JPH07188656A - Antioxidant and freshness-reserving agent from rice - Google Patents

Abstract

PURPOSE:To obtain an antioxidant and a freshness-reserving agent which are safe for a human body, low in cost, produced simply, and excellent in antioxidant and freshness-reserving effects. CONSTITUTION:An antioxidant and a freshness-reserving agent are obtd. from one of the following products or from rice contg. one of the following products: a ground germinated rice; an extract of rice or a germinated rice; a product obtd. by subjecting a hydrated rice or a hydrated germinated rice to enzymatic decomposition or to the action of koji; a product obtd. by subjecting rice or a germinated rice to enzymatic decomposition or to the action of koji before or during extraction or by subjecting the extract of rice or a germinated rice to enzymatic decomposition or to the action of koji; and a product obtd. by subjecting the extract of rice or a germinated rice or the product obtd. by sunjecting rice or a germinated rice to enzymatic decomposition or to the action of koji to an alcohol fermentation or to an org. fermentation.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an antioxidant and a freshness-retaining agent which are safe and can be used in a wide range of fields such as medicine, food and cosmetics by using rice or germinated rice.

[0002]

[Prior Art] Now that the distribution is complete,
A wide variety of products are coming to the market. Along with this, a change in quality that occurs over time has become a problem. For example, in the case of pharmaceuticals and cosmetics, depending on the substance, there is a risk that oxidation will occur over time, the effect of the active ingredient will change, or the substance will become a completely different substance. Also, in foods, oxidation may impair the flavor or the appearance. Therefore, in order to supply stable products to consumers, it is desired to develop an antioxidant that is safe and has an excellent antioxidant effect. However, in reality, only limited quinones, amines and phenols are generally used.

Recently, vitamin E, vitamin C and the like have been used for natural products. However, these are all synthetic products or substances isolated from nature,
Side effects caused by long-term eating, drinking, or applying are problematic. Therefore, recently, antioxidants derived from natural products have been developed with the aim of natural products, but the raw materials are expensive, it is difficult to obtain stable quality products, and there are still significant effects. The current situation is that it has not been developed. Furthermore, in fresh foods such as vegetables and fish, which lose their freshness in a short time, freshness is vital. When the freshness is lowered, the appearance and the like are deteriorated and the product value is lowered. Therefore, there is a long-awaited need for the appearance of products that can extend freshness for a day or even for an hour. However, as with antioxidants, natural products that have a remarkable freshness-maintaining effect have not yet emerged. Not not.

On the other hand, rice is not the staple food, but sake, shochu, amazake,
It has been used as an ingredient for mirin, vinegar, koji, etc., and has been indispensable for daily life since ancient times, but it has hardly been developed for new purposes. This may be due to the fact that rice was viewed as just a staple food, or at best viewed as a source of starch.
In addition, although bran bags are known as applications other than food, it is said that they are good for the skin even if they are bran bags, and they have only been used as they are, and there is no concept of an active ingredient.
There was no idea of using active ingredients.

[0005]

As described above, oxidation is a condition that must be prevented in all fields such as medicine, cosmetics and foods. Further, in fresh foods, the appearance of freshness-retaining agents has been eagerly awaited, and in addition, from the viewpoint of safety and side effects, there is an increasing demand for natural products, which are not isolated products. In other words, it is safe for the human body, inexpensive, and
The development of antioxidants and freshness-retaining agents that can be easily produced and have excellent antioxidant and freshness-retaining effects has been awaited.

[0006]

[Means for Solving the Problems] From the viewpoint of animal and plant harmony, the present inventors have conducted research on various plant components centering on rice, which is a staple food. In the process, it has become clear that rice has many unpredictable possibilities and effects. Therefore, we have conducted a comprehensive utilization study of rice, focusing on rice, which is used as a staple food and has been demonstrated to have the highest safety. As one of the themes, we conducted an intensive study on antioxidants and freshness-preserving agents from rice. In the process, the present inventors have already invented that what is obtained by water extraction or organic solvent extraction of rice becomes an excellent antioxidant and freshness-retaining agent (Japanese Patent Application No. 14-141999). However, as a result of further studies thereafter, an antioxidant and a freshness-retaining agent having higher effects were found at a lower cost from rice and germinated rice, and the present invention was completed.

