Method for producing a hydrophobic CNF dispersion, method for producing a hydrophobic CNF oily component-containing body

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 oil component-containing body, and cosmetics containing the hydrophobized CNF oil component-containing body.

Background Art

[0002] In recent years, the number of people troubled by sensitive skin and allergic constitutions has increased, and many people feel irritation from cosmetics and the like, and there is a demand for products with lower irritation.

[0003] Also, in the field of cosmetics, as oil thickeners for thickening liquid oil agents, dextrin fatty acid esters and 12-hydroxystearic acid are known. However, most of these are powders, have a high melting point, and require dispersion treatment at a high temperature of 75°C or higher. Further, depending on the compatibility with the oil component, the desired thickening effect may not be obtained. Furthermore, they were not satisfactory in terms of usability, such as being sticky after application and after rinsing.

[0004] Patent Document 1 describes a thickener containing a polyglycerol fatty acid ester that satisfies specific conditions for the purpose of providing a thickener capable of thickening an oil agent.

Prior Art Documents

Patent Documents

[0005]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0006] However, the thickener described in Patent Document 1 is a chemically synthesized product, and therefore may cause skin irritation for those with sensitive skin or allergies. Therefore, the present invention has been made in view of the above circumstances, and aims to provide a cosmetic product that uses sustainable raw materials, has a good feel, does not require high-temperature processing, and causes little skin irritation, as well as a cosmetic raw material with good dispersibility when incorporated into the cosmetic product.

[0007] Furthermore, the present invention aims to provide hydrophobized CNF that can be used as a raw material for cosmetics.

[0008] As a result of diligent research to achieve the above objective, the inventors have discovered that by utilizing the characteristic of CNF to be arranged in the same direction in a fluid and using a medialess disperser, it is possible to produce hydrophobic CNF with improved dispersibility in organic solvents by increasing the substitution reaction rate and degree of substitution while preventing damage to the CNF by applying horizontal shear stress. Furthermore, we found that the dispersibility of hydrophobized CNF in organic solvents can be improved by incorporating an oily component into the CNF. Furthermore, we found that cosmetics made from cosmetic ingredients containing the hydrophobic CNF in question have a pleasant feel and cause less skin irritation.

[0009] In other words, the present invention is a method for producing a hydrophobized CNF dispersion comprising at least a first step, a second step, and a third step, wherein the first step is to disperse hydrated CNF in an organic solvent to obtain a primary dispersion, the second step is to disperse the primary dispersion with vinyl esters or organic acid vinyl esters using a medialess disperser having a shear clearance of 10 μm or more and 23,000 μm or less to obtain a secondary dispersion, and the third step is to disperse the secondary dispersion in an alcohol, wherein the first step or the second step is characterized by adding a catalyst. [Effects of the Invention]

[0010] The present invention provides a cosmetic that has a pleasant feel and causes little skin irritation, and a cosmetic raw material that does not cause skin irritation and disperses well when incorporated into the cosmetic. Furthermore, a hydrophobic CNF is provided that can be used as a raw material for cosmetics and has improved dispersibility in organic solvents and oily components. [Brief explanation of the drawing]

[0011] [Figure 1] This is a cross-sectional view of a key part showing an example of a medialess distributed machine used in the second step of the present invention. [Figure 2] This figure shows the hydrophobic CNF powder obtained in Example 10 dispersed in ethylhexyl methoxycinnamate. [Figure 3] This figure shows the hydrophobic composite CNF powder obtained in Example 12 dispersed in polypropylene glycol. [Figure 4] This figure shows the results of viscosity evaluation 1 for hydrophobized CNF in Example 14. [Figure 5] This figure shows the results of viscosity evaluation 2 for hydrophobized CNF in Example 15. [Figure 6] This figure shows the results of viscosity evaluation using the hydrophobic composite CNF powder obtained in Example 16. [Modes for carrying out the invention]

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

[0013] (Definition of terms) Here, we define the main terms used in this invention. In this specification, the term "CNF" 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 composed of several single cellulose nanofibers bundled together in multiple layers. Furthermore, it includes not only cellulose fibers that do not branch in the longitudinal direction, but also those that do branch. Furthermore, the term "hydrophobized CNF" in this specification refers to CNF in which some of the hydroxyl groups of the CNF are esterified with vinyl esters and / or organic acid vinyl esters. Furthermore, the term "hydrophobized composite CNF" as used herein includes CNF in which some of the hydroxyl groups of the CNF are esterified with vinyl esters and / or organic acid vinyl esters, and the esterified CNFs are crosslinked with polyhydric alcohols and / or polyalkylene glycols, and / or CNF in which some of the hydroxyl groups of the esterified CNF are bonded. Furthermore, the term "hydrophobized CNF oily component-containing material" in this specification refers to a material containing at least the hydrophobized CNF and various oily components described later. Furthermore, the term "hydrophobic composite CNF oily component-containing material" in this specification refers to a material containing at least the hydrophobic composite CNF and various oily components described later. Furthermore, the term "hydrophobic CNF powder" in this specification refers to a hydrophobic CNF oily component-containing material in which the hydrophobic CNF component is between 20% and 99%. In other words, when the hydrophobic CNF component in the hydrophobic CNF oily component-containing material is set to 1, the ratio of hydrophobic CNF to the oily 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-based component-containing body, where the component of hydrophobized composite CNF in the hydrophobized composite CNF oil-based component-containing body is 20% or more and within 99%. In other words, when the component of hydrophobized composite CNF in the hydrophobized composite CNF oil-based component-containing body is regarded as 1, it refers to those in which the ratio of hydrophobized composite CNF to the oil-based component is in the range of 1:0.01 to 1:4. Furthermore, the "paste-like hydrophobized CNF oil-based component-containing body" in this specification refers to a hydrophobized CNF oil-based component-containing body, where the component of hydrophobized CNF in the hydrophobized CNF oil-based component-containing body is less than 20%. Furthermore, the "paste-like hydrophobized composite CNF oil-based component-containing body" in this specification refers to a hydrophobized composite CNF oil-based component-containing body, where the component of hydrophobized composite CNF in the hydrophobized composite CNF oil-based component-containing body is less than 20%.

[0014] (Method for producing hydrophobized CNF dispersion and hydrophobized composite CNF dispersion) The method for producing the 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 water-containing CNF in an organic solvent to obtain a primary dispersion. Also, the second step is a step of subjecting the primary dispersion and vinyl esters or vinyl organic acid esters to dispersion treatment using a media-less disperser with a clearance of the shearing part 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 with a hydrophobized CNF concentration of 2% to 30%. Furthermore, in the first step or the second step, there is a step of adding a catalyst.

[0015] The present invention provides a method for producing a hydrophobic CNF dispersion, which includes a step in the second step of dispersing the CNF using a medialess disperser with a shear clearance of 10 μm to 23,000 μm to obtain a secondary dispersion. This allows for the dispersion of CNF present in the primary dispersion obtained in the first step. As a result, in the secondary dispersion obtained in 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. Furthermore, the method for producing the hydrophobic composite CNF dispersion of the present invention differs from the method for producing the hydrophobic CNF dispersion in that a part of the second step is different, while the other first and third steps are the same as those of the method for producing the hydrophobic CNF dispersion.

[0016] <1st process> The objective of the first step is to obtain a primary dispersion by dispersing hydrated CNF in an organic solvent. This method improves the reactivity between the hydroxyl group of CNF and vinyl esters or organic acid vinyl esters. The first step will be explained in detail below.

[0017] First, a CNF dispersion is prepared, and the CNF and water are separated by solid-liquid separation to obtain hydrated CNF with a CNF content of approximately 2-40%. The method of solid-liquid separation is not particularly limited; for example, a centrifuge or filter press can be used. If a CNF dispersion with a CNF content of 2% or less is used, the hydrated CNF can be used as is. Further details about the CNF dispersion will be described later.

[0018] Next, if the obtained moisture-containing CNF has a moisture content of 15% or more, it is pulverized. The method of pulverization is not particularly limited. The pulverization method can be physically finely crushed, and for example, a compression crusher, shear crusher, impact crusher, roll mill, high-speed rotary mill, jet mill, etc., can be used. There are no particular restrictions on the degree of crushing, but it is preferable to pulverize the CNF so that the average particle size of the powder obtained is in the range of 0.1 to 5 cm.

[0019] Next, the obtained powdered CNF or CNF with a water content of 15% or less 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, devices capable of mixing while applying compressive and shearing forces include high-speed shear mills, blade-type kneaders, high-speed mixers (mechanohybrid), and high-performance fluidized bed mixers (FM mixers). The organic solvents mentioned above will be described later.

