Liquid cleaning agents and cleaning fluids

Abstract

To provide a liquid detergent and a cleaning liquid that has high detergency and suppressed coloration when exposed to light.SOLUTION: Provided is a liquid detergent that contains component (A): a phenolic antibacterial agent, component (B): one or more selected from fluorescent whitening agent and ultraviolet absorber, and component (C): an inorganic alkaline agent. The liquid detergent preferably further contains at least one of component (D): a surfactant and component (E): an inorganic reducing agent.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to liquid cleaning agents and cleaning fluids. [Background technology]

[0002] There are two general types of detergents for textile products, namely powder detergents and liquid detergents, which are used to clean clothing, etc. Demand for liquid detergents is growing because there is no risk of residual detergent remaining and they can be applied to clothing, etc. In recent years, due to the growing trend toward cleanliness, liquid detergents are required to not only remove dirt from the items being washed (cleaning power), but also to remove unpleasant odors that arise from the items being washed and to prevent the generation of unpleasant odors from the items being washed. Unpleasant odors from the items being washed are mainly caused by the proliferation of microorganisms that adhere to the fibers of the items being washed while they are being dried or stored. In order to prevent the growth of such microorganisms, liquid detergents containing antibacterial agents are known.

[0003] However, liquid cleaners containing phenolic antibacterial agents such as diclosan are not stable enough to light and may become discolored when exposed to light. Specifically, liquid cleaners containing phenolic antibacterial agents may become discolored and turn orange to red when exposed to fluorescent lights or sunlight. In view of this, as a liquid cleaning agent that is suppressed from discoloring even when exposed to light, for example, Patent Document 1 discloses a liquid cleaning agent that contains a phenol-based antibacterial agent, an inorganic reducing agent, and a surfactant. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] International Publication No. 2016 / 159368 Summary of the Invention [Problem to be solved by the invention]

[0005] However, there is still room for improvement in the light stability of liquid detergents containing phenolic antibacterial agents. In particular, alkaline agents are sometimes blended into liquid detergents to enhance their cleaning power, but when the pH of the liquid detergent increases due to the incorporation of alkaline agents, the liquid detergent becomes more susceptible to coloring when exposed to light. The present invention aims to provide a liquid detergent and cleaning solution that have high detergency and are suppressed from discoloring when exposed to light. [Means for solving the problem]

[0006] The present invention has the following aspects. [1] (A) component: a phenolic antibacterial agent, (B) component: one or more selected from fluorescent brightening agents and ultraviolet absorbers, (C) component: inorganic alkaline agent, A liquid cleaning agent comprising: [2] The liquid cleaning agent of [1], wherein the component (A) contains at least one of diclosan and triclosan. [3] Component (D): The liquid detergent according to [1] or [2] above, further comprising a surfactant. [4] Component (E): Any of the liquid cleaning agent according to [1] to [3] above, further containing an inorganic reducing agent. [5] The liquid cleaning agent according to any one of [1] to [4] above, wherein a mass ratio of the component (B) to the mass of the component (A) is 0.1 to 60. [6] The liquid detergent according to any one of [1] to [5] above, wherein at least a part of the component (C) is present in a solid state. [7] Component (F): Any of the liquid detergents according to [1] to [6] above, further comprising a structuring agent. [8] The liquid cleaning agent according to any one of [1] to [7] above, which has a pH of 8.5 or more at 25°C. [9] Any of the liquid cleaning agents according to [1] to [8] above, which is for use in textile products.

[10] A cleaning liquid that is an aqueous solution containing the liquid cleaning agent according to any one of [1] to [9], The content of the component (A) is 0.03 ppm by mass or more relative to the total mass of the cleaning solution, A cleaning solution having a content of the component (B) of 0.17 ppm by mass or more relative to the total mass of the cleaning solution. Effect of the Invention

[0007] According to the present invention, it is possible to provide a liquid cleaner and cleaning solution that have high detergency and are suppressed from discoloring when exposed to light. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0008] The present invention will be described in detail below. The liquid detergent of the present invention is a composition containing the following components (A), (B), and (C). The liquid detergent preferably further contains one or more of the following components (D), (E), and (F). The liquid detergent may further contain water. The liquid detergent may contain components (optional components) other than the components (A), (B), (C), (D), (E), (F), and water.

[0009] <Component (A)> Component (A) is a phenol-based antibacterial agent. Component (A) has an antibacterial effect and is a component that imparts antibacterial properties to textile products such as clothing after washing. Phenol-based means that the component (A) has a structure in which one or more hydrogen atoms of an aromatic hydrocarbon nucleus are substituted with a hydroxyl group. As the component (A), a compound having one or two benzene nuclei is preferred. Among them, as the component (A), a compound having a structure in which one or more hydrogen atoms of a benzene nucleus are substituted with a hydroxyl group is particularly preferred.

[0010] As the component (A), a phenol derivative or a diphenyl compound known as an antibacterial agent can be suitably used. Specific examples of the phenol derivative include 4-isopropyl-3-methylphenol and parachlorometaxylenol. Specific examples of the diphenyl compound include a 2-hydroxydiphenyl ether compound represented by the following formula (1) (hereinafter, also referred to as "compound (1)"). The component (A) may be used alone or in combination of two or more.

[0011] [ka]

[0012] In formula (1), Y is an oxygen atom or an alkylene group having 1 to 4 carbon atoms. V is a chlorine atom or a bromine atom. W is -SO2H, -NO2, or an alkyl group having 1 to 4 carbon atoms. z, g, and h each independently are an integer of 0 or 1 to 3. i is 0 or 1. j is 0 or 1. k is 0 or 1. The sum of h, i, and j is 4 or less. In addition, -(V)g means that g hydrogen atoms in the benzene ring are substituted with V. The same applies to -(V)h, -(W)i, -(OH)j, and -(OH)k.

[0013] The component (A) preferably contains the compound (1). The compound (1) is particularly prone to coloration when exposed to light, and is therefore preferred in that application of the present invention provides a significant effect. As compound (1), a compound in which Y is an oxygen atom or a methylene group, V is a chlorine atom or a bromine atom, j is 0, k is 0 or 1, z is 1, g is 0, 1 or 2, h is 0, 1 or 2, and i is 0 is more preferable. More preferred specific examples of compound (1) include monochlorohydroxydiphenyl ether (a compound in which Y is an oxygen atom, z is 1, V is a chlorine atom, one of g and h is 1 and the other is 0, i is 0, j is 0, and k is 0; common name: chlorophene), dichlorohydroxydiphenyl ether (a compound in which Y is an oxygen atom, z is 1, V is a chlorine atom, g is 1, h is 1, i is 0, j is 0, and k is 0; common name: diclosan), trichlorohydroxydiphenyl ether (a compound in which Y is an oxygen atom, z is 1, V is a chlorine atom, one of g and h is 1 and the other is 2, i is 0, j is 0, and k is 0; common name: triclosan), and benzylchlorophenol (a compound in which Y is a methylene group, z is 1, V is a chlorine atom, g is 0, h is 1, i is 0, j is 0, and k is 0).

[0014] Particularly preferred compounds (1) are 5-chloro-2-(2,4-dichlorophenoxy)phenol (trivial name: triclosan), 4,4'-dichloro-2-hydroxydiphenyl ether (trivial name: diclosan), and o-benzyl-p-chlorophenol (trivial name: chlorophene), respectively, according to the IUPAC nomenclature system; 5-chloro-2-(2,4-dichlorophenoxy)phenol (trivial name: triclosan) and 4,4'-dichloro-2-hydroxydiphenyl ether (trivial name: diclosan) are more preferred, and 4,4'-dichloro-2-hydroxydiphenyl ether (trivial name: diclosan) is the most preferred. The content of compound (1) is preferably 60 mass % or more, more preferably 80 mass % or more, and even more preferably 90 mass % or more, relative to the total mass of the component (A), and may be 100 mass %. The compound (1) may be used alone or in combination of two or more kinds.

[0015] The content of component (A) is preferably 0.01 to 2 mass% based on the total mass of the liquid detergent, more preferably 0.03 to 1 mass%, further preferably 0.05 to 0.5 mass%, particularly preferably 0.05 to 0.4 mass%, and most preferably 0.05 to 0.25 mass%. If the content of component (A) is equal to or greater than the lower limit, the antibacterial properties of the liquid detergent are more excellent. If the content of component (A) is equal to or less than the upper limit, coloring when exposed to light can be more suppressed. In addition, the cost is also excellent.

[0016] <(B) component> The component (B) is at least one selected from the group consisting of fluorescent brightening agents and ultraviolet absorbing agents. If the liquid detergent contains component (B), coloring of the liquid detergent when exposed to light can be suppressed even if the liquid detergent has a high pH. The reason for this is thought to be as follows. When a liquid detergent containing component (A) is exposed to light, a reaction occurs between the phenyl groups in component (A), causing the detergent to change color. If the liquid detergent contains component (B), the component (B) absorbs the light that hits the liquid detergent, suppressing the reaction between the phenyl groups, improving the stability against light and preventing coloring when exposed to light. The component (B) may be used alone or in combination of two or more.

[0017] Examples of the fluorescent whitening agent include stilbene, pyrazoline, coumarin, carboxylic acid, methine cyanine, dibenzothiophene-5-dioxide, azole, and derivatives of five- and six-membered heterocyclic compounds. Particularly preferred examples include biphenyl-type fluorescent whitening agents such as 4,4'-bis(2-sulfostyryl)biphenyl disodium salt and 4,4'-bis-(4-chloro-3-sulfostyryl)-biphenyl disodium salt; and stilbene-type fluorescent whitening agents such as 4,4'-bis((4-amino-6-morpholino-1,3,5-triazinyl-2)amino)stilbene-2,2'-disulfonate and 4,4'-bis((4-toluidino-6-morpholino-1,3,5-triazinyl-2)amino)stilbene-2,2'-disulfonate. These fluorescent whitening agents may be used alone or in combination of two or more.

[0018] As the fluorescent whitening agent, commercially available products can be used, for example, trade names "Whitex SA" and "Whitex SKC" manufactured by Sumitomo Chemical Co., Ltd.; trade names "Tinopal (registered trademark) AMS-GX", "Tinopal (registered trademark) DBS-X", "Tinopal (registered trademark) CBS-X", and "Tinopal (registered trademark) CBS-CL" manufactured by BASF; trade name "Lemonite CBUS-3B" manufactured by Khyati Chemicals; and trade name "Leucophor (registered trademark) DMA-X Conc" manufactured by ARCHROMA. Among these, Tinopal (registered trademark) CBS-X, Tinopal (registered trademark) CBS-CL, Tinopal (registered trademark) AMS-GX, and Leucophor (registered trademark) DMA-X Conc are preferred.

