; starch-based polymers such as carboxymethyl starch and methylhydroxypropyl starch; methylcellulose, ethylcellulose, methylhydroxypropylcellulose, carboxymethylcellulose, hydroxymethylcellulose, hydroxypropylcellulose, nitrocellulose, sodium cellulose sulfate, and carbo Examples of the water-soluble polymer include cellulose-based polymers such as sodium oxymethylcellulose, crystalline cellulose, cationized cellulose, and cellulose powder; alginic acid-based polymers such as sodium alginate and propylene glycol alginate; vinyl-based polymers such as polyvinyl methyl ether and carboxyvinyl polymer; acrylic polymers such as polyoxyethylene-based polymers, polyoxyethylene-polyoxypropylene copolymer-based polymers, sodium polyacrylate, polyethyl acrylate, polyacrylamide, and acryloyldimethyl taurate copolymers; other synthetic water-soluble polymers such as polyethyleneimine and cationic polymers; and inorganic water-soluble polymers such as bentonite, magnesium aluminum silicate, montmorillonite, beidellite, nontronite, saponite, hectorite, and silicic anhydride.

[0127] Among these, water-soluble thickeners that can be preferably used are one or a combination of two or more selected from plant-based polymers, microbial-based polymers, animal-based polymers, starch-based polymers, cellulose-based polymers, alginic acid-based polymers, polyoxyethylene-polyoxypropylene copolymer-based polymers, acrylic polymers, and inorganic water-soluble polymers.

[0128] Antiperspirant Antiperspirants include aluminum hydroxyhalides such as aluminum chlorohydrate and aluminum allantoin chlorohydrate, aluminum halides such as aluminum chloride, aluminum allantoin salt, tannic acid, persimmon tannin, potassium aluminum sulfate, zinc oxide, zinc paraphenolsulfonate, burnt alum, tetrachloro(Al / zirconium) hydrate, trichlorohydrex glycine(Al / zirconium), etc. Particularly preferred components that exhibit high effectiveness are aluminum hydroxyhalides, aluminum halides, and their complexes or mixtures with zirconyl oxyhalides and zirconyl hydroxyhalides (for example, tetrachloro(Al / zirconium) hydrate, trichlorohydrex glycine(Al / zirconium)).

[0129] · Preservatives · Disinfectants Preservatives and disinfectants include alkyl parahydroxybenzoate, benzoic acid, sodium benzoate, sorbic acid, potassium sorbate, phenoxyethanol, imidazolidinyl urea, salicylic acid, isopropylmethylphenol, carbolic acid, parachlormetacresol, hexachlorophene, benzalkonium chloride, chlorhexidine chloride, trichlorocarbanilide, iodopropynyl butylcarbamate, polylysine, photosensitizers, silver, and plant extracts.

[0130] ·Fragrance Fragrances include natural fragrances and synthetic fragrances. Natural fragrances include plant-based fragrances isolated from flowers, leaves, wood, peels, etc., and animal-based fragrances such as musk and civet. Synthetic fragrances include hydrocarbons such as monoterpenes, alcohols such as aliphatic alcohols and aromatic alcohols, aldehydes such as terpene aldehydes and aromatic aldehydes, ketones such as alicyclic ketones, esters such as terpene esters, lactones, phenols, oxides, nitrogen-containing compounds, acetals, etc.

[0131] ·salts Examples of salts include inorganic salts, organic acid salts, amine salts, and amino acid salts. Examples of inorganic salts include sodium salts, potassium salts, magnesium salts, calcium salts, aluminum salts, zirconium salts, and zinc salts of inorganic acids such as hydrochloric acid, sulfuric acid, carbonic acid, and nitric acid. Examples of organic acid salts include salts of organic acids such as acetic acid, dehydroacetic acid, citric acid, malic acid, succinic acid, ascorbic acid, and stearic acid. Examples of amine salts and amino acid salts include salts of amines such as triethanolamine, and salts of amino acids such as glutamic acid. In addition, salts of hyaluronic acid, chondroitin sulfate, and the like, as well as neutral salts of acids and alkalis used in pharmaceutical formulations, can also be used.

