JPH0395109A - Cosmetic for hair - Google Patents

Abstract

PURPOSE:To obtain a cosmetic for hair having high safety and stability and giving excellent smoothing effect, luster improving effect and wet effect, etc., to hair containing a modified transglutaminase(TGase) modified with a water-soluble substance. CONSTITUTION:Modified TGase modified with a water-soluble substance such as polyhydric alcohol, e.g. polyethylene glycol or glycerin, saccharides such as glucose, sucrose or polysaccharides e.g. alginic acid or CMC is contained in the objective cosmetic in an amount of 0.00001-1.0wt.% based on total weight of the cosmetic. Preferably 0.2-50 pts.wt. water-soluble substance is used to 1 pts. wt. TGase. The TGase densifies surface structure of the hair and water- retention activity of the hair is enhanced, then a flexibility and elasticity are imparted.

Description

[Detailed Description of the Invention] [Field of Industrial Application] The present invention is a novel method in which transglutaminase densifies the surface structure of the hair, thereby enhancing the moisture retention function of the hair and imparting flexibility and elasticity. Regarding hair cosmetics. [Prior Art] As interest in hair has increased, the frequency of use of hair dryers has increased, and the chances of damage to the hair surface due to repeated treatments such as cold perms from a young age have increased. Furthermore, due to the growing preference for cleanliness among young people, the number of times they wash their hair has increased in recent years, and the act of washing hair has become more susceptible to damage. Specifically, this kind of hair has peeling of the hair epidermis. A shedding phenomenon is observed, and furthermore, the precepts of the hair medulla inside the hair are exposed and eluted. In addition, the water content on and inside the hair decreases, and the smoothness of the surface is lost, which increases the dryness of the hair, worsens the texture, and increases the number of split ends.

Furthermore, the appearance loses its luster, causing a loss of beauty.

As a way to solve these hair problems, many attempts have been made to modify the surface of the hair and increase the internal moisture content by adding cationic surfactants or protein hydrolyzed peptides to rinses. However, none of these methods is effective in fundamentally improving damaged hair, and it is currently difficult to obtain beautiful, smooth hair.

[Problem to be solved by the invention]

As a result of intensive research aimed at solving the above-mentioned problems, the present inventors found that the above-mentioned drawbacks could be solved by a hair cosmetic obtained by blending modified transglutaminase modified with a water-soluble substance, and the present invention. was completed.

In other words, the purpose of the present invention is to provide excellent smoothness to the hair when used, without irritating the scalp (high safety), without changing odor or discoloration even when administered orally (good stability). The object of the present invention is to provide a hair cosmetic that exhibits a softening effect, a luster-improving effect, a moisturizing effect, and an elasticity-improving effect. (Means for solving ill!l) The present invention is a hair cosmetic characterized by containing modified transglutaminase modified with a water-soluble substance. Transglutaminase used in the present invention (EC2.3 ．．
2.13. TGa se (hereinafter abbreviated as TGa se) is one of the protein modification enzymes, and is a protein-modifying enzyme that binds between the T-carboxylamide group of the gluta ξ residue and the ε-aξ group of the lysine residue in protein 5 peptide. catalyzes a reaction, catalyzes a cross-linked reaction via an ε-(T-glutamyl)lysine bond,
TGase exists in various animal tissues and blood cells,
It is particularly involved in the coagulation reaction of blood-derived fibrin proteins and the keratinization reaction of epidermal cells and hair.

TGase used in the present invention is Mormont. Rat. pig. cow. It can be extracted and purified by known methods from liver serum, platelets, hair follicles, epidermis, etc. of mammalian animals such as sheep. 9 Also, those derived from microorganisms can also be used. Water-soluble substances used for modification include polyethylene glycol. Ethylene glycol Propylene glycol. glycerin. Polyhydric alcohols such as polyvinyl alcohol, sugars such as glucose, sugar, and fructose, and alginic acid. Carboxymethyl cellulose, starch. Examples include, but are not limited to, polyesters such as hydroxypropylcellulose. TGa s e and water-soluble ' used for modification! # The ratio of water-soluble substances to 1 part by weight of TGa is preferably 0. The amount is 2 to 50 parts by weight.

