WO2023013767A1 - Method for suppressing change in quality of perfume and inverted volatilization apparatus - Google Patents

Abstract

The present invention provides a method for suppressing change in quality of a perfume, the method being capable of suppressing a change in concentration of a perfume ingredient in a liquid composition containing the perfume to constantly maintain the formulation of the liquid composition when vaporizing the liquid composition using a stationary-type volatilization apparatus. This method serves to suppress a change in the quality of a perfume when vaporizing the perfume from a liquid composition containing the perfume, the method comprising vaporizing the liquid composition using an inverted volatilization apparatus, wherein the liquid composition contains 0.02% by mass or more of a perfume ingredient having a vapor pressure at 25° C of 0.00005kPa or higher.

Description

METHOD AND INVERTED VAPOLITION DEVICE FOR SUPPRESSING CHANGE IN PERFUME CHARACTERISTICS

The present invention relates to a method and an inverted volatilization device for suppressing changes in the fragrance quality of a fragrance, and more particularly, to volatilization of a liquid composition containing a fragrance using a volatilization device. ) and an inverted volatilization device.

A stationary volatilization device is known as a means of volatilizing an active ingredient from a liquid composition containing the active ingredient. A stationary volatilization device includes a storage container that stores a liquid composition, a liquid absorbing material that sucks up the liquid composition stored in the storage container, and a volatilization body that diffuses an active ingredient in the liquid composition that has been sucked up. there is Here, one of the liquid absorbing material and the volatilization body may serve as the other.

As such a volatilization device, for example, an upright volatilization device in which a liquid-absorbing material is provided at the top of a container and the liquid formulation is sucked up by capillary action of the liquid-absorbing material to volatilize the active ingredient, or a liquid-absorbing material is provided at the bottom of the container. Various inverted volatilization devices have been investigated in which the active ingredient is volatilized partially by utilizing gravity.

Since the upright volatilization device uses the capillary phenomenon of the liquid-absorbing material, if the liquid-absorbing material is clogged, the volatilization performance may change between the initial stage and the final stage. In the case of , the initial scent tends to disappear (or become weaker) than the final scent.
On the other hand, the inverted volatilization device can volatilize the active ingredient without going against gravity, so the liquid composition can be stably supplied to the absorbent material, and the effect of the active ingredient can be maintained from the beginning to the end of volatilization. can.

As an inverted volatilization device, for example, Patent Documents 1 and 2 disclose a bottle that contains a liquid formulation containing an active ingredient and is configured to supply the liquid formulation downward; and a volatilizer configured to volatilize into the air an active ingredient in a liquid formulation supplied from a volatilizer.

Japanese Patent Application Laid-Open No. 2020-99609 Japanese Patent Application Laid-Open No. 2020-99610

A fragrance contains a fragrance as an active ingredient, and a plurality of fragrance ingredients are combined to adjust the type and blending amount of the fragrance to form a desired fragrance. Some perfume ingredients have low palatability when used alone, but have a highly palatable aroma quality when combined with other perfume ingredients.
In volatilization of perfume using a volatilization device, the concentration balance of perfume components tends to change over time, and the fragrance quality (fragrance quality) of the perfume sometimes differs between the initial stage and the final stage of volatilization. Then, even if perfume ingredients are combined to form a highly palatable scent quality, the highly palatable scent at the beginning of volatilization may become unpalatable due to the loss of the concentration balance of the perfume components during volatilization. In some cases, the aroma quality was low.

No technology is known to suppress changes in fragrance quality in a liquid composition. The object of the present invention is to provide a method for suppressing changes in fragrance qualities of fragrances, which can keep the composition of a liquid composition constant by suppressing changes in the concentration of the fragrance ingredients.

The inventors have made extensive studies. As a result, it was found that by vaporizing a liquid composition containing a specific amount of a perfume component with a specific vapor pressure using an inverted volatilization device, it was possible to suppress changes in the flavor quality of the perfume, and to complete the present invention. Arrived.

That is, the present invention is characterized by the following.
(1) A method for suppressing a change in fragrance quality of a fragrance when volatilizing the fragrance from a liquid composition containing the fragrance, wherein the liquid composition has a vapor pressure of 0.00005 kPa or more at 25 ° C. and volatilizing the liquid composition using an inverted volatilization device.
(2) In the liquid composition, 0.02% by mass or more of a perfume component having a vapor pressure of 0.00005 kPa or more and less than 0.01 kPa at 25 ° C. and 0.01 kPa or more of a perfume component having a vapor pressure of 0.01 kPa or more at 25 ° C. .The method for suppressing changes in fragrance quality of the fragrance described in (1) above, wherein the fragrance is contained at a rate of 02% by mass or more.
(3) a bottle containing a liquid composition;
an inner plug that closes the bottom opening of the bottle in an inverted state;
a liquid-absorbent material that penetrates the inner plug and has a tip located inside and outside the bottle;
a lower container assembled to the bottom of the bottle in an inverted state;
a volatilization body housed in the lower container and in contact with the liquid-absorbing material,
The inverted volatilization device, wherein the liquid composition contains 0.02% by mass or more of a perfume component having a vapor pressure of 0.00005 kPa or more at 25°C.
(4) The liquid composition contains 0.02% by mass or more of a perfume component having a vapor pressure of 0.00005 kPa or more and less than 0.01 kPa at 25°C and 0.02% by mass or more of a perfume component having a vapor pressure of 0.01 kPa or more at 25°C. The inverted volatilization device according to (3) above, containing at a rate of 02% by mass or more.

According to the present invention, it is possible to suppress a change in the concentration of the fragrance component in the liquid composition, and to maintain the same fragrance quality from the initial stage to the final stage of volatilization. In addition, since the inverted volatilization device is used, the intensity of the scent can be kept constant, so that the same performance can be obtained from the beginning to the end of volatilization.
Moreover, according to the inverted volatilization device of the present invention, the fragrance can be volatilized without changing the scent quality of the fragrance from the beginning to the end of volatilization, so it is particularly suitable for aromatic agents.

FIG. 1 is an external perspective view showing an embodiment of an inverted volatilization device of the present invention. 2 is a longitudinal sectional view of the inverted volatilization device shown in FIG. 1. FIG. FIG. 3 is a single plan view of a volatilization body used in the inverted volatilization device shown in FIG. FIG. 4 is a schematic diagram for explaining the structures of the inverted volatilization device and the upright volatilization device used in the examples, and FIG. (b) is a cross-sectional view of an upright volatilization device.

The method of the present invention for suppressing changes in fragrance qualities of a fragrance suppresses changes in the fragrance qualities of the fragrance when volatilizing the fragrance from a liquid composition containing the fragrance. In the method of the present invention, a perfume component having a vapor pressure of 0.00005 kPa or more at 25° C. is contained in the liquid composition at a rate of 0.02% by mass or more, and the liquid composition is evaporated using an inverted volatilization device. volatilize.

In the upright volatilization device, a ventilation hole is provided in the inner plug to keep the pressure inside and outside the container containing the liquid composition constant. very quickly) will evaporate. Perfume ingredients are classified into top note, middle note and base note based on their volatility (vapor pressure). By using the liquid composition containing 0.02% by mass or more, clogging of the liquid absorbing material in the volatilization device with the component containing the liquid composition is suppressed, while the difference in volatilization speed of the perfume component is reduced. By using the volatilization device, it is possible to suppress volatilization of the perfume component from other than the volatilization material. As a result, it is possible to suppress a large change in the concentration balance of the perfume components in the perfume, thereby suppressing a change in the quality of the perfume.

(liquid composition)
The perfume contained in the liquid composition may consist of one perfume component, or may be a mixture of two or more perfume components. Further, the perfume may be a synthetic perfume, a natural perfume, or a blended perfume obtained by mixing a plurality of synthetic perfumes or natural perfumes.

In the present invention, a perfume component having a vapor pressure of 0.00005 kPa or more at 25°C is contained in the liquid composition at a rate of 0.02% by mass or more. Perfume ingredients having a vapor pressure of 0.00005 kPa or more at 25° C. include, for example, α-hexylcinnamaldehyde (vapor pressure 0.000064 kPa), dodecanal (vapor pressure 0.0001 kPa), propyl valerate (vapor pressure 0.001 kPa). , (E)-alpha-damascone (vapor pressure 0.0011 kPa), indole (vapor pressure 0.0016 kPa), citronellol (vapor pressure 0.0027 kPa), eugenol (vapor pressure 0.003 kPa), geraniol (vapor pressure 0.004 kPa ), l-menthol (vapor pressure 0.0085 kPa), citral (vapor pressure 0.012 kPa), isobornyl acetate (vapor pressure 0.013 kPa), decanal (vapor pressure 0.014 kPa), linalyl acetate (vapor pressure 0.015 kPa) , linalool (vapor pressure 0.021 kPa), nonanal (vapor pressure 0.049 kPa), geranyl isovalerate (vapor pressure 0.051 kPa), menthone (vapor pressure 0.067 kPa), phenethyl alcohol (vapor pressure 0.087 kPa), Camphor (vapor pressure 0.12 kPa), octanal (vapor pressure 0.16 kPa), limonene (vapor pressure 0.19 kPa), 1,8 cineol (vapor pressure 0.22 kPa), heptanal (vapor pressure 0.47 kPa), isoamyl acetate (vapor pressure 0.53 kPa), hexanal (vapor pressure 1.51 kPa), ethyl butyrate (vapor pressure 2.0 kPa), dihydromyrcenol and the like. These may be used individually by 1 type, and may combine 2 or more types.

