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WO2016167008A1 - Limonene-containing product, scented composition, and method for suppressing generation of deterioration odor - Google Patents

Limonene-containing product, scented composition, and method for suppressing generation of deterioration odor Download PDF

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Publication number
WO2016167008A1
WO2016167008A1 PCT/JP2016/052873 JP2016052873W WO2016167008A1 WO 2016167008 A1 WO2016167008 A1 WO 2016167008A1 JP 2016052873 W JP2016052873 W JP 2016052873W WO 2016167008 A1 WO2016167008 A1 WO 2016167008A1
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WIPO (PCT)
Prior art keywords
limonene
product
ppm
polyphenol
generation
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2016/052873
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French (fr)
Japanese (ja)
Inventor
たまみ 鈴木
善久 田中
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Asahi Breweries Ltd
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Asahi Breweries Ltd
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Filing date
Publication date
Priority claimed from JP2015174035A external-priority patent/JP6829935B2/en
Application filed by Asahi Breweries Ltd filed Critical Asahi Breweries Ltd
Publication of WO2016167008A1 publication Critical patent/WO2016167008A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • AHUMAN NECESSITIES
    • A23FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23LFOODS, FOODSTUFFS OR NON-ALCOHOLIC BEVERAGES, NOT OTHERWISE PROVIDED FOR; PREPARATION OR TREATMENT THEREOF
    • A23L2/00Non-alcoholic beverages; Dry compositions or concentrates therefor; Preparation or treatment thereof
    • AHUMAN NECESSITIES
    • A23FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23LFOODS, FOODSTUFFS OR NON-ALCOHOLIC BEVERAGES, NOT OTHERWISE PROVIDED FOR; PREPARATION OR TREATMENT THEREOF
    • A23L27/00Spices; Flavouring agents or condiments; Artificial sweetening agents; Table salts; Dietetic salt substitutes; Preparation or treatment thereof
    • A23L27/10Natural spices, flavouring agents or condiments; Extracts thereof
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/31Hydrocarbons
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/49Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/60Sugars; Derivatives thereof
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q13/00Formulations or additives for perfume preparations
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11BPRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
    • C11B9/00Essential oils; Perfumes

