JPH039984A - Preparation of natural antioxidant - Google Patents

Abstract

PURPOSE:To prepare a potent antioxidant without using any organic solvent by extracting a herb spice or a product of treatment thereof containing an antioxidant component with fluid CO2 in a supercritical state. CONSTITUTION:A herb spice, e.g. rosemary or sage, or a product of treatment thereof containing an antioxidant component, preferably one deodorized by CO2 in a supercritical state, is extracted with fluid CO2 in a supercritical state. Especially when extraction is conducted under a pressure of 200-450kg/cm<2> at 40-80 deg.C, a highly pure, potent antioxidant component can be obtained. The purpose antioxidant is prepared by transferring the antioxidant component from the spice or the product of treatment thereof to the fluid CO2 and separating the component from the fluid. The obtained antioxidant has a higher antioxidant power than that of an antioxidant prepared by the conventional method, i.e. extraction with an organic solvent.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a method for producing a natural antioxidant with high antioxidant power from herbal spices containing antioxidant components such as rosemary and sage.

[Conventional technology]

It has been known that herbal spices contain antioxidant components and have the effect of preventing the oxidation of oil- and fat-containing foods, and various studies have been conducted on this point ( JP-A-54-130485, JP-A No. 55-184
No. 35, No. 55-102508, No. 56-74177
No. 56-144078, No. 58-67794,
(U.S. Pat. No. 3,950,266, etc.). However, each herbal spice has its own strong flavor, so when these spices are directly added to foods, cosmetics, medicines, etc. as anti-acid agents, the flavor of the food changes,
In cosmetics, it affects the balance of fragrances, and in pharmaceuticals, it has a unique odor that restricts its use, causing various inconveniences.

In response, it has been proposed to remove essential oil components from herbal spices, recover odorless antioxidant components, and use these antioxidant components as antioxidants (U.S. Pat. No. 3,950,266, etc.). ). In this case, recovery of antioxidant components from herbal spices has conventionally been carried out by extraction using an organic solvent.

(Problem to be solved by the invention) However, antioxidant components extracted from herbal spices using organic solvents have the disadvantage that their antioxidant power is not necessarily sufficient, and therefore, they must be used in large amounts. In addition, the organic solvent may remain in the antioxidant component, which may pose a safety problem.

The present invention was made in view of the above circumstances, and is a method for producing an antioxidant with high antioxidant power from herbal spices without using an organic solvent or using as little amount of an organic solvent as possible. The purpose is to provide

[Means and effects for solving the problem] The present inventors,
In order to achieve the above objectives, as a result of intensive research into methods for obtaining natural antioxidants with high antioxidant power that can be added to foods, cosmetics, medicines, etc., we have found that herbal spices or processed products containing their antioxidant components When extracted with carbon dioxide in a supercritical state, the pressure is particularly 200 to 450 kg/cJ,
It was discovered that when extracted at a temperature of 40 to 80°C, an antioxidant component with higher purity and stronger antioxidant power can be obtained than that extracted with an organic solvent, and this led to the present invention. .

Therefore, the present invention extracts herbal spices or processed herbal spices containing antioxidant components with a fluid made of carbon dioxide in a supercritical state, and extracts the antioxidants contained in the herbal spices or processed products thereof. The present invention provides a method for producing an antioxidant component, which comprises transferring the antioxidant component into the fluid and then separating and recovering the antioxidant component from the fluid.

Here, the eight spices include rosemary sage,
Examples include thyme, marjoram, oregano, basil, etc., but are not limited to these as long as they contain antioxidant ingredients. Note that when herbal spices are subjected to direct extraction treatment, it is preferable to use the spices in powder form.

Furthermore, as a processed product of herbal spices containing antioxidant components, hot water extraction residues of herbal spices are used.

Essential oil extraction residue, oleoresin extracted with polar solvents such as ethyl ether, dioxane, acetone, ethanol, methanol, aqueous ethanol, ethyl acetate, propylene glycol, glycerin, etc. or its extraction residue, n-hexane, petroleum ether, ligroin, cyclohexane, Examples include oleoresins extracted with nonpolar solvents such as carbon tetrachloride, chloroform, dichloromethane, 1,2-dichloroethane, toluene, and benzene, or extraction residues thereof, and in particular, products deodorized with carbon dioxide in a supercritical state as described below. is preferably used.

