JP2001139423A - W/o-type emulston composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a W/O-type emulsion composition giving refreshing feeling to the skin in the treatment with the composition, forming durable make-up and having excellent emulsion stability. SOLUTION: The objective emulsion composition is produced by formulating 0.5-5.0 wt.% specific polyether-modified silicone, 7.0-60.0 wt.% oil component containing >=60 wt.% polysiloxane in the oil component, 3.0-60.0 wt.% powder subjected to the surface water-repelling treatment and 15.0-80.0 wt.% aqueous solution of ethyl alcohol having an ethyl alcohol/water weight ratio of 50/50 to 2/98.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a water-in-oil type emulsion composition, and more particularly, to a water-in-oil type emulsion which gives a refreshing sensation upon application, does not easily lose makeup after application, and has excellent emulsion stability. It relates to an emulsion composition.

[0002]

2. Description of the Related Art Emulsified cosmetics for makeup include foundations, eyeliners and mascaras.
When classified from emulsified systems, oil-in-water cosmetics (hereinafter referred to as O / W
It is called a type cosmetic. ) And water-in-oil cosmetics (hereinafter referred to as W /
It is referred to as an O-type cosmetic. ). Since these emulsified cosmetics contain water in their components as compared to oily cosmetics, when applied to the skin, they give a refreshing feeling and further suppress the oily feeling. In addition, they often have a liquid or cream shape, and have properties such as good spreadability on the skin and easy to obtain a uniform finish without unevenness.
In particular, W / O type cosmetics have a higher microbial resistance because the oil phase is a continuous phase as compared with O / W emulsified cosmetics, and leave an oil film with low moisture permeability on the skin surface during use. It protects the skin from drying over time and has excellent performance such as less re-emulsification even when it comes in contact with water by water bathing, water work, sweating, etc. are doing.

[0003]

However, it is difficult for conventional W / O type cosmetics to obtain a stable emulsification,
In order to stabilize, the amount of water contained in the dispersed phase is often limited, or an oil component with a high viscosity is often used, and when used in practice, the sticky or oily feeling is strong. was there. By the way, in order to obtain a refreshing feeling with little stickiness in an emulsified system, it is necessary to use an oil having a small oily content and a little stickiness. Polysiloxane represented by the following general formula (2), (3) or (4) (hereinafter referred to as silicone oil) forms an even thin film on the skin and gives a non-sticky smooth feel. It is known to be suitable as a component. However, these silicone oils have poor compatibility with ordinary surfactants and other oils, and have extremely poor emulsifiability, so that it is difficult to obtain a uniform and fine emulsified system. It is effective to use a system containing ethyl alcohol in order to impart a refreshing sensation at the time of coating. However, in general, the addition of ethyl alcohol has a drawback that the stability of the system is significantly reduced. Therefore, it has been very difficult in terms of stability to further incorporate ethyl alcohol into a polysiloxane-containing system which itself has poor stability.
In other words, despite the fact that W / O type cosmetics have superior performance as compared with O / W emulsified cosmetics, they lack refreshing feeling,
At present, it is not widely used as a cosmetic because it has low palatability due to usability such as stickiness. The present invention has been made in view of the above-mentioned problems of the prior art, and has as its object a highly stable, water-in-oil type that has a good refreshing feeling even after application and has a long lasting makeup. It is to provide an emulsion composition.

[0004]

Under these circumstances, the present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, using a specific polyether-modified silicone as an emulsifier, a silicone oil and a water-repellent powder. By adding an aqueous phase containing a certain concentration of ethyl alcohol to the oil phase containing the body under stirring, the aqueous phase is emulsified stably for a long time, giving a refreshing feeling at the time of application, and a makeup loss after application. It has been found that it is possible to obtain a water-in-oil type emulsion composition which is difficult and has excellent emulsion stability.

That is, the present invention provides the following components (a) to
A water-in-oil emulsion composition comprising (d) as an essential component. (A) General formula (1):

[0006]

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(Where a is 1 to 5, b is 30 to 90, c
Is 40 to 90, m is 10 to 300, n is 1 to 150, o
Represents an integer of 1 to 50, R ¹ represents an alkyl group having 6 to 26 carbon atoms, and R ² represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. ) Polyether-modified silicone represented by
0.5 to 5.0% by weight (b) General formula (2), (3) or (4):

[0008]

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[0009]

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[0010]

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(Wherein x is an integer of 4 to 100, z is an integer of 1 or more, y + z is an integer of 1 to 100, and q is an integer of 3 to 7). Oil component containing at least 60% by weight of the above oil component 7.0-7.0
60.0% by weight (c) Surface water-repellent treated powder 3.0 to 60.0% by weight (d) The weight ratio of ethyl alcohol and water is such that ethyl alcohol / water = 50/50 to 2/98. A certain ethyl alcohol aqueous solution 15.0-80.0% by weight

