JPH02298338A - Emulsion composition - Google Patents

Abstract

PURPOSE:To improve resistance to water, perspiration and sebum by preparing an emulsion composition by mixing an outer phase contg. fluorine modified silicone compound, an inner phase contg. water or alcohol and a lipophilic surfactant. CONSTITUTION:An emulsion composition is prepd by mixing an outer phase (component A) contg. at least one kind of fluorine modified silicone compounds shown by the formula I (wherein (n) and (m)are the average of 1-150 and 0-150, respectively, (a) is an integer of 0-5 and Rf represents 1-8C perphloroalkyl group) an inner phase (component B) contg. water and/or alcohol and lipophilic surfactant (component C). The above mixture is made, preferably with the ratio of the components A to B ranging from 5:1 to 1:5 and with the component C added thereto in an amt. of 0.5-20wt.% (per emulsion composition). As a suitable example for the component C, 14-22C sorbitam monofatty acid ester is available.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to an emulsion composition containing a fluorine-modified silicone compound in the outer phase and having excellent water resistance, sweat resistance, sebum resistance, and good feel and stability in use. More specifically, the present invention provides an emulsified composition that is useful as a base for cosmetics and pharmaceuticals, has excellent water resistance, sweat resistance, and sebum resistance, has good durability, and has good stability.

[Prior art] Conventional water-in-oil emulsion compositions are often known to be hydrocarbon-based such as liquid paraffin and squalane, and these are effective against rough skin because they cover the skin surface with an oil film and prevent water evaporation. It is thought that there is a certain amount of facial treatment, and it has not been released on the market as a facial product with a high treatment effect. Furthermore, in makeup products, it has been well marketed because it has excellent water repellency and has effects such as less fading of makeup. On the other hand, as silicone oils, dimethylpolysiloxane and methylphenylpolysiloxane are often used as oil phase components because they are smooth to use and have excellent water repellency.

[Problem to be Solved by the Invention 1] However, there is a strong desire to obtain an emulsion system that is even more water resistant and sebum resistant than those using dimethylpolysiloxane or methylphenylpolysiloxane, and has good durability. However, it is not obtained.

[Means for Solving the Problems] In view of these circumstances, the inventors of the present invention have made extensive studies and found that an outer phase containing a fluorine-modified silicone compound, an inner phase containing water and/or alcohol, and a specific lipophilic We have discovered that by using a surfactant, it is possible to obtain an emulsified composition that has good water resistance, sweat resistance, and sebum resistance when used as a base for cosmetics or pharmaceuticals.
The present invention has now been completed.

That is, the present invention provides (A) an external phase containing one or more fluorine-modified silicone compounds represented by the following general formula [I], (B) an internal phase containing water and/or alcohol, and (C) a parent phase. It is an emulsified composition containing an oily surfactant.

CH3CH3CH3CI+3 CH3-3i-0-(Si-0)r, -(Si-0),
, -5i-Ct131 1 1 l CH3(CH2), Rf CH3(Jh['I] (In formula [I], n and m are average numbers, n is a number of 1 to 150, and m is a number of O to 150. .a is an integer from O to 5, and Rf
represents a perfluoroalkyl group having 1 to 8 carbon atoms. ) Below, the structure of the present invention will be explained in detail.

Dimethylpolysiloxane and methylphenylpolysiloxane, which have been used to improve water resistance and sweat resistance, have not always had good oil and sebum resistance. The fluorine-modified silicone compound used in the present invention has improved oil resistance and sebum resistance by introducing a fluoroalkyl group into dimethylpolysiloxane represented by the following general formula [I].

CH3CH3CH3CH3 11I l CH3-3i-0-(Si-0)n -(Si-0)m
-Si-CH3C)13 (CH2), Rf CH3C
H3[I] (In formula [1], n and m are average numbers, n is 1 to 1501m is a number from O to 150, a is an integer from O to 5, and Rf
represents a perfluoroalkyl group having 1 to 8 carbon atoms. ) In order to impart oil resistance to the fluorine-modified silicone compound used in the present invention by adjusting the ratio of n, the ratio of n/(n+m
) is preferably from 0.05 to 1, and more preferably from 0.1 to 0.8, since a high fluorine modification rate increases oil resistance but deteriorates compatibility with other oils. Rf is a perfluoroalkyl group having 1 to 8 carbon atoms, which may be linear or branched, such as trifluoromethyl, pentafluoroethyl, heptafluoropropyl, nonafluorobutyl, heptadecafluorooctyl, and the like.