When the content of the perfume component having a vapor pressure of 0.00005 kPa or more at 25° C. in the liquid composition is 0.02% by mass or more, the concentration balance of the perfume component over time is less likely to be disturbed, and the effect of the present invention can be obtained. easy to get Perfume components having a vapor pressure of 0.00005 kPa or more at 25° C. are preferably contained in the liquid composition in an amount of 0.03% by mass or more, 0.05% by mass or more, 0.07% by mass or more, 0.09% by mass or more, 0.1% by mass or more, 0.12% by mass or more, 0.15% by mass or more, 0.18% by mass or more, 0.2% by mass or more, 0.25% by mass or more, 0 0.5% by mass or more, more preferably 0.75% by mass or more, and most preferably 1% by mass or more. In addition, if the amount of perfume is too large, the scent becomes too strong and gives an unpleasant feeling. % or less is more preferable, and 5% by mass or less is particularly preferable.

The perfume component having a vapor pressure of 0.00005 kPa or more at 25°C preferably contains a perfume component having a vapor pressure of 0.001 kPa or more at 25°C, more preferably 0.010 kPa or more. , more preferably 0.10 kPa or more. In addition, the upper limit of the vapor pressure of the perfume component is not particularly limited, but in order not to increase the difference in vapor pressure between the perfume components too much, the perfume component preferably has a vapor pressure of 6.0 kPa or less at 25 ° C. A fragrance component of 3.0 kPa or less is more preferable, and a fragrance component of 2.0 kPa or less is even more preferable.

A more preferable content of the perfume component in the liquid composition is a perfume having a vapor pressure of 0.001 kPa or more at 25° C. from the viewpoint of reducing the difference in volatilization rate of the perfume component and making it easier to obtain the effects of the present invention. It is preferable that the component is contained at 0.02% by mass or more and 10% by mass or less, and the fragrance component having a vapor pressure of 0.010 kPa or more at 25 ° C. is contained at 0.02% by mass or more and 10% by mass or less. More preferably, it contains 0.02% by mass or more and 10% by mass or less of a perfume component having a vapor pressure of 0.10 kPa or more at 25°C.

In the present invention, it is preferable that the liquid composition contains a combination of two or more fragrance components having different vapor pressures. If the vapor pressure of the perfume component is too high, the volatilization rate will increase, but by combining with a perfume component with a low vapor pressure, volatilization of the perfume component with too high a vapor pressure will be suppressed. Conversely, volatilization of a perfume component with a too low vapor pressure is promoted by combining it with a perfume component with a high vapor pressure. In other words, by combining perfume components with different vapor pressures, it becomes easier to adjust the volatility, and by containing a plurality of perfume components with different vapor pressures, the difference in vapor pressure between each perfume component in the liquid composition becomes smaller. It becomes easy to suppress the change of the fragrance quality of a fragrance|flavor. In addition, by containing a plurality of fragrance components, it is possible to form a variety of fragrance qualities and highly-preferred fragrance qualities.

When combining perfume ingredients with different vapor pressures, specifically, 0.02% by mass or more of a perfume component (middle note) having a vapor pressure of 0.00005 kPa or more and less than 0.01 kPa at 25 ° C. and steam at 25 ° C. It is preferable to combine and contain a perfume component (top note) having a pressure of 0.01 kPa or more at a ratio of 0.02% by mass or more.
More preferably, 0.02 to 5% by mass of the perfume component of the middle note and 0.02 to 5% by mass of the perfume component of the top note are combined. 02 to 4% by mass and 0.02 to 4% by mass of the top note fragrance component are more preferably combined, and 0.02 to 3% by mass of the middle note fragrance component and 0.02 to 3% by mass of the top note fragrance component are combined. It is particularly preferable to combine them at a ratio of 02 to 3% by mass, and it is particularly preferable to combine 0.02 to 2.5% by mass of the middle note fragrance component and 0.02 to 2.5% by mass of the top note fragrance component. is most preferred.

The content of perfume components having a vapor pressure of 0.00005 kPa or more at 25°C in the perfume is preferably 50% by mass or more. If the content of the perfume component having a vapor pressure of 0.00005 kPa or more at 25° C. is 50% by mass or more in the perfume (total perfume component), the difference in volatilization rate between the perfume components becomes small, so the perfume component It is possible to suppress a large change in the concentration balance of . A perfume component having a vapor pressure of 0.00005 kPa or more at 25° C. is contained in the perfume in an amount of 65% by mass or more, more preferably 80% by mass or more. Further, all of the perfume ingredients may be perfume ingredients having a vapor pressure of 0.00005 kPa or more at 25° C. (100% by mass), and the upper limit is not particularly limited.

In the present invention, the perfume may contain a perfume component having a vapor pressure of less than 0.00005 kPa at 25°C. Examples of perfume ingredients having a vapor pressure of less than 0.00005 kPa at 25°C include vanillin and ethyl vanillin.

According to the study of the present inventors, it was found that perfume ingredients with a vapor pressure of less than 0.00005 kPa at 25°C are less susceptible to volatilization depending on whether the volatilization device is upside down. Therefore, when the content of the perfume component having a vapor pressure of less than 0.00005 kPa at 25° C. increases, it becomes difficult to obtain the effects peculiar to the present invention by using the inverted volatilization device. In addition, when used in combination with a perfume component having a vapor pressure of 0.00005 kPa or more at 25 ° C., if the content of the perfume component having a vapor pressure of less than 0.00005 kPa at 25 ° C. increases, the concentration balance of the perfume component is lost. easier. Therefore, the content of the perfume component having a vapor pressure of less than 0.00005 kPa at 25° C. in the liquid composition is preferably 0.5% by mass or less, more preferably 0.2% by mass or less, and 0.2% by mass or less. 1% by mass or less is more preferable, 0.01% by mass or less is particularly preferable, and 0.001% by mass or less is most preferable. may be

The content of perfume components having a vapor pressure of less than 0.00005 kPa at 25°C in the perfume is preferably 50% by mass or less. If the content of the perfume component having a vapor pressure of less than 0.00005 kPa at 25°C is 50% by mass or less in the perfume (total perfume component), the perfume contains a perfume component having a vapor pressure of 0.00005 kPa or more at 25°C. Since it contains a large amount, the concentration balance of the perfume component over time is unlikely to be lost, and the desired effect of the present invention can be easily obtained. A perfume component having a vapor pressure of less than 0.00005 kPa at 25° C. is more preferably contained in the perfume at 35% by mass or less, more preferably at 20% by mass or less in the perfume, and 10% by mass in the perfume. % or less, more preferably 5% by mass or less, and most preferably 1% by mass or less. The lower limit of the content of the perfume component having a vapor pressure of less than 0.00005 kPa at 25°C in the perfume is not particularly limited, and may be 0% by mass.

The content of the perfume in the liquid composition varies depending on the size of the space in which the inverted volatilization device is installed and the duration of the effect, but the total amount of perfume ingredients should be 0.02% by mass or more in the liquid composition. is preferred. The content of the perfume in the liquid composition is more preferably 0.03% by mass or more, and 0.05% by mass or more, 0.07% by mass or more, 0.09% by mass or more, 0 0.1% by mass or more, 0.12% by mass or more, 0.15% by mass or more, 0.18% by mass or more, 0.2% by mass or more, 0.25% by mass or more, 0.5% by mass or more; 75% by mass or more is more preferable, and 1.0% by mass or more is most preferable. In addition, if the amount of perfume is too much, the fragrance becomes too strong and gives discomfort, so it is preferably 10% by mass or less, more preferably 8% by mass or less, further preferably 6% by mass or less, and 5% by mass or less. is particularly preferred.

The content of each fragrance component in the liquid composition can be measured by gas chromatography (GC) analysis, high performance liquid chromatography (HPLC) analysis, or the like. Also, the content of each perfume component in the perfume can be obtained by calculating the ratio from the measured content of all the perfume components in the liquid composition.

The liquid composition of the present invention may contain a surfactant in order to solubilize the perfume component. Examples of surfactants include surfactants such as nonionic surfactants, anionic surfactants, cationic surfactants and amphoteric surfactants.

