JPH0216794B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for producing a naturally sourced antioxidant component that exhibits excellent antioxidant properties when added to fats and oils or foods containing fats and oils. More specifically, an alcoholic solution containing antioxidant components of rosemary and/or sage is made into an alkaline hydroalcoholic solution with an alcohol concentration of about 80% by weight or less, and the solution is treated with a porous resin adsorbent, and the resulting treatment is The present invention relates to a method for producing naturally sourced antioxidant ingredients, which comprises making a liquid acidic and collecting the solid content formed. It has been known that herbal spices have an antioxidant effect on oils and fats, and many research reports have been made on rosemary and sage, which have particularly strong antioxidant properties. For example, when rosemary and sage powders, petroleum ether extracts of the powders, and ethanol extracts of the petroleum ether extraction residues were added to lard, remarkable antioxidant properties were observed for both [Food Res 17 , 46 (1952)], and when rosemary or sage is extracted with water or ethanol, the ethanol extract exhibits excellent antioxidant properties against lard, which is also found in spices. It is said that most of the antioxidant components are extracted by ethanol [Nutrition and Food 27 , (4), 181 (1974)]. However, oleoresins obtained by extracts obtained by the above methods, or by removing the solvent from the extract after extraction with an organic solvent such as hexane, acetone, methanol, ethanol, methylene chloride, or ethylene dichloride, Alternatively, essential oils obtained by means such as steam distillation have the characteristic flavor of spices derived from the raw materials rosemary and/or sage, so if they are added to foods and drinks for the purpose of preventing oxidation, It has a negative effect on the flavor of food and drinks. Therefore, the amount added is severely limited, resulting in insufficient antioxidant effects on the food and drink. In order to improve these drawbacks, various methods have been proposed for removing flavor components and color components from solvent extracts of rosemary or sage. For example, there is a method in which antioxidant substances are extracted by treating plants of the Lamiaceae family or Apiaceae family with a basic aqueous solution with a pH of 7 to 10 (Japanese Patent Publication No. 53-9395), or rosemary and/or sage is treated with a 40 to 60% concentration of rosemary and/or sage. Antioxidant components are extracted by treatment with aqueous methanol or aqueous ethanol, then water is added to the resulting extract to precipitate water-insoluble antioxidant components, and activated carbon is added and stirred, followed by filtration. A mixture of water-insoluble antioxidant components and activated carbon is obtained, this mixture is treated with methanol or ethanol to extract water-insoluble antioxidant components, and the solvent is distilled off from this extract to extract water-insoluble components. A method of obtaining a water-soluble antioxidant by obtaining an antioxidant component concentrate and, on the other hand, distilling off the solvent from the liquid obtained by passing through the mixture of the water-insoluble antioxidant component and activated carbon. JP-A-55-18435) has been proposed, but the antioxidant substances obtained by either method have a flavor characteristic of spices, and are not completely satisfactory. In order to further improve these drawbacks, various attempts have been made to add a deodorizing step to obtain tasteless and odorless antioxidant substances. For example, rosemary or sage powder is extracted with a low-boiling organic solvent, the resulting extract is concentrated, the concentrate is washed with hot water, and then the concentrate is dissolved in a low-boiling solvent such as methanol. An adsorbent such as activated carbon, activated clay, or silicic acid is added to the solution to decolorize it, and then the treated solution is concentrated, the resulting concentrate is dissolved or suspended in oils and fats, etc., and this is subjected to steam distillation or molecular A method for producing a tasteless and odorless antioxidant substance by removing aroma components through distillation treatment [USP. 3950266 (1976)], or by adding powdered rosemary, sage, or basil together with animal or vegetable oils. After heating at 80 to 180°C for about 30 minutes to 3 hours, insoluble solids are removed, and the obtained animal and vegetable oil layer is heated under reduced pressure at about 120 to 220°C for about 10 to 60 minutes to distill off aroma components. [USP. 3732111 (1973)], and furthermore, a method for producing antioxidant substances by adding distillation media such as monoglycerides and fats and oils to crushed plant materials containing oxidation inhibitors or low-boiling solvent extracts thereof. , a method for molecular distillation and collection of the distillation medium containing oxidation-inhibiting substances
