JP2020019819A - Skin cosmetic - Google Patents

Abstract

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 skin cosmetics.

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

JP 2012-126786 A

  However, the technique of Patent Document 1 described above is also improved in that it has excellent emulsifying power, emulsifying stability, and emulsifying stability when a salt is added, and also improves water resistance of a film when applied to skin or 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 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 copolymer portion is bonded via an amide bond,
It is intended to provide a skin cosmetic wherein the molecular weight of the EO / PO copolymer is from 600 to 10,000, and the content of PO in the EO / PO copolymer is from 6 to 80 mol%. .

Also, the present invention
The following components (A) to (C):
(A) a fine cellulose fiber composite,
(B) a skin cosmetic containing an oil having an SP value of 7.2 to 15 and (C) water,
The component (A) is a compound having an alkyl 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, and an alkyl halide or an alkyl sulfate. For providing a skin cosmetic, 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 via 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 excellent in the water resistance of the film when applied to skin etc. can be provided.

Hereinafter, embodiments of the present invention will be described.
In the present embodiment, the skin cosmetic is a composition containing the following components (A) to (C).
(A) Fine cellulose fiber composite (B) Oil agent with SP value of 7.2 to 15 (C) Water Hereinafter, each component will be described with specific examples. Each component can be used alone or in combination of two or more.
(Component (A))
The fine cellulose fiber composite of the component (A) is obtained by bonding a specific group to the carboxy group via an amide bond or an ester bond in the fine cellulose fiber having a carboxy group content of 0.1 to 3 mmol / g. It is a fine cellulose fiber composite.
First, the fine cellulose fibers will be described.

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

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

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

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

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

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

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

Next, as specific examples of the fine cellulose fiber composite in which a specific group is bonded to the carboxy group of the fine cellulose fiber via an amide bond or an ester bond, that is, the component (A), the following component (A1) ) And (A2). In the present embodiment, as the component (A), at least one 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 the component (A1) has an amine or an ethylene oxide / propylene oxide (EO / PO) copolymer having a hydrocarbon group having 2 to 24 carbon atoms in the carboxy group of the fine cellulose fiber described above. An amine is formed through an amide bond.

  Among amines that are amide-bonded to fine cellulose fibers, the amine having a hydrocarbon group having 2 to 24 carbon atoms includes an aliphatic hydrocarbon group having 2 to 24 carbon atoms or an aromatic hydrocarbon group having 2 to 24 carbon atoms. Amines.

<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 any of a saturated hydrocarbon group and an unsaturated hydrocarbon group. From the viewpoint of enhancement, a saturated hydrocarbon group is preferable. Further, the hydrocarbon group is preferably a linear or branched hydrocarbon group. The number of carbon atoms of the hydrocarbon group is 2 or more, and more preferably 3 or more, from the viewpoint of making the handleability preferable. In addition, from the viewpoint of increasing the availability, it is 24 or less, more preferably 18 or less, and further preferably 12 or less. The hydrocarbon group has 2 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, and still more preferably 3 to 12 carbon atoms. That is, as a suitable hydrocarbon group, a saturated or unsaturated, linear or branched hydrocarbon having preferably 2 to 24, more preferably 2 to 18, and even more preferably 3 to 12 carbon atoms. Groups.

Examples of the amine having an aliphatic hydrocarbon group having 2 to 24 carbon atoms include the above-described primary or secondary amine having an aliphatic hydrocarbon group.
Among them, as the primary amine, for example, a primary amine having 2 to 24 carbon atoms can be used. More specifically, as primary amines, ethylamine, propylamine, butylamine, pentylamine, hexylamine, heptylamine, octylamine, 2-ethylhexylamine, decylamine, dodecylamine, tridecylamine, tetradecylamine, octadecylamine And the like. 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, and specifically, ethylamine, propylamine, butylamine, pentylamine, hexylamine, heptylamine, Octylamine, 2-ethylhexylamine, decylamine, dodecylamine, tridecylamine, tetradecylamine, octadecylamine are exemplified. More preferred are primary amines 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. Among them, from the viewpoint of improving the reactivity with the carboxy group, preferably have 2 to 18 carbon atoms, more preferably 2 to 12 carbon atoms, further preferably 2 to 8 carbon atoms, and more preferably 2 to 2 carbon atoms. Primary amines having 6 linear or branched hydrocarbon groups are preferred.

  Examples of 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 the fine cellulose fiber via an amide bond include, for example, JP-A-2013-151636. Those described may 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 a primary amine or a secondary amine, but a primary amine is preferred from the viewpoint of improving the reactivity with a carboxy group.
The aromatic hydrocarbon group is selected, for example, from the group consisting of an aryl group and an aralkyl group. The aryl group and the aralkyl group may be substituted or unsubstituted aromatic rings.

