JP2017014116A - Skin Cosmetic - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a skin cosmetic which is excellent in emulsifying power, emulsification stability, and emulsification stability when a salt is added, and is excellent in water resistance of a film when applied to a skin or the like.SOLUTION: The skin cosmetic contains: a component (A) a fine cellulose fiber composite; a component (B) an oil agent having an SP value of 7.2 to 15; and a component (C) water; wherein the component (A) is the fine cellulose fiber composite in which a specific group is bonded to a carboxy group of a fine cellulose fiber having a carboxy group content of 0.1 to 3 mmol/g via an amide bond or an ester bond.SELECTED DRAWING: None

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 is also improved in that it has excellent emulsifying power, emulsifying stability and emulsifying stability when a salt is added, and improves the water resistance of the film when applied to the skin and the like. There was room for.

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 or ethylene oxide / propylene oxide (EO / PO) having a hydrocarbon group having 2 to 24 carbon atoms in a carboxy group of a fine cellulose fiber having a carboxy group content of 0.1 to 3 mmol / g. A fine cellulose fiber composite (A1) in which an amine having a copolymerized part is bonded through an amide bond,
The present invention provides a skin cosmetic in which the molecular weight of the EO / PO copolymer part is 600 to 10,000, and the PO content in the EO / PO copolymer part is 6 to 80 mol%. .

The present invention also provides:
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 a compound having an alkyl group having 2 to 24 carbon atoms in the carboxy group of a fine cellulose fiber having a carboxy group content of 0.1 to 3 mmol / g, and an alkyl halide and an alkyl sulfate ester. A skin cosmetic composition in which at least one selected from the group consisting of alkyl tosylate, alkyl mesylate, and alkyl triflate is a fine cellulose fiber composite (A2) bonded through an ester bond. It is.

  ADVANTAGE OF THE INVENTION According to this invention, while being excellent in emulsification power, emulsification stability, and the emulsion stability at the time of adding a salt, the skin cosmetics which are excellent in the water resistance of the film | membrane 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 (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))
In the fine cellulose fiber composite of component (A), a specific group is bonded to the carboxy group via an amide bond or an ester bond in a fine cellulose fiber having a carboxy group content of 0.1 to 3 mmol / g. It is a fine cellulose fiber composite.
First, the said fine cellulose fiber is demonstrated.

<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 number average fiber diameter of the fine cellulose fibers is preferably 200 nm or less, more preferably 100 nm or less, still more preferably 50 nm or less, even more preferably 20 nm or less, and even more preferably 10 nm or less, more More preferably, it is 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 in 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 a 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 bonding efficiency of the amide bond or the ester bond, the crystallinity of the fine cellulose fiber is preferably 90% or less, more preferably 85% or less, and further 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, specific examples of the fine cellulose fiber composite in which a specific group is bonded to the carboxy group of the fine cellulose fiber through an amide bond or an ester bond, that is, the component (A) include the following components (A1 ) And (A2). In the present embodiment, as the component (A), one or more selected from the group consisting of the following components (A1) and (A2) can be used.
First, the component (A1) will be described.

(Component (A1))
The fine cellulose fiber composite of component (A1) has an amine or ethylene oxide / propylene oxide (EO / PO) copolymer part having a hydrocarbon group having 2 to 24 carbon atoms in the carboxy group of the fine cellulose fiber described above. An amine is bonded through an amide bond.

  Among amines amide-bonded to fine cellulose fibers, the amine having a hydrocarbon group having 2 to 24 carbon atoms is an aliphatic hydrocarbon group having 2 to 24 carbon atoms or an aromatic hydrocarbon group having 2 to 24 carbon atoms. The amine which has is mentioned.

<Amine having an aliphatic hydrocarbon group having 2 to 24 carbon atoms>
The hydrocarbon group contained in the amine having an aliphatic hydrocarbon group having 2 to 24 carbon atoms may be either a saturated hydrocarbon group or an unsaturated hydrocarbon group, but it has the viewpoint of suppressing side reactions and the stability of the reaction. From the viewpoint of enhancing, a saturated hydrocarbon group is preferable. The hydrocarbon group is preferably a linear or branched hydrocarbon group. The number of carbon atoms of the hydrocarbon group is 2 or more, more preferably 3 or more, from the viewpoint of favorable handling properties. Moreover, from a viewpoint of improving availability, it is 24 or less, More preferably, it is 18 or less, More preferably, it is 12 or less. Moreover, carbon number of a hydrocarbon group is 2-24, More preferably, it is 2-18, More preferably, it is 3-12. That is, as a preferable hydrocarbon group, a saturated or unsaturated, linear or branched hydrocarbon having preferably 2 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, and further preferably 3 to 12 carbon atoms. Groups.

Examples of the amine having an aliphatic hydrocarbon group having 2 to 24 carbon atoms include the primary or secondary amine having the above-described aliphatic hydrocarbon group.
Among these, as the primary amine, for example, a primary amine having 2 to 24 carbon atoms can be used. More specifically, the primary amine is ethylamine, propylamine, butylamine, pentylamine, hexylamine, heptylamine, octylamine, 2-ethylhexylamine, decylamine, dodecylamine, tridecylamine, tetradecylamine, octadecylamine. Etc. From the viewpoint of improving the water resistance of the film formed by the skin cosmetic, a primary amine having 2 to 18 carbon atoms is preferable, specifically, ethylamine, propylamine, butylamine, pentylamine, hexylamine, heptylamine, Examples include octylamine, 2-ethylhexylamine, decylamine, dodecylamine, tridecylamine, tetradecylamine, and octadecylamine. More preferred is a primary amine having 3 to 12 carbon atoms, and specific examples include propylamine, butylamine, pentylamine, hexylamine, heptylamine, octylamine, 2-ethylhexylamine, decylamine and dodecylamine.