These can be obtained as commercial products such as those listed below. That is, examples of fluorine-modified silicone compounds include X-22-819 and X-2 manufactured by Shin-Etsu Chemical Co., Ltd.
2-820, X-22-821, X-22-822, F
L-100, FS1265 manufactured by Toray Silicone Co., Ltd.
etc. can be given.

The blending amount of the present fluorine-modified silicone compound can range from 1 to 95% of the emulsified composition, but is particularly preferably 5% or more.

An important aspect of the present invention is that an emulsion composition that takes advantage of the water resistance, sweat resistance, oil resistance, and sebum resistance of the present fluorine-modified silicone compound is obtained.

There is no particular problem with the lipophilic surfactant used in the present invention as long as it is a lipophilic surfactant normally used in cosmetics.
The following are preferable. That is, sorbitan monofatty acid esters, sorbitan difatty acid esters, glyceryl monofatty acid esters, glyceryl difatty acid esters, and alkyl groups having 1 carbon number.
Glyceryl monoalkyl ether of 4 to 22, glyceryl dialkyl ether, POE addition-cured castor bone addition molar number 2 to 8), polyglycerin fatty acid ester of polymerization degree of 2 to 10, polyglycerin alkyl ether and general formula [11, [21] , [31, and [4] One or a mixture of two or more polyoxyalkylene-modified organopolysiloxanes is used.

(Left below) Here, if the polyoxyalkylene group is 5% or less, it will dissolve in silicone oil and a sufficient effect will not be obtained, and if it is 40% or more, hydrophilicity will increase, which is not preferable.

Moreover, if the molecular weight is less than 2000, the emulsion composition will become unstable, which is not preferable. In carrying out the present invention, one or more of these activators may be used in any combination.

Furthermore, in the present invention, amino acids, amino acid salts,
A combination of one or more selected from polysaccharide sulfate and monosaccharide sulfate salts, oxyacids, and oxyacid salts, and a combination of water-swellable clay minerals and quaternary ammonium salt type cationic surfactants. In this case, the stability improved dramatically.

In addition, in the present invention, water and/or alcohol) L is added to the internal phase.
A mixed solution of , is used. The reason why the emulsion composition of the present invention is not described as a water-in-oil emulsion composition or an alcohol-in-oil emulsion composition is that the emulsion composition of the present invention straddles the range from the region where the main component of the internal phase is water to the region where the main component is alcohol. Neither expression is accurate. In other words, the emulsion composition of the present invention has good durability even when the main component of the internal phase changes, and if it is a good emulsion composition and is of a type that is shaken before use, it can be used as it is, and the stability is improved. If desired, by blending amino acids, amino acid salts, salts of polysaccharide sulfuric acid and monosaccharide sulfuric acid, oxyacid, and oxyacid salts, an emulsion composition that is sufficiently stable in a wide range of alcohol content in the internal phase can be obtained. .

Furthermore, the emulsified composition of the present invention has excellent water resistance, sweat resistance, and oil resistance even when a large amount of alcohol is blended, does not run off in water, and takes advantage of the cooling sensation of lower alcohol and the moisturizing effect of polyhydric alcohol. You can also expect the treatment to be effective.

