JP6731277B2 - Skin cosmetics - Google Patents

Description

The present invention relates to skin cosmetics.

As a technique relating to fibrous cellulose, there are techniques described in Patent Documents 1 to 3.
Patent Document 1 (JP-A-2015-157796) describes that cellulose nanofibers can be obtained by defibrating a dispersion fluid of cellulose by a high-pressure injection treatment of 100 to 245 MPa.

In Patent Document 2 (JP 2009-293167 A), a polybasic acid half-esterified cellulose is prepared by semi-esterifying a polybasic acid anhydride into a part of the hydroxyl groups of cellulose to introduce a carboxyl group. , A technique for producing nanofibers by making them fine fibers is described.

Patent Document 3 (Japanese Patent Laid-Open No. 2013-127141) discloses a technique of producing fine fibrous cellulose by treating a fiber raw material containing cellulose with an oxo acid of phosphorus or a salt thereof and then defibrating the cellulose. Have been described.

In addition, Patent Document 1 described above also describes using fibrous cellulose in the field of cosmetics. That is, according to the document, when fibrous cellulose obtained by the method described in the document is used as an emulsifier, the concentration of water and oil is lower than that of a general emulsifier, but the state in which water and oil are not separated for a long time. Since it can be maintained, the ratio of extra additives in cosmetics can be reduced.

JP, 2005-157796, A JP, 2009-293167, A JP, 2013-127141, A

Here, since the percutaneous absorption of the cosmetic and the active ingredient contained therein follows the concentration gradient between the cosmetic and the skin, high permeability occurs immediately after the cosmetic is applied to the skin, while the skin elapses over time. Penetration into water will decrease.
On the other hand, in recent years, there has been a demand for cosmetics that can be absorbed percutaneously gradually over a long period of time and have a sustained effect of the ingredients.
However, the techniques described in the patent documents mentioned above in the section of background art have not been examined from the viewpoint of enhancing the sustained release effect of the components in the cosmetic when the cosmetic is applied to the skin. Further, conventional cellulose-containing cosmetics have been used in a limited number of applications, such as being used as a detergent or having to be applied as a pack.

Therefore, the present invention provides a skin cosmetic having excellent sustained release of the components contained in the cosmetic.

The present inventor uses a combination of a cellulose suitable for a cosmetic formulation and a specific hydroxybenzenecarboxylic acid or a derivative thereof as a functional component, so that when the cosmetic is applied to the skin, the functional component It was found that sustained release is exhibited in percutaneous absorption.

That is, according to the present invention,
The following components (A) and (B):
(A) Fibrous carboxyalkylated cellulose,
(B) containing hydroxybenzenecarboxylic acid or a derivative thereof,
The component (A) has a carboxyalkyl-derived substituent derived from a carboxylic acid having a pKa of 4.70 or more and 4.90 or less in the hydroxyl groups at the 2, 3 or 6 positions of the cellulose skeleton,
There is provided a skin cosmetic in which the IOB value of the component (B) is 0.90 or more and 6.5 or less.

Further, according to the present invention, there is provided a method of using the skin cosmetic, which comprises the step of applying the skin cosmetic of the present invention described above to the skin.

According to the present invention, it is possible to provide a skin cosmetic having excellent sustained release of the components contained in the cosmetic.

Hereinafter, embodiments of the present invention will be described.
In this embodiment, the skin cosmetic contains the following components (A) and (B).
(A) Fibrous carboxyalkylated cellulose (B) Hydroxybenzenecarboxylic acid or derivative thereof And, the component (A) has a pKa of 4.70 or more and 4.90 in hydroxyl groups at the 2, 3 or 6 positions of the cellulose skeleton. It has a carboxyalkyl substituent derived from the following carboxylic acid, and the IOB value of the component (B) is 0.90 or more and 6.5 or less.

Hereinafter, each component will be described with reference to specific examples. Each component may be used alone or in combination of two or more.
In addition, in the present specification, “skin cosmetics” is also simply referred to as “cosmetics”.

(Component (A))
The component (A) is a fibrous carboxyalkylated cellulose, and has a carboxyalkyl-derived substituent derived from a carboxylic acid having a pKa of 4.70 or more and 4.90 or less at the hydroxyl group at the 2, 3 or 6 position of the cellulose skeleton. Have.
The origin of cellulose as the component (A) is not limited, and examples thereof include those derived from plant raw materials such as wood fibers (pulp).
The fibrous cellulose is cellulose that has been made into fine fibers and is preferably insoluble in water.

The component (A) has a carboxyalkyl-derived substituent group derived from a carboxylic acid having an acid dissociation constant pKa of 4.70 or more and 4.90 or less at the hydroxyl groups at the 2, 3 or 6 positions of the cellulose skeleton.
As a specific example of a carboxylic acid having a pKa of 4.70 to 4.90, acetic acid (pKa 4.77, Source: The Chemical Society of Japan, "Chemical Handbook Basic Edition", 5th revised edition, Maruzen, published in 2004 (hereinafter The same)), propionic acid (pKa4.874), butyric acid (pKa4.82), isobutyric acid (pKa4.86) and valeric acid (pKa4.86). Of these, the carboxylic acid is preferably acetic acid or propionic acid, and more preferably acetic acid, from the viewpoint of enhancing the sustained release effect of the component (B).