[0132] Antioxidants Examples of antioxidants include, but are not limited to, carotenoids, ascorbic acid and its salts, ascorbyl stearate, tocopherol, tocopherol acetate, tocopherol, pt-butylphenol, butylhydroxyanisole, dibutylhydroxytoluene, phytic acid, ferulic acid, thiotaurine, hypotaurine, sulfites, erythorbic acid and its salts, chlorogenic acid, epicatechin, epigallocatechin, epigallocatechin gallate, apigenin, campherol, myricetin, and quercetin.

[0133] pH adjuster Examples of pH adjusters include lactic acid, citric acid, glycolic acid, succinic acid, tartaric acid, dl-malic acid, potassium carbonate, sodium bicarbonate, and ammonium bicarbonate.

[0134] Chelating agents Examples of the chelating agent include alanine, edetate sodium salt, sodium polyphosphate, sodium metaphosphate, phosphoric acid, and the like.

[0135] · Cooling agent Cooling agents include L-menthol, camphor, menthyl lactate, and the like.

[0136] Anti-inflammatory Anti-inflammatory agents include allantoin, glycyrrhizinic acid and its salts, glycyrrhetinic acid and stearyl glycyrrhetinate, tranexamic acid, azulene, and the like.

[0137] ·Skin-beautifying ingredients Examples of skin-beautifying ingredients include whitening agents such as placenta extract, arbutin, glutathione, and saxifrage extract; cell activators such as royal jelly, photosensitizers, cholesterol derivatives, and calf blood extract; skin roughness improving agents; blood circulation promoters such as nonylic acid valenylamide, nicotinic acid benzyl ester, nicotinic acid β-butoxyethyl ester, capsaicin, zingerone, cantharides tincture, ichthammol, caffeine, tannic acid, α-borneol, tocopherol nicotinate, inositol hexanicotinate, cyclandelate, cinnarizine, tolazoline, acetylcholine, verapamil, cepharanthine, and γ-oryzanol; skin astringents; and antiseborrheic agents such as sulfur and thianthrol.

[0138] Vitamins Vitamins include vitamin A oil, retinol, retinol acetate, retinol palmitate, and other vitamin A derivatives; riboflavin, riboflavin butyrate, flavin adenine nucleotide, and other vitamin B2 derivatives; pyridoxine hydrochloride, pyridoxine dioctanoate, pyridoxine tripalmitate, and other vitamin B6 derivatives; and vitamin B 12 and its derivatives, vitamin B 15and derivatives thereof; vitamin C such as L-ascorbic acid, L-ascorbic acid dipalmitate, sodium L-ascorbic acid-2-sulfate, and dipotassium L-ascorbic acid phosphate diester; vitamin D such as ergocalciferol and cholecalciferol; vitamin E such as α-tocopherol, β-tocopherol, γ-tocopherol, dl-α-tocopherol acetate, dl-α-tocopherol nicotinate, and dl-α-tocopherol succinate; nicotinic acids such as nicotinic acid, benzyl nicotinate, and nicotinamide; vitamin H; vitamin P; pantothenic acids such as calcium pantothenate, D-pantothenyl alcohol, pantothenyl ethyl ether, and acetylpantothenyl ethyl ether; and biotin.

[0139] Amino acids Examples of amino acids include glycine, valine, leucine, isoleucine, serine, threonine, phenylalanine, arginine, lysine, aspartic acid, glutamic acid, cystine, cysteine, methionine, and tryptophan.

[0140] ·Nucleic acid Examples of nucleic acids include deoxyribonucleic acid.

[0141] ·hormone Examples of hormones include estradiol and ethenylestradiol.

[0142] ·Inclusion compounds Examples of the inclusion compound include cyclodextrin.

