JP7078353B2 - How to choose a fragrance for capsules - Google Patents

Description

The present invention relates to a method for selecting a perfume for capsules.

In fabric care, home care, and personal care products including perfume capsules, a method of optimizing the composition of the perfume in the capsule has been proposed for the purpose of improving the scent from the capsule adhering to the target surface.

For example, Patent Document 1 describes a method of enhancing the perfume effect by grouping perfume components according to the odor threshold concentration and encapsulating them in separate microcapsules. Patent Document 2 describes a method for selecting a capsule-encapsulated fragrance that adjusts the balance of vapor pressure by paying attention to the vapor pressure and boiling point of the fragrance material. Patent Document 3 describes a method for preparing a perfume capsule capable of suppressing leakage of the perfume by limiting the perfume contained in the core to a specific range of interfacial tension. Patent Document 4 describes a method for selecting a fragrance compound having a molecular weight smaller than 325 atomic weight units and having specific bulky structural characteristics as a fragrance composition for core-shell microcapsules. ..

Special Table 2015-533863 Gazette Special Table 2014-524973 Gazette Special Table 2015-502969 Gazette Japanese Unexamined Patent Publication No. 2008-63575

However, these methods are means for forming a stable fragrance emulsion when forming a shell in an aqueous solvent by suspension polymerization, and sufficient strong fragrance can be obtained from the capsule after adhering to the target surface. It was not taken into consideration. In particular, recently, there has been a demand for a stronger and refreshing scent from clothing when worn, and a fragrance capsule capable of more efficiently scenting a fragrance material that contributes to the scent is required. ..

Factors that affect the scent from the perfume capsule include the vapor pressure, boiling point, molecular weight, and polar moment of each perfume compound. LogT (odor threshold concentration), which is a parameter used in the method described in Patent Document 1, is an index showing odor intensity at a low concentration near the threshold of each fragrance compound, but is an index of fragrance volatilized from an actual fragrance capsule. The concentration is much higher than the threshold and does not necessarily match the perceived odor intensity. The value of the vapor pressure used in the invention described in Patent Document 2 is an estimated value from the molecular structure and the polar moment, and does not necessarily match the actual volatile behavior. Further, the interfacial tension of the fragrance compound used in the invention described in Patent Document 3 affects the ease of forming capsules and the stability of the shell, but is not related to the volatilization behavior of the fragrance. For example, Patent Document 3 describes that a perfume compound having an interfacial tension of 5 to 40 mN / m is preferable as a capsule core, but in reality, even a perfume compound having an interfacial tension of less than 5 mN / m is preferable. There are many fragrance compounds that exhibit excellent fragrance. Further, the degree of freedom in scent creation is limited only by the fragrance compound having a specific molecular structure as described in Patent Document 4.

Therefore, the present invention relates to a method for selecting a perfume for capsules, which can appropriately select a perfume compound having a superior fragrance standing than the conventional method for selecting a perfume for capsules.

The present inventors focused on three parameters, ClogP, logS, and Kovats Index, and by using these as indicators in combination, an appropriate fragrance compound having a superior fragrance standing compared to the conventional method for selecting a fragrance for capsules. I found that I could choose.

The present invention provides a method for selecting a perfume for capsules, which selects one or more perfume compounds satisfying the following conditions (a), (b) and (c) as the perfume compound used in the perfume composition for capsules. It is a thing.
(a) ClogP is 2 or more
(b) logS is -5.5 or more and less than -0.5
(c) Kovats Index is 1000 or more and less than 2000

Further, the present invention contains the following components (A) and (B), the content of the component (A) is 20% by mass or more, and the total amount of the component (A) and the component (B) is 80% by mass. The present invention provides the above-mentioned perfume composition for capsules.
(A) 1 or more fragrance compounds with ClogP of 2.0 or more, logS of -5.5 or more and less than -0.5, and Kovats Index of 1000 or more and less than 2000.
(B) A fragrance compound with a ClogP of 2.0 or higher, a logS of -5.5 or higher and less than -0.5, and a Kovats Index of 2000 or higher.

The method for selecting a fragrance for capsules of the present invention can predict the scent from capsules more accurately than the conventional method for selecting a fragrance for capsules, and can appropriately select a fragrance compound having excellent fragrance as a fragrance for capsules. ..

It is a figure which shows the Labeled Magnitude Scale (LMS). It is a figure which compared the predicted value and the measured value about the perfume release amount from the perfume composition 1 for a capsule.

〔index〕
ClogP is a 1-octanol / water partition coefficient of a chemical substance and is an index showing the hydrophobicity of a fragrance compound. The ClogP value in the present invention was calculated using software (The estimations Programs Interface for Windows ver4.11) jointly developed by the US Environmental Protection Agency and Syracuse, and Meylan, WM & Howard, PH (1995). It is obtained by the calculation method described in Journal of Pharmacological Sciences 84, 83-92.

logS is an index showing the solubility of a chemical substance in water, and "S" is the concentration (mol / L) of the saturated solution. The logS value in the present invention was calculated using ChemBioDraw Ultra 14.0, and a calculation module based on the chemoinformatics platform MOSES of Molecular Networks is used as the calculation method. MOSES is developed, maintained and owned by Molecular Networks GmbH (Erlangen, Germany).

