JPH11322568A - Skin cosmetic - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a skin cosmetic that has high water and oil repellency, excellent moisture retention durability and high stability due to use of a reduced amount of emulsifier by using a fluorinated organic compound having a specific degree of fluorine modification and polyols. SOLUTION: This skin cosmetic, preferably in the form of an oil-in-water type emulsion composition comprises (A) a fluorinated organic compound that is represented by the formula: R-X-(CH2 )n Rf (R is a 2-30C alkyl; Rf is a 3-20C fluorinated hydrocarbon group; X is an ester linkage or the like; n is 1 or 2), has 0.3-0.85 fluorine modification degree, defined as [number of fluorine atoms/(number of hydrogen atoms + number of fluorine atoms in the molecule)], for example, perfluoroctyl ethyl ether or the like, preferably in an amount of 0.01-5 wt.% based on the whole composition and (B) a polyol, for example, propylene glyccl or the like, in an amount of 0.1-10 wt.%. In a preferred embodiment, additionally, 0.1-5 wt.% of an oil agent, 0.1-5 wt.% of a surfactant and 0.01-5 wt.% of a thickener may be formulated thereto.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a skin cosmetic, and more particularly, to a stable emulsifier which has high water / oil repellency, excellent durability of moisturizing ability, and can be produced using a small amount of a general-purpose emulsifier. Related to cosmetics.

[0002]

2. Description of the Related Art Emulsion compositions are widely used in the fields of pharmaceuticals, cosmetics, and the like. In particular, when used as an external preparation for the skin, oil-in-water emulsion compositions are often used due to the refreshing feeling of use. ing. It is common practice to blend polyols as humectants in such external preparations for skin, but in such cases, in order to maintain the effect of the humectants, it is necessary that the polyols continue to be present on the skin. It is. However, since the cosmetic coating film on the skin is affected by sweating, sebum secretion, washing and the like, polyols also flow with time, and it has been difficult to maintain the effect for a long time.

[0003] For this reason, it has been practiced to incorporate a fluorine compound having water and oil repellency into skin cosmetics. However, such conventionally used fluorine compounds, particularly perfluoro compounds, themselves have low affinity for both the aqueous phase and the oil phase, and are very difficult to emulsify. Therefore, conventionally, in order to stably emulsify the fluorine compound, a polymer nonionic surfactant (polyoxyethylene-polyoxypropylene copolymer or the like), soybean or egg yolk phospholipid, a fluorine surfactant, etc. Surfactants have been developed.

[0004] However, for example, polyoxyethylene-polyoxypropylene copolymers give fine emulsified particles of a fluorine-based oil to a considerable extent, but they require a relatively large amount of emulsifier, and are not suitable for cosmetic applications. It is not satisfactory from the viewpoint of versatility, and an emulsion having sufficiently high stability has not been obtained with other emulsifiers.

It has been attempted to improve the stability of the emulsion by using various thickeners, fatty acids, etc. to increase the viscosity of the emulsion, but it is not satisfactory from the viewpoint of general versatility of the formulation. Did not.

[0006]

Therefore, a stable oil-in-water emulsified skin cosmetic composition having high water and oil repellency, excellent durability of moisturizing ability, and which can be produced by using a small amount of a general-purpose emulsifier. The development of was desired.

[0007]

Means for Solving the Problems The inventors of the present invention can obtain a skin cosmetic having excellent moisturizing ability by blending a polyol and a fluorinated organic compound having a fluorine modification rate within a certain range. In addition, the present inventors have found that the emulsifier can be emulsified stably by using an appropriate amount of a general-purpose emulsifier, thereby completing the present invention.

That is, the present invention provides the following components (A) and (B): (A) Fluorine modification rate [number of fluorine atoms in molecule / (number of hydrogen atoms in molecule + number of fluorine atoms in molecule)] ] Is 0.
It is intended to provide a skin cosmetic comprising a fluorinated organic compound (B) polyols of 3 to 0.85.

[0009]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The fluorinated organic compound of the component (A) needs to have a fluorine modification ratio of 0.3 to 0.85, preferably 0.3 to 0.8. If the fluorine modification rate is less than 0.3, sufficient water / oil repellency cannot be obtained,
If it exceeds 0.85, the emulsion stability becomes insufficient.

