FLAVOR OR AROMA DETERIORATION INHIBITOR CONTAINING THEANAPHTHOQUINONE AND ANALOGUES THEREOF AS ACTIVE INGREDIENT

Abstract

Provided is a deterioration inhibitor which, compared to prior art, is more effective against deterioration of the flavor or aroma of food, drinks, cosmetics, and the like caused by a variety of factors, and does not have any influence on the color of the food, drinks, cosmetics, and the like. This flavor or aroma deterioration inhibitor contains theanaphthoquinone and analogues thereof as an active ingredient.

Claims

1. A flavor or aroma deterioration inhibitor comprising a theanaphthoquinone and analogues thereof as an active ingredient.

2. The deterioration inhibitor according to claim 1, wherein the theanaphthoquinone and analogues thereof is a compound represented by the following formula (1) and the compound is any one or a combination of two or more thereof selected from a theanaphthoquinone wherein both substituents R.sub.1 and R.sub.2 are hydrogen in the formula, a theanaphthoquinone3′-O-gallate wherein substituent R.sub.1 is a galloyl group and R.sub.2 is hydrogen in the formula, a theanaphthoquinone3-O-gallate wherein substituent R.sub.1 is hydrogen and R.sub.2 is a galloyl group in the formula; or a theanaphthoquinone3,3′-di-O-gallate wherein both substituents R.sub.1 and R.sub.2 are galloyl groups in the formula ##STR00005##

3. The deterioration inhibitor according to claim 1 or 2, wherein the flavor or aroma is citrus flavor or aroma.

4. The deterioration inhibitor according to claim 1, wherein the flavor or aroma is based on citral.

5. A citrus-based flavor or fragrance composition comprising a citrus-based flavor or fragrance containing citral and the deterioration inhibitor according to claim 1.

6. (canceled)

7. An oral product comprising the citrus-based flavor or fragrance composition according to claim 5.

8. A cosmetic product having a citrus flavor or fragrance, comprising the deterioration inhibitor according to claim 1.

9. A cosmetic product comprising the citrus-based fragrance composition according to claim 5.

10. A method for inhibiting flavor or aroma deterioration of a fragrance composition, an oral product or a cosmetic product by adding the deterioration inhibitor according to claim 1 to a fragrance composition, an oral product or a cosmetic product.

11. The method for inhibiting deterioration according to claim 10, wherein the deterioration inhibitor is added in an amount of 0.0001 to 10 ppm as an active ingredient.

12. The method for inhibiting deterioration according to claim 10, wherein the flavor or aroma is citrus flavor or aroma.

13. The method for inhibiting deterioration according to claim 10, wherein the flavor or aroma is based on citral.

14. A method for inhibiting production of a deteriorated odor due to heat or with time of a flavor or fragrance composition, an oral product or a cosmetic product, comprising adding an effective amount of the deterioration inhibitor according to claim 1 to a flavor or fragrance composition, an oral product or a cosmetic product.

15. The method for inhibiting production of a deteriorated odor according to claim 14, wherein the deteriorated odor is a deteriorated odor due to p-cresol or p-methylacetophenone.

16. A method for producing the flavor or aroma deterioration inhibitor containing theanaphthoquinone and analogues thereof as an active ingredient according to claim 1, comprising autoxidizing theaflavin and analogues thereof.

17. The method for producing a flavor or aroma deterioration inhibitor containing theanaphthoquinone and analogues thereof as an active ingredient according to claim 16, comprising autoxidizing theaflavin and analogues thereof in a 10 to 50% ethanol aqueous solution.

18. The method for producing a flavor or aroma deterioration inhibitor containing theanaphthoquinone and analogues thereof as an active ingredient according to claim 16, comprising adjusting a pH of a reaction solution to 6 to 10.

19. The method for producing a flavor or aroma deterioration inhibitor containing theanaphthoquinone and analogues thereof as an active ingredient according to claim 16, wherein an autoxidation reaction temperature is 10 to 50° C.