Further, as specific examples of the substituent bonded to the oxygen atom at the 2, 3 or 6 position of the cellulose skeleton of the component (A), —CH ₂ COOH (carboxylalkyl substituent derived from acetic acid), —CH ₂ CH ₂ COOH( Propionic acid-derived carboxyalkyl substituent), —CH ₂ CH ₂ CH ₂ COOH (isobutyric acid-derived carboxyalkyl substituent), —CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ COOH (valeric acid-derived carboxyalkyl substituent), etc. The carboxyalkyl group of is mentioned. Among these, from the viewpoint of enhancing the sustained release effect of the component (B), the substituent is preferably —CH ₂ COOH, that is, carboxymethyl group, or —CH ₂ CH ₂ COOH, that is, carboxyethyl group, and more preferably carboxymethyl. It is a base.
From the same viewpoint, the component (A) is preferably fibrous carboxymethylated cellulose or fibrous carboxyethylated cellulose, and more preferably fibrous carboxymethylated cellulose.

In the component (A), the substitution degree of the carboxyalkyl group per anhydrous glucose unit constituting the cellulose skeleton (hereinafter, also simply referred to as “substitution degree”) improves the dispersion stability of the component (A) in the cosmetic. From the viewpoint of improving the sustained-release effect of the component (B), preferably 0.12 mmol/g or more, more preferably 0.30 mmol/g or more, still more preferably 0.60 mmol/g or more. And preferably 2.20 mmol/g or less, more preferably 2.16 mmol/g or less, even more preferably 2.00 mmol/g or less, still more preferably 1.95 mmol/g or less, particularly preferably 1 or less. It is 0.80 mmol/g or less, and more preferably 1.42 mmol/g or less.
Here, the substitution degree of the component (A) is measured by the method described later in the section of Examples.

In addition, from the viewpoint of improving the sustained-release effect of the component (B), and from the viewpoint of suppressing the occurrence of cosmetic discoloration such as shaving of cosmetics and disintegration of eraser-like residue after application to the skin, the component ( A) is preferably microfibrillar carboxyalkylated cellulose, more preferably microfibrillar carboxymethylated cellulose or microfibrous carboxyethylated cellulose, and still more preferably microfibrous carboxymethylated cellulose. It is cellulose.
Microfibrous carboxyalkylated cellulose is fibrous cellulose having a fiber diameter on the order of nanometers. The average fiber diameter of the carboxyalkylated cellulose in the form of fine fibers is determined from the viewpoints of improving the sustained release effect of the component (B), improving the production stability of the component (A), and adapting the cosmetic to the skin. From the viewpoint of improving the above, it is preferably 2 nm or more, more preferably 3 nm or more, further preferably 3.5 nm or more, still more preferably 8 nm or more, particularly preferably 9 nm or more, particularly preferably 10 nm or more. Yes, and more preferably 15 nm or more.
From the viewpoint of enhancing dispersibility in a dispersion medium such as water, the average fiber diameter of the component (A) is preferably 5000 nm or less, more preferably 200 nm or less, still more preferably 100 nm or less, still more preferably 50 nm. Or less, particularly preferably 40 nm or less.

The average fiber length of the component (A) is preferably 10 nm or more from the viewpoint of enhancing the sustained release effect of the component (B) and improving the sweat resistance and abrasion resistance of the cosmetic applied to the skin. It is more preferably 50 nm or more, further preferably 300 nm or more, even more preferably 500 nm or more, and particularly preferably 800 nm or more.
From the viewpoint of enhancing the dispersibility of the component (A) in a dispersion medium such as water, the average fiber length of the component (A) is preferably 2 mm or less, more preferably 300 μm or less, further preferably 100 μm or less, Even more preferably, it is less than 100 μm, particularly preferably 10 μm or less.

Further, the average aspect ratio (average fiber length/average fiber diameter) of the component (A) improves the balance between the sustained release effect of the component (B) and the dispersibility of the component (A) in a dispersion medium such as water. From the viewpoint, it is preferably 10 or more, more preferably 20 or more, even more preferably 50 or more, even more preferably 60 or more, particularly preferably 250 or more, and preferably 5000 or less, more preferably 1000 or more. Or less, more preferably 500 or less, even more preferably 400 or less, particularly preferably 300 or less.

Here, the average fiber diameter, the average fiber length and the average aspect ratio of the component (A) are measured by the following methods. That is, the average fiber diameter and the average fiber length of fibrous cellulose were analyzed using a field emission scanning electron microscope (FE-SEM) for 200 randomly selected fibers, and an arithmetic average of 200 was calculated. To do. The average aspect ratio is calculated by the following formula.
Average aspect ratio = average fiber length / average fiber diameter

From the viewpoint of enhancing the sustained release effect of the component (B), enhancing the dispersion stability of the component (A), and improving the compatibility of the cosmetic with the skin, the component (A) is preferably The average fiber diameter is 2 nm or more and 40 nm or less, and the average fiber length is 800 nm or more and 10000 nm or less. More preferably, the average fiber diameter and the average fiber length are in the above ranges, and the average aspect ratio is 250 or more and 300 or more. It is the following.

