Bleaching detergent composition and method for bleaching and cleaning mold stains

Abstract

Provided is a bleaching detergent composition that has excellent bleaching and cleaning performance against mold stains occurring in hydrophobic resin parts such as silicone resins, and further has excellent storage stability as concerns the bleaching and cleaning components and viscosity, thereby allowing the aforementioned effect to last for a long period of time.　Provided is a bleaching detergent composition characterized by including: component (a), 0.1-10 mass% of an alkali metal hypochlorite; component (b), 0.1-10 mass% of one or more quaternary ammonium salt-type surfactants selected from quaternary ammonium salts; component (c), an aromatic sulfonic acid or a salt thereof; component (d), an alkaline agent; and water, wherein the viscosity at 25°C is 1,000-100,000 mPa•s, and the pH of a 10 mass% aqueous solution at 25°C is 11-14.

Description

Bleach cleaning agent composition and method for bleaching and cleaning mildew stains

[0001] The present invention relates to a bleaching detergent composition and a method for bleaching and cleaning mildew stains.

[0002] In bathrooms, toilets, and kitchens, which are water-related residential facilities, water droplets adhere to the surfaces of the facilities due to splashes from faucets and showers during use, and the surfaces remain wet, creating an environment that is prone to the growth of bacteria and mold. Since mold stains are particularly difficult to remove sufficiently with cleaning agents whose main components are surfactants, chelating agents, abrasives, etc., bleaching compositions containing hypochlorite are generally used. Since the hard surfaces targeted by the above-mentioned bleaching compositions are not limited to horizontal surfaces but also include vertical surfaces, inclined surfaces, and various other surfaces, various product forms have been investigated to improve the adhesion and retention of bleaching components, such as foam spray types using trigger containers and gel types with high viscosity compositions.

[0003] Japanese Patent Application Laid-Open No. 2013-67806 discloses a chlorine-based bleaching composition containing (b) an alkali metal oxide and (c) a specific water-soluble solvent for use against mold growing on silicone resin-based caulking, and the examples disclose a technology in which the use of a specific cationic surfactant in combination provides even better results. Japanese Patent Application Laid-Open No. 2003-277796 discloses a bleaching composition containing (c) a tertiary amine oxide and (d) n-octyl sulfate, and which exhibits excellent thickening properties, storage stability, and viscosity controllability by specifying the contents and mass ratios of the components (c) and (d). Japanese Patent Application Laid-Open Publication No. 2007-137930 discloses a thickened bleaching composition containing an organic thickener, an alkali agent, a sulfonic acid compound, and its alkali metal salt, and having a viscosity of 1,000 to 10,000 mPa·s at 25°C, thereby exhibiting excellent storage stability, bleaching properties, adhesion, and rinsability. EP 0298172 A1 discloses a technology using a viscoelastic surfactant consisting of a surfactant ion of a hexadecyltrimethylammonium ion having 16 carbon atoms and an organic counterion of a p-toluenesulfonate ion, which associates with each other in sodium hypochlorite to exhibit thickening properties. The publication also discloses that the bleaching composition exhibits acceptable levels of bleaching stability, phase stability, and viscosity stability over long periods of time, and that the product can be used in the form of a non-mist spray or liquid that adheres to vertical surfaces without substantial dripping, and can be applied to a variety of substrates using a dispensing device.

[0004] Conventional chlorine-based bleaches have been sufficiently effective against mold stains adhering to tiles and joints. However, in recent years, there has been an increase in cases of mold growth on silicone resin-based caulking used in the joints of walls, bathtubs, etc., and it has been difficult to bleach or clean mold that has grown on these resin parts. JP 2013-67806 A discloses a liquid bleach cleaner composition that exhibits excellent bleaching power for bleaching mold that has grown on silicone resin-based caulking, but in recent years, further performance improvements have been required. JP 2003-277796 A and JP 2007-137930 A disclose techniques for thickening a composition to 1,000 mPa·s or more by using an amine oxide in combination with other agents or by using an organic thickener. EP 0298172 A1 discloses a thickening technique aimed at application to spray products using a dispensing device, and discloses a thickening technique for a composition having a viscosity of 15.85 mPa·s at room temperature from the viewpoint of ease of discharge, etc. -1 The goal is to achieve a viscosity of 500 mPa·s or less when measured at a shear rate of 1000 mPa·s. However, it has been found that these technologies are insufficient in terms of effectiveness against mold that has grown on hydrophobic resins, a characteristic that has become a requirement in recent years. Furthermore, compositions that have been made highly viscous to improve adhesion and retention on objects must also satisfy viscosity storage stability, so that the viscosity does not decrease when distributed, when in stock at stores, or when used at home. To date, no product has been found that combines an excellent bleaching effect against mold that has grown on hydrophobic resins with viscosity stability over time. Summary of the Invention

[0005] As a result of intensive research, the inventors of the present invention found that, because silicone resins are hydrophobic, they create an environment in which hydrophilic sodium hypochlorite is difficult to act on mold present on or inside the resin.Furthermore, they discovered that to solve this problem, it is important to achieve two goals: improving the retention of bleaching cleaning ingredients on hydrophobic surfaces and improving the effectiveness of the bleaching cleaning ingredients on mold, which led to the present invention.

[0006] The present invention aims to further overcome the problems of the prior art by providing a highly viscous bleaching detergent composition that exhibits excellent adhesion and retention on objects. The bleaching detergent composition has excellent bleaching and cleaning performance, decomposing and removing mold stains that have developed on hydrophobic resins, such as silicone resins, and bleaching mold-caused stains on objects. Furthermore, the bleaching and cleaning performance is maintained over a long period of time due to the excellent storage stability of the bleaching detergent components and viscosity. In this specification, "bleaching and cleaning" includes both cleaning of mold stains and bleaching of mold-caused stains. Furthermore, the performance of "bleaching and cleaning" is referred to as "bleaching and cleaning performance." The bleaching and cleaning performance can be measured, for example, by the mold removal rate described in

[0142] . The mold removal rate encompasses both the cleaning of mold stains and the bleaching of mold-caused stains as a mold remover.

[0007] The present invention relates to a composition comprising: (a) component: 0.1% by mass to 10% by mass of an alkali metal hypochlorite; and (b) component: 0.1% by mass to 10% by mass of a compound represented by the general formula (1), [R in the formula １ represents a linear or branched alkyl group having 8 to 22 carbon atoms. ２ represents a linear or branched alkyl group having 1 to 12 carbon atoms, or an aralkyl group having 7 to 12 carbon atoms. ３ and R ４ X may be the same or different and represent a linear or branched alkyl group having 1 to 4 carbon atoms. －represents a counter anion.], (c) component: aromatic sulfonic acid or a salt thereof, (d) component: alkaline agent, and water, wherein the bleach detergent composition has a viscosity of 1,000 mPa·s to 100,000 mPa·s at 25°C and a pH of a 10 mass% aqueous solution at 25°C of 11 to 14. The present invention also relates to a method for bleaching mildew stains, in which the bleach detergent composition is brought into contact with mildew stains that have developed on hydrophobic resin parts such as silicone resin-based caulking parts. The present invention further relates to a method for bleaching mildew stains, in which the bleach detergent composition is brought into contact with the mildew stains that have developed on hydrophobic resin parts such as silicone resin-based caulking parts. The present invention further relates to a bleach detergent composition comprising: (a) component: 0.1 mass% to 10 mass% of an alkali metal hypochlorite; (b) component: 0.1 mass% to 10 mass% of a compound represented by the general formula (1): [R in the formula １ represents a linear or branched alkyl group having 8 to 22 carbon atoms. ２ represents a linear or branched alkyl group having 1 to 12 carbon atoms, or an aralkyl group having 7 to 12 carbon atoms. ３ and R ４ X may be the same or different and represent a linear or branched alkyl group having 1 to 4 carbon atoms. － represents a counter anion.], component (c): an aromatic sulfonic acid or a salt thereof, component (d): an alkaline agent, and water, wherein the bleach detergent composition has a viscosity of from 1,000 mPa s to 100,000 mPa s at 25°C and a pH of from 11 to 14 in a 10% by mass aqueous solution at 25°C.

[0008] According to the present invention, the bleaching cleaning agent has excellent cleaning power against mold stains that have developed in hydrophobic resin parts such as silicone resins, and furthermore, the bleaching cleaning component and viscosity have excellent storage stability, so that the effect can be maintained for a long period of time.

[0009] 1 is a diagram showing a dispensing container with a sealing lid and a discharge outlet attached in a state where the sealing lid is removed, according to one embodiment of the present invention; and 2 is a diagram showing a dispensing container with a sealing lid and a discharge outlet attached in a state where the sealing lid is attached, according to one embodiment of the present invention.

[0010] First, the bleaching detergent composition of the present invention will be described. The bleaching detergent composition of the present invention contains an alkali metal salt of hypochlorous acid as a bleaching detergent component (a). Examples of alkali metals include lithium, sodium, potassium, etc. Sodium is preferred because of its easy availability. Sodium hypochlorite may be used in the form of an aqueous solution. Due to production, the aqueous sodium hypochlorite solution may contain an equimolar amount of sodium chloride. To ensure storage stability while maintaining the bleaching detergent performance of sodium hypochlorite, a low sodium chloride content is preferred. Specifically, the sodium chloride content is preferably 10 mol% to 60 mol%, and preferably 10 mol% to 40 mol%, relative to the sodium hypochlorite content. Sodium hypochlorite with reduced sodium chloride content is commercially available as low-calorie sodium hypochlorite. In addition, commercially available aqueous sodium hypochlorite solutions may contain an alkali metal hydroxide in advance to ensure storage stability. The bleaching detergent composition of the present invention may be used by blending it with a commercially available aqueous sodium hypochlorite solution.

