Method for inhibiting generation of odors caused by sebum dirt on textile product

Abstract

To provide a method for inhibiting the generation of odors caused by sebum dirt on a textile product.SOLUTION: A method for inhibiting the generation of odors caused by sebum dirt on a textile product comprises bringing the textile product into contact with an aqueous composition containing (a) a phenolic antioxidant and (b) a quaternary ammonium salt including a quaternary ammonium compound having an unsaturated hydrocarbon group.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a method for suppressing the generation of odor caused by sebum stains on textile products. [Background technology]

[0002] Dirt from human body such as sweat, sebum, and protein that adheres to textile products such as clothing is usually removed by washing, but as contamination and washing are repeated, dirt that cannot be removed by washing accumulates. It is known that such accumulated dirt causes odor problems due to bacterial metabolism, and it is common to deal with this by using ingredients such as bactericides in combination. However, it is difficult to suppress odor generation by applying bactericides alone, and it is particularly difficult to suppress odor generation due to oxidative decomposition of sebum with normal washing or bactericides.

[0003] Patent Document 1 describes a technology for suppressing odor caused by the oxidation of sebum, in which vesicles containing a phenolic antioxidant such as dibutylhydroxytoluene or butylhydroxyanisole encapsulated in a bilayer multilayer structure represented by a quaternary ammonium salt are dispersed. Patent Document 2 discloses a technology for improving the adsorption amount of an antioxidant to suppress the generation of unpleasant odors due to spontaneous autoxidation, and describes that fibers containing elastane promote the adsorption of antioxidants. Patent Document 3 discloses a technique for applying an antioxidant to a softener composition containing an ester-type cation. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Publication No. 10-131042 [Patent Document 2] Special Publication No. 2022-531561 [Patent Document 3] JP 2004-84143 A Summary of the Invention [Problem to be solved by the invention]

[0005] However, the conventional technology has not yet achieved a sufficient effect of suppressing the generation of odor caused by sebum stains on textile products, and there is a demand for a significant suppression of the generation of odor caused by sebum stains on textile products. In addition, the technology described in Patent Document 3 improves the stability of transparent fabric softeners, but does not disclose a technology that suppresses the oxidation of sebum and the like remaining on textile products and prevents the generation of odor caused by sebum stains. The present invention provides a method for suppressing the generation of odor caused by sebum stains on textile products. [Means for solving the problem]

[0006] The present invention relates to a method for suppressing the generation of odor caused by sebum stains on a textile product, which comprises contacting the textile product with an aqueous composition [hereinafter referred to as aqueous composition (A)] containing (a) a phenolic antioxidant [hereinafter referred to as component (a)] and (b) a quaternary ammonium salt containing a quaternary ammonium compound having an unsaturated hydrocarbon group [hereinafter referred to as component (b)]. Effect of the Invention

[0007] According to the present invention, there is provided a method for suppressing the generation of odor caused by sebum stains on textile products. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0008] The reason why the method of the present invention for suppressing the generation of odor caused by sebum stains on textile products is able to suppress the generation of odor caused by sebum stains is not clear, but is presumed to be as follows. The (a) component inhibits the oxidative decomposition of sebum, thereby reducing the amount of odor substances generated during the oxidative decomposition of sebum, but it has a low adsorption capacity to textile products by itself, and therefore it is considered that it does not fully exert the effect of inhibiting the generation of odor caused by sebum stains. It is known that general cationic surfactants are effective as such adsorption assistants, but their effect is not yet at a satisfactory level. The (b) component, which has many unsaturated bonds as in the present invention, can further promote the solubilization of the (a) component in the composition and its adsorption to textile products, and is considered to be able to inhibit the generation of odor caused by sebum stains. It is presumed that the synergistic effect of components (a) and (b) in the present invention effectively suppresses the generation of odor caused by sebum stains remaining on or adhering to textile products. The method of the present invention for suppressing the generation of odor caused by sebum stains on textile products is not limited to the above-mentioned mechanism of action.

[0009] <Method to suppress odor caused by sebum stains on textile products> The method of the present invention for suppressing the generation of odor caused by sebum stains on a textile product [hereinafter referred to as the method of the present invention] comprises contacting a textile product with an aqueous composition [hereinafter referred to as aqueous composition (A)] containing (a) a phenolic antioxidant [hereinafter referred to as component (a)] and (b) a quaternary ammonium salt including a quaternary ammonium compound having an unsaturated hydrocarbon group [hereinafter referred to as component (b)]. The method of the present invention can suppress the generation of odor from textile products stained with sebum, for example. The odor can be odor caused by sebum stains, such as odor caused by oxidative decomposition of sebum.

[0010] The method of the present invention may be a method for suppressing the generation of odor caused by sebum stains from a textile product having sebum stains attached thereto, by contacting the aqueous composition (A) with the textile product having sebum stains attached thereto. Sebum stains are stains caused by sebum secreted from the sebaceous glands of the human body, and examples of these include yellowing and darkening that occurs around collars and cuffs.

