JP4284236B2 - Oil-in-water emulsified cosmetic - Google Patents

Description

  The present invention relates to an oil-in-water emulsified cosmetic containing an oleamide-containing ceramide and having excellent emulsification stability.

  The stratum corneum that exists in the outermost layer of the skin suppresses the invasion of substances from the outside and the evaporation of moisture from the inside of the skin, and at the same time has the function of maintaining the skin's flexibility and smooth appearance by holding moisture. have. In the space between the stratum corneum constituting the stratum corneum, a lipid called a stratum corneum lipid (hereinafter referred to as stratum corneum ICL) exists so as to fill the gap of the stratum corneum.

  About 50% of the lipid composition of the stratum corneum ICL is ceramide, which is composed of cholesterol, cholesterol ester, fatty acid and the like. In general, when stratum corneum ICL, especially ceramide decreases, it is known to cause unfavorable skin conditions such as rough skin, dry skin, and aging skin. The lowered stratum corneum state can be improved.

However, since ceramide has strong crystallinity and a high melting point, it is difficult to stabilize in the preparation. When ceramides and other oil components are used in combination, a plurality of surfactants are used due to the difference in emulsifying properties. Must be used in combination, and the amount of surfactant used tends to be large.
As a method for stably blending ceramide without using a surfactant, Patent Document 1 describes a method using an oil agent having good compatibility with ceramide. However, in this method, it is difficult to use an oil component other than an oil agent having good compatibility with ceramide, and it is not sufficient to obtain a wide range of functions and feeling of use.

On the other hand, oil-in-water emulsified cosmetics have a visual and tactile refreshing feeling in addition to a refreshing feeling of use because the continuous phase is water. In such an oil-in-water emulsified cosmetic, when trying to emulsify ceramides together with other oily components, the feeling of use tends to be lowered or the emulsion stability tends to deteriorate.
JP-A-8-109121

  An object of the present invention is to provide an oil-in-water emulsified cosmetic containing an oily component containing ceramides and excellent in emulsion stability.

  When emulsifying oily components containing ceramides, the present inventor has excellent emulsification stability without impairing the emulsified state of ceramides by separately emulsifying ceramides and other oily components and then mixing them. It was found that an oil-in-water emulsified cosmetic was obtained.

The present invention relates to (A) sphingosine represented by the general formula (1), (B) an acidic compound selected from inorganic acids and organic acids having 5 or less carbon atoms, and (C) a ceramide represented by the general formula (2). An oil-in-water emulsified cosmetic comprising an emulsion containing a mixture, (D) an oily component selected from polar oils and hydrocarbon oils, and (E) an emulsion containing a surfactant. .
Sphingosines represented by the general formula (1):

(Wherein 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; Y represents methylene; A group, a methine group or an oxygen atom; X ¹ , X ² and X ³ each 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, Combined with the 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 represents an oxo group. When formed, X ³ is not present.); R ² and R ³ each independently represent 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 a hydroxy group A linear or branched saturated or unsaturated hydrocarbon group having 1 to 8 carbon atoms which may have a substituent selected from a ru group, a hydroxyalkoxy group, an alkoxy group and an acetoxy group; 2 or 3; the broken line indicates an unsaturated bond)
Ceramides represented by the general formula (2):