[0011] The bleach detergent composition of the present invention, component (a), is a composition containing an alkali metal hypochlorite. The amount of alkali metal hypochlorite is the amount of active ingredient at the time of production of the composition, and in the present application, is considered to correspond to the content in the composition. From the viewpoint of improving bleaching performance, the content of alkali metal hypochlorite is 0.1 mass% or more, preferably 0.5 mass% or more, more preferably 1 mass% or more, and even more preferably 1.5 mass% or more, of the total amount of the bleach detergent composition. From the same viewpoint, it is 10 mass% or less, preferably 7.5 mass% or less, more preferably 5 mass% or less, and even more preferably 3 mass% or less. In the present invention, the content of component (a) is determined based on the available chlorine concentration (Cl ) obtained by the method described in

[0144] . ２ ) is measured and converted into the formula weight of sodium hypochlorite (NaOCl).

[0012] Next, the quaternary ammonium salt surfactant of component (b) will be described. The bleaching detergent composition of the present invention is represented by the general formula (1) [R in the formula １ represents a linear or branched alkyl group having 8 to 22 carbon atoms. ２ represents a linear or branched alkyl group having 1 to 12 carbon atoms, or an aralkyl group having 7 to 12 carbon atoms. ３ and R ４ X may be the same or different and represent a linear or branched alkyl group having 1 to 4 carbon atoms. － represents a counter anion.]

[0013] Among these, from the viewpoint of improving bleaching and cleaning performance for mildew stains, one or more quaternary ammonium salt surfactants selected from quaternary ammonium salt surfactants represented by the following general formulas (1a) to (1c) are preferred. [R in the formula １ａ represents a linear or branched alkyl or alkenyl group having 14 to 22 carbon atoms. ２ａ , R ３ａ and R ４ａ X may be the same or different and represent a linear or branched alkyl group having 1 to 4 carbon atoms.ａ － indicates the counter anion.] [R in the formula １ｂ and R ２ｂ R may be the same or different and represent a linear or branched alkyl or alkenyl group having from 8 to 12 carbon atoms. ３ｂ and R ４ｂ X may be the same or different and represent a linear or branched alkyl group having 1 to 4 carbon atoms. ｂ － indicates the counter anion.] [R in the formula １ｃ represents a linear or branched alkyl or alkenyl group having 8 to 18 carbon atoms. ２ｃ represents an aralkyl group having 7 to 12 carbon atoms. ３ｃ and R ４ｃ X may be the same or different and represent a linear or branched alkyl group having 1 to 4 carbon atoms. ｃ － indicates the counter anion.]

[0014] First, the quaternary ammonium salt surfactant of general formula (1a) will be described. [R in the formula １ａ represents a linear or branched alkyl or alkenyl group having 14 to 22 carbon atoms. ２ａ , R ３ａ and R ４ａ X may be the same or different and represent a linear or branched alkyl group having 1 to 4 carbon atoms. ａ － indicates the counter anion.]

[0015] R １ａrepresents a linear or branched alkyl or alkenyl group having from 14 to 22 carbon atoms. From the viewpoint of improving bleaching and cleaning performance, a linear alkyl group is preferred. Specific examples include myristyl (C14), pentadecyl (C15), cetyl (C16), heptadecyl (C17), stearyl (C18), nonadecyl (C19), arachidyl (C20), heneicosanyl (C21), and behenyl (C22). Among these, from the viewpoint of improving bleaching and cleaning performance and easy availability, one or more selected from myristyl (C14), cetyl (C16), and stearyl (C18) groups are preferred, and one or more selected from cetyl and stearyl groups are more preferred.

[0016] R ２ａ , R ３ａ , and R ４ａ may be the same or different and represent straight-chain or branched alkyl groups having from 1 to 4 carbon atoms. Specific examples include a methyl group, an ethyl group, a propyl group, a 1-methylethyl group, a butyl group, a 1-methylpropyl group, a 2-methylpropyl group, and a 1,1-dimethylethyl group. Of these, from the viewpoints of improving bleaching and cleaning performance and easy availability, one or more selected from a methyl group and an ethyl group are preferred, and a methyl group is more preferred.

[0017] X ａ － represents a counter anion. Examples of the counter anion include inorganic anions such as fluoride ion, chloride ion, bromide ion, iodide ion, and hydroxide ion, and organic anions such as methyl sulfate ion, ethyl sulfate ion, acetate ion, and acetylacetonate ion. From the viewpoint of easy availability, inorganic anions are preferred, and chloride ion is more preferred.

[0018] Specific examples of the compound of general formula (1a) include one or more compounds selected from myristyltrimethylammonium salt, cetyltrimethylammonium salt, and stearyltrimethylammonium salt. ａ － may be a halide ion such as a chloride ion or a bromide ion, or an ethyl sulfate ion.

[0019] The quaternary ammonium salt surfactant of general formula (1a) may be used alone or in combination of two or more. When two or more types are used in combination, the mixing ratio (mass ratio) is not limited.

[0020] From the viewpoint of improving bleaching and cleaning performance, the content of cetyltrimethylammonium salt and stearyltrimethylammonium salt in the quaternary ammonium salt surfactant of general formula (1a) is preferably 50% by mass or more, more preferably 65% ​​by mass or more, even more preferably 80% by mass or more, and still more preferably 100% by mass.

[0021] From the viewpoint of improving bleaching and cleaning performance, it is preferable to use a mixture of cetyltrimethylammonium salt and stearyltrimethylammonium salt.

[0022] Next, the quaternary ammonium salt surfactant of general formula (1b) will be described. [R in the formula １ｂ and R ２ｂ R may be the same or different and represent a linear or branched alkyl or alkenyl group having from 8 to 12 carbon atoms. ３ｂ and R ４ｂ X may be the same or different and represent a linear or branched alkyl group having 1 to 4 carbon atoms. ｂ － indicates the counter anion.]

[0023] R １ｂ and R ２ｂ are the same or different and represent a linear or branched alkyl or alkenyl group having from 8 to 12 carbon atoms. From the viewpoint of improving bleaching and cleaning performance, a linear alkyl group is preferred. Specific examples include an octyl group (C8), a nonyl group (C9), a decyl group (C10), an undecyl group (C11), and a lauryl group (C12). Among these, from the viewpoints of good bleaching and cleaning performance and easy availability, one or more groups selected from the group consisting of an octyl group (C8), a decyl group (C10), and a lauryl group (C12) are preferred.

[0024] R ３ｂ and R ４ｂmay be the same or different and represent a linear or branched alkyl group having from 1 to 4 carbon atoms. Specific examples include a methyl group, an ethyl group, a propyl group, a 1-methylethyl group, a butyl group, a 1-methylpropyl group, a 2-methylpropyl group, and a 1,1-dimethylethyl group. Among these, from the viewpoints of improving bleaching and cleaning performance and easy availability, one or more selected from a methyl group and an ethyl group are preferred, and a methyl group is more preferred.

[0025] X ｂ － represents a counter anion. Examples of the counter anion include inorganic anions such as fluoride ion, chloride ion, bromide ion, iodide ion, and hydroxide ion, and organic anions such as methyl sulfate ion, ethyl sulfate ion, acetate ion, and acetylacetonate ion. From the viewpoint of easy availability, inorganic anions are preferred, and chloride ion is more preferred.

[0026] Specific examples of the compound of general formula (1b) include one or more compounds selected from N,N-dioctyl-N,N-dimethylammonium salt, N,N-didecyl-N,N-dimethylammonium salt, and N,N-didecyl-N-ethyl-N-methylammonium salt. ｂ － is a halide ion such as chloride ion or bromide ion, or an ethyl sulfate ion.

[0027] The quaternary ammonium salt surfactant of general formula (1b) may be used alone or in combination of two or more. When two or more types are used in combination, the mixing ratio (mass ratio) is not limited.

[0028] Next, the quaternary ammonium salt surfactant of general formula (1c) will be described. [R in the formula １ｃ represents a linear or branched alkyl or alkenyl group having 8 to 18 carbon atoms. ２ｃ represents an aralkyl group having 7 to 12 carbon atoms. ３ｃ and R ４ｃ X may be the same or different and represent a linear or branched alkyl group having 1 to 4 carbon atoms. ｃ －indicates the counter anion.]

[0029] R １ｃ represents a linear or branched alkyl or alkenyl group having from 8 to 18 carbon atoms. A linear alkyl group is preferred in terms of improving bleaching and cleaning performance. Specific examples include octyl (C8), nonyl (C9), decyl (C10), undecyl (C11), lauryl (C12), tridecyl (C13), myristyl (C14), pentadecyl (C15), cetyl (C16), heptadecyl (C17), stearyl (C18), nonadecyl (C19), arachidyl (C20), heneicosanyl (C21), and behenyl (C22). Among these, from the viewpoints of improving bleaching and cleaning performance and easy availability, one or more groups selected from octyl group (C8), decyl group (C10), lauryl group (C12), myristyl group (C14), cetyl group (C16), and stearyl group (C18) are preferred.

