JP2887681B2 - Manufacturing method of sheet cosmetics - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a method for producing a sheet-shaped cosmetic having good solubility in water.

(Prior art) Conventionally, as a so-called one-point cosmetic which is applied to the eyelids, outer corners of the eyes, forehead, mouth, neck and the like to impart appropriate moisture and “tension” to the skin, collagen hydrolyzate is formed into a film. A molded product or a nonwoven fabric impregnated with a collagen hydrolyzate and dried has been used.

Hyaluronic acid or its salt (hereinafter abbreviated as hyaluronic acid (salt)) has excellent properties as a moisturizer, so it activates skin cells, accelerates the turnover of aging skin, improves rough skin, and improves keratin. It is said to have a remarkable effect on the improvement effect, and to impart a moist feeling, a smooth feeling, a firmness and a luster to the skin, and to make the skin beautiful.

Magnesium phosphate, L-ascorbyl phosphate, has good stability to water and air, is absorbed percutaneously, and is easily hydrolyzed to L-ascorbic acid by enzymes such as phosphatase in the living body. It is said to have a whitening effect.

A mixture of hiluronic acid (salt) and magnesium-L-ascorbyl phosphate having such an effect is applied to small wrinkle-prone parts such as the eyelids, the outer corner of the eyes, the forehead, the mouth, the neck, and the like, so that the skin has a suitable amount of moisture and a "tension". It has been desired to use the composition as a one-point cosmetic having a whitening effect on the skin.

(Problems to be Solved by the Invention) However, the dried product of hyaluronic acid (salt) and magnesium L-ascorbyl phosphate is a powder, and a mixed aqueous solution of hyaluronic acid (salt) and magnesium L-ascorbyl phosphate is simply used as an aqueous solution. The sheet or film obtained by drying had very poor solubility in water or lotion, and could not be used as a one-point cosmetic.

The present invention provides hyaluronic acid (salt) having an excellent cosmetic effect as described above for use as a one-point cosmetic having a skin whitening effect while imparting moderate moisture and "tension" to the skin. An object of the present invention is to provide a method for producing a sheet-like or film-like cosmetic having good solubility in water or lotion, using magnesium phosphate-L-ascorbyl phosphate.

(Means for Solving the Problems) The present invention relates to hyaluronic acid or a salt thereof and phosphoric acid -L-
A method for producing a sheet-like cosmetic which is easily soluble in water, especially a lotion, comprising vacuum-drying an aqueous solution of ascorbyl magnesium and water in a thin layer.

The hyaluronic acid used in the present invention is present as a constituent component in connective tissues such as joints, vitreous body, umbilical cord, cartilage, skin, and bird crest, and is important for tissue flexibility, structure maintenance, cell metabolism regulation, and the like. Function. In addition, sodium hyaluronate is a high molecular substance, and its solution has strong viscoelasticity and water retention properties, so it can be widely used as a raw material for cosmetics, and it can be used as an ophthalmic treatment, eye drops, and arthrosis treatment. is there.

Hyaluronic acid (salt) is industrially produced by extracting from chicken crust, vitreous body of cow's eye, umbilical cord, or the like, or by culturing a microorganism capable of producing hyaluronic acid in a culture medium. A method (fermentation method) is being performed. The hyaluronic acid (salt) used in the present invention may be produced by an extraction method or a fermentation method.

At present, the molecular weight of hyaluronic acid (salt) industrially produced ranges from about 50,000 to about 3,000,000, but the molecular weight of hyaluronic acid (salt) used in the present invention is within this range. Any of them can be used.

L-Ascorbic acid (vitamin C) is widely distributed in the animal and plant kingdoms, and is particularly abundant in vegetables and fruits. L-ascorbic acid is known to have various physiological and pharmacological actions, and among them, its effect on dyschromatosis of the skin has long been known among cosmetics-related persons. The biggest factor that determines skin color is melamine pigment,
L-ascorbic acid is said to have the following two effects on melanin.

It reduces dopaquinone produced in the initial stage of melanin formation to dopa and suppresses melanin formation.

 Reduces melanin to a pale form.