In addition, in the present invention, herbal spices or processed products thereof are extracted with a fluid made of carbon dioxide in a supercritical state, and the extraction conditions are such that the pressure of carbon dioxide is increased to 200°C.
~450 kg/cJ and a temperature of 40 to 80°C are preferred. If the pressure is less than 200 kg/a, the extraction of antioxidant components may be insufficient;
Exceeding /a# may result in unreasonable equipment requirements. If the temperature is less than 40°C, the extraction of antioxidant components may become insufficient, and even if the temperature exceeds 80°C, no increase in the extraction efficiency of antioxidant components may be observed. In addition, the more preferable treatment pressure is 250 to 400 kg/aJ, and the treatment temperature is 40 to 400 kg/aJ.
The temperature is 60°C.

Here, an organic solvent can be mixed as an entrainer into the fluid made of carbon dioxide in a supercritical state, thereby improving the extraction efficiency of antioxidant components. Examples of this entrainer include aliphatic lower alcohols.

Aliphatic hydrocarbons, aromatic hydrocarbons, ketones, etc. can be used. Further, the amount of the entrainer mixed is preferably 2 to 20% by weight based on the weight of carbon dioxide. 2
If it is less than 20% by weight, the extraction efficiency of the antioxidant component may not increase, and if it exceeds 20% by weight, it may take time to distill off the entrainer. On the other hand, 2~
When the content is 20% by weight, the extraction efficiency can be sufficiently increased, and the amount of solvent used can be significantly reduced compared to conventional solvent extraction methods.

In the present invention, the antioxidant component is transferred into a fluid made of carbon dioxide in a supercritical state by the above-described extraction process, and then separated to obtain an antioxidant. In this case, the separation conditions are such that the pressure of carbon dioxide is from atmospheric pressure to 80k
g/aJ and the temperature is preferably 20 to 80°C.

If the pressure exceeds 80 kg/d, the separation and recovery of the antioxidant components may become insufficient, and if the temperature exceeds 80°C, which is higher than the extraction temperature, the separation and recovery of the antioxidant components may become insufficient. There is. In addition, more preferable separation conditions are that the pressure is atmospheric pressure to 60 kg/ad and the temperature is 25 to 60°C.

In the present invention, as a processed herbal spice containing the above-mentioned antioxidant component to be extracted.

Raw materials selected from herbal spices, their hot water extraction residues, essential oil collection residues, oleoresins extracted with polar solvents and their extraction residues, and oleoresins extracted with non-polar solvents and their extraction residues are extracted from carbon dioxide in a supercritical state. The extraction residue obtained by extracting with a fluid to remove odor components can be preferably used. In other words, this extraction residue has been extracted with supercritical carbon dioxide, which has almost completely removed odor components, so by extracting antioxidant components from this extraction residue, an odorless and antioxidant can provide strong antioxidants.

In this case, the above-mentioned extraction residue is extracted by extracting herbal spices, etc. with a fluid made of carbon dioxide in a supercritical state (deodorizing treatment).
However, the extraction conditions are preferably a carbon dioxide pressure of 90 kg/a (more than 200 kg/a) and a temperature of 40 to 8 o'c. However, if the amount exceeds 200 kg/-, the antioxidant component will be removed together with the odorous component, and the antioxidant component will be removed together with the odorous component. The yield of oxidizing components may be reduced, and if the temperature exceeds 80'C, the yield of antioxidant components may be reduced in the same manner as above.The more preferable pressure is 120 to 180 kg/cJ, and the temperature is 40°C. ~60'
It is C. Further, an entrainer can be mixed into the fluid used for this deodorizing process in the same manner as described above, thereby improving the deodorizing efficiency.

Thus, in the first stage the pressure is preferably 90 kg.
/an above 200 kg/a#, temperature 40-80℃
Extraction treatment (deodorization treatment) of odorous components is carried out using supercritical carbon dioxide at a pressure of 20%.
By extracting antioxidant components using carbon dioxide in a supercritical state at 0 to 450 kg/aI and a temperature of 40 to 80°C, an odorless and highly antioxidant natural antioxidant can be obtained. is a pressure box II [1 (90~
200 kglcr&) is selectively extracted and removed, while the antioxidant components are removed under relatively higher pressure (200 kglcr&) than the former.
00 to 450 kg/a+f) is based on the principle of extraction and separation.

