JP3108049B2 - Skin cosmetics - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a skin cosmetic containing a specific fluorine compound as an oil agent that remains on the skin for a long time.

[0002]

2. Description of the Related Art Emulsified compositions are frequently used in the fields of pharmaceuticals, cosmetics, etc., and particularly when used as an external preparation for the skin, a refreshing feeling can be obtained. An oil-in-water emulsion composition in which an oil component is dispersed in an aqueous phase is widely used. When such an oil-in-water emulsion composition is used as an external preparation for the skin, it is preferable that the composition remains on the skin for a long time. Such cosmetics and the like are required to have water resistance and oil resistance because they are exposed to perspiration and sebum secretion on the skin or washing with a detergent or the like.

However, in a conventional oil-in-water emulsion composition, for example, when it is applied to the skin, first, a thickening gelling agent or the like in an aqueous phase, which is an external phase, forms a film on the skin, and the oil is further added thereto. The phases will be arranged. Moreover,
Since the thickening gelling agent itself is hydrophilic, it is washed away by water and sweat, and despite having an oil content, it does not have sufficient water resistance, and it has poor retention on the coated surface. There was a problem. In addition, as the oil component generally used in the oil-in-water emulsion composition, semi-solid oil component, liquid oil component, solid oil component or a mixture thereof is used. Pigments and the like flow from the skin, making it difficult to maintain the effect for a long time.

As a measure for solving such problems, a fluorine-based oil having water repellency and low affinity for sebum, particularly a perfluoro compound in which all hydrogen atoms in the molecule have been replaced by fluorine atoms, has been used. An oil-in-water emulsion composition has been reported (JP-A-57-21812).

[0005] However, the above-mentioned fluorine-based oil components, especially perfluoro compounds, are non-hydrophilic and non-lipophilic, and are very difficult to emulsify. Therefore, surfactants such as high-molecular nonionic surfactants (such as polyoxyethylene-polyoxypropylene copolymer), soybean or egg yolk phospholipids, and fluorine-based surfactants have been devised.

However, a closer examination of these emulsifiers reveals that, for example, polyoxyethylene-polyoxypropylene copolymers can give considerably fine emulsified particles of a fluorine-based oil, but they are relatively large in amount. It was possible only in the presence of an emulsifier, and was not satisfactory from the viewpoint of application to cosmetics and versatility. Emulsions with sufficiently high stability have not been obtained with other surfactants. Attempts have also been made to improve the stability of the emulsion by increasing the viscosity of the emulsion using various thickeners and fatty acids, but this has never been satisfactory from the viewpoint of the versatility of the formulation.

Accordingly, an object of the present invention is to provide a skin cosmetic composition which is excellent in water repellency and oil repellency by incorporating a fluorine compound which can be easily emulsified with a small amount of a general-purpose surfactant.

[0008]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to achieve the above object, and as a result, have been used as a solvent for removing cosmetics containing a fluorine compound from the skin. The fluorine compound represented by the formula (1) can be emulsified by a general-purpose surfactant, has strong water and oil repellency, remains on the skin for a long time, and has an excellent skin care effect. And completed the present invention.

That is, the present invention provides the following general formula (1):

[0010]

## STR2 ## RX- (CH ₂ ) _n Rf (1)

(In the formula, R represents a hydrocarbon group, X represents an ether bond, n represents an integer, and Rf represents a fluorocarbon group or a fluorocarbon group having a hydrogen atom only at the terminal.)
And a skin cosmetic containing a fluorine-based compound represented by the formula:

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION The fluorine compound represented by the general formula (1) (hereinafter referred to as "fluorine compound (1)") used in the present invention can be easily emulsified and has strong water repellency and oil repellency. Having. In the general formula (1), the hydrocarbon group represented by R is preferably a straight-chain or branched-chain having 2 to 30 carbon atoms, particularly 2 to 20 carbon atoms. , Butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, docosyl, tetracosyl, hexacosyl, octakosyl, triaconsyl, ethenyl, propenyl,
Butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, ethynyl, propynyl,
Butynyl, pentynyl, hexynyl, heptynyl, octynyl, noninyl, decynyl groups and the like, among which a linear or branched alkyl group having 2 to 20 carbon atoms is more preferable, and ethyl, butyl, hexyl, octyl, decyl And dodecyl are particularly preferred. Further, the group represented by Rf is a fluorocarbon group or a fluorocarbon group in which a hydrogen atom is bonded only to a terminal carbon, and such a fluorocarbon group has 3 to 20 carbon atoms, particularly 3 to 18 carbon atoms. It is preferably a chain or branched perfluoroalkyl group or an ω-hydroperfluoroalkyl group. For example, a perfluoropropyl group, a perfluorobutyl group, a perfluoropentyl group,
Perfluorohexyl, perfluoroheptyl, perfluorooctyl, perfluorononyl, perfluorodecyl, perfluoroundecyl, perfluorostearyl and the like. The integer n is preferably 1 or 2. Further, the total carbon number of the fluorine compound (1) is 6 to 50, particularly 10 to prevent skin irritation.
Preferably it is 50.

The fluorine compound (1) in which X is an ether bond is, for example, an alcohol represented by Rf (CH ₂ ) _n OH represented by the following formula:

[0014]

Embedded image

Is produced by reacting the carbonyl compound represented by the formula (1) in a hydrogen atmosphere in the presence of a hydrogenation catalyst.

Preferred examples of the fluorine compound (1) include perfluorooctylethyl decyl ether, perfluorohexylethyl-1,3-dimethylbutyl ether, perfluorooctylethyl ethyl ether, perfluorostearyl methyl ethyl ether, perfluoropropyl Ethyl octyl ether, perfluorooctyl ethyl octyl ether, perfluorobutyl ethyl hexyl ether and the like can be mentioned. These fluorine compounds (1) can be used singly or as a mixture of two or more kinds. The compounding amount of the component in the cosmetic is 0.0001 to 20% by weight (hereinafter simply referred to as “the composition”). %), Particularly preferably 0.001 to 10%.

In the cosmetic of the present invention, optional components usually used in cosmetics, quasi-drugs, pharmaceuticals and the like may be appropriately compounded as needed, insofar as the effects of the present invention are not impaired. it can. Examples of such optional components include purified water, a surfactant, an oily component, a humectant, a thickener, and the like.

The surfactant may be any of nonionic, anionic, cationic and amphoteric surfactants. Examples of the nonionic surfactant include polyoxyethylene castor oil and hydrogenated castor oil derivatives such as polyoxyethylene castor oil and polyoxyethylene hydrogenated castor oil; polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan tetraoleate Polyoxyethylene sorbitan fatty acid esters such as polyoxyethylene glyceryl monostearate and polyoxyethylene glyceryl triisostearate; fatty acid esters of polyoxyethylene glycol; polyoxyethylene octyl dodecyl ether, polyoxyethylene lauryl ether, polyoxy Polyoxyethylene alkyl ethers such as ethylene cetyl ether, polyoxyethylene stearyl ether, and polyoxyethylene nonyl phenyl ether; In addition to polyoxyethylene addition type surfactant, polyglycerin alkyl ethers, polyglycerin fatty acid ester, and sucrose fatty acid esters.

The anionic surfactants include, for example, polyoxyethylene alkyl sulfate surfactants such as sodium polyoxyethylene lauryl ether sulfate and triethanolamine polyoxyethylene lauryl ether; sodium lauroyl sarcosine, lauroyl methyl alanine N-acyl amino acid salt surfactants such as sodium; sodium polyoxyethylene lauryl ether phosphate, sodium polyoxyethylene cetyl ether phosphate, dipolyoxyethylene alkyl ether phosphoric acid, tripolyoxyethylene alkyl ether phosphoric acid, dipoly Polio such as oxyethylene nonyl phenyl ether phosphate, sodium polyoxyethylene lauryl ether phosphate, sodium dipolyoxyethylene lauryl ether phosphate, etc. Shi ethylene alkyl ether phosphate-based surfactants, alkyl sulfate surfactant, alkyl phosphate-based surfactants, and the like fatty acid salt-based surfactant.