The polyether-modified silicone as the component (a) used in the present invention is an organopolysiloxane having a polyoxyalkylene group represented by the aforementioned general formula (1). The alkyl group of R ¹ has 6 to 2 carbon atoms.
And the alkyl group of R ² includes, for example, a methyl group, an ethyl group, an isopropyl group, an n-propyl group, a t-butyl group, an n-butyl group, and an n-pentyl group. Preferred specific examples of the polyether-modified silicone include, in the general formula (1), R ¹ having 10 to 20 carbon atoms, R ² being a hydrogen atom, a being 3, and b being 40 to 8;
0, c is 50 to 80, m is 10 to 300, n is 1 to 15
0 and o are 1 to 50. Among them, R ¹
Are preferably those having 16 carbon atoms. Further, the oxypropylene group of the polyether-modified portion is represented by —CH ₂ CH (C
H ₃ ) O— is desirable. Commercially available as the polyether-modified silicone of the present invention include:
For example, ABIL EM90 (TH.GOLDSCHMI
DTAG (trade name).

The applicant of the present application has previously developed a water-in-oil emulsion composition using a polyether-modified silicone having no alkyl-modified siloxane unit (Japanese Patent Application Laid-Open No. 9-1997).
No. 183710). Even when this polyether-modified silicone is used as an emulsifier, it gives a refreshing sensation during application and can be used as a water-in-oil type emulsion composition for makeup with excellent emulsification stability. Was inhibited. However, when the polyether-modified silicone, which is the component (a) of the present invention, is used, the system is more stable in the coexistence of the alcohol, so that more alcohol can be blended than before. As described above, when a large amount of alcohol is blended, the superiority of the component (A) of the present invention is recognized.

The component (a) of the present invention is 0.5 to 7.0% by weight, preferably 1.0 to 4.0% by weight in the water-in-oil emulsion composition.
% By weight. If the amount is more than 7.0% by weight, the effect has already reached saturation, which is uneconomical. If the amount is less than 0.5% by weight, the effect is weak, and particularly the long-term stability is poor.

The component (b) comprises at least 60.0% by weight of the polysilosan represented by the general formula (2), (3) or (4) and less than 40.0% of other oil components. However, among the polysiloxanes, preferred are those represented by the general formula (4). Since this polysiloxane has volatility and does not remain on the skin when actually used as a cosmetic, it does not have an oily feeling during use and can give a refreshing feeling. ) And (3) are more excellent in long-term stability. Examples of these readily available polysiloxanes include SH244, SH manufactured by Tore Silicone.
344, SH245, DC345, K manufactured by Shin-Etsu Chemical Co., Ltd.
F994, KF995, KF996, KF9956, TSF404, TSF405, TSF manufactured by Toshiba Silicone Co., Ltd.
406 and the like.

In the component (b), oil components other than polysiloxane include hydrocarbons such as liquid paraffin and squalane; natural animal and vegetable oils such as olive oil and jojoba oil; octyldodecyl myristate; IPP (isopropyl palmitate); Synthetic ester oils such as IPM (isopropyl myristate) and the like can be mentioned. When the amount of the polysiloxane in the component (b) is less than 60.0% by weight, the emulsified particles tend to be coarse and it is difficult to maintain long-term stability.

In the water-in-oil emulsion composition of the present invention, the component (b) contains 7.0 to 60.0% by weight, preferably 15.0 to 4%.
0.0% by weight is blended. If the oil component is less than 7.0% by weight, emulsification is unstable, and if it exceeds 60.0% by weight, the refreshing feeling and refreshing feeling due to the aqueous phase become poor, which is not preferable.

The component (c) is a known powder which has been subjected to a surface water repellent treatment. Examples of the powder include talc, sericite, mica, kaolin, silica, nylon powder, polyethylene powder, and silk powder. And colorants such as titanium oxide, iron oxide, zinc oxide, ultramarine, navy blue, chromium oxide, organic tar pigments, lakes, and the like; and composite pigments such as titanium mica and iron oxide coated mica. Examples of the surface water repellent include silicones, higher fatty acids, higher alcohols, fatty acid esters, metal soaps, amino acids, alkyl phosphoethers, and fluorine compounds.
Among the components (c), preferred are powders subjected to a water-repellent treatment using a higher fatty acid, a dextrin fatty acid ester, a fluorine compound, silicone or the like. The powder thus obtained has the strongest water repellency, and is resistant to water and sweat even when actually applied to an emulsion, and the makeup is most unlikely to be lost. Further, the emulsified particles are dense and have the longest stability. In addition, even when an untreated powder that is not subjected to water repellent treatment is used, a relatively stable emulsion can be obtained, but since the powder surface has a strong hydrophilicity, makeup loss due to water or sweat is very likely to occur. .

