JP2814567B2 - Method for producing natural antioxidants - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a method for producing a natural antioxidant having high antioxidant power from herbal spices containing antioxidant components such as rosemary and sage.

[Conventional technology]

Heretofore, it has been known that herbal spices contain an antioxidant component and have an effect of preventing the oxidation of oil- and fat-containing foods and the like, and various studies on this point have been made (Japanese Patent Application Laid-Open (JP-A) no. No. 54-130485, No. 55-18435, No. 55-1
02508, 56-74177, 56-144078, 58-6779
No. 4, U.S. Pat. No. 3,950,266). However, herbal spices have their own intense flavors, so when these spices are added directly to foods, cosmetics, pharmaceuticals, etc. as antioxidants, they change the flavor of the foods, A variety of inconveniences occur, such as affecting the balance of perfume and limiting the use of pharmaceuticals due to their unique odor.

On the other hand, it has been proposed to remove essential oil components from herbal spices, collect odorless antioxidant components, and use the antioxidant components as antioxidants (US Pat. No. 3,950,266). ). In this case, the recovery of the antioxidant component from the herb-based spice has been conventionally performed by an extraction treatment using an organic solvent.

[Problems to be solved by the invention]

However, antioxidant components collected from herbal spices using organic solvents have the drawback that their antioxidant power is not always sufficient, and for this reason, they must be used in large amounts and are economically economical. Be disadvantaged. Further, the organic solvent remains in the antioxidant component, which may cause a problem in terms of safety.

The present invention has been made in view of the above circumstances, and uses a high antioxidant and odorless antioxidant from herbal spices without using an organic solvent or using as little organic solvent as possible. It is intended to provide a method of manufacturing.

[Means and actions for solving the problem]

The present inventors have achieved intensive research on a method for obtaining a natural antioxidant having a high antioxidant power, which can be added to foods, cosmetics, pharmaceuticals, etc. When the treated product containing the antioxidant component is extracted with carbon dioxide in a supercritical state under the following conditions, the purity is higher than that extracted with an organic solvent, the antioxidant power is strong, and the odorless antioxidant component is Knowing that it can be obtained, the present invention has been accomplished.

Therefore, the present invention provides: (i) a herb spice or a processed product of an herb spice containing an antioxidant component as a raw material, and the pressure of the raw material is 90 kg / cm ^2.
More than 200 kg / cm ² , after removing the odorous component in the raw material by treating with a fluid consisting of supercritical carbon dioxide at a temperature of 40 to 80 ° C., the pressure is 200 to 450 kg / cm ² , the temperature is 40 ~ 80 ℃
Extraction with a fluid consisting of carbon dioxide in a supercritical state,
A method for producing an antioxidant, comprising: transferring an antioxidant component contained in the raw material into the fluid, and separating and recovering the antioxidant component from the fluid; and (ii) a herb system A spice or a herbal spice containing an antioxidant ingredient is used as a raw material, and the pressure of the raw material is 200 to 450.
kg / cm ² , a temperature of 40 to 80 ° C. After extracting with a fluid comprising supercritical carbon dioxide at a temperature of 40 to 80 ° C. to obtain an extract containing an antioxidant component and an odorous component contained in the raw material, The extract is treated with a fluid composed of carbon dioxide in a supercritical state at a pressure of 90 kg / cm ² or more and less than 200 kg / cm ² and a temperature of 40 to 80 ° C., and is removed by transferring the odorous component into the fluid. Providing a method for producing an antioxidant, which comprises extracting an extract containing the antioxidant component obtained as described above.

Here, examples of herbal spices include rosemary, sage, thyme, marjoram, oregano, basil, and the like, but are not limited thereto as long as they contain an antioxidant component. When the herbal spice is directly subjected to the extraction treatment, the spice is preferably used in the form of a powder.