(In the formula, R ⁷ represents a linear, branched or cyclic saturated or unsaturated hydrocarbon group or a 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 ⁵ , X ⁶ and X ⁷ each independently represent a hydrogen atom, a hydroxyl group or an acetoxy group, and X ⁴ 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, either X ⁵ and X ⁶ is a hydrogen atom, is .X ⁴ the other is absent when forming an oxo group, X ⁷ is absent);. R ⁸ and R ⁹ are each independently hydrogen atom, a hydroxyl group, a hydroxymethyl group or an acetoxymethyl group; R ¹⁰ represents a hydroxyl group, or a carbonyl group A linear, branched or cyclic saturated or unsaturated hydrocarbon group having 5 to 60 carbon atoms which may have an ether bond, ester bond or amide bond in the main chain, which may be substituted by a mino group R ¹¹ represents a hydrogen atom, or may have a substituent selected from a hydroxyl group, a hydroxyalkoxy group, an alkoxy group, and an acetoxy group, and is a linear or branched chain having 1 to 30 carbon atoms in total A saturated or unsaturated hydrocarbon group (provided that when R ⁷ is a hydrogen atom and Z is an oxygen atom, R ¹¹ is a hydrocarbon group having 10 to 30 carbon atoms in total, and R ⁷ is a hydrocarbon group) ¹¹ 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 present invention, (C) the ceramide represented by the general formula (2) is selected from (A) a sphingosine represented by the general formula (1) and (B) an inorganic acid and an organic acid having 5 or less carbon atoms. The oil-in-water obtained by mixing an emulsion obtained by emulsifying with an acidic compound and an emulsion obtained by emulsifying an oily component selected from (D) polar oil and hydrocarbon oil with (E) a surfactant. The present invention provides a method for producing a type emulsified cosmetic.

  The oil-in-water emulsified cosmetic of the present invention contains oily components including ceramides stably and is excellent in storage stability.

In the present invention, in emulsifying the oily component containing the ceramide represented by the general formula (2), the emulsified state of the ceramide is obtained by emulsifying the ceramide and the other oily component separately and mixing them. A stable oil-in-water emulsified cosmetic can be obtained without breaking.
Ceramides are substances that are difficult to emulsify because of their high crystallinity, and the surfactants that are emulsifiers are limited. Furthermore, when emulsification is performed in a state where it is mixed with other cosmetic oil components, depending on the type of the oil component or surfactant, it is in a dissolved state, making it difficult to maintain the emulsified state as a whole. Therefore, in order to maintain the emulsified state of ceramides, the amount of the surfactant is also increased.

However, when ceramides are emulsified with sphingosines and acidic compounds, a liquid crystal structure is formed, and crystallization of ceramide is suppressed, and a stable emulsified state is considered to be formed. The emulsion of ceramides emulsified with sphingosines, once formed into a stable emulsified state, can be mixed with oily components and other components that will inhibit the emulsion stability of ceramides. It seems that it tends to be hard to break. Therefore, emulsification of ceramides and emulsification of other oil components are separately performed and then mixed to obtain stability of the emulsification, and the emulsification method is simplified.
Furthermore, as the emulsifier for ceramides, since a sphingosine salt is used, the amount of the surfactant used in the entire cosmetic can be reduced, so that it is considered that an excellent feeling in use can be obtained.

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), natural or natural sphingosines represented by the following general formula (3) and derivatives thereof (hereinafter referred to as natural sphingosine) or the general formula (4) Pseudo-type sphingosines having a sphingosine structure represented by (hereinafter referred to as pseudo-type sphingosine) are preferred.
(I) A natural sphingosine represented by the general formula (3).

(Wherein R ¹² 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 ⁸ , X ⁹ and X ¹⁰ each independently represent a hydrogen atom, a hydroxyl group or an acetoxy group, and X ¹¹ 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 ⁸ and X ⁹ represents a hydrogen atom and the other does not exist.When X ¹¹ forms an oxo group, X ¹⁰ does not exist.); R ¹³ 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 Total carbon number Indicates to 4 straight or branched chain saturated or unsaturated hydrocarbon group; a represents a number of 2 or 3; indicates that the broken line may be an unsaturated bond)

R ¹² is preferably a straight-chain, branched-chain or cyclic saturated or unsaturated hydrocarbon group having 7 to 19 carbon atoms, and particularly a straight-chain 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 (3) 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 (4).

(Wherein R ¹⁷ 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 ⁴ 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 ¹⁷ , 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.
Further, when a is 2, R ₂ represents R ¹⁸ and R ¹⁹ , and when a is 3, R ₂ is R ¹⁸ , R ¹⁹ and R ²⁰ .

