JP2022068828A - Perfume scent-lingering property evaluation method, scent-lingering property imparting agent, and scent-lingering property improvement method - Google Patents

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

Application for application of Article 30, Paragraph 2 of the Patent Act Published in "The 64th Debate on Fragrances, Terpenes and Essential Oil Chemistry" issued on October 24, 2nd year of Reiwa.

The present invention is an evaluation method for searching for an aroma compound having a high residual aroma and a high residual aroma and a high contribution to aroma from a mixture of aroma compounds such as an odor substance, for example, a natural fragrance. In addition, a residual fragrance-imparting agent found using this method, and further, a fragrance composition that enhances the residual fragrance while having a similar fragrance tone by analyzing the characteristics of the aroma component using this method. Regarding how to improve.

In fragrance products such as perfumes, makeup products, skin care products, hair care products, toiletry products, household products, fragrances, etc., the long-lasting fragrance (having residual fragrance) is consumer satisfaction. It is an important factor to bring about a feeling of exhilaration and exhilaration, and to increase the commercial value. Therefore, improving the residual fragrance of aromatic products is important for the development of cosmetic fragrances (fragrances) used in aromatic products. Here, the residual scent refers to the property that the scent lasts for a long time or lasts.

In the fragrance industry, in order to overcome the problem that the fragrance disappears in a short time when using a fragrance ingredient with high volatility or low persistence, the fragrance ingredient is physically encapsulated in a microcapsule. A method of suppressing volatility of the active ingredient (Patent Document 1) and a method of using a derivative (profragrance) capable of extending the effect of the active ingredient (Patent Document 2) have been studied.

However, capsules and polymers used for encapsulated fragrances and professions are physically hard to break and have low biodegradability, which raises the problem of imposing a load on the natural environment.
Further, the pleasant sensation and the unpleasant sensation of the odor depend on the sensation of each individual, but the scent having excellent palatability and suitable for all people is less likely to cause unpleasant sensation to many people. Therefore, empirically, we have used fragrances that are excellent in both residual fragrance and palatability as fragrances used in fragrance products.
As such a technique, for example, the fragrance material of the compounded fragrance and the natural and synthetic fragrances used are attached to the fragrance paper, and the fragrance that leaves the odor on the odor paper for up to 2 hours, up to 6 hours, and 6 hours or more is selected. A method for formulating a fragrance has been proposed (Patent Document 3).

Further, when a natural fragrance is blended for the purpose of imparting residual fragrance to a fragrance fragrance, it is difficult to achieve both excellent fragrance tone and residual fragrance.
This is because the residual fragrance-contributing component in a natural fragrance composed of a wide variety of aroma components has not been clarified, and since some components are unnecessary for the residual fragrance, the balance between the residual fragrance and the target fragrance tone. Because it is difficult to take.
Therefore, a huge amount of trial and error was required to select the natural fragrance to be used and to adjust the blending amount, which also affected the cost of product development.

Therefore, a technique for enhancing only the residual fragrance without using a natural fragrance has been studied. For example, a method of sustaining a floral fruity green type scent by adding a retaining agent for adjusting the retention of a fragrant substance (Patent Document 4), a vinylpyrrolidone / vinyl acetate copolymer is used as an aroma extender. Method (Patent Document 5), Method using highly aromatic 1-methyl-3,4-dioxy (cycloacetonyl) benzene (Patent Document 6), Calculation log value (ClogP) ≧ 3.0 (P is octanol) / Water distribution coefficient) and a method using a persistent fragrance composition containing a component having a boiling point ≥250 ° C (Patent Document 7), a fragrance component that is solid and has low volatility at a temperature of 25 ° C and has a high residual scent. A method for producing a fragrance composition (Patent Document 8) and the like have been proposed.

In recent years, attention has been paid to the use of natural fragrance components that are highly palatable and have a low burden on the natural environment. However, there has been no means to search for and evaluate a long-lasting fragrance compound from natural fragrances and improve the fragrance composition based on the data, or to develop a fragrance composition having a high residual fragrance.

On the other hand, as a method for analyzing the aroma characteristics of each aroma component in a natural flavor, the aroma component in the coffee aroma concentrate is separated by gas chromatography (GC) and mixed with a coffee extract for evaluation for sensory evaluation. (Patent Document 9), the aroma component in the coffee aroma concentrate separated by GC and the headspace sample of the coffee extract are continuously mixed and the aroma thereof. (Patent Document 10), GCO analysis method for sensory evaluation (orfactometry) of aroma components separated by GC and aroma extract dilution analysis (AEDA) are combined to make each aroma component. (Patent Document 11) has been proposed in which the FD factor of the above is obtained, the threshold value of each aroma component is integrated with the FD factor, and the concentration of the trace aroma component in coffee beans is converted.