  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 below. One kind alone or two or more kinds may be contained in an amine having an aromatic hydrocarbon group. Among them, from the viewpoint of improving the dispersion stability of the skin cosmetic, a phenyl group, a biphenyl group, and a terphenyl group are preferable, and a phenyl group is more preferable.

  Examples of the aralkyl group include, 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 substituted with a substituent described below. And the like. One or more of these may be included in the amine. Among them, from the viewpoint of improving the dispersion stability of skin cosmetics, benzyl group, phenethyl group, phenylpropyl group, phenylpentyl group, phenylhexyl group, phenylheptyl group is preferable, benzyl group, phenethyl group, phenylpropyl group, Phenylpentyl and phenylhexyl are more preferred, and benzyl, phenethyl, phenylpropyl and phenylpentyl are even more preferred.

  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, still more preferably 13 or less, and further preferably 11 or less.

  As the substituent of the aryl group and the aralkyl group, those having a total carbon number of the entire aromatic hydrocarbon group including the substituent within the above-mentioned range are preferable. For example, a methyl group, an ethyl group, a propyl group, an isopropyl group Butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, hexyl and other alkyl groups having 1 to 6 carbon atoms; methoxy, ethoxy, propoxy, isopropoxy, butoxy A C1-C6 alkoxy group such as a group, isobutoxy group, sec-butoxy group, tert-butoxy group, pentyloxy group, isopentyloxy group, hexyloxy group; methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, Isopropoxycarbonyl group, butoxycarbonyl group, isobutoxycarbo An alkoxy-carbonyl group having 1 to 6 carbon atoms in an alkoxy group such as a carbonyl group, a sec-butoxycarbonyl group, a tert-butoxycarbonyl group, a pentyloxycarbonyl group, an isopentyloxycarbonyl group; a fluorine atom, a chlorine atom, and a bromine 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; Dialkylamino group. Note that the aromatic group itself may be bonded as a substituent.

  Among amines having an aromatic hydrocarbon group having 2 to 24 carbon atoms, those in which the aromatic hydrocarbon group and the N atom are bonded directly or via a linking group are preferable. As the linking group, a hydrocarbon group is preferable, and an alkylene group having preferably 1 to 6, more preferably 1 to 3 carbon atoms is used. For example, an ethylene group and a propylene group are preferable.

  Specific examples of the amine having an aromatic hydrocarbon group having 2 to 24 carbon atoms are described below. For example, examples of the amine having an aryl group include aniline, 4-biphenylylamine, diphenylamine, 2-aminonaphthalene, p-terphenylamine, 2-aminoanthracene, and 2-aminoanthraquinone. Among them, 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 them, benzylamine, phenethylamine, 5-phenylpentylamine, 6-phenylhexylamine, and 7-phenylheptylamine are preferable from the same viewpoint, and benzylamine, phenethylamine, 3-phenylpropylamine, 5-phenylpentylamine, and 6-phenylpentylamine are preferable. Phenylhexylamine is more preferred, and benzylamine, phenethylamine, 3-phenylpropylamine and 5-phenylpentylamine are even more preferred.

  A commercially available amine having an aromatic hydrocarbon group having 2 to 24 carbon atoms can be used, or an amine having an aromatic hydrocarbon group can be prepared according to a known method. For example, aniline can be produced by reducing nitrobenzene, and benzylamine can be produced by hydrogenating benznitrile.

<Amine having EO / PO copolymerization part>
Next, the amine having an ethylene oxide / propylene oxide (EO / PO) copolymer portion will be described.
First, in this specification, an amide bond of an amine having an ethylene oxide / propylene oxide (EO / PO) copolymer moiety to a carboxy group means that an EO / PO copolymer is bonded to a carboxy group having a carbon atom covalently bonded to a cellulose skeleton. It means a state in which the polymer part is amide-bonded.
And the molecular weight of the said EO / PO copolymer part is 600-10,000, and the content of PO in the EO / PO copolymer part is 6-80 mol%.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

The binding amount of the EO / PO amine in the fine cellulose fiber composite is determined based on the viewpoint of improving the handleability of the fine cellulose fiber composite, the viewpoint of improving the emulsion stability of the skin cosmetic, and the skin makeup applied to the skin and the like. From the viewpoint of improving the water resistance of the coating of the coating 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. / G or more, particularly preferably 0.5 mmol / g or more, even more preferably 0.8 mmol / g or more. Further, from the viewpoint of reactivity at the time of amide bond, the amount of EO / PO amine bound in the fine cellulose fiber composite is preferably 3 mmol / g or less, more preferably 2 mmol / g or less, and further preferably 1. 5 mmol / g or less. The binding amount of the EO / PO amine can be adjusted by the amount of amine added, the type of amine, the reaction temperature, the reaction time, the solvent, and the like.
In this embodiment, the binding amount of the EO / PO amine can be determined by infrared spectroscopy (Infrared (IR) Spectroscopy), and specifically, is determined by a method described in Examples described later.

