JPH07316011A - Cosmetic - Google Patents

Abstract

PURPOSE:To produce a cosmetic having excellent moisture-retention, feeling to the skin and make-up durability by compounding flaky silk fibroin powder with a mucopolysaccharide to improve the moisture-retention of the silk fibroin powder and compounding the produced composite powder having excellent feeling to a cosmetic base. CONSTITUTION:This silk fibroin powder compounded with a mucopolysaccharide is produced by adding an aqueous solution of silk fibroin to an aqueous solution of a mucopolysaccharide or its salt, thoroughly mixing the mixture, freeze-drying the obtained dispersion, subjecting the resultant dried material (silk fibroin containing mucopolysaccharide uniformly dispersed and occluded in the silk fibroin) to wet-heat treatment with saturated steam of >=80 deg.C to effect the denaturation of the silk fibroin and obtain a partially crosslinked silk fibroin insoluble in hot water (beta-type structure) and crushing the denaturated product to a prescribed size by a crusher such as a hammer mill. A cosmetic is prepared by compounding the powder (preferably flaky powder). The amount of the mucopolysaccharide or its salt in the cosmetic is preferably 0.01-20 pts.wt. based on 100 pts.wt. of the silk fibroin powder compounded with the mucopolysaccharide.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a cosmetic composition containing mucopolysaccharide-composite silk fibroin powder. More specifically, after mixing and lyophilizing a mixed solution of an aqueous silk fibroin solution and an aqueous solution of mucopolysaccharide or a salt thereof, a mucopolysaccharide-combined silk fibroin powder obtained by wet heat treatment with saturated steam at 80 ° C. or higher is added. Related to cosmetics.

[0002]

2. Description of the Related Art Silk fibroin has hitherto been known for its excellent properties such as appropriate hygroscopicity and moisturizing property, excellent affinity for skin and hair, and protective action. It has been used as a cosmetic base.

Although silk fibroin has such excellent characteristics, the function of silk fibroin as a component of the silk fibroin has been required to be further improved as the cosmetics have become more sophisticated and highly functional in recent years. One method for improving the function of silk fibroin powder is to combine it with a highly functional component, and one of the most desired functions obtained by that is a high moisturizing function.

On the other hand, the mucopolysaccharide contains hyaluronic acid, dermatan sulfate, chondroitin sulfate, heparan sulfate, and the like, and various proposals have been made regarding cosmetics containing them (for example, JP-A-55-153711 and JP-A-55).
No. 160712, JP-A-57-183707, JP-A-57-185208), all of them have a high moisturizing effect, but give an uncomfortable feeling such as sticky feeling and tightness to the skin. Since mucopolysaccharides are hydrophilic, there is a problem that they run off with sweat when using cosmetics.
By combining mucopolysaccharide and silk fibroin powder, it is expected that the function of conventional silk fibroin powder will be improved. Japanese Unexamined Patent Publication No. 1-144469 discloses a long chain fourth
An example in which a silk fibroin powder and hyaluronic acid are complexed with a quaternary ammonium type cationic activator (such as stearyltrimethylammonium chloride) is shown.
There is a problem that these active agents are included in the display components because they may cause skin irritation in some people.

In view of the above points, the present inventors freeze-dried a mixed solution of an aqueous silk fibroin solution and an aqueous solution of mucopolysaccharide or a salt thereof, and then heat-damp it with saturated steam at 80 ° C. or more to obtain a long chain. We succeeded in making silk fibroin powder highly functional and making it into a plate form without using a display component such as a quaternary ammonium type cationic activator. Then, by blending it, we succeeded in obtaining a cosmetic having high moisturizing properties.

Further, it has been found that the mucopolysaccharide-combined silk fibroin powder of the present invention has a plate-like shape and has a different feel as compared with the conventional spherical or amorphous silk powder.

[0007] That is, an object of the present invention is to provide a cosmetic composition in which mucopolysaccharide composite plate-like silk fibroin powder having an improved moisturizing function of the conventional silk fibroin powder and having an excellent feeling is blended.