The Kovats Index shows a retention index in gas chromatography calculated based on the retention time of alkanes, and is also an index showing the susceptibility of fragrances to volatilization. In the present invention, the value of the Kovats Index is calculated by the method described in Kovats, E., Helv. Chim. Acta, 41, 1915 (1958). Common non-polar phase columns are supplied under various trademarks such as HP-1 (Hewlett-Packard), CP Sil 5 CB (Chrompack), OV-1 (Ohio Valley) and Rtx-1 (Restek). 100% dimethylpolysiloxane, preferably 100% polyethylene glycol such as DB-WAX (Agilent) as the polar column.

[Component (A): Perfume compound satisfying conditions (a), (b) and (c)]
In the present invention, as the perfume compound used in the perfume composition for capsules, one or more perfume compounds satisfying the following conditions (a), (b) and (c) (hereinafter referred to as "component (A)"). Select. In the present invention, the fragrance compound of the component (A) is a synthetic fragrance.
(a) ClogP is 2 or more
(b) logS is -5.5 or more and less than -0.5
(c) Kovats Index is 1000 or more and less than 2000

In the present invention, the condition (a) for selecting a fragrance compound for capsules is ClogP of 2 or more, but preferably 2.05 or more from the viewpoint of improving the encapsulation rate in capsules. On the other hand, although there is no problem even if the upper limit of ClogP is high, it is preferably less than 8 and more preferably 6 or less for the same reason.

In addition, the condition (b) is that logS is -5.5 or more and less than -0.5, but it is preferably -5.1 from the viewpoint of stably producing a dispersion of a fragrance compound which is a core substance of suspension polymerization during capsule synthesis. It is more than that, and it is preferably -1 or less.

Further, the condition (c) is preferably 1040 or more, and preferably 1040 or more, from the viewpoint of improving the release amount of the fragrance compound when the capsule collapses on the surface of the object, although the Kovats Index is 1000 or more and less than 2000. It is less than 1950.

Examples of the fragrance compound of the component (A) satisfying the above conditions (a), (b) and (c) include the following acetals, alcohols, aldehydes, ethers, esters, ketones, sulfur-containing or nitrogen-containing compounds, and hydrocarbons. It is preferable to select two or more kinds selected from these.

Acetal: 2- (1-ethoxyethoxy) ethylbenzene, 3- (1-ethoxyethoxy) -3,7-dimethyl-1,6-octadien, 6,6-dimethoxy-2,5,5-trimethyl-2-hexene

Alcohol: 1-dodecanol, 2- (4-methyl-1-cyclohexyl-3-enyl) propan-2-ol, (Z) -6-nonen-1-ol, (Z) -3-methyl-5-( 2,2,3-trimethyl-1-cyclopenta-3-enyl) penta-4-en-2-ol, 1,8-cineole, 4-methyl-2- (2-methylpropyl) oxane-4-ol, 4-Propane-2-ylcyclohexane-1-ol, 3,7-dimethylocta-1,6-diene-3-ol, (4-propane2-ylcyclohexyl) mentanol, 2-methyl-6-methylidene octa-7 -En-2-ol, 2-methyl-4-phenylbutane-2-ol, 4-tert-butylcyclohexane-1-ol, 3,6-dimethyl-2-heptanol, 3,7-dimethyloctane-3- All, 2,6-dimethyloctane-2-ol, 4,7-methano-1H-inden-6-ol

Aldehydes: decanal, 2-methylundecanal, octanal, nonanal, (Z) -4-decenal, (Z) -4-heptenal, (Z) -6-nonen-1-al, 3,7-dimethyl-2, 6-octadienal, 3- (4-propane-2-ylphenyl) propanal, 3,6-dimethylcyclohexa-3-en-1-carbaldehyde, 2,2-dimethyl-3- (2-ethyl) Phenyl) Propanal, 3-Methyl-7-Propion-2-ylbicyclo [2,2,2] Octa-2-en-5-carbaldehyde, (E) -Dodeca-2-enoal, 8,8-dimethyl- 2,3,4,5,6,7-Hexahydro-1H-naphthalen-2-carbaldehyde, 4-prop-1-en-2-yl-cyclohexene-1-carbaldehyde, 3- (7,7-dimethyl) -4-bicyclo [3,1,1] hepte-3-enyl) propanal, 2-cyclohexylpropanal, 2,6,6-trimethylcyclohexa-1,3-dien-1-carbaldehyde, 2,6 , 10-trimethylundeca-9-enehyde, 3,5,5-trimethylhexanal, 2,4-dimethylcyclohexa-3-en-1-carbaldehyde, ethyl (1R, 6S) -2,2,6- Trimethylcyclohexane-1-carbaldehyde

Ether: 2-ethenyl-2-methyl-5-prop-1-en-2-yloxolane, 2,4-dimethyl-4-phenyloxolane, decahydro-2,6,6,7,8,8-hexamethyl- 2H-Indeno [4,5-b] furan, 2-butyl-4,6-dimethyl-5,6-dihydro-2H-pyran, phenoxybenzene, 2-ethenyl-2,6,6-trimethyloxane