Definitions

  • the present invention relates to a limonene-containing product, a fragrance composition, and a method for suppressing the generation of a deteriorated odor.
  • the aroma component contained in such a citrus flavor is converted to other components by heating or storing for a long time.
  • the following techniques are known as examples of countermeasures against such knowledge.
  • Patent Document 1 discloses an extract obtained by solvent extraction from karin, mango, mangosteen, mylobaran, pomegranate or cacao, or epi in order to suppress the production of p-methylacetophenone or the like that occurs when citral is heated.
  • a technique for adding catechin, epicatechin gallate, epigallocatechin gallate, enzyme-treated rutin, quercetin, ferulic acid, caffeic acid, rosmarinic acid, syringic acid or gallic acid is disclosed.
  • Patent Document 2 use of solvent extracts such as Ashitaba, Avocado, Psyllium, etc. to suppress the generation of odors from citral and citral-containing products (see Patent Document 2), and solvent extract from pericarp of periwinkle plants to suppress fragrance degradation A technique used as an agent is known (see Patent Document 3).
  • Patent Document 4 discloses a technique in which eriocitrin or an eriocitrin-containing material is used as an anti-degradation agent for flavor components of citral and limonene.
  • Patent Documents 1 to 3 have been shown to be able to suppress the generation of a deteriorated odor with respect to citral, but can suppress the deterioration with respect to limonene. It was unknown. Moreover, about the technique disclosed by patent document 4, it is shown that the residual rate of a limonene can be raised with the eriocitrin containing material which contains 30% of eriocitrin.
  • an addition amount of 200 ppm (60 ppm as an active ingredient) is required as the addition amount of the eriocitrin-containing material, and there is room for developing a technique capable of effectively suppressing the degradation of limonene even with a small amount.
  • the present inventors diligently studied and found that when a specific polyphenol is allowed to act on a product containing limonene, a very remarkable deterioration odor suppressing effect is exhibited. . Moreover, since the remarkable deterioration odor suppression effect
  • a limonene-containing product comprising limonene and a polyphenol component
  • a limonene-containing product is provided in which the polyphenol component is one or more polyphenol components selected from the group consisting of proanthocyanidins, ellagitannins, and gallotannins.
  • a fragrance composition containing limonene and a polyphenol component there is provided a fragrance composition wherein the polyphenol component is one or more polyphenol components selected from the group consisting of proanthocyanidins, ellagitannins and gallotannins.
  • a method for suppressing the generation of a deteriorated odor in a product containing limonene is to add a polyphenol component to the product, There is provided a method for inhibiting the generation of a deteriorated odor, wherein the polyphenol component is one or more polyphenol components selected from the group consisting of proanthocyanidins, ellagitannins and gallotannins.
  • generation of a degradation odor is suppressed by adding a specific polyphenol component with respect to the product containing limonene.
  • this specific polyphenol component can remarkably suppress the deterioration of limonene as compared with conventional additives, and can sufficiently exhibit the effect even when added in a small amount.
  • a product containing limonene a product in which the generation of the deteriorated odor is sufficiently suppressed can be realized.
  • generation suppression method which concerns on this embodiment is demonstrated.
  • generation suppression method of this embodiment is shown below.
  • the degradation odor production suppressing method is to add a specific polyphenol component to a product containing limonene, and thereby, when heating or long-term storage is performed on limonene.
  • production of the deterioration odor component which arises can be suppressed.
  • generation suppression method of this embodiment shows a very high degradation odor production suppression effect.
  • polyphenols are generally known to exhibit astringency. For example, when a small amount of polyphenol is added to limonene-containing products such as beverages and foods, a good aftertaste can be imparted. That is, since this polyphenol component exhibits a sufficient deterioration odor generation suppressing effect even with a limited addition amount, for example, it has a good aftertaste derived from the polyphenol component for limonene-containing products such as beverages and foods. While imparting, the deterioration of limonene can be suppressed.
  • the product containing limonene according to this embodiment can be appropriately selected from products that can contain limonene (hereinafter referred to as “limonene-containing product” or simply “ Also referred to as “product”). More specifically, examples of the product containing limonene include beverages and foods containing limonene, and cosmetics. In this embodiment, the product by which the production
  • Beverages include beverages such as soft drinks, alcoholic beverages, lactic acid bacteria beverages, fruitless beverages, beverages containing fruit juices, tea, green tea, and energy drinks, and foods include confectionery such as ice cream, strawberries, and gums, and dressings And other seasonings.
  • the cosmetics include perfumes, cosmetics, bathing agents, fragrances, detergents, mouthwashes, and the like.
  • generation suppression method of this embodiment is preferably used especially when a product is a drink.
  • the limonene-containing product is a beverage will be exemplified and the description will be continued.
  • the beverage according to this embodiment may be an alcoholic beverage or a non-alcoholic beverage.
  • the lower limit of the alcohol concentration as an alcoholic beverage is 1% or more, for example, Preferably it is 2% or more, More preferably, it is 3% or more.
  • the upper limit of the alcohol concentration as an alcoholic beverage is 25% or less, for example, Preferably it is 20% or less, More preferably, it is 18% or less.
  • the unit of alcohol concentration is volume (v / v)%.
  • the pH of the beverage when a drink is acidic, ie, when the pH of a drink is less than 7, the effect becomes remarkable.
  • the pH of the beverage can be less than 6, or the pH can be less than 5.
  • the pH of the beverage can be measured according to a known method. For example, it can be measured using a pH meter HM-30R manufactured by Toa DKK Corporation.
  • a pH adjuster can also be suitably added with respect to a drink.
  • the pH adjuster may be appropriately selected according to the product to be designed, and examples thereof include carboxylic acids such as citric acid and carboxylates such as sodium citrate. Moreover, what is necessary is just to adjust the addition amount of this pH adjuster, monitoring the pH of a product sequentially.
  • generation suppression method of this embodiment it suppresses producing
  • generation of p-cymene generated from limonene during heating or storage is suppressed.
  • the present inventors have found that the smell like kerosene derived from p-cymene causes the limonene aroma to be damaged.
  • the generation of this p-cymene can be effectively suppressed by the method for suppressing the generation of deteriorated odor of the present embodiment, it has been found that the aroma of limonene can be effectively maintained as a result.
  • the content of limonene in the entire product can be appropriately set according to the product to be designed.
  • the lower limit of the content of limonene is, for example, 0.05 ppm or more, preferably 0.1 ppm or more, more preferably 0.5 ppm or more, based on the entire product.
  • the upper limit of the content of limonene is, for example, 3,000 ppm or less, preferably 2,000 ppm or less, more preferably 1,000 ppm or less, based on the entire product.
  • ppm is a mass ratio.
  • generation suppression method of this embodiment can add combining various flavors other than said limonene according to the use etc. of a product.
  • the polyphenol component used in the degradation odor production suppressing method of the present embodiment is one or more polyphenol components selected from the group consisting of proanthocyanidins, ellagitannins, and gallotannins.
  • Proanthocyanidins are polyphenols having a structure in which a plurality of epicatechins, catechins, epigallocatechins, and gallocatechins are polymerized. Specific examples thereof include procyanidin A1 (Procyanidin A1), procyanidin A2 (Procyanidin A2), and procyanidin B1 (Procyanidin). B1), procyanidin B2 (Procyanidin B2), procyanidin B3 (Procyanidin B3), procyanidin C1 (Procyanidin C1), procyanidin C2 (Procyanidin C2), prodelphinidin B1 (Prodelphindin B1), Prodeldindin B1 idinB3) and the like.
  • the polymerization mode of catechin in the proanthocyanidins of the present embodiment is not limited to the above-described compound groups, and includes positional isomers thereof.
  • Some proanthocyanidins are galloylated and glycosylated, and these are considered to exhibit the same effect.
  • a derivative obtained by performing a specific chemical conversion on proanthocyanidins for the purpose of improving the effect of suppressing the generation of deteriorated odor can also be applied to the method for suppressing the generation of deteriorated odor.
  • procyanidin B2, procyanidin B1, and procyanidin C1 are particularly preferably used.
  • Examples of ellagitannins include compounds having a hexahydroxydiphenyl group, a sangisoruboyl group, and a galloyl group that give ellagic acid by hydrolysis. Specifically, punicalagin, punicalin, castalazine, vescalazine, eugeniiin, sanguiin H-1, sanguiin H-4 (Sanguin H-4) ), 2,3-hexahydroxydiphenoylglucose (2,3-hexahydroxydiphenoylglucose), 4,6-hexahydroxydiphenoylglucose (4,6-hexahydroxydiphenoylglucose), chebulagic acid, geraniin (Geraniin) Granatin A (Granatin A), Granatin B (Granatin B) Elaeocarpusin, Corilagin, Cornusinin A, Cornusinin B, Agrimoninin, Emburicanin (Emblicanin
  • punicalazine, punicalin, castalazine, bescalazine, eugeniin, telimaglandin I, and telimagrandin II are preferably used in the method for suppressing the generation of degraded odor of this embodiment.
  • punicalagin, eugeniin, and terimalangin I are particularly preferably used.
  • gallotannins examples include tannic acid, hamamelitannin, monogalloylglucose, digalloyllucose, trigalloylglucose, galloylglucose, galloyllucose, galloylglucose Ylglucose, hexagalloylglucose, heptagalloylglucose, octagalloylglucose, nonagalloylglucose Loylglucose), decagalloylglucose, undecagalloylglucose, dodecagalloylglucose and the like.
  • tannic acid and hamamelitannin are particularly preferably used among the gallotannins.
  • generation suppression method of this embodiment it achieves by adding said polyphenol component with respect to a limonene containing product.
  • the addition amount can be appropriately set according to the type of product to be applied, etc., but is, for example, 0.01 ppm or more, preferably 0.1 ppm or more, more preferably 0.5 ppm, with respect to the entire limonene-containing product. More preferably, it is 1 ppm or more.
  • the upper limit of the addition amount of a polyphenol component is not specifically limited, For example, it is 30,000 ppm or less with respect to the whole limonene containing product.
  • the upper limit of the amount of the polyphenol component added can be 3,000 ppm or less, more preferably 1,000 ppm or less, from the viewpoint of imparting a good aftertaste. More preferably 500 ppm or less.
  • the upper limit of the amount of polyphenol component added is 100 ppm or less, preferably 50 ppm or less, more preferably 10 ppm or less, More preferably, it can be 5 ppm or less.
  • Such a fragrance composition contains, for example, 0.001 part by mass or more of the above polyphenol component, more preferably 0.01 part by mass or more, and more preferably 100 parts by mass of limonene. It contains 0.1 parts by mass or more, particularly preferably 1 part by mass or more, and particularly preferably 10 parts by mass or more.
  • flavor composition which concerns on this embodiment does not necessarily need to be uniform as a whole, and the polyphenol component may be mixed with solid form.
  • the upper limit of the polyphenol component contained in the fragrance composition according to the present embodiment is, for example, 60,000,000 parts by mass or less, preferably 6,000,000 parts by mass with respect to 100 parts by mass of limonene. It is as follows.
  • limonene tends to be denatured when heated, stored for a long period of time, or in an environment having a low pH.
  • flavor composition of this embodiment deterioration of limonene can fully be suppressed by adding a polyphenol component.
  • the amount of the components contained in the beverage is quantified using gas chromatography (GC) analysis.
  • GC gas chromatography
  • the procedure for this analysis is as follows. (Sample preparation method) Weigh 50.0 g of the sample, add 100 ⁇ L of 2-octanol as an internal standard, and dilute with 50 mL of water. Separately, a solid phase (Oasis HLB 200 mg / 6 cc manufactured by Waters) that was sequentially conditioned with dichloromethane (5 mL), ethanol (5 mL), and water (20 mL) was prepared and included in the diluted sample obtained above. Adsorb all organic components.
  • Example 1 As a model solution, a beverage containing an alcohol concentration of 5.0% and limonene of 10 ppm was prepared, and the pH of this beverage was adjusted using citric acid and trisodium citrate so that the pH was 3.0. Here, the pH was measured using a pH meter HM-30R manufactured by Toa DKK Corporation. To this beverage, procyanidin B2, which is a polyphenol belonging to proanthocyanidins, was added so as to be 0.1 ppm of the whole beverage, and after sealing, it was allowed to stand at a temperature of 37 ° C. for 7 days. After standing, the amount of p-cymene contained in the beverage was quantified. The p-cymene content is shown in Table 1 as a ratio to the content in Comparative Example 1 described later.
  • Example 2 In the method of Example 1, the sample was allowed to stand in the same manner as in Example 1 except that the amount of procyanidin B2 was adjusted to 1.0 ppm, and the amount of p-cymene contained in the beverage was quantified. The results are shown in Table 1.
  • Example 3 To the beverage prepared in the same manner as in Example 1, punicalagin, a polyphenol belonging to ellagitannin, was added so as to be 0.1 ppm of the whole beverage, and sealed, and then at a temperature of 37 ° C. for 7 days. Left to stand. After standing, the amount of p-cymene contained in the beverage was quantified. The p-cymene content is shown in Table 1 as a ratio to the content in Comparative Example 1 described later.
  • Example 4 In the method of Example 3, the mixture was left standing in the same manner as in Example 3 except that the amount of punicaladine was adjusted to 1.0 ppm, and the amount of p-cymene contained in the beverage was quantified. The results are shown in Table 1.
  • Tannic acid which is a polyphenol belonging to gallotannin, was added to the beverage prepared in the same manner as in Example 1 so that the total amount of the beverage was 0.1 ppm, and the bottle was sealed and sealed at a temperature of 37 ° C. Let stand for days. After standing, the amount of p-cymene contained in the beverage was quantified. The p-cymene content is shown in Table 1 as a ratio to the content in Comparative Example 1 described later.
  • Example 6 In the method of Example 5, except that the amount of tannic acid added was adjusted to 1.0 ppm, the mixture was allowed to stand in the same manner as in Example 5 to quantify the amount of p-cymene contained in the beverage. The results are shown in Table 1.
  • Example 7 To the beverage prepared in the same manner as in Example 1, procyanidin B1, which is a polyphenol belonging to proanthocyanidins, was added so as to be 0.1 ppm of the whole beverage, and the cap was sealed, and at a temperature of 37 ° C. for 7 days. Left to stand. After standing, the amount of p-cymene contained in the beverage was quantified. The p-cymene content is shown in Table 2 as a ratio to the content in Comparative Example 1 described later.
  • Example 8 In the method of Example 7, the sample was allowed to stand in the same manner as in Example 7 except that the amount of procyanidin B1 added was adjusted to 1.0 ppm, and the amount of p-cymene contained in the beverage was quantified. The results are shown in Table 2.
  • Example 9 To the beverage prepared in the same manner as in Example 1, procyanidin C1, which is a polyphenol belonging to proanthocyanidins, was added so as to be 0.1 ppm of the whole beverage, and sealed at a temperature of 37 ° C. Let stand for 7 days. After standing, the amount of p-cymene contained in the beverage was quantified. The p-cymene content is shown in Table 2 as a ratio to the content in Comparative Example 1 described later.
  • Example 10 In the method of Example 9, the sample was allowed to stand in the same manner as in Example 9 except that the amount of procyanidin C1 added was adjusted to 1.0 ppm, and the amount of p-cymene contained in the beverage was quantified. The results are shown in Table 2.
  • Example 12 In the method of Example 11, the amount of p-cymene contained in the beverage was quantified by standing in the same manner as in Example 11 except that the amount of eugenin was adjusted to 1.0 ppm. The results are shown in Table 2.
  • Example 13 To the beverage prepared in the same manner as in Example 1, terimaglandin I, which is a polyphenol belonging to ellagitannin, was added so as to be 0.1 ppm of the whole beverage, sealed and then brought to a temperature of 37 ° C. Left for 7 days. After standing, the amount of p-cymene contained in the beverage was quantified. The p-cymene content is shown in Table 2 as a ratio to the content in Comparative Example 1 described later.
  • Example 14 In the method of Example 13, the sample was allowed to stand in the same manner as in Example 13 except that the amount of added terimaglandin I was adjusted to 1.0 ppm, and the amount of p-cymene contained in the beverage was quantified. . The results are shown in Table 2.
  • Example 15 Hamamelitannin, a polyphenol belonging to gallotannin, was added to the beverage prepared in the same manner as in Example 1 so that it would be 0.1 ppm of the whole beverage, and sealed at a temperature of 37 ° C. Let stand for 7 days. After standing, the amount of p-cymene contained in the beverage was quantified. The p-cymene content is shown in Table 2 as a ratio to the content in Comparative Example 1 described later.
  • Example 16 In the method of Example 15, the mixture was left standing in the same manner as in Example 15 except that the amount of hamamelitannin added was adjusted to 1.0 ppm, and the amount of p-cymene contained in the beverage was quantified. The results are shown in Table 2.
  • Comparative Example 1 The beverage prepared by the same method as in Example 1 was left standing by the same method as in Example 1 without adding anything, and the amount of each component contained in the beverage was quantified. The results of Comparative Example 1 are shown in Tables 1 and 2 as a control (100%).
  • generation suppression method of this invention can keep the aroma of limonene effectively. This method is useful for the development of various products such as foods and beverages containing limonene and cosmetics.
  • the limonene product of the present invention is sufficiently suppressed in the generation of a deteriorated odor, and can effectively bring a pleasant aroma to those who use it.

