JP7496053B2 - Fragrance composition - Google Patents

Description

The present invention relates to a fragrance composition containing metal-doped mesoporous silica and a fragrance.

Bad odors are an issue that haunts people's lives, such as those emanating from toilets, garbage bins, and garbage dumps in homes and stores, and from waste liquids discharged from various factories. Generally, the odorous components that cause bad odors are known to be basic odorous components such as ammonia and trimethylamine; acidic odorous components such as acetic acid and isovaleric acid; and sulfur-containing odorous components such as methyl mercaptan and hydrogen sulfide. Eliminating odors is important for a hygienic and comfortable life.

There are various types of deodorants, including those that use physical adsorption, those that use chemical adsorption, and those that use biological means. Examples of deodorants that use physical adsorption include porous inorganic materials such as activated carbon. Porous inorganic materials deodorise by encapsulating malodorous components within their pores.

In recent years, there has been an increasing need to eliminate unpleasant odors and enjoy pleasant scents in daily life. This has led to a demand for air freshener products, cosmetics, and consumer goods that have a deodorizing effect and also have a pleasant scent. However, porous inorganic materials such as activated carbon are unable to meet these needs because they not only eliminate bad odors but also pleasant scents.

Patent Document 1 discloses porous silica doped with a metal X, which is Mn or Cu. The porous silica of Patent Document 1 can deodorize sulfur-containing odors with high efficiency and is applicable to applications such as deodorants for permed hair and liquid deodorants, but there is room for improvement in terms of selective deodorization, etc.

JP 2020-15640 A

There is a demand for fragrance compositions that emit a pleasant scent and can selectively eliminate bad odors.

According to the present invention, the following is provided:
[1] A fragrance composition comprising a metal-doped mesoporous silica doped with a metal and a fragrance.
[2] The fragrance composition according to [1] above, wherein the metal comprises at least one selected from the group consisting of copper, manganese and cobalt.
[3] The fragrance composition according to [1] or [2] above, wherein the pore diameter of the metal-doped mesoporous silica is 1 to 50 nm.
[4] The fragrance composition according to any one of [1] to [3] above, which is in the form of a solid, liquid, gel, powder, sheet or film, foam or flake.
[5] A deodorant product or fragrance product comprising the fragrance composition according to any one of [1] to [4] above.
[6] The deodorant product or fragrance product according to the above [5], further comprising a binder.
[7] A fragrance device comprising a flow path for guiding an air flow and the fragrance composition according to any one of [1] to [4] above, the fragrance composition being disposed in the flow path.

The present invention provides an aromatic composition that emits a pleasant scent and can selectively eliminate bad odors.

1. Fragrance Composition The present invention provides a fragrance composition as one embodiment. The fragrance composition of this embodiment contains metal-doped mesoporous silica, which has a high deodorizing effect on malodors and a low deodorizing effect on other odors such as fragrance components derived from perfumes. Furthermore, the fragrance composition of this embodiment contains perfume. Therefore, it can emit a pleasant fragrance and selectively deodorize malodors.

In this specification, an odor component means a component that stimulates the olfactory receptors of animals such as humans, pets, and livestock when exposed to the odor. Preferably, it is a component that can stimulate the olfactory receptors of humans.

In this specification, odor components can be classified into malodorous components and other odor components. Malodorous components are components that stimulate the olfactory receptors of animals when they are smelled, causing discomfort to the animals. Malodorous components are, for example, volatile substances having a structure containing at least one atom selected from the group consisting of carbon atoms, hydrogen atoms, nitrogen atoms, and sulfur atoms and having a functional group terminal, or volatile substances having a structure containing sulfur atoms. The term "volatile substance" refers to organic compounds that exist in the form of gas in the atmosphere and have a boiling point of 50 to 260°C.
The malodor component is preferably at least one component selected from the group consisting of basic malodor components, acidic malodor components, sulfur-containing malodor components, and aldehyde-based malodor components. Most preferably, it is at least one component selected from the group consisting of basic malodor components, acidic malodor components, and sulfur-containing malodor components. Examples of basic malodor components include ammonia and trimethylamine. Examples of acidic malodor components include acetic acid and isovaleric acid. Examples of sulfur-containing malodor components include methyl mercaptan, hydrogen sulfide, tert-butyl mercaptan, cysteamine, thioglycolic acid, cysteine, and thiazolidine. Examples of aldehyde-based malodor components include acetaldehyde, nonenal, propionaldehyde, normal butyraldehyde, isobutyraldehyde, normal valeraldehyde, and isovaleraldehyde.

<Metal-doped mesoporous silica>
The fragrance composition of this embodiment includes metal-doped mesoporous silica. Metal-doped mesoporous silica is porous silica that is doped with a metal and has mesopores.

In metal-doped mesoporous silica, a metal is doped into the porous silica. "Doped" refers to a state in which the metal is incorporated into the position of the Si element in the _SiO4 framework of the silica.