[0011] <Component (a)> The component (a) is a phenol-based antioxidant. From the viewpoint of suppressing the generation of odor caused by sebum stains, the component (a) is preferably a hindered phenol-based antioxidant. From the viewpoint of suppressing the generation of odors due to sebum stains, the component (a) is preferably 2,6-di-t-butyl-4-methylphenol, pentaerythritol-tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], octadecyl-3-(3,5-di-t-butyl-hydroxyphenyl)propionate, 2,2'-methylenebis(4-methyl-6-t-butylphenol), 4,4'-ethylidenebis(3-methyl-6-t-butylphenol), triethylene glycol-bis[(3-t-butyl-5-methyl 2,6-Hexanediol-bis[3'-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 2,4-bis[(N-octylthio)-6-(4-hydroxy-3,5-di-t-butylanilino)]-1,3,5-triazine, 2,2-thio-diethylenebis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 2,2'-thiobis(4-methyl-6-t-butyl)phenol, 4,4'-thiobis(3-methyl-6-t-butyl)phenol and more preferably 2,6-di-t-butyl-4-methylphenol, pentaerythritol-tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], octadecyl-3-(3,5 octadecyl-3-(3,5-di-t-butyl-hydroxyphenyl)propionate, triethylene glycol-bis[(3-t-butyl-5-methyl-4-hydroxyphenyl)propionate], and methyl-3-(3,5-di-t-butyl-hydroxyphenyl)propionate. More preferably, octadecyl-3-(3,5-di-t-butyl-hydroxyphenyl)propionate, triethylene glycol-bis[(3-t-butyl-5-methyl-4-hydroxyphenyl)propionate], and methyl-3-(3,The preferred methyl 3-(3,5-di-t-butyl-hydroxyphenyl)propionate is one or more selected from the group consisting of methyl 3-(3,5-di-t-butyl-hydroxyphenyl)propionate, and more preferably methyl 3-(3,5-di-t-butyl-hydroxyphenyl)propionate.

[0012] The component (a) can be one or more phenolic antioxidants selected from compounds represented by the following general formula (a1) [hereinafter referred to as component (a1)]. [ka] [In the formula, R 1a is a tertiary butyl group or a hydrogen atom, R 2a , R 3a , R 5a are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or -C n H 2n COOR 6a R is an ester group represented by the formula: 4a is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or -C n H 2n COOR 6a Here, n is an integer of 1 to 5, and R 6a is a hydrocarbon group having 1 to 18 carbon atoms.

[0013] In general formula (a1), R 1a is preferably a tertiary butyl group. In general formula (a1), R 2a is preferably a tertiary butyl group, an ethyl group, a methyl group or a hydrogen atom, and more preferably a tertiary butyl group or a hydrogen atom. In general formula (a1), R 3a is a hydrogen atom, a methyl group, or -C n H 2n COOR 6a is preferred, and a hydrogen atom is more preferred. In general formula (a1), R 4a is a hydrogen atom, a methyl group, a methoxy group or -C n H 2n COOR 6ais preferred, and a methyl group, a methoxy group or -C n H 2n COOR 6a is more preferred. In general formula (a1), R 5a is a hydrogen atom, -C n H 2n COOR 6a or a tertiary butyl group, and more preferably a tertiary butyl group or a hydrogen atom. Also, R 1a , R 2a , R 3a , R 5a At least one of these is a tertiary butyl group. Also, R 3a , R 4a , R 5a At least one, preferably one, of the following is -C n H 2n COOR 6a and preferably R 3a , R 5a is a hydrogen atom, and R 4a Ga-C n H 2n COOR 6a is preferred. From the viewpoint of suppressing the generation of odor caused by sebum stains, n is 1 or more, preferably 2 or more, and 5 or less, preferably 4 or less. R 6a From the viewpoint of suppressing the generation of odor caused by sebum stains, the number of carbon atoms in R is preferably 1 or more and 18 or less, preferably 5 or less, and more preferably 2 or less. 6a is an alkyl or alkenyl group, preferably an alkyl group.

[0014] From the viewpoint of suppressing the generation of odor caused by sebum stains, the component (a1) is represented by the general formula (a1): R 1a and R 2a is a tertiary butyl group, R 3a and R 5a is a hydrogen atom, R 4a is an ester group represented by -C2H4COOCH3.

[0015] <(b) Component> Component (b) is a quaternary ammonium salt containing a quaternary ammonium compound having an unsaturated hydrocarbon group. Component (b) may be a quaternary ammonium salt containing only a compound having an unsaturated hydrocarbon group, a quaternary ammonium salt containing a quaternary ammonium compound having a saturated hydrocarbon group and a quaternary ammonium compound having an unsaturated hydrocarbon group, a quaternary ammonium salt having an unsaturated hydrocarbon group and a saturated hydrocarbon group in one compound, or a mixture thereof.