Esters: 3-acetoxy-1-octene, prop-2-enyl 2-cyclohexylacetate, prop-2-enyl heptanoate, prop-2-enyl 3-cyclohexylpropanoate, (Z) -3-hexene-1-ol Butyrate, (Z) -3-hexene-1-olhexanoate, (Z) -3-hexene-1-ol (2E) -2-methyl-2-butenoate, acetic acid 3,7-dimethyl-6- Octen-1-ol, Isobutyric Acid 3,7-Dimethyl-6-octenyl, 3,7-Dimethylocta-6-Enyl Acetate, Cyclopentylidene Methyl Acetate, Ethylphenylacetate, 2,6,6-trimethyl-2, Ethyl 4-cyclohexadiene-1-carboxylate, ethyl 2-methylbutyrate, (3,5-dimethyl-1-cyclohexyl-3-enyl) methyl acetate, (2-tert-butylcyclohexyl) ethyl carbonate, (3, 4,7,7) -Octahydro-4,7-methano-3aH-inden-3a-carboxylic acid ethyl ester, geranyl formate, butyric acid (E) -3,7-dimethyl-2,6-octadienyl, [(2E) -3,7-Dimethylocta-2,6-dienyl] acetate, [2- [1- (3,3-dimethylcyclohexyl) ethoxy] -2-methylpropyl] propanoate, hexyl acetate, propan-2-yl 2- Methylbutanoate, cyclooctylmethylcarbonate, (3-butyl-5-methyloxan-4-yl) acetate, (3-pentyloxan-4-yl) acetate, 3,7-dimethylocta-1,6-diene -3-Ilformate, 1,5-dimethyl-1-vinyl-4-hexenyl isobutyric acid, 3,7-dimethylocta-1,6-dien-3-ylacetate, ethyl 2-methylvalerate, 2-( 4-Methylcyclohexyl) propan-2-yl acetate, methyl 2-nonate, [(Z) -hexe-3-enyl] cyclopropanecarboxylate, butyl butyrate, [(2Z) -3,7-dimethylocta-2 , 6-Dienyl] Acetic acid, propylbutyrate, octyl acetate, (2-tert-butylcyclohexyl) acetate, 2-methoxyethylbenzene, ethyl-2-cyclohexylpropionate, 3-methylbuta-3-enyl 2,2-dimethyl Propanoate, [(E) -2-hexenyl] acetate, 3a, 4,5,6 , 7,7a-Hexahydro-4,7-methanodiene-6-ylacetate, methyl salicylate, (1-cyclohexa-2-methylpropan-2-yl) butanoate.

Ketone: 1- (2,4-dimethylcyclohexyl-3-en-1-yl) -2,2-dimethylpropan-1-one, 2,4,4,7-tetramethylocta-6-en-3- On, (E) -1- (2,6,6-trimethyl-1-cyclohexa-1,3-dienyl) buta-2-en-1-one, 1- (2,6,6-trimethyl-1-) Cyclohexi-3-enyl) buta-2-en-1-one, 4- (2,6,6-trimethyl-1-cyclohexen-1-yl) butane-2-one, 4,7-dimethylocta-6- En-3-one, 1- (5,5-dimethyl-1-cyclohexenyl) penta-4-en-1-one, 3-methyl-5-propylcyclohex-2-en-1-one, 4- (2,6,6-trimethylcyclohexen-1-yl) butane-3-en-2-one, (E) -1- (2,4,4-trimethylcyclohex-2-en-1-yl) butane -2-en-1-one, (Z) -3,4,5,6,6-pentamethylhepta-3-en-2-one, l-carboxyl, 4- (2-methylbutane-2-yl) Cyclohexane-1-one, 2-cyclohexyl-1,6-heptadiene-3-one

Sulfur-containing or nitrogen-containing compounds: 2-methyl-4-propyl-1,3-oxatian, 3,7-dimethylocta-6-enenitrile, 3,7-dimethylnona-2,6-dienenitrile, N- (5-) Methylheptan-3-iriden) hydroxylamine, 5-methyl-2- (2-sulfanylpropan-2-yl) cyclohexane-1-one, 4-methyl-2-propane-2-yl-1,3-thiazole)

Hydrocarbons: 1-methyl-4-propane-2-ylcyclohexa-1,3-diene, p-menta-1,4-diene, 1-methyl-4-propane-2-ylbenzene, 1-methyl- 4-Prop-1-ene-2-ylcyclohexene

Among the fragrance compounds of the above component (A), 4-methyl-2-propane-2-yl-1,3-thiazole, 5-methyl-2- (2-sulfanylpropan-2-yl) cyclohexane-1 -On, 6,6-dimethoxy-2,5,5-trimethyl-2-hexene, (Z) -3-methyl-5- (2,2,3-trimethyl-1-cyclopenta-3-enyl) penta- 4-en-2-ol, 2-ethenyl-2,6,6-trimethyloxane, (E) -dodeca-2-enoal, 2,2-dimethyl-3- (2-ethylphenyl) compound, 2 , 6,10-Methylundeca-9-enal, 2-cyclohexylpropanol, 3,6-dimethylcyclohexi-3-en-1-carbaldehyde, 4-prop-1-en-2-yl-cyclohexene- 1-Calvaldehide, 2,4-dimethyl-4-phenyloxolan, 2-ethenyl-2-methyl-5-prop-1-en-2-yloxolan, (Z) -3-hexene-1-olhexano Art, [(2Z) -3,7-dimethylocta-2,6-dienyl] acetate, 2-methoxyethylbenzene, 3-acetoxy-1-octene, ethylphenylacetate, prop-2-enyl 2-cyclohexylacetate, prop -2-Enyl heptanoate, 2-cyclohexyl-1,6-heptadiene-3-one, 1-methyl-4-propane-2-ylcyclohexa-1,3-diene, 1-methyl-4-propane-2- Ilbenzene and p-menta-1,4-diene are preferable, and one or more selected from these is preferably selected as the component (A).