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Abstract

This limonene-containing product includes limonene and a polyphenol component, wherein the polyphenol component is one or more selected from the group consisting of proanthocyanidins, ellagitannins, and gallotannins.

Description

リモネン含有製品、香料組成物および劣化臭生成抑制方法Limonene-containing product, perfume composition, and method of inhibiting deterioration odor production

 本発明は、リモネン含有製品、香料組成物および劣化臭生成抑制方法に関する。 The present invention relates to a limonene-containing product, a fragrance composition, and a method for suppressing the generation of a deteriorated odor.

 従来、シトラスフレーバーを飲料等に添加することにより、飲料等にレモンのような柑橘類特有の風味を加えることが広くなされている。また、このような柑橘類特有の風味を加えることにより、この飲料等を飲用した者にすっきりとした爽快感を与えることができる。 Conventionally, by adding citrus flavor to beverages and the like, it has been widely used to add flavors peculiar to citrus fruits such as lemons to beverages and the like. Moreover, the refreshing feeling can be given to the person who drank this drink etc. by adding such flavor peculiar to citrus fruits.

 ここで、このようなシトラスフレーバーに含まれる香気成分は、加熱を行うこと、あるいは長期的に保存することにより他の成分に変換されてしまうことが知られている。また、このような知見に対する対策を行った例として以下のような技術が知られている。 Here, it is known that the aroma component contained in such a citrus flavor is converted to other components by heating or storing for a long time. In addition, the following techniques are known as examples of countermeasures against such knowledge.

 たとえば、特許文献1にはシトラールを加熱等した際に生じる、p-メチルアセトフェノン等の生成を抑制するために、カリン、マンゴー、マンゴスチン、ミロバラン、ザクロまたはカカオから溶媒抽出された抽出物や、エピカテキン、エピカテキンガレート、エピガロカテキンガレート、酵素処理ルチン、クエルセチン、フェルラ酸、カフェー酸、ロズマリン酸、シリンガ酸または没食子酸を添加する技術が開示されている。 For example, Patent Document 1 discloses an extract obtained by solvent extraction from karin, mango, mangosteen, mylobaran, pomegranate or cacao, or epi in order to suppress the production of p-methylacetophenone or the like that occurs when citral is heated. A technique for adding catechin, epicatechin gallate, epigallocatechin gallate, enzyme-treated rutin, quercetin, ferulic acid, caffeic acid, rosmarinic acid, syringic acid or gallic acid is disclosed.

 その他、アシタバ、アボカド、オオバコ等の溶媒抽出物を用いてシトラールやシトラール含有製品の劣化臭の生成を抑制する技術(特許文献2参照)や、バンレイシ属植物の果皮の溶媒抽出物を香料劣化抑制剤として用いる技術が知られている(特許文献3参照)。 In addition, use of solvent extracts such as Ashitaba, Avocado, Psyllium, etc. to suppress the generation of odors from citral and citral-containing products (see Patent Document 2), and solvent extract from pericarp of periwinkle plants to suppress fragrance degradation A technique used as an agent is known (see Patent Document 3).

 また、特許文献4には、エリオシトリンまたはエリオシトリン含有物をシトラールやリモネンのフレーバー成分の劣化防止剤として用いる技術が開示されている。 Patent Document 4 discloses a technique in which eriocitrin or an eriocitrin-containing material is used as an anti-degradation agent for flavor components of citral and limonene.

特開2002-180081号公報Japanese Patent Laid-Open No. 2002-180081 特開2004-18613号公報JP 2004-18613 A 特開2004-292778号公報JP 2004-292778 A 特開2001-61461号公報JP 2001-61461 A

 本発明者らは、上述のシトラスフレーバーに含まれる香気成分のうち、リモネンを効果的に劣化抑制する技術の開拓を目指し、検討を行った。
 ここで、上記の文献のうち、特許文献1~3に開示される技術は、シトラールに対して劣化臭の生成を抑制することができることが示されているものの、リモネンに対して劣化を抑制できるかは不明であった。
 また、特許文献4に開示される技術について、エリオシトリンを30%含むエリオシトリン含有物によりリモネンの残存率を高めることができることが示されている。しかしながら、このエリオシトリン含有物の添加量として200ppm(有効成分として60ppm)もの添加量が必要となり、少量でも効果的にリモネンの劣化抑制ができる技術を開拓するだけの余地があった。
The present inventors have studied for the development of a technique for effectively suppressing degradation of limonene among the aroma components contained in the above-mentioned citrus flavor.
Here, among the above documents, the techniques disclosed in Patent Documents 1 to 3 have been shown to be able to suppress the generation of a deteriorated odor with respect to citral, but can suppress the deterioration with respect to limonene. It was unknown.
Moreover, about the technique disclosed by patent document 4, it is shown that the residual rate of a limonene can be raised with the eriocitrin containing material which contains 30% of eriocitrin. However, an addition amount of 200 ppm (60 ppm as an active ingredient) is required as the addition amount of the eriocitrin-containing material, and there is room for developing a technique capable of effectively suppressing the degradation of limonene even with a small amount.

 このような事情を鑑み、本発明はリモネンの香気を効果的に保つための劣化臭生成抑制方法、また、リモネンの劣化臭の生成が十分に抑制された製品を提供することを課題とする。 In view of such circumstances, it is an object of the present invention to provide a method for suppressing the generation of a deteriorated odor for effectively maintaining the aroma of limonene and a product in which the generation of a deteriorated odor of limonene is sufficiently suppressed.

 上記の課題を解決するために、本発明者らが鋭意検討したところ、リモネンを含有する製品に、特定のポリフェノールを作用させた際、極めて顕著な劣化臭抑制作用が発揮されることを見出した。
 また、このように顕著な劣化臭抑制作用をもたらすことから、限られた添加量であっても十分に劣化臭の生成を抑制することができる。
 また、このような知見に基づくことにより、リモネンを含有する製品として、その劣化臭の生成が十分に抑制された製品を実現することができる。
In order to solve the above-mentioned problems, the present inventors diligently studied and found that when a specific polyphenol is allowed to act on a product containing limonene, a very remarkable deterioration odor suppressing effect is exhibited. .
Moreover, since the remarkable deterioration odor suppression effect | action is brought about in this way, even if it is a limited addition amount, the production | generation of a deterioration odor can fully be suppressed.
Moreover, based on such knowledge, as a product containing limonene, a product in which the generation of the deteriorated odor is sufficiently suppressed can be realized.

 すなわち、本発明によれば、
 リモネンと、ポリフェノール成分とを含むリモネン含有製品であって、
 前記ポリフェノール成分は、プロアントシアニジン、エラジタンニンおよびガロタンニンからなる群から選ばれる1種又は2種以上のポリフェノール成分である、リモネン含有製品が提供される。
That is, according to the present invention,
A limonene-containing product comprising limonene and a polyphenol component,
A limonene-containing product is provided in which the polyphenol component is one or more polyphenol components selected from the group consisting of proanthocyanidins, ellagitannins, and gallotannins.

 また、本発明によれば、
 リモネンと、ポリフェノール成分とを含有する香料組成物であって、
 前記ポリフェノール成分は、プロアントシアニジン、エラジタンニンおよびガロタンニンからなる群から選ばれる1種又は2種以上のポリフェノール成分である、香料組成物が提供される。
Moreover, according to the present invention,
A fragrance composition containing limonene and a polyphenol component,
There is provided a fragrance composition wherein the polyphenol component is one or more polyphenol components selected from the group consisting of proanthocyanidins, ellagitannins and gallotannins.