The viscosity of the 1% by mass dispersion of the component (A) is preferably 900 mPa·s or more from the viewpoint of improving the sustained release of the component (B) and improving the compatibility of the cosmetic with the skin. Yes, more preferably 2000 mPa·s or more, further preferably 3000 mPa·s or more, preferably 4750 mPa·s or less, more preferably 4500 mPa·s or less, and further preferably 4000 mPa·s or less. ..
Further, from the viewpoint of improving the dispersion stability of the component (A), the viscosity of the 1% by mass dispersion liquid of the component (A) is preferably 10 mPa·s or more, more preferably 100 mPa·s or more, and further preferably It is 200 mPa·s or more, preferably less than 900 mPa·s, more preferably 850 mPa·s or less, still more preferably 830 mPa·s or less.
Here, the viscosity of the component (A) is a B-type viscometer (VISCOMETR TVB-10, rotor No. 4 manufactured by Toki Sangyo Co., Ltd.) for a dispersion liquid (dispersion medium: water) of 1% by mass of the component (A). Is measured under the conditions of 25° C., rotation speed 60 rpm, and 1 minute.

Further, the transparency of the component (A) is preferably 20% or more, more preferably 30% or more, further preferably 46% or more, from the viewpoint of improving the dispersion stability of the component (A), It is preferably 100% or less, more preferably 96% or less, still more preferably 94% or less.
Here, the transparency of the component (A) is the light transmittance (%) of a dispersion liquid (dispersion medium: water) of 0.1% by mass of the component (A), and is the ultraviolet/visible spectrophotometer U-3000. (Manufactured by Hitachi High-Tech Co., Ltd.) at 25° C., a wavelength of 660 nm, and a cell length of 10 mm.

As the component (A), from the viewpoint of improving the sustained release property of the component (B), improving the familiarity of the cosmetic to the skin, and easiness of availability, microfibers for general industry The carboxyalkylated celluloses of can be used. Specific examples of commercially available microfibrous carboxyalkylated cellulose include BiNFi-s series microfibrous carboxymethylated cellulose (manufactured by Sugino Machine Ltd.).
Further, as the component (A), those described in JP-A-2005-000977 or JP-A-2015-134873 can also be used.

The component (A) can be obtained, for example, by carboxyalkyl etherifying a cellulose raw material by a known method and then crushing it by a mechanical method or the like to obtain a fibrous substance having a predetermined fiber diameter.
When the component (A) is fibril-methyl carboxymethylated cellulose, the method described in, for example, JP-A-2015-000977 can be used as a method for producing the same. Specifically, the component (A) can be obtained by injecting a dispersion fluid of carboxymethyl cellulose at a high pressure of 100 to 245 MPa to cause it to collide with a collision hard body and disintegrate into a fine fibrous form.
In addition, when the component (A) is a microfibrous carboxymethylated cellulose, a microfibrous carboxymethylated cellulose is produced by using the carboxymethylation step, the defibration step, etc. described in JP-A-2015-134873. It can also be manufactured.

The content of the component (A) in the cosmetic is preferably 0.01% by mass or more, and more preferably from the viewpoint of further improving the sustainability of the sustained release effect of the component (B). Is 0.05% by mass or more, more preferably 0.1% by mass or more, even more preferably 0.15% by mass or more, and particularly preferably 0.2% by mass or more.
Further, from the viewpoint of further enhancing the smooth feeling of use of the cosmetic, the content of the component (A) in the cosmetic is preferably 10% by mass or less, and more preferably 5% by mass, based on the entire cosmetic. The amount is preferably 2% by mass or less, more preferably 1.5% by mass or less, still more preferably 1.2% by mass or less.

(Component (B))
The component (B) is hydroxybenzenecarboxylic acid or its derivative. The IOB value of the component (B) is 0.90 or more and 6.5 or less.

In this embodiment, since the component (B) is contained in the cosmetic together with the component (A), the component (B) is appropriately retained in the cosmetic and gradually released. Therefore, for example, immediately after the cosmetic is applied to the skin, the cosmetic gently acts on the skin, and the effect of the cosmetic after application to the skin can be continued with time.

The IOB value of the component (B) is 0.90 or more from the viewpoint of improving the balance between the effect of stably retaining the component (B) in the cosmetic and the effect of the sustained release of the component (B) by the cosmetic. And more preferably 0.95 or more, still more preferably 0.97 or more, still more preferably 1.0 or more, and 6.5 or less, more preferably 5.5 or less, and further preferably It is 4.5 or less, more preferably 2.0 or less, and particularly preferably 1.4 or less.
Here, the IOB value (Inorganic-Organic Balance) of the component (B) is the following formula:
IOB value=Σ inorganic value/Σ organic value. In the above formula, for each of the “inorganic value” and the “organic value”, for example, the “organic value” is 20 for one carbon atom in the molecule and 100 for the same hydroxyl group. As described above, based on the "inorganic value" and "organic value" set for each atom and functional group, the "inorganic value" and "organic value" of the atoms and functional groups that make up the organic compound such as an oil agent are calculated. It can be calculated by integrating the "sexuality value" (see Yoshida Koda, "Organic Conceptual Diagram -Basics and Applications-", pages 11 to 17, Sankyo Publishing Co., Ltd., 1984).
When the cosmetic contains a plurality of hydroxybenzenecarboxylic acids or derivatives thereof, the IOB value of the component (B) is a weighted average value obtained by multiplying each IOB value by the mass ratio.

