JP4832000B2 - Water-in-oil emulsion composition - Google Patents

Description

  The present invention relates to a water-in-oil emulsion composition having excellent stability and good usability.

  The water-in-oil emulsion composition has good affinity to the skin, and forms a film on the surface of the skin to prevent the evaporation of moisture, thereby protecting the skin from drying and imparting a treatment effect, etc. Due to its characteristics, it is widely used in cosmetics. In particular, when an oily agent having a high viscosity or a solid oily agent is used as the oil component, the protective effect of the skin can be enhanced, but there is a drawback that it is accompanied by a sticky feeling of use.

  In general, in order to obtain a refreshing feel while maintaining the characteristics of a water-in-oil emulsion composition, the amount of water is increased, silicone oil is used as an oil agent, or a powder that exhibits a refreshing feeling of use. It has been used. However, when emulsifying oily components including highly viscous oils and solid fats in particular, the surfactants that can be used as emulsifiers are limited, and it is necessary to add a large amount of surfactants, resulting in increased stickiness. There's a problem. Furthermore, such an oil agent makes it difficult to adjust the emulsified composition so as to obtain a refreshing feeling of use, such as increasing the amount of water or using silicone oil.

Therefore, various studies have been conducted in order to obtain a stable water-in-oil emulsion composition in a water-rich system. For example, Patent Document 1 describes a technique in which a sphingosine analog is cationized with a fatty acid and used as an emulsifier.
However, although the emulsion obtained here has good usability, it may become unstable when the temperature changes drastically, and is not sufficiently satisfactory in terms of stability.
JP 2005-2023 A

  An object of the present invention is to provide a water-in-oil type emulsion composition which is excellent in stability even when the temperature change is severe and has a good feeling in use.

  The present inventor used a salt formed of sphingosines originally present in the skin and a specific fatty acid as an emulsifier, and further added an oil-soluble antioxidant at a specific ratio, resulting in severe temperature changes. In some cases, it was found that a water-in-oil emulsion composition having excellent stability over time, less stickiness and uncomfortable feeling on the skin, and good usability can be obtained.

The present invention includes the following components (A) to (D):
(A) Sphingosines represented by the general formula (1)

(In the formula, R ¹ represents a linear, branched or cyclic saturated or unsaturated hydrocarbon group having 4 to 30 carbon atoms, which may be substituted by a hydroxyl group, a carbonyl group or an amino group; A methylene group, a methine group or an oxygen atom; each of X ¹ , X ² and X ³ independently represents a hydrogen atom, a hydroxyl group or an acetoxy group, and X ⁴ represents a hydrogen atom, an acetyl group or a glyceryl group Together with an adjacent oxygen atom to form an oxo group (provided that when Y is a methine group, ^one of X ¹ and X ² is a hydrogen atom and the other does not exist. X ⁴ is an oxo group) X ³ is not present when R.sup.3 is present.); R ² and R ³ each independently represents a hydrogen atom, a hydroxyl group, a hydroxymethyl group or an acetoxymethyl group; a R each independently represents a hydrogen atom. Or an amidino group or hydro A linear or branched saturated or unsaturated hydrocarbon group having 1 to 8 carbon atoms which may have a substituent selected from a sil group, a hydroxyalkoxy group, an alkoxy group and an acetoxy group; 2 or 3; the broken line indicates an unsaturated bond)
(B) an unsaturated fatty acid having 10 to 30 carbon atoms or a branched fatty acid having 10 to 30 carbon atoms,
(C) oily component,
(D) In oil containing an oil-soluble antioxidant and having a content ratio (mass ratio) of component (B) and component (D) of (B) / (D) = 100/1 to 1/100 An aqueous emulsion composition is provided.

  The water-in-oil emulsion composition of the present invention has excellent stability and good usability even when severe temperature changes occur. In addition, the odor and the color are not deteriorated even when the temperature is changed, and it is stable.

The sphingosine component (A) used in the present invention is represented by the general formula (1).
In the formula, R ¹ is a straight chain or branched chain having 4 to 30 carbon atoms, preferably 7 to 22 carbon atoms which may be substituted by a hydroxyl group, which may be substituted by a hydroxyl group, a carbonyl group or an amino group. It is a chain or cyclic saturated or unsaturated hydrocarbon group. In particular, a linear or branched alkyl group having 10 to 20 carbon atoms, a linear or branched alkyl group having 10 to 20 carbon atoms having a hydroxyl group at the Y-side end, and a branched chain in the case of a branched alkyl group. Are preferably methyl-branched. Specifically, a tridecyl group, a tetradecyl group, a pentadecyl group, a hexadecyl group, a 1-hydroxytridecyl group, a 1-hydroxypentadecyl group, an isohexadecyl group, and an isostearyl group are preferable.