Examples of nonionic surfactants include polyoxyalkylene hydrogenated castor oils such as polyoxyethylene hydrogenated castor oil, polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene oleyl ether, and polyoxyethylene decyl ether, poly Polyoxyalkylene alkyl ethers such as oxypropylene decyl ether, polyoxyalkylene fatty acid esters such as polyoxyethylene fatty acid esters, polyoxyalkylene glyceryl ether fatty acid esters such as polyoxyethylene glyceryl ether fatty acid esters, alkyl alkanolamides, alkyl polyglucosides, Sorbitan fatty acid esters, glycerin fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene polyoxypropylene glycol and the like are included.

Examples of anionic surfactants include alkyl sulfates, polyoxyethylene alkyl ether sulfates such as polyoxyethylene lauryl ether sulfate, sulfosuccinates, dialkyl sulfosuccinates, alkyl glucoside sulfates, N-acyl Amino acid salts, carboxylates, sulfonates, phosphate ester salts and the like are included.

Examples of cationic surfactants include alkylammonium salts.

Examples of amphoteric surfactants include alkylamidobetaine, alkyldimethylamine oxide, alkylbetaine, cocamidealkylhydroxysultaine, and the like.

When a surfactant is included, it is preferable to use a nonionic surfactant. Nonionic surfactants are suitable for solubilizing perfume ingredients, and can dissolve perfume ingredients even in small amounts, so that the amount of solubilizer used can be reduced. Therefore, it is difficult for the solubilizer to supplement the fragrance component or clog the liquid-absorbent material, and it is difficult to prevent the volatilization of the fragrance component. presumed to be

Examples of nonionic surfactants include polyoxyethylene hydrogenated castor oil having an average addition mole number of ethylene oxide (EO) of 30 to 80, polyoxyethylene alkyl ether having an alkyl group having a carbon number of 9 to 22, fatty acid having a carbon number of 12 to 18 polyoxyethylene sorbitan fatty acid esters, etc., and it is preferable to use at least one selected from the group consisting of these. Below, polyoxyethylene hydrogenated castor oil having an average number of added moles of ethylene oxide (EO) of 30 to 80, polyoxyethylene alkyl ether having an alkyl group having 9 to 22 carbon atoms, and polyoxyethylene having a fatty acid having 12 to 18 carbon atoms Sorbitan fatty acid ester is also called a specific nonionic surfactant. These specific nonionic surfactants have a high HLB value of 8 to 19 and are more suitable for solubilizing perfume ingredients, so that the amount of solubilizer used can be further reduced. Therefore, it is difficult for the fragrant component to be supplemented by the solubilizer and clogging of the absorbent material, and the effects of the present invention can be exhibited more effectively.

Specifically, as a polyoxyethylene hydrogenated castor oil having an average added mole number of ethylene oxide (EO) of 30 to 80, for example, a commonly available one is trade name "NIKKOL HCO-30" (E .O.30), "NIKKOLHCO-40" (E.O.40), "NIKKOL HCO-50" (E.O.50), "NIKKOL HCO-60" (E.O.60), etc. .
Examples of polyoxyethylene alkyl ethers having alkyl groups of 9 to 22 carbon atoms include polyoxyethylene decyl ether (alkyl group having 10 carbon atoms, E.O. 10), polyoxyethylene lauryl ether (alkyl group having carbon atoms of 12, E.O.10) and the like.
Examples of polyoxyethylene sorbitan fatty acid esters having 12 to 18 carbon atoms in fatty acids include polyoxyethylene sorbitan monolaurate (fatty acid carbon number 12, EO 20), polyoxyethylene sorbitan monopalmitate (fatty acid C16, E.O.20)) and the like.
Among them, polyoxyethylene hydrogenated castor oil having an average added mole number of ethylene oxide (EO) of 30 to 60, polyoxyethylene alkyl ether having an alkyl group having 9 to 12 carbon atoms, and polyoxyethylene having a fatty acid having 12 to 18 carbon atoms. It is more preferable to contain at least one selected from the group consisting of sorbitan fatty acid esters, polyoxyethylene hydrogenated castor oil having an average added mole number of ethylene oxide (EO) of 30 to 50, and an alkyl group having 10 to 12 carbon atoms. and at least one selected from the group consisting of polyoxyethylene alkyl ethers and polyoxyethylene sorbitan fatty acid esters of fatty acids having 12 to 18 carbon atoms.

The content of the surfactant in the liquid composition is preferably less than 6% by mass. If the content of the surfactant is too large, it tends to trap the perfume ingredients, clog the absorbent material, and cause a change in the concentration of the perfume ingredients. can suppress it. The content of the surfactant is preferably 0.01% by mass or more and less than 6% by mass, and 0.05% by mass or more and 6% by mass, from the viewpoint of the solubility of the fragrance ingredient and the durability of the effect of the fragrance ingredient. Less than is more preferable, 0.1% by mass or more and less than 6% by mass is more preferable, and 0.5 to 5% by mass is particularly preferable. Here, the content of the surfactant is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, still more preferably 0.1% by mass or more, and 0.5% by mass or more. Particularly preferred is less than 6% by weight, more preferably less than 5% by weight.

The specific nonionic surfactant is preferably contained in the surfactant in an amount of 50% by mass or more, more preferably 90% by mass or more, and the total amount of the surfactant is the specific nonionic surfactant. may

The liquid composition of the present invention may be prepared by dissolving the perfume described above in a solvent.
Examples of solvents include water, alcohol solvents, glycol ether solvents, ester solvents and the like.

Examples of water include purified water, ion-exchanged water, distilled water, filtered water, and sterilized water.

Examples of alcohol solvents include lower alcohols such as ethanol, normal propanol and isopropanol; polyhydric alcohols such as glycerin, ethylene glycol, propylene glycol and dipropylene glycol; and 3-methoxy-3-methyl-1-butanol. be done.

Examples of glycol ether solvents include propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, dipropylene glycol dimethyl ether, ethylene glycol monoisobutyl ether, diethylene glycol monoisobutyl ether, and diethylene glycol. Dibutyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol methyl ether acetate, ethylene glycol mono-n-propyl ether, ethylene glycol mono-iso-propyl ether, propylene glycol monomethyl ether , propylene glycol monopropyl ether and the like.

Examples of ester-based solvents include isopropyl myristate, hexyl laurate, and isopropyl palmitate.

Among these, water, ethanol, isopropanol, propylene glycol monomethyl ether, propylene glycol, dipropylene glycol, 3-methoxy-3-methyl-1-butanol are used from the viewpoint of solubility and volatility of perfume ingredients and versatility. is preferred.

The content of the solvent in the liquid composition is preferably 45-99% by mass, more preferably 50-95% by mass, and even more preferably 50-90% by mass.

When ethanol is used as a solvent, the ethanol content in the liquid composition is preferably less than 20% by mass, more preferably less than 19% by mass, even more preferably 18% by mass or less, and particularly 15% by mass or less. Preferably, 13% by mass or less is particularly preferable, and 10% by mass or less is most preferable. Ethanol has a very high vapor pressure at 25° C. Therefore, when the ethanol content is high, it affects the volatility of the perfume ingredients, and the concentration balance of the perfume ingredients tends to be lost. Therefore, the content of ethanol is preferably within the above range.

The liquid composition may contain components other than the perfume, surfactant, and solvent described above as long as they do not impair the effects of the present invention. Other components contained in the liquid composition include, for example, preservatives, pigments, pH adjusters, ultraviolet absorbers, antioxidants, chelating agents, viscosity adjusters, specific gravity adjusters, insect repellent/insecticidal components, and repellent components. , sterilization/sterilization ingredients, deodorant ingredients, and the like.

Examples of antiseptics include methylparaben, ethylparaben, phenoxyethanol, benzethonium chloride, organic nitrogen sulfur halogen compounds, PCMX, and TBZ.

Pigments include, for example, tar pigments, red iron oxide pigments, and natural pigments.

Examples of pH adjusters include organic acids such as citric acid, succinic acid, fumaric acid, lactic acid, salicylic acid, tartaric acid, malic acid, benzoic acid, sodium citrate, sodium monohydrogen phosphate, and potassium dihydrogen phosphate; acids, salts thereof, and the like.

Examples of ultraviolet absorbers include phenol derivatives such as BHT, bisphenol derivatives, phenyl-α-naphthylamine, arylamines such as condensates of phenetidine and acetone, and benzophenone compounds.

Examples of antioxidants include 2′-methylenebis(6-tert-butyl-4-ethylphenol) 2,6-di-tert-butyl-4-methylphenol (BHT), 2,6-di-tert- Butylphenol 2,2'-methylenebis(6-tert-butyl-4-methylphenol), 4,4'-methylenebis(2,6-di-tert-butylphenol), 4,4'-butylidenebis(6-tert-butyl -3-methylphenol), 4,4′-thiobis(6-tert-butyl-3-methylphenol), dibutylhydroxynon (DBH).

Chelating agents include, for example, ethylenediaminetetraacetic acid (EDTA), nitrilotriacetic acid, hydroxyethyliminodiacetic acid, dihydroxyethylglycine, hydroxyethylenediaminetriacetic acid, diethylenetriaminepentaacetic acid, triethylenetetraminehexaacetic acid, and salts thereof. be done.