The method of binding TGase and a water-soluble substance may be any commonly used method as described below, as long as it does not significantly impair the activity of TGase. For example, a method of bonding cyanuric chloride or glutaraldehyde to a hydroxyl group, amino group, etc. of a water-soluble substance. A method of introducing a reactive group into a male carboxyl group as an active ester and binding it to an enzyme, multi-v
A method in which M class is treated with cyanogen bromide to introduce an active group, or oxidized with periodine to form an aldehyde group, and then bonded with an enzyme. Further examples include methods using condensing agents such as carbodiimites. Some of the modified TGases obtained in this way are water-insoluble and some are water-soluble, but water-soluble ones are more preferable when incorporating them into hair cosmetics, considering the texture (roughness, etc.). .

In the present invention, the blending amount of modified TGase is 0.0% by weight based on the total amount of hair cosmetics. 0 0 0 0 1% by weight (hereinafter abbreviated as wt%)
Gara, 1. It is preferable to set it to O w t%. That is, 0. 0 0 0 0 1 w t
If it is less than %, the enzyme will not function sufficiently, and 1. 0wt
%, there is no improvement in effectiveness commensurate with the increase. The hair cosmetic of the present invention contains a moisturizing agent. Water-soluble polymer. Surfactant, water, 5 oils, wax, 1 fragrance. Colorants, preservatives. Antioxidants, bactericides, amino acids. Vitamins, hormones, ultraviolet absorbers, and other ingredients commonly used in cosmetics can be added as appropriate.

The hair cosmetics of the present invention include hair toninx and hair liquid. Hair cream, hair treatment. shampoo rinse. It is applied to hair spray, etc., but is not necessarily limited to this. [Examples and Comparative Examples] The present invention will be specifically described below with reference to Examples.

In addition, in the present invention, hair cosmetic smoothing effect test, gloss improvement effect test. Practical test. The oral stability test was conducted as follows.

(1) Smoothing effect test A commercially available hair bundle (2 g) was washed with shampoo and then degreased by reflux extraction with acetone for 2 hours using a Soxhlet extractor. Each hair bundle was immersed in 200 mffi of a 5% solution of Kumikaimono of Example 1 Comparative Example at room temperature for 1 hour, rinsed with tap water, and then air-dried indoors. Twenty hairs were randomly selected from this hair bundle, and their surface morphology was observed using a scanning electron microscope. The peeling state of the hair epidermis was judged according to the following criteria, and the smoothing effect was evaluated from the average value of 20 hairs.
Smoothing effect judgment criteria Evaluation score 5: No peeling 4: Slight peeling 3: Slight peeling 2: Moderate peeling 1: Significant drying (2) Gloss improvement effect Regarding the Moto IO book obtained by the same method as the above test, Using a spectrophotometer (manufactured by Murakami Color Research Institute), the incident angle was set at 60°, and the maximum reflection amount (mV) was measured as the acceptance angle was varied. The relative value (%) of the maximum reflection amount of the hair bundle treated with the sample to the maximum reflection amount of the untreated hair bundle is determined for 10 hair bundles,
The gloss effect was investigated from the average value. (3) A panel of 20 women specializing in practical tests used the samples once a day (in the evening) for a continuous month, and then evaluated the following items. Evaluation ItemsSmoothness2Number of people who said their hair became smoothWettability:Number of people who said their hair felt moisturizedElasticity:Number of people who felt their hair became tautFlexibility:Number of people who felt their hair became softStimulus Gender: Number of people who said they felt irritation on their scalp (4)
Seal the oral stability test sample. After being left in a constant temperature bath at 45°C for 3 months under light-shielded conditions, the presence or absence of changes in color and odor was observed. Example 1 Polyethylene glycol (average molecule ftl900)
5.0g, P-1 ditrophenyl oral formate 0.6
g was dissolved in 30rr+/2 acetonitrile, and then 0.3 g of triethynoleamine was added thereto. The second solution was stirred at room temperature for 24 hours, and then diluted with diethyl ether 20
0 mA was added and the mixture was left at 4°C for 24 hours to precipitate crystals. The crystals were filtered to obtain 4.5 g of activated polyethylene glycol.

