JP2546807B2 - Cosmetics - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial field of application) The present invention is to remove aging keratin and impart smoothness to the skin by enzymatic reaction by decomposing soil components and unnecessary waste products. However, the present invention relates to a novel cosmetic that imparts luster and a hair finishing effect to hair.

(Prior Art) Conventionally, various enzyme-containing cosmetics have been proposed that utilize the degrading action of skin stain components and aging keratin by hydrolases.

For example, in JP-A-58-77808 "Cream composition", a cosmetic in which a hydrolase is mixed with an emulsion has been proposed, but if the enzyme is mixed as it is with an emulsion containing water, the enzyme causes Therefore, the cosmetics are not preferable because they may cause discoloration or odor over time, or may cause skin irritation or allergies.

Further, in JP-A-63-130415, "Powder Cosmetics",
A powder cosmetic containing a hydrolase has been proposed, but it is not easy to use because it has to be mixed with water when used in order to express the enzyme activity, and the enzyme causes irritation and allergies to the skin. Is not preferable to give.

Further, in order to improve such drawbacks, the present inventors have
Japanese Patent Application No. 60-82022 “Emulsification type skin cosmetics” proposes an emulsification type cosmetic composition containing a powder of immobilized hydrolase. However, a cosmetic composition containing an immobilized enzyme varies depending on time. Even if the stability and skin irritation are improved, the immobilized enzyme does not dissolve in water, which gives a rough feeling during use and has a drawback that the feeling of use is unfavorable.

(Problems to be Solved by the Invention) The inventors of the present invention have conducted extensive studies as an improvement of the above-mentioned drawbacks of the prior art, and as a result, obtained by incorporating a modified hydrolase instead of a hydrolase or an immobilized hydrolase. The present invention has been completed by finding that the above-mentioned drawbacks can be solved by the cosmetics. That is, the object of the present invention is easy to use, highly safe so as not to cause irritation or allergy to the skin, does not cause a change in odor or discoloration with the passage of time, and aged against the skin. It is an object of the present invention to provide a cosmetic that removes calluses and imparts smoothness to hair, and imparts gloss and a finishing effect to hair.

(Means for Solving the Problems) The object of the present invention is achieved by a cosmetic comprising a water-soluble modified enzyme in which a hydrolase is modified with a water-soluble substance.

Examples of the hydrolase used in the present invention include, but are not limited to, protease, lipase, amylase, cellulase, muramidase and the like.
For example, pepsin, chymotrypsin, trypsin, rennin, buncreatin of animal origin, papain, promeline, ficin of plant origin, proteases produced by Aspergillus, Rhizopus, Bacillus of microbial origin and the like can be mentioned.

The lipase is not particularly limited, and examples thereof include pancreatic lipase, milk lipase, plant lipase, microbial lipase (filamentous fungal lipase, yeast lipase) and the like.

Amylase includes α-amylase, β-amylase, saccharified amylase and the like, and those extracted from pig pancreas, barley germ, sweet potato, barley, Bacillus spp, Aspergillus spp are commercially available, and they are commercially available. You can use it.

As the water-soluble substance used for modification, polyethylene glycol, ethylene glycol, propylene glycol,
Glycerin, polyhydric alcohols such as polyvinyl alcohol, sugars such as glucose, sucrose, fructose, alginic acid,
Examples include polysaccharides such as carboxymethyl cellulose, starch, and hydroxypropyl cellulose, but are not limited thereto.

The method for binding the enzyme and the water-soluble substance may be a method generally used as described below, and any method may be used as long as it does not significantly impair the activity of the enzyme. For example, a method of binding cyanuric chloride or glutaraldehyde to the hydroxyl group, amino group, etc. of a water-soluble substance, a method of introducing a reactive group using a carboxyl group as an active ester and binding with an enzyme, treating a polysaccharide with cyanogen bromide Then, a method of introducing an active group or forming an aldehyde group by periodate oxidation and then binding with an enzyme, and a method of using a condensing agent such as carbodiimides can be mentioned.

The ratio of the hydrolase and the water-soluble substance used for the modification is preferably 0.1 with respect to 1 part by weight of the hydrolase.
~ 50 parts by weight.