  Examples of the secondary amine include dimethylamine, diethylamine, diisopropylamine, dioctylamine, didecylamine, didodecylamine and the like.

  The primary or secondary amine having a hydrocarbon group having 2 to 24 carbon atoms can be used alone or in combination of two or more. In these, from a viewpoint of improving the reactivity with a carboxy group, Preferably it is C2-C18, More preferably, it is C2-C12, More preferably, it is C2-C8, More preferably, it is C2-C2. Primary amines having 6 linear or branched hydrocarbon groups are preferred.

  As a fine cellulose fiber composite in which an amine having an aliphatic hydrocarbon group having 2 to 24 carbon atoms is bonded to a carboxy group of a fine cellulose fiber via an amide bond, for example, JP-A-2013-151636 Those described can be used.

<Amine having an aromatic hydrocarbon group having 2 to 24 carbon atoms>
The amine having an aromatic hydrocarbon group having 2 to 24 carbon atoms may be either a primary amine or a secondary amine, but a primary amine is preferred from the viewpoint of improving reactivity with a carboxy group.
The aromatic hydrocarbon group is selected from the group consisting of an aryl group and an aralkyl group, for example. As the aryl group and the aralkyl group, the aromatic ring itself may be substituted or unsubstituted.

  Examples of the aryl group include a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, a biphenyl group, a triphenyl group, a terphenyl group, and a group in which these groups are substituted with a substituent described later. One kind alone or two or more kinds may be contained in an amine having an aromatic hydrocarbon group. Especially, a phenyl group, a biphenyl group, and a terphenyl group are preferable from a viewpoint of improving the dispersion stability of skin cosmetics, and a phenyl group is more preferable.

  As the aralkyl group, for example, a benzyl group, a phenethyl group, a phenylpropyl group, a phenylpentyl group, a phenylhexyl group, a phenylheptyl group, a phenyloctyl group, and an aromatic group of these groups are substituted with a substituent described later. Group etc. are mentioned, These may be contained individually by 1 type or 2 or more types in the said amine. Among these, from the viewpoint of improving the dispersion stability of skin cosmetics, benzyl group, phenethyl group, phenylpropyl group, phenylpentyl group, phenylhexyl group, phenylheptyl group are preferable, benzyl group, phenethyl group, phenylpropyl group, A phenylpentyl group and a phenylhexyl group are more preferable, and a benzyl group, a phenethyl group, a phenylpropyl group, and a phenylpentyl group are more preferable.

  The total carbon number of the aryl group and the aralkyl group is preferably 6 or more, more preferably 7 or more from the viewpoint of improving the dispersion stability of the skin cosmetic, and from the same viewpoint, 24 or less, more preferably It is 20 or less, more preferably 14 or less, further preferably 13 or less, and further preferably 11 or less.

  As the substituent of the aryl group and the aralkyl group, those in which the total number of carbon atoms of the entire aromatic hydrocarbon group including the substituent is within the above-described range are preferable, for example, methyl group, ethyl group, propyl group, isopropyl group Alkyl group having 1 to 6 carbon atoms such as butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, isopentyl group, hexyl group; methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy Group, an isobutoxy group, a sec-butoxy group, a tert-butoxy group, a pentyloxy group, an isopentyloxy group, a hexyloxy group and the like, an alkoxy group having 1 to 6 carbon atoms; a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, Isopropoxycarbonyl, butoxycarbonyl, isobutoxycarbo An alkoxy-carbonyl group having 1 to 6 carbon atoms of an alkoxy group such as a ru group, sec-butoxycarbonyl group, tert-butoxycarbonyl group, pentyloxycarbonyl group, isopentyloxycarbonyl group; fluorine atom, chlorine atom, bromine atom A halogen atom such as an iodine atom; an acyl group having 1 to 6 carbon atoms such as an acetyl group or a propionyl group; an aralkyl group; an aralkyloxy group; an alkylamino group having 1 to 6 carbon atoms; Of the dialkylamino group. In addition, the above-described aromatic group itself may be bonded as a substituent.

  In the amine having an aromatic hydrocarbon group having 2 to 24 carbon atoms, it is preferable that the aromatic hydrocarbon group and the N atom are 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.

  Specific examples of the amine having such an aromatic hydrocarbon group having 2 to 24 carbon atoms are given below. For example, the amine having an aryl group includes aniline, 4-biphenylylamine, diphenylamine, 2-aminonaphthalene, p-terphenylamine, 2-aminoanthracene, and 2-aminoanthraquinone. Of these, aniline, 4-biphenylylamine, diphenylamine, 2-aminonaphthalene, and p-terphenylamine are preferable, and aniline is more preferable from the viewpoint of improving the dispersion stability of the skin cosmetic. Examples of the amine having an aralkyl group include benzylamine, phenethylamine, 3-phenylpropylamine, 5-phenylpentylamine, 6-phenylhexylamine, 7-phenylheptylamine, and 8-phenyloctylamine. Among these, from the same viewpoint, benzylamine, phenethylamine, 5-phenylpentylamine, 6-phenylhexylamine and 7-phenylheptylamine are preferable, and benzylamine, phenethylamine, 3-phenylpropylamine, 5-phenylpentylamine, 6-phenylpentylamine, Phenylhexylamine is more preferable, and benzylamine, phenethylamine, 3-phenylpropylamine, and 5-phenylpentylamine are more preferable.

  A commercial item can also be used as an amine which has a C2-C24 aromatic hydrocarbon group, and the amine which has an aromatic hydrocarbon group can also be prepared in accordance with a well-known method. For example, aniline can be produced by reducing nitrobenzene, and benzylamine can be produced by hydrogenating benzonitrile.

