US 2011 O256283A1 (19) United States (12) Patent Application Publication (10) Pub. No.: US 2011/0256283 A1 Hashimoto et al. (43) Pub. Date: Oct. 20, 2011

(54) METHOD FOR PREVENTING (86). PCT No.: PCT/UP2009/071473 DECOMPOSITONADETERIORATION OF LIPOPHILIC COMPONENT IN THE S371 (c)(1), PRESENCE OF WATER (2), (4) Date: Jun. 21, 2011 (30) Foreign Application Priority Data (75) Inventors: Yasuharu Hashimoto, Osaka (JP); Jinji Shono, Osaka (JP); Akiko Dec. 24, 2008 (JP) ...... 2008-328262 Kamoi, Osaka (JP); Nobuaki Publication Classification Tsuge, Osaka (JP); Masaki (51) Int. Cl. Nakamura, Osaka (JP); Tadashi A2.3L 3/3454 (2006.01) Hamajima, Osaka (JP); Morihiro (52) U.S. Cl...... 426/330 Aoyagi, Osaka (JP); Nobuhide Nakagawa, Osaka (JP) (57) ABSTRACT Provided is a method for preventing decomposition/deterio ration of a lipophilic component due to interaction with water, (73) Assignee: HOUSE FOODS or due to interaction with light, enzymes, oxygen, or heat in CORPORATION, the presence of water. The method for preventing decompo Higashi-Osaka-shi (JP) sition/deterioration of the lipophilic component in the pres ence of water is characterized in that a complex comprising a (21) Appl. No.: 13/141.285 lipophilic component, a phytosterol ester, and a cyclodextrin is formed, and the aforementioned lipophilic component is preserved in the form of said complex in the presence of (22) PCT Filed: Dec. 24, 2009 Water. Patent Application Publication Oct. 20, 2011 Sheet 1 of 3 US 2011/0256283 A1

FIG. 1 CHANGE IN ALLYL AMOUNT STORED AT 50°C

-- EXAMPLE 1

EXAMPLE 1

0.06

0.04

0.02

OOO STORAGE PERIOD (DAYS)

FIG. 2

CHANGE IN CAPSAIC IN AMOUNT DUE an TO ENZYME REACTION G. 1.4 Z 12 9 10 1. 2 0.8 0.6 - n - -- EXAMPLE 2 g COMPARATIVE 04 - EXAMPLE 2 5 - A - REFERENCE 02 --- EXAMPLE 0.0 O ENZYME REACTION TIME (min) Patent Application Publication Oct. 20, 2011 Sheet 2 of 3 US 2011/0256283 A1

120

O O

8 O

6

4 O -- EXAMPLE 3 COMPARATIVE EXAMPLE 3-1 2 O -- COMPARATIVE EXAMPLE 3-2 OO ZERO DAY 1 DAY 5 DAYS 25 DAYS 40°C STORAGE PERIOD

FIG. 4 CHANGE IN GINGEROL AMOUNT 2 O

O O

60

40 -- EXAMPLE 4 2 O A COMPARATIVE EXAMPLE 4 O

ELAPSED TIME (WEEKS) Patent Application Publication Oct. 20, 2011 Sheet 3 of 3 US 2011/0256283 A1

