JP6615506B2 - Skin cosmetics - Google Patents

Description

  The present invention relates to a skin cosmetic.

As a technique for using cellulose fibers as a thickener, there is one described in Patent Document 1 (Japanese Patent Laid-Open No. 2012-126786).
In Patent Document 1, as a technique for solving the problem of providing a viscous aqueous composition that is excellent in shape retention, dispersion stability, salt resistance, and the like, and is excellent in emulsion stability, a specific maximum fiber diameter, Viscosity containing cellulose fiber having water average fiber diameter, carboxyl group amount and crystal structure, wherein the carboxyl group is a salt with a monoamine having an organic value of 300 or less in the organic conceptual diagram. An aqueous composition is described.

JP 2012-126786 A

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

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

  ADVANTAGE OF THE INVENTION According to this invention, the skin cosmetics which are excellent in the water resistance of the film | membrane when improving to emulsification power and emulsification stability and applying 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 (C) water having SP value of 7.2 to 15 Hereinafter, each component will be described with specific examples. Each component can be used alone or in combination of two or more.

(Ingredient (A))
The fine cellulose fiber composite of component (A) is an amine having an ethylene oxide / propylene oxide (EO / PO) copolymer part in the carboxy group in a fine cellulose fiber having a carboxy group content of 0.1 to 3 mmol / g. Are bonded as a salt. And the molecular weight of the said EO / PO copolymerization part is 600-10,000, Comprising: The content rate of PO in an EO / PO copolymerization part is 6-80 mol%.
In the present specification, “an amine having an ethylene oxide / propylene oxide (EO / PO) copolymerization part is bonded as a salt to a carboxy group” means that a carbon atom is covalently bonded to a cellulose skeleton, It means a state in which the EO / PO copolymer part is ionically bonded through an 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 component (A) is preferably 0.1 nm or more from the viewpoint of enabling the skin cosmetic to form a film having excellent water resistance. More preferably, it is 0.2 nm or more, further preferably 0.5 nm or more, still more preferably 0.8 nm or more, and still more preferably 1 nm or more. From the same viewpoint, the thickness 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, even more preferably 10 nm or less, and still more preferably 5 nm or less.
In the present specification, the number average fiber diameters 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 below. In general, the minimum unit of cellulose nanofibers prepared from higher plants is packed with 6 × 6 molecular chains in a nearly square shape, so the height analyzed by the AFM image is taken as the fiber width. Can do.

(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, more preferably from the viewpoint of improving the dispersion stability of the cellulose fiber. 0.6 mmol / g or more, more preferably 0.8 mmol / g or more. Further, from the viewpoint of improving the handleability of the fine cellulose fibers, the content of carboxy groups in the fine cellulose fibers is 3 mmol / g or less, preferably 2.5 mmol / g or less, more preferably 2 mmol / g or less, still more preferably. Is 1.8 mmol / g or less.
In addition, the fine cellulose fiber which is outside the range which requires carboxy group content to the fine cellulose fiber used by this embodiment may be included as an impurity unintentionally.
Further, the “carboxy group content” means the total amount of carboxy groups in cellulose constituting the fine cellulose fiber, 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 fibers is preferably 10 or more, more preferably 20 or more, and further preferably from the viewpoint of enabling the skin cosmetic to form a film having excellent water resistance. Is 50 or more, and even more preferably 100 or more. From the same viewpoint, the average aspect ratio of the fine cellulose fibers is preferably 1000 or less, more preferably 500 or less, still more preferably 400 or less, and even more preferably 350 or less.

  In the present specification, the average aspect ratio of the fine cellulose fibers is represented by the following formula (A) from the relationship between the cellulose fiber concentration in the dispersion in which the fine cellulose fibers are dispersed in water and the specific viscosity of the dispersion with respect to water. Thus, the aspect ratio of the cellulose fiber is calculated backward.

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

In addition, the above formula (A) is based on the viscosity formula (8.138) of the rigid rod-like molecule described in The Theory of Polymer Dynamics, M.DOI and DFEDWARDS, CLARENDON PRESS / OXFORD, 1986, P.312 and 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. ]. Moreover, in said viscosity formula (8.138), let a rigid rod-shaped molecule | numerator be a cellulose fiber.

(Crystallinity)
The degree of crystallinity of the fine cellulose fibers is preferably 30% or more, more preferably 35% or more, still more preferably 40% or more, and even more preferably 45% or more, from the viewpoint of improving the handleability of the fine cellulose fibers. It is. Further, from the viewpoint of improving the binding efficiency of ionic bonds, the crystallinity of the fine cellulose fibers is preferably 90% or less, more preferably 85% or less, and even more preferably 80% or less.
In the present specification, the crystallinity of cellulose is cellulose I-type crystallinity calculated by the Segal method from the diffraction intensity value by the X-ray diffraction method, and is defined by the following calculation 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). °) shows the diffraction intensity. ]
Cellulose I type refers to the crystal form of natural cellulose, and cellulose I type crystallinity refers to the proportion of the total cellulose area occupied by the amount of crystal region.

