Method for evaluating the residual fragrance properties of fragrances, residual fragrance imparting agent, and method for improving residual fragrance properties.

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 is an evaluation method for searching for aroma compounds with high residual aroma properties and aroma compounds with high residual aroma properties and high contribution to aroma from a mixture of odor substances, such as a mixture of aroma compounds such as natural fragrances. Further, the present invention relates to a residual aroma-imparting agent found using this method, and further to an improved method for analyzing the characteristics of aroma components using this method to improve the residual aroma properties while having a similar fragrance tone in a fragrance composition.

Background Art

[0002] In fragrance products such as perfumes, makeup products, skin care products, hair care products, toiletries, household products, and air fresheners, the long-lasting presence of a scent (having residual aroma) brings a sense of satisfaction, freshness, and elation to consumers, and is also an important factor in enhancing the product value. Therefore, improving the residual aroma properties of fragrance products is important for the development of cosmetic fragrances used in fragrance products. Here, residual aroma refers to the fact that the scent lasts for a long time or has the property of lasting.

[0003] In the fragrance industry, when using highly volatile or low-residual fragrance components, in order to overcome the problem that the scent disappears in a short time, methods such as encapsulating the fragrance components in microcapsules to physically suppress the volatilization of the fragrance components (Patent Document 1) and using derivatives (profragrances) that can extend the effect of the active ingredients (Patent Document 2) have been studied.

[0004] However, the capsules and polymers used in encapsulated fragrances and profragrances are physically difficult to break and have low biodegradability, thus posing a problem of imposing a burden on the natural environment. In addition, the pleasantness and unpleasantness of odors are influenced by individual sensations. However, a fragrance with excellent palatability that is suitable for everyone is less likely to give discomfort to many people. Therefore, empirically, fragrances that are excellent in both residual aroma and palatability have been used as fragrances for fragrance products. As an example of such a technology, a method has been proposed in which the fragrance materials and natural and synthetic fragrances used in the blended fragrance are applied to scented paper, and fragrances are selected to leave a scent on the scented paper for up to 2 hours, up to 6 hours, and more than 6 hours, in order to blend the fragrance (Patent Document 3).

[0005] Furthermore, when natural fragrances are added to perfumes to impart lingering scent, it is difficult to achieve both a good fragrance profile and long-lasting scent. This is because the components contributing to the lingering fragrance in natural fragrances, which are composed of a wide variety of aromatic compounds, have not been elucidated, and because they also contain components that are unnecessary for lingering fragrance, it is difficult to balance the lingering fragrance with the desired scent profile. Therefore, selecting the natural fragrances to use and adjusting their proportions required a great deal of trial and error, which also affected the costs of product development.

[0006] Therefore, technologies have been explored to enhance the lingering fragrance without using natural fragrances. For example, methods have been developed to prolong floral, fruity, and green fragrances by adding fixatives to adjust the retention of fragrant substances (Patent Document 4), using vinylpyrrolidone / vinyl acetate copolymer as a fragrance extender (Patent Document 5), using highly aromatic 1-methyl-3,4-dioxy(cycloacetonyl)benzene (Patent Document 6), using a long-lasting fragrance composition containing a calculated log value (ClogP) ≥ 3.0 (P is the octanol / water partition coefficient) and a boiling point ≥ 250°C (Patent Document 7), and at a temperature of 25°C... Methods for creating fragrance compositions with high residual fragrance using solid, low-volatility fragrance components have been proposed (Patent Document 8).

[0007] In recent years, there has been growing interest in and demand for the use of natural fragrance components that are highly palatable and have a low impact on the natural environment. However, until now, there has been no means to search for and evaluate highly persistent fragrance compounds from natural fragrances, and to improve fragrance compositions based on that data, or to develop fragrance compositions with high residual fragrance.

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

[0009] However, while the above methods can qualitatively and quantitatively identify the contained aroma components and the aroma compounds that constitute them, they do not provide an accurate method for evaluating the residual scent of aroma compounds in natural fragrances, nor do they lead to the discovery of fragrance components that are high in both residual scent and palatability. In short, while sensory evaluation methods are generally used to assess fragrance characteristics and gas chromatography (GC) is used to analyze fragrance components, these methods have made it difficult to identify the active ingredients and fragrance compounds that contribute to the lingering fragrance of natural fragrances, and to comprehensively search for components and fragrance compounds with high lingering fragrance.