As the fluorinated organic compound of the component (A), the following general formula (1): RX- (CH ₂ ) _n Rf (1)

[In the formula, R represents a linear or branched alkyl group having 2 to 30 carbon atoms, and Rf represents a linear or branched alkyl group having 3 to 20 carbon atoms which may have a hydrogen atom at a terminal carbon atom. X represents an ester bond (-COO- or-
OCO-), ether bond (-O-), amide bond (-NHCO- or -CONH-), urethane bond (-NHCOO- or -OCONH-), urea bond (-NHCONH-), group -CH (OH) CH ₂ O- or group -OCH ₂ CH (O
H)-, and n represents an integer of 1 or 2. ]

And a fluorine-modified silicone. Among them, a compound represented by the general formula (1) is more preferable.

In the general formula (1), examples of the alkyl group represented by R include an ethyl group, a linear or branched propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group and a nonyl group. Group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, eicosyl group, etc., among which those having 6 to 18 carbon atoms, For example, a hexyl group, an octyl group, a decyl group, a dodecyl group and the like are preferable.
Examples of the group represented by Rf include, for example, a linear or branched perfluoropropyl group, a perfluorobutyl group, a perfluoropentyl group, a perfluorohexyl group, a perfluoroheptyl group, a perfluorooctyl group, and a perfluorooctyl group. Fluorononyl group, perfluorodecyl group, perfluoroundecyl group, 1,1,2,2,3,3
4,4-octafluorobutyl group, 1,1,2,2
3,3,4,4,5,5-decafluoropentyl group,
1,1,2,2,3,3,4,4,5,5,6,6-dodecafluorohexyl group, 1,1,2,2,3,3
4,4,5,5,6,6,7,7-tetradecafluoroheptyl group, 1,1,2,2,3,3,4,4,5
5,6,6,7,7,8,8-hexadecafluorooctyl group and the like, among which those having 6 to 12 carbon atoms, for example, perfluorohexyl group, perfluorooctyl group, perfluorodecyl group , 1,1,2,2,3
3,4,4,5,5,6,6-dodecafluorohexyl group, 1,1,2,2,3,3,4,4,5,5,6
A 6,7,7,8,8-hexadecafluorooctyl group is preferred. X is preferably an ether bond or an ester bond, particularly preferably an ether bond.

The total number of carbon atoms of the fluorinated organic compound (1) is
It is preferably from 6 to 50, particularly preferably from 10 to 30.

Preferred examples of the fluorinated organic compound (1) include perfluorooctylethyl octyl ether, perfluorohexylethyl-1,3-dimethylbutyl ether, perfluorooctylethyl ethyl ether, perfluorodecylethyl octyl ether and the like. No.

Among the fluorinated organic compounds (1), compounds in which X is an ester bond include, for example, reacting a fatty acid R-COOH or a reactive derivative thereof with an alcohol represented by Rf (CH ₂ ) _n OH. It is manufactured by Further, a compound in which X is an ether bond is, for example, an alcohol represented by Rf (CH ₂ ) _n OH represented by the following formula:

[0017]

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

Among the components (A), the fluorine-modified silicone includes, for example, at least one of the partial structures represented by the following general formulas (2) to (5) and the partial structure represented by the following general formula (6) And the like.

[0020]

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[Wherein Rf¹And Rf^TwoAre the same or different
May be a linear or branched chain having 1 to 20 carbon atoms.
Fluoroalkyl group or H (CF_Two)_a-(A is an integer from 1 to 20
Linear ω-hydrogen perfluoro represented by
R represents a cycloalkyl group;^Three, R ⁶And R⁷Are the same or
It may be different, and may be a straight or branched chain having 1 to 20 carbon atoms.
A branched aliphatic hydrocarbon group or an alicyclic group having 5 to 10 carbon atoms
Or an aromatic hydrocarbon group;^FourIs a hydrogen atom, charcoal
Linear or branched aliphatic hydrocarbon having a prime number of 1 to 20
Group, alicyclic or aromatic hydrocarbon having 5 to 10 carbon atoms
Group, a perfluoroalkyl group having 1 to 20 carbon atoms or H (CF
_Two)_a-(A represents an integer of 1 to 20).
R represents a hydrogen perfluoroalkyl group;
^FiveRepresents a divalent hydrocarbon group having 2 to 6 carbon atoms; Y and
Z is a single bond, -CO- or a divalent hydrocarbon having 1 to 6 carbon atoms
B represents a number from 1 to 200; c represents a number from 2 to 16
And d and e each represent a number from 1 to 16, and f
Represents a number from 0 to 20, g represents a number from 0 to 200, h
Represents a number from 0 to 200]