[0020] (CNF dispersion) As a CNF dispersion that can be used in the present invention, one can refer to the method for producing fine fibers described in Japanese Patent Publication No. 6867613, the method for preparing cellulose nanofibers and cellulose nanocrystal aqueous solutions using cellulose as a natural polymer described in Japanese Patent Publication No. 6704551, or the method for producing fine fibers using other raw materials as components described in both publications.

[0021] These CNF dispersions may be prepared using one raw material alone or a mixture of two or more. Preferably, the polysaccharide raw material is pulp with an α-cellulose content of 60% to 99% by mass. A purity of 60% by mass or higher α-cellulose content makes it easier to adjust fiber diameter and length, suppressing entanglement between fibers. Compared to using materials with an α-cellulose content of less than 60% by mass, it exhibits higher thermal stability and better color suppression. On the other hand, using materials with a purity of 99% by mass or higher makes it difficult to defibrillate the fibers to the nanoscale.

[0022] The crystallinity of CNF is preferably 50 or higher. The crystallinity can be measured by methods such as X-ray diffraction. If the crystallinity is less than 50, the properties of the natural cellulose crystals cannot be fully utilized, and there is a risk of deterioration over time during storage due to spoilage, etc. The ACC method (Accelerated Collision Method in Water) can pulverize cellulose fibers to an average particle length of 10 μm, resulting in CNF with an average thickness of 3-200 nm and an average length of 0.1 μm or more. The average thickness and average fiber length are determined by observing and measuring the CNF using a scanning electron microscope (SEM), transmission electron microscope (TEM), etc., as appropriate, selecting 20 or more samples from the resulting photographs, and averaging them.

[0023] (organic solvent) As the organic solvent, a nonionic polar solvent containing N-methylpyrrolidone (hereinafter referred to as NMP), dimethylacetamide (hereinafter referred to as DMAc), dimethylformamide (hereinafter referred to as DMF), or dimethyl sulfoxide (hereinafter referred to as DMSO) can be used.

[0024] <Second process> The second step aims to obtain a secondary dispersion containing reaction products such as hydrophobized CNF by esterifying the hydroxyl groups present in CNF with vinyl esters or organic acid vinyl esters. Furthermore, hydrophobized CNF can be obtained by recovering the reaction products in the secondary dispersion obtained in the second step and purifying them. The second step will be explained in detail below.

[0025] In order to initiate the esterification reaction of hydroxyl groups present in CNF with vinyl esters or organic acid vinyl esters, the presence of a catalyst is essential. In the present invention, there are two forms in which the catalyst is added: one in which the catalyst is added in the second step, and the other in which the catalyst is added in the first step. The first embodiment is one in which a catalyst is added in the second step. After obtaining a primary dispersion in the first step, the water content of the primary dispersion is adjusted using the above-mentioned organic solvent and / or water so that the water content is in the range of 60% to 10% or less. Next, vinyl esters or organic acid vinyl esters are added. At this time, the vinyl esters or organic acid vinyl esters should be added in a ratio of 0.1 to 5.0 molar equivalents relative to the glucose unit equivalent amount of CNF contained in the primary dispersion. When producing a hydrophobic composite CNF dispersion, polyhydric alcohols and / or polyalkylene glycols and a crosslinking agent are further added. The amount of polyhydric alcohols and / or polyalkylene glycols relative to the CNF will be described later. Next, the catalyst is added to the CNF in the primary dispersion in an amount of 1 to 400 wt%, preferably 5 to 350 wt%, and more preferably 10 to 300 wt%. In this case, the esterification reaction begins when the catalyst is added. Alternatively, after obtaining a primary dispersion in the first step, the water content in the primary dispersion is adjusted within the range described above. Next, the catalyst is added to the CNF in the primary dispersion within the aforementioned range. Next, vinyl esters or organic acid vinyl esters are added in the aforementioned proportions. When producing hydrophobic composite CNF dispersions, polyhydric alcohols and / or polyalkylene glycols and crosslinking agents are further added. In such cases, the esterification reaction begins when vinyl esters, etc., are added.

[0026] The second embodiment is one in which, in the first step, the catalyst is added to the CNF in the primary dispersion within the range described above, and then the second step is carried out. In such cases, the esterification reaction is initiated when vinyl esters, etc., are added, similar to the latter part of the first embodiment described above.

[0027] Therefore, it is advisable to time the addition of catalysts, etc., so that the esterification reaction starts immediately before the start of the dispersion process using the medialess disperser described later. Furthermore, the dispersion process using a medialess disperser in this invention is understood to include not only the dispersion process using a medialess disperser, but also the esterification reaction. For the purpose of this explanation, the dispersion immediately before the addition of the catalyst or vinyl esters will be 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 carried out in the range of 1 minute to 5 hours, preferably 10 minutes to 4 hours, and more preferably 15 minutes to 3 hours. Vinyl esters or organic acid vinyl esters, polyhydric alcohols and / or polyalkylene glycols, crosslinking agents and catalysts will be discussed later.

[0028] Next, a secondary dispersion is obtained by dispersing the pre-processed secondary dispersion using a medialess disperser. Alternatively, the obtained secondary dispersion may be dispersed again using the medialess disperser. The medialess disperser used in the second step is not particularly limited, but it is preferable that it comprises a rotor, which is a rotating body, and a stator, which is a stationary surface. Furthermore, it is preferable that the medialess disperser has a mechanism for adding catalysts, crosslinking agents, etc., either immediately before or directly into the disperser. The rotor and stator are provided, and by adjusting the clearance between the rotor and the stator, or by adjusting the rotational speed of the rotor, the shear force applied to the pre-treatment secondary dispersion, the catalyst, and vinyl esters can be adjusted. Furthermore, you can choose from high-speed stirring blades, turbine / stator type stirrers, high-viscosity kneading plus high-speed stirring, swirling thin-film type high-speed stirring, in-line type dispersers / mixing type stirrers, etc. Furthermore, two or more medialess dispersers may be arranged in a continuous configuration, and they may be circulated with a stirring tank or the like. In addition, preliminary dispersion such as ultrasonic dispersion or kneading and stirring may be performed, and indirect heating and cooling using a stirring tank or the like, or direct heating using microwaves may be performed in combination. Examples of media-less distributing devices that can be used include "ClearStar" manufactured by Primix Corporation, "Disparizer" manufactured by Shinto Kogyo Co., Ltd., "Alria" manufactured by M-Technique Co., Ltd., and "FM Mixer" manufactured by Nippon Coke Industries Co., Ltd.

[0029] Here, the medialess distributor used in the second step will be described with reference to the drawings. Figure 1 is a cross-sectional view of a key part showing an example of a medialess distributor used in the second step of the present invention. In Figure 1, the medialess distributor 1 comprises 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 Figure 1, the minimum size of the gap 4 between the stator 2 and the rotor 3 is defined as clearance C. The clearance C is set to a size of 10 μm or more and 23,000 μm or less, more preferably 20 μm or more and 5,000 μm or less, and even more preferably 50 μm or more and 1,000 μm or less. If the clearance C is less than 10 μm, there is a possibility that larger CNF aggregates than clearance C may be present in the secondary dispersion before processing, or that concentration fluctuations may cause blockages within the equipment, or that the rotor and stator may come into contact due to eccentricity, potentially leading to a malfunction of the medialess disperser. On the other hand, if the clearance C exceeds 23,000 μm, the shear force may decrease.

[0030] In Figure 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 and the like can be uniformly dispersed, thereby improving the reaction efficiency.

[0031] Furthermore, the share rate in the second step described above is 1 × 10 (1 / s) or more. 8 It is preferable that it is (1 / s) or less, and 1 × 10 2 (1 / s) or more 1×10 7 It is more preferable that it be (1 / s) or less. If the above shear rate falls below 1 × 10 (1 / s), sufficient shear force cannot be obtained, and the catalyst, etc., will not be uniformly dispersed on the hydroxyl groups of the CNF aggregate in the secondary dispersion before treatment. On the other hand, if the above shear rate is 1 × 10 8 If the share rate exceeds (1 / s), the processing liquid during dispersion may become hot, which is undesirable. However, if the medialess disperser has a cooling function, the above share rate is 1 × 10⁻⁶. 8 There are cases where it may exceed (1 / s).

[0032] The above share rate is expressed by the following formula. Shear rate (1 / s) = Peripheral speed (m / s) / Clearance C (mm) × 1000 Peripheral speed (m / s) = π × rotor diameter (mm) × 1 / 1000 × rotational speed (rpm) × 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, as well as aromatic carboxylic acids such as vinyl benzoate.