Viscosity modifiers include, for example, xanthan gum, carrageenan, gelatin, gum arabic, pectin, carboxymethylcellulose, methylcellulose and the like.

Examples of specific gravity adjusters include sucrose fatty acid esters.

Examples of insect repellent/insecticide components include pyrethroid insecticides, organophosphorus insecticides, carbamate insecticides, insecticides derived from natural ingredients, and the like. Among these, pyrethroid insecticides having a vapor pressure of 2×10 ⁻⁴ Pa (25° C.) or higher are preferred as those that volatilize spontaneously.

Repellent components include, for example, N,N-diethyl-m-toluamide, dimethyl phthalate, dibutyl phthalate, p-menthane-3,8-diol, 2-ethyl-1,3-hexanediol, di-n-propyl iso cinchomelonate, p-dichlorobenzene, di-n-butylsuccinate, carane-3,4-diol, 1-methylpropyl-2-(2-hydroxyethyl)-1-piperidine carboxylate, 3-[acetyl ( propylamino)]ethyl propionate, allyl isothiocyanate, menthyl acetate, butylcyclohexyl acetate, butylcycloheptyl acetate and the like.

Examples of disinfecting/sterilizing components include phenoxyethanol, isopropylmethylphenol, thiabendazole, p-chloro-m-xylenol, triclosan, allyl isothiocyanate, methylisothiazolinone, dichloroisocyanurate, chlorine dioxide, acetic acid, and propionic acid. , lactic acid, citric acid, and malic acid.

Examples of deodorizing ingredients include lauryl methacrylate, geranyl crotonate, methylated cyclodextrin, and the like.

The content of other components in the liquid composition can be adjusted as appropriate within a range that does not impair the effects of the present invention.

The formulation of the liquid composition is not particularly limited as long as it does not impair the effects of the present invention, and can be appropriately adjusted according to the application.
For example, in the case of a fragrance, the formulation is as follows.
Perfume component with a vapor pressure of 0.00005 kPa or more at 25 ° C. 0.02 to 6% by mass
0 to 3% by mass of perfume ingredients having a vapor pressure of less than 0.00005 kPa at 25°C
Surfactant 0.05% by mass or more and less than 6% by mass Solvent 85 to 99% by mass
Total 100% by mass

A liquid composition can be prepared according to a conventional method. For example, a perfume component having a vapor pressure of 0.00005 kPa or more at 25 ° C. is contained in a solvent in an amount that is 0.02% by mass or more in the composition, solubilized, and if necessary, any other Mix the ingredients of If the ingredients are solid, they may be heated if necessary.

(Inverted volatilization device)
The inverted volatilization device of the present invention comprises a bottle containing a liquid composition, an inner plug that closes the bottom opening of the bottle in an inverted state, and a liquid-absorbing material that penetrates the inner plug and has a tip located inside and outside the bottle. and a lower container assembled to the bottom of the bottle in an inverted state, and a volatilization body housed in the lower container and in contact with the liquid-absorbing material, as a liquid composition having a vapor pressure of 0.00005 kPa or more at 25 ° C. It accommodates a liquid composition containing 0.02% by mass or more of a perfume component.

Hereinafter, the configuration of the inverted volatilization device of the present invention will be described with reference to the drawings.
As shown in FIGS. 1 and 2, the inverted volatilization device 10 of the present invention includes a bottle (container) 11 containing a liquid composition 13 therein, and a liquid composition 13 impregnated with the liquid composition 13. and a volatilization body 22 for volatilizing contained active ingredients. The bottle 11 is installed in an inverted state, and the bottom opening of the bottle 11 in the inverted state is closed by an inner plug 20. , and the exposed portion of the absorbent material 19 is in contact with the volatilization body 22 . The inverted volatilization device 10 further includes a lower container 12 , which is attached to the bottom of the bottle 11 and supports the bottle 11 and the volatilization body 22 .
In the inverted volatilization device 10 , the liquid composition 13 is supplied to the volatilization body 22 via the liquid absorbing material 19 by gravity, and the active ingredient volatilizes from the volatilization body 22 .

Liquid does not substantially leak from the wall surface of the bottle 11 . As the material for forming the bottle 11, one or more of plastic, paper, metal, ceramic, glass, and the like can be used as long as the liquid composition 13 does not leak. Further, when forming the bottle 11, the above materials may be mixed with a pigment or an ultraviolet absorber (blocking material), patterned, or a phosphorescent material, a light scattering material, glitter, or the like may be added. .

The lower container 12 forms the lower half of the main body of the inverted volatilization device 10 and supports the bottle 11 and the volatilization body 22 . A plurality of volatilization openings 15 are formed along the entire circumference of the side portion of the lower container 12 . The opening area of the volatilization opening 15 affects the amount of volatilization. The opening area of the volatilization opening 15 may be appropriately set according to the desired volatilization amount, but is preferably 5 to 200 cm ² , more preferably 10 to 100 cm ² , and particularly preferably 15 to 80 cm ² .

As shown in FIG. 2, the bottle 11 has an engaging portion 17 formed on the outer peripheral portion near the lower end to be fitted to the locking projection 16 formed on the lower container 12 . An opening 18 is formed at the lower end of the bottle 11, and the opening 18 is closed by an inner plug 20 to which a liquid absorbent material 19 is attached. In addition, a cap 21 indicated by phantom lines in FIG.

Various materials such as metal and plastic can be used for the inner plug 20, for example. When using metal, it is necessary to use packing or the like to prevent leakage. In addition, basically any resin may be used as long as it is made of plastic, and polyethylene is preferable in terms of economic efficiency and usability, and this polyethylene is not particularly limited, Linear low-density polyethylene, branched low-density polyethylene, or the like, or a mixture thereof may be used. Moreover, the mixing ratio is arbitrary. Moreover, a plasticizer is added as needed. This is to increase productivity.

The liquid absorbent material 19 is a liquid absorbent member that absorbs the liquid composition 13 . The material forming the absorbent material 19 may be either an inorganic material or an organic material, but is preferably a resin. ), polypropylene (hereinafter also referred to as PP), polyethylene (hereinafter also referred to as PE), and the like. In particular, the liquid absorbing material 19 should preferably have the property of allowing gas-liquid exchange. Here, the liquid-absorbent material having the property of exchanging gas and liquid means that the liquid composition 13 in the bottle 11 penetrates into the liquid-absorbent material and is discharged to the outside of the bottle 11, and air, etc., from the outside of the bottle 11 is discharged. gas permeates into the liquid-absorbing material and is discharged to the outside of the liquid-absorbing material inside the bottle 11 . The liquid-absorbent material having the property of allowing gas-liquid exchange is preferably a porous material, for example, a porous material using at least one selected from the group consisting of PET, PA, PP and PE. is preferred.

In the present invention, the absorbent material 19 is preferably formed containing fibers. The fibers have a thin and long shape, and the cross-sectional shape in the direction orthogonal to the long axis thereof is substantially circular. Gas-liquid exchange is performed by this gap.
The liquid composition 13 in the bottle 11 is supplied to the outside of the bottle through the liquid absorbent material 19 by gravity, but the amount of liquid discharged may increase due to temperature changes in the surrounding environment, pressure difference between the inside and outside of the bottle 11, etc. A phenomenon occurs in which the liquid composition is sucked inside. For example, when the air temperature rises, the air in the bottle 11 expands, so the liquid composition 13 is easily pushed out, and when the temperature drops, the liquid composition 13 held in the liquid absorbent material 19 is sucked into the bottle 11.例文帳に追加Further, when the liquid composition 13 becomes less, the inside of the bottle 11 becomes negative pressure, so an action of taking in air corresponding to the volume of the discharged liquid composition 13 works.

By increasing the fiber diameter of the fibers constituting the liquid absorbent material 19 or by combining different fiber diameters, it is possible to adjust the gaps between the fibers, thereby adjusting the flowability of the liquid composition and improving the flow of the liquid into the bottle. Since the return amount can be adjusted, even if the liquid composition leaks excessively from the bottle 11 , the liquid can be returned through the liquid absorbent material 19 .

The liquid return amount varies depending on the shape and size of the bottle 11 and the lower container 12, the amount of the liquid composition 13 that the volatilization body 22 can hold, the type of the liquid composition 13, the viscosity or amount used, and the usage environment such as temperature. Therefore, it is preferable to set a desired liquid return amount and adjust and determine the fiber diameter of the fibers constituting the liquid absorbent material 19 in consideration of the various factors described above.
Specifically, when the fiber diameter of at least some of the fibers is 6 denier or more, it becomes easier to increase the amount of liquid returned to the bottle. By including fibers having a large fiber diameter of 6 denier or more, the gaps between the fibers are widened, so that the liquid composition 13 can easily return into the bottle 11 via the absorbent material 19 . The absorbent material 19 preferably contains fibers with a fiber diameter of 8 denier or more, and more preferably contains fibers with a fiber diameter of 10 denier or more, in order to facilitate liquid return. Although the upper limit of the fiber diameter is not particularly limited, for example, 50 denier or less is preferable, 30 denier or less is more preferable, and 20 denier or less is even more preferable.