R ¹⁸ , R ¹⁹ and R ²⁰ 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 hydroxy, hydroxyalkoxy and al Examples thereof include an alkyl group having 1 to 8 carbon atoms having a substituent selected from alkoxy.
In particular, any one of R ¹⁸ and R ¹⁹ 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 ¹⁷ is an isostearyl group, X ⁴ is a hydrogen atom, R ¹⁸ is a hydrogen atom, R ¹⁹ 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 cosmetic 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 1.5% by mass.

The acidic compound selected from the inorganic acid of component (B) and organic acid having 5 or less carbon atoms used in the present invention forms a salt by the acid-base neutralization reaction with the amine group of sphingosine of component (A). It is considered that sphingosines become cationized and act as active agents. The state of the sphingosine salt can be confirmed by using, for example, infrared absorption spectroscopy or proton nuclear magnetic resonance spectroscopy, which is usually used to specify the structure of the compound.
Component (B) is preferably one having a pH of 0.1 mol / L aqueous solution at 25 ° C. of 1 or more and less than 7, particularly 1 to 6.5.

Examples of the inorganic acid include phosphoric acid, hydrochloric acid, nitric acid, sulfuric acid, perchloric acid, and carbonic acid, and phosphoric acid and hydrochloric acid are particularly preferable.
Examples of organic acids include monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, and valeric acid; dicarboxylic acids such as succinic acid, phthalic acid, fumaric acid, oxalic acid, malonic acid, and glutaric acid; glycolic acid, Examples thereof include oxycarboxylic acids such as citric acid, lactic acid, pyruvic acid, malic acid and tartaric acid; amino acids such as glutamic acid and aspartic acid.

  Of these, phosphoric acid, hydrochloric acid, succinic acid, citric acid, lactic acid, glutamic acid, aspartic acid and the like are preferable, and lactic acid, glutamic acid, aspartic acid and the like are particularly preferable.

  Two or more components (B) may be used in combination. The content of the component (B) in the cosmetic 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 1.5% by mass.

  In order to cationize the amine of (A) sphingosine, component (B) is 0.3 mol or more with respect to 1 mol of component (A), in particular 0.3-5 mol, more preferably 0.5-3 mol It is preferable to contain. For example, the pH of the aqueous solution mixed with the component (A) in an equimolar ratio is preferably 2 to 6 at 25 ° C. (measured with HORIBA pH METER F-22 after correction with a phthalate standard solution). The cationized sphingosine salt is considered to act as an active agent, suppress crystallization of ceramides having a strong correlation with the hydrophobic part of sphingosine, and form a stable emulsified state.

The ceramide of component (C) used in the present invention is represented by the general formula (2).
In the formula, R ⁷ is a linear group of 4 to 30 carbon atoms, preferably a hydroxyl group of 7 to 22 carbon atoms which may be substituted by 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 ⁵ , X ⁶ and X ⁷ each independently represent a hydrogen atom, a hydroxyl group or an acetoxy group. In particular, it is preferable that 0 to 1 of X ⁵ , X ⁶ and X ⁷ is a hydroxyl group and the remainder is a hydrogen atom. When Z is a methine group, only one of X ⁵ and X ⁶ is a hydrogen atom, and the other does not exist. X ⁴ is preferably a hydrogen atom or a glyceryl group.
R ⁸ and R ⁹ represent a hydrogen atom, a hydroxyl group, a hydroxymethyl group or an acetoxymethyl group, preferred R ⁸ is a hydrogen atom or a hydroxymethyl group, and preferred R ⁹ is a hydrogen atom.

R ¹⁰ may be substituted with a hydroxyl group, a carboxy group or an amino group,
A linear, branched or cyclic saturated or unsaturated hydrocarbon group having 5 to 60 carbon atoms, which may have an ether bond, an ester bond or an amide bond in the main chain. 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 ¹¹ 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 ⁷ is a hydrogen atom and Z is an oxygen atom, R ¹¹ is a hydrocarbon group having 10 to 30 carbon atoms in total. When R ⁷ is a hydrocarbon group, R ¹¹ is a hydrocarbon group having 1 to 8 carbon atoms in total. Among these, 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 (2) are particularly preferably ceramides represented by the following general formula (5) or (6).
(I) Natural or natural ceramides represented by the general formula (5) and derivatives thereof (hereinafter referred to as natural ceramide).