[0034] (Polyhydric alcohols and / or polyalkylene glycols) There are no particular restrictions on polyhydric alcohols and polyalkylene glycols as long as they have two or more hydroxyl groups. Examples of 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 can be used. Furthermore, polyalkylene glycols are linear polymer compounds having a repeating ether linkage structure in their main chain, and are produced, for example, by ring-opening polymerization of cyclic ethers. Specific examples of polyalkylene glycols include polymers such as polyethylene glycol and polypropylene glycol, ethylene oxide-propylene oxide copolymers and their derivatives. Any copolymer can be used, such as random copolymers, block copolymers, graft copolymers, and alternating copolymers. Furthermore, polyalkylene glycols with a molecular weight generally in the range of 200 to 100,000 can be used.

[0035] (Regarding the amount of polyhydric alcohol and / or polyalkylene glycol relative to CNF) It is preferable to bond polyhydric alcohols and / or polyalkylene glycols to the hydroxyl groups of CNF in an amount of 0.01% to 50%. If the amount of polyhydric alcohols and / or polyalkylene glycols is too small, a bulky hydrophobic composite CNF cannot be obtained when dispersed in an oily component, causing the CNFs to aggregate densely and resulting in excipient properties. On the other hand, if the amount of polyhydric alcohols and / or polyalkylene glycols is too large, the absolute amount of hydroxyl groups in the CNF that can effectively react decreases, making it difficult for the vinyl esters and / or organic acid vinyl esters to be introduced to the hydroxyl groups of CNF, resulting in poor compatibility with oily components. Furthermore, since polyalkylene glycols contain many hydrophilic ether bonds, this would be contrary to the purpose 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 CNF with the hydroxyl groups of polyhydric alcohols and / or polyalkylene glycols. 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 individually or in combination of two or more.

[0038] Isocyanate-based crosslinking agents include at least a polyisocyanate compound. Examples of polyisocyanate compounds 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 their biuret and isocyanurate forms, as well as adducts which are reaction products with low molecular weight 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 an alkaline catalyst, especially one with buffering properties, is preferred, and an alkali metal salt is preferred. Examples include disodium hydrogen phosphate, sodium acetate, and potassium carbonate.

[0040] <3rd process> The third step is a process aimed at obtaining a hydrophobic CNF dispersion with a hydrophobic CNF concentration of approximately 2-30% by dehydrating and washing the secondary dispersion containing hydrophobic CNF after the reaction in the second step, and then using an aqueous alcohol solution (hereinafter sometimes referred to as the dispersion medium). The third step will be explained in detail below.

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

[0042] (Washing process) Impurities such as organic solvents, unreacted substances, catalysts, and by-products that could not be removed in the dehydration step are washed with an aqueous alcohol solution. The type of alcohol is not particularly limited, but methanol or ethanol are preferred from the viewpoint of compatibility with the above substances. Furthermore, 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%, from the viewpoint of compatibility. The dehydration step and the washing step are performed alternately until the concentration of the organic solvent used in the first step of the obtained hydrophobic CNF dispersion is 1000 ppm or less.

[0043] (Hydrophobic CNF and hydrophobic composite CNF) The hydrophobic CNF and hydrophobic composite CNF according to the present invention can be obtained by recovering and purifying the reaction product obtained in the second step. Alternatively, they can be obtained by removing the aqueous alcohol solution from the obtained hydrophobic CNF dispersion or hydrophobic composite CNF dispersion. The hydrophobic CNF of the present invention has an average thickness of 3 to 200 nm and an average length of 0.1 μm or more, wherein 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 hydrophobized CNF is measured by the following substitution degree measurement.

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

[0045] (Hydrophobic composite CNF) The hydrophobic composite CNF of the present invention is a hydrophobic composite CNF comprising the steps of: dispersing hydrated CNF in an organic solvent to obtain a primary dispersion; adding a catalyst; adding polyhydric alcohols and / or polyalkylene glycols, a crosslinking agent, vinyl esters and / or organic acid vinyl esters; and dispersing and reacting the reaction using a medialess disperser with a shear clearance of 10 μm or more and 23,000 μm or less, and recovering the resulting reaction product.

[0046] In this invention, the invention of "hydrophobized composite CNF" is specified by its manufacturing method. The reason for this is explained below. There are at least two embodiments of the hydrophobic composite CNF of the present invention. Firstly, the unmodified hydroxyl groups within the cellobiose unit are esterified with vinyl esters and / or organic acid vinyl esters, resulting in hydrophobic composite CNFs 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, there exists a hydrophobic composite CNF in which the unmodified hydroxyl groups within the cellobiose unit are esterified with vinyl esters and / or organic acid vinyl esters, and two or more hydroxyl groups of polyhydric alcohols and / or polyalkylene glycols are bonded together, with this bonding between the unreacted hydroxyl groups in one CNF and the unreacted hydroxyl groups in another CNF. These hydrophobic composite CNFs are combined in certain proportions.

[0047] Here, in order to measure the degree of substitution of vinyl esters and / or organic acid vinyl esters esterified with hydroxyl groups, as described above, the esterified vinyl esters and / or organic acid vinyl esters are liberated using a sodium hydroxide solution and then calculated by titration. However, when this method is applied to hydrophobic composite CNF, the bonds between polyhydric alcohols and / or polyalkylene glycols are also released in the second hydrophobic composite CNF, making it impossible to accurately calculate the degree of substitution of polyhydric alcohols and / or polyalkylene glycols bonded to the hydroxyl groups in the hydrophobic composite CNF. Directly identifying the hydrophobic composite CNF of the present invention by its structure or properties would require an excessively large economic expenditure and time, making it practically impossible to uniquely identify it at the time of filing. Therefore, in the invention of the hydrophobic composite CNF, the manufacturing method is defined as the defining feature of the invention.

[0048] (Method for producing hydrophobic CNF oily component-containing material and hydrophobic CNF powder) (Method for producing hydrophobic composite CNF containing oily components and hydrophobic composite CNF powder) The method for producing a hydrophobic CNF oily component-containing material and the method for producing a hydrophobic composite CNF oily component-containing material according to the present invention differ only in whether a hydrophobic CNF dispersion is used or a hydrophobic composite CNF dispersion is used. Therefore, the hydrophobic CNF oily component-containing material will be described below. Furthermore, the method for producing hydrophobic CNF powder and the method for producing hydrophobic composite CNF powder according to the present invention differ only in whether a hydrophobic CNF dispersion is used or a hydrophobic composite CNF dispersion is used. Therefore, the hydrophobic CNF powder will be described below.

[0049] The method for producing a hydrophobized CNF oily component-containing material according to the present invention involves adding various oily components, as described later, to a hydrophobized CNF dispersion, and removing the dispersion medium in the hydrophobized CNF dispersion to approximately 50%, 40%, 30%, and 20% or less, thereby obtaining a hydrophobized CNF oily component-containing material. At this time, by adding various oily components in such a way that the proportion of hydrophobic CNF in the resulting hydrophobic CNF oily component-containing material is between 20% and 99%, a hydrophobic CNF powder can be obtained. Alternatively, when the hydrophobic CNF component in the resulting hydrophobic CNF oily component-containing material is set to 1, various oily components are added such that the ratio of hydrophobic CNF to the oily component is in the range of 1:0.01 to 1:4, thereby obtaining hydrophobic CNF powder. The method for removing the dispersion medium is not particularly limited, but it can be obtained, for example, by solvent replacement or drying. In the solvent substitution method, various oily components are added to a hydrophobic CNF dispersion, dispersed using a homogenizer or FM mixer, and then the hydrophobic CNF is recovered by settling using a centrifuge or the like. By repeating this series of operations several times, a hydrophobic CNF oily component-containing material can be obtained. This solvent substitution method can be mainly used when producing a paste-like hydrophobic CNF oily component-containing material. On the other hand, in the drying method, the product is obtained by adding various oily components to a hydrophobic CNF dispersion and removing the dispersion medium from the hydrophobic CNF dispersion using a dryer. More specifically, it is obtained by adding various oily components to a hydrophobic CNF dispersion, heating the dispersion medium in the hydrophobic CNF dispersion, drying it while stirring, and removing the dispersion medium. Known drying methods such as reduced pressure drying and vacuum drying can be used. This drying method can be used to produce both hydrophobic CNF powder and paste-like hydrophobic CNF containing oily components. The type of dryer used is not particularly limited, but equipment capable of simultaneous reduced pressure, heating, and stirring is desirable. The amount of oily component added to the hydrophobic CNF dispersion is not particularly limited, but it should be prepared so that the hydrophobic CNF content in the resulting hydrophobic CNF oily component-containing material is 1 to 99%. By incorporating a hydrophobized CNF oil component, good dispersibility can be obtained in solvents where dispersion of hydrophobized CNF dispersions was difficult.

