JPH0662951B2 - Water-soluble antioxidant - Google Patents

Description

TECHNICAL FIELD The present invention relates to a water-soluble antioxidant obtained from rice bran.

[Conventional technology]

As a negative factor for long-term storage of food, microbial contamination and oxidative deterioration of fats and oils components are mentioned, and as a preventive measure, various researches such as improvement of processing technology, modification of raw materials and food additives are being promoted. .

For oxidative deterioration of fats and oils in foods, a wide variety of objects such as foods using fats and oils and raw materials containing fats and oils can be considered.
While the westernization of eating habits is spreading and the use of highly reactive oils and fats is increasing along with the social tendency toward health and natural products, measures to prevent deterioration of oils and fats are an important issue for the food processing industry. I'm running.

Currently, as measures for preventing food oxidation, methods such as deoxidation (deoxidizer, vacuum packaging, inert gas filling, non-permeable packaging), improvement of physical environment such as light shielding, and methods using food additives are used alone or in combination. Used in. Of these, the antioxidant method using an antioxidant is the most common method,
Although the use of chemically synthesized products such as the carcinogenicity problem of BHA (Butylhydroxyanisole) has been recognized as effective in recent years, it tends to be avoided as it is targeted for social criticism, and it is an antioxidant substance from natural products. There is a situation where research to obtain

There are many reports on the antioxidant capacity of natural products, such as research on tocopherols, research on microorganisms themselves, and research on foods using various microorganisms such as miso and yeast such as miso and tempeh. In addition, the antioxidative ability of spices has attracted attention and has already been partially commercialized. Research on compounds such as aminocarbonyl compounds, amino acids, peptides, organic acids, and aminocarbonyl compounds, browning substances, reductones, flavones, and antioxidant properties of substances extracted from the plant and animal kingdom, including crude drugs, have been extensively researched. is there.

Among them, there are studies on antioxidants extracted from cereals such as rice and wheat, oryzanol, sesameol in sesame, caffeic acid in coffee beans, and gossypol in cottonseed, but they are still in practical use. It has not arrived. Of these, oryzanol originating from rice bran is a water-insoluble substance, which is different from a water-soluble antioxidant. On the other hand, although it is known that phytin, which is a water-soluble substance derived from rice bran, has an antioxidant action, its action is said to be a metal deactivator due to a chelating action, and it is generally used as a synergist and is used alone. Then its antioxidant power is not enough. The antioxidant activity of phytin is described in the following documents [Theory and practice of antioxidants, San-Shiu Shobo,
New Food Industry, Vol. 27, No. 10, issued November 30, 1984
No. 74-84 (1985)].

[Problems to be solved by the invention]

It goes without saying that the development of antioxidants is focused on oil-soluble substances because the target is oils and fats, but in the food field as a whole, trace amounts of oils and fats deteriorate even in water-soluble systems. It is considered to be a major cause of flavor deterioration,
It is a big problem and it is also used in oil and fat foods,
From a technical point of view such as how to incorporate it into the process, there is a strong need and strong demand for water-soluble antioxidants. However, in the present situation, a water-soluble antioxidant which is sufficiently satisfactory from the viewpoints of antioxidant effect, range of use, method of use, cost, etc. has not been put into practical use.

The present invention has been made in view of the above problems of the prior art, and its object is to provide a water-soluble antioxidant made from rice bran as a raw material, which is in the category of natural products. .

[Means for solving problems]

Briefly describing the present invention, the present invention relates to a water-soluble antioxidant, which is characterized by containing a water-soluble substance obtained by extracting a rice bran raw material with water or enzyme-containing water.

The water used in the present invention as the extraction solvent or the water in the enzyme-containing water may be ordinary water (including natural water) or more purified water, or may further contain salts (particularly salt) and / or a pH adjusting agent. You may have. In addition, examples of the enzyme used include enzyme agents such as protease and amylase.

The present invention will be described in detail below.

The rice bran to be used in the present invention may be any of commonly-known rice bran (white bran 90%), tiger bran (90-80%), and white bran (80% or more). In the present situation where the polishing rate is not always constant, so-called rice bran may be used, and the type and quality of rice do not matter.

In any case, the rice grain surface layer, called rice bran, is rich in many components such as proteins, vitamins, oils and fats, but it is difficult to store rice bran for a long time and the rice bran odor is disliked. The method is mainly used only for feed and raw materials for extracting oil. The rice bran raw material used in the present invention may be rice bran itself or defatted rice bran obtained by removing oil and fat components with hexane or another solvent.
Rice bran degreased with hexane shows no deterioration even after being stored at room temperature for 3 months, and is desirable as a practical raw material.