In the present invention, from the viewpoint of improving the fragrance intensity released when the capsule is disintegrated, the fragrance compound satisfying the conditions (a), (b) and (c), that is, the component (A) is 20 of the fragrance composition for capsules. Select the fragrance compound so that it is at least% by mass. The content of the component (A) in the fragrance composition for capsules is 20% by mass or more, preferably 25% by mass or more, more preferably 30% by mass or more, still more preferably 35% by mass or more, and also. It is preferably 95% by mass or less, more preferably 90% by mass or less, and further preferably 85% by mass or less.

[Component (B): Perfume compound satisfying conditions (a), (b) and (d)]
In the present invention, in addition to the above-mentioned component (A), as a perfume compound used in a perfume composition for capsules, one or more perfume compounds that further satisfy the following conditions (a), (b) and (d) (hereinafter, It is preferable to select "component (B)") and use it in combination with component (A). In the present invention, the fragrance compound of the component (B) is a synthetic fragrance.
(a) ClogP is 2 or more
(b) logS is -5.5 or more and less than -0.5
(d) Kovats Index is 2000 or higher

In the present invention, the condition (a) of the compound (B) is the same as the condition (a) of the compound (A), and the ClogP is 2 or more, but from the viewpoint of improving the encapsulation rate of the fragrance compound in the capsule. , Preferably 2.05 or higher. On the other hand, although there is no problem even if the upper limit of ClogP is high, it is preferably less than 8 and more preferably 6 or less for the same reason.

Further, the condition (b) is the same as the condition (b) in the compound (A), and the logS is -5.5 or more and less than -0.5, but the fragrance compound which is the core substance of suspension polymerization during capsule synthesis. From the viewpoint of stably producing the dispersion of, it is preferably -5.1 or more, and preferably -1 or less.

The third condition (d) for selecting the fragrance compound (B) uses the Kovats Index, which is the same index as the fragrance compound (A), but the range is 2000 or more, but the capsule collapses on the surface of the object. From the viewpoint of improving the amount of the fragrance compound released, the amount is preferably 4000 or less, more preferably 3000 or less, still more preferably 2800 or less.

Examples of the fragrance compound of the component (B) satisfying the above conditions (a), (b) and (d) include the following acetal, alcohol, aldehyde, ether, ester, ketone, lactone, sulfur-containing or nitrogen-containing compound. It is preferable that two or more kinds are selected from these.

Acetal: (4aR, 5R, 7aS, 9R)-Octahydro-2,2,5,8,8,9a-Hexamethyl-4H-4a, 9-Metanozureno [5,6-d] -1,3-dioxol

Alcohol: (E) -2-ethyl-4-(2,2,3-trimethyl-1-cyclopenta-3-enyl) buta-2-en-1-ol, 2-methoxy-4-propi-2-enyl Phenol, 2-methyl-4- (2,2,3-trimethylcyclopenta-3-en-1-yl) penta-4-en-1-ol, [(1R, 2S) -1-methyl-2-ol [[(1R, 3S, 5S) -1,2,2,-trimethyl-3-bicyclo [3.1.0] hexenyl] methyl] cyclopropyl] methanol, 3,7,11-trimethyldodeca-1,6,10 -Trien-3-ol, 1- (2,2,6-trimethylcyclohexyl) hexane-3-ol, 2-methyl-4-phenylpentane-1-ol, 3-methyl-5-phenylpentane-1-ol , 3-Phenylpropan-1-ol, (E) -2-Methyl-4- (2,2,3-triethyl-1-cyclopenta-3-enyl) Buta-2-en-1-ol, 6-isopropyl -3-Methylphenol

Aldehyde: 3- (4-tert-butylphenyl) propanol, 3- (4-methoxyphenyl) -2-methylpropanol, 3-ethoxy-4-hydroxybenzaldehyde, 3- (1,3-benzodioxol) -5-yl) -2-methylpropanol, 2- (phenylmethylidene) octanal, 3- (4-tert-butylphenyl) butanal, 4- (4-hydroxy-4-methylpentyl) cyclohex-3-ene -1-Calvaldehide, 2-Methyl-3- [4- (2-Methylpropyl) Phenyl] Propanal

Ether: (3aR, 5aS, 9aS, 9bR) -3a,6,6,9a-tetramethyl-2,4,5,5a,7,8,9,9b-octahydro-1H-benzo [e] [1] Benzofuran, 1,3,4,6,7,8-hexahydro-4,6,6,7,8,8-hexamethylcyclopent-2-benzopyran, 1,2-dimethoxy-4-prop-1-enyl Benzene, 2-ethoxynaphthalene, 2-methoxynaphthalene

Ester: 4-allyl-2-methoxyphenol acetate, (2-methoxy-4-prop-1-enylphenyl) acetate, ethyl 3-methyl-3-phenyloxylan-2-carboxylate, prop-2-enyl 2- (Phenoxy) Acetic Acid, 17-oxacycloheptadecane-6-en-1-one, pentyl 2-hydroxybenzoate, (4-methoxyphenyl) methyl acetate, [(Z) -hexe-3-enyl] 2-hydroxybenzoate , Cyclohexyl 2-hydroxybenzoate, ethyl 3-phenylpropyl-2-enoate, ethyl 3-phenyloxylan-2-carboxylate, 1,4-dioxacycloheptadecane-5,17-dione, diethylcyclohexane-1,4 -Dicarboxylate, (12E) -1-oxacyclohexadeca-12-en-2-one, hexyl 2-hydroxybenzoate, 3-methylbutyl 2-hydroxybenzoate, methyl-3-oxo-2-pentylcyclopentaneacetate , 16-oxacyclohexadecane-1-one, acetic acid (1-oxopropoxy) -1- (3,3, -dimethylcyclohexyl) ethyl ester

