JP2000219880A - Antioxidant - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an antioxidant having higher antioxidative activity, affecting no bad influence such as the change in appearance, taste or the like, and usable for many purposes by adding a tea extract, minerals and a surfactant. SOLUTION: This antioxidant contains (A) a tea extract, preferably (+)- catechin, (-)-epicatechin, (+)-gallocatechin, (-)-epigallocatechin, (-)-catechin gallate, (-)-epicatechin gallate, (-)-gallocatechin gallate and (-)-epigallocatechin gallate, (B) minerals (e.g. magnesium, potassium, sodium, calcium and the like), and (C) a surfactant (e.g. a polyglycerin fatty acid ester, lecithin, polyglycerin condensed ricinoleic acid ester, sorbitan fatty acid ester, sucrose fatty acid ester or the like). In the antioxidant, the component B is preferably added 1/100 to 1000 times the component A (by weight).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an antioxidant containing a tea extract, a mineral and a surfactant, and a method for producing the same.

[0002]

2. Description of the Prior Art It has been clarified that a tea extract has an excellent effect on preserving food quality, and that the effect is due to the bacteriostatic and antioxidant effects of catechins contained in the extract. . As a technique utilizing this effect, a technique utilizing a lipophilic emulsifier as a W / O type antioxidant (Japanese Patent Application Laid-Open No. 3-49315) and a technique using a combination with other plant components (Japanese Patent Application Laid-Open No. 2-92258). ) Or a technique for inclusion with cyclodextrin (JP-A-4-255792). However, these methods may not be able to obtain a satisfactory effect depending on the condition of the target food. That is, the preparations obtained by these methods have different solubility and dispersibility depending on the state of the dispersed phase, and thus may not have an antioxidant effect that can be used. Also, if you use a large amount of the formulation to obtain the effect,
Since the final product may have adverse effects such as the appearance of the product (such as cloudiness or browning of the product) and a change in flavor (expression of astringency or astringency), it has been difficult to use a large amount of the product. Therefore, an antioxidant capable of exhibiting an antioxidant effect with a smaller amount without changing the formulation form as much as possible has been desired.

[0003]

SUMMARY OF THE INVENTION The present invention enhances the antioxidant effect of the tea extract of a target food, and does not adversely affect the appearance and flavor of the tea extract, and can be used for various purposes. It is intended to provide an oxidizing agent.

[0004]

Means for Solving the Problems The present inventors have conducted intensive studies in view of the above-mentioned current situation, and as a result, have found that the above-mentioned problems can be solved by adding a tea extract, a mineral and a surfactant to the present invention. completed. That is, the present invention is an antioxidant characterized by containing a tea extract, a mineral and a surfactant.

[0005]

DETAILED DESCRIPTION OF THE INVENTION The raw material of the tea extract used in the present invention is not particularly limited, and green tea which is unfermented tea produced from leaves of Camellia sinensis, which is botanically a plant of the Camellia family. And oolong tea, a semi-fermented tea, and black tea, a fermented tea. Among them,
Preferably, green tea which is unfermented tea is used. The extract may be a tea leaf or a crushed tea leaf, a fraction extracted with water or hot water or an alcohol such as glycerin or ethanol, or a fraction obtained from an ethyl acetate-soluble fraction or an acetone-soluble fraction. And more preferably (+)-catechin, (-)-epicatechin, (+)
-Gallocatechin, (-)-epigallocatechin, (-)-
Catechin gallate, (-)-epicatechin gallate,
One or more catechins selected from the group consisting of (-)-gallocatechin gallate and (-)-epigallocatechin gallate are exemplified. The content of the catechins is not particularly limited, but is preferably contained in the tea extract to be used in an amount of 60% or more, more preferably 80% or more. In particular, it is preferable that the total amount of three types of (-)-epicatechin gallate, (-)-gallocatechin gallate and (-)-epigallocatechin gallate is contained in the tea extract to be used in an amount of 60% or more. . The total content of these catechins can be measured by a colorimetric method using iron tartrate, but in order to measure the composition of each catechin in detail, it is desirable to measure by reverse phase high performance liquid chromatography .