[0019] Examples of ultraviolet absorbents include 2H-benzotriazole, s-triazine, benzophenone, α-cyanoacrylate, oxanilide, benzoxazinone, benzoate, and α-alkylcinnamate. Particularly preferred are benzophenone-type ultraviolet absorbents such as 2-hydroxy-4-n-octyloxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sodium sulfonate, and 2,2'-dihydroxy-4,4'-dimethoxybenzophenone; 2-(5-methyl-2-hydroxyphenyl)benzotriazole, 2-[2-hydroxy-3,5-bis(α,α-dimethylbenzyl)phenyl]-2H-benzotriazole, and 2-(3-t-butyl-5-methyl-2-hydroxyphenyl)benzotriazole. benzotriazole-type ultraviolet absorbers such as 2-(2'-hydroxy-5'-t-octylphenyl)benzotriazole; and triazine-type ultraviolet absorbers such as 2,4-bis(2-hydroxy-4-butyloxyphenyl)-6-(2,4-bis-butyloxyphenyl)-1,3,5-triazine and 2-[4-[(2-hydroxy-3-(2'-ethyl)hexyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine. These ultraviolet absorbents may be used alone or in combination of two or more.

[0020] From the viewpoint of enhancing the cleaning power against yellow stains, a fluorescent whitening agent is preferred as the component (B). When an ultraviolet absorbent is used as the component (B), a benzophenone-type ultraviolet absorbent is preferred from the viewpoint of excellent solubility. In addition, benzotriazole-type ultraviolet absorbers and triazine-type ultraviolet absorbers have poor solubility. Therefore, when the liquid detergent contains at least one of a benzotriazole-type ultraviolet absorber and a triazine-type ultraviolet absorber as component (B), the liquid detergent may become cloudy. If the liquid detergent becomes cloudy, a light-shielding effect is obtained, which is preferable in terms of suppressing the reaction between phenyl groups.

[0021] The content of component (B) is preferably 0.05 to 5 mass% based on the total mass of the liquid detergent, more preferably 0.1 to 3 mass%, further preferably 0.1 to 1 mass%, and particularly preferably 0.1 to 0.5 mass%. When the content of component (B) is equal to or greater than the lower limit, the stability of the liquid detergent against light is improved, and coloring when exposed to light can be further suppressed. When the content of component (B) is equal to or less than the upper limit, the liquid detergent has excellent liquid stability and cost. The liquid stability means that the liquid detergent is less likely to solidify, separate, or separate when stored.

[0022] The mass ratio of component (B) to component (A), i.e., the mass ratio (B / A ratio) represented by component (B) / component (A), is preferably 0.1 to 60, more preferably 0.25 to 60, even more preferably 1 to 30, particularly preferably 1 to 10, and most preferably 2 to 10. When the B / A ratio is equal to or greater than the above lower limit, the stability of the liquid detergent against light is further improved, and coloring when exposed to light can be further suppressed. When the B / A ratio is equal to or less than the above upper limit, a sufficient antibacterial effect is easily obtained.

[0023] <(C) component> Component (C) is an inorganic alkaline agent. Component (C) is a component that imparts cleaning power, particularly cleaning power against sebum stains (sebum cleansing power), to the liquid detergent. An inorganic alkaline agent is a component that dissolves in whole or in part in water to exhibit basicity, and a 1% by mass aqueous solution has a pH of 8 or higher at 25° C. In the present invention, the inorganic alkaline agent does not include an inorganic reducing agent, which is component (E) described below. Specific examples of component (C) include carbonates such as sodium carbonate, sodium bicarbonate, double salts of sodium carbonate and sodium bicarbonate (sodium sesquicarbonate), potassium carbonate, potassium bicarbonate, etc.; silicates such as sodium metasilicate, layered sodium silicate, etc. Among these, sodium carbonate, potassium carbonate, sodium metasilicate, and layered sodium silicate are preferred from the viewpoint of further enhancing the cleaning power. The component (C) may be used alone or in combination of two or more types.

[0024] In the liquid detergent, the entirety of the (C) component may be dissolved, or at least a part of the (C) component may be present in a solid state. That is, some of the (C) component is dissolved in the liquid detergent, while some is not dissolved and exists in a solid state. The liquid detergent may contain an amount of the (C) component that exceeds the solubility. If at least a part of the (C) component is present in a solid state in the liquid detergent, the light-shielding effect of the (C) component in a solid state improves the stability of the liquid detergent against light, and coloring when exposed to light can be further suppressed. Hereinafter, in this specification, component (C) that is dissolved in the liquid detergent will be referred to as "component (C1)," and component (C) that exists in a solid state in the liquid detergent will be referred to as "component (C2)." The entire amount of component (C) may be blended directly into the liquid detergent, or an amount of component (C) not exceeding its solubility may be blended and dissolved in the liquid detergent, and the remaining amount may then be blended into the liquid detergent.

[0025] The surface of component (C2) may be modified. If the surface of component (C2) is modified, component (C2) does not dissolve, and the particle appearance (number of particles, particle size, etc.) can be maintained in a good condition, and the appearance stability of component (C2) is improved. In addition, component (C2) is less likely to precipitate, and dispersion stability is improved. Furthermore, the dissolution rate of component (C2) can be controlled. Methods for modifying the surface of component (C2) include, for example, a method in which an inorganic alkali agent is subjected to a baking treatment. In this specification, the inorganic alkaline agent whose surface has been modified is also referred to as a “modified alkaline agent.” In the present invention, sodium carbonate that partially contains sodium hydrogen carbonate and sodium sesquicarbonate is also considered to be a modified alkaline agent.

[0026] The surface of the (C2) component may be coated with a coating agent. That is, a coating layer may be formed on the surface of the (C2) component. If the surface of the (C2) component is coated with a coating agent, the (C2) component does not dissolve, and the particle appearance (number of particles, particle size, etc.) can be maintained in a good condition, and the appearance stability of the (C2) component is improved. In addition, the (C2) component is less likely to precipitate, and the dispersion stability is improved. Furthermore, the dissolution rate of the (C2) component can be controlled. However, when the liquid detergent of the present invention is used in a washing machine or automatic dispenser equipped with an automatic detergent dispenser, it is preferable that the surface of the (C2) component is not coated with a coating agent in order to prevent clogging of the dispenser pipe, syringe pump, etc. In this specification, an inorganic alkaline agent whose surface is coated with a coating agent is also referred to as a "coated alkaline agent".

[0027] The coating agent is preferably one that is difficult to dissolve in a liquid detergent and easily adheres to an inorganic alkaline agent, but is easily dissolved, swelled, disintegrated, or dispersed in a washing liquid obtained by diluting the liquid detergent with water, and is easily detached from the inorganic alkaline agent. Examples of the coating agent include hydroxypropylmethylcellulose, hydroxypropylcellulose, methylcellulose, hydroxyethylcellulose, polyacrylic acid or a salt thereof, acrylic acid-maleic acid copolymer or a salt thereof, acrylic acid-maleic anhydride copolymer or a salt thereof, fatty acid or a salt thereof, polyvinyl alcohol, pullulan, xanthan gum, starch, modified starch, sodium sulfate, calcium carbonate, aluminosilicate (zeolite, etc.), and titanium oxide. Among these, from the viewpoints of controlling the solubility in a liquid detergent and maintaining the particle appearance, hydroxypropylmethylcellulose, hydroxypropylcellulose, methylcellulose, hydroxyethylcellulose, polyacrylic acid or a salt thereof, acrylic acid-maleic acid copolymer or a salt thereof, acrylic acid-maleic anhydride copolymer or a salt thereof, fatty acid or a salt thereof, polyvinyl alcohol, pullulan, xanthan gum, starch, modified starch, sodium sulfate, and calcium carbonate are preferred, and hydroxypropylmethylcellulose, hydroxypropylcellulose, methylcellulose, polyacrylic acid or a salt thereof, acrylic acid-maleic acid copolymer or a salt thereof, acrylic acid-maleic anhydride copolymer or a salt thereof, and sodium sulfate are more preferred. The coating agent may be used alone or in combination of two or more kinds.

[0028] Coated alkali agents can be obtained by a variety of methods, including the fluidized bed granulation method, in which a coating agent is sprayed onto an inorganic alkali agent while fluidizing it, and then granulated and coated; the agitation granulation method, in which a coating agent is sprayed onto an inorganic alkali agent and then agitated with an agitator blade to granulate and coat it; the immersion agitation granulation method, in which an inorganic alkali agent is immersed in a coating agent and agitated, and the solvent is removed to obtain a granulated or coated material; the extrusion granulation method, in which a coating agent is added to an inorganic alkali agent, kneaded, and extruded with an extruder; the tumbling granulation method, in which a coating agent is sprayed onto the inorganic alkali agent while it is tumbling, and then granulated and coated; and the spray drying granulation method, in which a slurry containing an inorganic alkali agent and a coating agent is sprayed and dried. The coating agent may be used in the form of a solution by dissolving or dispersing it in any solvent.

[0029] Furthermore, a salt that sensitizes the coating agent (sensitizing salt) may be added to and mixed with the granules obtained by the above-mentioned method using any machine such as a mixer, a granulator, or a fluidized bed to produce a coated alkali agent. Here, the term "salt that sensitizes the coating agent" refers to a salt that increases the viscosity of the coating agent, gels the coating agent, or forms a film. Preferred examples of such sensitizing salts include polyvalent chlorides such as calcium chloride, magnesium chloride, and aluminum chloride; polyvalent sulfates such as magnesium sulfate and aluminum sulfate; polyvalent nitrates such as calcium nitrate and magnesium nitrate; polyvalent organic acid salts such as calcium acetate and calcium citrate; calcium oxide; calcium hydroxide; and sodium tetraborate. The sensitizing salt may be used alone or in combination of two or more kinds.

