JP2024092375A - Textile product treatment composition - Google Patents

Abstract

[Problem] To provide a textile product treatment composition that suppresses the growth of bacteria that cause malodorous components and has excellent masking properties, resulting in an excellent feeling of use and a clean feeling. [Solution] A composition containing (a) one or more specific quaternary ammonium salts (1), (b) one or more quaternary ammonium salts (2) different from the quaternary ammonium salts (1), and (c) microcapsules encapsulating a fragrance component (1) is produced and used as a textile product treatment composition. [Selected Figure] None

Description

The present invention relates to a textile product treatment composition.

In recent years, the value consumers seek in laundry products has expanded beyond the traditional dirt removal performance to include a variety of fragrances and hygienic properties such as antibacterial properties.

In particular, with regard to antibacterial properties, it has become clear that microorganisms that emerge when clothes are not completely dried produce unpleasant odors, and measures to address this are desirable. A specific example of a microorganism known is M. osloensis, which produces 4-methyl-3-hexenoic acid (4M3H), an unpleasant odor component, by assimilating ante-iso fatty acids that remain in clothing fibers and originate from sebum stains that cannot be completely removed even with careful washing (Patent Document 1).

Conventionally, measures to address the above-mentioned issues have included masking with fragrances, disinfection with detergents, and antibacterial treatment with fabric softeners. Patent Documents 2 and 3 disclose deodorizing fabric softener compositions that use biodegradable quaternary ammonium compounds and benzalkonium chloride. These prior art documents also disclose that the cause of the odor is bacterial.

Furthermore, Patent Documents 4 and 5 disclose technologies for liquid fabric softener compositions that contain capsules and monoalkyl cations, have high freeze recovery properties, and have good dispersibility of the encapsulated fragrances that are incorporated therein.

JP 2012-97367 A JP 2001-336065 A JP 2019-131943 A JP 2015-034371 A, JP 2015-227515 A

However, bacteria grow easily when the conditions for growth are right, and it is thought that, for example, by using sweat and sebum that accumulates over a long period of wear as nutrients, an unpleasant odor that is not noticeable immediately after wearing can be observed. In particular, M. osloensis (Moraxella osloensis) is known to be a bacterium that produces a characteristic unpleasant odor that reoccurs if the product becomes wet for a while after wearing it due to sweating or rain, even if the product has been treated and dried using a common antibacterial detergent or fabric softener, and therefore there is a need to suppress the growth of microorganisms for the long term.

In addition, textile product treatments that contain quaternary ammonium salts, such as fabric softener compositions, can become unstable depending on storage conditions, and when stored in direct sunlight, particularly in stores or at home, some of the components may condense and form a gel. In such cases, a concentration gradient of microcapsules in the composition is created, leading to uneven adsorption to clothing, and sufficient deodorizing effects through masking may not be expected.

The present invention provides a textile product treatment composition that suppresses the proliferation of M. osloensis, the main bacterium that produces 4-methyl-3-hexenoic acid (4M3H), a malodor component, and provides consumers with an excellent feeling of use and cleanliness through its excellent masking performance.

The present invention relates to a textile product treatment composition containing (a) one or more quaternary ammonium salts (1) represented by the following general formula (1), (b) one or more quaternary ammonium salts (2) represented by the following general formula (2), and (c) microcapsules encapsulating a fragrance component (1).

[In the formula, R ¹ is an alkyl group or alkenyl group having 12 to 22 carbon atoms. Y is -COO-, -CONR ⁵ -, -OCO-, or -NR ⁵ CO-. Here, R ⁵ is a hydrogen atom, an alkyl group or a hydroxyalkyl group having 1 to 3 carbon atoms. R ² is an alkylene group having 1 to 5 carbon atoms. Each R ³ is independently an alkyl group having 1 to 3 carbon atoms, -R ² -OH, or -R ² -Y-R ^1. However, when two or more kinds of quaternary ammonium salts (1) are contained, at least one Y is -COO- or -OCO-. R ⁴ is an alkyl group having 1 to 3 carbon atoms. X ^- is a counter anion.]

[In the formula, R ⁶ is an alkyl group or alkenyl group having 5 to 19 carbon atoms, R ⁷ is an alkylene group having 1 to 6 carbon atoms or -(O-R ¹¹ )n-. Here, R ¹¹ is an ethylene group or a propylene group, and n represents the average number of moles added, which is 1 to 10. T is -COO-, -OCO-, -CONH-, -NHCO- or a phenylene group. m is 0 or 1. R ¹⁰ represents an alkyl group having 1 to 3 carbon atoms, a benzyl group or a phenethyl group. R ⁸ is an alkyl group or an alkenyl group having 5 to 19 carbon atoms when R ¹⁰ is an alkyl group having 1 to 3 carbon atoms, and is an alkyl group having 1 to 3 carbon atoms when R ¹⁰ is a benzyl group or a phenethyl group. R ⁹ is an alkyl group having 1 to 3 carbon atoms. ^{Z -} is a counter anion.]

According to the present invention, it is possible to provide a textile product treatment composition that inhibits the proliferation of M. osloensis, the main bacterium responsible for producing 4-methyl-3-hexenoic acid (4M3H), one of the components that cause malodor, and imparts antibacterial effects to clothing. In addition, by maintaining a quality suitable for handling even after exposure to sunlight, it is possible to provide excellent masking performance due to the fragrance microcapsules. These antibacterial properties and the deodorizing effect due to masking make it possible to provide clothing that does not have a bad odor and has a pleasant, lively scent.

<Component (a)>
The textile product treatment composition of the present invention contains, as component (a), a quaternary ammonium salt (1) of the above general formula (1).

In the formula represented by the general formula (1), from the viewpoint of deodorizing effect and antibacterial effect, R ¹ is one or more hydrocarbon groups selected from saturated or unsaturated hydrocarbon groups having from 12 to 22 carbon atoms, and preferably one or more hydrocarbon groups selected from saturated or unsaturated hydrocarbon groups having from 15 to 19 carbon atoms. From the viewpoint of softening effect, preferred are a heptadecyl group, a pentadecyl group, an 8-heptadecenyl group, or an 8,11-heptadecedienyl group.
Such component (a) is generally used for the purpose of imparting a softening effect to textile products, but in the present invention, the synergistic action of components (b) and (c) described below can impart a high deodorizing effect to textile products.

From the viewpoint of deodorizing effect, ^R2 's each independently represent an alkylene group having 1 to 5 carbon atoms, preferably an ethylene group or a propylene group, and more preferably an ethylene group.

From the viewpoint of deodorizing effect, Y is preferably -COO- or -OCO-, and more preferably -COO-.

From the viewpoint of the efficiency of synthesis of the deodorant base, R ³ is preferably —R ² —Y—R ¹ , in which case Y is also preferably —COO— or —OCO—, more preferably —COO—.

Furthermore, ^R4 is an alkyl group having 1 to 3 carbon atoms, and from the viewpoint of the efficiency of synthesis of the deodorant base, is preferably a methyl group.

X ⁻ is a counter anion, and is preferably an anion selected from a halide ion, preferably a chloride ion, an alkyl sulfate ion having from 1 to 3 carbon atoms, a fatty acid ion having from 12 to 18 carbon atoms, and a benzenesulfonate ion which may be substituted with from 1 to 3 alkyl groups having from 1 to 3 carbon atoms, more preferably an anion selected from an alkyl sulfate ion having from 1 to 3 carbon atoms, and more preferably a monomethyl sulfate ion or a monoethyl sulfate ion.

Component (a), in which Y is preferably -COO-, can be prepared, for example, by a dehydration esterification reaction between a trialkanolamine having a hydroxyalkyl group with 1 to 3 carbon atoms, preferably triethanolamine, and a fatty acid, or an ester exchange reaction between the amine and a lower alcohol ester of a fatty acid, followed by a quaternization reaction with an alkylating agent. Component (a) can be produced by using a mixture of fatty acids with different carbon numbers or degrees of unsaturation as the fatty acid, or a mixture of fatty acid lower alcohol esters with different carbon numbers or degrees of unsaturation in the fatty acid moiety as the fatty acid lower alcohol ester.