This component (c) is present in the water-in-oil emulsion composition of the present invention in an amount of 3.0 to 60.0% by weight, preferably 7.0.
３30.0% by weight. If the amount is less than 3.0% by weight, the emulsified state is deteriorated, and the stability becomes poor.
In addition, they have poor coloring and are unsuitable as makeup cosmetics. If the content is more than 60.0% by weight, the powderiness is remarkable, and the refreshing feeling, which is the object of the composition of the present invention, becomes poor.

The aqueous solution of ethyl alcohol as the component (d) of the present invention has a weight ratio of ethyl alcohol / water of 50/5.
It is necessary to be in the range of 0 to 2/98, especially 35
/ 65 to 5/95. When the ratio of ethyl alcohol / water is smaller than 2/98, a refreshing feeling is not felt. When the ratio is larger than 50/50, emulsification becomes unstable and irritation to the skin increases.

This component (d) is contained in the water-in-oil emulsion composition of the present invention in an amount of 15.0 to 80.0% by weight, preferably 3 to 80.0% by weight.
0.0 to 70.0% by weight is blended. When the amount is less than 15.0% by weight, the refreshing feeling when actually used is poor, and when it is more than 80.0% by weight, the long-term stability is poor.

The component (d) contains, if necessary, glycerin, sorbitol, propylene glycol,
Moisturizers such as dipropylene glycol, 1,3-butylene glycol, sodium pyrrolidone carboxylate, polyoxyethylene methyl glucoside, polyoxypropylene methyl glucoside, glucose; amino acids such as glycine, serine, proline; anti-inflammatory agents, bactericides, vitamins Pharmaceutical agents and the like can be compounded.

The water-in-oil emulsion composition of the present invention is prepared, for example, as follows. First, the component (a) is added to the component (b) and stirred. Next, after the component (a) is dispersed, the component (c) is added, and the component (d) is added little by little with further stirring, and further stirred to obtain a desired water-in-oil emulsion composition. In the above method, the production temperature is 5
Any temperature up to 90 ° C. can be selected, and in any case, a stable water-in-oil emulsion composition can be obtained.

The water-in-oil emulsion composition of the present invention thus obtained is characterized in that, when the emulsified state of the emulsified particles is observed with a microscope, the powder is formed on the surface of the aqueous phase particles of 10 to 50 μm. The state of adsorption is observed. When the powder is present inside the particles, long-term emulsion stability is poor. Another characteristic of the emulsified particles is that they are very stable when left standing or shaken, but are easily broken when the solution is made into a thin film and given a light shear. This indicates that the same phenomenon occurs when actually applied to the skin.Thus, while it is a water-in-oil type, demulsification occurs immediately upon application, and the aqueous layer containing ethyl alcohol comes into contact with the skin. It is thought that it makes you feel cool.

The water-in-oil emulsion composition of the present invention can exhibit a desirable refreshing sensation regardless of whether it has a low viscosity and is fluid at room temperature or has a high viscosity. In addition, when the low-viscosity water-in-oil emulsion composition of the present invention is allowed to stand for a long time, a layer of an oil component may be slightly separated at the top. However, if the viscosity is such that it becomes uniform by gentle shaking, it can be used as a shaking type cosmetic.

The water-in-oil type emulsion composition of the present invention is not particularly limited as long as it is a cosmetic containing powder, but its main performance, that is, its refreshing sensation and difficulty in removing makeup, are clearly perceived. The use as a foundation is particularly preferred. In particular, the conventional summer liquid foundation is a suspension type in which untreated powder is dispersed in an aqueous phase containing ethanol (the powder sediments when left standing, and separates into two layers from the aqueous phase).
It is characterized by having a refreshing sensation, but has the disadvantage that makeup is easily lost due to water or sweat. The water-in-oil type emulsified composition of the present invention solves the problem, and is particularly preferable to be applied to a liquid foundation for summer.

[0027]

Next, the present invention will be described in more detail with reference to examples. Here, the compounding amount is% by weight. Examples 1 to 4 and Comparative Examples 1 to 5 Liquid foundations having the composition shown in Tables 1 and 2 were produced, the emulsified state immediately after the production, and the emulsion stability when stored at 0 ° C. and 50 ° C. for one week. Was examined. The results are shown in Tables 1 and 2. The manufacturing method and evaluation criteria are as follows.

