JP2002121538A - Thickener and cosmetic containing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an excellent polysaccharide-based thickener which exhibits a high thickening capability even when used in a small amount and does not exhibit a rapid decrease in viscosity by the rise of temperature; and a cosmetic containing the same. SOLUTION: This polysaccharide-based thickener is prepared by thermally treating, at 60-180 deg.C, a polysaccharide substantially comprising fucose, glucose, glucuronic acid, and rhamnose units in the form of an aqueous solution with a pH of 8 or higher. The cosmetic contains this thickener.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a microbial polysaccharide thickener having excellent emulsification / dispersion stabilization and high viscosity used in various emulsified products and solid dispersion products, and a cosmetic containing the same. It is about fees.

[0002]

2. Description of the Related Art Generally, emulsified products and dispersion products of fine solids include various thickening agents for the purpose of preventing separation of an emulsified system, preventing sedimentation and floating of a solid dispersion, and imparting an appropriate viscosity which is easy to handle. Agent is used. For example, in emulsions and lotions, low viscosity and good spreadability to apply thinly over a wide area,
Various viscosity characteristics are required depending on the purpose of use, such as the fact that creams and beauty essences have an appropriate viscosity for partial application, and pack cosmetics and massage cosmetics require a viscosity that does not run off. In addition, emulsified products and fine solid dispersion type products, etc., emulsify or disperse water and various insoluble materials such as oils, higher alcohols, pigments, etc., so that the emulsified or dispersed state is maintained for a long time. In order to prevent separation, a thickener is incorporated. However, depending on the thickener, cosmetics may have a "sticky feeling" and impair the commercial value.
There has been a demand for a thickener having no sticky feeling.

[0003] Thickening agents used in cosmetics include synthetic polymers such as acrylic acid polymers, processed natural products such as carboxymethylcellulose and methylcellulose, and carrageenan, guar gum, locust bean gum, gum arabic and gum karaya. Plant-derived polysaccharides,
Microbial polysaccharides such as xanthan gum have been used. In particular, conventionally processed natural products and microorganism-produced polysaccharides have been frequently used in order to obtain a high thickening effect with a relatively small amount. However, conventional thickeners have the drawbacks that the thickening action is not sufficient, and that the viscosity decreases rapidly with increasing temperature.

Therefore, a method for improving the viscosity characteristics of microorganism-produced polysaccharides has been proposed. For example, gellan gum, which is a microorganism-derived polysaccharide, and other polysaccharides have been proposed as a method for obtaining high viscosity by blending a low-concentration thickener. A method of increasing viscosity by blending (Japanese Patent Application Laid-Open No. 10-215795), a method of obtaining a high-viscosity xanthan gum by heating or moist heat-treating powdery xanthan gum (Japanese Patent Application Laid-Open Nos. 10-33125 and 2000-7705). ). However, a sufficiently satisfactory thickener has not yet been obtained, and higher performance is required.

[0005]

DISCLOSURE OF THE INVENTION The present invention solves the above-mentioned problems, and provides an excellent polysaccharide-based thickener which imparts a high viscosity in a small amount and does not rapidly decrease in viscosity due to an increase in temperature. The purpose is to provide cosmetics containing.

[0006]

Means for Solving the Problems In order to solve the above problems, the present inventors have conducted intensive studies on the improvement of various polysaccharide thickeners, and as a result, heating a specific polysaccharide in an aqueous alkaline solution. It has been found that the thickening performance is improved by the treatment, and the present invention has been completed.

[0007] That is, the invention according to claim 1 is characterized in that a polysaccharide containing substantially fucose, glucose, glucuronic acid, and rhamnose as constituent monosaccharides in an aqueous solution having a pH of 8 or more,
A thickener comprising a polysaccharide obtained by heat treatment at 60 to 180 ° C.

The invention according to claim 2 is the invention wherein the constituent monosaccharides of the polysaccharide are fucose: glucose: glucuronic acid: rhamnose = 1-2: 1-4: 1-2: 1-2 in a molar ratio. 1. The thickener according to item 1.

The invention according to claim 3 is the thickener according to claim 1, wherein the polysaccharide has a structure in which the main chain is composed of glucose, glucuronic acid, and rhamnose, and fucose is bonded to a side chain. It is.

A fourth aspect of the present invention is the thickener according to any one of the first to third aspects, wherein the polysaccharide is a polysaccharide produced by Alcaligenes L. strain B-16.