In addition, when a fraction containing antioxidant components and odorous components is obtained from herbal spices or their processed products by the method of the present invention, both of these fractions can be deodorized by the above-mentioned deodorizing method using carbon dioxide in a supercritical state. It is preferable to remove the components, and this also makes it possible to obtain a natural antioxidant that is odorless and has high antioxidant power.

The antioxidants obtained according to the present invention include fish oil, lard, tallow, head oil, chicken oil, soybean oil, linseed oil, cottonseed oil, safflower oil, rice oil, corn oil, coconut oil, palm oil,
Oils and fats made from animals and plants such as sesame oil, cacao oil, castor oil, peanut oil, butter, cheese, margarine, shortening, mayonnaise, dressing, ham, sausage, potato chips, fried rice crackers, fried ramen,
Added to curry roux, soy sauce, soft drinks, alcohol, fruit liquor, ketchup, jam, fish or meat paste products, other foods, hair cosmetics, skin cosmetics, cosmetics such as mouth cosmetics, pharmaceuticals, etc. can be used. In this case, the amount of the antioxidant of the present invention added is 0.0 of the total amount as a dry product.
005-1% by weight.

In particular, it is preferably 0.001 to 0.1% by weight.

The antioxidant according to the present invention may be used as it is, but if necessary, it may be made into powder or granule form by adding excipients such as starch or gelatin.
The antioxidant according to the present invention may also be dissolved and dispersed in oil, ethanol, propylene glycol, glycerin, or a mixture thereof to form a liquid form.The antioxidant according to the present invention may also contain a synergist component such as citric acid as necessary. You may.

〔Effect of the invention〕

As explained above, according to the present invention, by extracting antioxidant components using carbon dioxide in a supercritical state, the antioxidant components are more antioxidant than those produced by the conventional method (organic solvent extraction method). It is possible to obtain an antioxidant that has high potency and can effectively prevent the oxidation of oils and fats. In this case, 1. The antioxidant according to the present invention is extracted from natural herbal spices and uses carbon dioxide for extraction, so it is highly safe for the human body. 1. Currently, the safety of synthetic additives is a problem. It can be suitably used for foods including oil and fat products, cosmetics, medicines, etc. Furthermore, since the method of the present invention uses carbon dioxide, the manufacturing process is safer than conventional methods that use large amounts of organic solvents.

Next, the present invention will be concretely illustrated by examples, but the present invention is not limited to the following examples.

〔Example〕

FIG. 1 shows an example of an extraction and separation apparatus used in carrying out the present invention, in which 1 is an extraction tank, 2 is a separation tank, 3 is a Co2 cylinder, 4 is an extractant compressor, 5 is an entrainer container, 6 is a constant supply pump, 7 is a pressure control valve, 8 is a heat exchanger, 9 is a flow rate adjustment valve, 10 is a pressure holding valve, 11 is a gas flow meter, 1
2 is a weighing platform scale, 13 is an air release valve, 14 is a solvent path, and 15 is an extract recovery valve.

When producing an odorless natural antioxidant using this apparatus, the first step is to extract odorous components (deodorizing treatment), and the second step is to extract antioxidant components. In this case, first, herbal spices such as rosemary powder are 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 atmosphere release valve 13 and replaced with carbon dioxide.

Next, the pressure control valve 7 on the input side is set to the first stage treatment (deodorization) pressure, the flow rate adjustment valve 9 on the output side of the extraction tank 1 is fully closed, and the carbon dioxide compressor 4 and metering pump 6 (
(required when using an entrainer), and set the pressure in extraction tank 1 to the specified pressure (90 kg/cJ or more, 200 kg/cJ or more).
g/ad). At this time, a fixed amount of entrainer such as alcohol is delivered from the solvent container 5,
The mixed solvent, which is heated to a predetermined temperature (40 to 80°C) by mixing with carbon dioxide in the heat exchanger 8, is supplied in a constant quantity to the extraction tank 1, and the rosemary, etc. in the extraction tank 1 are Deodorizing herbal spices.

After that, the flow rate adjustment valve 9 is gradually opened to reduce the pressure, and the mixed solution containing the odorous components in the extraction tank 1 is introduced into the separation tank 2.
In the separation tank 2, the pressure is from atmospheric pressure to 80 kg/af and the temperature is from 20 to 80°C, separating both parts containing odorous components.
to recover.