  Next, the structure of the amine couple | bonded as a salt with the carboxy group of the fine cellulose fiber in a fine cellulose fiber composite is demonstrated.

<Amine having an EO / PO copolymer part>
In the fine cellulose fiber composite of the present embodiment, the carboxy group of the fine cellulose fiber described above is ionically bonded to an amine having an EO / PO copolymer part. Therefore, the amine in the present embodiment may be any one substituted by the EO / PO copolymerization part, and may be any of primary amine, secondary amine, and tertiary amine, but reaction with a carboxy group. From the viewpoint of properties, primary amines or secondary amines are preferred.

(EO / PO copolymerization part)
The EO / PO copolymerization part means a structure in which ethylene oxide (EO) and propylene oxide (PO) are polymerized randomly or in a block form. For example, when the amine is represented by the general formula (1) or (2) described later, ethylene oxide (EO) and propylene oxide (PO) have a random or block 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 copolymerization part is 6 mol% or more, preferably 12 mol% or more, more preferably 15 mol, from the viewpoint of improving the emulsion stability of the skin cosmetic. % Or more, more preferably 20 mol% or more, and from the same viewpoint, it is 80 mol% or less, preferably 70 mol% or less, more preferably 55 mol% or less, still more preferably 45 mol% or less, and even more. Preferably it is 35 mol% or less.

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

  The EO / PO copolymer part 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 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms is used. For example, ethylene group and propylene group are preferable.

  Examples of the amine having such an EO / PO copolymer part 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 form, and a is an average of EO It is a positive number indicating the added mole number, and b is a positive number indicating the average added mole number of PO. ]

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

[In the 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 blocked. E, g and i are the average addition moles of EO and are each independently a number from 1 to 50; f, h and j are the average addition moles of PO and are independently 1 It is a number of ~ 50. ]

Among these amines, the compound represented by the general formula (1) is preferable.
In the general formula (1), a represents the average added mole number of EO, and improves the emulsification stability of the skin cosmetic, and improves 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, still more 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, it is 70 or less, More preferably, it is 60 or less, More preferably, it is 55 or less.

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

In addition, the content (mol%) of PO in the EO / PO copolymerization part is the content of PO in the copolymerization part based on a and b described above when the amine is represented by the general formula (1). The rate can be calculated and can be calculated from the formula: b × 100 / (a + b).
When the amine is represented by the above general formula (2), the PO content (mol%) in the EO / PO copolymerization part can be similarly obtained from the formula: d × 100 / (c + d). Out.
When the amine is represented by the general formula (3), the PO content (mol%) in the EO / PO copolymer part is similarly expressed by the formula: (f + h + j) × 100 / (e + f + g + h + i + j) It can be obtained more.
A preferable 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 —CH ₂ CH (CH ₃ ) NH ₂ group. From the viewpoint of improving water resistance and the viewpoint of improving the water resistance of the skin cosmetic film applied to the skin or the like, hydrogen atoms are preferred. 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 represents the average added mole number of EO, and improves the emulsification stability of the skin cosmetic, and improves 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, even more preferably 20 or more, still more preferably 25 or more, From the viewpoint, it is preferably 70 or less, more preferably 50 or less. In the above general formula (2), d represents the average number of moles of PO added to improve the emulsification stability of the skin cosmetic, and the water resistance of the skin cosmetic film applied to the skin or the like. From the viewpoint of improving, it is preferably 1 or more, more preferably 2 or more, further preferably 3 or more, and from the same viewpoint, it is preferably 70 or less, more preferably 50 or less, even more preferably. Is 40 or less, more preferably 30 or less, even more preferably 25 or less, particularly preferably 20 or less, even more preferably 15 or less, and even 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 added mole number of EO, 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, even more preferably 15 or more, particularly preferably 20 or more, still more preferably 25 or more, and the same viewpoint Therefore, it is preferably 50 or less.
J in the general formula (3) represents the average number of moles of PO added to improve the emulsification 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, it is preferably 50 or less, more preferably 40 or less, still more preferably 30 or less, More preferably, it is 25 or less, Most preferably, it is 20 or less, More preferably, it is 15 or less, More preferably, it is 10 or less.
Moreover, as e and g in the said General formula (3), Preferably it is 1-30, More preferably, it is 10-30, As f and h, Preferably, preferably 1-25, More preferably, it is 5-25.

  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 hydroxyl terminal may be aminated. If necessary, the terminal can be made into a hydrogen atom by cleaving the alkyl ether with an acid. JP-A-3-181448 can be referred to for these production methods.

