Citral Degradation Flavor Inhibiting Composition

Abstract

This invention provides a composition effective in suppressing the deterioration of citral flavor. [Solution] A citral flavor-suppressing composition containing one or more compounds selected from the group consisting of 8-methyl-4-methylenenona-7-en-2-one and 4,8-dimethylnona-3,7-dien-2-one as an active ingredient. Preferably, it contains at least 8-methyl-4-methylenenona-7-en-2-one. Alternatively, preferably, the unpleasant flavor is due to p-cresol and / or p-methylacetophenone.

Description

Technical Field

[0001] The present invention relates to a composition for suppressing citral-degraded fragrance.

Background Art

[0002] Consumers' demands for the scent and taste (sometimes generally referred to as fragrance in this specification) of various consumer goods such as food and beverages and cosmetics are increasing, and a plurality of technologies for suppressing unpleasant fragrances have been proposed.

[0003] Citral is known as an aroma component of citrus fruits such as lemon and ginger. However, due to light, heat, changes over time, etc., the structure of citral changes (also referred to as degradation), and p-cresol, p-methylacetophenone, etc. are generated, and there is a problem that unpleasant fragrances (also referred to as degradation odors) caused by these products are generated. Methods for suppressing the degradation of fragrance (also referred to as citral-degraded fragrance in this specification) due to the generation of unpleasant fragrances have been studied.

[0004] As a method for suppressing the degraded fragrance caused by citral, for example, as a technique focusing on the above-mentioned p-cresol and p-methylacetophenone, by adding a flavor deterioration inhibitor characterized by comprising oxypeucedanin hydrate and / or byakangelicin to a flavor or food and beverage containing citral, suppressing the generation of p-methylacetophenone from citral and preventing the degradation of fragrance (Patent Document 1), or masking the unpleasant odors of p-cresol and p-methylacetophenone generated by the degradation of citral with a degradation odor masking agent for citral or a citral-containing product, which is characterized by containing one or more selected from the group consisting of ethyl pyruvate, methyl jasmonate, methyl dihydrojasmonate, diethyl malonate, methyl beta-naphthyl ketone, maltol isobutyrate, menthol, lauric acid, acetoin, cinnamyl acetate, benzyl acetate, and α-terpineol (Patent Document 2) have been proposed. [Prior art documents] [Patent Documents]

[0005] [Patent Document 1] Japanese Patent Publication No. 2010-99025 [Patent Document 2] Patent No. 6517010 [Overview of the Initiative] [Problems that the invention aims to solve]

[0006] However, conventional materials used to suppress the deterioration of citral flavor have not been sufficient to adequately address the suppression of citral flavor deterioration, and the discovery of more effective materials has been a challenge. Therefore, the objective of the present invention is to provide a composition useful for suppressing the deterioration of citral flavor deterioration. [Means for solving the problem]

[0007] In view of the above problems, the present inventors conducted diligent research and found that a composition containing one or more substances selected from the group consisting of 8-methyl-4-methylenenon-7-en-2-one and 4,8-dimethylnona-3,7-diene-2-one is useful in suppressing the deterioration of flavor caused by citral, leading to the present invention.

[0008] Thus, a brief overview of some of the representative inventions disclosed in this application is as follows: [1] A citral flavor degradation inhibitory composition comprising one or more substances selected from the group consisting of 8-methyl-4-methylenenona-7-en-2-one and 4,8-dimethylnona-3,7-dien-2-one as an active ingredient. [2] The citral degradation flavor suppression composition according to [1], comprising at least 8-methyl-4-methylenenona-7-en-2-one as the active ingredient. [3] The citral degradation flavor suppression composition according to [1], comprising 8-methyl-4-methylenenona-7-en-2-one and 4,8-dimethylnona-3,7-dien-2-one as the active ingredients. [4] The citral flavor degradation inhibitory composition according to any one of [1] to [3], wherein the degradation flavor is due to p-cresol and / or p-methylacetophenone. [5] A method for suppressing citral flavor degradation, comprising including a citral flavor degradation suppression composition containing one or more active ingredients selected from the group consisting of 8-methyl-4-methylenenona-7-en-2-one and 4,8-dimethylnona-3,7-dien-2-one in a citral-containing article. [6] The method for suppressing citral deterioration flavor according to [5], wherein the citral-containing article contains the active ingredient at a concentration of 1 ppt to 100 ppm (the total concentration of 8-methyl-4-methylenenona-7-en-2-one and 4,8-dimethylnona-3,7-dien-2-one if both are included) based on the total mass of the citral-containing article. [7] The method for suppressing citral deterioration flavor according to [6], wherein the concentration is 1 ppb to 500 ppb. [8] A citral-containing article comprising the addition of a citral-degradation flavor-suppressing composition described in any one of items [1] to [3]. [9] The citral-containing article according to [8], wherein the citral-containing article is a fragrance composition, food or beverage, cosmetic or health product. [Effects of the Invention]

[0009] The present invention provides a composition that is effective in suppressing the deterioration of citral's flavor. [Modes for carrying out the invention]

[0010] The present invention will be described in more detail below with specific examples. In this specification, "~" means a range including the lower and upper limits, concentration (ppt, ppb, ppm, etc.) and % represent mass concentration and mass %, respectively unless otherwise specified, and concentration refers to the concentration based on the total mass, i.e., the final concentration, unless otherwise specified.

[0011] [Citral Degradation Flavor Suppression Composition] A citral (also called 3,7-dimethyl-2,6-octadienal) flavor degradation suppression composition according to one embodiment of the present invention (which may also be simply referred to as the present flavor degradation suppression composition) is a composition comprising one or more compounds selected from the group consisting of 8-methyl-4-methylenenona-7-en-2-one and 4,8-dimethylnona-3,7-dien-2-one (which may also be referred to as the present active ingredient 1 or active ingredient 1, and as the latter as the present active ingredient 2 or active ingredient 2, and which may be collectively referred to as the present active ingredient) and can suppress the citral flavor degradation of an article containing citral (which may also be referred to as a citral-containing article) by incorporating it into the article.

[0012] In this specification, when referring to the inclusion of the flavor-deterioration-suppressing composition in a citral-containing article, it includes any of the following: adding the active ingredient to a citral-containing article to obtain a citral-containing article containing the active ingredient; adding a composition containing the active ingredient and citral to an article that does not contain citral to obtain a citral-containing article containing the active ingredient; or adding a composition containing the active ingredient and citral to an article that does contain citral to obtain a citral-containing article containing the active ingredient. The citral-containing article has its flavor deterioration suppressed by containing the active ingredient.

[0013] In this specification, “addition” includes at least one of simply adding to a substance by spraying, dropping, or other means, and mixing with a substance.

[0014] In this specification, "flavor" typically refers to sensations including smell and taste, and "degraded flavor" includes flavors that are perceived as unpleasant or alien due to changes (degradation) of citral. Specific examples include flavors derived from p-cresol and / or p-methylacetophenone (which may be referred to as degraded flavor compounds in this specification), which are compounds produced by the degradation of citral. Both of these compounds have low detection thresholds; p-cresol exhibits animalistic, medicinal, phenolic, and smoky aromas, while p-methylacetophenone exhibits fruity, strawberry, and almond-like aromas. Therefore, even trace amounts of these compounds in citral-containing articles can be perceived as unpleasant and lead to the recognition of citral-degraded flavor. Note that for articles that are not consumed (typically fragrance compositions and cosmetics), the term "aroma" (i.e., olfactory sensation) may be used as a description of flavor.