The type of doped metal (hereinafter sometimes referred to as metal X) may be selected according to the type of malodorous component to be deodorized. Specific examples of metal X include copper, manganese, cobalt, zinc, silver, calcium, iron, etc. For example, when sulfur-containing malodorous components are to be deodorized, metal X is preferably copper, manganese, cobalt, or iron. When malodorous components having a fatty acid structure or aldehyde-based malodorous components are to be deodorized, metal X is preferably cobalt, zinc, silver, or calcium. Metal X may be one type of metal or multiple types of metals.
In addition, although the acidic and basic malodorous components can be deodorized by the doped metal, they can also be deodorized by the inherent effect of the porous silica itself.

When multiple types of malodorous components are to be deodorized, a metal may be selected for each malodorous component, and the selected metals may be doped into the porous silica all at once. Alternatively, the selected metals may be doped into separate porous silicas to obtain multiple types of metal-doped mesoporous silica, which may then be combined in an appropriate ratio for use.

The metal X is preferably at least one selected from the group consisting of copper, manganese, and cobalt.

Doping porous silica with metal X can achieve higher malodor-eliminating properties than when metal X is present in granular form in porous silica without doping. This is believed to be because doping causes metal X to be present over the entire surface of the porous silica, which results in a larger contact area between the malodor components and metal X.
The term "present in the form of particles" refers to a state in which the metal is supported by the porous silica without being doped.

Moreover, the metal-doped mesoporous silica used in the fragrance composition of this embodiment is not only excellent at eliminating malodors, but can also quickly exert its excellent malodor eliminating properties.

In addition, when the fragrance composition is mixed into a liquid for use, if metal X is present without being doped, there is a risk that metal X will dissolve into the liquid as a metal ion. However, by doping metal X, it is possible to prevent metal X from being separated from the porous silica.

Furthermore, when metal X is contained in the porous silica in a doped form, the color that would be observed if metal X were present alone is reduced.

From the viewpoint of the balance between odor eliminating properties and ease of synthesis, the content of metal X in the metal-doped mesoporous silica is preferably 0.01 to 20 mass%, more preferably 0.01 to 10 mass%, and particularly preferably 0.1 to 5 mass%.

The metal-doped mesoporous silica preferably contains a metal other than metal X. The metal other than metal X may be doped or undoped.

An example of a metal different from metal X is metal Y, which is used to suppress hydrolysis of porous silica. Metal Y is preferably a metal selected from the group consisting of aluminum and zirconium. Aluminum is particularly preferred. From the viewpoint of increasing the hydrothermal durability of the metal-doped mesoporous silica, it is preferable that metal Y is also doped into the porous silica.

The content of metal Y in the metal-doped mesoporous silica is preferably 0.01 to 10 mass%, and more preferably 0.1 to 5 mass%. If the content of metal Y is too low, there is a risk that the specific surface area cannot be maintained during storage due to hydrolysis of the siloxane skeleton. If the content of metal Y is too high, there is a risk that a high specific surface area cannot be achieved.

At least a portion of the metal-doped mesoporous silica preferably has a chemical structure represented by the following formula 1.
(Formula 1): _{SiO2.aXOb /} 2.cYOd _/2
In formula 1, X represents metal X. Y represents metal Y. a represents a number greater than 0 and equal to or less than 0.1. c represents a number greater than 0 and equal to or less than 0.1. b and d represent the valences of metal X and metal Y, respectively.

It is preferable that at least a portion of the metal-doped mesoporous silica is irregular. Irregular shape means that it is multifaceted or has a rough, jagged surface. Irregular metal-doped mesoporous silica has the advantage that the metal-doped mesoporous silica adheres easily to fabrics when the fragrance composition of this embodiment is used in fabric products such as fabric detergents, fabric softeners, and ironing agents, or fabric deodorant products.

The specific surface area of the metal-doped mesoporous silica is preferably 500 m ² /g or more from the viewpoint of obtaining a high deodorizing effect. From the viewpoint of the strength for maintaining the pore structure, the upper limit of the specific surface area is preferably 2000 m ² /g or less. A more preferable specific surface area is 800 to 2000 m ² /g, and particularly 800 to 1600 m ² /g.

The pore diameter of the metal-doped mesoporous silica is preferably 1 to 50 nm, and from the viewpoint of enhancing selective deodorization, more preferably 2 to 10 nm. The pore diameter can be measured by gas adsorption method or small angle X-ray scattering method. It can be preferably measured by gas adsorption method. More preferably, it can be determined by the BJH method from the nitrogen gas adsorption isotherm.

The metal-doped mesoporous silica preferably has a selective deodorizing property represented by the following formula of 10 or more, and more preferably 10 to 30.
Selective deodorizing property=(B ₁ +B ₂ +B ₃ )/A
_B1 indicates the deodorizing amount (mmol/g) when 10 mg of metal-doped mesoporous silica was placed in a 500 ml container containing 1 μl of ammonia.
_B2 indicates the deodorizing amount (mmol/g) when 10 mg of metal-doped mesoporous silica was placed in a 500 ml container containing 1 μl of acetic acid.
_B3 indicates the deodorizing amount (mmol/g) when 10 mg of metal-doped mesoporous silica was placed in a 500 ml container containing 2 μl of methyl mercaptan.
A indicates the deodorizing amount (mmol/g) when 10 mg of metal-doped mesoporous silica is added to a 500 ml container containing 2 μl of an aromatic component. In this case, the aromatic component may be appropriately selected from a desired component, but is preferably at least one selected from the group consisting of limonene, pinene, cymene, terpinene, linalool, citral, ethyl butyrate, ethyl hexanoate, ethyl octanoate, ethyl decanoate, and terpineol. More preferably, it is at least one selected from (R)-(+)-limonene, ethyl butyrate, and α-terpineol. Particularly preferably, it is any one of (R)-(+)-limonene, ethyl butyrate, and α-terpineol. Most preferably, it is (R)-(+)-limonene.