 また、本発明によれば、
 リモネンを含有する製品における劣化臭生成抑制方法であって、
 当該方法は、前記製品に対して、ポリフェノール成分を添加するものであり、
 前記ポリフェノール成分は、プロアントシアニジン、エラジタンニンおよびガロタンニンからなる群から選ばれる1種又は2種以上のポリフェノール成分である、劣化臭生成抑制方法が提供される。
Moreover, according to the present invention,
A method for suppressing the generation of a deteriorated odor in a product containing limonene,
The method is to add a polyphenol component to the product,
There is provided a method for inhibiting the generation of a deteriorated odor, wherein the polyphenol component is one or more polyphenol components selected from the group consisting of proanthocyanidins, ellagitannins and gallotannins.

 本発明の劣化臭生成抑制方法においては、リモネンを含有する製品に対して、特定のポリフェノール成分を添加することで劣化臭の生成を抑制する。
 ここで、この特定のポリフェノール成分は、従来存在する添加剤よりも顕著にリモネンの劣化を抑制することができ、少量の添加であっても十分に効果を発揮することができる。
 また、このような知見に基づき、リモネンを含有する製品として、その劣化臭の生成が十分に抑制された製品を実現することができる。
In the degradation odor production | generation suppression method of this invention, the production | generation of a degradation odor is suppressed by adding a specific polyphenol component with respect to the product containing limonene.
Here, this specific polyphenol component can remarkably suppress the deterioration of limonene as compared with conventional additives, and can sufficiently exhibit the effect even when added in a small amount.
Moreover, based on such knowledge, as a product containing limonene, a product in which the generation of the deteriorated odor is sufficiently suppressed can be realized.

 以下、本発明を実施の形態に基づいて説明する。 Hereinafter, the present invention will be described based on embodiments.

(劣化臭生成抑制方法)
 まず、本実施形態に係る劣化臭生成抑制方法について説明する。
 本実施形態の劣化臭生成抑制方法は、以下に示されるものである。
 リモネンを含有する製品における劣化臭生成抑制方法であって、
 当該方法は、前記製品に対して、ポリフェノール成分を添加するものであり、
 前記ポリフェノール成分は、プロアントシアニジン、エラジタンニンおよびガロタンニンからなる群から選ばれる1種又は2種以上のポリフェノール成分である、劣化臭生成抑制方法。
(Deterioration odor production suppression method)
First, the degradation odor production | generation suppression method which concerns on this embodiment is demonstrated.
The degradation odor production | generation suppression method of this embodiment is shown below.
A method for suppressing the generation of a deteriorated odor in a product containing limonene,
The method is to add a polyphenol component to the product,
The method according to claim 1, wherein the polyphenol component is one or more polyphenol components selected from the group consisting of proanthocyanidins, ellagitannins, and gallotannins.

 すなわち、本実施形態に係る劣化臭生成抑制方法は、リモネンを含有する製品に対して、特定のポリフェノール成分を添加するものであり、これによって、リモネンに対して加熱や長期保存を行った際に生じる劣化臭成分の生成を抑制することができる。 That is, the degradation odor production suppressing method according to the present embodiment is to add a specific polyphenol component to a product containing limonene, and thereby, when heating or long-term storage is performed on limonene. Generation | occurrence | production of the deterioration odor component which arises can be suppressed.

 ここで、本実施形態の劣化臭生成抑制方法に用いられる特定のポリフェノール成分は、極めて高い劣化臭生成抑制作用を示す。
 一方、ポリフェノールは一般的に渋みを呈することが知られており、たとえば飲料や食品等のリモネン含有製品に対して、少量のポリフェノールを添加する場合は良好な後味を付与することができる。
 すなわち、このポリフェノール成分は限られた添加量であっても十分な劣化臭生成抑制作用を示すことから、たとえば、飲料や食品等のリモネン含有製品に対して、ポリフェノール成分に由来する良好な後味を付与しつつ、リモネンの劣化を抑制することができる。
Here, the specific polyphenol component used for the degradation odor production | generation suppression method of this embodiment shows a very high degradation odor production suppression effect.
On the other hand, polyphenols are generally known to exhibit astringency. For example, when a small amount of polyphenol is added to limonene-containing products such as beverages and foods, a good aftertaste can be imparted.
That is, since this polyphenol component exhibits a sufficient deterioration odor generation suppressing effect even with a limited addition amount, for example, it has a good aftertaste derived from the polyphenol component for limonene-containing products such as beverages and foods. While imparting, the deterioration of limonene can be suppressed.

(リモネンを含有する製品)
 本実施形態に係るリモネンを含有する製品は、リモネンを含ませることのできる製品の中から適宜選択することができる(以下、この「リモネンを含有する製品」について「リモネン含有製品」または、単に「製品」とも称する。)。
 このリモネンを含有する製品として、より具体的には、リモネンを含む飲料や食品、また、香粧品を挙げることができる。
 本実施形態においては、後述する特定のポリフェノール成分を含有させることによりリモネンに由来する劣化臭成分の生成が抑制された製品が提供される。
(Products containing limonene)
The product containing limonene according to this embodiment can be appropriately selected from products that can contain limonene (hereinafter referred to as “limonene-containing product” or simply “ Also referred to as “product”).
More specifically, examples of the product containing limonene include beverages and foods containing limonene, and cosmetics.
In this embodiment, the product by which the production | generation of the degradation odor component derived from limonene was suppressed by containing the specific polyphenol component mentioned later is provided.

 飲料としては、清涼飲料、アルコール飲料、乳酸菌飲料、無果汁飲料、果汁入り飲料、紅茶、緑茶、栄養ドリンクなどの飲料が挙げられ、食品としては、アイスクリームや飴、ガム等の菓子類、ドレッシング等の調味料類等が挙げられる。また、香粧品としては、香水や化粧品、入浴剤、芳香剤、洗剤、洗口剤等を例示することができる。
 これらのなかでも、本実施形態の劣化臭生成抑制方法は、製品が飲料である場合にとくに好ましく用いられる。
 以下、リモネン含有製品が飲料である場合を例示して、説明を続ける。
Beverages include beverages such as soft drinks, alcoholic beverages, lactic acid bacteria beverages, fruitless beverages, beverages containing fruit juices, tea, green tea, and energy drinks, and foods include confectionery such as ice cream, strawberries, and gums, and dressings And other seasonings. Examples of the cosmetics include perfumes, cosmetics, bathing agents, fragrances, detergents, mouthwashes, and the like.
Among these, the degradation odor production | generation suppression method of this embodiment is preferably used especially when a product is a drink.
Hereinafter, the case where the limonene-containing product is a beverage will be exemplified and the description will be continued.

 本実施形態に係る飲料としてはアルコール飲料であってもよく、またノンアルコール飲料であってもよい。なお、アルコール飲料としてのアルコール濃度の下限値は、たとえば1%以上であり、好ましくは2%以上であり、より好ましくは3%以上である。
 また、アルコール飲料としてのアルコール濃度の上限値は、たとえば25%以下であり、好ましくは20%以下である、より好ましくは18%以下である。ここで、アルコール濃度の単位は容量(v/v)%である。
The beverage according to this embodiment may be an alcoholic beverage or a non-alcoholic beverage. In addition, the lower limit of the alcohol concentration as an alcoholic beverage is 1% or more, for example, Preferably it is 2% or more, More preferably, it is 3% or more.
Moreover, the upper limit of the alcohol concentration as an alcoholic beverage is 25% or less, for example, Preferably it is 20% or less, More preferably, it is 18% or less. Here, the unit of alcohol concentration is volume (v / v)%.

 本実施形態に係る飲料のpHに関して、リモネンは、飲料のpHが低くなるほど、変性を起こしやすくなり、結果として、劣化臭を招く化合物を生成しやすくなる傾向がある。
 このことから、本実施形態に係る劣化臭生成抑制方法においては、飲料が酸性、すなわち、飲料のpHが7未満である場合に、その効果が顕著なものとなる。同様の観点から、飲料のpHを6未満とすることもできるし、pHを5未満とすることもできる。
 なお、飲料のpHは公知の方法に従って測定することができ、例えば、東亜ディーケーケー社製のpHメーター HM-30R等を用いて測定することができる。
Regarding the pH of the beverage according to the present embodiment, limonene tends to be denatured as the pH of the beverage is lowered, and as a result, it tends to easily generate a compound that causes a deteriorated odor.
From this, in the degradation odor production | generation suppression method which concerns on this embodiment, when a drink is acidic, ie, when the pH of a drink is less than 7, the effect becomes remarkable. From the same viewpoint, the pH of the beverage can be less than 6, or the pH can be less than 5.
The pH of the beverage can be measured according to a known method. For example, it can be measured using a pH meter HM-30R manufactured by Toa DKK Corporation.

 また、上記のようなpHに調整するために、適宜、飲料に対してpH調整剤を添加することもできる。このpH調整剤としては、設計する製品に合わせて適宜選択すればよいが、例えばクエン酸のようなカルボン酸やクエン酸ナトリウムのようなカルボン酸塩等が挙げられる。
 また、このpH調整剤は、製品のpHを逐次観測しながら、添加量を調整すればよい。
Moreover, in order to adjust to pH as mentioned above, a pH adjuster can also be suitably added with respect to a drink. The pH adjuster may be appropriately selected according to the product to be designed, and examples thereof include carboxylic acids such as citric acid and carboxylates such as sodium citrate.
Moreover, what is necessary is just to adjust the addition amount of this pH adjuster, monitoring the pH of a product sequentially.

