JP2020019820A - Skin cosmetics - Google Patents

Abstract

An object of the present invention is to provide a skin cosmetic which improves emulsifying power and emulsifying stability and has excellent water resistance of a film when applied to skin or the like.
The component (A) contains a fine cellulose fiber composite, the component (B) contains an oil having an SP value of 7.2 to 15 and the component (C) water, and the component (A) has a carboxy group content of 0.1%. A fine cellulose fiber composite comprising an amine having an ethylene oxide / propylene oxide (EO / PO) copolymerized part in a carboxy group of 1 to 3 mmol / g of fine cellulose fiber, which is bound as a salt, A skin cosmetic wherein the molecular weight of the copolymer is from 600 to 10,000 and the content of PO in the EO / PO copolymer is from 6 to 80 mol%.
[Selection diagram] None

Description

  The present invention relates to skin cosmetics.

As a technique using cellulose fibers as a thickener, there is a technique described in Patent Document 1 (Japanese Patent Application Laid-Open No. 2012-126786).
Patent Document 1 discloses a technique for solving the problem of providing a viscous aqueous composition having excellent shape retention, dispersion stability, salt resistance, and the like, and excellent emulsion stability. A cellulose fiber having a water average fiber diameter, a carboxyl group content, and a crystal structure, wherein the carboxyl group is a salt with a monoamine having an organic value of 300 or less in an organic conceptual diagram and a viscosity containing water. Aqueous compositions have been described.

JP 2012-126786 A

  However, the technique of Patent Document 1 described above still has room for improvement in improving the emulsifying power and the emulsifying stability and improving the water resistance of the film when applied to the skin or the like.

The present invention
The following components (A) to (C):
(A) a fine cellulose fiber composite,
(B) a skin cosmetic containing an oil having an SP value of 7.2 to 15 and (C) water,
The component (A) is characterized in that an amine having an ethylene oxide / propylene oxide (EO / PO) copolymer is bonded as a salt to a carboxy group of a fine cellulose fiber having a carboxy group content of 0.1 to 3 mmol / g. The EO / PO copolymer has a molecular weight of 600 to 10,000, and the PO content in the EO / PO copolymer is 6 to 80 mol%. And skin cosmetics.

  ADVANTAGE OF THE INVENTION According to this invention, the emulsification power and emulsification stability are improved, and the skin cosmetics which are excellent in the water resistance of a film when applied to skin etc. can be provided.

Hereinafter, embodiments of the present invention will be described.
In the present embodiment, the skin cosmetic is a composition containing the following components (A) to (C).
(A) Fine cellulose fiber composite (B) Oil agent with SP value of 7.2 to 15 (C) Water Hereinafter, each component will be described with specific examples. Each component can be used alone or in combination of two or more.

(Component (A))
The fine cellulose fiber composite of the component (A) is a fine cellulose fiber having a carboxy group content of 0.1 to 3 mmol / g, and an amine having an ethylene oxide / propylene oxide (EO / PO) copolymerized portion at the carboxy group. Are combined as a salt. And the molecular weight of the said EO / PO copolymer part is 600-10,000, and the content of PO in the EO / PO copolymer part is 6-80 mol%.
In the present specification, "an amine having an ethylene oxide / propylene oxide (EO / PO) copolymer moiety bonded to a carboxy group as a salt" means that a carbon atom is bonded to a carboxy group covalently bonded to a cellulose skeleton. It means a state in which the EO / PO copolymer portion is ion-bonded via the amine salt.
Hereinafter, the fine cellulose fibers constituting the component (A) will be described more specifically.

<Fine cellulose fiber>
(Number average fiber diameter)
The number average fiber diameter of the fine cellulose fibers constituting the fine cellulose fiber composite of the component (A) is preferably at least 0.1 nm from the viewpoint of enabling the skin cosmetic to form a film having excellent water resistance. , More preferably 0.2 nm or more, still more preferably 0.5 nm or more, even more preferably 0.8 nm or more, particularly preferably 1 nm or more. In addition, from the same viewpoint, it is preferably 200 nm or less, more preferably 100 nm or less, still more preferably 50 nm or less, still more preferably 20 nm or less, particularly preferably 10 nm or less, and still more preferably 5 nm or less.
In the present specification, the number average fiber diameter of the fine cellulose fiber and the fine cellulose fiber composite described later can be measured using an atomic force microscope (AFM). Is measured by the method described in Examples described later. In general, in the minimum unit of cellulose nanofiber prepared from higher plants, 6 × 6 molecular chains are packed in a substantially square shape, so the height analyzed by the AFM image is defined as the fiber width. Can be.

(Carboxy group content)
The carboxy group content of the fine cellulose fiber is an important factor for stably obtaining a cellulose fiber having a fine fiber diameter. In the present embodiment, the carboxy group content in the fine cellulose fiber is 0.1 mmol / g or more, preferably 0.4 mmol / g or more, and more preferably, from the viewpoint of improving the dispersion stability of the cellulose fiber. It is 0.6 mmol / g or more, more preferably 0.8 mmol / g or more. In addition, from the viewpoint of improving the handleability of the fine cellulose fiber, the carboxy group content in the fine cellulose fiber is 3 mmol / g or less, preferably 2.5 mmol / g or less, more preferably 2 mmol / g or less, and still more preferably. Is 1.8 mmol / g or less.
It should be noted that the fine cellulose fibers used in the present embodiment may unintentionally include fine cellulose fibers having a carboxy group content outside the above range as impurities.
The term "carboxy group content" refers to the total amount of carboxy groups in the cellulose constituting the fine cellulose fibers, and is specifically measured by the method described in Examples described later.

(Average aspect ratio)
The average aspect ratio (fiber length / fiber diameter) of the fine cellulose fiber is preferably 10 or more, more preferably 20 or more, and still more preferably, from the viewpoint of enabling the skin cosmetic to form a film having excellent water resistance. Is 50 or more, even more preferably 100 or more. From the same viewpoint, the average aspect ratio of the fine cellulose fiber is preferably 1,000 or less, more preferably 500 or less, further preferably 400 or less, and even more preferably 350 or less.

  In the present specification, the average aspect ratio of the fine cellulose fiber is determined by the following formula (A) from the relationship between the concentration of the cellulose fiber in the dispersion liquid in which the fine cellulose fiber is dispersed in water and the specific viscosity of the dispersion liquid to water. To calculate the aspect ratio of the cellulose fiber in reverse.

[In the above formula (A), η _SP is specific viscosity, π is pi, ln is natural logarithm, P is aspect ratio (fiber length L / fiber width b), γ = 0.8, ρ _S is dispersion medium density of ^{(kg / m 3), ρ} 0 is the density of cellulose crystal (kg / m ^3), C represents the mass concentration of cellulose _{(C = ρ / ρ S)} . ]

The above formula (A), The Theory of Polymer Dynamics, M.DOI and DFEDWARDS, CLARENDON PRESS · OXFORD, 1986, viscosity equation of rigid-rod molecules described P.312 and (8.138), Lb ² × [rho = relation M / N _a wherein, L is the fiber length, b is the fiber width (here, cellulose fiber cross section is a square.), [rho is the cellulose fiber concentration (kg / m ^3), M is molecular weight, _{N a} represents Avogadro's number. ] Is derived from In the above viscosity formula (8.138), the rigid rod-like molecules are cellulose fibers.