Y represents a methylene group (CH ₂ ), a methine group (CH), or an oxygen atom.
X ¹ , X ² , and X ³ each independently represent a hydrogen atom, a hydroxyl group, or an acetoxy group, and X ⁴ represents an oxo group together with a hydrogen atom, an acetyl group, a glyceryl group, or an adjacent oxygen atom. The substituent to be formed is shown. In particular, it is preferable that 0 to ¹ of X ¹ , X ² , and X ³ are hydroxyl groups, the remainder is a hydrogen atom, and X ⁴ is a hydrogen atom. When Y is a methine group, only ^one of X ¹ and X ² is a hydrogen atom, and the other does not exist. Also, when X ⁴ forms an oxo group, X ³ does not exist.

R ² and R ³ each independently represent a hydrogen atom, a hydroxyl group, a hydroxymethyl group or an acetoxymethyl group, and R ³ is particularly preferably a hydrogen atom.

A represents a number of 2 or 3, R represents R ⁴ and R ⁵ when a is 2, and R represents R ⁴ , R ⁵ and R ⁶ when a is 3.

R ⁴ , R ⁵ and R ⁶ are each independently a hydrogen atom or an amidino group, or may have a substituent selected from a hydroxyl group, a hydroxyalkoxy group, an alkoxy group and an acetoxy group. 1 to 8 linear or branched saturated or unsaturated hydrocarbon groups are shown. Here, the hydroxyalkoxy group that can be substituted with a hydrocarbon group is preferably a linear or branched hydroxyalkoxy group having 1 to 7 carbon atoms. Moreover, as an alkoxy group, a C1-C7 linear or branched alkoxy group is preferable. Examples of R ⁴ , R ⁵ and R ⁶ include a hydrogen atom; a linear or branched alkyl group such as methyl, ethyl, propyl, 2-ethylhexyl and isopropyl; an alkenyl group such as vinyl and allyl; an amidino group; Methyl, 2-hydroxyethyl, 1,1-dimethyl-2-hydroxyethyl, 2-hydroxypropyl, 2,3-dihydroxypropyl, 2-hydroxy-3-methoxypropyl, 2,3,4,5,6-penta Hydroxyhexyl, 1,1-bis (hydroxymethyl) ethyl, 2- (2-hydroxyethoxy) ethyl, 2-methoxyethyl, 1-methyl-2-hydroxyethyl, 3-hydroxypropyl, 3-methoxypropyl, 1 , 1-bis (hydroxymethyl) -2-hydroxyethyl and other hydroxyl groups, hydroxyalkoxy groups And a hydrocarbon group having 1 to 8 carbon atoms substituted by 1 to 6 selected from alkoxy groups.

  In particular, hydrogen atom or hydroxyl group such as methyl group, 2-hydroxyethyl, 1,1-dimethyl-2-hydroxyethyl, 1,1-bis (hydroxymethyl) ethyl, 2- (2-hydroxyethoxy) ethyl and hydroxy An alkyl group that may be substituted by 1 to 3 groups selected from alkoxy groups is preferred.

As the sphingosine represented by the general formula (1), naturally occurring sphingosine represented by the following general formula (2) or a synthetic product having the same structure, and derivatives thereof (hereinafter referred to as natural sphingosine) or Pseudo-type sphingosines having a sphingosine structure represented by the general formula (3) (hereinafter referred to as pseudo-type sphingosine) are preferable.
(I) A natural sphingosine represented by the general formula (2).

(In the formula, R ⁷ represents a linear, branched or cyclic saturated or unsaturated hydrocarbon group having 7 to 19 carbon atoms which may be substituted by a hydroxyl group; Y ₁ represents a methylene group or a methine group; X ⁵ , X ⁶ and X ⁷ each independently represent a hydrogen atom, a hydroxyl group or an acetoxy group, and X ⁸ represents a hydrogen atom or together with an adjacent oxygen atom, forms an oxo group ( However, when Y ₁ is a methine group, _one of X ⁵ and X ⁶ represents a hydrogen atom and the other does not exist.When X ⁸ forms an oxo group, X ⁷ does not exist.); R ⁸ Represents a hydroxymethyl group or an acetoxymethyl group; a R _{1 s} are each independently a hydrogen atom or an amidino group, or have a substituent selected from a hydroxyl group, a hydroxyalkoxy group, an alkoxy group and an acetoxy group 1 to 1 carbon total Of a linear or branched, saturated or unsaturated hydrocarbon group; a represents a number of 2 or 3; indicates that the broken line may be an unsaturated bond)

R ⁷ is preferably a linear, branched or cyclic saturated or unsaturated hydrocarbon group having 7 to 19 carbon atoms, particularly a linear saturated or unsaturated hydrocarbon group having 13 to 15 carbon atoms. Is preferred. a is preferably 2, and each R ₁ is independently a hydrogen atom or a linear or branched alkyl group having 1 to 4 carbon atoms.