On the other hand, J. The method of Connellan et al.
Of Biological History, Volume 246, 109
3, 1971) and Japanese Patent Application Laid-Open No. 175884/1984, TGase was obtained from the liver of Mormons.
was prepared. 0.0 for 500g of fresh guinea pig liver.
A homogenate was prepared using a polytron (manufactured by Kinematica) by adding 1.5 i of a 25 M sucrose solution,
A crude fraction of TGase was obtained from the supernatant by centrifugation.

This fraction was subjected to DEAE cellulose column chromatography-(2mM-.EDTA, 5mM
M} Squirrel Hydrochloric acid mild Ihl P H 7. 5)
and lO% agar a-sgel columnk 0'? Togura 74-
(Biogel, 0.5 M). Finally, TGa S e was obtained by ultrafiltration and freeze-drying.
I got it.

Purified transglutaminase 5 obtained in this way
Qmg to 0. 1 M phosphate buffer i (PH8.0)2
0 ml, and 100 mg of the above activated polyethylene glycol was added thereto, followed by stirring at room temperature for 24 hours. After adding 0.5 g of glycine to the obtained reaction solution and treating unreacted substances, the solution was purified by ultrafiltration, subjected to i4 condensation, and freeze-dried to obtain water-soluble modified TGase.

Next, a hair tonic was manufactured using the raw materials in the amounts shown in Table 1. First, the alcohol phase ingredients are uniformly dissolved, the water phase ingredients are added thereto, and the whole is stirred until the mixture becomes uniform. It is shown in Table 7. As is clear from Table 7, the hair toner of the present invention had excellent smoothing effect, gloss improvement effect, and practical properties, and its quality was stable even when stored orally. Comparative Example 1 1.0% by weight of TGase was used instead of modified TGase. Other than that, hair tonisoku was prepared in the same manner as in Example 1 (Comparative Example 1). The properties of the obtained hair tonic are shown in Table 7. As is clear from Table 7, hair tonisoku containing unmodified "l'Qase" (
Compared to comparative example l), Osamu! The hair tonic containing ITGase (Example 1) was less irritating to the skin and had better stability over time. Comparative Example 2 In Comparative Example 2, a hair tonic was prepared in the same manner as in Example 1, except that 1.0% by weight of polyethylene glycol (average molecular weight 1900) was used in place of modified TGase. The properties of the hair tonic obtained are shown in Table 7. As is clear from Table 7, hair tonic containing modified TGase (Example 2) has better smoothness and gloss than hair tonic containing no TGase (Comparative Example 2). Warm property, elasticity. It showed a significant effect on flexibility.

Example 2 Polyethylene glycol (average molecule 11900)
Instead, monomethoxypolyethylene glycol (average molecular weight [150000]) was used. Other than that, water-soluble modified TGase was obtained in the same manner as in the preparation of modified TGase in Example 1. Modified TGa of Example 1
Modified TGase prepared by the above method was used instead of se. Other than that, Hair Tonisoku was obtained in the same manner as in Example 1. Table 7 shows the properties of the obtained hair tony fuku.

As is clear from Table 7, the various properties of hair art Nisoku of the present invention were excellent.

Example 3 Monomethoxypolyethylene glycol (average molecule!5
0 0 0) 10 g”-Cyanuric chloride 1.1
g was dissolved in 80 ml of benzene, and 2.0 g of anhydrous sodium carbonate was added thereto. This solution was stirred at room temperature for 48 hours to react, and after filtering out insoluble materials, 100 m6 of petroleum ether was gradually added dropwise to obtain a white precipitate. This precipitate was repeatedly reprecipitated in a benzene-petroleum ether system to obtain 2-0-polyethylene glycol-4,6-dichloro-S-triazine.

5 mg of purified TGa se 2 obtained in Example 1
0. 1 M borax aqueous solution (pH 9.5) 5rnj! The above 2-0-polyethylene glycol-4.
400 mg of 6=dichloro-S-triazine was added.

This was stirred at room temperature for 1 hour, concentrated by ultrafiltration, and lyophilized to obtain water-soluble modified TGase. Next, a hair liquid was prepared in the same manner as in Example 1 using Raw Negative 4 in the amounts shown in Table 2.

Table 7 shows the properties of the obtained He7-liquid. As is clear from Table 7, the various properties of the hair liqueur of the present invention were excellent.

