JPH08301904A - Humectant comprising polysaccharide as effective component and cosmetic preparation containing the same - Google Patents

Abstract

PURPOSE: To obtain a humectant not only stable than conventional humectants and excellent in humectant performance but also active in tyrosinase inhibition by using as the effective component a polysaccharide composed of specific constituent saccharides at a specific molar ratio. CONSTITUTION: This humectant comprises as the effective component a polysaccharide composed of 4 constituent saccharides, D-gluculonic acid, L-rhamnose, D-galactose and D-glucose, at the following molar ratio: D-gluculonic acid : L-rhamnose : D-galactose : D-glucose = 0.8 to 1.2:2.4 to 3.6:0.8 to 1.2:0.8 to 1.2. The polysaccharide used herein has such a constituent saccharide residue bond structure and molar ratio as represented by the formula (wherein Rha, Gal, Glc and GlcUA are rhamnose residue, a galactose residue, a glucose residue and a glucuronate residue, respectively; and numerals each stand for a position of a glycoside bond). This humectant can be used as a treatment agent for production of clothes capable of moisture absorption and release, an additive for an improvement in the moisture retention of food, a moisture-conditioning subsidiary construction material, etc.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a moisturizing agent containing a polysaccharide as an active ingredient, and a cosmetic containing the same. Specifically, it relates to a moisturizer containing a polysaccharide having a tyrosinase inhibitory action as an active ingredient and a cosmetic containing the same.

[0002]

2. Description of the Related Art Hyaluronic acid, chitosan and the like have hitherto been generally used as moisturizers. For example, JP-A-63
No. 156,707 discloses a moisturizer having a molecular weight of 20.
Cosmetics containing at least 0,000 hyaluronic acid have been proposed. It is described that this humectant has a role of preventing irritation from the outside and rough skin, and also has a function of improving the usability of cosmetics.

In particular, it is said that the moisturizing agent as a cosmetic raw material desirably has a moisturizing rate in the range of 10 to 50% under normal environmental conditions of relative humidity of 40 to 80%. In addition, its moisturizing ability is also required to be less affected by changes in relative humidity (fragrance
Journal Extra Number No. 9 "Humectant Science" 1988
Year, p. 34 and others).

On the other hand, kojic acid, arbutin and the like are known to have tyrosinase inhibitory activity, and are incorporated in cosmetics as whitening agents.

[0005]

However, the moisturizing agent composed of hyaluronic acid has a serious drawback that it is difficult to obtain a stable moisturizing ability because the moisturizing ability greatly changes depending on humidity conditions.

Moisturizers such as glycerol and sodium pyrrolidonecarboxylate also have the same drawbacks as the above-mentioned hyaluronic acid and, moreover, have a low moisturizing property under low humidity conditions, and the moisturizer originally has its performance. Insufficient performance in the environment in which it must perform. Also, like hyaluronic acid, it has too high a hygroscopicity under high humidity conditions, so that it may give a sticky feeling or conversely remove water from the skin.

Moisturizers composed of chitosan have a serious drawback that they have low moisturizing properties under low humidity conditions where the most moisturizing ability is required.

No conventional humectant such as hyaluronic acid has tyrosinase inhibitory activity.
On the contrary, the moisturizing ability is not recognized in the conventional whitening agents such as kojic acid and arbutin.

[0009] As a result of intensive studies to provide a novel moisturizing agent, the present inventors have found that a specific polysaccharide produced by a Klebsiella bacterium has stable moisturizing properties and tyrosinase inhibitory activity. The present invention has been completed by discovering that it is a polysaccharide suitable for being blended in. That is, the object of the present invention is a moisturizing agent containing a polysaccharide having both excellent moisturizing ability and tyrosinase inhibitory activity as an active ingredient, and
It is intended to provide a cosmetic containing the moisturizer.

[0010]

The first gist of the present invention is as follows.
The constituent sugar consists of four kinds of D-glucuronic acid, L-rhamnose, D-galactose and D-glucose, and the constituent molar ratio is D-glucuronic acid: L-rhamnose: D.
-Galactose: D-glucose = 0.8-1.2:
2.4-3.6: 0.8-1.2: 0.8-1.2 exists in the moisturizer which uses the polysaccharide as an active ingredient.

The second aspect of the present invention resides in a cosmetic containing the above moisturizer.