Specific examples of the natural sphingosine represented by the general formula (2) include natural sphingosine, dihydrosphingosine, phytosphingosine, sphingadienin, dehydrosphingosine, dehydrophytosphingosine, and N-alkyl derivatives thereof (for example, N-methyl form) and the like.
These sphingosines may be either natural (D (+)) optically active or non-natural (L (-)) optically active, or a mixture of natural and non-natural types. May be used. The relative configuration of the above compound may be a natural configuration, a non-natural configuration other than that, or a mixture thereof.
In particular, PHYTOSPHINGOSINE (INCI name: 8th Edition) and the following formula are preferable.

These may be any of natural extracts and synthetic products, and commercially available products can be used.
Examples of commercially available natural sphingosine include D-Sphingosine (4-Sphingenine) (SIGMA-ALDRICH), DS-phytosphingosine (DOOSAN), and phytosphingosine (Cosmo Farm).

(II) A pseudo-type sphingosine represented by the general formula (3).

(In the formula, R ⁹ represents a linear, branched or cyclic saturated or unsaturated hydrocarbon group having 10 to 22 carbon atoms which may be substituted with a hydroxyl group; X ⁹ represents a hydrogen atom, an acetyl group or A glyceryl group; a R ₂ each independently represents a hydrogen atom or an amidino group, or a total carbon which may have a substituent selected from a hydroxyl group, a hydroxyalkoxy group, an alkoxy group and an acetoxy group A linear or branched saturated or unsaturated hydrocarbon group having a number of 1 to 8; a represents a number of 2 or 3)

Here, as R ⁹ , an iso-branched alkyl group having 14 to 20 carbon atoms is preferable, and an isostearyl group is particularly preferable. The isostearyl group is most preferably an isostearyl group obtained by using, as a raw material oil, an isosteal alcohol derived from a by-product during production of a dimer acid using a fatty acid derived from an animal or vegetable oil.
When a is 2, R ₂ represents R ¹⁰ and R ¹¹ , and when a is 3, R ₂ is R ¹⁰ , R ^11, and R ¹² .

R ¹⁰ , R ¹¹ and R ¹² are, for example, a hydrogen atom; a linear or branched alkyl group such as methyl, ethyl, propyl, 2-ethylhexyl and isopropyl; an alkenyl group such as vinyl and allyl; an amidino group; Methyl, 2-hydroxyethyl, 1,1-dimethyl-2-hydroxyethyl, 2-hydroxypropyl, 2,3-dihydroxypropyl, 2-hydroxy-3-methoxypropyl, 2,3,4,5,6-penta Hydroxyhexyl, 1,1-bis (hydroxymethyl) ethyl, 2- (2-hydroxyethoxy) ethyl, 2-methoxyethyl, 1-methyl-2-hydroxyethyl, 3-hydroxypropyl, 3-methoxypropyl, 1 , 1-bis (hydroxymethyl) -2-hydroxyethyl and the like hydroxyl groups, hydroxyalkoxy groups and the like And a C1-C8 alkyl group having a substituent selected from an alkoxy group.
In particular, one of R ¹⁰ and R ¹¹ is a hydrogen atom and the other is 2-hydroxyethyl, 1,1-dimethyl-2-hydroxyethyl, 1,1-bis (hydroxymethyl) ethyl, 2- (2- Secondary amines which are hydroxyethoxy) ethyl are preferred.

As pseudo-type sphingosine, R ⁹ is an isostearyl group, X ⁹ is a hydrogen atom, R ¹⁰ is a hydrogen atom, R ¹¹ is a 2-hydroxyethyl group, 1,1-bis (hydroxymethyl) ethyl group, 1,1 -It is preferable that 1-3 substituted by hydroxyl groups and hydroxyalkoxy groups such as dimethyl-2-hydroxyethyl group or 2- (2-hydroxyethoxy) ethyl group are substituted alkyl groups.
Specific examples of the pseudo-sphingosine include the following pseudo-sphingosines (i) to (iv).