Further, as a processed product of the herbal spice containing an antioxidant component, there are hot water extraction residue of the herb spice, essential oil collection residue, ethyl ether, dioxane, acetone, ethanol, methanol, aqueous ethanol, ethyl acetate, propylene glycol, Oleoresin extracted with a polar solvent such as glycerin or its extraction residue, extracted with a non-polar solvent such as n-hexane, petroleum ether, ligroin, cyclohexane, carbon tetrachloride, chloroform, dichloromethane, 1,2-dichloroethane, toluene and benzene Oleoresin or its extraction residue, etc., and in particular, a deodorized product using carbon dioxide in a supercritical state described below is suitably used.

In the present invention, the herbal spice or the processed product thereof is subjected to extraction treatment with a fluid composed of carbon dioxide in a supercritical state.
450450 kg / cm ^{2 at} a temperature of 40-80 ° C. If the pressure is less than 200 kg / cm ² , the extraction of the antioxidant component may be insufficient, and if the pressure exceeds 450 kg / cm ² , the equipment may be overloaded. When the temperature is lower than 40 ° C., the extraction of the antioxidant component may be insufficient, and when the temperature is higher than 80 ° C., the efficiency of extracting the antioxidant component may not be increased. In addition,
A more preferable processing pressure is 250 to 400 kg / cm ² , and a processing temperature is 40.
~ 60 ° C.

Here, an organic solvent can be mixed as an entrainer into the fluid composed of carbon dioxide in the supercritical state, whereby the extraction efficiency of the antioxidant component can be improved. As the entrainer, for example, aliphatic lower alcohols, aliphatic hydrocarbons, aromatic hydrocarbons, ketones and the like can be used. The mixing amount of the entrainer is preferably 2 to 20% by weight based on the weight of carbon dioxide. If the amount is less than 2% by weight, the extraction efficiency of the antioxidant component may not be increased. If the amount exceeds 20% by weight, the entrainer may be troublesome in the distillation process.
On the other hand, when the content is 2 to 20% by weight, the extraction efficiency can be sufficiently increased, and the amount of solvent used can be significantly reduced as compared with the conventional solvent extraction method.

In the present invention, an antioxidant is obtained by transferring an antioxidant component into a fluid composed of carbon dioxide in a supercritical state by the above-described extraction treatment, and then separating it.
In this case, the separation conditions are as follows:
/ cm ² , and the temperature is preferably 20 to 80 ° C. Pressure 80
separation and recovery of the antioxidant component exceeds kg / cm ² is may become insufficient, the temperature is above 80 ° C., separation and recovery of higher becomes the still antioxidant components from the extraction temperature is likely to be inadequate is there. In addition, more preferable separation conditions are that the pressure is atmospheric pressure to
60 kg / cm ² , temperature is 25-60 ° C.

In the present invention, as a processed product of the herbal spice containing the antioxidant component to be subjected to the extraction process, herbal spice, its hot water extraction residue, essential oil collection residue, oleoresin extracted with a polar solvent and its extraction residue, and A raw material selected from oleoresin extracted with a nonpolar solvent and its extraction residue is subjected to an extraction treatment with a fluid comprising carbon dioxide in a supercritical state, and an extraction residue from which odorous components have been removed can be suitably used.
That is, since the extraction residue is almost completely removed of odorous components by performing an extraction treatment with carbon dioxide in a supercritical state, the antioxidant components are collected from the extraction residue to obtain an odorless and antioxidant component. However, a strong antioxidant can be obtained.

In this case, the extraction residue is obtained by performing an extraction treatment (deodorization treatment) of a herb-based spice or the like with a fluid composed of carbon dioxide in a supercritical state. The extraction conditions are such that the pressure of carbon dioxide is 90 kg / cm ^2. 200 kg / cm of less than ^2, the temperature more than 40
~ 80 ° C. There may be a pressure insufficient extraction of odorous components is less than 90 kg / cm ^2, antioxidant components when to become 200 kg / cm ² or more antioxidant components and odorous components are present together It is removed together with the odorous component, and the yield of the antioxidant component may decrease. When the temperature exceeds 80 ° C., the yield of the antioxidant component may decrease similarly to the above. The more preferable pressure is 120 to 180 kg / cm ² and the temperature is 40 to 60.
° C. In addition, an entrainer can be mixed in the fluid used for the deodorization treatment in the same manner as described above, thereby improving the deodorization efficiency.

