Perfume scent-lingering property evaluation method, scent-lingering property imparting agent, and scent-lingering property improvement method

Abstract

To provide a novel method related to scent-lingering property and a scent-lingering property imparting agent, for example: a scent-lingering property evaluation method for specifying a high scent-lingering property fragrance compound contained in a fragrance component of an odor substance; a method for evaluating fragrance characteristics of the fragrance compound from a fragrance contribution degree and a scent-lingering property evaluation value; and a method for imparting scent-lingering property to a fragrance product.SOLUTION: A scent-lingering property evaluation method for selecting a high scent-lingering property compound in fragrance compounds contained in an odor substance includes: step 1 of leaving an odor substance at rest in a space with the condition of fixed temperature and moisture; step 2 of extracting a fragrance component contained in the odor substance after a predetermined time from the start of leaving-at-rest; step 3 of subjecting the extracted fragrance component to gas chromatography olfactometry (GCO) analysis, so as to detect presence / absence of odor for each fragrance compound constituting the fragrance component; step 4 of measuring the longest leaving-at-rest time (T) to detect the odor of each fragrance compound constituting the odor substance for each fragrance compound; and step 5 of using the longest leaving-at-rest time (Ta) to detect the odor of the specified fragrance compound A and the longest leaving-at-rest time (Tx) to detect the odor of the fragrance compound X with the longest T in the fragrance compounds constituting the odor substance in the step 4, so as to define a Ta / Tx value as a scent-lingering property evaluation value of the fragrance compound A contained in the odor substance.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to an evaluation method for searching for fragrance compounds with high lingering properties, or fragrance compounds that have high lingering properties and also contribute greatly to fragrance, from a mixture of odorous substances, for example, fragrance compounds such as natural fragrances. The present invention also relates to a fragrance lingering agent discovered using this method, and a method for improving a fragrance composition that has similar fragrance notes but has improved lingering properties by analyzing the properties of fragrance components using this method. [Background technology]

[0002] In aromatic products such as perfumes, makeup products, skin care products, hair care products, toiletry products, household products, and air fresheners, the long-lasting fragrance (fragrance lingering) is an important factor in providing consumer satisfaction, a sense of refreshment and elation, and in increasing the product value. Therefore, improving the fragrance lingering of aromatic products is important for the development of cosmetic fragrances (fragrances) used in aromatic products. Here, fragrance lingering and refers to the long-lasting or long-lasting quality of a fragrance.

[0003] In the fragrance industry, in order to overcome the problem of fragrance disappearing in a short period of time when using fragrance ingredients that are highly volatile or have low residual properties, methods have been considered that involve encapsulating the fragrance ingredients in microcapsules to physically suppress the volatilization of the fragrance ingredients (Patent Document 1) and using derivatives (professional fragrances) that can extend the effects of active ingredients (Patent Document 2).

[0004] However, the capsules and polymers used in encapsulated fragrances and pro-fragrances are difficult to break physically and have low biodegradability, which has raised the problem that they place a burden on the natural environment. In addition, whether a smell is pleasant or unpleasant depends on the senses of each individual, but a scent that is highly palatable and suitable for everyone is unlikely to cause discomfort to many people. Therefore, based on experience, fragrances that are both excellent in lingering power and palatability have been used as flavorings for fragrance products. As one such technique, for example, a method has been proposed for compounding fragrances in which the natural and synthetic fragrances used as the fragrance materials of the compounded fragrance are applied to scent paper and selected fragrances whose scent remains on the scent paper for up to 2 hours, up to 6 hours, or more than 6 hours (Patent Document 3).

[0005] Furthermore, when natural fragrances are blended with a fragrance for the purpose of imparting lingering fragrance, it is difficult to achieve both excellent fragrance tone and lingering fragrance. This is because the components that contribute to lingering fragrance in natural fragrances, which are made up of a wide variety of fragrance components, have not been clarified, and because they also contain components that are unnecessary for lingering fragrance, it is difficult to balance lingering fragrance with the desired fragrance tone. As a result, a huge amount of trial and error was required to select the natural fragrances to use and adjust the amounts used, which also affected the costs of product development.

[0006] Therefore, techniques have been developed to enhance the lingering fragrance without using natural fragrances. For example, there are a method of sustaining floral, fruity, and green fragrances by adding a retaining agent to adjust the retention of fragrant substances (Patent Document 4), a method of using vinylpyrrolidone / vinyl acetate copolymer as a fragrance extender (Patent Document 5), a method of using 1-methyl-3,4-dioxy(cycloacetonyl)benzene, which has a high aromaticity (Patent Document 6), a method of using a long-lasting fragrance composition containing ingredients with a calculated log value (ClogP) of 3.0 or more (P is the octanol / water partition coefficient) and a boiling point of 250°C or more (Patent Document 7), and a method of using a long-lasting fragrance composition containing ingredients with a calculated log value (ClogP) of 3.0 or more (P is the octanol / water partition coefficient) and a boiling point of 250°C or more (Patent Document 8). In addition, a method has been proposed in which a fragrance composition with long lingering fragrance is prepared by using a fragrance ingredient that is solid and has low volatility (Patent Document 8).