20. The method for producing a flavor or aroma deterioration inhibitor containing theanaphthoquinone and analogues thereof as an active ingredient according to claim 16, comprising adding 0.1 to 3 parts by mass of an acidic substance with respect to 100 parts by mass of a reaction solution to adjust a pH of the reaction solution to 1 to 5 and stopping an oxidation reaction.

21. The method for producing a flavor or aroma deterioration inhibitor containing theanaphthoquinone and analogues thereof as an active ingredient according to claim 16, wherein theaflavin and analogues thereof is theaflavin, theaflavin3-O-gallate, theaflavin3′-O-gallate, theaflavin3,3′-di-O-gallate or a combination of two or more thereof.

Description

EXAMPLES

[0096] The present invention will be specifically described below with reference to examples, but the present invention is not limited to the description of the Examples.

Production Example 1

[0097] To 3.9 g of theaflavin and analogues thereof containing composition (“Theaflavin TF40 (trade name)” containing 40% of theaflavin and analogues thereof, manufactured by Yaizu Suisankagaku Industry Co., Ltd.), 600 g of a 30% ethanol aqueous solution and 0.8 g of disodium hydrogen phosphate were added (pH 7.7), the mixture was stirred at 20° C. for 2.5 hours, and then 2.3 g of citric acid was added (pH 3.7).

[0098] The solution was concentrated under reduced pressure and then freeze-dried to obtain 7 g of brown powder (containing 3.9 g of a “crude product of theanaphthoquinone and analogues thereof”).

[0099] Next, 5 g of the above powder (containing 2.8 g of a “crude product of theanaphthoquinone and analogues thereof”) was purified by open column chromatography and high performance liquid chromatography to obtain 48 mg of theanaphthoquinone.

Production Example 2

[0100] A “black tea leaf extract” was prepared based on the description of “Extraction Example 4” in Patent Document 5 of existing technology.

[0101] 1000 g of a 95% ethanol aqueous solution was added to 50 g of black tea leaves, and the mixture was heated under reflux for 1 hour for extraction. After removing the insoluble substances by filtration, 5 g of activated carbon was added to the filtrate and the mixture was stirred at room temperature for 1 hour.

[0102] Activated carbon was removed by filtration and then the filtrate was concentrated under reduced pressure.

[0103] Subsequently, the concentrate was freeze-dried to obtain 10.3 g of brown powder (hereinafter referred to as “black tea leaf extract”).

Production Example 3

[0104] A “oxidation enzyme-treated tea extract” was prepared based on the description of “Extraction Example 1” in Patent Document 7 of existing technology.

[0105] 2000 g of water was added to 100 g of dried green tea leaves, and the mixture was heated under reflux for 1 hour. After removing the insoluble substances by filtration, 0.04 g of laccase (“Laccase Y120 (trade name)” manufactured by Amano Enzyme Co., Ltd.) was added to the filtrate (solid content of 1.5 to 2.5%), and the mixture was reacted at 55° C. for 4 hours.

[0106] After concentrating this enzyme-treated solution, 300 g of a 95% ethanol aqueous solution was added, and the mixture was heated under reflux for 30 minutes to carry out enzyme inactivation treatment. After cooling the reaction solution to −15° C., the insoluble substances were removed by filtration, and the filtrate was concentrated under reduced pressure and freeze-dried to obtain 16.5 g of a dark brown powder (hereinafter referred to as “oxidation enzyme-treated tea extract”).

Test Example 1 Quantification of Theanaphthoquinone and Analogues Thereof

[0107] Theaflavin and analogues thereof containing composition (Theaflavin TF40) that was a raw material of the active ingredient of the present invention, the crude product of theanaphthoquinone and analogues thereof containing the active ingredient of the present invention, theanaphthoquinone that was the active ingredient of the present invention, the black tea leaf extract and oxidation enzyme-treated tea extract that were products of existing technology, were each subjected to measurement of a theanaphthoquinone and analogues thereof content with high-speed liquid chromatography under the following measurement conditions.

[0108] Apparatus: “G1312B HPLC system” manufactured by Agilent Technologies Inc.