[0143] The cosmetic of the present invention is not particularly limited and can be applied to a variety of products, such as beauty serum, emulsion, cream, hair care, foundation, makeup base, sunscreen, concealer, blush, lipstick, gloss, balm, mascara, eye shadow, eyeliner, body makeup, deodorant, and nail cosmetics. Among these, makeup cosmetics such as emulsion, cream, hair care, and foundation, and cosmetics with sunscreen effects are particularly preferred. The cosmetic of the present invention can be in a variety of forms, such as liquid, cream, solid, paste, gel, mousse, soufflé, clay, powder, and stick. [Example]

[0144] The present invention will be described in more detail below using production examples, examples, production comparison examples, and comparative examples, but the present invention is not limited to the following production examples and examples. Unless otherwise specified, "%" in the composition is % by mass. Hydrophobic cellulose nanofibers and dispersions thereof are referred to as production examples and production comparison examples, and examples of cosmetics are referred to as examples and comparative examples.

[0145] [Production Example 1] <Production of Phosphite Group-Containing Hydrophobic Cellulose Nanofiber / KF-96A-6cs Dispersion> (Step 1) 100 g (weight of cellulose nanofiber: 1.0 g) of 1.0 mass% phosphite group-containing cellulose nanofiber / water dispersion (manufactured by Daio Paper Co., Ltd., average fiber diameter: 5 nm, light transmittance: 92%) and 400 g of N-methyl-2-pyrrolidone (NMP) were weighed into a 2 L descup and mixed using a high-speed dispersion mixer (manufactured by Silverson) to obtain a phosphite group-containing cellulose nanofiber / water-NMP mixed dispersion. Subsequently, sufficient dehydration was performed by distillation under reduced pressure to obtain a phosphite group-containing cellulose nanofiber / NMP dispersion. The amount of water contained at this time was 300 ppm.

[0146] (Step 2) 0.3 g of di-n-butyltin dilaurate was added as a urethane catalyst to the phosphite group-containing cellulose nanofiber / NMP dispersion obtained in Step 1, and the mixture was maintained at 80°C. 14.0 g of an isocyanate group-containing organopolysiloxane represented by the following formula (5) (feed weight of isocyanate group-containing organopolysiloxane / feed weight of cellulose nanofibers = 14.0) was added dropwise, and the reaction was continued by heating at 80°C for 3 hours. After confirming the disappearance of the band derived from the isocyanate groups by FT-IR, 1.0 g of ethanol was added to deactivate the unreacted isocyanate groups, yielding a phosphite group-containing hydrophobic cellulose nanofiber / NMP dispersion. [ka]

[0147] (Step 3) 2-propanol was added to the phosphite group-containing hydrophobic cellulose nanofiber / NMP dispersion obtained in Step 2, and the procedure of collecting the nanofibers by filtration was repeated three times to obtain a gel in which the phosphite group-containing hydrophobic cellulose nanofibers were swollen with 2-propanol. 100 g of KF-96A-6cs was added to the resulting gel, and the mixture was mixed homogenously using a high-speed dispersion mixer (Silverson). The remaining 2-propanol was then thoroughly removed by vacuum distillation, yielding a phosphite group-containing hydrophobic cellulose nanofiber / KF-96A-6cs dispersion. The physical properties of the resulting dispersion are listed in Table 1.

[0148] [Production Example 2] <Production of Phosphate Ester Group-Containing Cellulose Nanofiber / Methyl Trimethicone Dispersion> A phosphate group-containing hydrophobic cellulose nanofiber / methyl trimethicone dispersion was obtained by repeating the steps of Production Example 1, except that 100 g (weight of cellulose nanofiber: 1.0 g) of 1.0 mass% phosphite group-containing cellulose nanofiber / aqueous dispersion (manufactured by Daio Paper Co., Ltd., average fiber diameter: 5 nm, light transmittance: 92%) was replaced with 50 g (weight of cellulose nanofiber: 1.0 g) of 2.0 mass% phosphate ester group-containing cellulose nanofiber / aqueous dispersion (manufactured by Oji Paper Co., Ltd., average fiber diameter: 4 nm, light transmittance: 95%) and KF-96A-6cs was replaced with methyl trimethicone. The physical properties of the resulting dispersion are shown in Table 1.