[0010] Therefore, the inventors have discovered and provided a new method for searching for and evaluating highly lingering fragrance compounds from among the many components contained in fragrances that have been used and are familiar since ancient times, or fragrances with natural aromas that are well-liked by many people, that is, highly palatable natural fragrances. Furthermore, we have discovered and provided a method for evaluating aroma characteristics based on the correlation between the quantified data obtained by the residual fragrance evaluation method and the quantified data regarding the contribution of the compound to the aroma characteristics in natural fragrances; a residual fragrance imparting agent discovered by this method; a method for imparting residual fragrance to fragrance products; an aroma improvement method that is excellent in both residual fragrance and palatability; and a method for developing fragrance compositions using the 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] Japanese Patent Publication No. 2002-327193 [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] Japanese Patent Publication No. 2009-242298 [Patent Document 9] Japanese Patent Publication No. 2007-163198 [Patent Document 10] Japanese Patent Publication No. 2003-107067 [Patent Document 11] Japanese Patent Publication No. 2004-325116 [Non-patent literature]

[0012] [Non-Patent Document 1] Tetsujiro Horiuchi, "The Cutting Edge of Fragrance Measurement Using Analytical Instruments," Journal of the Japan Society of Cosmetic Scientists, Vol. 32, No. 3 (September 1998), pp. 253-262.

Summary of the Invention

Problems to be Solved by the Invention

[0013] The problem of the present invention is to provide a residual fragrance evaluation method for identifying and quantifying highly residual fragrance compounds contained in odor substances, a method for evaluating the fragrance characteristics of fragrance compounds contained in odor substances based on the fragrance contribution degree and the residual fragrance evaluation value, and various new means for improving the residual fragrance of fragrances such as residual fragrance imparting agents.

Means for Solving the Problems

[0014] That is, the present invention is as follows. 〔1〕The following steps, Step 1. A step of leaving an odor substance to stand in a space with constant temperature and humidity conditions; Step 2. A step of extracting the fragrance components contained in the odor substance after a predetermined time from the start of standing; Step 3. Subjecting the extracted fragrance components to gas chromatography-olfactometry (GCO) analysis to detect the presence or absence of odor for each fragrance compound constituting the fragrance components; Step 4. A step of measuring, for each fragrance compound, the longest standing time (T) during which the odor of each fragrance compound constituting the odor substance can be detected, and, Step 5. In Step 4, using the longest standing time (Ta) during which the odor of a specific fragrance compound A can be detected, and the longest standing time (Tx) during which the odor of the fragrance compound X having the longest T among the fragrance compounds constituting the odor can be detected, and using the Ta / Tx value as the residual fragrance evaluation value of the fragrance compound A contained in the odor substance; A residual fragrance evaluation method for selecting highly residual fragrance compounds of fragrance compounds contained in an odor substance, characterized by including the above.

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

[0016] [4] A fragrance composition containing the fragrance-imparting agent described in item 3 above (excluding a fragrance composition containing agarwood essential oil). [5] A method for imparting a lasting fragrance to a fragrance composition (excluding a fragrance composition containing agarwood essential oil) by incorporating the fragrance imparting agent described in item 3 above. [6] A method for imparting residual fragrance to a fragrance composition (excluding fragrance compositions containing agarwood essential oil) by incorporating dihydrocalanone represented by formula 1 into the fragrance composition in an amount of 0.00001 to 1%. [7] A fragrance product containing the fragrance composition described in item 4 above, with improved residual fragrance. [8] A fragrance product as described in item 7 above, which is a personal care product, household product, or quasi-drug, which is a perfume, makeup product, skincare product, haircare product, or toiletry product.

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

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

[11] A method for imparting the lingering fragrance described in item 10 above, wherein the fragrance product is a personal care product such as a perfume, makeup product, skincare product, haircare product, or 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 odor substance, 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 classified into compound group D and having a fragrance tone similar to that of the aroma compound b; An odor substance 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 with 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 searched for and clarified. 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, a huge amount of 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 in response to consumer needs can be timely carried out in a short time.