(Crystallinity)
The crystallinity of the fine cellulose fiber is preferably 30% or more, more preferably 35% or more, still more preferably 40% or more, and still more preferably 45% or more, from the viewpoint of improving the handleability of the fine cellulose fiber. It is. In addition, from the viewpoint of improving the binding efficiency of ionic bonds, the crystallinity of the fine cellulose fiber is preferably 90% or less, more preferably 85% or less, and further preferably 80% or less.
In addition, in this specification, the crystallinity of cellulose is a cellulose I-type crystallinity calculated by the Segal method from a diffraction intensity value by an X-ray diffraction method, and is defined by the following formula (B).
Cellulose type I crystallinity (%) = [(I _22.6 −I _18.5 ) / I _22.6 ] × 100 (B)
[In the above formula (B), I _22.6 is the diffraction intensity of the lattice plane (002 plane) (diffraction angle 2θ = 22.6 °) in X-ray diffraction, and I _18.5 is the amorphous portion (diffraction angle 2θ = 18.5). °) is shown. ]
In addition, the cellulose I type refers to a crystalline form of natural cellulose, and the cellulose I type crystallinity means a ratio occupied by a crystal region amount in the whole cellulose.

  Next, the configuration of the amine that binds as a salt to the carboxy group of the fine cellulose fiber in the fine cellulose fiber composite is described.

<Amine having EO / PO copolymerization part>
In the fine cellulose fiber composite of the present embodiment, the carboxy group of the fine cellulose fibers is ion-bonded to the amine having the EO / PO copolymer. Therefore, the amine in the present embodiment may be any of primary amines, secondary amines, and tertiary amines as long as it is substituted by the EO / PO copolymer part. From the viewpoint of properties, primary amines or secondary amines are preferred.

(EO / PO copolymerization section)
The EO / PO copolymer portion means a structure in which ethylene oxide (EO) and propylene oxide (PO) are polymerized in a random or block manner. For example, when the amine is represented by the following general formula (1) or (2), ethylene oxide (EO) and propylene oxide (PO) have a random or block-like chain structure. When the amine is an amine having a structure represented by the following general formula (3), (EO) e (PO) f, (EO) g (PO) h, and (EO) i (PO) ) J need not be chained.

  The PO content (mol%) in the EO / PO copolymer part is at least 6 mol%, preferably at least 12 mol%, more preferably at least 15 mol, from the viewpoint of improving the emulsion stability of the skin cosmetic. % Or more, more preferably 20% or more, and from the same viewpoint, it is 80% or less, preferably 70% or less, more preferably 55% or less, still more preferably 45% or less, and even more preferably. It is preferably at most 35 mol%.

The molecular weight of the EO / PO copolymer is at least 600, preferably at least 1,000, more preferably at least 1,500 from the viewpoint of improving the emulsion stability of the skin cosmetic, and from the same viewpoint, It is 10,000 or less, preferably 7,000 or less, more preferably 5,000 or less, still more preferably 4,000 or less, and even more preferably 3,000 or less.
Here, when the amine having an EO / PO copolymer is, for example, an amine having a structure represented by the following general formula (3), (EO) e (PO) f + (EO) g (PO ) Let the total molecular weight of h + (EO) i (PO) j be the molecular weight of the EO / PO copolymer. The PO content (mol%) in the EO / PO copolymer part and the molecular weight of the EO / PO copolymer part can be determined by calculating from the average number of moles added when producing the amine.

  The EO / PO copolymer and the amine are preferably bonded directly or via a linking group. As the linking group, a hydrocarbon group is preferable, and an alkylene group having preferably 1 to 6, more preferably 1 to 3 carbon atoms is used. For example, an ethylene group and a propylene group are preferable.

  Examples of the amine having such an EO / PO copolymer include those represented by the following general formulas (1) to (3).

[In the general formula (1), R ₁ represents a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, EO and PO are present randomly or in a block, and a is an average of EO. It is a positive number indicating the number of moles added, and b is a positive number indicating the average number of moles of PO added. ]

[In the above general formula (2), EO and PO are present at random or in a block shape, c represents an average number of moles of EO added, and independently represents a number of 1 to 70, and d represents an average number of PO. The number of moles added is independently 1 to 70. ]

[In the above general formula (3), n is 0 or 1, R ₂ represents a hydrogen atom or a linear or branched alkyl group having 1 to 3 carbon atoms, and EO and PO are randomly or Where e, g and i represent the average number of moles of EO and are independently a number from 1 to 50; f, h and j represent the average number of moles of PO and are independently 1 ~ 50. ]

Among these amines, the compound represented by the general formula (1) is preferable.
In the above general formula (1), a represents the average number of moles of EO added, and from the viewpoint of improving the emulsion stability of the skin cosmetic, and improving the water resistance of the skin cosmetic film applied to the skin and the like. From the viewpoint, it is preferably 1 or more, more preferably 11 or more, further preferably 15 or more, still more preferably 20 or more, particularly preferably 25 or more, and from the same viewpoint, preferably 100 or less. , More preferably 70 or less, still more preferably 60 or less, and even more preferably 55 or less.

  In the above general formula (1), b represents the average number of moles of PO added, from the viewpoint of improving the emulsion stability of the skin cosmetic and the water resistance of the skin cosmetic coating applied to the skin and the like. From the viewpoint of improvement, it is preferably 1 or more, more preferably 2 or more, and still more preferably 3 or more, and from the same viewpoint, preferably 50 or less, more preferably 40 or less, and still more preferably 30 or less. Hereinafter, it is even more preferably 25 or less, particularly preferably 20 or less, still more preferably 18 or less, and still more preferably 15 or less.

Further, when the amine is represented by the above general formula (1), the content (mol%) of PO in the EO / PO copolymerized section is determined from the a and b described above. The rate can be calculated, and can be obtained from the formula: b × 100 / (a + b).
When the amine is represented by the above general formula (2), the content (mol%) of PO in the EO / PO copolymer part can be similarly obtained from the formula: d × 100 / (c + d). Out.
When the amine is represented by the above general formula (3), the content (mol%) of PO in the EO / PO copolymer is similarly calculated by the formula: (f + h + j) × 100 / (e + f + g + h + i + j) More can be obtained.
The preferred range of the PO content is as described above.

R ₁ in the above general formula (1) represents a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, or a —CH ₂ CH (CH ₃ ) NH ₂ group. A hydrogen atom is preferred from the viewpoint of improving the water content and the water resistance of the skin cosmetic film applied to the skin and the like. The linear or branched alkyl group having 1 to 6 carbon atoms is preferably a methyl group, an ethyl group, an iso or normal propyl group.

  In the above general formula (2), c indicates the average number of moles of EO added, and from the viewpoint of improving the emulsion stability of the skin cosmetic, and improving the water resistance of the skin cosmetic film applied to the skin and the like. From the viewpoint, it is preferably 1 or more, more preferably 5 or more, still more preferably 11 or more, even more preferably 15 or more, particularly preferably 20 or more, and still more preferably 25 or more. From the viewpoint, it is preferably 70 or less, more preferably 50 or less. In the general formula (2), d represents the average number of moles of PO added, and the viewpoint of improving the emulsion stability of the skin cosmetic and the water resistance of the skin cosmetic coating applied to the skin and the like. From the viewpoint of improvement, it is preferably 1 or more, more preferably 2 or more, and still more preferably 3 or more, and from the same viewpoint, preferably 70 or less, more preferably 50 or less, and further more preferably Is 40 or less, even more preferably 30 or less, still more preferably 25 or less, particularly preferably 20 or less, still more preferably 15 or less, and still more preferably 10 or less.

