Method for adding fragrance to textile products

Abstract

To provide a method of adding fragrance to a textile product containing a cotton fiber which exhibits good fragrance when putting a treated textile product on, particularly when the treated textile product is moistened with water such as sweat.SOLUTION: A method of adding fragrance to a textile product containing a cotton fiber includes the following process (I) and process (II). Process (I) is a process of contacting (a) an aqueous composition containing a silica capsule (hereinafter referred to as a constituent (a)) containing specific fragrance composition (A) to a textile product containing a cotton fiber. Process (II) is a process of subjecting the textile product processed by a process (I) to drying processing in a gas having a temperature of 5°C or higher and lower than 90°C to break a silica capsule structure of the constituent (a) attached to the inside or the surface of the textile product.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a method for perfumery of textile products containing cotton fibers. [Background technology]

[0002] In recent years, consumer interest in scents when washing, drying, and wearing clothes has increased, and the market for liquid fabric softeners and fragrance additives that promote scent-related content has grown significantly. Among the situations in which scents are felt, the scent of clothing when worn is of particular interest, and active development has been underway for functional materials that enable consumers to experience scents all day while wearing clothing, and textile product treatment agents containing such materials.

[0003] Conventional techniques for improving the persistence of fragrances include microencapsulating fragrances and blending precursor fragrances. Fragrance microcapsules are particulate materials in which a core fragrance is enclosed by a wall material. Their role is to protect the core fragrance and, when physical force is applied to the capsule, the capsule wall breaks, releasing the core fragrance. As an example of such microcapsules, Patent Document 1 describes an encapsulated fragrance containing, as a core material, a fragrance composition having a flash point in the range of 50 to 130° C. Patent Document 1 also describes microcapsules containing a volatile component such as a highly volatile fragrance and an additive that has a higher melting point and is compatible with the volatile component. Patent Document 2 discloses a textile product treatment composition that contains a silicate ester compound of a perfume compound and a specific perfume, and improves the life of the perfume on fabrics. Patent Document 3 discloses a fragrance composition for fabric softeners containing a silicate ester compound and a specific highly persistent fragrance. Patent Document 4 discloses silica capsules containing an active ingredient obtained by a sol-gel method. Patent Document 5 describes silica capsules containing perfumes produced by the core-shell method, and discloses that they can be incorporated into liquid laundry detergents and fabric softeners. Patent Document 6 describes a method for producing silica capsules that contain active ingredients such as fragrances. Patent Document 7 (Kao Patent Publication No. 2021-80613) discloses a textile product treatment composition containing a fragrance composition that easily penetrates into fibers and gives off a fragrance by absorbing moisture such as sweat. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Laid-Open No. 2006-249326 [Patent Document 2] Japanese Patent Application Laid-Open No. 2009-256818 [Patent Document 3] Japanese Patent Application Laid-Open No. 2011-063674 [Patent Document 4] Special Publication No. 2003-534249 [Patent Document 5] Special Publication No. 2011-517323 [Patent Document 6] Japanese Patent Application Laid-Open No. 2015-128762 [Patent Document 7] Patent Publication No. 2021-80613 Summary of the Invention [Problem to be solved by the invention]

[0005] In recent years, fragrance preferences have become more diverse, and several technologies have been proposed to allow textiles to retain their fragrance for a long time, but the fragrances added to textile treatment agents are difficult to adsorb onto the textile, and remain on the surface of the textile, causing the scent to quickly diffuse into the air. Depending on the base, the scent may even disappear during drying. Conventional perfume microcapsules, such as those made of polymer resin, are attached to textiles and break when physical stress is applied, releasing the fragrance. Silica capsules containing perfume are also known, and although they are easily broken due to the thinness of the silica membrane, the perfume that penetrates into the pores of the silica provides a long-lasting fragrance. In addition, fragrance technology using fragrance precursors obtained by fatty acid esterification or silicate ester compounds is limited to alcohol-based fragrances, and does not work with other fragrance ingredients. In addition, the scent is limited and it is difficult to sense its spread. Furthermore, when the textile treatment agent is stored for a long period of time, the dispersibility of the perfume added to the textile treatment agent in water decreases, resulting in a significant decrease in the perfume imparting ability. Furthermore, when textile products onto which fragrance has been adsorbed are dried in a dryer, the capsules and fragrance precursors tend to collapse or decompose due to heat, and the fragrance tends to volatilize, reducing the persistence of the fragrance.

[0006] The present inventors have found that specific fragrance compounds easily penetrate into cotton fibers, and have filed a patent application in Patent Document 6. This technology can be effectively utilized in treatment methods in which the treatment solution is directly applied or sprayed onto the textile product, allowing it to absorb the treatment solution as is (also known as leave-on treatment methods), but when used in methods in which the textile product is soaked in finishing processes such as starching or softening in the washing process, it is necessary to increase the concentration of the fragrance in the aqueous solution used for soaking, and most of this is washed away with the water during dehydration, so the fragrance is not efficiently delivered to the textile product.

[0007] The present invention provides a fragrance imparting method that can be used in the immersion treatment of textile products containing cotton fibers, which gives off a good fragrance when the treated textile product is worn, particularly when the treated textile product is wetted with water due to perspiration or the like. [Means for solving the problem]

[0008] The present inventors have discovered that by contacting a textile product containing cotton fibers with an aqueous composition containing silica capsules encapsulating a fragrance composition containing a fragrance compound having specific properties, followed by drying, the structure of the silica capsules attached to the surface of the textile product collapses without substantial physical stress, facilitating the penetration of the fragrance compound into the cotton fibers, thereby enabling the fragrance compound to be efficiently retained in the textile product. They have also discovered that when the fibers absorb moisture, the fragrance intensity is significantly improved.

[0009] That is, the present invention relates to a method for perfumery of textile products containing cotton fibers, which comprises the steps (I) and (II). Step (I): (a) A step of contacting an aqueous composition containing silica capsules (hereinafter referred to as component (a)) enclosing the following fragrance composition (A) with a textile product containing cotton fibers. Step (II): A step of drying the textile product treated in step (I) in gas at a temperature of 5°C or higher but lower than 90°C to break down the silica capsule structure of component (a) attached to the surface or inside of the textile product. Fragrance composition (A): Fragrance composition (A) containing fragrance compounds (A1) having a log Kow value of 2.0 or more and 5.0 or less and a vapor pressure value at 25°C of 0.01 Pa or more and 3.63 Pa or less in an amount of 30% by mass or more and 85% by mass or less, and the fragrance composition (A) containing at least five fragrance compounds selected from the fragrance compounds (A1) below in an amount of 5% by mass or more and 65% by mass or less: (A1-1) γ-Undecalactone, 2-cyclohexylidene-2-phenylacetonitrile, damascenone, δ-damascone, α-methyl-β-(pt-butylphenyl)-propionaldehyde, β-ionone, myrrh aldehyde, ethyl tricyclo[5.2.1.0-2,6]decane-2-carboxylate, 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, dimethylbenzylcarbinyl butyrate, tricyclodecenyl propionate, amyl salicylate, γ-methyl ionone, α -Damascone, β-damascone, nerolin yarayara, 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 ketone, eugenol, lyral, dimethylbenzylcarbinyl acetate, iso-damascone, 2-cyclohexylidene-2-phenylacetonitrile, γ-decalactone, α-methyl-3,4-methylenedioxyhydrocinnamic aldehyde, 7-methyl-3,5-dihydro-2H-benzodioxepinone, tricyclodecynyl acetate, tricyclodecynyl propionate, allyl 2-pentyloxyglycolate [Effects of the Invention]

[0010] According to the present invention, there is provided a method for perfumery of textile products including cotton fibers, which gives off a good fragrance when the treated textile product is worn, particularly when the treated textile product is wetted with water due to perspiration or the like, and since a plurality of fragrances can be used equally, a wide variety of fragrances can be felt. DETAILED DESCRIPTION OF THE INVENTION

[0011] When textile products containing cotton fibers obtained by the fragrance imparting method of the present invention are moistened with water, their fragrance intensity is significantly improved compared to when they are dry. The reason for this is not entirely clear, but is presumed to be as follows. The inventors discovered that the specific fragrance compounds constituting fragrance composition (A) easily penetrate into the cotton fibers of textile products, and further found that they penetrate into the spaces between the fibril bundles that make up the cotton fibers. As a result, it is presumed that fragrance volatilization is suppressed, and the fragrance components in the fibers are replaced by water upon moisture absorption, resulting in the fragrance.

[0012] [Method for adding fragrance to textile products containing cotton fibers] The method for perfumery of a textile product containing cotton fiber of the present invention comprises steps (I) and (II). By applying step (II) to the textile product treated in step (I), it is possible to impart the property of giving off a strong fragrance when the textile product absorbs moisture or is wet. Hereinafter, the method for perfumery of textile products containing cotton fibers of the present invention will be referred to as the method of the present invention. Unless otherwise specified, the method of the present invention refers to this method.

[0013] <Process (I)> Step (I) of the present invention is (a) a step of contacting an aqueous composition containing silica capsules (hereinafter referred to as component (a)) enclosing the fragrance composition (A) with a textile product containing cotton fibers.

[0014] Contacting a textile product containing cotton fibers with an aqueous composition can be carried out by a commonly known method. This method involves immersing the textile product in the aqueous composition. Immersion can be carried out in a container such as a washbasin or tub, or in a washing machine. The textile product to be treated may be wet before treatment, or it may be contacted in a dry state. If the textile product is wet, it may be subjected to a dehydration procedure to remove excess water. If the textile product has already been immersed in an aqueous medium, a concentrated aqueous composition, which is a reduced-water version of the aqueous composition of the present invention, may be added to the aqueous medium in a proportion of 1 ml to 50 ml, designed to achieve a preferred fragrance composition concentration upon contact with the textile product, as described below. The concentrated aqueous composition may contain little water, or may be in the form of a fragrance composition dispersed in an organic solvent. The concentrated aqueous composition is used in a conventional textile product treatment composition, and may also be a textile product treatment composition, as described in detail below. Although it is possible to directly attach the aqueous composition of the present invention to the textile product to be scented by spraying it, the immersion method is more preferable because the silica capsules of the present invention may be broken by the mechanical force during the spraying operation.

[0015] When contacting a textile product with the aqueous composition of the present invention, the concentrated aqueous composition is added to a container containing water to prepare the aqueous composition of the present invention. In the first method, the concentration of the fragrance composition (A) in the aqueous composition is preferably 1 ppm or more, more preferably 3 ppm or more, and preferably 80 ppm or less, more preferably 20 ppm or less.

[0016] When using a washing machine or the like, the ratio of the textile product to be contacted with the aqueous composition of the present invention is preferably 5 L or more, more preferably 10 L or more, even more preferably 12 L or more, and preferably 30 L or less, more preferably 25 L or less, even more preferably 20 L or less per 1 kg of textile product.

[0017] In step (I), it is preferable that the aqueous composition of the present invention is brought into contact with the textile product at a temperature of preferably 5°C or higher, more preferably 10°C or higher, even more preferably 15°C or higher, and preferably 50°C or lower, more preferably 40°C or lower, even more preferably 30°C or lower.

[0018] The contact time between the textile product and the aqueous composition of the present invention is preferably 1 minute or more, more preferably 2 minutes or more, from the viewpoint of uniform adsorption of the fragrance onto the clothing, and is preferably 20 minutes or less, more preferably 10 minutes or less, from the viewpoint of suppressing evaporation of the fragrance during immersion. After step (I), it is preferable to carry out a dehydration treatment before proceeding to step (II).

[0019] <Aqueous composition> The aqueous composition of the present invention contains, as component (a), silica capsules containing the following fragrance composition (A) (hereinafter sometimes referred to as component (A)). Fragrance composition (A): Fragrance composition (A) containing fragrance compounds (A1) having a log Kow value of 2.0 or more and 5.0 or less and a vapor pressure value at 25°C of 0.01 Pa or more and 3.63 Pa or less in an amount of 30% by mass or more and 85% by mass or less, and the fragrance composition (A) containing at least five fragrance compounds selected from the fragrance compounds (A1) below in an amount of 5% by mass or more and 65% by mass or less: (A1-1) γ-Undecalactone, 2-cyclohexylidene-2-phenylacetonitrile, damascenone, δ-damascone, α-methyl-β-(pt-butylphenyl)-propionaldehyde, β-ionone, myrrh aldehyde, ethyl tricyclo[5.2.1.0-2,6]decane-2-carboxylate, 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, dimethylbenzylcarbinyl butyrate, tricyclodecenyl propionate, amyl salicylate, γ-methyl ionone, α -Damascone, β-damascone, nerolin yarayara, 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 ketone, eugenol, lyral, dimethylbenzylcarbinyl acetate, iso-damascone, 2-cyclohexylidene-2-phenylacetonitrile, γ-decalactone, α-methyl-3,4-methylenedioxyhydrocinnamic aldehyde, 7-methyl-3,5-dihydro-2H-benzodioxepinone, tricyclodecynyl acetate, tricyclodecynyl propionate, allyl 2-pentyloxyglycolate

[0020] The present inventors have searched for fragrances that are highly absorbed into textile products when the aqueous composition of the present invention comes into contact with the textile product. As a result, they have found that fragrance compounds (A1) that have common features in that they have water affinity, i.e., a log Kow of 2.0 or more and 5.0 or less (hereinafter, sometimes referred to as condition (1)), and relatively low volatility, i.e., a vapor pressure at 25°C of 0.01 or more and 3.63 Pa or less (hereinafter, sometimes referred to as condition (2)), are easily permeable into cotton fibers, and have found that fragrance compounds selected from the fragrance compounds (A1-1) described above are particularly effective.