[0016] From the viewpoint of the stability of the composition, the component (b) is a quaternary ammonium salt containing at least one unsaturated hydrocarbon group in an amount of preferably 5% by mass or more, more preferably 10% by mass or more, more preferably 15% by mass or more, and 100% by mass or less, preferably 95% by mass or less. The component (b) may be a quaternary ammonium salt containing at least one unsaturated hydrocarbon group in an amount of 100% by mass, that is, a quaternary ammonium salt consisting only of a quaternary ammonium salt having at least one unsaturated hydrocarbon group. The component (b) may also contain a quaternary ammonium salt having only a saturated hydrocarbon group.

[0017] The salt of component (b) is preferably a salt selected from the group consisting of iodides, bromides and chlorides of quaternary ammonium having an unsaturated hydrocarbon group, alkyl sulfate ester salts of quaternary ammonium having an unsaturated hydrocarbon group, having 1 to 3 carbon atoms, fatty acid salts having 12 to 18 carbon atoms, and benzenesulfonate salts which may be substituted with 1 to 3 alkyl groups having 1 to 3 carbon atoms, more preferably a salt selected from alkyl sulfate ester salts having 1 to 3 carbon atoms, and even more preferably a monomethyl sulfate or monoethyl sulfate.

[0018] The component (b) is one or more quaternary ammonium compounds (1b) selected from compounds represented by the following general formula (b1), and examples of the quaternary ammonium salts satisfy the following requirements 1 and 2. When there are two or more types of quaternary ammonium compounds (1b), R 1b , R 2b , R 3b , R4b , R 5b and X - may be the same or different. [ka]

[0019] [In the formula, R 1b is a linear, branched or cyclic alkyl or alkenyl group having 14 to 22 carbon atoms. Y is a -COO- group or a -OCO- group. R 2b is an alkylene group having 1 to 3 carbon atoms. 3b , R 4b each independently represents an alkyl group having 1 to 3 carbon atoms; -R 2b -OH or R 1b -YR 2b -, where R 3b and / or R 4b But R 1b -YR 2b -, R 1b and / or R 2b may be the same or different. 3b and / or R 4b But -R 2b -OH, R 2b may be the same or different. 5b is an alkyl group having 1 to 3 carbon atoms. - is an anion.]

[0020] Requirement 1: When the quaternary ammonium compound (1b) is one type, R 1b At least one of R is a linear, branched or cyclic alkenyl group having 14 to 22 carbon atoms. When the quaternary ammonium compound (1b) is of two or more types, R 1b At least one of the quaternary ammonium compounds is a linear, branched or cyclic alkenyl group having 14 to 22 carbon atoms. Requirement 2: The unsaturation rate defined by the following formula (1) is 20% by mass or more and 100% by mass or less. Unsaturation rate (mass%)=[(R 1b R is an alkenyl group1b (total mass of COOH) / (R 1b (1) (total mass of COOH) × 100

[0021] In general formula (b1), R 1b is a linear, branched or cyclic alkyl or alkenyl group having from 14 to 22 carbon atoms; from the viewpoint of inhibiting thickening, the alkyl group is preferably a pentadecanyl group or a heptadecanyl group, and the alkenyl group is preferably an 8-heptadecenyl group, an 8,11-heptadecadienyl group, an 8,11,14-heptadecatrienyl group, a 4,7,10,13-nonadecatetraenyl group, a 4,7,10,13,16-nonadecapentaenyl group, or a 3,6,9,12,15,18-heneicosahexaenyl group. In general formula (b1), Y is a -COO- group or a -OCO- group, and the -COO- group is preferred from the viewpoints of inhibiting thickening and facilitating availability of raw materials. In general formula (b1), R 2b is specifically a methylene group, an ethylene group or a propylene group, with the ethylene group being preferred in terms of easy availability of the raw material. In general formula (b1), R 3b and R 4b The alkyl group having 1 to 3 carbon atoms is specifically a methyl group, an ethyl group, or a propyl group. From the viewpoint of suppressing thickening, a methyl group is preferred. In general formula (b1), R 3b and R 4b -R 2b The -OH group is specifically a hydroxymethyl group, a 2-hydroxyethyl group, a 3-hydroxypropyl group, or a 2-hydroxypropyl group, with the 2-hydroxyethyl group being preferred in terms of easy availability of the raw material. In general formula (b1), R 5b Specifically, is a methyl group, an ethyl group, or a propyl group. From the viewpoint of suppressing thickening, a methyl group is preferred. In general formula (b1), X -is a counter anion, and is preferably an anion selected from an iodide ion, a bromide ion, a chloride ion, an alkyl sulfate ion having from 1 to 3 carbon atoms, a fatty acid ion having from 12 to 18 carbon atoms, and a benzenesulfonate ion which may be substituted with from 1 to 3 alkyl groups having from 1 to 3 carbon atoms, more preferably an anion selected from an alkyl sulfate ion having from 1 to 3 carbon atoms, and even more preferably a monomethyl sulfate ion or a monoethyl sulfate ion.

[0022] <Requirement 1> In terms of suppressing the generation of odor caused by sebum stains, when the component (b1) contains one type of quaternary ammonium compound (1b), R 1b In the case where the quaternary ammonium compound (1b) is two or more types, it is preferably a quaternary ammonium salt in which at least one of R 1b In the present invention, a quaternary ammonium salt containing at least one quaternary ammonium compound, at least one of which is a linear, branched or cyclic alkenyl group having 14 to 22 carbon atoms, is preferred.