At this time, during boat fishing, the pressure in 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 adjustment valve 9.

Further, the separated carbon dioxide containing odorous components is returned to the compressor 4 and recycled for use.

Next, as the second stage treatment, the residue in the extraction tank 1 was extracted and separated for antioxidant components (extraction pressure: 200 to 450
kg/cm2, extraction temperature: 40-80°C.

Separation pressure Crab atmospheric pressure ~ 80Icg/al1 Separation temperature: 20
~80°C). As a result, odorless antioxidant components are separated and recovered in the separation tank 2.

In this apparatus, the order of the two-step process described above can also be reversed. That is, in the first step, the antioxidant components are extracted and
Extraction and separation are carried out under separation conditions (pressure, temperature, 2 ditto), and a fraction containing antioxidant components and deodorizing components is obtained in separation tank 2. Next, in the second step, this fraction is put into extraction tank 1 and extracted and separated under deodorizing treatment conditions (pressure, temperature: same as above), so that odorless antioxidant components remain in extraction tank 1. At the same time, odor components are separated and recovered in the separation tank 2.

An experimental example using the apparatus shown in FIG. 1 will be shown below. In addition, actual i
llA-C are examples in which one-stage processing was performed, and Experiment 1 is an example in which two-stage processing was performed.

[Experiment example]

In order to find the optimal conditions to more efficiently obtain odorless antioxidant ingredients, we conducted experiments by changing the processing and separation conditions for various raw materials. An AOM test was conducted on each substance obtained (extraction tank residue, separation tank residue) to determine the antioxidant power, and a comprehensive evaluation was performed based on the antioxidant power, flavor, yield, etc. The results are shown in Tables 1 to 4 below.

In this case, the antioxidant power in the table below represents the time to reach POV = 30 when an AOM test is conducted with 0.01% solid content added as both components containing antioxidant components. . Here, the AOM test was conducted in accordance with "Standard Oil and Fat Analysis Test Methods, edited by Japan Oil Chemists'Association." The oil and fat used was lard (antioxidant-free, manufactured by Fuji Essential Oil Co., Ltd.), and the oil bath temperature was 97.8°C. In addition, the flavors in the table are based on undeodorized products.
, represents the average score (9 panelists) when evaluated using a 5-point system, with odorless products being 5. Therefore, the higher the antioxidant power value, the stronger the antioxidant power of the extraction tank residue or separated layer recovered material, and the higher the flavor value, the better the removal of fats and oils from the residue or recovered material. .

A1: Nα1-12 Using raw rosemary powder as a raw material, the treatment was performed by changing the pressure without using an entrainer.

Here, the extraction pressure was 80 to 450 kg/cif, and the separation pressure was 1 to 90 kg/cif.

Results: For deodorization, the processing pressure is 90-200 kg
/ffl was suitable. Moreover, in the case of extraction, a processing pressure of 200 to 450 kg/aJ was suitable.

B2: Nα13-18 As a raw material, a hot water treatment residue other than raw rosemary powder and oleoresin were treated without using an entrainer and at different treatment temperatures. Here, the processing temperature is set to 3
The temperature was 2 to 90°C.

Results: If the processing temperature during extraction is less than 40'C, the extraction of antioxidant components will be insufficient, and if it is above 80°C, no increase in the extraction efficiency of antioxidant components will be observed, so the extraction processing temperature should be set at 40-40°C. 80°C was suitable.

It was also possible to process materials other than rosemary powder.

C3: Using raw powder of Nα19-27 0-zumary, the treatment was carried out by changing the type and concentration of entrainer added. Here, ethanol, propane, n-hexane, acetone, and toluene were used as entrainers, and the concentration thereof was 1 to 25%.

Results: Both entrainers containing antioxidant components were efficiently obtained using either entrainer. Further, if the addition concentration is less than 2%, the extraction efficiency is poor, and a range of 2 to 20% is suitable.

D, 4:28-34 Based on the conditions obtained from experiments A-C, a two-step treatment was performed to more efficiently obtain an odorless antioxidant fraction. Ingredients other than rosemary include sage, thyme,
This was also done for marjoram. Raw materials: Rosemary (Nα28-30: hot water extraction residue, Nα31: yX powder) Nα28: Extraction → deodorization, with entrainer.