[0149] [Production Example 3] <Production of Carboxyl Group-Containing Cellulose Nanofiber / Methyl Trimethicone Dispersion> A carboxyl group-containing hydrophobic cellulose nanofiber / methyl trimethicone dispersion was obtained by repeating the steps of Production Example 1, except that 100 g (weight of cellulose nanofiber: 1.0 g) of 1.0 mass% phosphite ester group-containing cellulose nanofiber / aqueous dispersion (manufactured by Daio Paper Co., Ltd., average fiber diameter: 5 nm, light transmittance: 92%) was replaced with 50 g (weight of cellulose nanofiber: 1.0 g) of 2.0 mass% carboxyl group-containing cellulose nanofiber / aqueous dispersion (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., average fiber diameter: 3 nm, light transmittance: 95%) and KF-96A-6cs was replaced with methyl trimethicone. The physical properties of the resulting dispersion are shown in Table 1.

[0150] [Production Example 4] <Production of Phosphite Group-Containing Hydrophobic Cellulose Nanofiber / Decamethylcyclopentasiloxane Dispersion> The steps of Production Example 1 were repeated, except that "KF-96A-6cs" was replaced with "decamethylcyclopentasiloxane," to obtain a phosphite group-containing hydrophobic cellulose nanofiber / decamethylcyclopentasiloxane dispersion. The physical properties of the resulting dispersion are shown in Table 1.

[0151] [Production Example 5] <Production of Phosphite Group-Containing Hydrophobic Cellulose Nanofiber / Methyl Trimethicone Dispersion> A phosphite group-containing hydrophobic cellulose nanofiber / methyl trimethicone dispersion was obtained by repeating the steps of Production Example 1, except that "KF-96A-6cs" in Production Example 1 was replaced with "methyl trimethicone." The physical properties of the obtained dispersion are shown in Table 1.

[0152] [Production Example 6] <Production of Phosphite Group-Containing Hydrophobic Cellulose Nanofiber / Methyl Trimethicone Dispersion> "KF-96A-6cs" of Production Example 1 was replaced with "methyl trimethicone" and "isocyanate group-containing organopolysiloxane represented by formula (5) 14.0 g" to "an isocyanate group-containing organopolysiloxane represented by formula (6) 14.0 The steps of Production Example 1 were repeated, except that "0.3 g" of di-n-butyltin dilaurate was used as the urethane-forming catalyst, and "6.0 g of triethylamine" was used instead of "0.3 g of di-n-butyltin dilaurate" as the urethane-forming catalyst, to obtain a phosphite group-containing hydrophobic cellulose nanofiber / methyl trimethicone dispersion. The physical properties of the obtained dispersion are shown in Table 1. [ka]

[0153] [Production Example 7] <Production of Phosphite Group-Containing Hydrophobic Cellulose Nanofiber / Toluene Dispersion> The "KF-96A-6cs" of Production Example 1 was dissolved in "toluene" and "isocyanate group-containing organopolysiloxane represented by formula (5) 14.0 g" to "an isocyanate group-containing organopolysiloxane represented by formula (6) 14.0 The steps of Production Example 1 were repeated except for changing the amount of cellulose nanofibers to "g", thereby obtaining a phosphite group-containing hydrophobic cellulose nanofiber / toluene dispersion. The physical properties of the obtained dispersion are shown in Table 1.

[0154] [Production Example 8] <Production of Phosphite Group-Containing Hydrophobic Cellulose Nanofiber / 1-Butanol Dispersion> A phosphite group-containing hydrophobic cellulose nanofiber / 1-butanol dispersion was obtained by repeating the steps of Production Example 1, except that "KF-96A-6cs" was replaced with "1-butanol" and "N-methyl-2-pyrrolidone" was replaced with "N,N-dimethylformamide." The physical properties of the resulting dispersion are shown in Table 1.