[0023] <Requirement 2> From the viewpoint of suppressing the generation of odor due to sebum stains, the unsaturation rate of the (b1) component is 20% by mass or more, preferably 30% by mass or more, and more preferably 35% by mass or more, and from the same viewpoint, it is 100% by mass or less, preferably 90% by mass or less, and more preferably 80% by mass or less.

[0024] The unsaturation rate of the (b1) component is the R 1b Group R 1b When replaced with COOH, R 1b R is an alkenyl group 1b The total mass of COOH and R 1b It is calculated from the total mass of COOH using the above formula (1). The unsaturation rate of component (b1) is determined by the R 1b Compounds containing, for example, R 1b Of COOH, R 1bR is an alkenyl group 1b The total mass of COOH and R 1b It can be calculated from the total mass of COOH using the above formula (1). In the production of the quaternary ammonium compound of the general formula (b1) by an esterification reaction between an alkanolamine and a fatty acid or a fatty acid chloride or an ester exchange reaction between an alkanolamine and a lower alcohol ester of a fatty acid, followed by a quaternization reaction with a quaternizing agent, R 1b By optimizing the conditions, such as using COX (fatty acid, fatty acid chloride, or lower alcohol ester of fatty acid) at a molar ratio of 1.5 times or more to alkanolamine, it is possible to obtain an R of approximately 95% or more. 1b COX reacts with alkanolamine to give an ester. Therefore, one or more R 1b The unsaturation rate of COX may be used as the unsaturation rate. The unsaturation rate can also be calculated by measuring the iodine value. 1b When COX is used in excess relative to alkanolamine, one or more R 1b It is acceptable to measure the iodine value of COX and calculate it. 1b The iodine value of COX can be measured using the method described in the Iwanami Dictionary of Physics and Chemistry, 4th Edition, Iwanami Shoten.

[0025] <Composition of the aqueous composition (A)> The aqueous composition (A) contains component (a) in an amount of preferably 0.002% by mass or more, more preferably 0.0025% by mass or more, and even more preferably 0.005% by mass or more, from the viewpoint of suppressing the generation of odor caused by sebum stains, and from the same viewpoint, preferably 10% by mass or less, and more preferably 5% by mass or less.

[0026] The aqueous composition (A) contains component (b) in an amount of preferably 2% by mass or more, and more preferably 4% by mass or more, from the viewpoint of suppressing the generation of odor caused by sebum stains, and from the same viewpoint, preferably 40% by mass or less, more preferably 30% by mass or less, even more preferably 20% by mass or less, still more preferably 15% by mass or less, and even more preferably 13% by mass or less.

[0027] In the aqueous composition (A), the mass ratio of the content of the component (a) to the content of the component (b) [(a) / (b)] is, from the viewpoint of suppressing the generation of odor caused by sebum stains, preferably 0.0001 or more, more preferably 0.0002 or more, even more preferably 0.0005 or more, and still more preferably 0.001 or more, and from the same viewpoint, is preferably 5 or less, more preferably 1 or less, and even more preferably 0.1 or less.

[0028] <Water> The aqueous composition (A) may contain water. Examples of water include deionized water, tap water, groundwater, and water that has been subjected to sterilization or the like. Water is used in an amount such that the composition of the aqueous composition (A) is 100% by mass, as the balance other than the component (a), the component (b), and the optional components described below. From the viewpoint of storage stability, the aqueous composition of the present invention contains water in an amount of preferably 30% by mass or more, more preferably 40% by mass or more, even more preferably 50% by mass or more, and preferably 99.5% by mass or less, more preferably 99% by mass or less, even more preferably less than 98% by mass.

[0029] The aqueous composition (A) may contain, in addition to the components (a) and (b), optional components such as enzymes, other fabric softener substances, surfactants, stabilizers, oligomers, polymers, bactericides, antibacterial agents, fragrances, fluorescent agents, defoamers, chelating agents, colorants, and inorganic salts (excluding those that fall under the category of components (a) and (b)).

[0030] The method of the present invention can be applied to textile products that are soiled with sebum and / or that are at risk of becoming soiled with sebum. The textile product can be a textile product made of fibers, for example natural fibers, synthetic fibers, or semi-synthetic fibers.