  Commercially available products are also preferably used as amines having an EO / PO copolymerization part. Specific examples include Jeffamine M-2070, Jeffamine M-2005, Jeffamine M-1000, Surfamine B200, Surfamine L100 manufactured by HUNTSMAN. , Surfamine L200, Surfamine L207, Surfamine L300, XTJ-501, XTJ-506, XTJ-507, XTJ-508; BASF Corporation M3000, Jeffamine ED-900, Jeffine ED-2003D 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 amount of amine salt bound in the fine cellulose fiber composite is determined 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, still more preferably 0.1 mmol / g or more, and even more preferably 0.3 mmol / g. In particular, it is more preferably 0.5 mmol / g or more, still more preferably 0.8 mmol / g or more. In addition, from the viewpoint of reactivity during ionic bonding, the amount of amine salt bound in the fine cellulose fiber composite is preferably 3 mmol / g or less, more preferably 2 mmol / g or less, and even more preferably 1.5 mmol / g. g or less. The amount of amine salt bound can be adjusted by the amount of amine added, the type of amine, the reaction temperature, the reaction time, the solvent, and the like.
In the present embodiment, the amount of amine salt bound can be determined by infrared spectroscopy (Infrared (IR) Spectroscopy). Specifically, it can be determined by the method described in the examples described later.

<Method for producing 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 copolymerized part can be introduced into the fine cellulose fiber via an ionic bond. For example, a reaction of introducing an EO / PO copolymerization part via ionic bonds may be performed on fine cellulose fibers prepared in advance, or EO may be established via ionic bonds following the preparation of fine cellulose fibers. The reaction for introducing the / PO copolymerization part may be carried out. The fine cellulose fiber can be produced by a known method, for example, a method described in JP2011-140632A.

As a suitable manufacturing method, the manufacturing method containing the following process (i) and process (ii) is mentioned, for example.
Step (i): Oxidation of 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 amine having PO copolymerization part More specifically, as a preferred production method, a step of refinement described below after step (i) is performed to obtain a carboxy group-containing fine cellulose fiber. 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) can be mentioned.

  Hereinafter, based on the above-mentioned “first manufacturing mode”, a method for manufacturing a fine cellulose fiber composite will be described.

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

  In step (i), first, a slurry in which natural cellulose fibers are dispersed in water is prepared. The slurry is about 10 to 1000 times as much water (mass basis) as the raw material natural cellulose fiber (absolute drying basis: mass of natural cellulose fiber after being heated and dried at 150 ° C. for 30 minutes), It is obtained by processing with a mixer or the like. Examples of natural cellulose fibers 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. These 1 type can be used individually or in combination of 2 or more types. The natural cellulose fiber may be subjected to a treatment for increasing the surface area such as beating. Further, the cellulose I type crystallinity of the commercially available pulp is usually 80% or more.

(Oxidation process)
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 piperidine oxyl compounds having 1 or 2 carbon atoms, pyrrolidine oxyl compounds, imidazoline oxyl compounds, and azaadamantane compounds. preferable. Among these, piperidineoxyl compounds having an alkyl group having 1 or 2 carbon atoms are preferable from the viewpoint of reactivity, and 2,2 such as 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO). 4-hydroxy-2,2,6,6-tetraalkylpiperidine- such as 1,6,6-tetraalkylpiperidine-1-oxyl, 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, etc. -tert- alkyl nitroxyl compound, 4-acetamido -TEMPO, 4-carboxy -TEMPO, 4 Hosufonokishi -TEMPO and the like. Among these piperidine oxyl compounds, 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO), 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl, 4- Methoxy-2,2,6,6-tetramethylpiperidine-1-oxyl is more preferable, and 2,2,6,6 tetramethylpiperidine-1-oxyl (TEMPO) is more preferable.

  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 with respect to natural cellulose fiber (absolute dry basis). It is 9 mass%, More preferably, it is 0.1-8 mass%, More preferably, it is 0.5-5 mass%.

  An oxidizing agent can be used in the oxidation treatment of natural cellulose fibers. As the oxidizing agent, oxygen or air, peroxide, halogen, hypohalous acid, halous acid, perhalogenic acid and alkali metals thereof are used from the viewpoint of solubility and reaction rate when the solvent is adjusted to an alkaline region. Examples thereof include salts or alkaline earth metal salts, halogen oxides, nitrogen oxides and the like. Among these, alkali metal hypohalites are preferable, and specific examples include sodium hypochlorite and sodium hypobromite. The amount of the oxidizing agent used may be selected according to the degree of carboxy group substitution (oxidation degree) of the natural cellulose fiber, and the oxidation reaction yield varies depending on the reaction conditions. It can be set as the range used as about 1-100 mass% with respect to a cellulose fiber (absolute dry reference | standard).