The present invention will be described in detail below. The polysaccharide used in the present invention is an acidic heteropolysaccharide as is clear from the above constituent sugars. This polysaccharide usually has the following physical properties (1) to (4).

(1) Property: White fiber (freeze-dried product).

(2) Solubility: Soluble in water, dilute acid and dilute alkali, but insoluble in methanol, ethanol and acetone.

(3) Infrared absorption spectrum: 3400 cm -1
Near, around 1620 cm-1, 1100 cm-1, 1250 cm-1
And absorption around 2950 cm -1 are observed.

(4) Color reaction: all of the phenol-sulfuric acid method, the carbazole-sulfuric acid method and the m-phenylphenol method are positive.

The polysaccharide used in the present invention preferably has the following binding modes of constituent sugar residues and constituent molar ratios.

Embedded image

Preferably, the polysaccharide has a molecular weight of about 1 × 10 6 as measured by gel filtration chromatography.
^{It is 3} to 10 × 10 ⁶ .

The molecular weight of the polysaccharide used in the present invention and the type, constituent ratio and binding mode of the constituent sugars can be specified by ordinary chromatographic analysis, methylation analysis, Smith decomposition method, specific optical rotation measurement and the like. is there. In particular,
The following identification method is exemplified.

Measurement of molecular weight: For example, "As" manufactured by Asahi Kasei
ahipak GFA-7MF ”as a column, and 0.1
The molecular weight is measured using high-performance liquid chromatography in the GPC mode with an aqueous sodium nitrate solution as a mobile phase and a molecular weight-retention time standard curve prepared using pullulan of known molecular weight as a standard sample.

Constituent sugar and its constituent ratio: 2M trifluoroacetic acid (TFA) for the polysaccharide and the polysaccharide obtained by reducing the carboxyl group of the uronic acid residue in the polysaccharide.
Acid hydrolysis is carried out at 100 ° C. for 6 hours and then derivatized to alditol acetate. About each obtained derivative, 3% ECNSS-M coated "Ga
Gas chromatographic analysis is performed using “schrome Q” (manufactured by Wako Pure Chemical Industries, Ltd.) as a column. The constituent sugars of the polysaccharide and their constituent ratios are determined from the analytical results obtained for the polysaccharide and the reduced polysaccharide.

The polysaccharides used in the present invention are, for example, polysaccharide-producing Klebsiella oxytoca TNM3 strain (FE
It can be obtained by culturing RM BP-4669) or a mutant strain thereof and collecting a polysaccharide from the culture. Hereinafter, this manufacturing method will be described.

The polysaccharide obtained by the production method using Klebsiella oxytoca TNM3 strain is an acidic heteropolysaccharide and has a main repeating unit having a structure represented by the following formula.

[0024]

Embedded image

Klebsiella oxytoca TN used
The mycological properties of the M3 strain are shown in Tables 1-3.

[0026]

[Table 1] Bacteriological characteristics Various morphology Morphology Bacillus, colony is slightly mucoid Gram stain-Glucose OF F type motility-Catalase + oxidase-Gas production from glucose + Growth in KCN medium + Utilization of citrate ＋ Methyl red − VP +

[0027]

[Table 2] Production of Acid from Carbohydrate Glucose + Adonite + Arabinose + Dulcit + Lactose + Maltose + Mannitol + Rhamnose + Salicin + Sorbitol + Sucrose + Trehalose + Xylose + Glycerol + Inositol + Raffinose +

[0028]

[Table 3] Gelatin hydrolysis-malonate + gluconate + nitrate reduction + gas production from nitrate-urease + lysine decarboxylase + arginine dihydrolase-ornithine carboxylase-PAA-ONPG + hydrogen sulfide + esculin hydrolysis + indole + Extracellular specific polysaccharide production ability + (Producing ability of polysaccharide having the above specific repeating unit)

[0029] The above-mentioned mycological properties and the Vergiz Manual of Systematic Bacteriology Vol. 1 (BERGEY'S MANUAL OF Sys)
texture Biology Volu
Me 1, 1984) From the comparison with the data described on page 464, although there is no description regarding the extracellular specific polysaccharide production ability of Klebsiella oxytoca of the type culture, other properties are consistent. In addition, since there is no known strain producing a specific polysaccharide in Klebsiella oxytoca species, this strain is characterized by having the ability to produce a specific polysaccharide of Klebsiella oxytoca. Considered to be a new strain, Klebsiella
Oxytoca (Klebsiella oxytoca)
It is named TNM3 strain.