The modified hydrolase used in the present invention is water-soluble. The modified hydrolase which is insoluble in water is not preferable because it has a bad feel such as roughness when blended in cosmetics.

In the present invention, the amount of the modified hydrolase added is preferably 0.0001 to 5 parts by weight, based on 100 parts by weight of the total amount of the cosmetic. If the amount is less than 0.0001 part by weight, the function of the enzyme in cosmetics may not be sufficient. Further, even if it exceeds 5 parts by weight, the effect commensurate with the blending amount cannot be expected so much.

The cosmetics of the present invention include humectants, water-soluble polymers, surfactants, water, oils, waxes, fragrances, colorants, preservatives, antioxidants, bactericides, amino acids, vitamins, hormones, and ultraviolet absorbers. The components usually used in cosmetics can be appropriately blended.

(Effects of the Invention) The cosmetics of the present invention have been remedied by the drawbacks of the conventional cosmetics containing an enzyme or an immobilized enzyme, and are easy to use, and have excellent storage stability and skin stability, and can be applied to the skin. On the other hand, it is possible to remove aging keratin and impart smoothness to hair, and impart gloss and finishing effect to hair.

The cosmetics of the present invention include skin cream, skin milk,
Cleansing cream, cleansing milk, cold cream, cream soap, makeup base, skin lotion, milky lotion, pack, calamine lotion, T-zone essence, hand cream, essence powder, whitening powder, powder soap, solid soap, clear soap, Lip balm, lipstick,
Nutrition Essence, Creamy Foundation, Face Powder, Powder Eye Shadow, Powder Foundation, Nail Remover, Hair Tonic, Hair Liquid, Hair Cream, Hair Treatment, Scalp Treatment, Shampoo, Rinse, Hair Spray, Sun Oil, Sunscreen, Shaving Foam, Applied to shaving cream, baby oil, etc.

 Hereinafter, the present invention will be described specifically with reference to examples.

In addition, in the present invention, the practical test of the cosmetics and the stability over time were performed as follows.

(1) Practical test Twenty professional inspectors conducted a practical test once a day for three consecutive days and answered the questionnaire on the following test items.

Ease of use: The number of people who answered that it is easy to use.

Roughness during use: The number of people who reported feeling rough during use.

Irritation after use: The number of people who felt irritation on the skin (scalp) after use.

Smoothness after use: The number of people who responded that their skin (hair) became smooth after use.

Luster after use: The number of people who answered that the skin (hair) had gloss after use.

(2) Stability over time After sealing the sample and leaving it in a thermostatic chamber at 45 ° C for 3 months without light, the sample was observed for changes in color and odor.

[Example 1] 5.0 g of polyethylene glycol (average molecular weight 1900), P
After dissolving 0.6 g of -nitrophenyl chloroformate in 30 ml of acetonitrile, 0.3 g of triethylamine was added thereto. This solution was stirred at room temperature for 24 hours, 200 ml of diethyl ether was added, and the mixture was left at 4 ° C. for 24 hours to precipitate crystals. The crystals were separated by filtration to obtain 4.5 g of activated polyethylene glycol.

On the other hand, 50 mg of serine brotease (trade name: Esperase, Novo) produced by Bacillus was dissolved in 20 ml of 0.1M phosphate buffer (pH8.0), and 100 mg of the activated polyethylene glycol was further added to the solution at room temperature. It was stirred for 24 hours.
Glycine 0.5 g was added to the obtained reaction solution and after treatment of unreacted materials, the solution was purified by ultrafiltration and concentrated,
Lyophilized to obtain a water-soluble modified protease. This modified hydrolase was soluble in water.

Next, a skin cream was prepared from the raw materials having the blending amounts shown in Table 1. First, the oil phase component was uniformly heated and dissolved at 80 ° C., and the aqueous phase component that was also uniformly heated and dissolved at 80 ° C. was added thereto, cooled while stirring, and the above enzyme was added at 40 ° C.
It cooled to 0 degreeC and obtained the skin cream of this invention.

The properties of the obtained skin cream are shown in Table 3. Third
As is clear from the table, this skin cream was easy to use, had no irritation, and had an excellent effect of improving the skin properties after use, and the quality was stable even after storage over time.