[0015] In this specification, "suppression of degraded flavor" includes making the degraded flavor perceived from a citral-containing article weaker or substantially undetectable compared to when the degraded flavor suppressing composition is not included in the citral-containing article. As shown in the examples described below, when a citral-containing article containing the degraded flavor suppressing composition is subjected to abuse, the degraded flavor can be made weaker or substantially undetectable compared to when the degraded flavor suppressing composition is not included, thus it can be said that the generation of degraded flavor in citral-containing articles can be suppressed. Furthermore, as shown in another example, the flavor of compounds (preferably p-cresol and / or p-methylacetophenone) resulting from structural changes (also called degradation) of citral contained in a citral-containing article can also be made weaker or substantially undetectable compared to when the degraded flavor suppressing composition is not added. Therefore, "suppression of degraded flavor" includes both suppressing the generation of degraded flavor in a citral-containing article and suppressing the intensity of degraded flavor that has already occurred.

[0016] This unpleasant odor composition can also be used as a deterioration odor suppressing composition capable of imparting an odor. That is, as shown in the examples described later, not only can it suppress the odor due to citral deterioration, but it can also impart a citrus-like odor impaired by citral deterioration, and this unpleasant odor composition may exhibit both effects of suppressing deterioration odor derived from citral and imparting a citrus-like odor.

[0017] This deterioration odor suppressing composition may be used in combination with any known material that suppresses the generation of deterioration odor compounds (for example, p-cresol and / or p-methylacetophenone) due to the deterioration of citral, and an effect of suppressing the deterioration odor (that is, citral deterioration odor) caused by the deterioration odor compounds that cannot be completely suppressed from generation by the known generation suppressing material can be obtained.

[0018] The inclusion of one or more compounds selected from the group consisting of 8-methyl-4-methylene-nona-7-en-2-one and 4,8-dimethylnona-3,7-dien-2-one means any of the following aspects: an aspect including both 8-methyl-4-methylene-nona-7-en-2-one and 4,8-dimethylnona-3,7-dien-2-one; an aspect including 8-methyl-4-methylene-nona-7-en-2-one and not including 4,8-dimethylnona-3,7-dien-2-one; and an aspect not including 8-methyl-4-methylene-nona-7-en-2-one and including 4,8-dimethylnona-3,7-dien-2-one. From the viewpoint of a higher deterioration odor suppressing effect, preferably, this deterioration odor suppressing composition contains at least 8-methyl-4-methylene-nona-7-en-2-one, that is, it contains both 8-methyl-4-methylene-nona-7-en-2-one and 4,8-dimethylnona-3,7-dien-2-one, or it contains 8-methyl-4-methylene-nona-7-en-2-one and does not include 4,8-dimethylnona-3,7-dien-2-one.

[0019] A citral-containing article means any article that contains citral and as a result, may generate a deteriorated fragrance derived from citral due to light, heat, changes over time, or other factors. The generation of a deteriorated fragrance derived from citral means a state in which a fragrance derived from p-cresol and / or p-methylacetophenone, which are deteriorated fragrance compounds, can be felt, and in a citral-containing article, a state in which p-cresol is present at a concentration above its detection threshold and / or p-methylacetophenone is present at a concentration above its detection threshold is included. Specific examples include, but are not limited to, cases where p-cresol is generated at 1 ppb or more and / or p-methylacetophenone is generated at 1 ppb or more. The citral-containing article may consist essentially of only citral and its solvent or carrier.

[0020] The means for obtaining the active ingredient of this case is not particularly limited, but for 8-methyl-4-methylene-nona-7-en-2-one (the active ingredient 1 of this case), it can be obtained, for example, by two methods of <Reaction Route A> and <Reaction Route B> described below.

[0021] [Chemical Formula]

[0022] <Reaction Route A> The double bond of geranic acid or geranic acid ester (Formula (2)) is isomerized to the exo side with lithium diisopropylamide (LDA) or the like to generate a compound represented by Formula (3). Then, the compound represented by Formula (3) is converted to morpholine amide (Formula (4)). By methylating this morpholine amide (Formula (4)) and subjecting it to distillation purification, the target 8-methyl-4-methylene-nona-7-en-2-one (Formula (1)) is obtained. <00​​Geraneic acid or geraneic acid ester (formula (2)) is converted to morpholineamide (formula (6)). Then, the double bond of this morpholineamide (formula (6)) is isomerized to the exo side to convert it to the morpholineamide represented by formula (4). This morpholineamide (formula (4)) is methylated and purified by distillation to obtain the target product, 8-methyl-4-methylenenona-7-en-2-one (formula (1)).

[0023] The methylation method described above is not particularly limited, but it is preferable to use a Grignard reagent.

[0024] The active ingredient 1 obtained by the above synthesis method may be further purified using methods such as column chromatography or vacuum distillation, if necessary.

[0025] Active ingredient 1 has a citrus-like aroma and can be used not only as an active ingredient in the flavor-deterioration-suppressing composition, but also as a substitute for citral to impart a citrus-like flavor.

[0026] Of the active ingredients in this invention, 4,8-dimethylnona-3,7-dien-2-one (active ingredient 2) can be obtained by known synthetic methods or by using commercially available products. 4,8-dimethylnona-3,7-dien-2-one is known as a stable compound while exhibiting a citrus-like aroma (e.g., Japanese Patent Publication No. 2003-517052), and while 4,8-dimethylnona-3,7-dien-2-one exists in E and Z forms, in this invention, the E form, the Z form, or any mixture thereof in any proportion can be used as the active ingredient. In this specification, unless otherwise specified, the E form, the Z form, and any mixture thereof in any proportion are collectively referred to as 4,8-dimethylnona-3,7-dien-2-one or active ingredient 2. Commercially available 4,8-dimethylnona-3,7-dien-2-one is usually a mixture of the E and Z isomers, and when obtained by typical synthetic methods (for example, the methods described in JP 2001-181670 and JP 2012-158647), it is also usually a mixture of the E and Z isomers. Therefore, preferably, 4,8-dimethylnona-3,7-dien-2-one is a mixture of the E and Z isomers, and although the ratio is arbitrary, the E isomer is usually dominant in the mixture (approximately 60-90% or more of the mixture is the E isomer). Therefore, the ratio is preferably in the range of 5:5 to 9:1, more preferably 6:4 to 8:2, with 8:2 being a preferred specific example.

[0027] Active ingredient 2, like active ingredient 1, has a citrus-like aroma. In addition to being used as an active ingredient in the flavor-deterioration-suppressing composition, it can also be used as a substitute for citral to impart a citrus-like flavor. However, since it also has a floral aroma in addition to the citrus-like aroma, a floral flavor may also be imparted.

[0028] Examples of the flavor degradation suppression composition in this invention include various additives containing the active ingredient that can be added to various consumer goods such as food and beverages, cosmetics, and health and hygiene products. More specific examples include fragrance compositions containing the active ingredient, various animal and plant extracts, or fermented, enzyme-treated, or heat-treated products of various animal and plant raw materials that can be added to various consumer goods. These can take the form of water-soluble or oil-soluble solvent solutions, emulsified formulations, powder formulations, or other solid formulations (such as solid fats), but the present invention is not limited to these examples.

[0029] The flavor degradation suppression composition in question may contain, in addition to the active ingredient, any other components (specific examples will be described later), such as a solvent, dispersion medium, flavor-imparting components other than the active ingredient, and antioxidant components, but may also consist substantially of only the active ingredient. If the flavor degradation suppression composition in question contains components other than the active ingredient, the concentration of the active ingredient in the flavor degradation suppression composition in question can be arbitrarily determined according to the target of the addition and the aroma characteristics of the flavor degradation suppression composition.