FIG. 5 CHANGE IN SHO GAOL AMOUNT

120

1 OO

8 O

6 O

4. O -0- EXAMPLE 4 2 O "A" COMPARATIVE I EXAMPLE 4 O O 2 ELAPSED TIME (WEEKS)

FIG. 6 CHANGE IN PIPERINE AMOUNT

6 O

4. O

2 O ' A COMPARATIVE EXAMPLE 5 O O 2 ELAPSED TIME (WEEKS) US 2011/025,6283 A1 Oct. 20, 2011

METHOD FOR PREVENTING a cyclodextrin; and storing the lipophilic componentina form DECOMPOSITONADETERIORATION OF of the composite material in the presence of water. LIPOPHILIC COMPONENT IN THE PRESENCE OF WATER Effects of the Invention 0008. The present invention makes it possible to prevent TECHNICAL FIELD decomposition/deterioration, with time, of a lipophilic com ponent due to interaction with water, or due to interaction 0001. The present invention relates to a method for pre with light, an enzyme, oxygen, heat, or the like in the presence venting decomposition/deterioration of a lipophilic compo of water. This makes it possible to keep functionalities and nent. color of materials susceptible to decomposition, Such as com ponents of spices and unsaturated fatty acids, in beverages and high water content foods for a long period of time. BACKGROUND ART BRIEF DESCRIPTION OF THE DRAWINGS 0002 Lipophilic components are decomposed/deterio rated due to interaction with water, or interaction with light, 0009 FIG. 1 is a graph showing change in allyl amount in an enzyme, oxygen, heat, or the like in the presence of water. Example 1 and Comparative Example 1. With relation to a method for preventing such decomposition/ 0010 FIG. 2 is a graph showing change in capsaicin deterioration, Some food packaging materials have been pro amount in Example 2 and Comparative Example 2. posed (Patent Document 1) in which the antimicrobial effects 0011 FIG. 3 is a graph showing change in ratio of remain of isothiocyanate is retained even after heat drying in the ing capsinoids in Example 3, and Comparative Examples 3-1 following manner. Specifically, the stability of isothiocyanate and 3-2. is improved in Such a manner that isothiocyanate included in 0012 FIG. 4 is a graph showing change of gingerol being a cyclodextrin is kneaded with a synthesis resin to form films, stored in Example 4 and Comparative Example 4. sheets and trays, or contained in a printing ink or a paint, 0013 FIG. 5 is a graph showing change of shogaol being which is then printed or applied onto films. These are stable in stored in Example 4 and Comparative Example 4. dry state, but can not retain Sufficient storage stability in a 0014 FIG. 6 is a graph showing change of piperine being state where water content is high, for example, in beverages stored in Example 5 and Comparative Example 5. and high water content foods. 0003. Meanwhile, a hydrophilic composite material of an MODES FOR CARRYING OUT THE INVENTION L-ascorbic acid higher fatty acid ester imparted with stability 0015. A lipophilic component to which the present inven with time, and stability against heat can be obtained by adding tion is applied is a lipophilic component which undergoes a fat-soluble L-ascorbic acid higher fatty acid ester to water or decomposition/deterioration due to interaction with water, or a hydrophilic solution in which a cyclodextrin is dissolved, due to interaction with light, an enzyme, oxygen, heat, or the and stirring the mixture at 50 to 100°C. (Patent Document 2). like in the presence of water. Specific examples thereof However, this method has a problem that especially sub include mustard extracts containing allyl isothiocyanate; tur stances unstable in the presence of water are likely to undergo meric extracts such as curcumin; capsicum pepper extracts reaction Such as decomposition, because of contact with containing capsaicinoids, capsinoids, and the like; ginger water or the hydrophilic solvent, and besides because of expo extracts containing gingerol, shogaol, Zingerone, and the like; Sure to high-temperature during the inclusion. In addition, it pepper extracts containing piperine and the like; unsaturated cannot be said that the stability of the obtained composite fatty acids Susceptible to oxidation Such as docosahexaenoic material is sufficient. acid (DHA), eicosapentaenoic acid (EPA), and the like; and 0004 Patent Document 1: Japanese Patent Application so on. Mustard extracts containing allyl isothiocyanate have Publication No. Hei. 7-46973 Such a nature as to be easily decomposed with time in the 0005 Patent Document 2: Japanese Patent Application presence of water. Turmeric extracts Such as curcumin have Publication No. Hei 10-231224 Such a nature as to be easily decomposed with time due to interaction with light in the presence of water. Capsaicinoids have Such a nature as to be easily decomposed with time due SUMMARY OF THE INVENTION to interaction with an enzyme in the presence of water. Capsi noids have such a nature as to be easily decomposed with time Problems to be Solved by the Invention in the presence of water. Ginger extracts such as gingerol, shogaol, and Zingerone have such a nature as to be easily 0006 An object of the present invention is to provide a decomposed with time in the presence of water. Pepper method for preventing decomposition/deterioration of a lipo extracts such as piperine have such a nature as to be easily philic component due to interaction with water, or due to decomposed with time in the presence of water. Unsaturated interaction with light, an enzyme, oxygen, heat, or the like in fatty acids Such as docosahexaenoic acid and eicosapen the presence of water. taenoic acid have such a nature as to be decomposed/deterio rated with time due to interaction with oxygen in the presence Means for Solving the Problems of water. 0016. The phytosterol ester used in the present invention is 0007. The present invention provides a method for pre a Substance obtained by ester-bonding a fatty acid to a venting decomposition/deterioration of a lipophilic compo hydroxyl group in the sterol skeleton of a plant sterol. nent, the method comprising: forming a composite material Examples of a production method of the phytosterol ester containing the lipophilic component, a phytosterol ester, and include an enzymatic method utilizing an enzyme; and the US 2011/025,6283 A1 Oct. 20, 2011 like. Examples of the enzymatic method include a method of dextrin is, for example, preferably 0.01 to 1000 parts by obtaining the phytosterol ester by mixing the phytosterol and weight, and more preferably 0.1 to 100 parts by weight with the fatty acid and by causing reaction therebetween (at 30 to respect to one part by weight of the phytosterol ester. The 50° C. for approximately 48 hours), with a lipase or the like amount of water coexisting in producing the composite mate used as a catalyst; and the like. Other synthesis methods rial is, for example, preferably 0.01 to 100 parts by weight, include a method of obtaining the phytosterol ester by esteri and more preferably 0.1 to 10 parts by weight, with respect to fication which involves dehydration of a plant sterol produced one part by weight of the cyclodextrin. In addition, when the from soybean or the like with a fatty acid obtained from composite material of the present invention is produced, the rapeseed oil, corn oil, or the like, in the presence of a catalyst; mixing is preferably conducted under heating at 40 to 90°C., and the like. more preferably at 50 to 85°C. 0017 Examples of the plant sterol include sterols con 0022. In producing the composite material, the order of tained in vegetable fats and oils, and the like. For example, the adding and mixing water, the lipophilic component, the phy plant Sterol may be one extracted and purified from a Veg tosterol ester, and the cyclodextrin is not particularly limited. etable fat or oil of soybean, rapeseed, cottonseed, or the like. For example, the composite material is preferably formed as The plant sterol may be a mixture containing B-sitosterol, follows: the lipophilic component and the phytosterol ester campesterol, Stigmasterol, brassicasterol, fucosterol, dimeth (and water, when the dispersibility is poor) are mixed with ylsterol, and the like. For example, a Soybean Sterol contains each other to prepare a mixture, while the cyclodextrin cyclo 53 to 56% of sitosterol, 20 to 23% of campesterol and 17 to is dispersed in water to prepare another mixture; Subse 21% of Stigmasterol. As the plant sterol, one which is com quently the two mixtures are mixed with each other. However, mercially-available as “phytosterol F.' (produced by TAMA the order is not limited thereto, and, for example, the lipo BIOCHEMICAL CO.,LTD.) can also be used. philic component, the phytosterol ester, the cyclodextrin, and 0018. The fatty acid may be plant-derived, for example, water may be mixed with each other simultaneously. derived from rapeseed oil or palm oil, or animal-derived. 0023. In the mixing of the lipophilic component and the Examples of the fatty acid include myristic acid, Stearic acid, phytosterol ester, any mixing conditions and means can be palmitic acid, arachidonic acid, oleic acid, linoleic acid, C.