JPH0583560B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for simply and efficiently producing a substance from licorice that has the effect of suppressing the oxidation of oils and fats and the effect of suppressing the growth of microorganisms. Licorice is a herbal medicine that has been widely used since ancient times, and is currently used as a raw material for food sweeteners, tobacco flavorings, pharmaceuticals, etc. In particular, glycyrrhizin, a sweetening ingredient contained in licorice root, is It has attracted attention as an alternative sweetener in response to bans or regulations on the use of artificial sweeteners such as saccharin, and its usage is increasing. It is also already known that licorice contains antioxidant and antibacterial substances. For example, extracts extracted with water, lower alcohols such as methanol, ethanol, ether or acetone,
There are reports that it has antioxidant or antibacterial properties. However, when water is used as a solvent, both the antioxidant and antibacterial substances are poorly soluble in water, so the antioxidant power or antibacterial power of the obtained extract is extremely low. Furthermore, when lower alcohols or acetone are used as a solvent, the extraction efficiency of both antioxidant and antibacterial substances is good, but since these solvents are highly hydrophilic, in addition to antioxidants and antibacterial substances, they also extract odorous substances. , a large amount of impurities such as black-brown colored substances are extracted at the same time. As a result, when the obtained extract is added to fats and oils at an effective concentration as an antioxidant, problems arise with the color and odor of the fats, and furthermore, the quality of the fats and oils itself is impaired because they contain impurities that are insoluble in the fats. It turns out. Furthermore, if the obtained extract is added to food at an effective concentration as an antibacterial agent, the food will acquire color and odor and lose its value as a food. Thus, in practice it has not been possible to use this extract as an antioxidant or antibacterial agent. In view of the above, the present inventors have investigated a simple and efficient method for extracting antioxidant and antibacterial substances from licorice. It has been found that the simultaneous extraction of impurities as in the case of the present invention is reduced, the color and odor of the extract are improved, and an extract with improved antioxidant and antibacterial properties can be obtained. The present invention involves simultaneous extraction of impurities by extracting licorice or a residue obtained by extracting sweet components from licorice using an aqueous solvent using a ketone having 4 to 8 carbon atoms, preferably 5 to 8 carbon atoms as a solvent. This is a method for producing an antioxidant substance or an antibacterial substance with reduced oxidation and improved efficacy. Examples of the ketone having 4 to 8 carbon atoms used in the present invention include methyl ethyl ketone, methyl-
n-propyl ketone, diethyl ketone, methyl-
Examples include n-butyl ketone, methyl isobutyl ketone, methyl-n-amyl ketone, and ethyl-n-butyl ketone. Extraction using these solvents greatly suppresses the simultaneous extraction of impurities, removes substances that are insoluble in fats and oils, improves coloring and odor problems with fats and oils and foods, and improves efficacy. It can be used as an antioxidant or antibacterial agent. Furthermore, antioxidant substances and antibacterial substances in licorice are different substances, and for example, the purified product obtained by adsorbing and eluting the extract obtained by the present invention on a basic anion exchange resin or porous resin has antibacterial activity. Shows only
The present inventors have also revealed that it exhibits no antioxidant power. However, containing both an antioxidant substance and an antibacterial substance in the same extract makes it possible to apply it to a wide range of foods and has extremely high utility value. The licorice used as a raw material in the present invention may be untreated licorice, but the residue obtained by extracting sweet components such as glycyrrhizin using an aqueous solvent is advantageously used because it has few impurities and is easily available. When the extract containing ketones having 4 to 8 carbon atoms is concentrated to dryness and then ground, it has a high content of antioxidant or antibacterial substances and exhibits a light brown color, but the color and color are different compared to other extracts. A target substance with significantly improved odor is obtained in powder form and can be used as is as an antioxidant or antibacterial agent. The extract obtained according to the present invention has a wide range of applications in foods, and can be added to the following foods, for example. Foods expected to have antioxidant effects, such as animal edible oils and fats such as lard, tallow, and fish oil, vegetable edible oils and fats such as soybean oil, cottonseed oil, safflower oil, rice oil, corn oil, coconut oil, and palm oil, and fried noodles. Foods containing fats and oils such as fried sweets, dried sardines, dressings, butter, margarine, and toning.
Foods that are expected to have antibacterial effects, such as kamaboko, chikuwa, hanpen, fish ham/sausage, surimi,
Marine products such as dried seafood products and smoked fish products, meat products such as ham and sausages, sausages, bacon, and minced meat, noodles such as Chinese noodles, salads, hamburgers, shumai, gyoza, tsukudani,
Deli dishes such as boiled beans and rice cakes. It may also be added to foods that are expected to have both antioxidant and antibacterial effects, such as meat hams and sausages. The appropriate amount of the extract to be added is 0.002 to 0.2%, and preferably 0.005 to 0.1%, no matter which effect is expected. When used in fats and oils, it is preferable to use an appropriate amount dissolved in the fats and oils, and a suitable excipient may be added to form a formulation. When added to foods as an antibacterial substance, it may be formulated as a powder, as an ethanol or propylene glycol solution, or by adding excipients. In addition, by using in combination with a substance that has a shelf life extension effect, the shelf life can be further enhanced. Food preservatives that can be used in combination include, for example, synthetic preservatives (such as sorbic acid), glycine, condensed phosphates, ethyl alcohol, propylene glycol, lysozyme, glycerin fatty acid esters, sucrose fatty acid esters, sodium acetate, and organic acids. , its salt, etc. Example 1 Methyl ethyl ketone 1 was added to 100 g of shredded licorice, heated to 38° C. for 1 hour, and then separated into a liquid layer (2) and a residue. Methyl ethyl ketone 1 was further added to the residue, heated again to 38°C for 1 hour, and separated into a liquid layer (2) and a residue. The liquid layers () and () were combined, concentrated to dryness under reduced pressure, and then ground. Similar operations were performed using methyl isobutyl ketone, diethyl ketone, and ethyl-n-butyl ketone, and as comparative examples, toluene, methanol,
This was done using acetone and ethyl acetate. The yield, odor and color of the resulting extract are shown in Table 1. The color of the solution was determined by the color of an ethanol solution containing 0.1% extract based on the following criteria. ±: Extremely pale yellow +: Light yellow: Light orange: Light brown 〓: Brown The odor of the extract was determined according to the following criteria. +: Slight herbal medicine odor: Herbal medicine odor