  Two or more components (A) may be used in combination. The content of the component (A) in the composition of the present invention is preferably 0.001 to 10% by mass, particularly 0.005 to 3% by mass, and more preferably 0.01 to 3% by mass.

It is considered that the fatty acid of component (B) used in the present invention forms a salt by the neutralization reaction between the amino group of sphingosines and acid-base, and the sphingosines are cationized to act as activators. . The salt of sphingosines can be confirmed using, for example, infrared absorption spectroscopy or proton nuclear magnetic resonance spectroscopy, which is usually used for specifying the structure of a compound.
The chain length of the fatty acid is selected depending on the type of oil component to be emulsified and the viscosity of the emulsified composition. For example, in the case of an emulsion composition having a relatively low viscosity, an emulsion composition having a short chain length is used. In the case of a creamy emulsion composition having a high viscosity, a composition having a long chain length is used. An emulsified state is obtained.

The fatty acid of component (B) is an unsaturated fatty acid having 10 to 30 carbon atoms or a branched fatty acid, such as oleic acid, palmitooleic acid, linoleic acid, linolenic acid, ricinolenic acid, eicosapentaenoic acid, docosahexaenoic acid Unsaturated fatty acids; branched fatty acids such as isomyristic acid, isopalmitic acid and isostearic acid.
Among these, an unsaturated fatty acid having 12 to 18 carbon atoms or a branched fatty acid is particularly preferable, and among them, oleic acid, palmitooleic acid, linoleic acid, linolenic acid, isopalmitic acid, and isostearic acid are preferable. Isostearic acid is preferable from the viewpoint of use feeling.

Two or more types of fatty acids as the component (B) may be used in combination. The content of the component (B) in the composition of the present invention is preferably 0.001 to 10% by mass, particularly 0.005 to 6% by mass, and more preferably 0.01 to 3% by mass.
In addition, the component (B) is effective for cationizing the amino group part of the sphingosines of the component (A), and is 0.3 mol or more, particularly 0.3 to 5 mol per 1 mol of the component (A). It is preferable to contain 0.5 mol to 3 mol in order to improve the stability of the emulsion composition.
In the present invention, by using such a specific fatty acid as the component (B), particularly in a harsh environment, for example, when the temperature exceeds 60 ° C. when passing through the equator in a warehouse at the time of export, or in Hokkaido Sufficient emulsification stability can be obtained even when stored in a cold warehouse such as a winter warehouse.

  The oily component of component (C) used in the present invention can include synthetic and naturally-derived oily components that are usually used in cosmetics and are solid at 25 ° C., semi-solid, or liquid at 25 ° C. The oil component forms a continuous phase in the emulsion composition, and it is preferable that non-polar liquid oil is a main component from the viewpoint of emulsion stability over time.

  Nonpolar liquid oil (25 ° C.) includes, for example, hydrocarbon oils such as liquid paraffin and squalane; dimethylpolysiloxane, dimethylcyclopolysiloxane, methylphenylpolysiloxane, methylhydrogenpolysiloxane, higher alcohol-modified organopolysiloxane, etc. Silicone oil; fluoro oils such as fluoropolyether and perfluoroalkyl ether silicone. The content of the nonpolar oil is preferably 50% by mass or more, particularly 70% by mass or more, based on the whole oil component.

  Examples of liquid oil components other than non-polar oils include fatty acid esters such as diisostearyl malate, octyldodecyl lactate, isotridecyl isononanoate, isopropyl isostearate, octyldodecyl myristate; fatty acids such as neopentyl glycol dicaprate and alcohol Ester oils consisting of: amino acid derivatives; vegetable oils such as jojoba oil; and ester oils such as animal oils such as liquid lanolin.

  Examples of oily components that are solid or semi-solid at 25 ° C. include vegetable oils such as jojoba wax; waxes such as petrolatum, lanolin, ceresin, microcrystalline wax, carnauba wax, candelilla wax; ceramide and derivatives thereof, cholesterol and derivatives thereof, carbon Examples include those classified into intercellular lipids such as fatty acids of several 12-18.

  In the present invention, particularly from the viewpoint of the usability as an emulsified composition, it is preferable to contain intercellular lipids such as ceramide and derivatives thereof, cholesterol and derivatives thereof as oily components, and particularly contain ceramide and derivatives thereof. It is preferable from the viewpoint of improving the moisturizing effect. As ceramide and its derivatives, it is preferable to contain ceramides represented by the general formula (4).