In the present invention, the components having antioxidant and freshness-retaining effects contained in rice and germinated rice have not yet been elucidated, but rice and germinated rice treated as follows. Was found to exhibit antioxidant and freshness-retaining effects. Sprouted crushed rice as it is or containing it. Rice or germinated rice extract as it is or containing it. Enzyme-decomposed or hydrolyzed rice hydrolyzed as it is, or containing it. When extracting rice or sprouted rice, the one that has been subjected to enzymatic decomposition or koji before or at the same time as or after the extraction is used as it is or containing it. A product obtained by subjecting rice or germinated rice extract or koji which has been subjected to alcohol fermentation or organic acid fermentation to itself or containing it.

The rice used in the present invention is Japonica,
Regardless of indica rice, it refers to non-glutinous rice, brown rice such as sticky rice, and white rice, regardless of variety and type. Further, 92% or more of red rice bran or 92% or less of white rice bran, which appears during whitening, may be used, which is inexpensive and economical. Also,
Germinated rice is used. In addition, since the active ingredient is stable to heat and light, the above raw materials are dipping, steaming, roasting (all sand roasting, net roasting, hot air roasting, etc.),
The raw material treatment such as steam roasting, surface modification such as freeze-drying, photo-modification such as UV irradiation, pressure roasting such as Patrice, and frying may be performed, and the effect was not changed. Although rice and germinated rice are effective as they are, they are preferably crushed and used from the viewpoint of practical use. In order to pulverize the rice and the sprouted rice into powder, it may be carried out by a general method using a pulverizer or a rice mill.

When germinating rice, germinated rice is soaked in water or sprayed with water to germinate. The temperature for germination is 5 to 70 ° C. However, as long as it germinates,
Temperature and time do not matter. Further, when there is a risk of water spoiling during germination, it is preferable to replace the water so that it does not spoil, or to perform some kind of preservative. Here, germination refers to everything from just before germination to germinated ones.
The germinated rice is washed well before use. At this time, it may be dried before use. When extracting rice or sprouted rice, or subjecting it to enzymatic decomposition or koji, the raw material rice is pulverized into granules or powder to increase the surface area, resulting in higher efficiency. Although it is not necessary to grind, in this case, it takes a long time to decompose and extract the rice tissue.

When extracting rice or germinated rice with water,
High extraction temperature is efficient, but extraction can be sufficiently performed even at low temperature. However, in the case of a low temperature of 40 ° C. or lower, it is desirable to make PH acidic or alkaline, or add a preservative or alcohol to treat the rice so that it does not spoil. The extraction time may be long or short as long as the active ingredient can be extracted, and may be determined depending on the extraction temperature. The extraction may be carried out under pressure, at normal pressure, or under reduced pressure. In the case of water extraction, the most problematic is the gelatinization phenomenon. If it becomes pasty, not only the extraction efficiency will deteriorate, but it will be extremely difficult in actual work.
In order to prevent this, the reaction may be carried out by adding amylase or acidification may be carried out with hydrochloric acid or the like to cut the starch. By using this method, it can be sufficiently solved and there is no problem in practice.

Since the active ingredient in the extract is stable to acid and alkali, it is also effective to perform acid decomposition extraction or alkali decomposition extraction. In this case, neutralize if necessary,
Desalt. Also when extracting with an organic solvent, it is desirable to pulverize or pulverize rice as much as possible before extracting. The organic solvent may be a general organic solvent such as alcohol, acetone, n-hexane and methanol, but those harmful to the human body are preferably safe because it is necessary to completely remove the solvent after extraction. In addition, rice or germinated rice may be enzymatically decomposed or koji may be allowed to act. Enzymatic degradation here means starch degrading enzyme, proteolytic enzyme, lipolytic enzyme,
It refers to the action of one or more enzymes that act on rice, such as fiber degrading enzymes, lignin degrading enzymes, and pectin degrading enzymes. The type of koji mold and the variety and type of rice as koji do not matter.