Brief Explanation of Drawings

[0021] [Figure 1] This is a schematic diagram showing the relationship between standing time and sample number. [Figure 2] This is a correlation diagram between residual fragrance evaluation values ​​and fragrance contribution. [Modes for carrying out the invention]

[0022] In this invention, gas chromatography-olfactometry (GC-Olfactometry; abbreviated as GCO) analysis is performed by smelling the aroma compounds remaining in a sample of odor substances that have been left to stand for a specified period of time at the outlet of a gas chromatograph (GC), and superimposing the obtained information onto the GC information. By utilizing this method, we search for fragrance compounds that possess lingering scents, quantify their intensity (fragrance persistence), and evaluate them. Furthermore, AEDA (Aroma Extract Dilution Analysis) was used to determine the total odor of each aroma compound. By quantifying and evaluating the contribution of each fragrance to the body, and classifying (sorting) fragrance compounds using binary data of residual fragrance evaluation value and fragrance contribution, it is possible to identify and select active ingredients with high fragrance contribution and residual fragrance from among the many fragrance components contained in natural fragrances. The present invention will be described in detail below with reference to embodiments.

[0023] [1] Method for evaluating residual fragrance The present invention provides a method for evaluating residual fragrance to identify compounds with high residual fragrance content contained in odor substances, and consists of the following steps. In step 1, the odor substance is left to stand in a space where the temperature and humidity are kept constant. In step 2, the aromatic components contained in the odor substance are extracted after a predetermined time has elapsed since 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 odor for each aroma compound that makes up the aroma components. In step 4, the longest standing time (T) at which the odor of each aroma compound constituting the odor 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 constituting the odor substance, can be detected, are used, and the Ta / Tx value is used as the residual odor evaluation value for aroma compound A contained in the odor substance. The above process will be explained in more detail below.

[0024] (1) Regarding process 1 The odor substances subject to evaluation include natural plant-derived fragrances obtained from flowers, fruits, fruit juices, trees, vegetables, berries, seeds, spices, etc.; natural animal-derived fragrances obtained from ambergris, musk, knotweed, etc.; synthetic fragrances obtained by chemical or microbiological methods and composed of two or more aroma compounds; and food and beverages, cosmetics, etc. that have an odor and are available on the market. These odor substances may be purified and used by methods known in the field of fragrances, such as extraction, leaching, pressing, and distillation.

[0025] For evaluation, first, a sample is prepared by impregnating filter paper with odor substances. Then, considering the usage environment of the fragrance product, the temperature, humidity, and illuminance are adjusted to maintain constant conditions while the sample is standing. The space in which the sample is left to stand may be, for example, a constant temperature room, a constant temperature chamber, or a desiccator. By appropriately setting the temperature, humidity, and illuminance during the standing period, the lingering fragrance can be evaluated under various environmental conditions. For example, the temperature is 0-30°C, relative humidity is 40-90%, and illuminance is 0-100,000 lux. By using hair instead of filter paper during sample preparation, the lingering fragrance of hair care products such as hair dyes can be accurately evaluated. Similarly, by using clothing fabric, the lingering fragrance of household products such as detergents and fabric softeners can be accurately evaluated.

[0026] Here, fragrance products refer to perfumes, air fresheners, makeup products, toiletries, skincare products, haircare products, and household products, as listed below. "Perfume" refers to products such as eau de toilette, eau de parfum, and eau de cologne, and comes in bottle, roll-on, and spray types depending on its intended use.

[0027] Makeup products are used for aesthetic purposes, to enhance the beauty of the face, to protect the skin, and to provide enjoyment and satisfaction. This includes makeup cosmetics such as foundation, lipstick, lip balm, blush, eyeliner, mascara, eyeshadow, eyebrow pencil, loose powder, solid powder, nail polish, nail polish remover, etc.

[0028] "Skincare products" work by removing sweat and dirt, tightening the skin, maintaining proper nutrients and moisture, supporting a healthy skin condition, and protecting the skin from ultraviolet rays. The product line includes washing cream, vanishing cream, facial cleansing cream, cleansing cream, cold cream, sunscreen cream, lotion, toner, face mask, makeup remover, aftershave lotion, talcum powder, lip balm, hand cream, antiperspirant, and face care products (facial cleanser, makeup remover, cleansing oil, oil blotting paper, etc.).

[0029] "Hair care products" are used for cleansing and protecting hair and scalp, as well as for styling hair. They include shampoos, rinses and conditioners, tonics and hair oils that improve blood circulation in the scalp, pomades, sticks, hair liquids, setting lotions, hair gels, hair sprays, hair foams, hair waxes and other styling products, hair dyes such as hair color, hair manicures, bleaches, and gray hair dyes, hair styling agents such as perms and curling agents, and hair tonics and hair growth products such as hair treatments.