The absorbent material 19 may be composed of fibers having one type of fiber diameter, or may contain fibers having two or more types of fiber diameters in combination. It is preferable that fibers having a fiber diameter of 6 denier or more be contained in the absorbent material 19 in an amount of 10 mass % or more. By containing 10% by mass of fibers having a fiber diameter of 6 denier or more, the liquid composition 13 that has flowed out of the bottle 11 can easily return to the inside of the bottle, and the liquid composition 13 can be retained even if the environmental temperature or the like fluctuates. Excessive bleeding can be suppressed.
Fibers having a fiber diameter of 6 denier or more are contained in the absorbent material 19 in an amount of 25% by mass or more, since they are less likely to be affected by fluctuations in environmental temperature and the like, and the effects of the present invention can be obtained more remarkably. is more preferable, more preferably 30% by mass or more, particularly preferably 35% by mass or more, particularly preferably 40% by mass or more, particularly preferably 45% by mass or more, 50 It is most preferable to contain more than mass %.

The fiber diameter and content of the fibers contained in the absorbent material 19 can be measured using a scanning electron microscope or the like.

The liquid absorbent material 19 can be produced by a known method. Examples of the type of the liquid-absorbing material 19 include a liquid-absorbing material (so-called heat-sealable core) obtained by a method of thermoforming raw yarn, and a method in which raw yarn is thermoformed, impregnated with resin, dried, and dried. Liquid-absorbent materials (so-called synthetic fiber cores) obtained by a method of curing and producing, and the like.

The structure of the fibers constituting the absorbent material 19 is not particularly limited, and examples include a single system composed of one resin, and a core-sheath, sea-island, or side-by-side composite fiber composed of two or more resins.

The liquid absorbent material 19 preferably has a porosity of 20 to 90%. The porosity is preferably 20% or higher, more preferably 30% or higher, even more preferably 40% or higher, particularly preferably 50% or higher, particularly preferably 60% or higher, and most preferably 70% or higher. Moreover, the upper limit of the porosity is preferably 90% or less, more preferably 88% or less, and even more preferably 85% or less, from the viewpoint of moldability of the absorbent material.
The porosity of the absorbent material 19 can be measured by an Archimedes method, a mercury porosity method, a weight porosity method, or the like.

The size of the liquid absorbent material 19 can be appropriately set according to various conditions such as the amount of the liquid composition 13 inside the bottle 11 and the viscosity of the liquid composition 13 .
For example, when the liquid-absorbing material 19 is cylindrical, the diameter of the liquid-absorbing material 19 (the diameter of the cross section cut perpendicular to the axial direction) is preferably 2 to 15 mm, more preferably 4 to 12 mm, and 4 ~10 mm is particularly preferred.
In addition, the length (length in the axial direction) of the liquid absorbing material 19 is appropriately set in consideration of the size of the bottle 11 and the appearance of the inverted volatilization device, and is not particularly limited, but is, for example, 10 to 160 mm. is preferred, 10 to 50 mm is more preferred, 10 to 40 mm is even more preferred, and 18 to 36 mm is particularly preferred.

A volatilization body 22 is assembled in the lower container 12 at a position facing the liquid absorbing material 19 , and at least part of the liquid absorbing material 19 exposed outside the bottle 11 is in contact with the volatilization body 22 . In addition, the lower container 12 may have a liquid pool chamber 23 below the volatilization body 22, and when the lower container 12 has the liquid pool chamber 23, the volatilization body 22 has a liquid absorption part 26. .

In the inverted volatilization device 10 shown in FIGS. 1 and 2, the volatilization body 22 is integrally formed with the base portion 24, the four volatilization portions 25, and the liquid absorption portion 26, that is, integrally formed of the same material. It is. The volatilization body 22 is contained in the lower container 12 so as to be sandwiched between the lower end portion of the bottle 11 (that is, the liquid absorbent material 19 ) and the lower container 12 , and the liquid composition is discharged from the bottle 11 via the liquid absorbent material 19 . Receive 13 supplies.

The lower end surface of the liquid absorbing material 19 is in surface contact with the upper surface of the base portion 24 . The liquid composition 13 is transferred through the liquid absorbent material 19 by contact with the liquid absorbent material 19 , and the liquid composition 13 is volatilized from the four volatilization portions 25 .

The liquid absorption part 26 is bent so as to protrude from the bottom surface of the base part 24 toward the liquid pool chamber 23 . The liquid composition 13 stored in the liquid reservoir chamber 23 can be returned to the base 24 by the liquid absorption part 26 that constitutes a part of the volatilization body 22 .

As the volatilization body 22, any material can be used as long as it can hold the liquid composition 13 and volatilize the active ingredient of the liquid composition 13. Specifically, resin, pulp, or the like can be used. A porous material made of an inorganic material such as an organic material, glass fiber, glass powder, or the like can be used. Particularly preferable materials for the volatilization body 22 include pulp and non-woven fabric. Moreover, the volatilization body 22 may consist of several materials. For example, the volatilization body 22 is mainly made of pulp and bonded with a binder, and has a configuration in which tissue-like pulp materials, nonwoven fabrics, etc. are stretched on the front and back surfaces in order to improve the strength and shape retention of the surface. preferably. Further, by preliminarily holding a predetermined amount of the liquid composition 13 in the volatilization body 22, it is possible to obtain the effect of volatilizing the active ingredient of the held liquid composition 13 at the same time as opening at the start of use. good.

The thickness of the volatilization body 22 is preferably 2-12 mm, and more preferably 3-10 mm. Also, the volatilization body 22 may be made by mixing and adhering a component having a deodorizing function or an antibacterial function such as green tea powder, activated carbon powder, or coffee bean powder. Furthermore, the receptor (soluble or sparingly soluble) containing and held in a desired carrier with an active ingredient or additive is retained in the volatilization body 22, and the receptor is gradually dissolved by the supplied liquid composition 13. may As the volatilization body 22, polymer powder, polymer fiber, or the like having at least one of hydrophilicity and lipophilicity and having high liquid absorption ability may be used. In this case, the liquid pool chamber 23 can be minimized or omitted.

In such an inverted volatilization device 10, the liquid composition 13 stored in the bottle 11 is impregnated with the liquid absorbing material 19 and then impregnated with the volatilization body 22, whereby the bottle 11 is discharged quantitatively. be. Then, air containing the active ingredient of the liquid composition 13 is diffused to the outside from the four volatilization parts 25 of the volatilization body 22 through the volatilization openings 15 .

The inverted volatilization device of the present invention is not limited to the above-described embodiments, and can be modified and improved as appropriate. For example, in the above embodiment, the liquid absorbing material 19 is integrally formed, but the liquid absorbing portion 26 may be formed separately. Further, instead of the liquid pooling chamber 23 , a liquid absorbing portion having a volume equivalent to that of the liquid pooling chamber may be provided so as to be in contact with the volatilization body 22 .

Since the inverted volatilization device of the present invention accommodates a liquid composition containing 0.02% by mass or more of a perfume component having a vapor pressure of 0.00005 kPa or more at 25° C. as the liquid composition, volatilization This suppresses the change in the concentration of the perfume component in the liquid composition, thereby suppressing the change in the scent quality of the perfume, and keeping the scent quality unchanged from the initial stage to the final stage of volatilization.

Hereinafter, the present invention will be described in more detail with reference to the following examples, but the present invention is not limited to the following examples.

<Test Example 1: Example 1, Comparative Example 1>
1. Preparation of Liquid Composition Based on the formulation shown in Table 1, each component was mixed to prepare Liquid Composition 1A.
In addition, surfactant A in Table 1 contains 70% by mass of polyoxyethylene hydrogenated castor oil (E.O.40), 27% by mass of polyoxyethylene alkyl ether (10 carbon atoms, E.O.10), and 3% by weight of a dialkyl sulfosuccinate salt. The composition of Surfactant A is the same in Test Examples 2 to 7 and 9 to 11 below.

2. Preparation of test specimen 2-1. Test Specimen Using Inverted Volatilization Apparatus As an inverted volatilization apparatus, a device having the configuration shown in FIG. 4(a) was used. The inverted volatilization device 30 includes a bottle 31 containing a liquid composition 32, an inner plug 33 that closes the bottom opening of the bottle 31, and a liquid-absorbing material that penetrates the inner plug 33 and whose tip is located inside and outside the bottle 31. 35 , a volatilization body 37 in contact with the absorbent material 35 , and a lower container 39 located below the bottle 31 and the volatilization body 37 and supporting the bottle 31 . Details of each member in the device are shown in Table 2.
In the inverted volatilization device 30, the liquid composition 32 contained in the bottle 31 is supplied to the volatilization body 37 via the liquid absorbing material 35 by gravity, and the perfume component volatilized from the volatilization body 37 is volatilized in the lower container 39. is discharged from the opening 39a.
A bottle 31 was filled with 400 mL of the liquid composition 1A prepared above, and an inner plug 33 was attached to the bottom opening of the bottle 31 . A liquid absorbent material 35 was attached to the inner stopper 33, and finally the lower container 39 was fitted to the bottle 31 to obtain an inverted test sample.