Comparative Example 1 Instead of the modified hydrolase, 0.5 part by weight of Esperase and 1.0 part by weight of polyethylene glycol (average molecular weight 1900) were used. A skin cream was prepared in the same manner as in Example 1 except for the above. The properties of the obtained skin cream are shown in Table 3. As is clear from Table 3, the skin cream using an unmodified protease in place of the modified protease felt irritation after use and was inferior in stability over time.

Comparative Example 2 Instead of the modified hydrolase, a water-insoluble modified enzyme (immobilized enzyme) prepared as described below was used. A skin cream was obtained in the same manner as in Example 1 except for the above. The properties of the obtained skin cream are shown in Table 3. As is clear from Table 3, the skin cream containing a water-insoluble modification enzyme in place of the water-soluble modification enzyme was not preferable because it had a rough feeling during use and was inferior in smoothness after use. .

<Preparation method of water-insoluble modification enzyme> 20 parts by weight of calcium chloride is dissolved in 20 parts by weight of water, 80 parts by weight of methanol is mixed therein, and then 5 parts by weight of nylon powder (average particle size 6 to 10 μm) is added. Disperse, 50
Stirred at 30 ° C for 30 minutes. This is collected and washed with water, then 3.5M hydrochloric acid 10
It was immersed in 0 part by weight and stirred at 45 ° C. for 50 minutes. After washing with water, 10
It was immersed in 50 parts by weight of a 0.1 M sodium borate buffer solution (pH 8.5) containing 10% glutaraldehyde, and subsequently washed with the same buffer solution. This treated powder was added to 50 parts by weight of 0.05M sodium phosphate buffer (pH 7.5) containing 1 part by weight of Esperase, reacted at 10 ° C for 5 hours, and then washed with water to immobilize the carrier-bound type. A protease powder was obtained.

[Comparative Example 3] The blended raw materials as shown in Table 2 were enclosed in a polyethylene bag, and well mixed with stirring by hand until uniform, to obtain an essence powder.

2 g of the obtained essence powder was mixed with 20 g of water and applied to the face. The results are shown in Table 3. As is apparent from Table 3, powdery cosmetics containing a protease that is not modified by a water-soluble substance have improved stability over time, but mixing with water at the time of use causes the manifestation of activity. It is necessary in practice, not easy to use, and it causes skin irritation.

[Example 2] Instead of the modified hydrolase of Example 1, a modified hydrolase prepared by the following production method was used. A skin cream was obtained in the same manner as in Example 1 except for the above. The properties of the obtained skin cream are shown in Table 9. As shown in Table 9, various properties of this skin cream were excellent.

<Method for preparing modified hydrolase> Instead of polyethylene glycol (average molecular weight 1900), monomethoxy polyethylene glycol (average molecular weight 1900)
5000) was used. A water-soluble modified hydrolase was obtained in the same manner as in the preparation of the modified hydrolase of Example 1 except for the above.

Example 3 Monomethoxypolyethylene glycol (average molecular weight 50
00) 10 g and cyanuric chloride 1.1 g were dissolved in benzene 80 ml, and anhydrous sodium carbonate 2.0 g was added thereto. The solution was stirred at room temperature for 48 hours for reaction, the insoluble material was filtered off, and 100 ml of petroleum ether was gradually added dropwise to obtain a white precipitate. This precipitate was repeatedly reprecipitated with a benzene-petroleum ether system to give 2-0-polyethylene glycol-4,6-
Dichloro-S-triazine was obtained.

25 mg of lipase MY (manufactured by Meito Sangyo Co., Ltd.) was dissolved in 5 ml of 0.1 M borax aqueous solution (pH 9.5), and 400 mg of the above 2-0-polyethylene glycol-4,6-dichloro-S-triazine was added. This was stirred at room temperature for 1 hour, concentrated by ultrafiltration, and freeze-dried to obtain a water-soluble modified lipase. The modified hydrolase thus obtained was soluble in water.

Raw materials as shown in Table 4 were uniformly mixed to obtain a skin lotion. The characteristics are shown in Table 9. As shown in Table 9, the various properties of this skin lotion were excellent.