[0050] (Hydrophobic CNF oily component-containing material and hydrophobic CNF powder) The method for producing a hydrophobic CNF oily component-containing material and a hydrophobic CNF powder according to the present invention yields a hydrophobic CNF oily component-containing material and a hydrophobic CNF powder. The hydrophobic CNF oily component-containing material of the present invention contains hydrophobic CNF and an oily component according to the present invention. Furthermore, the hydrophobic CNF powder of the present invention is a hydrophobic CNF oily component-containing body, where the ratio of hydrophobic CNF to the oily component is 1:0.01 to 1:4 when the amount of hydrophobic CNF is set to 1. The hydrophobic CNF oily component-containing material and hydrophobic CNF powder according to the present invention can be redispersed in various oily components.

[0051] (Hydrophobic composite CNF containing oily components and hydrophobic composite CNF powder) The method for producing the hydrophobic composite CNF oily component-containing material and the hydrophobic composite CNF powder of the present invention yields the hydrophobic composite CNF oily component-containing material and the hydrophobic composite CNF powder. The hydrophobic composite CNF oily component-containing material of the present invention contains the hydrophobic composite CNF and an oily component according to the present invention. Furthermore, the hydrophobic composite CNF powder of the present invention is a hydrophobic composite CNF containing an oily component, wherein the ratio of the hydrophobic composite CNF to the oily component is 1:0.01 to 1:4 when the hydrophobic composite CNF is set to 1. The hydrophobic composite CNF containing oily component and the hydrophobic composite CNF powder according to the present invention can be redispersed in various oily components.

[0052] (Oily thickener) The hydrophobic CNF, hydrophobic CNF dispersion, hydrophobic CNF containing an oily component, hydrophobic CNF powder, hydrophobic composite CNF, hydrophobic composite CNF dispersion, hydrophobic composite CNF containing an oily component, and hydrophobic composite CNF powder of the present invention can be used as oily thickeners. For example, it can be used as an oily thickener by combining one or more known thickeners, gelling agents, hydrophobic agents, suspending agents, dispersants, temperature and mechanical stabilizers, anti-caking agents, flow improvers, dry silica, fused silica particles, etc. Examples of applications for the oily thickener according to the present invention include thickeners for oily paints and hydrophobic resins. It can also be used as an oil adsorbent, oil absorbent, or in emulsion oil compositions, and can be used to prevent deformation, prevent sagging, and improve abrasion resistance.

[0053] (Cosmetic raw materials) The hydrophobic CNF, hydrophobic CNF dispersion, hydrophobic CNF containing oily components, hydrophobic CNF powder, hydrophobic composite CNF, hydrophobic composite CNF dispersion, hydrophobic composite CNF containing oily components, and hydrophobic composite CNF powder of the present invention can be used as raw materials for cosmetics. By utilizing the hydrophobic CNF of the present invention, a high thickening effect can be achieved, and cosmetics with good usability and stability can be provided.

[0054] (Oily components) Examples of oily components that can be used in the hydrophobized CNF oily component-containing material or hydrophobized composite CNF oily component-containing material 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 tissue, collagen protein hydrolysates obtained by hydrolyzing bone and skin in the presence of acid, alkali, or enzyme, either individually or in combination, various low-polarity solvents such as benzene, and animal oils. Specific examples of oily components are listed below, but the present invention is not limited to these; any oily component that can be thickened with the hydrophobized CNF of the present invention can be used as an oily component of the present invention.

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

[0056] Examples of nonpolar 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 / polypyrropylene wax, squalene, squalane, pristane, and polyisoprene.

[0057] Examples of low-polarity organic compounds include: tripropylene glycol dieopentanoate, 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, glyceryl di-2-heptylundecanoate, trimethylolpropane tri-2-ethylhexanoate, trimethylolpropane triisostearate, pentaerythrityl tetra-2-ethylhexanoate, triethylhexanoic acid (Glycerin tri-2-ethylhexanoate), glycerin trioctanoate, glycerin triisopalmitate, trimethylolpropane triisostearate, cetyl 2-ethylhexanoate, 2-ethylhexyl palmitate, glycerin trimyristate, caprylic / capric triglyceride, caprylic / capric triglyceride, glyceryl tri-2-heptyl undecanoate, castor oil fatty acid methyl ester, oleyl oleate, acetoglyceride Examples include 2-heptyl undecyl palmitate, diisobutyl adipate, 2-octyldodecyl N-lauroyl-L-glutamic acid, di-2-heptyl undecyl 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, chymyl alcohol, stearyl alcohol, cetanol, cetostearyl alcohol, decyl alcohol, batyl alcohol, hexyldecanol, behenyl alcohol, myristyl alcohol, lauryl alcohol, and lanolin alcohol.

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

[0060] Examples of UV absorbers include a wide range of highly polar, oily UV absorbers commonly used in cosmetics. For example, ethylhexyl methoxycinnamate, benzoic acid derivatives such as 2-hydroxy-4-methoxybenzophenone and para-aminobenzoic acid, salicylic acid derivatives, cinnamic acid derivatives, dibenzoylmethane derivatives, β,β-diphenylacrylate derivatives, benzophenone derivatives, benzylidene camphor derivatives, phenylbenzimidazole derivatives, triazine derivatives, phenylbenzotriazole derivatives, anthranyl derivatives such as methyl anthranilate, imidazoline derivatives, benzalmalonate derivatives, and 4,4-diarylbutadiene derivatives are examples of such agents.

[0061] Examples of vegetable oils include mendofoam oil, safflower oil, castor 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 bran oil, olive oil, coconut oil, and sasanqua oil.

[0062] (Cosmetics) The cosmetic composition according to the present invention is a known cosmetic composition that contains an oily component. Furthermore, the present invention can be applied to a wide range of cosmetic forms, including makeup cosmetics, skin cosmetics, skin cleansers, UV protection cosmetics, skincare products, and hair cosmetics. Makeup products include makeup base, powder foundation, liquid foundation, cream foundation, stick foundation, eyeshadow, blush, concealer, lipstick, nail polish, mascara, theatrical makeup, face color, blush, eyeliner, eyebrow products, and nail treatments. Examples of skin cosmetics include lotions, emulsions (such as whitening emulsions), creams, serums, moisturizing lotions, face masks, emollient creams, moisturizing creams, and hand creams. Examples of skin cleansing agents include cleansing oils, hand washes, facial cleansers, body soaps, scalp washes, 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 lotions, sunscreen creams, sunscreen creams, sunscreen lotions, suntan cosmetics, after-sun care cosmetics, self-tanning cosmetics, tone-up products, sunscreen mists / sprays, gels, and powders. Hair cosmetics include hair creams, hair mists, shampoos, rinses, hair conditioners, rinse-in shampoos, hair styling products (hair foams, gel-type styling products, etc.), hair treatments, hair waxes, hair oils, and hair dyes. Furthermore, examples include pre-shave lotions, after-shave lotions, air fresheners, deodorants, toothpaste, ointments, compresses, mouthwashes, hair removal creams, and anti-aging creams.

[0063] The cosmetic composition of the present invention may, as needed, contain known raw materials that can be incorporated into ordinary cosmetic compositions, such as thickeners, gelling agents, hydrophobic agents, suspending agents, dispersants, temperature and mechanical stabilizers, anticaking agents, flow improvers, dry silica, fused silica particles, pigments, waxes, surfactants, humectants, preservatives, and bactericides.

[0064] As for pigments, there are no particular restrictions as long as they are commonly used in makeup cosmetics. Examples include inorganic pigments such as talc, mica, kaolin, silica, calcium carbonate, titanium dioxide, 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, and titanium-mica pearl pigments; organic pigments such as zirconium, barium, or aluminum lake, such as Red 201, Red 202, Orange 203, Yellow 205, Yellow 4, Yellow 5, Blue 1, Blue 404, and Green 3; natural pigments such as chlorophyll and β-carotene; and dyes.

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

[0066] Surfactants include nonionic, anionic, cationic, and amphoteric surfactants, but are not particularly limited. Any surfactant commonly used in cosmetics can be used, either alone or in appropriate combinations of two or more.

[0067] Examples of humectants 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; and glucose, glyceryl glucoside, betaine, hyaluronic acid, chondroitin sulfate, and polyoxypropylene methyl glucoside.