[0021] In the present invention, the log Kow (log P) value is a coefficient indicating the affinity of an organic compound for water and 1-octanol. The 1-octanol / water partition coefficient, log Kow, is the ratio of the equilibrium concentrations of a compound in each solvent in a two-phase liquid-phase equilibrium system of 1-octanol and water, and is expressed as their logarithmic value to the base 10. The log Kow (log P) value can be calculated by the "fragment constant" method, in which the structure is divided into fragments (atoms / functional groups) and the values ​​of each atomic group are summed (in some cases, a structural correction factor is used) to obtain an estimated value. In the present invention, the log Kow value calculated using EPI suite version 4.11, a chemical property prediction software available from the U.S. Environmental Protection Agency (EPA), is used.

[0022] In the present invention, the vapor pressure at 25°C is determined by an actual measurement or by estimating the vapor pressure from the boiling point, or, if the chemical is solid at room temperature, by estimating the vapor pressure from the melting point. Vapor pressure can be estimated by several known methods (such as the Antoine method, the Modified Grain method, and the Mackay method). In the present invention, the vapor pressure is calculated using MPBPWIN, which is included in the EPI suite available from the U.S. Environmental Protection Agency (EPA). If the average of the values ​​calculated by the Antoine method and the Grain method is displayed in the calculation results as the "Selected VP," the average value is used. If no "Selected VP" is displayed, the value calculated by the Modified Grain method is used.

[0023] The log Kow and vapor pressure (Pa; 25° C.) values ​​of the fragrance compound (A1-1) of the present invention are shown in Table 1.

[0024] [Table 1]

[0025] Among the above fragrance compounds (A1-1), fragrance compounds selected from the following fragrance compounds (A1-1S) are more preferred. (A1-1S) γ-Undecalactone, 2-cyclohexylidene-2-phenylacetonitrile, damascenone, δ-damascone, β-ionone, myrrh aldehyde, ethyl tricyclo[5.2.1.0-2,6]decane-2-carboxylate, citronellol, geraniol, α-ionone, patchouli alcohol, 6,7-dihydro-1,1,2,3,3-pentamethyl-4(5H)-indanone, methyl dihydrojasmonate, allylcyclohexyl propionate, tricyclodecene propionate Nyl, γ-methylionone, α-damascone, β-damascone, 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, lyral, iso-damascone, γ-decalactone, tricyclodecynyl acetate, tricyclodecynyl propionate, γ-decalactone, allyl 2-pentyloxyglycolate, allyl 2-pentyloxyglycolate

[0026] Among the fragrance compounds (A1-1) that satisfy the log Kow and vapor pressure requirements, the fragrance compound (A1-1S) is more preferred from the viewpoint of facilitating the perception of fragrance when the fabric swells with moisture due to sweating, etc. The fragrance compounds (A1-1S) may be used either alone or in combination of two or more. Of these, when formulating the fragrance composition of component (A), it is even more preferable from the viewpoint of scent recognition to include at least one essential component selected from the fragrance compounds (A1-1S) listed above: γ-undecalactone, 2-cyclohexylidene-2-phenylacetonitrile, damascenone, α-damascone, β-damascone, δ-damascone, iso-damascone, tricyclodecinyl acetate tricyclodecinyl propionate, ethyl tricyclo[5.2.1.0-2,6]decane-2-carboxylate, γ-decalactone, and allyl 2-pentyloxyglycolate.

[0027] In order to clarify the fragrance due to moisture absorption of cotton-containing textile products, the fragrance composition of component (A) of the present invention contains fragrance compound (A1) in an amount of 30% by mass or more, preferably 33% by mass or more, more preferably 35% by mass or more, even more preferably 37% by mass or more, and from the viewpoint of fragrance balance, 85% by mass or less, preferably 80% by mass or less, more preferably 75% by mass or less, even more preferably 70% by mass or less, and even more preferably 65% ​​by mass or less.

[0028] The fragrance composition of the component (A) of the present invention contains at least 5, preferably 7 or more, and more preferably 10 or more fragrance compounds selected from the fragrance compounds (A1-1) described above. Furthermore, the fragrance composition of component (A) of the present invention suitably contains at least three, preferably five or more, and more preferably seven or more fragrance compounds selected from the fragrance compounds (A1-1S) described above.

[0029] The fragrance composition of component (A) of the present invention contains the fragrance compound (A1-1) in an amount of 5% by mass or more, preferably 10% by mass or more, more preferably 20% by mass or more, even more preferably 30% by mass or more, still more preferably 35% by mass or more, and even more preferably 37% by mass or more, from the viewpoint of fragrance release when wet, and 65% by mass or less, preferably 60% by mass or less, and more preferably 55% by mass or less, from the viewpoint of fragrance balance. The fragrance composition of component (A) of the present invention contains the fragrance compound (A1-1S) in an amount of preferably 5% by mass or more, more preferably 10% by mass or more, even more preferably 20% by mass or more, and even more preferably 25% by mass or more in terms of fragrance release when wet, and preferably 65% ​​by mass or less, more preferably 60% by mass or less, and even more preferably 55% by mass or less in terms of fragrance balance.

[0030] The fragrance composition (A) of the present invention preferably further contains a fragrance compound (A2) having a log Kow value of 3.0 or more and a vapor pressure value at 25°C of more than 3.63 Pa.

[0031] The fragrance compound (A2) may be selected from the fragrance compounds (A2-1) below. (A2-1) Limonene, α-terpinene, γ-terpinene, citronellyl acetate, p,t-butylcyclohexyl acetate, o,t-butylcyclohexyl acetate, linalyl acetate, allyl heptanoate, tetrahydrolinalool, dihydromyrcenol, linalool, nonanal, decanal, geranyl acetate, rose oxide, methylnonylacetaldehyde, allyl caproate, terpinyl acetate, 1,8-cineole, citronellyl nitrile, ethyl 2-methylvalerate, α-pinene, β-pinene, allyl hexanoate, d-citronellal, neryl acetate, melonal, ethyl 2-cyclohexylpropionate, isocyclocitral

[0032] The log Kow and vapor pressure (Pa; 25°C) values ​​of the fragrance compound (A2-1) are also shown in Table 2.

[0033] [Table 2]

[0034] When the fragrance compound (A2) is used to treat fibers using water as a medium, specifically when it is used as a liquid fabric softener composition, it is preferable that the fragrance compound (A2) has a log Kow value of 3.0 or more from the viewpoint of its adsorption to fibers and of leaving a certain amount of the fragrance compound on the fibers until they dry, and that the fragrance compound has a log Kow value of preferably 5.0 or less from the viewpoint of its penetrability into the interior of highly hydrophilic fibers.

[0035] The fragrance compound (A2) must be volatile enough to ensure a gas phase concentration sufficient for scent recognition even when adsorbed in trace amounts, and therefore must have a vapor pressure of more than 3.63 Pa. In addition, from the viewpoint of the persistence of the fragrance compound on the fibers between treatment and drying, a fragrance compound with a vapor pressure of preferably 1000 Pa or less is preferred.

[0036] The fragrance compound (A2) has a log Kow value of 3.0 or more, preferably 3.5 or more, more preferably 4.0 or more, and preferably 5.0 or less, and a vapor pressure value at 25°C of more than 3.63 Pa and preferably 1000 Pa or less, more preferably 500 Pa or less, and even more preferably 250 Pa or less.

[0037] The fragrance compounds (A2) have a distinctive fragrance and are highly volatile, and therefore contribute greatly to the fragrance of the aqueous composition and the fragrance immediately after treatment with fibers. On the other hand, most of the compounds adsorbed to the fibers volatilize during the drying process, so they contribute little to the fragrance of the treated fibers. However, these fragrance compounds are present in trace amounts inside the fibers, and when the fibers swell due to the absorption of moisture during sweating, for example, they volatilize and blend with the fragrance compounds (A1), resulting in a more pleasant fragrance.

[0038] Since the fragrance compound (A2) has a high vapor pressure, it is sufficient for a trace amount of the fragrance compound (A2) to remain on the fiber in order to ensure a gas phase concentration sufficient for scent perception. However, since many of the fragrance compounds on the fibers volatilize during the period from treatment to drying, the fragrance composition of component (A) contains fragrance compound (A2), preferably fragrance compound (A2-1), in an amount of preferably 3% by mass or more, more preferably 5% by mass or more, even more preferably 10% by mass or more, and even more preferably 15% by mass or more in fragrance composition (A), and from the viewpoints of preventing excessive fragrance release upon absorption of water and ensuring fragrance persistence, preferably 70% by mass or less, more preferably 50% by mass or less, even more preferably 40% by mass or less, even more preferably 35% by mass or less, and even more preferably 30% by mass or less.

[0039] When the fragrance composition (A) of the present invention contains a fragrance compound (A2), from the viewpoint of further enhancing the fragrance release when fibers are swollen and immediately after fiber treatment, the total content of the fragrance compound (A1), preferably the fragrance compound (A1-1), more preferably the fragrance compound (A1-1S), and the fragrance compound (A2), preferably the fragrance compound (A2-1), in the fragrance composition (A), is, under the above-mentioned essential requirements, preferably 20% by mass or more, more preferably 30% by mass or more, even more preferably 35% by mass or more, still more preferably 45% by mass or more, still more preferably 55% by mass or more, and still more preferably 60% by mass or more; and from the viewpoint of fragrance preference, preferably 95% by mass or less, more preferably 90% by mass or less, and even more preferably 85% by mass or less.

[0040] When the fragrance composition (A) of the present invention contains a fragrance compound (A2), from the viewpoint of achieving both fragrance release when the fiber is swollen and fragrance release immediately after fiber processing, the mass ratio (A1) / (A2) of the content of fragrance compound (A1) to the content of fragrance compound (A2) in the fragrance composition (A) is preferably 0.1 or more, more preferably 0.2 or more, even more preferably 0.5 or more, still more preferably 1 or more, still more preferably 1.2 or more, and from the viewpoint of fragrance preference, it is preferably 50 or less, more preferably 30 or less, even more preferably 20 or less, still more preferably 10 or less, still more preferably 5 or less, still more preferably 4 or less.

[0041] Furthermore, in order to increase the freedom of fragrance creation, the fragrance composition of component (A) may contain, as a fragrance compound other than fragrance compounds (A1) and (A2), a fragrance compound that is generally known or known from patent documents, etc. to be used in textile product treatment agents [hereinafter, sometimes referred to as fragrance compound (A3)]. Examples of the fragrance compound (A3) other than the fragrance compounds (A1) and (A2) include octanal, hexyl acetate, benzyl acetate, isoamyl acetate, hexyl salicylate, benzyl salicylate, cyclohexyl salicylate, cis-3-hexenyl salicylate, Iso-E-Super, methyl anthranilate, ethylene brassylate, ambrettolide, vanillin, ethyl vanillin, isoeugenol, raspberry ketone, coumarin, heliotropin, 1- Examples of fragrance compounds include those selected from (spiro[4.5]decan-7-en-7-yl)pent-4-en-1-one, 1-(spiro[4.5]decan-6-en-7-yl)pent-4-en-1-one, cedryl methyl ether, Javanol (Givaudan), acetylcedrine, tripral, ethyl butyrate, ethyl-2-methylbutyrate, 2-(2-(4-methyl)-3-cyclohexynyl-(1)propylcyclopentanone, and cyclamen aldehyde.

[0042] The fragrance composition of component (A) may be used after being diluted with a solvent known in the fragrance industry as a diluent or fixative. Examples of the solvent include methanol, ethanol, ethylene glycol, glycerin, diethylene glycol monoethyl ether, propylene glycol, dipropylene glycol, dipropylene glycol monoethyl ether, 3-methoxy-3-methylbutanol, diethyl phthalate, isopropyl myristate, benzyl myristate, triethyl citrate, benzyl benzoate, benzyl alcohol, phenoxyethanol, diisobutyl adipate, hydrogenated methyl abietic acid, etc. In particular, when a concentrated solution containing a high concentration of component (A) is dissolved in water to prepare an aqueous composition, it is preferable to add a solvent from the viewpoint of ease of solubility or dispersion in water. However, when calculating the blending amount of the fragrance composition in the present invention, the calculation does not include the solvent used to dilute the fragrance. However, when a solvent is used, the proportion of the solvent in the total of component (A) and the solvent is preferably from 0 to 20% by mass in component (A).

[0043] The aqueous composition of the present invention contains, as component (a), microcapsules having a shell containing silica as a constituent and a core containing the fragrance composition (A) inside the shell. Silica is a substance whose structural unit is silicon dioxide. Hereinafter, microcapsules having a shell containing silica as a constituent are referred to as silica capsules. Furthermore, unless otherwise specified, when referring to a fragrance composition, it refers to the fragrance composition of component (A).