48281), raw materials such as herbal spices, their essential oil collection residues, oleoresins obtained by organic solvent extraction, or oleoresin extraction residues are extracted with a polar solvent such as ethanol to obtain an extract. Decolorization treatment is performed by adding an adsorbent such as activated carbon, diatomaceous earth, or acid clay, and then the solution portion obtained by separating this adsorbent is concentrated and then subjected to steam distillation treatment, and the insoluble portion in the steam distillation residue is collected. A method for producing a preservative (Japanese Unexamined Patent Publication No. 55-102508), raw materials such as herbal spices, their essential oil extraction residues, and oleoresin of herbal spices are mixed with a polar solvent and a non-polar solvent (volume ratio: 2: 98 to 50:50), the resulting extract is decolorized by adding an adsorbent such as activated carbon, diatomaceous earth, or acid clay, and then water is added to the solution obtained by separating this adsorbent to decolorize it. After separating into three layers: a polar solvent layer, a water-containing polar solvent layer, and a precipitate layer, an antioxidant substance is collected from each layer, and if necessary, steam distillation is performed to produce a preservative.
56-144078) and many other proposals have been made. However, all of the above methods are complicated for industrial production, and the antioxidant substances obtained by such methods are still unsatisfactory in terms of flavor. The present inventors have decolorized an alcoholic solution of anti-acid components of rosemary and/or sage by converting it into an alkaline hydroalcoholic solution with an alcohol concentration of approximately 80% by weight or less, and precipitating the pigment component. Then, by treating the solution with a porous styrene resin adsorbent, the aroma components can be removed, and by making the resulting treated solution acidic, a colorless, tasteless, and odorless naturally sourced antioxidant component can be obtained. They have discovered that it is possible to do this, and have completed the present invention. Therefore, it is an object of the present invention to produce colorless, tasteless, odorless, and highly antioxidant naturally-sourced antioxidants in a high yield and industrially advantageously from rosemary and/or sage antioxidant-containing materials. To provide a method for manufacturing. The above objects and many other objects and advantages of the present invention will become more apparent from the following description. The rosemary and/or sage antioxidant component-containing alcoholic solution used in the present invention can be obtained by extracting the rosemary and/or sage antioxidant component-containing material with alcohol. Examples of the rosemary and/or sage antioxidant component-containing materials include rosemary and/or sage.
or finely ground sage; residual essential oil extraction residue obtained by steam distilling the spice to obtain essential oil; or these materials can be processed into n-pentane, isopentane,
Extract with an organic solvent such as n-hexane, petroleum ether, ligroin, acetone, methyl acetate, ethyl acetate, methanol, ethanol, n-propanol, isopropanol, n-butanol, or a mixture of these, and remove the solvent from the extract. A preferred example is an oleoresin obtained by removing the oleoresin. Examples of alcohols used for extracting the rosemary and/or sage antioxidant component-containing material include methanol, ethanol, propanol, isopropanol, propylene glycol, glycerin, and multiple types of these alcohols. Examples include mixtures thereof and water-containing products thereof, with ethanol being particularly preferred. Extraction conditions for treating the above-mentioned rosemary and/or sage antioxidant component-containing material with alcohol can be selected as appropriate; for example, about 0.2 to about 50 times the weight of alcohol is added to the material. Afterwards, extraction can be carried out by allowing the mixture to stand for about 5 minutes to about 24 hours under normal pressure at room temperature to the boiling point temperature of the solvent used, or by stirring. In another extraction treatment mode, for example, the above-mentioned antioxidant component-containing material, particularly preferably a crushed product of rosemary and/or sage, or a crushed or shredded product of the essential oil extraction residue, is packed in an extraction column, A method of column extraction by continuously feeding alcohols from the upper or lower part of the column can also be exemplified. Still another preferable extraction treatment embodiment is a method in which alcohol is added to the above-mentioned antioxidant component-containing material and the mixture is heated at about 90° to about 180° C. under pressurized conditions. After the extraction, an alcoholic solution containing antioxidant components of rosemary and/or sage can be obtained by separating and removing insoluble solids, and if necessary, alcohol can be added to the