[0030] As an example of the concentration of the active ingredient in the flavor degradation suppression composition, if the flavor degradation suppression composition contains substantially only the active ingredient, or only the active ingredient and its solvent (specific examples are described later), the range can be exemplified as 10 ppb to 100%, and a preferred example is a range of 10 ppm to 99%. In this specification, the concentration of the active ingredient means one of the following unless otherwise specified. (A) The concentration of either 8-methyl-4-methylenenona-7-en-2-one or 4,8-dimethylnona-3,7-dien-2-one, alone, as the active ingredient in this case. (B) If both 8-methyl-4-methylenenona-7-en-2-one and 4,8-dimethylnona-3,7-dien-2-one are included, the total concentration of these is As an example of the concentration of the active ingredient in the flavor degradation suppression composition, if the flavor degradation suppression composition contains components other than the active ingredient and its solvent (details will be described later), the concentration can be arbitrarily determined according to the target of the flavor degradation suppression composition and its aroma characteristics, and should be set to an appropriate concentration so that it can be added to consumer goods at a concentration that suppresses flavor degradation. For example, the range for the unpleasant flavor improvement composition is 100ppt to 10%, preferably 1ppb to 10%, more preferably 100ppb to 10%. More specifically, the lower limit can be any of 100ppt, 1ppb, 10ppb, 100ppb, 1ppm, 10ppm, 100ppm, 0.1%, or 1%, and the upper limit can be any of 10%, 1%, 0.1%, 100ppm, 10ppm, 1ppm, 100ppb, 10ppb, or 1ppb, and the concentration can be within any combination of these lower and upper limits, but is not limited to these.

[0031] In other words, when the flavor degradation suppression composition contains 8-methyl-4-methylenenona-7-en-2-one or 4,8-dimethylnona-3,7-dien-2-one alone as the active ingredient, the concentration range is 100 ppt to 10%, preferably 1 ppb to 10%, and more preferably 100 ppb to 10%. When it contains both 8-methyl-4-methylenenona-7-en-2-one and 4,8-dimethylnona-3,7-dien-2-one, the total concentration range is 100 ppt to 10%, preferably 1 ppb to 10%, and more preferably 100 ppb to 10%.

[0032] Furthermore, although it depends on the formulation of the flavor degradation suppression composition, setting the concentration of the active ingredient in question to 100 ppt to 10% in the flavor degradation suppression composition makes it easier to obtain a flavor degradation suppression effect on consumer goods without the flavor derived from the active ingredient being excessively prominent. However, depending on the flavor degradation suppression composition, the flavor to which it is added, and other conditions, the active ingredient may be included at a concentration outside the range of 100 ppt to 10%.

[0033] In the present composition for suppressing deterioration of flavor, specific examples of other components that may be further included in addition to the active ingredient and its solvent include various types of fragrance compounds, fragrance compositions, pigments, vitamins, functional substances, fish extracts, livestock extracts, animal and plant extracts, animal and vegetable oils and fats, yeast extracts, animal and plant proteins, animal and plant protein hydrolysates, starch, dextrin, sugars, amino acids, nucleic acids, organic acids, solvents, emulsifiers, specific gravity adjusters, antioxidants, and the like. For example, natural essential oils, natural fragrances, and synthetic fragrances are listed in "Japan Patent Office Gazette, Collection of Well-Known and Conventional Technologies (Fragrances), Part II: Food Fragrances, published January 14, 2000," "Survey on the Actual Use of Food Fragrance Compounds in Japan" (FY2000 Ministry of Health and Welfare Research Report, Japan Fragrance Manufacturers Association, published March 2001), and "Synthetic Fragrances: Chemistry and Product Knowledge" (Revised and Enlarged Edition published December 20, 2016, edited by the Synthetic Fragrance Editorial Committee, Chemical Daily Co., Ltd.).

[0034] Examples of flavoring compounds include various compounds that contribute to the flavor of various plant and animal materials containing citral. Examples of such plant and animal materials include various citrus fruits such as lemon, orange, grapefruit, lime, mandarin, mandarin orange, kabosu, sudachi, hassaku, iyokan, yuzu, shikwasa, and kumquat; ginger; various soft fruits such as grapes; various tropical fruits such as guava and feijoa; olives; pistachios; quince; various spices or herbs such as marjoram and thyme; and various teas such as green tea, black tea, and oolong tea.

[0035] Specific examples of compounds include hydrocarbons such as osimene, limonene, α-phellandrene, terpinene, 3-carene, bisabolene, β-pinene, and valencene; 3-heptanol, 1-undecanol, 2-undecanol, 1-dodecanol, prenol, 10-undecene-1-ol, dihydrolinalool, tetrahydromugol, myrcenol, dihydromyrcenol, tetrahydromyrcenol, osimenol, terpineol, 3-thujanol, benzyl alcohol, β-phenylethyl alcohol, and α-phenylethyl alcohol. Alcohols such as ethyl alcohol, linalool, and cis-3-hexenol; acetaldehyde, n-hexanal, n-heptanal, n-octanal, n-nonanal, 2-methyloctanal, 3,5,5-trimethylhexanal, decanal, undecanal, 2-methyldecanal, dodecanal, tridecanal, tetradecanal, trans-2-hexenal, trans-4-decenal, cis-4-decenal, trans-2-decenal, 10-undecenal, trans-2-undecenal , trans-2-dodecenal, 3-dodecenal, trans-2-tridecenal, 2,4-hexadienal, 2,4-decadienal, 2,4-dodecadienal, 5,9-dimethyl-4,8-decadienal, dimethyloctanal, α-methylenecitronellal, citronellyloxyacetaldehyde, myrthenal, neral, α-or β-sinensal, mylacaldehyde, phenylacetaldehyde, octanal dimethyl acetal, nonanal dimethyl acetal, decanal dimethyl acetal Aldehydes such as ammonium acetal, decanal diethyl acetal, 2-methyl undecanal dimethyl acetal, citral dimethyl acetal, citral diethyl acetal, and citral propylene glycol acetal; ketones such as 3-heptanone, 3-octanone, 2-nonanone, 2-undecanone, 2-tridecanone, methylheptenone, dimethyloctenone, geranylacetone, 2,3,5-trimethyl-4-cyclohexenyl-1-methyl ketone, nerone, nootkatone, dihydronootkatone, and acetophenone;Propyl formate, octyl formate, linalyl formate, citronellyl formate, geranyl formate, neryl formate, terpinyl formate, ethyl acetate, isopropyl acetate, cis-3-hexenyl acetate, trans-2-hexenyl acetate, octyl acetate, nonyl acetate, decyl acetate, dodecyl acetate, dimethylundecadienyl acetate, osimenyl acetate, myrcenyl acetate, dihydromyrcenyl acetate, linalyl acetate, citronellyl acetate, geranyl acetate, neryl acetate, tetrahydromugol acetate, lavandulyl acetate, nerolidol acetate, dihydrocuminyl acetate, terpinyl acetate Citril acetate, nopyl acetate, dihydroterpinyl acetate, 2,4-dimethyl-3-cyclohexenylmethyl acetate, miraldyl acetate, betichol acetate, decenyl propionate, linalyl propionate, geranyl propionate, neryl propionate, terpinyl propionate, tricyclodecenyl propionate, styraryl propionate, octyl butyrate, neryl butyrate, cinnamyl butyrate, isopropyl isobutyrate, octyl isobutyrate, linalyl isobutyrate, neryl isobutyrate, linalyl isovalerate, terpinyl isovalerate, phenylethyl isovalerate Esters such as 2-methylpentyl 2-methylvalerate, methyl 3-hydroxyhexanoate, ethyl 3-hydroxyhexanoate, methyl octanoate, octyl octanoate, linalyl octanoate, methyl nonanoate, methyl undecylenate, linalyl benzoate, methyl cinnamate, isoprenyl angelicate, methyl geranate, triethyl citrate; phenols such as thymol, carvacrol, β-naphthol isobutyl ether; lactones such as γ-undecalactone, δ-dodecalactone; acetic acid, propionic acid, butyric acid, valeric acid, hexa Acids such as sanic acid, octanoic acid, decanoic acid, dodecanoic acid, 2-decenoic acid, and geranic acid; nitrogen-containing and sulfur-containing compounds such as methyl anthranilate, ethyl anthranilate, methyl N-methylanthranilate, methyl N-2'-methylpentylideneanthranilate, ligantral, dodecanenitrile, 2-tridecennitrile, geranylnitrile, citronellylnitrile, 3,7-dimethyl-2,6-nonadienonitrile, indole, 5-methyl-3-heptanone oxime, thiogeraniol, limonenthiol, and p-menthyl-8-thiol;Examples of known synthetic fragrance compounds include furfuryl alcohol, furfural, rose oxide, linalool oxide, menthofuran, theaspiran, and furan ether compounds such as 4,7-dihydro-2-isopentyl-2-methyl-1,3-dioxepin, and formulations can be made by arbitrarily combining and mixing these.