[0011] A fifth aspect of the present invention is a cosmetic comprising the thickener according to the first, second, third or fourth aspect incorporated into a cosmetic base material.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION The thickener of the present invention is obtained by substantially dispersing or dissolving a polysaccharide containing fucose, glucose, glucuronic acid, and rhamnose as constituent monosaccharides in an aqueous alkali solution and subjecting to heat treatment. .

The polysaccharide used in the present invention is a polysaccharide substantially containing fucose, glucose, glucuronic acid, and rhamnose as constituent monosaccharides, and is preferably glucose, glucuronic acid, rhamnose represented by the following formula (1): This is a polysaccharide comprising a main chain having a repeating structure consisting of: and a structure in which one fucose is branched into one glucose.

[0014]

Embedded image

The polysaccharide of the present invention is obtained as a polysaccharide produced by a microorganism. Generally, microorganisms often produce two or more kinds of polysaccharides. Therefore, even if other microorganisms are contained in addition to the polysaccharide used in the present invention, the effect of the polysaccharide of the present invention is hindered. If not, it does not preclude the inclusion of other polysaccharides.

The microorganism producing the polysaccharide of the present invention is not particularly limited.
Laterus B-16 strain bacteria (FERM BP-2015)
No.).

The production of the polysaccharide of the present invention is carried out, for example, in the case of a bacterium of Alcaligenes L. strain B-16 as follows.

The Alcaligenes strain B-16 bacterium is cultivated by an ordinary method for culturing microorganisms. For example, monosaccharides such as fructose, glucose and sucrose, natural macromolecules such as hemicellulose, starch and corn starch, olive Oils such as fats and oils, nitrogen sources such as urea, ammonium chloride, ammonium nitrate, inorganic nitrogen sources such as ammonium sulfate, tripton, yeast extract, meat extract, peptone, malt extract, etc. Initial p using a medium supplemented with inorganic salts such as magnesium sulfate and sodium chloride
The aeration and agitation liquid culture is performed for 3 to 10 days at H of 4 to 10 and a culture temperature of 15 to 40 ° C. After the culture, about twice (volume) or more of an organic solvent such as acetone, ethanol, isopropyl alcohol and the like is added to the culture solution, and the culture product is collected as insoluble aggregates.

It has been confirmed that at least two types of polysaccharides are contained in the polysaccharides produced by the Alcaligenes strain B-16 bacterium, and one of the polysaccharides is the polysaccharide of the present invention ( A polysaccharide having a structure in which one fucose is branched from one glucose in a repeating structure composed of glucose, glucuronic acid and rhamnose as shown in 1), and the other is represented by the following formula (2): Is a polysaccharide having a repeating structure substantially consisting of fucose and mannose as constituent monosaccharides. Y. Nohata, J .; Azu
ma, R .; Kurane, Carbohydrate
Research 293 , (1996) 213-22
2).

[0020]

Embedded image

Even if the polysaccharide represented by the formula (2) is contained in the polysaccharide of the formula (1) which is the polysaccharide of the present invention, its effect is not impaired. Without removing the saccharides, polysaccharides produced by the bacterium Alcaligenes latus B-16 can be used.

In the production of the thickener of the present invention, the concentration of the aqueous solution of the polysaccharide is 0.01 to 3% by weight, preferably 0.1% by weight.
It is a concentration of 1% to 1% by weight. If the concentration exceeds 3% by weight, the viscosity of the aqueous solution may be so high that the handleability may be deteriorated. On the other hand, if the concentration is less than 0.01% by weight, the concentration is low and the production efficiency is low, which is not preferable.

In the production of the thickener of the present invention, the pH of the aqueous solution of the polysaccharide is adjusted to 8 or more, preferably pH 11 or more, more preferably pH 1 by adding an alkaline substance.
2 or more. Under acidic conditions where the pH of the aqueous solution is less than 7, the molecular chain of the polysaccharide is severely cut, and the intended thickening effect of the present invention may not be obtained.

In the production of the thickener of the present invention, the temperature of the aqueous solution of the polysaccharide is from 60 ° C. to 180 ° C., preferably from 80 ° C.
To 160 ° C, more preferably 100 to 140 ° C.
If the temperature is lower than 60 ° C., the thickener of the present invention may not be obtained even if the heating time is lengthened. When the temperature exceeds 180 ° C.,
The decomposition of the polysaccharide may proceed excessively, which is not preferable. As a matter of course, when the temperature is 100 ° C. or higher, it is necessary to use a heat-resistant container for the heat treatment. The heating time is appropriately determined depending on the pH, the treatment temperature, and the desired viscosity characteristics, but is usually from 10 to 120 minutes.

