JPH0144231B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides oils and fats, food and drinks containing oils and fats,
Furthermore, the present invention relates to a fat-soluble natural source antioxidant liquid composition that is useful for preventing oxidation of fats and oils by adding it to health pharmaceuticals, cosmetics, essential oils, and the like. More particularly, the present invention relates to an antioxidant solution comprising at least one C ₆ -C ₁₂ saturated fatty acid triglyceride and a naturally occurring antioxidant component of rosemary and/or sage. Traditionally, synthetic antioxidants such as dibutylhydroxytoluene (BHT), butylhydroxyanisole (BHA), and propyl gallate have been used as antioxidants for oils and fats and oil-containing foods, but in recent years As the safety of antioxidants has become questionable, there has been a desire for highly safe natural antioxidants. Natural vitamin E (tocopherol) is widely used as such an antioxidant.
Other natural sources of antioxidants include, for example, organic solvent extracts of rosemary or sage that are decolorized and concentrated, then dispersed or dissolved in high-boiling oils and fats and then subjected to vacuum steam distillation or molecular distillation. Antioxidant compositions obtained by removing volatile impurities have been proposed (USP 3950266). The antioxidants obtained by this proposal have poor solubility in fats and oils, so it is not possible to obtain compositions with high concentrations, and the disadvantage is that the amount added to the final product, fats and oils or foods containing fats and oils, is large. be. As a proposal to improve these drawbacks, for example, a method for obtaining powdered antioxidant substances by decolorizing and deodorizing polar solvent extracts of herbal spices (Japanese Patent Application Laid-Open No. 1983-1999) has been proposed.
102508), or, for example, a method in which rosemary or sage is treated with hydroalcohol to obtain water-insoluble and water-soluble antioxidant substances separately (Japanese Patent Application Laid-open No. 102508).
55-18435) etc. have been proposed. However, although the antioxidant substances proposed by these proposals have a higher concentration, they still contain large amounts of impurities other than antioxidant substances, so they cannot be directly used in final products such as oil-based foods, such as oils and fats made from animals and plants. kind,
When added to oil- and fat-containing foods, drinks and other foods, medicines, cosmetics, etc., the insoluble portion must be removed, making use complicated and inconvenient. The present inventors have proposed an alternative to these proposals that exhibits even more improved fat solubility and does not require the complicated operation of removing insoluble substances, and that includes oils and fats, oil-containing foods, food and beverages, pharmaceuticals, cosmetics, etc. We conducted research to provide a naturally sourced antioxidant solution that is substantially free of insoluble matter and can be used in a wide variety of fields. As a result, the naturally sourced antioxidant components of rosemary and/or sage are extremely well soluble in a saturated fatty acid triglyceride consisting of at least one type of _C6 to _C12 saturated fatty acid triglyceride or any mixture of these triglycerides, and are insoluble. The present inventors have discovered that it is possible to form a solution containing substantially no components, and that this solution has excellent stability and forms a liquid dosage form with excellent stability without the generation of insoluble components over time. In addition, compared to conventional proposals in which these antioxidant components are dissolved or dispersed in natural edible oils and fats, it is possible to form liquid preparations in which these antioxidant components are dissolved in dramatically higher concentrations, and in addition, it is possible to form liquid preparations in which these antioxidant components are dissolved or dispersed in natural edible oils. It is essentially free from the disadvantages of antioxidant substances, which require complicated operations such as dissolution operations and insoluble matter removal operations, which are essential when added to final products such as oils and fats or foods containing oils and fats. It has been discovered that a lipid-soluble natural source antioxidant solution can be provided. Furthermore, the solvent used in the present invention consisting of _C6 - _C12 saturated fatty acid triglyceride or _C6 - _C12 saturated fatty acid triglyceride and alcohol has excellent oxidative stability compared to general edible fats and oils, It has been found to be extremely advantageous as a solvent for the naturally sourced antioxidant components of Marie and/or Sage. Accordingly, it is an object of the present invention to provide an antioxidant solution containing naturally sourced antioxidant components of rosemary and/or sage that exhibits excellent properties. 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 be done. Examples of materials containing antioxidant components of rosemary and/or sage include dried and pulverized products of rosemary and/or sage; remaining essential oil obtained by subjecting them to steam distillation or other processing to obtain essential oil. Collection residue; these materials can be collected, e.g.
