JPH046688B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to an improved formulation of an antibacterial substance extracted using an organic solvent from licorice or a residue obtained by extracting sweet components from licorice. Licorice has long been known as a herbal medicine, and is currently mainly used as a raw material for food sweeteners, tobacco flavorings, and pharmaceuticals, with glycyrrhizin, a water-soluble sweetening ingredient, being used in many ways. .
It is also known that licorice contains antibacterial substances in addition to glycyrrhizin. Since this antibacterial substance is sparingly soluble in water, it is difficult to uniformly disperse or dissolve it in food or cosmetics when used as a preservative for food or cosmetics. Therefore, when adding this antibacterial substance during the production of foods, etc., if sufficient attention is not paid to the above points, the expression of the preservative effect will vary. This antibacterial substance is methanol, ethanol,
Since it is relatively well soluble in organic solvents such as acetone and dichloromethane, it is possible to add it by dissolving it in these organic solvents, but these organic solvents may affect the quality of foods and cosmetics. Most organic solvents cannot be used in foods, so they are not practical. In view of the above points, the present inventors conducted research to improve the practicality of antibacterial substances extracted from licorice.
It has been found that an antibacterial preparation with improved solubility can be obtained by using a sucrose fatty acid ester having an HLB of 5 or more. The present invention provides a soluble compound consisting of an antibacterial substance extracted using an organic solvent from licorice or the residue obtained by extracting sweet ingredients from licorice using an aqueous solvent, and a sucrose fatty acid ester with an HLB of 5 or more. It is an improved antibacterial formulation. The antibacterial substance used in the present invention is extracted using an organic solvent from licorice or the residue obtained by extracting sweet components from licorice using an aqueous solvent. Examples of organic solvents include methanol, ethanol, acetone, dichloromethane, 1,2-dichloroethane, chloroform, benzene, toluene,
Examples include xylene, methyl ethyl ketone, methyl isobutyl ketone, and ethyl acetate. Further, a purified product obtained by adsorbing and eluting an antibacterial substance extracted with an organic solvent onto a basic anion exchange resin or a porous resin can also be used in the present invention. The HLB value is generally used to express whether a nonionic surfactant is hydrophilic or lipophilic. It is a fatty acid ester. Examples of the sucrose fatty acid ester include monoesters, diesters, or triesters such as sucrose stearate, sucrose palmitate, sucrose laurate, and sucrose oleate, singly or in mixtures. used as. If a sucrose fatty acid ester with an HLB lower than 5 is used, the solubility of the resulting preparation will be extremely low. In addition to sucrose fatty acid esters, surfactants that are permitted to be added to foods include sorbitan fatty acid esters, glycerin fatty acid esters, propylene glycol fatty acid esters,
Examples include soybean phospholipids. However, little improvement in solubility is observed in formulations using these surfactants. Furthermore, among the glycerin fatty acid esters, polyglycerol esters with high HLB showed a slight solubility improvement effect, but they themselves were paste-like at room temperature, and when processing licorice extract, they did not sufficiently improve solubility. If a rather large amount is used to obtain the desired effect, the resulting preparation does not solidify and remains a viscous oil, making it inconvenient to handle and not dispersible in water at all. In addition to the surfactants mentioned above, there are nonionic hydrophilic interfaces that are not approved for use in food products in Japan, but are widely used in other countries, and are also approved for use in pharmaceutical products in Japan. The active agent, polyoxyethylene sorbitan fatty acid ester, has a fairly high HLB, but it does not show any solubility improvement effect, and since it is also liquid at room temperature, the formulation will not solidify if used in large quantities, and it will hardly dissolve in water. Not dispersed. The reason why the solubility of licorice extract as an antibacterial substance is significantly improved by treatment with sucrose fatty acid ester has not yet been elucidated. When a licorice extract treated with sucrose fatty acid ester or an untreated licorice extract was dropped onto a water droplet placed on a slide glass and observed under a microscope, it was found that crystals were observed in the licorice extract treated with sucrose fatty acid ester. It is observed that the crystals break down into fine particles, whereas in unprocessed licorice extract, the crystals aggregate together,