The deodorizing capacity of the metal-doped mesoporous silica (B ₁ +B ₂ +B ₃ in the formula showing the selective deodorizing ability) is preferably 1 to 100 mmol/1g, and more preferably 10 to 100 mmol/1g.

The deodorizing amount of the metal-doped mesoporous silica (A in the formula showing the selective deodorizing property) is preferably 0.1 to 10 mmol/1g, more preferably 0.1 to 1 mmol/1g, and particularly preferably 0.1 mmol/1g or more and less than 1.00 mmol/1g.

In the metal-doped mesoporous silica, the ratio R represented by the following formula is preferably 3 or more, and more preferably 3 to 9.
Ratio R = ( _B1 + _B2 + _B3 ) / ( _A1 + _A2 + _A3 )
B ₁ to B ₃ are the same as B ₁ to B ₃ in the formula showing the selective deodorizing property.
_A1 indicates the deodorizing amount (mmol/g) when 10 mg of a powder sample was placed in a 500 ml container containing 2 μl of (R)-(+)-limonene.
_A2 indicates the amount of odor elimination (mmol/g) when 10 mg of a powder sample was placed in a 500 ml container containing 2 μl of ethyl butyrate.
_A3 indicates the deodorizing amount (mmol/g) when 10 mg of a powder sample was placed in a 500 ml container containing 2 μl of α-terpineol.

A in the formula showing the selective deodorizing property and A ₁ to A ₃ in the formula showing the ratio R can be measured with an odor monitor (for example, Handy Odor Monitor OMX-SR manufactured by Shin-Ei Technology Co., Ltd.). Specifically, a predetermined amount of the aroma component is placed in a 500 ml container, then 10 mg of metal-doped mesoporous silica is placed, and after one hour, the aroma component remaining in the container is measured using the odor monitor. In the same manner, the aroma component present in the container when no deodorant is used (blank) is measured. A and A ₁ to A ₃ are calculated by comparison with the blank measurement value.

_B1 to _B3 in the formula showing the selective deodorizing property and the formula showing the ratio R can be measured using a gas detector tube as shown in the examples described later. Specifically, a predetermined amount of malodorous components is placed in a 500 ml container, then 10 mg of metal-doped mesoporous silica is placed in the container, and after one hour, the concentration of the malodorous components remaining in the container is measured using a gas detector tube (e.g., manufactured by Gastec), and _B1 to _B3 are calculated by comparing with the initial concentration.

The unit of deodorizing amount is mmol/1g because, unlike other units such as ppm/1g, it is possible to eliminate the influence of molecular weight and makes it easier to compare the amount of deodorizing aromatics and the amount of deodorizing offensive odors.

Doping with metal X or metal Y is performed by dissolving a water-soluble metal salt containing metal X or metal Y in a solvent and mixing the resulting aqueous solution with porous silica or its precursor. When at least a portion of the metal-doped mesoporous silica is to be amorphous, amorphous porous silica or its precursor can be used as the raw material. Metal doping can be confirmed by measuring the chemical bond state using X-ray photoelectron spectroscopy or Raman spectroscopy.

The metal-doped mesoporous silica can be preferably obtained by a method comprising the following steps:
(A) A step of mixing a solvent, a surfactant, and a metal X-containing compound for doping with metal X to prepare a surfactant solution.
(B) A step of adding a silica source to a surfactant solution to generate micelles having the silica source accumulated on their surfaces.
(C) A step of condensing the accumulated silica source.
(D) After the condensation step, the micelles are recovered and calcined.
Each step will be described in detail below.

(A): Preparation of surfactant solution First, a surfactant and a metal doping compound are added to a solvent to prepare a surfactant solution. The surfactant solution is preferably stirred at room temperature (usually 20°C) or higher and 200°C or lower for 30 minutes to 10 hours. This causes the surfactant to form micelles.

For example, water can be used as the solvent. A mixture of water and an organic solvent such as ethanol or toluene can also be used as the solvent.

The amount of surfactant added is preferably 50 to 400 mmol/L, more preferably 50 to 150 mmol/L. Alternatively, the amount is preferably 0.01 to 5.0 mol, more preferably 0.05 to 1.0 mol per mol of the silica source to be added later.