(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 ¹² , X ¹³ and X ¹⁴ each independently represent a hydrogen atom, a hydroxyl group or an acetoxy group; X ¹⁵ 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 ¹² and X ¹³ is a hydrogen atom and the other does not exist. When X ¹⁵ forms an oxo group, X ¹⁴ 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 ¹⁵ 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 J. Lipid. Res., 35: 2069 (1994), porcine and human ceramides described in FIG.

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 include Ceramide I, Ceramide III, Ceramide IIIA, Ceramide IIIB, Ceramide IIIC, Ceramide VI (above, manufactured by Cosmo Farm), Ceramide TIC-001 (manufactured by Takasago Fragrance Co., Ltd.), CERAMIDE II (manufactured by Quest International), DS-Ceramide VI, DS-CLA-Phytoceramide, C6-Phytoceramide, DS-ceramide Y3S (manufactured by DOOSAN), and CERAMIDE2 (manufactured by Sederma).

(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 a hydrogen atom having 10 to 22 carbon atoms which may be substituted by a hydroxyl group; X ¹⁶ 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 represents a C1-C30 alkyl group)

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 ¹⁶ is a hydrogen atom, R ²⁶ is a pentadecyl group, R ²⁷ is a hydroxyethyl group; R ²⁵ is a hexadecyl group, X ¹⁶ is a hydrogen atom, and R ²⁶ is Preferred are pseudoceramides having a nonyl group, R ²⁷ is a hydroxyethyl group; or R ²⁵ is a hexadecyl group, X ¹⁶ 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 ⁴ is a hydrogen atom, R ²⁶ is a pentadecyl group, and R ²⁷ is a hydroxyethyl group.

The ceramides are preferably combined with the general formula (5) when the component (A) is the general formula (3), and with the general formula (6) when the component (A) is the general formula (4). In particular, it is preferable in terms of stability and effect to use COR ¹⁰ bonded to nitrogen in the general formula (2) with H as the general formula (1) of the component (A).

  Two or more components (C) may be used in combination. The content of the component (C) in the cosmetic of the present invention is preferably 0.001 to 20% by mass, particularly 0.01 to 15% by mass, and more preferably 0.1 to 10% by mass.

  In the oil-in-water emulsified cosmetic of the present invention, the content mass ratio ((A) + (B)) / (C) of the components (A), (B) and (C) is 0.0001 or more, particularly It is preferably 0.001 to 10, more preferably 0.01 to 6 from the viewpoint of stability over time.

  In the present invention, in addition to ceramides, as an oily component that can be emulsified with sphingosine salts, cholesterol and its derivatives, higher alcohols having a total carbon number of 10 to 50, total carbon Several 10-50 higher fatty acids can be included. These oily components are preferably emulsified with sphingosine salts together with ceramides from the viewpoint of compatibility with ceramides.

Examples of cholesterol derivatives include cholesterol sulfate, isostearyl cholesteryl ester, dihydrocholesterol, cholesteryl stearate, dehydrocholesterol, cholesteryl hydroxystearate, phytosterol and the like.
As the higher alcohol, those having a total carbon number of 9 to 25 are preferable. For example, stearyl alcohol, cetyl alcohol, isostearyl alcohol, lanolin acetate alcohol, polyoxyethylene lanolin acetate, hydrogenated lanolin alcohol, cetostearyl alcohol, batyl alcohol, Lanolin alcohol etc. are mentioned.
As the higher fatty acid, those having a total carbon number of 8 to 30, particularly 10 to 22 are preferable, and examples thereof include stearic acid, palmitic acid, myristic acid and the like.
Of these, stearyl alcohol, cetyl alcohol, batyl alcohol, cholesterol, stearic acid, palmitic acid, and myristic acid are particularly preferable.