In the general formula (3), the linear or branched alkyl group having 1 to 3 carbon atoms of R ₂ is preferably a methyl group or an ethyl group. When R ₂ is a methyl group or an ethyl group, n is preferably 1, and when R ₂ is a hydrogen atom, n is preferably 0.
In the above general formula (3), i represents the average number of moles of EO added, and the viewpoint of improving the emulsion stability of the skin cosmetic and the viewpoint of improving the water resistance of the skin cosmetic film applied to the skin and the like. Therefore, it is preferably 1 or more, more preferably 5 or more, still more preferably 11 or more, still more preferably 15 or more, particularly preferably 20 or more, and still more preferably 25 or more, and the same viewpoint. Therefore, it is preferably 50 or less.
In the general formula (3), j represents the average number of moles of PO added, from the viewpoint of improving the emulsion stability of the skin cosmetic and the viewpoint of improving the water resistance of the skin cosmetic film applied to the skin and the like. Therefore, it is preferably 1 or more, more preferably 2 or more, further preferably 3 or more, and from the same viewpoint, preferably 50 or less, more preferably 40 or less, still more preferably 30 or less, and It is more preferably 25 or less, particularly preferably 20 or less, still more preferably 15 or less, and even more preferably 10 or less.
In the formula (3), e and g are independently preferably 1 to 30, more preferably 10 to 30, and f and h are independently and preferably 1 to 25. More preferably, it is 5 to 25.

  The amine having an EO / PO copolymer moiety represented by the general formulas (1) and (2) can be prepared according to a known method. For example, a desired amount of ethylene oxide or propylene oxide may be added to propylene glycol alkyl ether, and then the terminal of the hydroxyl group may be aminated. If necessary, the terminal can be made a hydrogen atom by cleaving the alkyl ether with an acid. JP-A-3-181448 and the like can be referred to for the production method thereof.

  Commercially available products are also suitably used as the amine having an EO / PO copolymerization unit. Specific examples thereof include Jeffamine M-2070, Jeffamine M-2005, Jeffamine M-1000, Surfamine B200, and Surfamine L100 manufactured by HUNTSMAN. , Surfoamine L200, Surfoamine L207, Surfoamine L300, XTJ-501, XTJ-506, XTJ-507, XTJ-508; 4000, XTJ-510, Jeffamine T-3000, Jeffamine T-50 0, XTJ-502, XTJ-509, XTJ-510 and the like. These may be used alone or in combination of two or more.

The binding amount of the amine salt in the fine cellulose fiber composite is improved from the viewpoint of improving the handleability of the fine cellulose fiber composite, the viewpoint of improving the emulsion stability of the skin cosmetic, and the skin cosmetic applied to the skin and the like. From the viewpoint of improving the water resistance of the film, it is preferably 0.01 mmol / g or more, more preferably 0.05 mmol / g or more, further preferably 0.1 mmol / g or more, and still more preferably 0.3 mmol / g. The above is particularly preferably 0.5 mmol / g or more, more preferably 0.8 mmol / g or more. Further, from the viewpoint of reactivity at the time of ionic bonding, the binding amount of the amine salt in the fine cellulose fiber composite is preferably 3 mmol / g or less, more preferably 2 mmol / g or less, and still more preferably 1.5 mmol / g or less. g or less. The binding amount of the amine salt can be adjusted by the amount of the amine added, the type of the amine, the reaction temperature, the reaction time, the solvent, and the like.
In the present embodiment, the amount of amine salt bonded can be determined by infrared spectroscopy (Infrared (IR) Spectroscopy), and specifically, is determined by a method described in Examples described later.

<Production method of fine cellulose fiber composite>
The fine cellulose fiber composite can be produced according to a known method without limitation, as long as the EO / PO copolymer can be introduced into the fine cellulose fiber via ionic bonding. For example, a reaction of introducing an EO / PO copolymerized portion into fine cellulose fibers prepared in advance through an ionic bond may be carried out. A reaction for introducing a / PO copolymer portion may be performed. The fine cellulose fibers can be produced by a known method, for example, a method described in JP-A-2011-140632 or the like.

A preferred production method includes, for example, a production method including the following step (i) and step (ii).
Step (i): oxidizing natural cellulose fibers in the presence of an N-oxyl compound to obtain carboxy group-containing cellulose fibers Step (ii): carboxy group-containing cellulose fibers obtained in step (i) and EO / Step of mixing with an amine having a PO copolymer portion As a preferred production method, more specifically, a step of micronizing described below is performed after step (i) to obtain a carboxy group-containing fine cellulose fiber. There is a method of performing (ii) (first manufacturing mode), and a method of performing step (ii) after step (i) and then performing a miniaturization step (second manufacturing mode).

  Hereinafter, a method for producing a fine cellulose fiber composite will be described based on the above-mentioned "first production mode".

(Step (i))
Step (i) is a step of oxidizing natural cellulose fibers in the presence of an N-oxyl compound to obtain carboxy group-containing cellulose fibers.

  In the step (i), first, a slurry in which natural cellulose fibers are dispersed in water is prepared. The slurry is prepared by adding about 10 to 1000 times (by mass) water with respect to natural cellulose fibers as raw materials (absolute drying basis: mass of natural cellulose fibers after heating and drying at 150 ° C. for 30 minutes), It is obtained by processing with a mixer or the like. Examples of the natural cellulose fiber include wood pulp such as softwood pulp and hardwood pulp; cotton pulp such as cotton linter and cotton lint; non-wood pulp such as straw pulp and bagasse pulp; and bacterial cellulose. One of these can be used alone or in combination of two or more. The natural cellulose fiber may be subjected to a treatment such as beating to increase the surface area. The cellulose crystallization degree of the commercially available pulp is usually 80% or more.

(Oxidation treatment step)
Next, the natural cellulose fiber is oxidized in the presence of an N-oxyl compound to obtain a carboxy group-containing cellulose fiber (hereinafter sometimes simply referred to as “oxidation treatment”).

  Examples of the N-oxyl compound include one or more heterocyclic N-oxyl compounds selected from piperidineoxyl compounds having a C1 or C2 alkyl group, pyrrolidineoxyl compounds, imidazoline oxyl compounds, and azaadamantane compounds. preferable. Among these, from the viewpoint of reactivity, a piperidineoxyl compound having an alkyl group having 1 or 2 carbon atoms is preferable, and 2,2 such as 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) is preferable. , 6,6-tetraalkylpiperidine-1-oxyl and 4-hydroxy-2,2,6,6-tetraalkylpiperidine- such as 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl. 4-alkoxy-2,2,6,6-tetraalkylpiperidine-1-oxyl such as 1-oxyl, 4-methoxy-2,2,6,6-tetramethylpiperidine-1-oxyl, 4-benzoyloxy- 2,2,6,6-tetraalkylpiperidine-1-oxyl, 4-amino-2,2,6,6-tetraalkylpiperidine-1-oxyl and the like -tert- alkyl nitroxyl compound, 4-acetamido -TEMPO, 4-carboxy -TEMPO, 4 Hosufonokishi -TEMPO and the like. Among these piperidineoxyl compounds, 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO), 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl, Methoxy-2,2,6,6-tetramethylpiperidine-1-oxyl is more preferred, and 2,2,6,6 tetramethylpiperidine-1-oxyl (TEMPO) is even more preferred.