The surfactant is not particularly limited, and any of cationic, anionic, and nonionic surfactants can be used. Preferably, the surfactant is neutral or cationic, and more preferably, an alkyl ammonium salt. The alkyl ammonium salt is preferably one having 8 or more carbon atoms, and more preferably one having 12 to 18 carbon atoms in view of ease of industrial availability. Examples of the alkyl ammonium salt include hexadecyl trimethyl ammonium chloride, cetyl trimethyl ammonium bromide, stearyl trimethyl ammonium bromide, cetyl trimethyl ammonium chloride, stearyl trimethyl ammonium chloride, dodecyl trimethyl ammonium bromide, octadecyl trimethyl ammonium bromide, dodecyl trimethyl ammonium chloride, octadecyl trimethyl ammonium chloride, didodecyl dimethyl ammonium bromide, ditetradecyl dimethyl ammonium bromide, didodecyl dimethyl ammonium chloride, and ditetradecyl dimethyl ammonium chloride. The surfactant may be used alone or in combination of two or more.

The metal X doping compound is a substance that serves as a source of metal X to be doped into the porous silica. As the metal X doping compound, a water-soluble compound containing metal X is preferable. More preferably, chloride, nitrate, sulfate, etc. of metal X are used.

For example, when the metal X is iron, iron(III) chloride or the like is added as the metal X doping compound.
For example, when the metal X is copper, copper(II) nitrate, copper chloride, etc. are added as metal X doping compounds.
For example, when the metal X is manganese, manganese(II) chloride or the like is added as a metal X doping compound.
For example, when the metal X is cobalt, cobalt nitrate or the like is added as a compound for supplying the metal X.
For example, when the metal X is zinc, zinc nitrate or the like is added as the metal X supplying compound.
For example, when the metal X is silver, silver nitrate or the like is added as the metal X supplying compound.
For example, when the metal X is calcium, calcium carbonate or the like is added as a metal X supplying compound.
The metal X doping compound may be used alone or in combination of two or more kinds.

The amount of metal X doping compound added is preferably 0.001 to 1 mol, more preferably 0.001 to 0.5 mol, and particularly preferably 0.01 to 0.1 mol per mol of silica source.

(B): Addition of Silica Source Next, a silica source is added to the surfactant solution.

The silica source is not particularly limited as long as it is a raw material for silica, but examples include tetraethoxysilane, tetramethoxysilane, tetra-n-butoxysilane, and sodium silicate. These silica sources may be used alone or in combination of two or more. The silica source is preferably an alkoxysilane. The silica source is more preferably tetraethoxysilane. The organic functional groups on the silicon atoms are lost by hydrolysis and do not affect the structure of the compound. However, if the organic functional groups are bulky, the hydrolysis rate slows down, and there is a risk that the synthesis time will be long.

The amount of silica source added is not particularly limited, but is preferably, for example, 0.2 to 1.8 mol/L. Alternatively, when the solvent contains water, the concentration of the silica source is preferably, for example, 0.001 to 0.05 mol per 1 mol of water.

(C): Condensation of the silica source Next, the silica source is condensed. Specifically, the pH of the solution is increased or decreased until the silica source is condensed. For example, the silica source can be condensed by adding a basic aqueous solution and stirring. The stirring is performed, for example, for 1 hour or more, particularly 1 to 24 hours. By adding the basic aqueous solution, the silica source accumulated on the surface of the micelles is dehydrated and condensed to form a silica wall.
Examples of the basic aqueous solution include aqueous solutions of sodium hydroxide, sodium carbonate, ammonia, etc. The basic aqueous solution is preferably an aqueous sodium hydroxide solution. These basic aqueous solutions may be used alone or in combination of two or more. The basic aqueous solution is added so that the pH is preferably 8 to 14, more preferably 9 to 11 immediately after the addition. The addition of the basic aqueous solution accelerates the dehydration condensation reaction of the silica source.
As a result, the surface tension of the condensed parts increases, the silica walls become spherical, and then the spheres join together in layers, causing spinodal decomposition (phase separation). These structures are frozen by chemical crosslinking.

The silica source has the property of condensing even at low pH. Therefore, the silica source can be condensed by adding an acidic aqueous solution instead of a basic aqueous solution.

(D): Recovery and calcination of micelles Next, the micelles are recovered as precursors from the aqueous solution. In particular, when the silica source is condensed, micelles precipitate. The precipitate is then filtered off to recover the micelles as precursors. The recovered precursors are dried. After drying, the precursors are calcined to remove the organic components contained in the precursors. In other words, the surfactant that constituted the micelles is removed. This results in the formation of porous silica having pores. The calcination is carried out at a temperature equal to or higher than the decomposition temperature of the surfactant. The calcination temperature is, for example, 400 to 600°C.

By the above method, porous silica doped with metal X can be obtained. This method is one example, and the order of the steps may be changed, steps may be deleted, or new steps may be added. For example, in the above method, an example in which the metal X doping compound is added in step (A) has been described, but the metal X doping compound does not necessarily have to be added in step (A) and may be added to the solution at any stage before the firing in step (D). If the accumulated silica source and the metal X doping compound are mixed in the solution, the metal X derived from the metal X doping compound is incorporated into the silica source, and porous silica doped with metal X is obtained.

When producing metal-doped mesoporous silica containing metal Y in addition to metal X, a compound for doping metal Y may be added at any stage prior to step (D). The compound for doping metal Y is a substance that serves as a source of metal Y. As the compound for doping metal Y, a water-soluble compound containing metal Y is preferably used. More preferably, a chloride, nitrate, sulfate, or the like of metal Y is used.