[0008]

In order to achieve the above object, the present invention has the following constitution. That is, according to claim 1 of the present invention, a mucopolysaccharide composite silk obtained by freeze-drying a mixed solution of an aqueous silk fibroin solution and an aqueous solution of mucopolysaccharide or a salt thereof, and then subjecting it to wet heat treatment with saturated steam at 80 ° C or higher. It is a cosmetic product containing fibroin powder.

According to a second aspect of the present invention, the ratio of the mucopolysaccharide or its salt is 0.01 to 20 parts by weight with respect to 100 parts by weight of the mucopolysaccharide-combined silk fibroin powder. The cosmetics described in.

A third aspect of the present invention is the cosmetic composition according to the first aspect, characterized in that the mucopolysaccharide-combined silk fibroin powder has a plate shape.

The structure of the present invention will be described in detail below.

The mucopolysaccharides used in the present invention are hyaluronic acid, dermatan sulfate, chondroitin sulfate or heparan sulfate and salts thereof, which are alkali metal salts, alkaline earth metal salts, ammonium salts, alkanolamine salts or basic salts. Amino acid salts and the like can be mentioned. These mucopolysaccharides can be used from high molecular weight (500 to 2,000,000) to low molecular weight (1,000 to 10,000). Of these, hyaluronic acid is particularly preferable.

The amount of the mucopolysaccharide or salt thereof used in the present invention is preferably 0.01 to 20 parts by weight based on 100 parts by weight of silk fibroin powder. Within this range,
The moisturizing function of mucopolysaccharides is clearly recognized, while the silk fibroin powder has excellent properties such as the powder does not easily agglomerate.

The silk fibroin raw material used in the present invention includes eyebrows, raw silk, eyebrows waste, raw silk waste, screws, fried cotton,
According to a conventional method, silk cloth scraps, burettes and the like can be used by removing sericin in warm water or warm water containing an enzyme, if necessary, in the presence of an activator, and then drying.

The silk fibroin aqueous solution used in the present invention can be obtained according to the method disclosed in JP-A-1-144469. That is, it can be obtained by dissolving a raw material of silk fibroin in an aqueous solution of calcium, magnesium or zinc hydrochloride or nitrate and subjecting this to dialysis desalting.

Hereinafter, an example of a method for complexing silk fibroin powder will be described in detail. Add silk fibroin aqueous solution to the aqueous solution of mucopolysaccharide or its salt, mix well and disperse,
Then freeze-dry. Examples of the mixing method include a method of uniformly mixing using a mixing device such as a mixer.
In the freeze-drying treatment, for example, the aqueous solution is poured into a shallow vat-shaped container to a depth of 5 to 10 mm, and the whole is once rapidly cooled to −20 to −40 ° C. and frozen. Insert this into multiple stages in the shelf of the freeze dryer chamber, 0.5
Drying is performed under a reduced pressure of about torr, and at the end of about 0.05 torr. During vacuum drying, the heat of vaporization is replenished by the heater embedded in the shelf, and the temperature of the frozen product is within an appropriate range (eutectic point).
Adjust to.

The dried product thus obtained is one in which mucopolysaccharides are uniformly dispersed and occluded in silk fibroin, which is heat-treated by moistening and partially cross-linked hot water-insoluble silk fibroin (β type). Structure). Wet heat treatment is 8
It is carried out by a method of heat treatment with saturated steam of 0 to 120 ° C. Then, a mucopolysaccharide-combined silk fibroin powder is obtained by crushing to a desired size with a crusher such as a hammer mill or a jet mill.

The particles of the mucopolysaccharide-combined silk fibroin powder have a plate-like shape, and the particle diameter (average particle diameter) thereof is such that the major axis is usually 0.5 to 100 µ, preferably 1 to 60 µ, and particularly preferably 3 to. Adjusted to 30μ. Within this range, adhesion to skin, affinity, and extensibility are improved.

Examples of the cosmetics of the present invention include foundations, powders, face powders, eye shadows, lipsticks, nail colors, creams, hand creams, emulsions, lotions, preshave lotions, aftershave lotions, bath salts, soaps and bodies. Examples include soap, face wash, cleansing agent, deodorant agent and the like.