However, in any of the above methods, although the aroma component contained and the aroma compound constituting the aroma component can be qualified and quantified, the method for accurately evaluating the residual aroma of the aroma compound in the natural fragrance is not available. It was not possible to search for a fragrance component that had neither residual fragrance nor palatability.
In short, in general, a sensory evaluation method is used to evaluate the fragrance tone, and a gas chromatography (GC) analysis technique is used to analyze the fragrance component. In these methods, the residual fragrance contained in the natural fragrance is used. It was difficult to identify active ingredients and aroma compounds that contribute to the above, and to comprehensively search for ingredients and aroma compounds with high residual aroma.

Therefore, the present inventor has selected from among many components contained in fragrances that have been used for a long time and are familiar to people, or fragrances that are natural fragrances that many people like, that is, natural fragrances with high palatability. We have found and provided a new method for searching for and evaluating aroma compounds with high residual fragrance.
Further, 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 aroma characteristics to the natural fragrance of the compound, found by the method. We have found and provided a residual fragrance-imparting agent, a method for imparting residual fragrance to fragrance products, a fragrance improving method having excellent residual fragrance and palatability, and a method for developing a fragrance composition using a new method. ..

Special Table 2010-520928 Gazette Japanese Patent Publication No. 2008-531761 Japanese Unexamined Patent Publication No. 2002-327193 Japanese Patent No. 5025845 Special Table 2017-520543 Japanese Patent No. 501254 Special Table No. 10-507789 Gazette JP-A-2009-242298 Japanese Unexamined Patent Publication No. 2007-163198 Japanese Unexamined Patent Publication No. 2003-107067 Japanese Unexamined Patent Publication No. 2004-325116

Tetsujiro Horiuchi "Forefront of Fragrance Measurement with Analytical Instruments", Journal of Society of Cosmetic Chemists, Vol. 32, No. 3 (September 1998 issue), pp. 253-262

The subject of the present invention is a method for evaluating a residual scent for identifying and quantifying a compound having a high residual scent contained in an odorous substance, and an aroma of an aroma compound contained in the scent substance based on an aroma contribution and a residual aroma evaluation value. It is to provide a method for evaluating the characteristics and new means for improving the residual scent of a fragrance such as a residual scent imparting agent.

That is, the present invention is as follows.
[1] The following steps,
Process 1. The process of allowing odorous substances to stand in a space with constant temperature and humidity.
Process 2. The process of extracting the aroma component contained in the odorant after a predetermined time from the start of standing,
Process 3. A step of subjecting the extracted aroma component to gas chromatography orfactometry (GCO) analysis and detecting the presence or absence of an odor for each aroma compound constituting the aroma component.
Process 4. The step of measuring the longest standing time (T) at which the odor of each aroma compound constituting the odorant can be detected for each aroma compound, and
Process 5. In step 4, the longest standing time (Ta) in which the odor of the specific aroma compound A can be detected, and the longest static in which the odor of the aroma compound X having the longest T among the aroma compounds constituting the odor can be detected. A step of using the standing time (Tx) to set the Ta / Tx value as the residual aroma evaluation value of the aroma compound A contained in the odorant.
A method for evaluating a residual scent for selecting a compound having a high residual scent of an aroma compound contained in an odorant, which comprises.

で表されるジヒドロカラノン及び／又は
下記式２

で表される２－イソプロピリデン－１０－メチル－スピロ[４，５]－６－デセン－６－カルバルデヒドを有効成分とする残香性付与剤。 [2] The aroma characteristics of the aroma compound A are evaluated from the aroma contribution of the aroma compound A contained in the odorant and the residual aroma evaluation value (Ta / Tx) of the aroma compound A obtained by the method of claim 1. Method.
[3] The following formula 1

Dihydrocaranone represented by and / or the following formula 2

2-Isopropylidene-10-methyl-spiro [4,5] -6-decene-6-carbaldehyde as an active ingredient, which is a residual fragrance enhancer.

[4] A fragrance composition containing the residual fragrance-imparting agent according to 3 above (however, the fragrance composition containing an agarwood essential oil is excluded).
[5] A method for imparting residual fragrance to a fragrance composition (excluding a fragrance composition containing agarwood essential oil) by blending the residual fragrance-imparting agent according to 3 above.
[6] A fragrance composition by blending dihydrocaranone represented by the formula 1 in a fragrance composition so as to be 0.00001 to 1% (however, the fragrance composition containing agarwood essential oil is excluded). A method of imparting residual fragrance to.
[7] A fragrance product containing the fragrance composition according to 4 above and having improved residual aroma.
[8] The fragrance product according to 7 above, wherein the fragrance product is a perfume, a make-up product, a skin care product, a hair care product, a personal care product that is a toiletry product, a household product, or a quasi-drug.