Ketone: 1-[[(3R) -2,3,4,7,8,8aβ-hexahydro-3β, 6,8,8-tetramethyl-1H-3aα, 7α-methanoazulene] -5-yl] etanone , 1- (2,6,6, -trimethyl-1-cyclohex-2-enyl) hepta-1,6-dien-3-one, 8-methyl-1,5-benzodioxepin-3-one, 1- (6-tert-butyl-1,1-dimethyl-2,3-dihydroinden-4-yl) ethanoate, (9Z) -cycloheptadeca-9-en-1-one, (8E) -cyclohexa Deca-8-en-1-one, 4- (1,3-benzodioxol-5-yl) butane-2-one, 1- (2,3,8,8-tetramethyl-1,3, 4,5,6,7-Hexahydronaphthalen-2-yl) etanone, 1-naphthalene-2-yl etanone, (5E) -3-methylcyclopentadeca-5-en-1-one, 3-methylcyclopenta Deca-1-one, 5-cyclohexadecenenone, 2- [2- (4-methyl-1-cyclohexa-3-enyl) propyl] cyclopentane-1-one, 1- (spiro [4.5] deca-7- En-7-yl) Penta-4-en-1-one, 1- (3,5,5,6,8,8-hexamethyl-6,7-dihydronaphthalene-2-yl) etanone

(Lactone): 5-Heptyloxolan-2-one, 5-Pentyloxolan-2-one, 6-Pentyl-5,6-dihydropyran-2-one, 5-Hexyloxoran-2-one, 6 -Hexyloxan-2-one, 6-heptyloxan-2-one, 6-butyloxolan-2-one

Sulfur-containing or nitrogen-containing compounds: N- (1,5-dimethyl-8-bicyclo [3.2.1] octanylindene) hydroxylamine, 1H-indole, 6-butane-2-ylquinolin, (NE) -N- [ (6E) -2,4,4,7-Tetramethylnona-6,8-dien-3-ylinden] Hydroxylamine, Methyl 2-aminobenzoate, 2-Cyclohexylidene-2-phenyl acetonitrile)

In the present invention, from the viewpoint of improving the fragrance intensity released when the capsule is disintegrated, the fragrance compound satisfying the conditions (a), (b) and (d), that is, the component (B) is 5 of the fragrance composition for capsules. It is preferable to select the fragrance compound so as to have a mass% or more and 80% by mass or less. The content of the component (B) in the fragrance composition for capsules is preferably 5% by mass or more, more preferably 15% by mass or more, still more preferably 25% by mass or more, and preferably 80% by mass or less. It is more preferably 70% by mass or less, still more preferably 60% by mass or less.

In the present invention, from the viewpoint of improving the fragrance intensity released when the capsule is disintegrated, the fragrance compound satisfying the conditions (a), (b) and (c), that is, the component (A), and the conditions (a) and (b). ) And (d) can be selected, that is, the component (B) can be selected so that the total amount of the selected fragrance compounds is 80% by mass or more of the fragrance composition for capsules. preferable. The total content of the components (A) and (B) in the perfume composition for capsules is preferably 80% by mass or more, more preferably 85% by mass or more, and further preferably 90% by mass or more.

[Other fragrance materials]
For the fragrance composition for capsules, select a synthetic fragrance that does not correspond to the ingredients (A) and (B), or a fragrance derived from an essential oil and / or a natural product, as a fragrance further contained in addition to the ingredients (A) and (B). However, their content in the perfume composition for capsules is the capsule perfume, from the perspective of more accurately predicting the scent from the perfume capsule by the combination of perfume materials known by ClogP, logS and Kovats Index. From the viewpoint of predictability of fragrance from the above, it is preferably 10% by mass or less, more preferably 8% by mass or less, and further preferably 5% by mass or less.

The essential oils that may be further contained in the capsule fragrance composition include anis oil, elemi oil, olibanum oil, kanokosou oil, cardamon oil, galvanum oil, caraway oil, guaiyac oil, cumin oil, clove oil, coconut oil, etc. Cinnamon oil, ginger oil, sage oil, cedar leaf oil, nutmeg oil, basil oil, peppermint oil, bay oil, vetiver oil, bergamot oil, mandarin oil, mirror oil, eucalyptus oil, lime oil, lime oil, rosemary oil, rose Examples include oil, lavender oil, lavandin oil, orange oil, bergamot oil, lemon oil, lemongrass oil, davana oil and petitgrain oil.

[Fragrance composition for capsules]
The capsule fragrance composition of the present invention is prepared by using the method for selecting a capsule fragrance of the present invention described above, and contains the components (A) and (B), and the component (A) is contained. The content is 20% by mass or more, and the total amount of the component (A) and the component (B) is 80% by mass or more.

The content of the component (A) in the perfume composition for capsules of the present invention is 20% by mass or more, preferably 25% by mass or more, more preferably 30% by mass or more, still more preferably 35% by mass or more. Also, it is preferably 95% by mass or less, more preferably 90% by mass or less, and further preferably 80% by mass or less.