-li employed, as long as an appropriate dispersibility is achieved. nolenic acid, Y-linolenic acid, eicosapentaenoic acid, docosa 0024. After the cyclodextrin was added, a mixing device hexaenoic acid, palmitoleic acid, lauric acid, and the like. with high shearing force. Such as a kneader, is preferably used 0019 Preferred examples of the phytosterol ester include in order to achieve Sufficient kneading for obtaining the com phytosterols each obtained from a phytosterol derived from posite material. Soybean and a fatty acid derived from rapeseed oil; phytoster 0025. In the present invention, the lipophilic component is ols each obtained from a phytosterol derived from soybean or stored in the form of the thus obtained composite material in rapeseed and a fatty acid derived from palm oil; and the like. the presence of water. More specifically, for example, by The former include “San Sterol NO. 3 of San-Ei Gen F.F.I., adding the lipophilic component in the form of the thus Inc., and the like, and the latter include “phytosterol fatty acid obtained composite material to a food, a beverage, a pharma ester of TAMA BIOCHEMICAL CO.,LTD., and the like. ceutical drug, a cosmetic, or the like containing water, and 0020. The cyclodextrinused in the present invention refers then storing the mixture, decomposition/deterioration, with to a cyclic non-reducing maltooligosaccharide, whose con time, of a lipophilic component due to interaction with water, stitutional unit is glucose. Even though any one of C-cyclo or due to interaction with light, an enzyme, oxygen, heat, or dextrin with six glucose units, B-cyclodextrin with seven the like in the presence of water can be prevented. glucose units, and Y-cyclodextrin with eight glucose units may be used, Y-cyclodextrin is preferable since Y-cyclodextrin EXAMPLES is decomposed by human digestive enzymes and since Y-cy Example 1 clodextrin is easy to use for foods and beverages, particularly for beverages because of the its high solubility in water. 0026. To 5.67 parts by weight of a phytosterolester melted 0021. In the present invention, by forming the above-de by heating to 60° C., 0.63 parts by weight of a mustard scribed composite material of the lipophilic component, the essential oil was added, and dissolved thereinto. Meanwhile, phytosterol ester, and the cyclodextrin, and by storing the 62.4 parts by weight of Y-cyclodextrin and 31.3 parts by lipophilic component in the form of the composite material in weight of water (75°C.) were introduced into a mortar, and the presence of water, decomposition/deterioration, with mixed with a pestle, to obtain a paste. To this paste, the time, of a lipophilic component due to interaction with water, above-described phytosterol ester in which the mustard or due to interaction with light, an enzyme, oxygen, heat, or essential oil was dissolved was added, and the mixture was the like in the presence of water can be prevented. The com kneaded in a hot water (75°C.) for 10 minutes. After comple posite material herein can be produced by a method compris tion of the kneading, water in an amount equivalent to water ing a compositing step of forming a composite material by lost due to vaporization was added thereto, and the mixture mixing a lipophilic component, a phytosterol ester, and a was kneaded again to homogeneity. The blended amounts (g) cyclodextrin in the presence of water. For producing the com in Example 1 are shown in the following Table 1. posite material of the present invention, the amount of the Comparative Example 1 phytosterolester is preferably, for example, 0.5 to 30000 parts by weight with respect to one part by weight of the lipophilic 0027 Into a mortar, 66.24 parts by weight of Y-cyclodex component. Note that a higher proportion of the phytosterol trin, and 33.13 parts by weight of water (60°C.) were added, ester provides a greater effect of preventing the decomposi and mixed with each other using a pestle to obtain a paste. To tion. However, this results in a greater amount of the cyclo this paste, 0.63 parts by weight of a mustard essential oil was dextrin to be added, so that the relative proportion of the added, and the mixture was kneaded in a hot water (75°C.) for lipophilic component is reduced. The amount of the cyclo 10 minutes. After completion of the kneading, water in an US 2011/025,6283 A1 Oct. 20, 2011 amount equivalent to water lost due to vaporization was above-described phytosterol ester in which the capsicum added thereto, and the mixture was kneaded again to homo oleoresin was dissolved was added, and the mixture was geneity. The blended amounts (g) in Comparative Example 1 kneaded in a hot water (60°C.) for 10 minutes. After comple are shown in the following Table 1. tion of the kneading, water in an amount equivalent to water lost due to vaporization was added thereto, and the mixture TABLE 1. was kneaded again to homogeneity. The blended amounts (g) in Example 2 are shown in the following Table 2. Comparative Raw material Example 1 Example 1 Comparative Example 2 mustard essential oil 0.63g 0.63g (allyl isothiocyanate content: 0038 Into a mortar, 66.6 parts by weight of Y-cyclodex 97 weight percent) phytosterol ester 5.67g trin, and 33.33 parts by weight of water (60°C.) were added, (San Sterol NO. 3 of San-Ei and mixed with each other using a pestle to obtain a paste. To Gen F. F.I., Inc.) this paste, 0.07 parts by weight of a capsicum oleoresin was Y-cyclodextrin 62.40 g 66.24g added, and the mixture was kneaded in a hot water (60°C.) for Water 31.30 g 33.13g 10 minutes. After completion of the kneading, water in an amount equivalent to water lost due to vaporization was total 100.00 g 100.00 g added thereto, and the mixture was kneaded again to homo geneity. The blended amounts (g) in Comparative Example 2 are shown in the following Table 2. (Storage Method) 0028. To one part by weight of each of the samples TABLE 2 obtained in Example 1 and Comparative Example 1, 5 parts Comparative by weight of water was added, and uniformly dispersed Raw material Example 2 Example 2 therein. GC vials were filled up with the water-dispersion capsicum oleoresin 0.07 g. 0.07 g. composite material samples, then each were tightly closed (capsaicins content: with a cap, and sealed into an aluminum pouch. These vials 40 weight percent) were Stored at 50° C. phytosterol ester 3.50 g (San Sterol NO. 3 of San-Ei Gen F. F.I., Inc.) (GC Measurement) Y-cyclodextrin 64.30 g 66.60 g 0029. The samples stored for Zero days (at the beginning Water 32.13g 33.33 g of the storage), one day, and six days were diluted 100-fold with hexane, allowed to stand at room temperature for 16 to total 100.00 g 100.00 g 18 hours, and filtered through a 0.45-lum filter to prepare GC samples. For the GC measurement, a FID detector was used. The measurement was carried out under the following con (Enzyme Addition and Storage Method) ditions. 0039 Each of the samples obtained in Example 2 and 0030 Column: DB-WAX (Inner diameter: 0.53 mm, Comparative Example 2 was diluted 10-fold with a 50 mM Length: 30 m, Film thickness: 1 um) Tris buffer (capsaicin concentration: 0.0028%). To this, an 0031 Carrier gas: helium gas acylase was added to give a concentration of 0.05 u/ml. The 0032 Back pressure: 20 kPa mixture was shaken in a constant-temperature water bath at 0033. Injection temperature: 200° C. 37°C., to allow the reaction of the enzyme. 0034) Detector temperature: 220° C. 0040. Meanwhile, as Reference Example, a capsaicin 0035 Temperature rise conditions: Temperature was reagent (capsaicin content: 95% or higher) manufactured by raised from 100° C. to 180°C. (at a rate oftemperature rise of SIGMA was diluted with a 50 mM Tris buffer to have the 20°C/min) same capsaicin concentration (0.0028%) as Example 2 and 0036 FIG. 1 shows change in allyl concentration. As Comparative Example 2. To this, an acylase was added to give shown in FIG. 1, when the mustard essential oil was stored in a concentration of 0.05 u/ml. The mixture was shaken in a the presence of water in the form of the composite material constant-temperature water bath at 37°C. in the same manner which was formed together with the phytosterol ester and as Example 2 and Comparative Example 2, to allow the Y-cyclodextrin, the decomposition of allyl isothiocyanate in reaction of the enzyme. the oil was apparently prevented. Note that, the ratio of allyl isothiocyanate remaining after the 6-day storage was 60.2% (HPLC Measurement) in Example 1 and 15.5% in Comparative Example 1 with respect to that at the beginning of the storage. 0041. To 2 ml of each sample in which the reaction of the enzyme was allowed for 0 minutes (at the beginning of the Example 2 shaking), 30 minutes, or 60 minutes, 3 ml of water was added, and thus the volume thereof was adjusted to 5 ml. Moreover, 0037 To 3.5 parts by weight of a phytosterol ester heated 1 ml of 2.5NNaOH was added thereto, followed by heating in to 60° C. and dissolved, 0.07 parts by weight of capsicum boiling water at 100° C. for 10 minutes. After the heating, 20 oleoresin was added, and dissolved thereinto. Meanwhile, ml of methanol was added thereto. To this mixture, 1 ml of 64.3 parts by weight of Y-cyclodextrin and 32.13 parts by 2.5N HCl was added, and the volume was adjusted with weight of water (60° C.) were introduced into a mortar, and methanol to 50 ml. Then, the mixture was filtered through a mixed with a pestle, to obtain a paste. To this paste, the 0.45-lum filter, and used as a HPLC sample. For the HPLC US 2011/025,6283 A1 Oct. 20, 2011