<Amine having an EO / PO copolymer part>
Next, an amine having an ethylene oxide / propylene oxide (EO / PO) copolymer part will be described.
First of all, in this specification, an amine having an ethylene oxide / propylene oxide (EO / PO) copolymerization part is amide-bonded to a carboxy group means that an EO / PO copolymer is bonded to a carboxy group in which a carbon atom is covalently bonded to a cellulose skeleton. It means a state where the polymerized part is bonded with an amide bond.
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%.

<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 amide-bonded with 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, still 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; M3000, Jeffamine ED-900, Jeffine ED-2003, Jeffine ED-2003, 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 binding amount of EO / PO amine in the fine cellulose fiber composite is selected from the viewpoints of improving the handleability of the fine cellulose fiber composite, the emulsification stability of the skin cosmetics, and the skin makeup applied to the skin and the like. From the viewpoint of improving the water resistance of the coating film of the material, 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 or more, particularly preferably 0.5 mmol / g or more, still more preferably 0.8 mmol / g or more. Further, from the viewpoint of reactivity at the time of amide bonding, the binding amount of EO / PO amine 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. The amount of EO / PO amine binding can be adjusted by the amount of amine added, the type of amine, reaction temperature, reaction time, solvent, and the like.
In the present embodiment, the amount of EO / PO amine binding can be determined by infrared spectroscopy (Infrared (IR) Spectroscopy), but specifically, it can be determined by the method described in the examples below.

<Method for producing component (A1) fine cellulose fiber composite>
The fine cellulose fiber composite can be produced according to a known method without limitation as long as a hydrocarbon group or an EO / PO copolymerized part can be introduced into the fine cellulose fiber via an amide bond. For example, a reaction of introducing a hydrocarbon group or an EO / PO copolymerization part via an amide bond may be performed on a fine cellulose fiber prepared in advance, or an amide bond may be continued following the preparation of the fine cellulose fiber. You may perform reaction which introduce | transduces a hydrocarbon group or an EO / PO copolymerization part via. 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 the number of carbon atoms A step of amidation reaction with an amine having 2 to 24 hydrocarbon groups or an EO / PO copolymerization part. More specifically, as a suitable production method, more specifically, a refinement step described later after step (i) And a method of performing the step (ii) after making the carboxy group-containing fine cellulose fiber (first production form) and a method of performing the step (ii) after the step (i) and then performing the micronization step ( Second production form).

  Hereinafter, based on the above-mentioned “first manufacturing mode”, a method for manufacturing the fine cellulose fiber composite of component (A1) 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 (DMF), N, N-dimethylacetamide, dimethyl sulfoxide, and succinic acid methyltriglycol diester. These can be used alone or in admixture of two or more. From the viewpoint of improving the operability of the micronization treatment, water, alcohol having 1 to 6 carbon atoms, ketone having 3 to 6 carbon atoms, carbon Preferred are polar solvents such as lower alkyl ethers of formula 2-5, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, succinic acid methyltriglycol diester, 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) includes a carboxy group-containing fine cellulose fiber obtained through the above-described refinement step and an amine having a hydrocarbon group having 2 to 24 carbon atoms or an EO / PO copolymer part. Is an amidation reaction to obtain a fine cellulose fiber composite (A1). Specifically, the carboxy group contained in the carboxy group-containing fine cellulose fiber and the amino group of an amine having a hydrocarbon group having 2 to 24 carbon atoms or an EO / PO copolymerized portion are subjected to an amide bond. And a fine cellulose fiber composite in which a hydrocarbon group having 2 to 24 carbon atoms or an EO / PO copolymer part is connected through an amide bond is obtained.

  Examples of the amine having a hydrocarbon group having 2 to 24 carbon atoms or an EO / PO copolymerization part used in step (ii) include those described above for the fine cellulose fiber composite.

  From the viewpoint of improving reactivity, the amount of amine used is preferably 0.1 mol or more, more preferably 0.5 mol or more, with respect to 1 mol of carboxy group contained in the carboxy group-containing fine cellulose fiber. More preferably, it is 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, and even more preferably 10 mol or less. In addition, the amount of amine included in the above range may be subjected to the reaction at a time or may be divided and subjected to the reaction. When the amine is a monoamine, the above amine group and amine are the same.

  In the reaction between the carboxy group-containing fine cellulose fiber and the amine (hereinafter sometimes referred to as “condensation reaction” or “amide bond forming reaction”), a known condensing agent may be used.

  Although it does not limit as a condensing agent, synthetic chemistry series peptide synthesis (Maruzensha) P.I. 116, or a condensing agent described in Tetrahedron, 57, 1551 (2001), such as 4- (4,6-dimethoxy-1,3,5-triazin-2-yl) -4-methyl. Morpholinium chloride (hereinafter sometimes referred to as “DMT-MM”) and the like.

  Specific examples of the solvent in the condensation reaction include the solvent in the above-described refinement step, and it is preferable to select a solvent in which the amine used in the amidation reaction is dissolved, and more preferably N, N-dimethylformamide (DMF). ), Isopropyl alcohol (IPA).

  The reaction time and reaction temperature in the condensation reaction can be appropriately selected according to the type of amine and solvent used. From the viewpoint of increasing the reaction rate, the reaction time is preferably 1 to 24 hours, more preferably 10 to 20 hours. The reaction temperature is preferably 0 ° C. or higher, more preferably 5 ° C. or higher, and further preferably 10 ° C. or higher from the viewpoint of improving reactivity. Moreover, from a viewpoint of suppressing coloring of a fine cellulose fiber composite, Preferably it is 200 degrees C or less, More preferably, it is 80 degrees C or less, More preferably, it is 30 degrees C or less.