[0155] [Production Example 9] <Production of Phosphite Group-Containing Hydrophobic Cellulose Nanofiber / Methyl Trimethicone Dispersion> A phosphite group-containing hydrophobic cellulose nanofiber / methyl trimethicone dispersion was obtained by repeating the steps of Production Example 1, except that "KF-96A-6cs" in Production Example 1 was replaced with "methyl trimethicone," the charge weight of isocyanate group-containing organopolysiloxane / charge weight of cellulose nanofiber was changed to 4.5, and the urethane catalyst "di-n-butyltin dilaurate 0.3 g" was changed to "triethylamine 6.0 g." The physical properties of the obtained dispersion are shown in Table 1.

[0156] [Production Example 10] <Production of Phosphite Group-Containing Hydrophobic Cellulose Nanofiber / Methyl Trimethicone Dispersion> A phosphite group-containing hydrophobic cellulose nanofiber / methyl trimethicone dispersion was obtained by repeating the steps of Production Example 1, except that "KF-96A-6cs" in Production Example 1 was replaced with "methyl trimethicone," the charge weight of isocyanate group-containing organopolysiloxane / charge weight of cellulose nanofiber was changed to 28.0, and the urethane catalyst was changed from "0.3 g of di-n-butyltin dilaurate" to "6.0 g of triethylamine." The physical properties of the resulting dispersion are shown in Table 1.

[0157] [Comparative Manufacturing Example 1] <Production of a mixture of cellulose nanofibers containing phosphite ester groups and methyl trimethicone> The steps of Production Example 1 were repeated, except that "KF-96A-6cs" in Production Example 1 was replaced with "methyl trimethicone" and the "isocyanate group-containing organopolysiloxane represented by formula (5)" was not used, to obtain a phosphite group-containing cellulose nanofiber / methyl trimethicone mixture. The physical properties of the obtained mixture are shown in Table 1.

[0158] [Comparative Manufacturing Example 2] <Production of a mixture of phosphite group-containing hydrophobic cellulose nanofibers and methyl trimethicone> The steps of Production Example 1 were repeated, except that "KF-96A-6cs" was replaced with "methyl trimethicone" and "isocyanate group-containing organopolysiloxane represented by formula (5)" was replaced with "butyl isocyanate," to obtain a phosphite group-containing hydrophobic cellulose nanofiber / methyl trimethicone mixture. The physical properties of the obtained mixture are shown in Table 1.

[0159] [Comparative Manufacturing Example 3] <Production of a mixture of phosphite group-containing hydrophobic cellulose nanofibers and methyl trimethicone> The steps of Production Example 1 were repeated, except that "KF-96A-6cs" was replaced with "methyl trimethicone" and "isocyanate group-containing organopolysiloxane represented by formula (5)" was replaced with "dodecyl isocyanate," to obtain a phosphite group-containing hydrophobic cellulose nanofiber / methyl trimethicone mixture. The physical properties of the obtained mixture are shown in Table 1.

[0160] <Dispersibility> The cellulose nanofiber dispersions obtained in Production Examples 1 to 10 and the cellulose nanofiber mixtures obtained in Production Comparative Examples 1 to 3 were visually inspected for the presence or absence of cellulose nanofiber sedimentation. Cases where no sedimentation was observed were evaluated as ◯, and cases where sedimentation was observed were evaluated as ×. The results are shown in Table 1.

[0161] <Calculation of the average fiber diameter of hydrophobic cellulose nanofibers> The cellulose nanofiber dispersions obtained in Production Examples 1 to 10 were adjusted to a solids concentration of 0.01% by mass, dropped onto a copper grid, and dried to form observation samples, which were then observed under a transmission electron microscope. Three or more images in which fibers did not overlap were observed, and the diameters of 20 fibers per image were calculated. The average value was taken as the average fiber diameter, and the results are shown in Table 1.