separated insoluble solids residue to perform the above-mentioned process. The extraction process may be repeated in a similar manner. In the present invention, any of the above-mentioned extraction treatment methods may be employed, but the antioxidant component-containing material of rosemary and/or sage may include activated carbon, acid clay, silica, porous styrene resin, etc. After adding a solid adsorbent such as activated clay, extraction treatment with an alcohol may be carried out as described above, and a decolorized alcoholic solution containing an antioxidant component can be obtained by such a method. The alcohol solution containing antioxidant components of rosemary and/or sage used in the present invention can also be obtained by removing the organic solvent from the extract obtained by extracting the antioxidant component-containing material as described above with an organic solvent other than alcohol. , can be obtained by dissolving this material in alcohols, for example, by dissolving the material in non-polar solvents such as n-pentane, isopentane, petroleum ether, n-hexane, ligroin, methylene chloride, ethylene dichloride, ethyl ether, acetone, etc. , a polar solvent such as methyl acetate, ethyl acetate, or a mixed solvent of such a non-polar solvent and a polar solvent. Distill the solvent under reduced pressure to obtain a concentrate, and add about 0.5 to 300 times the weight of methanol, ethanol, n-propanol, isopropanol, propylene glycol, glycerin, a mixture thereof, or a water-containing mixture thereof. Add an alcohol, preferably ethanol, and thoroughly mix and stir. If necessary, remove insoluble substances by filtration, centrifugation, decantation, etc. to obtain an alcoholic solution containing antioxidant components. Obtainable. The method of the present invention can be carried out, for example, as follows. For example, about 1 to about
Add a 30% by weight aqueous alkaline solution, for example, an aqueous solution of sodium hydroxide, potassium hydroxide, sodium hydrogen carbonate, potassium hydrogen carbonate, barium hydroxide, disodium phosphate, or a mixture of multiple thereof, and add more water if necessary. Added alcohol concentration of about 80% by weight or less, preferably about 70% by weight or less,
The content is adjusted to about 20% by weight or more and the pH of the solution is adjusted to about 7 or more to form an alkaline hydroalcoholic solution of the antioxidant component. When the hydroalcohol concentration is 80% by weight or more, it is difficult to sufficiently remove coloring components and aromatic components, and when it is 20% or less, the yield of antioxidant components decreases, which is not preferable. The conditions for adding the alkaline aqueous solution can be selected as appropriate, but for example, add the rosemary and/or sage antioxidant component-containing alcohol solution to
This can be carried out by adding an aqueous alkali solution at a temperature of 0.degree. C. and stirring for about 10 minutes to about 3 hours. Through this treatment, a green pigment component is precipitated, and the pigment component is separated by solid-liquid separation means such as filtration, centrifugation, or decantation, thereby producing a decolorized alkaline alcohol solution containing an antioxidant component. and the separated dye can be recovered. Next, the above-mentioned alkaline hydrous alcohol solution is treated with a porous styrene resin adsorbent (hereinafter sometimes referred to as "porous polymer resin" or "porous resin") to remove aroma components. A processing liquid can be obtained. Such a porous styrene resin adsorbent is a porous resin obtained by polymerizing styrene as a main raw material, for example, by polymerizing styrene and divinylbenzene to increase the specific surface area and pore volume. Examples include porous synthetic resins and porous crosslinked polystyrene. The above porous polymer resin treatment method is as follows:
For example, this can be carried out by mixing and stirring an alkaline hydrous alcohol solution containing an antioxidant component and a porous polymeric resin, but preferably, the alkaline hydrous alcoholic solution containing an antioxidant component is added from the top of a column packed with a porous polymeric resin. A method of continuously passing the resin through a column and collecting the treated liquid from the bottom of the column is preferable, and such a method is also convenient for the use of young resin. The amount of the porous polymer resin to be used can be appropriately selected depending on the strength of the aroma of the alkaline hydroalcoholic solution containing the antioxidant component, but it is usually preferably about 0.001 to about 5 times the amount of the solution. By treating with the resin, a deodorized treatment liquid can be obtained. An acid is added to the treatment solution thus obtained to make the system acidic and to precipitate the antioxidant component. Examples of such acids include inorganic acids such as hydrochloric acid, sulfuric acid, and phosphoric acid; organic acids such as acetic acid, citric acid, malic acid, tartaric acid, and lactic acid; and mixtures thereof. The amount of acid to be added can be selected as appropriate, but it is preferable to add the acid in an amount necessary to neutralize the amount of alkali added to the alcoholic solution containing antioxidant components, for example, it can be added so that the pH is about 5 or less. . The solids precipitated by this operation are