[0068] Examples of preservatives and disinfectants include alkyl parahydroxybenzoates, benzoic acid, sodium benzoate, sorbic acid, potassium sorbate, imidazolidinyl urea, salicylic acid, isopropylmethylphenol, carbolic acid, parachlormethacresol, 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] 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] (Method for measuring DMSO) The concentration of DMSO in 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 dispersion device such as a stirrer or ultrasonic device. Next, using a gas chromatography-mass spectrometer, the solution after removing the hydrophobized CNF with a syringe filter was analyzed, and the concentration of DMSO contained in the hydrophobized CNF before dilution was calculated. The aforementioned dilution ratio was adjusted as appropriate 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 dispersions) A hydrophobized CNF dispersion using vinyl hexanoate was prepared by following the steps (A) to (F) below. Next, the degree of substitution of the obtained hydrophobized CNF was measured. (A) Bamboo pulp was used as the raw material and subjected to defibration treatment using the ACC method (water-based counter-impact method) to obtain a 1 wt% CNF dispersion with an average fiber diameter of 3 nm to 200 nm. Next, the CNF dispersion was dehydrated to a CNF concentration of 30 w / w% using a filter press (Kurita Machinery Works, Ltd., MF-A manual type), 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 Industries 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 moisture content after adding water was 40%, and the mixture was heated to 80°C. (D) Next, vinyl hexanoate was added in a proportion of 1.2 molar equivalents relative to the glucose unit amount of CNF contained in the primary dispersion. (E) Next, dispersion treatment was performed 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)). Then, potassium carbonate was added at a CNF ratio of 20%, and the reaction was carried out for 180 minutes using the FM mixer (under the same conditions as above) to obtain a secondary dispersion. (F) After the reaction was complete, the mixture was dehydrated using a Buchner funnel, and then washed multiple times with 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 obtained using an aqueous ethanol solution. Furthermore, the degree of substitution of the hydrophobic CNF was 0.71.

[0072] (Example 2) (Preparation of hydrophobic CNF dispersions) In Example 1, steps (B), (C), (D), and (F) were modified as follows to prepare a hydrophobized CNF dispersion using vinyl laurate. Next, the degree of substitution of the obtained hydrophobized CNF was measured. (B) Next, the powdered CNF was dispersed in DMSO for 1 hour using an FM mixer (Nippon Coke Industries 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 moisture content after adding water was 60%, and the mixture was heated to 80°C. (D) Next, vinyl laurate was added in a proportion of 1.2 molar equivalents relative to the glucose unit amount of CNF contained in the primary dispersion. (F) After the reaction was complete, the mixture was dehydrated using a Buchner funnel, and then washed multiple times with 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. Furthermore, the degree of substitution of the hydrophobic CNF was 1.09.

[0073] (Example 3) (Preparation of hydrophobic CNF dispersions) In Example 1, steps (B), (D), (E), and (F) were modified as follows to prepare a hydrophobized CNF dispersion using vinyl laurate. (B) Next, the powdered CNF was dispersed in DMSO for 1 hour using an FM mixer (Nippon Coke Industries 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 proportion of 1.2 molar equivalents relative to the glucose unit amount of CNF contained in the primary dispersion. (E) Next, dispersion treatment was performed using a Trimix (planetary mixer manufactured by Inoue Seisakusho Co., Ltd.) with a shear clearance of 23,000 μm (rotation speed: 102 rpm, diameter: 150 mm, peripheral speed: 0.8 m / s, shear rate: 35 (1 / s)). Then, potassium carbonate was added at a CNF ratio of 20%, and the reaction was carried out in the Trimix (under the same conditions as above) for 180 minutes to obtain a secondary dispersion. (F) After the reaction was complete, the mixture was dehydrated using a Buchner funnel, and then washed multiple times with 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. Furthermore, the degree of substitution of the hydrophobic CNF was 0.41.

[0074] (Example 4) (Preparation of hydrophobic CNF dispersions) In Example 1, steps (B), (C), (D), (E), and (F) were modified as follows to prepare a hydrophobized CNF dispersion using vinyl laurate. (B) Next, the powdered CNF was dispersed in DMSO for 1 hour using an FM mixer (Nippon Coke Industries 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 moisture content after adding water was 50%, and the mixture was heated to 80°C. (D) Next, vinyl laurate was added in a proportion of 5.0 molar equivalents relative to the glucose unit amount of CNF contained in the primary dispersion. (E) Next, the mixture was dispersed using a disparizer (Shinto Kogyo Co., Ltd. centrifugal disc mixer) with a shear clearance of 10 μm (rotation speed: 12000 rpm, diameter: 150 mm, peripheral speed: 94.2 m / s, shear rate: 9424778 (1 / s)). Then, potassium carbonate was added at a CNF ratio of 20%, and the reaction was carried out in the disparizer (under the same conditions as above) for 180 minutes to obtain a secondary dispersion. (F) After the reaction was complete, the mixture was dehydrated using a Buchner funnel, and then washed multiple times with an FM mixer and a 60% aqueous ethanol solution until the DMSO concentration reached 900 ppm. The washing was then stopped, and a hydrophobic CNF dispersion with a hydrophobic CNF concentration of 10% was obtained using an aqueous ethanol solution. Furthermore, the degree of substitution of the hydrophobic CNF was 1.79.

[0075] (Example 5) (Preparation of hydrophobic CNF dispersions) In Example 1, steps (A), (B), (C), (D), and (F) were modified as follows to prepare a hydrophobized CNF dispersion using vinyl laurate. (A) Coniferous tree pulp was used as the raw material instead of bamboo pulp. (B) Next, the powdered CNF was dispersed in DMSO for 1 hour using an FM mixer (Nippon Coke Industries 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 moisture content after adding water was 50%, and the mixture was heated to 80°C. (D) Next, vinyl laurate was added in a proportion of 1.2 molar equivalents relative to the glucose unit amount of CNF contained in the primary dispersion. (F) After the reaction was complete, the mixture was dehydrated using a Buchner funnel, and then washed multiple times with an FM mixer and a 30% aqueous ethanol solution until the DMSO concentration reached 980 ppm. The washing was then stopped, and a hydrophobic CNF dispersion with a hydrophobic CNF concentration of 5% was obtained using an aqueous ethanol solution. Furthermore, the degree of substitution of the hydrophobic CNF was 0.6.

[0076] (Example 6) (Preparation of hydrophobic CNF dispersions) In Example 1, steps (A), (B), (C), (D), and (F) were modified as follows to prepare a hydrophobized CNF dispersion using vinyl laurate. (A) Hardwood pulp was used as the raw material instead of bamboo pulp. (B) Next, the powdered CNF was dispersed in DMSO for 1 hour using an FM mixer (Nippon Coke Industries 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 moisture content after adding water was 20%, and the mixture was heated to 80°C. (D) Next, vinyl laurate was added in a proportion of 1.2 molar equivalents relative to the glucose unit amount of CNF contained in the primary dispersion. (F) After the reaction was complete, the mixture was dehydrated using a Buchner funnel, and then washed multiple times with 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. Furthermore, the degree of substitution of the hydrophobic CNF was 0.55.

[0077] (Example 7) (Preparation of hydrophobic CNF dispersions) In Example 1, steps (A), (B), (C), (D), and (F) were modified as follows to prepare a hydrophobized CNF dispersion using vinyl laurate. (A) Hardwood pulp was used as the raw material instead of bamboo pulp. (B) Next, the powdered CNF was dispersed in DMSO for 1 hour using an FM mixer (Nippon Coke Industries 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 moisture content after adding water was 30%, and the mixture was heated to 80°C. (D) Next, vinyl laurate was added in a proportion of 1.2 molar equivalents relative to the glucose unit amount of CNF contained in the primary dispersion. (F) After the reaction was complete, the mixture was dehydrated using a Buchner funnel, and then washed multiple times with an FM mixer and a 70% aqueous ethanol solution until the DMSO concentration reached 950 ppm. The washing was then stopped, and a hydrophobic CNF dispersion with a hydrophobic CNF concentration of 30% was obtained using an aqueous ethanol solution. Furthermore, the degree of substitution of the hydrophobic CNF was 0.5.

[0078] (Example 8) (Preparation of hydrophobic composite CNF dispersions) In Example 1, steps (B), (C), (D), and (F) were modified 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 Industries 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 moisture content after adding water was 10%, and the mixture was heated to 80°C. (D) Next, divinyl sebacate and vinyl propionate were added in amounts 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 amounts of 0.18 molar equivalents. (F) After the reaction was complete, the mixture was dehydrated using a Buchner funnel, and then washed multiple times with an FM mixer and a 60% aqueous ethanol solution until the DMSO concentration reached 500 ppm. The washing was then stopped, and a hydrophobic composite CNF dispersion with a hydrophobic composite CNF concentration of 5% was obtained using an aqueous ethanol solution.