After the alkali aqueous solution of the polysaccharide after the heat treatment is cooled to room temperature, an aqueous solution of an inorganic acid (for example, sulfuric acid or hydrochloric acid) is added to neutralize the solution, and about 3 times (volume) of acetone is stirred. An organic solvent such as ethanol, isopropyl alcohol or the like is added to precipitate the heat-treated polysaccharide as an aggregate, which is filtered and dried under reduced pressure to obtain the thickener of the present invention.

The rotational viscosity of the 0.1% by weight aqueous solution of the polysaccharide before the heat treatment is 310 mPa · s. However, the heat treatment at pH = 9, 120 ° C. for 120 minutes according to the method of the present invention. The rotational viscosity of the concentrated aqueous solution is 410 mPa · s.
It shows characteristics that greatly improve to 10 mPa · s.

The reason that the viscosity of the thickener of the present invention is increased by heating in an aqueous alkaline solution is that a part of the molecular chain of the polysaccharide is cleaved and the solubility in water is improved. It is considered that the viscosity increased.

The thickener of the present invention has a high viscosity in a small amount, has a small viscosity change with temperature, and is excellent in the emulsification stability of an emulsified product and the dispersion stability of a solid dispersion product. Pharmaceuticals, food, paints, inks, pesticides, etc.
It can be applied in a wide range of fields.

The present invention does not hinder the use of the polysaccharide of the present invention as a mixture with other thickeners as long as the effect is not impaired.

[0030]

The present invention will be specifically described below with reference to examples. However, the present invention is not limited to this.

[Culture of Bacteria of Alkaline Genestras B-16] The strain of Alkaline Genestras B-16 was cultured in a culture medium having the following composition. <Composition of culture medium> Glucose [Reagent manufactured by Wako Pure Chemical Industries, Ltd.] 40.0 g Dipotassium hydrogen phosphate [Reagent manufactured by Wako Pure Chemical Industries, Ltd.] 4.0 g Potassium dihydrogen phosphate [Wako Pure Chemical Industries, Ltd.] 2.0 g sodium chloride [Wako Pure Chemical Industries, Ltd. reagent] 0.1 g Magnesium sulfate [Wako Pure Chemical Industries, Ltd. reagent] 0.2 g potassium nitrate [Wako Pure Chemical Industries, Ltd.] 1.0 g yeast extract [manufactured by OXOID] 1.5 g

The above components were dissolved in ion-exchanged water, adjusted to pH 6.5 with sodium hydroxide and sulfuric acid, and the total amount was adjusted to 1 liter.

[0033] 150 mL of this medium was placed in a 500 mL Erlenmeyer flask, and sterilized by heating in an autoclave (121
(° C., 15 minutes). Subsequently, Alkaline GENESTRUS B-16 strain (FERM BP-20)
No. 15) was inoculated into the culture medium in an amount of one loopful of platinum,
Shaking culture (180 rpm) was performed for one day.

[Preparation of B-16 polysaccharide] After completion of the culture, about 3 volumes of isopropyl alcohol was added to the culture and mixed with stirring. The precipitated aggregate was collected by filtration, and dried under reduced pressure to obtain a B-16 polysaccharide.

[Preparation of Thickeners 1 to 8 of the Present Invention] The B-16 polysaccharide obtained by the above-mentioned method is converted into a 0.5 wt% aqueous solution, and a predetermined amount thereof is dissolved in a 1 mol / L aqueous sodium hydroxide solution. p
H, allowed to stand at room temperature overnight, and further maintained in an autoclave at a predetermined temperature for a predetermined time.
The mixture was neutralized using a mol / L aqueous sulfuric acid solution. After neutralization, about 3 times the volume of the aqueous solution of polysaccharide was added to isopropyl alcohol, and the precipitated aggregate was filtered and dried under reduced pressure to obtain thickeners 1 to 8 of the present invention.

[Preparation of thickener-9 of the present invention]
According to the method of No. 301904, the polysaccharide represented by the formula (2) was removed from the B-16 polysaccharide. That is,
4,000 ml of ion-exchanged water was added to 1,000 ml of the culture after the culture, and the pH was adjusted to 12 with a dilute aqueous sodium hydroxide solution. Next, an ion exchange resin: Diaion HPA-75 (OH ⁻ ) (manufactured by Nippon Rensui),
An adsorption treatment was carried out on a 2,000 ml column with a resin volume of not more than 8 to remove the low molecular component polysaccharide represented by the formula (2). Next, a thickener -9 was obtained in the same manner as the thickener -1.