The above-mentioned strain was obtained under the contract number "FERM B" at the Institute of Biotechnology, Institute of Biotechnology, Ministry of International Trade and Industry.
P-4669 ”has been deposited and stored internationally since May 18, 1994.

Klebsiella oxytoca TNM3 strain (F
The mutant strain of ERM BP-4669) is a radiation such as ultraviolet rays, X-rays, or ethyl methanesulfonic acid (EM).
S), N-methyl-N'-nitro-N-nitrosoguanidine (MNNG) and other chemical mutagens known in the art.
The presence or absence of the productivity of the above-mentioned polysaccharide can be easily determined by analyzing the culture solution of the strain.

In the above-mentioned production method, as a medium for culturing the above-mentioned microorganism, Klebsiera (Klebs) is used.
It is not particularly limited as long as it can grow a microorganism belonging to the genus iella) and produces a polysaccharide, and contains an appropriate amount of a carbon source, a nitrogen source, an inorganic salt and a trace nutrient source. And as carbon sources, glucose, lactose, maltose,
Xylose, mannitol, sucrose, rhamnose, arabinose, trehalose, raffinose and the like are used. As the nitrogen source, synthetic compounds such as nitrates, ammonium salts and urea, polypeptone, corn steep liquor, yeast extract, meat extract, defatted soybean extract, peptides and natural organic substances such as amino acids are used. As the inorganic salts, phosphates, potassium salts, sulfates, magnesium salts and the like are used. In the medium, if necessary, iron salt,
Calcium salt, manganese salt and the like can be added. Moreover, yeast extract, various vitamins, etc. are used as a micronutrient source.

The state of the medium may be solid or liquid. When a liquid medium is used, static culture may be used, but shaking culture and aeration-agitation culture can obtain the polysaccharide in higher yield. The pH at the time of culturing is not particularly limited as long as it can grow a microorganism and produce a polysaccharide, but a pH of 4 to 8 is usually suitable. The culture temperature is also not particularly limited, but usually 20 to 35 ° C is suitable. The culturing time is selected such that the production amount of the polysaccharide reaches the maximum, but usually 1 to 7 days is appropriate.

As a method for collecting polysaccharides from the culture obtained by the above-mentioned culture method, a conventionally known method applied to ordinary polysaccharides can be adopted. For example, first, cells are removed from the culture by centrifugation or filtration, and then an organic solvent such as methanol, ethanol, isopropanol, or acetone is added to the obtained culture solution to cause precipitation. Next, after dissolving the precipitate in water, dialysis is performed against water, and ventilation drying, hot air drying, spray drying,
The dialysis inner solution is dried by a method such as drum drying, reduced pressure drying, or freeze drying to recover the polysaccharide.

In addition to the above collection method, by ultrafiltration,
You may employ | adopt the method of removing the components other than polysaccharides from the said culture liquid, and providing the obtained concentrated liquid with the above-mentioned drying process. Further, if necessary, a highly purified purified product can be obtained by purifying according to a general polysaccharide purification method. As the purification method, various column chromatography such as ion exchange, gel filtration, affinity, etc., precipitation with a quaternary ammonium salt or salting out, precipitation with an organic solvent, etc. are adopted.

The degree of polymerization of the polysaccharide obtained by the above-mentioned production method can be changed by adjusting the conditions such as the medium composition at the time of production and the collecting method. Also, by using TFA, formic acid, hydrochloric acid, etc. and adjusting the conditions,
It can hydrolyze harvested and purified products. Therefore,
The molecular weight of the polysaccharide can be freely adjusted within the range of about 1 × 10 ³ to 10 × 10 ⁶ .

Particularly preferred polysaccharides used in the present invention are the above-mentioned Klebsiella oxytoca TNM3.
It is a polysaccharide obtained by the production method using.

The polysaccharide used in the present invention has an excellent moisturizing property that its moisturizing ability is less affected by humidity conditions, as compared with sodium hyaluronate, which is a typical moisturizing agent, Moreover, it also has tyrosinase inhibitory properties.