[0007] In recent years, there has been a growing demand for the use of natural fragrance ingredients that are highly palatable and have a low impact on the natural environment. However, there has been no means to search for and evaluate long-lasting fragrance compounds from natural fragrances and to improve fragrance compositions based on the data, or to develop fragrance compositions with long-lasting fragrance.

[0008] On the other hand, as methods for analyzing the aroma characteristics of each aroma component in a natural flavoring, there have been proposed a method in which aroma components in a coffee aroma concentrate are separated by gas chromatography (GC), mixed with a coffee extract for evaluation, and subjected to a sensory evaluation to measure the contribution of the separated aroma components (Patent Document 9), a method in which aroma components in a coffee aroma concentrate separated by GC are continuously mixed with a headspace sample of the coffee extract and the resulting aroma is evaluated (Patent Document 10), and a method in which the FD factor of each aroma component is determined by combining a GCO analysis method in which aroma components separated by GC are subjected to a sensory evaluation by olfactometry (olfactometry) with aroma extract dilution analysis (AEDA), and the concentration of trace aroma components in coffee beans is calculated by multiplying the FD factor by the threshold value of each aroma component (Patent Document 11).

[0009] However, although all of the above-mentioned methods can qualitatively and quantitatively determine the aroma components contained and the aroma compounds that constitute them, they are not methods for accurately evaluating the lingering of the aroma compounds in natural fragrances, and have not yet reached the point of discovering fragrance components that have both high lingering and high preference. In short, sensory evaluation methods are generally used to evaluate fragrance tones, and gas chromatography (GC) analytical techniques are used to analyze aroma components; however, these methods have made it difficult to identify the active ingredients and aroma compounds that contribute to the lingering fragrance contained in natural fragrances, and to comprehensively search for ingredients and aroma compounds with high lingering fragrance.

[0010] The present inventors have therefore discovered and provided a new method for searching for and evaluating aroma compounds with long lingering properties from among the many components contained in fragrances that have been used since ancient times and are familiar to many people, or fragrances that have natural fragrances that are well-liked by many people, i.e., highly palatable natural fragrances. Furthermore, the inventors have discovered and provided a method for evaluating fragrance characteristics based on the correlation between the quantified data obtained by the fragrance lingering evaluation method and the quantified data regarding the contribution of the compound to the fragrance characteristics in natural fragrances, a fragrance lingering agent discovered by the method, a method for imparting fragrance lingering to fragrance products, a method for improving fragrances that are excellent in both lingering and palatability, and a method for developing fragrance compositions using a new method. [Prior art documents] [Patent documents]

[0011] [Patent Document 1] Special Publication No. 2010-520928 [Patent Document 2] Special Publication No. 2008-531761 [Patent Document 3] JP 2002-327193 A [Patent Document 4] Patent No. 5025845 [Patent Document 5] Special Publication No. 2017-520543 [Patent Document 6] Patent No. 5011254 [Patent Document 7] Special Publication No. 10-507789 [Patent Document 8] JP 2009-242298 A [Patent Document 9] JP 2007-163198 A [Patent Document 10] JP 2003-107067 A [Patent Document 11] JP 2004-325116 A [Non-patent literature]

[0012] [Non-Patent Document 1] Tetsujiro Horiuchi, "The Frontline of Fragrance Measurement Using Analytical Instruments," Journal of the Japanese Society of Cosmetic Technologists, Vol. 32, No. 3 (September 1998), pp. 253-262 Summary of the Invention [Problem to be solved by the invention]

[0013] The objective of the present invention is to provide a method for evaluating odor lingering for identifying and quantifying compounds with high odor lingering contained in an odorous substance, a method for evaluating the odor characteristics of odor compounds contained in an odorous substance based on the odor contribution rate and odor lingering evaluation value, and new means for improving the odor lingering of fragrances, such as odor lingering imparting agents. [Means for solving the problem]

[0014] That is, the present invention is as follows. [1] The following steps: Step 1: The odorant is left to stand in a space with constant temperature and humidity conditions. Step 2: A step of extracting the aroma components contained in the odorous substance after a predetermined time from the start of standing; Step 3: subjecting the extracted aroma components to gas chromatography-olfactometry (GCO) analysis to detect the presence or absence of odor for each aroma compound that constitutes the aroma components; Step 4: measuring the longest standing time (T) at which the odor of each of the aroma compounds constituting the odor substance can be detected for each aroma compound; and Step 5: Using the longest standing time (Ta) at which the odor of a specific aroma compound A can be detected in step 4 and the longest standing time (Tx) at which the odor of aroma compound X, which has the longest T among the aroma compounds constituting the odor, can be detected, the Ta / Tx value is determined as an evaluation value of the lingering odor of aroma compound A contained in the odor substance; A method for evaluating lingering fragrance properties for selecting compounds having high lingering fragrance compounds contained in odorous substances, comprising:

[0015] [2] A method for evaluating the odor characteristics of an aroma compound A from the odor contribution degree of the aroma compound A contained in an odor substance and the odor persistence evaluation value (Ta / Tx) of the aroma compound A obtained by the method of claim 1. . [3] The following formula 1 [ka] Dihydrocalanone represented by the formula: The following formula 2 [ka] A lingering fragrance agent containing 2-isopropylidene-10-methyl-spiro[4,5]-6-decene-6-carbaldehyde as the active ingredient.