For example, when the metal Y is aluminum, aluminum chloride or the like is added as a compound for doping the metal Y.
For example, when the metal Y is zirconium, zirconium oxychloride or the like is added as a metal Y doping compound.
The metal Y doping compound may be used alone or in combination of two or more kinds.

The amount of the metal Y doping compound added is, for example, preferably 0.001 to 0.5 mol, more preferably 0.01 to 0.1 mol, per 1 mol of the silica source.

The content of metal-doped mesoporous silica in the fragrance composition of this embodiment is determined appropriately depending on the type of fragrance, the use of the fragrance composition, the type of malodorous component to be deodorized, etc., but is preferably 0.1 to 10 mass %, more preferably 0.5 to 2 mass %.

<Fragrance>
The fragrance composition of this embodiment contains a fragrance in addition to the metal-doped mesoporous silica.

The fragrance may be a natural fragrance, a synthetic fragrance, or a combination thereof, and may be a single fragrance or a blended fragrance. The fragrance may be described in various literature, for example, "Perfume and Flavor Materials of Natural Origin", Steffen Arctander, Allured Pub. Co. (1960), "Flower oils and Floral Compounds In Perfumery", Danute Pajaujis Anonis, Allured Pub. Co. (1993), "Perfume and Flavor Chemicals (aroma chemicals)", Vols. I and II, Steffen Arctander, Allured Pub. Co. (1994) can be used. Each of these is incorporated herein by reference. Representative examples of fragrances are listed below, but the fragrances are not limited to these.

Examples of natural fragrances include natural essential oils such as orange oil, lemon oil, lavender oil, lavandin oil, bergamot oil, patchouli oil, cedarwood oil, and peppermint oil.

Examples of synthetic fragrances include hydrocarbon terpenes such as pinene (α-pinene, β-pinene), limonene, cymene (p-cymene), terpinolene, terpinene (α-terpinene, γ-terpinene), α-phellandrene, myrcene, camphene, and o-cymene; heptanal, octanal, decanal, benzaldehyde, salicylic aldehyde, phenylacetaldehyde, citronellal, hydroxycitronellal, Aldehydes such as hydrotropic aldehyde, ligustral, citral, α-hexyl cinnamic aldehyde, α-amyl cinnamic aldehyde, lilial, cyclamen aldehyde, lyral, heliotropin, anisaldehyde, helional, vanillin, and ethyl vanillin; ethyl formate, methyl acetate, ethyl acetate, methyl propionate, methyl isobutyrate, ethyl isobutyrate, butyric acid, etc. Ethyl butyrate, propyl butyrate, isobutyl acetate, isobutyl isobutyrate, isobutyl butyrate, isobutyl isovalerate, ethyl 2-methyl valerate, isoamyl acetate, terpinyl acetate, isoamyl propionate, amyl propionate, amyl isobutyrate, amyl butyrate, amyl isovalerate, allyl hexanoate, ethyl acetoacetate, ethyl heptylate, heptyl acetate, methyl benzoate, ethyl benzoate, ethyl octylate, styraryl acetate, benzyl acetate, nonyl acetate, bornyl acetate, linalyl acetate, ortho-tert-butyl cyclohexyl acetate, linalyl benzoate, benzyl benzoate, triethyl citrate, ethyl cinnamate, methyl salicylate, hexyl salicylate, hexyl a Acetate, hexyl butyrate, menthyl acetate, terpinyl acetate, anisyl acetate, phenylethyl isobutyrate, methyl jasmonate, methyl dihydrojasmonate, ethylene brassylate, γ-undecalactone, γ-nonyl lactone, cyclopentadecanolide, coumarin, ethyl caproate, ethyl octanoate, ethyl decanoate, and other esters and lactones; anisole, p-cresyl methyl ether, dimethylhydroquinone, methyl eugenol, β-naphthol methyl ether, β-naphthol ethyl ether, anethole, diphenyl oxide, rose oxide, galaxolide, ambrox, and other ethers; isopropyl alcohol, cis-3-hexenol, heptanol, 2-octanol, dimetol, dihydromyrcenol, linalool, benzyl alcohol, citronellol, geraniol, Alcohols such as menthol, nerol, terpineol, tetrahydrogeraniol, l-menthol, cedrol, santalol, thymol, anise alcohol, phenylethyl alcohol, and hexanol; ketones such as diacetyl, menthone, isomenthone, thiomenthone, acetophenone, α- or β-damascone, α- or β-damascenone, α-, β- or γ-ionone, α-, β- or γ-methylionone, methyl-β-naphthyl ketone, benzophenone, tentalome, acetyl cedrene, α- or β-isomethylionone, α-, β- or γ-irone, maltol, ethyl maltol, cis-jasmone, dihydrojasmone, l-carvone, dihydrocarvone, and methyl amyl ketone; camphor, 1,8-cineole, allyl amyl glycolate, isopulegol, ligustral, and allyl caproate.

The fragrance may be used alone or in any combination of two or more kinds. Furthermore, the fragrance may be a fragrance composition further containing a solvent, a fragrance stabilizer, etc.