Next, the cosmetic of the present invention will be described.
The cosmetic of the present invention is obtained by blending the above-mentioned polysaccharide as a moisturizer. The content of the above-mentioned polysaccharide is usually 0.0001 to 20% by weight, preferably 0.001 to 10% by weight, based on the whole cosmetic. Compounding amount 0.0
If it is less than 001% by weight, the effect is not sufficiently exhibited, which is not preferable. In addition, if a high-molecular-weight polysaccharide is blended in an amount of more than 20% by weight, the resulting cosmetic composition may have a poor feeling in use.

The cosmetics of the present invention are, for example, water / oil type or oil / water type emulsified cosmetics, creams, lotions, lotions, oily cosmetics, lipsticks, foundations, hairnics, hair styling agents, hair nourishing agents, It can be used in various forms as a skin / hair cosmetic such as a hair restorer.

In the preparation of the cosmetics of the present invention, as oily components, for example, hydrocarbons such as liquid paraffin, paraffin wax, ceresin, squalane, waxes such as beeswax, whale wax, carnauba wax, olive oil, camellia oil, Jojoba oil, natural animal and vegetable oils such as lanolin,
Silicone oil, fatty acid, higher alcohol, and ester oil obtained by reacting these can be preferably used.

As the surfactant, polyoxyethylene alkyl ether, polyoxyethylene fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester,
Polyoxyethylene hydrogenated castor oil alkyl sulfate, polyoxyethylene alkyl sulfate, alkyl phosphate, polyoxyethylene alkyl phosphate, fatty acid alkali metal salt, sorbitan fatty acid ester, glycerol fatty acid ester and the like can be preferably used.

Furthermore, according to the type and purpose of the cosmetic,
As optional components, it is preferable to appropriately mix the following components.

Viscosity modifier: polyvinyl alcohol, carboxyvinyl polymer, carboxymethyl cellulose,
Polyvinylpyrrolidone, hydroxyethyl cellulose,
High molecular compounds such as methyl cellulose, natural gums such as gelatin and taracant gum, alcohols such as ethanol and isopropanol.

Moisturizers: propylene glycol, glycerol, 1,3-butylene glycol, dipropylene glycol, sorbitol, lactic acid, sodium lactate, sodium pyrrolidonecarboxylate and the like.

Preservatives: paraoxybenzoic acid ester, benzoic acid, sodium benzoate, sorbic acid, potassium sorbate, phenoxyethanol and the like.

[0047]

EXAMPLES The present invention will be described in more detail with reference to examples below, but the present invention is not limited to the following examples as long as the gist thereof is not exceeded.

Reference Example 1 (Production of Polysaccharide) 100 ml of the medium having the composition shown in Table 4 was placed in each of four 500 ml volume Sakaguchi flasks, and the medium having the composition shown in Table 5 was sterilized by wet heat at 121 ° C. for 20 minutes. 2 in a test tube using
Klebsiella oxytoca TNM3 strain (FERM BP-4669), which had been liquid-shaking culture for one day, was inoculated with one platinum loop of each strain and subjected to reciprocal shaking culture at 28 strokes at 110 strokes per minute and 28 ° C. for shaking.

[0049]

[Table 4] Medium composition (% by weight) Glucose 2.0% Polypeptone 0.1% Potassium monohydrogen phosphate 0.15% Magnesium sulfate heptahydrate 0.05% Vitamin B ₁ 0.0005% Biotin 0. 0000 6% calcium pantothenate 0.001% nicotinamide 0.0005% pH 6.5

[0050]

[Table 5] Medium composition (% by weight) Glucose 4% Polypeptone 0.2% Potassium monohydrogen phosphate 0.15% Magnesium sulfate heptahydrate 0.05% Vitamin B ₁ 0.0005% Biotin 0.000006% Calcium pantothenate 0.001% Nicotinamide 0.0005%

400 ml of the above-obtained culture solution was inoculated into a 15 liter jar fermenter containing 8 liters of the medium having the composition shown in Table 5 and sterilized in the same manner as above, and the temperature was 28 ° C. and the aeration rate was 5 5 under the condition of liter / minute
Aeration stirring culture was carried out for 95 hours while maintaining the pH in the system at 7 using an M sodium hydroxide aqueous solution. The rotation speed was 200 rpm until the 24th hour of culture, and 3 rpm thereafter.
It was set to 400 rpm until the 3rd hour and 700 rpm until the 95th hour.