measurement, a fluorescence detector was used. The mea pouch. Thereafter, the pouch was held in a constant-tempera Surement was carried out under the following conditions. ture water bath at 83° C. for 7 minutes to perform second 0042 Column: ODS (Senshu Scientific Co., Ltd.) sterilization. 0043 Flow rate: 1 ml/min 0044) Mobile phase: acetonitrile:TFA=1:1 Comparative Example 3-2 0045. Injection amount: 2 ul 0.052 Capsinoids extracted from “Natura' manufactured 0046) Detection: ex270, em330 by AJINOMOTO CO., INC., were used. 0047 FIG. 2 shows change in capsaicin concentration. As 0053. To 0.70 parts by weight of refined rapeseed oil shown in FIG. 2, when the capsicum oleoresin was stored in heated to 70° C., 0.35 parts by weight of a fat and fatty oil the presence of water in the form of the composite material containing the capsinoids was added, and dissolved thereinto. which was formed together with the phytosterol ester and On the other hand, 7.0 parts by weight of Y-cyclodextrin, and Y-cyclodextrin, the decomposition of capsaicin in the capsi 3.5 parts by weight of water were introduced into a mortar, cum oleoresin was apparently prevented. Note that, the ratio and mixed with each other in a hot water bath at 70° C. to of capsaicin remaining after the reaction of the enzyme for 60 obtain a paste. To this paste, 1.05 parts by weight of the minutes was 78.6% in Example 2, 58.9% in Comparative above-described oil phase in which the capsinoids were dis Example 2, and 2.0% in Reference Example with respect to Solved was added, and the mixture was kneaded in a hot water that at the beginning of the shaking. bath at 70° C. for 10 minutes. Thus, a composite material was prepared. Into 87.6 parts by weight of water, 11.55 parts by Example 3 weight of the obtained composite material, 0.56 parts by weight of citric acid, and 0.27 parts by weight of trisodium 0048 Capsinoids extracted from “Natura' manufactured citrate were dispersed, and the dispersion was stirred with a by AJINOMOTO CO., INC., were used. mixer for 30 seconds. Thus, a model beverage containing 0049. To 0.70 parts by weight of a phytosterol ester heated composite material was prepared. The model beverage con to 70° C., 0.35 parts by weight of a fat and fatty oil containing taining composite material was heated up to 93° C., and the capsinoids was added, and dissolved thereinto. Mean sterilized by being held at 90° C. for 3 minutes, and then filled while, 7.0 parts by weight of Y-cyclodextrin and 3.5 parts by into a pouch. Thereafter, the pouch was held in a constant weight of water were introduced into a mortar, and mixed temperature water bath at 83° C. for 7 minutes to perform with each other in a hot water bath at 70° C. to obtain a paste. second sterilization. To this paste, 1.05 parts by weight of the above-described oil phase in which the capsinoid was dissolved were added, and TABLE 3 the mixture was kneaded in a hot water bath at 70° C. for 10 Example Comparative Comparative minutes to prepare a composite material. Into 87.6 parts by Raw material (in part by weight) 3 Example 3-1 Example 3-2 weight of water, 11.55 parts by weight of the obtained com fat and fatty oil containing O3S O3S O.35 posite material, 0.56 parts by weight of citric acid, and 0.27 capsinoids parts by weight of trisodium citrate were dispersed, and the (extracted from “Natura dispersion was stirred with a mixer for 30 seconds. Thus, a manufactured by AJINOMOTO model beverage containing composite material was prepared. CO., INC.) B-sitosterol O.70 The model beverage containing composite material was refined rapeseed oil O.70 O.70 heated up to 93° C., and sterilized by being held at 90° C. for (manufactured by J-OIL MILLS, 3 minutes, and then filled into a pouch. Thereafter, the pouch INC.) was held in a constant-temperature water bath at 83°C. for 7 Y-cyclodextrin 7.0 7.0 Water 3.5 10.2 3.5 minutes to perform second sterilization. emulsifier O.33 (SWA-10D manufactured by Comparative Example 3-1 Mitsubishi-Kagaku Foods Corporation) citric acid O.S6 O.S6 O.S6 0050 Capsinoids extracted from “Natura' manufactured trisodium citrate 0.27 0.27 0.27 by AJINOMOTO CO., INC., were used. Water 87.6 87.6 87.6 0051) To 0.70 parts by weight of refined rapeseed oil heated to 70° C., 0.35 parts by weight of a fat and fatty oil total 100 100 1OO containing the capsinoids was added, and dissolved thereinto. To 10.2 parts by weight of water, 0.33 parts by weight of an 0054 The model beverages prepared in Example 3, and emulsifier (polyglycerin fatty acid ester SWA-10D manufac Comparative Examples 3-1 and 3-2 were stored at 40° C. tured by Mitsubishi-Kagaku Foods Corporation) and 1.05 After certain periods of time had elapsed, the capsinoids in parts by weight of the above-described oil phase in which the the samples were quantitatively determined by liquid chro capsinoid was dissolved were added, and the mixture was matography. For the ratio of remaining capsinoids, values emulsified with a mixer to prepare an emulsion. Into 87.6 determined after the beverages were stored for a day, 5 days, parts by weight of water, 11.58 parts by weight of the obtained and 25 days at 40°C. were represented by percentage, with a emulsion, 0.56 parts by weight of citric acid, and 0.27 parts by value of the capsinoids immediately after the start of the weight of trisodium citrate were dispersed, and the dispersion storage (zero days) being employed as 100%. FIG. 3 shows was stirred with a mixer for 30 seconds. Thus, an emulsion the results. As is apparent from FIG. 3, the decomposition of containing model beverage was prepared. The emulsion-con the capsinoids in the storage at 40° C. was more markedly taining model beverage was heated up to 93°C., and sterilized prevented in Example 3 than Comparative Examples 3-1 and by being held at 90° C. for 3 minutes, and then filled into a 3-2. From the results described above, it has been found that US 2011/025,6283 A1 Oct. 20, 2011 the present invention makes it possible to prevent the decom parts by weight of water, 0.23 parts by weight of the obtained position of capsinoids in the presence of water, and to emulsified preparation, 0.3 parts by weight of citric acid, and improve the stability thereof. 