(Preparation method) The powder and the oil phase were mixed and, after the powder was uniformly dispersed by stirring, an aqueous phase was added with stirring to emulsify. Then, it was filled in a glass container and left at room temperature.

(Evaluation criteria) Emulsion state ○: Good W / O state. Δ: Somewhat poor. ×: Poor. Stability ：: No change. Δ: Slightly separated. X: Separated.

[0030]

[Table 1] {Example 1 2 3 4} ────────────────────── Polyether-modified silicone ^{* 1)} 3.0 3.0 3.0 1.0 Decamethylcyclotetrasiloxane 15.0 15.0 − 15.0 Dimethylpolysiloxane (10 cSt) 5.0 5.0 30.0 5.0 Methylphenylpolysiloxane (20cSt) 10.0 5.0 − 10.0 Liquid paraffin − 5.0 − − Fragrance Trace Trace Trace Trace Trace Siliconized powder ^{* 2)} 15.0 15.0 15.0 15.0 Ethyl alcohol / water: 20/80 (W / W%) Remaining Amount Remaining Remaining Remaining Ethyl alcohol / water: 60/40 (W / W%)----───────────────────────── ────── Emulsified state ○ ○ ○ ○ Stability (storage at 50 ℃, 1 week) ○ ○ ○ ○ Stability (storage at 0 ℃, 1 week) ○ ○ ○ ○ ────────── ────────────────────

[0031]

[Table 2] {Comparative Example 1 2 3 4 5} ─────────────────────────────── Polyether-modified silicone ^{* 1)} 0.3 3.0 3.0 3.0 3.0 Decamethylcyclotetrasiloxane 15.0 6.0 4.0 15.0 4.0 Dimethylpolysiloxane (10cSt) 5.0 4.0 1.0 5.0 3.0 Methylphenylpolysiloxane (20cSt) 10.0--10.0 3.0 Liquid paraffin-20.0---Fragrance Trace Trace Trace Trace Trace Trace Siliconized powder ^{* 2)} 15.0 15.0 20.0 15.0 2.0 Ethyl alcohol / water: 20/80 (W / W%) Remaining Remaining Remaining Remaining-Remaining Ethyl alcohol / water: 60/40 (W / W%)---Remaining--乳化 Emulsified state △ △ △ △ △ Stability (store at 50 ℃, 1 week) △ △ △ × △ Stability (store at 0 ° C for 1 week) △ △ △ × ○ ───────────────────────────────────

* 1): In the general formula (1), a is 3, b
Is 40 to 70, c is 50 to 70, m is 10 to 300, n
Represents an integer of 1 to 150, o represents an integer of 1 to 50, R ¹ represents a carbon number of 16, and R ² represents a hydrogen atom. * 2): A powder having the following composition was used as a raw material powder, and 2% methyl hydrogen polysiloxane (KF99 manufactured by Shin-Etsu Chemical Co., Ltd.) was added to the powder, followed by heat treatment. Was used. Titanium oxide 8 parts Talc 4 parts Bengala 1.2 parts Yellow iron oxide 2.6 parts Black iron oxide 0.2 parts

As is clear from Tables 1 and 2, the liquid foundation of the present invention exhibited better stability than that of the comparative example.

Examples 5 to 8 and Comparative Examples 6 to 10 Foundations having the composition shown in Tables 3 and 4 were produced, and ten professional panelists evaluated the feeling of use by sensory evaluation. The evaluation criteria are as follows. The production method is Example 1
４4.

(Evaluation Criteria) ：: Eight or more out of ten evaluated as good. Good: 6 to 7 out of 10 evaluated as good. B: 4 to 5 persons among 10 persons evaluated that they were good. ×: Out of 10 people, 3 or less were evaluated as good.

[0036]

[Table 3] {Example 5 6 7 8} ────────────────────────── Polyether-modified silicone ^{* 3)} 3.5 3.5 3.5 3.5 Polyether-modified silicone ^{* 4)} − − − − Octamethyl Cyclotetrasiloxane 16.0 4.0 35.0 16.0 Decamethylcyclopentasiloxane 4.0 1.0 10.0 4.0 Methylphenylpolysiloxane (20cSt) 10.0 25.0 10.0 10.0 Fragrance trace trace trace trace trace Siliconized powder ^{* 2)} 12.0 12.0 20.0 50.0 Ethyl alcohol / water: 0 / 100 (W / W%)----Ethyl alcohol / water: 5/95 (W / W%)-Remaining--Ethyl alcohol / water: 20/80 (W / W%) Remaining---Ethyl Alcohol / water: 45/55 (W / W%)--Remaining Remaining ─────────────────────────────── ─ Refreshing feeling ◎ ◎ ◎ ○ Sticky ◎ ○ ○ ◎ Powderiness ◎ ◎ ◎ ○ ────────────────────────────── ───