The oily component selected from the polar oil and the hydrocarbon oil of component (D) used in the present invention is a component emulsified by a surfactant (E) described later.
Examples of polar oils include fatty acid esters such as diisostearyl malate, octyldodecyl lactate, isotridecyl isononanoate, isopropyl isostearate and octyldodecyl myristate; ester oils composed of fatty acids such as neopentyl glycol dicaprate and alcohol; amino acids Synthetic ester oils such as derivatives; vegetable oils such as olive oil and jojoba.

  Hydrocarbon oils include those which are liquid, semi-solid or solid at 25 ° C. and which are synthetic or naturally derived. Liquid hydrocarbon oils include liquid lanolin, liquid paraffin, squalane, etc .; semi-solid or solid hydrocarbon oils include waxes such as petrolatum, lanolin, ceresin, and microcrystalline wax.

  Two or more components (D) may be used in combination. The content of the component (D) in the cosmetic of the present invention is preferably 0.001 to 50% by mass, particularly 0.01 to 30% by mass, and more preferably 0.01 to 20% by mass.

  The component (E) surfactant emulsifies oily components other than ceramides, and is substantially not used for emulsification of ceramides. Surfactants include non-ionic surfactants, amphoteric surfactants, anionic surfactants, cationic surfactants, as well as alkyl-modified water-soluble substances such as hydroxyethyl cellulose, polyvinyl alcohol, alkyl-modified polyacrylic acid, and alkyl-modified polysaccharides. Polymeric surfactants such as polymers and natural surfactants such as saponins are included.

  Examples of the nonionic surfactant include polyoxyethylene hydrogenated castor oil, polyoxyethylene alkyl ether, and polyoxyethylene sorbitan fatty acid ester. Examples of the cationic surfactant include dimethyl distearyl ammonium chloride, monoalkyl trimethyl ammonium chloride, dialkyl dimethyl ammonium chloride and the like.

  Examples of the alkyl-modified water-soluble polymer include (meth) acrylic acid alkyl copolymers, alkyl-modified hydroxyethyl cellulose, and polysaccharide derivatives having a hydrophobic group and a hydrophilic group described in JP-A-11-12119. Commercially available alkyl-modified water-soluble polymers include alkyl acrylate copolymers such as Aculin 33 (ISP); Pemlen TR-1, Pemlen TR-2, Carbopol 1382, Carbopol ETD2020 (and above, Noveon) INC.), ACPEC HV-501ER (Sumitomo Seika Co., Ltd.) and other acrylic acid / alkyl methacrylate copolymers (including cross-linked type); Natrosol Plus 330CS, Polysurf 67 (above, belonging to Aqualon Group, Hercules Inc.) And alkyl-modified hydroxyethyl cellulose. Furthermore, as a derivative of (meth) acrylic acid / (meth) acrylic acid alkyl copolymer or a salt thereof, polyoxyethylene alkyl ether is ester-bonded to (meth) acrylic acid / (meth) acrylic acid alkyl copolymer, Polyoxyethylene alkyl ether ester copolymer of acrylic acid, methacrylic acid, alkyl acrylate, alkyl methacrylate, methacrylic acid (for example, alkyl acrylate, alkyl methacrylate, polyoxyethylene (20) stearyl ether copolymer (Aculin 22) (ISP)) can also be used.

Of these, nonionic surfactants, cationic surfactants, and alkyl-modified water-soluble polymers are preferable.
In particular, by using a fatty acid in addition to the ceramide of component (C), the oil component of component (D) can be stably emulsified using an alkyl-modified water-soluble polymer compound.

  Two or more types of component (E) may be used in combination. The content of the component (E) in the cosmetic of the present invention is preferably 0.01 to 20% by mass, particularly 0.01 to 5% by mass, and more preferably 0.01 to 3% by mass.

  The amount of water contained in the oil-in-water emulsified cosmetic of the present invention, that is, the total amount of water used for emulsifying ceramides and water used for emulsifying polar oil and hydrocarbon oil is It is preferably 5 to 99.9% by mass, particularly preferably 30 to 99.9% by mass.