[Table] Example 2 Add 500 ml of water to 100 g of shredded licorice, repeat the extraction twice for 3 hours at room temperature, then add 500 ml of methyl isobutyl ketone to the extraction residue, heat it to 40°C for 1 hour, and make a liquid. Separated into layers and residue. The liquid layer was concentrated to dryness under reduced pressure and then ground (No. 9). Furthermore, the liquid temperature
The same operation was performed at 90°C (No. 10). Further, as a comparative example, the same operation was performed using acetone and heating it to 40°C for 1 hour (No. 11). The yield, odor, and color of the resulting extract were evaluated in the same manner as in Example 1. The results are shown in Table 2.

[Table] Test Example 1 (Soybean oil) The extracts obtained in Examples 1 and 2 were added to soybean oil containing no antioxidant at a concentration of 0.05%,
The time required for the peroxide value (POV) to reach 30 was measured using the AOM test method. In addition, the coloring, odor effects, and solubility in fats and oils were observed upon addition. The results are shown in Table 3. In the table, Nos. 1 to 4, No. 9 and 10 represent the present invention, and Nos. 5 to 8 and No. 11 represent comparative examples. The properties upon addition of fats and oils were determined according to the criteria listed below. Colored odor (herbal medicine odor) −: Same as no additive −: Not felt at all ±: Slightly colored ±: Slightly felt +: Colored +: Sensed: Quite colored: Significantly felt: Strongly colored Insoluble material −: None +: Slight precipitation ±: Turbidity occurs ++: Considerable precipitation The overall evaluation was determined based on the results in Tables 1 to 3.

[Table] Test Example 2 (Fried noodles) Chinese noodles were fried for 60 seconds at a temperature of 170±10° C. using commercially available salad oil to which the extracts obtained in Examples 1 and 2 were added. The fried noodles were packaged in a polyethylene bag, stored at 60°C, and the oil was extracted with ethyl ether over time. The peroxide value (POV) of this oil was measured and the number of days required to reach POV30 was determined. For comparison, natural tocopherol and
BHT test plots were also investigated. The results are shown in Table 4.