n-pentane, isopentane, petroleum ether, ligroin, n-hexane, methylene chloride,
Ethylene dichloride, ethyl ether, acetone, methyl acetate, ethyl acetate, methanol, ethanol, n-propanol, isopropanol,
Extract with an organic solvent such as n-butanol or a mixture of multiple types of these, remove the solvent from the extract,
For example, oleoresin obtained by distillation under atmospheric pressure to reduced pressure conditions and its extraction residue can be mentioned. 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, an application filed on May 8, 1982 (patent application No. 1983-75988,
(Refer to Japanese Patent Application Laid-open No. 194973). According to the proposed manufacturing 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 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. Examples of natural source antioxidant ingredients obtained by other manufacturing methods include antioxidant ingredients obtained by the manufacturing method disclosed in detail in the title of the invention related to the application filed by the same applicant: "Method for producing natural source antioxidant ingredients": Showa
May 8, 1957 (Japanese Patent Application No. 75989, 1982)
(See Publication No. 194974). According to the production 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 them with a natural resin adsorbent, acidifying the resulting treatment solution, and collecting the solid content formed. 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, examples of antioxidant components obtained by other manufacturing methods include the antioxidant components obtained by the manufacturing method disclosed in detail in the title of the invention related to the application filed by the same applicant: "Method for producing natural source antioxidant components": May 8, 1981 (Patent Application No. 75990, Japanese Patent Application Publication No. 1983)
-Refer to Publication No. 194975). 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, an application in which the natural source antioxidant components of rosemary and/or sage obtained by the manufacturing method disclosed in detail in the title of the invention filed by the same applicant, ``Method for Extracting Natural Source Antioxidant Components,'' can also be used: Showa May 8, 1957 (Japanese Patent Application No. 75991, 1982)
(See Publication No. 194976). 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. In the present invention, the above-mentioned natural antioxidant components of rosemary and/or sage are added to C ₆ to _{C 12}
An antioxidant solution can be prepared by dissolving the antioxidant in at least one saturated fatty acid glyceride. As the C ₆ - _{C 12} saturated fatty acid triglyceride used in the present invention, a coconut oil fraction can be exemplified, but other examples include caproic acid triglyceride, caprylic acid triglyceride, capric acid triglyceride, lauric acid triglyceride, or a mixture of any plurality thereof. can do. Further examples include mixed fatty acid triglycerides of caproic acid, caprylic acid, capric acid, and lauric acid, and particularly preferred examples include mixed fatty acid triglycerides of caprylic acid and capric acid. Saturated fatty acid triglycerides with less than 6 carbon atoms are easily decomposed over time and are unstable, and saturated fatty acid triglycerides with more than 12 carbon atoms are difficult to dissolve the antioxidant substances extracted from rosemary and/or sage. It cannot be adopted for invention. The amount of the _C6 to _C12 saturated fatty acid triglyceride to be used can be selected as appropriate. For example, about 1 to about 100 parts by weight, preferably about 2 parts by weight, per 1 part by weight of solids in the rosemary and/or sage extract.
~50 parts by weight can be exemplified. The antioxidant liquid preparation of the present invention can contain at least one type of alcohol in addition to the above-mentioned C ₆ -C ₁₂ saturated aliphatic triglyceride. Examples of such alcohols include ethanol, propylene glycol, glycerin, and carbitols (e.g., C ₆ to _{C 4} diethylene glycol monoalkyl ether), with ethanol being particularly preferred. . Such alcohols and C ₆ to _{C 12}
Although the mixing ratio of saturated fatty acid triglycerides can be arbitrarily selected, for example, a weight ratio of 1:100 to 20:1 can _be exemplified.