The amino acids used in the present invention may be commonly known amino acids, such as monoamino monocarboxylic acids such as glycine, alanine, diaryne, leucine, isoleucine, serine, threonine, and phenylalanine, aspartic acid,
Examples include monoaminodicarboxylic acids such as glutamic acid, diaminomonocarboxylic acids such as arginine and lysine, and their salts, pyrrolidonecarboxylic acid and its salts, and the like. Among the various amino acids used in the present invention, acidic amino acids are preferably used, and glutamic acid, aspartic acid, and/or salts thereof are particularly preferably used. The polysaccharides and monosaccharide sulfates used in the present invention include sulfates of mucopolysaccharides such as chondroitin sulfate, keratosulfate, dermatan sulfate, polysaccharide sulfates such as dextran sulfate, maltitol sulfate, and monosaccharide sulfates such as sorbitol sulfate, respectively. Inorganic or organic salts such as salts, potassium salts, triethanolamine salts, and amino acid salts such as arginine, preferably sodium salts or potassium salts.

The oxyacids and oxyacid salts used in the present invention include hydroxyacetic acid, lactic acid, hydroxypropionic acid,
Examples include hydroxybutyric acid, hydroxyisobutyric acid, malic acid, tartronic acid, citric acid, isocitric acid, tartaric acid, and its sodium, potassium, and triethanolamine salts.

The amino acids, amino acid salts, salts of polysaccharide sulfuric acid and monosaccharide sulfuric acid, oxyacid, and oxyacid salts used in the present invention are formulated as an aqueous solution, and the concentration thereof is particularly preferably 0.1%.
~20%. The water-swellable clay mineral used in the present invention is a type of colloidal hydrated aluminum silicate having a three-layer structure, and is generally expressed by the following general formula %. Natural or synthetic montmorillonites (in which the (OH) group in the formula is substituted with fluorine) such as montmorillonite, sabonite, and hectorite (commercially available products include Veegum: Vanderbilt, Knivia Savonite; Kunimine) (Kogyosha, Labonite: Laborte, Smectite: Nippon Kayaku, etc.)
and synthetic mica known as sodium silicic mica or sodium or lithium taeniolite (commercially available products include dymonite; manufactured by Tobie Gyo Co., Ltd., etc.).

The quaternary ammonium salt type cationic surfactant used in the present invention has the following general formula (where RI is an alkyl group having 10 to 22 carbon atoms or a benzyl group, R2 is a methyl group or an alkyl group having 10 to 22 carbon atoms, R3 and R4 are an alkyl group or a hydroxyalkyl group having 1 to 3 carbon atoms, and X is a halogen atom or a methyl sulfate residue.

For example, dodecyltrimethylammonium chloride, myristyltrimethylammonium chloride, cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, aracyltrimethylammonium chloride, behenyltrimethylammonium chloride,
Myristyldimethylethylammonium chloride, Cetyldimethylethylammonium chloride, Stearyldimethylethylammonium chloride, Arakyldimethylethylammonium chloride, Behenyldimethylethylammonium chloride, Myristyldiethylmethylammonium chloride, Cetyldiethylmethylammonium chloride, Stearyldiethylmethylammonium chloride, Araki diethylmethylammonium chloride,
Behenyldiethylmethylammonium chloride, benzyldimethylmyristylammonium chloride, benzyldimethylcetylammonium chloride, benzyldimethylstearylammonium chloride, benzyldimethylbehenylammonium chloride, benzylmethylethylcetylammonium chloride, benzylmethylethylstearylammonium chloride, dibehenyldihydroxyethylammonium chloride , and corresponding bromides, as well as civalmitylpropylethylammonium methyl sulfate and the like.

In implementing the present invention, one or more of these may be arbitrarily selected.

The amount of water-swellable clay mineral and quaternary ammonium salt type cationic surfactant used in the present invention is adjusted depending on the internal phase ratio and viscosity of the emulsified composition to be obtained. The amount of surfactant is involved in emulsifying properties, and if it is too small, emulsifying properties will deteriorate, and as the amount of water-swellable clay minerals and quaternary ammonium salt type cationic surfactants increases, the viscosity will increase. Tend. Therefore, the blending amounts of polyoxyalkylene-modified organopolysiloxane, water-swellable clay mineral, and quaternary ammonium salt type cationic surfactant are 0.5-20% by weight, 0.1-5% by weight, and 0.0% by weight, respectively. .1 to 2% by weight is preferred.