[9] A method for imparting residual fragrance to a fragrance product by blending the fragrance composition according to 4 above.
[10] A method for imparting residual fragrance to a fragrance product by blending dihydrocaranone represented by the formula 1 in a fragrance product so as to have a concentration of 0.2 ppb to 1000 ppm.
[11] The method for imparting residual fragrance according to the above 10, wherein the fragrance product is a perfume, a make-up product, a skin care product, a hair care product, a personal care product that is a toiletry product, a household product, or a quasi-drug.

[12] The following steps,
Step 1: A step of specifying the residual scent evaluation value (P), the scent contribution (Q), and the scent tone by the method 1 above for each scent compound constituting the scent of the odorous substance.
Step 2: For each aroma compound, a compound having 0 <P <0.5 and 0 <Q <0.5 is used as a compound group A, and a compound having 0 <P <0.5 and 0.5 ≦ Q ≦ 1 is used. Compound group B, a compound having 0.5 ≦ P ≦ 1 and 0 <Q <0.5 as compound group C, and a compound having 0.5 ≦ P ≦ 1 and 0.5 ≦ Q ≦ 1 as compound group D. Sorting process,
Step 3: A step of replacing the aroma compound b classified in the compound group B with an aroma compound d classified in the compound group D and having a similar aroma tone to the aroma compound b.
A method for improving the aroma of an odorant, which is characterized by containing.

[13] For a large number of aroma compounds, a step of creating a database of the correlation between the residual aroma evaluation value and the aroma tone by the above 12 methods;
Next, when designing a fragrance composition whose fragrance tone changes with the passage of time, a step of selecting a constituent component from the above data;
A method for designing a fragrance composition, which comprises.

INDUSTRIAL APPLICABILITY According to the present invention, even a complex composition such as a natural fragrance or a natural essential oil can be searched for and elucidated a component having high importance in terms of both residual fragrance and contribution to fragrance, and the fragrance found thereby. By adding the compound as a residual fragrance enhancer to other fragrance compositions, the residual fragrance can be improved without causing discomfort.
Therefore, in the development of new fragrance compositions for fragrance products and the improvement and improvement of conventional products, the enormous amount of trial and error work and processes that have traditionally been required for selecting fragrances and determining the blending amount have been greatly shortened. , Simplification, efficiency and labor saving.
As a result, the labor, time and cost required for product development can be significantly reduced, and product design, development and improvement according to consumer needs can be performed in a short time and in a timely manner.

It is a schematic diagram of a standing time and a sample number. It is a correlation diagram of the residual fragrance evaluation value and the aroma contribution degree.

In the present invention, an aroma compound remaining in a sample of an odorous substance that has been allowed to stand for an arbitrary time is smelled at a gas chromatography (GC) outlet, and the obtained information is superimposed on the GC information. By utilizing a factometry (GC-Olfactometry; abbreviated as GCO) analysis method, an aroma compound having a residual scent is searched for, and its intensity (persistence of scent) is quantified and evaluated.
Furthermore, the contribution of each aroma compound to the entire odor is quantified and evaluated by AEDA (Aroma Extract Dilution Analysis), and the aroma compounds are classified (sorted) by the binary data of the residual aroma evaluation value and the aroma contribution. From many fragrance components contained in natural fragrances, an active ingredient having a high fragrance contribution and residual fragrance can be specified and selected.
Hereinafter, the present invention will be described in detail according to an embodiment.

[1] Residual scent evaluation method The residual scent evaluation method for identifying a compound having a high residual scent contained in an odorant according to the present invention comprises the following steps (steps).
In step 1, the odorant is allowed to stand in a space where the temperature and humidity are constant.
In step 2, the aroma component contained in the odorant is extracted after a predetermined time from the start of standing.
In step 3, the extracted aroma component is subjected to gas chromatography orfactometry (GCO) analysis, and the presence or absence of an odor is detected for each aroma compound constituting the aroma component.
In step 4, the longest standing time (T) at which the odor of each aroma compound constituting the odorous substance can be detected is measured for each aroma compound.
In step 5, in step 4, the longest standing time (Ta) at which the odor of the specific aroma compound A can be detected, and the odor of the aroma compound X having the longest T among the aroma compounds constituting the odorant are exhibited. The longest standing time (Tx) that can be detected is used, and the Ta / Tx value is used as the residual aroma evaluation value of the aroma compound A contained in the odorant.
Hereinafter, the above process will be described in more detail.