[0030] "Toiletries" include body care products such as soap, hand soap, bath salts, body wash, and lip balm; sunscreen, antiperspirant deodorants; shaving products (razors, hair removal razors, shaving foam, etc.); oral care products such as toothpaste, mouthwash, dental floss, and denture cleaner; wet wipes; disposable diapers; and feminine hygiene products.

[0031] "Household products" include laundry products such as detergents and fabric softeners, household and furniture products such as cleaners and waxes, kitchen products such as bleach and garbage deodorizers, and daily necessities such as office glue and paints, including liquid laundry detergent, powder laundry detergent, bar laundry soap, fabric softener, bleach for laundry, kitchen detergent, dishwasher detergent, These include bathroom cleaners, glass cleaners, mold removers, drain cleaners, fumigants, mosquito coils, insecticides, insect repellents, and toilet cleaners.

[0032] "Air fresheners" include water-based liquid air fresheners, oil-based liquid air fresheners, water-based gel air fresheners, oil-based gel air fresheners, fragrance sprays, fragrance aerosols, impregnated air fresheners, incense sticks, fragrance deodorizers, deodorizing sprays, and deodorizing aerosols.

[0033] (2) Regarding process 2 Next, as shown in Figure 1, the odor substance (Sn) remaining on the filter paper is collected after a certain period of time (Tn) from the start of standing. The standing time interval can be adjusted as appropriate depending on the purpose, but if the interval is too short, the number of experiments will increase and become complicated, and conversely, if it is too long, it will be difficult to distinguish between the residual scents of the aroma compounds, resulting in lower accuracy of the results. It is preferable to set the intervals at arithmetic or geometric intervals ranging from several tens of minutes to several hours. The recovery method is appropriately selected from methods such as solvent extraction, solid-phase extraction of headspace gas, and direct injection of headspace gas.

[0034] (3) Regarding steps 3-5 In the residual fragrance evaluation method of the present invention, a qualitative analysis of the fragrance components in the odor substance (Sn) after n hours (Tn) have elapsed from the start of standing (To) is performed by conventionally known GCO analysis. Here, GCO analysis is an analytical method that combines gas chromatography with detection methods using human olfaction. It involves branching the outlet of a gas chromatograph column, connecting one end to a detector (FID, MS, etc.) and the other end to a port that can detect odors, and controlling the apparatus so that detection can occur simultaneously at both the detector and the odor-sniffing port to analyze odor characteristics (Non-Patent Literature 1). A commercially available instrument can be used for GCO analysis as appropriate.

[0035] For each aroma component, the process is continued until the odor disappears, and GCO analysis is performed. The longest standing time (Tx) at which any component's odor can be detected is then measured. After the start of standing, the longest standing time (Ta) during which the odor of a specific aroma compound A can be detected, and the longest standing time (Tx) for aroma compound X among the aroma compounds constituting the odor substance, are defined as the Ta / Tx value (a value between 0 and 1) used to evaluate the residual odor of aroma compound A contained in the odor substance.

[0036] [2] Evaluation method using both residual fragrance evaluation value and fragrance contribution value By using both the residual fragrance evaluation value of the fragrance compound contained in the odor substance and the fragrance contribution of that fragrance compound, the fragrance characteristics of the fragrance compound can be evaluated more accurately, which can be useful for improving the fragrance of odor substances and developing new fragrances. In other words, the aroma contribution obtained by evaluating the aroma contribution of aroma compound A contained in the odor substance, and the residual scent evaluation value (Ta / Tx) of aroma compound A mentioned above, are used to determine the amount of aroma compound A contained in the odor substance. This is a method for evaluating the aroma properties of aroma compound A.

[0037] Dilution analysis can be used to measure the contribution of aroma. Dilution analysis is a method that uses GCO (Gas Coefficient of Spectroscopy), in which aroma components eluted from a GC column are smelled by a 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 analysis target are sequentially diluted at a predetermined magnification, and the GCO analysis is repeated for each component while increasing the dilution magnification sequentially until the odor disappears. The last dilution magnification at which the odor is felt for each component is defined as the FD factor of that component. That is, it is a method of identifying the components that can still be smelled until the end as the components with a high contribution degree.

[0039] The aroma contribution degree by CHARM analysis means that while performing AEDA, the time when the aroma 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 aroma 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 aroma property and contribution degree of each aroma compound contained in the odor substances.