It doesn't seem to be used to water. This probably suggests that the hydrophobic surface of the licorice extract becomes more compatible with water due to the treatment with the highly hydrophilic sucrose fatty acid ester, and that some of the licorice extract is also absorbed into the micelles of the sucrose fatty acid ester. It is thought that the solubility was improved by dissolving into the The preparation of the present invention is obtained by mixing an antibacterial substance extracted from licorice and a sucrose fatty acid ester having an HLB of 5 or more. Although the mixing method is not particularly limited, it is preferable to mix the licorice extract and the sugar fatty acid ester as homogeneously as possible. For example, the two substances can be mixed in a blender after being made into fine particles separately, the two substances can be ground and mixed at the same time using a ball mill, etc., the two substances can be dissolved in a solvent such as alcohol or acetone, and the solvent can be removed. Examples include a method in which both substances are precipitated by distillation, and then crushed or ground, and a method in which a fine powder of licorice extract is fluidized, a sugar fatty acid ester solution is sprayed onto it, and then dried. It will be done.
A preferred method is to dissolve both substances in a solvent, distill off the solvent to precipitate both substances, and then pulverize or grind the precipitate, since the operation is simple and in particular a homogeneous preparation of both substances can be obtained. After dissolving the sugar fatty acid ester in the organic solvent extract of licorice, the solvent may be distilled off. The amount of sucrose fatty acid ester used is 0.1 to 4 parts by weight, preferably 0.25 to 2 parts by weight, per 1 part by weight of licorice extract (antibacterial substance). When the amount of sucrose fatty acid ester is less than 0.1 part by weight, the solubility is better than that of untreated licorice extract, but it is not sufficient. As the amount of sucrose fatty acid ester increases, the solubility tends to improve, but the hygroscopicity of the prepared formulation increases, and moreover, the antibacterial activity of the licorice extract tends to decrease. In particular, if it exceeds 5 parts by weight, the antibacterial activity decreases significantly. The preparation of the present invention is added to foods alone or in the form of a combination preparation with other additives. This preparation is added directly to general foods as a powder, but
When brine is used, such as in the case of Chinese noodles, the present preparation may be added to the brine, dispersed and dissolved, and added to the flour. The preparation added in this manner exhibits extremely high solubility, dissolves rapidly in foods, and effectively exhibits the preservative effect of the antibacterial substance extracted from licorice. Experimental Example 1 10g of powdered licorice extract prepared by extraction using dichloromethane from the water-extracted residue of licorice and the first
1 g of the surfactant shown in the table was dissolved in 200 ml of ethanol or dichloromethane by heating, and the solvent was slowly distilled off using a rotary evaporator. After sufficiently removing the solvent in a vacuum desiccator, the residue was scraped off, thoroughly ground in an agate mortar, and passed through a 100-mesh sieve to obtain a fine powder preparation. 33 mg of this preparation was weighed out and stirred at a constant speed at 30°C.
(100ppm as licorice extract) to 300ml of water,
After continuing to stir for 10 minutes, the mixture was filtered by suction using a Millipore filter with a pore size of 0.2 μm. 50 ml of the liquid was taken, and after adjusting the pH of the liquid to around 3 with 1N HCl, it was transferred to a separating funnel and extracted twice with 80 ml of dichloromethane. The extracts were collected, dichloromethane was added to bring the total volume to 200 ml, and diluted appropriately, the absorbance at 270 nm was measured, and the solubility of the licorice extract was determined using a calibration curve. The state of dispersion in water when the formulation was added to water was also observed. The results are shown in Table 1. Sorbitan fatty acid ester has no solubility improvement effect, and polyoxyethylene sorbitan fatty acid ester has a slight improvement effect, but
It is smaller than sucrose fatty acid ester. Improvement effects are also observed with polyglycerol fatty acid esters. Attempts were made to prepare formulations by increasing the amount of surfactant used; None of them solidified at 0.5 parts by weight per 1 part by weight of licorice extract.