Thus, as the first stage, the pressure is 90 kg / cm ² or more and 200 k
g / cm ² , extraction of odorous components (deodorization treatment) with supercritical carbon dioxide at a temperature of 40 to 80 ° C, and as a second step, a pressure of 200 to 450 kg / cm ² and a temperature of 40 to Extraction of antioxidant components with supercritical carbon dioxide at 80 ° C can provide a natural antioxidant with high odorless and antioxidant properties, which is easily soluble in supercritical carbon dioxide. Pressure range with odorous components (including essential oil components) (90-200kg /
cm ² ) is based on the principle that, while being selectively extracted and removed, antioxidant components can be extracted and separated at a relatively higher pressure (200 to 450 kg / cm ² ) than the former.

When a fraction containing an antioxidant component and an odorous component is obtained from the herb-based spice or its processed product by the method of the present invention, the odor is obtained from this fraction by the deodorizing method using carbon dioxide in the supercritical state. It is preferable to remove the components, whereby a natural antioxidant having no odor and high antioxidant power can be obtained.

Antioxidants obtained by the present invention include fish oil, lard, tallow, head, chicken oil, soybean oil, linseed oil, lineseed oil, safflower oil, rice oil, corn oil, coconut oil, palm oil, Sesame oil, cocoa oil, castor oil, peanut oil, etc.
Fats and oils, butter, cheese, margarine,
Shortening, mayonnaise, dressing, ham, sausage, potato chips, fried rice cracker, fried ramen, curry roux, soy sauce, soft drink, sake, fruit wine, ketchup, jam, fish or meat meat products, other foods, or hair cosmetics, It can be used by being added to cosmetics such as skin cosmetics and oral cosmetics and pharmaceuticals. In this case, the added amount of the antioxidant of the present invention is 0.
[0005] The content is preferably set to 0005 to 1% by weight, particularly 0.001 to 0.1% by weight. The antioxidant according to the present invention may be used as it is, but if necessary, may be added into excipients such as starch, gelatin and the like to form a powder, granules, or oils and fats. It may be dissolved and dispersed in ethanol, propylene glycol, glycerin, or a mixture thereof to form a liquid. Further, the antioxidant according to the present invention may contain a synergist component such as citric acid, if necessary.

〔The invention's effect〕

As described above, according to the present invention, by extracting the antioxidant component under the above-mentioned conditions using carbon dioxide in a supercritical state, the antioxidant component produced by the conventional method (organic solvent extraction method) can be used. The antioxidant has a higher antioxidant power, can effectively prevent oxidation of fats and oils, and can provide an odorless antioxidant. In this case, the antioxidant according to the present invention is collected from natural herbal spices, and since it uses carbon dioxide for extraction, it is highly safe for the human body. It can be suitably used for foods including oils and fats products, cosmetics, medicines and the like. Also, since the method of the present invention uses carbon dioxide,
The safety in the manufacturing process is higher than the conventional method using a large amount of an organic solvent.

Next, the present invention will be specifically described by way of examples, but the present invention is not limited to the following examples.

〔Example〕

FIG. 1 shows an example of an extraction / separation apparatus used for carrying out the present invention. In the figure, 1 is an extraction tank, 2 is a separation tank, 3 is a CO ₂ cylinder, 4 is an extractant compressor, and 5 is an entrainer container. , 6 is a fixed-rate supply pump, 7 is a pressure control valve, 8 is a heat exchanger, 9 is a flow control valve, 10 is a holding pressure valve, 11 is a gas flow meter, 12 is a weighing platform scale, 13 is an atmospheric release valve, and 14 is a solvent. Path 15 is an extract collection valve.