[0030] The ratio of the coating layer to 100 parts by mass of the (C2) component is preferably 1 to 60 parts by mass, more preferably 3 to 50 parts by mass, and even more preferably 5 to 40 parts by mass. When the ratio of the coating layer is equal to or greater than the lower limit, the effect of coating the surface of the (C2) component is sufficiently obtained. When the ratio of the coating layer is equal to or less than the upper limit, the coating layer quickly dissolves, swells, disintegrates, or disperses in the washing liquid, preventing the (C2) component from remaining undissolved. In addition, the amount of the (C2) component per unit weight can be increased.

[0031] The particle size of component (C) is preferably 10 to 2000 μm, more preferably 100 to 1500 μm, and even more preferably 200 to 1000 μm. When the particle size of component (C) is equal to or greater than the lower limit, the dissolution rate is easily controlled, and the particle appearance is excellent. When the particle size of component (C) is equal to or less than the upper limit, the dissolution rate in water is improved. On the other hand, when control of the dissolution rate of the (C) component is not required, the particle size of the (C) component is preferably 200 μm or less, more preferably 100 μm or less. In particular, the particle size of the (C) component not coated on the surface is preferably less than 200 μm, more preferably less than 100 μm. If the particle size of the (C) component is equal to or less than the above upper limit, the (C2) component dissolves quickly when the liquid detergent is diluted with water. In addition, the solid (C2) component is unlikely to remain in the inlet of the washing machine or on the clothes after washing. Therefore, if the particle size of the (C) component is 200 μm or less, it is suitable for use in washing machines and automatic dispensers equipped with an automatic detergent dispensing function.

[0032] The particle size of the coated alkaline agent is preferably 10 to 2000 μm, more preferably 100 to 1500 μm, and even more preferably 200 to 1000 μm. If the particle size of the coated alkaline agent is equal to or greater than the lower limit, the dissolution rate is easily controlled and the particle appearance is excellent. If the particle size of the coated alkaline agent is equal to or less than the upper limit, the dissolution rate in water is improved. On the other hand, when control of the dissolution rate of the coated alkaline agent is not required, the particle size of the coated alkaline agent is preferably 200 μm or less, and more preferably 100 μm or less.

[0033] The particle size of component (C) and the particle size of the coated alkali agent are volume-based median sizes measured by a laser diffraction scattering method using a particle size distribution measuring device (e.g., Beckman Coulter, Inc., product name "LS 13 320"). The particle size may be measured by a dry method in which component (C) or the coated alkali agent is measured as is, or by a wet method in which component (C) or the coated alkali agent is dispersed in a solvent and measured.

[0034] The content of component (C) is preferably 1 to 20 mass%, more preferably 2 to 15 mass%, and even more preferably 3 to 10 mass%, based on the total mass of the liquid detergent. When the content of component (C) is equal to or more than the lower limit, the cleaning power is further increased. When the content of component (C) is equal to or less than the upper limit, the fluidity of the liquid detergent can be well maintained. In addition, the liquid stability at low temperatures is also excellent. When at least a part of component (C) is present in a solid state in the liquid detergent, the proportion of component (C2) is preferably 10 to 80 mass%, more preferably 15 to 70 mass%, and even more preferably 20 to 60 mass%, based on the total mass of component (C). When the proportion of component (C2) to the total mass of component (C) is equal to or less than the above upper limit, the liquid detergent has good fluidity and the particle appearance is beautiful.

[0035] <(D) component> Component (D) is a surfactant. If the liquid detergent contains component (D), its cleaning power will be enhanced. The component (D) is not particularly limited as long as it is a surfactant used in conventional liquid detergents, and examples thereof include nonionic surfactants, non-soap anionic surfactants, cationic surfactants, amphoteric surfactants, and semi-polar surfactants. As the component (D), one type of surfactant may be used, or two or more types of surfactants may be combined. From the standpoint of further enhancing the cleaning power, it is preferable that the component (D) contains a nonionic surfactant and a non-soap anionic surfactant. As the component (D), a nonionic surfactant and a non-soap anionic surfactant may be used in combination with one or more of a cationic surfactant, an amphoteric surfactant, and a semi-polar surfactant.

[0036] Examples of nonionic surfactants include polyoxyalkylene-type nonionic surfactants, alkylphenols, alkylene oxide adducts of fatty acids having 8 to 22 carbon atoms or amines having 8 to 22 carbon atoms, polyoxyethylene polyoxypropylene block copolymers, fatty acid alkanolamides, polyhydric alcohol fatty acid esters or alkylene oxide adducts thereof, alkylene oxide adducts of hydrogenated castor oil, sugar fatty acid esters, N-alkyl polyhydroxy fatty acid amides, and alkyl glycosides. The nonionic surfactant may be used alone or in combination of two or more kinds. As the nonionic surfactant, polyoxyalkylene type nonionic surfactants are preferred, and among them, in particular, a compound represented by the following general formula (2) (hereinafter also referred to as "compound (2)") and a compound represented by the following general formula (3) (hereinafter also referred to as "compound (3)") are more preferred, with compound (2) being even more preferred.

[0037] R 11 -O-[(EO) s / (A 11 O) t ]-(EO) u -R 12 (2) (In general formula (2), R 11 R is a straight or branched chain hydrocarbon group having 8 to 22 carbon atoms. 12 is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkenyl group having 2 to 6 carbon atoms. EO is an oxyethylene group. s is a number from 3 to 25 indicating the average number of EO repeats. A 11 O represents at least one of PO (oxypropylene group) and BO (oxybutylene group). t represents A 11 is a number between 0 and 6 indicating the average number of repeats of O. u is a number between 0 and 20 indicating the average number of repeats of EO.

[0038] R 11 The hydrocarbon group has 8 to 22 carbon atoms, preferably 10 to 18 carbon atoms, and more preferably 12 to 18 carbon atoms. R 12 is preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and more preferably a hydrogen atom. When u is 0, s is preferably an integer of 4 to 20, more preferably an integer of 5 to 16, and even more preferably an integer of 6 to 10. t is preferably an integer of 0 to 4, more preferably an integer of 0 to 2, and even more preferably 0. When u is 1 or more, s is preferably 4 to 16, more preferably 6 to 12, and further preferably 8 to 10. t is preferably 1 to 4, and more preferably 2 or 3. u is preferably 4 to 16, more preferably 6 to 12, and further preferably 8 to 10. If t is 1 or greater, then [(EO) s / (A 11 O) tIn the above, the distribution (arrangement order) of EO and PO, EO and BO, or EO, ​​PO and BO is not particularly limited, and they may be arranged in a block form or random form.

[0039] R 13 -X-[(EO) p / (A 12 O) q ]-(EO) r -R 14 (3) (In general formula (3), R 13 is a hydrocarbon group having 7 to 21 carbon atoms. -X- is -COO- or -CONH-. R 14 is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkenyl group having 2 to 6 carbon atoms. EO is an oxyethylene group. p is a number from 3 to 25 indicating the average number of EO repeats. A 12 represents at least one of PO (oxypropylene group) and BO (oxybutylene group). 12 is a number between 0 and 6 indicating the average number of repeats of O. r is a number between 0 and 20 indicating the average number of repeats of EO.

[0040] R 13 The hydrocarbon group has 7 to 21 carbon atoms, preferably 9 to 19 carbon atoms, and more preferably 11 to 17 carbon atoms. As -X-, -COO- is preferable. R 14 is preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and more preferably an alkyl group having 1 to 2 carbon atoms. When r is 0, p is preferably an integer of 6 to 22, more preferably an integer of 9 to 20, and even more preferably an integer of 12 to 18. q is preferably an integer of 0 to 4, more preferably an integer of 0 to 2, and even more preferably 0. When r is 1 or more, p is preferably 4 to 16, more preferably 6 to 12, and further preferably 8 to 10. q is preferably 1 to 4, and more preferably 2 or 3. r is preferably 4 to 16, more preferably 6 to 12, and further preferably 8 to 10. If q is 1 or greater, then [(EO) p / (A 12 O) qIn the above, the distribution (arrangement order) of EO and PO, EO and BO, or EO, ​​PO and BO is not particularly limited, and they may be arranged in a block form or random form.

[0041] The content of the nonionic surfactant is preferably 5 to 60 mass % based on the total mass of the liquid detergent, more preferably 10 to 50 mass %, further preferably 10 to 45 mass %, and particularly preferably 15 to 40 mass %. If the content of the nonionic surfactant is equal to or more than the lower limit, the cleaning power is further increased. If the content of the nonionic surfactant is equal to or less than the upper limit, the liquid stability at low temperatures is improved.

[0042] Examples of non-soap anionic surfactants include carboxylic acid type anionic surfactants such as linear alkylbenzene sulfonic acid or its salt (LAS), α-olefin sulfonic acid or its salt (AOS), linear or branched alkyl sulfate ester or its salt (AS), polyoxyalkylene alkyl (alkenyl) ether sulfate ester or its salt (AES), alkanesulfonic acid having an alkyl group or its salt, α-sulfofatty acid ester or its salt, internal olefin sulfonic acid or its salt (IOS), alkyl ether carboxylic acid or its salt, polyoxyalkylene ether carboxylic acid or its salt, alkylamide ether carboxylic acid or its salt, alkenylamide ether carboxylic acid or its salt, and acylamino carboxylic acid or its salt; and phosphate ester type anionic surfactants such as alkyl phosphate ester or its salt, polyoxyalkylene alkyl phosphate ester or its salt, polyoxyalkylene alkylphenyl phosphate ester or its salt, and glycerin fatty acid ester monophosphate ester or its salt. Examples of salt forms of non-soap anionic surfactants include alkali metal salts (sodium salts, potassium salts, etc.), alkaline earth metal salts (magnesium salts, etc.), and alkanolamine salts (monoethanolamine salts, diethanolamine salts, etc.). The non-soap anionic surfactant may be used alone or in combination of two or more kinds. As the non-soap anionic surfactant, LAS, AOS, AS, AES, and IOS are preferred, and among them, LAS, AES, and IOS are more preferred from the viewpoint of further enhancing the cleaning power. The liquid detergent preferably contains at least AES, and more preferably contains both LAS and AES.

[0043] The polyoxyalkylene alkyl(alkenyl) ether sulfate or its salt (AES) is represented by the following general formula (4). R 15 -O-[(EO) m / (PO) n ]-SO3 - Ma + (4) (In general formula (4), R 15 is a linear or branched alkyl group having 8 to 20 carbon atoms or a linear or branched alkenyl group having 8 to 20 carbon atoms. EO is an oxyethylene group. PO is an oxypropylene group. m is a number of 0.1 or more representing the average number of repetitions of EO. n is a number of 0 to 6 representing the average number of repetitions of PO. [(EO) m / (PO) n ] indicates that there is no restriction on the order of EO and PO, + is the counter cation.)