Specific fatty acids that are preferably used are fatty acids selected from stearic acid, palmitic acid, oleic acid, linoleic acid, or mixtures thereof, or fatty acids having a composition derived from palm oil, soybean oil, or olive oil.

The acid value of the fatty acid or fatty acid mixture used in producing component (a) is, in terms of the liquidity of the composition, preferably 180 mgKOH/g or more, more preferably 200 mgKOH/g or more, and is preferably 240 mgKOH/g or less, more preferably 210 mgKOH/g or less.
The iodine value of the fatty acid or fatty acid mixture used in producing component (a) is, in terms of the liquidity of the composition, preferably 30 g/100 g or more, more preferably 40 g/100 g or more, and is preferably 100 g/100 g or less, more preferably 95 g/100 g or less.
The acid value and iodine value of the fatty acid or fatty acid mixture are values measured by the method described in "Iwanami Physics and Chemistry Dictionary," 4th Edition, Iwanami Shoten.

The content of component (a) in the textile product treatment composition of the present invention is preferably 3% by mass or more, more preferably 5% by mass or more, even more preferably 8% by mass or more, and is preferably 20% by mass or less, more preferably 18% by mass or less, even more preferably 15% by mass or less, in terms of the ability to reduce the amount used per wash and the deodorizing effect.

<Component (b)>
The textile product treatment composition of the present invention contains, as component (b), a quaternary ammonium salt (2) of the above general formula (2).

In the formula represented by the general formula (2), from the viewpoints of deodorizing effect, antibacterial effect and light resistance, ^R6 is an alkyl or alkenyl group having 5 or more, preferably 7 or more, and 19 or less, preferably 17 or less, more preferably 15 or less, and most preferably 13 or less.

R ⁷ is an alkylene group having 1 to 6 carbon atoms or -(O-R ¹¹ )n-. When R ⁷ is an alkylene group, the number of carbon atoms is preferably 2 to 3 from the viewpoints of deodorizing effect, antibacterial effect and light resistance. When R ⁷ is -(O-R ¹¹ )n-, R ¹¹ is an alkylene group having 2 to 3 carbon atoms, preferably an ethylene group, and n represents the average number of moles added, preferably a number of 1 to 10, more preferably 5 or less.

T is -COO-, -OCO-, -CONH-, -NHCO-, or a phenylene group. m is 0 or 1. From the viewpoints of deodorizing effect, antibacterial effect, and light resistance, T is preferably -COO- or -OCO-, and m is preferably 0.

R ¹⁰ is an alkyl group having 1 to 3 carbon atoms, a benzyl group, or a phenethyl group.
^R8 is an alkyl group having 1 to 3 carbon atoms when ^R10 is a benzyl group or a phenethyl group, and is an alkyl group or alkenyl group having 5 or more, preferably 7 or more, and 19 or less, preferably 17 or less, more preferably 15 or less, and most preferably 13 or less, carbon atoms when ^R10 is an alkyl group having 1 to 3 carbon atoms.
From the viewpoints of deodorizing effect, antibacterial effect and light resistance, it is preferable that R ¹⁰ is a benzyl group and R ⁸ is a methyl group, or that R ¹⁰ is a methyl group and R ⁸ is an alkyl or alkenyl group having 5 to 13 carbon atoms.
When R ⁸ is an alkyl or alkenyl group having 5 to 19 carbon atoms, the number of carbon atoms is 5 or more, preferably 7 or more, and 19 or less, preferably 17 or less, more preferably 15 or less, and most preferably 13 or less.

R ⁹ is an alkyl group having 1 to 3 carbon atoms, and is preferably a methyl group from the viewpoints of deodorizing effect, antibacterial effect and light resistance.

Z ⁻ is a counter anion, and is preferably an anion selected from a halide ion, preferably a chloride ion, an alkyl sulfate ion having from 1 to 3 carbon atoms, a fatty acid ion having from 12 to 18 carbon atoms, and a benzenesulfonate ion which may be substituted with from 1 to 3 alkyl groups having from 1 to 3 carbon atoms, more preferably a methyl sulfate ion, an ethyl sulfate ion, or a halide ion, and more preferably a chloride ion.

The component (b) of the present invention not only has a deodorizing effect and an antibacterial effect, but also improves the light resistance of the textile product treatment agent containing the component (a). From the viewpoint of the deodorizing effect and the antibacterial effect, or from the viewpoint of improving the light resistance stability, the content of the component (b) in the textile product treatment composition is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, even more preferably 0.5% by mass or more, and is preferably 5% by mass or less, more preferably 3% by mass or less, even more preferably 2% by mass or less.

<Component (c)>
The textile product treatment composition of the present invention contains, as component (c), microcapsules encapsulating a fragrance component (1).

Specific examples of components of the shell of the microcapsule include silica, ethyl cellulose, hydroxypropyl methylcellulose, polyvinyl alcohol, gelatin, alginic acid, melamine, urea membrane, urethane membrane, CMC (cell membrane complex) membrane, etc. From the viewpoint of strength and release ability of the contained fragrance, silica is preferred as a component. Hereinafter, microcapsules having a shell containing silica as a component (c) are also referred to as silica capsules. The fragrance component (1) can be encapsulated in the silica capsule as a fragrance composition (1) containing one or more fragrance compounds.

<Shell>
The shell of the silica capsule of the present invention contains silica as a constituent component. The shell of the silica capsule of the present invention is characterized in that a part or substantially all of the structure constituting the shell is made of silica as a constituent component.
The shell of the silica capsule of the present invention is preferably formed by a sol-gel reaction using an alkoxysilane as a precursor.

In addition, the shell of the silica capsule of the present invention may contain inorganic polymer other than silica as a constituent component within a range that does not impair the effect of the present invention.In the present invention, inorganic polymer refers to a polymer containing inorganic elements.The inorganic polymer includes polymers consisting of only inorganic elements, polymers whose main chain consists of only inorganic elements and have organic groups as side chains or substituents, etc.
The inorganic polymer is preferably a metal oxide containing a metal element, and more preferably a polymer formed by a reaction similar to the above-mentioned sol-gel reaction of silica using a metal alkoxide [M(OR)x] as a precursor, where M is a metal element and R is a hydrocarbon group.
Examples of the metal element constituting the metal alkoxide include titanium, zirconium, aluminum, and zinc.

The alkoxysilane is preferably a tetraalkoxysilane from the viewpoints of increasing the encapsulation rate of the fragrance component (1) and of achieving good delivery performance.
From the viewpoint of promoting the sol-gel reaction, the tetraalkoxysilane is preferably one having an alkoxy group having from 1 to 4 carbon atoms, more preferably one or more selected from tetramethoxysilane, tetraethoxysilane, and tetraisopropoxysilane, even more preferably one or more selected from tetramethoxysilane and tetraethoxysilane, and still more preferably tetraethoxysilane.

(Manufacture of Silica Capsules)
From the viewpoints of increasing the encapsulation rate of the flavor compound, improving long-term retention, and favorably expressing the delivery performance of the flavor component (1), the shell of the silica capsule of the present invention preferably contains, as a constituent, silica formed by carrying out a sol-gel reaction in two stages. That is, the silica capsule of the present invention is preferably produced by a method including the following steps 1 and 2.
Step 1: A step of subjecting an emulsion obtained by emulsifying an aqueous phase component containing a cationic surfactant with an oil phase component containing a fragrance component (1) and a tetraalkoxysilane to a sol-gel reaction under acidic conditions to form silica capsules (1) having a core and a first shell containing silica as a constituent component, and obtaining an aqueous dispersion containing the silica capsules (1).
Step 2: A step of adding tetraalkoxysilane to the aqueous dispersion containing the silica capsules (1) obtained in step 1 to carry out a sol-gel reaction to form silica capsules (2) having a second shell that encapsulates the first shell.