The mineral used in the present invention is not particularly limited in its origin, but is preferably magnesium, potassium, sodium, calcium, zinc, chromium, manganese, aluminum, copper or a mineral salt. More preferred are copper, magnesium, zinc and mineral salts thereof. Although the form of the mineral salt is not particularly limited, halide salts, oxygenated salts,
Organic salts such as phosphates, carbonates, sulfates and amino acids are preferred, and chlorinated salts, oxygenated salts and carbonates are particularly preferred. More preferably, magnesium chloride, magnesium oxide, magnesium carbonate, zinc chloride, zinc oxide, and zinc carbonate are mentioned. The mixing ratio of these minerals or mineral salts is preferably from 1/100 to 1000 times (weight ratio), more preferably from 1/10 to 100 times, the amount of the tea extract. When the addition amount is 1/100 or less, the effect of improving the antioxidant property by the addition of the mineral is small, and when the addition amount is 1000 or more, the flavor unique to the mineral material may adversely affect the added product.

The surfactant used in the present invention includes monoglycerin fatty acid ester, monoglyceride derivative, polyglycerin fatty acid ester, polyglycerin condensed ricinoleate, sucrose fatty acid ester, sorbitan fatty acid ester, propylene glycol fatty acid ester,
Examples thereof include lecithin, saponin, calcium stearoyl lactate, oxyethylene higher aliphatic alcohol, monoforine fatty acid salt, polyoxyethylene sorbitan ester, and fatty acid salt. Preferably, one or more selected from the group consisting of polyglycerin fatty acid ester, lecithin, propylene glycol fatty acid ester, polyglycerin condensed ricinoleic acid ester, sorbitan fatty acid ester, and sucrose fatty acid ester, more preferably poly Glycerin fatty acid esters are exemplified. The polyglycerin which is a constituent component of the polyglycerin fatty acid ester used in the present invention is not particularly limited. For example, the synthesized polyglycerin is subjected to a molecular distillation purification method, a vacuum distillation method using a steam carrier, a simulated moving bed. Purified by liquid chromatography, etc.
It is preferable that the content of one kind of polyglycerin selected from tri, tetra, penta, hexa, hepta, octa, nona, and decaglycerin in the polyglycerin composition is 35% or more, more preferably 40% or more. In addition, when glycerin and diglycerin are contained, the alcohol portion in the surfactant becomes smaller, and the stability becomes worse.
The total content of glycerin and diglycerin is preferably less than 10% in the polyglycerin composition.

In the composition analysis of polyglycerin in the present invention, polymethylglycerol is converted into a derivative by trimethylsilylation, and then separated and quantified by GC (gas chromatography). GC
The analysis by the method can be easily performed by performing a temperature rise analysis at 10 ° C./min from 100 to 320 ° C. using a fused silica capillary tube in which a low-polar liquid phase such as methyl silicone is chemically bonded. . The identification of peaks on the gas chromatogram is performed, for example, by introducing a gas chromatograph into a double-focusing mass spectrograph, ionizing it by a method such as chemical ionization, and then measuring the ion. This can be easily performed by determining the molecular weight of the peak and further determining the degree of polymerization of glycerin from the chemical formula.
The polyglycerin fatty acid ester of the present invention can be obtained by esterifying the polyglycerin and a straight-chain or unsaturated fatty acid having 8 to 22 carbon atoms in a usual manner. The type of the ester is appropriately changed depending on the intended use of the composition. The mixing ratio of these surfactants is 1 to the mixture of tea extract and mineral.
The ratio is preferably from 1 / 10,000 to 100 times, more preferably from 1/1000 to 1: 1. If the addition amount is 1/10000 or less, the antioxidant improvement effect of the surfactant cannot be obtained, and if it is 100 or more times, the unique flavor of the surfactant may adversely affect the added product.