[0162] <Light transmittance> The cellulose nanofiber dispersions obtained in Production Examples 1 to 10 were diluted to a concentration of 0.2% by mass, filled into a square cell with an optical path length of 10 mm, and the light transmittance at a wavelength of 600 nm was measured using a UV-visible spectrophotometer (UV-1800, Shimadzu Corporation). The results are shown in Table 1.

[0163] <Viscosity measurement> The cellulose nanofiber dispersions obtained in Production Examples 1 to 10 were subjected to viscosity measurement after 1 minute using a B-type rotational viscometer (Brookfield) by rotating the rotor at 6 rpm. The results are shown in Table 1.

[0164] <Film-forming properties> The cellulose nanofiber dispersions obtained in Production Examples 2 to 10 and the cellulose nanofiber mixtures obtained in Production Comparative Examples 1 to 3 were dried in an oven at 105°C for 3 hours. After drying, the state of the solvent volatilization was visually observed and evaluated according to the following criteria. The results are shown in Table 1. Note that Production Example 1 was excluded from the evaluation of film-forming properties because it used a non-volatile oil. ◎: A colorless, transparent, and uniform film is obtained 〇: A uniform film with a white or cloudy appearance is obtained ×: No film was obtained (powdery), or a film with an uneven appearance (mottled) was obtained

[0165] [Table 1] *1: Organopolysiloxane ratio: Mass of mixed organopolysiloxane / Mass of cellulose nanofiber KF-96A-6cs: Dimethicone (kinematic viscosity at 25°C 6mm) 2 / s, manufactured by Shin-Etsu Chemical Co., Ltd.) TMF-1.5: Methyl trimethicone (Shin-Etsu Chemical Co., Ltd.) KF-995: Decamethylcyclopentasiloxane (Shin-Etsu Chemical Co., Ltd.)

[0166] As shown in Production Examples 1 to 10 in Table 1, hydrophobic cellulose nanofiber dispersions were obtained in which the transmittance was 80% or higher and the average fiber diameter of the cellulose nanofibers was 300 nm or less. Production Examples 4, 5, and 8 demonstrate high dispersibility even when the dispersant properties were different. Production Examples 2, 3, and 5 demonstrate high dispersibility even when the type of anionic functional group was different. Meanwhile, in Production Comparative Example 1, dispersion in methyl trimethicone was attempted without blocking the hydroxyl groups, but aggregates of cellulose nanofibers formed and precipitates were observed. Furthermore, in Production Comparative Examples 2 and 3, blocking with alkyl isocyanates not containing siloxane components was attempted, but precipitates were observed in both cases, and dispersibility did not improve. This demonstrates that blocking the hydroxyl groups of the hydrophobic cellulose nanofibers of the present invention with a siloxane structure containing an isocyanate group contributes to hydrophobicity and dispersibility in specific oils such as alcohols, silicone oils, and hydrocarbon oils.

[0167] (1) Characterization The cosmetics of Examples 1 to 12 and Comparative Examples 1 to 6 below were evaluated for their feel when used (non-sticky), refreshing feeling (moisturizing), applicability (good spreadability), and stability over time (condition after storage at 50°C for one month) according to the evaluation criteria shown in Table 2. The results were evaluated based on the average of the 10 panelists and in accordance with the following criteria. The results are shown in Tables 3 to 5.

[0168] [Table 2]

[0169] Judgment criteria ◎: Average score is 4.5 points or more ○: Average score is 3.5 points or more and less than 4.5 points △: Average score is between 2.5 and 3.5 points ×: Average score is 1.5 points or more but less than 2.5 points ××: Average score is less than 1.5 points

[0170] <Example> A W / O emulsion having the composition shown in Table 3 below was prepared. [Table 3] (Note 1) Polyether-modified silicone: KF-6017 (Shin-Etsu Chemical Co., Ltd.) (Note 2) Methyl trimethicone: TMF-1.5 (Shin-Etsu Chemical Co., Ltd.) The blending amounts are those of the blended products listed (same below).