  The amount of the N-oxyl compound is not limited as long as it functions as a catalyst, and is preferably 0.001 to 10% by mass, more preferably 0.01 to 10% by mass, based on natural cellulose fibers (absolute dry basis). It is 9% by mass, more preferably 0.1 to 8% by mass, still more preferably 0.5 to 5% by mass.

  In the oxidation treatment of the natural cellulose fiber, an oxidizing agent can be used. As the oxidizing agent, oxygen or air, peroxide, halogen, hypohalous acid, halogenous acid, perhalic acid and alkali metal thereof from the viewpoint of solubility and reaction rate when the solvent is adjusted to an alkaline region. Salts or alkaline earth metal salts, halogen oxides, nitrogen oxides and the like. Among these, alkali metal hypohalites are preferable, and specific examples thereof include sodium hypochlorite and sodium hypobromite. The amount of the oxidizing agent to be used may be selected according to the degree of carboxy group substitution (degree of oxidation) of the natural cellulose fiber, and cannot be unconditionally determined because the oxidation reaction yield varies depending on the reaction conditions. It can be in the range of about 1 to 100% by mass based on cellulose fibers (absolute dry basis).

  Further, in order to carry out the oxidation reaction more efficiently, a bromide such as sodium bromide or potassium bromide, or an iodide such as sodium iodide or potassium iodide can be used as a co-catalyst. The amount of the cocatalyst may be any effective amount capable of exerting its function, and is not limited.

  The reaction temperature in the oxidation treatment is preferably 50 ° C. or lower, more preferably 40 ° C. or lower, further more preferably 20 ° C. or lower, from the viewpoint of increasing the selectivity of the reaction and suppressing the side reaction. Is preferably −5 ° C. or higher.

  Further, the pH of the reaction system is preferably adjusted to the properties of the oxidizing agent. For example, when sodium hypochlorite is used as the oxidizing agent, the pH of the reaction system is preferably on the alkaline side, and is preferably pH 7 to 13. pH 10 to 13 is more preferred. The reaction time is preferably from 1 to 240 minutes.

  By performing the above-described oxidation treatment, a carboxy group-containing cellulose fiber having a carboxy group content in the range of 0.1 to 3 mmol / g can be obtained.

(Purification process)
The carboxy group-containing cellulose fiber obtained by the above-described oxidation reaction contains an N-oxyl compound such as TEMPO or a by-product salt used as a catalyst. Although the next step may be performed as it is, purification may be performed to obtain a carboxy group-containing cellulose fiber having high purity. As the purification method, an optimal method can be adopted depending on the type of the solvent in the oxidation reaction, the degree of oxidation of the product, and the degree of purification. For example, reprecipitation using water as a good solvent and methanol, ethanol, acetone or the like as a poor solvent, extraction of TEMPO or the like into a solvent that separates with water such as hexane, and ion exchange of salts, purification by dialysis, etc. No.

(Miniaturization process)
In the first production mode, after the above-described purification step, a step of miniaturizing the carboxy group-containing cellulose fiber obtained in step (i) is performed. In the miniaturization step, it is preferable to disperse the carboxy group-containing cellulose fiber that has undergone the above-described purification step in a solvent and perform a micronization treatment. By carrying out this refining step, a fine cellulose fiber having a number-average fiber diameter and an average aspect ratio in the above-mentioned ranges is obtained.

  Solvents as a dispersion medium include water, alcohols having 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms such as methanol, ethanol, and propanol; ketones having 3 to 6 carbon atoms such as acetone, methyl ethyl ketone, and methyl isobutyl ketone. Linear or branched saturated or unsaturated hydrocarbons having 1 to 6 carbon atoms; aromatic hydrocarbons such as benzene and toluene; halogenated hydrocarbons such as methylene chloride and chloroform; Alkyl ethers; polar solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide, and methyltriglycol diester succinate; These can be used alone or as a mixture of two or more, but from the viewpoint of the operability of the miniaturization treatment, water, alcohol having 1 to 6 carbon atoms, ketone having 3 to 6 carbon atoms, and 2 carbon atoms are preferable. To 5 lower alkyl ethers, polar solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide and methyltriglycol diester succinate are preferred, and water is more preferred from the viewpoint of reducing environmental load. The amount of the solvent used is not particularly limited as long as it is an effective amount capable of dispersing the carboxy group-containing cellulose fiber, but is preferably 1 to 500 times by mass, more preferably 2 to 200 mass times, based on the carboxy group-containing cellulose fiber. Use twice.

  In addition, a known disperser is suitably used as an apparatus used in the fine processing. For example, a disintegrator, a beater, a low-pressure homogenizer, a high-pressure homogenizer, a grinder, a cutter mill, a ball mill, a jet mill, a short-screw extruder, a twin-screw extruder, an ultrasonic stirrer, and a household juicer mixer can be used. Further, the solid content concentration of the reactant fiber in the micronization treatment is preferably 50% by mass or less.

  As the form of the carboxy group-containing fine cellulose fibers obtained after the micronization step, if necessary, a suspension in which the solid content concentration is adjusted (visually colorless, transparent or opaque liquid), or a dried powder (however, It is in the form of a powder in which fine cellulose fibers are agglomerated, and does not mean cellulose particles.) When the suspension is used, only water may be used as a dispersion medium, and a mixed solvent of water and another organic solvent (for example, alcohols such as ethanol) or a surfactant, an acid, or a base may be used. May be used.

  By such an oxidizing treatment and a micronizing treatment of the natural cellulose fiber, the hydroxyl group at the C6 position of the cellulose constituent unit is selectively oxidized to a carboxy group via an aldehyde group, and the carboxy group content is 0.1 to 3 mmol. / G of cellulose, preferably having a number average fiber diameter of 0.1 to 200 nm and having a fineness, preferably having a crystallinity of 30% or more. Here, the carboxy group-containing fine cellulose fiber (also referred to as “carboxy group-containing fine cellulose fiber” in this specification) has a cellulose I-type crystal structure. This means that the carboxy group-containing fine cellulose fibers used in the present embodiment are fibers obtained by oxidizing the surface of a naturally-derived cellulose solid raw material having an I-type crystal structure and miniaturizing the same. In step (i), after the natural cellulose fiber is oxidized, the carboxy group content can be adjusted by further reacting with an acid (for example, hydrochloric acid). May be performed in any of the above.

(Step (ii))
In the first production mode, the step (ii) is a step of mixing the carboxy group-containing fine cellulose fiber obtained through the above-described fine step with an amine having an EO / PO copolymer to form a fine cellulose fiber composite. This is the step of obtaining Specifically, a carboxy group-containing fine cellulose fiber and an amine having an EO / PO copolymer are mixed in a solvent.

  Examples of the amine having an EO / PO copolymer used in the step (ii) include those described above in the fine cellulose fiber composite.