  The oil-in-water emulsified cosmetic of the present invention may contain an oil component other than the components (C) and (D), and the oil component is substantially any emulsifier of a sphingosine salt or a surfactant. But it can be emulsified. Preferably, it is selected depending on the compatibility with the oil component emulsified with each emulsifier.

In addition to the above, the oily component can include substances usually used in cosmetics, that is, liquid, semi-solid or solid oily components derived from synthetic and natural sources.
Examples of the liquid oil include silicone oils such as dimethylpolysiloxane, dimethylcyclopolysiloxane, methylphenylpolysiloxane, methylhydrogenpolysiloxane, and higher alcohol-modified organopolysiloxane; fluorine oils such as fluoropolyether and perfluoroalkyl ether silicone. Etc.

  Examples of the semi-solid or solid oily component include alkyl glyceryl ethers such as glycerin monostearyl ether and glycerin monocetyl ether; waxes such as carnauba wax and candelilla wax.

  In the oil-in-water emulsified cosmetic of the present invention, in addition to the above components, ingredients used in ordinary cosmetics, for example, humectants such as glycine betaine, urea, amino acids; xanthan gum, hydroxyethyl cellulose, methyl cellulose, hydroxypropyl guar gum, etc. Water-soluble thickeners; 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; anhydrous silica Inorganic powders such as zinc oxide and titanium oxide; refreshing agents such as menthol and camphor; pH buffering agents, antioxidants, ultraviolet absorbers, preservatives, fragrances, bactericides, pigments and the like.

The oil-in-water emulsified cosmetic of the present invention comprises: (C) ceramides emulsified with a salt comprising (A) sphingosines and (B) acidic compounds; and (D) polar oils and hydrocarbon oils. It can manufacture by mixing with the emulsion obtained by emulsifying the oil-based component chosen from (E) surfactant.
For example, (A) sphingosines, (B) an acidic compound selected from inorganic acids and organic acids having 5 or less carbon atoms, and (C) ceramides are heated and dissolved at a temperature at which they can be dissolved. About 10% by mass of water is added to the solution and stirred with a propeller or the like (if necessary, a homomixer is used) to obtain a ceramide emulsion.

  On the other hand, an oil component selected from (D) polar oil and hydrocarbon oil, (E) surfactant, and the remaining water are stirred with a propeller (a homomixer if necessary) to obtain an OW emulsion. Thereafter, the ceramide emulsion is mixed with the OW emulsion, and the final oil-in-water emulsion cosmetic is obtained while stirring.

  In addition, when using components other than component (A)-(E), if the component to add is anionic, it is preferable to add, after the emulsion of ceramide becomes below melting | fusing point. The water-soluble component may be added at any stage after mixing the ceramide emulsion, the OW emulsion, or both.

  Thus, ceramides and other oil components are separately emulsified and mixed to suppress crystallization of the ceramides and to obtain a stable emulsified state.

  The oil-in-water emulsified cosmetic of the present invention is preferably used as, for example, lotion, milky lotion, beauty essence, UV protection cosmetic, makeup base, foundation, makeup cosmetic, and the like.

Examples 1-6, Comparative Examples 1-2
An oil-in-water emulsified cosmetic composition having the composition shown in Table 1 was produced by the following method. The resulting cosmetic was evaluated for storage stability. The results are also shown in Table 1.

(Production method)
Components (A) to (C) are dissolved by heating at 80 to 90 ° C., 10% by mass of water is added, and stirred with a propeller or the like to obtain a ceramide emulsion. Separately, components (D) and (E), the remaining water, and other components are stirred with a propeller to obtain an OW emulsion. The OW emulsion was mixed and stirred with a ceramide emulsion to obtain an oil-in-water emulsion cosmetic.