(In the formula, R ¹⁶ represents a linear, branched or cyclic saturated or unsaturated hydrocarbon group or hydrogen atom having 4 to 30 carbon atoms, which may be substituted by a hydroxyl group, a carbonyl group or an amino group. Z represents a methylene group, a methine group or an oxygen atom; X ⁹ , X ¹⁰ and X ¹¹ each independently represent a hydrogen atom, a hydroxyl group or an acetoxy group, and X ¹² represents a hydrogen atom, an acetyl group or a glyceryl group; or shown, together with the adjacent oxygen atom, forms an oxo group (provided that when Z is a methine group, one of X ⁹ and X ¹⁰ are hydrogen atoms, is .X ¹² to the other is not present when forming an oxo group, X ¹¹ is absent);. R ¹⁷ and R ¹⁸ are each independently hydrogen atom, a hydroxyl group, a hydroxymethyl group or an acetoxymethyl group; R ¹⁹ represents a hydroxyl group, a carbonyl Or a linear, branched or cyclic saturated or unsaturated hydrocarbon having 5 to 60 carbon atoms which may have an ether group, an ether bond, an ester bond or an amide bond in the main chain, which may be substituted by an amino group R ²⁰ represents a hydrogen atom, or may have a substituent selected from a hydroxyl group, a hydroxyalkoxy group, an alkoxy group and an acetoxy group, a straight chain or branched chain having 1 to 30 carbon atoms in total A saturated or unsaturated hydrocarbon group (where R ¹⁶ is a hydrogen atom, Z is an oxygen atom, R ²⁰ is a hydrocarbon group having 10 to 30 carbon atoms in total, and R ¹⁶ is a hydrocarbon group) R ²⁰ is a hydrocarbon group having 1 to 8 carbon atoms in total; the broken line indicates that it may be an unsaturated bond)

In the formula, R ¹⁶ is a straight chain having 4 to 30 carbon atoms, preferably 7 to 22 carbon atoms which may be substituted with a hydroxyl group, which may be substituted with a hydroxyl group, a carbonyl group or an amino group, A branched or cyclic saturated or unsaturated hydrocarbon group or a hydrogen atom.
Z represents a methylene group, a methine group or an oxygen atom.

X ⁹ , X ¹⁰ and X ¹¹ each independently represent a hydrogen atom, a hydroxyl group or an acetoxy group. In particular, it is preferable that 0 to 1 of X ⁹ , X ¹⁰ and X ¹¹ are hydroxyl groups and the remainder is a hydrogen atom. When Z is a methine group, only one of X ⁹ and X ¹⁰ is a hydrogen atom, and the other does not exist. X ¹² is preferably a hydrogen atom or a glyceryl group.
R ¹⁷ and R ¹⁸ represent a hydrogen atom, a hydroxyl group, a hydroxymethyl group or an acetoxymethyl group, preferred R ¹⁷ is a hydrogen atom or a hydroxymethyl group, and preferred R ¹⁸ is a hydrogen atom.

R ¹⁹ may be a hydroxyl group, a carboxyl group or an amino group, and the main chain may have an ether bond, an ester bond or an amide bond, a C 5-60 straight chain, branched chain or A cyclic saturated or unsaturated hydrocarbon group is shown. Preferably, the hydroxyl group or amino group may be substituted a linear, branched or cyclic saturated or unsaturated hydrocarbon group having 5 to 35 carbon atoms, or a hydroxyl group at the ω position of the hydrocarbon group In which a linear, branched, or cyclic saturated or unsaturated fatty acid having 8 to 22 carbon atoms, which may be substituted, is an ester bond or an amide bond. As the fatty acid to be bonded, isostearic acid, 12-hydroxystearic acid or linoleic acid is preferable.

R ²⁰ represents a hydrogen atom, or may have a substituent selected from a hydroxyl group, a hydroxyalkoxy group, an alkoxy group, and an acetoxy group. It is a saturated hydrocarbon group. When R ¹⁶ is a hydrogen atom and Z is an oxygen atom, R ²⁰ is a hydrocarbon group having 10 to 30 carbon atoms in total. When R ¹⁶ is a hydrocarbon group, R ²⁰ is a hydrocarbon group having 1 to 8 carbon atoms in total. In particular, a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms in which 1 to 3 groups selected from a hydroxyl group, a hydroxyalkoxy group and an alkoxy group may be substituted is preferable. Here, as a hydroxy alkoxy group and an alkoxy group, a C1-C7 thing is preferable.