[0030] R ２ｃ represents an aralkyl group having from 7 to 12 carbon atoms. Specific examples include a benzyl group, a (2-methylphenyl)methyl group, a (4-methylphenyl)methyl group, a (1-naphthyl)methyl group, a (2-naphthyl)methyl group, a phenylethyl group, a (2-methylphenyl)ethyl group, a (4-methylphenyl)ethyl group, a (1-naphthyl)ethyl group, and a (2-naphthyl)ethyl group. Of these, a benzyl group is preferred from the viewpoints of improving bleaching and cleaning performance and easy availability.

[0031] R ３ｃ and R ４ｃ may be the same or different and represent straight-chain or branched alkyl groups having from 1 to 4 carbon atoms. Specific examples include a methyl group, an ethyl group, a propyl group, a 1-methylethyl group, a butyl group, a 1-methylpropyl group, a 2-methylpropyl group, and a 1,1-dimethylethyl group. Of these, from the viewpoints of improving bleaching and cleaning performance and easy availability, one or more selected from a methyl group and an ethyl group are preferred, and a methyl group is more preferred.

[0032] X ｃ －represents a counter anion. Examples of the counter anion include inorganic anions such as fluoride ion, chloride ion, bromide ion, iodide ion, and hydroxide ion, and organic anions such as acetate ion and acetylacetonate ion. From the viewpoint of easy availability, inorganic anions are preferred, and chloride ion is more preferred.

[0033] Specific examples of the compound of general formula (1c) include, but are not limited to, alkyldimethylbenzylammonium salts, in which the alkyl group is one or more selected from octyl, lauryl, myristyl, cetyl, and stearyl groups, and benzalkonium chloride, which is known as a mixture thereof.

[0034] The quaternary ammonium salt surfactant of general formula (1c) may be used alone or in combination of two or more. When two or more types are used in combination, the mixing ratio (mass ratio) is not limited.

[0035] The quaternary ammonium salt surfactant of component (b) may be one selected from the quaternary ammonium salt surfactants (1a) to (1c), or two or more may be blended or contained independently or in admixture. When two or more types are used in admixture, there are no limitations on the blending ratio (mass ratio). When used in admixture, each quaternary ammonium salt surfactant may be one type, or two or more types may be mixed. From the viewpoint of improving bleaching and cleaning performance, it is preferable to use one or two or more selected from the quaternary ammonium salt surfactants (1a).

[0036] The bleach detergent composition of the present invention is a composition containing a quaternary ammonium salt surfactant as component (b). The amount of the quaternary ammonium salt surfactant is the amount in terms of active ingredient at the time of production of the composition, which corresponds to the content in the composition. From the viewpoint of improving bleaching performance, the content of the quaternary ammonium salt surfactant as component (b) is 0.1% by mass or more, preferably 0.5% by mass or more, more preferably 1% by mass or more, and even more preferably 2% by mass or more, of the total amount of the bleach detergent composition. From the same viewpoint, the content is 10% by mass or less, preferably 7.5% by mass or less, and more preferably 5% by mass or less.

[0037] The bleach detergent composition of the present invention may contain a quaternary ammonium salt surfactant other than component (b) within a range that does not impair the effects of the present invention. The content of the quaternary ammonium salt surfactant other than component (b) in the total quaternary ammonium salt surfactants is preferably 10% by mass or less, more preferably 1% by mass or less, and is preferably substantially 0% by mass.

[0038] Next, the aromatic sulfonic acid or salt thereof of component (c) will be described. Examples of aromatic sulfonic acids or salts thereof of component (c) include aromatic sulfonic acids or salts thereof such as benzene derivative sulfonic acids, naphthalene derivative sulfonic acids, biphenyl derivative sulfonic acids, and pyridine derivative sulfonic acids. In the present invention, the term "derivative" refers to a compound in which one or more hydrogen atoms bonded to an aromatic hydrocarbon group such as the benzene ring are substituted with a hydrocarbon group having 1 to 3 carbon atoms. From the viewpoints of improving bleaching and cleaning performance and easy availability, benzene derivative sulfonic acids or salts thereof are preferred. Among these, benzene derivative sulfonic acids or salts thereof represented by the general formula (2) [In the formula, n is an integer of 0 to 4. ５ represents an alkyl or alkenyl group having 1 to 3 carbon atoms. When n is 2 or more, R ５ may be the same or different, and M represents a hydrogen atom or a counter cation.] is preferred.

[0039] n is an integer of 0 or more and 4 or less, and is preferably 0, 1 or 2 from the viewpoint of improving bleaching and cleaning performance.

[0040] R ５ represents an alkyl group or alkenyl group having 1 to 3 carbon atoms. Specific examples include a methyl group, an ethyl group, a propyl group, a 1-methylethyl group, a vinyl group, and a 1-propenyl group. From the viewpoint of improving bleaching and cleaning performance, a methyl group or a vinyl group is preferred.

[0041] M represents a hydrogen atom or a counter cation. When M is a counter anion, it is sometimes called an aromatic sulfonate. Examples of the counter cation of the aromatic sulfonate include monovalent inorganic cations such as lithium ion, sodium ion, and potassium ion; divalent inorganic cations such as magnesium ion and calcium ion; trivalent inorganic cations such as aluminum; and organic cations such as mono-, di-, tri-, or tetra(alkyl having 1 to 4 carbon atoms)ammonium ion and mono-, di-, tri-, or tetra(aryl having 6 to 12 carbon atoms)ammonium ion.

[0042] From the viewpoint of improving bleaching and cleaning performance, inorganic cations are preferred, monovalent inorganic cations are more preferred, and sodium ions are even more preferred. Aromatic sulfonates having one or more of these counter cations may be blended or contained independently or in combination. When mixed, there is no particular limitation on the content ratio.

[0043] Furthermore, an aromatic sulfonic acid in which M is a hydrogen atom may be mixed with the above-mentioned aromatic sulfonate salt and used in combination. When mixed, the ratio of the contents is not particularly limited.

[0044] From the viewpoint of improving bleaching and cleaning performance, the aromatic sulfonic acid or salt thereof of component (c) is preferably one or more selected from p-toluenesulfonic acid or its sodium salt, and m-xylene-4-sulfonic acid or its sodium salt.

[0045] The bleach detergent composition of the present invention is a composition containing (c) an aromatic sulfonic acid or a salt thereof. The amount of aromatic sulfonic acid or a salt thereof is the amount in terms of active ingredient at the time of production of the composition, which corresponds to the content in the composition. From the viewpoint of improving bleaching performance, the content of aromatic sulfonic acid or a salt thereof as component (c) is preferably 0.1 mass% or more, more preferably 0.3 mass% or more, even more preferably 0.5 mass% or more, and even more preferably 0.8 mass% or more, based on the total amount of the bleach detergent composition. From the same viewpoint, the content of component (c) is preferably 10 mass% or less, more preferably 8 mass% or less, and even more preferably 6 mass% or less. Note that the content of component (c) in this application means the content in terms of aromatic sulfonic acid.

[0046] From the viewpoints of improving the viscosity immediately after preparation, the storage stability of the viscosity of component (a) and the bleaching detergent composition of the present invention, and bleaching cleaning performance, the molar ratio of the content of component (c) to the content of component (b), (c) / (b), is preferably 0.35 or more, more preferably 0.45 or more, even more preferably 0.5 or more, still more preferably 0.55 or more, and still more preferably 0.65 or more. From the same viewpoints, it is preferably 5 or less, more preferably 4.5 or less, even more preferably 4 or less, still more preferably 3.5 or less, and still more preferably 2.9 or less.

[0047] Next, the alkaline agent of component (d) will be described. Examples of alkaline agents include inorganic alkaline agents such as sodium hydroxide, sodium silicate, sodium bicarbonate, sodium carbonate, potassium hydroxide, potassium bicarbonate, and potassium carbonate, and organic alkaline agents such as ammonium hydroxide, monoethanolamine, diethanolamine, triethanolamine, and trishydroxymethylaminomethane. Inorganic alkaline agents are preferred in terms of availability. From the viewpoint of improving the storage stability of the alkaline agent in the bleach detergent and the storage stability of component (a), one or more selected from sodium hydroxide, sodium silicate, and potassium hydroxide are more preferred, and sodium hydroxide is even more preferred from the viewpoint of economy. These alkaline agents are preferably used as aqueous solutions in terms of convenience in production.

[0048] The bleach detergent composition of the present invention is a composition containing an alkaline agent (component (d)). The amount of the alkaline agent is the amount of the active ingredient at the time of production of the composition, which corresponds to the content in the composition. The content of the alkaline agent (component (d)) is related to the amount of hydroxide ions, i.e., free alkali, present in the bleach detergent composition of the present invention, and corresponds to the amount required for the pH of a 10% by weight aqueous solution of the bleach detergent composition at 25°C to satisfy the range described below. That is, from the viewpoint of improving the storage stability of viscosity and bleaching performance described below, the content of the alkaline agent (component (d)) relative to the bleach detergent composition is preferably 0.2% by weight or more, more preferably 0.4% by weight or more, even more preferably 0.6% by weight or more, and even more preferably 0.9% by weight or more. From the same viewpoint, the content is preferably 6.0% by weight or less, more preferably 5.0% by weight or less, and even more preferably 4.0% by weight or more. The content of component (d) in the bleaching detergent composition of the present invention is determined by measuring the free alkali (neutralization titration method, converted into sodium hydroxide) according to the standard for sodium hypochlorite for water supply (JWWA K120).