[0036] [Method for producing the flavor-deterioration-suppressing composition] One aspect of the present invention provides a method for producing a flavor degradation suppression composition, which includes adding the active ingredient to any composition that can be added to various consumer goods. Another aspect of the present invention also provides a method for producing another flavor degradation suppression composition by adding the flavor degradation suppression composition to another flavor-imparting composition. Examples of compositions that can be added to various consumer goods include compositions containing one or more selected from solvents, antioxidants, dyes, and other additives that can be added to food and beverages, cosmetics, and health and hygiene products.

[0037] The flavor-deterioration suppressing composition produced in this manner can be used as an additive composition for various consumer goods such as food and beverages, cosmetics, and health and hygiene products in the manufacture of various consumer goods.

[0038] Furthermore, the flavor-deterioration-suppressing composition may be in the form of an emulsified preparation, a powder preparation, or other solid preparation (such as solid fat).

[0039] There are no particular restrictions on the type of solvent used. Examples of water-soluble solvents include ethanol, methanol, acetone, tetrahydrofuran, acetonitrile, 2-propanol, methyl ethyl ketone, glycerin, ethylene glycol, propylene glycol, dipropylene glycol, hexyl glycol, benzyl benzoate, triethyl citrate, and diethyl phthalate. Of these, ethanol or propylene glycol are particularly preferred when used in food and beverages. Examples of oil-soluble solvents include vegetable oils and fats, animal oils and fats, refined oils and fats (for example, processed oils such as medium-chain fatty acid triglycerides and short-chain fatty acid triglycerides such as triacetin and trippropionine), harcoline, various essential oils, and triethyl citrate.

[0040] To obtain the flavor-deterioration-suppressing composition in question as an emulsified formulation, the active ingredient in question or a composition containing the active ingredient in question may be diluted with a vegetable oil as appropriate, and if necessary, a specific gravity adjuster (such as sucrose acetate isobutyrate) and an oil-soluble antioxidant may be added, and then it may be emulsified with a water-soluble solvent and an emulsifier. There are no particular restrictions on the emulsification method. By using various types of emulsifiers that have been conventionally used in food and beverages, such as fatty acid monoglycerides, fatty acid diglycerides, fatty acid triglycerides, propylene glycol fatty acid esters, sucrose fatty acid esters, polyglycerin fatty acid esters, lecithin, modified starch, sorbitan fatty acid esters, quillaja extract, gum arabic, tragacanth gum, guar gum, karaya gum, xanthan gum, pectin, alginic acid and its salts, carrageenan, gelatin, casein, quillaja saponin, and sodium caseinate, and performing emulsification using a homomixer, colloid mill, rotary disc homogenizer, high-pressure homogenizer, etc., a highly stable emulsified liquid can be obtained. The amount of emulsifiers used is not strictly limited and can be varied over a wide range depending on the type of emulsifier used, but generally, an amount of about 0.01 to about 100 parts by mass, preferably about 0.1 to about 50 parts by mass, per 1 part by mass of the active ingredient is appropriate. In addition, to stabilize the emulsification, the water-soluble solvent can be water or, in addition to water, one or more types of polyhydric alcohols such as glycerin, propylene glycol, sorbitol, maltitol, sucrose, glucose, trehalose, sugar solution, and reduced starch syrup.

[0041] Furthermore, the resulting emulsified liquid can be dried to produce a powder formulation if desired. During the powdering process, sugars such as gum arabic, trehalose, dextrin, sugar, lactose, glucose, starch syrup, and reduced starch syrup may be added as needed. The amounts used can be appropriately selected according to the desired characteristics of the powder formulation.

[0042] [Method for suppressing the deterioration of flavor in citral-containing articles] One aspect of the present invention provides a method for suppressing citral flavor degradation, which includes incorporating a citral flavor degradation suppression composition containing one or more active ingredients selected from the group consisting of 8-methyl-4-methylenenona-7-en-2-one and 4,8-dimethylnona-3,7-dien-2-one into a citral-containing article.

[0043] The inventors have confirmed that the active ingredient in citral-containing articles exhibits an inhibitory effect on the deterioration of flavor caused by deterioration flavor compounds in the citral-containing articles when its concentration is in the range of 1 ppt to 100 ppm. However, the concentration of the active ingredient is not limited to these concentrations, and the concentration of the active ingredient can be adjusted according to the concentration of deterioration flavor compounds and the desired degree of inhibitory effect. For example, the lower limit can be any of 1 ppt, 10 ppt, 100 ppt, 1 ppb, 10 ppb, 100 ppb, 500 ppb, 1 ppm, 5 ppm, 10 ppm, or 50 ppm, and the upper limit can be any of 100 ppm, 50 ppm, 10 ppm, 5 ppm, 1 ppm, 500 ppb, 100 ppb, 10 ppb, 1 ppb, 100 ppt, or 10 ppt, and the range can be any combination of these lower and upper limits. A preferred range is 1 ppb to 500 ppb.

[0044] In other words, when a citral-containing article contains either 8-methyl-4-methylenenona-7-en-2-one or 4,8-dimethylnona-3,7-dien-2-one as the active ingredient, the concentration range is 1 ppt to 100 ppm, preferably 1 ppb to 500 ppb. When both 8-methyl-4-methylenenona-7-en-2-one and 4,8-dimethylnona-3,7-dien-2-one are included, the total concentration range is 1 ppt to 100 ppm, preferably 1 ppb to 500 ppb.

[0045] Typical examples of citral-containing products include consumer products such as food and beverages, cosmetics, and health and hygiene products, as well as various additives used in the manufacture of consumer products. Examples of various additives include flavoring compositions containing citral, and more specifically, fragrance compositions and essential oils.

[0046] When a citral-containing article is a consumer product, the timing of adding the flavor degradation suppression composition to the product is arbitrary. The flavor degradation suppression composition itself may be added to various products such as food and beverages, cosmetics, and health and hygiene products, or it may be added to various consumer products in combination with one or more other flavoring compositions (for example, one or more selected from water-soluble flavor compositions, emulsified flavor compositions, any flavor compound, or natural essential oils (for example, flavor compounds described in the aforementioned "Japan Patent Office Gazette, Collection of Well-Known and Conventional Technologies (Fragrances) Part II Food Flavors," "Survey on the Actual Use of Food Flavor Compounds in Japan," and "Synthetic Fragrances: Chemistry and Product Knowledge").

[0047] The citral-containing articles to which this flavor-degradation-suppressing composition can be added are not particularly limited as long as they contain citral and may have any flavor (especially in the case of food and beverages, also called aroma). Examples of flavors include various citrus flavors such as lemon, orange, grapefruit, lime, mandarin, mandarin orange, kabosu, sudachi, hassaku, iyokan, yuzu, shikwasa, and kumquat; strawberry, blueberry, raspberry, apple, cherry, plum, apricot, and peach. Various fruit flavors such as pineapple, banana, melon, mango, papaya, kiwi, pear, grapes (grape, muscat, Kyoho, etc.), lychee, and passion fruit; milk flavors such as milk, yogurt, butter, and custard; vanilla flavor; various tea flavors such as green tea, matcha, hojicha, black tea, oolong tea, barley tea, corn tea, buckwheat tea, pu-erh tea, and herbal tea; coffee flavor; cola flavor; cocoa flavor; spearmint, peppermint, etc. Various mint flavors; various spice or herb flavors such as cinnamon, chamomile, cardamom, caraway, cumin, clove, pepper, coriander, sansho pepper, shiso, ginger, star anise, thyme, chili pepper, nutmeg, basil, marjoram, rosemary, bay leaf, wasabi, sansho pepper, garlic; various nut flavors such as almonds, cashews, walnuts; wine, brandy, whiskey, rum, gin, liqueur, sake, roasted Examples of articles include those having one or more of the following flavors: various alcoholic beverages (such as shochu and beer); various vegetable flavors such as carrots, tomatoes, cucumbers, onions, corn, and potatoes; various legume flavors such as soybeans, peas, and chickpeas; various meat flavors such as chicken, pork, beef, lamb, and horse meat; seafood flavors; broth (bouillon) flavors from vegetables, meat, and seafood; consommé flavors; caramel flavors; grain flavors such as barley and wheat; and vinegar flavors such as rice vinegar, black vinegar, and apple cider vinegar.