[0037]

[Table 4] Comparative Example 6 7 8 9 10 ─────────────────────────────── Polyether-modified silicone ^{* 3)} − 3.5 3.5 3.5 3.5 Polyether-modified silicone ^{* 4)} 3.5 − − − − Octamethylcyclotetrasiloxane 16.0 16.0 44.0 13.0 30.0 Decamethylcyclopentasiloxane 4.0 4.0 11.0 2.0 10.0 Methylphenylpolysiloxane (20cSt) 10.0 10.0 10.0 2.0 10.0 Flavors Minor Minor Minor Minor Minor Silicone treated powder ^{* 2)} 12.0 12.0 12.0 63.0 40.0 Ethyl alcohol / water: 0/100 (W / W%)-Remaining---Ethyl alcohol / water: 5/95 (W / W%)-----Ethyl alcohol / water: 20 / 80 (W / W%)-----Ethyl alcohol / water: 45/55 (W / W%) Remaining-Remaining Remaining Remaining ──────── ────────────────────────── Refreshing feeling △ × △ △ × Sticky × ◎ △ ◎ ○ Powderiness ◎ ◎ ◎ × ○ ── ─────────────────────────────────

* 3): In the general formula (1), a is 3, b
Is an integer of 70, c is 60, m is 100, n is 50, and o is 15, R ¹ has 16 carbon atoms, and R ² has a hydrogen atom. * 4): In the general formula (1), a is 3, b is 0, and c is 8.
-10, m is 30-40, n is 30-40, o is 2-5
Where R ¹ is a methyl group and R ² is a hydrogen atom.

As is clear from Tables 3 and 4, the foundation of the present invention had a stronger refreshing feeling, was less sticky and less powdery, and had good usability as compared with those of the comparative example.

Examples 9 to 12 and Comparative Examples 11 and 12 Liquid foundations having the compositions shown in Table 5 were prepared.
A panel of experts evaluated the appearance, feeling of use, water resistance and sweat resistance. In addition, the manufacturing method conformed to Examples 1-4 and the evaluation criteria conformed to Examples 5-8. The appearance was comprehensively evaluated for no change in properties such as color fringes, separation, and aggregation. The feeling of use is refreshing, sticky, and powdery.
The sensory evaluation was comprehensive. The water resistance was determined by observing the state of makeup loss after exposing the skin to which the sample was applied to running water for a certain period of time. As for the sweat resistance, the state of makeup loss after observation in a constant temperature and humidity room at 40 ° C. and 80% humidity for 1 hour was observed.

[0041]

Table 5 Example Comparative Example Composition (%) ９ 9 10 11 12 11 12 ──────────────────────────────── ─── Polyether-modified silicone ^{* 3)} 3.5 3.5 3.5 3.5 − 3.5 Polyether-modified silicone ^{* 4)} − − − − 3.5 − Decamethylcyclopentasiloxane 20.0 20.0 20.0 20.0 20.0 20.0 Methylphenyl polysiloxane (20 cSt) 7.0 7.0 7.0 7.0 7.0 7.0 Fragrance Trace Trace Trace Trace Trace Trace Trace Untreated powder ^{* 5)} -----20.0 Palmitic acid treated powder ^{* 6)} 20.0-----Dextrin Palmitate treated powder ^{* 7)} -20.0- ---Fluorine treated powder ^{* 8)} --20.0---Silicone treated powder ^{* 2)} ---20.0 20.0-Ethyl alcohol / water: 20/80 (W / W%) Remaining Remaining Remaining Remaining Remaining Remaining Remaining Remaining ────────────────────────────────外 観 Appearance ◎ ◎ ◎ ◎ △ ◎ Usability ◎ ◎ ◎ ◎ △ ○ Water resistance ◎ ◎ ◎ ◎ ◎ × Sweat resistance ◎ ◎ ◎ ◎ ◎ × ─────────────── ────────────────────

* 5): Same as the raw material powder of Example 1. * 6): A powder obtained by adding and mixing 2% of sodium palmitate to the raw material powder of Example 1 and performing a surface treatment. * 7): A material obtained by adding and mixing 2% of dextrin palmitic acid ester to the raw material powder of Example 1, followed by surface treatment. * 8): A powder obtained by adding and mixing 2% of a perfluoroalkyl phosphate to the raw material powder of Example 1 and subjecting it to a surface treatment.