[0049] The pH of a 10% by mass aqueous solution of the bleaching detergent composition of the present invention at 25°C is 11 or more, preferably 11.5 or more, and 14 or less, preferably 13 or less, from the viewpoint of improving bleaching and cleaning performance.

[0050] The viscosity of the bleaching detergent composition of the present invention at 25°C is 1,000 mPa·s or more, preferably 1,200 mPa·s or more, more preferably 3,000 mPa·s or more, even more preferably 5,000 mPa·s or more, and even more preferably 7,000 mPa·s or more, from the same viewpoint, 100,000 mPa·s or less, preferably 80,000 mPa·s or less, more preferably 50,000 mPa·s or less, and even more preferably 30,000 mPa·s or less. Furthermore, from the viewpoint of achieving both bleaching detergent performance and ease of handling, a viscosity of 1,000 mPa·s or more and 10,000 mPa·s or less is preferred. The viscosity of the present invention refers to a viscosity that is not limited by the elapsed time, such as immediately after production, during distribution, while in store inventory, or during home use. The viscosity may be at any time, and the elapsed time is not particularly limited.

[0051] The viscosity at 25°C can be measured using a Brookfield viscometer, specifically, by the method described in the Examples. The viscosity within the above range can be achieved by including a specific cationic surfactant (component (b)) and an aromatic sulfonic acid (component (c)) in specific amounts and ratios. Although the mechanism is unclear, it is presumed that the high viscosity is the result of a specific association state formed between the compounds due to hydrophobic interactions, electrostatic interactions, or the like. By having the above viscosity, the bleaching detergent composition can be applied in gel form or sprayed from a trigger container, even when the object to be cleaned of mold stains or bleached due to mold is a vertical or inclined surface. Furthermore, after application or spraying to a vertical or inclined surface, the bleaching detergent composition can be allowed to remain on the object for a period of time during which its effectiveness is maximized.

[0052] Another feature of the present invention is that the bleaching cleaning component and viscosity have excellent storage stability, allowing the effect to last for a long period of time. Conventionally, bleaching cleaning compositions containing hypochlorite have had the problem that, even if the viscosity is increased, the molecules that contribute to thickening are cleaved by the hypochlorite, causing a decrease in viscosity. In other words, the storage stability of the bleaching cleaning component and viscosity is low, resulting in poor lasting effect. The lasting effect of the present invention can be quantified, for example, by calculating the ratio of the bleaching cleaning performance after storage to the bleaching cleaning performance immediately after preparation of the bleaching cleaning composition as follows: Lasting effect (%) = (Bleaching cleaning performance after storage) / (Bleaching cleaning performance immediately after preparation) × 100. For example, when the mold removal rate described in

[0142] is used as an index of bleaching cleaning performance, the lasting effect can be calculated using the following formula: Lasting effect of mold removal rate (%) = (Mold removal rate after storage) / (Mold removal rate immediately after preparation) × 100

[0053] In order to adjust the viscosity of the bleaching detergent composition to the above-mentioned range, thickeners such as polyacrylates, cellulose derivatives, xanthan gum, guar gum, carboxymethyl cellulose, polyethylene glycol, and hydroxypropyl methyl cellulose may be blended or contained as other components. The bleaching detergent composition of the present invention may be substantially free of or contain no thickeners, i.e., may contain 0% by mass. When a thickener is blended or contained, from the viewpoint of storage stability of the bleaching detergent components and viscosity, the blending amount or content of the thickener is preferably 0.5% by mass or less, more preferably 0.3% by mass or less, and even more preferably 0.1% by mass or less. When the thickener is an ionic compound, the blending amount or content is expressed as a molecular weight equivalent of an acid or base type non-ionic compound.

[0054] The remainder of the bleach detergent composition of the present invention, other than components (a), (b), (c), (d), and other components, can be water. That is, the bleach detergent composition of the present invention is a composition containing water. The amount of water is the amount of water in terms of the active ingredient at the time of production of the composition, which corresponds to the content of water in the composition. From the viewpoints of the specific viscosity of the present invention and the solubility of the composition in water, the content of water in the composition is preferably 65% ​​by mass or more, more preferably 75% by mass or more, and even more preferably 80% by mass or more. From the same viewpoints, the content of water is preferably 98% by mass or less, more preferably 96% by mass or less, and even more preferably 94% by mass or less.

[0055] The bleaching detergent composition of the present invention may contain other additives such as foaming agents, foaming agents, penetrating agents, chelating agents, dispersants, binder resins, fragrances, antifungal agents, and antibacterial agents. That is, the bleaching detergent composition of the present invention is a composition containing these additives. The amount of the additives is the amount of active ingredients added at the time of production of the composition, which corresponds to the content in the composition. When these components are included, the content in the composition is preferably 10% by mass or less, more preferably 5% by mass or less, and even more preferably 3% by mass or less.

[0056] The bleaching detergent composition of the present application can be used as a mold remover for the purpose of cleaning mold stains and bleaching discoloration caused by mold. Examples of mold include black mold that tends to grow in wet areas, green mold that tends to grow on wood, and yellow mold that grows on glass, film, metal, etc. Specific examples include fungi of one or more microbial species selected from the fungi of the genera Cladosporium, Aspergillus, Candida, Penicillium, Alternaria, Phoma, Exophiala, and Aureobasidium.

[0057] Target objects for the mold remover include bathroom tile joints, walls and floors, washroom, kitchen, and toilet walls and floors, wallpaper, building materials, wood, flooring, decorative plywood for furniture and building materials, aluminum materials such as aluminum sashes and architectural aluminum panels, resin moldings, plumbing supplies, feed containers, air conditioning air duct components that constitute the air conditioning air ducts of air conditioners, steel products, house wrap, roofing materials, heat insulation materials, kitchenware, toilet supplies, indoor items, bedding, filters, toys, leather products such as synthetic leather and natural leather, etc. Target objects also include textile products such as fabrics and towels, resin films attached to walls, and laminates such as tarpaulins laminated on the resin films, etc.

[0058] It is particularly effective against black mold that grows on fixed objects such as tile joints, walls, floors, etc. in bathrooms, and walls and floors in washrooms, kitchens, toilets, etc. Furthermore, it is effective against black mold on hydrophobic resin parts such as polymer films such as polyvinyl chloride, olefin-based elastomers, polyurethane, and polyester, and silicone resin-based caulking parts.

[0059] Next, a method for bleaching and cleaning mold using the bleach detergent composition of the present application will be described. The types of mold and the target objects in the method for bleaching and cleaning mold using the bleach detergent composition of the present application can include the types of mold and the target objects exemplified in the description of the mold remover above. That is, the types of mold include black mold, green mold, yellow mold, etc., and specifically, for example, mold of one or more microbial species selected from the fungi of the genera Cladosporium, Aspergillus, Candida, Penicillium, Alternaria, Phoma, Exophiala, and Aureobasidium. It is also effective against black mold that grows on fixed objects such as tile joints, walls, floors, etc. in bathrooms, and on walls and floors in washrooms, kitchens, toilets, etc. Furthermore, it is effective against black mold on hydrophobic resin parts such as polymer films such as polyvinyl chloride, olefin-based elastomers, polyurethane, and polyester, and silicone resin-based caulking parts.

[0060] The bleaching detergent composition of the present application is also effective for bleaching discoloration caused by microorganisms other than mold, such as pink discoloration caused by specific yeasts or bacteria. Examples of yeasts that cause pink discoloration include one or more yeasts selected from the genera Rhodotorula, Rhodosporidium, Sporobolomyces, and Sporidiobolus. Examples of bacteria that cause pink discoloration include one or more bacteria selected from the genera Methylobacterium, Brevundimonas, and Microbacterium.

[0061] The bleach detergent composition of the present application has a moderate viscosity. Therefore, the composition becomes gel-like, which is particularly effective when the fixed object is on a vertical or inclined surface. When the bleach detergent composition of the present application is brought into contact with mold on an object, a discharge container that can pinpoint-apply the gel-like contents to the object can be used. As the discharge container, a tube container is preferably used from the viewpoints of ease of handling and application, taking safety into consideration. When a tube container is used, the hole diameter (diameter) of the tube container, when it has a perfect circle, is preferably 0.4 mm or more, more preferably 0.7 mm or more, and even more preferably 1.0 mm or more, from the viewpoint of easily dispensing the required amount. Furthermore, from the viewpoint of preventing the discharge of an amount greater than necessary, it is preferably 5.0 mm or less, more preferably 4.0 mm or less, and even more preferably 3.0 mm or less. That is, the area of ​​the perfect circle discharge port is preferably 0.13 mm or less. ２ More preferably, 0.38 mm ２ More preferably, 0.79 mm ２ or more, preferably 19.6 mm ２ Less than or equal to 12.6 mm, more preferably ２ Less than 7.1 mm, more preferably ２ Furthermore, if the outlet of the tube container is not a perfect circle but has another shape, such as an ellipse, a star, or a square, the area of ​​the outlet may be within the preferred range of the area of ​​the above-mentioned perfect circle outlet.