  In order to perform the oxidation reaction more efficiently, bromides such as sodium bromide and potassium bromide, iodides such as sodium iodide and potassium iodide, and the like can be used as a co-catalyst. The amount of the cocatalyst is not limited as long as it is an effective amount capable of exhibiting its function.

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

  Further, the pH of the reaction system is preferably matched to the nature 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 alkali side, preferably pH 7 to 13, A pH of 10 to 13 is more preferred. The reaction time is preferably 1 to 240 minutes.

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

(Purification process)
The carboxy group-containing cellulose fiber obtained by the oxidation reaction described above 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 can be performed to obtain a highly purified carboxy group-containing cellulose fiber. As the purification method, an optimum method can be employed depending on the type of 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, methanol, ethanol, acetone, etc. as a poor solvent, extraction of TEMPO into a solvent that is phase-separated from water such as hexane, purification by ion exchange of salts, dialysis, etc. Can be mentioned.

(Miniaturization process)
In a 1st manufacturing form, the process which refines | miniaturizes the carboxy-group containing cellulose fiber obtained by process (i) is performed after the refinement | purification process mentioned above. In the miniaturization process, it is preferable to disperse the carboxy group-containing cellulose fibers that have undergone the above-described purification process in a solvent, and perform the miniaturization process. By performing this refinement process, fine cellulose fibers having a number average fiber diameter and an average aspect ratio in the ranges described above can be obtained.

  The solvent as the dispersion medium is water, alcohol having 1 to 6 carbon atoms such as methanol, ethanol and propanol, preferably 1 to 3 carbon atoms; ketone 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; lower groups having 2 to 5 carbon atoms; Examples include alkyl ethers; polar solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, and methyltriglycol diester succinate. These can be used alone or in admixture of two or more, but from the viewpoint of the operability of the micronization treatment, water, alcohol having 1 to 6 carbon atoms, ketone having 3 to 6 carbon atoms, carbon number 2 Polar solvents such as -5 lower alkyl ethers, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, succinic acid methyltriglycol diester are preferable, and water is more preferable from the viewpoint of reducing environmental burden. The amount of the solvent used is not 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 with respect to the carboxy group-containing cellulose fiber. Use twice.

  Moreover, a well-known disperser is used suitably as an apparatus used by refinement | miniaturization processing. For example, a disaggregator, 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, a household juicer mixer, and the like can be used. Further, the solid content concentration of the reactant fiber in the refinement treatment is preferably 50% by mass or less.

  As the form of the carboxy group-containing fine cellulose fiber obtained after the refining step, the solid content concentration is adjusted as required (sustainably colorless and transparent or opaque liquid), or dry processed powder (however, It is also a powder form in which fine cellulose fibers are aggregated, and does not mean cellulose particles.). In the case of a suspension, only water may be used as a dispersion medium, and a mixed solvent of water and other organic solvents (for example, alcohols such as ethanol), surfactants, acids, bases, etc. May be used.

  By such oxidation treatment and refinement treatment of 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 crystallinity of preferably 30% or more can be obtained. Here, the fine cellulose fiber containing a carboxy group (also referred to as “carboxy group-containing fine cellulose fiber” in the present specification) has a cellulose I-type crystal structure. This means that the carboxy group-containing fine cellulose fiber used in the present embodiment is a fiber obtained by surface-oxidizing and refining a naturally-derived cellulose solid raw material having an I-type crystal structure. In step (i), after the natural cellulose fiber is oxidized, an acid (for example, hydrochloric acid) can be further reacted to adjust the carboxy group content, and the reaction can be performed before or after the refining treatment. Any of these may be performed.

(Step (ii))
In the first production mode, the step (ii) is performed by mixing the carboxy group-containing fine cellulose fiber obtained through the above-described micronization step with an amine having an EO / PO copolymerized portion, thereby producing a fine cellulose fiber composite. It is the process of obtaining. Specifically, a carboxy group-containing fine cellulose fiber and an amine having an EO / PO copolymer part are mixed in a solvent.

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

  The amount of the amine used can be determined by the amount of the desired amine salt bound in the fine cellulose fiber composite. From the viewpoint of reactivity, the amine is used with respect to 1 mol of the carboxy group contained in the carboxy group-containing fine cellulose fiber. The group is preferably 0.1 mol or more, more preferably 0.5 mol or more, further preferably 0.7 mol or more, and from the viewpoint of improving product purity, it is preferably 50 mol or less, more preferably 20 mol or less. More preferably, the amount is 10 mol or less. In addition, you may use for the reaction of the quantity of amine contained in the said range at once, or you may divide | segment and use for reaction. When the amine is a monoamine, the above amine group and 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), dimethyl sulfoxide (DMSO), N, N-dimethylacetamide, tetrahydrofuran (THF) , Succinic acid methyl triglycol diester, acetone, methyl ethyl ketone (MEK), acetonitrile, dichloromethane, chloroform, toluene, acetic acid and the like, and these can be used alone or in combination of two or more. Among these polar solvents, succinic acid methyl triglycol diester, ethanol, and DMF are preferable.