0.12 parts by weight of trisodium citrate were dispersed, and the dispersion was stirred with a mixer for 30 seconds. Thus, Pretreatment Method for Liquid Chromatography a ginger extract emulsified preparation-containing model 0055 Regarding each of Example 3 and Comparative beverage was prepared. The ginger extract emulsified prepa Example 3-2, 12.5g of the model beverage was centrifuged ration-containing model beverage was heated up to 93° C. (at 3000 rpm for 10 minutes), and then the supernatant was and sterilized by being held at 90° C. for 3 minutes, and then removed. To the deposit, 6 ml of DMSO (dimethylsulfoxide) filled into a pouch. Thereafter, the pouch was held in a con was added, and the mixture was ultrasonicated to dissolve the stant-temperature water bath at 83°C. for 5 minutes to per deposit. Moreover, the mixture was diluted with methanol to form second sterilization. In the prepared ginger extract 25 ml, filtered through a 0.45-lum filter, and then used as a test emulsified preparation-containing model beverage, the gin liquid. gerol component was 40.9 ppm, and the shogaol component 0056 Regarding Comparative Example 3-1, 5 g of the was 16.2 ppm. model beverage was sampled. The sample was diluted with methanol to 10 ml, filtered through a 0.45-lum filter, and then TABLE 4 used as a test liquid. Comparative 0057 Measurement Conditions for Liquid Chromatogra Raw material (in part by weight) Example 4 Example 4 phy ginger extract O.O15 0.058 A fluorescence detector was used. (Supercritical ginger extract gingerol: 0059 Column mightysil (250 mm, p2.0) 24.8%, shogaol: 10.7%, manufactured by 0060 Flow rate 0.2 ml/min Takasago International Corporation) ginger extract O.23 0061 Injection Amount 3 ul (emulsified preparation gingerol: 1.79%, 0062 Mobile Phase pH 3.3 TFA-water:acetonitrile=20:80 shogaol: 0.89%, manufactured by 0063 FLD Detector EX270 EM330 Takasago International Corporation) phytosterol ester O.18 Example 4 (San Sterol NO. 3 manufactured by San-Ei Gen F. F. I.) 0064. As a ginger extract, a Supercritical ginger extract edible fat and fatty oil O.12 Y-cyclodextrin 1.093 (gingerol: 24.8%, shogaol: 10.7%. Takasago International Water 1.093 Corporation) was used. citric acid O.3 O.3 0065. To 0.18 parts by weight of a phytosterol ester and trisodium citrate O.12 O.12 0.12 parts by weight of an edible fat and fatty oil, which were Water 97.08 99.35 heated to 80°C., 0.015 parts by weight of the ginger extract was added, and dissolved therein. On the other hand, 1.093 total 1OO 100 parts by weight of Y-cyclodextrin, and 1.093 parts by weight of water were mixed with a TK homomixer, while being 0067. The model beverages prepared in Example 4 and heated to 80°C. To this mixture, 0.315 parts by weight of the Comparative Example 4 were stored at 40°C. The gingerols above-described oil phase in which the ginger extract was and shogaols in the samples before the storage, stored for a dissolved was added. While continuously being heated to 80° week, and the stored for 2 weeks were quantitatively deter C., the resultant mixture was stirred with a TKhomomixer to mined by liquid chromatography. For the ratio of remaining conduct preliminary emulsification. After the preliminary gingerols and shogaols, values determined after the beverages emulsification, the mixture was passed through a high-pres were stored for a week and for 2 weeks were represented by sure homogenizer (LAB1000 manufactured by SMT Co., percentage, with values of the gingerols and shogaols before Ltd., pressure: 100 MPa). Thus, a ginger extract-containing the storage (zero weeks) being employed as 100%. FIGS. 4 composite material was prepared. Into 97.08 parts by weight and 5 show the results. As is apparent from FIGS. 4 and 5, the of water, 2.5 parts by weight of the obtained composite mate decomposition of the gingerols and especially the shogaols rial, 0.3 parts by weight of citric acid, and 0.12 parts by weight were prevented in Example 4 than Comparative Example 4. of trisodium citrate were dispersed, and the dispersion was From the results described above, it has been found that the stirred with a mixer for 30 seconds. Thus, a ginger extract present invention makes it possible to prevent the decompo model beverage containing composite material was prepared. sition of ginger extracts in the presence of water, and to The ginger extract model beverage containing composite improve the stability thereof. material was heated up to 93°C., and sterilized by being held Pretreatment Method for Liquid Chromatography at 90° C. for 3 minutes, and then filled into a pouch. There after, the pouch was held in a constant-temperature water bath 0068 Regarding Example 4, 25g of the model beverage at 83°C. for 5 minutes to perform second sterilization. In the was centrifuged (at 3000 rpm for 10 minutes), and then the prepared ginger extract model beverage containing compos supernatant was removed. To the deposit, 3 ml of DMSO ite material, the gingerol component was 36.1 ppm, and the (dimethyl sulfoxide) was added, and the mixture was ultra shogaol component was 15.4 ppm. sonicated to dissolve the deposit. Moreover, the mixture was diluted with methanol to 50 ml, filtered through a 0.45-lum Comparative Example 4 filter, and then used as a test liquid. 0069. Regarding Comparative Example 4, 25 g of the 0066. Here, an emulsified preparation obtained by emul model beverage was sampled. The sample was diluted with Sifying a ginger extract (gingerol: 1.79%, shogaol: 0.89%, methanol to 50 ml, filtered through a 0.45-lum filter, and then Takasago International Corporation) was used. Into 99.35 used as a test liquid. US 2011/025,6283 A1 Oct. 20, 2011