[0062] The bleach detergent composition of the present application can be filled into a discharge container having the above-mentioned discharge outlet to form a bleach detergent article. As shown in Figure 1, the bleach detergent composition of the present application can be filled into a discharge container 1 having the above-mentioned hole diameter 2 to form a bleach detergent article. When forming a bleach detergent article, from the viewpoint of convenience, the length 4 from the bottom of the discharge container to the tip of the discharge outlet is 60 to 250 mm, the maximum width 5 of the discharge container is 20 to 70 mm, and the capacity is 60 to 500 cm ３This is preferable because the product can be made by filling 60 to 500 g of the composition into a dispensing container 1, allowing multiple uses from one container. Furthermore, the container preferably has a sealable lid 3, which can be sealed as shown in FIG. 2, in order to suppress changes in the performance and physical properties of the bleach detergent composition over time. The container is preferably made of one or more materials selected from high-density polyethylene (HDPE) and low-density polyethylene (LDPE), with high-density polyethylene being more preferred. The above materials may be used alone or in combination, and may be molded into a single layer or multiple layers.

[0063] In addition, the bleaching detergent composition of the present invention is applied to the object at a concentration of 0.5 to 3 mL / cm ２ By applying this product, it is possible to effectively clean mold stains and bleach discoloration caused by mold.

[0064] The bleaching detergent composition of the present invention can more effectively clean mold stains and bleach discoloration caused by mold by applying it to an object and leaving it to remain on the object for a certain period of time. From the viewpoint of improving the bleaching effect, the leaving time is preferably 5 minutes or more, more preferably 30 minutes or more, even more preferably 50 minutes or more, still more preferably 120 minutes or more, and even more preferably 720 minutes (half a day) or more.

[0065] The bleaching detergent composition of the present application can be applied to an object on which mold has grown, left to stand for a certain period of time to allow the bleaching detergent composition to remain on the object, and then the object to which the bleaching detergent composition has been applied can be brought into contact with water to perform cleaning such as removing mold stains. Examples of the contact method include washing with water, which may be immersion or running water.

[0066] The present invention relates to a composition comprising: (a) component: 0.1% by mass to 10% by mass of an alkali metal hypochlorite; and (b) component: 0.1% by mass to 10% by mass of a compound represented by the general formula (1), [R in the formula １ represents a linear or branched alkyl group having 8 to 22 carbon atoms. ２represents a linear or branched alkyl group having 1 to 12 carbon atoms, or an aralkyl group having 7 to 12 carbon atoms. ３ and R ４ X may be the same or different and represent a linear or branched alkyl group having 1 to 4 carbon atoms. － represents a counter anion.], component (c): an aromatic sulfonic acid or a salt thereof, component (d): an alkaline agent, and water, wherein the bleach detergent composition has a viscosity of from 1,000 mPa s to 100,000 mPa s at 25°C and a pH of from 11 to 14 in a 10% by mass aqueous solution at 25°C.

[0067] The bleach detergent composition may be any of the components (a) to (d), water, and their amounts and contents, as well as other components, their amounts and contents, viscosity, and pH. The same embodiments as those exemplified for the bleach detergent composition containing components (a) to (d) and water can also be applied. The same embodiments can also be applied to a method for bleaching mildew, a bleach detergent article in which the bleach detergent composition is filled in a dispensing container, and a method for using the same.

[0068] <Aspects of the present invention> Examples of aspects of the present invention are shown below. The details described in the bleach detergent composition and the method for bleaching mildew stains of the present invention can be applied to these aspects with necessary modifications. Furthermore, the description of each aspect can be applied to other aspects with necessary modifications.

[0069] <1> (a) component: 0.1% by mass or more and 10% by mass or less of an alkali metal hypochlorite salt, (b) component: 0.1% by mass or more and 10% by mass or less of a general formula (1) [R in the formula １ represents a linear or branched alkyl group having 8 to 22 carbon atoms. ２ represents a linear or branched alkyl group having 1 to 12 carbon atoms, or an aralkyl group having 7 to 12 carbon atoms. ３ and R ４and (c) an aromatic sulfonic acid or a salt thereof; and (d) an alkaline agent; and water, wherein the viscosity at 25°C is from 1,000 mPa·s to 100,000 mPa·s, and the pH of a 10% by mass aqueous solution at 25°C is from 11 to 14.

[0070] <2> The bleaching detergent composition according to <1>, wherein the alkali metal of the alkali metal salt of hypochlorous acid (a) is selected from lithium, sodium, and potassium.

[0071] <3> The bleaching detergent composition according to <2>, wherein the alkali metal in the alkali metal salt of hypochlorous acid of the component (a) is sodium.

[0072] <4> The bleach detergent composition according to any one of <1> to <3>, wherein the content of the component (a) in the bleach detergent composition is, for example, 0.1% by mass, preferably 0.5% by mass or more, more preferably 1% by mass or more, even more preferably 1.5% by mass or more, and for example, 10% by mass or less, preferably 7.5% by mass or less, more preferably 5% by mass or less, even more preferably 3% by mass or less.

[0073] <5> The bleaching detergent composition according to any one of <1> to <4>, wherein the component (b) is one or more quaternary ammonium salt surfactants selected from quaternary ammonium salt surfactants represented by the following general formulas (1a) to (1c): [R in the formula １ａ represents a linear or branched alkyl or alkenyl group having 14 to 22 carbon atoms. ２ａ , R ３ａ and R ４ａ X may be the same or different and represent a linear or branched alkyl group having 1 to 4 carbon atoms. ａ － indicates the counter anion.] [R in the formula １ｂ and R ２ｂR may be the same or different and represent a linear or branched alkyl or alkenyl group having from 8 to 12 carbon atoms. ３ｂ and R ４ｂ X may be the same or different and represent a linear or branched alkyl group having 1 to 4 carbon atoms. ｂ － indicates the counter anion.] [R in the formula １ｃ represents a linear or branched alkyl or alkenyl group having 8 to 18 carbon atoms. ２ｃ represents an aralkyl group having 7 to 12 carbon atoms. ３ｃ and R ４ｃ X may be the same or different and represent a linear or branched alkyl group having 1 to 4 carbon atoms. ｃ － indicates the counter anion.]

[0074] <6> R １ａ is a linear alkyl group having 14 to 22 carbon atoms.

[0075] <7> R １ａ is a myristyl group (C14), a pentadecyl group (C15), a cetyl group (C16), a heptadecyl group (C17), a stearyl group (C18), a nonadecyl group (C19), an arachidyl group (C20), a heneicosanyl group (C21), or a behenyl group (C22).

[0076] <8> R ２ａ , R ３ａ , and R ４ａ and are the same or different and are linear or branched alkyl groups having from 1 to 4 carbon atoms.

[0077] <9> R ２ａ , R ３ａ , and R ４ａ are the same or different and are selected from a methyl group, an ethyl group, a propyl group, a 1-methylethyl group, a butyl group, a 1-methylpropyl group, a 2-methylpropyl group, and a 1,1-dimethylethyl group.

[0078] <10> X ａ－ is selected from an inorganic anion such as a fluoride ion, a chloride ion, a bromide ion, an iodide ion, or a hydroxide ion, a methyl sulfate ion, an ethyl sulfate ion, an acetate ion, or an acetylacetonate ion.

[0079] <11> The compound of general formula (1a) is one or more compounds selected from myristyltrimethylammonium salt, cetyltrimethylammonium salt, and stearyltrimethylammonium salt, and the counter anion X that forms these salts ａ － <11> The bleaching detergent composition according to any one of <5> to <10>, wherein is a halide ion such as a chloride ion or a bromide ion, or an ethyl sulfate ion.

[0080] <12> The bleach detergent composition according to any one of <5> to <11>, wherein the quaternary ammonium salt surfactant of general formula (1a) may be used alone or in combination of two or more thereof.

[0081] <13> The bleaching detergent composition according to any one of <5> to <12>, wherein the content of the cetyltrimethylammonium salt and the stearyltrimethylammonium salt in the quaternary ammonium salt surfactant of general formula (1a) is preferably 50% by mass or more, more preferably 65% ​​by mass or more, even more preferably 80% by mass or more, and still more preferably 100% by mass.

[0082] <14> The bleaching detergent composition according to any one of <5> to <13>, wherein the general formula (1a) is a mixture of a cetyltrimethylammonium salt and a stearyltrimethylammonium salt.

[0083] <15> R １ｂ and R ２ｂ and are the same or different linear alkyl groups having from 8 to 12 carbon atoms.

[0084] <16> R １ｂ and R ２ｂis selected from an octyl group (C8), a nonyl group (C9), a decyl group (C10), an undecyl group (C11), and a lauryl group (C12).

[0085] <17> R ３ｂ and R ４ｂ is selected from a methyl group, an ethyl group, a propyl group, a 1-methylethyl group, a butyl group, a 1-methylpropyl group, a 2-methylpropyl group, and a 1,1-dimethylethyl group.

[0086] <18> X ｂ － is selected from inorganic anions such as fluoride ion, chloride ion, bromide ion, iodide ion, and hydroxide ion, and organic anions such as methyl sulfate ion, ethyl sulfate ion, acetate ion, and acetylacetonate ion.

[0087] <19> The bleaching detergent composition according to any one of <5> to <18>, wherein the general formula (1b) is at least one selected from the group consisting of N,N-dioctyl-N,N-dimethylammonium salt, N,N-didecyl-N,N-dimethylammonium salt, and N,N-didecyl-N-ethyl-N-methylammonium salt.