The content of the component (B) in the fragrance composition for capsules is preferably 5% by mass or more, more preferably 15% by mass or more, still more preferably 25% by mass or more, and preferably 80% by mass or more. Hereinafter, it is more preferably 70% by mass or less, still more preferably 60% by mass or less.

The total amount of the components (A) and (B) in the capsule fragrance composition of the present invention is 80% by mass or more, preferably 85% by mass or more, more preferably 90% by mass or more, and further. It is preferably 95% by mass or more.

[Fragrance capsule]
As the capsule for encapsulating the perfume composition for capsules of the present invention, core-shell type microcapsules are preferable. The polymer forming the shell of the fragrance capsule is not particularly limited as long as it is a polymer that can be formed around the core by the process of interfacial polymerization, and is, for example, polyurea, polyamide, organic monomer or organic. Examples thereof include a hybrid polymer formed from an oligomer and an inorganic monomer or a mixture of the inorganic oligomer.

As the core substance, along with the capsule fragrance composition of the present invention, vegetable oils such as palm oil, palm kernel oil, cottonseed oil, soybean oil, corn oil, coconut oil, olive oil, Benihana oil, castor oil, and sunflower oil, and mixtures thereof. Dibutyl adipate, dibutyl phthalate, butyl benzyl adipate, benzyl octyl adipate, tricresyl phosphate, trioctyl phosphate and mixtures thereof; waxes with a melting point of 80 ° C or higher such as liquid paraffin, petrolatum (purified grease), carnauba wax, etc. In addition, it can contain linear or branched hydrocarbons having a boiling point of more than 90 ° C.

[Product aroma]
The perfume composition for capsules prepared by the method for selecting a perfume for capsules described above has an excellent scent from the capsule, and the perfume capsule containing this perfume composition for capsules is used. , Can be scented on various products. Examples of such products include fabric softeners, detergents, hair shampoos, conditioners, hair rinses, body cleansers, bar soaps, body shampoos and the like.

The method for analyzing the amount of fragrance released when the fragrance capsule is disintegrated and the Labeled Magnitude Scale (LMS) used for evaluating the sensory intensity of odor, which were adopted in the following examples and test examples, will be described.

(Analysis method of fragrance release amount when fragrance capsule collapses)
Prepare a 5 × 5 cm knitted cloth on which a predetermined amount of perfume capsules having a perfume composition as a core are adsorbed.
The dried knitted cloth is put into a 1 L fluororesin bag (Tedlar bag: registered trademark), and the fluororesin bag is plugged and sealed. A fluororesin bag is installed on a commercially available shaker (MMS-310 manufactured by Tokyo Rika Kikai Co., Ltd.), a weight is placed on the bag and pressure is applied, and the device is operated to destroy the fragrance capsule (condition: weight). Weight 5000g, shaking speed 100rpm, shaking time 10 seconds).
Introduce 1L of odorless air into the fluororesin bag and collect the fragrance volatilized in the fluororesin bag using Tenax-TA (GL Science) and diaphragm pump (GL Science, SP 208 Dual). ..
Quantitative analysis of the head space in the bag is performed by GC / MS for the perfume released from the perfume capsule due to the disintegration of the perfume capsule.

Gas chromatography analysis conditions Adsorption tube: Tenax TA (manufactured by GL Science)
GC: 6890N (manufactured by Agilent Technologies)
Column: DB-WAX 60.0m x 250μm x 0.25μm
Carrier gas: Helium (116.5kPa, 1.1mL / min)
Column temperature: After holding at 40 ° C for 3 minutes, raise the temperature to 70 ° C at 6 ° C / min and 240 ° C at 4 ° C / min, and hold for 20 minutes.
MS: 5975B (manufactured by Agilent Technologies)

(About Labeled Magnitude Scale (LMS))
The Labeled Magnitude Scale (LMS) is a sensory intensity scale developed by BGGreen (Chem. Senses., 1993, 18 (6), 683-702) by combining verbal markers and a logarithmic scale. LMS can directly and in detail measure the difference in sensory intensity depending on the measurement target, and is used for quantifying and comparing sensory intensity such as taste, smell, and touch. LMS indicates sensory intensity (“Barely Detectable”, “Weak”, “Barely Detectable”, “Weak”,” as shown in FIG. "Moderate", "Strong", "Very Strong") are labeled.

The strengths that the LMS values mean are shown below.
0-1.4: Almost no odor, 1.5-6.1: Weak odor, 6.2-17.2: Comfortable odor, 17.3-35.4: Strong odor, 35.5-53.3: Very strong odor, 53.4-100: Very strong odor

Examples 1 to 6 (Manufacturing of perfume composition for capsule and perfume microcapsule)
(Preparation of perfume composition for capsules)
The prescribed capsule fragrance compositions 1 to 6 were prepared using the method for selecting a capsule fragrance of the present invention. These formulations are shown in Tables 1-6, along with the ClogP, logS and Kovats Index for each perfume compound (“KI” indicates Kovats Index).