Further, in carrying out the above-mentioned extraction, the above-mentioned enzymatic decomposition and koji may be applied before the extraction, at the same time as the extraction, or after the extraction. In the present invention, at the same time as or after the above treatment, alcohol fermentation or lactic acid fermentation, and organic acid fermentation such as acetic acid fermentation,
It is also effective in the following points. First, if alcohol fermentation is performed, it is not foolish that there is no stickiness at the time of application, and it is easy to concentrate, so that the active ingredient is easily concentrated. Further, when lactic acid fermentation is used for applications such as beverages, the product of the present invention can be used as a seasoning liquid application of acetic acid fermentation to improve flavor, and acetic acid fermentation can be used as a wide range of applications by organic acid fermentation. You can If necessary, aeration fermentation with yeast, alcohol precipitation, saccharide removal by a synthetic adsorbent and the like may be performed. Further, when the red bran portion of 92% or more was examined, it was found that it was effective but weak. The product of the present invention obtained as described above is used as it is without separating the residue, or after being pressed and filtered.

The effectiveness of the product of the present invention as an antioxidant and a freshness-retaining agent will be shown below based on experimental results. First,
The effect of inhibiting the production of oxides by the product of the present invention was investigated by the rodan iron method. That is, the effect of inhibiting oxidation of linoleic acid, which is very easily oxidized by the product of the present invention, was investigated. The measuring method is as follows. Preparation of reagents (1) 0.2 M phosphate buffer (pH 7.0) (2) 2.6% linoleic acid ethanol solution (3) 75% ethanol solution (4) 30% ammonium thiocyanate (5) 0.02M chloride 35% hydrochloric acid solution of ferric iron

Method of operation 0.2 ml of sample solution, 0.2 M phosphate buffer 0.1
ml, water 0.5 ml, 2.6% linoleic acid ethanol solution 0.2 ml are added and mixed well, and the mixture is allowed to stand at 37 ° C. for 5 days. 50 μl of 75% ethanol solution, 4.85 ml of 75% ethanol solution, 50% of 30% ammonium thiocyanate
50 μl of 35% hydrochloric acid solution of 0.02 M ferric chloride
Are mixed, and after 5 minutes, the absorbance at 500 nm is measured. Use distilled water instead of the sample in the same manner as a control. The results are shown in Table 1.

[0015]

[Table 1]

As is clear from Table 1, the present inventor has found that the linoleic acid, which is highly susceptible to oxidation, has an excellent antioxidant effect. In addition, Examples 30 to 34
The product of the present invention obtained in 1. had a considerable effect, and an excellent effect was obtained by subjecting rice to alcohol fermentation, lactic acid fermentation, and acetic acid fermentation. Next, by the DPPH method,
The strength of the reducing action of the product of the present invention was examined. That is, the product of the present invention was reacted with DPPH, which is a stable radical, and the radical scavenging ability of the product of the present invention was investigated.

The method is as follows. Preparation of sample (1) Sample solution 1% w / v aqueous solution (2) 0.1M phosphate buffer (pH 6.5) (3) 99% ethanol solution (4) 5 × 10 ⁻⁴ M DPPH ethanol solution Operating method Sample solution 0.5 ml, 0.1 M phosphate buffer 2.0
ml, 99% ethanol solution 1.5 ml, 5 × 10 ⁻⁴
Mix 1.0 ml of M DPPH ethanol solution. Immediately after mixing, the absorbance at 525 nm is measured 3 hours later. The absorbance is measured in the same manner for distilled water instead of the sample and used as a control. The results are shown in Table 2.

[0018]

[Table 2]

As is clear from Table 2, in the case of using water as a control, the decrease in the absorbance caused by the reduction of DPPH was hardly recognized, whereas in the product of the present invention, the absorbance was considerably high. It showed a low value. This is because the stable radical of DPPH was reduced by the present invention and lost a unique color development, and it was clarified that the product of the present invention has an extremely effective antioxidant effect. Next, in order to examine the freshness-retaining effect of the product of the present invention, the product of the present invention obtained in Example 30 was sprayed on lettuce and tested. If you spray water on lettuce and leave it at room temperature, it will start to grow after 12 hours,
On the second day, the wound turned brown. However, the product of the present invention is 50
The lettuce that had been diluted two-fold and sprayed was fresh until 22 hours and did not discolor until the fourth day.