As is evident from Table 5, the liquid foundation of the present invention had good appearance and feeling of use, good water resistance and sweat resistance, and also had the property that the makeup was not easily dislodged.

Example 13 Eyeliner (1) Silicone-treated black iron oxide 20.0% by weight (2) Dimethylpolysiloxane 5.0 (3) Decamethylcyclopentasiloxane 22.0 (4) Vitamin E acetate 0.2 (5) Jojoba oil 2.0 (6) Fragrance 0.1 (7) Bentonite 3.0 (8) Polyether-modified silicone 3.0 (In the general formula (1), a = 3, b = 70, c = 55, m = 100, n = 50, o = 10, R ¹ = alkyl group having 18 carbon atoms, R ² = hydrogen atom) (9) 2% by weight ethyl alcohol aqueous solution remaining amount (10) 1,3-butylene glycol 10.0 (Production method) (1) to (8) were heated and stirred to emulsify, and (9) and (10) were added to obtain an eyeliner. This eyeliner is 40
It is stable for more than 1 month at ℃, 25 ℃ and 0 ℃ respectively, and has excellent usability with a refreshing feeling with a refreshing feeling. Both water resistance and sweat resistance are ◎, and it has excellent makeup durability It was.

Example 14 Hand cream (1) Dimethyl polysiloxane 20.0% by weight (2) Sorbitan fatty acid ester 1.0 (3) Vaseline 15.0 (4) Vitamin E acetate 0.2 (5) Paraben 0. 2 (6) Fragrance 0.1 (7) Polyether-modified silicone 3.0 (In the general formula (1), a = 3, b = 70, c = 60, m = 100, n = 60, R ¹ = carbon (8) alkyl group of formula 18, R ² = hydrogen atom (8) Silicone-treated talc 3.0 (9) 10% by weight aqueous solution of ethyl alcohol remaining amount (10) Propylene glycol 10.0 (production method) (1) to (8) And (9) to (10) were separately heated to 70 ° C., and (9) to (10) were added to (1) to (8) with stirring, emulsified, and then cooled to obtain a hand cream. This hand cream is stable at 40 ° C, 25 ° C, and 0 ° C for more than one month each, and has excellent usability with a refreshing feeling with a refreshing sensation. Both water resistance and sweat resistance are ◎. Yes, it was an excellent long-lasting makeup.

Example 15 Mascara (1) Isopar E 10.0% by weight (2) Vinyl acetate emulsion 8.0 (3) Polyether-modified silicone 2.5 (where a = 3 and b = 60, c = 70, m = 50, n = 80, o = 15, R ¹ = alkyl group having 18 carbon atoms, R ² = hydrogen atom) (4) Decamethylcyclopentapolysiloxane 40.0 (5) Paraben 0.1 (6) Fragrance 0.1 (7) Water-swellable clay mineral 3.0 (8) Palmitic acid-treated iron oxide black 3.1 (9) Propylene glycol 3.0 (10) 3% by weight aqueous solution of ethyl alcohol Remaining amount (Preparation method) (1) to (8), (9) and (10) are heated to 60 ° C, and (1) to
(9) and (10) were added to (8) with stirring to emulsify and then cooled to obtain mascara. This mascara is at 40 ° C, 25 ° C, 0
Each of them was stable for one month or more at ℃, and was excellent in usability with a refreshing feeling with a refreshing sensation. Both water resistance and sweat resistance were ◎, and the cosmetics were excellent in durability.

Example 16 Sunscreen Cream (1) Beeswax 1.0% by weight (2) Shortening 1.0 (3) Cetostearyl alcohol 2.0 (4) Decamethylcyclopentapolysiloxane 26.8 (5) p-Dimethylaminobenzoic acid 2-ethylhexyl ester 4.0 (6) 2-hydroxy-4-methoxybenzophenone 1.0 (7) Fragrance 0.1 (8) Polyether-modified silicone 3.0 (general formula (1) Where, a = 3, b = 70, c = 60, m = 150, n = 80, o = 20, R ¹ = alkyl group having 16 carbon atoms, R ² = hydrogen atom) (9) Paraben 0.1 ( 10) Ethanol 5.0 (11) Purified water Remaining (12) Sorbitan stearic acid ester 0.4 (13) Propylene glycol 5.0 (14) Dextrin palmitic acid ester treatment Ultrafine titanium oxide 8.0 (Production method) (1) to (8) and (9) to (13) were separately heated and stirred at 70 ° C., and (9) to (12) were added to (1) to (8) with stirring to emulsify. 14) was added, mixed and stirred, and cooled to obtain a W / O type sunscreen cream. This sunscreen cream is stable at 40 ° C, 25 ° C, and 0 ° C for more than one month each, and has a refreshing feeling, excellent usability with a refreshing feeling, water resistance, and sweat resistance. ◎, UV rays were prevented for a long time.