<Method for producing fine cellulose fiber composite of component (A1)>
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 copolymer 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 copolymerized portion into a previously prepared fine cellulose fiber via an amide bond may be performed, or the amide bond may be continuously prepared when preparing the fine cellulose fiber. May be introduced to introduce a hydrocarbon group or an EO / PO copolymerized portion through the reaction. The fine cellulose fibers can be produced by a known method, for example, a method described in JP-A-2011-140632 or the like.

A preferred production method includes, for example, a production method including the following step (i) and step (ii).
Step (i): Step of oxidizing natural cellulose fiber in the presence of an N-oxyl compound to obtain a carboxy group-containing cellulose fiber Step (ii): Carboxyl group-containing cellulose fiber obtained in step (i), and carbon number Step of amidating a 2 to 24 hydrocarbon group or an amine having an EO / PO copolymerized part. As a preferable production method, more specifically, a fine-pulverization step described later after the step (i) is used. A method in which the step (ii) is performed after forming the carboxy group-containing fine cellulose fiber (first production mode), and a method in which the step (ii) is performed after the step (i) and then the micronizing step is performed ( Second production mode).

  Hereinafter, a method for producing the fine cellulose fiber composite of the component (A1) will be described based on the above-mentioned “first production mode”.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

(Step (ii))
In the first production mode, the step (ii) includes the step of preparing a carboxy group-containing fine cellulose fiber obtained through the above-described fine step and an amine having a hydrocarbon group having 2 to 24 carbon atoms or an EO / PO copolymerized part. Is amidation-reacting to obtain a fine cellulose fiber composite (A1). Specifically, a carboxy group contained in the carboxy group-containing fine cellulose fiber is condensed with a hydrocarbon group having 2 to 24 carbon atoms or an amino group of an amine having an EO / PO copolymer to form an amide bond. A fine cellulose fiber composite formed and having a hydrocarbon group having 2 to 24 carbon atoms or an EO / PO copolymer unit linked via an amide bond is obtained.

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

  From the viewpoint of improving the reactivity, the amount of the amine is preferably 0.1 mol or more, more preferably 0.5 mol or more, based on 1 mol of the carboxy group contained in the carboxy group-containing fine cellulose fiber. It is still more preferably 0.7 mol or more, and from the viewpoint of increasing product purity, the amount is preferably 50 mol or less, more preferably 20 mol or less, and still more preferably 10 mol or less. The amount of the amine contained in the above range may be supplied to the reaction at one time or may be supplied to the reaction in a divided manner. When the amine is a monoamine, the above amine group and the 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.

  Examples of the condensing agent include, but are not limited to, synthetic chemistry series, Peptide Synthesis (Maruzensha) 116, or a condensing agent described in Tetrahedron, 57, 1551 (2001), for example, 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 micronization step, and it is preferable to select a solvent in which the amine used in the amidation reaction is dissolved. 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. The reaction time is preferably 1 to 24 hours, more preferably 10 to 20 hours, from the viewpoint of increasing the reaction rate. Further, the reaction temperature is preferably 0 ° C. or higher, more preferably 5 ° C. or higher, and still more preferably 10 ° C. or higher, from the viewpoint of improving the reactivity. From the viewpoint of suppressing the coloring of the fine cellulose fiber composite, the temperature is preferably 200 ° C or lower, more preferably 80 ° C or lower, further preferably 30 ° C or lower.

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

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

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

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

  The number average fiber diameter of the obtained fine cellulose fiber composite (A1) is preferably 0.1 nm or more, more preferably 0.1 nm, from the viewpoint of enabling the skin cosmetic to form a film having excellent water resistance. It is at least 2 nm, more preferably at least 0.5 nm, even more preferably at least 0.8 nm, particularly preferably at least 1 nm. Further, from the viewpoint of improving the water resistance when applied to the skin, more specifically, from the viewpoint of improving the water resistance of the formed film, the number average fiber diameter of the fine cellulose fiber composite is preferably 200 nm or less. Yes, more preferably 100 nm or less, still more preferably 50 nm or less, even more preferably 20 nm or less, particularly preferably 10 nm or less.