The pH of the resulting culture was adjusted to 10% with sulfuric acid.
The cells were adjusted to 5 and sterilized by moist heat at 121 ° C. for 60 minutes, and then the cells were removed by centrifugation. About the obtained culture supernatant,
Cross-flow ultrafiltration was repeated until components other than polysaccharides (residual medium components, etc.) were removed. For ultrafiltration, manufactured by Tosoh Corporation, ultrafiltration system "UF-LMS"
II ”(fraction molecular weight: 3 × 10 ⁶ ) was used. The concentrated solution that did not pass through the ultrafiltration membrane was freeze-dried to obtain about 21 g of a single polysaccharide per liter of the medium. The identity of the polysaccharide was confirmed using high performance liquid chromatography in GPC mode.

"Asahipak GFA-" manufactured by Asahi Kasei Corporation
7MF "as a column and high performance liquid chromatography using 0.1 M sodium nitrate aqueous solution as a mobile phase,
As a result of measuring the molecular weight of the above-mentioned polysaccharide, the retention time of the peak top of the chromatogram of the polysaccharide was found to be about 1.5 × 10 ⁶ in the molecular weight-retention time standard curve prepared using pullulan of known molecular weight as a standard sample. The value corresponding to

Further, the above-mentioned polysaccharide and the polysaccharide obtained by reducing the carboxyl group of the glucuronic acid residue are hydrolyzed to each constituent sugar, and then induced into alditol acetate, and then subjected to gas chromatography analysis. It was When the molar ratio of each constituent sugar was determined from the calibration curve prepared in advance and the peak area of each constituent sugar, D-glucuronic acid:
L-rhamnose: D-galactose: D-glucose =
It was 1: 3: 1: 1.

Reference Example 2 (Production of Polysaccharide) The pH of the culture obtained in the same manner as in Reference Example 1 was adjusted to 4.5 with 10% sulfuric acid, sterilized by moist heat at 121 ° C. for 100 minutes, and then centrifuged. The cells were removed. Then, the same treatment as in Reference Example 1 was performed to obtain about 19 g of a single polysaccharide per liter of the medium. However, for ultrafiltration, an ultrafiltration system “UF-LMSII” (fraction molecular weight: 1 × 10 ⁵ ) manufactured by Tosoh Corporation was used. Regarding the obtained polysaccharide, the molar ratio of constituent sugars was determined in the same manner as in Reference Example 1, and as a result, D-glucuronic acid: L-rhamnose: D-galactose: D-glucose = 1: 2.8: 1: 1. Met.
The molecular weight was 2 × 10 ⁵ .

Example 1 (Measurement of Moisturizing Ability in Low Humidity Environment) Each of the polysaccharides obtained in Reference Examples 1 and 2 was placed in a weighing tube and completely vacuum dried, and then the relative humidity was adjusted to 20% with potassium acetate. It was put in the adjusted desiccator and left for 3 days. The above operation was performed under a constant temperature of 20 ° C.

For comparison of moisturizing ability, commercially available moisturizing agents derived from chicken cob-derived sodium hyaluronate (manufactured by Kewpie, molecular weight: about 2 × 10 ⁶ ), sodium hyaluronate produced by microbial fermentation (manufactured by Kibun Food Chemifa) , Molecular weight: about 2 × 10 ⁶ ), chitosan (manufactured by Ajinomoto Co., Inc.), glycerol (manufactured by Wako Pure Chemical Industries, Ltd.) and sodium pyrrolidonecarboxylate, and commercially available polysaccharide xanthan gum (manufactured by Kelco), carrageenan (Dainippon Nihon). (Pharmaceutical company)
The same operation as described above was performed for the pullulan (manufactured by Hayashibara).

The moisturizing rate was calculated by the following formula by periodically measuring the sample weight. The results are shown in Table 6.

Moisture retention rate (%) = (A−B) / B × 100 (where A is the sample weight when it becomes constant, and B is the dry sample weight).