2-2. Test Specimen Using Upright Volatilization Apparatus As an upright volatilization apparatus, a device having the configuration shown in FIG. 4(b) was used. The upright volatilization device 40 includes a bottle 41 containing a liquid composition 42, an inner plug 43 closing an upper opening of the bottle 41, and a liquid absorbing liquid that penetrates through the inner plug 43 and whose tip is positioned inside and outside the bottle 41. A material 45 , a volatilization body 47 in contact with the absorbent material 45 , and an upper container 49 located above the bottle 41 and the volatilization body 47 and covering the volatilization body 47 . Details of each member in the device are shown in Table 2.
In the upright volatilization device 40, the liquid composition 42 contained in the bottle 41 is sucked up by capillary action of the liquid absorbent material 45 and supplied to the volatilization body 47, and the perfume component volatilized from the volatilization body 47 is stored in the upper container. 49 is discharged from the volatilization opening 49a.
400 mL of the liquid composition 1A prepared above was placed in a bottle 41, and an inner plug 43 was attached to the top opening of the bottle 41. A liquid absorbent material 45 was attached to the inner stopper 43, and finally the upper container 49 was fitted to the bottle 41 to obtain an upright test sample.

The rest of the liquid composition 1A was used as an initial liquid specimen for the following evaluations.

3. Confirmation of fragrance quality change of perfume The inverted test sample (Example 1) and the upright test sample (Comparative Example 1) prepared above were left to stand at 25 ° C. to start volatilization, and the liquid Composition 1A was volatilized to about 100 mL to obtain a terminal liquid specimen.
1 mL of the initial liquid sample or the final liquid sample and 1 mL of the internal standard solution (dibutyl phthalate 1 g/100 mL) were placed in a volumetric flask, and each volume was made up to 10 mL with acetone. The ethyl butyrate content of each sample was analyzed by gas chromatography (GC), and the initial value (%) was calculated from the peak areas of the initial liquid sample and the final liquid sample by the following formula.
vs. initial value (%) = (final liquid sample fragrance component peak area/internal standard peak area)/(initial liquid sample fragrance component peak area/internal standard peak area) x 100

The analysis method is shown below.
<GC analysis method>
Detector: hydrogen flame ionization detector Column: DB-17 (manufactured by Agilent) inner diameter 0.25 mm, length 30 m, film thickness 0.25 μm
Column temperature: After holding at 50°C for 5 minutes, the temperature was raised to 250°C at 8°C/min and held for 5 minutes Inlet temperature: 250°C
Detector temperature: 280°C
Carrier gas: Helium Flow rate: Adjusted so that the retention time of ethyl butyrate was 7 minutes.

4. Results The results are shown in Table 3 below. In Table 3, a case where the concentration change of the perfume component relative to the initial value was 90% or more was judged as "A (good)", and a case where it was less than 90% was judged as "B (bad)".

As can be seen from Table 3, when liquid composition 1A was volatilized using an upright volatilization device, the concentration of ethyl butyrate was 87% at the end of volatilization, whereas volatilization using an inverted volatilization device It was found that the concentration of ethyl butyrate was 96% and the change in the composition of the liquid composition was suppressed. Moreover, even when smelling the scent, when volatilizing using an inverted volatilization device, no change in the scent was observed.
A perfume component having a high vapor pressure, such as ethyl butyrate, is a perfume component that is felt first when one smells the scent, and that gives an impression of the scent. When volatilizing using an upright volatilization device, it is thought that the impression of the scent that is felt at the beginning is reduced. It is thought that the fragrance quality can be maintained.

<Test Example 2: Example 2, Comparative Example 2>
1. Preparation of Liquid Composition Based on the formulation shown in Table 4, each component was mixed to prepare Liquid Composition 2A.

2. Preparation of test specimens In the same manner as in Test Example 1, liquid composition 2A was used to prepare a test specimen using an inverted volatilization device (Example 2) and a test specimen using an upright volatilization device (Comparative Example 2). was made. Table 5 shows the details of the volatilization device.

3. Confirmation of Change in Aroma Quality of Perfume The contents of limonene and vanillin were analyzed by gas chromatography (GC) in the same manner as in Test Example 1, and the initial values were obtained from the peak areas of the initial and final samples. Regarding the analysis method, the flow rate was adjusted so that the retention time of limonene was about 12 minutes.
Table 5 shows the results.

As can be seen from Table 5, when the liquid composition 2A was volatilized using an upright volatilization device, in Comparative Example 2, the concentration of vanillin (vapor pressure at 25 ° C. 0.000016 kPa) was almost unchanged at the end of volatilization. On the other hand, the concentration of limonene (vapor pressure of 0.19 kPa at 25°C) decreased to 74%, and the concentration balance between limonene and vanillin in the liquid composition was lost. On the other hand, when the liquid composition 2A was volatilized using an inverted volatilization device, in Example 2, the concentration balance of limonene and vanillin remained almost unchanged even at the end of volatilization, and the change in aroma was suppressed. have understood. Moreover, even when smelling the scent, when volatilizing using an inverted volatilization device, no change in the scent was observed.
From this, when only perfume ingredients with a vapor pressure of less than 0.00005 kPa at 25 ° C. are used, even if volatilization is performed using an upright volatilization device, the concentration of the perfume is unlikely to change. It was found that when a perfume component having a vapor pressure of 0.00005 kPa or more at °C is used, changes in the fragrance quality of the perfume can be suppressed by volatilizing it using an inverted volatilization device.

<Test Example 3: Examples 3-4, Comparative Examples 3-4>
1. Preparation of Liquid Composition Based on the formulation shown in Table 6, each component was mixed to prepare Liquid Compositions 3A and 3B.

2. Preparation of test specimens In the same manner as in Test Example 1, liquid compositions 3A-3B were used to prepare test specimens using an inverted volatilization device (Examples 3-4) and test specimens using an upright volatilization device ( Comparative Examples 3 and 4) were produced. Table 7 shows the details of the volatilization device.

3. Confirmation of Aroma Quality Change of Perfume In the same manner as in Test Example 1, the contents of heptanal, octanal, nonanal, and decanal were analyzed by gas chromatography (GC), and the peak areas of the initial liquid specimen and the final liquid specimen were compared to the initial values. asked for
For the GC analysis, 1 mL of the initial liquid sample or the final liquid sample and 1 mL of the internal standard solution (dibutyl phthalate 1 g/100 mL) were placed in a volumetric flask and diluted to 10 mL with acetone.
Also, for the analysis method, the flow rate was adjusted so that the retention time of the internal standard solution was about 28 minutes.
Table 7 shows the results.

Examples 3 and 4 and Comparative Examples 3 and 4 are examples of using liquid compositions 3A and 3B in which the same perfume component was used, but the blending amount of the perfume component was changed. As can be seen from Table 7, when volatilization was performed using an upright volatilization device, the concentration of the perfume component decreased in all of Comparative Examples 3 and 4, and the concentration balance between the perfume components tended to collapse. When the inverted volatilization device was used, in all of Examples 3 and 4, the concentration of the perfume component was high even at the end of volatilization, and the concentration balance was maintained. Moreover, even when smelling the scent, when volatilizing using an inverted volatilization device, no change in the scent was observed.
From Example 4 and Comparative Example 4, when the content of a perfume component with a high vapor pressure such as a vapor pressure of 0.1 kPa or more at 25 ° C. is large, when volatilized using an upright volatilization device, the It was found that the decrease in the concentration of perfume ingredients with high vapor pressure was remarkable. Therefore, when the content of a perfume component having a high vapor pressure of 0.1 kPa or more at 25°C is high, it was found that vaporization using an inverted vaporization device is particularly effective.

<Test Example 4: Example 5, Comparative Example 5>
1. Preparation of Liquid Composition Based on the formulation shown in Table 8, each component was mixed to prepare Liquid Composition 4A.

2. Preparation of test specimens In the same manner as in Test Example 1, liquid composition 4A was used to prepare a test specimen using an inverted volatilization device (Example 5) and a test specimen using an upright volatilization device (Comparative Example 5). was made. Table 9 shows the details of the volatilization device.

3. Confirmation of fragrance change in fragrance In the same manner as in Test Example 1, the contents of limonene, linalyl acetate, dodecanal and α-hexyl cinnamaldehyde were analyzed by gas chromatography (GC), and the peaks of the initial liquid sample and the final liquid sample were analyzed. A pair initial value was obtained from the area.
For the GC analysis, 1 mL of the initial liquid sample or the final liquid sample and 1 mL of the internal standard solution (dibutyl phthalate 1 g/100 mL) were placed in a volumetric flask and diluted to 10 mL with acetone.
Also, for the analysis method, the flow rate was adjusted so that the retention time of the internal standard solution was about 28 minutes.
Table 9 shows the results.