[0044] An internal olefin sulfonic acid or a salt thereof (IOS) is a mixture of an alkene sulfonic acid represented by the following general formula (5) (hereinafter also referred to as "compound (5)") and a hydroxyalkane sulfonic acid represented by the following general formula (6) (hereinafter also referred to as "compound (6)") The internal olefin refers to an olefin in which the double bond is located inside the 2-position.

[0045] R 16 -CH=CH(CH2) x CH(SO3Mb)-R 17 (5) (In formula (5), R 16 is an alkyl group, and R 17is an alkyl group having 1 to 5 carbon atoms, and the total number of carbon atoms is 8 to 24. x is a number from 0 to 4, and Mb represents a counter ion.

[0046] The carbon number of the compound (5) is 8 to 24, preferably 10 to 20, more preferably 12 to 18, and even more preferably 14 to 18. When the carbon number is equal to or more than the lower limit, the lipophilicity of IOS is increased, and the function as a surfactant is enhanced. When the carbon number is equal to or less than the upper limit, the hydrophilicity of IOS is increased, and the function as a surfactant is enhanced.

[0047] R in Equation (5) 16 represents an alkyl group. 16 The number of carbon atoms is preferably 1 to 21, more preferably 3 to 17, and further preferably 7 to 15. R in Equation (5) 17 R represents an alkyl group having 1 to 5 carbon atoms. 17 The carbon number of is preferably 1 to 3. In the formula (5), x is an integer of 0 to 4, and preferably 0 to 2. When x is equal to or greater than the lower limit, the cleaning power is further increased. When x is equal to or less than the upper limit, the liquid stability is further increased. Examples of Mb in the formula (5) include sodium ion, potassium ion, magnesium ion, and ammonium ion.

[0048] R 18 -CH(OH)(CH2) y CH(SO3Mc)-R 19 (6) (In formula (6), R 18 is an alkyl group, and R 19 is an alkyl group having 1 to 5 carbon atoms, and the total number of carbon atoms is 8 to 24. y is a number from 0 to 4, and Mc represents a counter ion.

[0049] Compound (6) is a hydroxy form of compound (5). The carbon number of the compound (6) is 8 to 24, preferably 10 to 20, more preferably 12 to 18, and even more preferably 14 to 18. When the carbon number is equal to or more than the lower limit, the lipophilicity of IOS is increased, and the function as a surfactant is enhanced. When the carbon number is equal to or less than the upper limit, the hydrophilicity of IOS is increased, and the function as a surfactant is enhanced.

[0050] R in Equation (6) 18 represents an alkyl group. 18 The number of carbon atoms is preferably 2 to 22, more preferably 4 to 18, and further preferably 8 to 16. R in Equation (6) 19 R represents an alkyl group having 1 to 5 carbon atoms. 19 The carbon number of is preferably 1 to 3. In the formula (6), y is an integer of 0 to 4, and preferably 0 to 2. When y is equal to or greater than the lower limit, the cleaning power is further increased. When y is equal to or less than the upper limit, the liquid stability is further increased. Examples of Mc in the formula (6) include a sodium ion, a potassium ion, a magnesium ion, and an ammonium ion.

[0051] The mass ratio ((IO-2S) / (IO-1S) ratio) of IOS in which sulfonic acid groups are present at positions 2 to 4 ((IO-1S) component) to IOS in which sulfonic acid groups are present at positions 5 or higher is preferably 0.3 to 5, more preferably 1 to 3. When the (IO-2S) / (IO-1S) ratio is equal to or higher than the lower limit, the slipperiness of the object to be cleaned is further improved. When the (IO-2S) / (IO-1S) ratio is equal to or lower than the upper limit, the liquid stability is further improved. The (IO-1S) component is R in formula (5). 17 , R in Equation (6) 19 The (IO-2S) component is an IOS having 1 to 3 carbon atoms. 17 , R in Equation (6) 19 is an IOS having 4 or more carbon atoms.

[0052] IOS is obtained by sulfonating an internal olefin. The total number of carbon atoms in the internal olefin is 8 to 24, preferably 10 to 20, more preferably 12 to 18, and further preferably 14 to 18. Internal olefins can be obtained, for example, by isomerizing 1-olefins obtained by dehydrating 1-alcohols. When internal olefins are sulfonated, β-sultone is quantitatively produced, and a part of the β-sultone is converted to γ-sultone and olefin sulfonic acid, which are then converted to compound (5) and compound (6) in a neutralization hydrolysis step (e.g., J. Am. Oil Chem. Soc. 69, 39 (1992)). Here, the hydroxy group of the obtained compound (6) is located inside the alkane chain, and the double bond of the obtained compound (5) is located inside the olefin chain. The obtained product is mainly a mixture of these, and some of them may contain a trace amount of hydroxyalkanesulfonate having a hydroxy group at the end of the carbon chain or α-olefinsulfonate having a double bond at the end of the carbon chain. In this specification, these products and their mixtures are collectively referred to as IOS.

[0053] The mass ratio of compound (5) to the mass of compound (6) relative to 100 mass% of IOS, i.e., the mass ratio represented by compound (5) / compound (6) (compound (5) / compound (6) ratio) is preferably 1 / 99 to 50 / 50, more preferably 1 / 99 to 30 / 70, even more preferably 5 / 95 to 20 / 80, and particularly preferably 10 / 90 to 15 / 85. When the compound (5) / compound (6) ratio is equal to or greater than the lower limit, the liquid stability is further improved. When the compound (5) / compound (6) ratio is equal to or less than the upper limit, the cleaning power is further improved.

[0054] The content of the non-soap anionic surfactant is preferably 5 to 40% by mass, more preferably 10 to 40% by mass, further preferably 10 to 30% by mass, and particularly preferably 15 to 30% by mass, based on the total mass of the liquid detergent. If the content of the non-soap anionic surfactant is equal to or greater than the lower limit, the cleaning power is further increased. In addition, the anti-soap redeposition property is improved. If the content of the non-soap anionic surfactant is equal to or less than the upper limit, the fluidity of the liquid detergent is excellent and the liquid stability at low temperatures is improved.

[0055] The mass ratio of the nonionic surfactant to the mass of the non-soap anionic surfactant, i.e., the mass ratio expressed as nonionic surfactant / non-soap anionic surfactant (nonionic / anionic ratio), is preferably 0.1 to 3, more preferably 0.15 to 2, further preferably 0.2 to 1.5, and particularly preferably 0.25 to 1.3. When the nonionic / anionic ratio is within the above range, the liquid stability at low temperatures is improved. In addition, the liquid detergent is less likely to gel and can maintain its fluidity better. In addition, when a liquid detergent contains an enzyme, the enzyme stability may decrease if the liquid detergent contains a non-soap anionic surfactant as component (D). However, the enzyme stability can be maintained well if the nonionic / anionic ratio is within the above range.

[0056] Examples of the cationic surfactant include long-chain aliphatic amide alkyl tertiary amines or salts thereof, such as caprylic acid dimethylaminopropylamide, capric acid dimethylaminopropylamide, lauric acid dimethylaminopropylamide, myristic acid dimethylaminopropylamide, palmitic acid dimethylaminopropylamide, stearic acid dimethylaminopropylamide, behenic acid dimethylaminopropylamide, and oleic acid dimethylaminopropylamide; aliphatic ester alkyl tertiary amines or salts thereof, such as palmitate ester propyl dimethylamine and stearate ester propyl dimethylamine; palmitic acid diethanolaminopropylamide, stearic acid diethanolaminopropylamide; short-chain tetra (alkyl having 1 to 4 carbon atoms) ammonium salts, such as tetramethylammonium salt, tetraethylammonium salt, tetrapropylammonium salt, and tetrabutylammonium salt; octyltrimethylammonium salt, long-chain (C8-18 alkyl) tri-short-chain (C1 or C2 alkyl) ammonium salts such as ethyl ammonium salt, decyl trimethyl ammonium salt, dodecyl trimethyl ammonium salt, tetradecyl trimethyl ammonium salt, lauryl trimethyl ammonium salt, cetyl trimethyl ammonium salt, palmityl trimethyl ammonium salt, stearyl trimethyl ammonium salt, octyl dimethyl ethyl ammonium salt, decyl dimethyl ethyl ammonium salt, dodecyl dimethyl ethyl ammonium salt, tetradecyl dimethyl ethyl ammonium salt, lauryl dimethyl ethyl ammonium salt, cetyl dimethyl ethyl ammonium salt, stearyl dimethyl ethyl ammonium salt, octyl diethyl methyl ammonium salt, decyl diethyl methyl ammonium salt, dodecyl diethyl methyl ammonium salt, tetradecyl diethyl methyl ammonium salt, cetyl diethyl methyl ammonium salt, and stearyl diethyl methyl ammonium salt;Di-long chain (alkyl having 8 to 18 carbon atoms) di-alkyl ammonium salts such as dioctyl dimethyl ammonium salt, didecyl dimethyl ammonium salt, N,N-didecyl-N-methyl-poly(oxyethyl) ammonium salt, didodecyl dimethyl ammonium salt, ditetradecyl dimethyl ammonium salt, dicetyl dimethyl ammonium salt, distearyl dimethyl ammonium salt, dioctyl methyl ethyl ammonium salt, didecyl methyl ethyl ammonium salt, didodecyl methyl ethyl ammonium salt, ditetradecyl methyl ethyl ammonium salt, dicetyl methyl ethyl ammonium salt, and distearyl methyl ethyl ammonium salt. Examples of such ammonium salts include short chain (alkyl having 1 or 2 carbon atoms) ammonium salts; long chain (alkyl having 8 to 18 carbon atoms) di-short chain (alkyl having 1 or 2 carbon atoms) hydroxyalkyl (1 or 2 carbon atoms) ammonium salts such as stearyl dimethyl hydroxyethyl ammonium; di-short chain (alkyl having 1 or 2 carbon atoms) long chain (alkyl having 8 to 18 carbon atoms) ammonium salts having trialkoxysilyl alkyl groups (having 4 to 10 carbon atoms) such as [3(trimethoxysilyl)]propyl(dimethyl)octadecyl ammonium salts; amine nitrates; benzyl trimethyl ammonium salts; benzalkonium salts; and benzethonium salts. Examples of the salt form of the cationic surfactant include alkali metal salts (sodium salt, potassium salt, etc.), alkaline earth metal salts (magnesium salt, etc.), and alkanolamine salts (monoethanolamine salt, diethanolamine salt, etc.). The cationic surfactant may be used alone or in combination of two or more kinds.