[Step 1]
Step 1 is a step of subjecting an emulsion obtained by emulsifying an aqueous phase component containing a cationic surfactant with an oil phase component containing a fragrance component (1) and a tetraalkoxysilane to a sol-gel reaction under acidic conditions to form silica capsules (1) having a core and a first shell containing silica as a constituent component, and obtaining an aqueous dispersion containing the silica capsules (1).

Examples of cationic surfactants in step 1 include alkylamine salts and alkyl quaternary ammonium salts. The alkylamine salts are preferably salts of secondary amines or tertiary amines, more preferably salts of tertiary amines. The alkylamine salts and alkyl quaternary ammonium salts are compounds having at least one long-chain alkyl group, and optionally, preferably at least one group selected from long-chain alkyl groups, short-chain alkyl groups, and benzyl groups. The carbon number of the long-chain alkyl group is preferably 10 or more, more preferably 12 or more, even more preferably 14 or more, and preferably 22 or less, more preferably 20 or less, even more preferably 18 or less. The carbon number of the short-chain alkyl group is preferably 1 or more, and preferably 4 or less, more preferably 1 or 2, and even more preferably 1, that is, a methyl group.
Examples of the alkylamine salt include alkylamine salts in which the long-chain alkyl group has a carbon number within the above range, such as long-chain monoalkyl monomethyl secondary amine salts and long-chain monoalkyl dimethyl tertiary amine salts.
Examples of the quaternary ammonium salt include long-chain alkyl tri-short-chain alkyl quaternary ammonium salts, di-long-chain alkyl di-short-chain alkyl quaternary ammonium salts, and long-chain alkyl benzyl di-short-chain alkyl quaternary ammonium salts, each of which has a carbon number within the range described above.

Examples of the alkylamine salt include alkylamine acetates such as lauryl dimethyl ammonium acetate and stearyl dimethyl ammonium acetate.
Examples of alkyltrimethylammonium salts include alkyltrimethylammonium chlorides such as lauryltrimethylammonium chloride, cetyltrimethylammonium chloride, and stearyltrimethylammonium chloride; and alkyltrimethylammonium bromides such as lauryltrimethylammonium bromide, cetyltrimethylammonium bromide, and stearyltrimethylammonium bromide.
Examples of the dialkyldimethylammonium salt include dialkyldimethylammonium chlorides such as distearyldimethylammonium chloride; and dialkyldimethylammonium bromides such as distearyldimethylammonium bromide.
Examples of the alkylbenzyldimethylammonium salt include alkylbenzyldimethylammonium chloride and alkylbenzyldimethylammonium bromide.
Of these, the cationic surfactant is preferably a quaternary ammonium salt, more preferably an alkyltrimethylammonium salt having an alkyl group having from 10 to 22 carbon atoms, even more preferably an alkyltrimethylammonium chloride having an alkyl group having from 10 to 22 carbon atoms, still more preferably one or more selected from lauryltrimethylammonium chloride, stearyltrimethylammonium chloride, and cetyltrimethylammonium chloride, and even more preferably cetyltrimethylammonium chloride.

In step 1, in addition to the cationic surfactant, other emulsifiers may be included as long as they do not impair the effects of the present invention. Examples of other emulsifiers include polymer dispersants, nonionic surfactants, anionic surfactants, and amphoteric surfactants.

In step 1, the content of the cationic surfactant in the aqueous phase component is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, and even more preferably 0.4% by mass or more, from the viewpoint of dispersion stability of the emulsion droplets, and is preferably 10% by mass or less, more preferably 5% by mass or less, and even more preferably 2% by mass or less, from the viewpoint of suppressing the formation of emulsifier micelles due to excess emulsifier that does not contribute to the dispersion stability of the emulsion and improving the encapsulation efficiency.

The amount of the oil phase components relative to the total amount of the emulsion obtained in step 1 is preferably 5% by mass or more, more preferably 10% by mass or more, and even more preferably 15% by mass or more, from the viewpoint of production efficiency, and is preferably 50% by mass or less, more preferably 45% by mass or less, and even more preferably 40% by mass or less, from the viewpoint of obtaining a stable emulsion.

The amount of tetraalkoxysilane added in step 1 is preferably 10% by mass or more, more preferably 12% by mass or more, and even more preferably 14% by mass or more, based on the total amount of fragrance compounds in step 1, from the viewpoint of accelerating the sol-gel reaction and forming a sufficiently dense shell, and is preferably 60% by mass or less, more preferably 50% by mass or less, even more preferably 40% by mass or less, and even more preferably 35% by mass or less, from the viewpoint of preventing excess tetraalkoxysilane from remaining in the fragrance compounds.

Step 1 preferably includes the following steps 1-1 to 1-4.
Step 1-1: A step of preparing an aqueous phase component containing a cationic surfactant. Step 1-2: A step of mixing a fragrance and a tetraalkoxysilane to prepare an oil phase component. Step 1-3: A step of mixing and emulsifying the aqueous phase component obtained in step 1-1 and the oil phase component obtained in step 1-2 to obtain an emulsion. Step 1-4: A step of subjecting the emulsion obtained in step 1-3 to a first-stage sol-gel reaction to form a silica capsule (1) having a core and a first shell composed of silica.

The median diameter _D50 of the emulsion droplets in the emulsion in step 1 is preferably 0.1 μm or more, more preferably 0.2 μm or more, and even more preferably 0.3 μm or more, from the viewpoint of reducing the specific surface area relative to the environment outside the silica capsule and improving long-term retention, and is preferably 50 μm or less, more preferably 30 μm or less, even more preferably 10 μm or less, still more preferably 5 μm or less, and even more preferably 3 μm or less, from the viewpoint of the physical strength of the silica capsule (1).
The median diameter _D50 of the emulsion droplets can be measured by the method described in the Examples.

The initial pH of the sol-gel reaction in step 1 is preferably 3.0 or more, more preferably 3.3 or more, and even more preferably 3.5 or more, from the viewpoint of maintaining a balance between the hydrolysis reaction and the condensation reaction of the tetraalkoxysilane, and from the viewpoint of suppressing the formation of a highly hydrophilic sol and promoting the progress of encapsulation, and is preferably 4.5 or less, more preferably 4.3 or less, and even more preferably 4.1 or less, from the viewpoint of suppressing the simultaneous formation of a silica shell (1) and the aggregation of emulsion droplets and obtaining silica capsules (1) having a dense shell.

Depending on the strength of acidity or alkalinity of the oil phase components including the fragrance composition, any acidic or alkaline pH adjuster may be used from the viewpoint of adjusting the initial pH to a desired level.
The pH of the emulsion may be lower than the desired value, in which case it is preferable to adjust the pH using an alkaline pH adjuster, which will be described later.
That is, step 1-4 may preferably be the following step 1-4'.
Step 1-4': A step of adjusting the pH of the emulsion obtained in step 1-3 using a pH adjuster, carrying out a first-stage sol-gel reaction, forming silica capsules (1) having a core and a first shell, and obtaining an aqueous dispersion containing the silica capsules (1).

Examples of acidic pH adjusters include inorganic acids such as hydrochloric acid, nitric acid, and sulfuric acid, organic acids such as acetic acid and citric acid, and solutions in which cation exchange resins or the like have been added to water or ethanol, and preferred are hydrochloric acid, sulfuric acid, nitric acid, and citric acid.
Examples of alkaline pH adjusters include sodium hydroxide, sodium hydrogen carbonate, potassium hydroxide, ammonium hydroxide, diethanolamine, triethanolamine, trishydroxymethylaminomethane, and the like, with sodium hydroxide and ammonium hydroxide being preferred.