[0109] Column: “CAPCELL PAK (Registered Trademark)” C18 MG, 4.6 mm I.D. x 250 mm, manufactured by Osaka Soda Co., Ltd.

[0110] Column temperature: 40° C.

[0111] Eluent: A. Acetonitrile [0112] B. Water

TABLE-US-00001 Gradient condition 0 min..fwdarw. 10 min..fwdarw. 14.5 min..fwdarw. 23.5 min..fwdarw. 25 min. A. Acetonitrile 10% 11.35% 31.15% 32.05% 100% B. Water 90% 88.65% 68.85% 67.95%  0%

[0113] Flow speed: 1 ml/minute

[0114] Table 1 shows the content of each theanaphthoquinone and analogues thereof.

TABLE-US-00002 TABLE 1 Measurement results of theanaphthoquinone and analogues thereof contents Theanaphthoquinone- Objects to be measured Theanaphthoquinone 3′-gallate Theaflavin and analogues Not detected Not detected thereof containing composition (Theaflavin TF40) Crude product of 1.71% 1.84% theanaphthoquinone and analogues thereof Theanaphthoquinone  100% Not detected Black tea leaf extract Not detected Not detected Oxidation enzyme-treated Not detected Not detected tea extract

[0115] As shown in Table 1, the product of the present invention was found to contain theanaphthoquinone and analogues thereof not contained in the theaflavin and analogues thereof, black tea leaf extract, and oxidation enzyme-treated tea extract, which were obtained by prior art.

Test Example 2

[0116] The theanaphthoquinone of the present invention and theaflavin and analogues thereof containing composition (Theaflavin TF40) that was the raw material of the present invention, and black tea leaf extract and oxidation enzyme-treated tea extract that were products of existing technology, were evaluated for inhibition effect on production of p-cresol and p-methylacetophenone.

[0117] An acidic citral solution was prepared by adding citral to a buffer solution of pH 3.0 prepared with 1/10M citric acid-1/5 M disodium hydrogen phosphate so as to have a concentration of 10 ppm of citral.

[0118] To this solution, each of the theanaphthoquinone of the present invention, theaflavin and analogues thereof containing composition (Theaflavin TF40) that was a raw material of the present invention, black tea leaf extract and oxidation enzyme-treated tea extract that were products of existing technology, was added to each concentration in Table 2, and 18 g thereof each was packed in a glass vial of 20 ml volume (with a polytetrafluoroethylene cap).

[0119] Each vial was stored in a thermostatic bath (50° C.) for 7 days, and the amounts of p-cresol and p-methylacetophenone produced in each acidic citral solution were measured by high performance liquid chromatography under the following measurement conditions.

[0120] Apparatus: “G1312B HPLC system” manufactured by Agilent Technologies Inc.

[0121] Column: “CAPCELL PAK (Registered Trademark)” C18 MG, 4.6 mm I.D.×250 mm, manufactured by Osaka Soda Co. Ltd.

[0122] Column temperature: 40° C.

[0123] Eluent: A. Acetonitrile [0124] B. Water

TABLE-US-00003 Gradient condition 0 min..fwdarw. 25 min..fwdarw. 26 min. A. Acetonitrile 10% 100% 100% B. Water 90%  0%  0%

[0125] Flow speed: 1 ml/minute

[0126] For comparison, an acidic citral solution without addition of the product of the present invention was prepared, refrigerated for 7 days and stored at 50° C., and then measured in the same manner. Subsequently, relative values of amounts of p-cresol and p-methylacetophenone produced were determined with the amounts of p-cresol and p-methylacetophenone produced in the product without the addition, stored at 50° C. for 7 days, being as 100, respectively. The results are shown in Table 2.