As with kamaboko, it is most necessary to maintain the freshness of vegetables and the like, and in the extreme case, the freshness and the like of the vegetables are very effective even if they extend in time units. Furthermore, since the discoloration can be extended for 2 days, the product of the present invention also has a storage effect of maintaining freshness. Therefore, in order to exemplify this freshness-retaining effect, a test for tyrosinase activity inhibitory action was conducted, and the results are shown in Table 3. The operation method was as follows: substrate solution (0.04% tyrosine solution), buffer solution (Mcllvai)
1 ml each of ne Buffer pH 6.8) was accurately placed in an absorption cell, and 1 ml each of water and the product of the present invention
Each accurately, stir and mix, keep at 35 ° C, and after 5 minutes,
Zero-correction was performed by adjusting the absorbance scale to the wavelength of 475 nm, and then the tyrosinase solution (tyrosinase 5.3 m
g dissolved in 0.9% NaCl solution) 0.02 m
1 was added exactly, and immediately stirred and incubated.
The absorbance at this time was measured over time (every 5 minutes). The tyrosinase activity inhibition rate was calculated by the following formula, and the results are shown in Table 3.

[0021]

[Equation 1]

[0022]

[Table 3] As can be seen from Table 3, the product of the present invention was found to have a very remarkable effect on the tyrosinase activity inhibitory action. From this, it can be said that it is very effective as a freshness-retaining agent.

[0023]

【Example】

(Example 1) 1 kg of rice without germ was soaked in water at 25 ° C for 3 days to germinate rice. After thoroughly washing the germinated rice, it is dried at 50 ° C. for 24 hours, and then,
The product was finely pulverized to obtain 990 g of the product of the present invention. (Example 2) Brown rice was crushed to obtain a crushed brown rice product 500
g was obtained. 1500 ml of water was added to this pulverized product, PH was dropped with hydrochloric acid, and the mixture was left for 10 days. Then, it was squeezed with a squeezing machine to neutralize the resulting clear liquid to obtain 1200 ml of the product of the present invention and 760 g of a residue. (Example 3) Using 500 g of the product of the present invention obtained in Example 1, the same operation as in Example 3 was carried out to obtain another product of the present invention 11
90 ml was obtained.

Example 4 Brown rice was crushed by a crusher to obtain 500 g of crushed brown rice. Liquefaction enzyme 10g and water 1500ml were added to this ground product. Then, the temperature was gradually raised, and the mixture was boiled and extracted for 5 minutes and then cooled. Then, it was squeezed with a squeezing machine to obtain 1420 ml of the product of the present invention and 560 g of a residue. (Example 5) Using 500 g of the product of the present invention obtained in Example 1, the same operation as in Example 4 was carried out to obtain another product of the present invention 14
00 ml was obtained. (Example 6) Brown rice is crushed by a crusher to obtain crushed brown rice 500
g was obtained. 1500 ml of 2N-NaOH was added to this pulverized product and the mixture was left for 5 days. Then, it was squeezed with a squeezing machine to obtain 1350 ml of the clear liquid and 650 g of the residue. 1 of this clarified liquid
Neutralization with 0N-HCl gave 1480 ml of the product of the present invention.

Example 7 Using 500 g of the product of the present invention obtained in Example 1, the same operation as in Example 6 was carried out to obtain another 1490 ml of the product of the present invention. (Embodiment 8) Brown rice is crushed to obtain a crushed brown rice product 500
g was obtained. 1500 ml of 95% ethanol is added to this pulverized product.
Was added and left for 5 days. After that, squeeze with a wringer,
1300 ml of clear liquid and 650 g of residue were obtained. 2000 ml of water was added to this clarified solution, and the mixture was concentrated by a rotary evaporator to obtain 1500 ml of the product of the present invention. (Example 9) Using 500 g of the present invention product obtained in Example 1, the same operation as in Example 8 was carried out to obtain another invention product 15
00 ml was obtained.