Colorless, tasteless, and odorless antioxidant components can be obtained by separation by appropriate solid-liquid separation means such as filtration, centrifugation, or decantation, and further, by washing the antioxidant components with hot water, It can also be made into a powder by dehydration and drying. In addition, in the method of the present invention, the antioxidant component-containing alcohol solution as described above is treated with a solid adsorbent and/or with a cation exchange resin before being converted into an alkaline hydrous alcohol solution. Can be done. By such treatment, it is possible to obtain a highly purified and excellent antioxidant component. Examples of the solid adsorbent include activated carbon, diatomaceous earth, activated alumina, activated clay, acid clay, bentonite, microcrystalline cellulose, the above-mentioned porous polymer resin, or a mixture or combination of multiple types thereof, Preferred examples include activated carbon and/or porous polymer resin.
Furthermore, the most preferred example is porous polymer resin. In addition, as a cation exchange resin,
For example, strongly acidic cation exchange resins in which sulfonic acid groups are introduced into gel-type or porous three-dimensional polymeric substrates produced by polymerizing styrene and divinylbenzene, and weakly acidic cation exchange resins in which carboxyl groups are introduced into the polymeric substrates. Examples include cation exchange resins, and particularly preferred examples include strongly acidic cation exchange resins. Such solid adsorbent treatment or ion exchange resin treatment can be performed, for example, as follows. A solid adsorbent is added to the rosemary and/or sage antioxidant component-containing alcoholic solution, and the mixture is left standing or stirred at room temperature to the boiling point temperature of the alcoholic solution for about 10 minutes to about 30 hours. The amount of solid adsorbent used can be appropriately selected depending on the content of the water-insoluble pigment component in the alcohol solution, but usually the adsorbent is used in an amount at least equal to the content of the pigment component. It is preferable to perform a chemical treatment. Next, the solid adsorbent can be separated and removed from the treated product by filtration, decantation or centrifugation to obtain a treated liquid. In addition, when using a porous polymeric resin as a solid adsorbent, the resin is packed in a column, and an alcohol solution containing an antioxidant component is passed from the upper part of the column by the same operation as the porous resin treatment described above. A processing liquid with more pigment components removed can be obtained. Furthermore, when adsorbent treatment is performed using a porous polymeric resin, the natural green pigment adsorbed to the resin can be recovered by extracting the resin after the treatment with acetone. can. It is preferable to recover the green pigment from the porous polymer resin treated with a column such as the one described above. Next, acetone was passed through the column to elute the pigment component adsorbed on the resin, and extraction treatment with acetone was performed until the eluate flowing out from the bottom of the column became almost colorless. By distilling the acetone solution under normal pressure to reduced pressure to remove the solvent, an almost odorless natural green pigment can be recovered. Further, the cation exchange resin treatment of the antioxidant component-containing alcohol solution can be carried out in the same manner as in the case of porous polymer resin treatment using a column, for example. Furthermore, the treated solution obtained by treating the above-mentioned antioxidant component-containing alcohol solution with a cation exchange resin may be treated with a porous polymer resin, or the antioxidant component-containing solution has been decolorized by the solid adsorbent treatment as described above. The alcohol solution may be treated with a cation exchange resin. The amount of the cation exchange resin to be used can be appropriately selected depending on the aroma component content in the alcohol solution or the strength of the aroma of the solution, but is usually about 0.001 to about 0.001 to about the volume of the solution. 5 times the capacity is preferable,
By treating with the resin, a deodorized treatment liquid can be obtained. The bleached and/or deodorized rosemary and/or sage antioxidant component-containing alcoholic solution obtained by the solid adsorbent treatment and/or cation exchange resin treatment can be prepared in the same manner as in the above-described method.
