JP2834223B2 - Bath additive - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to a bathing agent which has no skin irritation and has an excellent bathing effect, particularly excellent in giving skin smoothness after use.

[Problems to be solved by conventional technology and invention]

Conventionally, inorganic salt compounds such as sodium sulfate, sodium bicarbonate, sodium carbonate, sodium chloride, potassium chloride, and magnesium sulfate have been used as the main components, to which flavors, coloring agents, various plant extracts, various surfactants, and oil components have been added. Bath salts containing the same are known. These bath additives impart aroma and color to the bath, refreshing the mood at the time of bathing, promote blood circulation with the enhancement of the warm bath effect, activate metabolism, and have coldness, low back pain, neuralgia, stiff shoulders, fatigue. It has an effect on recovery, etc., and is widely used in general.

Further, in order to further enhance the effect of bathing, bathing agents to which various additives are added to add various effects are known. Among them, attempts have been made to add various oils and alkali components for the purpose of smoothing the skin by bathing.

However, for products using oil, it is difficult to select a surfactant for dispersing and dissolving the oil,
There was a problem that it adhered to the skin too much or not at all. Further, there is a problem that the wall surface of the bathtub is stained depending on the quality or quantity of the oil.

On the other hand, the addition of an alkali component can provide skin smoothness, but during storage, other components used in bath additives, such as fragrances and pigments, deteriorate due to the alkali component. Cause problems such as skin irritation.

An object of the present invention is to provide a bath preparation composition which has no skin irritation at the time of use and is excellent in giving an excellent bathing effect, particularly, smoothness to the skin after use.

[Means for solving the problem]

The present invention is a bath preparation characterized by blending a highly viscous β-glucan, which is produced by culturing a microorganism belonging to the genus Macrohomopsis and has the following properties.

(A) The bonding mode is such that all the D-glucopyranose residues in the main chain are β-1,3 bonds, and the bond is branched at the C-6 position of the D-glucopyranose residue in the main chain; In addition, there is no β-1,4 bond in the D-glucopyranose residue in the side chain.

(B) The molecular weight is about 10 million daltons or more by high performance liquid chromatography using a molecular sieve column.

(C) The temperature dependence of viscosity has a constant viscosity between 5 ° C and 85 ° C at a concentration of 0.3% by weight or less, and a constant viscosity between 20 ° C and 85 ° C at a concentration exceeding 0.3% by weight. Having a viscosity of

(D) The viscosity is stable even by a 1 kg / cm ² autoclave heating (20 minutes) treatment at 121 ° C.

Β-glucan used in the present invention has the following physicochemical properties.

(1) Molecular weight: molecular sieving by high performance liquid chromatography (hereinafter abbreviated as HPLC) using an Asahipak GS-710 column (exclusion limit molecular weight measured by pullulan of 10 million) using a 50 mM sodium chloride solution as a mobile phase. Is performed, one peak is observed at a position near the exclusion limit. Therefore, the size of the molecule is 10 million daltons or more, which indicates an extremely large molecular size.

(2) Ultraviolet absorption spectrum: no absorption is shown.

(3) Infrared absorption spectrum: β- as shown in FIG.
It shows an absorption of about 900 cm ^-1 specific for glycosidic bonds.

(4) Solubility in solvents: soluble in water, soluble in 0.5N sodium hydroxide, 90% formic acid, insoluble in organic solvents such as methanol, acetone, chloroform, and ethyl acetate.

(5) Color reaction A) Phenol sulfuric acid reaction: + B) Iodine reaction:-C) Carbazole-sulfuric acid reaction:-D) Ninhydrin reaction:-(6) Basic, acidic, and neutral: aqueous solution of this substance of
pH is neutral.

(7) Substance color: White (8) Type of constituent sugars: Hydrolyzed with 2.5N trifluoroacetic acid for 8 hours
-HPLC using gel Sugar AXG column (Toyo Soda Co., Ltd.)
When it was analyzed by, it was recognized that only glucose was a main component.

(9) Degradability by enzyme: The polysaccharide used in the present invention is treated with the enzyme described below (2.5 Units of each enzyme, pH 5.0, 37 ° C, 0-24 hr reaction), and its hydrolytic ability is determined by thin-layer chromatography. Chromatography (developing solvent: n-butanol: acetic acid: ethyl ether: water = 9: 6: 3: 1) and Asahi
As a result of observation by pak GS-710 HPLC, α-amylase, β-amylase, and glucoamylase were not hydrolyzed at all, and only laminalinase showed resolution in both analytical methods.

(10) Viscosity a) Viscosity: The solution of the polysaccharide used in the present invention is a highly viscous neutral solution. When the viscosity is measured with a bismetron rotational viscometer, the viscosity is 1200 to 1700 centipoise (adapter No. 3, 60 rotations, 30 seconds) with a 1% aqueous solution.

B) Stability to heat: Shows stable high viscous flow at normal temperature, has a constant viscosity between 5 ° C and 85 ° C at a concentration of 0.3% by weight or less, and 20 ° C even at a concentration exceeding 0.3% by weight. ~ 85
It has a constant viscosity between ° C. Further, the viscosity is stable even by heating at 121 ° C. and heating at 1 kg / cm ² for 20 minutes. That is, when the above autoclave treatment was performed using a 0.3% by weight solution, the viscosity before the treatment was 207 cps.
After processing was 210 cps.