[0088] <20> The bleach detergent composition according to any one of <5> to <19>, wherein the quaternary ammonium salt surfactant of general formula (1b) may be used alone or in combination of two or more thereof.

[0089] <21> R １ｃ <21> The bleaching detergent composition according to any one of <5> to <20>, wherein is a linear alkyl group having from 8 to 18 carbon atoms.

[0090] <22> R １ｃis selected from octyl (C8), nonyl (C9), decyl (C10), undecyl (C11), lauryl (C12), tridecyl (C13), myristyl (C14), pentadecyl (C15), cetyl (C16), heptadecyl (C17), stearyl (C18), nonadecyl (C19), arachidyl (C20), heneicosanyl (C21), and behenyl (C22).

[0091] <23> R ２ｃ <23> The bleaching detergent composition according to any one of <5> to <22>, wherein is an aralkyl group having 7 to 12 carbon atoms.

[0092] <24> R ２ｃ is selected from a benzyl group, a (2-methylphenyl)methyl group, a (4-methylphenyl)methyl group, a (1-naphthyl)methyl group, a (2-naphthyl)methyl group, a phenylethyl group, a (2-methylphenyl)ethyl group, a (4-methylphenyl)ethyl group, a (1-naphthyl)ethyl group, and a (2-naphthyl)ethyl group.

[0093] <25> R ３ｃ and R ４ｃ is selected from a methyl group, an ethyl group, a propyl group, a 1-methylethyl group, a butyl group, a 1-methylpropyl group, a 2-methylpropyl group, and a 1,1-dimethylethyl group.

[0094] <26> X ｃ － is selected from inorganic anions such as fluoride ion, chloride ion, bromide ion, iodide ion, and hydroxide ion, and organic anions such as acetate ion and acetylacetonate ion.

[0095] <27> The bleaching detergent composition according to any one of <5> to <26>, wherein the general formula (1c) is an alkyldimethylbenzylammonium salt, and the alkyl group is at least one selected from an octyl group, a lauryl group, a myristyl group, a cetyl group, and a stearyl group.

[0096] <28> The bleach detergent composition according to any one of <5> to <27>, wherein the quaternary ammonium salt surfactant of general formula (1c) may be used alone or in combination of two or more thereof.

[0097] <29> The bleach detergent composition according to any one of <5> to <28>, wherein the component (b) may be one selected from the quaternary ammonium salt surfactants (1a) to (1c), or two or more selected from the quaternary ammonium salt surfactants (1a) to (1c) may be blended or contained independently or in combination.

[0098] <30> The bleach detergent composition according to any one of <1> to <29>, wherein the content of the quaternary ammonium salt surfactant as component (b) is preferably 0.5% by mass or more, more preferably 1% by mass or more, even more preferably 2% by mass or more, and from the same viewpoint, preferably 7.5% by mass or less, more preferably 5% by mass or less.

[0099] <31> The bleach detergent composition according to any one of <1> to <30>, wherein when the bleach detergent composition contains a quaternary ammonium salt surfactant other than component (b), the content of the quaternary ammonium salt surfactant other than component (b) in the total amount of quaternary ammonium salt surfactants is preferably 10% by mass or less, more preferably 1% by mass or less, and is preferably substantially 0% by mass.

[0100] <32> The bleach detergent composition according to any one of <1> to <31>, wherein the component (c) is selected from aromatic sulfonic acids such as benzene derivative sulfonic acids, naphthalene derivative sulfonic acids, biphenyl derivative sulfonic acids, and pyridine derivative sulfonic acids, or salts thereof.

[0101] <33> The component (c) is represented by the general formula (2) [In the formula, n is an integer of 0 to 4. ５represents an alkyl or alkenyl group having 1 to 3 carbon atoms. When n is 2 or more, R ５ may be the same or different. M represents a hydrogen atom or a counter cation.]. The bleaching detergent composition according to any one of <1> to <32>, wherein the benzene derivative sulfonic acid or a salt thereof is represented by the formula:

[0102] <34> The bleaching detergent composition according to <33>, wherein n is 0, 1 or 2.

[0103] <35> R ５ is selected from a methyl group, an ethyl group, a propyl group, a 1-methylethyl group, a vinyl group, and a 1-propenyl group.

[0104] <36> The bleach detergent composition according to any one of <33> to <35>, wherein M is selected from the group consisting of monovalent inorganic cations such as lithium ion, sodium ion, and potassium ion, divalent inorganic cations such as magnesium ion and calcium ion, trivalent inorganic cations such as aluminum, and organic cations such as mono-, di-, tri-, or tetra(alkyl having from 1 to 4 carbon atoms)ammonium ion and mono-, di-, tri-, or tetra(aryl having from 6 to 12 carbon atoms)ammonium ion.

[0105] <37> The bleaching detergent composition according to any one of <1> to <32>, wherein the component (c) is one or more selected from p-toluenesulfonic acid or a sodium salt thereof, and m-xylene-4-sulfonic acid or a sodium salt thereof.

[0106] <38> The bleach detergent composition according to any one of <1> to <37>, wherein the content of component (c) is, based on the total amount of the bleach detergent composition, preferably at least 0.1% by mass, more preferably at least 0.3% by mass, even more preferably at least 0.5% by mass, still more preferably at least 0.8% by mass, and preferably at most 10% by mass, more preferably at most 8% by mass, even more preferably at most 6% by mass.

[0107] <39> The bleach detergent composition according to any one of <1> to <38>, wherein the molar ratio of the content of the component (c) to the content of the component (b), (c) / (b), is preferably 0.35 or more, more preferably 0.45 or more, even more preferably 0.5 or more, still more preferably 0.55 or more, still more preferably 0.65 or more, and is preferably 5 or less, more preferably 4.5 or less, even more preferably 4 or less, still more preferably 3.5 or less, and still more preferably 2.9 or less.

[0108] <40> The bleach detergent composition according to any one of <1> to <39>, wherein the alkaline agent of component (d) is selected from inorganic alkaline agents such as sodium hydroxide, sodium silicate, sodium bicarbonate, sodium carbonate, potassium hydroxide, potassium bicarbonate, and potassium carbonate, and organic alkaline agents such as ammonium hydroxide, monoethanolamine, diethanolamine, triethanolamine, and trishydroxymethylaminomethane.

[0109] <41> The bleach detergent composition according to any one of <1> to <40>, wherein the content of the alkaline agent as component (d) is preferably 0.2% by mass or more, more preferably 0.4% by mass or more, even more preferably 0.6% by mass or more, still more preferably 0.9% by mass or more, and preferably 6.0% by mass or less, more preferably 5.0% by mass or less, and even more preferably 4.0% by mass or more.

[0110] <42> The bleach detergent composition according to any one of <1> to <41>, wherein the pH of a 10% by mass aqueous solution of the bleach detergent composition at 25°C is 11 or more, preferably 11.5 or more, and 14 or less, preferably 13 or less.

[0111] <43> The bleach detergent composition according to any one of <1> to <42>, wherein the viscosity of the bleach detergent composition at 25°C is preferably 1,200 mPa·s or more, more preferably 3,000 mPa·s or more, even more preferably 5,000 mPa·s or more, still more preferably 7,000 mPa·s or more, and preferably 80,000 mPa·s or less, more preferably 50,000 mPa·s or less, and still more preferably 30,000 mPa·s or less.

[0112] <44> The bleach detergent composition according to any one of <1> to <43>, wherein the water content of the bleach detergent composition is preferably 75% by mass or more, even more preferably 80% by mass or more, and preferably 98% by mass or less, more preferably 96% by mass or less, even more preferably 94% by mass or less.

[0113] <45> The bleach detergent composition according to any one of <1> to <44>, which may further contain additives such as a foaming agent, a foaming agent, a penetrating agent, a chelating agent, a dispersant, a binder resin, a fragrance, an antifungal agent, or an antibacterial agent.

[0114] <46> The bleach detergent composition according to any one of <1> to <45>, in which when other additives are contained, the content of such additives in the composition is preferably 10% by mass or less, more preferably 5% by mass or less, and even more preferably 3% by mass or less.

[0115] <47> The bleaching detergent composition according to any one of <1> to <46>, which is used as a mold remover.

[0116] <48> The bleaching detergent composition according to <47>, wherein the type of mold is selected from black mold that tends to grow in wet areas, green mold that tends to grow on wood, and yellow mold that grows on glass, film, metal, etc.

[0117] <49> The bleaching detergent composition according to <47>, wherein the type of mold is one or more microbial species selected from the group consisting of fungi of the genera Cladosporium, Aspergillus, Candida, Penicillium, Alternaria, Phoma, Exophiala, and Aureobasidium.

[0118] <50> The bleaching detergent composition according to any one of <47> to <49>, wherein the target object of the mold remover is black mold that has grown on fixed objects such as tile joints, walls, floors, etc. in a bathroom, or walls and floors of a washroom, kitchen, or toilet.

[0119] <51> The bleaching detergent composition according to any one of <47> to <50>, wherein the target of the mold remover is black mold on a hydrophobic resin part such as a polymer film of polyvinyl chloride, an olefin-based elastomer, polyurethane, or polyester, or a silicone resin-based caulking part.

[0120] <52> A method for bleaching and cleaning mold using the bleach detergent composition according to any one of <1> to <51>, in which the microbial species is one or more species selected from the group consisting of fungi of the genus Cladosporium, Aspergillus, Candida, Penicillium, Alternaria, Phoma, Exophiala, and Aureobasidium.