However, L-ascorbic acid is relatively stable when dried, but has the drawback that it is easily oxidized by air and light in an aqueous solution. Therefore, L-ascorbic acid is water-soluble, has high stability, and is easily incorporated into cosmetics. As a result of various studies on acid derivatives, magnesium L-ascorbyl phosphate having the following structural formula was developed as a cosmetic whitening ingredient. In the present invention, this magnesium L-ascorbyl phosphate is used.

The method of vacuum freeze-drying an aqueous solution of hyaluronic acid (salt) and magnesium L-ascorbyl phosphate in water in the form of a thin layer according to the present invention is performed as follows. First, a 0.05 to 2.0% by weight aqueous solution of hyaluronic acid (salt) is prepared. Hyaluronic acid (salt) is hardly soluble in water, and easily becomes so-called mamako. Therefore, hyaluronic acid (salt) is gradually added to the water while stirring well to completely dissolve it. To the thus obtained aqueous solution of hyaluronic acid (salt) of 0.05 to 2.0% by weight, magnesium L-ascorbyl phosphate is added and thoroughly stirred to completely dissolve. Since the solubility of magnesium L-ascorbyl phosphate is 15 to 20%, the amount to be added is 0.05 to 0.05% as the amount of magnesium L-ascorbyl phosphate.
It is desirable to make it about 15.0% by weight. In this case, a concentrated aqueous solution of magnesium L-ascorbyl phosphate may be separately prepared and mixed with an aqueous solution of hyaluronic acid (salt). In the present invention, the ratio of hyaluronic acid (salt) to magnesium L-ascorbyl phosphate can be arbitrarily changed, but practically, 0.1 to 0.1 part by weight of hyaluronic acid (salt) is used in an amount of 0.1 to 10 parts by weight of hyaluronic acid (salt). 50 parts by weight is desirable.

The water used for the production of the aqueous solution is not particularly limited, but those usually used for the production of cosmetics, for example, ion-exchanged water and distilled water are used. In addition, lotion can be used as water used for producing the aqueous solution.

The mixed aqueous solution of hyaluronic acid (salt) and magnesium L-ascorbyl phosphate thus obtained is poured into a shallow container having a flat bottom. When the mixed aqueous solution of viscous hyaluronic acid (salt) and magnesium L-ascorbyl phosphate forms a horizontal surface, it is cooled and pre-frozen. The pre-freezing temperature is desirably −20 to −40 ° C. This is placed in a vacuum freeze dryer and freeze dried under high vacuum.
Freeze drying shelf temperature ranges from room temperature to -20 ° C, vacuum degree is 1
Desirably less than torr. It may be heated during freeze-drying. When the dried product is taken out of the container, a white sheet (thin layer) mixture of hyaluronic acid (salt) and magnesium L-ascorbyl phosphate is obtained. Pre-freezing can also be performed in a vacuum freeze dryer. In this case, the operation from pre-freezing to freeze-drying can be continuously performed in a vacuum freeze-dryer.

Recently, cosmetics have been working to minimize the number of germs in products due to safety concerns, but have produced a mixture of hyaluronic acid (salt) in sheet form and magnesium L-ascorbyl phosphate with a low number of germs. In this case, a mixed aqueous solution of hyaluronic acid (salt) and magnesium L-ascorbyl phosphate is sterilized and filtered using a filter of about 0.5 μm. By freeze-drying the filtrate after sterilization filtration in a clean vacuum freeze dryer, a mixture of sheet-shaped hyaluronic acid (salt) and magnesium L-ascorbyl phosphate having a small number of bacteria can be obtained.

A freeze-dried product prepared from an aqueous solution having a low concentration of a mixed aqueous solution of hyaluronic acid (salt) and magnesium phosphate-L-ascorbic acid has a very low bulk density and thus a very low physical strength. Therefore, in order to obtain a sheet having practical physical strength, it is desirable to freeze-dry a mixed aqueous solution of hyaluronic acid (salt) and magnesium L-ascorbyl phosphate of about 0.1% by weight or more.
When freeze-drying an aqueous solution having a high concentration of a mixture of hyaluronic acid (salt) and magnesium L-ascorbyl phosphate, it is preferable to perform pre-freezing at a temperature of about -40 ° C. Freezing is not a necessary operation.

Sheet hyaluronic acid (salt) obtained by the method of the present invention
By adjusting the depth of the liquid layer of the mixed aqueous solution, a mixture having a desired thickness can be manufactured. Practically, those having a thickness of about 0.5 to 3.0 mm are easy to use as cosmetics.

