JPH0144233B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention aims to solve the problems caused by oxidation of foods and beverages (a term that includes luxury goods), pharmaceuticals, and cosmetics that contain easily oxidized components such as oily substances and aromatic substances. The present invention relates to safe complex antioxidants of natural sources suitable for effectively preventing deterioration and changes. More specifically, the present invention provides rosemary and/or
Alternatively, the present invention relates to a composite antioxidant characterized by containing a naturally sourced antioxidant component of sage and an organic solvent extract of tempeh (fermented soybean food) as active ingredients. Conventional oils and fats, aroma components, and other antioxidants include butylated hydroxyanisole (BHA), dibutylated hydroxytoluene (BHT),
Synthetic antioxidants such as nordihydroguaiaretic acid (NDGA) and gallic acid esters have been used, but their safety has been questioned in recent years, and safer natural sources are being sought instead. Various antioxidants have been studied. Uses of such naturally sourced antioxidants include, for example, natural vitamin E,
A number of proposals have been made, including the use of γ-oryzanol, rutin, quercetin, sezamol, sezamorin, gallic acid, and herbal spice extracts, and some of these have already been put into practical use. However, the above-mentioned naturally sourced antioxidants are not necessarily satisfactory in terms of economy, supply stability, and antioxidant effect. The present inventors have conducted various studies on excellent natural antioxidant substances, and have already established a method for producing natural antioxidant ingredients using sage and/or rosemary as raw materials, which are highly safe and have excellent antioxidant properties. made several proposals regarding the
-75989, patent application 1986-75990, patent application 1982-75991).
The present inventors have conducted extensive research into the development of naturally sourced antioxidants that can further improve the effects of the antioxidants obtained through the above proposal, and have found that the naturally sourced antioxidants of rosemary and/or sage and fermented It was discovered that by using both organic solvent extracts of tempeh, a type of soybean food, a significantly superior antioxidant effect that could not be expected from the effects of using each alone was demonstrated. did. It is already known that tempeh has antioxidant properties [Nature, 203, 870 (1964); Journal of
Food Science, Vol. 36, 798 (1971)]. However, the content of isoflavone compounds, which are considered to be antioxidant substances in tempeh, is small, and furthermore, tempeh extract alone has weak antioxidant power. Since it is necessary to add an extract of The present inventors have conducted various studies on complementary agents for the naturally sourced antioxidant components of rosemary and/or sage, and have found that the tempeh extract itself does not
It has been discovered that although it has no practical antioxidant power, it acts extremely effectively as a compensating agent for the antioxidant component. Therefore, an object of the present invention is to provide a composite antioxidant that is effective in preventing deterioration of oils and fats, aroma components, and other substances. The above objects and many other objects and advantages of the present invention will become more apparent from the following description. The naturally sourced antioxidant components of rosemary and/or sage used in the present invention can be collected from various antioxidant component-containing materials using solvent extraction treatment, adsorbent treatment, distillation treatment, or other separation unit means. can. Antioxidant component-containing materials of rosemary and/or sage that can be used in the present invention include:
For example, dried or pulverized products of rosemary and/or sage; residues from extracting essential oils by subjecting them to steam distillation or other treatments; Extraction with organic solvents such as , ligroin, n-hexane, methylene chloride, ethylene dichloride, ethyl ether, acetone, methyl acetate, ethyl acetate, methanol, ethanol, n-propanol, isopropanol, n-butanol, and mixtures of multiple types of these. death,
Examples include oleoresin and its extraction residue obtained by removing the solvent from the extract and distilling it off under, for example, atmospheric pressure or reduced pressure conditions. Naturally sourced antioxidant components of rosemary and/or sage can be obtained, for example, as an extract obtained by extracting the antioxidant component-containing material as exemplified above with an organic solvent, and further subjected to decolorization treatment, deodorization treatment, etc. be able to. Examples of organic solvents used in the above extraction process include:
For example, polar solvents such as methanol, ethanol, n-propyl alcohol, isopropyl alcohol, acetone, propylene glycol, glycerin, ethyl acetate, or, for example, n-pentane, n-hexane, cyclohexane, petroleum ether, ligroin, carbon tetrachloride, Examples include non-polar solvents such as methylene chloride, ethylene dichloride, benzene, toluene, etc., or mixtures of a plurality of these solvents, but extraction with ethanol is particularly preferred. Furthermore, the above-mentioned polar solvents can also be used in the form of a hydrous system, for example a hydrous solvent with a water content of about 10 to about 50%. Various extraction operations and extraction conditions can be selected, but for example, about 0.2 to about 50 times the weight of a polar solvent or a non-polar solvent is added to a material containing antioxidant components such as rosemary and/or sage, and the temperature ranges from room temperature to the boiling point temperature of the solvent used. For example, it can be left standing or stirred for about 5 minutes to about 24 hours. The extraction process can be carried out either batchwise or continuously. For example, an extraction column is packed with a material containing antioxidant components, such as crushed rosemary and/or sage, or crushed or shredded essential oil extraction residue. An example is a column extraction method in which an organic solvent such as an alcohol is continuously introduced into the column from the upper or lower part of the column for column extraction. After performing the extraction operation in this manner, insoluble solid residues are removed using, for example, centrifugation, filtration, compression, or other solid-liquid separation means.
