JP2010195925A - Antioxidant composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an antioxidant prepared with a simple method, having no influence on the taste of food and drink and high fading preventing effect on carotenoid-based pigments. <P>SOLUTION: The antioxidant contains grape juice as an effective ingredient, the antioxidant contains white grape juice as an effective ingredients, the antioxidant contains juice obtained from a meat part prepared by removing fruit skin and seeds from grape fruit as an effective ingredient and the antioxidant contains a non-adsorbed part as an effecting ingredient prepared by bringing the grape juice into contact with a synthetic adsorbent to remove the adsorbed part. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to an antioxidant. More specifically, the present invention relates to an antioxidant containing grape juice as an active ingredient and a method for preventing discoloration of carotenoid pigments by containing grape juice as an active ingredient.

  Carotenoid pigments are useful as natural pigments that are safe for the human body to be colored in red, orange and yellow, and are used, for example, in the fields of foods and drinks, cosmetics, health / pharmaceuticals, and are particularly widely used for coloring foods and drinks. Yes.

  However, carotenoid pigments are unstable with respect to oxygen, heat, etc., and are accompanied by a change in color tone and fading over time, resulting in a significant reduction in commercial value.

  In order to solve these drawbacks, several proposals have been made regarding the prevention of fading of carotenoid pigments or foods and beverages to which carotenoid pigments are added. For example, a method for preventing discoloration of paprika dye comprising adding rutin, quercetin, etc. (Patent Document 1), a method for preventing discoloration of paprika dye comprising adding morin (Patent Document 2), caffeic acid, ferulic acid, chlorogen Method for preventing fading of paprika pigment by adding acid or the like (Patent Literature 3), Method for preventing fading of paprika pigment comprising adding solvent extract such as hexane, ethanol, water such as rosemary and sage (Patent Literature 3) 4) Method for preventing discoloration of carotenoid pigment comprising adding solvent extract of tea (Patent Document 5), Method for preventing discoloration of food containing carotenoid pigment comprising adding γ-oryzanol (patent) Reference 6), Color stabilization method for astaxanthin-containing materials by the action of flavanol and kojic acid (patent) 7), a method for preventing discoloration of carotenoid pigments and the like comprising adding isochlorogenic acid or a salt thereof (Patent Document 8), and an amino acid-containing beverage colored with carotenoid pigments by using ascorbic acid and proanthocyanidins in combination. Many proposals such as a fading prevention method (Patent Document 9) have been made. However, it is difficult to say that the above method is sufficiently satisfactory in terms of fading prevention effect, ease of handling, influence on flavor of food and drink, and the like.

On the other hand, it is known that grapes, particularly grape fruits, have various functionalities, and it is known that these functionalities are due to polyphenol substances having a high antioxidant effect. Grape polyphenols include anthocyanins, which are pigment components contained in the peel, catechins and proanthocyanidins, which are contained in seeds, and resveratrols, which are stilbene-based polyphenols, that are mainly contained in seeds. Are known (Non-Patent Document 1).
However, there is no finding that only the juice of grapes has an antioxidant action such as an anti-fading action of carotenoid pigments.

Japanese Patent Laid-Open No. 51-112561 JP 54-52740 A Japanese Patent Laid-Open No. 57-117566 JP-A-57-102955 Japanese Patent Laid-Open No. 62-126953 Japanese Patent Laid-Open No. 4-166061 JP-A-8-332052 JP 2000-342219 A WO2005 / 104873

Fruit Juice Association Bulletin (488), 18-30, (1999)

  The problem to be solved by the present invention is to provide an antioxidant having a high effect of preventing discoloration of carotenoid pigments by a simple method, without affecting the taste of food and drink.

  The inventors of the present invention have conducted extensive research on a method for preventing discoloration of carotenoid pigments. Surprisingly, fading of carotenoid pigments can be suppressed by adding a small amount of white grape juice to a beverage colored with carotenoid pigments. I found out. And it turned out that this fading prevention effect is found not only in white grapes, but also in the juice of white, red and black grapes if the grapes are squeezed after removing the skin and seeds. . Furthermore, this anti-fading effect is not adsorbed by the synthetic adsorbent treatment of grape juice, but is contained in the non-adsorbed part, rather the non-adsorbed part is found to be more effective than the original fruit juice. Completed.

  Thus, the present invention provides an antioxidant comprising grape juice as an active ingredient. The present invention also provides the above antioxidant, wherein the grape juice is white grape juice. Furthermore, the present invention provides the antioxidant described above, wherein the grape juice is a fruit juice obtained from a fruit portion obtained by removing fruit skin and seeds from the grape fruit. Furthermore, the present invention provides the antioxidant described above, wherein the grape juice is a non-adsorbing portion obtained by bringing the grape juice into contact with a synthetic adsorbent and removing the adsorbing portion. Furthermore, the present invention provides a carotenoid pigment fading inhibitor comprising any one of the above antioxidants as an active ingredient. Furthermore, the present invention also provides a method for preventing discoloration of carotenoid pigments, which comprises adding any of the antioxidants described above.

It is a graph which shows the relationship between the addition amount of the grape juice which is the antioxidant of this invention, and the lycopene fading prevention effect.