(Evaluation methods)
(1) Storage stability:
Each oil-in-water emulsified cosmetic is filled in a glass bottle containing 50 mL, and after standing still for one month under three conditions of 50 ° C., room temperature (25 ° C.), and −5 ° C., the appearance is visually observed, Evaluation was made according to the following criteria.
○: Emulsion separation and crystal precipitation are not observed.
Δ: Slight emulsification separation and crystal precipitation are observed.
X: Separation of emulsification or crystal precipitation is observed.

  All of the oil-in-water emulsified cosmetics of Examples 1 to 6 were excellent in storage stability and good in use feeling. The comparative example 1 which does not contain the surfactant of a component (E) and the comparative example 2 which does not contain the acidic compound of a component (B) were inferior to stability of an emulsion.

Example 7 (milky lotion)
An emulsion having the composition shown in Table 2 was produced by the following method. The obtained emulsion was excellent in emulsification stability and usability.

(Production method)
Components (3) to (7), (11) and (13) are heated and dissolved at 90 ° C. Separately, components (1) and (2) and 5% by mass of water prepared by heating and dissolving at 90 ° C. were stirred with a propeller for 20 minutes, then stirred with a homomixer (7000 rpm) and stirred with a propeller. While cooling to 25 ° C., a ceramide emulsion is obtained.
Separately, components (8) to (10) are dispersed with a homomixer (7000 rpm) in the component (12) dissolved in the remaining water, and then the ceramide emulsion is added and mixed and stirred to obtain an emulsion. It was.

Example 8 (skin lotion)
A lotion having the composition shown in Table 3 was produced by the following method. The obtained lotion was excellent in emulsification stability and usability.

(Production method)
A part (about 3% by mass) of components (1), (3), (7) and (6) is heated and dissolved at 80 to 90 ° C. Separately, a component (2) and a part of water (about 6% by mass) dissolved by heating at 80 ° C. are gradually added while stirring with a propeller and held for 20 minutes. Further, water (about 50% by mass) heated to about 80 ° C. is added, and then cooled to 25 ° C. while stirring with a propeller to obtain a ceramide emulsion.
Separately, components (4), (5) and the remaining (6) were dissolved by heating at 80 to 90 ° C., then the remaining water was added little by little while stirring with a propeller, and cooled to 25 ° C., and then a ceramide emulsion Was added and mixed and stirred to obtain a lotion.

Example 9 (milky lotion)
An emulsion having the composition shown in Table 4 was produced by the following method. The obtained emulsion was excellent in emulsification stability and usability.

(Production method)
Components (3) to (7), (12) and (13) are heated and dissolved at 90 ° C. Separately, components (1) and (2) and 5% by mass of water prepared by heating and dissolving at 90 ° C. were stirred with a propeller for 20 minutes, then stirred with a homomixer (7000 rpm) and stirred with a propeller. While cooling to 25 ° C., a ceramide emulsion is obtained.
Separately, components (8) to (10) are dispersed with a homomixer (7000 rpm) in the component (11) dissolved in the remaining water, and then the ceramide emulsion is added and mixed and stirred to obtain an emulsion. It was.

Example 10
An emulsion having the composition shown in Table 5 was produced by the following method. The obtained emulsion was excellent in emulsification stability and usability.

(Production method)
Components (3) to (7), (12) and (13) are heated and dissolved at 90 ° C. Separately, components (1) and (2) and 5% by mass of water prepared by heating and dissolving at 90 ° C. were stirred with a propeller for 20 minutes, then stirred with a homomixer (7000 rpm) and stirred with a propeller. While cooling to 25 ° C., a ceramide emulsion is obtained.
Separately, components (8) to (10) are dispersed with a homomixer (7000 rpm) in the component (11) dissolved in the remaining water, and then a ceramide emulsion is added, and further component (14) is added, After mixing and stirring, an emulsion was obtained.

Example 11
An emulsion having the composition shown in Table 6 was produced by the following method. The obtained emulsion was excellent in emulsification stability and usability.