An alkaline hydroalcoholic solution with an alcohol concentration of approximately 80% by weight or less is prepared, and the solution is treated with a porous polymer resin.The resulting treatment liquid is acidified and the solid content formed is collected to produce a colorless and tasteless solution. , odorless natural source antioxidant ingredients can be obtained. The antioxidant substances obtained by the present invention include, 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, and sesame oil. , coconut oil, cottonseed oil, sunflower oil, peanut oil, palm oil,
Vegetable oils and fats such as palm kernel oil, coffee oil, and rice oil; oil-based foods such as butter, cheese, margarine, corn syrup, mayonnaise, and dressing; processed meat foods such as ham and sausage; processed seafood foods; fried noodles; Sweets, delicacies, Yakiniku sauce,
Foods such as dried vegetables, beverages such as milk drinks, soft drinks, and alcoholic beverages, as well as tablets,
Health medicines such as liquid oral medicines, powdered oral medicines, poultices, cosmetics such as soaps, detergents, shampoos, natural essential oil additives such as lemon oil, lime oil, grape oil, orange oil, etc. It can be used in a wide range of fields. Hereinafter, several embodiments of the method of the present invention will be illustrated in more detail with reference to Examples. Example 1 500 g of 95% ethanol was added to 100 g of sage powder and stirred at about 75° C. for 2 hours. Then, 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 701 g of a decolorized alkaline hydroalcoholic solution containing an antioxidant component and 1 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 (diameter 4 cm, height 20 cm) packed with 100 ml of HP-20) to obtain 780 g of a porous polymer resin treatment liquid. 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 (inventive product No. 1). Example 2 100g of rosemary powder and 1000g of n-hexane
was added and stirred at about 60°C for 3 hours. Next, insoluble solids were separated and removed by centrifugation, and the resulting hexane solution was distilled at about 70° C. under normal pressure to remove the solvent, yielding 5 g of rosemary oleoresin. Next, 200 g of 95% ethanol was added thereto, thoroughly stirred and mixed, and insoluble matter was filtered through paper to obtain 195 g of an alcoholic solution of rosemary oleoresin. Next, 2 g of activated carbon was added to this alcohol solution, stirred at room temperature for about 30 minutes, and then filtered through paper.
Glass column (diameter 3) packed with 50ml of SK-116)
cm, height 15 cm) from the top to obtain 215 g of ion exchange resin treatment solution. Next, 5 g of 10% sodium hydroxide aqueous solution and 200 g of water were added to this treatment solution to give an alcohol concentration of approximately 50.
% alkaline water-containing alcohol solution, and after removing insoluble matter from this solution, it was passed through the same porous polymer resin column as in Example 1 to obtain 465 g of an adsorbent-treated solution. Approximately 4g of 10% hydrochloric acid was added to this treatment solution to make the pH approx.
The antioxidant component was precipitated as 4.0, and the precipitate was washed twice with hot water at about 85° C. and then dried to obtain 3.2 g of colorless, tasteless, and odorless naturally sourced antioxidant component.