[0171] <Preparation of cosmetics> A: Component (1) was mixed uniformly. B: Component (2) was mixed uniformly. C: B was added to A and emulsified to obtain a W / O emulsion.

[0172] The results in Table 3 above show that the W / O emulsions of Examples 1 to 4 have good usability (non-sticky), refreshing feel (moisture), applicability (good spreadability), and stability over time (conditions after storage at 50°C for 1 month). On the other hand, in Comparative Example 1, when the cellulose nanofiber dispersion is not added, the feel derived from the cellulose nanofibers is not imparted, and the usability, refreshing feel, and applicability are impaired. Furthermore, when cellulose nanofibers dispersed in water are used in Comparative Example 2, the cellulose nanofibers are present in the internal phase of the water-in-oil emulsion, and do not affect the feel upon application, so the usability and refreshing feel are impaired.

[0173] A W / O emulsion having the composition shown in Table 4 below was prepared.

[0174] [Table 4] (Note 1) Polyether-modified silicone: KF-6017 (Shin-Etsu Chemical Co., Ltd.) (Note 2) Methyl trimethicone; TMF-1.5 (Shin-Etsu Chemical Co., Ltd.) The blending amounts are those of the blended products listed (same below).

[0175] <Preparation of cosmetics> A: Component (1) was mixed uniformly. B: Component (2) was mixed uniformly. C: B was added to A and emulsified to obtain a W / O emulsion.

[0176] The results in Table 4 above demonstrate that the W / O emulsions of Examples 5 to 8 had good usability (non-sticky), refreshing feel (moisture), application (good spreadability), and stability over time (storage at 50°C for 1 month). On the other hand, in Comparative Example 3, when the cellulose nanofiber dispersion was not added, the feel derived from the cellulose nanofibers was not imparted, resulting in a loss of usability, refreshing feel, and application. Furthermore, the increase in the aqueous phase worsened stability over time. This is because the cellulose nanofibers act as a thickener for the oil phase, thereby enhancing the stability of the entire system. Furthermore, when cellulose nanofibers dispersed in water were used in Comparative Example 4, the cellulose nanofibers were present in the internal phase of the water-in-oil emulsion, and did not affect the feel upon application, resulting in a loss of usability and refreshing feel. Furthermore, when cellulose nanofibers were used in the internal phase, they did not contribute to the stabilization of the entire system, resulting in a loss of stability over time.

[0177] An emulsion-type cream foundation having the composition shown in Table 5 below was prepared.

[0178] [Table 5] (Note 1) Cross-linked polyether-modified silicone: KSG-210 (Shin-Etsu Chemical Co., Ltd.) (Note 2) Crosslinked dimethylpolysiloxane: KSG-15 (Shin-Etsu Chemical Co., Ltd.) (Note 3) Polyether-modified silicone: KF-6017 (Shin-Etsu Chemical Co., Ltd.) (Note 4) Dimethylpolysiloxane: KF-96A-6cs (Shin-Etsu Chemical Co., Ltd.) (Note 5) Methyl trimethicone: TMF-1.5 (Shin-Etsu Chemical Co., Ltd.) (Note 6) Polymethylsilsesquioxane powder: KMP-590 (Shin-Etsu Chemical Co., Ltd.) (Note 7) Silicone treatment: KF-9909 treatment (Shin-Etsu Chemical Co., Ltd.)

[0179] <Preparation of cosmetics> Components (1) to (4), a portion of (5), (6) to (12), and (21) to (22) were mixed together until homogeneous. Components (13) to (14) and (16), which had been separately dissolved homogeneously in component (15), were gently added to this mixture and emulsified. Components (17) to (20), the remainder of (5), and (23) were added to this emulsion and mixed. This was filled into a specified container to prepare an emulsion-type cream foundation.