(1) About Step 1 The odorants to be evaluated are natural vegetable fragrances obtained from flowers, fruits, fruit juices, trees, vegetables, fruits, seeds, spices, etc., ambergris, and musk. (Musk), natural animal flavors obtained from ambergris, synthetic flavors obtained by chemical and microbial methods, composed of two or more aroma compounds, foods and drinks with commercially available odors Goods, fragrances, etc. These odorants may be purified and used by methods known in the fragrance field, such as extraction, leaching, squeezing, and distillation.

In the evaluation, first prepare a sample in which odorous substances are impregnated into filter paper, and then maintain constant conditions while the temperature, humidity, illuminance, etc. are kept still, considering the usage environment of the fragrance product. Adjust so that. The space to stand still is, for example, a constant temperature room, a constant temperature machine, a desiccator, or the like.
By appropriately setting the temperature, humidity, illuminance, etc. when standing still, it is possible to evaluate the residual fragrance in 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.
By using hair instead of filter paper when preparing samples, it is possible to accurately evaluate the residual fragrance of fragrances for hair care products such as hair dyes, and by using clothing fabrics, detergents and fabric softeners can be used. It is possible to accurately evaluate the residual fragrance of fragrances for house hold products.

Here, the fragrance product refers to a perfume, a fragrance, a make-up product, a toiletry product, a skin care product, a hair care product, and a household product as shown below.
"Perfume" refers to eau de toilette, eau de parfum, cologne, etc., and there are bottle type, roll type, and spray type according to the application.

"Makeup products" are used for the purpose of making the face look beautiful, protecting the skin, and bringing fun and satisfaction.
There are makeup cosmetics such as foundation, lipstick, lip cream, blusher, eyeliner, mascara, eyeshadow, eyebrow, eyebrow, powder powder, solid powder, nail enamel, nail polish, nail polish remover, etc.

"Skin care products" remove sweat and dirt, attract the skin, maintain proper nutrients and moisture, assist normal skin condition, and protect the skin from UV rays.
Washing cream, vanishing cream, face wash cream, cleansing cream, cold cream, sunscreen cream, milky lotion, lotion, pack, makeup remover, after shaving lotion, talcum powder, lip cream, hand cream, antiperspirant, face care (face wash) There are foam, makeup remover, cleansing oil, oil remover, etc.).

"Hair care products" are used for cleaning and protecting hair and scalp and setting hair, such as shampoo, conditioner, tonic and hair oil to improve blood circulation in scalp, pomade, tic, hair liquid, set lotion, etc. Hair styling products such as hair gels, hair sprays, hair foams and hair waxes, hair coloring agents such as hair coloring, hair manicure, bleaching and gray hair dyeing, hair deforming agents such as perms and curling agents, hair growth agents such as hair treatments, etc. be.

"Toiletries products" include body care products such as soaps, hand soaps, bathing agents, body shampoos, and lip balms, sunscreens, antiperspirant deodorants, shavings (razors, waste hair treatment razors, shaving foams, etc.), toothpaste, and washing. Oral care products such as mouthwash, dental floss, and artificial tooth cleaners, wet tissues, paper razors, sanitary products, etc.

"Household products" are clothing products such as detergents and soft finishes used in ordinary households, household and furniture products such as cleaners and waxes, and kitchen products such as bleaching agents and garbage deodorants. , Office glue, daily miscellaneous goods such as paints, liquid detergent for clothing, powder detergent for clothing, solid soap for clothing, soft finishing agent for clothing, bleaching agent for clothing, detergent for kitchen, detergent for dish dryer,
There are bath cleaners, glass cleaners, mold removers, drain pipe cleaners, smoke agents, mosquito coils, insecticides, insect repellents, toilet cleaners, etc.

"Air freshener" includes water-based liquid air freshener, oil-based liquid air freshener, water-based gel air freshener, oil-based gel air freshener, fragrance spray, fragrance aerosol, impregnated fragrance, incense, fragrance deodorant, deodorant spray, deodorant. There are odor aerosols and so on.

(2) Step 2 Then, as shown in FIG. 1, after a certain period of time (Tn) from the start of standing, the odorous substance (Sn) remaining on the filter paper is recovered. The interval of the standing time can be adjusted as appropriate according to the purpose, but if the interval is too short, the number of experiments will increase and it will be complicated. Become. It is preferably set at equal differences or geometric intervals in the range of 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.

