Hydrophobized CNF dispersion production method, and hydrophobized CNF oil-based component-containing body production method

Abstract

To provide: a cosmetic that uses sustainable materials, that provides an excellent use feeling, that does not require treatment at a high temperature, and that has a less stimulating feel to the skin; and a cosmetic material that is to be used therefor and that, when being blended in a cosmetic, has excellent dispersibility.SOLUTION: A hydrophobized CNF dispersion production method comprises at least a first step, a second step, and a third step, and is characterized in that: the first step is for obtaining a primary dispersion by dispersing, in an organic solvent, a CNF in a hydrous state; the second step is for obtaining a secondary dispersion by performing a dispersion process on the primary dispersion body and a vinyl ester or an organic acid vinyl ester by using a medialess disperser in which the clearance of a shearing part is 10-23,000 μm; the third step is for rinsing the secondary dispersion body and dispersing same into an alcohol aqueous solution; and a step for adding a catalyst is included in the first step or the second step.SELECTED DRAWING: Figure 1

Description

[Technical field]

[0001] The present invention relates to hydrophobized CNF, a hydrophobized CNF oily component-containing body, and cosmetics and the like containing the hydrophobized CNF oily component-containing body. [Background technology]

[0002] In recent years, the number of people suffering from sensitive skin or allergies has increased, and more people are feeling irritation from cosmetics and other products, creating a demand for products with less irritation.

[0003] In the field of cosmetics, dextrin fatty acid esters and 12-hydroxystearic acid are known as oil-based thickeners that thicken liquid oils. However, most of these are powders with high melting points, and require dispersion treatment at high temperatures of 75°C or higher. Depending on the compatibility with the oil component, the desired thickening effect may not be obtained. Furthermore, the feeling of use is unsatisfactory, such as stickiness after application and rinsing.

[0004] Patent Document 1 describes a thickener containing a polyglycerol fatty acid ester that satisfies specific conditions, with the aim of providing a thickener that is capable of thickening an oil agent. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Patent No. 6825066 Summary of the Invention [Problem to be solved by the invention]

[0006] However, the thickener described in Patent Document 1 is a chemically synthesized product, and may irritate the skin of those who suffer from sensitive skin or allergies. In view of the above circumstances, the present invention aims to provide a cosmetic preparation that uses sustainable raw materials, has a good feel when used, does not require high-temperature processing, and is less irritating to the skin, and a cosmetic raw material that has good dispersibility when blended into the cosmetic preparation for use therein.

[0007] Another object of the present invention is to provide hydrophobized CNF that can be used as a cosmetic raw material.

[0008] As a result of intensive research to achieve the above-mentioned objective, the inventors have discovered that it is possible to produce hydrophobic CNF that has improved dispersibility in organic solvents by utilizing the characteristic of CNF that aligns in the same direction in a fluid and using a media-less disperser to increase the substitution reaction rate and degree of substitution while preventing damage to the CNF by applying horizontal shear stress. We also found that the dispersibility of CNF in organic solvents can be improved by making hydrophobic CNF contain oily components. They also discovered that cosmetics made from cosmetic raw materials containing the hydrophobized CNF have a good feel when used and cause little irritation to the skin.

[0009] That is, the present invention is a method for producing a hydrophobized CNF dispersion having at least a first step, a second step, and a third step, in which the first step is a step of dispersing hydrous CNF in an organic solvent to obtain a primary dispersion, the second step is a step of dispersing the primary dispersion and vinyl esters or organic acid vinyl esters using a media-less disperser having a shear section clearance of 10 μm or more and 23,000 μm or less to obtain a secondary dispersion, and the third step is a step of dispersing the secondary dispersion in alcohol, and is characterized in that the first step or the second step includes a step of adding a catalyst. Effect of the Invention

[0010] According to the present invention, there are provided a cosmetic preparation which has a good feel when used and causes little irritation to the skin, and a cosmetic raw material which does not cause irritation to the skin when used therefor and has good dispersibility when blended into the cosmetic preparation. In addition, hydrophobized CNF is provided that can be used as a raw material for the cosmetic preparation and has improved dispersibility in organic solvents and oily components. [Brief description of the drawings]

[0011] [Figure 1] FIG. 2 is a cross-sectional view of a main part showing an example of a media-less disperser used in the second step of the present invention. [Diagram 2] This shows the state of the hydrophobized CNF powder obtained in Example 10 dispersed in ethylhexyl methoxycinnamate. [Diagram 3] FIG. 1 shows the state of the hydrophobized composite CNF powder obtained in Example 12 dispersed in polypropylene glycol. [Figure 4] FIG. 1 shows the results of viscosity evaluation 1 of hydrophobized CNF in Example 14. [Diagram 5] FIG. 1 shows the results of viscosity evaluation 2 of hydrophobized CNF in Example 15. [Figure 6] FIG. 13 shows the results of a viscosity evaluation performed using the hydrophobized composite CNF powder obtained in Example 16. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0012] Next, the embodiments of the present invention will be described in detail. However, the following embodiments are provided to aid in understanding the invention and are not intended to limit the present invention.

[0013] (Definition of terms) Here, the main terms used in the present invention will be defined. The term "CNF" in this specification refers to cellulose fibers with an average thickness of 3 to 200 nm and an average length of 0.1 μm or more, and includes so-called single cellulose nanofibers with an average width of 3 to 4 nm, and single cellulose nanofiber aggregates with an average width of 10 to 200 nm, which are formed by assembling several single cellulose nanofibers into multiple layers. In addition, there are not only cellulose fibers that are unbranched in the length direction, but also those that are branched. In addition, the term "hydrophobized CNF" in this specification refers to CNF in which some of the hydroxyl groups of the CNF have been esterified with vinyl esters and / or organic acid vinyl esters. Furthermore, the term "hydrophobized composite CNF" in this specification includes CNF in which some of the hydroxyl groups of the CNF are esterified using vinyl esters and / or organic acid vinyl esters, and the esterified CNFs are crosslinked via polyhydric alcohols and / or polyalkylene glycols and / or CNFs bonded to some of the hydroxyl groups of the esterified CNF. Furthermore, the term "hydrophobized CNF oil component-containing body" in this specification refers to a body containing at least the hydrophobized CNF and various oil components described below. Furthermore, the term "hydrophobized composite CNF oil component-containing body" in this specification refers to a body containing at least the hydrophobized composite CNF and various oil components described below. Furthermore, the term "hydrophobized CNF powder" in this specification refers to a hydrophobized CNF oil component-containing body in which the hydrophobized CNF component is 20% or more and 99% or less. In other words, when the hydrophobized CNF component in the hydrophobized CNF oil component-containing body is 1, the ratio of the hydrophobized CNF to the oil component is in the range of 1:0.01 to 1:4. Furthermore, the term "hydrophobized composite CNF powder" in this specification refers to a hydrophobized composite CNF oil component-containing body in which the hydrophobized composite CNF component is 20% or more and 99% or less. In other words, when the hydrophobized composite CNF component in the hydrophobized composite CNF oil component-containing body is 1, the ratio of the hydrophobized composite CNF to the oil component is in the range of 1:0.01 to 1:4. Furthermore, in this specification, "paste-like hydrophobized CNF oil-containing material" refers to a hydrophobized CNF oil-containing material in which the hydrophobized CNF component is less than 20%. Furthermore, in this specification, "paste-like hydrophobized composite CNF oil-component-containing material" refers to a hydrophobized composite CNF oil-component-containing material in which the hydrophobized composite CNF component accounts for less than 20%.

[0014] (Method of producing hydrophobized CNF dispersion and hydrophobized composite CNF dispersion) The method for producing a hydrophobized CNF dispersion of the present invention has at least a first step, a second step, and a third step. The first step is a step of dispersing hydrous CNF in an organic solvent to obtain a primary dispersion. The second step is a step of dispersing the primary dispersion and vinyl esters or organic acid vinyl esters using a media-less disperser having a shear section clearance of 10 μm or more and 23,000 μm or less to obtain a secondary dispersion. Furthermore, the third step is a step of dispersing the secondary dispersion in an aqueous alcohol solution to obtain a hydrophobized CNF dispersion having a hydrophobized CNF concentration of 2 to 30%. Furthermore, the first step or the second step includes a step of adding a catalyst.

[0015] The method for producing a hydrophobized CNF dispersion of the present invention includes a step of obtaining a secondary dispersion by dispersing the CNFs using a media-less disperser having a shear clearance of 10 μm or more and 23,000 μm or less in the second step, so that the CNFs present in the primary dispersion obtained in the first step can be dispersed. As a result, in the secondary dispersion obtained by carrying out the second step, the hydroxyl groups in the cellobiose units are esterified with vinyl esters or organic acid vinyl esters, and a substitution reaction proceeds. In addition, the method for producing a hydrophobized composite CNF dispersion of the present invention differs from the method for producing the hydrophobized CNF dispersion in that part of the second step is different, and the other steps, the first and third steps, are the same as the method for producing the hydrophobized CNF dispersion.

[0016] <1st process> The first step aims to disperse the hydrous CNF in an organic solvent to obtain a primary dispersion. In this way, the reactivity of the hydroxyl groups of the CNF with the vinyl esters or organic acid vinyl esters can be improved. The first step will now be described in detail.

[0017] First, a CNF dispersion is prepared, and the CNF dispersion is subjected to solid-liquid separation to separate CNF from water, resulting in hydrous CNF with a CNF content of about 2 to 40%. The manner of solid-liquid separation is not particularly limited. For example, a centrifuge, a filter press, or the like can be used. When a CNF dispersion with a CNF content of about 2% or less is used, it may be used as it is as hydrous CNF. The CNF dispersion will be described later.

[0018] Next, when the obtained water-containing CNF is about 15% or more, it is pulverized. Here, the mode of pulverization is not particularly limited. As a mode of pulverization, it is sufficient to physically pulverize finely, and for example, a compression crusher, a shear crusher, an impact crusher, a roll mill, a high-speed rotary mill, a jet mill, etc. can be used. In addition, there is no particular limit to the degree of pulverization, but it is preferable to pulverize so that the average particle size of the powder-like CNF obtained by pulverization is in the range of 0.1 to 5 cm.

[0019] Next, the obtained powdered CNF or CNF containing about 15% or less water is mixed with an organic solvent while applying compressive and shearing forces to obtain the primary dispersion. The CNF concentration in the primary dispersion is preferably in the range of 0.1 to 4.5 w / w, more preferably 2.5 to 3.5 w / w. Here, as a device capable of mixing while applying compressive force and shear force, a high-speed shear mill, a blade type kneader, a high-speed mixer Mechano Hybrid, a high-performance fluid mixer FM mixer, etc. can be used. The organic solvent will be described later.

[0020] (CNF dispersion) As examples of CNF dispersions that can be used in the present invention, reference can be made to the method for producing fine fibers described in Japanese Patent No. 6,867,613, the method for preparing cellulose nanofibers and cellulose nanocrystal aqueous solutions using cellulose as a natural polymer described in Japanese Patent No. 6,704,551, and the method for producing fine fibers derived from other raw materials, etc., described in both publications.