Note that the fine cellulose fiber composite preferably has the same degree of crystallinity as that of the fine cellulose fiber, since the crystallinity does not decrease due to the reaction in step (ii).
The amount of the amide bond in the obtained fine cellulose fiber composite, that is, the amount of the amine having a hydrocarbon group having 2 to 24 carbon atoms or the amine having EO / PO to the fine cellulose fiber composite is determined by the fine cellulose fiber composite. From the viewpoint of improving the handleability of the body, improving the emulsion stability of the skin cosmetic, and improving the water resistance of the skin cosmetic film applied to the skin and the like, preferably 0.01 mmol / g. Or more, more preferably 0.05 mmol / g or more, further preferably 0.1 mmol / g or more, even more preferably 0.3 mmol / g or more, particularly preferably 0.5 mmol / g or more, and still more preferably 0 mmol / g or more. 0.8 mmol / g or more. In addition, from the viewpoint of reactivity at the time of amide bond, the amount of amide bond 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. It is.

  As the fine cellulose fiber composite of the component (A1), at least one selected from the group consisting of EO / PO copolymers, secondary amines, and linear or branched alkylamines is preferably used. Is bonded via an amide bond, more preferably, one or more selected from the group consisting of an EO / PO copolymer, a secondary amine and a linear alkylamine 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. Are connected via The fine cellulose fiber composite of the 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 at an average bond amount of 0.3 mmol / g or more, and the average fiber diameter is 0.1 to 200 nm. (A1).
In the component (a1), the fine cellulose fibers can be the same as the fine cellulose fibers used in the fine cellulose fiber composite (A1).

  The hydrocarbon group in the fine cellulose fiber composite (a1) has 2 to 24 carbon atoms, more specifically, a saturated or unsaturated, linear or branched carbon having 2 to 24 carbon atoms. And a hydrogen group. Among them, the number of carbon atoms is preferably 20 or less, more preferably 18 or less, and still more preferably 12 or less, from the viewpoint of improving the strength of the film formed by the skin cosmetic. Further, from the viewpoint of improving the yellowing resistance (low coloration upon heating) of the component (a1) and improving the dispersion stability of the skin cosmetic, the hydrocarbon group in the fine cellulose fiber composite (a1) is The number of carbon atoms is preferably 3 or more. Moreover, the carbon number of the hydrocarbon group in the fine cellulose fiber composite (a1) is 2 to 24, more preferably 2 to 20, further preferably 2 to 18, and more preferably 3 to 12.

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

  The bonding amount of the hydrocarbon group in the fine cellulose fiber composite (a1) is intended to improve the yellowing resistance (low coloration upon heating) of the component (a1) and the dispersion stability of the skin cosmetic. Therefore, the average binding amount is 0.3 mmol / g or more, preferably 0.4 mmol / g or more, and more preferably 0.5 mmol / g or more. In addition, from the viewpoint of improving the strength of the film formed by the skin cosmetic, the amount is preferably 3 mmol / g or less, more preferably 2 mmol / g or less, and still more preferably 1 mmol / g or less. Further, the average bond amount of the hydrocarbon group is preferably 0.3 to 3 mmol / g, more preferably 0.4 to 2 mmol / g, and still more preferably 0.5 to 1 mmol / g.

  The fine cellulose fiber composite (a1) can be produced according to the method for producing 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. 0.2 mmol / g or more. In addition, from the viewpoint of improving the yellowing resistance (low coloration during heating) of the component (a1), it is preferably 2.8 mmol / g or less, more preferably 2.0 mmol / g or less, and still more preferably 1.5 mmol / g. / G or less. In addition, 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 enhancing the balance of the above effects. / G.

  In addition, 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 at least 0.5 nm, more preferably at least 0.8 nm, even more preferably at least 1 nm. In addition, from the viewpoint of improving the dispersion stability and the transparency of the skin cosmetic, preferably 200 nm or less, more preferably 100 nm or less, further preferably 50 nm or less, further preferably 20 nm or less, further more preferably 10 nm or less. It is. In addition, the average fiber diameter of the component (a1) is preferably 0.1 to 200 nm, more preferably 0.2 to 100 nm, further preferably 0.5 to 50 nm, and still more preferably, from the viewpoint of enhancing the balance of the above effects. It is 0.8-20 nm, more preferably 1-10 nm.

Next, the component (A2) will be described.
(Component (A2))
The fine cellulose fiber composite of the 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 comprises an alkyl halide, an alkyl sulfate, an 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 the component (A2) is obtained by bonding an alkyl having 2 to 24 carbon atoms to the carboxy group of the above fine cellulose fiber via an ester bond. As the component (A2), for example, those described in JP-A-2010-59571 can be used.

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

  Further, in the component (A2), the number of carbon atoms of the alkyl group bonded to the fine cellulose fiber via an ester group depends 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 to 24, more preferably 2 to 18, still more preferably 3 to 18, even more preferably a propyl, butyl, hexyl, decyl or hexadecyl group.

  In the fine cellulose fiber composite of the component (A2), the amounts of the ester group and the aldehyde group are determined based on the mass of the fine cellulose fiber composite 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.