  After the condensation reaction, 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 (A1) is preferably 0.1 nm or more, more preferably from the viewpoint of enabling the skin cosmetic to form a film having excellent water resistance. It is 2 nm or more, more preferably 0.5 nm or more, even more preferably 0.8 nm or more, and even 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.
The amount of amide bonds in the obtained fine cellulose fiber composite, that is, the amount of amine having 2 to 24 carbon groups or amine having EO / PO introduced into the fine cellulose fiber composite is From the viewpoint of improving the handleability of the body, 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, etc., preferably 0.01 mmol / g More preferably 0.05 mmol / g or more, still more preferably 0.1 mmol / g or more, still more preferably 0.3 mmol / g or more, even more preferably 0.5 mmol / g or more, and still more preferably 0. 0.8 mmol / g or more. In addition, from the viewpoint of reactivity during amide bonding, the amount of amide bonding 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 or less. It is.

  The fine cellulose fiber composite of component (A1) is preferably one or more selected from the group consisting of fine cellulose fibers, preferably an EO / PO copolymer part, a secondary amine, and a linear or branched alkylamine. Are bonded via an amide bond, more preferably one or more selected from the group consisting of an EO / PO copolymer part, a secondary amine, and a linear alkylamine are bonded via an amide bond. More preferably, one or more selected from the group consisting of an EO / PO copolymer part and a secondary amine are bonded via an amide bond, and even more preferably, the EO / PO copolymer part has an amide bond. It is connected through. The fine cellulose fiber composite of component (A1) preferably has a number average fiber diameter of 0.1 to 200 nm.

As a preferred component (A1), hydrocarbon groups having 2 to 24 carbon atoms are bonded to fine cellulose fibers via amide bonds with an average bond amount of 0.3 mmol / g or more, and the average fiber diameter is 0.1 to 200 nm. And a fine cellulose fiber composite (a1).
Also in the component (a1), the fine cellulose fiber can be the same as the fine cellulose fiber used in the fine cellulose fiber composite (A1).

  The hydrocarbon group in the fine cellulose fiber composite (a1) has 2 to 24 carbon atoms, and more specifically, a saturated or unsaturated, linear or branched carbon atom having 2 to 24 carbon atoms. A hydrogen group is mentioned. Especially, from a viewpoint of improving the intensity | strength of the film | membrane formed with skin cosmetics, carbon number becomes like this. Preferably it is 20 or less, More preferably, it is 18 or less, More preferably, it is 12 or less. Further, from the viewpoint of improving the yellowing resistance (less coloring during heating) of the component (a1) and the viewpoint of improving the dispersion stability of the skin cosmetic, the hydrocarbon group in the fine cellulose fiber composite (a1) The number of carbon atoms is preferably 3 or more. Moreover, carbon number of the hydrocarbon group in a fine cellulose fiber composite (a1) is 2-24, More preferably, it is 2-20, More preferably, it is 2-18, More preferably, it is 3-12.

  Specific examples of the hydrocarbon group include, for example, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, decyl, dodecyl, tridecyl. Group, tetradecyl group, hexadecyl group and the like. These may be connected singly or in combination of two or more at an arbitrary ratio via an amide bond.

  The amount of bonded hydrocarbon groups in the fine cellulose fiber composite (a1) is to improve the yellowing resistance (less coloration during heating) of the component (a1) and to improve the dispersion stability of the skin cosmetic. Therefore, the average bond amount is 0.3 mmol / g or more, preferably 0.4 mmol / g or more, more preferably 0.5 mmol / g or more. Moreover, from a viewpoint of improving the intensity | strength of the film | membrane formed with skin cosmetics, Preferably it is 3 mmol / g or less, More preferably, it is 2 mmol / g or less, More preferably, it is 1 mmol / g or less. Moreover, 0.3-3 mmol / g is preferable, as for the average bond amount of a hydrocarbon group, 0.4-2 mmol / g is more preferable, and 0.5-1 mmol / g is further more preferable.

  The fine cellulose fiber composite (a1) can be produced according to the production method of the fine cellulose fiber composite (A1).

  The carboxy group content in the obtained fine cellulose fiber composite (a1) is preferably 0 mmol / g or more, more preferably 0.1 mmol / g or more, and still more preferably, from the viewpoint of improving the dispersion stability of the skin cosmetic. It is 0.2 mmol / g or more. Further, from the viewpoint of improving yellowing resistance of the component (a1) (less coloring during heating), it is preferably 2.8 mmol / g or less, more preferably 2.0 mmol / g or less, and even more preferably 1.5 mmol. / G or less. The carboxy group content is preferably 0 to 2.8 mmol / g, more preferably 0.1 to 2.0 mmol / g, and still more preferably 0.2 to 1.5 mmol, from the viewpoint of increasing the balance of the above effects. / G.

  Further, the average fiber diameter of the fine cellulose fiber composite (a1) is preferably 0.1 nm or more, more preferably 0.2 nm or more, and still more preferably from the viewpoint of improving the strength of the film formed on the skin cosmetic. It is 0.5 nm or more, more preferably 0.8 nm or more, and still more preferably 1 nm or more. Further, from the viewpoint of improving the dispersion stability and enhancing the transparency of the skin cosmetic, 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, and even more preferably 10 nm or less. It is. The average fiber diameter of the component (a1) is preferably 0.1 to 200 nm, more preferably 0.2 to 100 nm, still more preferably 0.5 to 50 nm, and still more preferably, from the viewpoint of increasing the balance of the above effects. It is 0.8-20 nm, More preferably, it is 1-10 nm.

Next, the component (A2) will be described.
(Component (A2))
The fine cellulose fiber composite of component (A2) is a compound having an alkyl group having 2 to 24 carbon atoms in the carboxy group of the fine cellulose fiber described above, and an alkyl halide, alkyl sulfate, alkyl tosylate, At least one selected from the group consisting of alkyl mesylate and alkyl triflate is bonded via an ester bond.
That is, the fine cellulose fiber composite of component (A2) is obtained by bonding an alkyl having 2 to 24 carbon atoms via an ester bond to the carboxy group of the fine cellulose fiber described above. As the component (A2), for example, those described in JP 2010-59571 A can be used.