Measurement Conditions for Liquid Chromatography TABLE 5 0070 UV: 282 mm Comparative (0071 Column: ODS C18 (Senshu Scientific Co., Ltd.) Raw material (in part by weight) Example 5 Example 5 0072 Flow rate: 1.0 ml/min pepper extract O.OO64 0073. Injection amount: 20 ul (piperine powder piperine content: 92% or 0074 Analysis time: 30 minutes more, manufactured by Inabata Koryo Co., Ltd) 0075 Mobile phase: acetonitrile:water:THF (tetrahydro pepper extract O.15 furan)=45:50:5 (Piper longum of the Piperaceae family extract (piperines component: 300 to 1400 ppm, manufactured by Example 5 Maruzen Pharmaceuticals Co., Ltd.) phytosterol ester O.18 (San Sterol NO. 3 manufactured by San-Ei 0076. As a pepper extract, piperine powder (piperine con Gen F. F. I.) tent: 92% or more, Inabata Koryo Co., Ltd) was used. edible fat and fatty oil O.12 Y-cyclodextrin 1.097 0077. To 0.18 parts by weight of a phytosterol ester and Water 1.097 0.12 parts by weight of an edible fat and fatty oil, which were citric acid O.3 O.3 heated to 80°C., 0.0064 parts by weight of the pepper extract trisodium citrate O.12 O.12 was added, and dissolved therein. On the other hand, 1.097 Water 97.08 99.43 parts by weight of Y-cyclodextrin, and 1.097 parts by weight total 1OO 1OO of water were mixed with a TK homomixer, while being heated to 80°C. To this mixture, 0.3064 parts by weight of the 0080. The model beverages prepared in Example 5, and above-described oil phase in which the pepper extract was Comparative Example 5 were stored at 60°C. The piperines dissolved was added. While continuously being heated to 80° in the samples before the storage, stored for a week, and C., the resultant mixture was stirred with a TKhomomixer to stored for 2 weeks were quantitatively determined by liquid conduct preliminary emulsification. After the preliminary chromatography. For the ratio of remaining piperines, values emulsification, the mixture was passed through a high-pres determined after the beverages were stored for a week and for sure homogenizer (LAB1000 manufactured by SMT Co., 2 weeks were represented by percentage, with a value of the Ltd., pressure: 100 MPa). Thus, a pepper extract-containing piperines before the storage (Zero weeks) being employed as composite material was prepared. Into 97.08 parts by weight 100%. FIG. 6 shows the results. As is apparent from FIG. 6, of water, 2.5 parts by weight of the obtained composite mate the decomposition of the piperines was more prevented in rial, 0.3 parts by weight of citric acid, and 0.12 parts by weight Example 5 than Comparative Example 5. From the results of trisodium citrate were dispersed, and the dispersion was described above, it has been found that the present invention stirred with a mixer for 30 seconds. Thus, a pepper extract makes it possible to prevent the decomposition of piperines in model beverage containing composite material was prepared. the presence of water, and to improve the stability thereof. The pepper extract model beverage containing composite material was heated up to 93°C., and sterilized by being held Pretreatment Method for Liquid Chromatography at 90° C. for 3 minutes, and then filled into a pouch. There I0081 Regarding Example 5, 10 g of the model beverage after, the pouch was held in a constant-temperature water bath was centrifuged (at 3000 rpm for 10 minutes), and then the at 83°C. for 7 minutes to perform second sterilization. In the supernatant was removed. To the deposit, 3 ml of DMSO prepared pepper extract model beverage containing compos (dimethyl sulfoxide) was added, and the mixture was ultra ite material, the piperine amount was 62 ppm. sonicated to dissolve the deposit. Moreover, the mixture was diluted with methanol to 50 ml, filtered through a 0.45-lum filter, and then used as a test liquid. Comparative Example 5 I0082) Regarding Comparative Example 5, the sample was diluted with methanol, filtered through a 0.45-lum filter, and 0078 Here, a Piper longum of the Piperaceae family then used as a test liquid. extract (piperines content: 300 to 1400 ppm, Maruzen Phar I0083. Measurement Conditions for Liquid Chromatogra maceuticals Co., Ltd.) was used. phy 0079 Into 99.43 parts by weight of water, 0.15 parts by 0084 UV: 343 mm weight of the pepper extract, 0.3 parts by weight of citric acid, 0085 Column: YMCPack ODS-A and 0.12 parts by weight of trisodium citrate were dispersed, 008.6 Flow rate: 1.0 ml/min and the dispersion was stirred with a mixer for 30 seconds. I0087. Injection amount: 5ul Thus, a pepper extract model beverage containing composite I0088 Mobile phase: acetonitrile: water:THF (tetrahydro material was prepared. The pepper extract model beverage furan)=45:55:7 containing composite material was heated up to 93° C., and sterilized by being held at 90° C. for 3 minutes, and then filled Example 6 into a pouch. Thereafter, the pouch was held in a constant I0089. As an unsaturated fatty acid, a deodorized fish oil temperature water bath at 83° C. for 5 minutes to perform “DHA-22HG” containing 22% or more of DHA (manufac second sterilization. In the prepared pepper extract model tured by Maruha Nichiro Foods, Inc.) was used. beverage containing composite material, the piperine amount (0090. To 0.9 parts by weight of a phytosterol ester, 0.455 was 0.25 ppm. parts by weight of the deodorized fish oil containing DHA US 2011/025,6283 A1 Oct. 20, 2011