The reaction temperature of the sol-gel reaction in step 1 can be any value that is equal to or higher than the melting point and equal to or lower than the boiling point of the water contained in the aqueous phase, but from the viewpoint of controlling the balance between the hydrolysis reaction and the condensation reaction in the sol-gel reaction and forming a dense shell, it is preferable to set the temperature within a certain range. The range is preferably 5°C or higher, more preferably 10°C or higher, even more preferably 15°C or higher, and preferably 60°C or lower, more preferably 50°C or lower, and even more preferably 40°C or lower.

[Step 2]
Step 2 is a step in which tetraalkoxysilane is further added to the aqueous dispersion containing the silica capsules (1) obtained in step 1 to carry out a sol-gel reaction, thereby forming silica capsules (2) having a second shell that encapsulates the first shell.

The amount of tetraalkoxysilane added in step 2 is preferably 7% by mass or more, more preferably 10% by mass or more, and even more preferably 15% by mass or more, based on the fragrance compound in step 1, from the viewpoint of forming a second shell that encapsulates the first shell, and is preferably 200% by mass or less, more preferably 170% by mass or less, and even more preferably 150% by mass or less, from the viewpoint of suppressing the generation of silica sol that disperses in the aqueous phase and improving the dispersion stability of the silica capsules.

In step 2, the tetraalkoxysilane to be added to the aqueous dispersion containing the silica capsules (1) obtained in step 1 may be added all at once, may be added intermittently in portions, or may be added continuously. From the viewpoint of forming a highly dense second shell, however, it is preferable to add it dropwise continuously.
When the tetraalkoxysilane is added dropwise continuously, the drop time can be appropriately set depending on the scale of production. From the viewpoint of suppressing separation of the added tetraalkoxysilane from the aqueous dispersion, the drop time is preferably 5 minutes or more, more preferably 10 minutes or more, even more preferably 30 minutes or more, and is preferably 1200 minutes or less, more preferably 1000 minutes or less, even more preferably 500 minutes or less.

In the present invention, the total amount of tetraalkoxysilane added, i.e., the total amount of tetraalkoxysilane used in steps 1 and 2, is preferably 30% by mass or more, more preferably 35% by mass or more, even more preferably 40% by mass or more, and is preferably 250% by mass or less, more preferably 200% by mass or less, even more preferably 150% by mass or less, relative to the fragrance compound in step 1. By keeping the total amount of tetraalkoxysilane added within the above range, the encapsulated fragrance compound can be maintained for a long period of time.

In the present invention, the total amount of the fragrance compound and tetraalkoxysilane in step 1 relative to the total amount of the aqueous dispersion before the addition of tetraalkoxysilane in step 2 is, from the viewpoint of improving the long-term retention of the fragrance compound, preferably 20 mass% or less, more preferably 18 mass% or less, even more preferably 15 mass% or less, and even more preferably 10 mass% or less, and from the viewpoint of production efficiency, is preferably 2 mass% or more, more preferably 3 mass% or more, and even more preferably 5 mass% or more.
The adjustment of the total amount of the fragrance compound and tetraalkoxysilane in step 1 relative to the total amount of the aqueous dispersion before the addition of tetraalkoxysilane in step 2 may be performed in step 1 so that the amounts of the fragrance compound and tetraalkoxysilane in step 1 and the total amount of the aqueous dispersion obtained in step 1 are within the above-mentioned ranges, or may be performed by further adding water to the aqueous dispersion obtained in step 1 to dilute it.

From the viewpoint of production efficiency, the present invention may dilute the aqueous dispersion obtained in step 1 with water before the addition of tetraalkoxysilane in step 2. The total amount of the fragrance compound and tetraalkoxysilane in step 1 relative to the total amount of the aqueous dispersion obtained in step 1 before dilution is preferably 3 mass% or more, more preferably 5 mass% or more, even more preferably 10 mass% or more, still more preferably 15 mass% or more, and is preferably 50 mass% or less, more preferably 40 mass% or less, and even more preferably 30 mass% or less.
The dilution ratio is preferably 2 times or more, more preferably 2.5 times or more, and preferably 20 times or less, more preferably 10 times or less, more preferably 7 times or less.

The reaction temperature of the sol-gel reaction in step 2 can be selected arbitrarily as long as it is above the melting point and below the boiling point of water contained as the dispersion medium, but from the viewpoint of controlling the balance between the hydrolysis reaction and the condensation reaction in the sol-gel reaction and forming a dense shell, it is preferably 5°C or higher, more preferably 10°C or higher, even more preferably 15°C or higher, and preferably 60°C or lower, more preferably 50°C or lower, even more preferably 40°C. The sol-gel reaction in step 1 and the sol-gel reaction in step 2 may be carried out at different reaction temperatures.

In the present invention, in step 2, an organic polymer compound may be further added to the aqueous dispersion obtained in step 1 for the purpose of stabilizing the aqueous dispersion and suppressing aggregation. Here, the organic polymer compound means a compound having a weight average molecular weight of 5,000 or more.
The organic polymer compound includes a nonionic polymer, a cationic polymer, and an anionic polymer.
The nonionic polymer means a water-soluble polymer that has no electric charge in water. By using the nonionic polymer, it is possible to impart a function to the silica capsule (2) according to the application of the silica capsule.
When a nonionic polymer, cationic polymer, or anionic polymer is used as the organic polymer compound, for example, when the silica capsules of the present invention are used in a fabric treatment composition such as a fabric softener composition, improved adsorption of the silica capsules to fibers can be expected.
As used herein, the term "water-soluble polymer" refers to a polymer that, when dried at 105°C for 2 hours and allowed to reach a constant weight, dissolves in 100 g of water at 25°C in an amount of 1 mg or more.

Examples of the nonionic polymer include polymers having structural units derived from nonionic monomers, water-soluble polysaccharides (cellulose-based, gum-based, starch-based, etc.) and derivatives thereof.
Examples of nonionic monomers include (meth)acrylates having a hydrocarbon group derived from an aliphatic alcohol having 1 to 22 carbon atoms; styrene-based monomers such as styrene; aromatic group-containing (meth)acrylates such as benzyl (meth)acrylate; vinyl acetate; vinylpyrrolidone; vinyl alcohol; polyalkylene glycol (meth)acrylates such as polyethylene glycol mono(meth)acrylate; alkoxypolyalkylene glycol mono(meth)acrylates such as methoxypolyethylene glycol mono(meth)acrylate and octoxypolyethylene glycol mono(meth)acrylate; (meth)acrylamide, etc. Note that (meth)acrylate means acrylate or methacrylate. Similarly, (meth)acrylic means acrylic or methacrylic.

Examples of the cationic polymer include a polymer containing a quaternary ammonium salt group, a polymer having a nitrogen-based cationic group, a polymer that may become cationic by adjusting the pH, etc. By using a cationic polymer, the situation in which the silica capsules (1) obtained in step 1 tend to aggregate in the aqueous dispersion can be alleviated, and the generation of coarse particles, etc. can be suppressed in the subsequent step 2.
Examples of the cationic polymer include polydiallyldimethylammonium salts such as poly(diallyldimethylammonium chloride), poly(acrylic acid-co-diallyldimethylammonium chloride), poly(acrylamide-co-diallyldimethylammonium chloride), and poly(acrylamide-co-acrylic acid-co-diallyldimethylammonium chloride) and copolymers thereof, poly(2-(methacryloyloxy)ethyltrimethylammonium chloride), polyethyleneimine, polyallylamine, cationized cellulose, cationized guar gum, cationized tara gum, cationized fenugreek gum, and cationized locust bean gum. Among these, polydiallyldimethylammonium salts and copolymers thereof are preferred, and one or more selected from poly(diallyldimethylammonium chloride), poly(acrylic acid-co-diallyldimethylammonium chloride), and poly(acrylamide-co-acrylic acid-co-diallyldimethylammonium chloride) are more preferred, and poly(diallyldimethylammonium chloride) is even more preferred.