Example 4 Monomethoxypolyethylene glycol (average molecular weight 50
After dissolving 5.0 g of anhydrous benzene in 50 mj2 of anhydrous benzene, 2.5 g of anhydrous sodium carbonate was added and the mixture was refluxed for 30 minutes.
It was refluxed for 4 hours. After filtering the insoluble matter, petroleum ether 1
00 ml was gradually added and the resulting precipitate was washed several times with petroleum ether to obtain 2,4-bis(0-methoxypolyethylene glycol)-6-chloro-S-+-riazine.

On the other hand, 25 mg of Akin TQase obtained in Example 1 was added to 0
．． Dissolved in 5 ml of 1M borax aqueous solution (pH 9.5), further added 400 mg of the above 2.4-bis(0-methoxypolyethylene glycol)-6-chloro-S-triazine, and stirred at room temperature 25°C for 1 hour at RT. , purified by ultrafiltration. Concentrate and lyophilize to make water-soluble modified TGa
I got s e.

Next, a hair treatment cream was manufactured using the ingredients in the amounts shown in Table 3. First, the oil phase was uniformly heated and dissolved at 80°C, and a certain amount of the aqueous phase, which had also been uniformly heated and dissolved at 80°C, was added, cooled while stirring, and the above enzyme was added at 40°C. The hair treatment cream of the present invention was obtained by cooling to ℃.

Table 7 shows the properties of the hair treatment cream obtained. As is clear from Table 7, the various properties of this hair treatment cream were excellent. Example 5 After dissolving 2 g of carboxymethyl cellulose in 100 ml of water, 5 ml of a 10% cyanogen bromide solution was added dropwise while maintaining the pH at 10 with IN sodium hydroxide solution, and the mixture was reacted for 20 minutes. After the reaction, 4% sodium hydrogen carbonate solution was added to adjust the pH to 9. This contains 5% by weight of the purified Tease obtained in Example 1. 0 5 M
Add 100 ml of phosphorus l'l2 buffer (pH 8.5), react overnight, add 50 Qmg of glycine, leave for 2 hours, concentrate by ultrafiltration, and lyophilize to obtain water-soluble modified TGase. Obtained.

Next, Table 7 shows the properties of Hair 4 Lux obtained using the ingredients in the amounts shown in Table 4.

As is clear from Table 7, various properties of this hair milk were excellent. Example 6 100 mg of inulin was added to 0. It was dissolved in Qml of 1M sodium periodate solution I and stirred at room temperature 25°C for 16 hours. After purifying and concentrating by III extrafiltration, the solution was replaced with phosphate buffer (pH 8) to obtain l'Q m 1. Into the solution, 25 mg of TGase obtained in Example 1 was added.
was added, and after reacting overnight at room temperature, 0.0% of sodium borohydride was added. 5 mM was added, stirred for 1 hour, concentrated by ultrafiltration, and lyophilized to obtain water-soluble modified TGase.

Next, the raw materials shown in Table 5 were uniformly mixed and stirred to obtain the hair shampoo of the present invention. Dissolve in 20 ml and bring to pH 4 with IN hydrochloric acid. 7, 380 mg of 1-ethyl-3-(dimethylaminopropyl)carbodiimide hydrochloride and 20 mg of purified TGa se obtained in Example 1 were added, and the mixture was stirred at room temperature for 2 hours. After the reaction, 120 μl of acetic acid and 120 μl of monoethanolamine were added, stirred for 20 minutes, concentrated by ultrafiltration, and further freeze-dried to obtain water-soluble modified TGase.

Next, a hair rinse of the present invention was prepared in the same manner as in Example 4 using the raw materials shown in Table 6. The properties of the obtained He7-shampoo are shown in Table 7. As is clear from Table 7, the various properties of this hair shampoo were excellent. Example 7 Table 7 shows the properties of a hair rinse obtained by adding 200 mg of carboxymethyl cellulose to water. As is clear from Table 7, the hair rinse of the present invention [Effects of the Invention] As described above, the hair cosmetic of the present invention does not irritate the scalp (highly safe) and does not irritate the scalp over time. No odor or discoloration (good stability), and has an excellent smoothing effect on hair when used. Gloss improvement effect. Wetting effect. It showed elasticizing effect, softening effect, etc., and its action and effect were remarkable.

Claims (1)

[Claims] A hair cosmetic containing modified transglutaminase modified with a water-soluble substance.