[0048] In the present invention, the flavor of the citral-containing article may be an article that gives the impression of only one of the above-mentioned flavors, or an article that gives the impression of two or more flavors. Examples include an article that gives the impression of multiple fruit flavors, such as banana, peach, and apple (so-called mixed fruit flavored flavor compositions, food and beverages, cosmetics, etc.), an article that gives the impression of citrus flavor such as lemon and milk flavor (citrus-flavored lactic acid bacteria beverages, etc.), and an article that gives the impression of mint flavor or citrus flavor and cola flavor (mint or lemon-flavored cola beverages, etc.), but is not limited to these. When an article gives the impression of two or more flavors, it is preferable that it has one or more of the various flavors of citrus fruits, ginger, fruits, and herbs, and milk flavor, cola flavor, and fruit flavor, which can preferably be used in combination with these.

[0049] In particular, examples of citral-containing articles in which the present flavor degradation suppression composition can be suitably used include articles containing animal or plant materials that contain a relatively large amount of citral. Specific examples of such animal or plant materials include the various citrus fruits such as lemon, orange, grapefruit, lime, mandarin, mandarin orange, kabosu, sudachi, hassaku, iyokan, yuzu, shikwasa, and kumquat mentioned above; ginger; various soft fruits such as grapes; various tropical fruits such as guava and feijoa; olives; pistachios; quince; various spices or herbs such as marjoram and thyme; and various teas such as green tea, black tea, and oolong tea. Examples of citral-containing articles include, but are not limited to, various beverages containing one or more of these animal or plant materials that contain a relatively large amount of citral.

[0050] Specific examples of food and beverages include rice crackers, rice crackers, puffed rice crackers, mochi, manju, uiro, bean paste, yokan, mizuyokan, kintama, jelly, castella, candy, biscuits, crackers, potato chips, cookies, pies, pudding, frozen desserts, ice cream, ice milk, buttercream, custard cream, cream puffs, waffles, sponge cake, donuts, chocolate, chewing gum, caramel, candy, peanut paste or something similar. Other pastes, whipped cream and other confectionery or confectionery ingredients; bread, udon, ramen, Chinese noodles, sushi, mixed rice, fried rice, pilaf, gyoza wrappers, shumai wrappers, okonomiyaki, takoyaki and other breads, noodles, rice dishes, and other grains; pickles such as fermented rice bran pickles, pickled plums, fukujinzuke, bettara pickles, senmaizuke, rakkyo, miso pickles, takuan pickles, and pickling mixes for these; mackerel, sardines, saury, salmon, tuna, bonito, whale, flounder Fish such as sand eels and sweetfish; squid such as Japanese flying squid, spear squid, cuttlefish, and firefly squid; octopus such as common octopus and baby octopus; shrimp such as kuruma prawns, spot prawns, spiny lobsters, and black tiger prawns; crabs such as king crab, snow crab, swimming crab, and hairy crab; shellfish such as clams, cockles, scallops, oysters, and mussels; meats such as chicken, pork, beef, lamb, and horse meat; canned goods, boiled fish, tsukudani, surimi, and processed seafood products (chikuwa, kamaboko, etc.) (Fish cakes such as crab leg fish cakes), fried foods, tempura, curry, stew, beef stew, Hayashi rice sauce, meat sauce, mapo tofu, hamburgers, dumplings, instant rice mix, soups (corn soup, tomato soup, consommé soup, etc.), meatballs, braised pork, canned meat, boiled vegetables, Chikuzen-ni (a type of Japanese stew), oden (Japanese hot pot), hot pot dishes, take-out prepared foods, noodles such as ramen, soba, udon, and somen, and soups used with them, vegetable soups, and other processed foods made from animal and plant ingredients;Table salt, seasoned salt, soy sauce, powdered soy sauce, miso, powdered miso, moromi, hishio, furikake, ochazuke mix, margarine, mayonnaise, dressing, vinegar, sanbaizu, powdered sushi vinegar, Chinese seasoning mix, tempura dipping sauce, noodle soup (kombu dashi or katsuobushi dashi, etc.), sauce (medium-thick sauce, tomato sauce, etc.), ketchup, yakiniku sauce, curry roux, stew mix, soup base, dashi base (kombu dashi or katsuobushi dashi, etc.), compound seasonings, new mirin, mixed flours such as fried chicken flour and takoyaki flour, etc. Any seasonings, animal or plant-based broth-flavored foods and beverages to which these seasonings have been added; dairy products such as cheese, yogurt, butter, and fresh cream; fruit beverages using fruit juice, pulp, seeds, or peel of fruits such as apples, grapes, mangoes, peaches, and citrus fruits (grapefruit, oranges, lemons, etc.); vegetables such as tomatoes, bell peppers, celery, melons, bitter melons, carrots, potatoes, asparagus, bracken, and fiddlehead ferns, as well as vegetable beverages and vegetable soups containing these vegetables. Examples include: vegetable-containing foods and beverages; beverages such as coffee, cocoa, green tea, black tea, oolong tea, soft drinks, carbonated drinks, cola drinks, lactic acid bacteria drinks, milk-containing beverages (milk tea, café au lait, etc.), and fruit or fruit juice-containing beverages (fruit teas such as lemon tea and orange tea); beverages containing medicinal herbs and herbs; functional beverages such as cola drinks, sports drinks, honey drinks, vitamin supplements, mineral supplements, nutritional drinks, and nourishing drinks; non-alcoholic beverages such as alcohol-flavored beverages (non-alcoholic beer, non-alcoholic chuhai, etc.) with various alcoholic flavors (beer flavor, plum wine flavor, chuhai flavor, etc.); beer-flavored beverages (also called beer-flavored beverages) including wine, shochu, awamori, sake, beer, chuhai, cocktail drinks, sparkling wine, fruit wine, medicinal wine, and so-called "third beer"; other brewed alcoholic beverages (sparkling), liqueurs (sparkling), or alcoholic beverages containing these; and more.

[0051] Specific examples of cosmetics and health and hygiene products include perfumes such as eau de cologne, eau de toilette, eau de parfum, and parfum; hair care products such as shampoo, conditioner, and hair styling products (hair cream, pomade, etc.); cosmetics such as foundation, lipstick, lip balm, lip gloss, lotion, cosmetic emulsion, cosmetic cream, cosmetic gel, serum, and face masks; various preparations for suppressing scalp odor (scalp care products, etc.), various preparations for suppressing body odor (antiperspirant sprays, deodorant sheets, deodorant creams, deodorant sticks, etc.), and preparations for suppressing bad breath (mouthwash, toothpaste, breath fresheners, etc.). Examples include deodorant products such as masks with antiperspirant effects; bath additives such as inorganic salt-based, cooling, carbon dioxide-based, skincare-based, enzyme-based, and herbal-based products; sunscreens and other sun tanning cosmetics; facial cleansers such as face soaps and facial creams; body soaps and body washes; laundry soaps, laundry detergents, disinfectant detergents, deodorizing detergents, fabric softeners, dish soaps, and cleaning detergents; health and hygiene materials such as tissues and toilet paper; deodorizers for suppressing various unpleasant odors such as room odors and the smell of feces and urine; and air fresheners such as room fragrances. [Examples]

[0052] The present invention will be described in more detail below with reference to examples. However, the present invention is not limited to these examples.