The cationic group equivalent of the cationic polymer is preferably 1 meq/g or more, more preferably 3 meq/g or more, even more preferably 4.5 meq/g or more, and preferably 10 meq/g or less, more preferably 8 meq/g or less, from the viewpoint of dispersibility of the silica capsule (1), suppression of the generation of coarse particles, and improvement of long-term retention. The cationic polymer may contain an anionic group, and in that case, the anionic group equivalent contained in the cationic polymer is preferably 3.5 meq/g or less, more preferably 2 meq/g or less, even more preferably 1 meq/g or less. In the present invention, the cationic group equivalent of the cationic polymer is calculated based on the monomer composition.

Examples of the anionic polymer include polymers containing monomer units having a carboxyl group, polymers containing monomer units having a sulfonic acid group, and polymers that become anionic upon pH adjustment.
Examples of the anionic polymer include poly(meth)acrylic acid, polymaleic acid, poly((meth)acrylic acid-co-maleic acid), poly((meth)acrylic acid-co-maleic anhydride), poly((meth)acrylic acid-co-isobutylene), poly((meth)acrylic acid-co-styrene), poly(isobutylene-co-maleic acid), poly(styrene-co-maleic acid), carboxymethyl cellulose, etc. Incidentally, (meth)acrylic acid means acrylic acid or methacrylic acid.

The amount of the organic polymer compound added is preferably 0.05% by mass or more, more preferably 0.1% by mass or more, even more preferably 0.2% by mass or more, and is preferably 5% by mass or less, more preferably 3% by mass or less, even more preferably 2% by mass or less, relative to the aqueous dispersion obtained in step 1.

The silica capsules (2) obtained by step 2 are obtained in a state of being dispersed in water. By producing the above steps, most of the flavor component (1) can be encapsulated in the silica capsules, which can be used as is depending on the application. In some cases, the silica capsules can be separated and used. Separation methods that can be used include filtration and centrifugation.

<Core>
The core of the silica capsule according to the present invention comprises a perfume ingredient (1).
In the present invention, from the viewpoint of the release of fragrance when the fiber is moistened with moisture such as sweat, it is preferable that the proportion of fragrance compounds having a log P of 2.0 or more and 5.0 or less and a vapor pressure at 25° C. of 0.01 Pa or more and 8.00 Pa or less is 25 mass% or more of the total amount of fragrance compounds contained in the fragrance component (1).

In the present invention, the logP value is a coefficient indicating the affinity of an organic compound to water and 1-octanol. The 1-octanol/water partition coefficient P is the ratio of the equilibrium concentrations of a compound in each solvent when a trace amount of the compound is dissolved as a solute in a solvent consisting of two liquid phases, 1-octanol and water, and reaches distribution equilibrium, and is generally expressed in the form of their logarithm logP to the base 10. Nowadays, the value of "calculated logP (sometimes called ClogP)" calculated by a calculation program using fragment values of atomic groups determined by the number of atoms constituting the compound molecule and the type of chemical bond is widely used, and in the present invention, the value of ClogP is used when selecting a compound, but this value may be considered to be equivalent to the logP value obtained experimentally. The logP value used in this application is the ClogP value, and will be referred to as the ClogP value hereinafter.

Examples of fragrance compounds having a ClogP of 2.0 or more and 5.0 or less and a vapor pressure at 25°C of 0.01 Pa or more and 8.00 Pa or less include γ-undecalactone, 2-cyclohexylidene-2-phenylacetonitrile, damascenone, δ-damascone, α-methyl-β-(p-t-butylphenyl)-propionaldehyde, β-ionone, myrrhaldehyde, ethyltricyclo[5.2.1.0-2,6]decane-2 -Carboxylate (Fruitate), Citronellol, Geraniol, α-Ionone, Patchouli Alcohol, 6,7-Dihydro-1,1,2,3,3-Pentamethyl-4(5H)-Indanone, Methyl Dihydrojasmonate, Hexyl Cinnamic Aldehyde, Amyl Cinnamic Aldehyde, Allyl Cyclohexyl Propionate, Dimethyl Benzyl Carbinyl Butyrate, Tricyclodecenyl Propionate, Salicylic Acid amyl acetate, γ-methylionone, α-damascone, β-damascone, nerolin yarayara, 2,4,6-trimethyl-4-phenyl-1,3-dioxane, phenylhexanol, 2-methyl-4-(2,2,3-trimethyl-3-cyclopenten-1-yl)-2-buten-1-ol, dodecahydro-3a,6,6,9a-tetramethylnaphtho[2,1-b]furan, γ-nonalactone, methyl β-naphthyl Ketones, eugenol, lyral, dimethylbenzylcarbinyl acetate, iso-damascone, 2-cyclohexylidene-2-phenylacetonitrile, gamma-decalactone, alpha-methyl-3,4-methylenedioxyhydrocinnamic aldehyde, 7-methyl-3,5-dihydro-2H-benzodioxepinone, tricyclodecenyl acetate, tricyclodecenyl propionate, 2-phenyl Allyl butyloxyglycolate, 1-(2-tert-butylcyclohexyloxy)-2-butanol, citronellyloxyacetaldehyde, indole, 4-methyl-3-decen-5-ol, para-menthane-8-thiol-3-one, 3-(para-tert-butylphenyl)-propanal, ethyl cinnamate, 5-methyl-3-heptanone oxime, methyl anthranilate, terpineol, β-caryophyllene, citronellyl acetate, geranyl acetate, neryl acetate, [4-(t-butyl)cyclohexyl] acetate, tetrahydrogeraniol, 2-isobutyl-4-hydroxy-4-methyltetrahydropyranol (Florosa), α-dynascone, cis-jasmone, bicyclo[3.2.1]octane-8-1,5-dimethyloxime, 2,4-dimethyl-4,4α,5,9β-tetrahydroindeno[1,2- d]-m-dioxin, 3-(para-ethylphenyl)-2,2-dimethylpropanal, ethyl-2-tert-butylcyclohexyl-carbonate, hexyl benzoate, 4-acetoxy-3-amyltetrahydropyran, dodecyl aldehyde, dihydro-β-ionone, methyl cyclooctyl carbonate, ethyl methylphenyl glycidate, isoeugenol, methyl isoeugenol, diphenyl oxide, 2,2,5-trimethyl-5-pentyl cyclopentanone, thymol, nerolin bromeliad, 5,6-dimethyl-8-isopropenyl, bicyclo[4.4.0]-1-decen-3-one, 3-(4-isopropylphenyl)-propanal, 4-isopropylcyclohexanemethanol, methyl methyl anthranilate, dodecanenitrile, 3-dodecenal, and isopropyl myristate.

Fragrance compounds with a ClogP value of less than 2.0 can also be used as the fragrance compound of fragrance component (1). Examples of fragrance compounds with a ClogP value of less than 2.0 include coumarin (1.5), phenylethyl alcohol (1.6), cis-3-hexenol (1.6), raspberry ketone (1.5), and heliotropin (1.8). The numbers in parentheses are ClogP values.

Fragrance compounds having a ClogP value of more than 5.0 can also be used as the fragrance compound of fragrance component (1). Examples of fragrance compounds having a ClogP value of more than 5.0 include 2-[2-(4-methyl-3-cyclohexen-1-yl)propyl]cyclopentanone (5.1), 7-acetyl-1,2,3,4,5,6,7,8-octahydro-1,1,6,7-tetramethylnaphthalene (5.2), acetyl cedrene (5.2), nerolidol (5.7), benzyl alcohol (7.1), and caryophyllene (6.3). The numbers in parentheses are ClogP values.

Fragrance compounds with a vapor pressure of less than 0.01 Pa can also be used as the fragrance compound of fragrance component (1). Examples of fragrance compounds with a vapor pressure of less than 0.01 Pa include 1,4-dioxacycloheptadecane-5,17-dione (0.0000585) and ethylene brushylate (0.0000585). The numbers in parentheses indicate vapor pressure (units: Pa).