[0059]

[Table 6] Substance Moisture retention Polysaccharide obtained in Reference Example 1 12.1% Polysaccharide obtained in Reference Example 2 12.7% Sodium hyaluronate derived from chicken cob 12.0% Sodium hyaluronate 12.5% produced by microbial fermentation Chitosan 10.3% Glycerol 6.9% Sodium pyrrolidonecarboxylate 8.5% Xanthan gum 10.4% Carrageenan 9.3% Pullulan 8.8% ────────────────── ───────────

As is clear from the above results, the relative humidity 2
In a low humidity environment of 0%, the moisture retention of the polysaccharide used in the present invention is equal to or higher than that of hyaluronic acid, which is a typical humectant, and is generally used as a humectant. It shows higher values than chitosan, sodium glycerol and sodium pyrrolidonecarboxylate and commercial polysaccharides. Therefore, it can be seen that the humectant of the present invention has excellent properties in a low humidity environment.

Example 2 (Measurement of Moisturizing Ability in High Humidity Environment) Each of the polysaccharides obtained in Reference Examples 1 and 2 was placed in a weighing tube and completely vacuum dried, and then the relative humidity was adjusted with ammonium dihydrogen phosphate. It was placed in a desiccator adjusted to 92.9% and left for 3 days. The above operation was performed under a constant temperature of 30 ° C.

The same operations as above were carried out for the chicken cob-derived sodium hyaluronate used in Example 1, sodium hyaluronate produced by microbial fermentation, glycerol and sodium pyrrolidonecarboxylate.

The results are shown in Table 7. The method of calculating the moisture retention rate is the same as in the first embodiment.

[0064]

[Table 7] Substance Moisture retention Polysaccharide obtained in Reference Example 17.6% Polysaccharide obtained in Reference Example 2 56.5% Sodium hyaluronate derived from chicken cob 94.2% Sodium hyaluronate 96.9% produced by microbial fermentation Glycerol 139.1% Sodium pyrrolidonecarboxylate 218.3% ─────────────────────────────

Due to the widespread use of air conditioning, indoor environments such as offices have low temperature and low humidity even in summer, and cosmetics having a moisturizing property are required as in winter, but since the outdoor environment in summer is hot and humid, A moisturizer with high hygroscopicity gives a sticky feeling when going to work, going home, or going out for lunch.

However, as is apparent from the above results, the relative humidity of the polysaccharide used in the present invention is 92.9%.
Moisture retention rate under high humidity environment
It shows a lower value than conventional moisturizers, and there is no risk of giving a sticky feeling or absorbing water from the skin. It can be seen that the moisturizer of the present invention exhibits excellent properties even when exposed to a high humidity environment.

Example 3 (Measurement of Effect on Moisture Retention Ability Due to Change in Relative Humidity) The polysaccharides obtained in Reference Examples 1 and 2 were placed in weighing tubes and completely dried in vacuum, and then the relative humidity was adjusted to 79 by ammonium chloride. It was put in a desiccator adjusted to%, and left for 3 days. Next, it was transferred to a desiccator adjusted to a relative humidity of 31% with calcium chloride hexahydrate and left for 3 days. All of the above operations were performed at a constant temperature of 25 ° C.

The same operations as described above were carried out for the chicken comb-derived sodium hyaluronate and the sodium hyaluronate produced by microbial fermentation used in Example 1.

The results are shown in Table 8. The method of calculating the moisture retention rate is the same as in the first embodiment.

[0070]

[Table 8] Humidity retention substance at each relative humidity 79% 31% Difference Polysaccharide obtained in Reference Example 1 37% 25% 12% Polysaccharide obtained in Reference Example 2 35% 25% 10% Sodium hyaluronate 46% 27% 19% Sodium hyaluronate 41% 26% 15% ────────────────────────────────── ───

As is clear from the above results, all the substances had a relative humidity of 40 to 80% under a normal environment.
It has the generally required property of ~ 50% moisture retention. However, the influence of the change in relative humidity, that is, the difference in the moisture retention rate between the case where the relative humidity is 79% and the case where the relative humidity is 31%, is 19% for sodium hyaluronate derived from chicken cob, and hyaluronic acid produced by microbial fermentation. Sodium acid is 15%, whereas polysaccharides used in the present invention are as small as 12% to 10%. Therefore, the moisturizing agent containing a polysaccharide used in the present invention,
It can be seen that it is superior to various sodium hyaluronates in that it is not easily affected by changes in relative humidity.

