JPH0662385B2 - Emulsified composition - Google Patents

Description

TECHNICAL FIELD The present invention relates to an emulsion composition having silicone oil as an outer phase and a large amount of a polyhydric alcohol in an inner phase, and having good stability. More specifically, it relates to an emulsified composition which is useful as a base material for cosmetics and pharmaceuticals, has excellent water repellency, has a moist feeling, and has good stability.

[Prior Art] Conventionally, water-in-oil type emulsion compositions are well known to be liquid hydrocarbons such as liquid paraffin and squalane, and these are effective for rough skin because the skin surface is covered with an oil film to prevent water evaporation. It is considered that there is, and it is marketed as a facial treatment product with a high treatment effect. Further, makeup products are put on the market due to their excellent water repellency and the effect of not causing makeup damage. On the other hand, silicone oil is often used as an oil phase component because it has smooth usability and is excellent in water repellency.In particular, those containing volatile silicon have a volatile silicone oil that spreads well during application and spreads. Since it volatilizes and reduces the oil remaining on the width surface, it has good adhesion and is widely used because it is strong against sebum and sweat and does not easily collapse.

[Problems to be Solved by the Invention] However, silicone oil has a drawback that it is very difficult to obtain a stable water-in-oil type emulsion system, and it is An emulsified composition containing a large amount and having good stability has not been obtained. Furthermore, even if a stable emulsified composition is obtained, when a large amount of polyhydric alcohol is blended, the stability is markedly reduced and phenomena such as separation, syneresis and aggregation are observed, and the polyhydric alcohol is contained and stable. Such an emulsified composition is more difficult. So far, good stability, containing a large amount of polyhydric alcohol in the internal phase,
There was no method for obtaining an emulsion composition having silicone oil as an external phase.

[Means for Solving the Problems] As a result of intensive studies in view of such circumstances, the inventors of the present invention have found that in the outer phase containing silicon oil, an inner phase obtained by mixing an aqueous solution containing a specific salt with a polyhydric alcohol is used. It has been found that the use of the polyoxyalkylene-modified organopolysiloxane makes it possible to obtain an emulsion composition which is stable and has a good feel when used as a base material for cosmetics and pharmaceuticals, and thus completed the present invention.

That is, the present invention provides (A) an external phase containing silicone oil, and (B) salts of polysulfuric acid sulfate and monosulfuric acid sulfate, oxys,
An aqueous solution containing 0.1% by weight or more of one or more selected from oxyacid salts, and an internal phase containing polyhydric alcohol in an amount of 10 to 70% by weight based on the total amount of the composition, ( C) An emulsion composition containing one kind or a mixture of two or more kinds of polyoxyalkylene-modified organopolysiloxanes represented by the following general formulas [1], [2] and [3].

{In the general formulas [1], [2] and [3], R is a methyl group or a part thereof is a phenyl group, R'is hydrogen or a carbon number of 1 to 12
Alkyl group, p is a number from 1 to 5, q is a number from 2 to 3, x,
m and n are average numbers, and the polyoxyalkylene-modified organopolysiloxane has 5 to 5 polyoxyalkylene groups in the molecule.
40% by weight and the molecular weight of the polyoxyalkylene-modified organopolysiloxane is 2000 or more. } Below, the structure of this invention is explained in full detail.

The first point of the present invention was to select a good lipophilic nonionic surfactant for silicone oil. Conventionally,
Emulsified compositions using hydrocarbon oils include sorbitan monofatty acid ester, sorbitan difatty acid ester, glyceryl monofatty acid ester, glyceryl difatty acid ester, POE addition-hardened castor oil, polyglycerin fatty acid ester, etc. as lipophilic emulsifiers. Has been used. However, even if an attempt is made to make a water-in-oil type emulsion system in which a large amount of silicon is blended using these activators, a good emulsion system is not always obtained because the properties of the oil phase are different. Rather, our research has shown that most of them have stability problems. However, [1],
The activators having the structures [2] and [3] give a stable emulsion system by using an oil phase containing a large amount of silicone oil. In particular,
Of the activators having the structures [1], [2], and [3], the polyoxyalkylene group has a weight percentage of 5% to 40%, a molecular weight of 2000 or more, and is in a liquid or paste form. The stability was dramatically improved by combining one or more selected from salts of monosaccharide sulfuric acid, oxyacids, and oxyacid salts.