  Any grape varieties can be used as the raw material of the grape juice that can be used in the present invention. For example, white grape (for example, Muscat, Neo Muscat, Muscat of Alexandria, Niagara, Rosary) Bianco, Pittello Bianco, etc.), red grapes (eg Delaware, Rosario Rosso, Kai Road, Koshu, Beni Kanazawa, Beni Yamabiko etc.), black grapes (eg Kyoho, Pione, Berry A, Steuben, Campbell, etc.) Each variety can be exemplified, but grape juice can be used regardless of these varieties.

  As the grape juice that can be used in the present invention, a commercially available grape juice or a concentrate thereof can be used. These fruit juices are usually obtained by squeezing whole fruits, that is, including fruit skins and seeds. Such a squeezing method is a commonly practiced method and is easily available. In this case, known antioxidant components such as anthocyanins that are pigment components contained in the peel, catechins and proanthocyanidins contained in seeds, and resveratrols mainly contained in seeds are also contained in the fruit juice. Although it is included, it does not impede the effect of the present invention. However, since these known antioxidant components cause coloring and bitterness, it is preferable that they are reduced as much as possible or not contained so much. Some commercially available grape juices contain sodium sulfite as an antioxidant, but are preferably not added with sodium sulfite.

  The grape juice used in the present invention can be any of white grape, red grape and black grape as described above, but the influence on the taste of the final product due to the bitter taste of proanthocyanidins and the bitter taste of catechins In order to avoid the influence of unnecessary coloring of the final product by anthocyanins and proanthocyanidins, it is particularly preferable to use white grape juice.

  In addition, when squeezing fruit juice, the anthocyanins that are pigment components contained in the skin by squeezing after removing the fruit skin and seeds, catechins and proanthocyanidins contained in the seeds, mainly Although it has antioxidative properties such as resveratrol contained in seeds, it can avoid mixing into the juice of ingredients that cause coloring and bitter taste.

  In addition, grape juice is brought into contact with a synthetic adsorbent, and the adsorbed portion is removed to obtain a non-adsorbed portion, whereby anthocyanins, which are pigment components contained in the peel, catechins contained in seeds, contained in seeds The fruit juice from which proanthocyanidins, mainly resveratrol contained in seeds, and the like are removed can be obtained. Examples of synthetic adsorbents that can be used include styrene / divinylbenzene porous resin adsorbents and methacrylic ester synthetic resin adsorbents. Such synthetic adsorbents are easily available on the market. It can be obtained. Examples of the former include, for example, Diaion HP10, Diaion HP20, Diaion HP30, Diaion HP40, Diaion SP206, Diaion SP207 (above, manufactured by Mitsubishi Chemical Corporation); Amberlite XAD-2, Amberlite XAD- 4 (manufactured by Rohm &Haas); Hitachi Gel # 3010, Hitachi Gel # 3011, Hitachi Gel # 3019 (manufactured by Hitachi Chemical Co., Ltd.), and the like. Examples of the latter include, for example, Diaion HP1MG, Diaion HP2MG (manufactured by Mitsubishi Chemical Corporation), Amberlite XAD-7, Amberlite XAD-8 (manufactured by Rohm & Haas), and the like. Can do.

  Such a contact treatment with the synthetic adsorbent can adopt any form such as a batch type or a continuous treatment with a column, but generally a continuous treatment with a column filled with the synthetic adsorbent is adopted. .

  The conditions for the above contact treatment can be appropriately selected according to the type and concentration of grape juice. For example, as the conditions for the continuous treatment by the column, 1 to 50 volumes with respect to 1 volume of the synthetic tree adsorbent. Examples of the conditions are such that grape grape juice (straight juice equivalent) is passed at a liquid temperature of 10 ° C. to 30 ° C. and a flow rate of about SV = 1 to 5. A fraction that is particularly effective as an antioxidant in the present invention is a non-adsorbed portion after contact with a synthetic adsorbent as described above.

  There has never been any knowledge that the above-mentioned fractions of grape juice have anti-fading and anti-oxidation effects of carotenoid pigments, and this phenomenon can be found in anthocyanins, proanthocyanidins, catechins, resveratrols, etc. It is not clear whether this is due to the presence of an unknown antioxidant component other than the known antioxidant component, or a combined action due to components in the fruit juice. However, such a carotenoid pigment's anti-fading and antioxidant effects are not found in other fruit juices and are unique to grape juice.

  The grape juice obtained as described above can be used for various purposes as an antioxidant as it is, but is usually used after being concentrated. Concentration is performed by a normal method. For example, by distilling off water at a temperature of about 20 ° C. to about 90 ° C. under atmospheric pressure or reduced pressure, a concentrated fruit juice of Bx 40 ° to 80 ° can be obtained. it can. Furthermore, the grape juice concentrate of the present invention obtained as described above can be used in a wide range of fields in the form of powder as it is. Powdering can usually be performed by adding excipients such as lactose, dextrin and gum arabic and using a drying means such as vacuum drying or spray drying. In addition, when concentrated or powdered, if desired, for example, organic acids such as lactic acid, citric acid, malic acid, tartaric acid, vitamin C, chlorogenic acid, isochlorogenic acid, rutin, quercetin, morin, tea catechins, tannins Other antioxidants such as rosemary extract and sage extract can be added to form an antioxidant preparation.