[0031] The fibers may be either hydrophobic or hydrophilic. Examples of hydrophobic fibers include protein fibers (milk protein casein fibers, promix, etc.), polyamide fibers (nylon, etc.), polyester fibers (polyester, etc.), polyacrylonitrile fibers (acrylic, etc.), polyvinyl alcohol fibers (vinylon, etc.), polyvinyl chloride fibers (polyvinyl chloride, etc.), polyvinylidene chloride fibers (vinylidene, etc.), polyolefin fibers (polyethylene, polypropylene, etc.), polyurethane fibers (polyurethane, etc.), polyvinyl chloride / polyvinyl alcohol copolymer fibers (polycral, etc.), polyalkylene paraoxybenzoate fibers (benzoate, etc.), and polyfluoroethylene fibers (polytetrafluoroethylene, etc.). Examples of hydrophilic fibers include seed hair fibers (cotton, kapok, etc.), bast fibers (hemp, flax, ramie, hemp, jute, etc.), leaf vein fibers (Manila hemp, sisal, etc.), palm fibers, rush, straw, animal hair fibers (wool, mohair, cashmere, camel hair, alpaca, vicuna, angora, etc.), silk fibers (domestic silk, wild silk), feathers, and cellulosic fibers (rayon, polynosic, cupra, acetate, etc.). The fiber is preferably a fiber containing cotton fiber. From the viewpoint of adsorption of the agent, the content of cotton fiber in the fiber is preferably 5% by mass or more, more preferably 10% by mass or more, even more preferably 15% by mass or more, still more preferably 20% by mass or more, and even more preferably 100% by mass. In the present invention, the textile product means a fabric such as a woven fabric, knitted fabric, or nonwoven fabric using the hydrophobic or hydrophilic fiber, and an undershirt, T-shirt, dress shirt, blouse, slacks, hat, handkerchief, towel, knitwear, socks, underwear, tights, or other products obtained using the same. The textile product is preferably a textile product containing cotton fiber. The preferred embodiment of the content of cotton fiber in the textile product is the same as the content of cotton fiber in the above-mentioned fiber.

[0032] The method of the present invention will be described in detail with reference to specific examples. However, the method of the present invention for suppressing odor generation caused by sebum stains on textile products is not limited to the specific examples. The method of the present invention is a method for suppressing the generation of odor caused by sebum stains on a textile product by contacting the aqueous composition (A) of the present invention with the textile product. The aqueous composition (A) can be contacted with the textile product directly in the form of a stock solution or after diluting a concentrated solution of the aqueous composition (A) with water or the like. Examples of the embodiment of contacting the aqueous composition (A) of the present invention with a textile product include filling a container equipped with a sprayer with the aqueous composition (A) or a dilution thereof, spraying the aqueous composition (A) from the container onto the textile product to contact the aqueous composition (A) with the textile product, and immersing the textile product in the aqueous composition (A) or a dilution of the concentrated aqueous composition (A) to contact the textile product with the aqueous composition (A). In the immersion step of the textile product, mechanical force can also be applied to the textile product. Examples of the method of applying mechanical force to the textile product include a method of applying an external force by a water flow using a commercial washing machine or a household washing machine. After contacting the textile product with the aqueous composition (A), the textile product may be rinsed or dried, and it is preferable to dry the textile product.

[0033] In the method of the present invention, from the viewpoint of suppressing the generation of odor caused by sebum stains, component (a) is attached in an amount of preferably 0.001 μg or more, more preferably 0.005 μg or more, and even more preferably 0.2 μg or more per gram of textile product, and the upper limit is not particularly limited, but for example, 100 μg or less, or even 20 μg or less. The amount of component (a) attached per gram of textile product is determined by the method described below, in which component (a) attached to the textile product is extracted with methanol, and the component (a) contained in the methanol is measured by high performance liquid chromatography / mass spectrometry (HPLC-MS).

[0034] <Method for measuring the amount of component (a) attached per gram of textile product> The amount of component (a) attached to 1 g of a textile product is measured by immersing the component (a) attached to the textile product in methanol, applying ultrasonic vibrations to it for 30 minutes using an ultrasonic cleaner (As One ASU series), and extracting the component (a) attached to the textile product with methanol. The content of component (a) in this methanol is measured by high performance liquid chromatography / mass spectrometry (HPLC-MS). Specifically, component (a) is separated by high performance liquid chromatography (HPLC) and each is identified by mass spectrometry (MS). The content of component (a) is then calculated from the HPLC-MS peak area. The amount of component (a) attached per gram of textile product (μg) is then calculated from the content of component (a) thus determined. The apparatus and conditions used for the measurement are as follows: Equipment: Shimadzu Corporation "LCMS-2020" Column: Shimadzu Corporation "Shim-packXR-ODS", 2.0 x 100 mm, particle size: 2.2 μm Eluent A: 10 mM ammonium acetate added water Eluent B: 10 mM ammonium acetate in methanol Eluent C: 10 mM ammonium acetate in ethanol Gradient: 0 min (A / B / C = 60 / 20 / 20) → 3.01 to 10.0 min (0 / 50 / 50) → 10.01 to 15 min (60 / 20 / 20) ESI detection: positive ion detection m / z=310.0 Column temperature: 40℃ Flow rate: 0.5mL / min Injection volume: 5 μL

[0035] The temperature of the aqueous composition (A) to be contacted with the textile product is, from the viewpoint of liquid stability, preferably 0°C or higher, more preferably 5°C or higher, even more preferably 10°C or higher, and preferably 50°C or lower, more preferably 40°C or lower. In addition, the contact time between the textile product and the aqueous composition (A) is preferably 1 minute or more from the viewpoint of contact between the agent and the treated fabric, and the upper limit is not particularly limited, but is, for example, 60 minutes or less, or even 30 minutes or less.