The second point is the stable dispersion of polyhydric alcohol and water. In the present invention, salts of polysaccharide sulfate and monosaccharide sulfate in the internal phase,
A mixed solution of an aqueous solution of oxyacid and oxyacid salt and a polyhydric alcohol is used. Here, the water-in-oil type emulsion composition or the polyhydric alcohol-in-oil type emulsion composition was not described because the emulsion composition of the present invention is a polyhydric alcohol from the region where the main component of the internal phase is water. This is because it spans a certain area and neither expression is accurate. That is, the emulsion composition of the present invention is stable even if the main component of the internal phase changes, and the effect of blending the salts of polysaccharide sulfate and monosaccharide sulfate, oxyacid, and oxyacid salt is With respect to the amount of polyhydric alcohol, the stability was sufficiently improved in a wide range to give an emulsion composition having a moist feeling.

Further, the emulsion composition of the present invention is excellent in water repellency even if a large amount of polyhydric alcohol is blended, and it is expected that a treatment effect will be obtained in which the polyhydric alcohol does not run off and the moisturizing action of the polyhydric alcohol is applied.

Many of the polysaccharide sulfates according to the present invention have excellent effects on the skin. For example, sodium salts of chondroitin 4-sulfate and chondroitin 6-sulfate are found in the human dermis to improve the water retention and elasticity of skin tissue. It is known to be closely related. Further, for example, dextran sulfate ester is known to activate blood circulation and improve metabolism. Further, sorbitol sulfate, which is a monosaccharide sulfate used in the present invention, is expected to have an effect of preventing skin aging. Therefore, an emulsified composition which is stable by using salts of polysaccharide sulfate and / or monosaccharide sulfate having such excellent effects is very effective. Polysaccharides and monosaccharide sulfates used in the present invention include mucopolysaccharides such as chondroitin sulfate, keratosulfate, and dermatan sulfate, and dextran sulfate, sodium sulfate such as maltitol sulfate, and monosaccharide sulfates such as sorbitol sulfate. 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 are also used as cosmetics and pharmaceuticals as skin astringents and moisturizers, and most of them have an effective action on the skin. For example, lactic acid, tartaric acid, and citric acid are used as skin astringents, sodium lactate is used as a moisturizing agent, and sodium citrate is used as a sequestering agent and a pH adjusting agent. Therefore, an emulsion composition that is stable by using oxyacids and oxyacid salts having such effects is very effective. The oxyacids and oxyacid salts used in the present invention include hydroxyacetic acid, lactic acid, hydroxypropionic acid, hydroxybutyric acid, hydroxyisobutyric acid, malic acid, tartronic acid, citric acid, isocitric acid, tartaric acid and sodium, potassium and triacid thereof. Examples thereof include ethanolamine salt and the like.

The salts of polysaccharide sulfates and monosaccharide sulfates, oxyacids and oxyacid salts used in the present invention are blended as an aqueous solution, and the concentration thereof is 0.1% or more, but if it is less than 0.1%, the effect does not appear. When it is mixed in a large amount, if the solubility is exceeded, precipitation will occur, which is not preferable. The concentration of the aqueous solution used in the present invention is particularly preferably 1% to 20%.

The polyhydric alcohol used in the present invention may be one having two or more hydroxyl groups in the molecule and soluble in water, for example, polyethylene glycol, dipropylene glycol, 1,3-butylene glycol, propylene glycol. , Glycerin, sorbitol, maltitol and the like. The content of the polyhydric alcohol is 10 to 70% by weight in the emulsion composition. When it is less than 10% by weight, the moisturizing effect of the polyhydric alcohol is insufficient, and when it exceeds 70% by weight, the emulsion stability becomes poor.

The silicone oil used as the external phase in the present invention may be any one commonly used in cosmetics and pharmaceuticals, such as dimethylpolysiloxane, dimethylcyclopolysiloxane, methylphenylpolysiloxane, methylhydrogenpolysiloxane, and higher fatty acid-modified organopolysiloxane. Siloxane, higher alcohol-modified organopolysiloxane, trimethylsiloxysilicate, etc. can be exemplified, and in order to eliminate sticky feeling in use, volatile dimethylpolysiloxane having the following structures [4] and [5]. And dimethylcyclopolysiloxane. One or two or more of these may be arbitrarily selected and used.

The blending amount of silicone oil is related to the amount of other oil phase components, but when the amount of silicone oil is small, the properties of the oil phase are close to those of other blending components and a lipophilic active agent suitable for the oil phase used. And the polyoxyalkylene-modified organopolysiloxane of the present invention suitable for silicone oil becomes good. Therefore, it is particularly good if the silicone oil is 50% or more of the oil phase component.