[0079] (Example 9) (Preparation of a paste-like hydrophobic CNF oily component-containing material) 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 oily component was 19%. Next, using a stirrer (IKA EUROSTAR 20 DIGITAL (stirring rod: R1303)) and under conditions of a temperature of 80°C, the dispersion medium was removed from the hydrophobic CNF dispersion to obtain a paste-like hydrophobic CNF oily component-containing material.

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

[0081] (Example 11) (Preparation of hydrophobic CNF powder) Using the hydrophobic CNF dispersion obtained in Example 7, ethylhexyl methoxycinnamate was added so that the proportion of hydrophobic CNF in the resulting hydrophobic CNF powder was 90%. Next, using a stirrer (IKA EUROSTAR 20 DIGITAL (stirring rod: R1303)) and under conditions of a temperature of 80°C, the dispersion medium was removed from the hydrophobic CNF dispersion to obtain hydrophobic CNF powder.

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

[0083] (Example 13) (Evaluation of the dispersibility of hydrophobic CNF) The hydrophobic CNF obtained in Example 1 and Example 2 was prepared by adding 0.3 wt% of each of the following oils. Each oil was stirred, subjected to ultrasonic treatment for 30 minutes, and then allowed to stand. After one day, the dispersibility was visually evaluated using the evaluation criteria below. Table 1 shows the results for the hydrophobic CNF obtained in Example 1, and Table 2 shows the results for the hydrophobic CNF obtained in Example 2. Evaluation Criteria ◎: Dispersion stable 〇: Sedimentation after dispersion ×: Aggregation The types of oils used for the hydrophobized CNF obtained in Example 1 are as follows: • Isododecane (Kaneda Co., Ltd.: ISODODECANE) • 2-Octyldodecanol (Higher Alcohol Industry Co., Ltd.: Risonol 20SP) • Caprylic / capric triglyceride (BASF Japan Ltd.: Myritol 318) • Cetyl ethylhexanoate (BASF Japan Ltd.: Cetiol SN-1F) • Pentaerythrityl tetraethylhexanoate (Nisshin Oillio Group Ltd.: Saracos 5408) • Ethylhexyl methoxycinnamate (Nisshin Oillio Group Ltd.: Nomucoat TAB) • Ethylhexyl palmitate (Nikko Chemicals Co., Ltd.: NIKKOL IOP) The types of oils 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)) (CROPURE Japan Co., Ltd.) • Diisostearyl malate (Nippon Seika 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 hydrophobized CNF obtained in Example 1 was used to prepare samples in the concentrations shown in Table 3 below, in relation to 2-octyldodecanol (Lisonol 20SP: Higher Alcohol Industry Co., Ltd.), cetyl ethylhexanoate (Cetiol SN-1F: BASF Japan Ltd.), diisostearyl malate (Neosolue-DiSM: Nippon Seika Co., Ltd.), pentaerythrityl tetraethylhexanoate (Saracos 5408: Nisshin Oillio Group Ltd.), and ethylhexyl methoxycinnamate (Nomcoat TAB: Nisshin Oillio Group Ltd.). Each sample was shaken and stirred, then left to stand in a constant temperature bath (25°C) for 5 minutes. 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 of the oils had the effect of increasing their viscosity.

[0089] (Example 15) (Viscosity evaluation of hydrophobic CNF 2) Samples were prepared by adding the hydrophobic CNF obtained in Example 2 to olive oil (CROPURE OL-LQ-(JP)), cetyl ethylhexanoate (BASF Japan Ltd.: Cetiol SN-1F), diisostearyl malate (Nippon Seika Co., Ltd.: Neosolue-DiSM), diethyl sebacate (Nikko Chemicals Co., Ltd.: NIKKOL DES-SP), and ethylhexyl methoxycinnamate (Nisshin Oillio Group Ltd.: Nomucoat TAB) at the concentrations shown in Table 4 below. Each sample was shaken and stirred, then left to stand in a constant temperature bath (25°C) for 5 minutes. 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 of the oils had the effect of increasing their viscosity.

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

[0093] [Table 5]

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

[0095] (Evaluation of each cosmetic product) The following cosmetic formulations were prepared, and their formulation stability and feel (such as stickiness) were examined.

[0096] (Example 17) (Toner 1) Using the hydrophobic CNF dispersion obtained in Example 1, 2-octyldodecanol (oil component) was added so that the hydrophobic CNF content in the resulting cosmetic raw material was 2 wt%, thereby preparing cosmetic raw material 1. Next, the raw materials listed below were weighed, and lotion 1 was prepared using the following preparation method. The amount of hydrophobic CNF in lotion 1 was 0.005 wt%. Preparation method: Mix A. Further heat A to 80°C and dissolve uniformly. Meanwhile, mix B. Next, add B to the stirring of A and stir with a homomixer. Cool to room temperature and finish preparation. After using lotion 1, I found that it was not sticky, had a smooth texture, and the moisturizing effect lasted after use.

[0097] (Example 18) (Toner 2) Using the hydrophobic CNF dispersion obtained in Example 2, tri(caprylic / capric acid)glyceryl (oil component) was added so that the hydrophobic CNF content in the resulting cosmetic raw material was 2 wt%, thereby preparing cosmetic raw material 2. Next, the raw materials listed below were weighed, and lotion 2 was prepared using the following preparation method. The amount of hydrophobic CNF in lotion 2 was 0.005 wt%. Preparation method: Mix A. Further heat A to 80°C and dissolve uniformly. Meanwhile, mix B. Further heat B to 80°C and dissolve uniformly. Next, add B to the stirring A and stir with a homomixer. Cool to room temperature and finish preparation. After using lotion 2, I found that it wasn't sticky, had a smooth texture, and left my skin feeling moisturized for a long time after use. It was less sticky than some highly moisturizing lotions.

[0098] (Example 19) (emulsion) Using the hydrophobized CNF dispersion obtained in Example 1, ethylhexyl methoxycinnamate (oil component) was added to the resulting cosmetic raw material so that the hydrophobized CNF content in the raw material was 2 wt%, thereby preparing cosmetic raw material 3. Next, the raw materials listed below were weighed, and an emulsion was prepared using the following preparation method. The amount of hydrophobized CNF in the emulsion was 0.02 wt%. Preparation method: Mix A. Further heat A to 80°C and dissolve uniformly. Mix B. Further heat B to 80°C and dissolve uniformly. Meanwhile, mix C. Next, add A to the mixture of B being stirred and emulsify. The emulsion was non-sticky and had a smooth texture. Furthermore, the moisturizing effect lasted after use without any stickiness. In addition, cosmetic ingredient 3 did not inhibit emulsification.

[0099] (Example 20) (Moisturizing lotion) Using the hydrophobic CNF dispersion obtained in Example 2, diethyl sebacate (oil component) was added so that the hydrophobic CNF content in the resulting cosmetic raw material was 2 wt%, thereby preparing cosmetic raw material 4. Next, the raw materials listed below were weighed, and a moisturizing lotion was prepared using the following preparation method. The amount of hydrophobized CNF in the moisturizing lotion was 0.005 wt%. TIFF0007887463000009.tif52109 Preparation method: Mix A. Disperse uniformly and finish preparation. The moisturizing lotion had a non-sticky, easily spreadable texture. Furthermore, the moisturizing effect lasted after use.

[0100] (Example 21) (Cleansing oil 1) Using the hydrophobized CNF dispersion obtained in Example 1, cetyl ethylhexanoate (oil component) was added so that the hydrophobized CNF in the resulting cosmetic raw material was 2 wt%, thereby preparing cosmetic raw material 5. Next, the raw materials listed below were weighed, and cleansing oil was prepared using the following preparation method. The amount of hydrophobic CNF in cleansing oil 1 was 0.0006 wt%. Next, Examples 21-27 and Comparative Examples 1-3 were evaluated based on the following evaluation items and criteria 1-5. The results are shown in Table 6. TIFF0007887463000010.tif27108 Preparation method: Mix A. Disperse uniformly and finish preparation.