Example 4 Monomethoxyethylene glycol (average molecular weight 5000)
After dissolving 5.0 g in 50 ml anhydrous benzene, add 2.5 g anhydrous sodium carbonate and reflux for 30 minutes, then continue to use cyanuric chloride.
180 mg was added and the mixture was further refluxed for 24 hours. The insoluble material was filtered off, 100 ml of petroleum ether was gradually added, and the resulting precipitate was washed with petroleum ether several times to obtain 2,4-bis (0-methoxypolyethylene glycol) -6-chloro-S-triazine. It was

On the other hand, 25 mg of serine protease (Bioprase conc: Nagase Biochemical) produced from Bacillus was dissolved in 5 ml of 0.1 M borax aqueous solution (pH 9.5), and the above 2,4-bis (0
-Methoxypolyethylene glycol) -6-chloro-S
-Triazine (400 mg) was added, and the mixture was stirred at room temperature at 25 ° C for 1 hr, purified by ultrafiltration, concentrated, and lyophilized to give a water-soluble modified protease.

Then, a hair cream was prepared in the same manner as in Example 1 except that the raw materials were blended as shown in Table 5.

The properties of the obtained hair cream are shown in Table 9. Ninth
As is apparent from the table, the various properties of this hair cream were excellent.

[Example 5] 2 g of carboxymethyl cellulose was dissolved in 100 ml of water, and then 10% with 1N sodium hydroxide solution while keeping the pH at 10%.
5 ml of cyanogen bromide solution was added dropwise and reacted for 20 minutes. After the reaction, 4% sodium hydrogen carbonate solution was added to adjust the pH to 9. To this, 100 ml of 0.05M phosphate buffer (pH 8.5) containing 5% by weight of α-amylase (manufactured by Sigma) was added, reacted overnight, added with 500 mg of glycine, and allowed to stand for 2 hours.
It was concentrated by ultrafiltration and freeze-dried to obtain a water-soluble modified amylase.

Next, cleansing milk was prepared in the same manner as in Example 1 except that the raw materials were mixed in the amounts shown in Table 6.

The properties of the obtained cleansing milk are shown in Table 9.
As is clear from Table 9, various properties of this cleansing milk were excellent.

Example 6 Inulin 100 mg was added with 0.1 M sodium periodate solution 10 ml.
And was stirred at room temperature 25 ° C. for 16 hours. After purification and concentration by ultrafiltration, replace with phosphate buffer (pH 8) to make 10 ml. To this solution, 25 mg of lipase A "Amano" (manufactured by Amano Pharmaceutical Co., Ltd.) was added and reacted overnight at room temperature, then 0.5 mmol of sodium borohydride was added, stirred for 1 hour, concentrated by ultrafiltration, and lyophilized. Thus, a water-soluble modified lipase was obtained.

Next, the aqueous phase of the raw material as shown in Table 7 was uniformly heated and dissolved at 80 ° C for 1 hour, cooled with stirring, and the modified lipase was added at 40 ° C and cooled to 30 ° C to obtain cream soap. It was

The characteristics of the obtained cream soap are shown in Table 9. Ninth
As is apparent from the table, the various properties of this cream soap were excellent.

Example 7 200 mg of carboxymethyl cellulose was dissolved in 20 ml of water and adjusted to pH 4.7 with 1N hydrochloric acid, 1-ethyl-3- (dimethylaminopropyl) carbodiimide hydrochloride 380 mg and Esperase 20 mg were added, and the mixture was allowed to stand at room temperature for 2 hours. Stir for hours. After the reaction, 120 μ of acetic acid and 120 μ of monotetanolamine were added, stirred for 20 minutes, concentrated by ultrafiltration, and further lyophilized to obtain a water-soluble modified protease.

The raw materials as shown in Table 8 were uniformly mixed with stirring to obtain a powder foundation.

The characteristics of the obtained powder foundation are shown in Table 9. As is clear from Table 9, the various properties of this powder foundation were excellent.

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Claims (1)

(57) [Claims] 1. A cosmetic comprising a hydrolyzable enzyme modified with a water-soluble substance and a water-soluble modified enzyme incorporated therein.