In addition, substances which can be used in combination with the antioxidant of the present invention are not particularly limited, but include antioxidants such as tocopherol and vitamin C, pH adjusters, antibacterial / bactericides, pigments, fragrances and the like. Is mentioned. Further, depending on the dosage form, for example, a solvent can be used for a liquid preparation, and a bulking agent can be used for a powder preparation. further,
The antioxidant of the present invention can be widely used for various uses. If the minerals and surfactants to be blended are approved as food additives, they can be used for food applications. Next, the present invention will be described in detail with reference to Examples, but the present invention is not particularly limited thereby.

[0010]

Example 1 A green tea extract [trade name: Sanphenone GE-60, catechin content 80%, three kinds of catechins ((-)-epigallocatechin gallate, (-)) in 100 g of warm water at about 50 ° C.
-Gallocatechin gallate and (-)-epicatechin gallate) content: 60%, 20 g of Taiyo Kagaku Co., Ltd. and 20 g of magnesium chloride (manufactured by Wako Pure Chemical Industries, Ltd.) are dissolved, and triglycerin monostearate (product) Name: Sunsoft A-181C, HLB: 10, manufactured by Taiyo Chemical Co., Ltd.]
200 mg was added. Rotor-stator type emulsifier (product name: TK Homo mix) in a warm bath at 50 ° C.
er (Model: M SPEC.A), manufactured by Tokushu Kika Kogyo Co., Ltd.) at 5,000 rpm for 30 minutes, then transferred to a mold flask containing the contents, rapidly frozen, and then freeze-dried (FDU-810, Tokyo, Japan). Drying was carried out by Rika Co., Ltd.) to obtain 39.4 g of the product 1 of the present invention. Example 2 A green tea extract [trade name: Sanphenone GE-60, catechins content 80%, three kinds of catechins ((-)-epigallocatechin gallate, (-)) in 100 g of warm water at about 50 ° C.
-Gallocatechin gallate and (-)-epicatechin gallate) content: 60%, manufactured by Taiyo Kagaku Co., Ltd.) and 20 g of magnesium chloride, and enzymatically decomposed soy lecithin (trade name: San lecithin A, HLB: 12, sunshine) 200 mg (Chemical Co., Ltd.) was added. Rotor-stator type emulsifier (product name: TK Hom) in a warm bath at 50 ° C
o Mixer (Model: M SPEC.A), manufactured by Tokushu Kika Kogyo Co., Ltd.), stirred at 5,000 rpm for 30 minutes, transferred to a flask containing the contents, rapidly frozen, and then freeze-dried (FDU-810, It was dried with Tokyo Science Co., Ltd.) to obtain 38.7 g of the product 2 of the present invention.

Comparative Example 1 Green tea extract [trade name: Sanphenone GE-60, catechin content 80%, three kinds of catechins ((-)-epigallocatechin gallate, (-)) in 100 g of warm water at about 50 ° C.
-Gallocatechin gallate and (-)-epicatechin gallate) content: 60%, manufactured by Taiyo Kagaku Co., Ltd.] and 20 g of magnesium chloride, then transferred to a mold flask containing the contents, rapidly frozen, and then freeze-dried (FDU-81
0, manufactured by Tokyo Science Co., Ltd.).
2 g were obtained. Comparative Example 2 A green tea extract [trade name: Sanphenone GE-60, catechins content 80%, three kinds of catechins ((-)-epigallocatechin gallate, (-)) in 100 g of warm water at about 50 ° C.
-Gallocatechin gallate and (-)-epicatechin gallate) content 60%, manufactured by Taiyo Kagaku Co., Ltd.) 20 g and triglycerin monostearate (trade name: Sunsoft A-
181C, HLB: 10, manufactured by Taiyo Kagaku Co., Ltd.) 200 m
g was added. A rotor-stator type emulsifier (product name: TK Homo mixer (M
model: M SPEC. A), Tokushu Kika Kogyo Co., Ltd.
After stirring at 5,000 rpm for 30 minutes according to the method described above, the mixture was transferred to a mold flask containing the contents, rapidly frozen, and then freeze-dried (FDU).
-810, manufactured by Tokyo Science Co., Ltd.) to obtain 19.9 g of Comparative Product 2.