[0057] The content of the cationic surfactant is preferably 0.1 to 5 mass %, more preferably 0.2 to 3 mass %, based on the total mass of the liquid detergent. If the content of the cationic surfactant is within the above range, it is possible to further improve the softening, antibacterial and deodorizing effects of clothing.

[0058] Examples of amphoteric surfactants include alkyl betaine type, alkyl amide betaine type, imidazoline type, alkyl amino sulfone type, alkyl amino carboxylic acid type, alkyl amide carboxylic acid type, amide amino acid type, and phosphoric acid type amphoteric surfactants. The amphoteric surfactant may be used alone or in combination of two or more kinds.

[0059] Examples of semi-polar surfactants include alkylamine oxides and alkylamidopropyldimethylamine oxides. The semi-polar surfactant may be used alone or in combination of two or more kinds.

[0060] The content of component (D) is preferably 15 to 80 mass% based on the total mass of the liquid detergent, more preferably 15 to 70 mass%, further preferably 20 to 60 mass%, and particularly preferably 40 to 55 mass%. If the content of component (D) is equal to or greater than the lower limit, the cleaning power is further increased. If the content of component (D) is equal to or less than the upper limit, the liquid detergent is less likely to gel and the fluidity can be better maintained.

[0061] <(E) component> Component (E) is an inorganic reducing agent. If the liquid detergent contains component (E), coloring of the liquid detergent when exposed to light can be further suppressed. The reason for this is thought to be as follows. As mentioned above, when a liquid detergent containing component (A) is exposed to light, a reaction occurs between the phenyl groups in component (A), causing the liquid to change color. However, this reaction is inhibited by component (E), and component (E) itself does not become colored even when oxidized. The reducing agent means an agent that has the function of reducing a substance and oxidizes itself. The inorganic reducing agent means a reducing agent that does not contain a carbon atom.

[0062] Examples of the component (E) include sulfites such as sodium sulfite and potassium sulfite, pyrosulfites such as sodium pyrosulfite and potassium pyrosulfite, and hydrogen sulfites such as sodium hydrogen sulfite and potassium hydrogen sulfite. Among these, from the viewpoint of excellent liquid stability, sodium sulfite and potassium sulfite are preferred, and sodium sulfite is more preferred. The component (E) may be used alone or in combination of two or more types.

[0063] The content of component (E) is preferably 0.001 to 3 mass%, more preferably 0.02 to 1 mass%, and even more preferably 0.05 to 0.5 mass% based on the total mass of the liquid detergent. When the content of component (E) is equal to or greater than the lower limit, the stability of the liquid detergent against light is improved, and coloring when exposed to light can be further suppressed. Coloring of the composition due to storage at high temperatures can also be suppressed. When the content of component (E) is equal to or less than the upper limit, the liquid stability at low temperatures is improved.

[0064] The total content of the (B) and (E) components is preferably 0.06 to 5 mass%, more preferably 0.1 to 2 mass%, and even more preferably 0.3 to 1 mass%, based on the total mass of the liquid detergent. When the total content of the (B) and (E) components is equal to or greater than the above lower limit, the stability of the liquid detergent against light is improved, and coloring when exposed to light can be further suppressed. When the total content of the (B) and (E) components is equal to or less than the above upper limit, the liquid detergent has excellent liquid stability and cost.

[0065] The mass ratio of component (B) to component (E), i.e., the mass ratio (B / E ratio) represented by component (B) / component (E), is preferably 0.1 to 150, more preferably 0.2 to 50, and even more preferably 0.4 to 20. When the B / E ratio is equal to or greater than the lower limit, the stability of the liquid detergent against light is improved and coloring upon exposure to light can be further suppressed. When the B / E ratio is equal to or less than the upper limit, the liquid stability is improved and coloring of the composition upon storage at high temperatures can be suppressed.

[0066] <(F) Component> Component (F) is a structuring agent. The liquid detergent is structured by containing component (F), and therefore when the liquid detergent contains insoluble particles (such as the above-mentioned component (C2)), the dispersion stability of the insoluble particles is improved, the insoluble particles can be uniformly dispersed in the liquid detergent, and the state can be well maintained. In this specification, the term "structuring" refers to a state in which the viscosity changes before and after the application of force.

[0067] Examples of structuring agents include bacterial cellulose, non-bacterial cellulose, and compound (7) below. The structuring agent may be used alone or in combination of two or more.

[0068] Bacterial cellulose is cellulose produced by fermentation of bacteria of the genus Acetobacter. Examples of bacterial cellulose include so-called mesh-like bacterial cellulose, in which water-insoluble fibers are branched in a mesh-like manner and interdigitate with each other to form a network.

[0069] At least a portion of the bacterial cellulose may be coated with or mixed with a thickening agent. Examples of thickening agents include carboxymethylcellulose (CMC), modified CMC, xanthan products, pectin, alginates, gellan gum, welan gum, diutan gum, rhamsan gum, carrageenan, guar gum, agar, gum arabic, gum ghatti, gum karaya, gum tragacanth, tamarind gum, and locust bean gum. The thickener may be used alone or in combination of two or more kinds.

[0070] As the bacterial cellulose, commercially available products can be used, for example, the trade name "CELLULON (registered trademark)" manufactured by CPKelco US.

[0071] Non-bacterial cellulose is cellulose obtained from vegetables, fruits, and wood, and is also called cellulose fiber.

[0072] As the non-bacterial cellulose, commercially available products can be used, such as "Avicel (registered trademark)" manufactured by FMC Corporation, "Citri-Fi" manufactured by Fiberstar Corporation, and "Betafib" manufactured by Cosun Corporation.

[0073] Compound (7) is a compound (triglyceride component) represented by the following general formula (7).

[0074] [ka]

[0075] In formula (7), Z 1 ~Z 3 are each independently a hydrogen atom, a hydroxyl group, or a carboxyl group. 1 ~Z 3 may be the same or different. In formula (7), a+b=7-19, c+d=7-19, and e+f=7-19, preferably a+b=11-15, c+d=11-15, and e+f=11-15, and more preferably a+b=13-15, c+d=13-15, and e+f=13-15. When a+b, c+d, and e+f are each 7 or more, the volume of the hydrophobic group portion is sufficiently bulky, and the application cleaning power is enhanced. On the other hand, when a+b, c+d, and e+f are each 19 or less, the risk of solidification due to the volume of the hydrophobic group portion being bulky is reduced.

[0076] Compound (7) includes Z 1 ~Z 3 Compound (7-1) in which Z is a hydroxy group; 1 ~Z 3 is a hydrogen atom. As the compound (7-1), hydrogenated castor oil is particularly preferred, and as the compound (7-2), hydrogenated palm oil is particularly preferred. Hydrogenated castor oils include glycerides, particularly triglycerides, that contain an alkyl or alkenyl moiety having 10 to 22 carbon atoms that incorporates a hydroxyl group, such as trihydroxystearin, dihydroxystearin, and the like. Hydrogenated castor oil is obtained by hydrogenating castor oil to convert double bonds that may be present in the starting oil as ricinoleyl moieties, which are converted to saturated hydroxyalkyl moieties, such as hydroxystearyl. The hydrogenated castor oil may be processed in any suitable starting form, including but not limited to, being used in a solid state, a melt, or a mixture thereof.

[0077] As the hydrogenated castor oil, commercially available products can be used, such as "THIXCIN (registered trademark)" manufactured by Rheox, Inc. and "Custerwax A Flake" manufactured by NOF Corporation. As the hardened palm oil, commercially available products can be used, for example, the product name "Extremely Hardened Palm Oil A" manufactured by New Japan Chemical Co., Ltd.

[0078] As component (F), bacterial cellulose and non-bacterial cellulose are preferred, and bacterial cellulose is more preferred, because even a small amount can sufficiently enhance the dispersion stability of insoluble particles such as component (C2), and because a highly transparent liquid appearance is easily obtained.

[0079] The content of the component (F) is preferably from 0.02 to 2 mass %, more preferably from 0.04 to 1.5 mass %, and even more preferably from 0.05 to 1 mass %, based on the total mass of the liquid detergent. Furthermore, for example, when a bacterial cellulose preparation such as the commercially available product "CELLULON (registered trademark)" is used as component (F), the content of component (F) in the product as is (as is) is preferably 1 to 10 mass%, more preferably 2 to 8 mass%, and even more preferably 2.5 to 7 mass%, relative to the total mass of the liquid detergent. Here, "content of the product as it is" refers to the content of the product itself, including moisture and other substances contained in the product. When the content of component (F) is equal to or greater than the lower limit, the dispersion stability of insoluble particles such as component (C2) is improved. When the content of component (F) is equal to or less than the upper limit, the viscosity of the liquid detergent is lowered, improving ease of use and liquid stability.

[0080] <Water> As the water, purified water, ion-exchanged water, distilled water, tap water, etc. can be used. The water may be used alone or in combination of two or more kinds. The water content is not particularly limited, but in the case of a liquid detergent with a high surfactant concentration, the water content is preferably 7 to 40 mass %, more preferably 10 to 30 mass %, and even more preferably 15 to 28 mass %, based on the total mass of the liquid detergent. In particular, when the liquid detergent contains component (C2), if the water content is equal to or less than the upper limit above, component (C2) is less likely to dissolve in the liquid detergent, the particle appearance (particle number, particle size, etc.) can be well maintained, and the appearance stability of component (C2) is improved. In the case of a liquid detergent having a low surfactant concentration, the water content is preferably from 60 to 85 mass %, more preferably from 65 to 83 mass %, and even more preferably from 70 to 80 mass %. If the water content is equal to or greater than the lower limit, the viscosity of the liquid detergent can be reduced, improving usability and reducing the risk of ignition. Furthermore, the compatibility of the components is improved, improving manufacturability and liquid stability. If the water content is equal to or less than the upper limit, the cleaning power and liquid stability are improved. Note that "high surfactant concentration" means that the total content of surfactants in the liquid detergent is 40 mass% or more relative to the total mass of the liquid detergent. "low surfactant concentration" means that the total content of surfactants in the liquid detergent is less than 40 mass% relative to the total mass of the liquid detergent.