[0036] In the method of the present invention, the liquor ratio, which is the ratio of the mass (kg) of the textile product to the amount (liters) of the aqueous composition (A) or its dilution, i.e., the amount (liters) of the aqueous composition (A) or its dilution / mass (kg) of the textile product (hereinafter sometimes referred to as the liquor ratio), can be selected from 2 or more, 3 or more, 4 or more, 5 or more, and 100 or less, or 50 or less, from the viewpoint of further exerting the effects of the present invention. EXAMPLES

[0037] Aqueous compositions containing the components shown in Tables 4 to 6 were prepared using the following blended components, and the odor intensity was evaluated as described below.

[0038] <Composition ingredients> <Component (a)> Component (a-1): Methyl 3-(3,5-Di-tert-butyl-4-hydroxyphenyl)propionate, manufactured by Tokyo Chemical Industry Co., Ltd. Component (a-2): 3-5-di-t-butyl-4-hydroxytoluene, manufactured by Tokyo Chemical Industry Co., Ltd.

[0039] <(b) Component> Component (b-1): A cationic surfactant synthesized in Synthesis Example 1 below. Component (b-2): A cationic surfactant synthesized in Synthesis Example 2 below. Component (b-3): A cationic surfactant synthesized in Synthesis Example 3 below.

[0040] <Synthesis Example 1: Synthesis of component (b-1)> Triethanolamine and R of the composition shown in Table 1 1b COOH was used as the raw fatty acid. 1b The unsaturation percentage of COOH is 27% + 3% = 30%.

[0041] [Table 1]

[0042] Triethanolamine and R 1b COOH was added in the reaction molar ratio (R 1b 500g of a solution of COOH / triethanolamine (1.65 / 1) was charged into a 1L flask, nitrogen was introduced under stirring, and the resulting water was removed from the system using a dehydrator while heating to 180°C over about 3 hours. The temperature was kept at 180-230°C for another 5 hours, and a portion of the reaction product was sampled and its AV (acid value) was measured. After confirming that AV was 2.5mgKOH / g or less, the reaction product was cooled to room temperature. HPLC analysis revealed that the esterification product contained unreacted R 1b It contained 5% by mass of COOH. The total amino group nitrogen content of the obtained ester compound (based on the measurement method for total amino group nitrogen content in JIS K7245-2000) was determined, and a quaternization reaction was carried out with 0.96 equivalents of dimethyl sulfate relative to the equivalent number of amino groups obtained from the calculation. Specifically, 300 g of the esterification reaction product was charged into a 1 L flask, and heated to 50°C while stirring while introducing nitrogen. Dimethyl sulfate in an amount of 0.96 equivalents relative to the equivalent number of amino groups calculated from the total amino group nitrogen content was added dropwise from the dropping funnel over 1 hour, and the mixture was stirred at 50°C for another 2 hours. After the reaction was completed, the mixture was diluted with ethanol.

[0043] The composition ratio of each component in the obtained product was analyzed by HPLC and quantified using tetraoctylammonium bromide as an internal standard. As a result, the obtained product was found to contain 75% by mass of component (b-1), 10% by mass of ethanol, 12% by mass of unquaternized esterification reactants (as methyl sulfate), and 12% by mass of unreacted R. 1b The component (b-1) contains 2% by mass of COOH, a trace amount of triethanolamine quaternary salt and other trace components, and in the general formula (b1) of the component (b-1), -YR 2b - is -COO-C2H4-, R 3b and R 4b is -C2H4OH, R 5b is a methyl group, and X - The compound in which is a methyl sulfate ion is 28% by mass in the component (b-1), 2b - is -COO-C2H4-, R 3b R 1b -COO-C2H4-, R 4b is -C2H4OH, R 5b is a methyl group, and X - The compound in which is a methyl sulfate ion is 56% by mass in the component (b-1), 2b - is -COO-C2H4-, R 3b and R 4b R b1 -COO-C2H4-, R 5b is a methyl group, and X - The compound in which the ion is a methyl sulfate ion accounted for 16 mass% of component (b-1). The quaternization rate calculated from component (b-1) and the non-quaternized esterification reaction product (75÷(75+12)) was 86 mass%.

[0044] <Synthesis Example 2: Synthesis of component (b-2)> Triethanolamine and R of the composition shown in Table 2 1b COOH was used as the raw fatty acid. 1b The unsaturation percentage of COOH is 78% + 10% + 2% = 90%.