(3) Steps 3 to 5 In the method for evaluating residual fragrance of the present invention, the aroma component in the odorant (Sn) n hours after the start of standing (To) (Tn) by the conventionally known GCO analysis. Perform a qualitative analysis of.
Here, GCO analysis is an analysis method that combines gas chromatography and detection means by human sense of smell, branching the outlet of the column of the gas chromatograph, and one is to the detector (FID, MS, etc.). One is a method of analyzing odor characteristics by connecting to a port capable of smelling and controlling the device so that the detector and the smelling port can detect at the same time (Non-Patent Document 1).
As the device for GCO analysis, a commercially available device can be appropriately used.

Standing and GCO analysis are continued until the odor of each aroma component disappears, and the longest standing time (Tx) at which the odor of any component is felt is measured.
After the start of standing, the longest standing time (Ta) in which the odor of a specific aroma compound A can be detected, and the longest standing time (Tx) in which the odor can be detected among the aroma compounds constituting the odorous substance. ), The Ta / Tx value (a value in the range of more than 0 to 1) is used as the residual scent evaluation value of the aroma compound A contained in the odorant.

[2] Evaluation method using the residual scent evaluation value and the aroma contribution degree by using the residual scent evaluation value of the aroma compound contained in the odorant and the aroma contribution of the aroma compound together, the aroma characteristics of the aroma compound can be obtained. It can be evaluated more accurately and can be used for improving the aroma of odorous substances and developing new fragrances.
That is, from the aroma contribution obtained by evaluating the aroma contribution of the aroma compound A contained in the odorant and the residual aroma evaluation value (Ta / Tx) of the aroma compound A described above, the aroma compound contained in the odorant. This is a method for evaluating the aroma characteristics of A.

A dilution analysis method can be used as a method for measuring the aroma contribution. The dilution analysis method is a method using GCO that smells the aroma component eluted from the GC column with the human nose, and includes AEDA (Aroma Extract Dilution Analysis) and CHARM (Combined Hedonic Aroma Response Measurement) analysis.

The aroma contribution by AEDA means that the odorous substances of the analysis target are sequentially diluted at a predetermined magnification, the dilution ratio is increased sequentially, and the GCO analysis is repeated until the odor disappears for each component, and the odor is felt for each component at the end. The dilution ratio of the above is taken as the FD factor of the component. In other words, it is a method of identifying a component whose odor is felt until the end as a component having a high degree of contribution.

The scent contribution by CHARM analysis is a method of simultaneously recording the time when the scent is felt while performing AEDA, and two-dimensionally recording the scent contribution of each component as the peak area (Charm Value) of the chromatogram. ..

By arranging the residual scent Ta / Tx obtained by GCO analysis of the scent component in the odor substance after standing and the scent contribution required by the dilution analysis method, each scent compound contained in the scent substance It is possible to comprehensively evaluate the residual scent and the degree of contribution.

FIG. 2 shows an evaluation example based on the residual aroma evaluation value (Ta / Tx) and the aroma contribution.
The classification of A to D in FIG. 2 is as follows.
A: Aroma compound with low residual aroma evaluation value and low aroma contribution B: Aroma compound with low residual aroma evaluation value but high aroma contribution C: Aroma compound with high residual aroma evaluation value but low aroma contribution D: Residual aroma Aroma compounds with high sexual evaluation values and high aroma contribution

Further, when the residual fragrance evaluation value is quantified as P and the aroma contribution is quantified as Q (here, 0 <P ≦ 1 and 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 having 0.5 ≦ P ≦ 1 and 0.5 ≦ Q ≦ 1 are compounded in the compound group D.
Can be classified as. When the P value is higher than 0.5 (for example, P> 0.7), the residual fragrance property is excellent, and when the Q value is higher than 0.5 (for example, P> 0.7), the fragrance contribution is excellent. ..

[3] Aroma imparting agent The present inventor makes full use of the above-mentioned residual fragrance evaluation method, residual fragrance evaluation value and two-dimensional evaluation method of aroma contribution, and has been used since ancient times and has high palatability. ), Various aroma compounds contained in) were analyzed and examined.
Among the aroma compounds contained in agarwood, dihydrocaranone and 2-isopropyridene-10-methyl-spiro [4,5] -6-decene-6-carbaldehyde are effective as fragrance residual aroma-imparting agents. I found that. In particular, dihydrocaranone was excellent in both residual aroma and aroma contribution.
Agarwood is a basic plant of the genus Aquilaria of the family Thymelaeaceae, and is a sap produced from the bark to prevent the invasion of bacteria against wounds on trees. The essential oil extracted from agarwood contains many components such as terpene alcohol.

Dihydrocaranone has the structure of the following formula 1 and has woody and fumigation. Although it is known to be an aroma component contained in agarwood and the like, its use as an agar compound is not known.