[0016] [4] A fragrance composition comprising the residual fragrance imparting agent according to the above item 3 (excluding fragrance compositions containing agarwood essential oil). [5] A method for imparting lingering fragrance to a fragrance composition (excluding fragrance compositions containing agarwood essential oil) by blending the lingering fragrance imparting agent described in 3 above. [6] A method for imparting residual fragrance to a fragrance composition (excluding fragrance compositions containing agarwood essential oil) by blending dihydrocalanone represented by formula 1 in the fragrance composition at a concentration of 0.00001 to 1%. [7] A fragrance product containing the fragrance composition described in 4 above, and having improved fragrance retention. [8] The fragrance product according to the above item 7, which is a personal care product such as a perfume, a makeup product, a skin care product, a hair care product, or a toiletry product, a household product, or a quasi-drug.

[0017] [9] A method for imparting lingering fragrance to a fragrance product by blending the fragrance composition described in 4 above.

[10] A method for imparting residual fragrance to a fragrance product by blending dihydrocalanone represented by formula 1 in the fragrance product at a concentration of 0.2 ppb to 1000 ppm.

[11] The method for imparting a lingering fragrance as described in the above item 10, wherein the fragrance product is a personal care product such as a perfume, a makeup product, a skin care product, a hair care product, or a toiletry product, a household product, or a quasi-drug.

[0018]

[12] The following steps: Step 1: For each aroma compound that constitutes the fragrance of the odorant, a step of specifying the residual fragrance evaluation value (P), the aroma contribution degree (Q), and the fragrance tone by the method of 1 above; Step 2: For each aroma compound, compounds with 0 < P < 0.5 and 0 < Q < 0.5 are classified as compound group A, compounds with 0 < P < 0.5 and 0.5 ≤ Q ≤ 1 are classified as compound group B, compounds with 0.5 ≤ P ≤ 1 and 0 < Q < 0.5 are classified as compound group C, and compounds with 0.5 ≤ P ≤ 1 and 0.5 ≤ Q ≤ 1 are classified as compound group D; Step 3: A step of substituting the aroma compound b classified into compound group B with an aroma compound d that is classified into compound group D and has a fragrance tone similar to that of the aroma compound b; An odorant fragrance improvement method characterized by including the above.

[0019] 〔13〕A step of creating a database of the correlation between the residual fragrance evaluation value and the fragrance tone by the method of 12 above for a large number of aroma compounds; Next, when designing a fragrance composition whose fragrance tone changes over time, a step of selecting components from the said data; A fragrance composition design method characterized by including the above.

Effect of the Invention

[0020] According to the present invention, even for a complex composition such as a natural fragrance or natural essential oil, components that are highly important in terms of both residual fragrance and contribution to aroma can be explored and elucidated. By adding the aroma compounds thus found as residual fragrance imparting agents to other fragrance compositions, the residual fragrance can be improved without causing discomfort. Therefore, in the development of new fragrance compositions for fragrance products, the improvement and enhancement of conventional products, the enormous trial-and-error work and processes that have been required for the selection and determination of blending amounts of fragrances can be significantly shortened, simplified, made more efficient, and labor-saving. As a result, the labor, time, and cost spent on product development can be significantly reduced, and moreover, product design, development, and improvement that meet consumer needs can be timely carried out in a short time.

Brief Description of the Drawings

[0021] [Figure 1] FIG. 1 is a schematic diagram of settling time and sample number. [Diagram 2] FIG. 1 is a correlation diagram between fragrance lingering evaluation value and fragrance contribution degree. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0022] In the present invention, the aroma compounds remaining in a sample of an odorant that has been left to stand for a given period of time are smelled at the outlet of a gas chromatograph (GC), and the obtained information is superimposed on the GC information in a gas chromatography-olfactometry (GC-Olfactometry) analysis. By utilizing this method, we search for lingering fragrance compounds and quantify and evaluate their strength (lasting scent). In addition, the entire odor of each aroma compound was analyzed by AEDA (Aroma Extract Dilution Analysis). By quantifying and evaluating the degree of contribution to the body and classifying (sorting) aroma compounds using the binary data of aroma lingering evaluation value and aroma contribution degree, it is possible to identify and select active ingredients with high aroma contribution degree and aroma lingering degree from the many fragrance ingredients contained in natural fragrances. The present invention will be described in detail below with reference to the embodiments.

[0023] [1] Evaluation method for residual fragrance The odor lingering evaluation method of the present invention for identifying compounds with high odor lingering properties contained in odorous substances comprises the following steps. In step 1, the odorant is placed in a space with constant temperature and humidity. In step 2, the aroma components contained in the odorous substance are extracted after a predetermined time from the start of standing. In step 3, the extracted aroma components are subjected to gas chromatography-olfactometry (GCO) analysis to detect the presence or absence of an odor for each of the aroma compounds that make up the aroma components. In step 4, the longest standing time (T) during which the odor of each aroma compound constituting the odorous substance can be detected is measured for each aroma compound. In step 5, the longest standing time (Ta) at which the odor of a specific aroma compound A can be detected in step 4 and the longest standing time (Tx) at which the odor of aroma compound X, which has the longest T among the aroma compounds that make up the odorous substance, can be detected are used, and the Ta / Tx value is determined as the lingering evaluation value of aroma compound A contained in the odorous substance. The above steps will now be described in more detail.