The fine cellulose fiber composite of component (A2) has the same type I crystal structure as natural cellulose, for example.
The fine cellulose fiber composite of component (A2) preferably has a number average fiber diameter of 0.1 to 200 nm.

  In the component (A2), the number of carbon atoms of the alkyl group bonded to the fine cellulose fiber via an ester group is based on the viewpoint of improving the dispersion stability of the skin cosmetic and the strength of the film formed by the skin cosmetic. From the viewpoint of improving, it is 2-24, More preferably, it is 2-18, More preferably, it is 3-18, More preferably, they are a propyl group, a butyl group, a hexyl group, a decyl group, or a hexadecyl group.

  In the fine cellulose fiber composite of component (A2), the amount of the ester group and aldehyde group is such that the ester group and the aldehyde group with respect to the mass of the fine cellulose fiber composite are from the viewpoint of improving the dispersion stability of the skin cosmetic. Is preferably 0.1 to 2.2 mmol / g, more preferably 0.5 to 1.5 mmol / g.

The amount of ester bonds in the fine cellulose fiber composite of component (A2) is preferably 0.01 mmol / g or more, more preferably 0.05 mmol / g, from the viewpoint of improving the handleability of component (A2). More preferably, it is at least 0.1 mmol / g, even more preferably at least 0.3 mmol / g, even more preferably at least 0.5 mmol / g, even more preferably at least 0.8 mmol / g. From the viewpoint of esterification reactivity when obtaining the component (A2), the ester bond amount in the fine cellulose fiber composite is preferably 3 mmol / g or less, more preferably 2 mmol / g or less, and still more preferably. It is 1.5 mmol / g or less.
In the present embodiment, the ester bond amount can be determined by solid-state NMR (Nuclear Magnetic Resonance).

<Method for producing component (A2) fine cellulose fiber composite>
As a manufacturing method of a component (A2), the manufacturing method including the following process (i), process (iii), and process (iv) is mentioned, for example.
Step (i): Step of obtaining a carboxy group-containing cellulose fiber by oxidizing natural cellulose fibers in the presence of an N-oxyl compound (iii) Step of treating fine cellulose fibers with an organic onium compound Step (iv): Step A compound having a cellulose fiber treated with an onium compound in (iii) and an alkyl group having 2 to 24 carbon atoms, and comprising an alkyl halide, an alkyl sulfate ester, an alkyl tosylate, an alkyl mesylate, and an alkyl triflate Reacting with at least one selected from the group for esterification

Here, process (i) is the same as process (i) mentioned above in the manufacturing method of component (A1).
Similarly to the method for producing component (A1), also in the method for producing component (A2), the step (iii) and the step are carried out after the step (i) is followed by a refinement step to obtain a carboxy group-containing fine cellulose fiber. A method of performing (iv) (first manufacturing mode), or a method of performing steps (iii) and (iv) after step (i) and then performing a miniaturization step (second manufacturing mode); It is preferable to do.

Hereinafter, step (iii) will be described.
Step (iii) is made hydrophobic by adding an organic onium compound having an onium structure such as organic ammonium or organic phosphonium to react with the carboxyl group of the fine cellulose fiber obtained in step (i). ) Process to process.
As the step (iii), for example, a hydrophobizing treatment described in JP 2010-59571 A can be used.

Hereinafter, step (iv) will be described.
In the step (iv), the fine cellulose fiber obtained in the step (iii) is reacted with at least one selected from the group consisting of alkyl halide, alkyl sulfate, alkyl tosylate, alkyl mesylate and alkyl triflate. This is an alkyl esterification step for esterification.
As the step (iv), for example, an esterification reaction described in JP 2010-59571 A can be used.

The solvent used in the alkyl esterification step is not limited, but it is preferable to select a solvent that is excellent in dispersibility of the fine cellulose fiber subjected to the hydrophobization treatment in step (iii) or that does not inhibit the transesterification reaction. A solvent can be used individually or in combination of 2 or more types.
Specific examples of the solvent include esters such as ethyl acetate, n-butyl acetate and γ-butyrolactone; ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone; aliphatic or aromatic hydrocarbons such as toluene, xylene and cyclohexane; diethyl Examples include ethers such as ether, dioxane, and tetrahydrofuran; polar solvents such as dimethylacetamide, dimethylformamide, N-methylpyrrolidone, and dimethylsulfoxide. For example, when the N-onium compound used for the hydrophobization treatment in the step (iii) is an alkylonium compound, from the viewpoint of enhancing the dispersibility of fine cellulose fibers, preferably dimethylacetamide, dimethylformamide, N-methylpyrrolidone or Dimethyl sulfoxide.

  The amount of the solvent used can be determined according to the amount of fine cellulose fibers subjected to the alkyl esterification reaction, the addition amount of the reaction reagent, and the like. From the viewpoint of stably carrying out the alkyl esterification reaction, the fine cellulose concentration is preferably 0.01 to 50% by mass, more preferably 0.5 to 20% by mass, and even more preferably 1.0 to 10% by mass. It is.

The reaction temperature of the alkyl esterification reaction can be set according to the boiling point of the solvent, the thermal stability of the hydrophobized fine cellulose fiber, and preferably from room temperature (25 ° C., the same shall apply hereinafter) to 200 ° C. Yes, more preferably 50 ° C to 150 ° C, still more preferably 70 ° C to 120 ° C. Moreover, when employ | adopting the comparatively high reaction temperature of 100 degreeC or more, the fine cellulose fiber processed with the alkylphosphonium compound from a viewpoint of improving heat resistance is used preferably.
Moreover, the reaction container used for the alkyl esterification reaction is not limited.
Moreover, reaction time becomes like this. Preferably it is 0.1 to 30 hours, More preferably, it is 1 to 20 hours.