[0044] The shell of the silica capsule of component (a) of the present invention contains silica as a constituent component. The shell of the silica capsule of the present invention is characterized in that 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 the present invention, the "sol-gel reaction" refers to a reaction in which an alkoxysilane undergoes hydrolysis and polycondensation to form silica, a component of the shell, through a sol and a gel state. Specifically, for example, tetraalkoxysilane is hydrolyzed, and a silanol compound undergoes a dehydration condensation reaction and a dealcoholization condensation reaction to generate a siloxane oligomer, and the dehydration condensation reaction further proceeds to form silica.

[0045] In addition, the shell of the silica capsule of the present invention may contain an inorganic polymer other than silica as a constituent component, as long as the effect of the present invention is not impaired. In the present invention, the inorganic polymer refers to a polymer containing an inorganic element. Examples of the inorganic polymer include a polymer consisting only of inorganic elements, a polymer whose main chain is composed only of inorganic elements and has an organic group as a side chain or substituent, and the like. The inorganic polymer is preferably a metal oxide containing a metal element or a metalloid element, and more preferably a polymer formed by a reaction similar to the sol-gel reaction of silica using a metal alkoxide [M(OR)x] as a precursor, where M is a metal or metalloid element and R is a hydrocarbon group. Examples of metal or semimetal elements constituting the metal alkoxide include titanium, zirconium, aluminum, and zinc.

[0046] The alkoxysilane is preferably a tetraalkoxysilane from the viewpoint of increasing the encapsulation rate of the fragrance composition and exhibiting 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.

[0047] (Manufacturing of silica capsules) From the viewpoints of increasing the encapsulation rate of the fragrance composition, improving the long-term retention, and achieving good delivery performance of the fragrance composition, the shell of the silica capsule of the present invention preferably contains, as a constituent, silica formed by a two-stage sol-gel reaction. 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 composition and a tetraalkoxysilane to a sol-gel reaction under acidic conditions to form silica capsules (1) having a core and a first shell composed of silica, 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, thereby forming silica capsules having a second shell that encapsulates the first shell.

[0048] [Process 1] Step 1 is a step of subjecting an emulsion obtained by emulsifying an aqueous phase component containing a cationic surfactant with a fragrance composition containing an alcohol-based fragrance compound and an oil phase component containing a tetraalkoxysilane to a sol-gel reaction under acidic conditions to form silica capsules (1) having a core and a first shell composed of silica as a constituent component, and obtaining an aqueous dispersion containing the silica capsules (1).

[0049] Examples of cationic surfactants used 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 a long-chain alkyl group, a short-chain alkyl group, and a benzyl group. 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, and 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, i.e., a methyl group. Examples of alkylamine salts include alkylamine salts in which the long-chain alkyl group has the 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 quaternary ammonium salts 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 long-chain alkyl group and a short-chain alkyl group within the above-mentioned range of carbon number.

[0050] Examples of alkylamine salts include alkylamine acetates such as lauryl dimethylamine acetate and stearyl dimethylamine 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 dialkyldimethylammonium salts include dialkyldimethylammonium chlorides such as distearyldimethylammonium chloride; and dialkyldimethylammonium bromides such as distearyldimethylammonium bromide. Examples of alkylbenzyldimethylammonium salts 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 with 10 to 22 carbon atoms, even more preferably an alkyltrimethylammonium chloride having an alkyl group with 10 to 22 carbon atoms, even more preferably one or more selected from lauryltrimethylammonium chloride, stearyltrimethylammonium chloride, and cetyltrimethylammonium chloride, and even more preferably cetyltrimethylammonium chloride.

[0051] In step 1, other emulsifiers may be contained in addition to the cationic surfactant, provided that the effects of the present invention are not impaired. Examples of other emulsifiers include polymer dispersants, nonionic surfactants, anionic surfactants, and amphoteric surfactants.

[0052] 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 emulsified 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 by excess emulsifier that does not contribute to the dispersion stability of the emulsion and improving encapsulation efficiency.

[0053] The amount of 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.

[0054] 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, relative to the total amount of the fragrance composition 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 composition.

[0055] Step 1 preferably includes the following steps 1-1 to 1-4. Step 1-1: Preparing an aqueous phase component containing a cationic surfactant Step 1-2: A step of mixing a fragrance composition containing an alcohol-based fragrance compound with 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 silica capsules having a core and a first shell composed of silica.

[0056] The stirring means used in preparing the emulsion is not particularly limited, and may be a homogenizer, high-pressure disperser, ultrasonic disperser, etc., which have a strong shearing force. Also, a homomixer, such as "Disper" (trade name, manufactured by Primix Corporation), "Clearmix" (trade name, manufactured by M Technique Co., Ltd.), or "Cavitron" (trade name, manufactured by Pacific Machinery Works, Ltd.) may be used.

[0057] Median diameter D of the emulsion droplets in the emulsion of step 1 50 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 storage stability, and is preferably 50 μm or less, more preferably 30 μm or less, even more preferably 10 μm or less, even 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. Median diameter of emulsion droplets D 50 can be measured by the method described in the Examples.

[0058] The initial pH of the sol-gel reaction in step 1 is preferably 3.0 or higher, more preferably 3.3 or higher, and even more preferably 3.5 or higher, from the viewpoint of maintaining a balance between the hydrolysis reaction and condensation reaction of the tetraalkoxysilane, and from the viewpoint of suppressing the formation of a highly hydrophilic sol and promoting the progress of encapsulation. The initial pH is preferably 4.5 or lower, more preferably 4.3 or lower, and even more preferably 4.1 or lower, from the viewpoint of suppressing the simultaneous formation of a silica shell and the aggregation of emulsified droplets and obtaining silica capsules with a dense shell.

[0059] 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 to adjust the initial pH to a desired level. The pH of the emulsion may fall below the desired value, in which case it is preferable to adjust it 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 to form silica capsules (1) having a core and a first shell, and obtaining an aqueous dispersion containing the silica capsules (1).

[0060] 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 of cation exchange resins added to water or ethanol, among which hydrochloric acid, sulfuric acid, nitric acid, and citric acid are preferred. Examples of alkaline pH adjusters include sodium hydroxide, sodium bicarbonate, potassium hydroxide, ammonium hydroxide, diethanolamine, triethanolamine, and trishydroxymethylaminomethane, with sodium hydroxide and ammonium hydroxide being preferred.

[0061] 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 water contained as 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, 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.

[0062] [Process 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 having a second shell that encapsulates the first shell.

[0063] 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, relative to the fragrance composition 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 formation of silica sol that disperses in the aqueous phase and improving the dispersion stability of the silica capsules.

[0064] 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 divided amounts, or may be added continuously. However, from the viewpoint of forming a highly dense second shell, it is preferable to add it dropwise continuously. When the tetraalkoxysilane is added dropwise continuously, the dropwise addition time can be set appropriately depending on the scale of production, but from the viewpoint of suppressing separation of the added tetraalkoxysilane from the aqueous dispersion, it is preferably 5 minutes or more, more preferably 10 minutes or more, even more preferably 30 minutes or more, and preferably 1200 minutes or less, more preferably 1000 minutes or less, even more preferably 500 minutes or less.

[0065] In the present invention, the total amount of tetraalkoxysilane added, i.e., the total amount of tetraalkoxysilane added in Step 1 and Step 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 composition in Step 1. By keeping the total amount of tetraalkoxysilane added within the above range, the encapsulated fragrance composition can be preserved for a long period of time.

[0066] In the present invention, the total amount of the fragrance composition and tetraalkoxysilane in Step 1 relative to the total amount of the aqueous dispersion before the addition of the tetraalkoxysilane in Step 2 is preferably 20% by mass or less, more preferably 18% by mass or less, even more preferably 15% by mass or less, and even more preferably 10% by mass or less, from the viewpoint of improving the long-term shelf life of the fragrance composition, and is preferably 2% by mass or more, more preferably 3% by mass or more, and even more preferably 5% by mass or more, from the viewpoint of production efficiency. The adjustment of the total amount of the fragrance composition and tetraalkoxysilane in Step 1 relative to the total amount of the aqueous dispersion before the addition of the tetraalkoxysilane in Step 2 may be performed by carrying out Step 1 so that the amounts of the fragrance composition and tetraalkoxysilane in Step 1 and the total amount of the aqueous dispersion obtained in Step 1 fall within the above-mentioned ranges, or may be performed by further adding water to the aqueous dispersion obtained in Step 1 to dilute it.

[0067] In the present invention, from the viewpoint of production efficiency, the aqueous dispersion obtained in Step 1 may be diluted with water before the addition of the tetraalkoxysilane in Step 2. The total amount of the fragrance composition and tetraalkoxysilane in Step 1 relative to the total amount of the aqueous dispersion obtained in Step 1 before dilution is preferably 3% by mass or more, more preferably 5% by mass or more, even more preferably 10% by mass or more, still more preferably 15% by mass or more, and is preferably 50% by mass or less, more preferably 40% by mass or less, and even more preferably 30% by 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.

[0068] The reaction temperature for the sol-gel reaction in step 2 can be selected arbitrarily as long as it is equal to or higher than the melting point and equal to or lower than 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, the reaction temperature 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.

[0069] 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. Examples of the organic polymer compound include nonionic polymers, cationic polymers, and anionic polymers. The nonionic polymer refers to a water-soluble polymer that has no charge in water. By using a nonionic polymer, it is possible to impart a function to the silica capsule depending on the intended use 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 textile product treatment composition such as a 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.

[0070] Examples of nonionic polymers 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" refers to either acrylate or methacrylate. Similarly, "(meth)acrylic" refers to either acrylic or methacrylic. The nonionic polymer is preferably one or more selected from polyvinylpyrrolidone, copolymers of vinylpyrrolidone with other nonionic monomers such as vinylpyrrolidone / vinyl acetate copolymer, and cellulose polymers such as hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxypropyl methyl cellulose, and hydroxyethyl methyl cellulose, and more preferably one or more selected from polyvinylpyrrolidone and hydroxypropyl cellulose.

[0071] Examples of cationic polymers include polymers containing quaternary ammonium salt groups, polymers having nitrogen-based cationic groups, polymers that can become cationic by adjusting the pH, etc. By using a cationic polymer, it is possible to alleviate the situation in which the silica capsules (1) obtained in step 1 tend to aggregate in the aqueous dispersion, and it is possible to suppress the generation of coarse particles, etc. in the subsequent step 2. Examples of cationic polymers 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), as well as 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, with one or more selected from poly(diallyldimethylammonium chloride), poly(acrylic acid-co-diallyldimethylammonium chloride), and poly(acrylamide-co-acrylic acid-co-diallyldimethylammonium chloride) being more preferred, and poly(diallyldimethylammonium chloride) being even more preferred.

[0072] 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 viewpoints of dispersibility of the silica capsules (1), suppression of the generation of coarse particles, and improvement of long-term retention. The cationic polymer may contain anionic groups, 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.

[0073] Examples of anionic polymers 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 anionic polymers include poly(meth)(acrylic acid), poly(maleic 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. Note that (meth)acrylic acid means acrylic acid or methacrylic acid.

[0074] In step 2, 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 amount of the aqueous dispersion obtained in step 1.

[0075] The silica capsules obtained in step 2 are dispersed in water. Depending on the application, they can be used as they are, but in some cases, the silica capsules are separated and used. Separation methods such as filtration and centrifugation can be used.

[0076] Silica capsules (a) containing the fragrance composition (A) of the present invention, for example, silica capsules produced as described above, are attached to textile products in an aqueous medium and then break down towards the end of the process as water evaporates from the textile product, allowing the contents to penetrate into the textile product.

[0077] The silica capsules, which are component (a) of the present invention, are preferably silica capsules having a core containing the fragrance composition, a first shell encapsulating the core, and a second shell encapsulating the first shell, from the viewpoint of stably retaining the contents within the aqueous composition of the present invention and breaking down upon drying after being attached to a textile product in an aqueous medium. The first shell of the silica capsule of the present invention encapsulates the core, contains silica as a constituent component, and preferably has an average thickness of 5 nm or more and 20 nm or less, and the second shell encapsulates the first shell, contains silica as a constituent component, and preferably has an average thickness of 10 nm or more and 100 nm or less. The average thickness of the first and second shells of the silica capsules can be measured by observation with a transmission electron microscope (TEM). Specifically, the thickness of the first and second shells is measured on a photograph under a transmission electron microscope. This operation is performed with the field of view changed five times. The distribution of the average thickness of the first and second shells is determined from the obtained data. The magnification of the transmission electron microscope is generally between 10,000 and 100,000 times, but is adjusted appropriately depending on the size of the silica capsules. Here, a transmission electron microscope (TEM) such as the "JEM-2100" (manufactured by JEOL Ltd.) can be used.

[0078] The median diameter D of the silica capsule according to the present invention 50 From the viewpoint of improving the long-term storage property and improving the dispersion stability of the silica capsules, the particle size is preferably 0.1 μm or more, more preferably 0.5 μm or more, and even more preferably 1 μm or more, and from the viewpoint of improving the physical strength and long-term storage property of the silica capsules, the particle size is preferably 100 μm or less, more preferably 50 μm or less, even more preferably 30 μm or less, and even more preferably 10 μm or less. Silica capsule median diameter D 50 can be measured by the method described in the Examples.