[0021] These raw materials for the CNF dispersion may be used alone or in combination of two or more. As the raw polysaccharide, it is preferable to use pulp with an α-cellulose content of 60% to 99% by mass. If the purity is 60% or more by mass of α-cellulose, the fiber diameter and fiber length can be easily adjusted, and entanglement of the fibers can be suppressed. Compared with the use of a material with an α-cellulose content of less than 60% by mass, the thermal stability is high and the coloring suppression effect is good. On the other hand, if a material with an α-cellulose content of 99% or more by mass is used, it becomes difficult to defibrate the fibers to the nano level.

[0022] The crystallinity of CNF is preferably at least 50. The crystallinity can be measured by X-ray diffraction or the like, and if the crystallinity is less than 50, the properties of natural cellulose crystals cannot be fully utilized, and there is a risk of deterioration over time during storage due to spoilage or the like. By using the ACC method (underwater head-on collision method), cellulose fibers can be pulverized to an average particle length of 10 μm, resulting in CNFs with an average thickness of 3 to 200 nm and an average length of 0.1 μm or more. The average thickness and average fiber length are measured by appropriately selecting a scanning electron microscope (SEM), a transmission electron microscope (TEM), etc., observing and measuring the CNFs, selecting 20 or more from the resulting photographs, and averaging each of these.

[0023] (Organic solvent) As the organic solvent, a non-ionic polar solvent including N-methylpyrrolidone (hereinafter referred to as NMP), dimethylacetamide (hereinafter referred to as DMAc), dimethylformamide (hereinafter referred to as DMF), or dimethylsulfoxide (hereinafter referred to as DMSO) can be used.

[0024] <Second process> The second step is a step for the purpose of obtaining a secondary dispersion containing reaction products such as hydrophobized CNF by esterifying the hydroxyl groups present in the CNF with vinyl esters or organic acid vinyl esters. In addition, the reaction products in the secondary dispersion obtained in the second step are recovered and purified to obtain hydrophobized CNF. The second step will now be described in detail.

[0025] The presence of a catalyst is essential to initiate the esterification reaction of the hydroxyl groups present in CNF with vinyl esters or organic acid vinyl esters. In the present invention, the step of adding a catalyst can be carried out in two modes, that is, in the second step, or in the first step, as described below. The first embodiment is an embodiment in which a catalyst is added in the second step. After obtaining the primary dispersion in the first step, the water content in the primary dispersion is adjusted using the organic solvent and / or water so that the water content is within the range of any one of 60% to 10%. Next, vinyl esters or organic acid vinyl esters are added. At this time, the vinyl esters or organic acid vinyl esters are preferably added in a ratio of 0.1 to 5.0 molar equivalents relative to the glucose unit amount of the CNF contained in the primary dispersion. When producing a hydrophobized composite CNF dispersion, polyhydric alcohols and / or polyalkylene glycols and a crosslinking agent are further added. The amount of polyhydric alcohol and / or polyalkylene glycol relative to the CNF is described later. Next, a catalyst is added in an amount of 1 to 400 wt%, preferably 5 to 350 wt%, more preferably 10 to 300 wt%, based on the CNF in the primary dispersion. In this case, the esterification reaction starts when the catalyst is added. Alternatively, after the primary dispersion is obtained in the first step, the water content in the primary dispersion is adjusted to fall within the above-mentioned range. A catalyst is then added to the CNF in the primary dispersion in the ranges described above. Then, the vinyl esters or organic acid vinyl esters are added in the above-mentioned proportions. When producing a hydrophobized composite CNF dispersion, polyhydric alcohols and / or polyalkylene glycols and a crosslinking agent are further added. In such cases, the esterification reaction starts when vinyl esters or the like are added.

[0026] In the second embodiment, in the first step, a catalyst is added to the CNF in the primary dispersion in the range described above, and then the second step is carried out. In this case, as in the latter part of the first embodiment, the esterification reaction starts when a vinyl ester or the like is added.

[0027] Therefore, it is advisable to time the addition of the catalyst etc. so that the esterification reaction is started immediately before the start of the dispersion treatment using a media-less disperser, which will be described later. The dispersion treatment with the media-less disperser in the present invention is understood to include the above-mentioned esterification reaction in addition to the dispersion treatment using a media-less disperser. For the sake of explanation, the dispersion immediately before the addition of the catalyst or vinyl esters is referred to as the pre-treatment secondary dispersion. The reaction temperature is in the range of 25°C to 100°C, preferably 60°C to 95°C, and more preferably 70°C to 90°C. The reaction time is within a range of 1 minute to 5 hours, preferably 10 minutes to 4 hours, and more preferably 15 minutes to 3 hours. The vinyl esters or organic acid vinyl esters, polyhydric alcohols and / or polyalkylene glycols, crosslinking agents and catalysts will be described later.

[0028] The pre-processed secondary dispersion is then subjected to a dispersion treatment using a media-less disperser to obtain a secondary dispersion. The obtained secondary dispersion may be dispersed again using the media-less disperser. The media-less dispersing machine used in the second step is not particularly limited, but is preferably equipped with a rotor as a rotating body and a stator as a fixed surface. In addition, it is preferable that the media-less dispersing machine is equipped with a mechanism for adding catalysts, crosslinking agents, etc., either immediately adjacent to the media-less dispersing machine or directly into the machine. By providing the rotor and the stator, the shear force applied to the untreated secondary dispersion, the catalyst, vinyl esters, etc. can be adjusted by adjusting the clearance between the rotor and the stator and adjusting the rotation speed of the rotor. In addition, you can choose from high-speed mixing blades, turbine / stator type mixers, high-viscosity kneading plus high-speed mixing, rotating thin film type high-speed mixing, in-line type disperser / mixer type mixer, etc. Two or more types of media-less dispersers may be arranged in a continuous manner, or may be circulated with a stirring tank, etc. Furthermore, coarse dispersion such as ultrasonic dispersion or kneading and stirring may be combined as preliminary dispersion, and indirect heating and cooling using a stirring tank, etc. or direct heating using microwaves may be combined. Examples of the media-less dispersing machine that can be used include the "Clearstar" manufactured by Primix Corporation, the "Disperser" manufactured by Shinto Kogyo Co., Ltd., the "Aruria" manufactured by M-Technique Co., Ltd., and the "FM Mixer" manufactured by Nippon Coke and Engineering Co., Ltd.

[0029] Here, the media-less dispersing machine used in the second step will be described with reference to the drawings. Fig. 1 is a cross-sectional view of a main part showing an example of the media-less dispersing machine used in the second step of the present invention. In Fig. 1, the media-less disperser 1 includes a stator 2 and a rotor 3 that rotates inside the stator 2. A gap 4 is formed between the stator 2 and the rotor 3. In Fig. 1, the minimum size of the gap 4 between the stator 2 and the rotor 3 is defined as a clearance C. The clearance C is set to a value not less than 10 μm and not more than 23000 μm, and the clearance C is more preferably not less than 20 μm and not more than 5000 μm, and further preferably not less than 50 μm and not more than 1000 μm. If the clearance C is smaller than 10 μm, when CNF aggregates larger than the clearance C are present in the secondary dispersion before processing or when there are fluctuations in concentration, this may cause blockages inside the equipment, or the rotor and stator may come into contact due to eccentricity, which may cause the media-less disperser to break down. On the other hand, if the clearance C exceeds 23,000 μm, the shear force may become small.

[0030] In FIG. 1, by rotating the rotor 3 and passing the mixed liquid through the gap 4 between the stator 2 and the rotor 3 in the direction of the arrow, horizontal shear stress can be applied to the pre-treatment secondary dispersion in the present invention, and the catalyst, etc. can be uniformly dispersed, thereby improving the reaction efficiency.

[0031] In addition, the share rate in the second step is 1×10(1 / s) or more and 1×10 8 (1 / s) or less, and 1×10 2 (1 / s) or more 1×10 7 It is more preferable that it is equal to or less than (1 / s). If the shear rate is less than 1×10 (1 / s), sufficient shear force cannot be obtained, and the catalyst, etc. cannot be uniformly dispersed in the hydroxyl groups of the CNF aggregates in the pre-treatment secondary dispersion. 8 If the shear rate exceeds 1×10 (1 / s), the processing liquid may become too hot during the dispersion process, which is not preferable. However, if the media-less disperser has a cooling function, the above shear rate is 1×10 8 In some cases it may be acceptable to exceed (1 / s).

[0032] The share rate is expressed by the following formula. Shear rate (1 / s) = peripheral speed (m / s) / clearance C (mm) x 1000 Circumferential speed (m / s) = π x rotor diameter (mm) x 1 / 1000 x rotation speed (rpm) x 1 / 60

[0033] (Vinyl esters or organic acid vinyl esters) Examples of vinyl esters or organic acid vinyl esters used in the present invention include vinyl esters of linear or branched C2-20 aliphatic carboxylic acids such as vinyl acetate, vinyl butyrate, vinyl stearate, vinyl laurate, vinyl myristate, vinyl propionate, and vinyl versaticate, and aromatic carboxylic acids such as vinyl benzoate.

[0034] (Polyhydric alcohols and / or polyalkylene glycols) The polyhydric alcohols and polyalkylene glycols are not particularly limited as long as they have two or more hydroxyl groups. Examples of the polyhydric alcohols include glycerin, diglycerin, polyglycerin, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, trimethylolpropane, pentaerythritol, and 1,3-butanediol, and one or more of these may be used. Polyalkylene glycol is a linear polymeric compound having a repeating structure of ether bonds in the main chain, and is produced, for example, by ring-opening polymerization of cyclic ether. Specific examples of polyalkylene glycol include polymers such as polyethylene glycol and polypropylene glycol, ethylene oxide-propylene oxide copolymers and derivatives thereof, etc. As the copolymer, any copolymer such as a random copolymer, a block copolymer, a graft copolymer, or an alternating copolymer can be used. The molecular weight of the polyalkylene glycol that can be used is generally within the range of 200 to 100,000.

[0035] (Amount of polyhydric alcohol and / or polyalkylene glycol relative to CNF) It is recommended that polyhydric alcohol and / or polyalkylene glycol be bonded to the hydroxyl groups of CNF in an amount of 0.01% to 50%. If the amount of polyhydric alcohol and / or polyalkylene glycol is small, a bulky hydrophobic composite CNF composite cannot be obtained when dispersed in an oily component, and the CNFs will gather together densely, resulting in syneresis. On the other hand, if the amount of polyhydric alcohol and / or polyalkylene glycol is large, the absolute amount of hydroxyl groups in CNF that can react effectively will be small, making it difficult for the vinyl esters and / or organic acid vinyl esters to be introduced into the hydroxyl groups of CNF, resulting in incompatibility with the oily component. In addition, polyalkylene glycol contains many hydrophilic ether bonds, which is contrary to the object of the present invention.