  In the step (iv), it is preferable to carry out an alkyl esterification reaction by adding the hydrophobized fine cellulose fiber to an organic solvent, followed by dispersion treatment, and then adding an alkyl halide. For the dispersion treatment, for example, a shearing device such as a homogenizer can be used.

  As alkylating agents used in the alkyl esterification reaction, alkyl halides; alkyl sulfates such as dimethyl sulfate and diethyl sulfate; alkyl tosylates such as methyl p-toluenesulfonate; alkyl mesylate such as methyl methanesulfonate; trifluoromethane Examples include alkyl triflates such as methyl sulfonate. Of these, alkyl halides are preferred from the viewpoint of price and the like. Specific examples of the alkyl halide include methyl chloride, ethyl chloride, propyl chloride, butyl chloride, hexyl chloride, decyl chloride, hexadecyl chloride, octadecyl chloride, cholesteryl chloride, cholesteryl chloride, polyfluoroalkyl chloride having 2 to 24 carbon atoms, and the like. Chloride: methyl bromide, ethyl bromide, propyl bromide, butyl bromide, hexyl bromide, decyl bromide, hexadecyl bromide, okdacil bromide, cholesteryl bromide, cholesteryl bromide, poly C2-C24 Bromide such as fluoroalkyl bromide; methyl iodide, ethyl iodide, propyl iodide, butyl iodide, hexyl iodide, decyl iodide, hexadecyl iodide, octadecyl iodide, cholesteryl iodide, cholesteryl iodide, 2 carbon atoms ~ 24 iodides such as polyfluoroalkyliodide; etc. Among these, from the viewpoint of excellent reactivity and handling property, it is preferably bromide.

  After the alkyl esterification reaction, an appropriate post-treatment may be performed to remove unreacted alkylating agent and the like. As a post-treatment method, for example, filtration, centrifugation, dialysis, or the like can be used.

  Moreover, the fine cellulose fiber composite (A2) obtained by the above can also be used as a component in skin cosmetics in the state of the dispersion liquid after performing a post-process similarly to the case of a component (A1). Alternatively, the solvent can be removed from the dispersion by a drying treatment or the like to obtain a dry powdery fine cellulose fiber composite, which can be used. Specific examples of the powdered fine cellulose fiber composite include those described above for the component (A1).

  Further, the number average fiber diameter of the obtained fine cellulose fiber composite (A2) is preferably 0.1 nm or more, more preferably from the viewpoint of enabling the skin cosmetic to form a film having excellent water resistance. It is 0.2 nm or more, more preferably 0.5 nm or more, even more preferably 0.8 nm or more, and even 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 (A2) is preferably It is 200 nm or less, more preferably 100 nm or less, still more preferably 50 nm or less, even more preferably 20 nm or less, and even more preferably 10 nm or less.

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 include (isostearic acid / myristic acid) glyceryl (for example, Kasper's Exepar DG-MI, SP value: 9.32), monomyristic acid diglycerin (for example, Nikko Chemical Co., Ltd.) Ceralkyl alcohol manufactured, SP value: 11.88), polyglyceryl isostearate (for example, Cosmol 41 manufactured by Nisshin Oil Rio Co., SP value: 11.37), polyglyceryl diisostearate (for example, Cosmol 42 manufactured by Nisshin Oil Rio Co., 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-ethylhexa 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), methoxycinnamate ethylhexyl (for example, DSM Nutrition, Inc.) 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. Therefore, the emulsifying power, the emulsification stability, and the emulsification stability when the salt is added are excellent. A skin cosmetic is obtained. In particular, an emulsion excellent in salt resistance can be obtained by using a combination of components (A) to (C). 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 1-27)
Fine cellulose fiber composites used in Examples and Comparative Examples described below were produced and evaluated by the following methods. Composition of fine cellulose fiber used in each production example and hydrocarbon group or EO / PO copolymerized part or amide bond alkyl group bonded to amide bond to this, and characteristics of fine cellulose fiber composite obtained in each production example Are shown in Tables 1 to 3.

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, and then TEMPO 1.25 mass%, sodium bromide 12.5 mass%, sodium hypochlorite 28 with respect to 100 g of the pulp mass. .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 (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 (solid content concentration 5.4% by mass) obtained in Preparation Example 2 of fine cellulose fibers. Subsequently, an amine having an EO / PO copolymer part of the type shown in Table 1 is added in an amount corresponding to 5 mol of amine groups with respect to 1 mol of carboxy groups of fine cellulose fibers, and 4- (4,6) which is a condensing agent. -Dimethoxy-1,3,5-triazin-2-yl) -4-methylmorpholinium chloride (DMT-MM) 3.78 g was charged and dissolved in 300 g of IPA. The reaction solution was reacted at room temperature (25 ° C.) for 14 hours. After completion of the reaction, the mixture was filtered, washed with ion exchange water, the DMT-MM salt was removed, washed with acetone, and the solvent was replaced, whereby the fine cellulose fiber was linked to the EO / PO copolymer via an amide bond. A cellulose fiber composite was obtained.

(Production Example 11)
A beaker equipped with a magnetic stirrer and a stirrer was charged with 40 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, propylamine was charged in an amount corresponding to 1.2 mol of amine group with respect to 1 mol of carboxy group of fine cellulose fiber, 0.34 g of 4-methylmorpholine, 1.98 g of DMT-MM as a condensing agent, and 300 g of DMF. Dissolved in. The reaction was allowed to react for 14 hours at room temperature (25 ° C.). After completion of the reaction, the mixture is filtered, washed with ethanol to remove the DMT-MM salt, and solvent-substituted with ion-exchanged water, whereby a fine cellulose fiber composite in which an amine is linked to the fine cellulose fiber via an amide bond. A dispersion was obtained.

