JPH07118306A - Water-in-oil emulsion containing sulfated polysaccharide - Google Patents

Abstract

PURPOSE:To obtain a water-in-oil emulsion which contains a sulfated polysaccharide or its salt and is excellent in temp. stability, protection of the skin, and retention of the moistness and softness of the skin. CONSTITUTION:This water-in-oil emulsion is characterized by containing a polysulfated mucopolysaccharide or its salt.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a water-in-oil (hereinafter abbreviated as W / O) emulsion composition useful as a cosmetic or a pharmaceutical.

[0002]

2. Description of the Related Art Conventionally, as a base for creams and the like, a W / O type emulsion in which oil particles are generally contained in oil is better than an O / W type emulsion in which oil particles are contained in water. In comparison, it is known to be excellent in many points such as protection of skin, moisturization and maintenance of flexibility.

However, the W / O type emulsion composition has some problems such as stability of quality. To improve the stability, the amount of oil or the viscosity is increased. Although the stability is improved, as a result, defects such as stickiness of the cream and oiliness appear. As a solution to this, a method of adding dextrin or diglycerin and diglyceryl monooleate (JP-A-55-31038 and JP-A-55-31037).
Issue). However, its stability is not very high, and there is a problem in that it lacks stability due to changes in temperature, components, and the like. Also, a method of adding a mixture of oleic acid monoglyceride, sorbitol and water (Japanese Patent Publication No. 48-15798) or a method of adding a mixture of an aqueous solution of a glycerin fatty acid ester or the like which is liquid at room temperature and an amino acid or its salt (Japanese Patent Publication No. 2139
No. 3) has been proposed, but both methods require a two-step manufacturing process, and quality control is difficult in actual production.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide a W / O type emulsion composition which is excellent in temperature stability and is also excellent in skin protection, moisturizing and maintaining flexibility.

[0005]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventor has found that the W / O type emulsion composition is blended with a sulfated polysaccharide to provide a physicochemical stability. It has excellent properties, is excellent in skin protection, moisturizing and softness maintenance, etc., and it is possible to obtain a W / O type emulsion composition which can be produced in one step, thus completing the present invention.

That is, the present invention provides a water-in-oil emulsion composition containing a sulfated polysaccharide or a salt thereof.

Further, the present invention also provides a water-in-oil emulsion composition in which the sulfated polysaccharide is a polysulfate of mucopolysaccharide.

In the present invention, the sulfated polysaccharides are the main monosaccharides constituting D-glucosamine, D-galactosamine, D-glucuronic acid, L-iduronic acid, D-glucose, D-galactose, D-xylose. Which is obtained by sulfating a polymer having one or more of the monosaccharides as a repeating unit, and the sulfate group has an average of 0.55 to 5 molecules per monosaccharide molecule, preferably an average of 0. 6 to 2.9
The number of molecules is more preferably 0.7 to 2 molecules. When the above-mentioned sulfated polysaccharide is a mucopolysaccharide having a sulfate group, an average of 0.55 to 5 molecules per monosaccharide molecule, preferably an average of 0.6 to 2.9 molecules, more preferably an average of 0.7 to There are two molecules.

The average molecular weight of the sulfated polysaccharide or its salt is about 1000 to 10,000,000, preferably about 5,000 to 1,000,000, and more preferably 1.
It is about 0000 to 100,000.

Specific examples of the sulfated polysaccharide include heparin,
Examples include mucopolysaccharides such as chondroitin sulfate D and chondroitin sulfate E, which are called chondroitin polysulfate, and keratan polysulfate, and those obtained by sulfating chitin or hyaluronic acid. In addition, starch, cellulose, guar gum, gum arabic, konjac Examples thereof include sulfated polysaccharides such as mannan, agar agarose, and amylopectin, which may be used alone or in combination.

The sulfation reaction is carried out as follows. First,
10 to 30 ml of ice-cold solvent for 1 g of raw material polysaccharide
Prepare and add a sulphating agent to this for 2 to 6 g of raw material polysaccharide.
Add double. To this solution, add 1g of raw material polysaccharide,
Sulfation is carried out by reacting at -100 ° C for 1-10 hours. As the solvent to be used, pyridine, N, N-dimethylformamide, N, N-dialkylacrylamide, etc. can be used, and as the sulfating agent, chlorosulfonic acid, triethylamine-sulfatrioxide complex salt, etc. can be used.