The ceramides represented by the general formula (4) are particularly preferably ceramides represented by the following general formula (5) or (6).
(I) Naturally derived ceramides represented by the general formula (5) or a synthetic product having the same structure, and derivatives thereof (hereinafter referred to as natural ceramides).

(In the formula, R ²¹ represents a linear, branched or cyclic saturated or unsaturated hydrocarbon group having 7 to 19 carbon atoms which may be substituted by a hydroxyl group; Z ₁ represents a methylene group or a methine group; X ¹³ , X ¹⁴ and X ¹⁵ each independently represent a hydrogen atom, a hydroxyl group or an acetoxy group; X ¹⁶ represents a hydrogen atom or together with an adjacent oxygen atom, forms an oxo group. (However, when Z ₁ is a methine group, _one of X ¹³ and X ¹⁴ is a hydrogen atom and the other does not exist. When X ¹⁶ forms an oxo group, X ¹⁵ does not exist.) R ²² represents a hydroxymethyl group or an acetoxymethyl group; R ²³ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; R ²⁴ has 5 to 30 carbon atoms which may be substituted by a hydroxyl group Linear, branched or cyclic saturated or unsaturated hydrocarbon groups Or a linear or branched saturated or unsaturated fatty acid having 8 to 22 carbon atoms which may be substituted with a hydroxyl group at the ω-terminal of the alkyl group; Indicates that it may be an unsaturated bond.)

Preferably, R ²¹ is a linear alkyl group having 7 to 19 carbon atoms, more preferably 13 to 15 carbon atoms; R ²⁴ is a linear alkyl group having 9 to 27 carbon atoms which may be substituted by a hydroxyl group, or linoleic acid Is a straight-chain alkyl group having 9 to 27 carbon atoms with an ester bond. X ¹⁶ preferably represents a hydrogen atom or forms an oxo group together with an oxygen atom. In particular, R ²⁴ is preferably tricosyl, 1-hydroxypentadecyl, 1-hydroxytricosyl, heptadecyl, 1-hydroxyundecyl, or a nonacosyl group in which linoleic acid is ester-bonded to the ω position.

  Specific examples of natural ceramides include ceramides Type 1 to 7 in which sphingosine, dihydrosphingosine, phytosphingosine or sphingadienin is amidated (for example, J. Lipid Res., 24: 759 (1983), FIG. And porcine and human ceramides described in FIG. 4 of J. Lipid. Res., 35: 2069 (1994)).

Furthermore, these N-alkyl bodies (for example, N-methyl body) are also included.
These ceramides may be either natural (D (−)) optically active or non-natural (L (+)) optically active, or a mixture of natural and nonnatural. May be used. The relative configuration of the above compound may be a natural configuration, a non-natural configuration other than that, or a mixture thereof. In particular, compounds of CERAMIDE1, CERAMIDE2, CERAMIDE3, CERAMIDE5, CERAMIDE6II (above, INCI, 8th Edition) and those represented by the following formula are preferable.

These may be any of natural extracts and synthetic products, and commercially available products can be used.
Such commercially available natural ceramides are Ceramide I, Ceramide III, Ceramide IIIA, Ceramide IIIB, Ceramide IIIC, Ceramide VI (above, Cosmo Farm), Ceramide TIC-001 (Takasago Inc.), CERAMIDE II (Quest International), DS-Ceramide VI, DS-CLA-Phytoceramide, C6-Phytoceramide, DS-ceramide Y3S (DOOSAN), CERAMIDE2 (Cedama).

(II) A pseudo-ceramide represented by the general formula (6).

(In the formula, R ²⁵ represents a linear, branched or cyclic saturated or unsaturated hydrocarbon group or hydrogen atom having 10 to 22 carbon atoms which may be substituted with a hydroxyl group; X ¹⁷ represents a hydrogen atom; Represents an acetyl group or a glyceryl group; R ²⁶ is a linear, branched or cyclic saturated or unsaturated hydrocarbon group having 5 to 22 carbon atoms which may be substituted with a hydroxyl group or an amino group, Or a hydrocarbon group having an ester bond with a linear or branched saturated or unsaturated fatty acid having 8 to 22 carbon atoms which may be substituted with a hydroxyl group at the ω-terminal; R ²⁷ represents a hydrogen atom; Or a hydroxyl group, a hydroxyalkoxy group, an alkoxy group or an acetoxy group which may be substituted is an alkyl group having 1 to 30 carbon atoms in total.