In the above formulas, Rf¹And Rf^TwoPar indicated by
As the fluoroalkyl group, any of a straight chain and a branched chain
However, for example, CF_Three-, C_TwoF_Five-, CF_Three(CF_Two)_Three-, CF_Three(C
F_Two)_Five-, CF_Three(CF_Two)₇-, CF_Three(CF_Two)₉-, (C_ThreeF₇) C (CF_Three)_Two-
Linear ω-hydrogen perfluoroalkyl
H (CF_Two)_Two-, H (CF_Two)_Four-, H (CF_Two)₆-, H (CF_Two)
₈-Especially those having 6 to 20 carbon atoms
Is preferred. R^Three, R⁶And R⁷A hydrocarbon group represented by
Are, for example, methyl, ethyl, propyl,
Tyl, pentyl, hexyl, heptyl, octyl
Linear alkyl groups such as phenyl, nonyl, and decyl;
Propyl group, s-butyl group, t-butyl group, neopentyl
Group, 1-ethylpropyl group, 2-ethylhexyl group, etc.
Branched-chain alkyl group; cyclopentyl group, cyclohexyl
Cyclic alkyl groups such as phenyl group, naphthyl group, etc.
And aromatic hydrocarbon groups.
A chain or branched chain aliphatic hydrocarbon group is preferred. R^Fourage
Is a hydrogen atom or a perfluoroalkyl having 6 to 20 carbon atoms.
Kill group or ω-hydrogen perfluoroalkyl
Preferred is a thiol group. R^FiveAnd a divalent hydrocarbon group represented by
Is a linear or branched alkylene group having 2 to 4 carbon atoms
Preferred are ethylene and propylene groups.
Y and Z are each a single bond —CO— or a divalent group having 1 to 4 carbon atoms.
Are preferred. b is 1 to 100, especially 1 to 1
The number of 0 is preferable, and the number of c is preferably 2 to 10, especially 2 to 5.
Preferably, d and e are each 2 to 10, especially 1 to 6
Is preferred, f is preferably a number of 0 to 5, and g is 0 to 10
0, particularly preferably a number of 0 to 10; h is 0 to 100;
Is preferably a number from 0 to 10.

As the fluorine-modified silicone having such a partial structure, for example, the following general formula (7)

[0024]

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[In the formula, h, R ⁶ and R ⁷ have the same meanings as described above, and A ¹ and A ^{2 each} represent a partial structure selected from the general formulas (2) to (5), Which represents a bond] or the following general formula (8)

[0026]

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[In the formula, h, R ⁶ and R ⁷ have the same meanings as described above, and A ³ represents a partial structure selected from the general formulas (2) to (5). In addition, two h may be the same or different. ] Can be cited. In addition,
The arrangement of the structural units of the fluorine-modified silicone (8) is as follows:
It may be alternating, block or random.

Preferred examples of the fluorine-modified silicone include the partial structure represented by the general formula (3) and the general formula (6)
JP-A-5-247214 having a partial structure represented by the following formula:
JP-A-6-184, which has a partial structure represented by general formula (4) and a partial structure represented by general formula (6).
No. 312, a fluorine-modified silicone having a degree of polymerization of 2 to 200, commercially available FSL-30 manufactured by Asahi Glass Co., Ltd.
0, X-22-819, X-22 manufactured by Shin-Etsu Chemical Co., Ltd.
820, X-22-821, X-22-822 and FL
-100, Toray Dow Corning Silicone FS-
1265 and the like.

The fluorinated organic compound as the component (A) can be used alone or in combination of two or more. The amount of the fluorinated organic compound in the total composition is from 0 to 30% from the viewpoint of the stability of the emulsion.
0001 to 20% by weight, 0.001 to 10% by weight, particularly preferably 0.01 to 5% by weight.