[0024] (1) Regarding step 1 The odor substances to be evaluated include natural plant-based fragrances obtained from flowers, fruits, fruit juices, trees, vegetables, nuts, seeds, spices, etc.; natural animal-based fragrances obtained from ambergris, musk, joints, etc.; synthetic fragrances obtained by chemical or microbial methods and consisting of two or more odorous compounds; and foods, beverages, cosmetics, etc. that have odors available on the market. These odorants may be purified by known methods in the field of fragrances, such as extraction, percolation, squeezing, distillation, and the like.

[0025] For the evaluation, first, a sample is prepared by permeating a filter paper with an odorant, and then, taking into consideration the environment in which the fragrance product will be used, the temperature, humidity, illuminance, etc. are adjusted so as to maintain certain conditions while the sample is left standing. The space in which the sample is left standing may be, for example, a thermostatic room, a thermostatic machine, a desiccator, etc. By appropriately setting the temperature, humidity, illuminance, etc. during standing, it is possible to evaluate the lingering fragrance under various environments. For example, the temperature is 0 to 30°C, the relative humidity is 40 to 90%, and the illuminance is 0 to 100,000 lux. When preparing samples, using hair instead of filter paper allows for accurate evaluation of the lingering scent of fragrances for hair care products such as hair dyes, while using clothing fabric allows for accurate evaluation of the lingering scent of fragrances for household products such as detergents and fabric softeners.

[0026] Here, fragrance products refer to perfumes, air fresheners, makeup products, toiletry products, skin care products, hair care products, and household products, as described below. "Perfume" refers to eau de toilette, eau de parfum, eau de cologne, etc., and comes in bottle, roll, and spray types depending on the purpose.

[0027] "Makeup products" are used for the aesthetic purpose of making the face look beautiful, for the protective purpose of protecting the skin, and for the purpose of providing enjoyment and satisfaction. Products include makeup cosmetics such as foundation, lipstick, lip balm, blush, eyeliner, mascara, eye shadow, eyebrow pencil, eyebrow pencil, powder powder, solid powder, nail enamel, nail polish, nail polish remover, etc.

[0028] "Skin care products" have functions such as removing sweat and dirt, tightening the skin, maintaining proper nutrients and moisture, supporting normal skin condition, and protecting the skin from ultraviolet rays. Products include washing cream, vanishing cream, facial wash cream, cleansing cream, cold cream, sunscreen cream, milk lotion, toner, pack, makeup remover, aftershave lotion, talcum powder, lip balm, hand cream, antiperspirant, and face care (facial cleanser, makeup remover, cleansing oil, blotting paper, etc.).

[0029] "Hair care products" are products used for cleaning and protecting hair and scalp, as well as styling hair, and include shampoos, rinses, conditioners, tonics that improve blood circulation in the scalp, hair oils, pomades, balms, hair liquids, setting lotions, hair gels, hair sprays, hair foams, hair wax and other hair styling products, hair dyes such as hair color, hair manicure, bleach and gray hair dye, hair transformation products such as perms and curling agents, hair treatments and other hair growth products, etc.

[0030] "Toiletries" include body care products such as soap, hand soap, bath salts, body shampoo, and lip balm, sunscreen, antiperspirant deodorants, shaving products (razors, shaving razors, shaving foam, etc.), toothpaste, mouthwash, dental floss, denture cleaner and other oral care products, wet tissues, disposable diapers, and sanitary products.

[0031] "Household products" include laundry products such as detergents and fabric softeners used in ordinary households, home and furniture products such as cleaners and waxes, kitchen products such as bleach and food waste deodorizers, and daily miscellaneous products such as office glue and paints. These products include liquid laundry detergent, powder laundry detergent, solid laundry soap, fabric softener, laundry bleach, kitchen detergent, detergent for dish dryers, Products include bath cleaners, glass cleaners, mold removers, drain cleaners, fumigants, mosquito coils, insecticides, insect repellents, toilet cleaners, and more.

[0032] "Fragrance" includes aqueous liquid fragrances, oil-based liquid fragrances, aqueous gel fragrances, oil-based gel fragrances, fragrance sprays, fragrance aerosols, impregnated fragrances, incense, fragrance deodorants, deodorant sprays, deodorant aerosols, and the like.

[0033] (2) Regarding step 2 Next, as shown in Figure 1, after a certain time (Tn) from the start of the standing, the odorant (Sn) remaining on the filter paper is collected. The standing time interval can be adjusted appropriately depending on the purpose, but if the interval is too short, the number of experiments will increase and it will become complicated, and conversely, if it is too long, it will be difficult to determine the difference in the lingering properties between the aroma compounds, resulting in low accuracy of the results. It is preferable to set the interval at equal or proportional intervals, from several tens of minutes to several hours. The recovery method is appropriately selected from solvent extraction, solid-phase extraction of headspace gas, direct injection of headspace gas, and the like.