  The temperature during mixing is preferably 0 ° C. or higher, more preferably 5 ° C. or higher, further preferably 10 ° C. or higher, from the viewpoint of improving the reactivity of the amine. Moreover, from the viewpoint of suppressing 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 amine and solvent to be used, but from the viewpoint of improving the reactivity of the amine, it is preferably 0.01 hours or more, more preferably 0.1 hours or more, and still more preferably Is 1 hour or longer, preferably 48 hours or shorter, more preferably 24 hours or shorter.

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

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

  The fine cellulose fiber composite thus obtained can be used as a component in the skin cosmetic in the state of the dispersion after the post-treatment, or the solvent is removed 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 in which fine cellulose fiber composites are aggregated, and does not mean cellulose particles.

  Examples of the powdered fine cellulose fiber composite include, for example, a dried product obtained by directly drying a dispersion of the fine cellulose fiber composite; a powder obtained by pulverizing the dried product by a mechanical treatment; and a dispersion of the fine cellulose fiber composite. What was pulverized by the well-known spray-drying method; What pulverized the dispersion liquid of the fine cellulose fiber composite by the well-known freeze-drying method, etc. are mentioned. The spray drying method is a method in which a dispersion of 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 enabling the skin cosmetic to form a film having excellent water resistance. More preferably, it is 0.5 nm or more, still more preferably 0.8 nm or more, and still more preferably 1 nm or more. 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. More preferably 100 nm or less, still more preferably 50 nm or less, still more preferably 20 nm or less, and even more preferably 10 nm or less.

  In addition, since a crystallinity does not fall by reaction of process (ii), it is preferable that a fine cellulose fiber composite has a crystallinity degree comparable as the crystallinity degree of a fine cellulose fiber.

  As described above, the fine cellulose fiber composite contained in the skin cosmetic of the present embodiment is a fine cellulose fiber in which an EO / PO copolymer part is ionically bonded via an amine salt, and is a number average fiber. A thing with a diameter of 0.1-200 nm is preferable.

In the present embodiment, the content of the component (A) in the skin cosmetic is, for example, 0.1 mass relative 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, and even more preferably 0.5% by mass or more.
Further, from the viewpoint of enabling the skin cosmetic to form a film having excellent water resistance and making the use of the skin cosmetic suitable, the content of the component (A) in the skin cosmetic is: For example, it is 4% by mass or less, preferably 3% by mass or less, more preferably 2% by mass or less, and still more preferably 1.5% by mass or less.

Next, the component (B) will be described.
(Ingredient (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, which is a substance constant given by δ = (E / V) ^1/2 (J / cm ³ ) from the molecular cohesive energy E and molecular volume V of the liquid. From this value, the relative height 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 the present embodiment, when the oil agent is a mixture, the SP value of the oil agent of component (B) is obtained as a weighted average, that is, the sum of products of the SP value and the mass fraction of each component. In addition, the SP value is calculated according to the representative structure for those that cannot specify the structural formula such as natural products and polymers.