Test Example 1 (Study of synergistic effect by oxygen electrode method) Inventive products 1, 2, Comparative products 1, 2, commercially available green tea extract [trade name: Sanphenone GE-60, catechin content 80
%, Three kinds of catechins ((-)-epigallocatechin gallate, (-)-gallocatechin gallate and (-)-
Epicatechin gallate) content 60%, Taiyo Kagaku Co., Ltd.
Manufactured) and commercially available magnesium chloride (Wako Pure Chemical Industries, Ltd.)
Was evaluated by measuring the amount of decrease in oxygen accompanying the lipid peroxidation reaction in the linoleic acid micelle solution. That is,
Biological dissolved oxygen meter (Oxy) equilibrated to 37 ° C in the dark
graph8; 50 mM linoleic acid solution (solvent: 50 mM Tris-HCl buffer containing 0.5 M sodium dodecyl sulfate (p.p.) in a reaction cell of Central Chemical Co., Ltd.)
H7.4)) was added thereto, and air was blown into the mixture under oxygen saturation with stirring for about 10 minutes.
Was added. Thereafter, AMVN (2,2′-azobis (2,
20 μl of a methanol solution (concentration: 1 M) of 4-dimethylvaleronitrile)) was added, and the oxygen concentration in the cell after the addition was measured. At this time, as shown in FIG. 1, a linear form occurs between the amount of dissolved oxygen (vertical axis) and the consumption time (horizontal axis).
The degree of slope of this equation is defined as (R), and the consumption time (Rp) when no antioxidant is added and the consumption time (Rp) when an antioxidant is added
When expressed as a ratio (Rp '/ Rp), the higher the antioxidant property, the smaller the ratio (Rp' / Rp). Test results (n =
3) is shown in Table 1.

[0013]

[Table 1] As is clear from Table 1, the commercial green tea extract, the commercial magnesium chloride, the products 1 and 2 of the present invention more than the comparative products 1 and 2
Was confirmed to have about 1.5 to 2 times higher antioxidant properties.

Test Example 2. (Effect on the effect of preventing salmon fillet from fading) Inventive products 1 and 2, Comparative products 1 and 2, commercially available green tea extract [trade name: Sanphenone GE-60, catechin content 80
%, Three kinds of catechins ((-)-epigallocatechin gallate, (-)-gallocatechin gallate and (-)-
Epicatechin gallate) content 60%, Taiyo Kagaku Co., Ltd.
Manufactured) and commercially available magnesium chloride (Wako Pure Chemical Industries, Ltd.)
Was evaluated for the anti-fading effect of red salmon fillets. After thawing the frozen red salmon, the head, spine, and tail fin were removed to prepare cuts (three grated). 0.05% of Comparative Products 1 and 2 and Invention Products 1 and 2 against 12% saline
After adding, stirring and mixing well, it was immersed in a dark place at 4 ° C. for 12 hours. After that, drain the fillet and seal it in a vinyl bag.
It was stored at 10 ° C. under fluorescent light irradiation (4000 lux).
Fillet color tone 1,2,3,4 days after the start of storage (red)
The degree of fading was visually checked, and the average value of evaluation scales of 10 persons was calculated and compared. Table 2 shows the test results.

[0015]

[Table 2] As is clear from Table 2, it was confirmed that the red color of the salmon fillets of the present invention products 1 and 2 was retained for a long time from the commercially available green tea extract, the commercially available magnesium chloride, and the comparative products 1 and 2.