(Production Example 12)
In Production Example 11, except that hexylamine was used instead of propylamine, the production was carried out according to the method described in Production Example 11, and a fine cellulose fiber composite in which hexyl groups were connected to fine cellulose fibers via amide bonds. Was prepared.

(Production Example 13)
In Production Example 11, except that octadecylamine was used instead of propylamine, the production was carried out according to the method described in Production Example 11, and a fine cellulose fiber composite in which octadecyl groups were connected to fine cellulose fibers via amide bonds. Was prepared.

(Production Example 14)
A fine cellulose fiber composite produced in accordance with the method described in Production Example 11 except that dioctylamine was used in place of propylamine in Production Example 11, and the dioctyl group was linked to the fine cellulose fiber via an amide bond. Was prepared.

(Production Example 15)
A fine cellulose fiber composite produced in accordance with the method described in Production Example 11 except that didodecylamine was used in place of propylamine in Production Example 11, and the didodecyl group was linked to the fine cellulose fiber via an amide bond. The body was prepared.

(Production Example 16)
In Production Example 11, except that aniline was used instead of propylamine, a fine cellulose fiber composite produced according to the method described in Production Example 11 and having phenyl groups linked to fine cellulose fibers via amide bonds was prepared. Prepared.

(Production Example 17)
In Production Example 11, except that benzylamine was used instead of propylamine, a fine cellulose fiber composite in which benzyl groups were connected to fine cellulose fibers via an amide bond in accordance with the method described in Production Example 11 was obtained. .

(Production Example 18)
In Production Example 11, except that methylamine was used instead of propylamine, a fine cellulose fiber composite in which methyl groups were linked to fine cellulose fibers via amide bonds was obtained according to the method described in Production Example 11. .

(Production Example 19)
In Production Example 11, except that heptacosylamine was used instead of propylamine, a fine cellulose fiber composite in which heptacosyl groups were linked to fine cellulose fibers via amide bonds in accordance with the method described in Production Example 11 was obtained. It was.

(Production Example 20)
The fine cellulose fiber dispersion (solid content concentration: 5.0% by mass) obtained in Preparation Example 2 for fine cellulose fibers is placed in a beaker equipped with stirring blades, and the solid content concentration is adjusted to 1.0% by mass with ion-exchanged water. Dilution was performed to prepare a dispersion. This dispersion was adjusted to a pH of around 8.0 with a 10% aqueous solution of tetrabutylammonium hydroxide (manufactured by Wako Pure Chemical Industries, Ltd.) to obtain organic onium-treated fine cellulose (hereinafter referred to as “finely modified cellulose”). It was. This finely modified cellulose was lyophilized.

  1.0 part by mass of the finely modified cellulose was transferred to a beaker, 100 parts by mass of dimethylformamide was added, and the dispersion treatment was performed for 10 minutes with a homogenizer. Furthermore, after adding 10.2 parts by mass of propyl iodide as an alkylating agent, the reaction temperature was set to 25 ° C. and the reaction was carried out for about 48 hours. The reaction product was washed with methanol and then dried under reduced pressure overnight to obtain a fine cellulose fiber composite in which propyl groups were connected to fine cellulose fibers via ester bonds. The average binding amount of propyl groups in the fine cellulose fiber composite was 0.73 mmol / g.

(Production Example 21)
A fine cellulose fiber composite in which hexyl groups are linked to fine cellulose fibers via ester bonds in accordance with the method of Production Example 20, except that 10.2 parts by mass of propyl iodide is changed to 12.7 parts by mass of hexyl iodide. Got the body. The average binding amount of hexyl groups in the fine cellulose fiber composite was 0.67 mmol / g.

(Production Examples 22 to 27)
According to the method described in JP 2010-59571 A, a fine cellulose fiber composite in which an alkyl group was connected to a fine cellulose fiber via an ester bond was obtained by the following procedure.

(Production Example 22)
100 parts by mass of the carboxy group-containing fine cellulose fiber dispersion obtained in Preparation Example 1 for fine cellulose fibers was placed in a beaker equipped with stirring blades, and heated and stirred at 70 ° C. Here, as an N-onium compound, a solution prepared by dissolving 11 parts by mass of tri-n-butylhexadecylphosphonium bromide (manufactured by Nippon Kasei Kogyo Co., Ltd.) with 300 parts by mass of ion-exchanged water was added and stirred at 70 ° C. for 3 hours. A solid was separated from the mixture by filtration, washed 3 times with methanol and 3 times with water, to obtain onium-treated fine cellulose fibers. The obtained fine cellulose fiber was dried under reduced pressure all day and night.

  Next, 1.0 part by mass of the obtained finely modified cellulose was transferred to a beaker, 100 parts by mass of DMF, and 6.9 parts by mass of butyl bromide as an alkylating agent were added, followed by dispersion treatment for 10 minutes with a homogenizer. . The reaction temperature was set to 85 ° C. and the reaction was allowed to proceed for about 24 hours. The reaction product was washed with methanol and water, and then dried under reduced pressure overnight to obtain a fine cellulose fiber composite in which butyl groups were linked to fine cellulose fibers via ester bonds. The amount of ester groups measured by the solid NMR method in this fine cellulose fiber composite was 0.78 mmol / g.

(Production Example 23)
A fine cellulose fiber composite in which hexyl bromide was used as an alkylating agent except that 8.3 parts by mass of hexyl bromide was used, and the operation was performed in accordance with Production Example 22, and hexyl groups were linked to fine cellulose fibers via ester bonds. Got. The amount of ester groups measured by solid state NMR in the obtained fine cellulose fiber composite was 0.79 mmol / g.