[0079] The silica capsules according to the present invention are preferably blended as a silica capsule slurry when preparing the textile product treatment composition, which is the concentrated aqueous composition of the present invention. From the viewpoint of improving the dispersibility of the silica capsule slurry in the components mixed when preparing the textile product treatment composition, a surfactant selected from a cationic surfactant, a nonionic surfactant, and an anionic surfactant may be added to the silica capsule slurry.

[0080] The silica capsules of component (a) may be partially aggregated to the extent that the fragrance is not impaired.

[0081] The aqueous composition of the present invention contains component (a) as a fragrance composition (A) encompassed by component (a) in an amount of preferably 0.01 ppm or more, more preferably 0.05 ppm or more, even more preferably 0.1 ppm or more, and preferably 20 ppm or less, more preferably 10 ppm or less, even more preferably 5 ppm or less.

[0082] In addition to the silica capsules (a) containing component (A), the aqueous composition of the present invention may also contain other fragrance precursors, such as known microencapsulated fragrance particles and the silicate ester fragrance precursors described in JP 2009-256818 A. These fragrance precursors and microencapsulated fragrances are not included in the concentration specification of component (A) of the present invention.

[0083] The aqueous composition of the present invention preferably contains water. The water is preferably distilled water or deionized water. From the viewpoint of ease of use, the aqueous composition of the present invention preferably contains water in an amount of 50% by mass or more, more preferably 65% ​​by mass or more, even more preferably 70% by mass or more, and preferably 99.9% by mass or less, more preferably 99.5% by mass or less, even more preferably 99% by mass or less.

[0084] The aqueous composition of the present invention may contain a water-soluble organic solvent (hereinafter also referred to as component (b)) from the viewpoint of the stability of the composition itself, the stability or water solubility of the concentrated aqueous composition before dilution (herein, the concentrated aqueous composition may also be referred to as a textile product treatment agent, which may be a known textile product treatment agent such as a fabric softener), or as an accompanying component of component (A). In the present invention, the term "water-soluble" for component (b) means that 20 g or more dissolves in 100 g of deionized water at 20° C. Furthermore, in the present invention, "dissolution" means that no separation or clouding occurs, and specifically, means that the light transmittance at UV600 nm is 85% or more, as measured using a UV-2550 ultraviolet-visible spectrophotometer (manufactured by Shimadzu Corporation).

[0085] Specific examples of component (b) include lower alcohols (having 2 to 4 carbon atoms) such as ethanol and isopropanol, polyhydric alcohols (having 2 to 12 carbon atoms) such as ethylene glycol, propylene glycol, glycerin and sorbitol, monoethyl or monobutyl ether of ethylene glycol, monoethyl or monobutyl ether of propylene glycol, monoethyl or monobutyl ether of diethylene glycol, monoethyl or monobutyl ether of dipropylene glycol, benzyl alcohol, benzyloxyethanol, ethylene oxide or propylene oxide adducts of phenolic compounds, and monoalkyl monoglyceryl ethers having an alkyl group having 5 to 8 carbon atoms, and these may be used alone or in combination. From the viewpoint of ensuring the solubility of component (A) in the aqueous composition, component (b) is preferably at least one selected from ethylene glycol, propylene glycol, phenoxyethanol, ethanol, ethylene glycol monoethyl ether, and propylene glycol monoethyl ether, and more preferably at least one selected from ethylene glycol, propylene glycol, and ethanol.

[0086] The aqueous composition of the present invention may contain a surfactant as component (c). Examples of the surfactant include one or more selected from cationic surfactants, nonionic surfactants, anionic surfactants, and amphoteric surfactants. In the present invention, however, cationic surfactants are preferred, and quaternary ammonium salt-type cationic surfactants are more preferred, from the viewpoint of enhancing the adsorption of component (a) to textile products during immersion in the treatment. In this regard, cationic surfactants are also preferred because they can be used as fabric softeners and disinfectants, and cationic surfactants known as fabric softeners can be used.

[0087] Examples of the cationic surfactant of component (c) include tertiary amine salt-type cationic surfactants which are acid salts of hydrochloric acid, sulfuric acid, or hydroxycarboxylic acid, and which preferably have 10 or more, preferably 12 or more, carbon atoms and one to three (two or less in the case of amines) unsaturated or saturated linear hydrocarbons having 22 or less, preferably 22 or less, carbon atoms, which may be separated by ester bonds or amide bonds, and the remaining organic groups are alkyl or hydroxyalkyl groups having 1 to 3 carbon atoms, and the hydroxyalkyl group may have an oxyethylene group or oxypropylene group with a degree of polymerization of 1 to 40 between the nitrogen atoms, or are benzyl groups, preferably methyl, ethyl, hydroxyethyl, or benzyl groups; and quaternary ammonium salt-type cationic surfactants which are obtained by quaternizing the tertiary amine with an alkylating agent, and which have an anion, preferably a chloride ion, a methyl sulfate ion, or an ethyl sulfate ion as a counter ion. It is known that cationic surfactants are produced as a mixture of two or more cationic surfactants. For example, a quaternary ammonium salt compound may be used as a mixture of compounds having one, two, or three of the long-chain hydrocarbon groups that are hydrophobic groups, and may contain unquaternized tertiary amine salts, unreacted fatty acids, and other by-products.

[0088] Examples of component (c) include quaternary ammonium salt compounds represented by the following general formula (c1) (hereinafter also referred to as component (c1)), which are well known as softening bases that take biodegradability into consideration, and it is more preferable to use these as the main base.

[0089] [ka]

[0090] [In the formula, R 11c , R 12c , R 13c are each independently a residue (acyl group) obtained by removing OH from a fatty acid having 16 to 22 carbon atoms, or a hydrogen atom. 11c , R 12c , R 13cAt least one of R is an acyl group. 14c is an alkyl group having 1 to 3 carbon atoms, and X - is an anion.

[0091] Since component (c1) is a quaternized triethanolamine fatty acid ester, it is composed of three different quaternary compounds with acylation degrees of 1, 2, and 3. From the viewpoints of storage stability and lingering fragrance duration of the composition, the average acylation ratio of component (c1) is preferably 1.3 or more, more preferably 1.5 or more, and preferably 2.0 or less, more preferably 1.95 or less. The average acylation degree can be adjusted by the reaction ratio of fatty acid to triethanolamine and the reaction ratio with an alkylating agent during quaternization, as well as the reaction conditions.

[0092] In the present invention, the following ratios are preferred for the components constituting component (c1). A compound having an acylation degree of 1, i.e., R in general formula (c1) 11c is an acyl group, and R 12c and R 13c is a hydrogen atom [hereinafter referred to as component (c11)], the proportion of which is 5% by mass or more, preferably 10% by mass or more, more preferably 15% by mass or more, and preferably 45% by mass or less, more preferably 40% by mass or less, and even more preferably 35% by mass or less, of the total amount of the quaternary ammonium salt represented by general formula (c1). A compound having an acylation degree of 2, i.e., R in general formula (c1) 11c and R 12c is an acyl group, and R 13c is a hydrogen atom [hereinafter referred to as component (c12)], is preferably 30% by mass or more, more preferably 35% by mass or more, even more preferably 40% by mass or more, and preferably 75% by mass or less, more preferably 70% by mass or less, even more preferably 65% ​​by mass or less, of the total amount of the quaternary ammonium salt represented by general formula (c1). A compound having an acylation degree of 3, i.e., R in general formula (c1) 11c , R 12c and R13c is an acyl group [hereinafter referred to as component (c13)], the proportion of which is preferably 5% by mass or more, more preferably 8% by mass or more, even more preferably 10% by mass or more, and preferably 40% by mass or less, more preferably 30% by mass or less, even more preferably 25% by mass or less, of the total amount of the quaternary ammonium salt represented by general formula (c1).

[0093] Although components (c12) and (c13) are effective in adsorbing fragrances to textile products, they affect the storage stability of the textile product treatment composition. Therefore, it is preferable that component (c1) has a composition in which a moderate amount of component (c11) remains. Furthermore, while satisfying the above ratio, the content of component (c12) in component (c1) is greater than that of component (c13), and more preferably, the difference between the content (% by mass) of component (c12) and the content (% by mass) of component (c13) is preferably 15% by mass or more, more preferably 20% by mass or more, and even more preferably 25% by mass or more.

[0094] In general formula (c1), R 14c is preferably a methyl group or an ethyl group. In general formula (c1), X - is preferably an anion selected from a halogen ion such as a chlorine ion, an alkyl sulfate ion having from 1 to 3 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 alkyl sulfate ion having from 1 to 3 carbon atoms, and more preferably a methyl sulfate ion or an ethyl sulfate ion.

[0095] The component (c1) used in the present invention can be obtained by quaternizing an esterification reaction product obtained by a method of dehydrating esterification of a fatty acid with triethanolamine (referred to as the dehydration esterification method) or a method of transesterification of a fatty acid lower alkyl ester (wherein the lower alkyl is a methyl, ethyl, or propyl group) with triethanolamine (referred to as the transesterification method) with an alkylating agent. To obtain a mixture satisfying the ratios of components (c11) to (c13) of the component (c1) of the present invention, for example, the mixture can be obtained by quaternizing a mixture of triethanolamine fatty acid esters reacted at a molar ratio of fatty acid or fatty acid lower alkyl ester to triethanolamine of preferably 1.3:1 or more, more preferably 1.5:1 or more, and preferably 2.0:1 or less, more preferably 1.95:1 or less.

[0096] When a selective hydrogenation reaction is carried out to obtain component (c1), a mixture of geometric isomers of unsaturated bonds is formed. In the component (c1) of the present invention, the cis / trans (molar ratio) is preferably 25 / 75 or more, more preferably 50 / 50 or more, and preferably 100 / 0 or less, more preferably 95 / 5 or less.

[0097] In the dehydration esterification method, the esterification reaction temperature is preferably 140°C to 230°C, and the reaction is carried out while removing condensed water. To promote the reaction, a conventional esterification catalyst may be used, such as an inorganic acid such as sulfuric acid or phosphoric acid, an inorganic oxide such as tin oxide or zinc oxide, or an alcoholate such as titanium tetrapropoxide. The progress of the reaction is monitored by measuring the acid value (AV) and saponification value (SV) according to the method described in JIS K0070-1992. The esterification reaction is terminated when the AV reaches 10 mgKOH / g or less, preferably 6 mgKOH / g or less. The SV of the resulting mixture of ester compounds is preferably 110 mgKOH / g or more, more preferably 130 mgKOH / g or more, and preferably 210 mgKOH / g or less, more preferably 190 mgKOH / g or less.

[0098] In the transesterification method, the reaction is preferably carried out at a temperature of 50°C or higher, more preferably 100°C or higher, and preferably 150°C or lower, while removing the resulting lower alcohol. To accelerate the reaction, inorganic alkalis such as sodium hydroxide and potassium hydroxide, or alkoxy catalysts such as methylate and ethylate, can also be used. The progress of the reaction is preferably monitored by directly quantifying the amount of fatty acid lower alkyl ester using gas chromatography or the like. It is preferable to terminate the reaction when the amount of unreacted fatty acid lower alkyl ester is 10 area% or less, particularly 6 area% or less, based on the amount of the charged fatty acid lower alkyl ester on the gas chromatography chart. The resulting mixture of ester compounds preferably has an SV of 110 mgKOH / g or higher, more preferably 130 mgKOH / g or higher, and preferably 210 mgKOH / g or less, more preferably 190 mgKOH / g or less.

[0099] The ester compound thus obtained is then quaternized. Suitable alkylating agents for quaternization include methyl chloride, dimethyl sulfate, and diethyl sulfate. When using methyl chloride as the alkylating agent, no particular solvent is required. However, when using a solvent, a solution containing 10% to 50% by mass of a solvent such as ethanol or isopropanol relative to the ester compound is charged into a pressure reactor such as a titanium autoclave, and the methyl chloride is introduced under pressure at a temperature of 30°C to 120°C under a sealed condition to carry out the reaction. Since some of the methyl chloride may decompose and generate hydrochloric acid during this reaction, adding a small amount of an alkaline agent is preferred to promote the reaction more efficiently. The molar ratio of methyl chloride to the ester compound is preferably 1 to 1.5 equivalents of methyl chloride per equivalent of amino groups in the ester compound.

[0100] The molar reaction ratio of dimethyl sulfate and / or diethyl sulfate to the ester compound is preferably 0.9 equivalents or more, more preferably 0.95 equivalents or more, and preferably 1.1 equivalents or less, more preferably 0.99 equivalents or less, of dimethyl sulfate and / or diethyl sulfate relative to 1 equivalent of the amino group of the ester compound.