Of the component (B), the hydroxybenzenecarboxylic acid derivative is preferably one or more selected from the group consisting of hydroxybenzenecarboxylic acid salts, hydroxybenzenecarboxylic acid esters and salts thereof, and more preferably 2 One or more selected from the group consisting of -hydroxybenzenecarboxylic acid ester, 4-hydroxybenzenecarboxylic acid ester and salts thereof.
Specific examples of the counter ion constituting the salt include alkali metals such as sodium and potassium; alkaline earth metals such as calcium and magnesium; metals other than the above, such as titanium; ammonium; monoethanolamine, diethanolamine, triethanolamine and the like. And cations derived from basic amino acids such as arginine and lysine, and preferably ions derived from a metal selected from the group consisting of sodium, magnesium and titanium.
Component (B) is preferably one or more selected from the group consisting of hydroxybenzenecarboxylic acid, hydroxybenzenecarboxylic acid ester and salts thereof.

As specific examples of the component (B), 2-hydroxybenzenecarboxylic acid (IOB1.89), 2-hydroxybenzenecarboxylic acid dipropylene glycol (IOB1.13), 2-hydroxybenzenecarboxylic acid Na (IOB5.46). , Titanium 2-hydroxybenzenecarboxylate (IOB3.32), methyl 2-hydroxybenzenecarboxylate (IOB1.09), acetamidephenyl 2-hydroxybenzenecarboxylate (IOB1.30), ethylene glycol 2-hydroxybenzenecarboxylate (IOB1.30). 2-hydroxybenzenecarboxylic acid such as IOB1.53), diphenhydramine 2-hydroxybenzenecarboxylic acid (IOB1.52) or a derivative thereof; and 4-hydroxybenzenecarboxylic acid (IOB1.89), methyl 4-hydroxybenzenecarboxylic acid Na (IOB4.22), 4-hydroxybenzenecarboxylic acid ethyl Na (IOB3.75), 4-hydroxybenzenecarboxylic acid propyl Na (IOB3.38), 4-hydroxybenzenecarboxylic acid isobutyl Na (IOB3.21), 4- Butyl hydroxybenzenecarboxylate Na (IOB3.07), methyl 4-hydroxybenzenecarboxylate (IOB1.09), ethyl 4-hydroxybenzenecarboxylate (IOB0.97), isopropyl 4-hydroxybenzenecarboxylate (IOB0.92) 4-hydroxybenzenecarboxylic acid or a derivative thereof.

From the viewpoint of enhancing the sustained release effect of the component (B), the component (B) is preferably ethylene glycol 2-hydroxybenzenecarboxylate, 4-hydroxybenzenecarboxylic acid, methyl 4-hydroxybenzenecarboxylate and 4-hydroxybenzene. One or more selected from the group consisting of ethyl carboxylate;
More preferably, it is one or more selected from the group consisting of ethylene glycol 2-hydroxybenzenecarboxylate, methyl 4-hydroxybenzenecarboxylate and ethyl 4-hydroxybenzenecarboxylate;
More preferably, it is one or two selected from the group consisting of methyl 4-hydroxybenzenecarboxylate and ethyl 4-hydroxybenzenecarboxylate;
More preferably, it is methyl 4-hydroxybenzenecarboxylate, or methyl 4-hydroxybenzenecarboxylate and ethyl 4-hydroxybenzenecarboxylate;
Even more preferably, it is methyl 4-hydroxybenzenecarboxylate.

The content of the component (B) in the skin cosmetic is from the viewpoint of improving the balance between the effect of stably retaining the component (B) in the cosmetic and the effect of the cosmetic releasing the component (B) slowly. , Preferably 0.02% by mass or more, more preferably 0.05% by mass or more, further preferably 0.1% by mass or more, still more preferably 0.15% by mass or more, based on the entire cosmetic; , Preferably 10% by mass or less, more preferably 6% by mass or less, further preferably 5% by mass or less, even more preferably 4% by mass or less, particularly preferably 3% by mass or less, and further preferably 1% by mass. It is as follows.

Further, the mass ratio ((B)/(A)) of the content of the component (B) to the content of the component (A) in the cosmetic is an effect of stably retaining the component (B) in the cosmetic. From the viewpoint of improving the balance between the effect of the cosmetic and the sustained release of the component (B), it is preferably 0.01 or more, more preferably 0.1 or more, further preferably 0.2 or more, and It is more preferably 0.5 or more, preferably 100 or less, more preferably 50 or less, further preferably 20 or less, still more preferably 5 or less, and particularly preferably 1 or less.