The ratio of the mucopolysaccharide-combined silk fibroin powder blended in the cosmetic of the present invention varies depending on the characteristics of the product, but it has a high moisturizing property, gives a smooth and refreshing good feel, and has a makeup lasting effect. In order to obtain a good cosmetic, it is preferable to add 0.1 to 99.5 parts by weight, more preferably 0.5 to 10 parts by weight to 100 parts by weight of the cosmetic.

The cosmetics of the present invention include, in addition to the mucopolysaccharide-combined silk fibroin powder, powders conventionally used in cosmetics,
A colorant, an oil agent, a moisturizing agent, a surfactant, an ultraviolet absorber, a bactericide, a fragrance, a solvent, an antiseptic and the like can be simultaneously mixed. In particular, regarding the powders, conventionally known inorganic powders, organic powders, pigments, and composite powders thereof, powders subjected to surface treatment such as silicone treatment, fluorine compound treatment, metal soap treatment, and oil treatment. Is mentioned. In some cases, the mucopolysaccharide-combined silk fibroin powder of the present invention can be further surface-treated by the conventionally known surface treatment method described above.

[0022]

The present invention will be described in detail below with reference to Examples and Comparative Examples.

Evaluation of Moisture Absorption Performance A powder which has been sufficiently dried in advance is dried at 23 ° C. and 70% R.A.
H. The sample was allowed to stand under the temperature and humidity conditions of 1 above, and the moisture absorption amount of powder (ratio to the weight of powder) was measured with respect to time.

Evaluation of Moisture Retaining Performance A powder which has been sufficiently moisture-absorbed in advance is dried at 23 ° C. and 28% R.V.
H. The sample was allowed to stand under the temperature and humidity conditions of No. 1, and the amount of water released from the powder (the ratio to the amount of water initially absorbed) was measured.

Evaluation of Sensory Properties Regarding the cosmetics of Examples and Comparative Examples, they were dried in Kanagawa Prefecture in February 1994 under outdoor conditions (10 ° C., 32%) under daytime conditions.
R. H. ) A sensory test was conducted by a total of 10 women aged 25 to 55 years, and the moistness, dryness, dryness and makeup lasting of the cosmetics were evaluated. The evaluation method was to apply the cosmetics of Examples and Comparative Examples to the left and right faces,
We obtained answers in a questionnaire format as to which was better for each evaluation item. The number of people who answered that the example was excellent was taken as the evaluation result of the sensory characteristics. In addition,
Regarding the dry feeling, the number of people who answered that the Example did not have a dry feeling was taken as the evaluation result.

Production Example 1 Raw silk waste was used as a raw material for silk fibroin.
0 parts by weight of a solution of 30 parts by weight of Marcel soap and 3000 parts by weight of purified water was stirred and scoured at 95 to 98 ° C. for 3 hours,
Residual glue is reduced to less than 0.1% by weight, and after washing with water 80 ° C
It was blown dry. On the other hand, calcium chloride (CaCl ₂ ·
100 parts by weight of 2H ₂ O) was mixed with 100 parts by weight of purified water to prepare 200 parts by weight of 38% by weight calcium chloride aqueous solution, and the mixture was heated to 110 ° C. 40 parts by weight of scoured raw silk waste was added to this with stirring with a kneader for 5 minutes, and further stirred for 30 minutes to completely dissolve it.

Then, 2000 pieces of regenerated cellulose-based hollow fibers having an inner diameter of 200 μ, a membrane pressure of 20 μ and a length of 500 mm are bundled,
Using a hollow fiber type dialysis device in which both ends of the solution are focused and fixed (sealed) without closing the hollow hole, the solution is introduced at a rate of 0.31 hour and dialyzed with deionized water. A high-purity silk fibroin aqueous solution was obtained.
The silk fibroin aqueous solution had a fibroin concentration of 5.75.
% By weight, the residual calcium chloride was 0.001% by weight.

Subsequently, while 300 parts by weight of a 38% by weight hyaluronic acid aqueous solution was being heated, 2000 parts by weight of the silk fibroin aqueous solution was added and mixed by stirring. Then, the aqueous solution was rapidly cooled to −40 ° C., and initially 0.5 torr
At the end, it was dried under a reduced pressure of 0.05 torr.