(Production method)
Components (4) to (9), (15) and (16) are heated and dissolved at 90 ° C. Separately, components (1) to (3) and 5% by mass of water prepared by heating and dissolving at 90 ° C. were stirred with a propeller for 20 minutes, then stirred with a homomixer (7000 rpm) and stirred with a propeller. While cooling to 25 ° C., a ceramide emulsion is obtained.
Separately, components (10) to (13) are dispersed with a homomixer (7000 rpm) in the component (14) dissolved in the remaining water, and then the ceramide emulsion is added and mixed and stirred to obtain an emulsion. It was.

Example 12
An emulsion having the composition shown in Table 7 was produced by the following method. The obtained emulsion was excellent in emulsification stability and usability.

(Production method)
Components (4) to (9), (14) and (15) are heated and dissolved at 90 ° C. Separately, components (1) to (3) and 5% by mass of water prepared by heating and dissolving at 90 ° C. were stirred with a propeller for 20 minutes, then stirred with a homomixer (7000 rpm) and stirred with a propeller. While cooling to 25 ° C., a ceramide emulsion is obtained.
Separately, components (10) to (12) are dispersed with a homomixer (7000 rpm) in the component (13) dissolved in the remaining water, and then the ceramide emulsion is added and mixed and stirred to obtain an emulsion. It was.

Claims (2)

(A) Sphingosine represented by the general formula (1), (B) an acidic compound selected from inorganic acids and organic acids having 5 or less carbon atoms, and (C) a ceramide represented by the general formula (2) An oil-in-water emulsified cosmetic comprising an emulsion, (D) an oily component selected from polar oils and hydrocarbon oils, and (E) an emulsion containing a surfactant.
Sphingosines represented by the general formula (1):

(Wherein 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; Y represents methylene; A group, a methine group or an oxygen atom; X ¹ , X ² and X ³ each 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, Combined with the 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 represents an oxo group. When formed, X ³ is not present.); R ² and R ³ each independently represent 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 a hydroxy group A linear or branched saturated or unsaturated hydrocarbon group having 1 to 8 carbon atoms which may have a substituent selected from a ru group, a hydroxyalkoxy group, an alkoxy group and an acetoxy group; 2 or 3; the broken line indicates an unsaturated bond)
Ceramides represented by the general formula (2):

(In the formula, R ⁷ represents a linear, branched or cyclic saturated or unsaturated hydrocarbon group or a 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 ⁵ , X ⁶ and X ⁷ each independently represent a hydrogen atom, a hydroxyl group or an acetoxy group, and X ⁴ 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, either X ⁵ and X ⁶ is a hydrogen atom, is .X ⁴ the other is absent when forming an oxo group, X ⁷ is absent);. R ⁸ and R ⁹ are each independently hydrogen atom, a hydroxyl group, a hydroxymethyl group or an acetoxymethyl group; R ¹⁰ represents a hydroxyl group, or a carbonyl group A linear, branched or cyclic saturated or unsaturated hydrocarbon group having 5 to 60 carbon atoms which may have an ether bond, ester bond or amide bond in the main chain, which may be substituted by a mino group R ¹¹ represents a hydrogen atom, or may have a substituent selected from a hydroxyl group, a hydroxyalkoxy group, an alkoxy group, and an acetoxy group, and is a linear or branched chain having 1 to 30 carbon atoms in total A saturated or unsaturated hydrocarbon group (provided that when R ⁷ is a hydrogen atom and Z is an oxygen atom, R ¹¹ is a hydrocarbon group having 10 to 30 carbon atoms in total, and R ⁷ is a hydrocarbon group) ¹¹ is a hydrocarbon group having 1 to 8 carbon atoms in total); the broken line indicates that it may be an unsaturated bond)   (C) The ceramide represented by the general formula (2) is emulsified with an acidic compound selected from (A) a sphingosine represented by the general formula (1) and (B) an inorganic acid and an organic acid having 5 or less carbon atoms. The oil-in-water emulsification according to claim 1, wherein an emulsion obtained by emulsifying an oily component selected from (D) polar oil and hydrocarbon oil with (E) a surfactant is mixed. A method for producing cosmetics.