Example 17 Sunscreen lotion (1) 28.0% by weight of dimethylpolysiloxane (2) olive oil 4.0 (3) liquid paraffin 1.5 (4) octyl methoxycinnamate 3.0 (5) paraben 0.1 (6) Fragrance 0.1 (7) Silicone-treated titanium oxide 6.0 (8) Polyether-modified silicone 2.5 (In the general formula (1), a = 3, b = 60, c = 55, m = 30, n = 60, o = 20, R ¹ = alkyl group having 16 carbon atoms, R ² = hydrogen atom) (9) 30% by weight aqueous solution of ethyl alcohol remaining amount (10) Diglycerin stearate 0.3 (11) Propylene glycol 5.0 (Production method) (1) to (8) and (9) to (11), (1) to (8) to (9) to (11)
Was added while stirring to emulsify and then cooled to obtain a W / O type sunscreen lotion. This lotion is 40
It is stable for more than 1 month at ℃, 25 ℃ and 0 ℃ respectively, and has excellent usability with a refreshing feeling with a refreshing feeling. Both water resistance and sweat resistance are ◎, and it has excellent makeup durability It was.

Example 18 Pre-Make Lotion (1) Liquid paraffin 10.0% by weight (2) Polyether-modified silicone 2.5 (in the general formula (1), a = 3, b = 60, c = 55, m = 30, n = 60, o = 20, R ¹ = alkyl group having 16 carbon atoms, R ² = hydrogen atom) (3) Trimethylsiloxysilicate 3.0 (4) Decamethylcyclopentapolysiloxane 30.0 ( 5) Octyl methoxycinnamate 1.5 (6) Fragrance 0.1 (7) Paraben 0.1 (8) Fluorinated talc 3.0 (9) Spherical nylon powder 1.0 (10) 10% by weight aqueous solution of ethyl alcohol Remaining amount (11) Polyethylene glycol 1.4 (12) Propylene glycol 8.0 (Preparation method) (1)-(9) and (10)-(12) are separately heated and stirred at 70 ° C, and (1)- (10)-(12) was added to (9) with stirring to emulsify, and then cooled to pre-make-up lotion Was manufactured. This lotion was stable at 37 ° C., 25 ° C., and 0 ° C. for more than one month each. In addition, both the water resistance and the sweat resistance were rated as な が ら, and the makeup was excellent in durability while having a refreshing feeling. Then, when the powdery foundation was applied repeatedly, the makeup durability was improved as compared with the case where the powdery foundation was applied without the lotion.

Example 19 Foundation (1) Cyclic polysiloxane (q = 5 in general formula (4)) 20.0% by weight (2) Trimethylsiloxysilicic acid 3.0 (3) Vitamin E acetate 0.1 (4) ) Polyether-modified silicone 3.5 (in the general formula (1), a = 3, b = 70, c = 60, m = 100, n = 60, o = 15, R ¹ = alkyl group having 16 carbon atoms, (R ² = hydrogen atom) (5) Bentonite 0.6 (6) Fluorine-treated titanium dioxide 5.8 (7) Fluorine-treated talc 4.2 (8) Fluorine-treated iron oxide 2.1 (9) 15% by weight ethyl alcohol Aqueous solution Remaining amount (10) Propylene glycol 8.0 (11) Paraben 0.1 (Production method) (1) to (8) are stirred, and (9) to (11) are heated and stirred at 70 ° C., and (1) After (9) to (11) were added to to (8) with stirring to emulsify, a foundation was produced. This foundation was stable at 37 ° C., 25 ° C., and 0 ° C., respectively, for one month or more. In addition, it had a refreshing refreshing feeling, and both the water resistance and the sweat resistance were ◎, indicating that the cosmetics were excellent in durability.