【table】

[Table] Test Example 3 Each of the obtained extracts was soaked in a paper disk for antibiotic assay (manufactured by Toyo Kagaku Sanyaku) for 50 liters, and then added to a pressure-sterilized Antibiotics Medime-5 agar medium ( 4 x 10 ⁴ spores of Bacillus subtilis IAM-1069 were added to Difco).
ml on a flat plate and heat at 4℃ for 40 minutes.
After cooling for a minute, culturing was carried out at 37°C, and antibacterial activity was assayed by measuring the zone of inhibition. The antibacterial activity of No. 7 acetone extract as a comparative example was set as 100%, and the results of determining the relative activity strength are shown in Table 5.

【table】

[Table] Test Example 4 (Casing Kamaboko) 2.5% salt, 0.8% chemical seasoning, 5% starch, and 10% ice water were added to 4 kg of frozen pollack surimi.
The batter was prepared by cutting with a silent cutter for 10 minutes. Add the additives shown in Table 6 to 2 kg of this battered meat, mix for 5 minutes in a small crusher, and then add polyvinylidene chloride film (folded diameter 48
Approximately 100 g of each sample was filled into a tube (mm) and boiled at 90°C for 30 minutes. After cooling, 10 bottles from each group were stored at 30°C and observed with the inner eye to determine the preservative effect. The following 5-level scoring system was used as the evaluation criteria, and the average score was 1.
The number of days until this point was reached was defined as the effective number of storage days. The color and flavor of the obtained kamaboko were also judged to be good or bad. The results are shown in Table 6.

【table】

【table】

[Table] Test Example 5 (Steamed Chinese noodles) To 500 g of strong flour, add 160 ml of Baume 3-degree water (12.3 ml of Baume 35-degree water, 147.7 ml of water), 4 g of natural pigment (crocin) and a predetermined amount of preservative.
After mixing for a minute, the noodles were made into noodles (4-inch rolling, No. 10 cut), steamed at 100°C for 3 minutes, washed with water, steamed for 3 minutes, and sealed in a sterile bag. Further, secondary heating was performed at 85°C for 30 minutes, and after cooling, the steamed Chinese noodles were sensory evaluated and the preservative effect when stored at 30°C was investigated. A sensory test of the steamed Chinese noodles was conducted by comparing the color tone (yellow tone for Chinese noodles) and flavor (taste and smell) with the additive-free group. As a criterion for the preservative effect, the following 5-level scoring method was used, and the number of days until the average score reached 1 point was taken as the effective storage period. The result is the 7th
Shown in the table.

【table】

[Table] Test Example 6 (Boiled beans) 500g of soybeans were soaked in water overnight, swollen and steamed, then mixed with 20g of kelp, seasoning liquid (75ml of soy sauce, 100g of sugar,
After adding 400 ml of water and a prescribed drug and heating in a pot for 1 hour, the resulting boiled beans were left to cool in the refrigerator overnight. Next, approximately 30 g of the solid material and approximately 20 g of the seasoning liquid were placed in a sterile bag and packaged, and then stored at 30° C., and the number of viable bacteria, mold, and yeast was measured over time to determine the preservative effect. For microbial testing, 10 g of sample was added with 90 ml of sterile physiological saline and passed through a stomacher as the sample stock solution.The number of viable bacteria was determined using a standard agar medium after culturing at 37℃ for 48 hours, and the number of mold and yeast was determined using potato dextrose agar. The measurement was carried out after culturing in a medium at 30°C for 5 days. General viable bacteria count, mold or yeast count
The number of days until reaching ¹⁰⁵ pieces/g was defined as the effective storage period. The results are shown in Table 8.

【table】

Claims (1)

[Scope of Claims] 1. Licorice or a residue obtained by extracting sweet components from licorice using an aqueous solvent, using a ketone having 4 to 8 carbon atoms as a solvent to extract licorice A method for producing antioxidant and antibacterial substances. 2. The method according to claim 1, wherein the solvent is a ketone having 5 to 8 carbon atoms.