[0045] [Table 2]

[0046] Triethanolamine and R 1b COOH was added in the reaction molar ratio (R 1b 500g of a solution mixed with COOH / triethanolamine (1.87 / 1) was charged into a 1L flask, nitrogen was introduced under stirring, and the resulting water was removed from the system using a dehydrator while heating to 180°C over about 3 hours. The temperature was kept at 180-230°C for another 5 hours, and a portion of the reaction product was sampled and its AV (acid value) was measured. After confirming that AV was 2.5mgKOH / g or less, the reaction product was cooled to room temperature. HPLC analysis revealed that the esterification product contained unreacted R 1b It contained 1% by mass of COOH. The total amino group nitrogen content of the obtained ester compound (based on the measurement method for total amino group nitrogen content in JIS K7245-2000) was determined, and a quaternization reaction was carried out with 0.96 equivalents of dimethyl sulfate relative to the equivalent number of amino groups obtained from the calculation. Specifically, 300 g of the esterification reaction product was charged into a 1 L flask, and heated to 50°C while stirring while introducing nitrogen. Dimethyl sulfate in an amount of 0.96 equivalents relative to the equivalent number of amino groups calculated from the total amino group nitrogen content was added dropwise from the dropping funnel over 1 hour, and the mixture was stirred at 50°C for another 2 hours. After the reaction was completed, the mixture was diluted with ethanol.

[0047] The composition ratio of each component in the obtained product was analyzed by HPLC and quantified using tetraoctylammonium bromide as an internal standard. As a result, the obtained product contained 66% by mass of component (b-2), which is component (b), 15% by mass of ethanol, 17% by mass of unquaternized esterification reactants (as methyl sulfate), and 17% by mass of unreacted R. 1b COOH 1 mass %, a trace amount of triethanolamine quaternary salt and other trace components, among which in the general formula (b1), -YR 2b - is -COO-C2H4-, R 3b and R 4b is -C2H4OH, R 5b is a methyl group, and X -The compound in which is a methyl sulfate ion is 22% by mass in the component (b-2), 2b - is -COO-C2H4-, R 3b R 1b -COO-C2H4-, R 4b is -C2H4OH, R 5b is a methyl group, and X - The compound in which is a methyl sulfate ion is 58% by mass in the component (b-2), 2b - is -COO-C2H4-, R 3b and R 4b R 1b -COO-C2H4-, R 5b is a methyl group, and X - The compound in which the ion is a methyl sulfate ion accounted for 20 mass% of component (b-2). The quaternization rate calculated from component (b-2) and the non-quaternized esterification reaction product (66÷(66+17)) was 80 mass%.

[0048] <Synthesis Example 3: Synthesis of component (b-3)> Triethanolamine and R 1b Component (b-3) was synthesized in the same manner as in Synthesis Example 2, except that fatty acids having the following composition were used as COOH. Palmitic acid: 45% by weight Stearic acid: 55% by weight In the (b-3) component, the ratio of mono- / di- / tri-isomers was 22% by mass / 58% by mass / 20% by mass, the amount of unreacted fatty acid was 0.5% by mass, and the quaternization rate was 80% by mass. The unsaturation rate of the fatty acid used in the synthesis of the (b-3) component was 0%.

[0049] <(c) component> (c) Component: A fragrance composition as described in Table 3.

[0050] [Table 3]

[0051] <How to evaluate odor intensity> (1) Preparation of soiled cloth A 6 cm x 6 cm TC broadcloth (Tanigasshi Shoten; 65% polyester, 35% cotton) was coated with 20 μL of a liquid mixture of squalene (Tokyo Chemical Industry Co., Ltd.) and oleic acid (Fujifilm Wako Pure Chemical Industries, Ltd.) in a 1:1 mass ratio to prepare a contaminated cloth.

[0052] (2) Coating process A solution prepared by diluting the aqueous composition shown in Table 4 with ion-exchanged water was applied to the soiled cloth (6 cm x 6 cm) prepared in (1) so that the amount of the aqueous composition applied was 500 μL. The solution was left for 18 hours under conditions of 20°C and 43% RH, and then dried. The soiled cloth was then placed in a vial, capped, and aged at 50°C for 18 hours.

[0053] (3) Immersion treatment Five pieces of soiled cloth (6 cm x 6 cm) prepared in (1) were treated at 85 rpm for 3 minutes in a tergotometer (Ueshima, MS-8212). A total of 15 g of TC broadcloth (Tanigashou Shoten; polyester 65%, cotton 35%) was added to the same bath for rinsing, and the bath ratio was adjusted to 30 using city water (20°C). The rinsing conditions were that the aqueous composition shown in Table 5 or Table 6 was poured in, and the water temperature was 20°C. After that, the soiled cloth after rinsing was dehydrated for 2 minutes using a two-layer washing machine, and then left to dry for 18 hours under conditions of 20°C and 43% RH. The dried soiled cloth was placed in a vial, capped, and aged at 50°C for 18 hours.

[0054] (4) Evaluation method for odor intensity An expert panel evaluated the odor of the soiled cloth treated in (2) and the soiled cloth treated in (3), and evaluated the odor intensity of the Examples and Comparative Examples based on the following evaluation. Aqueous compositions rated as "○" or "△" for odor intensity significantly suppressed the generation of odor caused by sebum stains, and aqueous compositions rated as "○" for odor intensity particularly significantly suppressed the generation of odor caused by sebum stains. [Odor Intensity Evaluation Index] ○: No unpleasant odor. △: Slightly unpleasant odor. ×: There is an unpleasant odor.