[0036] (Crosslinking agent) The crosslinking agent in the present invention is not particularly limited as long as it bonds the hydroxyl groups of the CNF with the hydroxyl groups of the polyhydric alcohol and / or polyalkylene glycol. Specifically, divinyl esters, isocyanate-based crosslinking agents, etc. can be used.

[0037] Examples of divinyl esters include divinyl adipate, divinyl sebacate, divinyl glutarate, diallyl phthalate, diallyl malate, and diallyl succinate. These may be used alone or in combination of two or more.

[0038] The isocyanate-based crosslinking agent contains at least a polyisocyanate compound. Examples of the polyisocyanate compound include aromatic polyisocyanates such as tolylene diisocyanate, diphenylmethane diisocyanate, and xylylene diisocyanate, aliphatic polyisocyanates such as hexamethylene diisocyanate, alicyclic polyisocyanates such as isophorone diisocyanate and hydrogenated diphenylmethane diisocyanate, and biuret and isocyanurate forms thereof, as well as adducts which are reaction products with low-molecular active hydrogen-containing compounds such as ethylene glycol, propylene glycol, neopentyl glycol, trimethylolpropane, and castor oil.

[0039] (catalyst) The catalyst in the present invention is not particularly limited, but is preferably an alkaline catalyst, particularly one having a buffering effect, and is preferably an alkali metal salt, such as disodium hydrogen phosphate, sodium acetate, or potassium carbonate.

[0040] <3rd process> The third step is a step in which the secondary dispersion containing the hydrophobized CNF after the reaction in the second step is dehydrated and washed, and then an aqueous alcohol solution (hereinafter sometimes referred to as the dispersion medium) is used to make a hydrophobized CNF dispersion with a hydrophobized CNF concentration of approximately 2 to 30%. The third step will now be described in detail.

[0041] (Dehydration process) After the reaction, the secondary dispersion containing the hydrophobized CNF is subjected to solid-liquid separation to separate the hydrophobized CNF from the organic solvent, unreacted substances, catalyst, and by-products. The manner of solid-liquid separation is not particularly limited. For example, a centrifuge, a filter press, etc. can be used.

[0042] (Cleaning process) Impurities such as organic solvents, unreacted substances, catalysts, and by-products that were not completely removed in the dehydration step are washed away using an aqueous alcohol solution. The type of alcohol is not particularly limited, but methanol, ethanol, etc. are preferred from the viewpoint of compatibility with the above substances. Similarly, from the viewpoint of compatibility, the alcohol concentration in the aqueous alcohol solution is preferably 1 to 100%, more preferably 30 to 90%, and even more preferably 50 to 70%. The dehydration step and the washing step are alternately performed until the concentration of the organic solvent used in the first step in the resulting hydrophobized CNF dispersion becomes 1000 ppm or less.

[0043] (Hydrophobic CNF and hydrophobic composite CNF) The hydrophobized CNF and hydrophobized composite CNF according to the present invention can be obtained by recovering and purifying the reaction product obtained in the second step, or by removing the aqueous alcohol solution from the obtained hydrophobized CNF dispersion or hydrophobized composite CNF dispersion. The hydrophobic CNF of the present invention is CNF having an average diameter of 3 to 200 nm and an average length of 0.1 μm or more, in which the hydroxyl groups of the CNF are esterified with vinyl esters and / or organic acid vinyl esters, and the degree of substitution is 0.41 to 1.79. The degree of substitution of the hydrophobized CNF is measured by the following degree of substitution measurement.

[0044] (Degree of substitution measurement) In the present invention, the degree of substitution of the hydrophobized CNF in the hydrophobized CNF dispersion is measured by the following method. To 10 ml of 1% (w / w) hydrophobized CNF dispersion, add an equal amount of 10 ml of ethanol to disperse. Next, add 10 ml of 0.5N sodium hydroxide solution to the dispersion using a whole pipette, and react and hydrolyze at 80°C for 60 minutes. After the reaction is complete, cool to stop the reaction. After adding a few drops of phenolphthalein solution, add 0.1N hydrochloric acid using a burette to titrate the amount of acid generated by hydrolysis of the ester. Calculate the degree of substitution (DS) from the titration value.

[0045] (Hydrophobic composite CNF) The hydrophobized composite CNF of the present invention is a hydrophobized composite CNF that includes a step of dispersing hydrous CNF in an organic solvent to obtain a primary dispersion, a step of adding a catalyst, a step of adding polyhydric alcohols and / or polyalkylene glycols, a crosslinking agent, vinyl esters and / or organic acid vinyl esters, a step of dispersing and reacting using a media-less disperser having a shear section clearance of 10 μm or more and 23,000 μm or less, and a step of recovering the obtained reaction product.

[0046] In this invention, the invention of "hydrophobized composite CNF" is specified by its manufacturing method as a specific feature. The reason for this will be explained below. There are at least two embodiments of the hydrophobized composite CNF of the present invention: First, the chemically unmodified hydroxyl groups in the cellobiose units are esterified using vinyl esters and / or organic acid vinyl esters, and hydrophobized composite CNFs exist in which two or more hydroxyl groups of polyhydric alcohols and / or polyalkylene glycols are bonded to the unreacted hydroxyl groups in one CNF and the unreacted hydroxyl groups in another CNF. Secondly, the unmodified hydroxyl groups in the cellobiose units are esterified using vinyl esters and / or organic acid vinyl esters, and the hydroxyl groups of two or more molecules of polyhydric alcohols and / or polyalkylene glycols are bonded to each other, resulting in hydrophobized composite CNFs in which the hydroxyl groups are bonded to unreacted hydroxyl groups in one CNF and unreacted hydroxyl groups in another CNF. These hydrophobized composite CNFs are then combined in a certain ratio.

[0047] Here, in order to measure the degree of substitution of vinyl esters and / or organic acid vinyl esters formed with hydroxyl groups via ester bonds, as described above, a sodium hydroxide solution is used to liberate the vinyl esters and / or organic acid vinyl esters formed with ester bonds, and the liberated vinyl esters are titrated to calculate the degree of substitution. However, when such a method is applied to hydrophobized composite CNF, the bonds between the polyhydric alcohols and / or polyalkylene glycols in the second hydrophobized composite CNF are also released, making it impossible to accurately calculate the degree of substitution of the polyhydric alcohols and / or polyalkylene glycols bonded to the hydroxyl groups in the hydrophobized composite CNF. In order to directly identify the hydrophobic composite CNF of the present invention by its structure or properties, it would require excessive economic expenditure and time to carry out the identifying work, and it would be practically difficult to uniquely identify it at the time of filing. Therefore, in the invention of the hydrophobic composite CNF, the manufacturing method is set as the invention specifying matter.

[0048] (Method of producing hydrophobized CNF oil component-containing body and hydrophobized CNF powder) (Method of manufacturing hydrophobized composite CNF oil component-containing body and hydrophobized composite CNF powder) The manufacturing method of the hydrophobized CNF oil-containing body of the present invention and the manufacturing method of the hydrophobized composite CNF oil-containing body differ only in whether a hydrophobized CNF dispersion or a hydrophobized composite CNF dispersion is used, so below we will explain the hydrophobized CNF oil-containing body. In addition, the only difference between the manufacturing method of the hydrophobized CNF powder and the manufacturing method of the hydrophobized composite CNF powder of the present invention is whether a hydrophobized CNF dispersion or a hydrophobized composite CNF dispersion is used, so the following description will focus on the hydrophobized CNF powder.

[0049] The method for producing the hydrophobized CNF oil-containing material of the present invention involves adding various oil-containing components described below to the hydrophobized CNF dispersion and removing the dispersion medium in the hydrophobized CNF dispersion to approximately 50%, 40%, 30%, or 20% or less to obtain the hydrophobized CNF oil-containing material. In this case, by adding various oily components in such a ratio that the hydrophobic CNF components in the resulting hydrophobic CNF oil-containing material are 20% or more and 99% or less, a hydrophobic CNF powder is obtained. Alternatively, when the content of hydrophobized CNF in the obtained hydrophobized CNF oil component-containing body is taken as 1, various oil components are added so that the ratio of hydrophobized CNF to the oil components is in the range of 1:0.01 to 1:4, thereby obtaining hydrophobized CNF powder. The method for removing the dispersion medium is not particularly limited, but may be, for example, a solvent replacement method or a drying method. In the case of the solvent replacement method, various oily components are added to the hydrophobized CNF dispersion, dispersed using a stirring device such as a homogenizer or FM mixer, and then the hydrophobized CNF that has been precipitated using a centrifuge or the like is collected. By repeating this series of operations several times, a hydrophobized CNF oily component-containing body can be obtained. This solvent replacement method can be mainly adopted when producing a paste-like hydrophobized CNF oily component-containing body. On the other hand, in the case of the drying method, various oily components are added to the hydrophobized CNF dispersion, and the dispersion medium in the hydrophobized CNF dispersion is removed using a dryer. More specifically, various oily components are added to the hydrophobized CNF dispersion, and the dispersion medium in the hydrophobized CNF dispersion is heated and dried while stirring, and the dispersion medium is removed. The drying method can be a known method such as reduced pressure drying or vacuum drying. This drying method can be used to produce both hydrophobized CNF powder and paste-like hydrophobized CNF oily component-containing bodies. The dryer to be used is not particularly limited, but is preferably one that can simultaneously reduce pressure, heat, and stir. The amount of oily component to be added to the hydrophobized CNF dispersion is not particularly limited, but may be adjusted so that the hydrophobized CNF content in the resulting hydrophobized CNF oily component-containing body is 1 to 99%. By making the hydrophobized CNF oil-containing material, it is possible to obtain good dispersibility in solvents in which it was difficult to disperse the hydrophobized CNF dispersion.

[0050] (Hydrophobic CNF oil-containing body and hydrophobic CNF powder) The method for producing hydrophobized CNF oil-containing body and hydrophobized CNF powder of the present invention makes it possible to obtain hydrophobized CNF oil-containing body and hydrophobized CNF powder. The hydrophobized CNF oil component-containing body of the present invention contains the hydrophobized CNF of the present invention and an oil component. In addition, the hydrophobized CNF powder of the present invention is a hydrophobized CNF oil component-containing body, in which, when the hydrophobized CNF is taken as 1, the ratio of the hydrophobized CNF to the oil component is 1:0.01 to 1:4. The hydrophobized CNF oil component-containing body and hydrophobized CNF powder of the present invention can be redispersed in various oil components.

[0051] (Hydrophobic composite CNF containing oily components and hydrophobic composite CNF powder) The method for producing hydrophobized composite CNF oil-containing body and hydrophobized composite CNF powder of the present invention makes it possible to obtain hydrophobized composite CNF oil-containing body and hydrophobized composite CNF powder. The hydrophobized composite CNF oil component-containing body of the present invention contains the hydrophobized composite CNF of the present invention and an oil component. In addition, the hydrophobized composite CNF powder of the present invention is a hydrophobized composite CNF containing an oily component, and when the hydrophobized composite CNF is taken as 1, the ratio of the hydrophobized composite CNF to the oily component is 1:0.01 to 1:4. The hydrophobized composite CNF oil component-containing body and hydrophobized composite CNF powder of the present invention can be redispersed in various oil components.