[0101] The aqueous composition of the present invention may contain other reaction products generated during the production of component (c1). For example, specific examples of unquaternized amines include amines of a fatty acid triester structure and amines of a fatty acid diester structure. Depending on the production method, a reaction product containing a total of amines of a fatty acid triester structure and amines of a fatty acid diester structure in an amount of 5 to 30 parts by mass per 100 parts by mass of component (c1) can be obtained. On the other hand, since amines of a fatty acid monoester structure are easily quaternized, their content in the reaction product is usually 0.5 parts by mass or less per 100 parts by mass of component (c1). Furthermore, triethanolamine that has not been converted into a fatty acid ester and quaternized triethanolamine are contained in a total amount of 0.5 to 3 parts by mass per 100 parts by mass of component (c1), of which 90% by mass or more is the quaternized product. Unreacted fatty acids may also be present. When a reaction product containing component (c1) is used, such unreacted components and side reaction components may be contained in the textile product treatment composition as long as they do not impair the effects of the present invention.

[0102] When a mixture containing components (c11), (c12), and (c13) is used as component (c1), the proportions of components (c11), (c12), (c13), and amine compounds in the mixture can be determined using a high-performance liquid chromatograph (also called HPLC) and a charged aerosol detector (also called CAD). For a measurement method using CAD, please refer to "Technology and Applications of the Corona CAD Charged Aerosol Detector" (Fukushima et al., Chromatography, Vol. 32, No. 3 (2011)).

[0103] The component (c1) of the present invention preferably contains, as an essential component, a quaternary ammonium salt compound [hereinafter referred to as component (c1-1)] in which, when the acyl group is considered to be a fatty acid, the proportion of oleic acid, linoleic acid, and linolenic acid in all fatty acids constituting the acyl group is preferably 60% by mass or more, more preferably 70% by mass or more, even more preferably 75% by mass or more, even more preferably 80% by mass or more, even more preferably 90% by mass or more, and preferably 100% by mass or less, more preferably 98% by mass or less, and even more preferably 95% by mass or less.

[0104] Component (c1-1) is a quaternary ammonium salt compound in which, when the acyl groups are considered to be fatty acids, the proportion of oleic acid in all fatty acids constituting the acyl groups is preferably 50% by mass or more, more preferably 60% by mass or more, even more preferably 65% ​​by mass or more, still more preferably 70% by mass or more, still more preferably 75% by mass or more, and preferably 100% by mass or less, more preferably 95% by mass or less, and even more preferably 90% by mass or less. Note that the conditions for including components (c11), (c12), and (c13) as component (c1) described above also apply to component (c1-1).

[0105] Examples of fatty acids that constitute the acyl group of the component (c1-1) include stearic acid, palmitic acid, and elaidic acid in addition to oleic acid, linoleic acid, and linolenic acid.

[0106] When component (c1-1) is used as component (c1), it is preferable to use a quaternary ammonium salt compound (hereinafter also referred to as component (c1-2)) that differs from component (c1-1) in the composition of the fatty acids that make up the acyl groups. Component (c1-2) is preferably a quaternary ammonium compound represented by the general formula (c1) and obtained in the same manner as component (c1-1), except for the fatty acid composition that makes up the acyl groups. Specifically, when the acyl groups are considered to be fatty acids, a quaternary ammonium salt compound in which the proportion of unsaturated fatty acids is 50% by mass or less, and preferably 40% by mass or less, of the total fatty acids that make up the acyl groups is preferred. The lower limit of the proportion of unsaturated fatty acids in the quaternary ammonium salt compound may be 10% by mass or more of the total fatty acids that make up the acyl groups.

[0107] The component (c1-2) is R in the general formula (c1). 11c , R 12c and R 13c The fatty acids constituting the acyl groups are preferably those obtained by saponifying an oil or fat selected from beef tallow, palm oil, sunflower oil, soybean oil, rapeseed oil, safflower oil, cottonseed oil, corn oil, and olive oil. Fatty acid compositions obtained from beef tallow, palm oil, and sunflower oil are particularly preferred from the viewpoint of flexibility. Furthermore, because these oils contain a large amount of alkenyl groups having two or more carbon-carbon unsaturated bonds, they can be produced by, for example, crystallization as described in JP-A-4-306296, vacuum distillation of methyl esters as described in JP-A-6-41578, or a method of controlling the proportion of fatty acids having two or more carbon-carbon unsaturated bonds by selective hydrogenation as described in JP-A-8-99036. For example, hardened beef tallow is obtained by saturating fatty acids derived from beef tallow by hydrogenation, and is sometimes referred to as semi-hardened, since only a portion of the fat or oil is hardened. The above-mentioned conditions for including the components (c11), (c12) and (c13) as the component (c1) are also applicable to the component (c1-2).

[0108] The component (c) may include a cationic surfactant other than the component (c1) (hereinafter also referred to as the component (c2)).

[0109] Specific examples of component (c2) include tertiary amine compounds and acid salts thereof, in which one or two of the groups bonded to the nitrogen atom are alkyl or alkenyl groups having from 10 to 22 carbon atoms, and the remaining groups are alkyl groups having from 1 to 4 carbon atoms, which may have a hydroxyl group, benzyl groups, or preferably methyl groups, as well as quaternized products of the above tertiary amine compounds. Among these, cationic surfactants having one alkyl or alkenyl group having from 10 to 22 carbon atoms and one benzyl group are preferred, from the viewpoint of imparting a bactericidal effect to the aqueous composition of the present invention. As the alkylating agent used for the quaternization of the compound, the compounds described in the component (c1) can be used.

[0110] The component (c2) is preferably one or more cationic surfactants selected from the following (I) to (IV), more preferably a cationic surfactant selected from (II) to (IV). (I) a dilong-chain alkyl or alkenyl dimethyl ammonium salt having an alkyl or alkenyl group with 10 to 22 carbon atoms [hereinafter referred to as component (c2-1)], (II) Mono-long-chain alkyl or alkenyl trimethylammonium salts having an alkyl or alkenyl group with 10 to 22 carbon atoms [hereinafter referred to as component (c2-2)] (III) Mono-long-chain alkyldimethylbenzylammonium salts having an alkyl or alkenyl group with 10 to 22 carbon atoms [hereinafter referred to as component (c2-3)] (IV) Acid salt of an amine compound represented by formula (c2-4) [hereinafter referred to as component (c2-4)]

[0111] [ka]

[0112] [In the formula, R 21cis an alkyl group having 13 to 19 carbon atoms or an alkenyl group having 13 to 19 carbon atoms, and R 22c is an alkylene group having 1 to 6 carbon atoms, and R 23c , R 24c are each independently an alkyl group having 1 to 3 carbon atoms.

[0113] The acid of the acid salt of the amine compound represented by the general formula (c2-4) can be an inorganic acid or an organic acid. Examples of inorganic acids include hydrochloric acid and sulfuric acid. Examples of organic acids include alkyl sulfuric acids having 1 to 3 carbon atoms, mono- or polycarboxylic acids having 1 to 10 carbon atoms, and mono- or polysulfonic acids having 1 to 20 carbon atoms. Specific examples of organic acids include methyl sulfuric acid, ethyl sulfuric acid, p-toluenesulfonic acid, (o-, m-, p-)xylenesulfonic acid, benzenesulfonic acid, dodecylbenzenesulfonic acid, glycolic acid, citric acid, benzoic acid, and salicylic acid.

[0114] Specific examples of component (c2) include didecyldimethylammonium chloride, lauryltrimethylammonium chloride, myristyltrimethylammonium chloride, lauryldimethylbenzylammonium chloride, dimethylaminopropyl stearyl amide salt, and dimethylaminopropyl palmitylamide salt.

[0115] The component (c) may include a nonionic surfactant (hereinafter also referred to as component (c3)).

[0116] As the component (c3), a nonionic surfactant having an alkyl or alkenyl group having from 8 to 20 carbon atoms and an oxyalkylene group is preferred, and a nonionic surfactant represented by the following general formula (c3) is more preferred. R 31c -A-〔(R 32c O) x -R 33c 〕 y (c3) [In the formula, R 31cis an alkyl or alkenyl group having 8 or more, preferably 10 or more, carbon atoms and 18 or less, preferably 16 or less, carbon atoms; R 32c is an alkylene group having 2 or 3 carbon atoms, preferably an ethylene group, and R 33c is an alkyl group having 1 to 3 carbon atoms or a hydrogen atom; x is a number of 2 or more, preferably 5 or more, more preferably 10 or more, and 100 or less, preferably 80 or less, more preferably 60 or less; A is -O-, -COO-, -CON<, or -N<; when A is -O- or -COO-, y is 1; and when A is -CON< or -N<, y is 2.

[0117] Specific examples of the compound of general formula (c3) include compounds represented by the following formulae (c3-1) to (c3-3). R 31c -O-(C2H4O) k -H (c3-1) [In the formula, R 31c is the above R 31c k is a number equal to or greater than 8, preferably equal to or greater than 10, and equal to or less than 100, preferably equal to or less than 60. R 31c -O-[(C2H4O) s (C3H6O) t ]-H (c3-2) [In the formula, R 31c is the above R 31c The letters s and t each independently represent a number of 2 or more, preferably 5 or more, and 40 or less, and (C2H4O) and (C3H6O) may be a random or block adduct. The bonding order of (C2H4O) and (C3H6O) is not important.]

[0118] [ka]

[0119] (In the formula, R 31c is the above R 31cA is -N< or -CON<, u and v are each independently a number of 0 to 40, and u+v is a number of 5 to 60, preferably 40 or less. R 33c is an alkyl group having 1 to 3 carbon atoms or a hydrogen atom.

[0120] The aqueous composition of the present invention preferably contains, as component (c), one or more selected from component (c1), component (c2), and component (c3).

[0121] The aqueous composition of the present invention may contain, as component (d), a fragrance other than the fragrance composition included in component (a). Component (d) may include a conventional fragrance (sometimes referred to as an external fragrance) that is dispersed or dissolved in the aqueous composition and is not encapsulated or derivatized. The external fragrance may generally refer to the fragrance compositions described in the examples of textile treatment agents, particularly softener compositions, and may be formulated for known purposes. The external fragrance of component (d) may also be a fragrance composition consisting of fragrance compounds that meet the same requirements as component (A) of the present invention. In addition, the aqueous composition of the present invention may contain, as component (d), in addition to the outer fragrance, microcapsules in which a fragrance compound is encapsulated in a shell (sometimes called a husk) made of a material other than the silica capsule (a), or a fragrance precursor. The combined use of component (d) with component (A) allows for greater freedom in fragrance design than ever before. Microcapsules or fragrance precursors containing a fragrance compound encapsulated in a shell (sometimes called a shell) made of a material other than the silica capsule (a) of component (d), can be sustained-release fragrances such as silicate ester compounds described in JP 2014-125685 A and ester compounds of alcohol-based fragrance compounds with aliphatic monocarboxylic acids or aliphatic dicarboxylic acids described in JP 8-502522 A, or capsule fragrances such as microcapsule fragrances described in JP 2015-200047 A.

[0122] The aqueous composition of the present invention may contain an inorganic salt as component (e). As the inorganic salt, from the viewpoint of improving storage stability, one or more types selected from sodium chloride, calcium chloride, and magnesium chloride are preferred.

[0123] The aqueous composition of the present invention may contain a water-insoluble silicone compound as component (f). In this specification, the term "water-insoluble" for component (f) means that the amount of silicone compound that dissolves in 1 L of ion-exchanged water at 20°C is 1 g or less. Specific examples of component (f) include silicone compounds such as dimethylpolysiloxane, quaternary ammonium-modified dimethylpolysiloxane, amino-modified dimethylpolysiloxane, amide-modified dimethylpolysiloxane, epoxy-modified dimethylpolysiloxane, carboxy-modified dimethylpolysiloxane, polyoxyalkylene-modified dimethylpolysiloxane, and fluorine-modified dimethylpolysiloxane.

[0124] The component (f) preferably has a weight average molecular weight of 1,000 or more, more preferably 3,000 or more, and even more preferably 5,000 or more, and is preferably 1,000,000 or less, and a viscosity at 25°C of preferably 2 mm 2 / s or more, preferably 500 mm 2 / s or more, more preferably 1,000 mm 2 / s or more, and preferably 1 million mm 2 Preferably, the siloxane is one or more selected from dimethylpolysiloxane, amino-modified dimethylpolysiloxane, amide-modified dimethylpolysiloxane, and polyoxyalkylene (polyoxyethylene and / or polyoxypropylene, preferably polyoxyethylene)-modified dimethylpolysiloxane, each of which has a viscosity of 1 / s or less. The weight average molecular weight of component (f) is a value measured by gel permeation chromatography using polystyrene as a standard substance.

[0125] The amino equivalent of the amino-modified dimethylpolysiloxane (amino equivalent is the molecular weight per nitrogen atom) is preferably 1,500 g / mol or more, more preferably 2,500 g / mol or more, even more preferably 3,000 g / mol or more, and preferably 40,000 g / mol or less, more preferably 20,000 g / mol or less, even more preferably 10,000 g / mol or less.

[0126] The aqueous composition of the present invention may contain a chelating agent as component (g). Specific examples of the chelating agent include one or more selected from ethane-1-hydroxy-1,1-diphosphonic acid, ethylenediaminetetraacetic acid, methylglycine diacetic acid, hydroxyethyliminodiacetic acid, ethylenediaminedisuccinic acid, L-glutamic acid-N,N-diacetic acid, N-2-hydroxyethyliminodiacetic acid, citric acid, succinic acid, and salts thereof. As the salt, alkali metal salts and ammonium salts are preferred, and sodium salts and potassium salts are more preferred.