The polyols of the component (B) include, for example, propylene glycol, isoprene glycol,
3-butanediol, dipropylene glycol, glycerin, diglycerin, triglycerin, polyglycerin, trimethylolpropane, erythritol, pentaerythritol, sorbitan, sorbitol, glucose, maltitol, saccharose, trehalose, a sugar or a sugar derivative ethylene oxide or Examples include propylene oxide adducts and polyethylene glycols, and particularly preferred are ethylene oxide adducts of sugar derivatives such as glycerin, sorbitol, maltitol, and polyoxyethylene methyl glycoside.

The polyols of the component (B) can be used alone or in combination of two or more. The amount of the polyols varies depending on the intended use feeling, consistency and the like. It is preferably from 01 to 20% by weight, particularly preferably from 0.1 to 10% by weight.

The cosmetic of the present invention contains, in addition to the above essential components,
Various components generally used in cosmetics, for example, oils, surfactants, thickeners, water, pH adjusters, preservatives, antioxidants, and the like can be appropriately compounded as long as the effects of the present invention are not impaired.

As the oil agent, 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 erucate, isostearyl octoate, isodecyl pivalate, isodecyl isononanoate, ersyl erucate, octyl dodecyl oleate, isostearyl pivalate, isostearyl isostearate, isosetyl isostearate, erucate Isostearyl,
Octyldodecyl erucate, isopropyl oleate,
Octyldodecyl dimethyloctanoate, hexyldecyl dimethyloctanoate, oleyl myristate, stearyl erucate, ethyl oleate, decyl oleate, isocetyl stearate, octyl stearate, octyl dodecyl stearate, isostearyl palmitate, isocetyl palmitate, Octyl palmitate,
Isostearyl myristate, isocetyl myristate, isotridecyl myristate, octyl dodecyl myristate, isostearyl laurate, hexyl isostearate, myristyl isostearate, lauryl isostearate, 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, myristate Methyl, methyl laurate, propylene glycol dinonanoate, diisopropyl sebacate, glyceryl trioctanoate, glyceryl tricaprate, diisobutyl adipate, neopentyl glycol dicaprate, propylene glycol dicaprate, dihexyl adipate, glyceryl triacetyl ricinoleate, adipic acid Diisopropyl, glyceryl tricaprate, diglyceryl triisostearate, diethyl sebacate , Diglyceryl monomyristate 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, diglyceryl monoisostearate diglyceryl monomyristate, silicone oil and the like. Preferred are isotridecyl acid, neopentyl glycol dicaprate, diglyceryl monoisostearate, and the like.

These oils can be used alone or in combination of two or more kinds.
It is preferably from 1 to 10% by weight, particularly preferably from 0.1 to 5% by weight.

As the surfactant, any of a nonionic surfactant, an anionic surfactant, a cationic surfactant, and an amphoteric surfactant can be used. It is preferred to use agents, especially polyoxyethylene hydrogenated castor oil or derivatives thereof.

These surfactants can be used alone or in combination of two or more, and the amount is preferably 0.01 to 10% by weight, more preferably 0.1 to 6% by weight in the total composition. .

Examples of the thickener include various clay minerals such as montmorillonite, inorganic compounds such as silica, polyethylene glycol, alginate, xanthan gum, carboxyvinyl polymer, hydroxyethyl cellulose, hydroxymethyl cellulose, and cationized cellulose. It is preferable to add 0.001 to 10% by weight, particularly 0.01 to 5% by weight in the cosmetic of the present invention.

The skin cosmetic of the present invention is prepared according to a conventional method.
It can be produced by appropriately blending (A) a fluorinated organic compound, (B) a polyol, and other optional components, and the dosage form is an emulsion cosmetic, particularly an oil-in-water emulsion cosmetic. It can be widely applied to basic cosmetics such as creams, milky lotions and beauty essences, makeup cosmetics such as foundations, and further hair cosmetics.

[0039]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the invention is limited thereto.