The alcohols used in the present invention include lower alcohols such as ethanol and isopropanol, and/or polyhydric alcohols that have two hydroxyl groups in the molecule and are soluble in water, such as polyethylene glycol, dipropylene glycol, 1.3-butylene glycol,
Examples include propylene glycol, glycerin, sorbitol, maltitol, etc. The amount of alcohol blended is preferably 5 to 50% by weight in the emulsified composition.

In addition to fluorine-modified silicone compounds, silicone oils can be cited as the oils that can be blended into the external phase in the present invention. The silicone oils used here are those normally used in cosmetics and pharmaceuticals and have good compatibility with fluorine-modified silicone compounds, such as dimethylpolysiloxane, dimethylcyclopolysiloxane, methylphenylpolysiloxane, methylhydrogenpolysiloxane, and higher fatty acids. Modified organopolysiloxanes, higher alcohol-modified organopolysiloxanes, trimethylsiloxysilicate, etc. can be exemplified, and in particular, when eliminating the sticky feeling during use, volatile dimethylpolysiloxanes having the structures shown in [51 and [6] below can be used. Examples include siloxane and dimethylcyclopolysiloxane. One, two or more, or two or more of these may be arbitrarily selected and used.

CH3CH3 CH3-SiO-5iO-CH3[5]0(Si(CH
3)20)i i=1~4 C113CH3CH3 CH3-Si-0-(Si-0)j-3i-CH3[6
] CH3CH3CH3 j = 1 to 3 In addition, the mixing ratio of (A) the external phase containing the fluorine-modified silicone compound and (B) the internal phase containing water and/or alcohol used in the present invention is the same as that contained in (A). A good emulsified composition can be obtained by adjusting the amount of fluorine-modified silicone compound used, the type and amount of oil phase components, the amount of water and alcohol (B), and the amount of lipophilic surfactant (C). However, a preferable weight ratio of (A):(B) is 5:1 to 1:5, and a particularly preferable range is 2:1 to 2.

In addition, the mixing ratio of water and alcohol blended into the internal phase is 9:
A ratio of 1 to 1:9 is preferred, and a ratio of 5:1 to 3 is particularly preferred. Roughly speaking, at a mixing ratio of 2:3 to 3:2, a region that becomes a transparent emulsion composition appears, and it is possible to impart characteristics in appearance.

The amount of lipophilic surfactant blended into the emulsion composition is 0.5~2.
O is preferably 0%, and particularly preferably 1 to 10%. Furthermore, the emulsified composition of the present invention may contain commonly used components within a range that does not impair the effects of the present invention. For example, moisturizers such as sodium hyaluronate are used as aqueous phase components, and petrolatum, lanolin, ceresin, silicone wax, microcrystalline wax, carnauba wax, candelilla wax, higher fatty acids, etc. are used as oil phase components.
Solid and semi-solid oils such as higher alcohols, liquid oils such as squalane, liquid paraffin, ester oils, and triglycerides, surfactants such as cationic surfactants, anionic surfactants, and nonionic surfactants, and vitamin E1. Drugs such as vitamin E acetate, astringents, antioxidants, preservatives, fragrances, PH regulators such as dibasic sodium phosphate, thickeners such as dextrin fatty acid esters, ultraviolet absorbers, talc, kaolin, mica, silica , inorganic powders such as magnesium silicate, calcium silicate, aluminum silicate, hydrated iron oxide, hydroxyapatite, organic powders such as nylon powder, polyethylene powder, benzoguanamine powder, tetrafluoroethylene powder, boron nitride, titanium oxide, oxidized titanium, etc. Zinc, iron oxide, iron titanate,
Loess, mango violet, cobalt violet,
Inorganic pigments such as chromium hydroxide, chromium oxide, cobalt titanate, navy blue and ultramarine blue, var pigments such as titanium oxide coated mica, titanium oxide coated talc, fish scale foil, tar-based pigments made into lakes, and natural pigments made into lakes. These inorganic powders, organic powders, inorganic pigments, and organic pigments that have been hydrophobized with silicone, organic compounds, etc. can be blended into the emulsion composition of the present invention.

Next, examples according to the present invention will be described, but these are merely examples and do not limit the scope of the present invention in any way. In addition, the blending amounts in the examples are weight %.