[0053] [Example 1] Synthesis of the active ingredient 8-methyl-4-methylenenona-7-en-2-one One of the active ingredients in this study, 8-methyl-4-methylenenona-7-en-2-one (active ingredient 1), was synthesized through the following steps in Examples 1-1 to 1-3 (synthesis route A). In the reaction equation, if an isomer other than the exo isomer is produced, the position of the double bond of the isomer other than the exo isomer is indicated by a dashed line. <Example 1-1: Conversion of geranic acid to exo-isogeranic acid>

[0054] [ka]

[0055] 2.0 L of tetrahydrofuran (THF) was placed in a 5 L four-diameter flask and cooled with ice under a nitrogen atmosphere. Sodium hydride (60%, 84.0 g, 2.10 mol) was added, followed by the dropwise addition of geranic acid (337 g, 2.00 mol) over 40 minutes. After stirring at the same temperature for 30 minutes, lithium diisopropylamide (LDA, 2.0 mol / L tetrahydrofuran solution, 1.15 L, 2.30 mol) was added dropwise over 75 minutes. After 1 hour and 20 minutes at the same temperature, the mixture was poured into dilute hydrochloric acid to stop the reaction, and layer separation was performed. The resulting organic layer and the extract obtained by extracting the separated aqueous layer with toluene were combined and washed three times with saturated saline solution. The resulting organic layer was subjected to vacuum distillation to obtain a crude product (411 g) from which the solvent had been removed under reduced pressure. This crude product yielded 280 g (1.67 mol, yield 83.4%, exo-isogeranic acid (compound of formula (3) above, where R is H)) of exo-isogeranic acid (67.4%). <Example 1-2: Conversion of exo-isogeranic acid to exo-isogeranamide>

[0056] [ka]

[0057] Pyridine (136 g, 1.71 mol) and toluene (920 mL) were placed in a 3 L 4-diameter flask and cooled on ice under a nitrogen atmosphere. The starting material, exo-isogeranic acid (262 g, 1.56 mol) obtained in Example 1-1, was then added. Next, pivaloyl chloride (207 g, 1.71 mol) was added, and after raising the temperature to room temperature for 1.5 hours, it was returned to ice cooling. Morpholine (305 g, 3.50 mol) was then added. The reaction was completed after 1 hour at the same temperature, and the reaction solution was poured into dilute hydrochloric acid. After layer separation, the obtained organic layer and the extract obtained by extracting the separated aqueous layer with toluene were combined and washed sequentially with 20% saline solution, 20% sodium carbonate aqueous solution, and 20% saline solution. The solvent was removed from the obtained organic layer under reduced pressure to obtain a crude product (394 g) of exo-isogeranic acid morpholineamide (the compound represented by formula (4) above). <Example 1-3: Conversion of exo-isogeranamide to active ingredient 1>

[0058] [ka]

[0059] In a 3L 4-diameter flask, the crude purified exo-isogeranic acid morpholineamide (394g) obtained in Examples 1-2 and anhydrous tetrahydrofuran (1.0L) were charged and cooled on ice under a nitrogen atmosphere. Methylmagnesium chloride (3.0 mol / L tetrahydrofuran solution, 624mL, 1.87 mol) was added dropwise over 50 minutes. The reaction was completed at the same temperature for 4.5 hours, and the reaction mixture was poured into 20% ammonium chloride water. After layer separation, the obtained organic layer and the extract obtained by extracting the separated aqueous layer with ethyl acetate were combined and washed with dilute hydrochloric acid. The obtained organic layer was washed twice with 5% sodium bicarbonate water, then with 20% saline solution, and dried over anhydrous magnesium sulfate. After filtration, the solvent was removed under reduced pressure, and the obtained crude purified product was purified by precision distillation under reduced pressure to obtain 90g of 8-methyl-4-methylenenona-7-en-2-one (purity 95.5%). This was chosen as one of the active ingredients for use in the following examples. <<Physical properties of 8-methyl-4-methylenenona-7-en-2-one synthesized in Example 1>> 1 H-NMR (400MHz, CDCl3): δ1.60(s,3H),1.68(s,3H),2.03-2.12(m,4H),2.16(s,3H),3.12(s,2H),4.88(s,1H),4.97(s,1H),5.08(m,1H). 13 C-NMR (100MHz, CDCl3): δ17.7,25.7,26.0,29.1,36.0,51.8,114.1,123.5,132.0,142.9,207.2. MS(EI,70eV) m / z:43(58),69(100),81(19),108(49),123(39),151(5),166(4). A 1% ethanol solution of the obtained 8-methyl-4-methylenenona-7-en-2-one was prepared and had five well-trained panelists with more than 10 years of experience smell it and comment on the aroma they perceived. All five responded that it smelled like citrus.

[0060] [Example 2] Production example of the flavor degradation suppression composition. An ethanol solution of 8-methyl-4-methylenenona-7-en-2-one obtained in Example 1 was prepared at any concentration to obtain a composition for suppressing the deterioration of flavor in citral-containing articles according to one aspect of the present invention (Product 1-1). The aroma of Product 1-1 in a 1% ethanol solution was citrusy. In addition, commercially available 4,8-dimethylnona-3,7-dien-2-one (a mixture of E and Z isomers, E:Z isomer = 8:2) was prepared, and an ethanol solution of it at any concentration was prepared to obtain a composition for suppressing the deterioration of flavor in citral-containing articles according to one aspect of the present invention (Product 1-2). The aroma of Product 1-2 in a 1% ethanol solution was citrusy with a slight rose-like nuance. These were used in the following examples as one aspect of the present deterioration of flavor suppression composition.

[0061] [Example 3] Confirmation of the effect of suppressing deterioration flavor 1 (Test to suppress deterioration odor caused by abuse of citral-containing articles) A lemon-scented fragrance composition (hereinafter referred to as "basic lemon fragrance") was prepared according to the formulation shown in Table 1 below. The amount of citral in the basic lemon fragrance was approximately 0.25%.

[0062] [Table 1]

[0063] In addition, a sugar-acid solution was prepared by dissolving citric acid and granulated sugar in water (Bx3.0°, pH2.7, acidity 0.2%asC.A).

[0064] Then, a lemon-flavored solution was prepared by adding a basic lemon flavoring at a concentration of 0.1% by mass (approximately 2.5 ppm as citral concentration) to the sugar-acid solution. This was called the basic lemon-flavored beverage and was designated as control product 2. Control product 2 is one form of a citral-containing article.

[0065] Next, product 1-1 or product 1-2 of the present invention was added to control product 2 so that the concentration of the active ingredient in control product 2 was as shown in Table 2 below, thereby obtaining a citral-containing article according to one embodiment of the present invention (products 2-1 to 2-14 of the present invention).

[0066] Then, an abuse test was conducted in which control product 2 and products 2-1 to 2-14 of the present invention were placed in transparent containers and left to stand for one week in a light-shielded constant temperature bath at 50°C. After the abuse test, control product 2 produced approximately 25 ppb of p-cresol and approximately 25 ppb of p-methylacetophenone.

[0067] Then, the deteriorated flavor of the abused products 2-1 to 2-14 of the present invention were evaluated by 12 well-trained panelists with more than 10 years of experience, based on the following criteria, compared to control product 2 after abuse. "The deteriorated flavor is the same as control product 2" = 1 point meant that the deteriorated flavor was equivalent to the deteriorated flavor perceived from control product 2 (including p-cresol-like flavor and p-methylacetophenone-like flavor), and "The deteriorated flavor is almost imperceptible" = 4 points meant that the deteriorated flavor was equivalent to that of control product 2 immediately after preparation without abuse. (Standard) Regarding the deterioration of flavor compared to the control product. "Almost no noticeable deterioration in flavor" = 4 points "Degraded flavor is noticeable, but clearly weaker than the control product" = 3 points "Degraded flavor is slightly weaker than the control product" = 2 points "The deterioration in flavor is the same as the control product" = 1 point Table 2 shows the average evaluation scores of the 12 panelists.