An extract containing naturally occurring antioxidant components of rosemary and/or sage can be obtained. If necessary, a polar solvent or a non-polar solvent may be further added to the insoluble solid content extraction residue and the same operation may be repeated for extraction. In the present invention, a concentrated extract containing natural antioxidant components of rosemary and/or sage obtained by concentrating the extract obtained from rosemary and/or sage by the method as exemplified above and removing the solvent is used. can use things. Further, the extract obtained by the above method is desirably decolorized using an adsorbent such as activated carbon, activated alumina, silica gel, bentonite, acid clay, or diatomaceous earth, and then concentrated. Furthermore, the concentrate obtained by the above method may be deodorized by steam distillation or other means before use. The natural antioxidant components of rosemary and/or sage used in the present invention can be extracted and collected from the antioxidant component-containing material as described above. It is preferable to use an antioxidant component obtained using a method for producing an odorless rosemary and/or sage antioxidant component. For example, the title of the invention related to the application filed by the same applicant is “Process for producing natural source antioxidant ingredients” (Patent Application No. 75988-1988).
Antioxidant components obtained by the manufacturing method disclosed in detail in . According to the proposed production method, for example, a material containing antioxidant components of rosemary and/or sage selected from rosemary and/or sage, its essential oil extraction residue, and its oleoresin is extracted with alcohol. or a solution obtained by removing the organic solvent from the extract obtained by extracting the material with an organic solvent other than alcohol, and dissolving this in alcohol; rosemary and/or as exemplified above. By treating an alcoholic solution containing antioxidant components of sage with a solid adsorbent and a cation exchange resin, it is possible to obtain naturally sourced antioxidant components of rosemary and/or sage of excellent quality. As a natural source antioxidant ingredient obtained by another manufacturing method, an antioxidant obtained by a manufacturing method disclosed in detail in the title of the invention related to the application filed by the same applicant, ``Method for producing a natural source antioxidant ingredient'' (Japanese Patent Application No. 75989/1989). Oxidizing components can be mentioned. According to the manufacturing method of this proposal, an alcoholic solution containing antioxidant components of rosemary and/or sage similar to those exemplified in the previous proposal is made into an alkaline hydroalcoholic solution with an alcohol concentration of about 80% by weight or less, and the solution is made into a porous Excellent quality naturally sourced antioxidant components of rosemary and/or sage can be obtained by treating the rosemary and/or sage with a natural resin adsorbent, acidifying the resulting treatment solution, and collecting the solid content. can. In this production method, the antioxidant component-containing alcoholic solution can be treated with a solid adsorbent and/or with a cation exchange resin before being made into the alkaline hydrous alcoholic solution. Furthermore, as an antioxidant component obtained by another manufacturing method, there is an antioxidant component obtained by a manufacturing method disclosed in detail in the title of the invention related to the application filed by the same applicant, "Method for manufacturing natural source antioxidant components" (Japanese Patent Application No. 75990/1983). Oxidizing components can be mentioned. According to the proposed manufacturing method, the antioxidant of rosemary and/or sage, such as a material containing an antioxidant component of rosemary and/or sage, selected from rosemary and/or sage, its essential oil extraction residue, and its oleoresin. Naturally sourced antioxidant components of excellent quality can be obtained by extracting the oxidized component-containing material with an organic solvent such as those already exemplified in the presence of a solid adsorbent. In this embodiment, an alcohol is used as the organic solvent, and the treatment liquid obtained by extraction with the alcohol can be treated with a cation exchange resin. Furthermore, the title of the invention related to the application filed by the same applicant is “Method for Extracting Natural Source Antioxidant Components” (Patent Application No. 57-75991).