As salts of sulfated polysaccharides, sodium salts,
Examples thereof include alkali metal salts such as potassium salts, alkaline earth metal salts such as calcium and magnesium, and a plurality of these salts are also included.

The concentration of the sulfated polysaccharide or its salt in the emulsified composition is about 0.05% by weight to 1.0% by weight, preferably about 0.1% by weight to 0.5% by weight. is there. The emulsion composition of the present invention usually contains a surfactant, an oil component and water in addition to the sulfated polysaccharide or its salt.

In the present invention, examples of the above-mentioned surfactant include a cationic surfactant, an anionic surfactant, an amphoteric surfactant and a nonionic surfactant, which are used alone. Alternatively, they may be used in combination.

Specific examples of the cationic surfactant include cetyltrimethylammonium chloride, lauryldimethylbenzylammonium chloride, tetrabutylammonium chloride, dioctadecyldimethylammonium chloride, and the like. Anionic surfactants Include sodium alkylbenzene sulfonate, sodium dodecyl sulfate, sodium coconut alcohol ethoxy sulfate, sodium α-olefin sulfonate, and the like, and nonionic surfactants include polyoxyethylene alkyl ether, polyoxyethylene alkylphenol ether, and sorbitan. Fatty acid ester, glycerin fatty acid ester, sucrose fatty acid ester and the like can be mentioned, and as the zwitterionic surfactant, N-alkyl-N, N-dimethy! Ammonium betaine, imidazoline type amphoteric surface active agents and the like.

The above-mentioned oil components are hydrocarbons, oils and fats, waxes, fatty acids, higher alcohols, ester oils and the like, which can be used without particular limitation, and may be blended in an appropriate combination according to the purpose of use. it can. Examples of hydrocarbons include liquid paraffin, squalane, synthetic squalane, white petrolatum, ceresin wax, solid paraffin, and microcrystalline wax.
Examples of the oils and fats include olive oil, soybean oil, and wax, examples of the waxes include beeswax, lanolin, etc., examples of the fatty acids include stearic acid, oleic acid, etc., and examples of the higher alcohols include cetanol, Octyldodecanol and the like can be mentioned, and as the esters,
Examples include cetyl lactate and isopropyl myristate.

The amount of the oil phase component is not particularly limited,
Considering the feeling surface, 10 to 90% by weight, especially 15 to 9%
It is 0% by weight, preferably 25 to 50% by weight.

The amount of water is not particularly limited, but is 10-9.
0% by weight, especially 15-85% by weight, preferably 40-7
It is 5% by weight.

If desired, oil-soluble and water-soluble substances may be added to the present emulsion composition. For example, the components normally used in cosmetics and pharmaceuticals such as moisturizers, thickeners, preservatives, sequestering agents, ultraviolet absorbers, drugs, dispersants, and pH adjusters are added in an amount of about 0.01 to 20% by weight. Can be blended.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples.

[0021]

【Example】

Example 1 (1) to (5) were weighed in as follows and heated to about 75 ° C. to obtain an oil phase. Next, weigh (6) and (7),
The aqueous phase, which was heated to about 75 ° C., was gradually added using a homomixer and emulsified. This was cooled to make an ointment.

The chondroitin polysulfate used in the examples is based on the Japanese Pharmacopoeia Standard (1993) heparin-like substance.

(1) Squalane 15% (2) Ceresin 3% (3) White petrolatum 3% (4) White beeswax 1% (5) Diglyceryl dioleate 4% (6) Chondroitin polysulfate 0.5% ( 7) Purified water (added so that the total amount is 100%) Comparative Example 1 Except that chondroitin polysulfate was removed from Example 1,
An ointment was prepared in the same manner as in Example 1.

Comparative Example 2 An ointment was prepared in the same manner as in Example 1 except that 10% of diglycerin was added instead of chondroitin polysulfate from Example 1.

Comparative Example 3 An ointment was prepared in the same manner as in Example 1 except that 10% of dextrin (average molecular weight 990) was added instead of chondroitin polysulfate.

Comparative Example 4 An ointment was prepared in the same manner as in Example 1 except that 10% of dextrin (average molecular weight 2300) was added in place of chondroitin polysulfate from Example 1.

Comparative Example 5 An ointment was prepared in the same manner as in Example 1 except that 10% of dextrin (average molecular weight 8500) was added instead of chondroitin polysulfate.

Table 1 shows the results of the stability tests of Example 1 and Comparative Examples 1-5. The stability test was conducted as follows.