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

[0042] Furthermore, when the residual aroma property evaluation value is quantified as P and the aroma contribution degree is quantified as Q (where 0 < P ≤ 1 and 0 < Q ≤ 1), Compounds with 0 < P < 0.5 and 0 < Q < 0.5 belong to compound group A, Compounds with 0 < P < 0.5 and 0.5 ≤ Q ≤ 1 belong to compound group B, Compounds with 0.5 ≤ P ≤ 1 and 0 < Q < 0.5 belong to compound group C, Compounds satisfying 0.5 ≤ P ≤ 1 and 0.5 ≤ Q ≤ 1 are grouped as compound group D. They can be classified as follows. Furthermore, compounds with a P value higher than 0.5 (for example, P>0.7) have superior residual fragrance properties, and compounds with a Q value higher than 0.5 (for example, P>0.7) have superior fragrance contribution.

[0043] [3] Aroma-imparting agent The inventors of this invention used the aforementioned residual fragrance evaluation method and a two-dimensional evaluation method of residual fragrance evaluation value and fragrance contribution to analyze and examine various fragrance compounds contained in agarwood (a representative fragrant wood) that has been used since ancient times and is highly palatable. Furthermore, among the aroma compounds contained in agarwood, dihydrocalanone and 2-isopropylidene-10-methyl-spiro[4,5]-6-decene-6-carbaldehyde were found to be effective as fragrance-residualing agents. In particular, dihydrocalanone showed excellent properties in both residual fragrance and fragrance contribution. Agarwood is derived from plants of the Aquilaria genus in the Thymelaeaceae family, and it is a fungal agent used to treat wounds on the wood. It is a sap secreted from the bark to defend against intrusion. The essential oil extracted from agarwood contains many components, including terpene alcohols.

[0044] Dihydrocalanone has the structure shown in Formula 1 below and possesses a woody, smoky fragrance. Although it is known to be an aromatic component found in agarwood such as Kyara, its use as an aromatic compound is unknown. [ka]

[0045] 2-Isopropylidene-10-methyl-spiro[4,5]-6-decene-6-carbaldehyde (J-GLOBALID: 200907023404424459, Nikkaji number: J664.750B) is the compound of formula 2 below. It is an aromatic compound with a structure and a woody scent. Its use as an aromatic compound has not been previously known. [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) Prepare seven pieces of filter paper with a diameter of 1 cm, each containing 5 μL of Thai agarwood essential oil (commercially available). Then, at room temperature (25°C), each filter paper was allowed to stand for 6 hours, 12 hours, 24 hours, 48 ​​hours, 96 hours, and 192 hours before being collected in a vial. 1 mL of dichloromethane was added to each vial, and solvent extraction was performed for 10 minutes to obtain samples S0, S6, and S. 12 ,S 24 ,S 48 S 96 S 192 I obtained it.

[0048] (Evaluation of lingering fragrance) Samples extracted at each time interval were subjected to GCO analysis under the conditions described below to evaluate the presence or absence of odor, its intensity, and its fragrance (character). Ta is the longest standing time at which the scent of fragrance component A can be perceived, and among the odor substances, it is the longest standing time. The standing time of the fragrance component whose odor could be detected was defined as Tx, and the residual fragrance evaluation value (Ta / Tx) was calculated. In Test Example 1, Tx was 96.

[0049] (Evaluation of the contribution to aroma) Thai agarwood essential oil was subjected to GCO (Global Coherence Occlusion), and the FD factors of each odor component were determined using the AEDA (Autonomous Physician-Assisted Aromatherapy) method. A sample was obtained by diluting Thai agarwood essential oil 256 times with 1 mL of dichloromethane. This sample was sequentially diluted four times, and measured using GCO until the odor could no longer be detected. Furthermore, the dilution ratio at which the odor of each aroma compound could no longer be detected (1 / 4) was determined. n ) From FD Factory Turn n was found. Next, the ratio of the FD factor of each aroma compound to the highest FD factor among the odor substances was evaluated as the aroma contribution (Q).

[0050] (GCO analysis conditions) Equipment: 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) Heating conditions: 40°C to 210°C at a rate of 5°C / min Carrier gas: He (1 ml / min)

[0051] Table 1 summarizes the residual fragrance evaluation values ​​and fragrance contributions for each fragrance compound detected from agarwood essential oil. "RI" in the table indicates the Retention Index.