Example 4 (Evaluation of Tyrosinase Inhibitory Ability) In 2.4 ml of 0.1 M phosphate buffer (pH 6.5),
0.1 ml of a solution of mushroom-derived tyrosinase dissolved in 0.05 M phosphate buffer (pH 6.5) at a concentration of 2000 U / ml, and the polysaccharide obtained in Reference Example 1 in 0.05 M phosphate buffer 300 μg in (pH 6.5)
0.1 ml of a solution dissolved at a concentration of / ml was added, and 0.4 ml of a solution prepared by dissolving L-tyrosine at a concentration of 1.5 mM in 0.05 M phosphate buffer (pH 6.5) was added. In addition, the reaction was started and incubated at 25 ° C for 10 minutes. Then, the absorbance at 475 nm was measured by an ultraviolet-visible spectrophotometer. Furthermore, the above operation was performed without adding the polysaccharide, and the absorbance was measured in the same manner to give a blank value.

The same procedure was performed for the polysaccharide obtained in Reference Example 2. Further, for comparison, the same operation was performed using kojic acid (manufactured by Tokyo Chemical Industry Co., Ltd.). The tyrosinase inhibition rate was calculated by the following formula. The results are shown in Table 9 as relative values when the value of kojic acid was 1.0.

[0074]

[Number 2] tyrosinase inhibition rate _{(%) = (OD 2 -OD} 1)
/ OD ₂ × 100 (where, OD ₁ represents the absorbance at 475 nm when the sample was added, and OD ₂ represents the absorbance at 475 nm when the sample was not added (blank).)

[0075]

[Table 9] Substance Tyrosinase inhibition rate Polysaccharide obtained in Reference Example 0.2 Polysaccharide obtained in Reference Example 2 0.3 Kojic acid 1.0 ────────────────── ─────────────

As is clear from the above results, although the activity is weaker than that of kojic acid, the polysaccharide used in the present invention has tyrosinase inhibitory activity and is expected to be used as a whitening agent.

Example 5 (Preparation of Polysaccharide-Containing Lotion) Lotion was prepared according to the formulation shown in Table 10 below. That is, (1), (2), (3), (5) and (6) were dissolved in (10) with heating and returned to room temperature, and then (7) was subjected to (4), (8) and (6). What melt | dissolved 9) was slowly added and solubilized, and it filtered and obtained the lotion. A lotion was similarly prepared for the polysaccharide obtained in Reference Example 2.

[0078]

Table 1 (1) Polysaccharide obtained in Reference Example 1 0.5% by weight (2) 1,3-butylene glycol 2.5% by weight (3) Glycerol (86%) 0.5% by weight (4 ) Polyoxyethylene hydrogenated castor oil (40EO) 0.5 wt% (5) Lactic acid 0.05 wt% (6) Sodium lactate 0.7 wt% (7) Ethanol 7.0 wt% (8) Paraoxy Methyl benzoate 0.1% by weight (9) Perfume 0.05% by weight (10) Purified water 88.1% by weight

Example 6 (Preparation of polysaccharide-containing emulsion) An emulsion was prepared according to the formulation shown in Table 11 below. That is, first, (1) to (8) and (12) are heated and dissolved,
It was kept at 70 ° C (oil phase). Then, (9) to (11) were heated and dissolved in (13), and this was gradually added to the above oil phase to emulsify and slowly cooled to obtain an emulsion. An emulsion was similarly prepared for the polysaccharide obtained in Reference Example 2.

[0080]

Table 1 (1) Liquid paraffin 4.0 wt% (2) Squalane 4.0 wt% (3) Cetanol 0.5 wt% (4) Stearic acid 1.5 wt% (5) Sorbitan monooleate 1 0.0 wt% (6) Polyoxyethylene sorbitan monooleate (20 EO) 1.0 wt% (7) Glycerol monostearate 0.5 wt% (8) Ethyl paraoxybenzoate 0.2 wt% ( 9) Glycerol 3.0% by weight (10) 1,3-butylene glycol 5.0% by weight (11) Polysaccharide obtained in Reference Example 1 0.3% by weight (12) Perfume 0.05% by weight (13) ) Purified water 78.95% by weight

Example 7 (Preparation of polysaccharide-containing cream) A cream was prepared according to the formulation shown in Table 12 below. That is, first, (1) to (7) and (11) were melted by heating and kept at 70 ° C (oil phase). Then, (8) to (1
(0) was dissolved in (12) by heating, and the above oil phase was gradually added thereto with stirring, followed by homomixer treatment and then rapid cooling to obtain a cream. A cream was prepared in the same manner for the polysaccharide obtained in Reference Example 2.