Nα29: Extraction → deodorization, no entrainer.

NQ 30: Deodorization → extraction, with entrainer.

Nα31: Deodorization → extraction, no entrainer.

Ingredients: Herbal spices other than rosemary (raw powder) Nα32: Sage, extraction → deodorization, with entrainer.

&33: Thyme, extraction → deodorization, with entrainer.

&34: Marjoram, extraction → deodorization, with entrainer.

Results: It was possible to efficiently obtain odorless antioxidants and components containing other components either in the order of extraction → deodorization or deodorization → extraction. Furthermore, by performing the two-step treatment on raw materials other than rosemary, it was possible to efficiently obtain odorless fractions containing antioxidant components.

Furthermore, it was found that these antioxidants were much stronger than those of natural vitamin E (Emix 80 manufactured by Eisai) and BHA, which are generally used as antioxidants (see Table 5).

No. 5 table Main extension time: Time to reach POV=30.

Moreover, the additional time is minus 21 hours without additives.

From the results shown in Tables 1 to 5 above, it is confirmed that antioxidant components and odorous components can be successfully extracted by extracting herbal spices or their processed products with supercritical carbon dioxide. Ta. In addition, in this case, the extraction and separation treatment of antioxidant components is performed at an extraction pressure of 200 to 450 kg/c.
o? , extraction temperature 40-80℃, separation pressure atmospheric pressure ~8
0kg/c+J, the separation temperature is 20 to 80℃, and the extraction and separation treatment of odorous components is performed at an extraction pressure of 90kg/- or more20
0 kg/(d less than
It was found that a temperature of 0°C was appropriate.

Finally, a formulation example is shown.

[Formulation example]

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

Emulsion stabilizer 50g Sucrose 400g Seasoning Log Various spices 40g Water 1640g Acetic acid solution 500g Egg yolk 200g Salt 150g Sodium citrate 5g Vegetable salad oil 2000g In this case, the above dressing contains 3 g of the antioxidant obtained in the above experiment &28 * 1-5 g * O-15g
6 g of eBHAo and 3 g of tocopherol were added to each dressing, and the Pov value (peroxide value) was measured immediately after the production of each dressing and after the dressing was stored at 40°C for 32 days, and its stability (antioxidant property) was investigated. . The results are shown in Table 6. The POv value was measured using 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 N(128) exhibited much stronger antioxidant power than BHA, which was said to have a strong antioxidant power even in conventional amounts.

In addition, the dressing to which &28 was added had no change in aroma, taste, or color tone due to the addition, and maintained good quality.

Table 6 POv value when added to dressing

[Brief explanation of the drawing]

FIG. 1 is a schematic diagram showing an example of an extraction/separation apparatus used for carrying out the present invention. 1... Extraction tank, 2... Separation tank, 3... Co8 cylinder, 4... Extraction compressor, 5...
・Entrainer container, 6...Quantitative supply pump, 7...Pressure control valve, 8-
...Heat exchanger, 9...Flow rate adjustment valve, 10...
Pressure holding valve, 11... Gas flow meter, 12... Weighing platform scale, 13... Atmospheric release valve. 14...Solvent path, 15...Extract collection valve.

Claims (1)

[Claims] 1. Herbal spices or processed products of herbal spices containing antioxidant components are extracted with a fluid made of carbon dioxide in a supercritical state, and the herbal spices or processed products thereof include A method for producing an antioxidant, which comprises transferring the antioxidant component into the fluid and then separating and recovering the antioxidant component from the fluid. 2. The manufacturing method according to claim 1, wherein the fluid is carbon dioxide in a supercritical state at a pressure of 200 to 450 kg/cm^2 and a temperature of 40 to 80°C. 3. The manufacturing method according to claim 1 or 2, wherein an organic solvent is mixed into the fluid as an entrainer. 4. Processed products of herbal spices containing antioxidant components include herbal spices, their hot water extraction residues, essential oil collection residues, oleoresins extracted with polar solvents and their extraction residues, and oleoresins extracted with nonpolar solvents. The manufacturing method according to claim 1, 2 or 3, wherein the extraction residue is obtained by extracting a raw material selected from the extraction residue and the extraction residue thereof with a fluid consisting of carbon dioxide in a supercritical state.