[0127] The aqueous composition of the present invention may contain, as other components (hereinafter also referred to as component (h)), antioxidants such as butylhydroxytoluene (BHT) from the viewpoint of suppressing deterioration of the substrate, and dyes and pigments commonly used in textile product treatment compositions from the viewpoint of aesthetics and preventing discoloration during long-term storage. Furthermore, antibacterial and antifungal agents commercially available under the trade name Proxel may also be used. Benzoic acid and its salts may also be used as antibacterial and antifungal agents.

[0128] The aqueous composition used in step (I) of the present invention may contain the fragrance composition as component (A), which is the essential part of the present invention, and water, as well as the components (b) to (h) as described above.

[0129] In the aqueous composition of the present invention, when immersion treatment is performed, the content of component (b) is preferably 0.8 ppm or more, more preferably 2 ppm or more, even more preferably 3 ppm or more, and preferably 100 ppm or less, more preferably 50 ppm or less, even more preferably 10 ppm or less. In the aqueous composition of the present invention, when coating or spray treatment is performed, the content of component (b) is preferably 30,000 ppm or more, more preferably 40,000 ppm or more, even more preferably 50,000 ppm or more, and preferably 100,000 ppm or less, more preferably 80,000 ppm or less, even more preferably 70,000 ppm or less.

[0130] In the aqueous composition of the present invention, when immersion treatment is performed, the content of component (c) is preferably 10 ppm or more, more preferably 20 ppm or more, even more preferably 30 ppm or more, and preferably 800 ppm or less, more preferably 200 ppm or less, even more preferably 100 ppm or less.

[0131] In the aqueous composition of the present invention, the total content of components (A) and (d) is preferably 1 ppm or more, more preferably 2 ppm or more, and even more preferably 4 ppm or more when immersion treatment is performed, and from the viewpoint of stably dissolving the fragrance component in the composition, it is preferably 120 ppm or less, more preferably 60 ppm or less, and even more preferably 20 ppm or less. Furthermore, in the aqueous composition of the present invention, the total content of components (A) and (d) is preferably 150 ppm or more, more preferably 250 ppm or more, and even more preferably 400 ppm or more when coating or spraying treatment is performed, and from the viewpoint of stably dissolving the fragrance component in the composition, it is preferably 1500 ppm or less, more preferably 1000 ppm or less, and even more preferably 600 ppm or less.

[0132] When the aqueous composition of the present invention contains component (d), the mass ratio (d) / (A) of the content of component (d) to the content of component (A) is preferably 0.002 or more, more preferably 0.02 or more, even more preferably 0.1 or more, still more preferably 0.5 or more, still more preferably 1 or more, still more preferably 3 or more, and preferably 100 or less, more preferably 50 or less, still more preferably 25 or less, still more preferably 10 or less, and still more preferably 5 or less.

[0133] In the aqueous composition of the present invention, when immersion treatment is performed, the content of component (e) is preferably 0.01 ppm or more, more preferably 0.1 ppm or more, even more preferably 0.3 ppm or more, and preferably 20 ppm or less, more preferably 5 ppm or less, even more preferably 2 ppm or less. Furthermore, in the aqueous composition of the present invention, when a coating or spray treatment is carried out, the content of component (e) is preferably 100 ppm or more, more preferably 300 ppm or more, even more preferably 500 ppm or more, and preferably 3000 ppm or less, more preferably 2000 ppm or less, even more preferably 1000 ppm or less.

[0134] In the aqueous composition of the present invention, when immersion treatment is performed, the content of component (f) is preferably 0.01 ppm or more, more preferably 0.03 ppm or more, even more preferably 0.05 ppm or more, and preferably 2 ppm or less, more preferably 1 ppm or less, even more preferably 0.5 ppm or less. Furthermore, in the aqueous composition of the present invention, when a coating or spray treatment is carried out, the content of component (f) is preferably 1 ppm or more, more preferably 5 ppm or more, even more preferably 10 ppm or more, and preferably 100 ppm or less, more preferably 75 ppm or less, even more preferably 50 ppm or less.

[0135] In the aqueous composition of the present invention, when immersion treatment is performed, the content of component (g) is preferably 0.01 ppm or more, more preferably 0.03 ppm or more, even more preferably 0.05 ppm or more, and preferably 1 ppm or less, more preferably 0.75 ppm or less, even more preferably 0.5 ppm or less. Furthermore, in the aqueous composition of the present invention, when a coating or spray treatment is carried out, the content of component (g) is preferably 10 ppm or more, more preferably 100 ppm or more, even more preferably 500 ppm or more, and preferably 3000 ppm or less, more preferably 2000 ppm or less, even more preferably 1500 ppm or less.

[0136] The aqueous composition of the present invention can be prepared by diluting a concentrated aqueous composition with water. The concentrated aqueous composition of the present invention may be a textile product treatment composition such as a known fabric softener. The concentrations of component (A) and optional components (b) to (g) in the concentrated aqueous composition or textile product treatment composition of the present invention are preferably as follows:

[0137] In the concentrated aqueous composition or textile product treatment composition of the present invention, the content of the fragrance composition (A) contained in component (a) is preferably 0.01% by mass or more, more preferably 0.03% by mass or more, even more preferably 0.05% by mass or more, and still more preferably 0.1% by mass or more, from the viewpoint of the amount of fragrance remaining after washing treatment and drying, and is preferably 3.0% by mass or less, more preferably 2.0% by mass or less, even more preferably 1.5% by mass or less, still more preferably 1.0% by mass or less, and still more preferably 0.5% by mass or less, from the viewpoint of storage stability and balance with other fragrance additives.

[0138] When the concentrated aqueous composition or textile product treatment composition of the present invention contains component (b), the content of component (b) is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, even more preferably 1% by mass or more, and preferably 4% by mass or less, more preferably 3% by mass or less.

[0139] When the concentrated aqueous composition or textile product treatment composition of the present invention contains component (c), the content of component (c) is preferably 0.5% by mass or more, more preferably 1% by mass or more, even more preferably 5% by mass or more, still more preferably 10% by mass or more, and preferably 25% by mass or less, more preferably 20% by mass or less, even more preferably 17% by mass or less, and still more preferably 14% by mass or less.

[0140] When the concentrated aqueous composition or textile product treatment composition of the present invention contains component (d), the total content of component (d) and component (A) is preferably 0.1 mass% or more, more preferably 0.3 mass% or more, even more preferably 0.45 mass% or more, still more preferably 0.8 mass% or more, and preferably 7.5 mass% or less, more preferably 4.0 mass% or less, even more preferably 3.0 mass% or less, and still more preferably 1.5 mass% or less.

[0141] When the concentrated aqueous composition or textile product treatment composition of the present invention contains component (d), the mass ratio (d) / (A) of the content of component (d) to the content of component (A) is preferably 0.002 or more, more preferably 0.02 or more, even more preferably 0.1 or more, still more preferably 0.5 or more, still more preferably 1 or more, still more preferably 3 or more, and preferably 100 or less, more preferably 50 or less, still more preferably 25 or less, still more preferably 10 or less, and still more preferably 5 or less.

[0142] When the concentrated aqueous composition or textile product treatment composition of the present invention contains component (e), the content of component (e) is preferably 0.005% by mass or more, more preferably 0.015% by mass or more, and preferably 0.5% by mass or less, more preferably 0.3% by mass or less, even more preferably 0.1% by mass or less, and still more preferably 0.05% by mass or less.

[0143] When the concentrated aqueous composition or textile product treatment composition of the present invention contains component (f), the content of component (f) is preferably 0.005% by mass or more, more preferably 0.01% by mass or more, and preferably 0.05% by mass or less, more preferably 0.04% by mass or less.

[0144] When the concentrated aqueous composition or textile product treatment composition of the present invention contains component (g), the content of component (g) is preferably 0.005% by mass or more, more preferably 0.01% by mass or more, and preferably 0.05% by mass or less, more preferably 0.04% by mass or less.

[0145] As mentioned above, the aqueous composition used in step (I) may be a concentrated aqueous composition obtained by reducing the amount of water in the aqueous composition, which is then diluted with water before use. As mentioned above, the concentrated aqueous composition may be a commonly known textile product treatment composition, such as a fabric softener composition, starch, or styling agent. Other examples include UV inhibitor treatments that are known to be used in laundry finishing and are disclosed in patents and other publications: UV inhibitors that block UV rays; dye auxiliaries that impart fluorescent dyes; stain resistant agents that make fabrics less susceptible to staining; bactericidal and antibacterial agents that impart bactericidal, virucidal, antibacterial, or antiviral properties to fabrics; allergen removers that suppress the adhesion and development of allergens such as pollen and PM2.5, and soot and dust; and fragrances primarily intended to impart fragrance to fabrics. When these compositions are diluted and used, the component (A) of the present invention can be used to finish textile products that exhibit the present effects. Therefore, when diluting these treatments, the aqueous composition of the present invention may contain components other than the components (b) to (h) described above. Care should be taken to determine the components so as not to significantly impair the present effects.

[0146] The aqueous composition of the present invention may also be used as a disinfectant / antibacterial agent for textile products or as a deodorizer for eliminating malodors. While the present invention can also be used as a fragrance, component (A), particularly the fragrance compound (A1), can be designed to not emit a fragrance when dried using the fragrance-imparting method of the present invention, so its use in combination with a deodorizer is effective. Even when other fragrances are used in combination, the composition may be either a deodorizer that eliminates malodors or a composition with fragrance-imparting properties. Other examples include allergen inhibitors that suppress the adhesion and development of allergens such as pollen and PM2.5, as well as soot and dust; pest repellents that suppress the adhesion or approach of mosquitoes, mites, and other insects; specific odor inhibitors that suppress the adhesion of cigarette smoke, body odor, or food odors such as grilled meat; and stain inhibitors. Therefore, when these treatments are used by coating or spraying, the aqueous composition of the present invention may contain ingredients other than the aforementioned components (b) to (h), and the ingredients can be carefully selected so as not to significantly impair the present effects.

[0147] The aqueous composition of the present invention is more preferably used as a finishing agent such as a fabric softener, or as a fragrance or deodorizer. In this case, the aqueous composition may contain base materials and various components known to be used for each purpose, as long as the effects of each are not impaired.

[0148] When the aqueous composition of the present invention is used as a fragrance or deodorant, the pH of the aqueous composition is preferably 4.0 or more and 9.5 or less at 20°C. From the viewpoint of liquid phase stability, the pH of the aqueous composition of the present invention is more preferably 4.5 or more, even more preferably 5.0 or more, and more preferably 9.0 or less, even more preferably 8.5 or less at 20°C. The pH can be adjusted by adding an acid such as hydrochloric acid or an alkali such as sodium hydroxide. The pH is measured at 20°C in accordance with JIS K 3362;2008, item 8.3.

[0149] When the aqueous composition of the present invention is used as a fabric softener, it preferably contains the surfactant component (c1) described above, and may also contain other additives such as a softening aid in the form of a polyhydric alcohol fatty acid ester, such as glycerin, sorbitol, or pentaerythritol, an organic acid such as citric acid or a salt thereof, an organic acid such as hydrochloric acid or a salt thereof, the above-mentioned antioxidant, the above-mentioned preservative, a colorant, and an ultraviolet absorber.

[0150] When the aqueous composition of the present invention is used as a fabric softener, the pH of the aqueous composition, particularly the concentrated aqueous composition or textile treatment composition, is preferably 2.0 or more and 4.0 or less at 20°C. From the viewpoint of liquid phase stability, the pH of the aqueous composition of the present invention is more preferably 2.5 or more, even more preferably 2.7 or more, and more preferably 3.8 or less, even more preferably 3.5 or less at 20°C. The pH can be adjusted by adding an acid such as hydrochloric acid or an alkali such as sodium hydroxide. The pH is measured at 20°C according to JIS K 3362;2008, item 8.3.

[0151] The textile products that can be subjected to the fragrance application method of the present invention include textile products containing cotton fibers, such as 100% cotton textile products, and spun yarns, woven fabrics, knitted fabrics, and nonwoven fabrics obtained by blending cotton fibers with other fibers through blending, interweaving, intertwisting, etc. Specific examples of other fibers that can be used include one or more selected from natural cellulose fibers such as ramie, flax, pulp, and bacterial cellulose fibers; natural protein fibers such as silk and wool; regenerated cellulose fibers such as viscose rayon, cuprammonium rayon, and solvent-spun rayon; semi-synthetic fibers such as acetate and triacetate; and synthetic fibers such as polyester, polyamide, acrylic, polyethylene, and polypropylene. The textile products may be pre-dyed, roll-dyed or printed using reactive dyes, vat dyes or the like. When mixed with other fibers, the content of cotton fiber is preferably 20% by mass or more, more preferably 30% by mass or more, and even more preferably 50% by mass or more, from the viewpoint of odor generation upon moisture absorption. Examples of textile products that can be used in the present invention include fabrics such as woven fabrics, knitted fabrics, and nonwoven fabrics made from the above-mentioned cotton fibers and blended fibers, and products made from them, such as undershirts, T-shirts, dress shirts, blouses, slacks, hats, handkerchiefs, towels, knitwear, socks, underwear, tights, and bedding.