(Making fragrance microcapsules)
130.2 g of a 1 mass% aqueous solution of polyvinyl alcohol (Gosenol GH-20, manufactured by Nippon Synthetic Chemical Industry Co., Ltd .; polymerization degree 2000, saponification degree 86.5 to 89.0 mol%) as an aqueous phase, and the fragrance composition shown in Tables 1 to 6 as an organic phase. 21 g, 4.55 g of methacrylic acid, 1.51 g of methyl methacrylate, 2.92 g of ethylene glycol dimethacrylate, and 0.12 g of 2,2'-azobis (2,4-dimethylvaleronitrile (V-65, manufactured by Wako Pharmaceutical Co., Ltd.)) were prepared. ..
After stirring at 3500 rpm for 5 minutes, the mixture was stirred at 4000 rpm for 5 minutes and emulsified. Nitrogen was purged at 22 kPa for 1 minute, and this was repeated 3 times. The temperature was raised to 65 ° C. at 1 ° C./min and polymerization was carried out for 5 hours. After further aging at 75 ° C. for 3 hours, the mixture was cooled to obtain 6 kinds of perfume microcapsules.

Test Example 1 (Drivation of prediction formula for fragrance release amount)
A 5 × 5 cm knitted cloth having the perfume capsules of Examples 1 to 3 adsorbed equivalent to 0.2 to 30.0 μg / cm ² was prepared, and the perfume released from the perfume capsule due to the disintegration of the perfume capsule was used as the perfume capsule according to the above method. Quantitative analysis was performed for each amount of adsorbed. From the results of this quantitative analysis, it was found that the relationship between the adsorption amount of the perfume capsule and the release amount of the perfume compound A at the time of capsule disintegration (gas phase concentration; ng / L air) is expressed by the following equation (1). ..

Here, the relationship between the adsorbed amount (Ab) of the perfume capsule and the variables (a, b) is
a = 1.03 × Ab
b = 3874 x Ab ^-0.8
By substituting this into Equation 1, it was found that the amount of fragrance compound released can be expressed by the following equation (2) and is related to the Kovats Index of fragrance compound A.

Further, the following equation (3) was obtained by multiplying Equation 2 by the blending amount of the fragrance compound A. From this formula, the amount (gas phase concentration) of the specific perfume compound A released from the perfume capsule at the time when the perfume capsule remaining on the target surface disintegrates can be calculated.

Test Example 2 (Derivation of intensity curve of each fragrance compound corresponding to gas phase concentration)
Introduce 0.5 mL of each fragrance into a 3L polyethylene odor bag (purchased from AS ONE), introduce odorless air into the odor bag, collect the head space from the odor bag that has been left to stand overnight, and use another fluororesin bag. Smell bags of various concentrations were prepared.
The perfume volatilized in the fluororesin bag was collected using Tenax-TA and a sampling pump, and the head space in the bag was quantitatively analyzed by GC / MS.
A fluororesin bag with a known concentration was connected to a dilution / mixing device for odor identification (manufactured by Shimadzu Corporation), and the odor intensity for each concentration emitted from the device was evaluated by 14 specialized panels using LMS.
From the evaluation results, the sensory intensity corresponding to the gas phase concentration of the fragrance represented by the following equation (4) was obtained.

The coefficients p, q, and r are the values of the sensory intensity calculated by substituting the gas phase concentration obtained for each fragrance compound into the equation (4), which is the average value of the sensory evaluations of the 14 specialized panels. It was determined by minimizing the sum of squares of the residuals between the predicted value and the measured value (least squares method) so as to approximate.
The decision was made using the solver, which is an add-in program of Microsoft's Excel 2010 (ver14.0), which is a spreadsheet software program.

Example 7
Does the data obtained by the gas phase concentration prediction formula (Equation (3)) released from the perfume capsule when the perfume capsule collapses and the intensity curve corresponding to the gas phase concentration (Equation (4)) actually contribute to odor? It was confirmed by gas phase concentration analysis and sensory evaluation at the time of capsule disintegration.

(Confirmation of predicted value and actual amount of fragrance released from fragrance capsule)
A 5 × 5 cm knitted cloth to which the perfume capsule of Example 1 was adsorbed equivalent to 2.5 μg / cm ² was prepared, and the perfume released from the perfume capsule by the disintegration of the perfume capsule was quantitatively analyzed according to the above method. For each fragrance compound, the values calculated from the above formula and the analysis results are shown in FIG.
From FIG. 2, it was confirmed that the calculated value was almost the same as the actual amount of volatilization.

(Confirmation by sensory evaluation)
The fluororesin bag in which the fragrance capsule was destroyed was connected to a dilution / mixing device for odor identification (manufactured by Shimadzu Corporation), and the odor strength emitted from the device was evaluated by a specialized panel (14 people) using the LMS evaluation scale. The results are shown in Table 7.

From Table 7, it was confirmed that the sensory intensity value calculated by the formula (4) and the sensory evaluation were almost the same for all the perfume capsules.

Example 8 (Sensory evaluation with softener)
A perfume capsule containing the perfume composition 1, 4 or 5 for capsules was perfumeed with 0.175% by mass with respect to the softener dough.
4.6 g of fabric softener and 100% cotton towel were added to 23 L of water, and this was treated by washing for 6 minutes, dehydration for 3 minutes, and drying overnight.
The treated towel was stimulated by pulling or rubbing it by hand, and the scent intensity before and after it was evaluated from the top of the acrylic box (40 cm x 40 cm x 30 cm). The evaluation was carried out by 7 specialized panels. The results are shown in Table 8.
The evaluation uses a 6-step odor intensity display, and the evaluation scale is shown below.
0: Odorless, 1: Smell that can be finally perceived, 2: Smell that can be easily perceived, 3: Smell that can be easily perceived, 4: Strong scent, 5: Strong scent

Here, the perfume compositions 1 and 4 are set so that the predicted odor intensity is strong, and the perfume composition 5 is set so that the predicted odor intensity is weak. When evaluating the scent from the capsule, the stimulus applied to the garment when actually wearing the garment was assumed, and the scent was evaluated by adding two kinds of stimuli, expansion and contraction and friction, to the towel treated with the softener.
As a result, in the perfume compositions 1 and 4 having a strong expected odor intensity, strong fragrance was observed even with a weak stimulus of the degree of expansion and contraction, but in the fragrance composition 5, fragrance was not observed only by expansion and contraction, and a stronger stimulus was observed. By adding the rubbing, a weak scent was observed, and the expected strength results were obtained for each scent capsule.