[0052] (Oily thickener) The hydrophobized CNF, hydrophobized CNF dispersion, hydrophobized CNF oil component-containing body, hydrophobized CNF powder, hydrophobized composite CNF, hydrophobized composite CNF dispersion, hydrophobized composite CNF oil component-containing body, and hydrophobized composite CNF powder of the present invention can be used as an oil-based thickener. For example, the oil-based thickener may be used in combination with one or more of known thickeners, gelling agents, hydrophobizing agents, suspending agents, dispersants, temperature and mechanical stabilizers, anti-caking agents, flow improvers, dry silica, fused silica particles, etc. Examples of applications of the oil-based thickener of the present invention include a thickener for oil-based paints and a thickener for hydrophobic resins. It can also be used as an oil adsorbent, an oil absorbent, and an oil composition for emulsions, and can also be used to prevent deformation, dripping, and improve abrasion resistance.

[0053] (Cosmetic raw materials) The hydrophobized CNF, hydrophobized CNF dispersion, hydrophobized CNF oil component-containing body, hydrophobized CNF powder, hydrophobized composite CNF, hydrophobized composite CNF dispersion, hydrophobized composite CNF oil component-containing body, and hydrophobized composite CNF powder of the present invention can be used as raw materials for cosmetics. By using the hydrophobized CNF, etc. of the present invention, a high thickening effect can be exhibited, and cosmetics with good usability and stability can be provided.

[0054] (Oily ingredients) Examples of oily components that can be used in the hydrophobized CNF oily component-containing body or hydrophobized composite CNF oily component-containing body according to the present invention include silicone oil, non-polar organic compounds and low-polarity organic compounds, higher alcohols, higher fatty acids, polyhydric alcohols, polyalkylene glycols, ultraviolet absorbers, vegetable oils, mineral oils, seed extract oils, oils separated, refined and liquefied from natural gas or petroleum, fatty oils obtained from animal subcutaneous tissues, collagen protein hydrolysates obtained by hydrolyzing bones and skins in the presence of acids, alkalis, and enzymes, either alone or in combination, various solvents with low polarity such as benzene, animal oils, etc. Specific examples of oily components are listed below, but the present invention is not limited to these, and any oily component that can be thickened by the hydrophobized CNF of the present invention can be used as the oily component of the present invention.

[0055] Examples of silicone oils include linear polysiloxanes (e.g., dimethicone), methyltrimethicone, methylphenylpolysiloxane, diphenylpolysiloxane, etc.); cyclic polysiloxanes (e.g., octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, etc.), silicone resins forming a three-dimensional network structure, silicone rubber, various modified polysiloxanes (amino-modified polysiloxanes, polyether-modified polysiloxanes, alkyl-modified polysiloxanes, fluorine-modified polysiloxanes, etc.), and the like.

[0056] Examples of non-polar organic compounds include liquid paraffin (mineral oil), light liquid isoparaffin, heavy liquid isoparaffin, petrolatum, n-paraffin, isoparaffin, isododecane, isohexadecane, polyisobutylene, hydrogenated polyisobutylene, polybutene, ozokerite, ceresin, microcrystalline wax, paraffin wax, polyethylene wax, polyethylene-polypropylene wax, squalene, squalane, pristane, polyisoprene, etc.

[0057] Examples of low polarity organic compounds include tripropylene glycol dineopentanoate, isononyl isononanoate, isopropyl myristate, cetyl octanoate, octyldodecyl myristate, isopropyl palmitate, butyl stearate, hexyl laurate, myristyl myristate, decyl oleate, hexyldecyl dimethyloctanoate, cetyl lactate, myristyl lactate, lanolin acetate, isocetyl stearate, isocetyl isostearate, 12-hydroxystearate, Cholesteryl phosphate, cetyl ethylhexanoate, ethylene glycol di-2-ethylhexanoate, dipentaerythritol fatty acid ester, N-alkyl glycol monoisostearate, neopentyl glycol dicaprate, diisostearyl malate, glycerin di-2-heptylundecanoate, trimethylolpropane tri-2-ethylhexanoate, trimethylolpropane triisostearate, pentaerythrityl tetra-2-ethylhexanoate, triethylhexanoyl Glyceryl tri-2-ethylhexanoate, glyceryl trioctanoate, glyceryl triisopalmitate, trimethylolpropane triisostearate, cetyl 2-ethylhexanoate, 2-ethylhexyl palmitate, glyceryl trimyristate, caprylic / capric triglyceride, caprylic / capric triglyceride, tri-2-heptylundecanoic acid glyceride, castor oil fatty acid methyl ester, oleyl oleate, acetoglyceride , 2-heptylundecyl palmitate, diisobutyl adipate, N-lauroyl-L-glutamic acid-2-octyldodecyl ester, di-2-heptylundecyl adipate, ethyl laurate, di-2-ethylhexyl sebacate, 2-hexyldecyl myristate, 2-hexyldecyl palmitate, 2-hexyldecyl adipate, diisopropyl sebacate, 2-ethylhexyl succinate, triethyl citrate, and ethylhexyl palmitate.

[0058] Examples of higher alcohols include isostearyl alcohol, oleyl alcohol, octyldodecanol, octyl alcohol, chimyl alcohol, stearyl alcohol, cetanol, cetostearyl alcohol, decyl alcohol, batyl alcohol, hexyldecanol, hexyldecanol, behenyl alcohol, myristyl alcohol, lauryl alcohol, and lanolin alcohol.

[0059] Examples of higher fatty acids include lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, oleic acid, undecylenic acid, tallic acid, isostearic acid, linoleic acid, linoleic acid, eicosapentaenoic acid (EPA), and docosahexaenoic acid (DHA).

[0060] The ultraviolet absorbent can be a wide variety of oil-based ultraviolet absorbents with high polarity that are generally used in cosmetics.For example, benzoic acid derivatives such as ethylhexyl methoxycinnamate, 2-hydroxy-4-methoxybenzophenone, and paraaminobenzoic acid, salicylic acid derivatives, cinnamic acid derivatives, dibenzoylmethane derivatives, β,β-diphenylacrylate derivatives, benzophenone derivatives, benzylidene camphor derivatives, phenylbenzimidazole derivatives, triazine derivatives, phenylbenzotriazole derivatives, anthranil derivatives such as methyl anthranilate, imidazoline derivatives, benzalmalonate derivatives, and 4,4-diarylbutadiene derivatives can be exemplified.

[0061] Examples of vegetable oils include almond oil, safflower oil, castor oil, safflower oil, jojoba oil, sunflower oil, almond oil, sesame oil, canola oil, corn oil, soybean oil, peanut oil, mink oil, avocado oil, camellia oil, macadamia nut oil, rice oil, olive oil, coconut oil, and camellia oil.

[0062] (Cosmetics) The cosmetic according to the present invention is a known cosmetic that contains an oily component. The cosmetic composition of the present invention can be widely applied in the form of makeup cosmetics, skin cosmetics, skin cleansing agents, UV protection cosmetics, skin care products, hair cosmetics, and the like. Examples of makeup cosmetics include makeup bases, powder foundations, liquid foundations, cream foundations, stick foundations, eye shadows, blushers, concealers, lipsticks, nail polishes, mascaras, grease guns, face colors, blushers, eyeliners, eyebrow products, and nail treatments. Examples of skin cosmetics include skin lotions, milky lotions (such as whitening milky lotions), creams, beauty essences, moisturizing lotions, face packs, emollient creams, moisture creams, and hand creams. Skin cleansers include cleansing oils, hand cleansers, facial cleansers, body soaps, scalp cleansers, hand cleaners, scrubs, peeling agents, cleansing creams, cleansing balms, cleansing gels, cleansing milks, cold creams, vanishing creams, massage creams, and the like. Examples of UV protection cosmetics include sunscreen emulsions, sunscreen creams, sunscreen lotions, suntan cosmetics, after-sun care cosmetics, self-tanning cosmetics, tone-up products, sunscreen mists / sprays, gels, powders, etc. Examples of hair cosmetics include hair creams, hair mists, shampoos, rinses, hair conditioners, rinse-in-shampoos, hair styling products (hair foams, gel-type hair styling products, etc.), hair treatment products, hair waxes, hair oils, and hair dyes. Further examples include pre-shave lotions, after-shave lotions, fragrances, deodorants, dentifrices, ointments, compresses, mouthwashes, hair removal creams, anti-aging creams, and the like.

[0063] The cosmetic preparation of the present invention may contain, as necessary, known raw materials that can be blended into ordinary cosmetic preparations, such as thickeners, gelling agents, hydrophobizing agents, suspending agents, dispersing agents, temperature and mechanical stabilizers, anti-caking agents, flow improvers, dry silica, fused silica particles, pigments, waxes, surfactants, moisturizers, preservatives and disinfectants.

[0064] The pigment is not particularly limited as long as it is one generally used in makeup cosmetics. For example, inorganic pigments such as talc, mica, kaolin, silica, calcium carbonate, titanium oxide, zinc oxide, red iron oxide, yellow iron oxide, black iron oxide, ultramarine, Prussian blue, carbon black, cobalt violet, chromium oxide, chromium hydroxide, cobalt titanate, bismuth oxychloride, titanium-mica pearl pigments, etc.; organic pigments such as zirconium, barium or aluminum lakes such as Red No. 201, Red No. 202, Orange No. 203, Yellow No. 205, Yellow No. 4, Yellow No. 5, Blue No. 1, Blue No. 404, Green No. 3, etc.; natural pigments such as chlorophyll, β-carotene, etc.; dyes, etc.

[0065] Examples of waxes include synthetic hydrocarbon waxes such as ceresin, microcrystalline wax, and polyethylene wax, plant-derived waxes such as carnauba wax, ozokerite, rice wax, rice bran wax, jojoba wax, and candelilla wax, animal-derived waxes such as whale wax, beeswax, and snow wax, silicone wax, etc. These waxes can be used alone or in combination of two or more kinds.

[0066] The surfactant may be a nonionic, anionic, cationic or amphoteric surfactant, but is not particularly limited thereto, and any surfactant that is used in ordinary cosmetics may be used. One type may be used alone, or two or more types may be used in appropriate combination.

[0067] Examples of moisturizing agents include lower alcohols such as ethanol and isopropanol; sugar alcohols such as sorbitol, maltose, and xylitol; polyhydric alcohols such as butylene glycol, dibutylene glycol, propylene glycol, dibutylene glycol, pentylene glycol, decanediol, hexanediol, erythritol, glycerin, diglycerin, and polyethylene glycol; glucose, glyceryl glucoside, betaine, hyaluronic acid, chondroitin sulfate, and polyoxypropylene methyl glucoside.