The content of the fragrance in the fragrance composition of this embodiment is determined appropriately depending on the type of fragrance, the purpose of the fragrance composition, the type of malodorous component to be deodorized, etc., but is preferably 0.01 to 1 mass %, more preferably 0.1 to 0.5 mass %.

The fragrance composition of this embodiment may be in any state, for example, a solid, liquid, gel, powder, sheet or film, foam, or flake.

The fragrance composition of this embodiment may contain other materials in addition to the metal-doped mesoporous silica and the fragrance.

When the fragrance composition of this embodiment is in liquid form, it may contain other ingredients such as alcohol, water, etc.

When the fragrance composition of this embodiment is made into a gel, it may contain other materials such as a superabsorbent resin, a dye, a preservative, and water.

When the fragrance composition of this embodiment is in the form of a sheet or film, for example, a paper, cloth, resin sheet or film, etc., into which metal-doped mesoporous silica has been previously kneaded, may be impregnated with a fragrance dissolved in a solvent.

The fragrance composition of this embodiment can be produced by mixing the metal-doped mesoporous silica, the fragrance, and any other ingredients that may be used, by known means.

<Applications>
The fragrance composition of this embodiment can be used as a deodorant or fragrance by itself.

Deodorants or air fresheners are used in items that require the elimination of bad odors and the release of fragrance. For example, they can be used in a variety of items, including chests of drawers, closets, clothing cases, shoe cabinets, trash cans, kitchen sinks and their drains, toilets and their drains, cars, refrigerators, freezers, food storage containers, food storage bags, bath and sink drains, and air conditioners.

It can also be used on fabrics such as clothing, underwear, stockings, socks, bags, futons, futon covers, cushions, blankets, carpets, curtains, sofas, air filters, air purifier filters, masks, diapers, toilet seats, car floor mats and seats, car air conditioner filters, etc.

The fragrance composition of this embodiment can also be used in a deodorant product or fragrance product by being contained in a container, supported on a carrier, or placed in a device. Examples of deodorant products or fragrance products include a free-standing type, a type filled in a spray container (hereinafter sometimes referred to as a spray deodorant product or spray fragrance product), a type filled in an aerosol can (hereinafter sometimes referred to as an aerosol deodorant product or aerosol fragrance product), and a sheet-type type. Examples of fragrance products include a fragrance device that is equipped with a flow path that guides an air flow and the fragrance composition of this embodiment, and in which the fragrance composition of this embodiment is placed in the flow path.

When the fragrance composition of this embodiment is used in a spray deodorant product or a spray air freshener product, for example, the metal-doped mesoporous silica and the fragrance, together with any other additives, may be mixed in a solvent or dispersion medium such as water or alcohol to form a fragrance composition, and the fragrance composition may be filled into a spray container or the like. As the spray container, a known type such as a trigger spray container may be used.

When the fragrance composition of this embodiment is used in an aerosol deodorant product or an aerosol fragrance product, for example, the metal-doped mesoporous silica and the fragrance, together with any other additives, may be mixed in a solvent or dispersion medium such as water or alcohol to form a fragrance composition, and the fragrance composition may be filled into an aerosol can or the like together with a propellant. Any known propellant may be used, such as LPG, DME, carbon dioxide, or HFC.

When the fragrance composition of this embodiment is used in a spray deodorant product, a spray air freshener product, an aerosol deodorant product, or an aerosol air freshener product, it is preferable that the fragrance composition of this embodiment contains a binder as another additive in order to improve adhesion to the target object. Examples of binders include urethane resins, acrylic resins, aminoplast resins, epoxy resins, glyoxal resins, and ethylene urea resins. Urethane resins and acrylic resins are preferred, and urethane resins are particularly preferred. As such urethane resins, polyurethane emulsions or water-soluble urethane resins are preferably used. The content of the binder can be appropriately determined depending on the composition of the fragrance composition of this embodiment, but is preferably 0.1 to 10% by mass from the viewpoint of a balance between ease of adhesion and ease of cleaning.

When the fragrance composition of this embodiment is used in a fragrance device, the fragrance composition of this embodiment is usually placed in a flow path that guides airflow, preferably inside the flow path that guides airflow, or at the exit or entrance of the flow path, and particularly preferably inside the flow path. The fragrance device is preferably equipped with a blower such as a fan to facilitate contact of the fragrance composition of this embodiment with air, or to facilitate sending air that has come into contact with the fragrance composition of this embodiment to the outside.

In addition to deodorant products and fragrance products, the fragrance composition of this embodiment may be contained in products in fields that use fragrances and require deodorizing properties, such as cosmetics and consumer goods.

The cosmetics may be cosmetics for any purpose, but are preferably cosmetics for hair (for hair in the case of animals other than humans), facial cosmetics, fragrance cosmetics, or body cosmetics. Examples of cosmetics for hair (for hair) include shampoo, rinse, conditioner or treatment, hairspray, hair wax, etc. Examples of cosmetics for the face include basic cosmetics such as face wash cream, cold cream, massage cream, milky lotion, lotion, beauty essence, pack, makeup remover, etc.; finishing cosmetics such as foundation, face powder, talcum powder, lipstick, lip balm, blusher, eyeliner, mascara, eye shadow, eyebrow pencil, nail enamel, enamel remover, etc. Examples of fragrance cosmetics include perfume, solid perfume, fragrance powder, etc. Examples of body cosmetics include body cleansers, body powders, deodorant products (antiperspirants, etc.), bath additives, body lotions, sunscreens, hand creams, etc.