In the present embodiment, from the viewpoint of enhancing the sustained release effect of the component (B), enhancing the dispersion stability of the component (A), and improving the compatibility of the cosmetic with the skin, the components (A) and The combination of (B) is preferably such that the average fiber diameter of the component (A) is 2 nm or more and 40 nm or less, the average fiber length is 800 nm or more and 10000 nm or less, and the IOB value of the component (B) is 0.90. Greater than or equal to 1.4 and less;
More preferably, the component (A) has an average fiber diameter and an average fiber length in the above ranges, an average aspect ratio of 250 or more and 300 or less, and the component (B) is methyl 4-hydroxybenzenecarboxylate or 4-hydroxybenzenecarboxylate. One or two selected from the group consisting of ethyl hydroxybenzenecarboxylate;
More preferably, the component (A) has an average fiber diameter and an average fiber length in the above ranges, an average aspect ratio of 250 or more and 300 or less, and the component (B) is methyl 4-hydroxybenzenecarboxylate, or Methyl 4-hydroxybenzenecarboxylate and ethyl 4-hydroxybenzenecarboxylate;
Even more preferably, the component (A) has an average fiber diameter and an average fiber length in the above ranges, an average aspect ratio of 250 or more and 300 or less, and the component (B) is methyl 4-hydroxybenzenecarboxylate. ..

In this embodiment, the cosmetic may contain components other than the above.
For example, the cosmetic may contain a dispersion medium such as water. The content of the dispersion medium such as water can be, for example, the balance of the cosmetic except components other than water.

Further, the cosmetic may contain a solvent (dispersion medium) other than water, and examples of such a solvent include alcohols having 1 to 4 carbon atoms such as ethanol and 2-propanol. From the viewpoint of improving the followability to the movement of the film formed by applying the cosmetic of the present embodiment to the skin, the content of the alcohol having 1 to 4 carbon atoms in the cosmetic is Is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, still more preferably 1% by mass or more, preferably 10% by mass or less, more preferably 8% by mass or less. , And more preferably 5 mass% or less.

In addition, in the present embodiment, the cosmetic contains a large amount of vitamins, deodorants, antiperspirants, cooling agents, fragrances, warming agents, glycerin, etc. within a range where a sustained release effect of the component (B) can be obtained. If necessary, components other than the components (A) and (B), such as a polyhydric alcohol or other moisturizers, oils, and pH adjusters, which are usually added to cosmetics, may be included.
From the viewpoint of improving the followability to the movement of the film formed by applying the cosmetic of the present embodiment to the skin, the content of the polyhydric alcohol in the cosmetic is preferably 0. 1% by mass or more, more preferably 1% by mass or more, further preferably 2% by mass or more, preferably 10% by mass or less, more preferably 8% by mass or less, further preferably 6% by mass. It is as follows.

Next, a method for manufacturing a cosmetic material according to this embodiment will be described.
The cosmetic in the present embodiment can be manufactured by a predetermined procedure depending on the form of the skin cosmetic. For example, the method for producing a cosmetic may include a step of dispersing the component (A) in a dispersion medium containing water to obtain a dispersion liquid, and a step of dissolving or dispersing the component (B) in the dispersion liquid. ..

The form of the obtained cosmetic can be a lotion, a solution, an emulsion, a cream, an ointment, a gel, and the like, and more specifically, an emulsion, a lotion, and a gel.
Further, it is preferable that the cosmetic material forms a film on the skin when applied to the skin.

Since the cosmetic of the present embodiment contains the specific components (A) and (B), it is excellent in the sustained release property of the component (B) after the cosmetic is applied to the skin.
More specifically, in the present embodiment, since the component (B) in the cosmetic material moderately interacts with the component (A), the component (B) is excessively applied immediately after the cosmetic material is applied to the skin. It is possible to suppress transient penetration at a high concentration. Therefore, the action of the cosmetic immediately after being applied to the skin can be made mild and, for example, excessive irritation to the skin can be suppressed. Although the detailed reason for this is not clear, the component (B) is a component (A) due to the interaction between the benzene ring of the hydroxybenzenecarboxylic acid or its derivative having a specific IOB value and the component (A), which is the component (A). This is probably because B) is trapped.
In addition, in the present embodiment, since the component (B) in the cosmetic material appropriately interacts with the component (A), the component (B) is gradually released from the cosmetic material. Therefore, after applying the cosmetic to the skin, the component (B) can be gradually absorbed through the skin over a long period of time. Therefore, the durability of the effect of the component (B) in the cosmetic can be obtained.