 本実施形態の劣化臭生成抑制方法においては、加熱時や保存時において、劣化成分がリモネンから生成することを抑制する。
 たとえば、本実施形態の劣化臭生成抑制方法においては、加熱時や保存時においてリモネンから発生するp-サイメンの生成を抑制する。
 本発明者らは、このp-サイメンに由来する灯油のような臭いがリモネンの香気を損なう原因となることを見出した。また、本実施形態の劣化臭生成抑制方法によりこのp-サイメンの生成を効果的に抑制できることから、結果として、効果的にリモネンの香気を保つことができることを見出した。
In the degradation odor production | generation suppression method of this embodiment, it suppresses producing | generating a degradation component from limonene at the time of a heating and a preservation | save.
For example, in the deteriorated odor generation suppressing method of the present embodiment, generation of p-cymene generated from limonene during heating or storage is suppressed.
The present inventors have found that the smell like kerosene derived from p-cymene causes the limonene aroma to be damaged. Moreover, since the generation of this p-cymene can be effectively suppressed by the method for suppressing the generation of deteriorated odor of the present embodiment, it has been found that the aroma of limonene can be effectively maintained as a result.

 本実施形態において、製品の全体におけるリモネンの含有量は、設計する製品に合わせて適宜設定することができる。
 このリモネンの含有量の下限値としては、たとえば製品の全体に対して0.05ppm以上であり、好ましくは0.1ppm以上であり、より好ましくは0.5ppm以上である。
 また、リモネンの含有量の上限値は、たとえば製品の全体に対して3,000ppm以下であり、好ましくは2,000ppm以下であり、より好ましくは1,000ppm以下である。ここで、ppmは質量比である。
In the present embodiment, the content of limonene in the entire product can be appropriately set according to the product to be designed.
The lower limit of the content of limonene is, for example, 0.05 ppm or more, preferably 0.1 ppm or more, more preferably 0.5 ppm or more, based on the entire product.
Further, the upper limit of the content of limonene is, for example, 3,000 ppm or less, preferably 2,000 ppm or less, more preferably 1,000 ppm or less, based on the entire product. Here, ppm is a mass ratio.

 なお、本実施形態の劣化臭生成抑制方法は、製品の用途等に応じて、上記のリモネン以外にも各種フレーバーを組み合わせて加えることができる。 In addition, the deterioration odor production | generation suppression method of this embodiment can add combining various flavors other than said limonene according to the use etc. of a product.

(ポリフェノール成分)
 続いて、本実施形態の劣化臭生成抑制方法に用いられるポリフェノール成分について説明する。
(Polyphenol component)
Then, the polyphenol component used for the degradation odor production | generation suppression method of this embodiment is demonstrated.

 本実施形態の劣化臭生成抑制方法に用いられるポリフェノール成分は、プロアントシアニジン、エラジタンニンおよびガロタンニンからなる群から選ばれる1種又は2種以上のポリフェノール成分である。 The polyphenol component used in the degradation odor production suppressing method of the present embodiment is one or more polyphenol components selected from the group consisting of proanthocyanidins, ellagitannins, and gallotannins.

 プロアントシアニジンは、エピカテキン、カテキン、エピガロカテキン、ガロカテキンが複数個重合した構造を有するポリフェノールであり、その具体例としては、プロシアニジンA1(Procyanidin A1)、プロシアニジンA2(Procyanidin A2)、プロシアニジンB1(Procyanidin B1)、プロシアニジンB2(Procyanidin B2)、プロシアニジンB3(Procyanidin B3)、プロシアニジンC1(Procyanidin C1)、プロシアニジンC2(Procyanidin C2)、プロデルフィニジンB1(ProdelphinidinB1)、プロデルフィニジンB2(ProdelphinidinB2)、プロデルフィニジンB3(ProdelphinidinB3)等が挙げられる。
 また、本実施形態のプロアントシアニジンにおけるカテキンの重合態様としては、上で列挙した化合物群の態様に限定されるものでなく、その位置異性体も含まれるものである。また、プロアントシアニジンにはガロイル化されたもの、配糖体化されたものも存在しており、これらも同様の効果を示すと考えられる。
 また、劣化臭生成抑制作用の向上等を目的として、プロアントシアニジンに対して特定の化学変換を行った誘導体も本実施形態の劣化臭生成抑制方法に適用することができる。
 本実施形態の劣化臭生成抑制方法においては、上記のプロアントシアニジンのうち、プロシアニジンB2、プロシアニジンB1、プロシアニジンC1がとくに好ましく用いられる。
Proanthocyanidins are polyphenols having a structure in which a plurality of epicatechins, catechins, epigallocatechins, and gallocatechins are polymerized. Specific examples thereof include procyanidin A1 (Procyanidin A1), procyanidin A2 (Procyanidin A2), and procyanidin B1 (Procyanidin). B1), procyanidin B2 (Procyanidin B2), procyanidin B3 (Procyanidin B3), procyanidin C1 (Procyanidin C1), procyanidin C2 (Procyanidin C2), prodelphinidin B1 (Prodelphindin B1), Prodeldindin B1 idinB3) and the like.
In addition, the polymerization mode of catechin in the proanthocyanidins of the present embodiment is not limited to the above-described compound groups, and includes positional isomers thereof. Some proanthocyanidins are galloylated and glycosylated, and these are considered to exhibit the same effect.
In addition, a derivative obtained by performing a specific chemical conversion on proanthocyanidins for the purpose of improving the effect of suppressing the generation of deteriorated odor can also be applied to the method for suppressing the generation of deteriorated odor.
In the degradation odor production suppressing method of the present embodiment, among the above-mentioned proanthocyanidins, procyanidin B2, procyanidin B1, and procyanidin C1 are particularly preferably used.

 エラジタンニンとしては加水分解によりエラグ酸を与える、ヘキサヒドロキシジフェニル基、サングイソルボイル基、ガロイル基を有する化合物が挙げられる。
 具体的には、プニカラジン(Punicalagin)、プニカリン(Punicalin)、カスタラジン(Castalagin)、ベスカラジン(Vescalagin)、オイゲニイン(Eugeniin)、サングイインH-1(Sanguiin H-1)、サングイインH-4(Sanguiin H-4)、2,3-ヘキサヒドロキシジフェノイルグルコース(2,3-hexahydroxydiphenoylglucose)、4,6-ヘキサヒドロキシジフェノイルグルコース(4,6-hexahydroxydiphenoylglucose)、ケブラグ酸(Chebulagic acid)、ゲラニイン(Geraniin)、グラナチンA(Granatin A)、グラナチンB(Granatin B)、エラエオカルプシン(Elaeocarpusin)、コリラギン(Corilagin)、コルヌシインA(Cornusiin A)、コルヌシインB(Cornusiin B)、アグリモニイン(Agrimoniin)、エンブリカニン(Emblicanin)、プニグルコニン(Punigluconin)、テリマグランジンI(Tellimagrandin I)、テリマグランジンII(Tellimagrandin II)、カスアリクチン(Casuarictin)、ペデュンクラギン(Pedunculagin)、ケブリン酸(Chebulic acid)等が挙げられる。
 本実施形態の劣化臭生成抑制方法においては、上記のエラジタンニンのうち、プニカラジン、プニカリン、カスタラジン、ベスカラジン、オイゲニイン、テリマグランジンI、テリマグランジンIIが好ましく用いられる。また、これらの中でもプニカラジン、オイゲニイン、テリマグランジンIがとくに好ましく用いられる。
Examples of ellagitannins include compounds having a hexahydroxydiphenyl group, a sangisoruboyl group, and a galloyl group that give ellagic acid by hydrolysis.
Specifically, punicalagin, punicalin, castalazine, vescalazine, eugeniiin, sanguiin H-1, sanguiin H-4 (Sanguin H-4) ), 2,3-hexahydroxydiphenoylglucose (2,3-hexahydroxydiphenoylglucose), 4,6-hexahydroxydiphenoylglucose (4,6-hexahydroxydiphenoylglucose), chebulagic acid, geraniin (Geraniin) Granatin A (Granatin A), Granatin B (Granatin B) Elaeocarpusin, Corilagin, Cornusinin A, Cornusinin B, Agrimoninin, Emburicanin (Emblicanin), Unglicinin, P , Telimagrandin II, Casuaricin, Pedunculagin, Chebulic acid, and the like.
Of the above-mentioned ellagitannins, punicalazine, punicalin, castalazine, bescalazine, eugeniin, telimaglandin I, and telimagrandin II are preferably used in the method for suppressing the generation of degraded odor of this embodiment. Of these, punicalagin, eugeniin, and terimalangin I are particularly preferably used.