TABLE-US-00004 TABLE 2 Measurement results of amounts (%) of p-cresol and p-methylacetophenone produced Additives Temperature p-Cresol p-Methylacetophenone Additive-free Refrigeration  0  0 Additive-free 50° C. 100 100 Theanaphthoquinone 50° C. 96 100 10 ppb Theanaphthoquinone 50° C.  76  82 20 ppb Theanaphthoquinone 50° C.  61  54 40 ppb Theanaphthoquinone 50° C.  24  22 100 ppb Theanaphthoquinone 50° C.  16  8 200 ppb Theaflavin and analogues 50° C.  86  62 thereof containing composition (Theaflavin TF40) 320 ppb Theaflavin and analogues 50° C.  66  40 thereof containing composition (Theaflavin TF40) 640 ppb ppb Black tea leaf extract 50° C.  92  20 5 ppm Oxidation enzyme-treated 50° C.  99  72 tea extract 2 ppm

[0127] From the results in Table 2, it was found that the theanaphthoquinone of the present invention significantly inhibited the production of deteriorated odor, and the effect was remarkable at a concentration of 20 to 200 ppb.

Test Example 3

[0128] The crude product of theanaphthoquinone and analogues thereof of the present invention, theaflavin and analogues thereof containing composition (Theaflavin TF40) that was a raw material of the present invention, and black tea leaf extract and oxidation enzyme-treated tea extract that were products of existing technology, were evaluated for inhibition effect on production of p-cresol and p-methylacetophenone in the same manner.

[0129] Purified water was added to 80 g of granulated sugar, 0.8 g of citric acid, 0.4 g of sodium citrate, and 1 g of a 1% citral solution to adjust the total amount to 1000 g. To this solution, each of the crude product of theanaphthoquinone and analogues thereof of the present invention, the theaflavin and analogues thereof containing composition (Theaflavin TF40) that was the raw material of the present invention, and the black tea leaf extract and oxidation enzyme-treated tea extract that were products of existing technology, was added to each concentration shown in Table 3, the mixture was sterilized at 70° C. for 10 minutes, and then filled in a can to prepare a lemon-tasted beverage.

[0130] The above lemon beverages were each stored at 50° C. for 7 days in a thermostatic bath, and the amounts of p-cresol and p-methylacetophenone produced in each lemon-tasted beverage were measured by high performance liquid chromatography.

[0131] For comparison, a lemon beverage without addition of the product of the present invention was prepared, refrigerated for 7 days and stored at 50° C., and then measured in the same manner. Subsequently, relative values of amounts of p-cresol and p-methylacetophenone produced were determined with the amounts of p-cresol and p-methylacetophenone produced in the product without the addition, stored at 50° C. for 7 days, being as 100, respectively. The results are shown in Table 3.

TABLE-US-00005 TABLE 3 Amounts of p-cresol and p-methylacetophenone produced Additives Temperature p-Cresol p-Methylacetophenone Additive-free Refrigeration  0  0 Additive-free 50° C. 100 100 Crude product of 50° C.  61  28 theanaphthoquinone and analogues thereof 320 ppb Crude product of 50° C.  21  11 theanaphthoquinon and analogues thereof e 640 ppb Theaflavin and 50° C.  81  57 analogues thereof containing composition (Theaflavin TF40) 320 ppb Theaflavin and 50° C.  54  38 analogues thereof containing composition (Theaflavin TF40) 640 ppb ppb Black tea leaf extract 50° C.  84  30 5 ppm Oxidation enzyme- 50° C.  87  43 treated tea extract 2 ppm

[0132] From the results in Table 3, it was found that by adding the product of the present invention containing a crude product of theanaphthoquinone and analogues thereof to the lemon-tasted beverage, the amounts of p-cresol and p-methylacetophenone produced were significantly reduced as compared with those of the products with the added theaflavin and analogues thereof containing composition (Theaflavin TF40) containing no theanaphthoquinone and analogues thereof, the added black tea leaf extract, and the added oxidation enzyme-treated tea extract.

Test Example 4

[0133] The lemon-tasted beverage of Test Example 3 was subjected to organoleptic evaluation with eight proficient panelists. Control lemon-tasted beverages that were a refrigerated product without addition of the product of the present invention (evaluation score set to 1 point) and a product stored at 50° C. for 7 days without addition of the product of the present invention (evaluation score set to 5 points), were used, and the degree of deterioration of the flavor was evaluated for each lemon-tasted beverage. The results are shown in Table 4.