The production of the water-soluble antioxidant from the rice bran raw material according to the present invention is generally performed as follows. That is, raw or defatted rice bran is suspended in water, left at room temperature, and then filtered to obtain a water extract of rice bran. When used as an antioxidant, this extracted aqueous solution is effective as it is, but when added to food,
Unpleasant odors such as rice bran odor are a problem and should be removed. For example, the odor can be removed by heating and concentrating it more than twice. Further, as a food additive, there are problems such as the amount added and the storability due to contamination of various bacteria, etc. Although these are taken into consideration to make a paste, it is practical to use it as a dried product by a conventional method. In any case, it goes without saying that the higher the dehydration rate, the greater the effect for the same amount of use. In addition, the concentration step may make a positive contribution to the antioxidant power such as an aminocarbonyl product, but since the degree of coloring is large, a decolorizing method using activated carbon or the like is also used.

The antioxidant power was measured by oxidizing the oxidation of linoleic acid in 70% aqueous ethanol solution with the rhodane iron colorimetric method (OD.
The number of days required to give an OD. value of 0.3 by colorimetric determination in m) was displayed as the number of induction days, and various antioxidant substances were compared. Therefore, if the amount of the sample used is the same, the number of days of induction is longer in the sample having stronger antioxidant titer. Hereinafter, the antioxidant titer in the present specification is represented by the number of days of induction in this water system, unless otherwise specified.

The standard reaction solution is Was performed under the constant temperature of 50 ° C. Next, 200 g of defatted bran was suspended in 1000 ml of water, and then 30
The results of examination on the water-extracted substance that was agitated for minutes and passed through are shown (Table-1 to Table-4 and FIG. 1).

Table 1 shows the general components of the water extract material.

Each component other than acid is shown in the amount in 100 ml.

The antioxidative activity of this aqueous solution, its 4-fold concentrated solution, and the freeze-dried product were examined and shown in Table 2. In Table 2,% is
In the case of 1 and 2, it is V / V, and in the case of 3, it is W / V.

Thus, it was clarified that the water extract material of rice bran had a very strong antioxidant power. Although there is a positive correlation between the amount added and the antioxidant titer, the antioxidant mechanism itself has not been fully elucidated, and it is expected that it will differ depending on the reaction system and the target oil or fat. The antioxidant activity of BHA in this system was 18 days after induction at an addition amount of 0.005%.

Further, FIG. 1 shows the antioxidant titers of raw rice bran and defatted rice bran in aqueous extraction by rhodane iron colorimetric measurement values, but it was found that they all have equivalent titers. That is, Fig. 1 shows the titer of antioxidants obtained from defatted rice bran and raw rice bran in days (days,
Horizontal axis) and rhodane iron colorimetry (OD at 500 nm, vertical axis)
It is a graph which shows the relationship with. In FIG. 1, a circle mark means degreased bran and a cross mark means raw bran.

Table 3 shows M. Method of M. Latta et al. [Journal of Agricultural Food Chemistry (J. Agr. Food. Chem) 1980, Volume 28, 13
13 to 1315], and shows the relationship between the apparent phytin content (all calculated as sodium phytate) and the antioxidant titer.

As is clear from Table-3, 0.76% (W / V) in the water extract,
1.74% (W / V) of apparent phytin was extracted in the 0.65N hydrochloric acid aqueous solution, but there was no difference in the antioxidant power of each dried product. Further, the antioxidative power was 9 days at the same content as the hydrochloric acid aqueous solution using the reagent sodium phytate. From the above, it became clear that the efficacy of the antioxidant according to the present invention is not solely due to phytin.

Table 4 is a comparison of the antioxidant titers of the extract substances obtained by allowing various proteases to act during water extraction of defatted rice bran as a 4-fold concentrate.

The enzyme treatment conditions are as shown below.

1) 100 g of enzyme preparation for 200 g of defatted bran water suspension
Addition of mg 2) Stirring reaction at 55 ° C for 3 hours 3) Reaction is completed, 4) Liquid is boiled to inactivate enzyme to make antioxidant.

As is clear from Table 4, there was no difference in the antioxidant power, and it was found that an antioxidant having a sufficient titer could be obtained by the water extraction method.

In addition, after reacting defatted rice bran with a liquefied amylase, saccharified amylase, protease, etc. were used, or the water-soluble substance obtained by allowing rice malt to act on defatted rice bran was examined for its antioxidant ability, It is understood that there is no great difference from the case of simply using the water extraction method, the production method, the period, the cost, etc. need not be taken into consideration, and a sufficient effect can be exhibited by at least the extraction substance obtained by the water extraction as in the present invention. Ivy.