[0068] [Table 2]

[0069] As shown in Table 2, it was confirmed that adding the present flavor-degrading suppression composition (product 1-1 or 1-2 of the present invention) to a citral-containing article suppresses the generation of unpleasant flavors in that article. Furthermore, all 12 panelists responded that when product 1-1 of the present invention (active ingredient 1: 8-methyl-4-methylenenona-7-en-2-one) was added, products 2-3, 2-4, and 2-5, and when product 1-2 of the present invention (active ingredient 2: 4,8-dimethylnona-3,7-dien-2-one) was added, products 2-10 and 2-11, had a good balance between suppression of flavor degradation and flavor impartment by the active ingredients themselves, resulting in a desirable lemon flavor.

[0070] Furthermore, in the case of product 1-1 of the present invention (active ingredient 1: 8-methyl-4-methylenenona-7-en-2-one), when the concentration exceeds 1 ppm, and in the case of product 1-2 of the present invention (active ingredient 2: 4,8-dimethylnona-3,7-dien-2-one), when the concentration exceeds 500 ppb, the flavor of the active ingredient itself is imparted while the deterioration of flavor is suppressed, and a slightly floral citrus-like flavor is emphasized. Thus, when it is desired to clearly impart a citrus-like flavor, it is possible to add the active ingredient at a concentration above a certain level.

[0071] Furthermore, a composition can be obtained by adding either Product 1-1 or Product 1-2 of the present invention obtained in Example 2 to a basic lemon flavor containing citral as shown in Table 1 of Example 3, and this composition can be used as the flavor degradation suppression composition containing the active ingredient of the present invention, thereby obtaining the same effects as in Example 3.

[0072] [Example 4] Confirmation of the effect of suppressing deterioration flavor 2 (Test to suppress deterioration odor caused by abuse of citral-containing articles) As one form of a citral-containing product, commercially available lemon juice (5% fruit juice, hereinafter referred to as "basic lemon juice") was prepared. Hereinafter referred to as "basic lemon juice."

[0073] On the other hand, Product 1-1 of the present invention was blended with the basic lemon flavoring prepared in Example 3 so that the concentration of active ingredient 1 was 0.01% by mass to obtain a citral degradation flavor suppression composition according to one aspect of the present invention (Product 3-1 of the present invention). Furthermore, Product 1-2 of the present invention was blended with the basic lemon flavoring prepared in Example 3 so that the concentration of active ingredient 2 was 0.01% by mass to obtain a citral degradation flavor suppression composition according to one aspect of the present invention (Product 3-2 of the present invention).

[0074] Next, Product 3-1 of the present invention was added to the basic lemon juice at a concentration of 0.1% by mass to obtain a lemon beverage according to one embodiment of the present invention (Product 3-3 of the present invention, with a concentration of active ingredient 1 of 100 ppb). Furthermore, Product 3-2 of the present invention was added to the basic lemon juice at a concentration of 0.1% by mass to obtain a lemon beverage according to one embodiment of the present invention (Product 3-4 of the present invention, with a concentration of active ingredient 1 of 100 ppb).

[0075] On the other hand, a control lemon beverage was obtained by adding basic lemon flavoring to basic lemon juice to a concentration of 0.1% by mass, and this was designated as control product 3-1.

[0076] Next, abuse tests were conducted on products 3-3 and 3-4 of the present invention, as well as control product 3-1. In the abuse test, products 3-3 and 3-4 of the present invention and control product 3-1 were each placed in a transparent container and left to stand for one week in a light-shielded constant temperature bath at 50°C, similar to the abuse test in Example 3. Subsequently, the flavors of products 3-3 and 3-4 after abuse were evaluated by five well-trained panelists with more than 10 years of experience, compared to the flavor of control product 3-1 after abuse. As a result, all five panelists responded that they did not perceive the heterogeneous, degraded flavors, such as the p-cresol-like chemical flavor and the p-methylacetophenone-like fruity flavor, that were present in control product 3-1, in product 3-3. In product 3-4, two panelists responded that they did not perceive any flavors, while three panelists responded that they were slightly perceived but significantly suppressed.

[0077] [Example 5] Confirmation of the effect of suppressing deterioration of flavor 3 (effect of suppressing deterioration of flavor compounds) Commercially available carbonated water was mixed with p-cresol at a concentration of 100 ppb, p-methylacetophenone at 100 ppb, or p-cresol and p-methylacetophenone at 100 ppb each (total concentration 200 ppb). The samples were then divided into three control products: control product 4-1 contained 100 ppb of p-cresol, control product 4-2 contained 100 ppb of p-methylacetophenone, and control product 4-3 contained 100 ppb each of p-cresol and p-methylacetophenone (all were forms of citral-containing products that exhibited degraded flavor).

[0078] On the other hand, an ethanol solution of 8-methyl-4-methylenenona-7-en-2-one prepared in Example 2 at any concentration (Product 1-1 of the present invention), and an ethanol solution of 4,8-dimethylnona-3,7-dien-2-one at any concentration (Product 1-2 of the present invention) were prepared.

[0079] Then, product 1-1 of the present invention (active ingredient 1: 8-methyl-4-methylenenona-7-en-2-one) or product 1-2 of the present invention (active ingredient 2: 4,8-dimethylnona-3,7-dien-2-one) was added to control products 4-1 to 4-3 as shown in Table 3 below to obtain a beverage according to one embodiment of the present invention (products 4-1 to 4-18 of the present invention).

[0080] Next, a sensory evaluation was conducted on the suppression of deterioration flavor of products 4-1 to 4-18 of the present invention. In the sensory evaluation, 12 well-trained panelists with more than 10 years of experience were asked to score the p-cresol-like flavor and / or p-methylacetophenone-like flavor of the products of the present invention compared to control products 4-1 to 4-3, according to the following criteria. (Reference) Regarding the p-cresol-like and / or p-methylacetophenone-like flavor compared to the control product. "Almost imperceptible" = 4 points "Can be felt, but clearly weaker than the control product" = 3 points "Slightly weaker than the control product" = 2 points "Same as the control product" = 1 point Table 3 shows the average evaluation scores of the 12 panelists.

[0081] [Table 3]

[0082] As shown in Table 3, it was confirmed that the active ingredient in question can suppress deterioration of flavor at concentrations in the range of at least 1 ppt to 1 ppm. Furthermore, as can be seen from the evaluation scores, it was confirmed that active ingredient 1 showed a higher inhibitory effect than active ingredient 2.

[0083] [Example 6] Confirmation of the effect of suppressing deterioration of flavor 4 (effect of suppressing deterioration of flavor compounds) The basic lemon-like flavor composition prepared in Example 3 was added to carbonated water at a concentration of 0.1% by mass to obtain a basic lemon-flavored beverage. To this, as representative examples of degraded flavor compounds, p-cresol was added at a concentration of 100 ppb, p-methylacetophenone at 100 ppb, or p-cresol and p-methylacetophenone at 100 ppb each (total concentration 200 ppb). The sample containing 100 ppb of p-cresol was designated as control sample 5-1, the sample containing 100 ppb of p-methylacetophenone as control sample 5-2, and the sample containing 100 ppb each of p-cresol and p-methylacetophenone as control sample 5-3 (all are embodiments of citral-containing articles).

[0084] On the other hand, an ethanol solution of 8-methyl-4-methylenenona-7-en-2-one prepared in Example 2 at any concentration (Product 1-1 of the present invention), and an ethanol solution of 4,8-dimethylnona-3,7-dien-2-one at any concentration (Product 1-2 of the present invention) were prepared.

[0085] Then, product 1-1 of the present invention (active ingredient 1: 8-methyl-4-methylenenona-7-en-2-one) or product 1-2 of the present invention (active ingredient 2: 4,8-dimethylnona-3,7-dien-2-one) was added to control products 5-1 to 5-3 as shown in Table 4 below to obtain a lemon-flavored beverage according to one embodiment of the present invention (products 5-1 to 5-30 of the present invention).