Test Example 3 (Effects of Blood Lipids on Inhibition of Peroxidation) Products 1 and 2 of the present invention, Comparative Products 1 and 2, a commercially available green tea extract [trade name: Sanphenone GE-60, catechin content 80
%, Three kinds of catechins ((-)-epigallocatechin gallate, (-)-gallocatechin gallate and (-)-
Epicatechin gallate) content 60%, Taiyo Kagaku Co., Ltd.
Manufactured) and commercially available magnesium chloride (Wako Pure Chemical Industries, Ltd.)
Was evaluated by the blood lipid peroxidation inhibitory effect of the ingestion of each case. Seven groups of eight male Wistar rats (5-week-old) in groups of eight were prepared, and a standard diet (group VII) and an arteriosclerosis-forming diet (IV) having the composition (% by weight) shown in Table 3 were prepared.
Group I) was administered.

[0017]

[Table 3] Arteriosclerotic diets include 1.5% cholesterol and 0.5 cholic acid to increase serum cholesterol levels.
% And linoleic acid 5% for the purpose of increasing serum lipid peroxide levels. Both feeds were stored in a freezer at −20 ° C. and fresh feeds were given daily in the experiments. The food was given to each animal individually and the intake was measured daily.
Food intake was about 18-20 g / day for each group.

The vitamin mixture per 100 g of feed is
V. A: 3000 (IU); D ₂: 300 (I
U), V. B₁Hydrochloride: 0.5 (mg); B₂:
0.6 (mg), V.I. B₆Hydrochloride: 0.5 (mg),
V. B₁₂: 0.5 (μg); E: 1.0 (m
g), V.I. K₃: 0.5 (mg), calcium pantothenate
Um: 2.0 (mg), niacin: 2.0 (mg),
p-Aminobenzoic acid: 2.0 (mg), d-biotin:
0.01 (mg), folic acid: 0.05 (mg), inosito
100 mg, choline hydrochloride: 150 mg
contains. The salt mixture is 100 g of carbonated carbonate per 100 g of feed.
Cium: 1200mg, dipotassium phosphate: 1300m
g, calcium phosphate (dihydrate): 300 mg, sulfuric acid
408 mg of magnesium (heptahydrate), sodium chloride
System: 672 mg, iron citrate: 112 mg, potassium iodide
: 3.2 mg, manganese sulfate (tetrahydrate): 20 m
g, zinc chloride: 1.0 mg, copper sulfate (pentahydrate): 1.
Contains 2 mg. In addition, distilled water (V
Group II, free drinking water) and invention products 1, 2, comparative products 1, 2,
Commercially available green tea extract (trade name: Sanphenon GE-60,
Catechin content 80%, manufactured by Taiyo Chemical Co., Ltd.) and commercially available
Magnesium chloride (manufactured by Wako Pure Chemical Industries, Ltd.) in distilled water
A fixed amount of the dissolved solution (groups I to VI) was forcibly administered. I
Table 4 shows the daily dose classification and the dose in the groups VI to VI.
Followed.

[0019]

[Table 4]

Rats were bred for 14 weeks at room temperature 25 ± 2 ° C., relative humidity 55 ± 5%, irradiation time 12 hours.
In the meantime, blood was fasted the night before the experiment started, every other week overnight and on the last night. During the breeding period, body weight was measured every week, and after fasting every two weeks, 0.2 ml of blood was collected from the fundus of the rat under ether anesthesia, serum was separated, and lipid peroxide in serum was determined. It was measured. In addition, lipid peroxide was used in the form of Yagi [Yagi et al, Bioche.
m. Med. , 15, 212 (1976)] and a thiobarbituric acid-reactive substance (TBAR).
S) It was expressed by the amount. The values obtained are expressed as average values, II
The Student's t-test was applied to the test of the significant difference between the experimental value and the group. FIG. 2 shows the weight change of each group. According to this, compared with the body weight of the VII group (the standard diet administration group), I to VI
The body weight gain of the group (the group receiving the atherosclerotic diet) was suppressed.
In addition, no significant difference was observed between the groups I to VI. FIG. 3 shows the time course of the serum lipid peroxide values of the groups I to VI measured every two weeks. Lipid peroxide levels in group II gradually increased over the course of the experiment. On the other hand, the lipid peroxide values of the groups I and III to VI showed a decreasing tendency after the 8th week as compared with the group II. In particular, the effect of reducing the lipid peroxide value in the VI group was remarkable, showing a low value after the sixth week, and a significant difference was observed between the group II and the group II. That is, the ingestion of the product 2 of the present invention confirmed a remarkable effect of suppressing peroxidation of blood lipids.