When producing odorless natural antioxidants with this device,
In the first step, the odorous component is extracted (deodorized), and in the second step, the antioxidant component is extracted. In this case, first, an herb-based spice such as rosemary powder is put into the extraction tank 1. Subsequently, carbon dioxide is sent out from the carbon dioxide cylinder 3, and the air in the solvent path 14 including the extraction tank 1 and the separation tank 2 is released by the atmospheric release valve 13 and replaced with carbon dioxide.

Next, the input side pressure control valve 7 is subjected to the first stage processing (deodorization).
While setting the pressure, the flow rate control valve 9 on the output side of the extraction tank 1 is fully closed, and the carbon dioxide compressor 4 and the metering pump 6
(Required when using an entrainer)
The pressure in the extraction tank 1 is increased to a predetermined pressure (90 kg / cm ² or more and less than 200 kg / cm ² ). At this time, a fixed amount of entrainer such as alcohol is sent out from the solvent container 5 and the heat exchanger 8
The mixed solvent is mixed with carbon dioxide to form a mixed solvent. The mixed solvent heated to a predetermined temperature (40 to 80 ° C.) is supplied to the extraction tank 1 in a constant amount, and the herb spices such as rosemary in the extraction tank 1 are removed. Deodorize.

Thereafter, the flow control valve 9 is gradually opened to reduce the pressure, and the mixed solution containing the odorous component in the extraction tank 1 is introduced into the separation tank 2, and the pressure in the separation tank 2 is changed from the atmospheric pressure to 80 kg / cm ² , Separates and collects fractions containing odorous components under the conditions of 20-80 ° C.

At this time, generally, the pressure of the separation tank 2 is maintained at a constant pressure by the pressure holding valve 10, and the flow rate of the mixed solvent is quantitatively controlled by the flow rate adjusting valve 9.

Further, the carbon dioxide from which the fraction containing the odorous component has been separated is returned to the compressor 4 and recycled.

Next, as a second stage treatment, the residue in the extraction tank 1 is subjected to extraction and separation conditions for antioxidant components (extraction pressure: 200 to 450 kg / c).
m ² , extraction temperature: 40 ~ 80 ° C, separation pressure: atmospheric pressure ~ 80kg / c
m ² , separation temperature: 20-80 ° C.). Thereby, the odorless antioxidant component is separated and collected in the separation tank 2.

In the present apparatus, the order of the above-described two-stage processing can be reversed. That is, in the first stage, the extraction / separation treatment is performed under the conditions for extracting / separating the antioxidant component (pressure and temperature: the same as above), and a fraction containing the antioxidant component and the deodorant component is obtained in the separation tank 2. Next, in the second stage, this fraction is extracted from the extraction tank 1
And extracted under deodorizing treatment conditions (pressure, temperature: same as above)
By performing the separation treatment, the odorless antioxidant component remains in the extraction tank 1 and the odorous component is separated and collected in the separation tank 2.

Hereinafter, an experimental example using the apparatus of FIG. 1 will be described. Experiments A to C are examples in which one-stage processing was performed, and Experiment D is an example in which two-stage processing was performed.

(Experimental example)

In order to find the optimum conditions for obtaining an odorless antioxidant component more efficiently, experiments were conducted on various raw materials by changing the conditions of treatment and separation. An AOM test was performed on each of the obtained substances (residues in the extraction tank and residues in the separation tank) to determine the antioxidant power, and a comprehensive evaluation was made based on the antioxidant power, flavor and yield. The results are shown in Tables 1 to 4 below.

In this case, the antioxidant power in the following table indicates the time required to reach POV = 30 when the AOM test was conducted by adding 0.01% in terms of solid content as a fraction containing an antioxidant component.
Here, the AOM test was carried out in accordance with “Standard Oil and Fat Analysis Test Method, edited by the Japan Oil Chemists' Society”. The oil used was lard (free from antioxidants: Fuji Essential Oil), and the oil bath temperature was 97.8 ° C. The flavors in the table are 1 for undeodorized products and 5 for odorless products.
Average score (paneler 9)
Name). Therefore, the larger the value of the antioxidant power, the stronger the antioxidant power of the extraction tank residue or the separated layer recovered material,
The higher the value of the flavor, the better the odorous component is removed from the residue or the recovered material.