Examples of consumer goods include the fabrics described above; fabric products such as fabric detergents, fabric softeners, and ironing agents; sheet or film products such as medical wrapping paper and film, food wrapping paper and film, freshness-preserving paper and film, wallpaper, tissue paper, toilet paper, garbage bags, and wet towels; nursing care products such as diapers and portable toilets; and pet supplies. Preferably, the fragrance composition of this embodiment is contained in fabrics or fabric products.

2. Cosmetics or consumer goods Up to this point, a fragrance composition has been described as one embodiment of the present invention, but as another embodiment of the present invention, there is provided a cosmetic or consumer goods comprising a metal-doped mesoporous silica and a fragrance. In the manufacturing process of the cosmetic or consumer goods of this embodiment, the metal-doped mesoporous silica and the fragrance may be blended together or separately.

The cosmetic or consumer product of this embodiment, like the fragrance composition, selectively deodorizes malodors and does not deodorize other odors such as fragrance components derived from fragrances. The characteristics, physical properties, and manufacturing method of the metal-doped mesoporous silica and fragrance contained in the cosmetic or consumer product of this embodiment are as described in Section 1. Fragrance composition. In addition, the explanation of other materials that can be used optionally, and the explanation of the cosmetic and consumer product are also as described in Section 1. Fragrance composition.

However, the amount of metal-doped mesoporous silica contained in the cosmetic or consumer product of this embodiment is preferably 0.1 to 10% by mass, and more preferably 0.5 to 2% by mass.

The amount of fragrance contained in the cosmetic or consumer product of this embodiment is preferably 0.01 to 1% by mass, and more preferably 0.1 to 0.5% by mass.

3. Metal-doped mesoporous silica As yet another embodiment of the present invention, there is provided a metal-doped mesoporous silica that is doped with a metal and is used in fragrance-containing cosmetics or fragrance-containing consumer goods. The characteristics, properties, and production method of the metal-doped mesoporous silica of this embodiment are as described in the section 1. Fragrance composition. In addition, the description of the fragrance and other materials that can be used optionally, deodorant products, fragrance products, cosmetics, and consumer goods are also as described in the section 1. Fragrance composition.

The following describes examples of the present invention. However, the present invention should not be construed as being limited to these examples.

Example 1
Hexadecyltrimethylammonium chloride as a surfactant, copper chloride as a compound for doping metal X, and aluminum chloride as a compound for doping metal Y were added to water as a solvent, and the mixture was stirred at 100° C. for 1 hour. After the aqueous solution was cooled to room temperature, tetraethoxysilane was added as a silica source and stirred. Sodium hydroxide was then added as a condensation catalyst and stirred. The amount of each compound added was the following amount per mole of tetraethoxysilane.
Surfactant (hexadecyltrimethylammonium chloride): 0.225 mol Metal X doping compound (copper chloride): 0.0204 mol Metal Y doping compound (aluminum chloride): 0.0482 mol Water: 125 mol Sodium hydroxide: 0.195 mol The solid product was filtered from the obtained suspension, dried, and then fired to remove organic components, thereby obtaining metal-doped mesoporous silica. The obtained metal-doped mesoporous silica was used as the powder sample of Example 1. The specific surface area of the powder sample of Example 1 was 1100 m ² /g, and the pore size was 2.51 nm. The specific surface area and pore size were determined by the BJH method from the nitrogen gas adsorption isotherm at liquid nitrogen temperature.

<Comparative Example 1>
Activated carbon powder (Kuraray Coal (registered trademark) GG) manufactured by Kuraray Co., Ltd. was prepared as a powder sample of Comparative Example 1.

<Comparative Example 2>
Activated carbon powder (CAS RN: 7440-44-0) manufactured by Tokyo Chemical Industry Co., Ltd. was prepared as a powder sample of Comparative Example 2.

<Comparative Example 3>
Mesoporous silica MCM-41 (CAS RN: 7631-86-9) manufactured by Sigma-Aldrich was prepared as a powder sample for Comparative Example 3. The specific surface area of this powder sample was 894 m ² /g and the pore diameter was 2.61 nm. The specific surface area and pore diameter were determined by the BJH method from the nitrogen gas adsorption isotherm at liquid nitrogen temperature.

<Deodorizing properties>
The following odor components were prepared:

Three 500 mL Erlenmeyer flasks were prepared, and the amount (μl) of (R)-(+)-limonene shown in the table below was dropped into each Erlenmeyer flask and allowed to volatilize. 10 mg of the powder samples of Example 1, Comparative Example 1, and Comparative Example 2 were added to separate Erlenmeyer flasks. The amount of (R)-(+)-limonene in the Erlenmeyer flasks after one hour was measured using an odor monitor (Handy Odor Monitor OMX-SR, Shin-Ei Technology Co., Ltd.). In the same manner, the aromatic components present in the container when no deodorant was used (blank) were measured. The deodorizing amount of (R)-(+)-limonene was calculated by comparing with the blank measurement value.
In the same manner, the deodorizing amounts of ethyl butyrate and α-terpineol were calculated.