  The grape juice concentrate or grape juice powder obtained in this way can be used as an antioxidant for preventing deterioration of fragrances, in particular for preventing deterioration of citral by light and heat, and for preventing discoloration of pigments. It is particularly effective in preventing discoloration of carotenoid pigments, and further in preventing discoloration when a carotenoid preparation emulsified and water-soluble is added to an acidic beverage. The carotenoid pigment having an anti-fading effect by the antioxidant of the present invention is not particularly limited as long as it is a carotenoid pigment, but α-carotene, β-carotene, δ-carotene, lycopene, astaxanthin, canthaxanthin, lutein, crotine, bixin , Β-apocarotenal, Anato pigment, paprika pigment, tomato pigment, shrimp pigment, crab pigment, marigold pigment, saffron pigment, Haematococcus alga pigment and the like.

  The antioxidant of the present invention may be added directly to the final product. However, by containing it in the dye preparation or the fragrance preparation, the anti-fading of the dye preparation and the fragrance deterioration of the fragrance preparation are also prevented. be able to.

  When the antioxidant of the present invention is added to a dye preparation or a fragrance preparation, the addition amount is 1% by mass to 500% in the dye preparation or the fragrance preparation when the grape juice is converted to straight (Bx11 °: Japanese Agricultural Standard). % By mass, preferably 5% by mass to 500% by mass, more preferably 20% by mass to 500% by mass (the content exceeds 100% because concentrated juice can be used) . When the addition amount is less than 1% by mass, the effect of preventing the fading of the dye and the effect of preventing the deterioration of the fragrance cannot be obtained sufficiently. Moreover, it is difficult to add over 500% by mass in the preparation because of the concentration.

  In addition, when added directly to the final product containing a carotenoid pigment or fragrance, the addition amount is 0.1% by mass to 20% by mass, preferably 0.5% by mass in the final product when grape juice is converted into a straight equivalent. % To 15% by mass, more preferably 1% to 10% by mass. When the addition amount is less than 0.1% by mass, the effect of preventing the fading of the dye and the effect of preventing the deterioration of the fragrance cannot be obtained sufficiently. Moreover, when adding over 20 mass% in a formulation, the taste derived from grape juice will appear in a final product, and it is unpreferable.

As the final product to which the antioxidant of the present invention can be added, beverages such as soft drinks, fruit juice drinks, carbonated drinks, milk drinks, fermented milk drinks, etc. are preferable, but other examples include drops, candy, chocolate, Foods and drinks such as ice cream, sherbet, jelly, rice cake, processed meat, grilled meat, pickles, etc .; feeds; And cosmetics such as soaps, detergents, and shampoos. In these fields, they are useful as antioxidants for preventing discoloration of carotenoid pigments and preventing deterioration of fragrances.
Hereinafter, the present invention will be described more specifically with reference to examples.

Reference Example 1 Preparation of Lycopene Dye Formulation As an aqueous phase, 100 g of decaglycerin monooleate (HLB12) and 30 g of purified water were added to 800 g of glycerin, sterilized by heating at 80 ° C. to 90 ° C. for 15 minutes, and then cooled to 50 ° C. Separately, 50 g of lycopene crystals (manufactured by Hasegawa Koryo Co., Ltd.) are suspended in 20 g of sorbitan monooleate (HLB4.3) to form an oil phase part, which is added to the water phase part prepared previously, and TK-disperser (primics ( The product was mixed at 5000 rpm for 5 minutes. Subsequently, using a Ultra Apex mill (manufactured by Kotobuki Kogyo Co., Ltd.), a liquid pigment preparation was obtained by repeating pulverization for 45 times under the following conditions (reference product 1, lycopene content 5 mass%). The average particle size of lycopene contained in the obtained pigment preparation was 202 nm, the particle size distribution was sharp, the color tone was red, and the dispersion state was good.
<Crushing conditions>
Mill: Ultra Apex Mill peripheral speed: 10m / s
Bead filling rate: 85%
Zirconia bead particle size: φ0.2mm
<Analysis conditions>
Average particle diameter: Dynamic light scattering particle size distribution analyzer ELS-800 (Otsuka Electronics)
Particle size distribution state: Optical microscope observation color tone: Visual dispersion state: Optical microscope observation

Reference example 2
Grape transparent concentrated fruit juice Bx56 ° (Muscat fruit juice manufactured by Tokyo Food Techno Co., Ltd., 1/5 concentrated fruit juice, no sodium sulfite added), which is a commercial product, was designated as Product 1 of the present invention.

Example 1 Preparation of beverage added with grape juice as an anti-fading agent Isomerized sugar Bx 75 ° 225 g, citric acid: 0.9 g, sodium citrate: 0.7 g (brix 17 ° (refractive when 1000 ml with water) 0.02 g of Reference product 1 and 5.9 g of the product 1 of the present invention (3% in beverages in terms of straight fruit juice) are added to the sugar base), which is a pH 3.9 beverage base, and the whole amount is added with water. Was sterilized by heating at 95 ° C. for 30 seconds, cooled to 88 ° C., filled into a 350 ml heat-resistant PET bottle, and then cooled to 25 ° C. to obtain a beverage sample (Product 2 of the present invention). .