Example 10 Brown rice was crushed to obtain 500 g of crushed brown rice. 300 g of koji and 1500 ml of water were added to this pulverized product, and the mixture was left at 55 ° C. for 20 hours. Then, squeezing with a squeezing machine, 1230 ml of the present invention product and 100 residues
0 g was obtained. (Example 11) Using 500 g of the present invention product obtained in Example 1, the same operation as in Example 10 was carried out to obtain another 1210 ml of the present invention product. (Example 12) Brown rice is crushed to obtain a crushed brown rice product 50
0 g was obtained. 2 g of protease and 150 water
0 ml was added and the mixture was left at 50 ° C. for 20 hours. Then, the product was squeezed with a squeezing machine to obtain 1310 ml of the product of the present invention and 670 g of a residue.

(Example 13) Using 500 g of the product of the present invention obtained in Example 1, the same operation as in Example 12 was carried out,
Another 1380 ml of the product of the present invention was obtained. (Example 14) Brown rice is crushed to obtain 50 crushed brown rice.
0 g was obtained. 2 g of lipolytic enzyme and 150 water
0 ml was added and the mixture was left at 50 ° C. for 20 hours. Then, it was squeezed with a squeezing machine to obtain 1290 ml of the product of the present invention and 680 g of a residue. (Example 15) The same operation as in Example 14 was carried out using 500 g of the product of the present invention obtained in Example 1 to obtain 1360 ml of another product of the present invention.

Example 16 Brown rice was crushed to obtain 500 g of crushed brown rice. Fiber-degrading enzyme 2 in this crushed product
g and 1500 ml of water were added, and the mixture was left at 50 ° C. for 20 hours. Then, the product was squeezed with a squeezing machine to obtain 1330 ml of the product of the present invention and 650 g of a residue. (Example 17) The same operation as in Example 16 was carried out using 500 g of the product of the present invention obtained in Example 1 to obtain 1370 ml of another product of the present invention. (Example 18) Brown rice was crushed to obtain a crushed brown rice product 50
0 g was obtained. 2g starch degrading enzyme and 150g water
0 ml was added and the mixture was left at 55 ° C. for 20 hours. Then, it was squeezed with a squeezing machine to obtain 1380 ml of the product of the present invention and 600 g of a residue.

Example 19 The same operation as in Example 18 was carried out using 500 g of the product of the present invention obtained in Example 1,
Another 1400 ml of the product of the present invention was obtained. (Example 20) Brown rice is crushed to obtain a crushed brown rice product 50
0 g was obtained. Add 2 g of pectin-degrading enzyme and 1 part of water to this ground product.
500 ml was added and left at 50 ° C. for 20 hours. After that, squeezing with a squeezing machine, 1320 ml of the present invention product and residue 660
g was obtained. (Example 21) Using 500 g of the present invention product obtained in Example 1, the same operation as in Example 20 was carried out to obtain another 1300 ml of the present invention product.

Example 22 Brown rice was crushed to obtain 500 g of crushed brown rice. Proteolytic enzyme 2 in this crushed product
g, lipolytic enzyme 2 g, fiber degrading enzyme 2 g, starch degrading enzyme 2 g, pectin degrading enzyme 2 g and 1500 ml of water were added, and the mixture was allowed to stand at 50 ° C. for 20 hours. Then, it was squeezed with a squeezing machine to obtain 1420 ml of the product of the present invention and 560 g of a residue. (Example 23) Using 500 g of the product of the present invention obtained in Example 1, the same operation as in Example 22 was carried out to obtain another 1440 ml of the product of the present invention. (Example 24) The same operation as in Example 22 was carried out to obtain 2000 g of an enzymatic decomposition product of rice. Then, the temperature was gradually raised, and the mixture was boiled and extracted for 5 minutes and then cooled. Then, it was squeezed with a squeezing machine to obtain 1400 ml of the product of the present invention and 550 g of a residue.