C) Stability to acids and alkalis: exhibits relatively stable viscosity in the pH range of 2 to 13.

D) Stability to salts: borate, acetate, sulfate,
It exhibits a certain viscosity and is stable in the presence of any of salts such as sodium salt, potassium salt, calcium salt and magnesium salt.

(11) Bonding Mode The polysaccharide used in the present invention is dissolved in dimethyl sulfoxide, and then is converted to a methyl derivative by the box guard method using methylsulfonyl carbanion and methyl iodide. , Acetate, and fixed and quantitative analysis by a combination of gas chromatography and mass spectrometer, the following products were observed.

About 2.5 to 3.5 mol of 2,4,6-tri-O-methyl-D-glucose, 2,4-di-glucose per 1.0 mol of 2,3,4,6-tetra-O-methyl-D-glucose O-methyl-D-glucose about 1.5 to 2.5 moles Comprehensively judging the above results, β used in the present invention
-Glucan has no β-1,4 bond in the main bond of the side chain D-glucopyranose remnant, and this side chain has β β
It is a neutral polysaccharide having a structure of branching at the C-6 position of the D-glucopyranose residue in the main chain repeating 1,3 bonds.

(12) Moisture transpiration test Put a certain amount of water into the sample bottles of the four groups, attach the second base paper (thin paper with wax used for the transcript) to the mouths of the bottles, and put the hyaluronic acid on the base paper of each group. 1% solution,
Hyaluronic acid 0.5% solution, polysaccharide 1 used in the present invention
% Solution and a 0.5% solution of the polysaccharide used in the present invention were applied in a predetermined amount, and the weight of the sample bottle was measured over time to determine the amount of water evaporation.

In addition, the thing which applied water to the paper was set as a control, and 3
The measurement was performed using a number of samples.

 The results are shown below.

The polysaccharide used in the present invention was found to have a more effective moisture evaporation suppression effect than hyaluronic acid having a moisturizing effect.

(13) Safety test A sensitizing test of the polysaccharide used in the present invention (Maximizati
on method, sample concentration; induction 1% (twice), induction 0.5% and 1
%), None of the 10 guinea pigs were found to be positive.

In addition, the photosensitizing test (Ad
When the juvant-Strip method, sample concentration; induction 1%, induction 0.5% and 1%) were performed, none of the 10 guinea pigs was found to be positive.

As described above, the polysaccharide used in the present invention was a highly safe polysaccharide with low sensitization.

(14) Other characteristic properties The polysaccharide used in the present invention is tasteless and odorless. Also,
The polysaccharide used in the present invention has a smooth feel as a sensory property when applied. Hereinafter, a culture method and a purification method of β-glucan used in the present invention will be described.

The microorganism used in the present invention belongs to the genus Macrohomopsis and is, for example, a contract of Microfabrication Research 9366.
No. KAB55 deposited as Macrophomopsis. Details of the physicochemical properties of this strain are described in JP-A-64-63370.

Carbon sources used for culturing the polysaccharide-producing bacteria used in the present invention include glucose, glycerin, maltose, starch, lactose, sucrose, fructose, molasses, and the like. Nitrogen sources include corn steep liquor, yeast extract, and the like. Dried yeast, oatmeal meat extract, casein hydrolyzate, ammonium salt, nitrate, Pharmamedie (absorbent cottonseed flour) and the like. Other additives include inorganic salts such as sodium chloride, magnesium, calcium, and phosphoric acid. Further, the medium may contain trace amounts of metal salts such as iron, copper, and manganese, if necessary.

The culture can also be carried out by shaking culture, submerged aeration culture, stirring culture, or rotating drum culture in a usual aqueous medium containing the above culture medium.

Culture conditions are pH 3.5 to 9.0, preferably pH 5.0 to 8.0, and the culture temperature is 10 to 40 ° C, preferably 20 to 35 ° C, usually for 3 to 7 days. The polysaccharide used in the present invention is obtained from the culture thus obtained. The culture solution is treated by a suitable method such as filtration or centrifugation to remove the microbial cells, and an appropriate precipitant such as ethanol, methanol, isopropanol, propanol, acetone or the like is added to the resulting filtrate or supernatant. To precipitate the polysaccharide used in the present invention. The precipitate is separated by an appropriate method such as filtration or centrifugation, and then redissolved in water. After repeated precipitation with a precipitant, dialysis and lyophilization give a purified polysaccharide. .

In the present invention, the compounding amount of β-glucan is preferably 0.1% to 5% by weight (hereinafter abbreviated as wt%), more preferably 0.5% to 3% by weight in a powdered bath agent. In the case of a liquid bath agent, it is preferably 0.1% to 3% by weight, more preferably 0.1% to 3% by weight.
5% to 1% by weight. Below this range, smoothness on the skin cannot be expected so much, which is not preferable. Also, powdered bathing agents, when dissolved in warm water at 5% by weight or more, have poor dispersibility, and liquid bathing agents at 3% by weight or more tend to become highly viscous, so that β-glucan is uniform. It is not preferable because dissolution becomes difficult.