Table 1 shows the treatment conditions of the thickeners 1 to 9 of the present invention.
Summarized in

[Thickener used for comparison] Thickener-10: B-16 polysaccharide prepared by the above culture method was used. Thickener-11: A 0.5 wt% aqueous solution of B-16 polysaccharide was adjusted to pH 13 with an aqueous sodium hydroxide solution.
After standing at room temperature overnight, the mixture was neutralized with a 1 mol / L sulfuric acid aqueous solution, and about 3 times the volume of isopropyl alcohol of the aqueous solution was added with stirring to collect the resulting aggregates and dried under reduced pressure. Thickener-11 was obtained. Thickener-12: A 0.5 wt% aqueous solution of B-16 polysaccharide was adjusted to pH 6 using sodium hydroxide and sulfuric acid. Leave at room temperature overnight, and autoclave for 1 hour.
After heating at 20 ° C. for 20 minutes, the mixture was cooled to room temperature, neutralized with a 1 mol / L aqueous sodium hydroxide solution, and stirred.
About 3 times the volume of the aqueous solution of isopropyl alcohol was added. The precipitated aggregate is recovered, dried under reduced pressure, and used as a thickener -12.
I got Xanthan gum-1: A commercially available product ["KELZAN" (trade name): manufactured by Sanseki Co., Ltd.] was used. Xanthan gum-2: Xanthan gum-1 left in a 120 ° C. dry heater for 20 minutes. Xanthan gum-3: 0.5 wt of xanthan gum-1
% Aqueous solution and 1 mol / L sodium hydroxide
Adjusted to H13. The mixture was allowed to stand at room temperature overnight, further heated at 120 ° C. for 20 minutes in an autoclave, cooled to room temperature, and neutralized with 1 mol / L sulfuric acid. After the neutralization, about 3 times the volume of the aqueous solution of isopropyl alcohol was added with stirring. The precipitated aggregate was recovered and dried under reduced pressure for 6 hours. Polyvinyl alcohol (PVA): a commercial product [“DENKA P
VAB-17 "(trade name): manufactured by Denki Kagaku Kogyo KK].

[Measurement of Viscosity] 0.2 g of a thickener and 199.8 g of water were added to a 200 mL tall beaker, and the mixture was stirred and dispersed at 8000 rpm for 10 minutes using a small homomixer.
A 0.1% by weight aqueous solution was obtained. The aqueous solution is heated at 30 ° C. and 50
After standing for 24 hours in a thermostat at 80 ° C. and 80 ° C., the viscosity was measured at each temperature with a B-type rotational viscometer (30 rpm, 1 minute). The results are shown in Table 1.

[0040]

[Table 1]

Comparing the viscosities of aqueous solutions of the same concentration, the thickener of the present invention has a higher viscosity than xanthan gum and PVA.
And the change in viscosity due to the difference in temperature is small. Furthermore, the thickener of the present invention is less affected by temperature. Also, a thickener
As is clear from the test results performed on 1-8 and thickener -9, even when the B-16 polysaccharide and the polysaccharide from which the polysaccharide represented by the formula (2) has been removed are treated under the same conditions. Similar results were shown.

[Application to Cosmetics] An O / W cream, a lotion, and a body gel were prepared with the following composition. (Preparation of O / W cream) <Components> (% by weight) Cetanol 3.0 2. 2. Stearic acid 2.0 Squalane 8.0 4. Lanolin 1.05. Glycerin monostearate 3.0 6. Octyldodecanol 5.0 7. 7. Thickener Predetermined concentration Glycerin 2.0 9. Sorbitol 10.0 10. Sodium cetyl sulfate 1.0 11. Purified water residue (total 100%)

The components 1 to 6 were completely dissolved at 80 ° C. to obtain a mixture 1. Also, 7 to 11 are uniformly dispersed,
The mixture was heated to 80 ° C. to obtain a mixture 2. Mixture 2 to mixture 1
And a small homomixer for 10 minutes at 80 ° C and 80 ° C.
After stirring and dispersing at 00 rpm to emulsify, the mixture was cooled to room temperature to obtain an O / W cream. The viscosity of the final product is 2,40
The compounding amount of the thickener was set so as to be 0 to 3,200 mPa · s.