[0134] It is noted that the average organoleptic evaluation scores shown in Table 4 are the average values scored in each panel as ranked according to the following criteria.

[0135] The scoring criteria are based on the following evaluation criteria for the off-taste and off-odor (p-cresol-like (chemical odor), p-methylacetophenone-like (cinnamon odor)).

[0136] Very strong perception: 5 points

[0137] Strong perception: 4 points

[0138] Perceivable: 3 points

[0139] Weak perception: 2 points

[0140] Not perceivable: 1 point

Test Example 5

[0141] The degree of coloring was evaluated for each lemon-tasted beverage of Test Example 4. The degree of coloring was defined as an absorbance at a wavelength of 450 nm for each lemon beverage, and the results are shown in Table 4.

TABLE-US-00006 TABLE 4 Evaluation results of organoleptic evaluation and coloring for off-taste and off-odor Degree of coloring Degree of p-Cresol- p-Methylacetophenone- (abs. coloring Additives Temperature like like 450 nm) (visually) Additive-free Refrigeration 1 1 0.0215 No coloring Additive-free 50° C. 5 5 0.0294 No coloring Crude product of 50° C. 3 3 0.0352 No theanaphthoquinone coloring and analogues thereof 320 ppb Crude product of 50° C. 2 2 0.0461 Coloring theanaphthoquinone and analogues thereof 640 ppb Black tea leaf 50° C. 3 3 0.0493 Coloring extract 5 ppm Oxidation 50° C. 4 4 0.0332 No enzyme-treated coloring tea extract 2 ppm

[0142] From the results in Table 4, by adding the crude product of theanaphthoquinone and analogues thereof of the present invention to the lemon-tasted beverage, the deteriorated odors of p-cresol and p-methylacetophenone-like odor were found to be remarkably inhibited as compared with those of the black tea leaf extract and the oxidation enzyme-treated tea extract, and the crude product of theanaphthoquinone and analogues thereof exhibited the above effect at a concentration that did not affect the color of the beverage.

Test Example 6 Lotion

[0143] A lotion was prepared by a routine procedure, compounding the following components in the prescribed amounts below.

TABLE-US-00007 1,3-butylene glycol  60.0 g Glycerin  40.0 g Oleyl alcohol  1.0 g POE (20) sorbitan monolauric acid ester  5.0 g POE (15) lauryl alcohol ether  5.0 g 95% ethanol 100.0 g Methylparaben  1.0 g Gardenia yellow pigment  0.1 g Purified water 783.9 g

[0144] To 1,000 g of the model base described above, 2.0 g of lemon fragrance, and each of the crude product of theanaphthoquinone and analogues thereof of the present invention, theaflavin and analogues thereof containing composition (Theaflavin TF40) which was the raw material of the present invention, black tea leaf extract and the oxidation enzyme-treated tea extract that were products of existing technology, were added to each concentration shown in Table 5 and stored at 50° C. for 7 days in a thermostatic bath.

[0145] Each of the obtained mixture was subjected to organoleptic evaluation by ten proficient panelists.

[0146] For comparison, a refrigerated product without addition of the product of the present invention (evaluation score set to 1 point) and a product stored at 50° C. for 7 days without addition of the product of the present invention (evaluation score set to 5 points), were used, and each lotion was evaluated for the degree of deterioration of the lotion smell. The results are shown in Table 5.

[0147] Incidentally, the average organoleptic evaluation scores in Table 5 are average values scored in each panel according to the following criteria. The scoring criteria are based on the following evaluation criteria for the off-taste and off-odor (p-cresol-like (chemical odor), p-methylacetophenone-like (cinnamon odor)).