[0068] Examples of preservatives and disinfectants include alkyl esters of paraoxybenzoic acid, benzoic acid, sodium benzoate, sorbic acid, potassium sorbate, imidazolidinyl urea, salicylic acid, isopropylmethylphenol, carbolic acid, parachlormetacresol, phenoxyethanol, hexachlorophene, benzalkonium chloride, chlorhexidine chloride, trichlorocarbanilide, polylysine, 1,2-pentanediol, 1,2-hexanediol, 1,3-propanediol, 1,2-octanediol, and 1,2-decanediol. EXAMPLES

[0069] EXAMPLES The present invention will be specifically described below with reference to examples and comparative examples, but the present invention is not limited to these.

[0070] (DMSO measurement method) The concentration of DMSO in the step of each Example (F) was measured based on the following measurement method. Each hydrophobic CNF dispersion is diluted 10 to 100 times in acetone and dispersed using a dispersing device such as a stirrer or ultrasonic. Next, the liquid after removing the hydrophobic CNF with a syringe filter was analyzed using a gas chromatography mass spectrometer, and the concentration of DMSO contained in the hydrophobic CNF before dilution was calculated. The dilution ratio was appropriately adjusted during the analysis. The measurement conditions for the gas chromatography mass spectrometer are as follows. Gas chromatograph mass spectrometer: Agilent 5975GC / MS, manufactured by Agilent Technologies, Inc. Column: Agilent Technologies, DB-WAX 0.25mm x 30m x 0.25μm Inlet temperature: 200℃ Injection method: Split Temperature conditions: 40℃ (1 minute) ~ 10℃ / min → 250℃ (8 minutes) Carrier gas flow rate: He 1.2 ml / min Ion source temperature: 230℃

[0071] Example 1 (Preparation of hydrophobic CNF dispersion) A hydrophobized CNF dispersion using vinyl hexanoate was prepared by carrying out the following steps (A) to (F). The degree of substitution of the resulting hydrophobized CNF was then measured. (A) Bamboo pulp was used as the raw material and defibrated using the ACC method (underwater counter collision method) to obtain a 1 wt% dispersion of CNF with an average fiber diameter of 3 nm to 200 nm. Next, the CNF dispersion was dehydrated using a filter press (Kurita Machinery Works, Ltd., MF-A manual type) to a CNF concentration of 30 w / w%, and the obtained CNF was crushed to obtain powdered CNF. (B) Next, the powdered CNF was dispersed in DMSO for 1 hour using an FM mixer (Nippon Coke and Engineering Co., Ltd., FM10C / I) to obtain a primary dispersion (DMSO dispersion) with a CNF concentration of 2.7 w / w%. (C) Next, water was added to the primary dispersion so that the water content after the addition of water was 40%, and this was heated to 80°C. (D) Next, vinyl hexanoate was added in a ratio of 1.2 molar equivalents relative to the glucose unit amount of CNF contained in the primary dispersion. (E) Next, a dispersion process was carried out using an FM mixer with a shear clearance of 1000 μm (rotation speed: 1200 rpm, diameter: 160 mm, peripheral speed: 10.1 m / s, shear rate: 10053 (1 / s)). Potassium carbonate was then added at a ratio of 20% to the CNF, and the reaction was carried out for 180 minutes in the FM mixer (conditions were the same as above) to obtain a secondary dispersion. (F) After the reaction was completed, the mixture was dehydrated using a Buchner funnel and then washed multiple times using an FM mixer and a 50% aqueous ethanol solution. When the DMSO concentration reached 950 ppm, the washing was stopped and a hydrophobic CNF dispersion with a hydrophobic CNF concentration of 2% was prepared using an aqueous ethanol solution. In addition, the degree of substitution of the hydrophobic CNF was 0.71.

[0072] Example 2 (Preparation of hydrophobic CNF dispersion) Of steps (A) to (F) in Example 1, steps (B), (C), (D), and (F) were changed as follows to prepare a hydrophobic CNF dispersion using vinyl laurate. The degree of substitution of the resulting hydrophobized CNF was then measured. (B) Next, the powdered CNF was dispersed in DMSO for 1 hour using an FM mixer (Nippon Coke and Engineering Co., Ltd., FM10C / I) to obtain a primary dispersion (DMSO dispersion) with a CNF concentration of 2.3 w / w%. (C) Next, water was added to the primary dispersion so that the water content after the addition of water was 60%, and this was heated to 80°C. (D) Next, vinyl laurate was added in a ratio of 1.2 molar equivalents relative to the glucose unit amount of CNF contained in the primary dispersion. (F) After the reaction was completed, the mixture was dehydrated using a Buchner funnel and then washed multiple times using an FM mixer and a 60% aqueous ethanol solution. When the DMSO concentration reached 500 ppm, the washing was stopped and a hydrophobic CNF dispersion with a hydrophobic CNF concentration of 5% was obtained using an aqueous ethanol solution. In addition, the degree of substitution of the hydrophobic CNF was 1.09.

[0073] Example 3 (Preparation of hydrophobic CNF dispersion) Of steps (A) to (F) in Example 1, steps (B), (D), (E), and (F) were changed as follows to prepare a hydrophobic CNF dispersion using vinyl laurate. (B) Next, the powdered CNF was dispersed in DMSO for 1 hour using an FM mixer (Nippon Coke and Engineering Co., Ltd., FM10C / I) to obtain a primary dispersion (DMSO dispersion) with a CNF concentration of 3.5 w / w%. (D) Next, vinyl laurate was added in a ratio of 1.2 molar equivalents relative to the glucose unit amount of CNF contained in the primary dispersion. (E) Next, a dispersion process was carried out using a Trimix (Inoue Seisakusho Co., Ltd. planetary mixer) with a shear section clearance of 23,000 μm (rotation speed: 102 rpm, diameter: 150 mm, peripheral speed: 0.8 m / s, shear rate: 35 (1 / s)), after which potassium carbonate was added at a ratio of 20% to the CNF, and a reaction was carried out for 180 minutes in a Trimix (conditions were the same as above) to obtain a secondary dispersion. (F) After the reaction was completed, the mixture was dehydrated using a Buchner funnel and then washed multiple times using an FM mixer and a 50% aqueous ethanol solution. When the DMSO concentration reached 50 ppm, the washing was stopped and a hydrophobic CNF dispersion with a hydrophobic CNF concentration of 2% was obtained using an aqueous ethanol solution. In addition, the degree of substitution of the hydrophobic CNF was 0.41.

[0074] Example 4 (Preparation of hydrophobic CNF dispersion) Of steps (A) to (F) in Example 1, steps (B), (C), (D), (E), and (F) were changed as follows to prepare a hydrophobic CNF dispersion using vinyl laurate. (B) Next, the powdered CNF was dispersed in DMSO for 1 hour using an FM mixer (Nippon Coke and Engineering Co., Ltd., FM10C / I) to obtain a primary dispersion (DMSO dispersion) with a CNF concentration of 3.0 w / w%. (C) Next, water was added to the primary dispersion so that the water content after the addition of water was 50%, and this was heated to 80°C. (D) Next, vinyl laurate was added in a ratio of 5.0 molar equivalents relative to the glucose unit amount of CNF contained in the primary dispersion. (E) Next, a dispersion process was carried out using a dispersizer (Shinto Kogyo Co., Ltd., centrifugal disc mixer) with a shear clearance of 10 μm (rotation speed: 12,000 rpm, diameter: 150 mm, peripheral speed: 94.2 m / s, shear rate: 9,424,778 (1 / s)), after which potassium carbonate was added at a ratio of 20% to the CNF, and a reaction was carried out for 180 minutes in a dispersizer (conditions were the same as above) to obtain a secondary dispersion. (F) After the reaction was completed, the mixture was dehydrated using a Buchner funnel and then washed multiple times using an FM mixer and a 60% aqueous ethanol solution. When the DMSO concentration reached 900 ppm, the washing was stopped and a hydrophobic CNF dispersion with a hydrophobic CNF concentration of 10% was prepared using an aqueous ethanol solution. In addition, the degree of substitution of the hydrophobic CNF was 1.79.

[0075] Example 5 (Preparation of hydrophobic CNF dispersion) Of steps (A) to (F) in Example 1, steps (A), (B), (C), (D), and (F) were changed as follows to prepare a hydrophobic CNF dispersion using vinyl laurate. (A) Softwood pulp was used instead of bamboo pulp. (B) Next, the powdered CNF was dispersed in DMSO for 1 hour using an FM mixer (Nippon Coke and Engineering Co., Ltd., FM10C / I) to obtain a primary dispersion (DMSO dispersion) with a CNF concentration of 2.5 w / w%. (C) Next, water was added to the primary dispersion so that the water content after the addition of water was 50%, and this was heated to 80°C. (D) Next, vinyl laurate was added in a ratio of 1.2 molar equivalents relative to the glucose unit amount of CNF contained in the primary dispersion. (F) After the reaction was completed, the mixture was dehydrated using a Buchner funnel and then washed multiple times using an FM mixer and a 30% aqueous ethanol solution. When the DMSO concentration reached 980 ppm, the washing was stopped and a hydrophobic CNF dispersion with a hydrophobic CNF concentration of 5% was obtained using an aqueous ethanol solution. In addition, the degree of substitution of the hydrophobized CNF was 0.6.

[0076] Example 6 (Preparation of hydrophobic CNF dispersion) Of steps (A) to (F) in Example 1, steps (A), (B), (C), (D), and (F) were changed as follows to prepare a hydrophobic CNF dispersion using vinyl laurate. (A) Hardwood pulp was used instead of bamboo pulp. (B) Next, the powdered CNF was dispersed in DMSO for 1 hour using an FM mixer (Nippon Coke and Engineering Co., Ltd., FM10C / I) to obtain a primary dispersion (DMSO dispersion) with a CNF concentration of 3.0 w / w%. (C) Next, water was added to the primary dispersion so that the water content after the addition of water was 20%, and this was heated to 80°C. (D) Next, vinyl laurate was added in a ratio of 1.2 molar equivalents relative to the glucose unit amount of CNF contained in the primary dispersion. (F) After the reaction was completed, the mixture was dehydrated using a Buchner funnel and then washed multiple times using an FM mixer and a 90% aqueous ethanol solution. When the DMSO concentration reached 300 ppm, the washing was stopped and a hydrophobic CNF dispersion with a hydrophobic CNF concentration of 5% was obtained using an aqueous ethanol solution. In addition, the degree of substitution of the hydrophobic CNF was 0.55.

[0077] Example 7 (Preparation of hydrophobic CNF dispersion) Of steps (A) to (F) in Example 1, steps (A), (B), (C), (D), and (F) were changed as follows to prepare a hydrophobic CNF dispersion using vinyl laurate. (A) Hardwood pulp was used instead of bamboo pulp. (B) Next, the powdered CNF was dispersed in DMSO for 1 hour using an FM mixer (Nippon Coke and Engineering Co., Ltd., FM10C / I) to obtain a primary dispersion (DMSO dispersion) with a CNF concentration of 4.0 w / w%. (C) Next, water was added to the primary dispersion so that the water content after the addition of water was 30%, and this was heated to 80°C. (D) Next, vinyl laurate was added in a ratio of 1.2 molar equivalents relative to the glucose unit amount of CNF contained in the primary dispersion. (F) After the reaction was completed, the mixture was dehydrated using a Buchner funnel and then washed multiple times using an FM mixer and a 70% aqueous ethanol solution. When the DMSO concentration reached 950 ppm, the washing was stopped and a hydrophobic CNF dispersion with a hydrophobic CNF concentration of 30% was prepared using an aqueous ethanol solution. In addition, the degree of substitution of the hydrophobized CNF was 0.5.