[0055] (5) Method for measuring the adhesion amount of component (a) per 1 g of cloth (2) One white cloth treated in (3) was immersed in 10 mL of methanol and irradiated with ultrasonic waves for 30 minutes using an ultrasonic cleaner (AS ONE ASU series). The obtained solution was subjected to LC / MS (liquid chromatography / mass spectrometry) under the following conditions, and the adhesion amount of component (a) attached to 1 g of cloth was measured based on a separately prepared calibration curve.

[0056] <LC / MS measurement conditions> The apparatus and conditions used for the measurement are as follows. Apparatus: "LCMS-2020" manufactured by Shimadzu Corporation Column: "Shim-packXR-ODS" manufactured by Shimadzu Corporation, 2.0 × 100 mm, particle size: 2.2 μm Eluent A: Water added with 10 mM ammonium acetate Eluent B: Methanol solution added with 10 mM ammonium acetate Eluent C: Ethanol solution added with 10 mM ammonium acetate Gradient: 0 min (A / B / C = 60 / 20 / 20) → 3.01 - 10.0 min (0 / 50 / 50) → 10.01 - 15 min (60 / 20 / 20) ESI detection: Positive ion detection m / z = 310.0 Column temperature: 40 °C Flow rate: 0.5 mL / min Injection volume: 5 μL

[0057]

Table 4

[0058]

Table 5

[0059]

Table 6

Claims

1. A method for suppressing the generation of odor caused by sebum stains on a textile product, comprising contacting the textile product with an aqueous composition [hereinafter referred to as aqueous composition (A)] containing (a) a phenolic antioxidant [hereinafter referred to as component (a)] and (b) a quaternary ammonium salt containing a quaternary ammonium compound having an unsaturated hydrocarbon group [hereinafter referred to as component (b)].

2. 2. The method for suppressing odor generation due to sebum stains on textile products according to claim 1, wherein the component (a) is adhered to the textile product in an amount of 0.2 μg to 20 μg per 1 g of the textile product.

3. 3. The method for suppressing the generation of odor caused by sebum stains on textile products according to claim 1 or 2, wherein the component (a) is one or more compounds selected from the group consisting of compounds represented by the following general formula (a1): 【Chemistry 1】 [In the formula, R １ａ is a tertiary butyl group or a hydrogen atom, R ２ａ , R ３ａ , R ５ａ are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or -C ｎ H ２ｎ COOR ６ａ R is an ester group represented by the formula: ４ａ is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or -C ｎ H ２ｎ COOR ６ａ Here, n is an integer of 1 to 5, and R ６ａ is a hydrocarbon group having 1 to 18 carbon atoms.

4. The method for suppressing the generation of odor caused by sebum stains on a textile product according to any one of claims 1 to 3, wherein the component (b) is one or more quaternary ammonium compounds (1b) selected from compounds represented by the following general formula (b1), and satisfies the following requirements 1 and 2. 【Chemistry 2】 [In the formula, R １ｂ is a linear, branched or cyclic alkyl or alkenyl group having 14 to 22 carbon atoms. Y is a -COO- group or a -OCO- group. ２ｂ is an alkylene group having 1 to 3 carbon atoms. ３ｂ , R ４ｂ each independently represents an alkyl group having 1 to 3 carbon atoms; ２ｂ -OH or R １ｂ -Y-R ２ｂ -, where R ３ｂ and / or R ４ｂ But, R １ｂ -Y-R ２ｂ -, R １ｂ and / or R ２ｂ may be the same or different. ３ｂ and / or R ４ｂ But, -R ２ｂ When —OH, R ２ｂ may be the same or different. ５ｂ is an alkyl group having 1 to 3 carbon atoms. － is an anion.] Requirement 1: When the quaternary ammonium compound (1b) is one kind, R １ｂ At least one of R is a linear, branched or cyclic alkenyl group having 14 to 22 carbon atoms. １ｂ At least one of the quaternary ammonium compounds is a linear, branched or cyclic alkenyl group having 14 to 22 carbon atoms. Requirement 2: The unsaturation rate defined by the following formula (1) is 20% by mass or more and 100% by mass or less. Unsaturation rate (mass%) = [(R １ｂ R is an alkenyl group １ｂ Total mass of COOH) / (R １ｂ (total mass of COOH) × 100 (1)

5. The method for suppressing the generation of odor caused by sebum stains on a textile product according to any one of claims 1 to 4, comprising filling a container equipped with a sprayer with the aqueous composition (A) and spraying the aqueous composition (A) from the container to bring the aqueous composition (A) into contact with the textile product.

6. A method for suppressing the generation of odor caused by sebum stains on a textile product according to any one of claims 1 to 4, which comprises immersing the textile product in the aqueous composition (A).

7. 7. The method for suppressing the generation of odor caused by sebum stains on a textile product according to any one of claims 1 to 6, wherein in the aqueous composition (A), the mass ratio of the content of component (a) to the content of component (b) [(a) / (b)] is 0.0001 or more and 0.1 or less.

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