Examples of the amphoteric surfactant include alkyl betaine and alkyl amide betaine. Examples of the cationic surfactant include di-long-chain alkyl quaternary ammonium salts, mono-long-chain alkyl quaternary ammonium salts, di-long-chain alkyl polyoxyethylene quaternary ammonium salts, bis (hydroxyalkyl) quaternary ammonium salts, and amides. / Quaternary ammonium salts having an ester bond.

Specific examples of the oily component include squalane,
Ethyl arachidonic acid, ethyl linolenate, isononyl isononanoate, octyl isopalmitate, isopropyl linoleate, octyl isoperargonate, oleyl linoleate, isotridecyl isononanoate, ethyl linoleate, isopropyl isostearate, isocetyl octanoate, oleyl eica Isostearyl octanoate,
Isodecyl pivalate, Isodecyl isononanoate, Elsyl eica, Octyldodecyl oleate, Isostearyl pivalate, Isostearyl isostearate,
Isocetyl isostearate, isostearyl eica, octyl dodecyl eica, isopropyl oleate, octyl dodecyl dimethyl octanoate, hexyl decyl dimethyl octoate, oleyl myristate, stearyl eica, ethyl oleate, decyl oleate, isocetyl stearate, Octyl stearate,
Octyldodecyl stearate, isostearyl palmitate, isocetyl palmitate, octyl palmitate, isostearyl myristate, isocetyl myristate, isotridecyl myristate, octyldodecyl myristate, isostearyl laurate, hexyl isostearate, myristyl isostearate, isostearin Lauryl acid, stearyl oleate, cetyl oleate, isobutyl stearate, isobutyl palmitate, isopropyl palmitate, octyl myristate, isodecyl laurate, butyl isostearate, octyl pelargonate, isopropyl myristate, isoamyl laurate, isohexyl laurate ,
Myristyl neopentanoate, isobutyl pelargonate,
Lauryl palmitate, decyl myristate, ethyl stearate, ethyl palmitate, butyl myristate, ethyl laurate, methyl myristate, methyl laurate, propylene glycol dinonanoate, diisopropyl sebacate, glyceryl trioctanoate, glyceryl tricaprate, adipin Diisobutyl acid, neopentyl glycol dicaprate, propylene glycol dicaprate, dihexyl adipate, glyceryl triacetyl ricinoleate, diisopropyl adipate, glyceryl tricaprate, diglyceryl triisostearate, diethyl sebacate, diglyceryl monoisostearate , Butyl adipate, dibutyl adipate, diisostearyl malate, octyl oxystearate Octyl methoxycinnamate, octyl dodecyl lactate, isostearyl lactate, oleyl lactate, methyl ricinoleate, octyl paradimethylaminobenzoate, myristyl lactate, dl-α-tocopherol, dl-α-tocopherol nicotinate, lauryl lactate, monoisostearin And diglyceryl monomyristate.

Of these, isotridecyl isononanoate, neopentyl glycol dicaprate, diglyceryl monomyristate monoisostearate and the like are particularly preferred.

Examples of the humectant include propylene glycol, isopropylene glycol, 1,3-butanediol, dipropylene glycol, glycerin, diglycerin, triglycerin, polyglycerin, trimethylolpropane, erythritol, pentaerythritol,
Sorbitan, sorbitol, glucose, maltitol, saccharose, trehalose, ethylene oxide or propylene oxide adducts of sugars or sugar derivatives, polyethylene glycol, ethanol and the like, especially glycerin, sorbitol, maltitol, polyoxyethylene methyl glucoside and the like An ethylene oxide adduct of a sugar derivative and ethanol are preferred. These are used alone or in combination of two or more.

Specific examples of the thickener include specific inorganic compounds and polymer substances. Examples of the inorganic compound include various clay minerals such as montmorillonite and silica. Examples of the polymer substance include polyethylene glycol, alginate, xanthan gum, carboxyvinyl polymer, hydroxyethyl cellulose, hydroxymethyl cellulose, and cationized cellulose.