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, it is 12 or less, more preferably 10.2 or less, and still more preferably 9.99 or less.
Moreover, from a viewpoint of improving the emulsification power in skin cosmetics, SP value of a component (B) becomes like this. Preferably it is 7.5-12, More preferably, it is 7.8-10.2, More preferably, it is 8. It is 0 to 9.5, 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, fatty acid triglycerides, and the like (poly) glycerin fatty acid esters, etc. Of which SP value is 7.2-15. Further, as the component (B), an ultraviolet absorber, a bactericidal agent, a whitening agent or the like having an SP value of 7.2 to 15 can also be used. These may be vegetable oils.
Component (B) is preferably a hydrocarbon, a higher fatty acid, a higher alcohol, an ether, an ester, the hydrocarbon, a higher fatty acid, a higher alcohol, an ether, an ultraviolet absorber other than the ester, the hydrocarbon, a higher fatty acid. , One or more selected from the group consisting of bactericides 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), as specific examples of hydrocarbons, squalane (for example, Nikko Chemicals, SP value: 8.34), liquid paraffin (for example, Kaneda Hicoll K-350, SP value: 8.51). ).
Specific examples of higher fatty acids include oleic acid (for example, EXTRA OLEIN-80, SP value: 9.14 manufactured by Kao Corporation), stearic acid (for example, Lunac S-50 manufactured by Kao Corporation, SP value: 9.12), palmitic acid Acid (for example, Lunac P-95KC manufactured by Kao Corporation, SP value: 9.18), myristic acid (for example, Lunac MY-98KC manufactured by Kao Corporation, SP value: 9.26), linoleic acid (for example, manufactured by 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, ceralkyl alcohol manufactured by Nikko Chemicals, SP value: 10.46).
Specific examples of monoesters include octyldodecyl lactate (for example, Nisshin Oilio Cosmol 13, SP value: 9.40), sesquioleate sorbitan (for example, Nisshin Oilio Cosmol 82, SP value: 10.07). ), Isopropyl palmitate (for example, EXOPARL IPP manufactured by Kao Corporation, SP value: 8.54), isostearyl myristate (for example, Cosmol 812 manufactured by Nisshin Oilio Co., SP value: 8.55), butyl stearate (for example, Butyl stearate K manufactured by Kawaken Fine Chemical Co., 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., Inc.) El Dew SL-205, SP value: 9.52) .
As specific examples of diesters, diisostearyl malate (for example, Cosmol 222 manufactured by Nisshin Oillio Co., SP value: 9.36), neopentyl glycol dicaprate (for example, Esthemol NO-1, manufactured by Nisshin Oilio Co., SP) Value: 8.87), neopentyl glycol diethylhexanoate (for example, Nisshin Oilio Cosmol 525, SP value: 8.79).
Specific examples of (poly) glycerin fatty acid esters and the like include (isostearic acid / myristic acid) glyceryl (for example, Kasper's Exepar DG-MI, SP value: 9.32), monomyristic acid diglycerin (for example, Nikko Chemical). Seracyl alcohol manufactured by Co., Ltd., SP value: 11.88), polyglyceryl isostearate (for example, Cosmol 41 manufactured by Nisshin Oil Rio Co., Ltd., SP value: 11.37), polyglyceryl diisostearate (for example, Cosmol 42 manufactured by Nisshin Oil Co., Ltd.), SP value: 9.91), polyglyceryl triisostearate (for example, Nisshin Oillio Cosmol 43, SP value: 9.25), tetraisostearate polyglyceryl (for example Nisshin Oilio Cosmol 44, 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 ultraviolet absorbers 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), diethylaminohydroxybenzoyl benzoate Acid hexyl (for example, BASF Ubinal A plus, SP value: 10.69), ethylhexyl triazone (for example, BASF Ubinal T150, SP value: 11.51), ethyl hexyl methoxycinnamate (for example, DSM Nutrition Corporation) Pulsol MCX, SP value: 9.91), bisethylhexyloxyphenol methoxyphenyl triazine (for example, Tinosolv S manufactured by BASF, SP value: 12.00).
Specific examples of bactericides other than the hydrocarbons, higher fatty acids, higher alcohols, ethers and esters include isopropylmethylphenol (for example, IPMP manufactured by Osaka Kasei Co., Ltd., SP value: 11.50), triclosan (for example, BASF Corporation) 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 manufactured by Kao Corporation, SP value: 10.43). .
Specific examples of vegetable oils include jojoba oil (SP value: 8.6) and olive oil (SP value: 9.3).

  The oil agent of component (B) may be used alone or in combination of two or more. In addition, 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 emulsification stability and making the usability when applied to the skin suitable. % By mass or more, more preferably 4% by mass or more, further preferably 6% by mass or more, and preferably 40% by mass or less, more preferably 30% by mass or less, still more preferably 20% by mass or less. Even more preferably, it is 19% by mass or less.

  In this embodiment, the skin cosmetic may contain an oil whose SP value is not within 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.

(Ingredient (C))
Ingredient (C) is water. As water, ion exchange 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. Moreover, content of a component (C) becomes like this. Preferably it is 50 mass% or more, More preferably, it is 75 mass% or more.

The skin cosmetic in the present embodiment can be produced 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. Moreover, the manufacturing method of skin cosmetics may include the process of preparing the emulsion by mixing the water phase containing component (A) and (C), and the oil phase containing component (B).
The obtained 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, solution, emulsion, cream, ointment, gel, pack, powder, stick, etc., more specifically, Examples include emulsions, lotions, packs, and gels.

In the present embodiment, by using the components (A) to (C) in combination, the emulsification power and the emulsion stability are excellent, and a film can be formed by applying to the skin and the like. A skin cosmetic excellent in water resistance can be obtained.
More specifically, in this embodiment, a fine cellulose fiber composite having a specific structure and characteristics of 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 crystal can be improved, so that a skin cosmetic excellent in emulsifying power and emulsion stability can be obtained. Furthermore, by using the component (A), a coating film of a skin cosmetic can be formed when applied to the skin or the like. And while being able to disperse | distribute and hold | maintain a component (B) in the formed coating film, it is excellent also in the water resistance of the coating film itself. For this reason, it becomes possible to leave a component (B) on skin for a long time, for example with respect to perspiration.