The embodiments of the present invention and the desired products are as follows. (1) An antioxidant comprising a tea extract, a mineral and a surfactant. (2) The antioxidant according to (1), wherein the tea is selected from one or more of green tea, oolong tea, and black tea. (3) The tea extract contains one or more catechins selected from the group consisting of catechin, epicatechin, gallocatechin, epigallocatechin, catechin gallate, epicatechin gallate, gallocatechin gallate and epigallocatechin gallate The antioxidant according to (1) above. (4) The above-mentioned (1), wherein the tea extract contains 60% or more of three kinds of catechins {(−)-epicatechin gallate, (−)-gallocatechin gallate and (−)-epigallocatechin gallate}. Antioxidants as described. (5) The above (1), wherein the mineral contains one or more selected from the group consisting of magnesium, potassium, sodium, calcium, zinc, chromium, manganese, aluminum, copper and compounds containing these. Antioxidants. (6) The antioxidant according to the above (1), wherein the mineral is magnesium chloride, magnesium oxide, magnesium carbonate, zinc chloride, zinc oxide, zinc carbonate. (7) Mineral content is 1/100 of tea extract
The antioxidant according to the above (1), which is up to 1000 times. (8) The surfactant is monoglyceride, monoglyceride derivative, polyglycerin fatty acid ester, polyglycerin condensed ricinoleate, sucrose fatty acid ester,
Contains one or more selected from the group consisting of sorbitan fatty acid esters, propylene glycol fatty acid esters, lecithin, saponins, calcium stearoyl lactate, oxyethylene higher fatty alcohols, monoforine fatty acid salts, polyoxyethylene sorbitan esters, and fatty acid salts The antioxidant according to (1) above. (9) The antioxidant according to the above (1), wherein the mixing ratio of the surfactant is 1/10000 to 100 times the amount of the mixture of the tea extract and the mineral. (10) A food containing the antioxidant according to (1) in an amount of 0.005% or more.

[0022]

According to the present invention, it is possible to enhance the antioxidant effect of a tea extract by using a mineral and a surfactant in combination with a tea extract conventionally recognized as an antioxidant. , Is a great contribution to the food industry.

[0023]

[Brief description of the drawings]

FIG. 1 is a diagram showing the relationship between the amount of dissolved oxygen obtained by an oxygen electrode method and the oxygen consumption time.

FIG. 2 is a diagram showing changes in body weight of each group.

FIG. 3 is a graph showing changes in serum lipid peroxide.

Continuation of the front page (72) Inventor Reka Raju Juneja 9-5 Akabori Shinmachi, Yokkaichi-shi, Mie Taiyo Kagaku Co., Ltd. F-term (reference) 4B021 MC03 MK02 MK05 MK08 MK21 MK22 MK25 MK28 4H025 AA18 AC04 AC05

Claims (4)

[Claims] 1. An antioxidant comprising a tea extract, a mineral and a surfactant. 2. The tea extract is (+)-catechin, (−)-
Epicatechin, (+)-gallocatechin, (-)-epigallocatechin, (-)-catechin gallate, (-)-epicatechin gallate, (-)-gallocatechin gallate and (-)-epigallocatechin gallate The antioxidant according to claim 1, wherein the antioxidant is at least one member selected from the group. 3. The mineral according to claim 1, wherein the mineral is one or more selected from the group consisting of magnesium, potassium, sodium, calcium, zinc, chromium, manganese, aluminum, copper and compounds containing these. Antioxidants. 4. The antioxidant according to claim 1, wherein the amount of the antioxidant is 0.0.
Food containing more than 05%.