[0152] As described above, examples of methods for contacting the aqueous composition of the present invention with a textile product include a method of applying the aqueous composition of the present invention to the textile product, and a method of immersing the textile product in an aqueous composition prepared by diluting the concentrated aqueous composition of the present invention with water. The treatment in step (I) can be carried out using a washing machine. For example, when used as a fragrance, the treatment can be carried out in an environment containing a detergent during the washing step, as long as the effects of the present invention are not impaired. It can be added together with the detergent before the washing step, or it can be added before or after the rinsing step after the washing step. In the present invention, it is preferable to contact the textile product with the aqueous composition of the present invention at the timing of adding the softener. Specifically, it is preferable to add the aqueous composition of the present invention after one or more rinsing steps after the washing step. In this case, since the textile product already contains water, the concentrated aqueous composition of the present invention should be used taking into account the amount of water stored. Alternatively, as mentioned above, the concentrated aqueous composition may be the softener composition itself.

[0153] When a textile product is immersed in the aqueous composition of the present invention, after the textile product has been brought into contact with the aqueous composition of the present invention by immersion, excess water and components may be removed using a dehydrator, if necessary.

[0154] The aqueous composition of the present invention may be a textile fragrance composition, and may be applied to textiles as is or after dilution. The textile fragrance composition of the present invention preferably contains water. The textile fragrance composition of the present invention may be the aqueous composition of the present invention described in the method of the present invention. The matters described for the aqueous composition of the present invention can be applied to the textile fragrance composition of the present invention.

[0155] <Process (II)> Step (II) is a step in which the textile product treated in step (I) is dried in a gas at a temperature of 5°C or higher but lower than 90°C, thereby breaking down the structure of the silica capsules of component (a) that have adhered to the surface or interior of the textile product. As mentioned above, when the contact method in step (I) is immersion, it is preferable to provide a dehydration step after step (I). In the case of immersion, dehydration methods include simply placing the textile on a mesh to remove the water, as well as physical dehydration methods such as centrifugal dehydration using a washing machine, dehydration by twisting and squeezing the textile by hand, and dehydration by passing the textile through two or more rollers. In the present invention, the dehydration step performed between steps (I) and (II) is sometimes referred to as step (I'). When the contact method in step (I) is immersion, the water content of the textile product before step (II) is preferably 0.6 to 0.7 kg per 1 kg of dried textile product. When the contact method in step (I) is immersion, the aqueous composition may be diluted by adding water or a solvent after step (I). However, it is preferable that the concentration of component (A) in the aqueous composition solution that contacts the textile product does not exceed the range specified in the present invention until step (II).

[0156] An important requirement of step (II) is that the silica capsules collapse upon drying. Since the fragrance compound (A1) of the present invention has the property of easily penetrating deep into textile products containing cotton fibers, the silica capsules attached to the textile products are collapsed by drying in gas in step (II), making it easier for the encapsulated fragrance compound (A1) to penetrate into the interior of the textile products. In step (II), the drying temperature is 5°C or higher, preferably 7°C or higher, more preferably 10°C or higher, from the viewpoint of preventing the volatilization of the fragrance compound that has collapsed during drying. It is preferably a temperature below which the fragrance compound (A1) does not volatilize before penetrating into the textile product, and is 90°C or lower, preferably 80°C or lower, more preferably 70°C or lower. The drying process may be performed using a dryer, but the upper temperature limit is preferably within this range. Heat treatment after the drying process makes it easier for the fragrance compound (A1) to penetrate into the interior of the fiber. In this regard, reference can be made to JP 2021-80613 A.

[0157] <Process (III)> The method for perfumery of textile products containing cotton fibers of the present invention can further include, after step (II), step (III) in which the drying treatment of step (II) is continued or the textile product is heated to dry the textile product. In step (III), a drying treatment may be carried out after step (II), or the textile product may be heated by ironing to remove wrinkles, but it is preferable to avoid wetting the textile product with water, spray-type starch, etc. [Example]

[0158] The components used in the examples and comparative examples are shown below.

[0159] <Component (a)> The fragrance compositions shown in Tables 3a, 3b, and 3c were prepared as fragrance composition (A) or fragrance composition (A') (comparison component of fragrance composition (A)). Silica capsules (a1-1) to (a1-6) and (a2-1) to (a2-4) containing fragrance composition (A) or fragrance composition (A') were prepared using these compositions according to the following Synthesis Example (a-1).

[0160] [Table 3a]

[0161] [Table 3b]

[0162] [Table 3c]

[0163] [Synthesis Example (a-1): Synthesis of Silica Capsule (a-1)] (Process 1) An aqueous phase component was obtained by diluting 0.91 g of Coatamine 60W (trade name, manufactured by Kao Corporation, cetyltrimethylammonium chloride, active ingredient 30% by mass) with 224.13 g of ion-exchanged water. An oil phase component was prepared by mixing 60.03 g of fragrance composition (A) or fragrance composition (A') in the formulation shown in Table 3 with 15.10 g of tetraethoxysilane (hereinafter also referred to as "TEOS") to this aqueous phase component, and the mixture was emulsified for 10 minutes at a rotation speed of 9,000 rpm using a homomixer (manufactured by HsiangTai, model: HM-310, the same applies hereinafter) to obtain an emulsion. The median diameter D of the emulsified droplets at this time was 1.06 g. 50 was 1.3 μm. The pH of the resulting emulsion was adjusted to 3.7 using a 1% by mass aqueous solution of sulfuric acid, and then the emulsion was transferred to a separable flask equipped with a stirring blade and a condenser. The emulsion was stirred for 24 hours while maintaining the liquid temperature at 30°C, yielding an aqueous dispersion containing silica capsules (1-1) having a core made of fragrance composition (A) or fragrance composition (A') in Table 3 and a first shell made of silica.

[0164] (Process 2) To 280.0 g of the aqueous dispersion obtained in step 1, 8.4 g of TEOS was added over 420 minutes. After the dropwise addition, the mixture was stirred for an additional 17 hours to form a second shell encapsulating the first shell, thereby obtaining an aqueous dispersion containing silica capsules (I) in which the fragrance composition (A) or fragrance composition (A') shown in Table 3 was encapsulated in amorphous silica. The median diameter D of the silica capsules (I) was 50 The median diameter D of the emulsion droplets and silica capsules (I) was 2.1 μm. 50 was measured using a laser diffraction / scattering particle size distribution analyzer "LA-960" (trade name, manufactured by Horiba, Ltd.). A flow cell was used for the measurement, and the medium was set to water and the refractive index was set to 1.40-0i. An emulsion or an aqueous dispersion containing silica capsules was added to the flow cell, and measurements were carried out at a concentration where the transmittance was around 90%, and the median diameter D 50 asked for. The thickness of the first shell was approximately 5 nm, and the thickness of the second shell was 5 to 30 nm.

[0165] <(b) Component> (b-1): Ethylene glycol (b-2): Propylene glycol

[0166] <(c) component> [Synthesis Example c1-2: Production of (c1-2)] A quaternary ammonium salt compound represented by general formula (c1) was prepared as component (c1), in which the fatty acid composition constituting the acyl group was component (c1-2). Specifically, triethanolamine and a fatty acid represented by RCOOH (composition described below) were esterified at a reaction molar ratio (fatty acid / triethanolamine) of 1.65 / 1 to obtain an esterification reaction product containing the amine compound represented by general formula (c1). The esterification reaction product contained 5% by mass of unreacted fatty acid (the composition is described below). After a quaternization reaction with dimethyl sulfate was carried out so that the methyl group was 0.96 equivalents relative to the amine of the amine compound in the esterification reaction product, ethanol was added. In this manner, a reaction product containing a quaternary ammonium salt compound [hereinafter referred to as component (c1-2)] was prepared.

[0167] The reaction product obtained was analyzed by HPLC for the composition ratio of each component, and quantified using tetraoctylammonium bromide as an internal standard. As a result, the reaction product obtained contained 75% by mass of component (c1-2) represented by general formula (c1), 10% by mass of ethanol, 12% by mass of unreacted amine (as methyl sulfate), 2% by mass of unreacted fatty acid, a trace amount of triethanolamine quaternary salt, and other trace components. Of the component (c1-2), the R 11c is an acyl group, and R 12c and R 13c is a hydrogen atom, and R 14c is a methyl group, and X - is methyl sulfate [hereinafter referred to as (c1-2-1)] accounts for 28% by mass of the component (c1-2), and in the general formula (c1), R 11c and R 12c is an acyl group, and R 13c is a hydrogen atom, and R 14c is a methyl group, and X -is methyl sulfate [hereinafter referred to as (c1-2-2)] accounts for 56% by mass of the components, and in the general formula (c1), R 11c , R 12c and R 13c is an acyl group, and R 14c is a methyl group, and X - The compound (c1-2) in which methyl sulfate was used [hereinafter, may be referred to as (c1-2-3)] accounted for 16 mass % of the (c1-2) component. The quaternization rate was 80 mass %.

[0168] The composition of the RCOOH used in the reaction to produce component (c1-2) is shown below. Palmitic acid: 45% by mass Stearic acid: 25% by mass Oleic acid: 27% by mass Linoleic acid: 3% by mass The above composition was determined by analyzing the fatty acids used as raw materials by gas chromatography, and the area percentage of each fatty acid was considered to be mass percentage. The amounts of the components in the compositions in Tables 6 and 7 are converted into concentrations of the (c1-2) component.

[0169] [Synthesis Example c1-1: Preparation of (c1-1)] Triethanolamine and a fatty acid having a composition represented by RCOOH, which will be described later, were subjected to an esterification reaction at a reaction molar ratio (fatty acid / triethanolamine) of 1.87 / 1 to obtain an esterification reaction product containing an amine compound represented by general formula (c1). The esterification reaction product contained 1% by mass of unreacted fatty acid (the composition is described below). A quaternization reaction was carried out with dimethyl sulfate so that the methyl group was 0.96 equivalents relative to the amine of the amine compound in the esterification reaction product, and then ethanol was added. In this manner, a reaction product containing the quaternary ammonium salt compound represented by general formula (c1), which is component (c1) [hereinafter referred to as component (c1-1)], was prepared.

[0170] The reaction product obtained was analyzed by HPLC for the composition ratio of each component, and quantified using tetraoctylammonium bromide as an internal standard. As a result, the reaction product obtained contained 66 mass % of component (c1-1), which is component (c1), 15 mass % of ethanol, 17 mass % of unreacted amine salt (as methyl sulfate), 1 mass % of unreacted fatty acid, a trace amount of triethanolamine quaternary salt, and other trace components, among which, in general formula (c1), R 11c is an acyl group, and R 12c and R 13c is a hydrogen atom, and R 14c is a methyl group, and X - is methyl sulfate [hereinafter, may be referred to as (c1-1-1)] in the component (c1-1), and 11c and R 12c is an acyl group, and R 13c is a hydrogen atom, and R 14c is a methyl group, and X - is methyl sulfate [hereinafter, may be referred to as (c1-1-2)] in the component (c1-1), and 11c , R 12c and R 13c is an acyl group, and R 14c is a methyl group, and X - The compound (c1-1) in which methyl sulfate was used [hereinafter, may be referred to as (c1-1-3)] accounted for 20 mass % of the component (c1-1). The quaternization rate was 80 mass %.

[0171] The composition of the RCOOH used in the reaction to produce component (c1-1) is shown below. Oleic acid: 80% by mass Linoleic acid: 10% by mass Linolenic acid: 2% by mass Stearic acid: 2% by mass Palmitic acid: 6% by mass The above composition was determined by analyzing the fatty acids used as raw materials by gas chromatography, and the area percentage of each fatty acid was considered to be mass percentage. The amounts of the components in the compositions in Tables 6 and 7 are converted into concentrations of the (c1-1) component.

[0172] (c3-1): A compound in which an average of 30 moles of ethylene oxide is added to lauryl alcohol, that is, in the general formula (c3-1), R 31c is a linear alkyl group having 12 carbon atoms and bonded to an oxygen atom. 31c A nonionic surfactant in which the carbon atom in is a primary carbon atom and k is 30. (c2-4): dimethylaminopropyl stearyl amide salt

[0173] <(d) component> (d0-1): The fragrance composition (d0-1) shown in Table 4 as the outer fragrance

[0174] [Table 4]

[0175] (d1-1): Si(O-Geranyl)4 as a silicate ester fragrance precursor In addition, "Geranyl" in (d1-1) represents a group obtained by removing one hydroxyl group from geraniol (primary allylic alcohol fragrance, logP 2.4).

[0176] The (d1-1) was synthesized according to the following Synthesis Example d1-1.

[0177] (Synthesis Example d1-1: Synthesis of Si(O-Geranyl)4) 27.08 g (0.13 mol) of tetraethoxysilane, 72.30 g (0.47 mol) of geraniol, and 0.485 mL of a 2.8 mass % sodium methoxide methanol solution were placed in a 200 mL four-neck flask and stirred at 110 to 120° C. for 2 hours while distilling off ethanol under a nitrogen stream. After 2 hours, the pressure in the vessel was gradually reduced to 8 kPa, and the mixture was stirred for another 4 hours at 117-120°C while distilling off ethanol. After 4 hours, the mixture was cooled, the vacuum was released, and then filtered to obtain 76.92 g of a yellow oil containing a geraniol silicate ester fragrance precursor.