[0052] [Table 1]

[0053] Based on the above results, the relationship between the residual fragrance evaluation value and the fragrance contribution of each fragrance compound was classified according to Figure 2. Aroma compounds were classified as D if they had a high contribution to the aroma, meaning they had a high contribution to the aroma of agarwood essential oil and also had a high residual scent evaluation value; C if they had a low contribution to the aroma but a high residual scent evaluation value; B if they had a high contribution to the aroma but a low residual scent evaluation value; and A if they had a low contribution to the aroma and a low residual scent evaluation value. The aroma compounds that were classified into A to D and identified are summarized in Table 2.

[0054] The classifications A through D are as follows: A: Compounds where 0 < residual fragrance evaluation value < 0.5 and 0 < fragrance contribution < 0.5 B: Compounds where 0 < residual fragrance evaluation value < 0.5 and 0.5 ≤ fragrance contribution ≤ 1. C: Compounds where 0.5 ≤ residual fragrance evaluation value ≤ 1 and 0 < fragrance contribution < 0.5. Compounds where D: 0.5 ≤ residual fragrance evaluation value ≤ 1 and 0.5 ≤ fragrance contribution ≤ 1

[0055] [Table 2]

[0056] [Test Example 2] Floral-type fragrance composition Floral-type fragrance compositions (manufactured by Ogawa Fragrance Co., Ltd.) prepared according to the formulations listed in Table 4 were mixed with dihydrocalanone (manufactured by Ogawa Fragrance Co., Ltd.), which was classified in Test Example 1 as an aroma compound with high fragrance contribution and long-lasting fragrance, at the concentrations listed in Table 3. The mixture was then dropped onto filter paper in the same manner as in Test Example 1, and the long-lasting fragrance after standing 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 5 below.

[0057] [Table 3]

[0058] [Table 4]

[0059] [Table 5]

[0060] The evaluation details are as follows: Fragrance Residue Evaluation: The numbers in the table represent the number of evaluators. Evaluation 1: The lingering fragrance is the same as in Comparative Example 1. Rating 2: The lingering scent has slightly improved. Rating 3: The lingering scent has improved significantly. The appropriate concentration of dihydrocalanone was 0.00001 to 1%, preferably 0.00001 to 0.1%, more 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 formulations listed in Table 7 was mixed with dihydrocalanone (manufactured by Ogawa Fragrance Co., Ltd.) classified in Test Example 1 at the concentrations listed in Table 6. The mixture was dropped onto filter paper in the same manner as in Test Example 1, and the residual fragrance after standing for 12 hours under the same conditions was evaluated by 10 pre-trained expert panelists. The evaluation results are shown in Table 8 below.

[0062] [Table 6]

[0063] [Table 7]

[0064] [Table 8]

[0065] The evaluation is as follows: Fragrance Residue Evaluation: The numbers in the table represent the number of evaluators. Evaluation 1: The lingering fragrance is the same as in Comparative Example 4. Rating 2: The lingering scent has slightly improved. Rating 3: The lingering scent has improved significantly. The appropriate concentration of dihydrocalanone was 0.00001 to 1%, preferably 0.00001 to 0.1%, more 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 Oriental-type fragrance compositions (manufactured by Ogawa Fragrance Co., Ltd.) prepared according to the formulations listed in Table 10 were mixed with dihydrocalanone (manufactured by Ogawa Fragrance Co., Ltd.) classified in Test Example 1 at the concentrations listed in Table 9. The mixture was then dropped onto filter paper in the same manner as in Test Example 1, and the residual fragrance after standing 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 evaluation is as follows: Fragrance Residue Evaluation: The numbers in the table represent the number of evaluators. Evaluation 1: The lingering fragrance is the same as in Comparative Example 7. Rating 2: The lingering scent has slightly improved. Rating 3: The lingering scent has improved significantly. The appropriate concentration of dihydrocalanone was 0.00001 to 1%, preferably 0.00001 to 0.1%, more 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 conducted on fruity, citrus, amber, and herbal fragrance compositions with scent profiles other than those mentioned above. It was confirmed that the inclusion of dihydrocalanone in all fragrance profiles improved the lingering scent of the fragrance composition.

[0072] Furthermore, in the aforementioned Test Example 1, 2-isopropylidene-10-methyl-spiro[4,5]-6-decene-6-carbaldehyde, which was classified as an aroma compound with a low contribution but high residual fragrance, was also subjected to evaluation tests similar to those for dihydrocalanone. It was confirmed that incorporating it into various types of fragrance compositions has a similar effect in improving residual fragrance, and that using dihydrocalanone and 2-isopropylidene-10-methyl-spiro[4,5]-6-decene-6-carbaldehyde in combination is also effective.