[0180] The results in Table 5 above show that the emulsion cream foundations of Examples 9 to 12 have good usability (non-sticky), refreshing feel (moisture), application (good spreadability), and stability over time (conditions after storage at 50°C for 1 month). On the other hand, in Comparative Example 5, when the cellulose nanofiber dispersion is not added, the feel derived from the cellulose nanofibers is not imparted, and the usability, refreshing feel, and application are impaired. Furthermore, when cellulose nanofibers dispersed in water are used in Comparative Example 6, the cellulose nanofibers are present in the internal phase because it is a water-in-oil emulsion, and do not affect the feel upon application, so the usability and refreshing feel are impaired.

[0181] The present invention is not limited to the above-described embodiments. The above-described embodiments are merely examples, and anything that has substantially the same configuration as the technical idea described in the claims of the present invention and that exhibits similar effects is included within the technical scope of the present invention.

Claims

1. Hydrophobic cellulose nanofibers, (A) cellulose nanofibers, and (B) Isocyanate group-containing organopolysiloxane wherein the isocyanate group-containing organopolysiloxane is bonded to the hydroxyl groups of the cellulose nanofibers via urethane bonds, the (A) cellulose nanofiber further has an anionic functional group, and the anionic functional group is selected from a carboxymethyl group, a sulfate ester group, a phosphate ester group, a phosphite ester group, and a xanthate ester group; The hydrophobic cellulose nanofiber, characterized in that the (B) isocyanate group-containing organopolysiloxane is represented by the following general formula (1) or (2): 【Chemical 1】 (In the formula, R 1 is a monovalent alkyl group having 1 to 6 carbon atoms, and R 2 is independently an alkyl group having 1 to 6 carbon atoms, a phenyl group, a trimethylsiloxy group, an ethyldimethylsiloxy group, a phenyldimethylsiloxy group, a vinyldimethylsiloxy group, a chloromethyldimethylsiloxy group, or a 3,3,3-trifluoropropyldimethylsiloxy group; m is an integer from 1 to 10; and a is an integer from 0 to 1.) 【Chemistry 2】 (wherein R 2 is the same as defined above, m is an integer of 1 to 10, and n is an integer of 1 to 500.)

2. The hydrophobic cellulose nanofiber according to claim 1, characterized in that a 0.2 mass% aqueous dispersion of the cellulose nanofibers having anionic functional groups has a light transmittance of 80% or more at 600 nm, and the fiber width of the cellulose nanofibers having anionic functional groups in the aqueous dispersion is 300 nm or less.

3. The hydrophobic cellulose nanofiber according to claim 1 or 2, characterized in that the isocyanate group-containing organopolysiloxane represented by the general formula (1) is tristrimethylsiloxysilylpropyl isocyanate.

4. A hydrophobic cellulose nanofiber dispersion, characterized in that the hydrophobic cellulose nanofibers according to any one of claims 1 to 3 are dispersed in an oil agent (C).

5. The hydrophobic cellulose nanofiber dispersion according to claim 4, characterized in that the (C) oil agent is one or more selected from the group consisting of aliphatic alcohols, silicone oils, and hydrocarbon oils.

6. The hydrophobic cellulose nanofiber dispersion according to claim 4 or 5, characterized in that the mass ratio of the (C) oil agent to the hydrophobic cellulose nanofibers is 1:0.0001 to 1:0.

5.

7. The hydrophobic cellulose nanofiber dispersion according to any one of claims 4 to 6, characterized in that a 0.2 mass% silicone oil dispersion of the hydrophobic cellulose nanofiber dispersion has a light transmittance of 70% or more at 600 nm.

8. A cosmetic preparation comprising the hydrophobic cellulose nanofiber dispersion liquid according to any one of claims 4 to 7.

9. The cosmetic preparation according to claim 8, wherein the hydrophobic cellulose nanofiber dispersion is used as an emulsion composition.

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