[0178] (d2-1): Ester of lauric acid and ethyl vanillin

[0179] The compound (d2-1) was synthesized according to the following Synthesis Example d2-1.

[0180] [Synthesis Example d2-1: Production of ester of lauric acid and ethyl vanillin] Under a nitrogen atmosphere, 8.95 g (0.041 mol) of lauric acid chloride and 40 mL of dichloromethane were placed in a 300 mL four-neck flask and cooled to 0°C. Meanwhile, 6.80 g (0.041 mol) of ethyl vanillin, 4.35 g (0.043 mol) of triethylamine, and 40 mL of dichloromethane were placed in a 100 mL dropping funnel. The mixture was added dropwise to the flask over 40 minutes, maintaining the reaction temperature between -5°C and 0°C. After the addition was complete, the mixture was stirred at room temperature (25°C) for 2 hours. 10 mL of saturated aqueous ammonium chloride solution was added to the flask to terminate the reaction. 150 mL of diethyl ether was added, and the resulting white solid was removed by filtration. The filtrate was transferred to a separatory funnel. 100 mL of ion-exchanged water was added to the separatory funnel, and the aqueous layer was extracted three times with 50 mL of diethyl ether. The extracted solution was collected, washed with saturated brine, and dried over sodium sulfate. After removing the solvent under reduced pressure, 14.20 g (yield 99%) of a pale yellow solid ester of lauric acid and ethyl vanillin was obtained. The final product was confirmed by NMR and IR to be the target compound.

[0181] (d3-1): Fragrance-containing microcapsule slurry obtained in the following Production Example d3-1

[0182] [Production Example d3-1: Production of (d3-1)] 1.7 g of diisobutylene-maleic anhydride copolymer (Demol EP, 25% solids, Kao Corporation) was neutralized with hydrochloric acid and further diluted with ion-exchanged water to obtain an aqueous solution with a solids content of 3% and a pH of 4.3. Next, 36 g of fragrance (d3-1) with the composition shown in Table 5, containing 90 parts by weight of alcohol-based fragrance compounds (geraniol, terpineol, and tetrahydrolinalool) per 1000 parts by weight of fragrance, was added to 100 g of the diisobutylene-maleic anhydride copolymer aqueous solution, and the mixture was emulsified using a homomixer and heated to 50°C. Next, an aqueous solution containing 12 g of partially methylolated melamine resin (trade name Cymel 385, 80% solids, Cytec Industries Inc.) and 35 g of ion-exchanged water was added dropwise. The mixture was maintained at 50°C for 2 hours, then at 70°C for 1 hour, and then at 80°C for 3 hours to complete the encapsulation. Thereafter, the mixture was allowed to cool, yielding a microcapsule slurry having an average particle size of 7 μm and an active ingredient content of 30% by mass.

[0183] [Table 5]

[0184] <(e) component> (e-1): Calcium chloride

[0185] <Component (f)> (f-1): Aqueous emulsion of dimethylpolysiloxane produced in Synthesis Example f-1 below.

[0186] [Production of Synthesis Example f-1] 5 g of polyoxyethylene lauryl ether having an average addition mole number of 5 moles was dissolved in dimethylpolysiloxane (viscosity at 25°C: 500,000 mm 2300 g of (s) was added while applying a high shear force, and stirring was continued under a high shear force for another 10 minutes. Thereafter, 30 g of ion-exchanged water was added, and then 2 g of sodium polyoxyethylene lauryl ether sulfate with an average added molar number of 2 moles and 15 g of polyoxyethylene myristyl ether with an average added molar number of 40 moles were added. Stirring was continued for 30 minutes under a high shear force, and then 248 g of water was added and stirred to obtain an aqueous emulsion [(f-1)] of dimethylpolysiloxane. The volume-average particle diameter of the emulsified particles in (f-1) was 500 nm. Also, the content of dimethylpolysiloxane in (f-1) was 50% by mass. The volume-average particle diameter was measured at 20 °C using an electrophoretic light scattering photometer (manufactured by Otsuka Electronics Co., Ltd., model ELS-8000) with the aqueous emulsion dispersed in ethanol.

[0187] <Component (g)> Component (g-1): Trisodium methylglycinediacetate

[0188] <Component (h)> Component (h-1): Proxel BDN (manufactured by Arch Chemical Japan)

[0189] <pH adjuster> To adjust the pH of the concentrated aqueous composition, sodium hydroxide, citric acid, and hydrochloric acid were used as appropriate as needed.

[0190] <Example 1 and Comparative Example 1> [Preparation of concentrated aqueous composition] A concentrated aqueous composition was prepared by mixing each component so as to have the formulation composition shown in Table 6. Specifically, it is as follows. The mass% of the composition in the table is the mass% of the active ingredient. A 300 mL beaker was charged with ion-exchanged water in an amount equivalent to 85% by mass of the amount required to produce a 200 g concentrated aqueous composition, along with components (f), (g), and (h), as needed, and a pH adjuster, and a water bath was used to adjust the temperature of the ion-exchanged water to 60±2°C to prepare a mixed solution. The stirring blades used were three blades, with the long side at a 90° angle relative to the central axis of rotation of a 5 mm diameter stirring rod, the long side / short side of the blades being 3 cm / 1.5 cm, and the blades installed at a 45° angle relative to the plane of rotation. The mixture, whose temperature had been adjusted to 60±2°C, was stirred (300 rpm) with the stirring blade. Component (c), which had been heated and dissolved at 65°C, was added to the mixture over a period of 3 minutes, and after the addition was completed, the mixture was stirred for 15 minutes. Next, the mixture was cooled to 30±2°C using a 5°C water bath. To this was sequentially added silica capsules containing fragrance composition (A) or fragrance composition (A'), component (e), and component (d), and the mixture was stirred for 5 minutes. Further, ion-exchanged water was added to the mixture to a final mass of 200 g, and the mixture was stirred for 5 minutes to obtain a concentrated aqueous composition. The visible light transmittance of the obtained concentrated aqueous compositions was measured. Specifically, a glass cell with an optical path length of 10 mm was used as the measurement cell, and ion-exchanged water was placed in a control cell, and the measurement was performed using an ultraviolet-visible spectrophotometer (UV-2500PC manufactured by Shimadzu Corporation). The visible light transmittance (wavelength 660 nm) of the concentrated aqueous compositions obtained in the examples and comparative examples was all less than 10%, and they were emulsion-type concentrated aqueous compositions.

[0191] [Fragrance evaluation] Seventeen pairs of underwear (Gunze men's round-neck short-sleeved shirts, size L) were washed five times in a Hitachi NW-6CY fully automatic washing machine using a commercially available weak alkaline detergent (Kao Attack), and then dried indoors to remove excess detergent. The washing conditions for each cycle were: detergent concentration 0.0667% by mass, tap water 47 L, water temperature 20°C, wash time 10 minutes, rinse cycle 2 times, and spin cycle 6 minutes.

[0192] An aqueous composition was prepared by adding 0.867 g (10 g / 1.5 kg of underwear) of the concentrated aqueous composition shown in Table 6 to 4 L of tap water in a Panasonic Corporation electric bucket N-BK2-A. One piece of underwear washed as described above was then added and stirred for 5 minutes. The underwear treated with the aqueous composition was then dehydrated for 3 minutes in the spin tub of a Hitachi, Ltd. twin-tub washing machine, and then hung on hangers to dry for 24 hours at 20°C and 40% RH.

[0193] A 20cm x 20cm piece of fabric was cut from the undergarments treated as described above and used for fragrance evaluation. The evaluation method was to first smell the fragrance in a dry state, then wet the fabric with 10-20% owf water using a spray and then fold the fabric in quarters. After leaving it to stand for a few seconds, the fabric was opened and the fragrance at the intersection of the folds was smelled. The difference in fragrance intensity between the dry and wet states and the expressiveness of the fragrance were evaluated, and this was used to assess the effectiveness of the moisture fragrance. Evaluation was carried out by five expert panelists who evaluate fragrances. Evaluation was based on the following criteria, and the average of the five evaluations was used as the evaluation result. The results are shown in Table 6.

[0194] <Evaluation criteria> (Evaluation criteria for fragrance intensity) 3: Large difference in fragrance intensity 2: Small difference in fragrance intensity 1: No noticeable difference in scent intensity

[0195] (Evaluation criteria for fragrance expression) 3: Enjoy a rich and varied aroma 2: I feel a slightly varied scent 1: The scent is flat

[0196] [Table 6]

[0197] Table 7 below shows formulation examples of concentrated aqueous compositions of the present invention. By treating textile products with an aqueous composition prepared from the concentrated aqueous composition shown in Table 7, the treated textile products can emit a pleasant fragrance when wet with water due to sweating or the like.

[0198]

Table 7

Claims

1. A method for perfumery of a textile product containing cotton fibers, comprising the following steps (I) and (II): Step (I): (a) A step of contacting an aqueous composition containing silica capsules (hereinafter referred to as component (a)) enclosing the following fragrance composition (A) with a textile product containing cotton fibers. Step (II): A step of drying the textile product treated in step (I) in a gas at 5°C or higher but lower than 90°C to break down the silica capsule structure of component (a) attached to the surface or inside of the textile product. Fragrance composition (A): Fragrance composition (A) containing fragrance compounds (A1) having a log Kow value of 2.0 or more and 5.0 or less and a vapor pressure value at 25°C of 0.01 Pa or more and 3.63 Pa or less, in an amount of 30% by mass or more and 85% by mass or less, and wherein the fragrance compounds (A1) contain at least five fragrance compounds selected from the following fragrance compounds (A1-1), in an amount of 5% by mass or more and 65% by mass or less, (A1-1) γ-Undecalactone, 2-cyclohexylidene-2-phenylacetonitrile, damascenone, δ-damascone, α-methyl-β-(pt-butylphenyl)-propionaldehyde, β-ionone, myrrh aldehyde, ethyl tricyclo[5.2.1.0-2,6]decane-2-carboxylate, 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, dimethylbenzylcarbinyl butyrate, tricyclodecenyl propionate, amine salicylate , γ-methylionone, α-damascone, β-damascone, nerolin yarayara, 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 ketone, eugenol, lyral, dimethylbenzylcarbinyl acetate, iso-damascone, γ-decalactone, α-methyl-3,4-methylenedioxyhydrocinnamic aldehyde, 7-methyl-3,5-dihydro-2H-benzodioxepinone, tricyclodecynyl acetate, tricyclodecynyl propionate, allyl 2-pentyloxyglycolate

2. A method for perfumery of a textile product containing cotton fiber according to claim 1, wherein the fragrance composition (A) contains seven or more fragrance compounds selected from the fragrance compounds (A1-1) described above.

3. A method for perfumery of a textile product containing cotton fiber according to claim 1 or 2, wherein the fragrance composition (A) contains 20% by mass or more but not more than 65% by mass of a fragrance compound selected from the fragrance compounds (A1-1) described above.

4. A method for perfumery of a textile product containing cotton fiber according to any one of claims 1 to 3, wherein the fragrance composition (A) contains five or more fragrance compounds selected from the following fragrance compounds (A1-1S): (A1-1S) γ-Undecalactone, 2-cyclohexylidene-2-phenylacetonitrile, damascenone, δ-damascone, β-ionone, myrrh aldehyde, ethyl tricyclo[5.2.1.0-2,6]decane-2-carboxylate, citronellol, geraniol, α-ionone, patchouli alcohol, 6,7-dihydro-1,1,2,3,3-pentamethyl-4(5H)-indanone, methyl dihydrojasmonate, allylcyclohexyl propionate, tricyclodecene propionate Nyl, γ-methylionone, α-damascone, β-damascone, 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, lyral, iso-damascone, γ-decalactone, tricyclodecynyl acetate, tricyclodecynyl propionate, γ-decalactone, allyl 2-pentyloxyglycolate, allyl 2-pentyloxyglycolate

5. A method for perfumery of a textile product containing cotton fiber according to claim 4, wherein the fragrance composition (A) contains seven or more fragrance compounds selected from the fragrance compounds (A1-1S) described above.

6. A method for perfumery of a textile product containing cotton fiber according to claim 4 or 5, wherein the fragrance compound (A1-S) is contained in a fragrance composition (A) in an amount of 20% by mass or more and 65% by mass or less.

7. 7. A method for perfumery of textile products containing cotton fibers according to claim 1, further comprising, after step (II), step (III) of drying the textile product by continuing the drying treatment of step (II) or by heating the textile product.

8. 8. The method for perfumery of a textile product containing cotton fibers according to claim 1, wherein the fragrance composition (A) further contains 3% by mass or more and 70% by mass or less of a fragrance compound (A2) having a log Kow value of 3.0 or more and a vapor pressure value at 25°C of more than 3.63 Pa.

9. 9. The method for perfumery of textile products containing cotton fibers according to claim 1, wherein step (I) is a step of immersing the textile products in the aqueous composition.

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