Further, (A) the external phase containing silicone oil used in the present invention and (B) one or more selected from the salts, oxys, and oxyacid salts of polysaccharide sulfuric acid and monosaccharide sulfuric acid are added to 0.1 The mixing ratio of the aqueous solution containing at least wt% and the internal phase containing the polyhydric alcohol is such that the amount of silicon contained in (A) and the salts of polysaccharide sulfate and monosaccharide sulfate contained in (B), oxyacid By adjusting the amount of the oxyacid salt and the amount of the (C) polyoxyalkylene-modified organopolysiloxane, a stable emulsion composition having a good feeling in use can be obtained, and (A): (B) is preferable. The range of (A) :( B) is 2: 1 to 1: 5, and the particularly preferred range is 1: 2 to 2: 7.

The mixing ratio of the aqueous salt solution to the polyhydric alcohol blended in the internal phase is preferably 5: 1 to 1: 9, and particularly preferably 3: 1 to 3: 7. Further, in the mixing ratio of 2: 3 to 3: 2, when the outer phase is only silicone oil, a region that becomes a transparent emulsion composition appears and appearance characteristics can be imparted.

The content of the polyoxyalkylene-modified organopolysiloxane is preferably 0.5 to 20% in the emulsion composition,
10% is particularly preferred.

Further, the emulsified composition of the present invention may contain components that are usually used, as long as the effects of the present invention are not impaired. For example, moisturizers such as sodium hyaluronate as an aqueous phase component, petroleum jelly, lanolin, ceresin, silicone wax, microcrystalline wax, carnauba wax, candelilla wax, higher fatty acid as an oil phase component,
Solid / semi-solid oils such as higher alcohols, liquid oils such as squalane, liquid paraffin, ester oil and triglyceride, cationic surfactants, anionic surfactants, surfactants such as nonionic surfactants, vitamin E , Agents such as vitamin E acetate, astringents, antioxidants, preservatives, fragrances, pH adjusting agents such as dibasic sodium phosphate, thickeners such as organically modified montmorillonite, ultraviolet absorbers, talc, kaolin, mica, Silica, magnesium silicate,
Calcium silicate, aluminum silicate, hydrated iron oxide,
Inorganic powder such as hydroxyapatite, nylon powder, polyethylene powder, benzoguanamine powder, tetrafluoroethylene powder, organic powder such as boron nitride, titanium oxide, zinc oxide, iron oxide, iron titanate, ocher, mango violet, cobalt violet, water Chromium oxide, chromium oxide, cobalt titanate,
Inorganic pigments such as dark blue and ultramarine blue, titanium oxide coated mica, titanium oxide coated talc, pearl pigments such as fish scale foil, laked tar-based pigments and laked natural pigments, and inorganic powders, organic powders and inorganic pigments A pigment, an organic pigment obtained by subjecting a pigment, an organic pigment to a hydrophobic treatment with silicon, an organic compound, or the like can be blended in the emulsion composition of the present invention.

[Examples] 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.

Example 1 Creamy emulsion composition After heating and stirring A to 70 ° C., this is added to B which has been heated to 70 ° C. in advance and emulsified and dispersed. Then, the mixture is stirred and cooled to room temperature to obtain the desired emulsified composition.

Comparative Examples 1 to 3 are manufactured according to Example 1.

Comparative Example 1 Creamy emulsion composition [Comparative Example 2] Creamy emulsion composition [Comparative Example 3] Creamy emulsion composition Comparative Example 4 Creamy emulsion composition The stability test results of Example 1 and Comparative Examples 1 to 4 are shown in Table 1. As for the test results, the appearance after 1 month and 2 months of being left in a constant temperature bath of 0 ° C., room temperature and 37 ° C. was judged by the following evaluation criteria.

(Stability) ○: Separation, no aggregation Δ: Separation, slight aggregation ×: Separation, aggregation Only Example 1 of the present invention had good stability.

Example 2 Creamy emulsion composition The manufacturing method is the same as in Example 1.

[Comparative Example 5] Creamy emulsion composition The manufacturing method is the same as in Example 1.

Comparative Example 6 Creamy emulsion composition The manufacturing method is the same as in Example 1.

[Comparative Example 7] Creamy emulsion composition The manufacturing method is the same as in Example 1.

The stability test results of Example 2 and Comparative Examples 5 to 7 were performed in the same manner as in Example 1. The results are shown in Table 2.