The dried product thus obtained was subjected to heat denaturation treatment with saturated steam at 110 ° C. for 15 minutes to modify it into a hot water-insoluble β-type structure. This was pulverized with an atomizer to obtain hyaluronic acid-composite silk fibroin powder (hyaluronic acid content 1% by weight). Figure 1 shows a photograph taken with a scanning electron microscope.
Shown in. It can be seen from FIG. 1 that the particle shape of the powder is plate-like.

With respect to the hyaluronic acid composite silk fibroin powder obtained in Production Example 1, the moisture absorption performance was evaluated.
The result is shown in FIG.

From the results shown in FIG. 2, it can be seen that the hyaluronic acid-composite silk fibroin powder used in the present invention has higher hygroscopicity than the conventional silk powder.

With respect to the hyaluronic acid composite silk fibroin powder obtained in Production Example 1, the moisturizing performance was evaluated.
The result is shown in FIG.

From the results shown in FIG. 3, it can be seen that the hyaluronic acid-composite silk fibroin powder used in the present invention is excellent in moisture retention.

Example 1. Foundation A composition of Table 1 was used to prepare a foundation. The hyaluronic acid composite silk fibroin powder used was that produced in Production Example 1.

[0035]

[Table 1]

(Production Method) After the powders were mixed by using a mixer, an oil agent component was added and further mixed. After passing the obtained mixed powder through 60 mesh, it was stamped on a metal plate using a metal mold to obtain a product.

Comparative Example 1 A trial production of a foundation was carried out in the same manner except that 3% zinc myristate-treated talc was used in place of the hyaluronic acid composite silk fibroin powder of Example 1.

Comparative Example 2 A trial production of a foundation was carried out in the same manner except that spherical silk powder was used instead of the hyaluronic acid-composite silk fibroin powder of Example 1.

The sensory characteristics of the examples and comparative examples were evaluated. The results are shown in Table 2.

[0040]

[Table 2]

From the results shown in Table 2, the examples in which the hyaluronic acid-combined silk fibroin powder of the present invention was blended were richer in moistness and less in dryness than Comparative Example 1 in which zinc myristate-treated talc was blended. I also found that it was excellent in holding makeup. It was also found that it had a smoother feeling than Comparative Example 2 in which the conventional spherical silk powder was blended.

[0042]

INDUSTRIAL APPLICABILITY As described above, the present invention provides a mucopolysaccharide obtained by freeze-drying a mixture of an aqueous silk fibroin solution and an aqueous solution of mucopolysaccharide or a salt thereof and subjecting it to wet heat treatment with saturated steam at 80 ° C. or higher. It is a cosmetic product containing a composite plate-like silk fibroin powder, and has excellent moisturizing function, touch and makeup retention.

[Brief description of drawings]

FIG. 1 is a scanning electron micrograph showing the particle structure of hyaluronic acid-combined silk fibroin powder obtained in the present invention.

FIG. 2 shows the hygroscopic performance of the hyaluronic acid-combined silk fibroin powder obtained in the present invention.

FIG. 3 shows the moisturizing performance of the hyaluronic acid composite silk fibroin powder obtained in the present invention.

[Explanation of symbols]

 ● Hyaluronic acid composite silk fibroin powder △ Silk powder

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Kiyoshi Otoi 1623 Nakamaruko Nakamaruko, Gunma-cho, Nagano Prefecture Kanebo Silk Elegance Co., Ltd. Silk Research Center

Claims (3)

[Claims] 1. After freeze-drying a mixed solution of an aqueous silk fibroin solution and an aqueous solution of mucopolysaccharide or a salt thereof, 8
A cosmetic comprising a mucopolysaccharide-combined silk fibroin powder obtained by wet heat treatment with saturated steam at 0 ° C or higher. 2. A mucopolysaccharide complex silk fibroin powder 10
The ratio of the mucopolysaccharide or a salt thereof is 0.01 to 20 parts by weight with respect to 0 parts by weight.
Cosmetics described in. 3. The cosmetic according to claim 1, wherein the mucopolysaccharide-combined silk fibroin powder has a plate shape.