was added. The mixture was heated to 70° C. with stirring, thereto and mixed therewith. Then the mixture was heated up and the deodorized fish oil was dissolved therein. Thus, a to 93°C. with stirring, then introduced into a colorless trans phytosterol ester in which the deodorized fish oil containing parent glass container, and then cooled. Thus, a packaged DHA was dissolved was prepared. Separately, 10 parts by beverage was produced. Note that the pH of the beverage was weight of Y-cyclodextrin and 5 parts by weight of water (90° 3.4. C.) were mixed with each other to prepare a mixture (paste). To the mixed paste, the phytosterol ester in which the deodor (Evaluation of Beverages) ized fish oil containing DHA was dissolved was added. By 0.095 The packaged beverages were placed in a thermo using a mortar, the mixture was kneaded for 10 minutes, while static chamber (“SANYO GROWTH CABINET at a tem being heated to 70° C. to prepare a composite material. To the perature of 25°C. and an illuminance of 10000 lx), and stored composite material, 82.895 parts by weight of water was for 6 days. After the storage, the odor (fishy odor) of the added with mixing. Subsequently, 0.5 parts by weight of citric beverages was Subjected to sensory evaluation. The blending acid and 0.25 parts by weight of trisodium citrate were added ratios and the results of the sensory evaluation are shown in thereto, and mixed therewith. Furthermore, the resultant mix the following Table 6. From these results, it has been found ture was stirred with a homomixer at 5000 rpm for 2 minutes that deterioration of the deodorized fish oil containing DHA to obtain a homogeneous white liquid. The white liquid was can be prevented by the present invention. heated up to 93° C. with stirring, then introduced into a colorless transparent glass container, and then cooled. Thus, a packaged beverage was produced. Note that the pH of the TABLE 6 beverage was 3.4. Comparative Comparative Example 6 Example 6-1 Example 6-2 Comparative Example 6-1 blending deodorized fish oil O.4S5 O4S5 O.45S ratio (“DHA-22HG 0091. As an unsaturated fatty acid, a deodorized fish oil (in part by (Maruha Nichiro “DHA-22HG” containing 22% or more of DHA (manufac weight) Foods, Inc.)) tured by Maruha Nichiro Foods, Inc.) was used. phytosterol ester O.9 O.9 (“San Sterol NO. 0092. To 0.9 parts by weight of a phytosterol ester, 0.455 3” (San-Ei Gen parts by weight of the deodorized fish oil containing DHA F. F. I.)) was added. The mixture was heated to 70° C. with stirring, refined rapeseed O.9 and the deodorized fish oil was dissolved therein. Thus, a oil (manufactured by phytosterol ester in which the deodorized fish oil containing J-OIL MILLS, DHA was dissolved was prepared. Separately, 0.5 parts by INC.) weight of an emulsifier was dissolved in 14.5 parts by weight Y-cyclodextrin 10 of water (at 70° C.). To the emulsion, the phytosterol ester in emulsifier O.S O.S (“ryoto ester SWA which the deodorized fish oil containing DHA was dissolved 1OD'Mitsubishi was added, and the mixture was stirred with a homomixer at Kagaku Foods 5000 rpm for 10 minutes to prepare an emulsion. To the Corporation) emulsion, 82.895 parts by weight of water was added with Water 5 14.5 14.5 (anhydrous) citric O.S O.S O.S mixing, and Subsequently 0.5 parts by weight of citric acid acid and 0.25 parts by weight of trisodium citrate were added trisodium citrate O.25 O.25 O.25 thereto and mixed therewith. Then, the mixture was heated up Water 82.895 82.895 82.895 to 93°C. with stirring, then introduced into a colorless trans total 1OO 1OO 1OO parent glass container, and then cooled. Thus, a packaged sensory evaluation (fishy odor) almost no strong odor strong odor beverage was produced. Note that the pH of the beverage was odor was was noticed was noticed 3.4. noticed Comparative Example 6-2 0093. As an unsaturated fatty acid, a deodorized fish oil Example 7 “DHA-22HG” containing 22% or more of DHA (manufac 0096. As an unsaturated fatty acid, a deodorized fish oil tured by Maruha Nichiro Foods, Inc.) was used. “DHA-22HG” containing 22% or more of DHA (manufac 0094) To 0.9 parts by weight of refined rapeseed oil, 0.455 tured by Maruha Nichiro Foods, Inc.) was used. parts by weight of the deodorized fish oil containing DHA (0097. To 0.9 parts by weight of a phytosterol ester, 0.455 was added. The mixture was heated to 70° C. with stirring, parts by weight of the deodorized fish oil containing DHA and the deodorized fish oil was dissolved therein. Thus, was added. The mixture was heated to 70° C. with stirring, refined rapeseed oil in which the deodorized fish oil contain and the deodorized fish oil was dissolved therein. Thus, a ing DHA was dissolved was prepared. Separately, 0.5 parts by phytosterol ester in which the deodorized fish oil containing weight of an emulsifier was dissolved in 14.5 parts by weight DHA was prepared. Separately, 10 parts by weight of Y-cy of water (at 70° C.). To the emulsion, the refined rapeseed oil clodextrin and 5 parts by weight of water (90°C.) were mixed in which the deodorized fish oil containing DHA was dis with each other to prepare a mixture (paste). To the mixed solved was added, and the mixture was stirred with a homo paste, the phytosterol ester in which the deodorized fish oil mixer at 5000 rpm for 10 minutes to prepare an emulsion. To containing DHA was dissolved was added. By using a mortar, the emulsion, 82.895 parts by weight of water was added with the mixture was kneaded for 10 minutes, while being heated mixing, and Subsequently 0.5 parts by weight of citric acid to 70° C. to prepare a composite material. To the composite and 0.25 parts by weight of trisodium citrate were added material, 82.895 parts by weight of water was added with US 2011/025,6283 A1 Oct. 20, 2011