In addition, the amount of the ester bond in the fine cellulose fiber composite of the component (A2) is preferably 0.01 mmol / g or more, more preferably 0.05 mmol / g, from the viewpoint of improving the handleability of the component (A2). The above is more preferably 0.1 mmol / g or more, still more preferably 0.3 mmol / g or more, particularly preferably 0.5 mmol / g or more, and still more preferably 0.8 mmol / g or more. In addition, from the viewpoint of the reactivity of esterification when obtaining the component (A2), the amount of ester bonds 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.
In the present embodiment, the amount of the ester bond can be determined by solid-state NMR (Nuclear Magnetic Resonance).

<Method for producing fine cellulose fiber composite of component (A2)>
Examples of the method for producing the component (A2) include a method including the following step (i), step (iii), and step (iv).
Step (i): Step of oxidizing natural cellulose fibers in the presence of an N-oxyl compound to obtain carboxy group-containing cellulose fibers Step (iii) Step of treating fine cellulose fibers with an organic onium compound Step (iv): Step (Iii) a compound having an alkyl group having 2 to 24 carbon atoms and a cellulose fiber treated with an onium compound and comprising an alkyl halide, an alkyl sulfate, an alkyl tosylate, an alkyl mesylate and an alkyl triflate; Reacting with at least one selected from the group to esterify

Here, the step (i) is the same as the step (i) described above in the method for producing the component (A1).
In the same manner as in the method for producing the component (A1), in the method for producing the component (A2), a micronizing step is performed after the step (i) to obtain a carboxy group-containing fine cellulose fiber. A method of performing (iv) (first manufacturing mode) or a method of performing step (iii) and step (iv) after step (i), and then performing a miniaturization step (second manufacturing mode). Is preferred.

Hereinafter, the step (iii) will be described.
Step (iii) is hydrophobized (lipophilic) 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). ) This is the processing step.
As the step (iii), for example, a hydrophobic treatment described in JP-A-2010-59571 can be used.

Hereinafter, the 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 an alkyl halide, an alkyl sulfate, an alkyl tosylate, an alkyl mesylate, and an alkyl triflate. This is an alkyl esterification step for esterification.
As the step (iv), for example, an esterification reaction described in JP-A-2010-59571 can be used.

Although the solvent used in the alkyl esterification step is not limited, it is preferable to select a solvent having excellent dispersibility of the fine cellulose fibers subjected to the hydrophobizing treatment in the step (iii) or a solvent which does not inhibit the transesterification reaction. The solvents can be used alone or in combination of two or more.
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 and aromatic hydrocarbons such as toluene, xylene and cyclohexane; Ethers such as ether, dioxane and tetrahydrofuran; and polar solvents such as dimethylacetamide, dimethylformamide, N-methylpyrrolidone, dimethylsulfoxide and the like. For example, when the N-onium compound used in the hydrophobizing treatment in the step (iii) is an alkylonium compound, it is preferably dimethylacetamide, dimethylformamide, N-methylpyrrolidone or dimethylacetamide from the viewpoint of increasing the dispersibility of the fine cellulose fibers. Dimethyl sulfoxide.

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

The reaction temperature of the alkyl esterification reaction can be set in accordance with the boiling point of the solvent, the thermal stability of the hydrophobized fine cellulose fibers, and the like, and is preferably from room temperature (25 ° C., the same applies hereinafter) to 200 ° C. Yes, more preferably 50C to 150C, even more preferably 70C to 120C. When a relatively high reaction temperature of 100 ° C. or higher is employed, fine cellulose fibers treated with an alkylphosphonium compound are preferably used from the viewpoint of improving heat resistance.
Further, the reaction vessel used for the alkyl esterification reaction is not limited.
The reaction time is preferably 0.1 to 30 hours, more preferably 1 to 20 hours.

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

  Examples of the alkylating agent used in the alkyl esterification reaction include alkyl halides; alkyl sulfates such as dimethyl sulfate and diethyl sulfate; alkyl tosylate such as methyl p-toluenesulfonate; alkyl mesylate such as methyl methanesulfonate; 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, cholestaryl chloride, and polyfluoroalkyl chloride having 2 to 24 carbon atoms. Chloride; methyl bromide, ethyl bromide, propyl bromide, butyl bromide, hexyl bromide, decyl bromide, hexadecyl bromide, okdacil bromide, cholesteryl bromide, cholesteryl bromide, poly having 2 to 24 carbon atoms 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, carbon number 2 Iodides such as polyfluoroalkyl iodine; 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 method of the post-treatment, for example, filtration, centrifugation, dialysis and the like can be used.