Naturally sourced antioxidant components of rosemary and/or sage obtained by the process disclosed in detail in 2003, No. According to this proposed manufacturing method, rosemary and/or
Or, by subjecting the sage antioxidant component-containing material to an organic solvent extraction treatment as already exemplified at about 90°C to about 180°C under pressurized conditions and collecting the treated liquid,
High quality natural source antioxidant ingredients can be obtained. The organic solvent can be a polar organic solvent or a water-containing product thereof as already exemplified, and
The extraction process can be performed under an inert gas atmosphere. Furthermore, natural source antioxidant ingredients of rosemary and/or sage obtained by the manufacturing method detailed in the patent application entitled "Antioxidant Liquid Agent" (Japanese Patent Application No. 57-91281) filed by the same applicant, Antioxidant solutions obtained by dissolving in at least one of C ₆ to _{C 12} saturated fatty acid glycerides can also be used. According to this proposal, inventions related to the same applicant as mentioned above (Japanese Patent Application Nos. 57-075988, 57-075989,
57-075990, 57-075991) is dissolved in a C ₆ - _{C 12} saturated fatty acid triglyceride or a mixture of the triglyceride and alcohol. By doing so, it is possible to obtain a liquid preparation in which the naturally sourced antioxidant component is dissolved at a high concentration. Furthermore, the organic solvent extract of tempeh used in the present invention can be obtained, for example, by extracting tempeh, which is known as the most important fermented soybean food in Southeast Asia, especially Indonesia, with an organic solvent. can. Such tempeh is available on the market and furthermore,
For example, black soybeans, yellow soybeans, etc. are soaked in water overnight, their skins are removed, and then vapor-deposited, drained, spread, and cooled.
oligosporus (NRRL2710, IFO8631,
ATCC22959), R.oryzae (ATCC8466), R.
arrhizus (IFO5780), R. stolonifer (AHU6529)
Inoculated with bacteria such as
It can be obtained by fermentation for about 10 days. In the present invention, the tempeh obtained as described above can be used as it is as an extraction raw material, or the tempeh can be dried in the form of a dried product by an appropriate drying method such as sky drying or aerated drying. It can also be used. Examples of the organic solvent for extracting the tempeh include the polar solvent or non-polar solvent used to extract the antioxidant components of the rosemary and/or sage;
Furthermore, mixtures of these can be exemplified,
Particularly preferred examples include polar solvents such as ethanol, methanol, and acetone. In addition, the extraction operation and extraction conditions can be carried out under exactly the same conditions as the above-mentioned method for extracting the natural source antioxidant components of rosemary and/or sage, and after extraction, the solvent can be removed to obtain a concentrate. . Further, the organic solvent extract of tempeh can be subjected to decolorization and deodorization treatment by adsorbent treatment or steam distillation, if necessary, at any stage of the extraction process. The composite antioxidant of the present invention contains natural antioxidant components of rosemary and/or sage and an organic solvent extract of tempeh as active ingredients. The blending ratio of the two components can be arbitrarily selected, for example, a blending ratio of about 1:20 to about 10:1, preferably about 1:10 to about 5:1.
1 can be exemplified. The composite antioxidant of the present invention can be in the form of a mixture in which the antioxidant components of rosemary and/or sage and the organic solvent extract of tempeh are mixed in advance, or both can be separately mixed in the above-mentioned ratio for the purpose. It can also be added to a substance to form a composite antioxidant on the spot in the substance to be added. Furthermore, the composite antioxidant of the present invention may be used in the form of a liquid dissolved in alcohols, fats and oils, etc., if desired, or an emulsion obtained by emulsifying this with a thickening agent such as gum arabic, dextrin, gelatin, etc. Alternatively, the emulsion can be used in the form of powder or granules by spray drying or the like. The composite antioxidant of the present invention can be added to foods, drinks, pharmaceuticals, cosmetics, etc. that contain substances that are susceptible to deterioration or deterioration, such as oily substances or aromatic substances, to achieve excellent antioxidant effects. Can be done. The timing of addition of the antioxidant can be selected as appropriate, and it can be added at any time during or after the manufacturing process of foods, drinks, pharmaceuticals, cosmetics, etc. Examples of food/drinks, pharmaceuticals, and cosmetics containing easily oxidizable substances such as the above-mentioned oily substances and aromatic substances include the following food/drinks, pharmaceuticals, and cosmetics. For example, animal fats and oils such as lard, head, chicken oil, tallow, milk fat, fish oil, liver oil, safflower oil, soybean oil, corn oil, rapeseed oil, sesame oil,
Vegetable oils and fats such as coconut oil, cottonseed oil, sunflower oil, peanut oil, palm oil, palm kernel oil, coffee oil, rice oil; Oil-based foods such as butter, cheese, margarine, corn syrup, mayonnaise, dressing, etc.; Ham Processed meat foods such as sausages, bacon, corned beef, and canned meat; Processed seafood foods such as kamaboko, hanpen, fish sausage, and dried fish; Other processed foods such as fried noodles, fried sweets, yakiniku sauce, milk drinks, soft drinks, etc. Food and beverages; Japanese and Western confectionery;
Candy products, various desserts, confectionery products such as chewing gum, chiyocolate, and kutsky; Or pharmaceutical products such as tablets, liquid and powder oral preparations, patches, and oral preparations; Perfumes, colognes, creams, lotions, lipsticks, and pomades. It can be used in a wide range of fields, such as cosmetics such as hair liquids, hair creams, hair sprays, shampoos, soaps and detergents; natural essential oils such as lemon oil, lime oil and grapefruit oil; The composite antioxidant of the present invention includes rosemary and/or
Alternatively, it contains a naturally sourced antioxidant component of sage and an organic solvent extract of tempeh as active ingredients, but if desired, other additives can be added and used in combination. Such additives include naturally occurring antioxidants such as vitamin E, oryzanol, phytic acid, lecithin and rutin, flavonoids such as quercetin, naringenin, gossypetin, mixtures thereof; synergists such as citric acid, L- ascorbic acid, and glycine, alanine, serine,
Valine, leucine, threonine, isoleucine,
Examples include amino acids such as methionine, tryptophan, histidine, lysine, arginine, glutamic acid, and aspartic acid, and mixtures thereof. The amount of the composite antioxidant of the present invention to be added to the above-mentioned foods and drinks, medicines, and cosmetics is sufficient in a relatively small amount, and can be appropriately selected.