 ガロタンニンとしては、タンニン酸(tannic acid)、ハマメリタンニン(Hamamelitannin)、モノガロイルグルコース(monogalloylglucose)、ジガロイルグルコース(digalloylglucose)、トリガロイルグルコース(trigalloylglucose)、テトラガロイルグルコース(tetragalloylglucose)、ペンタガロイルグルコース(pentagalloylglucose)、ヘキサガロイルグルコース(hexagalloylglucose)、ヘプタガロイルグルコース(heptagalloylglucose)、オクタガロイルグルコース(octagalloylglucose)、ノナガロイルグルコース(nonagalloylglucose)、デカガロイルグルコース(decagalloylglucose)、ウンデカガロイルグルコース(undecagalloylglucose)、ドデカガロイルグルコース(dodecagalloylglucose)等が挙げられる。
 本実施形態の劣化臭生成抑制方法においては、上記のガロタンニンのうち、タンニン酸、ハマメリタンニンがとくに好ましく用いられる。
Examples of gallotannins include tannic acid, hamamelitannin, monogalloylglucose, digalloyllucose, trigalloylglucose, galloylglucose, galloyllucose, galloylglucose Ylglucose, hexagalloylglucose, heptagalloylglucose, octagalloylglucose, nonagalloylglucose Loylglucose), decagalloylglucose, undecagalloylglucose, dodecagalloylglucose and the like.
In the degradation odor production suppressing method of the present embodiment, tannic acid and hamamelitannin are particularly preferably used among the gallotannins.

 本実施形態の劣化臭生成抑制方法においては、上記のポリフェノール成分をリモネン含有製品に対して添加することで達成される。
 その添加量は、適用させる製品の種類等に応じ適宜設定することができるが、リモネン含有製品全体に対して、たとえば0.01ppm以上であり、好ましくは0.1ppm以上、より好ましくは0.5ppm以上、さらに好ましくは1ppm以上である。ポリフェノール成分の添加量をこのように設定することでリモネンの劣化を十分に抑制することができる。
 また、ポリフェノール成分の添加量の上限値はとくに限定されないが、たとえばリモネン含有製品全体に対して30,000ppm以下である。
 また、リモネン含有製品が飲料や食料品である場合、良好な後味を付与する観点から、このポリフェノール成分の添加量の上限値を3,000ppm以下とすることができ、より好ましくは1,000ppm以下とすることができ、さらに好ましくは500ppm以下とすることができる。
 また、上記のポリフェノール成分は従来存在する添加剤よりも顕著にリモネンの劣化を抑制することができるため、ポリフェノール成分の添加量の上限値は100ppm以下、好ましくは50ppm以下、より好ましくは10ppm以下、さらに好ましくは5ppm以下とすることができる。これにより、リモネン含有製品の香気を効果的に保ちつつ、リモネン含有製品の本来の風味をより効果的に保つことができる。
In the degradation odor production | generation suppression method of this embodiment, it achieves by adding said polyphenol component with respect to a limonene containing product.
The addition amount can be appropriately set according to the type of product to be applied, etc., but is, for example, 0.01 ppm or more, preferably 0.1 ppm or more, more preferably 0.5 ppm, with respect to the entire limonene-containing product. More preferably, it is 1 ppm or more. By setting the addition amount of the polyphenol component in this way, the deterioration of limonene can be sufficiently suppressed.
Moreover, the upper limit of the addition amount of a polyphenol component is not specifically limited, For example, it is 30,000 ppm or less with respect to the whole limonene containing product.
In addition, when the limonene-containing product is a beverage or a food product, the upper limit of the amount of the polyphenol component added can be 3,000 ppm or less, more preferably 1,000 ppm or less, from the viewpoint of imparting a good aftertaste. More preferably 500 ppm or less.
In addition, since the above polyphenol component can significantly suppress the deterioration of limonene as compared with the existing additives, the upper limit of the amount of polyphenol component added is 100 ppm or less, preferably 50 ppm or less, more preferably 10 ppm or less, More preferably, it can be 5 ppm or less. Thereby, the original flavor of a limonene containing product can be kept more effectively, maintaining the aroma of a limonene containing product effectively.

(香料組成物)
 上述の劣化臭生成抑制方法においては、リモネンを含有する製品に対して、特定のポリフェノールを添加する態様を示したが、他の実施形態として、事前にリモネンと、ポリフェノール成分とを含有する香料組成物を調製しておき、この香料組成物を各種製品に添加することで所望の効果を発現することもできる。
(Fragrance composition)
In the above-described degradation odor production suppressing method, a mode in which a specific polyphenol is added to a product containing limonene has been shown, but as another embodiment, a fragrance composition containing limonene and a polyphenol component in advance. A desired effect can also be expressed by preparing this product and adding this fragrance composition to various products.

 このような香料組成物は、たとえばリモネン100質量部に対して、上記のポリフェノール成分を0.001質量部以上含むものであり、より好ましくは0.01質量部以上含むものであり、さらに好ましくは0.1質量部以上、殊更好ましくは1質量部以上、特に好ましくは10質量部以上含むものである。
 なお、本実施形態に係る香料組成物は、必ずしも全体として均一である必要はなく、ポリフェノール成分が固体状で混合されていてもよい。
 また、本実施形態に係る香料組成物に含まれるポリフェノール成分の上限値は、たとえば、リモネン100質量部に対して、60,000,000質量部以下であり、好ましくは6,000,000質量部以下である。
Such a fragrance composition contains, for example, 0.001 part by mass or more of the above polyphenol component, more preferably 0.01 part by mass or more, and more preferably 100 parts by mass of limonene. It contains 0.1 parts by mass or more, particularly preferably 1 part by mass or more, and particularly preferably 10 parts by mass or more.
In addition, the fragrance | flavor composition which concerns on this embodiment does not necessarily need to be uniform as a whole, and the polyphenol component may be mixed with solid form.
Moreover, the upper limit of the polyphenol component contained in the fragrance composition according to the present embodiment is, for example, 60,000,000 parts by mass or less, preferably 6,000,000 parts by mass with respect to 100 parts by mass of limonene. It is as follows.

 ここで、先述の通り、リモネンは加熱時や長期保存時、また、pHの低い環境におかれることにより、変性を招きやすくなる。これに対し、本実施形態の香料組成物においては、ポリフェノール成分を添加することで十分にリモネンの劣化を抑制することができる。
 この香料組成物に関する具体的な態様として、香料組成物を不活性ガスとともに容器に収容した上で密閉し、冷暗所に保管することが、シトラスフレーバー固有の香気を保つ観点から好ましい態様である。
Here, as described above, limonene tends to be denatured when heated, stored for a long period of time, or in an environment having a low pH. On the other hand, in the fragrance | flavor composition of this embodiment, deterioration of limonene can fully be suppressed by adding a polyphenol component.
As a specific embodiment relating to this fragrance composition, it is a preferable embodiment from the viewpoint of keeping the fragrance unique to the citrus flavor by sealing the fragrance composition together with an inert gas in a container and storing it in a cool and dark place.

 以上、本発明の実施形態について述べたが、これらは本発明の例示であり、上記以外の様々な構成を採用することもできる。 As mentioned above, although embodiment of this invention was described, these are illustrations of this invention and various structures other than the above can also be employ | adopted.

 以下、実施例を用いて本発明を詳細に説明するが、本発明はこれらの実施例の記載に何ら限定されるものではない。 Hereinafter, the present invention will be described in detail using examples, but the present invention is not limited to the description of these examples.

 まず、本実施例項において、飲料中に含まれる成分の量はガスクロマトグラフィ(GC)分析を用いて定量を行っている。この分析の手順は以下に示す通りである。
(サンプル作製方法)
 試料を50.0g秤量し、内部標準として2-オクタノールを100μL添加した上で、50mLの水で希釈を行う。これとは別にジクロロメタン(5mL)、エタノール(5mL)、水(20mL)にて順次コンディショニングを行った固相(Waters社製Oasis HLB 200mg/6cc)を準備し、上で得られた希釈試料に含まれる有機成分を全量吸着させる。その後、ジクロロメタン5mLにて溶出を行い、この溶出液を無水硫酸ナトリウムで脱水し、その上清をスピッツ管に移注して窒素パージにて200μLまで濃縮し、分析用のサンプルを作製する。なお、試料調製は2点並行して行う。
(定量方法)
 この分析用のサンプルは以下に示す条件にて、GC分析を行う。試料中の成分量は内部標準として用いた2-オクタノールのピークとの面積比から計算する。また、同一試料について2点並行で行った分析値の平均値を試料中の成分量であるものとして定量を行う。
(GC条件)
機器名:Agilent Technologies社製 5973inert Mass Selective Detector
カラム:DB-WAX(60m×0.25mm,0.25μm)
オーブン温度:40℃(1min)-(3℃/min)-210℃(3min)
流量:1mL/min
インジェクション温度:250℃
インジェクション量:1μL
スプリット比:10:1
First, in the present Example section, the amount of the components contained in the beverage is quantified using gas chromatography (GC) analysis. The procedure for this analysis is as follows.
(Sample preparation method)
Weigh 50.0 g of the sample, add 100 μL of 2-octanol as an internal standard, and dilute with 50 mL of water. Separately, a solid phase (Oasis HLB 200 mg / 6 cc manufactured by Waters) that was sequentially conditioned with dichloromethane (5 mL), ethanol (5 mL), and water (20 mL) was prepared and included in the diluted sample obtained above. Adsorb all organic components. Thereafter, elution is performed with 5 mL of dichloromethane, and the eluate is dehydrated with anhydrous sodium sulfate. The supernatant is transferred to a Spitz tube and concentrated to 200 μL with a nitrogen purge to prepare a sample for analysis. Sample preparation is performed in parallel at two points.
(Quantitative method)
This analysis sample is subjected to GC analysis under the following conditions. The amount of components in the sample is calculated from the area ratio with the 2-octanol peak used as the internal standard. Further, quantification is performed assuming that the average value of the analysis values performed in parallel on the same sample at two points is the amount of the component in the sample.
(GC condition)
Device name: 5973inert Mass Selective Detector manufactured by Agilent Technologies
Column: DB-WAX (60 m × 0.25 mm, 0.25 μm)
Oven temperature: 40 ° C. (1 min) − (3 ° C./min)−210° C. (3 min)
Flow rate: 1 mL / min
Injection temperature: 250 ° C
Injection volume: 1 μL
Split ratio: 10: 1