(Product of the present invention No. 2) Example 3 1200 g of 95% ethanol was added to a mixed powder of 80 g of rosemary and 120 g of sage, and the mixture was stirred and extracted at about 60° C. for 5 hours. Next, insoluble solids are separated by centrifugation and an alcoholic solution containing antioxidant components is prepared.
Obtained 1100g. Furthermore, 400 g of 90% ethanol by weight was added to the above extraction residue, and the mixture was stirred and extracted at approximately 80°C for 2 hours. After removing the insoluble solids, an alcohol solution was obtained.
Obtained 400g. Next, combine the above alcohol solution and add it in advance.
A glass column (diameter 4 cm, height 20 cm) filled with 200 ml of porous polymer resin (trade name, Diaion HP-50) soaked in 93% ethanol, followed by a strongly acidic cation exchange resin soaked in 93% ethanol in advance. (Product name Diaion SK-1B) 200
Glass column (diameter 4 cm, height 20
The treatment solution is continuously flowed from the top of each cm).
Obtained 1670g. Furthermore, after the above alcohol solution has been treated, acetone is added from the top of the porous resin column.
After flowing 250 g of the resin to desorb the dye component adsorbed on the resin, the acetone solution was distilled under normal pressure to remove the solvent, yielding 2 g of a green dye. On the other hand, by adding an alkaline aqueous solution to the above treatment liquid,
It was treated in the same manner as in Example 1 to obtain 17.0 g of colorless, tasteless, and odorless antioxidant component powder. (Product of the present invention No. 3) Example 4 420 g of an alcoholic solution containing an antioxidant component obtained by the same manufacturing method as Example 1 was added to a strongly acidic cation exchange resin column (the same column used in Example 3). ) to obtain 480 g of treatment liquid. Next, 12 g of 10% sodium hydroxide aqueous solution and 300 g of 10% sodium hydroxide solution were added to this treatment solution.
The pH was adjusted to 11.5 and the mixture was stirred to precipitate the green pigment, which was then filtered through paper to obtain 850 g of the decolorized liquid.
I got it. On the other hand, the separated precipitate was washed with water and dried to obtain 1.1 g of a crude green pigment. Next, the decolorized liquid was treated with a porous polymer resin column (the same column used in Example 1), and the same procedure as in Example 1 was carried out to obtain a colorless, tasteless, and odorless natural source antioxidant component.
6.5g was obtained. Example 5 Table 1 shows the results of measuring the antioxidant effect of adding 0.02% of the antioxidant substance obtained by the method of the present invention to lard. The measurement method was the AOM method, in which clean air was sent at 97.8°C at a rate of 2.33ml/sec into each test tube containing 20g of lard added with the present invention until the peroxide value (POV) reached 30. The time was measured.

[Table] From the results shown in Table 1, all of the products of the present invention had significantly higher antioxidant properties than tocopherols.

Claims (1)

[Scope of Claims] 1. An alcoholic solution containing an antioxidant component of rosemary and/or sage is made into an alkaline hydroalcoholic solution with an alcohol concentration of about 80% by weight or less,
A natural source dye is characterized in that the precipitated dye is separated and recovered, the resulting solution is treated with a porous styrene resin adsorbent, and the resulting treated solution is then acidified to collect the solid content formed. Method for producing oxidizing components. 2. Before making the alkaline hydroalcoholic solution,
The method according to claim 1, characterized in that the alcohol solution containing antioxidant components is treated with a solid adsorbent and/or a cation exchange resin. 3. The antioxidant component-containing alcoholic solution is obtained by extracting the antioxidant component-containing material of rosemary and/or sage selected from rosemary and/or sage, its essential oil extraction residue, and the oleorange 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. The method described in item 1 or 2. 4. The method according to claim 2, wherein the solid adsorbent is activated carbon and/or porous styrene resin adsorbent. 5. The solid adsorbent is a porous styrene resin adsorbent, and the resin adsorbent treated with the solid adsorbent is extracted with acetone to recover the natural green pigment adsorbed on the adsorbent. The manufacturing method according to claim 2.