2-Isopropylidene-10-methyl-spiro [4,5] -6-decene-6-calbaldehide (J-GLOBALID: 200907023404424459, Nikkaji number: J664.750B) has the structure of the following formula 2 and is woody. It is an aroma component having an incense. Until now, its use as an aroma compound has not been known.

Next, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples.

[Test Example 1] Agarwood essential oil (sample preparation)
Prepare 7 sheets of odorous substance in which 5 μL of Thai-produced liquid-liquid essential oil (commercially available) was dropped on a filter paper having a diameter of 1 cm, and immediately after standing at room temperature of 25 ° C., 6 hours, 12 hours, 24 hours, 48 hours, 96 hours, Each filter paper that had been allowed to stand for 192 hours was collected in a vial, 1 mL of dichloromethane was added thereto, and solvent extraction was performed for 10 minutes to obtain samples S ₀ , S ₆ , S ₁₂ , S ₂₄ , S ₄₈ , S ₉₆ , and S ₁₉₂ . rice field.

(Evaluation of residual fragrance)
The samples extracted after each elapsed time were subjected to GCO analysis under the conditions described below, and the presence or absence of odor, intensity, fragrance tone (character) and the like were evaluated.
The longest standing time at which the scent of the aroma component A can be felt is Ta, the longest standing time among the odorants, and the standing time of the fragrance component at which the odor can be detected is Tx, and the residual fragrance evaluation value (Ta / Tx) is set. I asked. In Test Example 1, Tx was 96.

(Evaluation of aroma contribution)
Thai agarwood essential oil was applied to GCO, and the FD factor of each component in which the odor was felt was determined by using the AEDA method.
A sample was obtained by diluting Thai agarwood essential oil 256 times with 1 mL of dichloromethane. This sample was then sequentially diluted 4-fold and measured with GCO until no odor was felt. Furthermore, the FD factor n was determined from the dilution rate (1/4 ⁿ ) when the odor of each aroma compound was no longer felt.
Then, the ratio of the FD factor of each aroma compound to the highest FD factor among the odorants was evaluated as the aroma contribution (Q).

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

Table 1 summarizes the residual aroma evaluation values and aroma contributions for each aroma compound detected in the agarwood essential oil. "RI" in the table indicates the Retention Index.

From the above results, the relationship between the residual aroma evaluation value and the aroma contribution degree was classified according to FIG. 2 for each aroma compound.
Among the agarwood essential oils, the aroma compound having a high aroma contribution, that is, the aroma compound having a high aroma contribution to the aroma and having a high residual aroma evaluation value is D, the aroma compound having a low aroma contribution but a high residual aroma evaluation value is C, and the aroma contribution. Aroma compounds having a high degree but a low residual aroma evaluation value were classified as B, and aroma compounds having a low aroma contribution and a low residual aroma evaluation value were classified as A. Next, the aroma compounds classified into A to D and identified are summarized in Table 2.

The classification of A to D is as shown below.
A: A compound having 0 <residual aroma evaluation value <0.5 and 0 <aroma contribution <0.5,
B: A compound having 0 <residual fragrance evaluation value <0.5 and 0.5 ≦ aroma contribution ≦ 1.
C: 0.5 ≤ residual fragrance evaluation value ≤ 1 and 0 <aroma contribution <0.5 compound,
D: A compound having 0.5 ≦ residual fragrance evaluation value ≦ 1 and 0.5 ≦ aroma contribution ≦ 1.

[Test Example 2] Floral type fragrance composition A floral type fragrance composition (manufactured by Ogawa & Co., Ltd.) prepared according to the formulation shown in Table 4 is used as an aroma compound having a high aroma contribution and a high residual aroma in Test Example 1. The classified dihydrocaranone (manufactured by Ogawa & Co., Ltd.) was mixed at the concentrations shown in Table 3, dropped onto a 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 determined in advance. It was evaluated by 10 professional panelists who trained in Japan.
The evaluation results are shown in Table 5 below.

The contents of the evaluation are as follows.
Residual fragrance evaluation: The numbers in the table represent the number of evaluators.
Evaluation 1: Residual aroma is the same as in Comparative Example 1.
Evaluation 2: The residual fragrance was slightly increased.
Evaluation 3: The residual scent was significantly increased.
The composition of dihydrocaranone is preferably 0.00001 to 1%, preferably 0.00001 to 0.1%, more preferably 0.00001 to 0.01%, and particularly preferably 0.00005 to 0.005. %, Especially preferably 0.0001 to 0.002%.

[Test Example 3] Musk-type fragrance composition The musk-type fragrance composition (manufactured by Ogawa fragrance Co., Ltd.) prepared according to the formulation shown in Table 7 is mixed with dihydrocaranone (manufactured by Ogawa fragrance Co., Ltd.) classified in Test Example 1. The mixture was mixed at the concentrations shown in Table 6. The residue was dropped on a 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 specialized panelists who had been trained in advance.
The evaluation results are shown in Table 8 below.