The amount of C ₁₂ saturated fatty acid triglyceride to be used can be selected as appropriate. For example, about 0.1 parts to about 100 parts, preferably about 2 parts to about 50 parts by weight, based on 1 part of the solid content in the extract obtained by extracting rosemary and/or sage with an organic solvent. can do. It consists of at least one C ₆ - _{C 12} saturated fatty acid triglyceride of the present invention and a naturally sourced antioxidant component of rosemary and/or sage, and may further contain at least one alcohol. The natural antioxidant liquid preparation is prepared by dissolving naturally occurring antioxidant components of rosemary and/or sage, which can be obtained as described above, in the above-mentioned specific triglyceride and, if desired, in the triglyceride and alcohol. It can be obtained by At this time, the C ₆ - C ₁₂ saturated fatty acid triglyceride or the C ₆ - _{C 12} saturated fatty acid triglyceride and alcohol may be added after the production of the natural antioxidant ingredient from rosemary and/or sage, or may be added during the production process. It may be added at any stage during the process to form an antioxidant solution. For example, rosemary and/or
Or extract antioxidant components from sage with an organic solvent,
It can be added after solid-liquid separation to remove and concentrate the solvent. Alternatively, after solid-liquid separation, it may be added before or after decolorization treatment and concentrated. Additionally, or after solid-liquid separation, it can be added to the decolorized concentrate for subsequent deodorization. Furthermore, in the present invention, the organic solvent extract of rosemary and/or sage and the _C6 - _C12 saturated fatty acid triglyceride or the _C6 - _C12 saturated fatty acid triglyceride and the alcohol may be mixed under any conditions. For example, it can be carried out at room temperature or
The antioxidant composition can be obtained by stirring at 150° C. for about 1 minute to about 5 hours. Furthermore, after the completion of mixing and stirring, the mixture may be filtered if necessary. The amount of the antioxidant liquid agent of the present invention added to fats and oils or foods containing fats and oils can be selected as appropriate. I can give an example. The naturally sourced antioxidant liquid agent of the present invention, which does not substantially contain insoluble matter, can be added alone to oils and fats or oil-containing foods, but if necessary, it can be added in combination with tocopherols and other known natural antioxidant substances. You can also. Furthermore, citric acid, hydroxy acid, phosphoric acid, known as synergists,
It can also be used in combination with phytic acid and the like. Furthermore, the natural source antioxidant liquid preparation of the present invention may be in the form of an emulsion with natural protective colloids such as gum arabic, starch, gelatin or surfactants, if necessary, in addition to the liquid form. be able to.
Furthermore, a solid dosage form containing the liquid preparation of the present invention may be obtained by subjecting the emulsion to a powder or granulation product by subjecting the emulsion to a method such as spray drying. The antioxidant liquid preparation of the present invention is a natural source that provides excellent antioxidant performance in a wide range of fields of use, such as oils and fats, oil- and fat-containing foods, food and drink products, feed and feed products, health and pharmaceutical products, and cosmetics. Useful as an antioxidant. For example, animal fats such as lard, head, chicken oil, tallow, butterfat, fish oil, liver oil, marine animal oil; safflower oil, soybean oil, corn oil, cottonseed oil,
Vegetable oils such as rapeseed oil, sunflower oil, sesame oil, peanut oil, coconut oil, palm oil, palm kernel oil, olive oil, rice oil; Oil-based foods such as butter, cheese, margarine, corn syrup, mayonnaise, dressing; Fish, meat, ham, etc. Processed foods containing fats and oils such as sausages; Foods containing fats and oils such as instant noodles and fried sweets; Foods such as delicacies, grilled meat sauce, and dried vegetables;
Beverages such as milk drinks, soft drinks, and alcoholic beverages; or antioxidants in health medicines such as tablets, liquid oral medicines, powdered oral medicines, and poultices; and antioxidants in soaps, detergents, and shampoos. It is useful as an antioxidant in cosmetics. EXAMPLES Below, several embodiments of the antioxidant composition of the present invention will be illustrated in more detail with reference to Examples. Example 1 A mixture of 200g sage powder, 16g activated carbon and 1600g 95% ethanol was stirred at about 75-80°C for 2 hours. Next, insoluble solids were separated and removed by centrifugation, and the resulting extract was distilled under normal pressure to remove the solvent, resulting in a colorless antioxidant component concentrate 45
I got g. Next, 100 g of C ₆ - C ₁₂ saturated fatty acid triglyceride was added to this concentrate, stirred for 10 minutes at room temperature,
132 g of antioxidant composition was obtained. (Product of the present invention No. 1) Example 2 500 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 490 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, the water-insoluble solids were collected by paper filtration and vacuum dried at 50-60℃/0.4-0.02mmHg to obtain colorless, tasteless, and odorless antioxidant component concentrate 8.