[0034] (3) Steps 3 to 5 In the method for evaluating lingering fragrance of the present invention, a qualitative analysis of the aroma components in an odor substance (Sn) after n hours (Tn) have elapsed since the start of standing (To) is performed using a conventionally known GCO analysis. Here, GCO analysis is an analytical technique that combines gas chromatography and human olfactory detection, in which the outlet of the gas chromatograph column is branched, one end is connected to a detector (FID, MS, etc.) and the other end is connected to a port that can sniff odors, and the device is controlled to allow simultaneous detection by the detector and the sniffing port to analyze odor characteristics (Non-Patent Document 1). As the device for GCO analysis, a commercially available device can be appropriately used.

[0035] For each aroma component, the standing time and GCO analysis are continued until the odor is no longer detectable, and the longest standing time (Tx) during which any component can be smelled is measured. If the longest standing time (Ta) at which the odor of a specific aroma compound A can be detected after the start of standing is taken as the standing time (Tx) of the longest standing time (Tx) of aroma compound X at which the odor of the aroma compounds constituting the odorous substance can be detected, then the Ta / Tx value (a value ranging from 0 to 1) is taken as the evaluation value of the lingering odor of aroma compound A contained in the odorous substance.

[0036] [2] Evaluation method using both lingering odor evaluation value and odor contribution degree By using the lingering evaluation value of the aroma compound contained in an odorous substance in combination with the aroma contribution degree of the aroma compound, the aroma characteristics of the aroma compound can be evaluated more accurately, which can be useful for improving the aroma of odorous substances and developing new fragrances. That is, the odor contribution of the odor compound A contained in the odorant is evaluated and the odor contribution is calculated based on the odor lingering evaluation value (Ta / Tx) of the odorant A described above. This is a method for evaluating the odor characteristics of an aroma compound A.

[0037] Dilution analysis can be used to measure aroma contribution. Dilution analysis is a method that uses a GCO to smell the aroma components eluted from a GC column with the human nose, and includes AEDA (Aroma Extract Dilution Analysis) and CHARM (Combined Hedonic Aroma Response Measurement) analysis.

[0038] The aroma contribution degree by AEDA means that the odor substances of the object to be analyzed are successively diluted at a predetermined magnification, and the GCO analysis is repeated for each component while increasing the dilution magnification successively until the odor disappears. The last dilution magnification at which the odor is felt for each component is taken as the FD factor of that component. That is, it is a method of identifying the components with a high contribution degree as the components that can still be smelled until the end.

[0039] The aroma contribution degree by CHARM analysis means that while performing AEDA, the time when the smell is felt is simultaneously recorded, and the contribution degree of the odor of each component is taken as the peak area (Charm Value) of the chromatogram and is a method of recording two-dimensionally.

[0040] By organizing the residual fragrance property Ta / Tx obtained by GCO analysis of the aroma components in the odor substances after standing, and the aroma contribution degree obtained by the dilution analysis method, it is possible to comprehensively evaluate the residual fragrance property and contribution degree of each aroma compound contained in the odor substances.

[0041] An evaluation example based on the residual fragrance property evaluation value (Ta / Tx) and the aroma contribution degree is shown in Fig. 2. In Fig. 2, the classification from A to D is as follows. A: Aroma compounds with a low residual fragrance property evaluation value and a low aroma contribution degree B: Aroma compounds with a low residual fragrance property evaluation value but a high aroma contribution degree C: Aroma compounds with a high residual fragrance property evaluation value but a low aroma contribution degree D: Aroma compounds with a high residual fragrance property evaluation value and a high aroma contribution degree

[0042] Furthermore, when the residual fragrance property evaluation value is quantified as P and the aroma contribution degree is quantified as Q (here, 0 < P ≤ 1, 0 < Q ≤ 1), Compounds with 0 < P < 0.5 and 0 < Q < 0.5 are compound group A, Compounds with 0 < P < 0.5 and 0.5 ≤ Q ≤ 1 are compound group B, Compounds with 0.5 ≤ P ≤ 1 and 0 < Q < 0.5 are compound group C, Compounds satisfying 0.5≦P≦1 and 0.5≦Q≦1 are classified into compound group D, The compound can be classified as follows: The higher the P value is, the better the lingering fragrance, and the higher the Q value is, the better the compound's fragrance contribution.

[0043] [3] Fragrance imparting agent The present inventors have utilized the above-mentioned fragrance lingering evaluation method and the two-dimensional evaluation method of fragrance lingering evaluation value and fragrance contribution degree to analyze and examine various fragrance compounds contained in agarwood (a representative fragrant wood), which has been used since ancient times and is highly palatable. They found that dihydrocalanone and 2-isopropylidene-10-methyl-spiro[4,5]-6-decene-6-carbaldehyde were effective as lingering agents for fragrances among the aromatic compounds contained in agarwood. In particular, dihydrocalanone was excellent in both lingering and fragrance contribution. Agarwood is derived from the Aquilaria genus of the Thymelaeaceae family, and is a fungus that grows on wounds in wood. It is a sap secreted from the bark to protect against the invasion of insects. The essential oil extracted from agarwood contains many components, including terpene alcohol.