The contents of the evaluation are as follows.
Residual fragrance evaluation: The numbers in the table represent the number of evaluators.
Evaluation 1: The residual scent is the same as in Comparative Example 4.
Evaluation 2: The residual fragrance was slightly increased.
Evaluation 3: The residual scent was significantly increased.
The composition of dihydrocaranone is preferably 0.00001 to 1%, preferably 0.00001 to 0.1%, more preferably 0.00001 to 0.01%, and particularly preferably 0.00005 to 0.005. %, Especially preferably 0.0001 to 0.002%.

[Test Example 4] Oriental type fragrance composition The oriental type fragrance composition (manufactured by Ogawa fragrance Co., Ltd.) prepared according to the formulation shown in Table 10 is combined with the dihydrocaranone (manufactured by Ogawa fragrance Co., Ltd.) classified in Test Example 1. ) Was mixed at the concentrations shown in Table 9, dropped onto a 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 specialized panelists who had been trained in advance. ..
The evaluation results are shown in Table 11 below.

The contents of the evaluation are as follows.
Residual fragrance evaluation: The numbers in the table represent the number of evaluators.
Evaluation 1: The residual fragrance is the same as that of Comparative Example 7.
Evaluation 2: The residual fragrance was slightly increased.
Evaluation 3: The residual scent was significantly increased.
The composition of dihydrocaranone is preferably 0.00001 to 1%, preferably 0.00001 to 0.1%, more preferably 0.00001 to 0.01%, and particularly preferably 0.00005 to 0.005. %, Especially preferably 0.0001 to 0.002%.

Similar evaluation tests were conducted on fruity type, citrus type, amber type, and herbal type fragrance compositions other than the above, and by blending dihydrocaranone in any of the fragrance types, the residual fragrance of the fragrance composition It was confirmed that the effect of improving is brought about.

Further, in Test Example 1, 2-isopropylidene-10-methyl-spiro [4,5] -6-decene-6-carbaldehyde, which was classified as an aroma compound having a low contribution but a high residual fragrance, was also used. By conducting the same evaluation test as dihydrocaranone and blending it into various types of fragrance compositions, there is a similar residual improvement effect, dihydrocaranone and 2-isopropyridene-10-methyl-spiro [4,5 ] It was confirmed that the combined use of -6-decene-6-calbaldehide was effective.

By using the residual aroma evaluation technique of the present invention, it becomes possible to easily screen an aroma compound having a high residual aroma and its aroma tone. As a result, when there is no desirable group D in the fragrance of FIG. 2, the fragrance can be improved by supplementing the fragrance with an aroma compound having a fragrance tone of group B and a high residual fragrance.
In addition, by using aroma compounds having different residual fragrances, it is possible to develop cosmetic fragrances whose fragrance tone changes over time.
By creating a database of screened residual fragrance and fragrance tone, it is possible to develop new fragrances by selecting the fragrance compound to be used from the viewpoint of residual fragrance.

[Example 16] Application of dihydrocaranone to perfume According to the formulation shown in Table 12 below, a fragrance sample was prepared by mixing the floral fragrance prepared in Example 5 of Test Example 2 with ethanol.
The perfume sample remained a floral type perfume with a scent tone, and a favorable residual scent was maintained.

[Example 17] Application of dihydrocaranone to fragrances According to the formulation in Table 13, a spray type in which methylparaben, the floral fragrance prepared in Example 2, polyoxyethylene (POE) hardened castor oil, ethanol, and water are mixed in this order. Aromas were prepared.
The favorable residual scent persisted while maintaining the floral type scent-like fragrance.

[Example 18] Application of dihydrocaranone to skin care products According to the formulation shown in Table 14, 1,3-butylene glycol, glycerin, and methyl paraoxybenzoate were dissolved in ethanol and mixed with water to make a lotion base. , A pre-uniformly mixed PEG-20 sorbitan cocoate and the floral type fragrance prepared in Example 1 were added to prepare a lotion.
A favorable residual scent persisted with the floral type scented lotion.

[Example 19] Application of dihydrocaranone to hair care products According to the formulation in Table 15, the water-based base is weighed in a beaker, mixed uniformly while heating at 85 ° C., and then the activity of Na cocoyl glutamate and the like is stirred while stirring. The agent was added and uniformly dissolved, and 1% citric acid water and water were added and uniformly mixed. Finally, a shampoo was prepared by adding the floral type fragrance of Example 2 to the obtained mixture.
The floral type scented shampoo remained, and the favorable residual scent persisted.