(実施例1)
 モデル液として、アルコール濃度5.0%、リモネン10ppmを含む飲料を用意し、この飲料のpHを、クエン酸およびクエン酸三ナトリウムを用いてpHが3.0となるように調整した。なお、ここでpHは東亜ディーケーケー社製のpHメーター HM-30Rを用いて測定した。
 この飲料に対し、プロアントシアニジンに属するポリフェノールであるプロシアニジンB2を飲料全体の0.1ppmとなるように添加し、密栓した上で、37℃の温度にて7日間静置した。静置後、飲料に含まれるp-サイメンの量を定量した。
 このp-サイメンの含有量について、後述する比較例1における含有量との比として表1に示した。
(Example 1)
As a model solution, a beverage containing an alcohol concentration of 5.0% and limonene of 10 ppm was prepared, and the pH of this beverage was adjusted using citric acid and trisodium citrate so that the pH was 3.0. Here, the pH was measured using a pH meter HM-30R manufactured by Toa DKK Corporation.
To this beverage, procyanidin B2, which is a polyphenol belonging to proanthocyanidins, was added so as to be 0.1 ppm of the whole beverage, and after sealing, it was allowed to stand at a temperature of 37 ° C. for 7 days. After standing, the amount of p-cymene contained in the beverage was quantified.
The p-cymene content is shown in Table 1 as a ratio to the content in Comparative Example 1 described later.

(実施例2)
 実施例1の方法において、プロシアニジンB2の添加量を1.0ppmに調整する以外は、実施例1と同様の方法で静置を行い、飲料中に含まれるp-サイメンの量を定量した。結果は表1に示した。
(Example 2)
In the method of Example 1, the sample was allowed to stand in the same manner as in Example 1 except that the amount of procyanidin B2 was adjusted to 1.0 ppm, and the amount of p-cymene contained in the beverage was quantified. The results are shown in Table 1.

(実施例3)
 実施例1と同様の方法で調製した飲料に対して、エラジタンニンに属するポリフェノールであるプニカラジンを、飲料全体の0.1ppmとなるように添加し、密栓した上で、37℃の温度にて7日間静置した。静置後、飲料に含まれるp-サイメンの量を定量した。
 このp-サイメンの含有量について、後述する比較例1における含有量との比として表1に示した。
(Example 3)
To the beverage prepared in the same manner as in Example 1, punicalagin, a polyphenol belonging to ellagitannin, was added so as to be 0.1 ppm of the whole beverage, and sealed, and then at a temperature of 37 ° C. for 7 days. Left to stand. After standing, the amount of p-cymene contained in the beverage was quantified.
The p-cymene content is shown in Table 1 as a ratio to the content in Comparative Example 1 described later.

(実施例4)
 実施例3の方法において、プニカラジンの添加量を1.0ppmに調整する以外は、実施例3と同様の方法で静置を行い、飲料中に含まれるp-サイメンの量を定量した。結果は表1に示した。
Example 4
In the method of Example 3, the mixture was left standing in the same manner as in Example 3 except that the amount of punicaladine was adjusted to 1.0 ppm, and the amount of p-cymene contained in the beverage was quantified. The results are shown in Table 1.

(実施例5)
 実施例1と同様の方法で調製した飲料に対して、ガロタンニンに属するポリフェノールであるタンニン酸を、飲料全体の0.1ppmとなるように添加し、密栓した上で、37℃の温度にて7日間静置した。静置後、飲料に含まれるp-サイメンの量を定量した。
 このp-サイメンの含有量について、後述する比較例1における含有量との比として表1に示した。
(Example 5)
Tannic acid, which is a polyphenol belonging to gallotannin, was added to the beverage prepared in the same manner as in Example 1 so that the total amount of the beverage was 0.1 ppm, and the bottle was sealed and sealed at a temperature of 37 ° C. Let stand for days. After standing, the amount of p-cymene contained in the beverage was quantified.
The p-cymene content is shown in Table 1 as a ratio to the content in Comparative Example 1 described later.

(実施例6)
 実施例5の方法において、タンニン酸の添加量を1.0ppmに調整する以外は、実施例5と同様の方法で静置を行い、飲料中に含まれるp-サイメンの量を定量した。結果は表1に示した。
(Example 6)
In the method of Example 5, except that the amount of tannic acid added was adjusted to 1.0 ppm, the mixture was allowed to stand in the same manner as in Example 5 to quantify the amount of p-cymene contained in the beverage. The results are shown in Table 1.

Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001

(実施例7)
 実施例1と同様の方法で調製した飲料に対し、プロアントシアニジンに属するポリフェノールであるプロシアニジンB1を飲料全体の0.1ppmとなるように添加し、密栓した上で、37℃の温度にて7日間静置した。静置後、飲料に含まれるp-サイメンの量を定量した。
 このp-サイメンの含有量について、後述する比較例1における含有量との比として表2に示した。
(Example 7)
To the beverage prepared in the same manner as in Example 1, procyanidin B1, which is a polyphenol belonging to proanthocyanidins, was added so as to be 0.1 ppm of the whole beverage, and the cap was sealed, and at a temperature of 37 ° C. for 7 days. Left to stand. After standing, the amount of p-cymene contained in the beverage was quantified.
The p-cymene content is shown in Table 2 as a ratio to the content in Comparative Example 1 described later.

(実施例8)
 実施例7の方法において、プロシアニジンB1の添加量を1.0ppmに調整する以外は、実施例7と同様の方法で静置を行い、飲料中に含まれるp-サイメンの量を定量した。結果は表2に示した。
(Example 8)
In the method of Example 7, the sample was allowed to stand in the same manner as in Example 7 except that the amount of procyanidin B1 added was adjusted to 1.0 ppm, and the amount of p-cymene contained in the beverage was quantified. The results are shown in Table 2.

(実施例9)
 実施例1と同様の方法で調製した飲料に対して、プロアントシアニジンに属するポリフェノールであるプロシアニジンC1を、飲料全体の0.1ppmとなるように添加し、密栓した上で、37℃の温度にて7日間静置した。静置後、飲料に含まれるp-サイメンの量を定量した。
 このp-サイメンの含有量について、後述する比較例1における含有量との比として表2に示した。
Example 9
To the beverage prepared in the same manner as in Example 1, procyanidin C1, which is a polyphenol belonging to proanthocyanidins, was added so as to be 0.1 ppm of the whole beverage, and sealed at a temperature of 37 ° C. Let stand for 7 days. After standing, the amount of p-cymene contained in the beverage was quantified.
The p-cymene content is shown in Table 2 as a ratio to the content in Comparative Example 1 described later.

(実施例10)
 実施例9の方法において、プロシアニジンC1の添加量を1.0ppmに調整する以外は、実施例9と同様の方法で静置を行い、飲料中に含まれるp-サイメンの量を定量した。結果は表2に示した。
(Example 10)
In the method of Example 9, the sample was allowed to stand in the same manner as in Example 9 except that the amount of procyanidin C1 added was adjusted to 1.0 ppm, and the amount of p-cymene contained in the beverage was quantified. The results are shown in Table 2.

(実施例11)
 実施例1と同様の方法で調製した飲料に対して、エラジタンニンに属するポリフェノールであるオイゲニインを、飲料全体の0.1ppmとなるように添加し、密栓した上で、37℃の温度にて7日間静置した。静置後、飲料に含まれるp-サイメンの量を定量した。
 このp-サイメンの含有量について、後述する比較例1における含有量との比として表2に示した。
(Example 11)
Eugeniin, which is a polyphenol belonging to ellagitannin, was added to the beverage prepared in the same manner as in Example 1 so that the total amount of the beverage was 0.1 ppm, and sealed, and then at a temperature of 37 ° C. for 7 days. Left to stand. After standing, the amount of p-cymene contained in the beverage was quantified.
The p-cymene content is shown in Table 2 as a ratio to the content in Comparative Example 1 described later.

(実施例12)
 実施例11の方法において、オイゲニインの添加量を1.0ppmに調整する以外は、実施例11と同様の方法で静置を行い、飲料中に含まれるp-サイメンの量を定量した。結果は表2に示した。
Example 12
In the method of Example 11, the amount of p-cymene contained in the beverage was quantified by standing in the same manner as in Example 11 except that the amount of eugenin was adjusted to 1.0 ppm. The results are shown in Table 2.