  Further, the fine cellulose fiber composite (A2) obtained as described above can be used as a component in a skin cosmetic in a state of a dispersion liquid after post-treatment, similarly to the case of the component (A1). Alternatively, the solvent may be removed from the dispersion by a drying treatment or the like to obtain a dried powdery fine cellulose fiber composite, which can be used. Specific examples of the powdery 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 at least 0.1 nm, more preferably at least 0.1 nm, from the viewpoint of enabling the skin cosmetic to form a film having excellent water resistance. It is at least 0.2 nm, more preferably at least 0.5 nm, even more preferably at least 0.8 nm, particularly preferably at least 1 nm. Further, from the viewpoint of improving the water resistance when applied to the skin, and 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, particularly 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 with respect to the entire skin cosmetic from the viewpoint of enabling the skin cosmetic to form a film having excellent water resistance. % Or more, preferably 0.2% by mass or more, more preferably 0.3% by mass or more, even more preferably 0.5% by mass or more.
In addition, from the viewpoint of enabling the skin cosmetic to form a film having excellent water resistance and optimizing the feeling of use of the skin cosmetic, the content of the component (A) in the skin cosmetic is controlled by the skin cosmetic. It is, for example, 4% by mass or less, preferably 3% by mass or less, more preferably 2% by mass or less, even more preferably 1.5% by mass or less based on the whole.

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

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

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

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

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

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

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

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

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

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

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

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

  Next, examples of the present invention will be described.

(Production Examples 1 to 27)
The fine cellulose fiber composites used in Examples and Comparative Examples described later were produced by the following methods and evaluated. Structure of the fine cellulose fiber used in each production example and the hydrocarbon group or EO / PO copolymerized portion or ester-bonded alkyl group bonded thereto, and the characteristics of the 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 Carboxyl Group-Containing Fine Cellulose Fiber Obtained by Acting N-Oxyl Compound on Natural Cellulose)
Bleached kraft pulp of softwood (Flecher Challenge Canada, trade name "Machenzie", CSF 650 ml) was used as natural cellulose fiber. As TEMPO, a commercially available product (free radical, 98% by mass, manufactured by ALDRICH) was used. A commercially available product (manufactured by Wako Pure Chemical Industries, Ltd.) was used as sodium hypochlorite. A commercial product (manufactured by Wako Pure Chemical Industries, Ltd.) was used as sodium bromide.

  First, 100 g of bleached kraft pulp fiber of softwood was sufficiently stirred with 9900 g of ion-exchanged water, and then 1.25 mass% of TEMPO, 12.5 mass% of sodium bromide, 28 mg of sodium hypochlorite were added to 100 g of the pulp. 0.4% by weight were added in this order. Using a pH stud, 0.5 M sodium hydroxide was added dropwise to maintain the pH at 10.5. After the reaction was performed for 120 minutes, the dropping of sodium hydroxide was stopped to obtain oxidized pulp. The obtained oxidized pulp was sufficiently washed using ion-exchanged water, and then dehydrated. Thereafter, 3.9 g of oxidized pulp and 296.1 g of ion-exchanged water were mixed, and the mixture was refined twice at 245 MPa using a high-pressure homogenizer (Starburst Lab HJP-25005, manufactured by Sugino Machine Co., Ltd.) to obtain a carboxy group. A fine cellulose fiber dispersion (solid content: 1.3% by mass) was obtained. The number average fiber diameter of this fine cellulose fiber was 3.3 nm, and the carboxy group content was 1.4 mmol / g.

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

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

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

(Production of fine cellulose fiber composite)
A beaker equipped with a magnetic stirrer and a stirrer was charged with 35 g of the carboxy group-containing fine cellulose fiber dispersion obtained in Preparation Example 2 of fine cellulose fibers (solid content concentration: 5.4% by mass). Subsequently, an amine having an EO / PO copolymer of the type shown in Table 1 was added in an amount corresponding to 5 mol of amine groups per 1 mol of carboxy groups of the fine cellulose fibers, and 4- (4,6) as a condensing agent. -Dimethoxy-1,3,5-triazin-2-yl) -4-methylmorpholinium chloride (DMT-MM) (3.78 g) was charged and dissolved in IPA (300 g). The reaction solution was reacted at room temperature (25 ° C.) for 14 hours. After the completion of the reaction, the mixture was filtered, washed with ion-exchanged water, the DMT-MM salt was removed, washed with acetone and solvent-substituted, whereby the EO / PO copolymer was linked to the fine cellulose fiber via an amide bond. A cellulose fiber composite was obtained.

(Production Example 11)
In a beaker equipped with a magnetic stirrer and a stirrer, 40 g of the carboxy group-containing fine cellulose fiber dispersion obtained in Preparation Example 2 of fine cellulose fibers (solid content concentration: 5% by mass) was charged. Subsequently, propylamine was added in an amount corresponding to 1.2 mol of amine groups per 1 mol of carboxy groups of fine cellulose fibers, 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 at room temperature (25 ° C.) for 14 hours. After completion of the reaction, the mixture was filtered, washed with ethanol to remove DMT-MM salts, and solvent-exchanged with ion-exchanged water, whereby a fine cellulose fiber composite in which an amine was connected to the fine cellulose fiber through an amide bond. A dispersion was obtained.