Moreover, since the cosmetic of this embodiment contains the components (A) and (B), the cosmetic applied to the skin can form a film on the skin. Further, according to the present embodiment, for example, it is possible to obtain a film having excellent abrasion resistance, being resistant to rubbing and scratching, and having a good feeling in use.
More specifically, according to the present embodiment, it is possible to form a film that is water resistant and strong against rubbing, for example, even when the cosmetic is a hydrophilic cosmetic. Therefore, it has excellent resistance to sweating and rubbing of the skin, and the action of the cosmetic on the skin can be maintained for a long time.
Further, by using the cosmetic of the present embodiment, for example, it is possible to form a strong film. For this reason, for example, rubbing of the skin by the collar is reduced, and it is possible to prevent the collar stain, that is, the adhesion of the skin horny layer melanin pigment, so that the collar stain preventing ability can be exhibited.
Further, by using the cosmetic of the present embodiment, for example, sweat generated after applying the cosmetic to the skin can be diffused into the film of the cosmetic. Then, the generated sweat spreads on the film of the cosmetic and wets the film of the cosmetic to increase the surface area of the sweat exposed to the outside air. Therefore, for example, it is possible to make the sweat excellent in quick-drying after sweating. It will be possible. Further, this also makes it possible to suppress body odor.

Next, a method of using the cosmetic will be described.
The method of using the cosmetic according to the present embodiment includes, for example, a step of applying the cosmetic to the skin, and preferably a step of applying the cosmetic to the skin. More specifically, the method of using the cosmetic may include the step of applying the cosmetic to the skin to form a film.
Further, the cosmetic material in the present embodiment may be used for forming a film on the skin.

The embodiments of the present invention have been described above, but these are examples of the present invention, and various configurations other than the above can be adopted.

First, in the following examples, the following materials were used as cellulose.
(Fibrous cellulose)
As the fibrous cellulose, the following components (A1) to (A6), (A'1) and (A'2) were used.
(A1) Fibrous carboxymethylated (CMized) cellulose: BiNFi-s TFO-10002, manufactured by Sugino Machine Limited (average fiber diameter: 20 nm, average fiber length: 1100 nm, average aspect ratio: 55, dispersion of 1 mass% Liquid viscosity: 800 mPa·s, transparency: 82%, carboxymethyl substitution degree: 2.16 mmol/g)
(A2) Fibrous carboxymethyl cellulose: average fiber diameter: 4 nm, average fiber length: 1000 nm, average aspect ratio: 250, viscosity of a 1% by weight dispersion liquid: 3900 mPa·s, transparency: 94%, carboxymethyl substitution Degree: 1.42 mmol/g, the manufacturing method will be described later.
(A3) Fibrous carboxymethylated cellulose: average fiber diameter: 25 nm, average fiber length: 900 nm, average aspect ratio: 36, viscosity of 1% by weight dispersion: 250 mPa·s, transparency: 54%, carboxymethyl substitution Degree: 1.31 mmol/g, and the manufacturing method is the same as in (A2).
(A4) Fibrous carboxymethylated cellulose: average fiber diameter: 10 nm, average fiber length: 2400 nm, average aspect ratio: 240, viscosity of a dispersion liquid of 1 mass% 900 mPa·s, transparency: 72%, carboxymethyl substitution degree : 1.62 mmol/g, and the manufacturing method is the same as in (A2).
(A5) Fibrous carboxymethyl cellulose: average fiber diameter: 30 nm, average fiber length: 8400 nm, average aspect ratio: 280, viscosity of dispersion liquid of 1 mass%: 4750 mPa·s, transparency: 46%, carboxymethyl substitution Degree: 1.72 mmol/g, and the manufacturing method is the same as in (A2).
(A6) Fibrous carboxyethylated (CE-ized) cellulose: average fiber diameter: 15 nm, average fiber length: 6000 nm, average aspect ratio: 400, viscosity of 1% by mass dispersion liquid: 4400 mPa·s, transparency: 72% , Carboxyethyl substitution degree: 1.92 mmol/g, and the production method will be described later.
(A′1) KMN-01: Oxidized cellulose fine fiber, manufactured by Kao Corporation (average fiber diameter: 3.3 nm, average fiber length: 830 nm, average aspect ratio: 251.5, viscosity of 1% by mass dispersion liquid: 2600 mPas) -S, transparency: 95%, carboxy group content: 1.4 mmol/g, the manufacturing method will be described later.)
(A'2) Serish FD-200L: Microfibrillated fibrous cellulose, manufactured by Daicel Finechem Co., Ltd. (average fiber length: 3 to 0.5 mm, viscosity of 1% by mass dispersion: 2000 mPa·s, transparency: 12%).
(Other cellulose)
The following components (A'3) to (A'5) were used as the other cellulose.
(A′3) Sunrose SLD-FM: fine powdery sodium carboxymethyl cellulose, manufactured by Nippon Paper Industries (average particle size: 20 μm)
(A′4) CMC Daicel 1190: Water-soluble carboxymethyl cellulose, manufactured by Daicel Finechem Co., Ltd. (viscosity of 1% by mass dispersion liquid: 1520 mPa·s, molecular weight: 680,000, carboxymethyl substitution degree: 3.45 mmol/g)
(A′5) HEC Daicel SE850: Water-soluble hydroxyethylated cellulose, manufactured by Daicel Finechem (viscosity of 1% by mass dispersion: 2800 mPa·s, average molecular weight: 1.15 million, degree of etherification: 1.3)