[0081] <Optional ingredients> Examples of optional components include water-miscible organic solvents, builder components other than components (C) and (E), chelating agents, pH adjusters, viscosity reducers and solubilizing agents, enzymes, thickeners other than component (F), alkali agents other than component (C), higher fatty acids or salts thereof, preservatives, antioxidants, enzyme stabilizers, texture improvers, dye transfer inhibitors, redeposition inhibitors, colorants, emulsifying agents, fragrances, discoloration inhibitors, hydrotropes, bleaching agents, pearling agents, and extracts of natural products and the like. The optional components may be used alone or in combination of two or more.

[0082] A water-miscible organic solvent is an organic solvent that dissolves at least 25 g in 1 L of water at 25°C. Examples of water-miscible organic solvents include alcohols such as ethanol, glycerin, 1-propanol, 2-propanol, 1-butanol, and 3-methoxy-3-methyl-1-butanol (Solfit, product name); glycols such as propylene glycol (PG), butylene glycol, and hexylene glycol; polyglycols such as diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycols having a molecular weight of about 200 to 1000, and dipropylene glycol; and alkyl ethers such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether (butyl carbitol), and diethylene glycol dimethyl ether. Among these, from the viewpoints of low odor, easy availability, and fluidity of the liquid detergent, ethanol, glycerin, 3-methoxy-3-methyl-1-butanol, propylene glycol, polyethylene glycols having a molecular weight of about 200 to 1000, and diethylene glycol monobutyl ether (butyl carbitol) are preferred, and ethanol, glycerin, and propylene glycol are more preferred. The water-miscible organic solvent may be used alone or in combination of two or more. From the viewpoints of enzyme stability (residual activity), appearance stability, and fluidity of the liquid detergent, it is preferable to use propylene glycol and glycerin in combination. The content of the water-miscible organic solvent is preferably from 5 to 50 mass %, more preferably from 10 to 40 mass %, and even more preferably from 10 to 25 mass %, based on the total mass of the liquid detergent.

[0083] Builder components other than the components (C) and (E) (hereinafter also referred to as "other builder components") include, for example, sodium chloride, potassium chloride, sodium sulfate, potassium sulfate, ammonium chloride, ammonium sulfate, sodium tetraborate, sodium pyrophosphate, sodium tripolyphosphate, sodium hydroxide, potassium hydroxide, aluminosilicates (e.g., zeolite, etc.), and the like. The other builder components may be used alone or in combination of two or more. Other builder ingredients may be dissolved in the liquid detergent or may be present in the solid state. The content of other builder components is preferably 20% by mass or less, more preferably 0.5 to 10% by mass, based on the total mass of the liquid detergent.

[0084] The chelating agent is preferably, for example, a chelating agent having a trivalent or tetravalent carboxylic acid group or a salt thereof. Specific examples thereof include citric acid or a salt thereof, and an aminocarboxylic acid-based chelating agent or a salt thereof. An aminocarboxylic acid refers to a compound containing at least one primary, secondary or tertiary amino group and at least one carboxyl group in one molecule, and an aminocarboxylic acid-based chelating agent refers to a chelating agent that is an aminocarboxylic acid. The aminocarboxylic acid chelating agent can be one known in the field of cleaning agents.Specific examples include methylglycine diacetate (MGDA), methylglycine diacetate, L-glutamic acid diacetate (GLDA), L-glutamic acid diacetate, diethylenetriamine pentaacetate (DTPA), diethylenetriamine pentaacetate, ethylenediamine succinic acid (EDDS), ethylenediamine succinate, 3-hydroxy-2,2'-iminodisuccinic acid (HIDS), 3-hydroxy-2,2'-iminodisuccinic acid, L-aspartic acid-N,N-diacetate (ASDA), and L-aspartic acid-N,N-diacetate.Among these, citric acid or its salt, MGDA or its salt are preferred, and trisodium methylglycine diacetate is more preferred. The chelating agent may be used alone or in combination of two or more kinds. The content of the chelating agent is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and even more preferably 0.1% by mass or more, based on the total mass of the liquid detergent. If the content of the chelating agent is equal to or more than the lower limit, the cleaning power improving effect, the liquid stability improving effect, and the discoloration preventing effect are easily obtained.

[0085] Examples of pH adjusters include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; basic amino acids such as arginine and lysine; ammonia; and acid agents such as sulfuric acid, hydrochloric acid, phosphoric acid, and citric acid. Among these, sodium hydroxide, sulfuric acid, and hydrochloric acid are preferred. The pH adjusters may be used alone or in combination of two or more. The amount of pH adjuster added may be appropriately determined so as to adjust the liquid detergent to a desired pH.

[0086] Examples of the viscosity reducing agent and solubilizing agent include aromatic sulfonic acid or its salt. Specifically, examples of the aromatic sulfonic acid include toluenesulfonic acid, xylenesulfonic acid, cumenesulfonic acid, substituted or unsubstituted naphthalenesulfonic acid, and their salts. Examples of the aromatic sulfonic acid salt include sodium salt, potassium salt, calcium salt, magnesium salt, ammonium salt, and alkanolamine salt. The viscosity reducing agent and the solubilizing agent may be used alone or in combination of two or more kinds. The content of the viscosity reducer and solubilizer is preferably 0.1 to 15% by mass based on the total mass of the liquid detergent.

[0087] If a liquid cleaner contains enzymes, it has better cleaning power against sebum, protein and food stains. Here, enzyme refers to an enzyme preparation. As the enzyme, a liquid enzyme preparation or a solid (granular) enzyme preparation may be used. When a solid enzyme preparation is used, it is preferable that a part or the whole of the solid preparation is present in the liquid detergent in a solid state from the viewpoint of the stability of the enzyme.

[0088] Examples of the enzyme include protease, amylase, lipase, cellulase, and mannanase. Examples of proteases include protease preparations available from Novozymes under the trade names Savinase 16L, Savinase Ultra 16L, Savinase Ultra 16XL, Savinase Evity 16L, Everlase 16L TypeEX, Everlase Ultra 16L, Esperase 8L, Alcalase 2.5L, Alcalase Ultra 2.5L, Liquanase 2.5L, Liquanase Ultra 2.5L, Liquanase Ultra 2.5XL, Coronase 48L, Progress Uno 100L, Deozyme, Savinase Evity 12T, and Kannase Evity 24T; and protease preparations available from DuPont under the trade names EFFECTENZ P150, EFFECTENZ P100, and PREFERENZ P100. Examples of amylase include amylase preparations available from Novozymes under the trade names Termamyl 300L, Termamyl Ultra 300L, Duramyl 300L, Stainzyme 12L, Stainzyme Plus 12L, Amplify 12L, Amplify Prime 100L, and Stainzyme Plus 12T; available from DuPont under the trade name EFFECTENZ S100; available from Amano Enzyme Co., Ltd. under the trade name Pullulanase Amano; and available from Seikagaku Corporation under the trade name DB-250. Examples of lipase include lipase preparations available from Novozymes under the trade names Lipex 100L, Lipolase 100L, Lipex 100T, and the like. Examples of cellulases include cellulase preparations available from Novozymes under the trade names Endolase 5000L, Celluzyme 0.4L, Carezyme 4500L, and Celluclean 4500T, and those available from DuPont under the trade name REVITALENTZ 2000. Examples of mannanase include mannanase preparations available from Novozymes under the trade names Mannaway 4L and Mannaway 4.0T. Examples of multi-enzymes that contain two or more types of enzymes include Medley Core 210L, Medley Core 200L, Medley Boost 300L, Medley Advance 200T, Medley Glow 200L, Medley Brilliant 100L, Medley Essential 150L, ​​Medley Core 200T, Medley CleanR, Medley Essential 200T, Medley SmartR, Medley Advance 200T, Medley Boost 200L, Medley Boost 200T, and Medley SuperioR 100T. The enzymes may be used alone or in combination of two or more.

[0089] The enzyme content is preferably 0.1 to 5 mass %, more preferably 0.3 to 3 mass %, and even more preferably 0.4 to 2.5 mass %, based on the total mass of the liquid detergent. If the enzyme content is within the above range, the detergency is further enhanced and it is also economically advantageous.

[0090] Examples of thickeners other than component (F) (hereinafter also referred to as "other thickeners") include acrylic polymers, xanthan gum, and carrageenan. Commercially available acrylic polymers include, for example, the Carbopol (registered trademark) series manufactured by Lubrizol Co. Examples of the Carbopol series include Carbopol ETD 2623, Carbopol EZ3, Carbopol EZ4, Carbopol Ultrez20, Carbopol Ultrez21, and Carbopol Aqua 30. The other thickening agents may be used alone or in combination of two or more. The content of the other thickener is preferably 6 mass % or less, more preferably 0.2 to 4 mass %, based on the total mass of the liquid detergent.

[0091] Examples of alkali agents other than component (C) (hereinafter also referred to as "other alkali agents") include alkanolamines such as monoethanolamine, diethanolamine, triethanolamine, 2-amino-2-methyl-1-propanol, 2-amino-2-methyl-1,3-propanediol, isopropanolamine, diisopropanolamine, etc. Among these, monoethanolamine, diethanolamine, triethanolamine, isopropanolamine, and diisopropanolamine are preferred. The other alkaline agents may be used alone or in combination of two or more. The content of the other alkaline agent is preferably 0.5 to 10 mass %, more preferably 1 to 5 mass %, based on the total mass of the liquid detergent. The other alkaline agents may be used as pH adjusters.

[0092] If a liquid detergent contains a higher fatty acid or its salt, the defoaming property is enhanced. Note that "defoaming property" refers to the property of suppressing foaming when the liquid detergent is used for washing, specifically when the liquid detergent is diluted with tap water or the like before use. Examples of higher fatty acids or salts thereof include single fatty acids or salts thereof, such as caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, isostearic acid, hydroxystearic acid, oleic acid, and behenic acid; mixed fatty acids or salts thereof, such as coconut oil fatty acid and beef tallow fatty acid; and the like. As the higher fatty acid, lauric acid, myristic acid, palmitic acid, and coconut oil fatty acid are preferred, and coconut oil fatty acid is more preferred. Examples of salt forms of higher fatty acids include alkali metal salts (sodium salt, potassium salt, etc.), alkaline earth metal salts (magnesium salt, etc.), and alkanolamine salts (monoethanolamine salt, diethanolamine salt, etc.). The higher fatty acid or a salt thereof may be used alone or in combination of two or more kinds. The content of the higher fatty acid or its salt is preferably 0.5 to 10 mass %, more preferably 2 to 8 mass %, and even more preferably 3 to 5 mass %, based on the total mass of the liquid detergent. If the content of the higher fatty acid or its salt is equal to or more than the above lower limit, the defoaming property is improved. If the content of the higher fatty acid or its salt is equal to or less than the above upper limit, the liquid stability at low temperatures is improved.