When pouring a mixed aqueous solution of hyaluronic acid (salt) and magnesium phosphate-L-ascorbic acid into a shallow container having a flat bottom, a release paper treated with a silicone resin is spread on the bottom of the container, and the mixture is dried into a sheet. The operation of taking out is smoothly performed.

 Lyophilization is performed under a high vacuum of about 0.05 torr.

Hyaluronic acid (salt) in sheet form of the present invention and phosphoric acid -L-
When making a mixture of ascorbyl magnesium, the mixed aqueous solution contains surfactants, extenders, pigments, dyes, chelating agents,
Antioxidants, ultraviolet absorbers, fragrances, etc. can be added.

The mixture of sheet-shaped hyaluronic acid (salt) and magnesium L-ascorbyl phosphate obtained by the method of the present invention has a feature that it is very soluble in water or lotion. In the area where the corners of the eyes are moistened with lotion in advance,
When the sheet-shaped cosmetic of the present invention cut into an appropriate shape and size such as a teardrop, a half-moon, an oval or the like is applied, the sheet is rapidly dissolved and the concentrated hyaluronic acid (salt) and phosphoric acid-L- It becomes a solution of a mixture of ascorbyl magnesium. If the sheet does not completely dissolve due to lack of water or lotion, add an appropriate amount of water or lotion from the top of the sheet and allow it to completely dissolve. Conversely, the sheet-shaped cosmetic composition of the present invention cut into teardrops may be attached to a portion such as the outer corner of the eye, and the surface thereof may be moistened with water or lotion. Dissolving is more complete when the sheet moistened with water or lotion is gently pressed with a fingertip. After a certain period of time, if you wash your face with water, it will be easily hyaluronic acid (salt)
And magnesium phosphate-L-ascorbyl phosphate are soluble in water and can be removed from the skin.

The sheet-shaped cosmetic obtained by the method of the present invention can be used for parts other than the outer corner of the eye, such as the eyelids, forehead, mouth, and neck, where small wrinkles are likely to appear. Of course, it can be used for other parts. The part used as cosmetics is hyaluronic acid (salt)
With the beauty effect of the present invention, appropriate "moisturizing" and "tension" are imparted to the skin, and the skin is whitened by the whitening effect of magnesium phosphate-L-ascorbyl.

(Effects of the Invention) According to the present invention, it is possible to produce a cosmetic comprising a mixture of hyaluronic acid (salt) and magnesium L-ascorbyl phosphate in a sheet form having excellent solubility in water or lotion. It can be used to improve skin roughness, keratin, turnover of stratum corneum quickly, and skin effect, etc., based on a mixture of hyaluronic acid (salt) and magnesium phosphate-L-ascorbyl. It is possible to produce a one-point cosmetic having an excellent anti-aging effect.

(Example) Example 1 0.50 g of hyaluronic acid (molecular weight: 1.2 million) was dissolved in 100 ml of pure water. To this solution, 1.0 g of magnesium L-ascorbyl phosphate was added and completely dissolved with good stirring. This mixed solution was filtered with a 0.45 μm filter. The filtrate was put into an aluminum vat so as to have a thickness of 2 mm, and preliminarily frozen by a freeze dryer (manufactured by Labconco, stopper ring tray dryer) cooled to -40 ° C. After pre-freezing, freeze-dried for 20 hours at a vacuum of 0.05 torr,
1.32 g of a mixture of sheet hyaluronic acid and magnesium L-ascorbyl phosphate was obtained. This was cut into a rectangle having a length of 3 cm and a width of 4 cm to obtain a sheet-shaped cosmetic having a side of 32 mg.

When this sheet-shaped cosmetic was put into a petri dish filled with water, it absorbed water and dissolved within a very short time.

Comparative Example 1 0.50 g of hyaluronic acid (molecular weight: 1.2 million) was dissolved in 100 ml of pure water. To this solution, 1.0 g of magnesium L-ascorbyl phosphate was added and completely dissolved with good stirring. This mixed solution was filtered with a 0.45 μm filter. The filtrate was put into an aluminum vat so as to have a thickness of 2 mm, and dried in a thermostatic dryer at a temperature of 60 ° C. for 16 hours. 1.40 g of a mixture of hyaluronic acid and magnesium L-ascorbyl phosphate in the form of a film was obtained. This was cut into a rectangle 3 cm long and 4 cm wide.