[0078] Example 8 (Creation of hydrophobic composite CNF dispersion) Of the steps (A) to (F) in Example 1, steps (B), (C), (D), and (F) were changed as follows to prepare a hydrophobic composite CNF dispersion. (B) Next, the powdered CNF was dispersed in DMSO for 1 hour using an FM mixer (Nippon Coke and Engineering Co., Ltd., FM10C / I) to obtain a primary dispersion (DMSO dispersion) with a CNF concentration of 0.1 w / w%. (C) Next, water was added to the primary dispersion so that the water content after the addition of water was 10%, and this was heated to 80°C. (D) Next, divinyl sebacate and vinyl propionate were added in a ratio of 1.2 molar equivalents each relative to the glucose unit amount of CNF contained in the primary dispersion, and polyethylene glycol was added in a ratio of 0.18 molar equivalents. (F) After the reaction was completed, the mixture was dehydrated using a Buchner funnel and then washed multiple times using an FM mixer and a 60% aqueous ethanol solution. When the DMSO concentration reached 500 ppm, the washing was stopped and an aqueous ethanol solution was used to prepare a hydrophobic composite CNF dispersion with a hydrophobic composite CNF concentration of 5%.

[0079] Example 9 (Preparation of paste-like hydrophobic CNF oil-containing body) Using the hydrophobized CNF dispersion obtained in Example 1, ethylhexyl methoxycinnamate was added so that the proportion of hydrophobized CNF in the resulting paste-like hydrophobized CNF oil component-containing material was 19%. Next, using a stirrer (IKA EUROSTAR 20 DIGITAL (stirring rod: R1303), the dispersion medium in the hydrophobic CNF dispersion was removed at a temperature of 80°C, and a paste-like hydrophobic CNF oil component-containing body was obtained.

[0080] Example 10 (Creation of hydrophobic CNF powder) Using the hydrophobized CNF dispersion obtained in Example 4, ethylhexyl methoxycinnamate was added so that the proportion of hydrophobized CNF in the resulting hydrophobized CNF powder was 20%. Next, the dispersion medium in the hydrophobic CNF dispersion was removed using a stirrer (IKA EUROSTAR 20 DIGITAL (stirring rod: R1303) at a temperature of 80°C, thereby obtaining hydrophobic CNF powder. Next, ethylhexyl methoxycinnamate was added to the obtained hydrophobized CNF powder to redisperse the hydrophobized CNF powder. The results are shown in Figure 2. From Figure 2, it was revealed that the hydrophobized CNF powder according to the present invention can be redispersed in an oily component.

[0081] Example 11 (Creation of hydrophobic CNF powder) Using the hydrophobized CNF dispersion obtained in Example 7, ethylhexyl methoxycinnamate was added so that the proportion of hydrophobized CNF in the resulting hydrophobized CNF powder was 90%. Next, the dispersion medium in the hydrophobic CNF dispersion was removed using a stirrer (IKA EUROSTAR 20 DIGITAL (stirring rod: R1303) at a temperature of 80°C, thereby obtaining hydrophobic CNF powder.

[0082] Example 12 (Creation of hydrophobic composite CNF powder) Using the hydrophobized composite CNF dispersion obtained in Example 8, polypropylene glycol was added so that the proportion of hydrophobized composite CNF in the resulting hydrophobized composite CNF powder was 30%. Next, the dispersion medium in the hydrophobic composite CNF dispersion was removed using a stirrer (IKA EUROSTAR 20 DIGITAL (stirring rod: R1303) at a temperature of 80°C, thereby obtaining a hydrophobic composite CNF powder. Next, polypropylene glycol was added to the obtained hydrophobized composite CNF powder to redisperse the hydrophobized composite CNF powder. The results are shown in Figure 3. From Figure 3, it was revealed that the hydrophobized composite CNF powder according to the present invention can be redispersed in an oily component.

[0083] (Example 13) (Evaluation of dispersibility of hydrophobic CNF) The hydrophobized CNF obtained in Example 1 and Example 2 was adjusted to 0.3 wt% in each of the following oils, and each oil was stirred, ultrasonicated for 30 minutes, and allowed to stand. After one day, the dispersibility was evaluated visually using the following evaluation criteria. Table 1 shows the results for the hydrophobized CNF obtained in Example 1, and Table 2 shows the results for the hydrophobized CNF obtained in Example 2. Evaluation criteria ◎: Dispersion stable 〇: Settling after dispersion ×: Coagulation The types of oil used for the hydrophobized CNF obtained in Example 1 are as follows. Isododecane (Kaneda Co., Ltd.: ISODODECANE), 2-Octyldodecanol (Kyushu Alcohol Kogyo Co., Ltd.: Lisonol 20SP) Caprylic / capric triglyceride (BASF Japan Ltd.: Myritol 318), Cetyl ethylhexanoate (BASF Japan Ltd.: Cetiol SN-1F) Pentaerythrityl tetraethylhexanoate (Nisshin Oillio Group Co., Ltd.: Salacos 5408) Ethylhexyl methoxycinnamate (Nomcoat TAB: Nisshin Oillio Group Co., Ltd.) Ethylhexyl palmitate (Nikko Chemicals Co., Ltd.: Nikkol IOP) The types of oil used for the hydrophobized CNF obtained in Example 2 are as follows: Mineral oil (MORESCO Corporation: MORESCO White P-70(M)) Olive oil (CROPURE OL-LQ-(JP)) Diisostearyl malate (Nippon Fine Chemicals Co., Ltd.: Neosolue-DiSM) Diethyl sebacate (Nikko Chemicals Co., Ltd.: NIKKOL DES-SP) Dimethicone (Shin-Etsu Chemical Co., Ltd.: KF-96A-6CS) Ethylhexyl palmitate (Nikko Chemicals Co., Ltd.: Nikkol IOP)

[0084] [Table 1]

[0085] [Table 2]

[0086] Example 14 (Viscosity evaluation of hydrophobic CNF 1) The hydrophobic CNF obtained in Example 1 was used to prepare samples at the concentrations shown in Table 3 below with 2-octyldodecanol (Kyushu Alcohol Industry Co., Ltd.: Lisonol 20SP), cetyl ethylhexanoate (BASF Japan Ltd.: Cetiol SN-1F), diisostearyl malate (Nippon Fine Chemicals Co., Ltd.: Neosolue-DiSM), pentaerythrityl tetraethylhexanoate (Nisshin Oillio Group Ltd.: Salacos 5408), and ethylhexyl methoxycinnamate (Nisshin Oillio Group Ltd.: Nomcoat TAB). Each sample was shaken and stirred, then allowed to stand in a thermostatic chamber (25° C.) for 5 minutes, and the viscosity was measured using a viscometer (Toki Sangyo Co., Ltd.: TVB-15M, rotor M4) at a rotation speed of 6 rpm.

[0087] [Table 3]

[0088] The results are shown in Table 3 and Figure 4. It was found that adding a small amount of hydrophobic CNF to any oil had the effect of thickening the oil.

[0089] Example 15 (Viscosity evaluation of hydrophobic CNF 2) The hydrophobic CNF obtained in Example 2 was mixed with olive oil (Croda Japan: CROPURE OL-LQ-(JP)), cetyl ethylhexanoate (BASF Japan: Cetiol SN-1F), diisostearyl malate (Nippon Fine Chemicals: Neosolue-DiSM), diethyl sebacate (Nikko Chemicals: NIKKOL DES-SP), and ethylhexyl methoxycinnamate (Nissin Oillio Group: Nomcoat TAB) at the concentrations shown in Table 4 below to prepare samples. Each sample was shaken and stirred, then allowed to stand in a thermostatic chamber (25° C.) for 5 minutes, and the viscosity was measured using a viscometer (Toki Sangyo Co., Ltd.: TVB-15M, rotor M4) at a rotation speed of 6 rpm.

[0090] [Table 4]

[0091] The results are shown in Table 4 and Figure 5. It was found that adding a small amount of hydrophobic CNF to any oil had the effect of thickening the oil.

[0092] (Example 16) (Evaluation of viscosity of hydrophobic composite CNF powder) The hydrophobic composite CNF powder obtained in Example 12 was dispersed in ethylhexyl methoxycinnamate (Nomcoat TAB, Nisshin Oillio Group, Ltd.) and olive oil (CROPURE OL-LQ-(JP), Croda Japan, Ltd.) for 10 minutes using a handheld homogenizer (IKA T10 ULTRA-TURRAX; shaft generator (S10D-7G-KS-110)) to prepare samples with hydrophobic composite CNF concentrations of 0.5%, 1.0%, 1.5%, and 2.0%. Next, each sample was shaken and stirred, and then allowed to stand for 5 minutes, and the storage modulus (Pa) was measured using a rheometer (Anton Paar: MCR92, cone plate 50 mm 1°). The measurement results are shown in Table 5 and Figure 6. From Table 5 and Figure 6, it is clear that the hydrophobic composite CNF powder according to the present invention has sufficient gelling ability for both ethylhexyl methoxycinnamate and olive oil.

[0093] [Table 5]

[0094] (Manufacturing of cosmetic raw materials) The cosmetic raw materials (hydrophobized CNF oil component-containing bodies) of Examples 17 to 35 were prepared by the following method. Various oily components were added to the hydrophobized CNF dispersion obtained in Example 1 or Example 2, and dispersed using a homogenizer (IKA ULTRA-TURRAX T18 digital (shaft S18N-19G 12,000 rpm 15 minutes). The hydrophobic CNF was then precipitated using a centrifuge (Kubota Shoji Co., Ltd. Model 7000, 23,830 rpm, 4.5 hours). The precipitate was then collected and the same procedure was repeated twice. Next, an oily component was added to the obtained hydrophobized CNF sediment to reach a predetermined concentration, and the mixture was dispersed using a homogenizer (IKA ULTRA-TURRAX T18 digital shaft S18N-19G 12,000 rpm for 1 minute).

[0095] (Evaluation of each cosmetic product) The following cosmetics were prepared and their formulation stability and texture (presence or absence of stickiness, etc.) were examined.

[0096] (Example 17) (Lotion 1) Using the hydrophobized CNF dispersion obtained in Example 1, 2-octyldodecanol (oil component) was added so that the hydrophobized CNF in the resulting cosmetic raw material was 2 wt %, to prepare cosmetic raw material 1. Next, the raw materials shown below were weighed and prepared according to the following preparation method to prepare lotion 1. The amount of hydrophobized CNF in lotion 1 was 0.005 wt%. TIFF2025024008000007.tif51108 Preparation method: Mix A. Heat A to 80°C and dissolve homogeneously. Meanwhile, mix B. Next, add B to the stirring A and stir with a homomixer. Cool to room temperature to complete preparation. After using lotion 1, it was confirmed that it was not sticky and spread easily, and that the skin remained moisturized after use.