[0101] (Example 22) (Cleansing Oil 2) Cosmetic raw material 5 and the raw materials listed below were weighed, and cleansing oil 2 was prepared using the same preparation method as cleansing oil 1. The amount of hydrophobic CNF in cleansing oil 2 was 0.008 wt%. TIFF0007887463000011.tif27109

[0102] (Example 23) (Cleansing Oil 3) Cosmetic raw material 5 and the raw materials listed below were weighed, and cleansing oil 3 was prepared using the same preparation method as cleansing oil 1. The amount of hydrophobic CNF in cleansing oil 3 was 0.0136 wt%. TIFF0007887463000012.tif27108

[0103] (Example 24) (Cleansing oil 4) Cosmetic raw material 5 and the raw materials listed below were weighed, and cleansing oil 4 was prepared using the same preparation method as cleansing oil 1. The amount of hydrophobic CNF in cleansing oil 4 was 0.25 wt%. TIFF0007887463000013.tif27108

[0104] (Example 25) (Cleansing oil 5) Using the hydrophobized CNF dispersion obtained in Example 1, cetyl ethylhexanoate (oil component) was added so that the hydrophobized CNF in the resulting cosmetic raw material was 7.8 wt%, thereby preparing cosmetic raw material 6. Next, the raw materials listed below were weighed, and a cleansing oil was prepared using the same preparation method as for cleansing oil 1. The amount of hydrophobic CNF in cleansing oil 5 was 1.0 wt%. TIFF0007887463000014.tif28109

[0105] (Example 26) (Cleansing oil 6) Using the hydrophobized CNF dispersion obtained in Example 1, cetyl ethylhexanoate (oil component) was added so that the hydrophobized CNF in the resulting cosmetic raw material was 15.1 wt%, thereby preparing cosmetic raw material 7. Next, the raw materials listed below were weighed, and a cleansing oil was prepared using the same preparation method as for cleansing oil 1. The amount of hydrophobic CNF in cleansing oil 6 was 2.0 wt%. TIFF0007887463000015.tif28109

[0106] (Example 27) (Cleansing Oil 7) Using the hydrophobized CNF dispersion obtained in Example 2, cetyl ethylhexanoate (oil component) was added so that the amount of hydrophobized CNF in the resulting cosmetic raw material was 2 wt%, thereby preparing cosmetic raw material 8. Next, the raw materials listed below were weighed, and cleansing oil 7 was prepared using the same preparation method as for cleansing oil 1. The amount of hydrophobic CNF in cleansing oil 7 was 0.0006 wt%. TIFF0007887463000016.tif27109

[0107] (Prescription example 1) (Cleansing oil 8) Using the hydrophobized CNF dispersion obtained in Example 1, a preparation was made in which hydrophobized CNF was present in cetyl ethylhexanoate (oil component) at a concentration of 18.2 wt%, and this was used as cosmetic raw material 9. Next, the raw materials listed below were weighed, and a cleansing oil was prepared using the same preparation method as for cleansing oil 1. The amount of hydrophobic CNF in cleansing oil 8 was 2.5 wt%. TIFF0007887463000017.tif27108

[0108] (Comparative Example 1) (Cleansing Oil 9) Without formulating the cosmetic raw materials according to the present invention, the raw materials listed below were weighed, and cleansing oil 9 was prepared using the same preparation method as cleansing oil 1. The amount of hydrophobic CNF in cleansing oil 9 was 0 wt%. TIFF0007887463000018.tif19109

[0109] (Comparative Example 2) (Cleansing oil 10) Using CNF prepared by the method described below, a mixture was prepared so that the hydrophobized CNF in cetyl ethylhexanoate (oil component) was 2 wt%, and this was used as raw material 1 for cleansing oil. 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 coniferous trees, 0.0125g of TEMPO(2,2,6,6-tetramethylpiperidine-1-oxyradical) and After dispersing 0.125g of sodium bromide in 100ml of water, A 13% sodium hypochlorite solution, Add 5.0 mmol of sodium hypochlorite per 1 g of pulp. The reaction was initiated at room temperature. The pH inside the meter during the reaction is 0.5 mol / l sodium hydroxide aqueous solution, A 0.5 mol / l hydrochloric acid solution was added dropwise to maintain the pH at 10. After reacting for 2 hours, the reaction product was filtered and washed with water to obtain TEMPO oxidized pulp. The aforementioned TEMPO-oxidized pulp was dispersed in distilled water, and the resulting sample, at a concentration of 1% by mass, was subjected to defibrillation using a homogenizer to obtain a cellulose nanofiber aqueous dispersion (average fiber width 3-8 nm). TIFF0007887463000019.tif2079

[0110] (Evaluation item 1: Ease of dropping) After applying multiple coats of black oil-based marker to a whiteboard, the cleaning power was evaluated by applying the aforementioned cleansing oil to a cloth and rubbing it multiple times. (Evaluation Criterion 1) ◎: Oil-based black marker stains can be removed with fewer than 10 rubs. ○: The oil-based black marker stain won't come off unless you rub it hard more than 10 times. ×: Even after rubbing it more than 10 times, the oil-based black marker stain hardly comes off.

[0111] (Evaluation item 2: Pleasant texture) The cleansing oils 1-10 were actually used and evaluated for their oily, squeaky feel. (Evaluation Criterion 2) ◎: When applied to the skin, there was no oily, sticky feeling. ○: When applied to the skin, there was a slight oily, squeaky feeling. ×: When applied to the skin, it felt oily and sticky.

[0112] (Evaluation Item 3: Ease of Use (Doesn't become boring)) The cleansing oils 1-10 were actually used on the skin and evaluated for their ease of use (not dripping). (Evaluation Criterion 3) ○: When applied to the skin, it helps to prevent it from dripping. ×: When applied to the skin, it either does not drip at all or drips immediately.

[0113] (Evaluation item 4: Ease of improvement) The aforementioned cleansing oils 1-10 were actually used on the skin and evaluated for their spreadability. (Evaluation Criterion 4) ◎: When applied to the skin, it spreads evenly across the entire face. ○: When applied to the skin, it spreads to a certain extent. ×: Does not spread when applied to the skin.

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

[0115] [Table 6]

[0116] By incorporating the hydrophobic CNF according to the present invention, the cleansing power was improved, making it possible to easily remove makeup with water.

[0117] (Example 28) (Liquid foundation 1) Using the hydrophobic CNF dispersion obtained in Example 2, ethylhexyl methoxycinnamate (oil component) was added to the resulting cosmetic raw material so that the hydrophobic CNF content in the raw material was 2 wt%, thereby preparing cosmetic raw material 10. Next, the raw materials listed below were weighed, and liquid foundation 1 was prepared using the following preparation method. The amount of hydrophobic CNF in liquid foundation 1 was 0.064 wt%. JPEG0007887463000021.jpg85133 Preparation method: Mix A and disperse uniformly. Meanwhile, mix B and dissolve uniformly. Next, add C to the stirring of B and disperse uniformly. Then, add A and disperse uniformly to complete the preparation. After using liquid foundation 1, I found that it spread easily and the makeup applied well.

[0118] (Example 29) (Liquid foundation 2) Using the hydrophobic CNF dispersion obtained in Example 2, pentaerythrityl tetraethylhexanoate (oil component) was added so that the hydrophobic CNF content in the resulting cosmetic raw material was 2 wt%, thereby preparing cosmetic raw material 11. Next, the raw materials listed below were weighed, and liquid foundation 2 was prepared using the following preparation method. The amount of hydrophobic CNF in liquid foundation 2 was 0.06 wt%. JPEG0007887463000022.jpg65133 Preparation method: Mix B and disperse uniformly. Add C to the mixture of B while stirring, disperse uniformly, and finish the preparation. After using Liquid Foundation 2, I found that it spread easily and the makeup applied well.

[0119] (Example 30) (Hair cream) Using the hydrophobic CNF dispersion obtained in Example 1, olive oil (oil component) was added so that the amount of hydrophobic CNF in the resulting cosmetic raw material was 2 wt%, thereby preparing cosmetic raw material 12. Next, the raw materials listed below were weighed, and hair cream was prepared using the following preparation method. The amount of hydrophobic CNF in the hair cream was 0.006 wt%. JPEG0007887463000023.jpg101133 Preparation method: Mix A. Heat to 80°C and dissolve uniformly. Mix B. Heat to 80°C and dissolve uniformly. Add B to the mixture of A being stirred and emulsify. Cool to room temperature and finish preparation. After using the hair cream, I found it to be non-greasy and had a smooth texture that spread easily. Furthermore, it reduced dryness and kept my hair moisturized for a long time.

[0120] (Example 31) (Hair mist) Using the hydrophobic CNF dispersion obtained in Example 1, dimethicone (an oily component) was added to the resulting cosmetic raw material so that the hydrophobic CNF content in the raw material was 2 wt%, thereby preparing cosmetic raw material 13. Next, the raw materials listed 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%. JPEG0007887463000024.jpg85133 Preparation method: Mix A. Further heat to 80°C and dissolve uniformly. Mix B and dissolve uniformly. Add A to the mixture of B, disperse uniformly, and finish preparation. After using the hair mist, I found it wasn't sticky and had a smooth, easily spreadable texture. Furthermore, it reduced dryness and kept my hair feeling silky smooth for a long time.