  The amount of the amine to be used can be determined depending on the amount of the desired amine salt bound in the fine cellulose fiber composite, but from the viewpoint of reactivity, the amine is added to 1 mol of the carboxy group contained in the carboxy group-containing fine cellulose fiber. The group is preferably at least 0.1 mol, more preferably at least 0.5 mol, even more preferably at least 0.7 mol, and from the viewpoint of improving product purity, preferably at most 50 mol, more preferably at most 20 mol. More preferably, the amount is 10 mol or less. The amount of the amine contained in the above range may be supplied to the reaction at once, or may be divided and supplied to the reaction. When the amine is a monoamine, the above amine group and the amine are the same.

  As the solvent, it is preferable to select a solvent in which the amine to be used is dissolved. For example, ethanol, isopropanol, N, N-dimethylformamide (DMF), dimethylsulfoxide (DMSO), N, N-dimethylacetamide, tetrahydrofuran (THF) , Succinic acid methyltriglycol diester, acetone, methyl ethyl ketone (MEK), acetonitrile, dichloromethane, chloroform, toluene, acetic acid, etc., and these can be used alone or in combination of two or more. Among these polar solvents, methyl succinate triglycol diester, ethanol and DMF are preferred.

  The temperature at the time of mixing is preferably 0 ° C. or higher, more preferably 5 ° C. or higher, and still more preferably 10 ° C. or higher, from the viewpoint of improving the reactivity of the amine. In addition, from the viewpoint of suppressing the coloring of the fine cellulose fiber composite, the temperature during mixing is preferably 50 ° C or lower, more preferably 40 ° C or lower, and further preferably 30 ° C or lower. The mixing time can be appropriately set according to the type of the amine and the solvent to be used, but from the viewpoint of improving the reactivity of the amine, is preferably 0.01 hour or more, more preferably 0.1 hour or more, and still more preferably. Is 1 hour or more, preferably 48 hours or less, more preferably 24 hours or less.

  After the formation of the salt, post-treatment may be appropriately performed to remove unreacted amine, condensing agent and the like. As a method of the post-treatment, for example, filtration, centrifugation, dialysis and the like can be used.

  In the second manufacturing mode, the steps described above can be performed by a method according to the first manufacturing mode except that the steps (i), (ii), and the miniaturization step are performed in this order.

  The fine cellulose fiber composite thus obtained can be used as a component in skin cosmetics in the form of a dispersion after post-treatment, or by removing a solvent from the dispersion by a drying treatment or the like. It is also possible to obtain a dried powdery fine cellulose fiber composite and use it. Here, “powder” is a powder form in which the fine cellulose fiber composite is aggregated, and does not mean cellulose particles.

  Examples of the powdery fine cellulose fiber composite include a dried product obtained by drying a dispersion of the fine cellulose fiber composite as it is; a product obtained by pulverizing the dried product by mechanical treatment; and a dispersion of the fine cellulose fiber composite. Powdered powders by a known spray-drying method; powdered powders of a dispersion of fine cellulose fiber composites by a known freeze-drying method; The spray drying method is a method in which a dispersion liquid of a fine cellulose fiber composite is sprayed in the air and dried.

  The number average fiber diameter of the obtained fine cellulose fiber composite is preferably 0.1 nm or more, more preferably 0.2 nm or more, from the viewpoint of allowing the skin cosmetic to form a film having excellent water resistance. More preferably, it is at least 0.5 nm, even more preferably at least 0.8 nm, particularly preferably at least 1 nm. Further, from the viewpoint of improving the water resistance when applied to the skin, more specifically, from the viewpoint of improving the water resistance of the formed film, the number average fiber diameter of the fine cellulose fiber composite is preferably 200 nm or less. Yes, more preferably 100 nm or less, still more preferably 50 nm or less, even more preferably 20 nm or less, particularly preferably 10 nm or less.

  Note that the fine cellulose fiber composite preferably has the same degree of crystallinity as that of the fine cellulose fiber, since the crystallinity does not decrease due to the reaction in step (ii).

  As described above, the fine cellulose fiber composite contained in the skin cosmetic of the present embodiment is obtained by ion-bonding the EO / PO copolymer to the fine cellulose fiber via an amine salt, as described above. Those having a diameter of 0.1 to 200 nm are preferred.

In the present embodiment, the content of the component (A) in the skin cosmetic is, for example, 0.1 mass with respect to the entire skin cosmetic from the viewpoint of enabling the skin cosmetic to form a film having excellent water resistance. % Or more, preferably 0.2% by mass or more, more preferably 0.3% by mass or more, even more preferably 0.5% by mass or more.
In addition, from the viewpoint of enabling the skin cosmetic to form a film having excellent water resistance and optimizing the feeling of use of the skin cosmetic, the content of the component (A) in the skin cosmetic is controlled by the skin cosmetic. It is, for example, 4% by mass or less, preferably 3% by mass or less, more preferably 2% by mass or less, even more preferably 1.5% by mass or less based on the whole.

Next, the component (B) will be described.
(Component (B))
Component (B) is an oil having an SP value of 7.2 to 15 (cal / cm ³ ) ^1/2 .
The SP value is a solubility parameter δ and is a material constant given by δ = (E / V) ^1/2 (J / cm ³ ) from the molecular cohesion energy E and the molecular volume V of the liquid. From this value, the relative polarity of the substance can be estimated. The SP value is determined by actual measurement or calculation by various methods. In the present embodiment, according to the method of Fedors, J. BRANDR UP al "POLYMER HANDBOOK-4 ^th" (JHON WILEY & SONS, issued INC 1999 years), determined using the parameters given in Section VII685～686.
In this embodiment, when the oil agent is a mixture, the SP value of the oil agent of the component (B) is obtained as a weighted average, that is, the sum of the product of the SP value of each component and the mass fraction. In addition, for natural substances and polymers whose structural formula cannot be specified, the SP value is calculated according to the representative structure.

The SP value of the component (B) is 7.2 or more, preferably 7.8 or more, more preferably 8.0 or more, and 15 or less from the viewpoint of improving the emulsion stability of the skin cosmetic. , Preferably 12 or less, more preferably 10.2 or less, and still more preferably 9.99 or less.
Further, from the viewpoint of improving the emulsifying power of the skin cosmetic, the SP value of the component (B) is preferably 7.5 to 12, more preferably 7.8 to 10.2, and further preferably 8. 0 to 9.5, still more preferably 8.2 to 8.6.

Specific examples of component (B) include: hydrocarbons; higher fatty acids; higher alcohols; ethers; monoesters such as fatty acid monoesters, diesters, fatty acid monoglycerides, fatty acid diglycerides, (poly) glycerin fatty acid esters such as fatty acid triglycerides, and the like. Which have an SP value of 7.2 to 15. Further, as the component (B), an ultraviolet absorbent, a bactericide, a whitening agent, or the like having an SP value of 7.2 to 15 can be used. These may be vegetable oils.
Component (B) is preferably a hydrocarbon, a higher fatty acid, a higher alcohol, an ether, an ester, an ultraviolet absorber other than the above hydrocarbon, a higher fatty acid, a higher alcohol, an ether, or an ester, the hydrocarbon, a higher fatty acid And one or more selected from the group consisting of fungicides other than higher alcohols, ethers and esters, and whitening agents other than the hydrocarbons, higher fatty acids, higher alcohols, ethers and esters.