Example 1 O / W type emulsified cosmetics having the compositions shown in Tables 1 and 2 were prepared by a conventional method, and the emulsion stability, water repellency, oil repellency and moisture retention were evaluated by the following evaluation methods. The results are shown in Tables 1 and 2.

<Emulsion stability> After preparation,
The condition after storage at 0 ° C. and 40 ° C. for 3 months was visually observed and evaluated according to the following criteria. ◎: Completely emulsified at any temperature. ：: Almost completely emulsified at any temperature. Δ: Some separation was observed at any temperature. ×: Completely separated at any temperature.

<Water repellency / oil repellency> 50 μl of a cosmetic was applied to the surface of a tanned leather, allowed to stand overnight at room temperature and room humidity, and the contact angle of water and squalane in the cosmetic application area was measured the next day. It was evaluated according to the standard. Water repellency ：: Water contact angle of 60 ° or more ×: Water contact angle of less than 60 ° Oil repellency ：: Squalane contact angle of 70 ° or more ：: Squalane contact angle of 50 ° or more and less than 70 ° △: Squalane contact angle of 30 ° or more and less than 50 ° ×: Squalane contact angle less than 30 °

<Moisturizing Ability> Ten women, aged 20 to 50, whose skin is rough on the cheeks in winter, are applied with different cosmetics on the left and right cheeks for two weeks. The following items were tested the day after two weeks had elapsed. Skin Conductance After washing the face with warm water of 37 ° C. and resting in a room at a temperature of 20 ° C. and a humidity of 40% for 20 minutes, the water content of the stratum corneum was measured with a skin conductance meter (manufactured by IBS). The smaller the conductance value, the more rough the skin.

Skin roughness score Skin roughness was observed with the naked eye, evaluated according to the following criteria, and determined by the average value. 5: No rough skin is observed. 4: Slight skin roughness is observed. 3: Rough skin is observed. 2: Severe rough skin is observed. 1: Severe rough skin is observed.

[0045]

[Table 1]

[0046]

[Table 2]

[0047]

Industrial Applicability The skin cosmetic of the present invention is a stable emulsified cosmetic having high water and oil repellency, excellent durability of moisturizing ability, and which can be produced using a small amount of a general-purpose emulsifier.

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[Submission date] July 13, 1999

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That is, the present invention relates to the following components (A) and (B): (A) a fluorine modification ratio represented by the following general formula (1) [the number of fluorine atoms in a molecule / (the number of hydrogen atoms in a molecule) + The number of fluorine atoms in the molecule)] is 0.3 to 0.85. The present invention provides a skin cosmetic comprising (B) a polyol.

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And the like.

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Claims (4)

[Claims] 1. The following components (A) and (B): (A) the fluorine modification ratio [the number of fluorine atoms in a molecule / (the number of hydrogen atoms in a molecule + the number of fluorine atoms in a molecule)] is 0 .
A skin cosmetic comprising a fluorinated organic compound (B) polyol having a content of 3 to 0.85. 2. The fluorinated organic compound of the component (A) is represented by the general formula (1) RX- (CH ₂ ) _n Rf (1) wherein R is a straight or branched chain having 2 to 30 carbon atoms. Rf represents a linear or branched fluorocarbon group having 3 to 20 carbon atoms which may have a hydrogen atom at a terminal carbon atom, and X represents an ester bond (-COO- or -OCO -), Ether bond (-O-), amide bond (-NHCO- or -CONH-),
Urethane bond (-NHCOO- or -OCONH-), urea bond (-NHC
ONH-), group -CH (OH) CH ₂ O- or a group -OCH ₂ CH (OH) - indicates, n
Represents an integer of 1 or 2. ] The skin cosmetic according to claim 1, which is represented by the formula: 3. Component (B) is propylene glycol,
Isoprene glycol, 1,3-butanediol, dipropylene glycol, glycerin, diglycerin, triglycerin, polyglycerin, trimethylolpropane, erythritol, pentaerythritol, sorbitan, sorbitol, glucose, maltitol, saccharose, trehalose, sugar or sugar 3. The skin cosmetic according to claim 1, which is selected from a derivative of ethylene oxide or a propylene oxide adduct, and polyethylene glycol. 4. An oil-in-water emulsion composition according to claim 1.
The skin cosmetic according to any one of the above.