I got g. 8g of this antioxidant ingredient concentrate contains C ₆ ~
Add 80g of _C12 saturated fatty acid triglyceride, 95~
The antioxidant composition was dissolved by stirring at 97°C for 1 hour.
Obtained 88g. (Product of the present invention No. 2) Example 3 500 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. Then add 10 to this solution
% aqueous sodium hydroxide solution was gradually added at room temperature to make it alkaline, and then 250 g of water was added to adjust the alcohol concentration to about 65% to precipitate the green pigment. Next, the precipitate was removed by filtration to obtain 710 g of a decolorized alkaline hydroalcoholic solution containing an antioxidant component and 1.5 g of a crude green pigment. Next, a porous polymer resin (trade name: Diaion) that has been soaked in approximately 65% hydrous alcohol
The above alkaline water-containing alcohol solution was dropped from the top of a glass column (4 cm in diameter, 20 cm in height) packed with 100 ml of HP-20) to obtain 780 g of a porous polymer resin treatment solution. Next, while stirring the above treatment solution, 9 g of 10% hydrochloric acid was gradually added to adjust the pH to approximately 3.5.
The mixture was stirred at room temperature for 30 minutes to precipitate insoluble antioxidant components. Next, this insoluble solid was filtered through paper, washed with water, and dried under reduced pressure to obtain 6.1 g of a colorless, tasteless, and odorless antioxidant component. Next, the above antioxidant component was added to a mixed solvent of 14 g of 95% alcohol and 40 g of C ₆ - _{C 12} saturated fatty acid triglyceride and heated at 70°C.
The mixture was stirred for 30 minutes to dissolve, and filtered through warm paper to obtain 59 g of an antioxidant composition. (Product of the present invention No. 3) Example 4 1 kg of rosemary powder and 5 kg of 95% ethanol were placed in an autoclave, and heated to 100 to 105°C after replacing with nitrogen.
The mixture was stirred for 1 hour. After cooling, insoluble solids were removed by centrifugation, 200 g of C ₆ - C ₁₂ saturated fatty acid triglyceride was added to the extract, and after stirring at room temperature for 10 minutes, ethanol was distilled off under reduced pressure. 495 g of oxidizing agent composition was obtained. (Product of the present invention No. 4) Reference example 1 Antioxidant compositions obtained in Examples 1 to 4 of the present invention
Nos. 1 to 4 were added to lard, and the antioxidant effects were compared using the AOM method. That is, lard with no antioxidant added was used as a control, and antioxidant composition No. 1 according to the present invention, 0.08% (as an antioxidant concentrate) was added to it.
0.02%); No. 2, 0.2% (same as above 0.02%); No. 3, 0.2
% (0.02% as above); No. 4 and 0.2% (0.02% as above) were added respectively to examine the antioxidant effect. For comparison, a sample containing 0.02% natural tocopherolmics (manufactured by Eisai Co., Ltd., natural vitamin E) was also tested. Weigh 20g of the sample into a test tube, and add 97.8g of the sample to the test tube.
The sample was placed in a constant temperature bath at ℃, and 2.33 ml of cleaned air was passed through it per second, and the time required for the POV (peroxide value) to reach 30 was measured. The results are shown in Table 1. As is clear from the results in Table 1, the antioxidant composition according to the present invention was found to have superior antioxidant effects compared to tocopherols. 【table】

Claims (1)

[Scope of Claims] An antioxidant liquid preparation comprising at least one 1 C ₆ to _{C 12} saturated fatty acid triglyceride and a naturally sourced antioxidant component of rosemary and/or sage. Claim 1, characterized in that the composition comprises at least one type of saturated fatty acid triglyceride of 2 _C6 to _C12 , a naturally sourced antioxidant component of rosemary and/or sage, and at least one type of alcohol. Antioxidant liquid agent.