Among the components (B), specific examples of hydrocarbons include squalane (for example, Nikko Chemicals, SP value: 8.34), and liquid paraffin (for example, Hi-Kol K-350, manufactured by Kaneda Corporation, SP value: 8.51) ).
Specific examples of the higher fatty acid include oleic acid (for example, EXTRA OLEIN-80 manufactured by Kao Corporation, SP value: 9.14), stearic acid (for example, Lunac S-50 manufactured by Kao Corporation, SP value: 9.12), palmitin Acids (for example, Kao Corporation Lunac P-95KC, SP value: 9.18), myristic acid (for example, Kao Corporation Lunac MY-98KC, SP value: 9.26), linoleic acid (for example, NOF Corporation) Linoleic acid 90, SP value: 9.17).
Specific examples of the higher alcohol include oleyl alcohol (for example, oleyl alcohol VP, SP value: 9.47, manufactured by Higher Alcohol Industry Co., Ltd.).
Specific examples of ethers include monooleyl glyceryl ether (for example, Seraquil alcohol manufactured by Nikko Chemicals, SP value: 10.46).
As specific examples of the monoester, octyl dodecyl lactate (for example, Cosmall 13, manufactured by Nisshin Oillio, SP value: 9.40), sorbitan sesquioleate (for example, Cosmole 82, manufactured by Nisshin Oillio, SP value: 10.07) ), Isopropyl palmitate (for example, Exepearl IPP manufactured by Kao Corporation, SP value: 8.54), isostearyl myristate (for example, Cosmall 812, manufactured by Nisshin Oillio Co., SP value: 8.55), butyl stearate (for example, Butyl stearate K, manufactured by Kawaken Fine Chemical Co., Ltd., SP value: 8.61), cetyl lactate (for example, Cerafil 28, manufactured by ASP Japan, SP value: 9.6), lauroyl sarcosine isopropyl (for example, manufactured by Ajinomoto Co.) Eldue SL-205, SP value: 9.52) .
Specific examples of the diester include diisostearyl malate (for example, Cosmall 222 manufactured by Nisshin Oillio Co., SP value: 9.36), and neopentyl glycol dicaprate (for example, Estemol NO-1 and SP manufactured by Nisshin Oillio Co., Ltd.) Value: 8.87) and neopentyl glycol diethylhexanoate (for example, Cosmall 525 manufactured by Nisshin Oillio, SP value: 8.79).
Specific examples of (poly) glycerin fatty acid esters and the like include (isostearic acid / myristic acid) glyceryl (for example, Exepearl DG-MI manufactured by Kao Corporation, SP value: 9.32), diglycerin monomyristate (for example, Nikko Chemical) Seraquil alcohol, SP value: 11.88), polyglyceryl isostearate (for example, Cosmall 41 manufactured by Nisshin Oillio, SP value: 11.37), polyglyceryl diisostearate (for example, Cosmall 42 manufactured by Nisshin Oillio, SP value: 9.91), polyglyceryl triisostearate (for example, Cosmall 43 manufactured by Nisshin Oillio, SP value: 9.25), polyglyceryl tetraisostearate (for example, Cosmole 44 manufactured by Nisshin Oillio, SP value: 8) .88), tri-2-ethylhexyl Phosphate glyceryl (e.g., Nisshin OilliO Co. T.I.O, SP value: 9.1) and the like.
Specific examples of the ultraviolet absorber other than the hydrocarbons, higher fatty acids, higher alcohols, ethers, and esters include ethylhexyl methoxycinnamate (for example, Ubinal MC80 manufactured by BASF, SP value: 10.00), and diethylaminohydroxybenzoyl benzoate. Hexyl acid (for example, Ubinal A plus, manufactured by BASF, SP value: 10.69), ethylhexyl triazone (for example, Ubinal T150, manufactured by BASF, SP value: 11.51), ethylhexyl methoxycinnamate (for example, DSM Nutrition Co., Ltd.) Manufactured by PARSOL MCX, SP value: 9.91), and bisethylhexyloxyphenol methoxyphenyl triazine (for example, Tinosolve S, manufactured by BASF; SP value: 12.00).
Specific examples of the bactericides other than the hydrocarbons, higher fatty acids, higher alcohols, ethers and esters include isopropylmethylphenol (for example, IPMP manufactured by Osaka Kasei Co., SP value: 11.50), triclosan (for example, BASF) Irgasan DP 300, SP value: 12.75).
Specific examples of whitening agents other than the hydrocarbons, higher fatty acids, higher alcohols, ethers, and esters include ethylpentylmethoxychromone (for example, MA-293, SP value: 10.43, manufactured by Kao Corporation). .
Specific examples of vegetable oils include jojoba oil (SP value: 8.6) and olive oil (SP value: 9.3).

  The oil agent of the component (B) may be used alone or in combination of two or more. Further, the content of the component (B) in the skin cosmetic is preferably 2 in total with respect to the entire skin cosmetic from the viewpoint of improving the emulsion stability and optimizing the feeling of use when applied to the skin. % By mass or more, more preferably 4% by mass or more, still more preferably 6% by mass or more, and preferably 40% by mass or less, more preferably 30% by mass or less, and still more preferably 20% by mass or less. And still more preferably 19% by mass or less.

  In the present embodiment, the skin cosmetic may contain an oil having an SP value outside the above range. Also in this case, it is preferable that the weighted average of the SP values of the entire oil component in the skin cosmetic is in the range of 7.2 to 15.

(Component (C))
Component (C) is water. As the water, ion-exchanged water, distilled water, or the like can be used. The water content is, for example, the remaining amount of the components (A) and (B) and other components in the skin cosmetic. Further, the content of the component (C) is preferably 50% by mass or more, and more preferably 75% by mass or more.

The skin cosmetic in the present embodiment can be manufactured by a predetermined procedure according to the form of the skin cosmetic. For example, the method for producing a skin cosmetic may include a step of mixing and stirring the components (A) to (C) to prepare an emulsion. Further, the method for producing a skin cosmetic may include a step of preparing an emulsion by mixing an aqueous phase containing the components (A) and (C) with an oil phase containing the component (B).
The resulting emulsion, for example, an oil-in-water emulsion composition, can be used as a skin cosmetic.

  The form of the skin cosmetic in the present embodiment can be a lotion, a solution, an emulsion, a cream, an ointment, a gel, a pack, a powder, a stick, and more specifically, Emulsions, lotions, packs and gels are included.

In the present embodiment, by using the components (A) to (C) in combination, the emulsifying power and the emulsifying stability are excellent, and the film can be applied to the skin or the like to form a film. A skin cosmetic with excellent water resistance can be obtained.
More specifically, in the present embodiment, a fine cellulose fiber composite having the specific structure and characteristics of the component (A) is used. By using the component (A), the emulsifying power of the oil-soluble liquid and the solubilizing power of the oil-soluble crystals can be improved, so that a skin cosmetic having excellent emulsifying power and emulsion stability can be obtained. Further, by using the component (A), a film of a skin cosmetic can be formed when applied to the skin or the like. The component (B) can be dispersed and held in the formed coating film, and the coating film itself has excellent water resistance. For this reason, for example, it becomes possible to allow the component (B) to remain on the skin for a long time against sweating.