(実施例13)
 実施例1と同様の方法で調製した飲料に対して、エラジタンニンに属するポリフェノールであるテリマグランジンIを、飲料全体の0.1ppmとなるように添加し、密栓した上で、37℃の温度にて7日間静置した。静置後、飲料に含まれるp-サイメンの量を定量した。
 このp-サイメンの含有量について、後述する比較例1における含有量との比として表2に示した。
(Example 13)
To the beverage prepared in the same manner as in Example 1, terimaglandin I, which is a polyphenol belonging to ellagitannin, was added so as to be 0.1 ppm of the whole beverage, sealed and then brought to a temperature of 37 ° C. Left for 7 days. After standing, the amount of p-cymene contained in the beverage was quantified.
The p-cymene content is shown in Table 2 as a ratio to the content in Comparative Example 1 described later.

(実施例14)
 実施例13の方法において、テリマグランジンIの添加量を1.0ppmに調整する以外は、実施例13と同様の方法で静置を行い、飲料中に含まれるp-サイメンの量を定量した。結果は表2に示した。
(Example 14)
In the method of Example 13, the sample was allowed to stand in the same manner as in Example 13 except that the amount of added terimaglandin I was adjusted to 1.0 ppm, and the amount of p-cymene contained in the beverage was quantified. . The results are shown in Table 2.

(実施例15)
 実施例1と同様の方法で調製した飲料に対して、ガロタンニンに属するポリフェノールであるハマメリタンニンを、飲料全体の0.1ppmとなるように添加し、密栓した上で、37℃の温度にて7日間静置した。静置後、飲料に含まれるp-サイメンの量を定量した。
 このp-サイメンの含有量について、後述する比較例1における含有量との比として表2に示した。
(Example 15)
Hamamelitannin, a polyphenol belonging to gallotannin, was added to the beverage prepared in the same manner as in Example 1 so that it would be 0.1 ppm of the whole beverage, and sealed at a temperature of 37 ° C. Let stand for 7 days. After standing, the amount of p-cymene contained in the beverage was quantified.
The p-cymene content is shown in Table 2 as a ratio to the content in Comparative Example 1 described later.

(実施例16)
 実施例15の方法において、ハマメリタンニンの添加量を1.0ppmに調整する以外は、実施例15と同様の方法で静置を行い、飲料中に含まれるp-サイメンの量を定量した。結果は表2に示した。
(Example 16)
In the method of Example 15, the mixture was left standing in the same manner as in Example 15 except that the amount of hamamelitannin added was adjusted to 1.0 ppm, and the amount of p-cymene contained in the beverage was quantified. The results are shown in Table 2.

(比較例1)
 実施例1と同様の方法で調製した飲料に対して、何も添加することなく、実施例1と同様の方法で静置を行い、飲料中に含まれる各成分の量を定量した。この比較例1の結果を対照(100%)として表1および表2に示した。
(Comparative Example 1)
The beverage prepared by the same method as in Example 1 was left standing by the same method as in Example 1 without adding anything, and the amount of each component contained in the beverage was quantified. The results of Comparative Example 1 are shown in Tables 1 and 2 as a control (100%).

Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002

 以上の表1、2の結果から、リモネンを有する飲料に対して、プロアントシアニジン、エラジタンニン、ガロタンニンのいずれかのポリフェノール成分を加えることで、リモネンの劣化を顕著に抑制することができることが認められる。このポリフェノール成分の添加量は従来提案されていたものよりも少ないものであり、本願で用いられるポリフェノール成分の効果の顕著性が認められる。 From the results of Tables 1 and 2 above, it is recognized that the deterioration of limonene can be remarkably suppressed by adding any polyphenol component of proanthocyanidins, ellagitannins and gallotannins to beverages having limonene. The addition amount of the polyphenol component is smaller than that conventionally proposed, and the remarkable effect of the polyphenol component used in the present application is recognized.

 本発明の劣化臭生成抑制方法は、リモネンの香気を効果的に保つことができる。この方法は、リモネンを含む飲食品や香粧品など、種々の製品の開発に有用である。
 また、本発明のリモネン製品は、十分に劣化臭の生成が抑制されたものであり、これを使用する者に、心地よい香気を効果的にもたらすことができる。
The degradation odor production | generation suppression method of this invention can keep the aroma of limonene effectively. This method is useful for the development of various products such as foods and beverages containing limonene and cosmetics.
In addition, the limonene product of the present invention is sufficiently suppressed in the generation of a deteriorated odor, and can effectively bring a pleasant aroma to those who use it.

 この出願は、2015年4月13日に出願された日本出願特願2015-081560号および2015年9月3日に出願された日本出願特願2015-174035号を基礎とする優先権を主張し、その開示の全てをここに取り込む。 This application claims priority based on Japanese Patent Application No. 2015-081560 filed on April 13, 2015 and Japanese Patent Application No. 2015-174035 filed on September 3, 2015. , The entire disclosure of which is incorporated herein.

Claims (10)

 リモネンと、ポリフェノール成分とを含むリモネン含有製品であって、
 前記ポリフェノール成分は、プロアントシアニジン、エラジタンニンおよびガロタンニンからなる群から選ばれる1種又は2種以上のポリフェノール成分である、リモネン含有製品。
A limonene-containing product comprising limonene and a polyphenol component,
The limonene-containing product, wherein the polyphenol component is one or more polyphenol components selected from the group consisting of proanthocyanidins, ellagitannins and gallotannins.
 請求項1に記載のリモネン含有製品であって、
 前記製品の全体に対して、前記リモネンを0.05ppm以上3,000ppm以下含む、リモネン含有製品。
The limonene-containing product according to claim 1,
A limonene-containing product containing 0.05 to 3,000 ppm of the limonene with respect to the entire product.
 請求項1または2に記載のリモネン含有製品であって、
 前記製品全体に対して、前記ポリフェノール成分を0.01ppm以上30,000ppm以下含むことを特徴とする、リモネン含有製品。
A limonene-containing product according to claim 1 or 2,
A limonene-containing product comprising the polyphenol component in an amount of 0.01 ppm to 30,000 ppm with respect to the entire product.
 請求項1ないし3のいずれか一項に記載のリモネン含有製品であって、
 飲料又は食品である、リモネン含有製品。
A limonene-containing product according to any one of claims 1 to 3,
Limonene-containing products that are beverages or foods.
 リモネンと、ポリフェノール成分とを含有する香料組成物であって、
 前記ポリフェノール成分は、プロアントシアニジン、エラジタンニンおよびガロタンニンからなる群から選ばれる1種又は2種以上のポリフェノール成分である、香料組成物。
A fragrance composition containing limonene and a polyphenol component,
The perfume composition, wherein the polyphenol component is one or more polyphenol components selected from the group consisting of proanthocyanidins, ellagitannins and gallotannins.
 リモネンを含有する製品における劣化臭生成抑制方法であって、
 当該方法は、前記製品に対して、ポリフェノール成分を添加するものであり、
 前記ポリフェノール成分は、プロアントシアニジン、エラジタンニンおよびガロタンニンからなる群から選ばれる1種又は2種以上のポリフェノール成分である、劣化臭生成抑制方法。
A method for suppressing the generation of a deteriorated odor in a product containing limonene,
The method is to add a polyphenol component to the product,
The method according to claim 1, wherein the polyphenol component is one or more polyphenol components selected from the group consisting of proanthocyanidins, ellagitannins, and gallotannins.
 請求項6に記載の劣化臭生成抑制方法であって、
 前記製品は、前記リモネンを前記製品の全体に対して0.05ppm以上3,000ppm以下含む、劣化臭生成抑制方法。
It is a degradation odor production | generation suppression method of Claim 6, Comprising:
The said product contains the said limonene 0.05 ppm or more and 3000 ppm or less with respect to the whole said product, The degradation odor production | generation suppression method.
 請求項6または7に記載の劣化臭生成抑制方法であって、
 前記製品全体に対して、前記ポリフェノール成分を0.01ppm以上30,000ppm以下添加することを特徴とする、劣化臭生成抑制方法。
It is the degradation odor production | generation suppression method of Claim 6 or 7,
A degradation odor production suppressing method, wherein the polyphenol component is added in an amount of 0.01 ppm to 30,000 ppm with respect to the entire product.
 請求項6ないし8のいずれか一項に記載の劣化臭生成抑制方法であって、
 前記製品は飲料又は食品である、劣化臭生成抑制方法。
It is a degradation odor production | generation suppression method as described in any one of Claim 6 thru | or 8, Comprising:
The method according to claim 1, wherein the product is a beverage or food.
 請求項6ないし9のいずれか一項に記載の劣化臭生成抑制方法であって、
 当該方法は、p-サイメンの生成を抑制するものである、劣化臭生成抑制方法。
A method for suppressing the generation of a deteriorated odor according to any one of claims 6 to 9,
The method is a method for suppressing the generation of degraded odor, which suppresses the generation of p-cymene.
PCT/JP2016/052873 2015-04-13 2016-02-01 Limonene-containing product, scented composition, and method for suppressing generation of deterioration odor Ceased WO2016167008A1 (en)

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