Next, the usage method of skin cosmetics is demonstrated.
The method for 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 excluding the scalp. More specifically, it may include the step of applying a skin cosmetic to the skin, preferably the skin excluding the scalp to form a film.
Further, the skin cosmetic in the present embodiment may be, for example, a sunburn suppressing cosmetic, an ultraviolet protection cosmetic, a whitening cosmetic, an antiperspirant cosmetic, an anti-inflammatory cosmetic, etc., depending on the nature of the component (B). Can be used to obtain.

In this embodiment, skin cosmetics 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.
Moreover, in this embodiment, skin cosmetics are surfactants, oil agents other than a component (B), moisturizer, antiseptic | preservative, deodorant, antiperspirant, cooling sensation agent, warm feeling as components other than the above Agents, anti-inflammatory agents, preservatives, perfumes and the like.
Furthermore, as long as the effect is not spoiled for skin cosmetics, the component normally mix | blended with cosmetics or an external preparation can be utilized suitably. For example, alcohols other than the above, antioxidants, pH adjusters, chelating agents, dyes, emulsion stabilizers, astringents, refreshing agents, vitamins, amino acids and the like can be mentioned. These may be used alone or in combination of two or more.
Each component may have other functions in addition to the above-described function as one agent. For example, vitamins may function as an anti-inflammatory agent.

  Next, examples of the present invention will be described.

(Production Examples 1-10)
Fine cellulose fiber composites used in Examples and Comparative Examples described below were produced and evaluated by the following methods. Table 1 shows the structure of the fine cellulose fibers and EO / PO copolymerized portions used in each production example, and the characteristics of the fine cellulose fiber composites obtained in each production example.

Preparation Example 1 of Fine Cellulose Fiber (Dispersion of carboxy group-containing fine cellulose fiber obtained by allowing N-oxyl compound to act on natural cellulose)
Conifer bleached kraft pulp (Fletcher Challenge Canada, trade name “Machenzie”, CSF 650 ml) was used as natural cellulose fiber. As TEMPO, a commercially available product (ALDRICH, Free radical, 98% by mass) was used. As sodium hypochlorite, a commercially available product (manufactured by Wako Pure Chemical Industries, Ltd.) was used. 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 coniferous trees was sufficiently stirred with 9900 g of ion-exchanged water. .4% by weight was added in this order. Using a pH stud, 0.5 M sodium hydroxide was added dropwise to maintain the pH at 10.5. After carrying out the reaction for 120 minutes, dropping of sodium hydroxide was stopped to obtain oxidized pulp. The oxidized pulp obtained using ion-exchanged water was sufficiently washed and then dehydrated. Thereafter, 3.9 g of oxidized pulp and 296.1 g of ion-exchanged water were mixed, and the refining treatment was performed twice at 245 MPa using a high-pressure homogenizer (manufactured by Sugino Machine, Starburst Lab HJP-2 5005). A contained fine cellulose fiber dispersion (solid concentration 1.3 mass%) was obtained. The number average fiber diameter of the fine cellulose fibers 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)
Add 4085 g of ion-exchanged water to 4088.75 g of the carboxy group-containing fine cellulose fiber dispersion obtained in Preparation Example 1 (solid content concentration: 1.3% by mass) in a beaker to obtain a 0.5% by mass aqueous solution. The mixture was stirred at room temperature (25 ° C.) for 30 minutes. Subsequently, 245 g of 1M hydrochloric acid aqueous solution was added and reacted at room temperature (25 ° C.) for 1 hour. After completion of the reaction, the precipitate was reprecipitated with acetone, filtered, and then washed with acetone / ion exchange water to remove hydrochloric acid and salts. Finally, acetone was added and filtered to obtain an acetone-containing acid-type cellulose fiber dispersion (solid content concentration: 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 exchange water to remove hydrochloric acid and salts. After solvent substitution with acetone, the solvent substitution with IPA was performed to obtain an IPA-containing acid-type cellulose fiber dispersion (solid content concentration 5.0% by mass) in a state where the carboxy group-containing fine cellulose fibers were swollen. This fine cellulose fiber had an average fiber diameter of 3.3 nm and a carboxy group content of 1.4 mmol / g.

(Production Examples 1-10)
(Production of amine having EO / PO copolymerization part (EO / PO copolymer amine))
132 g of propylene glycol tertiary butyl ether was charged into a 1 L autoclave, heated to 75 ° C., added with 1.2 g of flaky potassium hydroxide, and stirred until dissolved. Next, in order to obtain the constituent parts of the EO / PO copolymerization 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 Was reacted at 110 ° C. at 0.34 MPa, and then 7.14 g of Magnesol 30/40 (magnesium silicate, manufactured by Dallas Group) was added to neutralize at 95 ° C. Tertiary butyl-p-cresol (0.16 g) was added and mixed, followed by filtration to obtain a polyether as an EO / PO copolymer.