For example, an amount of about 0.0001 to about 5% by weight can be added to foods, drinks, pharmaceuticals, cosmetics, etc. that contain substances that easily deteriorate or deteriorate, such as oily substances and aromatic substances, and more preferably. An example of the amount added is about 0.01 to about 2% by weight. The composite antioxidant of the present invention will be explained in more detail with reference to Examples below. Reference Example 1 500 g of 95% ethanol was added to 100 g of sage powder, and the mixture was stirred at about 75° C. for 2 hours. Next, insoluble solids were separated and removed by centrifugation to obtain an alcoholic solution containing antioxidant components. Next, 5 g of activated carbon was added to this solution, stirred at room temperature for about 30 minutes, and then filtered through paper.Then, the resulting activated carbon treatment solution was filled with 200 ml of a strongly acidic cation exchange resin (trade name Dowex 50W) soaked in ethanol in advance. The solution was dropped from the top of a glass column (4 cm in diameter, 20 cm in height) to obtain 510 g of an ion exchange resin treatment solution. Next, the above treated solution was concentrated to about 50g at about 80℃ under normal pressure, and 300g of hot water at about 85℃ to 90℃ was added to it for 10 minutes.
After mixing and stirring for a minute, filter through paper to collect water-insoluble solids, and vacuum dry at 50-60℃/0.4-0.02mmHg to obtain a colorless, tasteless, and odorless antioxidant component concentrate (A).
7.5g was obtained. Reference Example 2 After washing 200 g of soybeans with water, they were soaked in water overnight.
After removing the skin, it was cut in half and steamed for 30 minutes.
After the water was thoroughly drained and the mixture was spread on a paper towel and allowed to cool, freeze-dried spores of Rhiopus oligosporus (ATCC22959) were sprinkled on the mixture and thoroughly mixed. The inoculated beans were packed into an aluminum tray (height 2 cm) in which holes (approximately 0.6 mm in diameter) were made with a needle at 1 cm intervals, and the surface was covered with a wrap that also had holes made in the same way. After culturing in a 30°C incubator for 6 days, the cells were freeze-dried. The obtained dried tempeh was pulverized, 500 g of ethanol was added to 100 g of the pulverized material, and the mixture was stirred and extracted at 50° C. for 1 hour, followed by solid-liquid separation. Ethanol was distilled off from the separated liquid under reduced pressure to obtain 20 g of tempeh extract (B). Example 1 The anti-acid component of sage obtained in Reference Example 1 (A) and the tempeh extract obtained in Reference Example 2 (B) were added to lard, and the mixture was purified at 2.33 ml per second at 97.8°C using the AOM method. By blowing air, the peroxide value (POV)
The time taken to reach 30meq/Kg was measured. For comparison, a similar test was conducted on natural vitamin E (manufactured by Eisai Co., Ltd.). The mutual effect of the antioxidant components of sage and tempeh extract was evaluated using the following method. Let the time (hr) extended compared to the non-additive control group (control) at each addition rate of sage antioxidant component, tempeh extract, and a mixture of both be [S], [T], and [S + T], respectively. , [S+T]/[S]+[T]×100 (%) as a mutual effect. The results are shown in Table 1. The product of the present invention showed a significant synergistic effect compared to when the sage antioxidant component and tempeh extract were used alone. 【table】

Claims (1)

[Claims] 1. A composite antioxidant characterized by containing a natural source antioxidant component of rosemary and/or sage and an organic solvent extract of tempeh as active ingredients.