(Example 25) The same operation as in Example 24 was carried out using 500 g of the product of the present invention obtained in Example 1,
1420 ml of another product of the present invention was obtained. (Example 26) Brown rice was crushed to obtain a crushed brown rice product 50
0 g was obtained. To this crushed product, 300 g of koji and 1500 ml of 40% ethanol were added, and the mixture was left at 55 ° C. for 48 hours. After that, squeeze with a squeezing machine and clarified liquid 1300 ml and residue 850
g was obtained. Then, 1000 ml of water was added to the clarified liquid, and the mixture was concentrated by a rotary evaporator to obtain the product 13 of the present invention.
00 ml was obtained. (Example 27) The same operation as in Example 26 was carried out using 500 g of the present invention product obtained in Example 1 to obtain another 1300 ml of the present invention product.

(Example 28) In the same manner as in Example 4, 2000 g of a rice extract was obtained. To this extract, 2 g of proteolytic enzyme, 2 g of lipolytic enzyme, 2 g of fiber degrading enzyme, 2 g of starch degrading enzyme, 2 g of pectin degrading enzyme were added, and the mixture was heated at 50 ° C for 2
It was left for 4 hours. After that, the product of the present invention 14
00 ml and 580 g of residue were obtained. (Example 29) The same operation as in Example 28 was carried out using 500 g of the present invention product obtained in Example 1 to obtain another 1390 ml of the present invention product. (Example 30) In the same manner as in Example 24, 2000 g of an enzyme-decomposed extract of rice was obtained. Yeast was added to this enzyme-decomposed extract, and alcoholic fermentation was carried out for 16 days. Then, it was squeezed with a squeezing machine to obtain 1880 ml of the product of the present invention and 80 g of a residue.

(Example 31) The same operation as in Example 30 was carried out using 500 g of the product of the present invention obtained in Example 1,
Another 1800 ml of the product of the present invention was obtained. (Example 32) In the same manner as in Example 24, 2000 g of an enzyme-decomposed extract of rice was obtained. The enzyme-decomposed extract was sterilized by boiling, cooled to 37 ° C., 200 ml of a starter in which lactic acid bacteria had been cultured in advance was added, and the mixture was well stirred and sealed, and
Lactic acid fermentation was performed at 7 ° C for 2 days. Then, it was squeezed with a squeezing machine to obtain 1380 ml of the product of the present invention and 590 g of a residue. (Example 33) Using 500 g of the present invention product obtained in Example 1, the same operation as in Example 32 was carried out to obtain another 1400 ml of the present invention product.

Example 34 80 ml of 95% ethanol was added to 1000 ml of the product of the present invention obtained in Example 24, and acetic acid fermentation was carried out for 20 days. Then, filtration was performed to obtain 990 ml of the product of the present invention. (Example 35) Using 500 g of the present invention product obtained in Example 1, the same operation as in Example 34 was carried out to obtain another 1000 ml of the present invention product.

[0035]

As is apparent from the above data,
By using rice or germinated rice, an antioxidant and a freshness-retaining agent having an extremely excellent antioxidant action can be easily obtained. Moreover, since rice has been the staple food until now, little development has been done for its intended use in new fields other than food. Furthermore, the fact that rice has been the staple food has proved its safety. Therefore, the present invention provides antioxidants and freshness-retaining agents that are excellent in antioxidant effect and freshness-retaining effect and can be used in a wide range of fields such as pharmaceuticals, cosmetics, foods, etc. It was found that it can be obtained,
It is extremely meaningful to find new uses for rice, which is said to be overproduction of rice, and to increase consumption by improving the image of rice.

Claims (5)

[Claims] 1. An antioxidant and a freshness-retaining agent which are obtained by crushing sprouted rice as it is or containing it. 2. An antioxidant and a freshness-retaining agent comprising rice or an extract of germinated rice as it is or containing it. 3. An antioxidant and a freshness-retaining agent, which is obtained by enzymatically decomposing or hydrolyzing rice hydrolyzed with hydrolyzed rice, or containing it. 4. Extraction of rice or sprouted rice is carried out before or at the same time as or after extraction with enzymatic decomposition or koji, as it is, or as an antioxidant containing the same, Freshness-retaining agent. 5. An antioxidant or an extract of rice or germinated rice, or a product obtained by subjecting it to enzymatic decomposition or koji, which has been subjected to alcohol fermentation or organic acid fermentation as it is or containing it. Freshness-retaining agent.