The volatilization devices used in Example 5 and Comparative Example 5 have the same specifications for each member, and the difference is whether they are inverted volatilization or upright volatilization. As can be seen from Table 9, in the case of upright volatilization, the concentration of the perfume component decreased in Comparative Example 5, but in the case of inverted volatilization, all the perfume components remained at high concentrations in Example 5, and the concentration balance was also good. was maintained. In addition, even when smelling the scent, when volatilizing using an inverted volatilization device, no change in the scent was observed.

<Test Example 5: Examples 6 to 7, Comparative Examples 6 to 7>
1. Preparation of Liquid Composition Based on the formulation shown in Table 10, each component was mixed to prepare Liquid Composition 5A.

2. Preparation of test specimens In the same manner as in Test Example 1, liquid composition 5A was used to prepare test specimens using an inverted volatilization device (Examples 6 and 7) and test specimens using an upright volatilization device (Comparative Example 6-7) were prepared. The details of the volatilization device are shown in Table 11.

3. Confirmation of Aroma Quality Change of Perfume In the same manner as in Test Example 1, the contents of limonene and phenethyl alcohol were analyzed by gas chromatography (GC), and the initial values were obtained from the peak areas of the initial liquid sample and the final liquid sample. .
For the GC analysis, 1 mL of the initial liquid sample or the final liquid sample and 1 mL of the internal standard solution (dibutyl phthalate 1 g/100 mL) were placed in a volumetric flask and diluted to 10 mL with acetone.
Also, for the analysis method, the flow rate was adjusted so that the retention time of the internal standard solution was about 28 minutes.
Table 11 shows the results.

Examples 6 and 7 differ from each other only in the length of the absorbent material of the inverted volatilization device. As can be seen from Table 11, in all of Examples 6 and 7, the perfume component remained at a high concentration, and the concentration balance was maintained. Comparative Examples 6 and 7 differed from each other only in the specifications of the diameter of the absorbent material of the upright volatilization device, but in each case the concentration of the perfume component decreased. From these results, the significance of volatilization using an inverted volatilization device was confirmed. In addition, even when smelling the scent, when volatilizing using an inverted volatilization device, no change in the scent was observed.

<Test Example 6: Examples 8-9, Comparative Examples 8-9>
1. Preparation of Liquid Composition Based on the formulation shown in Table 12, each component was mixed to prepare Liquid Compositions 6A and 6B.

2. Preparation of test specimens In the same manner as in Test Example 1, liquid compositions 6A-6B were used to prepare test specimens using an inverted volatilization device (Examples 8-9) and test specimens using an upright volatilization device ( Comparative Examples 8-9) were produced. The details of the volatilization device are shown in Table 13.

3. Confirmation of Change in Aroma Quality of Perfume Limonene content was analyzed by gas chromatography (GC) in the same manner as in Test Example 1, and the initial value was calculated from the peak areas of the initial and final liquid samples.
For the GC analysis, 1 mL of the initial liquid sample or the final liquid sample and 1 mL of the internal standard solution (dibutyl phthalate 1 g/100 mL) were placed in a volumetric flask and diluted to 10 mL with acetone.
Also, for the analysis method, the flow rate was adjusted so that the retention time of the internal standard solution was about 28 minutes.
The results are shown in Table 13.

The liquid composition 6A is a formulation containing 0.1% by mass of perfume, and the liquid composition 6B is a formulation containing 0.5% by mass of perfume. As can be seen from Table 13, both liquid composition 6A and liquid composition 6B were volatilized using an inverted volatilization device, and it was found that the change in fragrance quality of the perfume could be suppressed. Moreover, even when smelling the scent, when volatilizing using an inverted volatilization device, no change in the scent was observed.

<Test Example 7: Examples 10 to 15, Comparative Examples 10 to 11>
1. Preparation of Liquid Composition Based on the formulation shown in Table 14, each component was mixed to prepare Liquid Compositions 7A to 7H. The liquid composition 7A has the same formulation as the liquid composition 6B of Test Example 6.

2. Preparation of test specimens In the same manner as in Test Example 1, liquid compositions 7A to 7H were used to prepare test specimens (Examples 10 to 15, Comparative Examples 10 to 11) using an inverted volatilization device. The details of the volatilization device are shown in Table 15.

3. Confirmation of aroma quality change of fragrance In the same manner as in Test Example 1, the content of limonene or α-hexylcinnamaldehyde was analyzed by gas chromatography (GC), and the peak areas of the initial liquid sample and the final liquid sample were compared to the initial value. asked for
For the GC analysis, 1 mL of the initial liquid sample or the final liquid sample and 1 mL of the internal standard solution (dibutyl phthalate 1 g/100 mL) were placed in a volumetric flask, and the volume was adjusted to 5 mL with acetone.
Also, for the analysis method, the flow rate was adjusted so that the retention time of the internal standard solution was about 28 minutes.
Table 15 shows the results.

Liquid compositions 7A and 7E contain 0.5% by mass of fragrance, liquid compositions 7B and 7F contain 0.1% by mass of fragrance, liquid compositions 7C and 7G contain 0.05% by mass of fragrance, liquid composition 7D, 7H is a formulation containing 0.01% by weight of perfume. As can be seen from Table 15, when 0.01% by mass or less of a fragrance component having a vapor pressure of 0.00005 kPa or more at 25°C is contained, it is difficult to suppress changes in fragrance quality of the fragrance.

<Test Example 8: Examples 16 to 21>
1. Preparation of Liquid Composition Based on the formulation shown in Table 16, each component was mixed to prepare Liquid Compositions 8A to 8F.
The surfactants include polyoxyethylene hydrogenated castor oil with an average added mole number of ethylene oxide (EO) of 40, polyoxyethylene decyl ether (EO 10) with an alkyl group having 10 carbon atoms, and fatty acid carbon number. of 12 polyoxyethylene sorbitan monolaurate (E.O.20) was used.

2. Preparation of test specimens In the same manner as in Test Example 1, liquid compositions 8A to 8F were used to prepare test specimens (Examples 16 to 21) using an inverted volatilization device. The details of the volatilization device are shown in Table 17.

3. Confirmation of fragrance quality change of perfume 3-1. Confirmation by liquid composition analysis In the same manner as in Test Example 1, the content of limonene or α-hexylcinnamaldehyde was analyzed by gas chromatography (GC), and the initial value was calculated from the peak areas of the initial liquid sample and the final liquid sample. rice field.
For the GC analysis, 1 mL of the initial liquid sample or the final liquid sample and 1 mL of the internal standard solution (dibutyl phthalate 1 g/100 mL) were placed in a volumetric flask and diluted to 10 mL with acetone.
Also, for the analysis method, the flow rate was adjusted so that the retention time of the internal standard solution was about 28 minutes.

3-2. Confirmation by gas phase analysis Two test specimens prepared above were prepared, one of them was left to stand under 25 ° C. conditions, volatilization was started, and the liquid composition was volatilized until it reached about 100 mL, and a terminal sample was obtained. . The test sample that was not volatilized was used as the initial sample.
A terminal sample or an initial sample was placed in a Tedlar bag with a volume of 10 L, sealed, and allowed to stand for 1 hour. After 1 hour, an organic solvent injection needle NeedlEx (manufactured by Shinwa Kako Co., Ltd.) was inserted into the Tedlar bag to collect 100 mL of internal air. The collected air was analyzed by gas chromatography (GC), and the initial value (%) was calculated from the peak areas of the initial sample and the final sample according to the following formula.
vs. initial value (%) = peak area of final sample/peak area of initial sample x 100

The analysis method in gas phase analysis is shown below.
<GC analysis method>
Detector: hydrogen flame ionization detector Column: DB-17 (manufactured by Agilent) inner diameter 0.25 mm, length 30 m, film thickness 0.25 μm
Column temperature: After holding at 50°C for 5 minutes, the temperature was raised to 250°C at 8°C/min and held for 5 minutes Inlet temperature: 200°C
Detector temperature: 280°C
Carrier gas: Helium Flow rate: For Examples 16-18, the retention time of limonene was adjusted to about 10 minutes, and for Examples 19-21, the retention time of α-hexylcinnamaldehyde was about 24 minutes. adjusted accordingly.

4. Results The results are shown in Table 17 below. Judgment in Table 17 is determined as "A (good)" when the liquid composition analysis is 90% or more of the initial value and the gas phase analysis is 90% or more of the initial value, and otherwise "B (poor)". )” was determined.

Liquid compositions 8A-8F are formulations with varying types of surfactants.
As can be seen from Table 17, no significant change in liquid composition was observed regardless of the type of surfactant. In addition, in Examples 16 to 21, both the liquid composition analysis and the gas phase analysis showed that the concentration change of the fragrance component relative to the initial value was 90% or more, and it was confirmed that the concentration change of the fragrance component was suppressed. .

<Test Example 9: Examples 22 to 26>
1. Preparation of Liquid Composition Based on the formulation shown in Table 18, each component was mixed to prepare Liquid Compositions 9A to 9E.