[0148] Very strong perception: 5 points

[0149] Strong perception: 4 points

[0150] Perceivable: 3 points

[0151] Weakly perception: 2 points

[0152] Not perceivable: 1 point

TABLE-US-00008 TABLE 5 Evaluation results of heating test of lotion Organoleptic evaluation Additives Temperature average score Additive-free Refrigeration 1.0 Additive-free 50° C. 5.0 Theaflavin and 50° C. 1.7 analogues thereof- containing composition (Theaflavin TF40) 640 ppb Crude product of 50° C. 1.3 theanaphthoquinone and analogues thereof 640 ppb Black tea leaf extract 5 ppm 50° C. 1.9 Oxidation enzyme-treated 50° C. 2.1 tea extract 2 ppm

[0153] From the results in Table 5, it was found that by adding the crude product of theanaphthoquinone and analogues thereof of the present invention to the lotion, the deteriorated odors of the p-cresol and p-methylacetophenone-like odors were remarkably inhibited as compared with those of the products with the added theaflavin and analogues thereof containing composition (Theaflavin TF40) containing no theanaphthoquinone and analogues thereof, the added black tea leaf extract, and the added oxidation enzyme-treated tea extract.

Test Example 7 Vegetable Juice Beverage

[0154] Distilled water was added to 84 g of carrot turbid juice (36° Bx) and 86 g of orange concentrated fruit juice (64° Bx) to adjust the total amount to 1000 g. To this mixture each of the crude product of theanaphthoquinone and analogues thereof of the present invention, the black tea leaf extract and the oxidation enzyme-treated tea extract that were products of existing technology, was added to the respective concentrations shown in Table 6, and each mixture was filled in a glass container, sterilized at 90° C. for 30 minutes to prepare a vegetable juice beverage.

[0155] The obtained vegetable juice beverage was subjected to organoleptic evaluation by 6 experienced panelists. Control vegetable juice beverages that were the unsterilized product (evaluation score set to 1 point) and the sterilized product without addition of the product of the present invention (evaluation score set to 5 points) were used, and the degree of deterioration of the flavor of each vegetable juice beverage was evaluated. The results are shown in Table 6.

[0156] It is noted that the average organoleptic evaluation scores in Table 6 are average values scored in each panel according to the following criteria.

[0157] The scoring criteria are based on the following evaluation criteria for the off-taste and off-odor (earthy odor, lipstick-like odor) generated due to deterioration of carotenoids.

[0158] Very strong perception: 5 points

[0159] Strong perception: 4 points

[0160] Perceivable: 3 points

[0161] Weak perception: 2 points

[0162] Not perceivable: 1 point

TABLE-US-00009 TABLE 6 Organoleptic evaluation results of heating test of vegetable juice beverages Organoleptic Organoleptic evaluation evaluation Sterilization average score average score Additives temperature (off-odor) (off-taste) Non-sterilization — 1.0 1.0 Additive-free 90° C. 5.0 5.0 Crude product of 90° C. 2.6 3.0 theanaphthoquinone and analogues thereof 1.3 ppm Crude product of 90° C. 2.3 2.5 theanaphthoquinone and analogues thereof 3.2 ppm Black tea leaf 90° C. 3.3 3.3 extract 5 ppm Oxidation 90° C. 3.2 3.6 enzyme-treated tea extract 2 ppm

[0163] From the results in Table 6, it was found that by adding the crude product of theanaphthoquinone and analogues thereof of the present invention to each vegetable juice beverage, the deteriorated odors of the earthy odor and the lipstick-like odor generated due to the deterioration of carotenoids were remarkably inhibited as compared with those of the black tea leaf extract and the oxidation enzyme-treated tea extract.

INDUSTRIAL APPLICABILITY

[0164] By using the theanaphthoquinone and analogues thereof of the present invention in citral or the product containing citral, the production of deteriorated odors derived from citral due to change with time or due to heat can be effectively inhibited while the color of food and drinks, cosmetics, and the like is not affected.

[0165] Furthermore, the theanaphthoquinone and analogues thereof of the present invention has a remarkable effect on the deterioration of carotenoids and can inhibit the production of off-taste and off-odor (earthy odor, lipstick-like odor) due to the deterioration of carotenoids.

[0166] Thus, use of the deteriorated odor production inhibitor of the present invention efficiently inhibits the production of deteriorated odor that gradually progresses at each stage of the production, distribution, and storage period in the oral product, and maintains the fresh feeling, which thereby can maintain the quality of the product inexpensively and stably for a long period of time.