[0097] (Example 18) (Lotion 2) Cosmetic raw material 2 was prepared by adding tri(caprylic / capric acid)glyceryl (oil component) to the hydrophobized CNF dispersion obtained in Example 2 so that the hydrophobized CNF in the resulting cosmetic raw material was 2 wt%. Next, the raw materials shown below were weighed and lotion 2 was prepared by the following preparation method. The amount of hydrophobized CNF in lotion 2 was 0.005 wt%. TIFF2025024008000008.tif68109 Preparation method: Mix A. Heat A to 80°C and dissolve homogeneously. Meanwhile, mix B. Heat B to 80°C and dissolve homogeneously. Next, add B to the stirred A and stir with a homomixer. Cool to room temperature to complete preparation. When using lotion 2, it was not sticky and spread easily. In addition, the moist feeling continued after use, and it was less sticky than the more moisturizing lotion.

[0098] (Example 19) (emulsion) Using the hydrophobized CNF dispersion obtained in Example 1, ethylhexyl methoxycinnamate (oil component) was added so that the hydrophobized CNF in the resulting cosmetic raw material was 2 wt% to prepare cosmetic raw material 3. Next, the raw materials shown below were weighed and an emulsion was prepared using the method described below. The amount of hydrophobic CNF in the emulsion was 0.02 wt%. TIFF2025024008000009.tif85108 Preparation method: Mix A. Heat A to 80°C and dissolve homogeneously. Mix B. Heat B to 80°C and dissolve homogeneously. Meanwhile, mix C. Next, add A while stirring B and emulsify. After using the emulsion, it was not sticky and had a smooth texture. After use, the skin remained moisturized and not sticky. Furthermore, Cosmetic Raw Material 3 did not inhibit emulsification.

[0099] (Example 20) (Moisturizing lotion) Using the hydrophobized CNF dispersion obtained in Example 2, diethyl sebacate (oil component) was added so that the hydrophobized CNF in the resulting cosmetic raw material was 2 wt% to prepare cosmetic raw material 4. Next, the raw materials shown below were weighed and a moisturizing lotion was prepared by the following preparation method. The amount of hydrophobized CNF in the moisturizing lotion was 0.005 wt%. TIFF2025024008000010.tif52109 Preparation method: Mix A. Disperse uniformly to complete preparation. After using the moisturizing lotion, it was not sticky and had a stretchy feel. In addition, the moist feeling continued after use.

[0100] Example 21 (Cleansing oil 1) Using the hydrophobic CNF dispersion obtained in Example 1, cetyl ethylhexanoate (oil component) was added so that the hydrophobic CNF in the resulting cosmetic raw material was 2 wt% to prepare cosmetic raw material 5. Next, the raw materials shown below were weighed and cleansing oils were prepared using the following preparation method. The amount of hydrophobic CNF in cleansing oil 1 was 0.0006 wt%. Next, Examples 21 to 27 and Comparative Examples 1 to 3 were evaluated based on the following evaluation items and evaluation criteria 1 to 5. The results are shown in Table 6. TIFF2025024008000011.tif27108 Preparation method: Mix A. Disperse uniformly to complete preparation.

[0101] Example 22 (Cleansing Oil 2) Cosmetic raw material 5 and the raw materials shown below were weighed, and cleansing oil 2 was prepared in the same manner as cleansing oil 1. The amount of hydrophobized CNF in cleansing oil 2 was 0.008 wt%. TIFF2025024008000012.tif27109

[0102] (Example 23) (Cleansing Oil 3) Cosmetic raw material 5 and the raw materials shown below were weighed, and cleansing oil 3 was prepared in the same manner as cleansing oil 1. The amount of hydrophobized CNF in cleansing oil 3 was 0.0136 wt%. TIFF2025024008000013.tif27108

[0103] Example 24 (Cleansing Oil 4) Cosmetic raw material 5 and the raw materials shown below were weighed, and cleansing oil 4 was prepared in the same manner as cleansing oil 1. The amount of hydrophobized CNF in cleansing oil 4 was 0.25 wt%. TIFF2025024008000014.tif27108

[0104] (Example 25) (Cleansing Oil 5) Using the hydrophobic CNF dispersion obtained in Example 1, cetyl ethylhexanoate (oil component) was added so that the hydrophobic CNF in the resulting cosmetic raw material was 7.8 wt% to prepare cosmetic raw material 6. Next, the raw materials shown below were weighed, and cleansing oils were prepared using the same preparation method as for cleansing oil 1. The blending amount of hydrophobized CNF in cleansing oil 5 was 1.0 wt%. TIFF2025024008000015.tif28109

[0105] (Example 26) (Cleansing Oil 6) Using the hydrophobic CNF dispersion obtained in Example 1, cetyl ethylhexanoate (oil component) was added so that the hydrophobic CNF in the resulting cosmetic raw material was 15.1 wt% to prepare cosmetic raw material 7. Next, the raw materials shown below were weighed, and cleansing oils were prepared using the same preparation method as for cleansing oil 1. The blending amount of hydrophobized CNF in cleansing oil 6 was 2.0 wt%. TIFF2025024008000016.tif28109

[0106] Example 27 (Cleansing Oil 7) Using the hydrophobic CNF dispersion obtained in Example 2, cetyl ethylhexanoate (oil component) was added so that the hydrophobic CNF in the resulting cosmetic raw material was 2 wt% to prepare cosmetic raw material 8. Next, the raw materials shown below were weighed, and Cleansing Oil 7 was prepared in the same manner as Cleansing Oil 1. The amount of hydrophobized CNF in Cleansing Oil 7 was 0.0006 wt%. TIFF2025024008000017.tif27109

[0107] (Prescription Example 1) (Cleansing Oil 8) The hydrophobic CNF dispersion obtained in Example 1 was used to prepare a cosmetic raw material 9, with the hydrophobic CNF being 18.2 wt% in cetyl ethylhexanoate (oil component). Next, the raw materials shown below were weighed, and cleansing oils were prepared using the same preparation method as for cleansing oil 1. The blending amount of hydrophobized CNF in cleansing oil 8 was 2.5 wt%. TIFF2025024008000018.tif27108

[0108] Comparative Example 1 (Cleansing Oil 9) Without using the cosmetic raw material according to the present invention, the raw materials shown below were weighed out and cleansing oil 9 was prepared using the same preparation method as cleansing oil 1. The amount of hydrophobized CNF in cleansing oil 9 was 0 wt%. TIFF2025024008000019.tif19109

[0109] Comparative Example 2 (Cleansing Oil 10) Using the CNF prepared by the method described below, the hydrophobized CNF was adjusted to 2 wt% in cetyl ethylhexanoate (oil component) to prepare cleansing oil raw material 1. Cleansing oil 10 was prepared using the same preparation method as cleansing oil 1. The amount of TEMPO oxidized CNF in cleansing oil 10 was 0.0006 wt%. -method- 1g (dry weight) of bleached kraft pulp derived from softwood 0.0125 g of TEMPO (2,2,6,6-tetramethylpiperidine-1-oxy radical), 0.125g of sodium bromide was dispersed in 100ml of water, A 13% aqueous solution of sodium hypochlorite Add sodium hypochlorite to 1 g of pulp so that the amount is 5.0 mmol. The reaction was started at room temperature. The pH in the meter during the reaction was adjusted with 0.5 mol / l sodium hydroxide solution and The pH was maintained at 10 by dropwise addition of 0.5 mol / l aqueous hydrochloric acid solution. After reacting for 2 hours, the reaction product was filtered and washed with water to obtain TEMPO oxidized pulp. The TEMPO oxidized pulp was dispersed in distilled water, and the resulting sample was adjusted to 1% by mass, and then defibrated using a homogenizer to obtain an aqueous dispersion of cellulose nanofibers (average fiber width: 3 to 8 nm). TIFF2025024008000020.tif2079

[0110] (Evaluation item 1: Ease of removal) After applying multiple layers of oil-based black marker to a whiteboard, the cleansing oil was applied to a cloth and the cleaning power was evaluated based on the number of times the cloth was rubbed. (Evaluation Criteria 1) ◎: Black marker marks come off after less than 10 rubs ○: Black marker marks do not come off unless rubbed hard 10 times or more ×: The oil-based black marker marks are barely removed even after rubbing 10 times or more.

[0111] (Evaluation item 2: Texture) The above cleansing oils 1 to 10 were actually used and evaluated for the squeaky feeling of the oil. (Evaluation Criteria 2) ◎: No oily feeling when applied to skin ○: There was a slight oily feeling when applied to the skin. ×: There was an oily feeling when applied to the skin.

[0112] (Evaluation item 3: Ease of use (not getting dull)) The cleansing oils 1 to 10 were actually applied to the skin and evaluated for ease of use (non-sagging). (Evaluation Criteria 3) 〇: Prevents dripping when applied to the skin ×: When applied to the skin, it does not drip at all or drips immediately.

[0113] (Evaluation item 4: Ease of stretching) The cleansing oils 1 to 10 were actually applied to the skin and evaluated for ease of spread. (Evaluation Criteria 4) ◎: When applied to the skin, it spreads evenly over the entire face. 〇: Spreads to some extent when applied to the skin ×: Does not spread when applied to the skin

[0114] (Evaluation item 5: Mixing) The presence or absence of emulsification of the cleansing oil was evaluated. (Rating Criteria 5) ◎: No cloudiness was observed ×: Emulsified and cloudy

[0115] [Table 6]

[0116] By incorporating the hydrophobized CNF of the present invention, the cleansing power was improved and makeup could be easily removed with water.

[0117] (Example 28) (Liquid Foundation 1) Using the hydrophobized CNF dispersion obtained in Example 2, ethylhexyl methoxycinnamate (oil component) was added so that the hydrophobized CNF in the resulting cosmetic raw material was 2 wt%, and cosmetic raw material 10 was prepared. Next, the raw materials shown below were weighed and prepared by the following preparation method to prepare Liquid Foundation 1. The blending amount of hydrophobic CNF in Liquid Foundation 1 was 0.064 wt%. JPEG2025024008000022.jpg85133 Preparation method: A is mixed and uniformly dispersed. Meanwhile, B is mixed and uniformly dissolved. Next, C is added while stirring B and uniformly dispersed. Furthermore, A is added and uniformly dispersed, and the preparation is completed. After using Liquid Foundation 1, I found it spread well and made my makeup sit nicely on the skin.