Only Example 2 of the present invention had good stability.

Next, the usability of the conventional cream (Comparative Examples 8 to 10) and the cream of the present invention (Examples 1 and 2) was tested.

[Comparative Example 8] Creamy emulsion composition B is heated and dissolved at 70 ° C., and then added and emulsified in A which is heated at 70 ° C. Then, the mixture is stirred and cooled to room temperature to obtain the desired emulsified composition.

[Comparative Example 9] Emulsion composition using hydrocarbon-based oil The manufacturing method is the same as in Example 1.

[Comparative Example 10] Creamy emulsion composition The manufacturing method is the same as in Example 1.

Table 3 shows the usability test results of Examples 1-2 and Comparative Examples 8-10.
Shown in. As an evaluation method, 20 panelists were used and evaluated according to the following evaluation criteria.

(Evaluation method) The number of people who answered good is 15 or more ○ The number of people who answered good is 7 to 14 △ The number of people who answered good is 6 or less × Conventional oil-in-water type and water-in-oil type emulsion compositions have drawbacks such as stickiness, and when the amount of polyhydric alcohol is small, they are not sufficiently moist. The emulsified composition of the present invention was epoch-making because it had a moist feel to use and was hard to drop in water.

Next, Tables 4 and 5 show the relationship between the weight% of the polyoxyalkylene group of the polyoxyalkylene-modified organopolysiloxane, the average molecular weight, and the stability.

Next, application of the emulsion composition of the present invention will be described with reference to Examples.

[Example 11] Hand cream After heating and dissolving B at 70 ° C. with stirring, A previously heated to 70 ° C. is added and emulsified and dispersed. Then, the mixture is stirred and cooled to room temperature to obtain the target hand cream.

[Example 12] Makeup base After heating and dissolving B at 70 ° C. with stirring, C is added and dispersed, and heated at 70 ° C. in advance and A is added to emulsify and disperse. Then, the mixture is stirred and cooled to room temperature to obtain the intended makeup base.

[Example 13] Cleansing lotion After heating and dissolving B at 70 ° C. with stirring, A previously heated to 70 ° C. is added and emulsified and dispersed. Then, the mixture is stirred and cooled to room temperature to obtain the desired cleansing lotion.

Example 14 Eye Wrinkle Cream After heating and dissolving B at 70 ° C. with stirring, A previously heated to 70 ° C. is added and emulsified and dispersed. Then, the mixture is stirred and cooled to room temperature to obtain the target eye wrinkle cream.

The emulsion compositions of Examples 3 to 14 were all excellent in stability and usability.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Shigenori Kumagai 1050 Shinba-cho, Kohoku-ku, Yokohama-shi, Kanagawa Shiseido Research Institute Co., Ltd. Shiseido Research Institute Co., Ltd. (56) Reference JP-A-56-79614 (JP, A) JP-A-55-47613 (JP, A) JP-A-54-24959 (JP, A) JP-A-51-46588 (JP , A) JP-B-48-2766 (JP, B1) JP-B-55-39576 (JP, B2) Fragrance Journal, Volume 56 (1982) P. 19-25, 32-42

Claims (3)

[Claims] 1. An (A) external phase containing silicone oil,
(B) One or two or more selected from the salts, oxys, and oxyacid salts of polysaccharide sulfates and monosaccharide sulfates can be used in an amount of 0.
An aqueous phase containing 1% by weight or more, and an internal phase containing polyhydric alcohol in an amount of 10 to 70% by weight based on the total amount of the composition,
(C) An emulsion composition containing one or a mixture of two or more polyoxyalkylene-modified organopolysiloxanes represented by the following general formulas [1], [2], and [3]. {In the general formulas [1], [2] and [3], R is a methyl group or a part thereof is a phenyl group, R'is hydrogen or a carbon number of 1 to 12
Alkyl group, p is a number from 1 to 5, q is a number from 2 to 3, x,
m and n are average numbers, and the polyoxyalkylene-modified organopolysiloxane has 5 to 5 polyoxyalkylene groups in the molecule.
40% by weight and the molecular weight of the polyoxyalkylene-modified organopolysiloxane is 2000 or more. } 2. The emulsion composition according to claim 1, wherein (A) :( B) is 2: 1 to 1: 5 and (C) is 0.5 to 20% based on the total weight. object. 3. The emulsified composition according to claim 1, wherein the silicone oil content in the outer phase containing silicone oil is 50% by weight or more.