Experiment A (Table 1: Nos. 1 to 12) The raw material of rosemary was used as a raw material, and the treatment was carried out by changing the pressure without using an entrainer. here,
The extraction pressure was 80-450 kg / cm ² and the separation pressure was 1-90 kg / cm ² .

Result: For deodorization, a processing pressure of 90-200 kg / cm ² was suitable. In the case of extraction, the processing pressure is 200 to 450 kg / c.
m ² was suitable.

Experiment B (Table 2: Nos. 13 to 18) As a raw material, other than the raw powder of rosemary hydrothermal treatment residue,
The oleoresin was processed at a different processing temperature without using an entrainer. Here, the processing temperature
32-90 ° C.

Result: When the treatment temperature at the time of extraction is lower than 40 ° C., the extraction of the antioxidant component is insufficient, and at 80 ° C. or higher, the extraction efficiency of the antioxidant component does not increase. ° C
Was suitable.

 In addition, it was possible to process non-rosemary powder.

Experiment C (Table 3: Nos. 19 to 27) Using the raw powder of rosemary, the type of entrainer
The treatment was carried out with the addition concentration changed. Here, ethanol, propane, n-hexane, acetone, and toluene were used as entrainers, and the added concentration was 1 to 25%.

Result: The fraction containing the antioxidant component was efficiently obtained by using any of the entrainers. Moreover, the addition concentration is 2
%, The extraction efficiency was poor, and 2 to 20% was suitable.

Experiment D (Table 4: 28 to 34) Based on the conditions obtained from Experiments A to C, a two-stage treatment was carried out so as to obtain an odorless antioxidant fraction more efficiently. Raw materials were also used for sage, thyme and marjoram other than rosemary.

Raw material: Rosemary (No.28-30: Hot water extraction residue, No.3
1: Original powder) No.28: Extraction → deodorization, with entrainer.

 No.29: Extraction → deodorization, no entrainer.

 No.30: Deodorization → extraction, with entrainer.

 No.31: Deodorization → extraction, no entrainer.

Raw material: Herbal spices other than rosemary (raw powder) No.32: Sage, extraction → deodorization, entrainer.

 No.33: Thyme, extraction → deodorization, with entrainer.

No.34: Marjoram, extraction → deodorization, with entrainer.

Result: A fraction containing an odorless antioxidant component could be efficiently obtained in any order of extraction → deodorization → deodorization → extraction. Also, by performing the two-step treatment on raw materials other than rosemary, a fraction containing an odorless antioxidant component could be efficiently obtained.

Furthermore, the antioxidant power was found to be much stronger than that of natural vitamin E (Eisai: Emix 80) and BHA which are generally used as antioxidants (see Table 5).

From the results of Tables 1 to 5 above, it was confirmed that the antioxidant component and the odorous component were favorably extracted by extracting the herbal spice or the processed product thereof with carbon dioxide in a supercritical state. Was. In this case, antioxidant extraction and separation processes for component extraction pressure 200 to 450 kg / cm ^2, the extraction temperature of 40 to 80 ° C., the separation pressure atmospheric ~80kg / cm ^2, a separation temperature of 20 to 80 ° C. and then, the extraction and separation process of the odorous components 90 kg / cm ² or more 200 kg / cm of less than ² extraction pressure, extraction temperature 40 to 80 ° C.,
It has been found that it is appropriate to set the separation pressure at atmospheric pressure to 80 kg / cm ² and the separation temperature at 20 to 80 ° C.

 Finally, a formulation example is shown.