(Production Example 12)
A fine cellulose fiber composite in which a hexyl group is connected to a fine cellulose fiber via an amide bond in Production Example 11 except that hexylamine is used in place of propylamine in the same manner as in Production Example 11. Was prepared.

(Production Example 13)
A fine cellulose fiber composite produced in accordance with the method described in Production Example 11 except that octadecylamine was used instead of propylamine in Production Example 11, and an octadecyl group was linked to the fine cellulose fiber via an amide bond. 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 instead of propylamine in Production Example 11, and a dioctyl group was connected 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 instead of propylamine in Production Example 11, and a didodecyl group was connected 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 in place of propylamine, a fine cellulose fiber composite in which a phenyl group was connected to a fine cellulose fiber via an amide bond was produced according to the method described in Production Example 11. Prepared.

(Production Example 17)
A fine cellulose fiber composite having a benzyl group linked to a fine cellulose fiber via an amide bond was obtained according to the method described in Production Example 11, except that benzylamine was used instead of propylamine in Production Example 11. .

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

(Production Example 19)
A fine cellulose fiber composite in which a heptacosyl group is linked to a fine cellulose fiber via an amide bond according to the method described in Production Example 11 except that heptacosylamine is used instead of propylamine in Production Example 11 Was.

(Production Example 20)
The fine cellulose fiber dispersion (solid content: 5.0% by mass) obtained in Preparation Example 2 of the fine cellulose fiber is put into a beaker equipped with stirring blades, and the solid content is adjusted to 1.0% by mass with ion-exchanged water. After dilution, a dispersion was prepared. 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 an organic onium-treated fine cellulose (hereinafter, referred to as “finely modified cellulose”). Was. This finely modified cellulose was freeze-dried.

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

(Production Example 21)
Except that 10.2 parts by mass of propyl iodide was changed to 12.7 parts by mass of hexyl iodide, a fine cellulose fiber composite in which a hexyl group was linked to a fine cellulose fiber via an ester bond in accordance with the method of Production Example 20 I got a 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-A-2010-59571, a fine cellulose fiber composite in which an alkyl group is linked to a fine cellulose fiber via an ester bond was obtained by the following procedure.

(Production Example 22)
100 parts by mass of the dispersion liquid of the carboxy group-containing fine cellulose fiber obtained in Preparation Example 1 of the fine cellulose fiber was put into a beaker equipped with a stirring blade and heated and stirred at 70 ° C. Here, as an N-onium compound, a solution in which 11 parts by mass of tri-n-butylhexadecylphosphonium bromide (manufactured by Nippon Kasei Kogyo Co., Ltd.) was dissolved in 300 parts by mass of ion-exchanged water was added, and the mixture was stirred at 70 ° C. for 3 hours. The solid was filtered off from the mixture, washed three times with methanol and three times with water, to obtain onium-treated fine cellulose fibers. The obtained fine cellulose fibers were 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, and then a dispersion treatment was performed for 10 minutes with a homogenizer. . The reaction temperature was set at 85 ° C., and the reaction was performed for about 24 hours. The reaction product was washed with methanol and water, and dried under reduced pressure all day and night to obtain a fine cellulose fiber composite in which butyl groups were connected to fine cellulose fibers via ester bonds. The amount of ester groups measured by the solid-state NMR method in this fine cellulose fiber composite was 0.78 mmol / g.

(Production Example 23)
Except for using 8.3 parts by mass of hexyl bromide as the alkylating agent, the same operation as in Production Example 22 was carried out to obtain a fine cellulose fiber composite in which hexyl groups were linked to fine cellulose fibers via ester bonds. I 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)
Except for using 11.1 parts by mass of decyl bromide as the alkylating agent, the same operation as in Production Example 22 was carried out, and the fine cellulose fiber composite in which decyl groups were linked to fine cellulose fibers via ester bonds. I 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)
Except for using 15.3 parts by mass of hexadecyl bromide as the alkylating agent, the same operation as in Production Example 22 was carried out, and the fine cellulose fiber composite in which hexadecyl groups were linked to the fine cellulose fibers via ester bonds. I 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 for using 4.7 parts by mass of methyl bromide as the alkylating agent, the same operation as in Production Example 22 was carried out, and the fine cellulose fiber composite in which a methyl group was connected to the fine cellulose fibers via an ester bond was used. I 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)
Except for using 23.0 parts by mass of heptacosyl bromide as the alkylating agent, the same procedure as in Production Example 22 was repeated, except that the heptacosyl group was linked to the fine cellulose fiber via an ester bond. I 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 was added to the fine cellulose fiber or the fine cellulose fiber composite to prepare a dispersion having a concentration of 0.0001% by mass, and the dispersion was dropped on mica (mica) and dried to obtain an observation sample. Using an atomic force microscope (AFM, Nanoscope III Tapping mode AFM, manufactured by Digital Instrument Co., Ltd., probe: Point Probe (NCH) manufactured by Nanosensors Co., Ltd.), the fiber height of the cellulose fiber in the observation sample was measured. It was measured. At that time, five or more fine cellulose fibers or fine cellulose fiber composites were extracted from a microscope image in which the cellulose fibers could be confirmed, and the average fiber diameter was calculated from the fiber height.