Comparative Example 1
In Example 1, a beverage sample was obtained in the same manner as in Example 1 except that the product 1 of the present invention was not added (Comparative product 1).

Comparative Example 2
In Example 1, a beverage sample was obtained in the same manner as in Example 1 except that 0.2 g of vitamin C was used instead of the product 1 of the present invention (Comparative product 2).

Example 2 Confirmation of lycopene fading prevention effect of grape juice In order to make the beverages of the present invention product 1 and comparative products 1 to 2 in contact with air, they were opened in a clean bench, and 1 / of the beverages After removing 3 amounts and replacing the upper 1/3 of the container with air, it was sealed again and irradiated with a fluorescent lamp using a light stability tester (LST-2000: manufactured by Tokyo Rika Kikai Co., Ltd.) (15 , 000 Lx-55 ° C) for 72 hours. The samples before and after the abuse test were subjected to color difference measurement using transmitted light (a quartz cell of width × depth × height: 40 mm × 20 mm × 50 mm) with a color difference meter (SD-5000: manufactured by Nippon Denshoku Industries Co., Ltd.). The results are shown in Table 1.

  L value represents lightness, 100 represents white, and 0 represents black. When the a value is large, the red value is strong when the value of + is large, and when the b value is large, the yellow value is strong. ΔE represents the difference between the two colors, and is calculated as the square root of the total value obtained by adding the squares of the differences between the values of L, a, and b. When ΔE is less than 3, almost no difference is observed with the naked eye, when ΔE is about 5 to 10, a slight difference is recognized, and when ΔE is about 20, a clear difference is recognized.

  As shown in Table 1, Comparative Product 1 to which no antioxidant was added had a ΔE before and after abuse of 40, severe discoloration, and the L value after abuse became 86.5 and almost transparent. However, the color change due to the abuse of the product 2 of the present invention to which the grape juice of the present invention was added was ΔE of 4.2 and a slight color fading was observed. (Muscat juice) was confirmed to have a fading prevention effect. Further, Comparative Product 2 added with vitamin C, which is very commonly used in beverages as an antioxidant, was able to suppress the fading of the pigment, but the a value was lower than the decrease in b value (-0.9). It was relatively greatly reduced (-3.6), the color tone was slightly brown, and the appearance of the beverage was changed.

Comparative Example 3
In Example 1, instead of the present invention product 1 (5.9 g), Valencia transparent fruit juice Bx66 ° (Tokyo Food Techno Co., Ltd. Valencia orange fruit juice, 1/5 concentrated fruit juice) 5.0 g (in straight fruit juice equivalent) 3%) Except for use, the same operation as in Example 1 was performed to obtain a beverage sample (Comparative product 3).

Comparative Example 4
In Example 1, it replaced with grape transparent fruit juice Bx56 degrees (5.9g), and lemon transparent fruit juice Bx45.3 degrees (Tokyo food techno lemon juice, 1/5 concentrated fruit juice) 5.3g (straight fruit juice conversion drink) Except for use, a beverage sample was obtained in the same manner as in Example 1 (Comparative product 4).

Example 3 Comparison of lycopene anti-fading effect between grape juice and other juices The present invention product 2, comparative product 1, comparative product 2, comparative product 3 and comparative product 4 were tested for light stability in the same manner as in Example 2. A fluorescent lamp irradiation (15,000 Lx-55 ° C.) 72 hours abuse test was conducted using a machine (LST-2000: manufactured by Tokyo Rika Kikai Co., Ltd.). The samples before and after the abuse test were subjected to color difference measurement using transmitted light (a quartz cell of width × depth × height: 40 mm × 20 mm × 50 mm) with a color difference meter (SD-5000: manufactured by Nippon Denshoku Industries Co., Ltd.). The results are shown in Table 2.

  As shown in Table 2, as in Example 1, Comparative Product 1 to which no antioxidant was added was severely fading and became almost transparent, but the product 2 of the present invention to which grape juice was added. It was confirmed that grape juice (muscat juice) has an effect of preventing fading. Further, Comparative Product 2 added with vitamin C, which is very commonly used in beverages as an antioxidant, was able to suppress the fading of the pigment, but was slightly less effective than grape juice. On the other hand, Valencia orange juice (Comparative product 3) and Lemon juice (Comparative product 4) showed no anti-fading effect.

Example 4
After washing commercially available black grape fruit (Campbell), the skin and seeds are removed, squeezed, sterilized at 85 ° C. for 10 minutes, cooled at 25 ° C., filtered through diatomaceous earth, adjusted to 11 ° Bx, and almost colorless. A clear black grape juice was obtained. A beverage sample was obtained in the same manner as in Example 1 except that 30 g of this black grape juice was used in place of the product 1 (5.9 g) of the present invention in Example 1 (Product 3 of the present invention).