[0093] Examples of preservatives include 2-bromo-2-nitropropane-1,3-diol, 3-iodopropynyl butylcarbamate, zinc pyrithione, sodium pyrithione, octylisothiazolin-3-one, 1,2-benzisothiazolin-3-one (BIT), 5-chloro-2-methylisothiazolin-3-one (CMIT), 2-methylisothiazolin-3-one (MIT), ethoxylated cocoamine, octanediol, benzyl alcohol, phenoxyethanol, and sodium benzoate. The preservatives may be used alone or in combination of two or more. The content of the preservative is preferably 0.001 to 2% by mass based on the total mass of the liquid detergent.

[0094] If the liquid detergent contains an antioxidant, it can suppress the absorption of oxygen in the head space of the container in which the liquid detergent is stored, and it can also suppress fading and discoloration due to light and heat. Examples of the antioxidant include monophenol-based antioxidants such as dibutylhydroxytoluene and butylhydroxyanisole; bisphenol-based antioxidants such as 2,2'-methylenebis(4-methyl-6-t-butylphenol); and polymeric phenol-based antioxidants such as dl-α-tocopherol. Among these, monophenol-based antioxidants and polymeric antioxidants are preferred. Among the monophenol-based antioxidants, dibutylhydroxytoluene is particularly preferred. Among the polymeric phenol-based antioxidants, dl-α-tocopherol is particularly preferred. The antioxidants may be used alone or in combination of two or more. The content of the antioxidant is preferably 0.01 to 2% by mass based on the total mass of the liquid detergent.

[0095] Examples of the enzyme stabilizer include boric acid, borax, formic acid or a salt thereof, lactic acid or a salt thereof, calcium chloride, calcium sulfate, and other calcium salts. The enzyme stabilizer may be used alone or in combination of two or more kinds. The content of the enzyme stabilizer is preferably 2% by mass or less based on the total mass of the liquid detergent.

[0096] Examples of the feel improver include silicones such as dimethyl silicone, polyether-modified silicone, and amino-modified silicone. The texture improver may be used alone or in combination of two or more kinds. The content of the texture improver is preferably 5% by mass or less based on the total mass of the liquid detergent.

[0097] Examples of dye transfer inhibitors include polyvinylpyrrolidone, carboxymethylcellulose, and polyalkyleneamines. The dye transfer inhibitor may be used alone or in combination of two or more kinds. The content of the dye transfer inhibitor is preferably 3% by mass or less based on the total mass of the liquid detergent.

[0098] Examples of the anti-redeposition agent include water-soluble polymers having at least one repeating unit selected from the group consisting of alkylene terephthalate units and alkylene isophthalate units, and at least one repeating unit selected from the group consisting of oxyalkylene units and polyoxyalkylene units. Specific examples of such water-soluble polymers include the product name "TexCare SRN-100" (manufactured by Clariant, mass average molecular weight 2000 to 3000), the product name "TexCare SRN-300" (manufactured by Clariant, mass average molecular weight 7000), the product name "Repel-O-Tex Crystal" (manufactured by Rhodia), and the product name "Repel-O-Tex QC" (manufactured by Rhodia). Among these, TexCare SRN-100 is preferred because of its high solubility in water and excellent liquid stability. From the viewpoint of ease of handling, it is preferable to use a product called TexCare SRN-170 (manufactured by Clariant) which is commercially available as a 70% aqueous solution of the above-mentioned TexCare SRN-100 as the re-soiling inhibitor. In addition to the above, examples of the anti-redeposition agent that can be used include alkylene oxide adducts of polyalkyleneimines and alkylene oxide adducts of polyalkyleneamines. Specific examples include the product name "Sokalan HP20" (manufactured by BASF). The anti-redeposition agent may be used alone or in combination of two or more kinds. The content of the anti-redeposition agent is preferably 0.01 to 5% by mass based on the total mass of the liquid detergent.

[0099] The colorant is not particularly limited, and examples thereof include dyes described in the "Legal Dyes Handbook" (Japan Cosmetic Industry Association) and dyes in which the end of the chromophore structure has been chemically modified with a water-soluble polymer or the like. Specifically, CI Acid Red 138, CI Acid Red 260, CI Acid Red 106, Acid Yellow 203 (Yellow No. 203), Acid Blue 9, Blue No. 1, Blue No. 205, Green No. 3, Levanyl (registered trademark) Violet (Levanyl (registered trademark) Violet), Liquitint (registered trademark) BLUE SE (Liquitint (registered trademark) Blue SE), Liquitint (registered trademark) BLUE HP (Liquitint (registered trademark) Blue HP), Liquitint (registered trademark) BLUE MC (Liquitint (registered trademark) Blue MC), Liquitint (registered trademark) VIOLET CT (Liquitint (registered trademark) Violet CT), Liquitint (registered trademark) VIOLET LS (Liquitint (registered trademark) Violet LS), Liquitint (registered trademark) VIOLET DD (Liquitint (registered trademark) Violet DD), Liquitint(R) GREEN SA, Liquitint(R) Bright Yellow, Liquitint(R) YELLOW SY, Liquitint(R) YELLOW LP, Liquitint(R) BRILLIANT ORANGE, Liquitint(R) PINK AL, Liquitint(R) RED ST, Liquitint(R) RED MX, CI77007 (Pigment Blue 29, L-280 BLUE U), CI74160 (Pigment Blue 15), CIExamples of the pigments include general-purpose dyes and pigments such as CI 77346 (Pigment Blue 28), CI 77343 (Pigment Blue 36), CI 74260 (Pigment Green 7), CI 74265 (Pigment Green 36), WA-S Color Green, CI 21090 (Pigment Yellow 12, Yellow No. 205), CI 56110 (Pigment Red 254), CI 12490 (Pigment Red 5), Labracol 040 (F) Red, and PIGMOSOL (registered trademark). In this specification, "CI" is an abbreviation for Color Index. The colorant may be used alone or in combination of two or more kinds. The content of the colorant is preferably 0.00005 to 1.0 mass %, more preferably 0.00005 to 0.01 mass %, based on the total mass of the liquid detergent. If the content of the colorant is equal to or more than the lower limit, the liquid detergent can be sufficiently colored, and if the content is equal to or less than the upper limit, pigmentation on the washed items is unlikely to occur, making it easier to obtain a liquid detergent with excellent dispersion stability.

[0100] Examples of the emulsifier include polystyrene emulsion and polyvinyl acetate emulsion, and generally, emulsions with a solid content of 30 to 50% by mass are preferably used.Specific examples include polystyrene emulsion (product name: Saibinol (registered trademark) RPX-196 PE-3, solid content 40% by mass, manufactured by Saiden Chemical Industry Co., Ltd.), Opulyn 301, Acusol OP 301, etc. The emulsifier may be used alone or in combination of two or more kinds. The content of the emulsifier is preferably 0.001 to 0.5% by mass based on the total mass of the liquid detergent.

[0101] Examples of the flavoring agent include those described in "Synthetic Flavors: Chemistry and Product Knowledge" by Indo Genichi, published by The Chemical Daily in 1996, and "Perfume and Flavor Chemicals" by STEFFEN ARCTANDER, published by MONTCLAIR, NJ in 1969. More specifically, examples of the flavoring agent include synthetic flavors, natural flavors derived from animals or plants, blended flavors containing natural flavors and / or synthetic flavors, and flavoring ingredients described in JP-A-2002-146399. The flavoring agent may be incorporated as a capsule flavoring encapsulated in a capsule formed of a polymer compound. The flavoring agent may be used alone or in combination of two or more kinds. The content of the fragrance is preferably 0.01 to 2% by mass based on the total mass of the liquid detergent.

[0102] <Physical Properties> (pH) The pH of the liquid detergent at 25°C is preferably 8.5 or more, more preferably 8.5 to 11, even more preferably 8.5 to 10.5, and particularly preferably 8.5 to 10. If the pH of the liquid detergent is equal to or higher than the above lower limit, the cleaning power is further enhanced. If the pH of the liquid detergent is equal to or lower than the above upper limit, damage to textile products such as clothing can be prevented. The pH of the liquid cleaner can be adjusted, if necessary, by adding a pH adjuster. The pH of a liquid detergent is measured at 25°C using a pH meter (manufactured by DKK-TOA Corporation, product name "HM-30G").

[0103] <Manufacturing method> The method for producing the liquid detergent is not particularly limited, and the liquid detergent can be produced in accordance with a conventional method. For example, a liquid detergent can be produced by mixing components (A), (B), and (D), a portion of water, and one or more optional components other than the pH adjuster, adjusting the pH to a predetermined value using a pH adjuster as necessary, and then mixing the mixture with component (C) and, as necessary, components (E) and (F) and the remaining water.

[0104] <How to use> Methods for using liquid detergents include, for example, putting the liquid detergent into the liquid detergent inlet of a washing machine and then running the washing machine, putting the liquid detergent into water together with the items to be washed when washing, immersing the items to be washed in a cleaning liquid prepared by dissolving the liquid detergent in water in advance, applying the liquid detergent directly to the items to be washed and leaving it for, for example, 3 minutes to 24 hours, and then washing as usual.