[0121] (Example 32) (UV Milk) Using the hydrophobic CNF dispersion obtained in Example 1, mineral oil (oil component) was added so that the amount of hydrophobic CNF in the resulting cosmetic raw material was 2 wt%, thereby preparing cosmetic raw material 14. Next, the raw materials listed below were weighed, and UV milk was prepared using the following preparation method. The amount of hydrophobized CNF in the UV milk was 0.57 wt%. JPEG0007887463000025.jpg74133 Preparation method: Mix A and disperse uniformly. Mix B and dissolve uniformly. Disperse A and B uniformly to complete the preparation. The UV milk was non-greasy and had a smooth, easily spreadable texture. It also contributed to improved dispersibility of titanium dioxide and did not inhibit emulsification. Furthermore, it left minimal white residue.

[0122] (Example 33) (UV gel) Using the hydrophobic CNF dispersion obtained in Example 2, isododecane (an oily component) was added to the resulting cosmetic raw material so that the hydrophobic CNF content in the raw material was 2 wt%, thereby preparing cosmetic raw material 15. Next, the raw materials listed below were weighed, and a UV gel was prepared using the following preparation method. The amount of hydrophobized CNF in the UV gel was 0.02 wt%. JPEG0007887463000026.jpg121133 Preparation method: Mix A. Further heat to 80°C and disperse uniformly. Mix B. Further heat to 80°C and dissolve uniformly. Add B to A while stirring and emulsify. Cool to room temperature and finish preparation. The UV gel was non-sticky and had a smooth, easily spreadable texture. It also contributed to improved dispersibility of titanium dioxide and did not inhibit emulsification. Furthermore, it left minimal white residue.

[0123] (Example 34) (UV lotion) Using the hydrophobic CNF dispersion obtained in Example 2, mineral oil (oil component) was added so that the amount of hydrophobic CNF in the resulting cosmetic raw material was 2 wt%, thereby preparing cosmetic raw material 16. Next, the raw materials listed below were weighed, and a UV lotion was prepared using the following preparation method. The amount of hydrophobized CNF in the UV lotion was 0.3 wt%. JPEG0007887463000027.jpg106133 Preparation method: Mix A. Further heat to 80°C and dissolve uniformly. Mix B. Further heat to 80°C and disperse uniformly. Add B to the stirring of A and emulsify. Cool to room temperature and finish preparation. The UV lotion was non-greasy and had a smooth, easily spreadable texture. It also contributed to improved titanium dioxide dispersion and did not inhibit emulsification. Furthermore, it left minimal white residue.

[0124] (Example 35) (BB cream) To the hydrophobized CNF dispersion obtained in Example 1, cetyl ethylhexanoate (oil component) was added so that the hydrophobized CNF in the resulting cosmetic raw material amounted to 20 wt%. Next, using a stirrer (IKA EUROSTAR 20 DIGITAL (stirring rod: R1303)) and under conditions of a temperature of 80°C, the dispersion medium was removed from the hydrophobic CNF dispersion to obtain cosmetic raw material 17 (hydrophobic CNF powder). Next, the raw materials listed below were weighed, and BB cream was prepared using the following preparation method. The amount of hydrophobic CNF in the BB cream was 2.0 wt%. Preparation method: Mix A and finish preparation. The BB cream spread easily and smoothly, making it very easy to apply. It also had a good thickness. Furthermore, it settled at an appropriate time after application, which was good. When actually used on the face, it didn't leave a white cast, which was good. Finally, after adjustment, no clumping was observed, indicating excellent stability.

Claims

1. A method for producing a hydrophobic CNF dispersion comprising at least a first step, a second step, and a third step, The first step is to disperse hydrated CNF in an organic solvent to obtain a primary dispersion. The second step involves dissolving the primary dispersion and a vinyl ester, wherein the clearance of the shear portion is 10 μm or more and 23,000 μm or less, and the shear rate is 1 × 10 (1 / s) or more. 8 This is a process to obtain a secondary dispersion by performing a distributed processing using a medialess distributor with a processing time of (1 / s) or less. The third step is to wash the secondary dispersion and disperse it in an aqueous alcohol solution. A method for producing a hydrophobic CNF dispersion, characterized by having a step of adding a catalyst in the first or second step.

2. A method for producing a hydrophobic composite CNF dispersion comprising at least a first step, a second step, and a third step, The first step is to disperse hydrated CNF in an organic solvent to obtain a primary dispersion. The second step involves dissolving the primary dispersion with a polyhydric alcohol and / or polyalkylene glycol, a crosslinking agent, and a vinyl ester, wherein the clearance of the shear portion is 10 μm or more and 23,000 μm or less, and the shear rate is 1 × 10 (1 / s) or more. 8 This is a process to obtain a secondary dispersion by performing a distributed processing using a medialess distributor with a processing time of (1 / s) or less. The third step is to wash the secondary dispersion and disperse it in an aqueous alcohol solution. A method for producing a hydrophobic composite CNF dispersion, characterized by having a step of adding a catalyst in the first or second step.

3. A step of adding an oily component to the hydrophobic CNF dispersion described in claim 1, A step to remove the dispersion medium from the hydrophobic CNF dispersion, A method for producing a hydrophobized CNF oily component-containing product, characterized by having the following characteristics.

4. A step of adding an oily component to the hydrophobic composite CNF dispersion according to claim 2, A step to remove the dispersion medium from the hydrophobic composite CNF dispersion, A method for producing a hydrophobic composite CNF oily component-containing body, characterized by having the following characteristics.

5. A step of adding an oily component to the hydrophobic CNF dispersion described in claim 1, A method for producing hydrophobic CNF powder, comprising the step of removing the dispersion medium from the hydrophobic 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 set to 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 hydrophobic composite CNF dispersion according to claim 2, A method for producing hydrophobic composite CNF powder, comprising the step of removing the dispersion medium in the hydrophobic composite CNF dispersion, A method for producing hydrophobic composite CNF powder, characterized in that, when the amount of hydrophobic composite CNF in the obtained hydrophobic composite CNF powder is set to 1, the ratio of hydrophobic composite CNF to the oily component is 1:0.01 to 1:

4.

7. A method for producing hydrophobic CNF comprising at least a first step and a second step, The first step is to disperse hydrated CNF in an organic solvent to obtain a primary dispersion. The second step involves dissolving the primary dispersion and a vinyl ester, wherein the clearance of the shear portion is 10 μm or more and 23,000 μm or less, and the shear rate is 1 × 10 (1 / s) or more. 8 This is a process to obtain a secondary dispersion by performing a distributed processing using a medialess distributor with a processing time of (1 / s) or less. Hydrophobized CNF 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 hydrophobic composite CNF comprising at least a first step and a second step, wherein the first step is a step of dispersing hydrated CNF in an organic solvent to obtain a primary dispersion, The second step involves dissolving the primary dispersion with a polyhydric alcohol and / or polyalkylene glycol, a crosslinking agent, and a vinyl ester, wherein the clearance of the shear portion is 10 μm or more and 23,000 μm or less, and the shear rate is 1 × 10 (1 / s) or more. 8 This is a process to obtain a secondary dispersion by performing a distributed processing using a medialess distributor with a processing time of (1 / s) or less. The first or second step includes a step of adding a catalyst, A hydrophobic composite CNF obtained by recovering the reaction product in the secondary dispersion obtained in the second step and purifying it.

9. A hydrophobic CNF oily component-containing body comprising the hydrophobic CNF described in claim 7 and an oily component.

10. A hydrophobic composite CNF containing an oily component, comprising the hydrophobic composite CNF described in claim 8.

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

4.

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

4.

13. An oily thickener containing the hydrophobic CNF described in claim 7, the hydrophobic CNF oily component-containing body described in claim 9, or the hydrophobic CNF powder described in claim 11.

14. An oily thickener containing the hydrophobic composite CNF described in claim 8, the hydrophobic composite CNF oily component-containing body described in claim 10, or the hydrophobic composite CNF powder described in claim 12.

15. A cosmetic composition containing the hydrophobic CNF described in claim 7, the hydrophobic CNF oily component-containing material described in claim 9, or the hydrophobic CNF powder described in claim 11.

16. A cosmetic composition containing the hydrophobic composite CNF described in claim 8, the hydrophobic composite CNF oily component-containing material described in claim 10, or the hydrophobic composite CNF powder described in claim 12.

17. The cosmetic according to claim 15, which is one of the following: a makeup cosmetic, a skin cosmetic, a skin cleanser, a UV protection cosmetic, a skincare product, or a hair cosmetic.

18. The cosmetic according to claim 16, which is one of the following: a makeup cosmetic, a skin cosmetic, a skin cleanser, a UV protection cosmetic, a skincare product, or a hair cosmetic.

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