Example 1 After heating and stirring creamy emulsion composition A to 700°C, it was preheated to 70°C.
Add to the heated water and emulsify and disperse.

Thereafter, the mixture is stirred and cooled to room temperature to obtain the desired emulsion composition.

Comparative Example 1 was manufactured according to Example 1.

Table-2 Comparison of stability Observe by leaving in a constant temperature bath at 0°C1 room temperature and 37°C.

O: No separation or aggregation △: Slightly present X: No I present Example 1 of the present invention had good conditions and stability immediately after trial production.

Next, the usability of the conventional cream emulsion composition and the cream emulsion composition of the present invention was tested.

After heating and stirring B to 70°C, add C and perform a dispersion treatment. Then, add A, which had been previously heated to 70°C, and emulsify and disperse. Thereafter, the mixture was stirred and cooled to room temperature to obtain the desired emulsion composition. Comparative Example 1.2 was produced according to Example 2.

Comparative Example 3 Water-in-oil breast panel using hydrocarbon oil
20 people 15 or more people answered ``Good'' O Tsuno 7 to 14 people Δ ノ! 6 people or less

Kaolin 5.0% Sericite 7.4 Talc 3.0 Zinc oxide 3.0 Titanium oxide 10.0 Iron oxide yellow 1.0 Iron oxide world 0.4 Iron oxide black 0.2 Heat and stir B to 70°C After that, C is added and dispersed, and then A, which has been heated to 70°C in advance, is added and emulsified and dispersed. Thereafter, the mixture is stirred and cooled to room temperature to obtain the desired emulsified foundation.

Example 4 Emulsified foundation sericite 8.03 Titanium oxide 6.0 Iron oxide yellow 0.6 Iron oxide world 0.25 Iron oxide black 0.12 After heating B to 70°C and stirring, add and disperse, Next, C was added and stirred, and then A, which had been previously heated to 70'C, was added and emulsified and dispersed. Thereafter, the mixture is stirred and cooled to room temperature to obtain the desired emulsified foundation.

Example 5 Blush titanium oxide 4.0 Iron oxide 1.0 Sericite 2.0 After heating and stirring A to 70°C, add and disperse, then dissolve B in some ion-exchanged water. Added. This is added to C which has been preheated to 70°C and emulsified and dispersed. Thereafter, the mixture is stirred and cooled to room temperature to obtain the desired blush.

Fine particle titanium oxide 3.0 Cobalt titanate 0.5 Talc 1゜5 Nylon powder 1.0 (particle size 5 microns) After heating and stirring B to 70°C, add and disperse, then add C and stir After that, A, which had been heated to 70°C in advance, was added and emulsified and dispersed. Thereafter, the mixture is stirred and cooled to room temperature to obtain the desired makeup base.

Particulate titanium oxide 10.0 Sericite 4.35 Zinc oxide 5.0 Yellow iron oxide 0.5 Iron oxide 0.15 Nylon powder 5.0 A was heated to 70°C, the mixture was added and dispersed, Thereafter, B is dissolved in some ion-exchanged water and added. This is added to C, which has been previously heated to 70'C, and emulsified and dispersed. Thereafter, the mixture is stirred and cooled to room temperature to obtain the desired sunscreen.

Example 8 Ointment B was heated to 70°C and stirred, and then A, which had been previously heated to 70'C, was added and emulsified and dispersed. Thereafter, the mixture was stirred and cooled to room temperature to obtain the desired makeup base.

The emulsified compositions of Examples 3 to 8 were all excellent in water resistance, sweat resistance, oil resistance, and sebum resistance, and had good stability and feel when used.

Claims (1)

[Claims] (1) (A) an external phase containing one or more fluorine-modified silicone compounds represented by the following general formula [I]; (B) an internal phase containing water and/or alcohol; and (C) lipophilicity. An emulsified composition characterized by containing a surfactant. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [I] (In the formula [I], n and m are average numbers, and n is 1 to 150, m
is a number from 0 to 150. a is an integer from 0 to 5, R
f represents a perfluoroalkyl group having 1 to 8 carbon atoms. )