The bathing agent of the present invention is not limited to the description of the examples described below, and can be appropriately mixed with other components such as a fragrance, a coloring agent, a medicinal component, a surfactant and the like as long as the object of the present invention is achieved. It is.

〔Example〕

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

A human skin patch test and a moisturizing test were performed to evaluate skin irritation during use and smoothness after use. The method is described below. (Human skin patch test) A sample of 0.05 g was applied to the forearm flexion side skin of 25 subjects with a diameter of 1.0
After 24 hours of obstruction application using a patch test bandage with a cm-shaped lint cloth, the skin condition of 25 subjects was evaluated and determined for each sample according to the following criteria.
The judgment result was taken from the number of people who evaluated (±) or more by using the one with the strongest reaction 1 hour or 24 hours after the bandage removal.

(Moisturizing Test) A sensory test was conducted by 20 testee males and females to test the moisturizing properties. Evaluation is "moist after use"
And the number of respondents.

Examples 1-4, Comparative Example 1 Powdered Bath Agent Powdered bath agents of Examples and Comparative Examples were prepared by changing the blending amount of β-glucan, and the above-mentioned various tests were performed. Production of Glucan The following medium 30 was placed in a 50-jar fermenter, and one strain of KAB55 belonging to the genus Macrophomopsis (microfabrication research contract No. 9366) pre-cultured for 3 days in the following composition medium was inoculated at 25 ° C. The cells were cultured at an aeration rate of 1.0 vvm for 4 days.

(Composition) Glucose 3000 g Pharmamedia 150 g KH ₂ PO ₄ 30 g MgSO ₄ .7H ₂ O 90 g tap water 30 (prepared to pH 6 with NaOH) The obtained culture solution is subjected to continuous centrifugation at 10,000 rpm to remove cells, An equal amount of 60% ethanol was added to the obtained supernatant to precipitate a polysaccharide. This was centrifuged at 10,000 rpm for 5 minutes to obtain a polysaccharide. The obtained polysaccharide was dissolved in water again, and the above operation was repeated to give a tasteless, odorless, white, highly viscous β-
25 g of glucan was obtained.

In the above composition, sodium sulfate, sodium chloride, Blue No. 1, β-glucan, and sodium bicarbonate were sequentially charged into a horizontal cylindrical mixer and mixed until uniform. Next, POE (10) oleyl ether and a fragrance were mixed to form a uniform solution. This solution was gradually dropped into a horizontal cylindrical mixer, and uniformly stirred and mixed to obtain a bath agent.

(Iii) Characteristics Table 1 shows the results of testing the various characteristics according to the examples and comparative examples.

Examples 5 to 6, Comparative Example 2, Liquid Bath Agent A liquid bath agent was prepared using the β-glucan used in Example 1, and various tests were performed.

Perfume, yellow No.4, POE in order to polyethylene glycol
(20) Sorbitan monolaurate and β-glucan were charged and uniformly dissolved to obtain a bath agent.

(Ii) Characteristics The results of testing various characteristics in the same manner as in Example 1 are shown in Table 1.

As shown in Table 1, the powdered and liquid bath agents of Examples 1 to 6 containing β-glucan were Comparative Examples 1 to 2.
It was excellent in moisturizing properties and highly safe as compared with.

[Effects of the Invention] As described above, the bath preparation of the present invention has no skin irritation and provides an excellent bathing effect, particularly an excellent bath preparation in terms of imparting smoothness to the skin.

[Brief description of the drawings]

FIG. 1 is a diagram showing an infrared absorption spectrum of a polysaccharide used in the present invention.

Continuation of the front page (56) References JP-A-64-63370 (JP, A) JP-A-63-156714 (JP, A) JP-A-3-2202 (JP, A) JP-A-62-205008 (JP) , A) Brian C .; Sutton, "The Coelomycetes Fungi Imperfecti whit Pycnidia Acervulli and Stromata", Commonwealth bycologial, Tn. 294-297 (58) Field surveyed (Int. Cl. ⁶ , DB name) A61K 7/00-7/50 BIOSIS (DIALOG)

Claims (1)

(57) [Claims] 1. A bath preparation comprising a highly viscous β-glucan produced by culturing a microorganism belonging to the genus Macrohomopsis and having the following properties: (A) The bonding mode is such that all the D-glucopyranose residues in the main chain are β-1,3 bonds, and the bond is branched at the C-6 position of the D-glucopyranose residue in the main chain; In addition, there is no β-1,4 bond in the D-glucopyranose residue in the side chain. (B) The molecular weight is about 10 million daltons or more by high performance liquid chromatography using a molecular sieve column. (C) The temperature dependence of viscosity has a constant viscosity between 5 ° C and 85 ° C at a concentration of 0.3% by weight or less, and a constant viscosity between 20 ° C and 85 ° C at a concentration exceeding 0.3% by weight. Having a viscosity of (D) The viscosity is stable even by a 1 kg / cm ² autoclave heating (20 minutes) treatment at 121 ° C.