Example 20 Cream Foundation (1) Cyclic polysiloxane (q = 5 in the general formula (4)) 20.0% by weight (2) Dimethylpolysiloxane 3.0 (3) Trimethylsiloxysilicic acid 2.0 ( 4) Polyether-modified silicone 3.0 (in the general formula (1), a = 3, b = 70, c = 60, m = 100, n = 60, o = 15, R ¹ = alkyl group having 16 carbon atoms) , R ² = hydrogen atom) (5) Octyl methoxycinnamate 2.0 (6) Silicone treated titanium dioxide 8.0 (7) Silicone treated sericite 5.0 (8) Silicone treated iron oxide 2.0 (9) Butylene glycol 5.0 (10) 30% by weight aqueous solution of ethyl alcohol Remaining amount (11) Paraben 0.1 (Production method) (1) to (8) are stirred, and (9) to (11) are heated and stirred at 70 ° C. Then, (9) to (11) were added to (1) to (8) with stirring and emulsified, followed by cream fan It was obtained Shon. This cream foundation was stable at 37 ° C., 25 ° C., and 0 ° C. for more than one month each. In addition, it had a refreshing refreshing feeling, and both the water resistance and the sweat resistance were ◎, indicating that the cosmetics were excellent in durability.

Example 21 Foundation (1) Dimethylpolysiloxane 20.0% by weight (2) Methylphenylpolysiloxane 12.0 (3) Squalane 5.0 (4) Behenyl alcohol 1.0 (5) Fragrance 0.1 ( 6) Paraben 0.1 (7) Octyl methoxycinnamate 2.5 (8) Polyether-modified silicone 4.0 (In the general formula (1), a = 3, b = 65, c = 55, m = 150, n = 80, o = 20, R ¹ = alkyl group having 16 carbon atoms, R ² = hydrogen atom) (9) Silicone treated titanium dioxide 5.8 (10) Silicone treated sericite 4.2 (11) Silicone treated oxidation Iron 2.1 (12) Butylene glycol 5.0 (13) 20% by weight aqueous solution of ethyl alcohol Remaining (Preparation method) (1) to (11) and (12) to (13) are separately heated and stirred to make uniform. , (1) to (11) were added to (12) to (13) with stirring to emulsify, To prepare a foundation to retirement.
This foundation is stable at 40 ° C., 25 ° C. and 0 ° C. for at least one month each, and has excellent usability with a refreshing feeling with a refreshing feeling, and both water resistance and sweat resistance are ◎. It was excellent in long-lasting makeup.

[0053]

As described above, the water-in-oil emulsion composition of the present invention has a refreshing sensation at the time of application, has no oily feeling after application, and has a refreshing feeling of use. Further, it has an effect that makeup is not easily dislodged by water or sweat.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) A61K 7/035 A61K 7/035 7/42 7/42 // B01J 13/00 B01J 13/00 A (72 ) Inventor Sadaki Takada 1050 Nippa-cho, Kohoku-ku, Yokohama-shi, Kanagawa F-term in Shiseido Daiichi Research Center (reference) 4C083 AA082 AA122 AB051 AB052 AB171 AB172 AB232 AB242 AB432 AB442 AB471 AC012 AC022 AC072 AC101 AC102 AC122 AC212 AC241 AC342 AC442 AC482 AD072 AD092 AD161 AD162 AD171 AD172 AD241 AD662 BB25 CC01 CC05 CC11 CC12 CC14 CC19 DD32 EE06 EE17 4G065 AA01 AB03X AB10Y AB12X AB28Y BB01 BB03 CA04 DA02 EA01 EA02

Claims (3)

[Claims] 1. A water-in-oil emulsion composition comprising the following components (a) to (d) as essential components. (A) General formula (1): (Where a is 1 to 5, b is 30 to 90, c is 40 to 9)
0, m is 10 to 300, n is 1 to 150, o is 1 to 50
R ¹ is an alkyl group having 6 to 26 carbon atoms, R ²
Represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. )
Polyether-modified silicone represented by 0.5 to 5.
0% by weight (b) General formula (2), (3) or (4): Embedded image Embedded image (Where x is 4 to 100, z is an integer of 1 or more, and y + z
Represents an integer of 1 to 100, and q represents an integer of 3 to 7. )) In the oil component.
Oil component containing not less than 7.0% by weight 7.0 to 60.0% by weight (c) Surface-repellent treated powder 3.0 to 60.0% by weight (d) The weight ratio of ethyl alcohol to water is ethyl alcohol / Water = 50/50 to 2/98 ethyl alcohol aqueous solution 15.0 to 80.0% by weight 2. The powder according to claim 1, wherein the component (c) is a powder subjected to a surface water repellent treatment with a surface water repellent agent selected from the group consisting of higher fatty acids, dextrin fatty acid esters, fluorine compounds and silicones. A water-in-oil emulsion composition. 3. The component (a) is a compound represented by the formula (1), wherein R ¹ is an alkyl group having 16 carbon atoms, R ² is a hydrogen atom, a is 3, b
Is 40 to 80, c is 50 to 80, m is 10 to 300, n
The water-in-oil type emulsion composition according to claim 1 or 2, wherein o is 1 to 150 and o is 1 to 50.