[0044] Dihydrocalanone has the structure of the following formula 1 and has a woody, fumigating aroma. It is known to be an aroma component contained in the fragrant wood aloeswood, but its use as an aroma compound is not known. [ka]

[0045] 2-Isopropylidene-10-methyl-spiro[4,5]-6-decene-6-carbaldehyde (J-GLOBALID: 200907023404424459, Nikkaji number:J664.750B) is a compound represented by the following formula 2. It has the structure and is a fragrance component with a woody scent. Its use as a fragrance compound has not been known until now. [ka] EXAMPLES

[0046] The present invention will now be described in more detail with reference to examples, but the present invention is not limited to these examples.

[0047] [Test Example 1] Agarwood essential oil (Sample preparation) Seven pieces of odorant were prepared by dropping 5 μL of Thai agarwood essential oil (commercially available) onto filter paper with a diameter of 1 cm. After leaving the filter paper at room temperature (25°C) for 6, 12, 24, 48, 96, and 192 hours, the filter paper was collected in a vial, and 1 mL of dichloromethane was added to the vial for 10 minutes to perform solvent extraction. Samples S0, S6, and S7 were extracted. 12 ,S 24 ,S 48 , S 96 , S 192 obtained.

[0048] (Evaluation of lingering fragrance) The samples extracted after each elapsed time were subjected to GCO analysis under the conditions described below to evaluate the presence or absence of odor, its intensity, and fragrance tone (character), etc. The longest standing time during which the odor of aroma component A can be sensed is Ta, the longest time among all odor substances. The time that the fragrance component was allowed to stand until the odor could be detected was defined as Tx, and the fragrance lingering evaluation value (Ta / Tx) was calculated. In Test Example 1, Tx was 96.

[0049] (Evaluation of Aroma Contribution) Thai agarwood essential oil was subjected to GCO, and the FD factors of each odor component were determined using the AEDA method. A sample was obtained by diluting Thai agarwood essential oil 256 times with 1 mL of dichloromethane. The sample was then diluted 4-fold and measured with GCO until the odor was no longer detectable. n ) from FD Fac Turn asked. Next, the ratio of the FD factor of each odor compound to the highest FD factor among odorants was evaluated as the odor contribution (Q).

[0050] (GCO analysis conditions) Instrument: Agilent 6850 series gas chromatograph Detector: Thermal Conductivity Detector (TCD) (Agilent Technologies, Palo Alto, USA) Column: Fused silica column (30m×0.25mm id,coated with a 0.25 μm film of DB-Wax; J & W Scientific, Folsom, USA) Temperature rise conditions: 40℃ to 210℃ at a rate of 5℃ / min Carrier gas: He (1ml / min)

[0051] The retention evaluation score and aroma contribution of each aroma compound detected in agarwood essential oil are summarized in Table 1. "RI" in the table stands for Retention Index.

[0052] [Table 1]

[0053] From the above results, the relationship between the lingering evaluation value and the degree of odor contribution for each aroma compound was classified according to Figure 2. Aroma compounds with a high aroma contribution, i.e., a high aroma contribution to the aroma of agarwood essential oil and a high lingering evaluation value, were classified as D, aroma compounds with a low aroma contribution but a high lingering evaluation value were classified as C, aroma compounds with a high aroma contribution but a low lingering evaluation value were classified as B, and aroma compounds with a low aroma contribution and a low lingering evaluation value were classified as A. The aroma compounds that could be identified and classified into A to D are summarized in Table 2.

[0054] The classifications A to D are as follows: A: Compounds with 0<Odor lingering evaluation value<0.5 and 0<Odor contribution rate<0.5, B: Compounds with 0<Odor Lingering Evaluation Value<0.5 and 0.5≦Odor Contribution Degree≦1; C: A compound having a lingering odor evaluation value of 0.5 or less and a lingering odor evaluation value of 1 or less and a 0 or less odor contribution degree of 0.5 or less. D: Compounds with 0.5≦Odor lingering evaluation value≦1 and 0.5≦Odor contribution degree≦1

[0055] [Table 2]

[0056] [Test Example 2] Floral-type fragrance composition A floral type fragrance composition (manufactured by Ogawa Fragrance Co., Ltd.) prepared according to the formula shown in Table 4 was mixed with dihydrocalanone (manufactured by Ogawa Fragrance Co., Ltd.), which was classified in Test Example 1 as a fragrance compound with high fragrance contribution and long lingering properties, at the concentrations shown in Table 3. The mixture was dropped onto filter paper in the same manner as in Test Example 1, and the lingering properties after leaving it for 12 hours under the same conditions were evaluated by 10 expert panelists who had been trained in advance. The evaluation results are shown in Table 5 below.

[0057] [Table 3]

[0058] [Table 4]

[0059] [Table 5]

[0060] The evaluation results are as follows: Evaluation of lingering fragrance: The numbers in the table indicate the number of evaluators. Evaluation 1: Fragrance lingering was the same as in Comparative Example 1. Rating 2: Slightly improved lingering fragrance. Rating 3: The lingering scent has improved significantly. The blending amount of dihydrocalanone is suitably 0.00001 to 1%, preferably 0.00001 to 0.1%, further preferably 0.00001 to 0.01%, particularly preferably 0.00005 to 0.005%, and even more preferably 0.0001 to 0.002%.