mixing. Subsequently, 0.5 parts by weight of citric acid and peroxide values were measured (measurement method: acetic 0.25 parts by weight of trisodium citrate were added thereto, acid-isooctane method). The blending ratios and the results of and mixed therewith. Furthermore, the resultant mixture was the sensory evaluation are shown in the following Table 7. stirred with a homomixer at 5000 rpm for 2 minutes to obtain From these results, it has been found that deterioration of the a homogeneous white liquid. The white liquid was heated up deodorized fish oil containing DHA can be prevented by the to 93°C. with stirring, then introduced into a colorless trans present invention. parent glass container, and then cooled. Thus, a packaged beverage was produced. Note that the pH of the beverage was TABLE 7 3.4. Comparative Comparative Example 7 Example 7 Example 7 blending ratio deodorized fish oil O.45S O.45S 0098. As an unsaturated fatty acid, a deodorized fish oil (in part by (“DHA-22HG (Maruha “DHA-22HG” containing 22% or more of DHA (manufac weight) Nichiro Foods, Inc.)) tured by Maruha Nichiro Foods, Inc.) was used. phytosterol ester O.9 (“San Sterol NO. 3 (San-Ei 0099 10 parts by weight of Y-cyclodextrin and 5 parts by Gen F. F. I.)) weight of water (90° C.) were mixed with each other to Y-cyclodextrin 10 10 prepare a mixture (paste). To the mixed paste, the phytosterol Water 5 5 ester in which the deodorized fish oil containing DHA was (anhydrous) citric acid O.S O.S dissolved was added. By using a mortar, the mixture was trisodium citrate O.25 O.25 kneaded for 10 minutes, while being heated to 70° C. to Water 82.895 83.795 prepare a composite material. To the composite material, total 100 1OO 82.895 parts by weight of water was added with mixing. sensory evaluation (fishy odor) almost no strong odor odor was was noticed Subsequently, 0.5 parts by weight of citric acid and 0.25 parts noticed by weight of trisodium citrate were added thereto, and mixed peroxide value (meq/kg) 58 618 therewith. Furthermore, the resultant mixture was stirred with a homomixer at 5000 rpm for 2 minutes to obtain a homoge 1. A method for preventing decomposition/deterioration of neous white liquid. The white liquid was heated up to 93° C. a lipophilic component in the presence of water, comprising: with stirring, then introduced into a colorless transparent forming a composite material containing the lipophilic glass container, and then cooled. Thus, a packaged beverage component, a phytosterol ester, and a cyclodextrin; and was produced. Note that the pH of the beverage was 3.4. storing the lipophilic component in a form of the composite (Evaluation of Beverages) material in the presence of water. 2. The method according to claim 1, wherein the lipophilic 0100. The packaged beverages were placed in a thermo component is selected from the group consisting of mustard static chamber (“SANYO GROWTH CABINET at a tem extracts, capsicum pepper extracts, ginger extracts, pepper perature of 25°C. and an illuminance of 10000 lx), and stored extracts, unsaturated fatty acids, and turmeric extracts. for 6 days. After the storage, the odor (fishy odor) of the beverages was Subjected to sensory evaluation. Furthermore, c c c c c