[0086] As a comparative example, geranyl acetate, known to contribute to citrus-like aroma, was added to each of the control products 5-1 to 5-3 at a concentration of 1 ppb to obtain comparative lemon-flavored beverages (comparative product 5-1, comparative product 5-2, and comparative product 5-3).

[0087] Then, a sensory evaluation was conducted on the suppression of deterioration flavor in the present invention products 5-1 to 5-30 and comparative products 5-1 to 5-3. In the sensory evaluation, 12 well-trained panelists with more than 10 years of experience were asked to comment on the p-cresol-like flavor and / or p-methylacetophenone-like flavor of the present invention products and comparative products compared to the lemon-flavored beverages of control products 5-1 to 5-3, and to score them according to the following criteria. (Reference) Regarding the p-cresol-like and / or p-methylacetophenone-like flavor compared to the control product. "Almost imperceptible" = 4 points "Can be felt, but clearly weaker than the control product" = 3 points "Slightly weaker than the control product" = 2 points "Same as the control product" = 1 point Table 4 shows the average scores and representative comments of the 12 panelists.

[0088] [Table 4]

[0089] As shown in Table 4, it was confirmed that the flavor degradation suppression composition can suppress the flavor degradation of citral-containing articles. [Example 7] Confirmation of the effect of suppressing deterioration of flavor 5: Effect of suppressing deterioration of flavor on deterioration components In Example 6, the concentrations of p-cresol, p-methylacetophenone, and their combined concentration, which are degraded flavor compounds, were changed to 1 ppm, as shown in Table 5 below, to make the degraded flavor very strong. In addition, the concentration of the active ingredient in question was changed as shown in Table 5 below. The degraded flavor-inhibiting effect of the degraded flavor-inhibiting composition in question on citral was confirmed by sensory evaluation by 12 well-trained panelists with more than 10 years of experience.

[0090] [Table 5]

[0091] As a result, it was confirmed that even at a high concentration of degraded flavor compounds, i.e., 1 ppm, where the degraded flavor is strongly perceived, the degraded flavor was effectively suppressed by the degraded flavor suppression composition. [Example 8] Effect of combining the two active ingredients in this case The effect of suppressing deterioration of flavor when 8-methyl-4-methylenenona-7-en-2-one (active ingredient 1) and 4,8-dimethylnona-3,7-dien-2-one (active ingredient 2) are used in combination was confirmed.

[0092] First, commercially available body fragrance products labeled as citrus and floral (also known as floral citrus or citrus floral) were prepared. To these, p-cresol and p-methylacetophenone were added to a concentration of 100 ppb to obtain a control lemon-scented cosmetic product (control product 7-1).

[0093] Then, as shown in Table 6 below, two products, Product 1-1 (ethanol solution of active ingredient 1) and Product 1-2 (ethanol solution of active ingredient 2), were added to obtain a lemon-like cosmetic product according to one embodiment of the present invention (Products 7-1 to 7-3).

[0094] Next, a sensory evaluation was conducted on the suppression of deterioration in flavor for products 7-1 to 7-3 of the present invention. In the sensory evaluation, five well-trained panelists with more than 10 years of experience were asked to comment on the aroma of the products of the present invention compared to control product 7-1. Representative comments are shown in Table 6.

[0095] [Table 6]

[0096] As shown in Table 6, the deterioration of flavor was effectively suppressed in all of the products of the present invention. This confirms that the deterioration of flavor is effectively suppressed not only when using active ingredient 1 alone or active ingredient 2 alone, but also when using active ingredients 1 and 2 in any ratio.

[0097] Furthermore, it was confirmed that the comments differed depending on the ratio of active ingredients 1 and 2, and that the ratio could be arbitrarily determined according to the desired inhibitory effect based on the respective efficacy characteristics of the active ingredients. [Example 9] Example of the ratio of E-isomer and Z-isomer of the active ingredient 2. Ethanol solutions of 4,8-dimethylnona-3,7-dien-2-one (active ingredient 2, E-isomer:Z-isomer = approximately 8:2) prepared in Example 2 (Product 1-2 of the present invention). In addition, as other examples of 4,8-dimethylnona-3,7-dien-2-one (active ingredient 2), ethanol solutions of a mixture of the E-isomer and Z-isomer with a ratio of approximately 7:3 (Product 8-1 of the present invention) and a mixture with a ratio of approximately 9:1 (Product 8-2 of the present invention) were prepared.

[0098] On the other hand, commercially available lemon juice was mixed with p-cresol (a representative example of a degraded flavor compound) at a concentration of 100 ppb, p-methylacetophenone (100 ppb), or p-cresol and p-methylacetophenone at 100 ppb each (total concentration of 200 ppb). The sample containing 100 ppb of p-cresol was designated as control product 8-1, the sample containing 100 ppb of p-methylacetophenone as control product 8-2, and the sample containing 100 ppb each of p-cresol and p-methylacetophenone as control product 8-3 (all were forms of citral-containing products in which degraded flavors occurred).

[0099] Then, as shown in Table 7 below, product 1-2 (E-isomer:Z-isomer = approximately 8:2), product 8-1 (E-isomer:Z-isomer = approximately 7:3), and product 8-2 (E-isomer:Z-isomer = approximately 9:1) were added to control products 8-1 to 8-3, respectively, so that the concentration of each active ingredient was 1 ppb, to obtain beverages according to one embodiment of the present invention (products 8-3 to 8-11).

[0100] Next, a sensory evaluation was conducted on the suppression of deterioration flavor of products 8-3 to 8-11 of the present invention. In the sensory evaluation, five well-trained panelists with more than 10 years of experience evaluated the p-cresol-like flavor and / or p-methylacetophenone-like flavor of the products of the present invention compared with each of the control products 8-1 to 8-3.

[0101] [Table 7]

[0102] As a result, all panelists commented that there was no difference in the flavor degradation suppression effect among the inventive products 8-3 to 8-5, 8-6 to 8-8, and 8-9 to 8-11, regardless of the ratio of E-isomers to Z-isomers, and that they were equivalent, confirming that the flavor degradation suppression effect is achieved regardless of the ratio of E-isomers to Z-isomers.

Claims

1. A citral flavor degradation suppression composition comprising one or more substances selected from the group consisting of 8-methyl-4-methylenenona-7-en-2-one and 4,8-dimethylnona-3,7-dien-2-one as an active ingredient.

2. The citral degradation flavor suppression composition according to claim 1, comprising at least 8-methyl-4-methylenenona-7-en-2-one as the active ingredient.

3. The citral degradation flavor suppression composition according to claim 1, comprising 8-methyl-4-methylenenona-7-en-2-one and 4,8-dimethylnona-3,7-dien-2-one as the active ingredients.

4. The citral flavor degradation suppression composition according to any one of claims 1 to 3, wherein the aforementioned flavor degradation is due to p-cresol and / or p-methylacetophenone.

5. A method for suppressing citral flavor degradation, comprising incorporating a citral flavor degradation suppression composition containing one or more active ingredients selected from the group consisting of 8-methyl-4-methylenenona-7-en-2-one and 4,8-dimethylnona-3,7-dien-2-one into a citral-containing article.

6. The method for suppressing citral-induced flavor degradation according to claim 5, wherein the citral-containing article is in which the active ingredient is added at a concentration of 1 ppt to 100 ppm (or the total concentration thereof if both 8-methyl-4-methylenenona-7-en-2-one and 4,8-dimethylnona-3,7-dien-2-one are included) based on the total mass of the citral-containing article.

7. The method for suppressing citral-induced flavor degradation according to claim 6, wherein the concentration is 1 ppb to 500 ppb.

8. A citral-containing article comprising the citral-degradation flavor-suppressing composition described in any one of claims 1 to 3.

9. The citral-containing article according to claim 8, wherein the citral-containing article is a fragrance composition, food or beverage, cosmetic, or health and hygiene product.

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