[0121] <53> A method for bleaching and cleaning mold using the bleach detergent composition according to any one of <1> to <51>, wherein the object is black mold that has grown on fixed objects such as tile joints, walls, floors, etc. in a bathroom, or walls and floors of a washroom, kitchen, or toilet.

[0122] <54> The method for bleaching and cleaning mold according to <52> or <53>, wherein the object is black mold on a hydrophobic resin part such as a polymer film of polyvinyl chloride, an olefin-based elastomer, polyurethane, or polyester, or a silicone resin-based caulking part.

[0123] <55> Apply the bleaching detergent composition to the object at a concentration of 0.5 to 3 mL / cm ２ <52> to <54>, the method for bleaching and cleaning mold according to any one of <52> to <54>, wherein by applying the method, cleaning of mold stains and bleaching of discoloration caused by mold are effectively performed.

[0124] <56> The method for bleaching and cleaning mold according to any one of <52> to <55>, in which the bleaching detergent composition is applied to an object and then left to stand for a certain period of time to allow the bleaching detergent composition to remain on the object, thereby cleaning the mold stains and bleaching discoloration caused by mold, wherein the leaving time is preferably 5 minutes or more, more preferably 30 minutes or more, even more preferably 50 minutes or more, still more preferably 120 minutes or more, and still more preferably 720 minutes (half a day) or more.

[0125] <57> A method for bleaching and cleaning pinkish discoloration caused by yeast or bacteria, using the bleaching detergent composition according to any one of <1> to <51>.

[0126] <58> The bleaching and washing method according to <57>, wherein the yeast causing the pinkish discoloration is one or more yeasts selected from the genera Rhodotorula, Rhodosporidium, Sporobolomyces, and Sporidiobolus.

[0127] <59> The bleaching and washing method according to <57>, wherein the bacteria causing the pinkish coloration are one or more bacteria selected from the genus Methylobacterium, the genus Brevundimonas, the genus Microbacterium, and the like.

[0128] <60> A bleaching detergent article, in which the bleaching detergent composition according to any one of <1> to <51> is filled in a discharge container having a discharge opening.

[0129] <61> The bleach detergent article according to <60>, wherein the discharge container is a tube container.

[0130] <62> The area of ​​the discharge port of the tube container is preferably 0.13 mm ２ More preferably, 0.38 mm ２ More preferably, 0.79 mm ２ or more, preferably 19.6 mm ２ Less than or equal to 12.6 mm, more preferably ２Less than 7.1 mm, more preferably ２ The bleaching detergent article according to <60> or <61>, which is:

[0131] <63> The bleach detergent article has a length from the bottom of the discharge container to the tip of the discharge outlet of 60 to 250 mm, a maximum width of the discharge container of 20 to 70 mm, and a capacity of 60 to 500 cm ３ The bleaching detergent article according to any one of <60> to <62>, wherein the composition is filled in an amount of 60 to 500 g into a dispensing container to produce a product, thereby enabling multiple uses from one container.

[0132] <64> (a) component: 0.1% by mass or more and 10% by mass or less of an alkali metal hypochlorite salt, (b) component: 0.1% by mass or more and 10% by mass or less of a general formula (1) [R in the formula １ represents a linear or branched alkyl group having 8 to 22 carbon atoms. ２ represents a linear or branched alkyl group having 1 to 12 carbon atoms, or an aralkyl group having 7 to 12 carbon atoms. ３ and R ４ X may be the same or different and represent a linear or branched alkyl group having 1 to 4 carbon atoms. － represents a counter anion.], component (c): an aromatic sulfonic acid or a salt thereof, component (d): an alkaline agent, and water, wherein the bleach detergent composition has a viscosity of 1,000 mPa·s or more and a pH of 11 or more and 14 or less at 25°C in a 10% by mass aqueous solution.

[0133] EXAMPLES The present invention will be described in detail below with reference to examples and comparative examples, but the present invention is not limited to the following descriptions.

[0134] The components used are as follows: (a) Component (a-1) Sodium hypochlorite: "Low-coating sodium hypochlorite" (sodium hypochlorite content 12.5% ​​by mass), manufactured by Nankai Chemical Industry Co., Ltd.

[0135] (b) Component (b-1) Myristyltrimethylammonium chloride: manufactured by Tokyo Chemical Industry Co., Ltd. (b-2) Cetyltrimethylammonium chloride: manufactured by Tokyo Chemical Industry Co., Ltd. (b-3) Stearyltrimethylammonium chloride: manufactured by Tokyo Chemical Industry Co., Ltd.

[0136] Component (c) (c-1) p-toluenesulfonic acid: PTS-70 manufactured by Meiyu Sangyo Co., Ltd. (c-2) m-xylene-4-sulfonic acid: SXA-60 manufactured by Itochu Chemical Frontier Co., Ltd. (c-3) sodium p-toluenesulfonate: SXA-60 manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. Component (d): sodium hydroxide Component (e): thickener acrylic acid / C10-C30 alkyl acrylic acid copolymer: Carbopol EDT2020 manufactured by Lubriol Corporation

[0137] The bleach detergent compositions shown in Table 1 were prepared using the above components, and the pH and viscosity immediately after preparation were measured. Furthermore, 200 g of the composition was filled into a tube container (5 mm diameter), sealed, and left at room temperature for one week. After opening the tube with the top facing downward, the composition was visually confirmed to be a gel-like liquid by confirming that it had not dripped due to gravity for one minute or more. The content of each component in Table 1 indicates the content (active component) of each component in 100 parts by mass of the bleach detergent composition, expressed as % by mass. <Preparation Example> Using Example 1 as an example, the preparation method is described below. A predetermined amount of sodium hydroxide (component (d)) was added to an amount of ion-exchanged water necessary to make the total bleach detergent composition 100% by mass, and dissolved. A predetermined amount of p-toluenesulfonic acid (component (c)) as a 70% by mass aqueous solution, and cetyltrimethylammonium chloride and stearyltrimethylammonium chloride (component (b)) were sequentially added to the resulting aqueous sodium hydroxide solution, and the mixture was stirred and dissolved until a highly viscous composition was uniformly obtained. The pH of the composition before adding sodium hypochlorite was confirmed in advance, and then a predetermined amount of sodium hypochlorite (component (a)) was added and thoroughly stirred to obtain a bleaching detergent composition.

[0138] <Appearance> Each bleach detergent composition was filled into the tube container and held upright, and the appearance of the composition, such as a gel-like liquid or a low-viscosity liquid, was visually evaluated by judging dripping when the composition was held upright. <pH Measurement Method> Each bleach detergent composition was prepared as a 10% by mass aqueous solution using ion-exchanged water, and the pH was measured at 25°C. The pH value at 25°C was measured using a pH meter (manufactured by DKK-TOA) one minute after immersing the electrode of the pH meter in the aqueous solution.

[0139] <Viscosity Measurement Method> The viscosity of each bleach detergent composition produced was measured using a Brookfield viscometer TVB-10M with a rotor M4 at 30 rpm for 1 minute at 25°C. For compositions with a high viscosity of 20,000 mPa·s or more that could not be measured under the above conditions, the rotation speed was changed to 12 rpm or 6 rpm, and the measured value was used. The measurement was carried out after maintaining the composition at 25°C for 30 minutes. For compositions in which bubbles were observed, the composition was left to stand overnight to defoam before measurement.

[0140] Compositions of Examples 1 to 7 and Comparative Examples 1 to 4 shown in Table 1 were produced in accordance with the above production examples. Visual inspection of the compositions of Examples 1 to 7 and Comparative Examples 3 and 4 using tube containers confirmed that all were gel-like liquids. On the other hand, the compositions of Comparative Examples 1 and 2 dripped as soon as the opening of the tube was tilted directly downward, indicating that they were low-viscosity liquids. As will be described later, the compositions of Comparative Examples 3 and 4 showed a decrease in viscosity after storage at 50°C for 20 days, which is an accelerated test condition equivalent to long-term storage at room temperature.

[0141] Using some of the bleach detergent compositions in Table 1, the mold removal rate immediately after production was measured as an index of bleach cleaning performance. Furthermore, the mold removal rate, viscosity, and residual rate of sodium hypochlorite (component (a)) were measured after storing the bleach detergent compositions at 50°C for 20 days. Furthermore, the storage stability of the gel liquid was confirmed by evaluating the dripping property when the composition filled in a tube container (diameter φ1 mm) was held directly downward as described above.