Next, a method for using the skin cosmetic will be described.
The method of using the skin cosmetic in the present embodiment includes, for example, a step of applying the skin cosmetic to the skin, preferably to the skin except for the scalp. More specifically, the method may include a step of applying a skin cosmetic to the skin, preferably to the skin except for the scalp to form a film.
Further, the skin cosmetic according to the present embodiment may be, for example, a cosmetic for sunburn suppression, a cosmetic for ultraviolet protection, a cosmetic for whitening, a cosmetic for antiperspirant, a cosmetic for anti-inflammatory, etc. according to the properties of the component (B). Can be used to get

In this embodiment, the skin cosmetic may contain components other than the above.
For example, the skin cosmetic may contain a solvent other than water, and examples of such a solvent include lower alcohols having 2 to 5 carbon atoms such as ethanol and 2-propanol.
Further, in the present embodiment, the skin cosmetic is a surfactant other than the above, a surfactant, an oil agent other than the component (B), a humectant, a preservative, a deodorant, an antiperspirant, a cooling agent, a warm feeling Agents, anti-inflammatory agents, preservatives, fragrances and the like.
Furthermore, as long as the effect is not impaired, the component normally mix | blended with cosmetics or an external preparation can be used suitably for skin cosmetics. For example, alcohols, antioxidants, pH adjusters, chelating agents, pigments, emulsion stabilizers, astringents, cooling agents, vitamins, amino acids and the like other than those described above are exemplified. These may be used alone or in combination of two or more.
In addition, each component may have another function in addition to the function as one agent described above, and for example, vitamins may also function as an anti-inflammatory agent.

  Next, examples of the present invention will be described.

(Production Examples 1 to 10)
The fine cellulose fiber composites used in Examples and Comparative Examples described later were produced by the following methods and evaluated. Table 1 shows the structure of the fine cellulose fiber and the EO / PO copolymer used in each production example, and the characteristics of the fine cellulose fiber composite obtained in each production example.

Preparation Example 1 of Fine Cellulose Fiber (Dispersion of Carboxyl Group-Containing Fine Cellulose Fiber Obtained by Acting N-Oxyl Compound on Natural Cellulose)
Bleached kraft pulp of softwood (Flecher Challenge Canada, trade name "Machenzie", CSF 650 ml) was used as natural cellulose fiber. As TEMPO, a commercially available product (free radical, 98% by mass, manufactured by ALDRICH) was used. A commercially available product (manufactured by Wako Pure Chemical Industries, Ltd.) was used as sodium hypochlorite. A commercial 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 1.25 mass% of TEMPO, 12.5 mass% of sodium bromide, 28 mg of sodium hypochlorite were added to 100 g of the pulp. 0.4% by weight were added in this order. Using a pH stud, 0.5 M sodium hydroxide was added dropwise to maintain the pH at 10.5. After the reaction was performed for 120 minutes, the dropping of sodium hydroxide was stopped to obtain oxidized pulp. The obtained oxidized pulp was sufficiently washed using ion-exchanged water, and then dehydrated. Thereafter, 3.9 g of oxidized pulp and 296.1 g of ion-exchanged water were mixed, and the mixture was refined twice at 245 MPa using a high-pressure homogenizer (Starburst Lab HJP-25005, manufactured by Sugino Machine Co., Ltd.) to obtain a carboxy group. A fine cellulose fiber dispersion (solid content: 1.3% by mass) was obtained. The number average fiber diameter of this fine cellulose fiber was 3.3 nm, and the carboxy group content was 1.4 mmol / g.

Preparation Example 2 of fine cellulose fiber (carboxy group-containing fine cellulose fiber dispersion obtained by acid-type treatment)
In a beaker, 4085 g of ion-exchanged water was added to 4088.75 g (solid content concentration: 1.3% by mass) of the carboxy group-containing fine cellulose fiber dispersion obtained in Preparation Example 1 to form a 0.5% by mass aqueous solution, and the mixture was stirred with a mechanical stirrer. The mixture was stirred at room temperature (25 ° C.) for 30 minutes. Subsequently, 245 g of a 1 M aqueous hydrochloric acid solution was charged and reacted at room temperature (25 ° C.) for 1 hour. After the completion of the reaction, the precipitate was reprecipitated with acetone, filtered, and then washed with acetone / ion-exchanged water to remove hydrochloric acid and salts. Finally, acetone was added and the mixture was filtered to obtain an acetone-containing acid-type cellulose fiber dispersion liquid (solid content: 5.0% by mass) in which carboxy group-containing fine cellulose fibers were swollen in acetone. After completion of the reaction, the mixture was filtered, and then washed with ion-exchanged water to remove hydrochloric acid and salts. After solvent replacement with acetone, solvent replacement with IPA was performed to obtain an IPA-containing acid-type cellulose fiber dispersion liquid (solid content concentration: 5.0% by mass) in which the carboxy group-containing fine cellulose fibers were swollen. The average fiber diameter of this fine cellulose fiber was 3.3 nm, and the carboxy group content was 1.4 mmol / g.

(Production Examples 1 to 10)
(Production of amine having EO / PO copolymerized part (EO / PO copolymerized amine))
132 g of propylene glycol tertiary butyl ether was charged into a 1 L autoclave, heated to 75 ° C., 1.2 g of flaky potassium hydroxide was added, and the mixture was stirred until dissolved. Then, in order to obtain the constituent parts of the EO / PO copolymerized part shown in Table 1, ethylene oxide (EO) having a mole number a shown in Table 1 and propylene oxide (PO) having a mole number (b-1) shown in Table 1 were obtained. Was reacted at 110 ° C. at 0.34 MPa. Then, 7.14 g of Magnesol 30/40 (magnesium silicate, manufactured by Dallas Group) was added and neutralized at 95 ° C., and the obtained product was treated with After adding and mixing 0.16 g of tertiary butyl-p-cresol, the mixture was filtered to obtain a polyether as an EO / PO copolymer.

On the other hand, the EO / PO copolymer obtained above was placed in a 1.250 mL tubular reaction vessel filled with a catalyst of nickel oxide / copper oxide / chromium oxide (molar ratio: 75/23/2) (manufactured by Wako Pure Chemical Industries, Ltd.). Polymer polyether (8.4 mL / min), ammonia (12.6 mL / min), and hydrogen (0.8 mL / min) were supplied. The temperature of the vessel was maintained at 190 ° C. and the pressure was maintained at 14 MPa. The crude effluent from the vessel was distilled off at 70 ° C. and 3.5 mmHg for 30 minutes. 200 g of the obtained aminated polyether and 93.6 g of a 15% hydrochloric acid aqueous solution were charged into a flask, and the reaction mixture was heated at 100 ° C. for 3.75 hours to cleave tertiary butyl ether with an acid. The product was neutralized with 144 g of a 15% aqueous solution of potassium hydroxide. Next, the neutralized product was distilled off under reduced pressure at 112 ° C. for 1 hour, followed by filtration to obtain a monoamine having an EO / PO copolymer part represented by the general formula (1). In the obtained monoamine, the EO / PO copolymer portion and the amine are directly bonded, and R ₁ in the general formula (1) is a hydrogen atom.
The molecular weight of the amine copolymer is, for example, in the case of the amine of Production Example 1,
2200 (= 44 × 50) +754 (= 58 × 13) = 2954
It was calculated.