(Formulation example)

Based on the above findings, an emulsified dressing having the following formulation was blended and its antioxidant power was evaluated.

Emulsion stabilizer 50 g Sucrose 400 g Seasoning 10 g Various spices 40 g Water 1640 g Acetic acid solution 500 g Egg yolk 200 g Food salt 150 g Sodium citrate 5 g Plant salad oil 2000 g , 1.5g, 0.15g, BHA0.6g, tocopherol 3g
Was added, and the POV value (peroxide value) was measured immediately after the production of each dressing and after storing these dressings for 32 days at 40 ° C., and their stability (antioxidant properties) was examined. The results are shown in Table 6. The POV value was measured according to an improved method of the Lea method [Oil Chemistry, 19 (15), 340 (1970)].

As is clear from the results in Table 6, it was found that No. 28 exhibited much higher antioxidant power than BHA, which was conventionally said to have the strongest antioxidant power.

In addition, the dressing to which No. 28 was added did not show any change in aroma, taste, and color tone due to the addition, and maintained good quality.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a schematic diagram showing an example of an extraction / separation device used for carrying out the present invention. 1 ...... extraction tank, 2 ...... separating tank, 3 ...... CO ₂ cylinder, 4 ...... extractant compressor, 5 ...... entrainer vessel, 6 ...... metering pump, 7 ...... pressure control valve, 8 ... ... heat exchanger, 9 ... flow control valve, 10 ... pressure holding valve, 11 ... gas flow meter, 12 ... weighing platform scale, 13 ... atmospheric release valve, 14 ... solvent path, 15 ... extract recovery valve.

──────────────────────────────────────────────────続 き Continuation of the front page (51) Int.Cl. ⁶ Identification symbol FI C11B 5/00 C11B 5/00 (72) Inventor Toshihiko Matsuya 1 Kurose-cho, Ise-shi, Mie (56) References JP-A-61- 209567 (JP, A) JP-A-59-176385 (JP, A) JP-A-61-286332 (JP, A) JP-A-57-22682 (JP, A) (58) Fields investigated (Int. ⁶ , DB name) C09K 15/34

Claims (4)

(57) [Claims] 1. A herb-based spice or a processed product of an herb-based spice containing an antioxidant component is used as a raw material, and the raw material is subjected to a pressure of 90%.
kg / cm ² or more and less than 200 kg / cm ² , the temperature is 40 to 80 ° C. After removing the odorous components in the raw material by treating with a fluid composed of carbon dioxide in a supercritical state, the pressure is 200 to 450 kg / cm ² , the temperature is 40
Extracting with a fluid consisting of carbon dioxide in a supercritical state at ~ 80 ° C, transferring the antioxidant component contained in the raw material into the fluid, and separating and recovering the antioxidant component from the fluid. A method for producing an antioxidant, comprising: 2. A herb-based spice or a processed product of an herb-based spice containing an antioxidant component is used as a raw material.
0 to 450 kg / cm ² , a temperature of 40 to 80 ° C. After extracting with a fluid comprising supercritical carbon dioxide at a temperature of 40 to 80 ° C. to obtain an extract containing an antioxidant component and an odorous component contained in the raw material , the extract pressure 90 kg / cm ² or more 200 kg / cm lower than ^2, the temperature is 40-8
Treated with a fluid consisting of carbon dioxide in a supercritical state at 0 ° C.,
A method for producing an antioxidant, comprising extracting an extract containing the antioxidant component obtained by removing the odorous component by transferring the odorous component into the fluid. 3. The method according to claim 1, wherein an organic solvent is mixed with the fluid as an entrainer. 4. A processed product of an herbal spice containing an antioxidant component is extracted with a herbal spice, its hot water extraction residue, essential oil collection residue, oleoresin extracted with a polar solvent and its extraction residue, and a nonpolar solvent. 4. An extraction residue obtained by extracting a raw material selected from oleoresin and its extraction residue with a fluid comprising carbon dioxide in a supercritical state.
The manufacturing method as described.