[0142] <Measurement of Mold Removal Rate> Test pieces were prepared by solidifying silicone caulking commonly used in households (manufactured by Konishi, product name: Bond Silicone Coke White, product number: #55778) at room temperature (25°C) and cutting it into approximately 1.5 cm squares. An environmental isolate of the genus Cladosporium, Cladosporium sp. PA-4, which is a filamentous fungus that prefers the living environment, was cultured for one month at 25°C using potato dextrose agar medium (prepared according to the instructions using Potato Dextrose Agar Reagent manufactured by Becton Dickinson Co.), and mold was allowed to grow on the entire surface of the silicone caulking. Test pieces with mold stains that had penetrated the surface and interior of the silicone caulking were collected and cut into approximately 5 mm squares to prepare evaluation samples. The bleach detergent composition was filled into a tube (1 mm diameter) and 100 μL of the composition was extruded onto the evaluation sample prepared by the above method. After leaving it for 60 minutes, it was washed with water and air-dried. The removal rate was calculated by image analysis before and after treatment. Image analysis was performed using the scanner function of a RICOH printer (MP C5504), capturing an image of the sample, measuring the gray value using Image J, and using the following calculation formula: Mold removal rate (%) = [(gray value after treatment) - (gray value before treatment)] / [(gray value of new silicone piece) - (gray value before treatment)] × 100. The mold removal rate after 20 days of storage of the bleach detergent composition in a sealed container at 50°C was also measured in the same manner. A higher value indicates better mold removal ability. The sustained effect of mold removal rate was calculated using the following formula: Sustained effect of mold removal rate (%) = (mold removal rate after storage) / (mold removal rate immediately after preparation) × 100

[0143] <Residual percentage of component (a) after storage at 50°C for 20 days> As an accelerated test aimed at predicting the remaining amount of the bleaching detergent component after long-term storage at room temperature, the bleaching detergent composition was stored at 50°C for 20 days, and the remaining available chlorine concentration was measured by the following method. The ratio of the remaining available chlorine concentration after storage to the initial available chlorine concentration was defined as the residual percentage of component (a). A larger value indicates better storage stability of the bleaching detergent component.

[0144] <Method for measuring available chlorine concentration> 0.3 g of the bleaching detergent composition was mixed with 100 mL of ion-exchanged water and stirred for about 10 minutes to completely dissolve. 0.2 g of potassium iodide (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), 20 mL of 10% sulfuric acid (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), and 5 drops of starch indicator (manufactured by Sigma-Aldrich Co., Ltd.) were added to the mixture and completely dissolved. The mixture was then titrated with 0.1 M sodium thiosulfate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) using a titration burette. The available chlorine concentration in the cleaning solution was calculated from the amount of sodium thiosulfate used in the titration.

[0145] The viscosity after storage at 50°C for 20 days was measured in accordance with the method for measuring the viscosity of the bleach detergent composition immediately after production.

[0146] The results of the measurements and evaluations are shown in Table 1. The content of component (d) (sodium hydroxide) in the table is a value measured using the free alkali measurement (neutralization titration method) of the sodium hypochlorite standard for water supply (JWWA K120) and converted into the amount of sodium hydroxide. The value in parentheses is the blending amount (mass%) of component (d).

[0147] As shown in Table 1, in the Examples, high mold removal rates were achieved by using bleaching cleaning compositions containing predetermined amounts of components (a), (b), (c), and (d) and water. The sustained mold removal rate after 20 days of storage at 50°C ranged from 52% (Example 7) to 81% (Example 6), demonstrating remarkable superiority. No significant decrease in viscosity was observed, and evaluation of dripping properties using tube containers confirmed that all compositions were gel-like liquids. Furthermore, 48% or more of the sodium hypochlorite in component (a) remained after 20 days of storage at 50°C.

[0148] As described above, the viscosities of Comparative Examples 1 and 2 immediately after production were less than 5 mPa·s. In Comparative Example 3, in which the alkaline agent (d) was not added and the pH of the 10% by mass aqueous solution immediately after production was 10, the mold removal rate and viscosity immediately after production were good values, but after 20 days of storage at 50°C, no component (a) remained, and the mold removal ability was 0%. The same tendency as in Comparative Example 3 was observed in Comparative Example 4, in which components (b) and (c) were not added but a polymeric thickener was added instead. Furthermore, the viscosity of Comparative Examples 3 and 4 dramatically decreased after storage, and in an evaluation of dripping properties using a tube container, the liquid dripped when the tube opening was tilted directly downward, indicating that the liquid was a low-viscosity liquid.

[0149] Table 2 shows the pH and viscosity immediately after production of the compositions produced according to the above Production Examples.

[0150] Table 2 shows the pH and viscosity immediately after production of the compositions produced according to the above Production Examples. Visual inspection of each composition using a tube container confirmed that all were gel-like liquids. These compositions also achieved a high mold removal rate, stable viscosity, component (a) residual rate, and sustained mold removal rate.

[0151] 1 Discharge container, 2 Discharge outlet, 3 Sealing lid, 4 Length from the bottom of the discharge container to the tip of the discharge outlet, 5 Maximum width of the discharge container

Claims

1. (a) component: 0.1% by mass or more and 10% by mass or less of an alkali metal hypochlorite salt, (b) component: 0.1% by mass or more and 10% by mass or less of a general formula (1) [R in the formula １ represents a linear or branched alkyl group having 8 to 22 carbon atoms. ２ represents a linear or branched alkyl group having 1 to 12 carbon atoms, or an aralkyl group having 7 to 12 carbon atoms. ３ and R ４ X may be the same or different and represent a linear or branched alkyl group having 1 to 4 carbon atoms. － represents a counter anion.], component (c): an aromatic sulfonic acid or a salt thereof, component (d): an alkaline agent, and water, wherein the bleach detergent composition has a viscosity of from 1,000 mPa·s to 100,000 mPa·s at 25°C and a pH of from 11 to 14 in a 10% by mass aqueous solution at 25°C.

2. The bleaching detergent composition according to claim 1, wherein the quaternary ammonium salt surfactant of general formula (1) is one or more quaternary ammonium salt surfactants selected from the quaternary ammonium salt surfactants of general formulas (1a) to (1c). [R in the formula １ａ represents a linear or branched alkyl group having 14 to 22 carbon atoms. ２ａ , R ３ａ and R ４ａ X may be the same or different and represent a linear or branched alkyl group having 1 to 4 carbon atoms. ａ － indicates the counter anion.] [R in the formula １ｂ and R ２ｂ R may be the same or different and represent a linear or branched alkyl group having from 8 to 12 carbon atoms. ３ｂ and R ４ｂ X may be the same or different and represent a linear or branched alkyl group having 1 to 4 carbon atoms. ｂ － indicates the counter anion.] [R in the formula １ｃ represents a linear or branched alkyl group having 8 to 18 carbon atoms. ２ｃ represents an aralkyl group having 7 to 12 carbon atoms. ３ｃ and R ４ｃ X may be the same or different and represent a linear or branched alkyl group having 1 to 4 carbon atoms. ｃ － indicates the counter anion.] 3. A bleaching detergent composition according to claim 2, wherein component (b) is one or more quaternary ammonium salt surfactants selected from quaternary ammonium salt surfactants of general formula (1a).

4. (b) Component is R １ａ The bleach detergent composition according to claim 2, wherein the surfactant is one or two quaternary ammonium salt surfactants selected from quaternary ammonium salt surfactants of general formula (1a), wherein 5. (b) As component, R １ａ 3. The bleach detergent composition according to claim 2, wherein a quaternary ammonium salt surfactant of general formula (1a) is used in combination with the surfactant, wherein R is a linear or branched alkyl group having 16 or 18 carbon atoms.

6. A bleaching detergent composition according to any one of claims 1 to 5, which uses a combination of cetyltrimethylammonium salt and stearyltrimethylammonium salt as component (b).

7. A bleaching detergent composition according to any one of claims 1 to 6, wherein component (c) is a benzene derivative sulfonic acid or a salt thereof.

8. A benzene derivative sulfonic acid or its salt represented by the general formula (2) [In the formula, R ５ represents an alkyl or alkenyl group having 1 to 3 carbon atoms; n is an integer of 0 to 4, and when n is 2 or more, R ５ and may be the same or different; M represents a hydrogen atom or a counter cation; and the benzenesulfonic acid or salt thereof is of the formula:

9. A bleaching cleaning agent composition described in any one of claims 1 to 8, wherein the molar ratio (c) / (b) of the content of component (c) to the content of component (b) is 0.35 or more and 5 or less.

10. A bleaching detergent composition described in any one of claims 1 to 9, wherein the content of component (d) in the bleaching detergent composition is 0.5 mass% or more and 5.0 mass% or less.

11. A bleaching detergent composition according to any one of claims 1 to 10, having a viscosity at 25°C of 3,000 mPa·s or more and 100,000 mPa·s or less.

12. A bleaching detergent composition according to any one of claims 1 to 11, which is used as a mold remover.

13. A method for bleaching and cleaning mold stains, comprising contacting the bleaching detergent composition according to any one of claims 1 to 12 with mold that has grown on a hydrophobic resin part.

14. A method for bleaching and cleaning mold stains, comprising contacting the bleaching detergent composition according to any one of claims 1 to 12 with mold and leaving it for 5 minutes or more.

15. (a) component: 0.1% by mass or more and 10% by mass or less of an alkali metal hypochlorite salt, (b) component: 0.1% by mass or more and 10% by mass or less of a compound represented by the general formula (1) [R in the formula １ represents a linear or branched alkyl group having 8 to 22 carbon atoms. ２ represents a linear or branched alkyl group having 1 to 12 carbon atoms, or an aralkyl group having 7 to 12 carbon atoms. ３ and R ４ X may be the same or different and represent a linear or branched alkyl group having 1 to 4 carbon atoms. － represents a counter anion.], component (c): an aromatic sulfonic acid or a salt thereof, component (d): an alkaline agent, and water, wherein the bleach detergent composition has a viscosity of from 1,000 mPa s to 100,000 mPa s at 25°C, and a pH of a 10% by mass aqueous solution at 25°C of from 11 to 14.

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