Of the above, the method for producing the fibrous carboxymethylated cellulose of the component (A2) is as follows.
To a stirrer with which pulp can be mixed, pulp (NBKP (softwood bleached kraft pulp) manufactured by Nippon Paper Industries Co., Ltd.) is added in a dry mass of 200 g, and sodium hydroxide is added in a dry mass of 111 g to give a pulp solid content of 20% (w/ v) was added. Then, after stirring for 30 minutes at 30° C., 216 g (as active ingredient conversion) of sodium monochloroacetate was added. After stirring for 30 minutes, the temperature was raised to 70° C. and the mixture was stirred for 1 hour. Then, the reaction product was taken out, neutralized and washed to obtain a carboxymethylated pulp having a degree of carboxymethyl substitution per glucose unit of 1.42 mmol/g. Then, the carboxymethylated pulp was made to have a solid content of 1% with water, and fibrillated by treating it with a high-pressure homogenizer 5 times at 20° C. and a pressure of 150 MPa to obtain fibrous carboxymethylated cellulose.
The obtained fibrous carboxymethylated cellulose had an average fiber length of 1000 nm, an average fiber diameter of 4 nm, and an average aspect ratio of 250.
Further, in the above production method, the fibrous carboxymethylated cellulose of the components (A3) to (A5) was obtained by changing the addition amount of sodium monochloroacetate and changing the treatment pressure of the high-pressure homogenizer.

The fibrous carboxyethylated cellulose of the above component (A6) is the same as that of the component (A2), except that 242 g of sodium 3-chloropropionate (active ingredient equivalent) is used in place of sodium monochloroacetate in the method for producing the above component (A2). ) Was manufactured according to the manufacturing method of.
The obtained fibrous carboxyethylated cellulose had an average fiber length of 6000 nm, an average fiber diameter of 15 nm, and an average aspect ratio of 400.

The method for producing the oxidized cellulose microfiber (KMN-01) of the above component (A′1) is as follows.
Bleached kraft pulp of conifer (Fletcher Challenge Canada, trade name "Machenzie", CSF 650 ml) was used as a natural cellulose fiber. As the TEMPO, a commercially available product (Free radical, 98 mass% manufactured by ALDRICH) was used. A commercially available product (manufactured by Wako Pure Chemical Industries, Ltd.) was used as sodium hypochlorite. A commercially available product (manufactured by Wako Pure Chemical Industries, Ltd.) was used as sodium bromide.
First, 100 g of bleached kraft pulp fiber of softwood was sufficiently stirred with 9900 g of ion-exchanged water, and then TEMPO 1.25% by mass, sodium bromide 12.5% by mass, sodium hypochlorite 28. 4 mass% was added in this order. Using a pH stat, 0.5 M sodium hydroxide was added dropwise to maintain the pH at 10.5, and an oxidation reaction was performed. After the oxidation reaction was carried out for 120 minutes, the dropping was stopped to obtain oxidized pulp. The oxidized pulp was thoroughly washed with ion-exchanged water, and then dehydrated. Then, 3.9 g of oxidized pulp and 296.1 g of ion-exchanged water were stirred for 10 minutes with a mixer (Vita-Mix-Blender ABSOLUTE, manufactured by Osaka Chemical Co., Ltd.). The fiber was refined by the operation to obtain a dispersion liquid of cellulose fine fibers. The solid content concentration of the dispersion was 1.3% by mass. This cellulose fine fiber had an average fiber diameter of 3.3 nm, an average fiber length of 830 nm, an average aspect ratio of 251.5, and a carboxy group content of 1.4 mmol/g.

The evaluation method of fibrous cellulose is shown below.
(Method for measuring the degree of substitution of carboxyalkyl group per anhydroglucose unit)
About 2.0 g of fibrous carboxyalkylated (CA-ized) cellulose (absolutely dried) was precisely weighed and put in a 300 mL Erlenmeyer flask with a stopper. 100 mL of a solution prepared by adding 100 mL of special grade concentrated nitric acid to 1000 mL of nitric acid methanol was added and shaken for 3 hours to convert the carboxyalkylated cellulose salt (CA-modified cellulose) into hydrogenated CA-modified cellulose. 1.5-2.0 g of hydrogenated CA cellulose (extra dried) was precisely weighed and put in a 300 mL Erlenmeyer flask with a ground stopper. The hydrogenated CA cellulose was wetted with 15 mL of 80% methanol, 100 mL of 0.1 N NaOH was added, and the mixture was shaken at room temperature for 3 hours. Excess NaOH was back titrated with 0.1 N H ₂ SO ₄ using phenolphthalein as an indicator. The degree of substitution (DS) was calculated by the following formula.
A=[(100×F′−(0.1 N H ₂ SO ₄ )(mL)×F)×0.1]/(absolute dry mass (g) of hydrogenated CA cellulose)
DS=0.162×A/(1-0.058×A)
A: 1N NaOH amount (mL) required for neutralizing 1 g of hydrogenated CA cellulose
F': 0.1N H ₂ SO ₄ factor F: 0.1N NaOH factor