(Production of fine cellulose fiber composite)
In a beaker equipped with a magnetic stirrer and a stirrer, 35 g of the carboxy group-containing fine cellulose fiber dispersion obtained in Preparation Example 2 of fine cellulose fibers (solid content concentration: 5% by mass) was charged. Subsequently, each of the amines of the type shown in Table 1 obtained by the above-described method was charged in an amount corresponding to 5 mol of the amine group per 1 mol of the carboxy group of the fine cellulose fiber, and dissolved in 300 g of ethanol. The reaction solution was reacted at room temperature (25 ° C.) for 6 hours. After the completion of the reaction, the mixture was filtered, washed with acetone, and solvent-exchanged with ion-exchanged water to obtain a fine cellulose fiber composite dispersion in which an amine salt was bonded to fine cellulose fibers.

(Average fiber diameter of fine cellulose fiber and fine cellulose fiber composite)
Water was added to the fine cellulose fiber or the fine cellulose fiber composite to prepare a dispersion having a concentration of 0.0001% by mass, and the dispersion was dropped on mica (mica) and dried to obtain an observation sample. Using an atomic force microscope (AFM, Nanoscope III Tapping mode AFM, manufactured by Digital Instrument Co., Ltd., probe: Point Probe (NCH) manufactured by Nanosensors Co., Ltd.), the fiber height of the cellulose fiber in the observation sample was measured. It was measured. At that time, five or more fine cellulose fibers or fine cellulose fiber composites were extracted from a microscope image in which the cellulose fibers could be confirmed, and the average fiber diameter was calculated from the fiber height.

(Carboxy group content of fine cellulose fiber and fine cellulose fiber composite)
A fine cellulose fiber or a fine cellulose fiber composite having a dry mass of 0.5 g is placed in a 100 mL beaker, and ion-exchanged water or a mixed solvent of methanol / water = 2/1 is added thereto to make a total of 55 mL. 5 mL was added to prepare a dispersion, and the dispersion was stirred until the fine cellulose fibers or the fine cellulose fiber composite were sufficiently dispersed. 0.1M hydrochloric acid was added to this dispersion to adjust the pH to 2.5-3, and a 0.05M aqueous sodium hydroxide solution was added using an automatic titrator (trade name "AUT-50" manufactured by Toa DKK Inc.). The solution was dropped into the dispersion under the condition of a waiting time of 60 seconds, and the conductivity and the pH value were measured every minute, and the measurement was continued until the pH reached about 11, thereby obtaining a conductivity curve. From the conductivity curve, the sodium hydroxide titer was determined, and the carboxy group content of the fine cellulose fiber or the fine cellulose fiber composite was calculated by the following equation.
Carboxyl group content (mmol / g) = sodium hydroxide titration x concentration of aqueous sodium hydroxide solution (0.05 M) / mass of cellulose fiber (0.5 g)

(Amount of amine salt in fine cellulose fiber composite)
The dried fine cellulose fiber or the fine cellulose fiber composite is measured by an attenuated total reflection (ATR) method using an infrared absorption spectrometer (IR) Nicolet 6700 (manufactured by Thermo Fisher Scientific), The amine bond amount was calculated by the following equation.
Amine binding amount (mmol / g) = 1.4 × [1- - 1720cm of (peak intensity of 1720 cm ^-1 of the fine cellulose fibers minute peak intensity of 1720 cm ^-1 of the cellulose fiber composite) ÷ (fine cellulose fiber composite ^-1 peak intensity)]
Peak intensity at 1720 cm ^-1 : peak intensity derived from carbonyl group of carboxylic acid

(Examples 1 to 7, Comparative Examples 1 to 5)
The skin cosmetics shown in Tables 2 and 3 were prepared, and the emulsifying power, emulsifying stability, and film water resistance were evaluated by the following methods. The evaluation results are shown in Tables 2 and 3.

(Method of preparing skin cosmetics)
Skin cosmetics of each example were prepared so as to contain the components shown in Tables 2 and 3 at the concentrations shown in the same tables. Specifically, a dispersion liquid of the fine cellulose fiber composite of the component (A) or other components of the component (A) ′ is added to an oil agent and ion-exchanged water, and the mixture is emulsified with stirring at 4500 rpm for 5 minutes at 60 ° C. using a homomixer Mark II. The oil-in-water emulsion composition thus obtained was used as the skin cosmetic of each example.

(Emulsification test)
The emulsified product of the skin cosmetic obtained in each example was placed in a test tube having a diameter of 3 cm * 30 cm and a height of 20 cm, and allowed to stand at 25 ° C. The volume% of the emulsified layer after 6 hours was calculated from the height measurement. The higher the volume percentage, the better the emulsifying ability.

(Emulsion stability)
500 g of the skin cosmetic emulsion obtained in each example was placed in a 30 cm long test tube, and the emulsified layer was left standing at 25 ° C. for 6 hours and the emulsified layer was stored in a 50 ° C. constant temperature bath for 5 days. Emulsification stability was determined from the difference in volume% of the layers. The evaluation criteria are shown below.
++: Decrease of less than 10% +: Decrease of 10% or more and less than 40%-: Decrease of 40% or more

(Coating water resistance)
0.1 mg of the skin cosmetic of each example was applied to a slide glass plate, uniformly stretched with a bar coder, and dried for 30 minutes to form a film. Thereafter, the glass plate was immersed in a water bath at 37 ° C., and the water was kept gently stirred for 80 minutes while maintaining the water temperature at 37 ° C. After the completion, the glass plate was slowly taken out and allowed to dry for 30 minutes or more, and then the residual property of the film was visually determined. The criteria are shown below.
++: film remains 80% or more +: 40% or more and less than 80% remains-: less than 40% remains

  From Tables 2 and 3, the skin cosmetics obtained in each Example are excellent in emulsifying power and emulsifying stability because they contain a fine cellulose fiber composite having a specific structure and characteristics, and are coated to form a film. It can be seen that the film can be formed and the film has excellent water resistance.

Claims (4)

The following components (A) to (C):
(A) a fine cellulose fiber composite,
(B) a skin cosmetic containing an oil having an SP value of 7.2 to 15 and (C) water,
The component (A) is characterized in that an amine having an ethylene oxide / propylene oxide (EO / PO) copolymer is bonded as a salt to a carboxy group of a fine cellulose fiber having a carboxy group content of 0.1 to 3 mmol / g. The EO / PO copolymer has a molecular weight of 600 to 10,000, and the PO content in the EO / PO copolymer is 6 to 80 mol%. , Skin cosmetics.   The skin cosmetic according to claim 1, wherein the number average fiber diameter of the fine cellulose fibers is 0.1 to 200 nm.   The skin cosmetic according to claim 1 or 2, wherein the amount of the amine bound in the fine cellulose fiber composite is 0.01 to 3 mmol / g.   The component (B) is selected from the group consisting of hydrocarbons, higher fatty acids, higher alcohols, ethers, esters, other ultraviolet absorbers, other fungicides, and other whitening agents; or The skin cosmetic according to any one of claims 1 to 3, wherein the cosmetic is two or more types.