In addition, as the fragrance compound of the fragrance component (1), a fragrance compound having a vapor pressure of more than 8.00 Pa can be used. Examples of fragrance compounds having a vapor pressure of more than 8.00 Pa include ethyl 2-methylbutyrate (1070), ethyl 2-methylpentanoate (384), limonene (193), allyl 2-pentyloxyglycolate (19.7), 2,4-dimethyl-3-cyclohexenylcarboxaldehyde (46.9), linalool (11.1), linalyl acetate (17.5), tetrahydrolinalool (9.51), 1,8-cineole (208), isobornyl acetate (14.3), ocimene (358), cis-3-hexenol (125), triplral (46.9), and styraryl acetate (14.9). The numbers in parentheses are vapor pressures (units: Pa).

From the viewpoint of deodorizing effect, the content of component (c) in the textile product treatment composition of the present invention is, as the fragrance component (1) in the microcapsules, preferably 0.02% by mass or more, more preferably 0.07% by mass or more, even more preferably 0.1% by mass or more, and preferably 1.0% by mass or less, more preferably 0.7% by mass or less, even more preferably 0.5% by mass or less.

Furthermore, the microcapsules of component (c) may contain one or more selected from diluents, solvents, and solidifying agents in addition to the fragrance component (1). Examples of diluents or solvents include ethylene glycol, propylene glycol, dipropylene glycol, and glycerin, and also include fatty acid alcohols, lower alcohol esters of fatty acids, and glycerin esters of fatty acids.

<Component (d)>
The textile product treatment composition of the present invention preferably further contains a fragrance component (2) as component (d).
Examples of the fragrance component (2) include natural or synthetic fragrances that are generally used in textile product treatment compositions, and for example, the fragrances described in "Synthetic Fragrances: Chemistry and Product Knowledge" by Genichi Indo, published by The Chemical Daily in 1969, and "Perfume and Flavor Chemicals" by STEFFEN ARCTANDER, published by MONTCLAIR, N.J. in 1969 can be used.
The fragrance used in the present invention is an organic compound known to be used as a fragrance, and the fragrances described in "Practical Knowledge of Fragrances and Fragrances" (by Nakajima Mototaka, published by Sangyo Tosho Co., Ltd. on June 21, 1995) can be used in appropriate combination according to the fragrance tone and application.
Furthermore, as the fragrance, a fragrance component having a hydroxyl group described in JP-A-2009-256818 can be used in combination as a silicate ester for the purpose of improving the duration and lingering of a fragrance. Also, fragrance components and fragrance compositions described in patent documents for fabric softeners, starches, styling agents, or other finishing agents known as laundry finishing agents can be used.

Examples of fragrance compounds that can be suitably used as the fragrance component (2) in the present invention include ethers such as fatty acid ethers, aromatic ethers (excluding hydroxyphenyl ethers), and the like; oxides such as fatty acid oxides, oxides of terpenes, and the like; acids such as acetals, ketals, phenols, hydroxyphenyl ethers, fatty acids, terpene carboxylic acids, hydrogenated aromatic carboxylic acids, aromatic carboxylic acids, and the like; acid amides, nitro musks, nitriles, amines, pyridine, quinoline, pyrrole, indole, and other nitrogen-containing compounds.
The fragrance component (2) can be used as a fragrance composition (2) containing one or more of these fragrance compounds.

When the textile product treatment composition of the present invention contains component (d), the content of component (d) is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, even more preferably 0.5% by mass or more, and preferably 2% by mass or less, more preferably 1.5% by mass or less. In addition, the mass ratio of component (d) to component (c), component (c)/component (d), is 0.01 or more, preferably 0.03 or more, and 2 or less, preferably 1 or less, particularly preferably 0.5 or less, from the viewpoints of light resistance and deodorizing effect.

<Component (e)>
The textile product treatment composition of the present invention preferably contains, as component (e), a nonionic surfactant selected from the following general formula (e-1) and general formula (e-2).
R ^1g -O-[(C ₂ H ₄ O) _s (C ₃ H ₆ O) _t ]-H (e-1)
[In the formula, R ^1g is an alkyl or alkenyl group having 8 or more, preferably 10 or more, and 18 or less, preferably 16 or less, carbon atoms. s and t are the average number of moles added, s being 6 or more, preferably 10 or more, and 50 or less, preferably 40 or less, and t being 0 or more, preferably 1 or more, and 5 or less, preferably 3 or less. The ethylene groups (C ₂ H ₄ O) and propylene groups (C ₃ H ₆ O) are bonded in a random or block manner.]

[In the formula, R ^2g is an alkyl or alkenyl group having 8 or more, preferably 10 or more, carbon atoms and 18 or less, preferably 16 or less. -A< is -N< or -C(O)N<, u and v are each independently a number of 0 or more and 40 or less, and u+v is a number of 5 or more and 60 or less. R ^3g and R ^4g are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.]

When the textile product treatment composition of the present invention contains component (e), the content is preferably 0.5% by mass or more, more preferably 1% by mass or more, from the viewpoint of light resistance, and is preferably 10% by mass or less, more preferably 5% by mass or less.

The textile product treatment composition of the present invention may contain an inorganic salt as component (f) from the viewpoint of improving storage stability. As the inorganic salt, from the viewpoint of improving storage stability, one or more kinds selected from sodium chloride, calcium chloride, and magnesium chloride are preferable.
When the textile product treatment composition of the present invention contains component (f), the content thereof is preferably 0.01 mass % or more, more preferably 0.05 mass % or more, and preferably 1 mass % or less, more preferably 0.5 mass % or less.

The textile product treatment composition of the present invention preferably further contains an acidic compound as component (g) from the viewpoint of adjusting the pH of the textile product treatment composition concentrate to 2.5 or more and 4.0 or less for the purpose of suppressing hydrolysis of the quaternary ammonium salt (1), which is component (a).
Examples of the acidic compound include inorganic acids and organic acids. Specific examples of inorganic acids include hydrochloric acid and sulfuric acid. Specific examples of organic acids include monovalent or polyvalent carboxylic acids having 1 to 10 carbon atoms, or monovalent or polyvalent sulfonic acids having 1 to 20 carbon atoms. More specifically, examples of the acidic compound include one or more selected from methylsulfuric acid, ethylsulfuric acid, p-toluenesulfonic acid, (o-, m-, p-)xylenesulfonic acid, benzenesulfonic acid, dodecylbenzenesulfonic acid, glycolic acid, methylglycine diacetic acid, ethylenediaminetetraacetic acid, citric acid, benzoic acid, and salicylic acid. Among these, one or more selected from methylglycine diacetic acid, ethylenediaminetetraacetic acid, and citric acid are preferred.
There is no particular limitation on the amount of the acidic compound to be added, and it can be used appropriately so that the pH falls within the above range.

The textile product treatment composition of the present invention may contain a chelating agent as component (h) from the viewpoint of suppressing changes in hue, fading of dyes, and deterioration of fragrance during long-term storage. Preferred examples of the chelating agent include ethane-1-hydroxy-1,1-diphosphonic acid, ethylenediaminetetraacetic acid, methylglycinediacetic acid, hydroxyethyliminodiacetic acid, ethylenediaminedisuccinic acid, L-glutamic acid-N,N-diacetic acid, N-2-hydroxyethyliminodiacetic acid, citric acid, succinic acid, and alkali metal salts and ammonium salts thereof, such as sodium salts and potassium salts.
When the textile product treatment composition of the present invention contains component (h), the content thereof is preferably 0.001 mass % or more, more preferably 0.005 mass % or more, and preferably 0.5 mass % or less, more preferably 0.1 mass % or less.

<Component (i)>
In the textile product treatment composition of the present invention, an antioxidant such as butylhydroxytoluene (BHT) can be used from the viewpoint of suppressing deterioration of the substrate, and dyes and pigments generally used in textile product treatment compositions can be used from the viewpoint of aesthetics and preventing coloration during long-term storage. Furthermore, a preservative, antibacterial, and antifungal agent commercially available under the trade name Proxel BDN can also be used. Benzoic acid and its salts can also be used as preservative, antibacterial, and antifungal agents.