Example 5
After washing commercially available black grape fruit (Pione) with water, the pericarp and seeds are removed, squeezed, sterilized at 85 ° C. for 10 minutes, cooled at 25 ° C., filtered through diatomaceous earth, adjusted to 11 ° Bx, almost colorless. A clear black grape juice was obtained. A beverage sample was obtained in the same manner as in Example 1 except that 30 g of this black grape juice was used in place of the product 1 (5.9 g) of the present invention in Example 1 (Product 4 of the present invention).

Example 6
After washing commercially available white grape fruit (Rosario Bianco), the skin and seeds are removed, squeezed, sterilized at 85 ° C. for 10 minutes, cooled to 25 ° C., filtered through diatomaceous earth, adjusted to 11 ° Bx, A colorless and transparent white grape juice was obtained. A beverage sample was obtained in the same manner as in Example 1 except that 30 g of this white grape juice was used in place of the product 1 (5.9 g) of the present invention in Example 1 (Product 5 of the present invention).

Example 7
After washing commercially available white grape fruits (Niagara), the skin and seeds are removed, squeezed, sterilized at 85 ° C. for 10 minutes, cooled to 25 ° C., filtered through diatomaceous earth, adjusted to 11 ° Bx, and almost colorless. A clear white grape juice was obtained. A beverage sample was obtained in the same manner as in Example 1 except that 30 g of this white grape juice was used in place of the product 1 (5.9 g) of the present invention in Example 1 (Product 6 of the present invention).

Example 8
After washing the commercially available red grape fruit (Kai Road), the skin and seeds were removed, pressed, sterilized at 85 ° C. for 10 minutes, cooled at 25 ° C., filtered through diatomaceous earth, adjusted to 11 ° Bx, A colorless and transparent white grape juice was obtained. A beverage sample was obtained in the same manner as in Example 1 except that 30 g of this red grape juice was used in place of the product 1 (5.9 g) of the present invention in Example 1 (Product 7 of the present invention).

Example 9 Comparison of lycopene fading prevention effect of various grape juices Inventive products 2 to 7 were fluorescent using a light stability tester (LST-2000: manufactured by Tokyo Rika Kikai Co., Ltd.) in the same manner as in Example 2. Irradiation (15,000 Lx-55 ° C.) 72 hour abuse test was performed. The samples before and after the abuse test were subjected to color difference measurement using transmitted light (a quartz cell of width × depth × height: 40 mm × 20 mm × 50 mm) with a color difference meter (SD-5000: manufactured by Nippon Denshoku Industries Co., Ltd.). The results are shown in Table 3.

  As shown in Table 3, ΔE before and after abuse of lycopene-colored beverages to which fruit juices other than the peels and seeds of commercially available grapes were added was about 3 to 7 (about a degree of fading), The same lycopene discoloration preventing effect as that of the product 1 of the present invention was also confirmed.

Example 10 Fractionation of grape juice Juice 2000 (g) was added with 2000 g of water and charged with 2000 ml of SP-207 (Mitsubishi Chemical's styrene divinylbenzene synthetic adsorbent) at room temperature at SV = 2. The fruit juice in the column was extruded with 4000 ml of water to obtain a passing liquid, and concentrated under reduced pressure with a rotary evaporator to obtain 2000 g of a Bx55 ° concentrate (Product 8 of the present invention).
Subsequently, 4000 g of 10 (W / W)% aqueous ethanol solution, 4000 g of 30 (W / W)% aqueous ethanol solution, and 4000 g of 95 (W / W)% aqueous ethanol solution were sequentially passed at SV = 2. Each desorption solution was obtained. The obtained desorption liquid is concentrated under reduced pressure on a rotary evaporator (finished in a fluid state so as not to completely remove the solvent. If there is an insoluble substance, dissolve by adding 95% ethanol or water. ), Comparative product 5 (10% ethanol desorption part 44.0 g), comparative product 6 (30% ethanol desorption part 45.2 g), and comparative product 7 (95% ethanol desorption part 69.6 g).

Example 11 Comparison of effect of preventing lycopene fading of each fraction of grape juice In the sample preparation in Example 1, 11.8 g of the present invention 1 and 8 of the present invention 8 instead of the present product 1 (5.9 g) 11.8 g, Comparative product 5 0.26 g, Comparative product 6 0.27 g or Comparative product 7 0.41 g Obtained (each addition amount was 6% in terms of straight fruit juice in terms of yield from grape juice Bx 56 °. The present product 9, the present product 10, the comparative product 8, and the comparative product, respectively. 9 and comparative product 10). Each beverage was subjected to a fluorescent light irradiation (15,000 Lx-55 ° C.) 72 hour abuse test using a light stability tester (LST-2000: manufactured by Tokyo Rika Kikai Co., Ltd.) in the same manner as in Example 2. went. The samples before and after the abuse test were subjected to color difference measurement using transmitted light (a quartz cell of width × depth × height: 40 mm × 20 mm × 50 mm) with a color difference meter (SD-5000: manufactured by Nippon Denshoku Industries Co., Ltd.). The results are shown in Table 4.