The skin cosmetic of the present invention can be produced by mixing, stirring, etc. the fluorine compound (1) and other components according to a conventional method. The dosage form of the present invention can be arbitrarily selected from creams, ointments, emulsions, lotions, solutions, and gels.

The skin cosmetic of the present invention is excellent in emulsion stability and forms a coating film having excellent water repellency and oil repellency on the skin. Therefore, it is particularly preferably used as a skin care cosmetic.
In particular, it is preferably used as a skin care cosmetic to be applied to undressed skin.

[0027]

Next, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the following Examples.

Synthesis Example 1 2- (perfluorohexyl) ethanol 1 was placed in a 70 ml autoclave equipped with a hydrogen gas inlet tube and a stirrer.
8.2 g (0.05 mol), 20 g (0.20 mol) of 4-methyl-2-pentanone, 5% Pd-C as a catalyst
(PH 7.2) 0.36 g, hydrogen pressure 50 kg / c
The mixture was stirred at 150 ° C. for 7 hours at m ² . After completion of the reaction, the catalyst was removed by filtration, and excess 4-methyl-2 was removed under reduced pressure.
Pentanone was removed. Further purification is performed by silica gel column chromatography, and 18.4 g of desired perfluorohexylethyl-1,3-dimethylbutyl ether is obtained.
(0.041 mol). The isolation yield was 82%.

Examples 1 to 8 and Comparative Examples 1 to 4 Cosmetics were produced according to a conventional method using the formulations shown in Tables 1 and 2.

[0030]

[Table 1]

[0031]

[Table 2]

Test Example 1 The emulsified state, water repellency and oil repellency of the cosmetic obtained above were evaluated according to the following evaluation criteria. The results are shown in Tables 1 and 2. In addition, the emulsion stability was visually observed after storage for 3 months at -5 ° C to 40 ° C after preparation. The water repellency and oil repellency were measured by applying 50 μl of the cosmetic obtained above on a tanned leather and allowing it to stand at room temperature and room humidity overnight, and measuring the contact angle of water and squalane in the cosmetic application area the next day. And water repellent /
Oil repellency was evaluated. The evaluation results were based on the following criteria. (Evaluation criteria) ・ Emulsification stability ◎: Completely emulsified ○: Almost completely emulsified △: Slightly insufficient emulsification ×: Not emulsified at all ・ Water / oil repellency ◎: Contact with water Angle 60 ° or more, Squalane contact angle 70 °
○: Water contact angle of 60 ° or more, squalane contact angle of 50 °
Not less than 70 ° Δ: water contact angle 50 ° or more, squalane contact angle 30 °
Not less than 50 ° C: Contact angle of water 50 ° or more, Contact angle of squalane 30 °
Less than

From Tables 1 and 2, it was confirmed that the cosmetics of Examples 1 to 8 were superior to the cosmetics of Comparative Examples 1 to 4 in both emulsified state, water repellency and oil repellency.

[0034]

The cosmetic of the present invention contains a fluorine compound which can be easily emulsified with a general-purpose surfactant,
It has excellent water repellency and oil repellency. The cosmetic of the present invention is particularly useful as a skin care cosmetic.

──────────────────────────────────────────────────続 き Continuation of the front page (72) Inventor Shinji Yano 1334 Minato, Wakayama City, Wakayama Pref. Kao Corporation Laboratory (56) References JP-A-8-291045 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) A61K 7/48 A61K 7/00

Claims (3)

(57) [Claims] 1. The following general formula (1): R—X— (CH2) nRf (1) (wherein, R represents a hydrocarbon group, X represents an ether bond, and n represents an integer. Wherein Rf represents a fluorocarbon group or a fluorocarbon group having a hydrogen atom only at the terminal.) 2. The fluorine-based compound represented by the general formula (1) has a total carbon number of 6 to 50, R is a linear or branched hydrocarbon group having 2 to 30 carbon atoms, and n is The skin cosmetic according to claim 1, which is 1 or 2, wherein Rf is a linear or branched fluorocarbon group having 3 to 20 carbon atoms or a fluorocarbon group having only a hydrogen atom at a terminal. 3. The composition according to claim 1, which is a skin care cosmetic.
The skin cosmetic according to the above item.