[0082]

[Table 12] (1) Vaseline 8.0 wt% (2) Lanolin 2.0 wt% (3) Squalane 20.0 wt% (4) Cetanol 5.0 wt% (5) Glycerol monostearate 2.0 % By weight (6) sorbitan polyoxyethylene monolaurate (20 EO) 2.0% by weight (7) ethyl paraoxybenzoate 0.2% by weight (8) polysaccharide obtained in Reference Example 1 0.5% by weight % (9) Glycerol (86%) 5.0% by weight (10) 1,3-butylene glycol 5.0% by weight (11) Perfume 0.1% by weight (12) Purified water 50.2% by weight

Example 8 (Preparation of pack containing polysaccharide) A pack was prepared according to the formulation shown in Table 13 below. That is, (2), (3), (4) and (6) were added to (8) and dissolved by stirring, and then (1) was added and dissolved by heating.
Further, (5) in which (7) was dissolved was added and dissolved to obtain a pack. A pack was prepared in the same manner for the polysaccharide obtained in Reference Example 2.

[0084]

[Table 13] (1) Polyvinyl alcohol 18.0 wt% (2) Polyethylene glycol 2.0 wt% (3) 1,3-Butylene glycol 5.0 wt% (4) Polysaccharide obtained in Reference Example 1 0.5% by weight (5) Ethanol 8.0% by weight (6) Ethyl paraoxybenzoate 0.1% by weight (7) Perfume 0.05% by weight (8) Purified water 66.35% by weight

Example 9 (Preparation of polysaccharide-containing essence) An essence was prepared according to the formulation shown in Table 14 below.
That is, (1) to (8) were dissolved in (10) by heating, and then (9) was added to solubilize it to obtain an essence. In addition, the essence was similarly prepared for the polysaccharide obtained in Reference Example 2.

[0086]

Table 14 (1) Polysaccharide obtained in Reference Example 1 1.5% by weight (2) 1,3-butylene glycol 20.0% by weight (3) Glycerol (86%) 15.0% by weight (4 ) Polyethylene glycol 5.0 wt% (5) Polyoxyethylene hexadecyl ether (20 EO) 0.1 wt% (6) Citric acid 0.05 wt% (7) Sodium citrate 0.5 wt% ( 8) Ethyl paraoxybenzoate 0.2% by weight (9) Perfume 0.1% by weight (10) Purified water 58.05% by weight

[0087]

INDUSTRIAL APPLICABILITY According to the present invention described above, there is provided a moisturizing agent which is more stable and excellent in moisturizing ability than conventional moisturizing agents and also has tyrosinase inhibitory activity. Since the humectant has both properties, it is particularly advantageous when incorporated into cosmetics. The moisturizing agent of the present invention can be used as a treating agent in the production of absorbent and desorptive clothing, an additive for improving the moisturizing ability of foods, a humidity adjusting auxiliary material for construction, and the like. Further, since the polysaccharide used in the present invention has a tyrosinase inhibitory ability, it can be used in fields other than the cosmetics field such as the prevention of browning of meat and the blackening of cultured fish.

Claims (4)

[Claims] 1. The constituent sugar is composed of four kinds of D-glucuronic acid, L-rhamnose, D-galactose and D-glucose, and the constituent molar ratio is D-glucuronic acid: L-.
Rhamnose: D-galactose: D-glucose = 0.
8-1.2: 2.4-3.6: 0.8-1.2: 0.8
A moisturizer containing a polysaccharide of 1.2 as an active ingredient. 2. The moisturizing agent according to claim 1, wherein the binding mode of each constituent sugar residue of the polysaccharide and the molar ratio thereof are as follows. Embedded image (However, Rha, Gal, Glc and GlcUA are
Each represents a rhamnose residue, a galactose residue, a glucose residue and a glucuronic acid residue, and the numbers indicate the positions of glycosidic bonds. ) 3. The moisturizer according to claim 1, wherein the molecular weight of the polysaccharide measured by gel filtration chromatography is about 1 × 10 ³ to 10 × 10 ⁶ . 4. A cosmetic containing the moisturizing agent according to claim 1.