About 5 g in a 10 ml spitz tube with a stopper
The ointment was filled in, and after centrifugation at 3000 rpm for 10 minutes, it was stored in a thermostat at -20 ° C and 60 ° C for 2 weeks. Then, these were centrifuged at 3000 rpm for 10 minutes, the amount of the separation layer (lower part: water separation) was measured, and the volume was shown as 5 g.

[0030]

[Table 1]

Example 2 (1) to (7) were weighed and heated to about 75 ° C. to obtain an oil phase. Next, (8) to (10) were weighed and heated to about 75 ° C. to obtain an aqueous phase, which was gradually added using a homomixer and emulsified. This was cooled to make an ointment.

(1) Squalane 5% (2) Ceresin 3% (3) White Vaseline 4% (4) White beeswax 0.5% (5) Octyldodecyl myristate 0.5% (6) Stearic acid 1% ( 7) Diglyceryl dioleate 6% (8) Chondroitin polysulfate 0.1% (9) Glycerin 10% (10) Purified water (added so that the total amount becomes 100%) Comparative Example 6 From Example 2 Except for removing chondroitin polysulfate,
An ointment was prepared in the same manner as in Example 2.

Examples 3 to 6 Ointments were produced in the same manner as in Example 2 except that the chondroitin polysulfate of Example 2 was added as shown in Table 2.

Table 2 shows the results of stability tests of Examples 2 to 6 and Comparative Example 6. The stability test was performed in the same manner as the test in Table 1. However, the storage period is -20 ℃ ・ 1 month, 60 ℃ ・
It went in two weeks.

[0035]

[Table 2]

Example 7 (1) to (5) were weighed and heated to about 75 ° C. to obtain an oil phase. Next, (6) to (8) were weighed and heated to about 75 ° C. to obtain an aqueous phase, which was gradually added using a homomixer and emulsified. This was cooled to make an ointment.

(1) Squalane 17% (2) Ceresin 4% (3) White petrolatum 4% (4) White beeswax 1% (5) Diglyceryl dioleate 4% (6) Chondroitin polysulfate 0.05% ( 7) Glycerin 10% (8) Purified water (added so that the total amount becomes 100%) Comparative Example 7 Except that chondroitin polysulfate was removed from Example 7,
An ointment was produced in the same manner as in Example 7.

Examples 8 to 11 Ointments were produced in the same manner as in Example 7 except that the chondroitin polysulfate of Example 7 was added as shown in Table 3.

Table 3 shows the results of the stability tests of Examples 7 to 11 and Comparative Example 7. The stability test was performed in the same manner as the test in Table 1. However, the storage period is -20 ℃, 1 month, 60 ℃
・ I went in 3 weeks.

[0040]

[Table 3]

FIG. 1 shows the results of measuring the water content of the skin using an impedance meter. The measurement was performed on the following three groups.

1) W / O type ointment administration group containing 0.3% sulfated polysaccharide 2) O / W type ointment administration group containing 0.3% sulfated polysaccharide 3) No treatment group As a result, 0.3% sulfuric acid The W / O type ointment administration group containing the modified polysaccharide showed a significantly higher skin water content than the O / W type ointment administration group containing the 0.3% sulfated polysaccharide and the untreated group. From this, it can be said that the present invention can provide an emulsified composition excellent in moisturizing the skin, which is a characteristic of the W / O type emulsified composition.

[0043]

INDUSTRIAL APPLICABILITY According to the present invention, a water-in-oil type emulsion composition is blended with a sulfated polysaccharide or a salt thereof so that the W / O type emulsion composition does not lose its characteristics such as moisturizing properties. It was possible to improve the temperature stability.

[0044]

[Brief description of drawings]

FIG. 1 shows the moisturizing effect on the skin of guinea pigs.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Office reference number FI technical display location C08B 37/00 H 7433-4C 37/10 7433-4C // A61K 7/00 N 7/48 ( 72) Inventor, Hiroshi Takei, 2700-8, Hinatsuma-cho, Hikone, Shiga Prefecture (72) Inventor, Koichi Hiraoka, 3-7-10, Akasakadai, Sakai-shi, Osaka

Claims (2)

[Claims] 1. A water-in-oil emulsion composition containing a sulfated polysaccharide or a salt thereof. 2. The water-in-oil emulsion composition according to claim 1, wherein the sulfated polysaccharide is a polysulfate of mucopolysaccharide.