The textile product treatment composition of the present invention is suitable for textile products such as clothing and bedding. The clothing is used to wash clothing such as clothes, towels, bedding, and textile products for bedding (sheets, pillowcases, etc.). Other washable textile products can also be subject to washing as clothing in the present invention. In the present invention, textile products refer to fabrics such as woven fabrics, knitted fabrics, and nonwoven fabrics using these various fibers, and textile products obtained using them, such as undershirts, T-shirts, dress shirts, hats, handkerchiefs, towels, and masks. Preferred textile products are woven fabrics such as woven fabrics and knitted fabrics, and woven textile products.

<Examples and Comparative Examples>
The present invention will be described in detail below with reference to examples and comparative examples, but the present invention is not limited to the following descriptions.

Component (a) <Synthesis Example 1: Synthesis of component (a)>
A fatty acid having an acid value of 206.9 mgKOH/g, which was prepared from palm oil as a raw material, was subjected to a dehydration esterification reaction with triethanolamine at a reaction molar ratio of 1.65/1 (fatty acid/triethanolamine), to obtain a condensation product containing N,N-dialkanoyloxyethyl-N-hydroxyethylamine as a main component.
Next, the amine value of this condensate was measured, and 0.95 equivalents of dimethyl sulfate was used relative to the condensate to perform quaternization according to a standard method, to obtain a mixture of ester-type dialkylammonium salts containing 10% by mass of ethanol, the main component of which was N,N-dialkanoyloxyethyl-N-hydroxyethyl-N-methylammonium methyl sulfate, as the quaternary ammonium salt (1) of component (a). However, the term "alkanoyl" used here includes the meaning of residues derived from unsaturated fatty acids, such as alkenoyl, in addition to saturated fatty acids, since alkanoyl is a fatty acid residue of palm oil as a raw material. The preparation procedure and reaction conditions were performed according to Synthesis Example 2 of JP2010-209493A.

Component (b) As the component (b), the following compound was used as a quaternary ammonium salt (2).
(b-1) benzalkoum chloride (b-2) didecyldimethylammonium chloride Furthermore, (b-3) trimethyllaurylammonium chloride was also used as a comparative compound for the above (b-1) and (b-2).

Component (c) As the fragrance component (1) encapsulated in the silica capsules of component (c), a fragrance composition containing the fragrance compounds shown in Table 1 in the indicated contents was used. The proportion of fragrance compounds having a ClogP of 2.0 or more and 5.0 or less and a vapor pressure of 0.01 Pa or more and 8.00 Pa or less in fragrance component (1) was 31.5 mass %. The fragrance components in Table 1 are referred to as fragrance components (1-1).

<Synthesis Example 1> Synthesis of (c) (Step 1)
An aqueous phase component was obtained by diluting 1.49 g of Coatamin 60W (trade name, manufactured by Kao Corporation, cetyltrimethylammonium chloride, active content 30% by mass) with 88.52 g of ion-exchanged water. An oil phase component prepared by mixing 24.13 g of the fragrance component (1) in the blending ratio shown in Table 1 and 6.01 g of tetraethoxysilane (hereinafter also referred to as "TEOS") was added to this aqueous phase component, and the mixture was emulsified using a homomixer (manufactured by HsiangTai, model: HM-310, the same applies below) at a rotation speed of 6,500 rpm for 5 minutes and then at a rotation speed of 8,000 rpm for 5 minutes to obtain an emulsion. The median diameter D ₅₀ of the emulsified droplets at this time was 1.09 μm.
The pH of the obtained emulsion was adjusted to 3.7 using 0.2 N hydrochloric acid, and then transferred to a separable flask equipped with a stirring blade and a cooler. While maintaining the liquid temperature at 30°C, the mixture was stirred for 24 hours to obtain an aqueous dispersion containing silica capsules (1) having a core made of fragrance component (1) and a first shell made of silica.

(Step 2)
305.58 g of water was added to 100.22 g of the aqueous dispersion obtained in step 1, and the resulting mixture was stirred at a liquid temperature of 30° C., while 24 g of TEOS was added. Stirring was continued for 24 hours, followed by cooling, to obtain an aqueous dispersion containing silica capsules (2) in which a second shell encapsulating the first shell was formed and the fragrance component (1) was encapsulated in amorphous silica. The median diameter D ₅₀ of the silica capsules (2) was 3.0 μm. The median diameter D ₅₀ of the emulsion droplets and silica capsules (2) was measured using a laser diffraction/scattering type particle size distribution measuring device "LA-960" (trade name, manufactured by Horiba, Ltd.). The measurement was performed using a flow cell, with the medium being water and the refractive index set to 1.40-0i. The aqueous dispersion containing the emulsion or silica capsules was added to the flow cell, and the measurement was performed at a concentration showing a transmittance of approximately 90%, and the median diameter D ₅₀ was calculated on a volume basis.
The thickness of the first shell was about 5 nm, and the thickness of the second shell was 5 to 30 nm.

Component (d) A fragrance composition containing the fragrance compounds shown in Table 2 in the amounts shown was used as component (d). The fragrance component in Table 2 is referred to as fragrance component (2-1).

Component (e) As the nonionic surfactant of component (e), polyoxyethylene lauryl ether having an average added mole number of oxyethylene groups of 30 moles was used.

Calcium chloride was used as the inorganic salt of component (f).

Citric acid was used as the acidic compound (g).

Trisodium methylglycine diacetate was used as the chelating agent for component (h).

Proxel BDN (manufactured by Arch Chemical Japan) was used as component (i).

<Preparation of Textile Product Treatment Composition>
A 300 mL glass beaker (inner diameter 7 cm, height 11 cm) was charged with ion-exchanged water in an amount equivalent to 90% of the amount required for a finished textile product treatment composition with a mass of 200 g, as well as components (e), (g), (h) and (i), and the temperature of the ion-exchanged water was adjusted to 60±2°C using a water bath.
Next, a stirring blade (turbine-type stirring blade, three blades, blade length 2 cm) attached to a Three-One Motor (manufactured by Shinto Scientific Co., Ltd., "TYPE HEIDON 1200G") was placed at a height of 1 cm from the bottom of the beaker, and while stirring at a rotation speed of 300 rpm, a quaternary ammonium salt mixture as component (a) that had been melted and mixed in advance at 65°C was added, and then the mixture was stirred at 300 rpm for 10 minutes while heating at 60±2°C.
Next, the mixture was cooled to 30±2°C using a 5°C water bath. Components (b), (c), (d), and (f) were added in sequence and stirred for 5 minutes. Ion-exchanged water was then added to the mixture to a final mass of 200g, and the mixture was stirred for 5 minutes to obtain a textile product treatment composition. The pH was adjusted to 3.5.
The content of each component in each composition is shown in Table 3 for the Examples and Comparative Examples (units are parts by mass).

The following two tests were carried out on the textile product treatment compositions obtained in Examples 1 to 8 and Comparative Examples 1 to 6.

[Deodorization test]
Used undergarments (100% cotton, T-shirts) that had been washed and used for six months to one year and collected from ordinary households were used. 4.5 L of city water adjusted to 20°C was poured into an electric bucket-type washing machine ("MiniMini", model number: NA-35) manufactured by National (Panasonic Corporation), and the textile product treatment composition of the Examples and Comparative Examples was added in an amount of 10 g per 1.5 kg of cotton undergarments and stirred for one minute. Then, one piece of cotton undergarment was added and stirred for another 5 minutes. The undergarments were dehydrated for 5 minutes in the dehydration tub of a two-tub washing machine, and immediately after dehydration, the undergarments were wrapped in plastic wrap, sealed in a plastic bag with a zipper, and stored in a high-temperature oven at 30°C for 5 hours to generate a damp odor. Then, the undergarments were dried for 24 hours in a room at 20°C/60% RH.
A cloth measuring 20 cm x 20 cm was cut from the prepared underwear and used for deodorization evaluation by 10 odor evaluation panelists. After moistening the cloth with 10-20% o.w.f. water using a spray, the cloth was folded in four and left to stand for a few seconds, then opened and the scent at the intersection of the folds was smelled and rated as follows:
+3: A pleasant fragrance with a strong sense of dynamism.
+2: The scent has a strong sense of dynamism.
+1: I don't feel much dynamism in the scent.
0: The fragrance has no vibrancy.