  As shown in Table 4, a strong lycopene fading preventing effect was observed in the non-adsorbed portion of the synthetic adsorbent of the present invention, and the fractions desorbed from the adsorbed portion were 10% ethanol desorbed portion, 30% ethanol desorbed portion, and 95% ethanol desorbed. Not so much in any of the departments.

Example 12 Comparison with various antioxidants In Example 1, in place of grape transparent fruit juice Bx56 ° (5.9 g), various antioxidants were added as antioxidant functional substances so as to be 50 ppm in the beverage. Except that, the same operation as in Example 1 was performed to obtain each antioxidant-added beverage sample shown in Table 5. Each beverage was subjected to a fluorescent light irradiation (15,000 Lx-55 ° C.) 72 hour abuse test using a light stability tester (LST-2000: manufactured by Tokyo Rika Kikai Co., Ltd.) in the same manner as in Example 2. went. The samples before and after the abuse test were subjected to color difference measurement using transmitted light (a quartz cell of width × depth × height: 40 mm × 20 mm × 50 mm) with a color difference meter (SD-5000: manufactured by Nippon Denshoku Industries Co., Ltd.). The results are shown in Table 5.

  As shown in Table 5, the grape juice of the present invention had the most excellent anti-fading effect. In addition, resveratrol and pine bark anthocyanidins have an effect on ΔE after abuse, which is close to that of white grape juice, but as shown in Table 5, the b value has increased, and it is recognized that both have browned. It was. Therefore, the comparison in Table 5 showed that white grape juice was the most excellent as a lycopene anti-fading agent.

  Considering the above results together with the results of Example 11, the anti-fading effect of the lycopene of the present invention is due to the action other than polyphenolic substances such as anthocyanidins, proanthocyanidins, catechins, resveratrols, etc. It was suggested that there is a high possibility.

Example 13 Confirmation of Grape Juice Concentration and Lycopene Fading Prevention Effect The relationship between the amount of grape juice added in Example 1 and the fading prevention effect was examined. In Example 1, the beverage sample shown in Table 6 was obtained by performing exactly the same operation as in Example 1 except that the addition amount of the product 1 of the present invention was changed to 5.9 g to be 11.8 g or 17.7 g. It was. Each beverage was subjected to a fluorescent light irradiation (15,000 Lx-55 ° C.) 130-hour abuse test using the light stability tester (LST-2000: manufactured by Tokyo Rika Kikai Co., Ltd.) in the same manner as in Example 2. It was. The samples before and after the abuse test were subjected to color difference measurement using transmitted light (a quartz cell of width × depth × height: 40 mm × 20 mm × 50 mm) with a color difference meter (SD-5000: manufactured by Nippon Denshoku Industries Co., Ltd.). The results are shown in Table 6. Further, FIG. 1 illustrates Table 6 as a diagram.

  As shown in Table 6 and FIG. 1, when the abuse time was extended to 130 hours, the fading of the product 1 of the present invention was as in Example 2, Example 3, Example 9, Example 11 and Example 12 (abuse time 72 hours). However, in the present invention product 11 and the present product product 12 with increased grape juice addition amount, fading is suppressed, and as the amount of grape juice addition increases, the fading prevention effect also increases, but about 6% addition in straight conversion It was confirmed that the carotenoid pigment was sufficiently discolored by 6% as a blending amount in the beverage.

Reference Example 3 Preparation of β-carotene pigment preparation 100 g of decaglycerin monooleate (HLB12) and 30 g of purified water were added to 800 g of glycerin as an aqueous phase, and the mixture was sterilized by heating at 80 ° C. to 90 ° C. for 15 minutes and then cooled to 50 ° C. Separately, 20 g of β-carotene (manufactured by Kuraray Co., Ltd.) is added to 80 g of MCT (manufactured by ODO Nisshin Oillio Group Co., Ltd.) and stirred for 20 minutes at an internal temperature of 105 ° C. to 115 ° C. under a nitrogen stream to obtain a uniform solution. It was. This was added to the previously prepared aqueous phase part, preliminarily dispersed, and then emulsified at 15 MPa using a high-pressure homogenizer to prepare a yellow-orange water-soluble carotene preparation (Reference product 2).

Reference example 4
100 g of paprika oleoresin (manufactured by Hasegawa Fragrance Co., Ltd.) and 100 g of MCT (manufactured by ODO Nisshin Oillio Group Co., Ltd.) are added and mixed, and then added to a mixed solution of 100 g of decaglycerin monooleate (HLB12) and 700 g of glycerin. The mixture was sterilized by heating for 15 minutes and then cooled to 40 ° C. Using a TK-homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.), emulsification was carried out until the average particle size became 1 μm or less to obtain a paprika pigment preparation for food coloring (reference product 3).

Reference Example 5
100 g of marigold oleoresin (manufactured by Hasegawa Fragrance Co.) 100 g of MCT (manufactured by ODO Nisshin Oillio Group) is added and mixed, and then added to a mixture of 100 g of decaglycerin monooleate (HLB12) and 700 g of glycerin, The mixture was sterilized by heating at 95 ° C for 15 minutes and then cooled to 40 ° C. Using a TK-homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.), the emulsion was emulsified until the average particle size became 1 μm or less to obtain a marigold pigment preparation for food coloring (Reference product 4).