(Production Example 24)
As the alkylating agent, except that 11.1 parts by mass of decyl bromide was used, the same procedure as in Production Example 22 was followed, and a fine cellulose fiber composite in which a decyl group was linked to a fine cellulose fiber via an ester bond. Got. The amount of ester groups measured by solid-state NMR in the obtained fine cellulose fiber composite was 0.8 mmol / g.

(Production Example 25)
As the alkylating agent, except that 15.3 parts by mass of hexadecyl bromide was used, the same procedure as in Production Example 22 was followed, and a fine cellulose fiber composite in which hexadecyl groups were linked to fine cellulose fibers via ester bonds. Got. The amount of ester groups measured by solid-state NMR in the obtained fine cellulose fiber composite was 0.78 mmol / g.

(Production Example 26)
Except having used 4.7 mass parts of methyl bromides as an alkylating agent, it operated according to manufacture example 22, and the fine cellulose fiber composite_body | complex which connected the methyl group to the fine cellulose fiber via the ester bond. Got. The amount of ester groups measured by solid-state NMR in the obtained fine cellulose fiber composite was 0.76 mmol / g.

(Production Example 27)
As the alkylating agent, except that 23.0 parts by mass of heptacosyl bromide was used, the same procedure as in Production Example 22 was followed, and a fine cellulose fiber composite in which heptacosyl groups were linked to the fine cellulose fiber via an ester bond. Got. The amount of ester groups measured by solid-state NMR in the obtained fine cellulose fiber composite was 0.78 mmol / g.

[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)

[Introduced amount of amide bond in fine cellulose fiber composite]
The average bond amount of hydrocarbon groups in the fine cellulose fiber composite was calculated by the following formula.
Bond amount of amide group (mmol / g) = Carbon group content before introduction of hydrocarbon group or EO / PO copolymer (mmol / g) -Fine after introduction of hydrocarbon or EO / PO copolymerization Carboxy group content in cellulose fiber (mmol / g)

[Introduction amount of ester bond in fine cellulose fiber composite]
The proportion of the carboxy group in the fine cellulose fiber esterified, that is, the esterification rate is determined by DD / MAS (Dipolar Decoupling / Magic Angle Spinning) method using solid-state NMR in accordance with the description in JP-A-2010-59571. Calculated by

(Examples 1-20, Comparative Examples 1-9)
The skin cosmetics shown in Tables 4 to 7 were prepared, and the emulsifying power, the emulsifying stability and the water resistance of the film were evaluated by the following methods. An evaluation result is combined with Table 4-Table 7, 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 4 to 7 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

(Emulsion stability against salt addition)
In order to include the components shown in Tables 4 to 7 at the concentrations shown in the same table, the fine cellulose fiber composite dispersion of component (A) or component (A) ′ in oil agent, sodium chloride 5 wt% ion-exchanged water Other components were added, and the mixture was stirred and emulsified at 4500 rpm for 5 minutes using a homomixer Mark II (manufactured by Primix) at a temperature of 60 ° C. to prepare 500 g. The obtained emulsion was put in a 30 cm long test tube, and the emulsion stability was determined from the difference between the volume% of the emulsion layer after 6 hours and the volume% of the emulsion layer after 6 hours of the tuned product without sodium chloride. Was judged. The evaluation criteria are shown below.
++: Less than 10% reduction by adding sodium chloride +: 10% or more reduction by less than 40% by addition of sodium chloride-: Reduction by 40% or more by addition of sodium chloride

(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%

In Tables 4 to 7, the following components were used.
* 1 Squalane / Nikko Chemical Co., Ltd. * 2 Liquid paraffin: Haicol K-350 / Kaneda Co., Ltd. * 3 Isopropyl palmitate: Exepal IPP / Kao Corporation * 4 Dicaprate neopentyl glycol: Estemol N01 / Nisshin Oilio Co., Ltd. * 5 Polyglyceryl diisostearate: Cosmol 42 / Nisshin Oilio Co., Ltd. * 6 Ethylhexyl methoxycinnamate: Ubinal MC80 / BASF Co. * 7 Monooleyl glyceryl ether: Seraquil alcohol / Nikko Chemical Co., Ltd. * 8 (Isostearic acid / Myristic acid ) Glyceryl: Exepal DG-MI / Kao Co., Ltd. * 9 Isostearyl myristate: Cosmol 812 / Nisshin Oilio Co., Ltd. * 10 Monomyristate diglycerin: Seraquil alcohol / Nikko Chemical Co., Ltd. * 11 HE (Hydroxyethylcellulose): Daicel HEC / Daicel FineChem Ltd. * 12 CMC (carboxymethyl cellulose): CMC Daicel 1222 / Daicel FineChem Ltd.

  From Table 4 to Table 7, since the skin cosmetics obtained in each Example include a fine cellulose fiber composite having a specific structure and characteristics, emulsification power, emulsion stability, and emulsion stability when a salt is added. In addition to being excellent in properties, it can be applied to form a film, 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 agent having an SP value of 7.2 to 15, and (C) water,
The component (A) is an amine or ethylene oxide / propylene oxide (EO / PO) having a hydrocarbon group having 2 to 24 carbon atoms in a carboxy group of a fine cellulose fiber having a carboxy group content of 0.1 to 3 mmol / g. A fine cellulose fiber composite (A1) in which an amine having a copolymerized part is bonded through an amide bond,
A skin cosmetic, 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%. 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 a compound having an alkyl group having 2 to 24 carbon atoms in the carboxy group of a fine cellulose fiber having a carboxy group content of 0.1 to 3 mmol / g, and an alkyl halide and an alkyl sulfate ester. Skin fine cosmetics, wherein at least one selected from the group consisting of alkyl tosylate, alkyl mesylate, and alkyl triflate is a fine cellulose fiber composite (A2) bonded through an ester bond.   The skin cosmetic according to claim 1 or 2, wherein the number average fiber diameter of the fine cellulose fibers is 0.1 to 200 nm.   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.