[0073] By using the residual fragrance evaluation technology of the present invention, it becomes possible to easily screen for highly residual fragrance compounds and their fragrance profiles. As a result, if the desired group D is not present in the fragrance shown in Figure 2, the fragrance of the fragrance can be improved by supplementing it with a highly residual fragrance compound from group B with a suitable fragrance profile. Furthermore, by using fragrance compounds with different residual properties, it becomes possible to develop cosmetic fragrances whose scent changes over time. By creating a database of screened residual scents and fragrance profiles, it becomes possible to develop new fragrances by selecting fragrance compounds based on their residual scent properties.

[0074] [Example 16] Application of dihydrocalanone to perfume A fragrance sample was prepared by mixing the floral fragrance prepared in Example 5 of Test Example 2 with ethanol, according to the formulation shown in Table 12 below. The fragrance sample maintained a pleasant lingering scent, retaining the floral fragrance profile of the perfume.

[0075] [Table 12]

[0076] [Example 17] Application of dihydrocalanone to fragrances A spray-type fragrance was prepared by sequentially mixing methylparaben, the floral fragrance prepared in Example 2, polyoxyethylene (POE) hydrogenated castor oil, ethanol, and water according to the formulation in Table 13. The floral-type fragrance remained, leaving a pleasant lingering scent.

[0077] [Table 13]

[0078] [Example 18] Application of dihydrocalanone to skincare products According to the formulation in Table 14, 1,3-butylene glycol, glycerin, and methyl parahydroxybenzoate were dissolved in ethanol and mixed with water to prepare a lotion base. To this base, pre-mixed PEG-20 sorbitan cocoate and the floral fragrance prepared in Example 1 were added to prepare the lotion. The lotion retained its floral fragrance, leaving a pleasant aftertaste.

[0079] [Table 14]

[0080] [Example 19] Application of dihydrocalanone to hair care products Following the formulation in Table 15, the aqueous base was measured into a beaker and mixed uniformly while being heated at 85°C. Then, while stirring, an activator such as sodium cocoyl glutamate was added and dissolved uniformly, and 1% citric acid solution and water were added and mixed uniformly. Finally, the floral fragrance of Example 2 was added to the resulting mixture to prepare the shampoo. The shampoo retained its pleasant floral fragrance, and the lingering scent was long-lasting.

[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, mixed uniformly while being heated to 80°C, and then phase B, which had been mixed uniformly at 80°C, was added and stirred with a homomixer. Finally, the fragrance from Example 2 was added to the resulting mixture to prepare a fabric softener. The pleasant floral scent of the fabric softener lingered for a long time.

[0083] [Table 16]

[0084] Fragrance compositions containing dihydrocalanone as a fragrance-residual agent demonstrated sustained fragrance retention in fragrance products where the fragrance concentration ranged from 0.2% (Example 18) to 10% (Example 16). Therefore, the appropriate concentration of dihydrocalanone in fragrance products was 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 most preferably 2 ppb to 2 ppm.

Claims

1. Formula 1 below 【Chemistry 1】 Dihydrocalanone and / or represented by Formula 2 below 【Chemistry 2】 A fragrance imparting agent comprising 2-isopropylidene-10-methyl-spiro[4,5]-6-decene-6-carbaldehyde as the active ingredient.

2. A method for imparting a lingering fragrance to a fragrance composition (excluding a fragrance composition containing agarwood essential oil) by incorporating the lingering fragrance imparting agent described in claim 1.

3. A method for imparting residual fragrance to a fragrance composition (excluding fragrance compositions containing agarwood essential oil) by incorporating dihydrocalanone represented by Formula 1 in an amount of 0.00001 to 1%.

4. A method for imparting a lingering fragrance to a fragrance product by incorporating the lingering fragrance imparting agent described in claim 1.

5. A method for imparting a lingering fragrance to a fragrance product by incorporating dihydrocalanone represented by Formula 1 in a concentration of 0.2 ppb to 1000 ppm.

6. The method for imparting lingering fragrance according to claim 5, wherein the fragrance product is a personal care product such as a perfume, makeup product, skincare product, haircare product, or toiletry product, a household product, or a quasi-drug.

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