[Table] Experimental Example 2 10g of powdered licorice extract extracted directly from licorice using benzene and HLB shown in Table 2
Noshiyose sugar fatty acid ester (manufactured by Mitsubishi Kasei Foods Co., Ltd.) 5
g was dissolved in 200 ml of ethanol by heating, and the solvent was slowly distilled off using a rotary evaporator.
Thereafter, a preparation was prepared in the same manner as in Experimental Example 1. Next, 10g of the same licorice extract is shown in Table 2.
The mixture was placed in a ball mill with 5 g of HLB sucrose fatty acid ester, mixed for 1 hour, and passed through a 100 mesh sieve to obtain a fine powder mixture. These formulations were tested for solubility in water at 30°C. The state of dispersion in water when the formulation was added to water was also observed. The results are shown in Table 2.

[Table] Experimental Example 3 Powdered licorice extract extracted from the water-extracted residue of licorice using acetone and HLB14-15 sucrose fatty acid ester P-1570 (manufactured by Mitsubishi Kasei Foods Co., Ltd.) The amount shown in the table was added to 200 ml of ethanol and dissolved, and the ethanol was slowly distilled off using a rotary evaporator. Hereinafter, Example 1
A formulation was prepared in the same manner as above, and its solubility in water at 30°C was tested. The state of dispersion in water was also observed. The formulation contains 100ppm of licorice extract.
Added to water so that The results are shown in Table 3. The solubility increases as the amount of sucrose fatty acid ester used increases. Although the solubility is improved by using 0.05 parts by weight of sucrose fatty acid ester per 1 part by weight of licorice extract, it is not sufficient.

【table】

[Table] Experimental example 4 Bacillus subtilis spores were used as the test bacteria.
The antibacterial activity of the preparation obtained in Experimental Example 3 was measured. Dissolve the untreated licorice extract or preparation in ethanol to prepare a 5000 ppm solution of licorice extract. Dilute this solution with ethanol to 500~
Make a solution of 5000 ppm licorice extract. After sterilizing 98ml of ordinary agar medium (PH7.0) using the usual method,
Cool to 50-60°C, add 1 ml of ethanol solution of licorice extract and 1 ml of Bacillus subtilis spore solution at 2 x 10 ⁶ cells/ml, mix well, and dispense 15-20 ml each into sterilized chalets. Solidified. This was cultured at 37°C for 2 days, and the presence or absence of bacterial growth was observed to determine the minimum growth inhibitory concentration. The result is the fourth
Shown in the table. As the amount of sucrose fatty acid ester used increases, the antibacterial activity of the licorice extract decreases. In particular, if 5 parts by weight or more of sucrose fatty acid ester is used per 1 part by weight of licorice extract, the reduction is remarkable.

[Table] As a result of the above comparative experiments, the conditions of the present invention were selected. Example 1 8 kg of frozen pollack surimi, 2.5% salt,
0.8% chemical seasoning, 5% starch, and 10% ice water were added, and the mixture was cut with a silent cutter for 10 minutes to prepare batter. Add untreated licorice extract, ethanol solution of licorice extract, or the preparation prepared in Experimental Example 3 to 1 kg of this batter as 0.02 licorice extract.
% and mixed for 5 minutes in a small sieve machine.
About 100 g each was filled into a tube (mm) and boiled at 90°C for 30 minutes. After cooling, 10 bottles per test group were stored at 30°C, and the preservative effect was determined by visually observing the storage stability. The following 5-level scoring system was used as the judgment criteria,
The time required to reach 1 point as an average score was defined as the effective storage days. Immediately after production, the product was cut into rings and the state of the cross section was observed to determine whether licorice extract remained in the form of spots. The results are shown in Table 5.

【table】

[Table] Example 2 4 g of natural pigment (crocin) and the chemicals shown in Table 6 were added to 160 ml of Baume 3 degree sprinkling water (12.3 ml of Baume 35 degree water and 147.7 ml of water) and dispersed and dissolved. Add to 500g of strong flour, knead for 5 minutes in a kneader, make noodles (roll 4 inches, cut out No. 10), steam for 3 minutes at 100℃, wash with water, steam again for 3 minutes, and then put about 40g in a sterile plastic bag. Each was enclosed. This was then subjected to secondary heating at 85°C for 30 minutes, and after cooling, 10 bags were selected and stored at 30°C to examine their preservative effect. The following 5-level scoring method was used as the criterion for determining the preservative effect, and the time required to reach 1 point as the average score was defined as the number of effective storage days. The results are shown in Table 6. The licorice extract used was obtained by extracting the water-extracted residue of licorice with acetone.

【table】

【table】

【table】

[Table] Addition amount: % of wheat flour
SE: Shisucrose fatty acid ester

Claims (1)

[Claims] 1. A product with improved solubility consisting of an antibacterial substance extracted using an organic solvent from licorice or the residue obtained by extracting sweet ingredients from licorice using an aqueous solvent, and a sucrose fatty acid ester with an HLB of 5 or more. Antibacterial preparations.