Next, the results of examining the extraction time, the extraction temperature, the pH, and the salt concentration for the water extraction conditions in the present invention are shown in Table-
Although shown in Nos. 5, -6, -7, and -8, there was no effective difference under various conditions, and there was no combined effect of the conditions. The antioxidant power was determined by adding 0.1% (V / V) to the standard reaction solution using the extract under each condition.

Table 9 shows the results when ethanol was added as water extraction conditions.

As described above, in the water extraction of the water-soluble antioxidant obtained from rice bran, the results of examination of various conditions during water extraction, combined use of various enzymatic reaction actions such as amylase and protease,
Even if there was a difference in the effect on the flavor as a food additive for each, there was no extreme difference in the effect on the antioxidant potency, so at least a sufficient antioxidant effect was obtained by water extraction. It was revealed that a water-extracted substance having

〔Example〕

Next, regarding the effect of adding the water-soluble antioxidant according to the present invention,
More specific examples will be described, but it goes without saying that the target food, the amount added, the method of use, the method for producing an antioxidant, etc. are not limited to these examples.

Example 1 500 g of defatted rice bran was suspended in 2500 ml of water, and the suspension was stirred at 30 ° C. for 1 hour.
After stirring for 2 hours and solid-liquid separation, 2200 ml of a water extract was obtained. Using a vacuum vacuum distiller, 50
Concentration to 0 ml gave a water soluble antioxidant.

Using this antioxidant, we examined the antioxidation of semi-dried fish.

After removing the internals of the sardine, open it up and soak it in water containing 1% (V / V) antioxidant, soak it in water for 30 minutes, wash it with water and dry it at 20 ° C for 3 hours to obtain a semi-dried sardine product. It was 5 ° C
After storing for 3 days in the sardine, the semi-dried sardines were homogenized, and the POV was measured by a conventional method. As shown in the results in Table-10, a clear strong antioxidant effect was recognized as compared with the case where no antioxidant was added.

The POV (peroxide value) was measured by the method described in "Food Analytical Method", page 551 [Kosoh Co., Ltd., issued October 20, 1982].

Example 2 200 g of raw rice bran was suspended in 500 ml of water, stirred at 25 ° C. for 5 hours, and then solid-liquid separated to obtain a water extract 3
70 ml was obtained. This was freeze-dried to obtain about 30 g of a water-soluble antioxidant.

The antioxidant effect of lard was investigated using this antioxidant. After adding 0 g, 0.25 g, and 0.5 g of antioxidants to 50 g of lard and kneading, the time-dependent change in POV under sunlight was measured. The results are shown in FIG. That is, FIG. 2 is a graph showing the relationship between the number of days of storage (days, horizontal axis) and the POV value (vertical axis), and ○ marks, × marks, and Δ marks show the antioxidant addition amount of 0 g and 0.25 g, respectively. , 0.5 g. As is clear from FIG. 2, the antioxidant of the present invention has a strong antioxidant effect.

Example 3 600 g of defatted rice bran was suspended in water 6, stirred at 50 ° C. for 30 minutes, and then solid-liquid separated to obtain a water extract 5.
Got 6. By vacuum concentration under reduced pressure, about 120 g of a paste-like water-soluble antioxidant having a water content of 25% was obtained.

This antioxidant was added to the cuties based on the formulation shown in Table-11, and the oil and fat deterioration of the cuties was examined by POV measurement.

The results are shown in FIG. That is, FIG. 3 is a graph showing the relationship between the number of days of storage (days, horizontal axis) and the POV value (vertical axis), where ○ indicates no antioxidant added, and × indicates 1% antioxidant (W / W).
The case of addition is shown. As shown in FIG. 3, it was found that the antioxidant 1% additive clearly has a stronger antioxidant effect than the antioxidant-free additive.

〔The invention's effect〕

As described in detail above, the water-soluble antioxidant of the present invention is characterized by containing a water-soluble substance obtained by extracting a rice bran raw material with water or enzyme-containing water, and has a strong antioxidant power. However, it has excellent effects as an antioxidant, an anti-fading agent and a freshness-retaining agent.

[Brief description of drawings]

FIG. 1 is a graph comparing the titers of antioxidants obtained from defatted rice bran and raw rice bran, and FIG. 2 is the POV time course when the antioxidant of the present invention was added to lard and stored in sunlight. FIG. 3 is a graph showing the change, and FIG. 3 is a graph showing the time-dependent change in POV during storage by adding the antioxidant of the present invention to KUTSUKI.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Hideo Morita, Inventor Hideo Morita, 3-4-1, Seta, Otsu, Shiga Prefecture, Central Research Laboratory, Mina Shuzo Co., Ltd. (56)

Claims (1)

[Claims] 1. A water-soluble antioxidant, comprising a water-soluble substance obtained by extracting a rice bran raw material with water or enzyme-containing water.