When this film was placed in a petri dish with water, it swelled but did not dissolve even after 10 minutes.

Example 2 Sodium hyaluronate produced by a fermentation method (molecular weight: 1
200,000) was dissolved in purified water 5. To this sodium hyaluronate solution was added 190 g of magnesium L-ascorbyl phosphate, and the mixture was stirred and completely dissolved. This mixed solution was filtered with a 0.45 μm filter. Pour the filtrate into an aluminum vat to a thickness of 2 mm, and
Freeze dryer (Kyowa Co., Ltd., vacuum freeze dryer RL)
-2412BS). After the preliminary freezing was completed, the mixture was freeze-dried for 2 days at a degree of vacuum of 0.05 torr to obtain 180 g of a sheet-like mixture of sodium hyaluronate and magnesium L-ascorbin phosphate. This was cut into a rectangle having a length of 3 cm and a width of 4 cm to obtain a sheet-shaped cosmetic.

When this sheet-like cosmetic was put in a petri dish filled with water, it absorbed water and dissolved within a very short time.

Comparative Example 2 A filtrate of a mixed solution of sodium hyaluronate and magnesium L-ascorbyl phosphate similar to that used in Example 2 was placed in an aluminum vat so as to have a thickness of 2 mm, and heated in a thermostatic drier. Dry at 60 ° C. for 8 hours. 5.4 kg of a film-like mixture of sodium hyaluronate and magnesium L-ascorbyl phosphate was obtained. This is 3cm long,
It was cut into rectangles 4 cm wide.

When this film was placed in a petri dish filled with water, it was not completely dissolved even after 10 minutes.

Example 3 Sheet-shaped sodium hyaluronate of the present invention and phosphoric acid-
The effect of the cosmetic comprising the mixture of L-ascorbyl magnesium was tested by a use test. The usage test was conducted with 10 black and white women as panelists.
The sheet-like cosmetic comprising the mixture of sodium hyaluronate and magnesium L-ascorbyl phosphate obtained under the conditions of Example 2 was molded into a mask shape by hollowing out the eyes, nose and mouth.

In the test, after washing the face every night, an appropriate amount of lotion having the composition shown in Table 1 was applied to the face, and the above-mentioned molded sheet-like cosmetic was stuck thereon. When the lotion was insufficient and the sheet could not be completely dissolved, an appropriate amount of lotion was soaked from above the sheet and pressed completely with a fingertip to completely dissolve. One night, it was kept in that state, and the next morning, the face was washed with water, and the cosmetics were washed off.

The test was conducted over two months, and the panelists themselves evaluated the effectiveness of the three items listed in Table 2 for their effectiveness. The results are as shown in Table 2.

Table 1 Composition of lotion (wt%) Ethanol 8.0% Propylene glycol 4.0% Glycerin 3.0% Polyoxyethylene oleyl alcohol ether 1.0% Sodium citrate 0.1% Methyl p-oxybenzoate 0.1% Ion-exchanged water As is clear from the results in Table 2, the sheet-like cosmetic comprising the mixture of sodium hyaluronate and magnesium phosphate-L-ascorbic acid of the present invention was found to have moisturizing, firming and whitening effects on the skin. .

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-58-216109 (JP, A) JP-A-61-37710 (JP, A) JP-A-60-116618 (JP, A) JP-A-62 129212 (JP, A) (58) Fields investigated (Int. Cl. ⁶ , DB name) A61K 7/00-7/50

Claims (3)

(57) [Claims] (1) hyaluronic acid or a salt thereof and phosphoric acid-L-
A method for producing a water-soluble sheet-like cosmetic, comprising vacuum-drying an aqueous solution comprising ascorbyl magnesium in a thin layer. 2. An amount of magnesium L-ascorbyl phosphate 0.1 to 50 parts by weight per 1 part by weight of hyaluronic acid or a salt thereof.
2. The method according to claim 1, wherein an aqueous solution in which both are dissolved in water at a ratio of parts by weight is freeze-dried in a thin layer. 3. The method according to claim 1, wherein the water is a lotion.