(Examples 1 to 10, Comparative Examples 1 to 6)
The components shown in Table 1 were mixed at room temperature (25° C., the same applies below) to prepare a skin cosmetic, and the retained amount of the component in the cosmetic was evaluated. The evaluation results are also shown in Table 1.
A dispersion liquid was prepared by dispersing cellulose of any of the components (A1) to (A6) or (A′1) to (A′4) in water. The component (B) or (B′) was dissolved in the obtained dispersion liquid to obtain a sample. The concentration of each component in the sample is as shown in Table 1.
The obtained sample was filtered through a membrane filter (manufactured by ADVANTEC, DISMIC, PTFE membrane filter 25HPO45AN), and the concentration of the component (B) or (B′) contained in the obtained filtrate was measured. Further, the ratio of the component (B) or (B′) retained in the skin cosmetics of each example was calculated from the obtained quantitative value of the concentration by the following formula.
Retention amount (%) of component (B) or (B′)=(addition amount−quantitative value)/addition amount×100

From Table 1, it can be seen that the skin cosmetics obtained in each example are superior in the retention effect of the component (B) as compared with those in each comparative example.

(Examples 11 to 14, Comparative Examples 7 to 12)
The components shown in Table 2 were mixed at room temperature to prepare a skin cosmetic, and the usability of the cosmetic and the permeability of the components in the cosmetic to the skin were evaluated. The evaluation results are also shown in Table 2.
A dispersion liquid was prepared by dispersing the cellulose of any of the components (A1), (A2), (A4), (A6) or (A'2) to (A'5) in water. Ingredient (B) or (B') was dissolved in the obtained dispersion to obtain a skin cosmetic of each example. The concentration of each component in the cosmetic is as shown in Table 2.

The cosmetics obtained by one professional panelist were applied to the upper arm of a person (40 μL/4 cm ² ), and it was evaluated whether or not the cosmetics could be applied uniformly as the usability when applied to the skin.
In addition, 1 hour or 6 hours after application, after washing the cosmetic on the skin surface with a hot water bath, the component (B) or (B′) that has penetrated into the skin is recovered by the cup shake method (solvent: water). The content of the hydroxybenzenecarboxylic acid derivative contained in the recovered sample solution was quantified by high performance liquid chromatography (HPLC) by the method and conditions described below.
Then, the permeation amount (%) into the skin with respect to the applied amount of the component (B) or (B′) was calculated from the obtained quantitative value. Evaluations were made for the cases where the elapsed time after applying the cosmetic to the skin was 1 hour and 6 hours, respectively.

(HPLC measurement method)
(Measurement condition)
The following conditions were used using a high performance liquid chromatograph with an ultraviolet absorption detector.
Column: L-column ODS 5 μm, 4.6×150 mm (manufactured by Chemical Substance Evaluation Organization)
Column temperature: 40°C
Mobile phase: methanol/5 mmol L ^-1 citric acid (6:4)
Flow rate: 1.0 mL/min
Injection volume: 10 μL
Measurement wavelength: 254 nm
(Quantification method)
For each hydroxybenzenecarboxylic acid used in the examples or comparative examples, a calibration curve was prepared in advance under the above conditions.
Next, for each sample solution collected from the skin surface in each example, HLPC measurement was performed under the above conditions, and the concentration (μg/mL) of the hydroxybenzenecarboxylic acid derivative in the sample solution was determined using a calibration curve. Based on the formula, the hydroxybenzenecarboxylic acid derivative content (g/kg) was calculated.
Hydroxybenzenecarboxylic acid derivative content (g/kg)=C/(25×W)
(In the above formula, C is the concentration (μg/mL) of the hydroxybenzenecarboxylic acid derivative in the sample liquid, and W is the sampled amount (g) of the sample liquid (10 μL).)

From Table 2, the skin cosmetics obtained in each example were uniformly applied to the skin to form a film. Then, in the skin cosmetics obtained in each example, as compared with those in each comparative example, excessive penetration of the component (B) after 1 hour from application of the cosmetic to the skin was suppressed, It can be seen that the component (B) is continuously permeated 6 hours after the application of the dye to the skin.

Claims (4)

The following components (A) and (B):
(A) Fibrous carboxyalkylated cellulose,
(B) containing hydroxybenzenecarboxylic acid or a derivative thereof,
The component (A) has a carboxyalkyl-derived substituent derived from a carboxylic acid having a pKa of 4.70 or more and 4.90 or less in the hydroxyl groups at the 2, 3 or 6 positions of the cellulose skeleton,
The average fiber diameter of the component (A) is 2 nm or more and 40 nm or less,
The average fiber length of the component (A) is 800 nm or more and 10000 nm or less,
Ri der IOB value is 0.97 to 2.0 of the component (B),
Wherein Ru Der mass ratio of the content ((B) / (A) ) is 0.1 or more 1.33 or less of the component (B) to the content of the component (A), skin cosmetics. The skin cosmetic according to claim 1, wherein the component (A) contains fibrous carboxymethylated cellulose or fibrous carboxyethylated cellulose. The skin cosmetic according to claim 1 or 2 , wherein the component (B) is one or more selected from the group consisting of hydroxybenzenecarboxylic acid, hydroxybenzenecarboxylic acid ester and salts thereof. A method of using a skin cosmetic, comprising the step of applying the skin cosmetic according to any one of claims 1 to 3 to the skin.