Reference Example 6
100 g of MCT (manufactured by ODO Nisshin Oillio Group) and 100 g of SAIB were added to 80 g of a commercially available astaxanthin-containing oil (astaxanthin content: 5%). As an aqueous phase, 60 g of decaglycerin monooleate (HLB12) and 100 g of purified water were added to 560 g of glycerin, and the mixture was sterilized by heating at 90 ° C. to 95 ° C. for 15 minutes and then cooled to 40 ° C. The mixture was emulsified using a TK-homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.) to obtain an emulsion having an average particle size of 1 μm or less (reference product 5: astaxanthin content 0.4%).

Example 14 Confirmation of effect of addition to various carotenoid pigments In Example 1, the same procedure as in Example 1 was performed except that the pigment preparation shown in Table 7 below was used instead of Reference product 1 (0.2 g). This was done to obtain beverage samples containing various dye preparations. Each beverage was subjected to a fluorescent light irradiation (15,000 Lx-55 ° C.) 120-hour abuse test using a light stability tester (LST-2000: manufactured by Tokyo Rika Kikai Co., Ltd.) in the same manner as in Example 2. It was. The samples before and after the abuse test were subjected to color difference measurement using transmitted light (a quartz cell of width × depth × height: 40 mm × 20 mm × 50 mm) with a color difference meter (SD-5000: manufactured by Nippon Denshoku Industries Co., Ltd.). The results are shown in Table 7.

  As shown in Table 7, the addition of the white grape juice of the present invention prevented fading of any beverage colored with any carotenoid pigment. In addition, β-carotene, paprika oleoresin, and marigold dyes are relatively stable even without the addition of an antioxidant, so they do not show a significant effect. However, lycopene and astaxanthin with poor stability prevent discoloration. In particular, a great effect was seen.

Example 15 Preparation of Citral Containing Beverage Synthesis of Grape Transparent Concentrated Juice Bx56 ° (Muscat Juice, Tokyo Food Techno Co., Ltd.) obtained in Invention Product 1 and Example 10 in the beverage base formulation shown in Table 8 below. The adsorbent fractions (invention product 8, comparative product 5, comparative product 6 and comparative product 7) were added in the amounts shown in Table 9 below, sterilized by heating at 95 ° C. for 30 seconds, and then cooled to 88 ° C. Then, after filling a 200 ml transparent glass container with a full amount, it was stoppered and cooled to 25 ° C. to obtain a beverage sample.

Example 16 Effect on Stabilization of Citral The inventive products 17-18 and comparative products 24-27 were subjected to a light stability test at 10 ° C. (LST-2000: manufactured by Tokyo Rika Kikai Co., Ltd.) as a light stability test. ) Was subjected to fluorescent light irradiation (15,000 Lx-55 ° C.) for 7 days. Further, as a thermal stability test, it was stored in the dark at 35 ° C. for 2 days and 4 days, and at 50 ° C. for 7 days. Each beverage after storage was measured for citral content. Moreover, about the heat abuse article, it measured also about the p-methyl acetophenone content considered to be the off-flavor substance produced | generated by deterioration of citral.

The citral and p-methylacetophenone contents were measured using HPLC under the conditions shown below.
(Analysis conditions)
Apparatus: WATERS HPLC System
Column: TSKgel ODS-100S, 3.0 × 150 mm (TOSOH)
Mobile phase: Liquid A (water: phosphoric acid = 995: 5),
Liquid B (water: acetonitrile: phosphoric acid = 95: 900: 5)
30% B in A → 100% B (20 minutes, linear gradient)
Flow rate: 0.7 ml / min Detection: Waters 2996 Photodiode Array
Detector
Citral (240nm)
p-methylacetophenone (257 nm)
Injection volume: 20 μl
The analysis results of citral after light abuse are shown in Table 10, and the analysis results of citral and p-methylacetophenone after heat abuse are shown in Table 11.

As shown in Table 10, a beverage to which grape juice was added (present product 17), a beverage to which a synthetic adsorbent non-adsorbing portion for grape juice was added (present product 18), and a synthetic juice adsorbed 10% ethanol for grape juice Both the beverage added with the desorption part (Comparative product 25) and the beverage added with the synthetic adsorbent adsorbed 30% ethanol desorption part of grape juice (Comparative product 26) compared with the additive-free product, the residual rate of citral after light abuse It was a little expensive. Among these, the residual ratio of citral was particularly high in the non-adsorbed portion of the synthetic adsorbent. In addition, none of these beverages felt the off-flavors derived from grape juice. On the other hand, the beverage (comparative product 27) to which the 95% ethanol desorbing part adsorbing the synthetic adsorbent of grape juice was reduced, and a slightly bitter taste was produced while the residual ratio of citral was lowered.
From these results, it was confirmed that grape juice and the synthetic adsorbent non-adsorbing portion of grape juice have not only the effect of preventing discoloration of carotenoid pigments but also the effect of preventing photodegradation of citral.