(Preparation of Lotion) <Blending Components> (% by Weight) Ethanol 8.0 2. 2. Polyoxyethylene hydrogenated castor oil (addition of 60 moles of ethylene oxide) 2.0 Methyl paraben 0.1 4. Perfume 0.05 5. Glycerin 10.0 6. 6. Thickener predetermined concentration Purified water residue (total 100%)

The components 1 to 4 were uniformly dissolved, and the mixture 3
Was prepared, and 5 to 7 were uniformly dispersed to prepare a mixture 4. Add Mixture 4 to Mixture 3 and add 1 with a small homomixer.
The mixture was stirred and mixed at 8000 rpm for 0 minutes to obtain a uniform lotion. Also, the viscosity of the final product is 150-250 mPa
-The compounding amount of the thickener was set so as to be s.

(Preparation of Body Gel) <Blending Components> (% by Weight) Thickener Predetermined concentration 2. 2. Polyoxyethylene hydrogenated castor oil (addition of 60 moles of ethylene oxide) 1.0 Glycerin 1.0 4. Porous nylon powder 2.05. Ethanol 2.0 6. Potassium hydroxide 0.3 7. Methyl paraben 0.18. Purified water residue (total 100%)

The blending component 1 was dissolved in 8, and other components such as glycerin were sequentially added and mixed by stirring with a small homomixer at 8000 rpm for 10 minutes and neutralized with potassium hydroxide to obtain a gel for body. Also, the viscosity of the final product is 1
The compounding amount of the thickener was set so as to be 4,000 to 18,000 mPa · s.

(Evaluation) "Sticky feeling", "Smoothness",
"Viscosity change" and "presence or absence of separation" were compared. (1) Stickiness: Evaluated by a sensory test. Evaluation criteria: Those who rated "less sticky" were: ：: 9 or more out of 10 〇: 6 to 8 out of 10 ×: 5 or less out of 10 (2) Smoothness: Evaluated by sensory test did. Evaluation criteria: Those who evaluated that there was "smoothness": ：: 9 or more out of 10 〇: 6 to 8 out of 10 ×: 5 or less out of 10 (3) Viscosity change: cylindrical sample bottle (Cross-sectional area: 16 cm ² × height: 10 cm), and allowed to stand at 30 ° C. for 3 months. ：: No decrease in viscosity was observed. X: Viscosity decreased. (4) Separation: Cylindrical sample bottle (cross-sectional area 16 cm ² ×)
After being left at 30 ° C. for 3 months, the state of separation between the oil phase and the aqueous phase was observed, and the presence or absence of separation was visually judged. ：: Separation was not observed X: Separation was observed

The results are shown in Table 2.

[0050]

[Table 2]

O prepared by using the thickener of the present invention
/ W cream, lotion, and gel for body were excellent in feeling of use such as "stickiness" and "smoothness", and a product having no separation and having no problem in viscosity stability was obtained.

[0052]

As described above, the thickener of the present invention can produce a high-viscosity product in a small amount compared with the conventional thickener. In addition, cosmetics using the thickener of the present invention have not only a "sticky feeling" but also an improved "smoothness" and not only improved product characteristics, but also product separation and viscosity change. And the quality of the product could be improved.

 ──────────────────────────────────────────────────の Continuing on the front page (72) Inventor Tomomi Kuromiya Yokkaichi-shi, Mie Prefecture 6-6-9 Inside Yokkaichi Research Laboratories, Hakuto Co., Ltd. ) Inventor Toyofumi Miya, 6952, Omejima, Oita Prefecture, 6952, 3F F-term (reference) 4C083 AB032 AB052 AC022 AC072 AC102 AC122 AC132 AC242 AC392 AC432 AC482 AC782 AD072 AD211 AD212 AD512 BB60 CC02 CC04 CC05 DD27 DD33 DD41 EE01 EE06 EE07

Claims (5)

[Claims] 1. A polysaccharide substantially containing fucose, glucose, glucuronic acid, and rhamnose as constituent monosaccharides,
A thickener comprising a polysaccharide obtained by heat-treating an aqueous solution having H of 8 or more at 60 to 180 ° C. 2. The constituent monosaccharides of the polysaccharide are fucose: glucose: glucuronic acid: rhamnose = 1 to 2:
The thickener according to claim 1, wherein the ratio is from 1 to 4: 1 to 2: 1 to 2. 3. The thickener according to claim 1, wherein the polysaccharide is composed of glucose, glucuronic acid, and rhamnose as a main chain, and has a structure in which fucose is bonded to a side chain. 4. The method according to claim 1, wherein the polysaccharide is alkaligenes latus.
4. A polysaccharide produced by the B-16 strain.
The thickener as described. 5. A cosmetic comprising the thickener according to claim 1, 2, 3, or 4 incorporated in a cosmetic base.