R ²⁶ is particularly nonyl, tridecyl, pentadecyl, an undecyl group in which linoleic acid is ester-bonded to the ω position, a pentadecyl group in which linoleic acid is ester-bonded to the ω position, and a pentadecyl group in which 12-hydroxystearic acid is ester-bonded to the ω position. An undecyl group in which methyl branched isostearic acid is amide-bonded at the ω position is preferred.

R ²⁷ is an alkyl having a total carbon number of 10 to 30, preferably a total carbon number of 12 to 20, which may be substituted by a hydroxyl group, hydroxyalkoxy group, alkoxy group or acetoxy group when R ²⁵ is a hydrogen atom. When R ²⁵ is a linear, branched or cyclic saturated or unsaturated hydrocarbon group having 10 to 22 carbon atoms which may be substituted with a hydroxyl group, What shows a C1-C8 alkyl group which the hydroxyl group, the hydroxy alkoxy group, an alkoxy group, or an acetoxy group may substitute is preferable. The hydroxyalkoxy or alkoxy group R ²⁷ preferably has 1 to 7 carbon atoms.

In general formula (6), R ²⁵ is a hexadecyl group, X ¹⁷ is a hydrogen atom, R ²⁶ is a pentadecyl group, R ²⁷ is a hydroxyethyl group; R ²⁵ is a hexadecyl group, X ¹⁷ is a hydrogen atom, and R ²⁶ is R ²⁶ Preferred are pseudoceramides having a nonyl group, R ²⁷ is a hydroxyethyl group; or R ²⁵ is a hexadecyl group, X ¹⁷ is a glyceryl group, R ²⁶ is a tridecyl group, and R ²⁷ is a 3-methoxypropyl group. Particularly preferred is 6) wherein R ²⁵ is a hexadecyl group, X ¹⁷ is a hydrogen atom, R ²⁶ is a pentadecyl group, and R ²⁷ is a hydroxyethyl group.

  The ceramides are preferably contained in the oil component in an amount of 0.0001 to 50% by mass, particularly 0.001 to 20% by mass, and more preferably 0.01 to 15% by mass.

  Component (E) may be used in combination of two or more, and particularly preferably contains a hydrocarbon oil and a solid / semi-solid oily component at 25 ° C., and ceramide as a solid / semi-solid oily component at 25 ° C. and its It is preferable from a viewpoint of a usability | use_condition and a moisturizing effect improvement to include what is classified into intracellular lipids, such as a derivative | guide_body, cholesterol and its derivative (s), and a C12-C18 fatty acid. The content of the component (C) in the composition of the present invention is preferably 20 to 99% by mass, particularly 30 to 93% by mass, and more preferably 35 to 85% by mass.

  The oil-soluble antioxidant of component (D) used in the present invention is not particularly limited as long as it is usually used in cosmetics. For example, tocopherol, tocopherol acetate, dl-α-tocopherol, oryzanol; stearic ascorbate Examples include vitamin C derivatives such as acid esters and ascorbyl palmitate; coenzyme Q10, coenzyme Q10 derivatives, and α-lipoic acid. Among these, tocopherol, tocopherol acetate, and dl-α-tocopherol are particularly preferable.

Two or more components (D) may be used in combination. The content of the component (D) in the composition of the present invention is preferably 0.001 to 10% by mass, particularly 0.001 to 5% by mass, and more preferably 0.01 to 5% by mass.
The content ratio (mass ratio) of the component (B) and the component (D) is (B) / (D) = 100/1 to 1/100, preferably 5/1 to 1/10, particularly preferably 1. / 1-1 / 3. Outside this range, the odor stability is poor.

  The amount of water contained in the water-in-oil emulsion composition of the present invention is preferably 1 to 80% by mass, particularly 7 to 70% by mass, and more preferably 15 to 60% by mass in the total composition.

  In the water-in-oil emulsion composition of the present invention, in addition to the above components, components used in ordinary cosmetics such as 1,3-butylene glycol, propylene glycol, dipropylene glycol, glycerin, diglycerin, sorbitol, Moisturizers such as maltitol, polyethylene glycol, glycine betaine, xylitol, trehalose, urea, amino acids; water-soluble thickeners such as xanthan gum, hydroxyethyl cellulose, methyl cellulose, hydroxypropyl guar gum; oil-soluble polymers such as fatty acid dextrin and fatty acid inulin ; Medicinal agents such as allantoin and tocopherol acetate; organic powders such as cellulose powder, nylon powder, crosslinked silicone powder, crosslinked methylpolysiloxane, porous cellulose powder, porous nylon powder; Inorganic powders such as zinc oxide and titanium oxide; plant extracts such as eucalyptus extract; whitening agents such as chamomile extract; refreshing agents such as menthol and camphor; pH buffering agents, antioxidants, UV absorbers, preservatives, fragrances , Fungicides, pigments and the like can be included.