[Example 20] Application of dihydrocaranone to household products According to the formulation in Table 16, Phase A was weighed in a beaker, mixed uniformly while heating at 80 ° C, and then uniformly mixed at 80 ° C. B. The phase was added and stirred with a homomixer.
Finally, the fragrance of Example 2 was added to the obtained mixture to prepare a softener.
A favorable residual scent persisted while remaining a floral type fragrance-like softener.

The fragrance composition containing dihydrocaranone as a residual fragrance enhancer is a fragrance product blended in a fragrance product so that the concentration of the fragrance added is 0.2% (Example 18) to 10% (Example 16). It was confirmed that the residual fragrance persisted.
Therefore, the formulation of dihydrocaranone in the fragrance product is preferably 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 particularly preferably 2 ppb. It was ~ 2 ppm.

Claims (13)

The following process,
Process 1. The process of allowing odorous substances to stand in a space with constant temperature and humidity.
Process 2. The process of extracting the aroma component contained in the odorant after a predetermined time from the start of standing,
Process 3. A step of subjecting the extracted aroma component to gas chromatography orfactometry (GCO) analysis and detecting the presence or absence of an odor for each aroma compound constituting the aroma component.
Process 4. The step of measuring the longest standing time (T) at which the odor of each aroma compound constituting the odorant can be detected for each aroma compound, and
Process 5. In step 4, the longest standing time (Ta) in which the odor of the specific aroma compound A can be detected, and the longest static in which the odor of the aroma compound X having the longest T among the aroma compounds constituting the odor can be detected. A step of using the standing time (Tx) to set the Ta / Tx value as the residual aroma evaluation value of the aroma compound A contained in the odorant.
A method for evaluating a residual scent for selecting a compound having a high residual scent of an aroma compound contained in an odorant, which comprises. A method for evaluating the aroma characteristics of the aroma compound A from the aroma contribution of the aroma compound A contained in the odorant and the residual aroma evaluation value (Ta / Tx) of the aroma compound A obtained by the method of claim 1. Equation 1 below

Dihydrocaranone represented by and / or the following formula 2

2-Isopropylidene-10-methyl-spiro [4,5] -6-decene-6-carbaldehyde as an active ingredient, which is a residual fragrance enhancer. A fragrance composition containing the residual fragrance-imparting agent according to claim 3 (excluding the fragrance composition containing an agarwood essential oil). A method for imparting residual fragrance to a fragrance composition (excluding a fragrance composition containing agarwood essential oil) by blending the residual fragrance-imparting agent according to claim 3. By blending the dihydrocaranone represented by the formula 1 in the fragrance composition so as to be 0.00001 to 1%, the fragrance composition (excluding the fragrance composition containing agarwood essential oil) has a residual fragrance. How to grant. A fragrance product containing the fragrance composition according to claim 4, which has an improved residual fragrance. The fragrance product according to claim 7, wherein the fragrance product is a perfume, a make-up product, a skin care product, a hair care product, a personal care product which is a toiletry product, a household product, or a quasi-drug. A method for imparting residual fragrance to a fragrance product by blending the fragrance composition according to claim 4. A method of imparting residual fragrance to a fragrance product by blending dihydrocaranone represented by the formula 1 in a fragrance product so as to have a concentration of 0.2 ppb to 1000 ppm. The method for imparting residual fragrance according to claim 10, wherein the fragrance product is a perfume, a make-up product, a skin care product, a hair care product, a personal care product that is a toiletry product, a household product, or a quasi-drug. The following process,
Step 1: A step of specifying the residual scent evaluation value (P), the scent contribution (Q), and the scent tone by the method of claim 1 for each scent compound constituting the scent of the odorous substance.
Step 2: For each aroma compound, a compound having 0 <P <0.5 and 0 <Q <0.5 is used as a compound group A, and a compound having 0 <P <0.5 and 0.5 ≦ Q ≦ 1 is used. Compound group B, a compound having 0.5 ≦ P ≦ 1 and 0 <Q <0.5 as compound group C, and a compound having 0.5 ≦ P ≦ 1 and 0.5 ≦ Q ≦ 1 as compound group D. Sorting process,
Step 3: A step of replacing the aroma compound b classified in the compound group B with an aroma compound d classified in the compound group D and having a similar aroma tone to the aroma compound b.
A method for improving the aroma of an odorant, which is characterized by containing. A step of creating a database of the correlation between the residual aroma evaluation value and the aroma tone by the method of claim 12 for a large number of aroma compounds;
Next, when designing a fragrance composition whose fragrance tone changes with the passage of time, a step of selecting a constituent component from the above data;
A method for designing a fragrance composition, which comprises.

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