[0061] [Test Example 3] Musk-type fragrance composition A musk-type fragrance composition (manufactured by Ogawa Fragrance Co., Ltd.) prepared according to the recipe in Table 7 was mixed with dihydrocalanone (manufactured by Ogawa Fragrance Co., Ltd.) classified in Test Example 1 at the concentration shown in Table 6. As in Test Example 1, the mixture was dropped onto filter paper, and the lingering fragrance after being left to stand for 12 hours under the same conditions was evaluated by 10 expert panelists who had been trained in advance. The evaluation results are shown in Table 8 below.

[0062] [Table 6]

[0063] [Table 7]

[0064] [Table 8]

[0065] The contents of the evaluation are as follows: Evaluation of lingering fragrance: The numbers in the table indicate the number of evaluators. Evaluation 1: Fragrance lingering is the same as in Comparative Example 4. Rating 2: Slightly improved lingering fragrance. Rating 3: The lingering scent has improved significantly. The blending amount of dihydrocalanone is suitably 0.00001 to 1%, preferably 0.00001 to 0.1%, further preferably 0.00001 to 0.01%, particularly preferably 0.00005 to 0.005%, and even more preferably 0.0001 to 0.002%.

[0066] [Test Example 4] Oriental-type fragrance composition An oriental-type fragrance composition (manufactured by Ogawa Fragrance Co., Ltd.) prepared according to the formula shown in Table 10 was mixed with dihydrocalanone (manufactured by Ogawa Fragrance Co., Ltd.) classified in Test Example 1 at the concentrations shown in Table 9. The mixture was dropped onto filter paper in the same manner as in Test Example 1, and the residual fragrance after being left to stand for 12 hours under the same conditions was evaluated by 10 expert panelists who had been trained in advance. The evaluation results are shown in Table 11 below.

[0067] [Table 9]

[0068] [Table 10]

[0069] [Table 11]

[0070] The contents of the evaluation are as follows: Evaluation of lingering fragrance: The numbers in the table indicate the number of evaluators. Evaluation 1: Fragrance lingering is the same as in Comparative Example 7. Rating 2: Slightly improved lingering fragrance. Rating 3: The lingering scent has improved significantly. The blending amount of dihydrocalanone is suitably 0.00001 to 1%, preferably 0.00001 to 0.1%, further preferably 0.00001 to 0.01%, particularly preferably 0.00005 to 0.005%, and even more preferably 0.0001 to 0.002%.

[0071] Similar evaluation tests were also conducted on fragrance compositions of fruity, citrus, amber and herbal types other than those mentioned above, and it was confirmed that the incorporation of dihydrocalanone has the effect of improving the lingering fragrance of the fragrance composition in any fragrance type.

[0072] Furthermore, 2-isopropylidene-10-methyl-spiro[4,5]-6-decene-6-carbaldehyde, which was classified in Test Example 1 as a fragrance compound with low contribution but high lingering power, was also subjected to the same evaluation test as dihydrocalanone, and it was confirmed that the same lingering power was achieved by adding it to various types of fragrance compositions, and that the combined use of dihydrocalanone and 2-isopropylidene-10-methyl-spiro[4,5]-6-decene-6-carbaldehyde was also effective.

[0073] The technology for evaluating lingering fragrance of the present invention makes it possible to easily screen for lingering fragrance compounds and their fragrance tones. As a result, if the fragrance in Figure 2 does not contain the desired Group D, it is possible to improve the fragrance by supplementing the fragrance with a Group B fragrance compound that has a lingering fragrance tones instead. In addition, by using fragrance compounds with different lingering properties, it will be possible to develop cosmetic fragrances whose scent changes over time. By compiling the screened fragrance lingering properties and fragrance notes into a database, it will be possible to develop new fragrances by selecting the fragrance compounds to be used from the perspective of fragrance lingering properties.

[0074] [Example 16] Application of dihydrocalanone to perfume According to the formulation in Table 12 below, the floral fragrance prepared in Example 5 of Test Example 2 above was mixed with ethanol to prepare a fragrance sample. The fragrance sample had a pleasant lingering scent that remained a floral-type perfume.

[0075] [Table 12]

[0076] [Example 17] Application of dihydrocalanone to fragrances According to the recipe in Table 13, methylparaben, the floral fragrance prepared in Example 2, polyoxyethylene (POE) hydrogenated castor oil, ethanol, and water were mixed in that order to prepare a spray-type air freshener. The fragrance had a floral scent and the pleasant lingering scent lasted.

[0077] [Table 13]

[0078] [Example 18] Application of dihydrocalanone to skin care products According to the formulation in Table 14, 1,3-butylene glycol, glycerin, and methyl paraoxybenzoate were dissolved in ethanol and mixed with water to prepare a lotion base. To this was added PEG-20 sorbitan cocoate and the floral-type fragrance prepared in Example 1, which had been uniformly mixed in advance, to prepare a lotion. The lotion had a floral scent and the pleasant lingering scent lasted.