[0118] (Example 29) (Liquid Foundation 2) Using the hydrophobized CNF dispersion obtained in Example 2, pentaerythrityl tetraethylhexanoate (oil component) was added so that the hydrophobized CNF in the resulting cosmetic raw material was 2 wt%, and cosmetic raw material 11 was prepared. Next, the raw materials shown below were weighed and prepared by the following preparation method to prepare Liquid Foundation 2. The blending amount of hydrophobic CNF in Liquid Foundation 2 was 0.06 wt%. JPEG2025024008000023.jpg65133 Preparation method: Mix B and disperse uniformly. While stirring B, add C and disperse uniformly to complete the preparation. When I used Liquid Foundation 2, I found it spread well and made my makeup sit nicely on the skin.

[0119] (Example 30) (Hair cream) Using the hydrophobized CNF dispersion obtained in Example 1, olive oil (oil component) was added so that the hydrophobized CNF in the resulting cosmetic raw material was 2 wt % to prepare cosmetic raw material 12. Next, the raw materials shown below were weighed and a hair cream was prepared according to the following preparation method. The amount of hydrophobic CNF in the hair cream was 0.006 wt%. JPEG2025024008000024.jpg101133 Preparation method: Mix A. Heat further to 80°C and dissolve uniformly. Mix B. Heat further to 80°C and dissolve uniformly. Add B while stirring A and emulsify. Cool to room temperature to complete preparation. After using the hair cream, it was not sticky and spread easily. It also prevented dryness and left my hair feeling moisturized.

[0120] (Example 31) (Hair mist) Using the hydrophobized CNF dispersion obtained in Example 1, dimethicone (oil component) was added so that the hydrophobized CNF in the obtained cosmetic raw material was 2 wt %, to prepare cosmetic raw material 13. Next, the raw materials shown below were weighed and a hair mist was prepared using the following preparation method. The amount of hydrophobic CNF in the hair mist was 0.005 wt%. JPEG2025024008000025.jpg85133 Preparation method: Mix A. Heat to 80°C and dissolve uniformly. Mix B and dissolve uniformly. While stirring B, add A and disperse uniformly to complete preparation. After using the hair mist, it was not sticky and spread easily. It also prevented dryness and left my hair feeling smooth.

[0121] Example 32 (UV Milk) Using the hydrophobized CNF dispersion obtained in Example 1, mineral oil (oil-based component) was added so that the hydrophobized CNF in the resulting cosmetic raw material was 2 wt %, to prepare cosmetic raw material 14. Next, the ingredients shown below were weighed and UV milk was prepared according to the preparation method described below. The amount of hydrophobic CNF in the UV milk was 0.57 wt%. JPEG2025024008000026.jpg74133 Preparation method: Mix A and disperse uniformly. Mix B and dissolve uniformly. Disperse A and B uniformly to complete preparation. When using UV milk, the product was not sticky and had good spreadability. It also contributed to improving the dispersion of titanium dioxide and did not inhibit emulsification. Furthermore, it was less likely to leave a white cast.

[0122] (Example 33) (UV Gel) Cosmetic raw material 15 was prepared by adding isododecane (oil component) to the hydrophobized CNF dispersion obtained in Example 2 so that the hydrophobized CNF in the resulting cosmetic raw material was 2 wt%. Next, the raw materials shown below were weighed and a UV gel was prepared using the following preparation method. The amount of hydrophobic CNF in the UV gel was 0.02 wt%. JPEG2025024008000027.jpg121133 Preparation method: Mix A. Heat further to 80°C and disperse uniformly. Mix B. Heat further to 80°C and dissolve uniformly. Add B while stirring A and emulsify. Cool to room temperature to complete preparation. When using the UV gel, it was not sticky and had good spreadability. It also contributed to improving the dispersibility of titanium dioxide and did not inhibit emulsification. Furthermore, it was less likely to leave a white cast.

[0123] (Example 34) (UV lotion) Using the hydrophobized CNF dispersion obtained in Example 2, mineral oil (oil-based component) was added so that the hydrophobized CNF in the resulting cosmetic raw material was 2 wt %, to prepare cosmetic raw material 16. Next, the raw materials shown below were weighed and a UV lotion was prepared by the following preparation method. The amount of hydrophobic CNF in the UV lotion was 0.3 wt%. JPEG2025024008000028.jpg106133 Preparation method: Mix A. Heat to 80°C and dissolve uniformly. Mix B. Heat to 80°C and disperse uniformly. While stirring A, add B and emulsify. Cool to room temperature to complete preparation. When the UV lotion was used, it was not sticky and spread easily. It also contributed to improving the dispersibility of titanium dioxide and did not inhibit emulsification. Furthermore, it was unlikely to leave a white cast.

[0124] (Example 35) (BB Cream) Cetyl ethylhexanoate (oil component) was added to the hydrophobic CNF dispersion obtained in Example 1 so that the hydrophobic CNF content in the resulting cosmetic raw material was 20 wt %. Next, using a stirrer (IKA EUROSTAR 20 DIGITAL (stirring rod: R1303), the dispersion medium was removed from the hydrophobic CNF dispersion at a temperature of 80°C, yielding cosmetic raw material 17 (hydrophobic CNF powder). Next, the raw materials shown below were weighed and a BB cream was prepared according to the preparation method described below. The amount of hydrophobic CNF in the BB cream was 2.0 wt%. Preparation method: Mix A and complete preparation. When using the BB cream, it spread quickly and was easy to apply. It also had a good thickness. After applying it to the skin, it spread at the right time, which was good. When actually using it on the face, it did not leave a white cast, which was good. Furthermore, after adjustment, no clumping was observed, and it had excellent stability.

Claims

1. A method for producing a hydrophobized CNF dispersion, comprising at least a first step, a second step, and a third step, The first step is a step of dispersing hydrous CNF in an organic solvent to obtain a primary dispersion, the second step is a step of dispersing the primary dispersion and a vinyl ester using a media-less disperser having a shear rate of 1×10 (1 / s) or more and 1×10 8 (1 / s) or less to obtain a secondary dispersion, The third step is a step of washing the secondary dispersion and dispersing it in an alcohol aqueous solution, A method for producing a hydrophobized CNF dispersion, characterized in that the first step or the second step includes a step of adding a catalyst.

2. A method for producing a hydrophobized composite CNF dispersion, comprising at least a first step, a second step, and a third step, The first step is a step of dispersing hydrous CNF in an organic solvent to obtain a primary dispersion, the second step is a step of dispersing the primary dispersion, a polyhydric alcohol and / or a polyalkylene glycol, a crosslinking agent, and a vinyl ester using a media-less disperser having a shear rate of 1×10 (1 / s) or more and 1×10 8 (1 / s) or less to obtain a secondary dispersion; The third step is a step of washing the secondary dispersion and dispersing it in an alcohol aqueous solution, A method for producing a hydrophobic composite CNF dispersion, characterized in that the first step or the second step includes a step of adding a catalyst.

3. Adding an oil component to the hydrophobized CNF dispersion according to claim 1; removing the dispersion medium from the hydrophobized CNF dispersion; A method for producing a hydrophobized CNF oil-containing body, comprising the steps of:

4. A step of adding an oily component to the hydrophobized composite CNF dispersion according to claim 2; A step of removing the dispersion medium from the hydrophobized composite CNF dispersion; A method for producing a hydrophobic composite CNF oil-containing body, comprising the steps of:

5. Adding an oil component to the hydrophobized CNF dispersion according to claim 1; A method for producing a hydrophobized CNF powder, comprising a step of removing a dispersion medium from a hydrophobized CNF dispersion, A method for producing hydrophobic CNF powder, characterized in that when the amount of hydrophobic CNF in the obtained hydrophobic CNF powder is 1, the ratio of hydrophobic CNF to the oily component is 1:0.01 to 1:

4.

6. A step of adding an oily component to the hydrophobized composite CNF dispersion according to claim 2; A method for producing a hydrophobic composite CNF powder, comprising a step of removing a dispersion medium from a hydrophobic composite CNF dispersion, A method for producing hydrophobic composite CNF powder, characterized in that when the hydrophobic composite CNF in the obtained hydrophobic composite CNF powder is taken as 1, the ratio of hydrophobic composite CNF to the oily component is 1:0.01 to 1:

4.

7. A method for producing hydrophobized CNF comprising at least a first step and a second step, The first step is a step of dispersing hydrous CNF in an organic solvent to obtain a primary dispersion, the second step is a step of dispersing the primary dispersion and a vinyl ester using a media-less disperser having a shear rate of 1×10 (1 / s) or more and 1×10 8 (1 / s) or less to obtain a secondary dispersion, The hydrophobized CNF is obtained by adding a catalyst in the first or second step, recovering the reaction product in the secondary dispersion obtained in the second step, and purifying it.

8. A method for producing hydrophobized composite CNF, comprising at least a first step and a second step, the first step being a step of dispersing hydrous CNF in an organic solvent to obtain a primary dispersion, the second step is a step of dispersing the primary dispersion, a polyhydric alcohol and / or a polyalkylene glycol, a crosslinking agent, and a vinyl ester using a media-less disperser having a shear rate of 1×10 (1 / s) or more and 1×10 8 (1 / s) or less to obtain a secondary dispersion; The first step or the second step includes a step of adding a catalyst, The reaction product in the secondary dispersion obtained in the second step is recovered and purified to obtain hydrophobic composite CNF.

9. A hydrophobized CNF oil component-containing body containing the hydrophobized CNF according to claim 7 and an oil component.

10. A hydrophobic composite CNF oil component-containing body comprising the hydrophobic composite CNF according to claim 8 and an oil component.

11. A hydrophobic CNF powder characterized in that, when the content of hydrophobic CNF in the hydrophobic CNF oil component-containing body described in claim 9 is 1, the ratio of hydrophobic CNF to the oil component is 1:0.01 to 1:

4.

12. A hydrophobic composite CNF powder characterized in that, when the component of hydrophobic composite CNF in the hydrophobic composite CNF oil component containing body described in claim 10 is 1, the ratio of hydrophobic composite CNF to the oil component is 1:0.01 to 1:

4.

13. An oil-based thickener comprising the hydrophobized CNF according to claim 7, or the hydrophobized CNF oil component-containing body according to claim 9, or the hydrophobized CNF powder according to claim 11.

14. An oil-based thickener comprising the hydrophobic composite CNF according to claim 8, or the hydrophobic composite CNF oil component-containing body according to claim 10, or the hydrophobic composite CNF powder according to claim 12.

15. A cosmetic preparation comprising the hydrophobized CNF according to claim 7, or the hydrophobized CNF oil component-containing body according to claim 9, or the hydrophobized CNF powder according to claim 11.

16. A cosmetic preparation comprising the hydrophobized composite CNF according to claim 8, or the hydrophobized composite CNF oil component-containing body according to claim 10, or the hydrophobized composite CNF powder according to claim 12.

17. The cosmetic according to claim 15, which is any one of a makeup cosmetic, a skin cosmetic, a skin cleanser, an ultraviolet ray protection cosmetic, a skin care product, and a hair cosmetic.

18. The cosmetic according to claim 16, which is any one of a makeup cosmetic, a skin cosmetic, a skin cleanser, an ultraviolet ray protection cosmetic, a skin care product, and a hair cosmetic.

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