In addition to the above, if a foul odor was detected, a score was added according to the following criteria.
-1: Slightly foul odor.
-2: There is a foul odor.
-3: A strong foul odor is felt.
A score was calculated for each panelist, and the average score of the 10 panelists was used to evaluate the product as follows:
⊚: 2.2 points or more ◯: 1.6 to 2.2 points △: 1 to 1.6 points ×: 1 point or less The results are shown in Table 3.

[Light resistance test]
The test was carried out using a low-temperature cycle xenon fade meter (XL75, manufactured by Suga Test Instruments Co., Ltd.). A container (PE, PA mixed) filled with 400 g of a sample prepared to a specified composition was placed in the tester with the maximum surface area facing the lamp, and light was irradiated under the following irradiation conditions. The tester was then stopped and left as it was for 18 hours (1 cycle). After 11 cycles, the tester was carefully removed from the tester without moving the internal liquid.
(Irradiation conditions)
・Set illuminance: 42W/ ^m2
Set radiation time: 6 hours (integrated irradiance: 0.9 MJ/m ² )
Black panel temperature: 45°C

This was observed by 10 evaluation panelists and scored as follows:
+2: Significantly less gel-like matter than the standard (Comparative Example 1).
+1: Less gel-like matter than standard.
0: A gel-like substance was formed to the same extent as the standard.
The evaluation was made based on the average scores of 10 panelists as follows:
⊚: 1.6 points or more ◯: 1.2 to 1.6 points or more △: 0.8 to 1.2 points ×: 0.8 points or less The results are shown in Table 3.

All of the compositions of Examples 1 to 8 gave good results in the deodorizing test. No deodorizing effect was observed in Comparative Example 1, which did not contain the components (b) and (c), Comparative Example 2, which did not contain the component (a), Comparative Example 3, which did not contain the component (b), and Comparative Example 4, which did not contain the component (c). Furthermore, Comparative Examples 5 and 6, which used lauryltrimethylammonium chloride having three methyl groups as the component (b), had a deodorizing effect inferior to that of Examples 1 to 8.
Furthermore, Examples 1 to 8 produced less gel-like matter than Comparative Example 1, which was used as the standard. Comparative Examples 2 and 4 also produced less gel-like matter, but Comparative Example 3, which did not contain component (b), and which used lauryltrimethylammonium chloride having three methyl groups as component (b), produced more gel-like matter than Examples 1 to 8.
From the above results, it is clear that by using the components (a) to (c) specified in the present application, a good deodorizing effect and suppression of gelation after exposure to sunlight are achieved, and the problem of the present application is solved.

Table 4 shows an example of a formulation that has the effect of the present invention. Note that components (c-1) to (c-3) and components (d-1) to (d-3) are the components shown in Table 5, where (c-1) is the same component as (c) above, and (c-2) and (c-3) were produced according to Examples 7 and 14 of International Patent No. 2021/132726, respectively.

Claims (19)

A textile product treatment composition comprising: (a) one or more quaternary ammonium salts (1) represented by the following general formula (1); (b) one or more quaternary ammonium salts (2) represented by the following general formula (2); and (c) a microcapsule encapsulating a fragrance component (1).

[In the formula, R ¹ is an alkyl group or alkenyl group having 12 to 22 carbon atoms. Y is -COO-, -CONR ⁵ -, -OCO-, or -NR ⁵ CO-. Here, R ⁵ is a hydrogen atom, an alkyl group or a hydroxyalkyl group having 1 to 3 carbon atoms. R ² is an alkylene group having 1 to 5 carbon atoms. Each R ³ is independently an alkyl group having 1 to 3 carbon atoms, -R ² -OH, or -R ² -Y-R ^1. However, when two or more kinds of quaternary ammonium salts (1) are contained, at least one Y is -COO- or -OCO-. R ⁴ is an alkyl group having 1 to 3 carbon atoms. X ^- is a counter anion.]

[In the formula, R ⁶ is an alkyl group or alkenyl group having 5 to 19 carbon atoms, R ⁷ is an alkylene group having 1 to 6 carbon atoms or -(O-R ¹¹ )n-. Here, R ¹¹ is an ethylene group or a propylene group, and n represents the average number of moles added, which is 1 to 10. T is -COO-, -OCO-, -CONH-, -NHCO- or a phenylene group. m is 0 or 1. R ¹⁰ represents an alkyl group having 1 to 3 carbon atoms, a benzyl group or a phenethyl group. R ⁸ is an alkyl group or an alkenyl group having 5 to 19 carbon atoms when R ¹⁰ is an alkyl group having 1 to 3 carbon atoms, and is an alkyl group having 1 to 3 carbon atoms when R ¹⁰ is a benzyl group or a phenethyl group. R ⁹ is an alkyl group having 1 to 3 carbon atoms. ^{Z -} is a counter anion.] The textile product treatment composition according to claim 1, wherein Y is -COO-. The fiber product treatment composition according to claim 2, wherein R ³ is —R ² —COO—R ¹ . The fiber product treating composition according to any one of claims 1 to 3, wherein X ⁻ is a chloride ion. The textile product treatment composition according to any one of claims 1 to 4, wherein m is 0. The fiber product treatment composition according to claim 5, wherein R ¹⁰ is a benzyl group. 6. The fiber product treatment composition according to claim 5, wherein ^R10 is an alkyl group having 1 to 3 carbon atoms, and ^R8 is an alkyl or alkenyl group having 5 to 19 carbon atoms. The fiber product treating composition according to any one of claims 1 to 7, wherein Z ^{1 -} is a chloride ion. The textile product treatment composition according to any one of claims 1 to 8, wherein the microcapsules of component (c) are microcapsules having a shell (second shell) containing silica and a core (first shell) containing a fragrance compound inside the shell and silica encapsulating the core. The textile product treatment composition according to any one of claims 1 to 9, wherein the median diameter _D50 of the microcapsules of component (c) is 0.1 µm or more and 50 µm or less. The textile product treatment composition according to any one of claims 1 to 10, wherein the shell of the microcapsule of component (c) contains silica as a constituent formed by a sol-gel reaction of an alkoxysilane. The textile product treatment composition according to claim 11, which contains silica as a constituent formed by carrying out the sol-gel reaction in two stages. The textile product treatment composition according to claim 11 or 12, wherein the alkoxysilane is tetraethoxysilane. The textile product treatment composition according to any one of claims 1 to 13, wherein the fragrance component (1) of the component (c) contains one or more fragrance compounds, and the proportion of fragrance compounds having a log P of 2.0 to 5.0 and a vapor pressure at 25°C of 0.01 Pa to 8.00 Pa is 25 mass% or more of the total amount of fragrance compounds. The textile product treatment composition according to any one of claims 1 to 14, containing 3% by mass or more and 20% by mass or less of component (a), 0.1% by mass or more and 5% by mass or less of component (b), and 0.005% by mass or more and 0.5% by mass or less of the fragrance component (1) of component (c). The textile product treatment composition according to claims 1 to 15 further comprises, as component (d), a fragrance component (2) containing one or more fragrance compounds not encapsulated in microcapsules. The textile product treatment composition according to any one of claims 1 to 16, further comprising a nonionic surfactant as component (e). A method for suppressing odors from indoor drying, comprising contacting the textile product treatment composition according to any one of claims 1 to 17 with clothing during washing and then drying the clothing indoors. A deodorant composition containing the textile product treatment composition according to any one of claims 1 to 17.