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

(Introduction amount of amide bond in the fine cellulose fiber composite)
The average binding amount of the hydrocarbon groups in the fine cellulose fiber composite was calculated by the following equation.
Bonding amount of amide group (mmol / g) = carboxy group content (mmol / g) in fine cellulose fiber before introduction of hydrocarbon group or EO / PO copolymer-fine particle after introduction of hydrocarbon or EO / PO copolymerization Carboxyl group content in cellulose fiber (mmol / g)

(Introduction amount of ester bond in the fine cellulose fiber composite)
The ratio of the esterification of the carboxy group in the fine cellulose fiber, that is, the esterification ratio, is determined by the DD / MAS (Dipolar Decoupling / Magic Angle Spinning) method using solid-state NMR according to the description in JP-A-2010-59571. Was calculated by

(Examples 1 to 20, Comparative Examples 1 to 9)
The skin cosmetics shown in Tables 4 to 7 were prepared, and the emulsifying power, the emulsion stability, and the water resistance of the film were evaluated by the following methods. The evaluation results are also shown in Tables 4 to 7.

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

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

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

(Emulsion stability against salt addition)
The dispersion of the fine cellulose fiber composite or the component (A) ′ of the component (A) in an oil agent, 5% by weight of sodium chloride ion-exchanged water so as to include the components shown in Tables 4 to 7 at the concentrations described in the same table. Other components were added, and the mixture was 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 placed in a test tube having a length of 30 cm, and the emulsion stability was determined from the difference between the volume% of the emulsified layer after 6 hours and the volume% of the emulsified layer after 6 hours of the synchronized product without sodium chloride added. Was determined. The evaluation criteria are shown below.
++: Decrease of less than 10% by addition of sodium chloride +: Decrease of 10% or more and less than 40% by addition of sodium chloride-: Decrease of 40% or more by addition of sodium chloride

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

In Tables 4 to 7, the following components were used.
* 1 Squalane / Nikko Chemical * 2 Liquid paraffin: Hicoll K-350 / Kaneda * 3 Isopropyl palmitate: Exepearl IPP / Kao * 4 Neopentyl glycol dicaprate: Estemol N01 / Nisshin Oilio * 5 Polyglyceryl diisostearate: Cosmall 42 / Nisshin Oillio Co., Ltd. * 6 Ethylhexyl methoxycinnamate: Ubinal MC80 / BASF * 7 Monooleyl glyceryl ether: Seracyl alcohol / Nikko Chemical * 8 (Isostearic acid / myristic acid) ) Glyceryl: Exepearl DG-MI / Kao Corporation * 9 Isostearyl myristate: Cosmall 812 / Nissin Oilio Corporation * 10 Diglycerin monomyristate: Serakyl alcohol / Nikko Chemical Corporation * 11 HE (Hydroxyethylcellulose): Daicel HEC / Daicel FineChem Ltd. * 12 CMC (carboxymethyl cellulose): CMC Daicel 1222 / Daicel FineChem Ltd.

  From Tables 4 to 7, since the skin cosmetics obtained in each Example contain a fine cellulose fiber composite having a specific structure and properties, emulsifying power, emulsifying stability and emulsifying stability when a salt is added. It has excellent properties, can form a film by being applied, and has excellent water resistance.

Claims (4)

The following components (A) to (C):
(A) a fine cellulose fiber composite,
(B) a skin cosmetic containing an oil having an SP value of 7.2 to 15 and (C) water,
The component (A) is 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 copolymer portion is bonded via an amide bond,
Skin cosmetics, wherein the molecular weight of the EO / PO copolymer is from 600 to 10,000, and the content of PO in the EO / PO copolymer is from 6 to 80 mol%. The following components (A) to (C):
(A) a fine cellulose fiber composite,
(B) a skin cosmetic containing an oil having an SP value of 7.2 to 15 and (C) water,
The component (A) is a compound having an alkyl 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, and an alkyl halide or an alkyl sulfate. Skin 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 via 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, other ultraviolet absorbers, other fungicides, and other whitening agents; or The skin cosmetic according to any one of claims 1 to 3, wherein the cosmetic is two or more types.