  The water-in-oil emulsion composition of the present invention is produced by heating and dissolving the components (A) to (D), and then adding water and other components to emulsify.

  The water-in-oil emulsion composition of the present invention can be applied as cosmetics, pharmaceuticals and the like, and is particularly preferably used as cosmetics, for example, emulsions, creams, foundations, hair creams, etc., especially in creamy cosmetics. .

Examples 1-6, Comparative Examples 1-2
A water-in-oil emulsion composition having the composition shown in Table 1 was produced by the following method. About the obtained emulsion composition, cycle stability, odor stability, color stability, stability, and a usability | use_condition were evaluated. The results are also shown in Table 1.

(Production method)
The oil phase component including components (A), (B), (C), (D) and (E) is dissolved by heating and stirring at 80 to 90 ° C. Ingredients were added. The mixture was further cooled to room temperature with stirring to obtain a water-in-oil emulsion composition.

(Evaluation methods)
(1) Cycle stability:
Each emulsified composition was put in a storage box having a cycle of -15 ° C to 60 ° C for 24 hours, allowed to stand for 6 days, returned to room temperature, and evaluated according to the following criteria.
A: No emulsification separation was observed, and there was no change in appearance.
○: No emulsification separation was observed, but the appearance slightly changed.
X: Separation of emulsification was observed, and the appearance was greatly changed.

(2) Stability:
Each emulsion composition was allowed to stand at 50 ° C. for 1 week, and then the appearance was visually evaluated according to the following criteria.
A: No emulsification separation was observed, and there was no change in appearance.
○: No emulsification separation was observed, but the appearance slightly changed.
X: Separation of emulsification was observed, and the appearance was greatly changed.

(3) Color stability:
The sample after the cycle test storage was subjected to sensory evaluation according to the following criteria.
A: Almost no change.
○: Slightly discolored.
X: Discolored.

(4) Odor stability:
The sample after the cycle test storage was subjected to sensory evaluation according to the following criteria.
A: Almost no change.
○: Smell slightly changed.
X: There is a strange odor.

(5) Feeling of use:
A “smooth feeling” when each cycle test product was applied to the face by 10 expert panelists was sensory-evaluated and judged according to the following criteria.
A: Nine or more people evaluated it as good (good).
○: Seven to eight people evaluated it as good (good).
X: 6 or less evaluated as good (good).

Claims (2)

The following components (A) to (D):
(A) 0.001 to 10% by mass of sphingosine represented by the general formula (1) ,

(In the formula, R ¹ represents a linear, branched or cyclic saturated or unsaturated hydrocarbon group having 4 to 30 carbon atoms, which may be substituted by a hydroxyl group, a carbonyl group or an amino group; A methylene group, a methine group or an oxygen atom; each of X ¹ , X ² and X ³ independently represents a hydrogen atom, a hydroxyl group or an acetoxy group, and X ⁴ represents a hydrogen atom, an acetyl group or a glyceryl group Together with an adjacent oxygen atom to form an oxo group (provided that when Y is a methine group, ^one of X ¹ and X ² is a hydrogen atom and the other does not exist. X ⁴ is an oxo group) X ³ is not present when R.sup.3 is present.); R ² and R ³ each independently represents a hydrogen atom, a hydroxyl group, a hydroxymethyl group or an acetoxymethyl group; a R each independently represents a hydrogen atom. Or an amidino group or hydro A linear or branched saturated or unsaturated hydrocarbon group having 1 to 8 carbon atoms which may have a substituent selected from a sil group, a hydroxyalkoxy group, an alkoxy group and an acetoxy group; 2 or 3; the broken line indicates an unsaturated bond)
(B) C10-30 unsaturated fatty acid or C10-30 branched fatty acid 0.001-10 mass% ,
(C) Oil component 20-99 mass% ,
(D) Oil-soluble antioxidant 0.001-10 mass%
The component (B) is 0.5 to 3 mol per 1 mol of the component (A), and the content ratio (mass ratio) of the component (B) and the component (D) is (B) / ( D) A water-in-oil emulsion composition in which 100/1 to 1/100.   The water-in-oil emulsion composition according to claim 1, wherein the component (C) comprises a solid or semi-solid oily component at 25 ° C.