Claims (7)

For capsules containing the following components (A) and (B), the content of the component (A) is 20% by mass or more, and the total amount of the component (A) and the component (B) is 80% by mass or more. Fragrance composition.
(A) Ethyl 2-methylpentanoate, 1,8-cineole, hexyl acetate, 3,6-dimethylcyclohexa-3-en-1-carbaldehyde, ethyl-2-cyclohexylpropionate, (3,4, 7,7)-Octahydro-4,7-methano-3aH-inden-3a-carboxylic acid ethyl ester, 1- (5,5-dimethyl-1-cyclohexenyl) penta-4-en-1-one, 4, 7-methano-1H-inden-6-ol, ethyl 2-methylbutyrate, ethyl 2-methylvalerate, 2-methyl-4-propyl-1,3-oxatian, 3,7-dimethyloctane-3-ol , 2,4-Dimethylcyclohexa-3-en-1-carbaldehyde, (2-tert-butylcyclohexyl) ethyl carbonate, ethylhexanoate, (2-tert-butylcyclohexyl) acetate, phenoxybenzene, 1-methyl -4-Prop-1-en-2-ylcyclohexene, octanal, nonanal, prop-2-enyl heptanoate, decalal, 3,7-dimethylocta-6-enyl acetate, 3,7-dimethylocta-6-enenitrile, 1- (2,6,6-trimethyl-1-cyclohex-3-enyl) buta-2-en-1-one, 2,4-dimethyl-4-phenyloxolane, prop-2-enyl 3-cyclohexylpropa Noate, 4- (2,6,6-trimethylcyclohexen-1-yl) buta-3-en-2-one, propan-2-yl 2-methylbutanoate, 3,6-dimethylcyclohexi-3 -En-1-carbaldehyde, 2-methylundecanal, 3- (7,7-dimethyl-4-bicyclo [3,1,1] hepte-3-enyl) propanal, methyl salicylate, 3a, 4,5 , 6,7,7a-Hexahydro-4,7-methanodiene-6-ylacetate, prop-2-enyl 2-cyclohexylacetate , 1 -methyl-4-prop-1-en-2-ylcyclohexane, 3,7 -Dimethylocta-1,6-diene-3-ol, 3,7-dimethylocta-1,6-diene-3-yl acetate, 2- (4-methylcyclohexyl) propan-2-yl acetate, N-( 5-Methylheptane-3-iriden) hydroxylamine, 3,7-dimethyl-2,6-octadienal, [(2E) -3,7-dimethylocta-2,6-dienyl] acete G, (E) -1- (2,6,6-trimethyl-1-cyclohexa-1,3-dienyl) buta-2-en-1-one, (E) -dodeca-2-enal, (1- Cyclohexyl-2-methylpropan-2-yl) butanoate, p-menta-1,4-diene, 2- (4-methyl-1-cyclohexyl-3-enyl) propan-2-ol, and [(2Z)- 3,7-Dimethylocta-2,6-dienyl] One or more fragrance compounds selected from acetate
(B) 3,6,6,9-tetramethyl-2,4,5,5,7,8,9,9-octahydro-1H-benzobenzofuran, 3- (4-tert-butylphenyl) compound, 5-Heptyloxolan-2-one, 3-ethoxy-4-hydroxybenzaldehyde, 5-cyclohexadecenenone, hexyl 2-hydroxybenzoate, 2-methoxynaphthalene, ethyl 3-methyl-3-phenyloxylan-2-carboxylate , 1- (Spiro [4.5] Deca-7-en-7-yl) Penta-4-en-1-one, (12E) -1-oxacyclohexadeca-12-en-2-one, Cyclohexyl2- Hydroxybenzoate, and (3aR, 5aS, 9aS, 9bR) -3a,6,6,9a-tetramethyl-2,4,5,5a,7,8,9,9b-octahydro-1H-benzo [e] [ 1] One or more fragrance compounds selected from benzofurans The perfume composition for capsules according to claim 1, wherein the content of the component (A) is 20% by mass or more and 95% by mass or less. The perfume composition for capsules according to claim 1 or 2, wherein the components (A) and (B) are synthetic perfumes. The perfume composition for capsules according to any one of claims 1 to 3, wherein the content of the perfume derived from the essential oil and / or the natural product is 10% by mass or less. The perfume composition for capsules according to any one of claims 1 to 4, which is encapsulated in core-shell type microcapsules. A method for perfume a product using a perfume capsule containing the perfume composition for capsules according to any one of claims 1 to 5. The perfume method according to claim 6, wherein the product to be perfused is selected from a softener, a laundry detergent, a hair shampoo, a hair conditioner, a hair rinse and a body shampoo.

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