  As shown in Table 11, the beverage with added grape juice (present product 17) and the beverage with added non-adsorbed portion of grape juice (produced product 18) citral after heat abuse compared to the additive-free product The survival rate of was high. On the other hand, a beverage (comparative product 25) added with a 10% ethanol desorbing part adsorbing a synthetic adsorbent of grape juice and a beverage (comparative product 26) containing a synthetic adsorbent adsorbing 30% ethanol desorbing part of a grape juice and synthesizing grape juice The beverage to which the adsorbent adsorbed 95% ethanol desorbing part was added (Comparative Product 27) had almost the same citral residual rate as that in the case of no addition. From this result, it was confirmed that the grape juice of the present invention and the synthetic adsorbent non-adsorbing portion of the grape juice also have an effect of preventing thermal degradation of citral.

  On the other hand, with respect to the amount of p-methylacetophenone produced, the beverage added with grape juice (present product 17) was also added with any fraction obtained by treating grape juice with a synthetic adsorbent (present product 18, comparison). The products 25 to 28) were also less produced than the additive-free products. Among these, the amount of p-methylacetophenone produced in the beverage added with the non-adsorbed portion of the grape juice synthetic adsorbent (Product 18 of the present invention) was slightly higher, but compared with the additive-free product (Comparative Product 24), It was confirmed that the grape juice of the present invention and the synthetic adsorbent non-adsorbing portion of the grape juice also had an effect of preventing p-methylacetophenone production due to thermal decomposition of citral.

Example 17 Preparation of a pigment preparation containing grape juice Reference product 1 (containing 5% lycopene) 3.3 g and the present invention product 1 (Grape transparent concentrated fruit juice Bx56 ° (Muscat juice manufactured by Tokyo Food Techno Co., 1/5 concentrated fruit juice) 96.7 g was mixed, sterilized by heating at 95 ° C. for 30 seconds, cooled to 25 ° C. and filled to obtain a pigment preparation (Invention product 19: lycopene content 0.165%, Grape juice content 482.5%).

Example 18 Preparation of a pigment preparation containing a synthetic adsorbent non-adsorbing part of grape juice Reference product 1 (containing 5% lycopene) 3.3 g and the present product 8 (grape transparent concentrated fruit juice Bx56 ° synthetic adsorbent non-adsorbing part) 96.7 g was mixed, sterilized by heating at 95 ° C. for 30 seconds, cooled to 25 ° C. and filled to obtain a pigment preparation (Product 20 of the present invention: lycopene content 0.165%, grape juice content 482.5) %).

Comparative Example 5 Preparation of pigment preparation diluted with liquid sugar Reference product 1 (containing 5% lycopene) 3.3 g and sugar-mixed fructose glucose liquid sugar (Bx75 °) 96.7 g were mixed, and sterilized by heating at 95 ° C. for 30 seconds. After cooling to 25 ° C. and filling, a pigment preparation was obtained (Comparative product 28: lycopene content 0.165%).

Example 19 Preparation of beverage and confirmation of anti-fading effect Isomerized sugar Bx 75 ° 225 g, citric acid: 0.9 g, sodium citrate: 0.7 g (Brix 17 ° when measured with water to 1000 ml (by refractometer) Value), which becomes a beverage base material having a pH of 3.9), 0.6 g of each of the present invention product 19, the present product 20 or the comparison product 28 is added, and the total volume is made up to 1000 ml with water, and then 95 ° C. for 30 seconds. After heat sterilization, the mixture was cooled to 88 ° C., filled in a 350 ml heat-resistant PET bottle, and then cooled to 25 ° C. to obtain a beverage sample. Each beverage is opened in a clean bench, 1/3 of the beverage is extracted, the upper 1/3 in the container is replaced with air, and then sealed again, and the light stability tester (LST-2000: Fluorescent lamp irradiation (15,000 Lx-55 ° C.) 72 hours abuse test was conducted using Tokyo Rika Kikai Co., Ltd. The samples before and after the abuse test were subjected to color difference measurement using transmitted light (a quartz cell of width × depth × height: 40 mm × 20 mm × 50 mm) with a color difference meter (SD-5000: manufactured by Nippon Denshoku Industries Co., Ltd.). The results are shown in Table 12.

  As shown in Table 12, the beverage containing the lycopene dye preparation (invention product 19) containing grape juice and the lycopene dye preparation (invention product 20) containing the synthetic adsorbent non-adsorbing part of the grape juice were added. Compared with the drink which added the lycopene pigment preparation (Comparative product 28) without a grape ingredient, the drink was remarkably suppressed in fading and extremely stable against light.

Claims (6)

  An antioxidant containing grape juice as an active ingredient.   The antioxidant according to claim 1, wherein the grape juice is white grape juice.   The antioxidant according to claim 1 or 2, wherein the grape juice is a fruit juice obtained from a fruit portion obtained by removing fruit skin and seeds from the grape fruit.   The antioxidant according to any one of claims 1 to 3, wherein the grape juice is a non-adsorbed portion obtained by bringing grape juice into contact with a synthetic adsorbent and removing the adsorbed portion. .   An anti-fading agent for carotenoid pigments, comprising the antioxidant according to any one of claims 1 to 4 as an active ingredient.   A method for preventing discoloration of a carotenoid pigment, comprising adding the antioxidant according to any one of claims 1 to 4.

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