[0079] [Table 14]

[0080] [Example 19] Application of dihydrocalanone to hair care products According to the recipe in Table 15, the aqueous base was weighed into a beaker and mixed uniformly while heating at 85°C, and then an activator such as sodium cocoyl glutamate was added with stirring and dissolved uniformly, and 1% citric acid water and water were added and mixed uniformly. Finally, the floral type fragrance of Example 2 was added to the obtained mixture to prepare a shampoo. The shampoo had a floral scent and the pleasant lingering scent lasted.

[0081] [Table 15]

[0082] [Example 20] Application of dihydrocalanone to household products According to the formulation in Table 16, phase A was weighed into a beaker and mixed uniformly while heating at 80°C, and then phase B, which had been mixed uniformly at 80°C, was added and stirred with a homomixer. Finally, the fragrance of Example 2 was added to the resulting mixture to prepare a fabric softener. The fabric softener had a floral-type scent and the pleasant lingering scent lasted.

[0083] [Table 16]

[0084] The fragrance composition containing dihydrocalanone as a fragrance lingering agent was confirmed to have a long-lasting fragrance when blended in a fragrance product so that the fragrance concentration in the fragrance product was 0.2% (Example 18) to 10% (Example 16). Therefore, the blending amount of dihydrocalanone in fragrance products is suitably 0.2 ppb to 1000 ppm, preferably 0.2 ppb to 100 ppm, more preferably 0.2 ppb to 10 ppm, particularly preferably 1 ppb to 5 ppm, and even more preferably 2 ppb to 2 ppm.

Claims

1. The following steps: Step 1: A step of leaving the odorant in a space with constant temperature and humidity conditions; Step 2: A step of extracting aroma components contained in the odorous substance after a predetermined time from the start of standing; Step 3: subjecting the extracted aroma components to gas chromatography-olfactometry (GCO) analysis to detect the presence or absence of odor for each aroma compound constituting the aroma components; Step 4. A step of measuring the longest standing time (T) at which the odor of each of the aroma compounds constituting the odor substance can be detected for each aroma compound; and Step 5. In step 4, the longest standing time (Ta) at which the odor of a specific aroma compound A can be detected and the longest standing time (Tx) at which the odor of an aroma compound X having the longest T among the aroma compounds constituting the odor can be detected are used, and the Ta / Tx value is used as an evaluation value of the lingering odor of the aroma compound A contained in the odorous substance; A method for evaluating lingering fragrance properties for selecting compounds having high lingering fragrance compounds contained in odorous substances, comprising:

2. A method for evaluating the odor characteristics of an aroma compound A from the odor contribution degree of the aroma compound A contained in an odor substance and the odor lingering evaluation value (Ta / Tx) of the aroma compound A obtained by the method of claim 1.

3. The following formula 1 【Chemistry 1】 Dihydrocalanone represented by the formula: The following formula 2 【Chemistry 2】 The present invention relates to a fragrance-imparting agent having as an active ingredient 2-isopropylidene-10-methyl-spiro[4,5]-6-decene-6-carbaldehyde represented by the formula:

4. A fragrance composition comprising the residual fragrance imparting agent according to claim 3 (excluding fragrance compositions containing agarwood essential oil).

5. A method for imparting residual fragrance to a fragrance composition (excluding fragrance compositions containing agarwood essential oil) by blending the residual fragrance imparting agent according to claim 3.

6. A method for imparting residual fragrance to a fragrance composition (excluding fragrance compositions containing agarwood essential oil) by blending dihydrocalanone represented by formula 1 in the fragrance composition at a concentration of 0.00001 to 1%.

7. A fragrance product containing the fragrance composition according to claim 4 and having improved fragrance retention.

8. 8. The fragrance product according to claim 7, which is a personal care product such as a perfume, a makeup product, a skin care product, a hair care product, or a toiletry product, a household product, or a quasi-drug.

9. A method for imparting lingering fragrance to a fragrance product by blending the fragrance composition according to claim 4.

10. A method for imparting lingering fragrance to a fragrance product by blending dihydrocalanone represented by formula 1 in the fragrance product at a concentration of 0.2 ppb to 1000 ppm.

11. The method for imparting a lingering fragrance according to claim 10, wherein the fragrance product is a personal care product such as a perfume, a makeup product, a skin care product, a hair care product, or a toiletry product, a household product, or a quasi-drug.

12. The following steps: Step 1: A step of determining the residual odor evaluation value (P), odor contribution degree (Q) and odor note for each of the odor compounds constituting the odor of an odor substance according to the method of claim 1; Step 2: classifying, for each aroma compound, compounds satisfying 0<P<0.5 and 0<Q<0.5 into compound group A, compounds satisfying 0<P<0.5 and 0.5≦Q≦1 into compound group B, compounds satisfying 0.5≦P≦1 and 0<Q<0.5 into compound group C, and compounds satisfying 0.5≦P≦1 and 0.5≦Q≦1 into compound group D; Step 3: replacing the aroma compound b classified in compound group B with an aroma compound d classified in compound group D and having a similar odor note to the aroma compound b; A method for improving the aroma of an odorous substance, comprising:

13. A step of compiling a database of correlations between the fragrance notes and the fragrance lingering evaluation values ​​obtained by the method of claim 12 for a large number of fragrance compounds; Then, selecting components from the data when designing a fragrance composition whose fragrance note changes over time; A method for designing a fragrance composition comprising the steps of:

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