In addition, three 500 mL Erlenmeyer flasks were prepared, and the amount (μl) of ammonia shown in the table below was dropped into each Erlenmeyer flask and allowed to volatilize. 10 mg of the powder samples of Example 1, Comparative Example 1, and Comparative Example 2 were added to each Erlenmeyer flask. The amount of ammonia in the Erlenmeyer flask after one hour was measured using a gas detector tube (manufactured by Gastec). The amount of ammonia deodorized was calculated by comparing with the initial concentration.
In the same manner, the deodorizing amounts of acetic acid and methyl mercaptan were calculated.
The amount of ammonia and acetic acid dropped was small so that the initial concentrations would be similar to those of the other odor components.
The results are shown in the table below.

The initial concentration (ppm) values in the above table were calculated from the drop amounts using the following formula.
In the formula, M represents the molecular weight (g/mol). T represents the room temperature (°C) during the experiment. P represents the room pressure (hPa) during the experiment. During the experiment, the room temperature was 20°C and the room pressure was 1,013 hPa.

The powder of Example 1 had odor eliminating properties equal to or greater than those of the activated carbons of Comparative Examples 1 and 2.

In the Erlenmeyer flask to which the powder of Example 1 was added, significantly more aromatic components remained than in the Erlenmeyer flask to which the activated carbon of Comparative Examples 1 and 2 was added, and the aromatic and deodorizing properties of the powder of Example 1 were lower than those of the activated carbon of Comparative Examples 1 and 2.

Based on the following formula, the selective deodorizing properties of the powders of Example 1, Comparative Example 1, and Comparative Example 2 were calculated. The results are shown in the table below.
Selective deodorizing property=(B ₁ +B ₂ +B ₃ )/A
In the formula, _B1 represents the amount of ammonia deodorization (mmol/g).
_B2 indicates the deodorizing amount of acetic acid (mmol/g).
_B3 indicates the deodorizing amount of methyl mercaptan (mmol/g).
A indicates the deodorizing amount of the aromatic component (mmol/g).

Based on the following formula, the ratio R of the total amount of malodor removal to the total amount of aroma removal was calculated for the powders of Example 1, Comparative Example 1, and Comparative Example 2. The results are shown in the table below.
Ratio R = ( _B1 + _B2 + _B3 ) / ( _A1 + _A2 + _A3 )
B ₁ to B ₃ have the same meaning as B ₁ to B ₃ in the formula showing the selective deodorizing property.
_A1 indicates the deodorizing amount (mmol/g) of (R)-(+)-limonene.
_A2 indicates the deodorizing amount of ethyl butyrate (mmol/g).
_A3 indicates the deodorizing amount of α-terpineol (mmol/g).

<Deodorizing speed>
Two 500 mL Erlenmeyer flasks were prepared, and hydrogen sulfide gas was prepared in each Erlenmeyer flask using a permeator so that the initial concentration was 19 ppm. 10 mg of the powder samples of Example 1 and Comparative Example 3 were added to each Erlenmeyer flask. The amount of hydrogen sulfide in the Erlenmeyer flask after 5 minutes was measured using a gas detector tube (manufactured by Gastec).
The results are shown in the table below.

The powder of Example 1 has a faster deodorizing speed than the powder of Comparative Example 3. Since there is no significant difference in the specific surface area and pore size between the powder of Example 1 and the powder of Comparative Example 3, it is believed that the faster deodorizing speed of the powder of Example 1 is due to the effect of metal doping.

Considering all the above-mentioned various properties, it was found that when a composition containing the metal-doped mesoporous silica powder of Example 1 and a fragrance was prepared, such a composition could effectively emit an aroma derived from the fragrance and selectively and quickly deodorize bad odors.

Claims (8)

A fragrance composition comprising a metal-doped mesoporous silica and a fragrance ,
the metals are copper and aluminum;
The content of the fragrance in the fragrance composition is 0.01 to 1% by mass,
The content of the metal-doped mesoporous silica in the fragrance composition is 0.1 to 10 mass % . The fragrance composition according to claim 1 , wherein the pore diameter of the metal-doped mesoporous silica is from 1 to 50 nm. 3. The fragrance composition according to claim 1, wherein the content of copper in the metal-doped mesoporous silica is 0.01 to 10 mass %. The fragrance composition according to any one of claims 1 to 3, wherein the content of the aluminum in the metal-doped mesoporous silica is 0.01 to 10 mass %. The fragrance composition according to any one of claims 1 to 4 , which is in the form of a solid, liquid, gel, powder, sheet or film, foam or flake. A deodorant or fragrance product comprising the fragrance composition according to any one of claims 1 to 5 . 7. The deodorant or fragrance product of claim 6 , further comprising a binder. The present invention is provided with a flow path for guiding an air flow and the fragrance composition according to any one of claims 1 to 5 ,
The fragrance device, wherein the fragrance composition is disposed in the flow path.