On the other hand, in the 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 container temperature 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 potassium hydroxide solution. Next, the neutralized product was distilled off under reduced pressure at 112 ° C. for 1 hour and filtered to obtain a monoamine having an EO / PO copolymer part represented by the general formula (1). In the obtained monoamine, the EO / PO copolymer part and the amine are directly bonded, and R ₁ in the general formula (1) is a hydrogen atom.
The molecular weight of the amine copolymerization part is, for example, in the case of the amine of Production Example 1,
2200 (= 44 × 50) +754 (= 58 × 13) = 2954
And calculated.

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

[Average fiber diameter of fine cellulose fiber and fine cellulose fiber composite]
Water is added to fine cellulose fibers or fine cellulose fiber composites to prepare a dispersion having a concentration of 0.0001% by mass, and the dispersion is dropped onto mica (mica) and dried as an observation sample. Using an atomic force microscope (AFM, Nanoscope III Tapping mode AFM, manufactured by Digital instrument, and probe using Nano Probes Point Probe (NCH)), the fiber height of the cellulose fiber in the observed sample was measured. It was measured. At that time, in the microscopic image in which the cellulose fibers can be confirmed, five or more fine cellulose fibers or fine cellulose fiber composites were extracted, and the average fiber diameter was calculated from their fiber heights.

[Carboxy group content of fine cellulose fiber and fine cellulose fiber composite]
Take a fine cellulose fiber or a fine cellulose fiber composite with a dry mass of 0.5 g in a 100 mL beaker, add ion-exchanged water or a mixed solvent of methanol / water = 2/1 to make a total of 55 mL, and 0.01M sodium chloride aqueous solution there 5 mL was added to prepare a dispersion, and the dispersion was stirred until the fine cellulose fiber or the fine cellulose fiber composite was sufficiently dispersed. 0.1M hydrochloric acid was added to this dispersion to adjust the pH to 2.5-3, and 0.05M sodium hydroxide aqueous solution was added using an automatic titrator (trade name “AUT-50” manufactured by Toa DKK Corporation). The solution was dropped into the dispersion under the condition of a waiting time of 60 seconds, and the electric conductivity and pH value were measured every minute, and the measurement was continued until the pH was about 11, and an electric conductivity curve was obtained. From this conductivity curve, the sodium hydroxide titration amount was determined, and the carboxy group content of the fine cellulose fiber or fine cellulose fiber composite was calculated according to the following formula.
Carboxy group content (mmol / g) = sodium hydroxide titration × sodium hydroxide aqueous solution concentration (0.05 M) / mass of cellulose fiber (0.5 g)

[Amount of bound amine salt in fine cellulose fiber composite]
The dried fine cellulose fiber or fine cellulose fiber composite was 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 according to the following formula.
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 1-7, Comparative Examples 1-5)
The skin cosmetics shown in Table 2 and Table 3 were prepared and evaluated for emulsifying power, emulsifying stability, and film water resistance by the following methods. An evaluation result is combined with Table 2 and Table 3, and is shown.

(Method for preparing skin cosmetics)
The 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 table. Specifically, the fine cellulose fiber composite dispersion of component (A) or other component (A) ′ is added to oil agent and ion-exchanged water, and the mixture is emulsified with stirring at a temperature of 60 ° C. using a homomixer Mark II at 4500 rpm for 5 minutes. The oil-in-water emulsion composition thus obtained was used as a skin cosmetic for each example.

(Emulsifying power test)
The emulsion of the skin cosmetic obtained in each example was placed in a test tube having a diameter of 3 cm * 30 cm in length 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%, the better the emulsifying ability.

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

(Film water resistance)
0.1 mg of the skin cosmetic material 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 37 ° C. water bath, and light agitation was continued for 80 minutes while keeping the water temperature at 37 ° C. After the completion, the glass plate was slowly taken out, allowed to stand for 30 minutes or more and dried, and then the film persistence was judged visually. Judgment criteria are shown below.
++: Remaining 80% or more of film +: Remaining 40% or more and less than 80%-: Remaining less than 40%

  From Table 2 and Table 3, since the skin cosmetics obtained in each Example include a fine cellulose fiber composite having a specific structure and characteristics, the skin cosmetic is excellent in emulsifying power and emulsion stability, and applied to form a film. It can be seen that 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 with an SP value of 7.2 to 15 (cal / cm ³ ) ^1/2 and (C) water,
The component (A) is an amine having an ethylene oxide / propylene oxide (EO / PO) copolymer part bonded to a carboxy group of a fine cellulose fiber having a carboxy group content of 0.1 to 3 mmol / g as a salt. A fine cellulose fiber composite, wherein the EO / PO copolymer part has a molecular weight of 600 to 10,000, and the PO content in the EO / PO copolymer part 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 a binding amount of the amine 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, ultraviolet absorbers other than those described above, fungicides other than those described above, and whitening agents other than those described above or The skin cosmetic according to any one of claims 1 to 3, wherein there are two or more kinds.