2. Preparation of test specimens In the same manner as in Test Example 1, liquid compositions 9A to 9E were used to prepare test specimens (Examples 22 to 26) using an inverted volatilization device. The details of the volatilization device are shown in Table 19.

3. Confirmation of fragrance quality change of perfume 3-1. Confirmation by liquid composition analysis In the same manner as in Test Example 1, the content of isoamyl acetate, geraniol, or vanillin was analyzed by gas chromatography (GC), and the initial value was obtained from the peak areas of the initial liquid sample and the final liquid sample. .
For the GC analysis, 1 mL of the initial liquid sample or the final liquid sample and 1 mL of the internal standard solution (dibutyl phthalate 1 g/100 mL) were placed in a volumetric flask and diluted to 10 mL with ethanol.
Regarding the analysis method, nitrogen was used as a carrier gas, and the flow rate was adjusted so that the retention time of the internal standard solution was about 28 minutes.

3-2. Confirmation by vapor phase analysis For Examples 24 and 26, vapor phase analysis was also performed.
The content of isoamyl acetate, geraniol or vanillin was analyzed by gas chromatography (GC) in the same manner as the confirmation by gas phase analysis in Test Example 8.
Regarding the analysis method, nitrogen was used as a carrier gas, and the retention time of isoamyl acetate was adjusted to about 10 minutes.

4. Results The results are shown in Table 19 below. In Table 19, the overall judgment is "A (good)" when all the initial values in the concentration change of the perfume component are 90% or more, and otherwise "B (poor)". bottom.

Liquid compositions 9A to 9E are formulations in which three perfume components (top note, middle note, base note) with different vapor pressures are used and the content is changed.
As can be seen from Table 19, all of Examples 22 to 26 were able to suppress the change in aroma quality, and it was found that an excellent effect of suppressing the change in aroma quality was obtained.

<Test Example 10: Examples 27-28>
1. Preparation of Liquid Composition Based on the formulation shown in Table 20, each component was mixed to prepare Liquid Compositions 10A to 10B.

2. Preparation of Test Specimens In the same manner as in Test Example 1, liquid compositions 10A and 10B were used to prepare test specimens (Examples 27 and 28) using an inverted volatilization device. The details of the volatilization device are shown in Table 21.

3. Confirmation of flavor change of fragrance In the same manner as in Test Example 1, the content of isoamyl acetate, geraniol or vanillin was analyzed by gas chromatography (GC), and the initial value was calculated from the peak areas of the initial liquid sample and the final liquid sample. asked.
For the GC analysis, 1 mL of the initial liquid sample or the final liquid sample and 1 mL of the internal standard solution (dibutyl phthalate 1 g/100 mL) were placed in a volumetric flask and diluted to 10 mL with ethanol.
Regarding the analysis method, nitrogen was used as a carrier gas, and the flow rate was adjusted so that the retention time of the internal standard solution was about 28 minutes.
The results are shown in Table 21.

Liquid compositions 10A-10B are formulations with varying amounts of ethanol.
As can be seen from Table 21, in all of Examples 27 and 28, an excellent effect of suppressing changes in aroma quality was confirmed.

<Test Example 11: Examples 29 to 35>
1. Preparation of Liquid Composition Based on the formulation shown in Table 22, each component was mixed to prepare Liquid Compositions 11A to 11G.
Surfactant B in Table 21 is composed of 50% by mass of polyoxyethylene hydrogenated castor oil (E.O.60), 49% by mass of polyoxyethylene secondary alkyl ether, and 1% by mass of sodium dioctyl sulfosuccinate. Become.

2. Preparation of test specimens In the same manner as in Test Example 1, liquid compositions 11A to 11G were used to prepare test specimens (Examples 29 to 35) using an inverted volatilization device. The details of the volatilization device are shown in Table 23.

3. Confirmation of Change in Aroma Quality of Fragrance In the same manner as in Test Example 1, the content of each fragrance component was analyzed by gas chromatography (GC), and the initial value was obtained from the peak areas of the initial liquid sample and the final liquid sample.
For the GC analysis, 1 mL of the initial liquid sample or the final liquid sample and 1 mL of the internal standard solution (dibutyl phthalate 1 g/100 mL) were placed in a volumetric flask and diluted to 10 mL with ethanol.
As for the analysis method, helium was used as a carrier gas, and the flow rate was adjusted so that the retention time of the internal standard solution was about 28 minutes.
The results are shown in Table 23. Also in Table 23, the overall judgment was "A (good)" when all the perfume ingredients contained were 90% or more of the initial value, and "B (poor)" in other cases.

Liquid compositions 11A to 11G are formulations using combinations of perfume ingredients having different vapor pressures.
As can be seen from Table 23, all of Examples 29 to 35 contain 0.02% by mass or more of a fragrance component having a vapor pressure of 0.00005 kPa or more at 25 ° C., thereby obtaining an excellent effect of suppressing changes in fragrance quality. I understand.

<Test Example 12: Examples 36-37>
1. Preparation of Liquid Composition Based on the formulation shown in Table 24, each component was mixed to prepare Liquid Compositions 12A to 12B.

2. Preparation of Test Specimens In the same manner as in Test Example 1, liquid compositions 12A and 12B were used to prepare test specimens (Examples 36 and 37) using an inverted volatilization device. The details of the volatilization device are shown in Table 25.

3. Confirmation of fragrance quality change of perfume 3-1. Confirmation by liquid composition analysis The limonene content was analyzed by gas chromatography (GC) in the same manner as in Test Example 1, and the initial value was obtained from the peak areas of the initial liquid sample and the final liquid sample.
For the GC analysis, 1 mL of the initial liquid sample or the final liquid sample and 1 mL of the internal standard solution (dibutyl phthalate 1 g/100 mL) were placed in a volumetric flask and diluted to 10 mL with acetone.
As for the analysis method, helium was used as a carrier gas, and the flow rate was adjusted so that the retention time of the internal standard solution was about 28 minutes.

3-2. Confirmation by gas phase analysis In the same manner as confirmation by gas phase analysis in Test Example 8, the content of limonene was analyzed by gas chromatography (GC).
Regarding the analysis method, nitrogen was used as a carrier gas, and the retention time of limonene was adjusted to about 10 minutes.

4. Results The results are shown in Table 25 below. The determination in Table 25 is the same as in Test Example 8.

Liquid compositions 12A-12B are formulations with varying amounts of surfactant.
When the content of the surfactant increases, it becomes easier to supplement the fragrance component, so it tends to become difficult to suppress the change in fragrance quality.

Although the present invention has been described in detail and with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention. This application is based on a Japanese patent application (Japanese Patent Application No. 2021-129918) filed on August 6, 2021, the contents of which are incorporated herein by reference.

REFERENCE SIGNS LIST 10 inverted volatilization device 11 bottle 12 lower container 13 liquid composition 15 volatilization opening 16 locking protrusion 17 engaging portion 18 opening 19 liquid absorbing material 20 middle plug 21 cap 22 volatilization body 23 liquid pool chamber 24 base 25 volatilization Part 26 liquid absorption part 27 bottom plate 30 inverted volatilization device 31 bottle 32 liquid composition 33 middle plug 35 liquid absorption material 37 volatilization body 39 lower container 39a volatilization opening 40 upright volatilization device 41 bottle 42 liquid composition 43 medium Stopper 45 Absorbent material 47 Volatile body 49 Upper container 49a Opening for volatilization

Claims (4)

A method for suppressing a change in the fragrance quality of a fragrance when volatilizing the fragrance from a liquid composition containing the fragrance,
The liquid composition contains a perfume component having a vapor pressure of 0.00005 kPa or more at 25° C. at a rate of 0.02% by mass or more, and the liquid composition is volatilized using an inverted volatilization device. A method for suppressing changes in aroma quality. In the liquid composition, 0.02% by mass or more of a fragrance component having a vapor pressure of 0.00005 kPa or more and less than 0.01 kPa at 25°C and 0.02 mass of a fragrance component having a vapor pressure of 0.01 kPa or more at 25°C % or more, the method of suppressing the change of the fragrance quality of the fragrance according to claim 1. a bottle containing a liquid composition;
an inner plug that closes the bottom opening of the bottle in an inverted state;
a liquid-absorbent material that penetrates the inner plug and has a tip located inside and outside the bottle;
a lower container assembled to the bottom of the bottle in an inverted state;
a volatilization body housed in the lower container and in contact with the liquid-absorbing material,
The inverted volatilization device, wherein the liquid composition contains 0.02% by mass or more of a perfume component having a vapor pressure of 0.00005 kPa or more at 25°C. The liquid composition contains 0.02% by mass or more of a fragrance component having a vapor pressure of 0.00005 kPa or more and less than 0.01 kPa at 25°C and 0.02% by mass of a fragrance component having a vapor pressure of 0.01 kPa or more at 25°C. The inverted volatilization device according to claim 3, containing at the above ratio.

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