[0105] The cleaning solution is an aqueous solution containing a liquid cleaning agent, i.e., the cleaning solution is an aqueous solution containing the above-mentioned components (A), (B), and (C), water, and, as necessary, one or more of the components (D), (E), and (F), and optional components. The content of each component in the cleaning solution is as follows: The content of the component (A) is preferably 0.03 ppm by mass or more, more preferably 0.03 to 6.7 ppm by mass, even more preferably 0.1 to 3.3 ppm by mass, still more preferably 0.17 to 1.7 ppm by mass, particularly preferably 0.17 to 1.3 ppm by mass, and most preferably 0.17 to 0.8 ppm by mass, relative to the total mass of the cleaning liquid. The content of the component (B) is preferably 0.17 ppm by mass or more, more preferably 0.17 to 17 ppm by mass, even more preferably 0.3 to 10 ppm by mass, still more preferably 0.3 to 3.3 ppm by mass, and particularly preferably 0.3 to 1.7 ppm by mass, relative to the total mass of the cleaning liquid. The mass ratio of component (B) to component (A), i.e., the mass ratio (B / A ratio) represented by component (B) / component (A), is preferably 0.1 to 60, more preferably 0.25 to 60, even more preferably 1 to 30, particularly preferably 1 to 10, and most preferably 2 to 10. The content of the component (C) is preferably from 3.3 to 67 ppm by mass, more preferably from 6.7 to 50 ppm by mass, and even more preferably from 10 to 33 ppm by mass, relative to the total mass of the cleaning liquid. The mass ratio of the nonionic surfactant to the mass of the non-soap anionic surfactant, i.e., the mass ratio expressed as nonionic surfactant / non-soap anionic surfactant (nonionic / anionic ratio), is preferably from 0.1 to 3, more preferably from 0.15 to 2, even more preferably from 0.2 to 1.5, and particularly preferably from 0.25 to 1.3. The content of the component (D) is preferably from 50 to 700 ppm by mass, more preferably from 100 to 500 ppm by mass, and even more preferably from 150 to 300 ppm by mass, relative to the total mass of the cleaning liquid.

[0106] It is also preferable to use a washing machine equipped with an automatic detergent dispenser, which has been put into practical use in recent years. The automatic detergent dispenser is a device that automatically dispenses liquid detergent from a tank containing the liquid detergent into the washing tub via a dust filter installed at the bottom of the tank and a dispenser pipe. A measuring means such as a syringe pump is installed in the dispenser pipe, so that a fixed amount set according to the amount of laundry can be transferred from the tank to the washing tub. Using an automatic detergent dispenser not only saves you the trouble of measuring out the detergent, but also prevents liquid detergent from getting on your hands when measuring out the detergent, or from spilling and soiling the washing machine or surrounding area.

[0107] It is also preferable to use an automatic dispenser that can automatically dispense a predetermined amount of liquid. When an automatic dispenser is used, it is also preferable because it is possible to accurately measure even a small amount of liquid detergent, making it easier to achieve sufficient cleaning power and avoiding waste due to overuse. Some automatic dispensers on the market use infrared sensors to automatically dispense liquid detergent without the need to touch a switch, etc. By using such an automatic dispenser, the user can measure out the liquid detergent simply by holding the container in one hand, greatly reducing the burden on the user.

[0108] In addition, when using an automatic dispenser, it is also preferable to receive the liquid detergent dispensed into a soft container and then directly put the soft container into the washing machine, so that the entire amount of the dispensed liquid detergent can be reliably dissolved in the cleaning liquid. Examples of materials for the soft container that can be directly put into the washing machine include silicone resin, polyvinyl chloride, elastomer, soft polyester, soft polypropylene, polyurethane, and the like.

[0109] Examples of items to be washed include textile products such as clothing, dishcloths, towels, sheets, curtains, etc. The material of the textile products is not particularly limited, and may be any of natural fibers such as cotton, silk, wool, etc., and chemical fibers such as polyester, polyamide, etc. When the liquid detergent is used by dissolving it in water, it is preferable to dilute it, for example, 5 to 6000 times (by volume). The liquor ratio, which is the amount of water per amount of clothes (mass of cleaning liquid during washing / mass of clothes), is preferably 5 or more for drum-type washing machines and 10 or more for top-loading washing machines. The liquid detergent is suitable as a detergent for textile products. In particular, if the liquid detergent contains an uncoated component (A) and the particle size of the component (A) is less than 200 μm, more preferably less than 100 μm, it is suitable for use in washing machines and automatic dispensers equipped with an automatic detergent dispensing function.

[0110] <Action and effect> The liquid detergent of the present invention described above contains components (A), (B), and (C), and therefore has excellent cleaning power and antibacterial properties. In addition, the liquid detergent of the present invention has excellent stability against light, so it is difficult to discolor even when exposed to light, and can maintain its aesthetic appearance for a long period of time. Furthermore, when component (B) is a fluorescent whitening agent, it can impart a white appearance to clothing. In particular, if at least a portion of component (C) exists in a solid state in the liquid detergent, the liquid detergent contains an amount of component (C) that exceeds its solubility, and the cleaning power is further enhanced. When the liquid detergent is used for washing, it is diluted with water, so that component (C) that exists in a solid state gradually dissolves in the washing liquid, increasing the concentration of component (C) around it, and it acts at a high concentration on dirt and textile products, thereby exerting a high cleaning power. EXAMPLES

[0111] The present invention will be described in detail below with reference to examples, but the present invention is not limited to the following description. The raw materials used in this example are as follows: It should be noted that Examples 16 to 20 are reference examples.

[0112] "Raw materials used" As component (A), the compound shown below was used. A-1: Diclosan (4,4'-dichloro-2-hydroxydiphenyl ether) (manufactured by BASF, trade name "TINOSAN (registered trademark) HP100").

[0113] As component (B), the compound shown below was used. B-1: 4,4'-bis(2-sulfostyryl)biphenyl disodium salt (manufactured by BASF, trade name "Tinopal (registered trademark) CBS-X"). B-2: 4,4'-bis((4-amino-6-morpholino-1,3,5-triazinyl-2)amino)stilbene-2,2'-disulfonic acid salt (manufactured by ARCHROMA, trade name "Leucophor (registered trademark) DMA-X Conc"). B-3: 2,2'-dihydroxy-4,4'-dimethoxybenzophenone (manufactured by BASF under the trade name "Uvinul (registered trademark) 3049"). B-4: Sodium 2-hydroxy-4-methoxybenzophenone-5-sulfonate (manufactured by Sankyo Kasei Co., Ltd., trade name "Dilyser S"). B-5: 2-(3-t-butyl-5-methyl-2-hydroxyphenyl)-5-chlorobenzotriazole (manufactured by BASF under the trade name "Tinuvin (registered trademark) 326"). B-6: 2,4-bis(2-hydroxy-4-butyloxyphenyl)-6-(2,4-bis-butyloxyphenyl)-1,3,5-triazine (manufactured by BASF under the trade name "Tinuvin (registered trademark) 460").

[0114] As component (C), the compound shown below was used. C-1: Sodium carbonate (manufactured by Soda Ash Japan Co., Ltd., product name "granular ash"). · C-2: Sodium hydrogen carbonate (manufactured by Qingdao Haiwan Co., Ltd., product name "Sodium hydrogen carbonate"). C-3: Layered sodium silicate (manufactured by Tokuyama Corporation, product name "Purifeed").

[0115] As component (D), the compound shown below was used. D-1: Polyoxyethylene alkyl ether (manufactured by Lion Specialty Chemicals Corporation, trade name "Rheox CL-70"; in general formula (2), R 11 is a linear alkyl group having 12 carbon atoms (C12) and a linear alkyl group having 14 carbon atoms (C14) (mass ratio of C12:C14=75:25), and R 11 The carbon atom of R is a primary carbon atom. 12 is a hydrogen atom, s is 7, t is 0, and u is 0. D-2: Polyoxyethylene alkyl ether (manufactured by Lion Chemical Co., Ltd., trade name "LMAO-90"; in general formula (2), R 11 is a linear alkyl group having 12 carbon atoms (C12) and a linear alkyl group having 14 carbon atoms (C14) (mass ratio of C12:C14=75:25), and R 11 The carbon atom of R is a primary carbon atom. 12 is a hydrogen atom, s is 15, t is 0, and u is 0. D-3: A nonionic surfactant obtained by block-addition of 8 moles of ethylene oxide, 2 moles of propylene oxide, and 8 moles of ethylene oxide to natural alcohol (mass ratio of C12 primary alcohol / C14 primary alcohol = 7 / 3). D-4: Linear alkylbenzene sulfonic acid having an alkyl group having 10 to 14 carbon atoms (manufactured by Lion Specialty Chemicals Co., Ltd., trade name "Lipon (registered trademark) LH-200"). D-5: Polyoxyalkylene alkyl ether sulfate (in general formula (4), R 15 is a linear alkyl group having 12 carbon atoms (C12) and a linear alkyl group having 14 carbon atoms (C14) (mass ratio of C12:C14=75:25), m is 1, n is 0, Ma is sodium, and the proportion of compounds in which m is 0 and n is 0 in the entire AES is 43 mass%. Compound (4) synthesized by the following synthesis method. · D-6: IOS. Sodium internal olefin sulfonate synthesized by the following synthesis method, hydroxy content is 85 mass%. Synthesized by the following synthesis method. D-1, D-2, and D-3 are nonionic surfactants, and D-4, D-5, and D-6 are non-soap anionic surfactants.

[0116] (Synthesis of D-5) Into a 4-L autoclave, 400 g of Procter & Gamble Co.'s CO1270 alcohol (a mixture of a carbon number 12 alcohol and a carbon number 14 alcohol in a mass ratio of 75 / 25) was charged as the raw material alcohol, and 0.8 g of potassium hydroxide catalyst was charged as the reaction catalyst. The atmosphere inside the autoclave was replaced with nitrogen, and the temperature was raised with stirring. Subsequently, 91 g of ethylene oxide was introduced while maintaining the temperature at 180° C. and the pressure at 0.3 MPa or less, and reacted to obtain an alcohol ethoxylate. Analysis using a gas chromatograph: GC-5890 manufactured by Hewlett-Packard, a detector: a flame ionization detector (FID), and a column: Ultra-1 (manufactured by HP, L25m×φ0.2mm×T0.11μm) showed that the average number of moles of ethylene oxide added in the obtained alcohol ethoxylate was 1.0. In addition, the amount of compounds to which ethylene oxide was not added (those that ultimately became component (b-0)) was 43% by mass relative to the entire alcohol ethoxylate obtained. Next, 237g of the alcohol ethoxylate obtained above was placed in a 500mL flask equipped with a stirrer, and after replacing with nitrogen, 96g of liquid sulfuric anhydride (sulfan) was slowly added dropwise while maintaining the reaction temperature at 40°C. After the dropwise addition was completed, stirring was continued for 1 hour (sulfation reaction) to obtain polyoxyethylene alkyl ether sulfate. This was then neutralized with an aqueous sodium hydroxide solution to obtain D-5.

[0117] (Synthesis of D-6) The internal olefin mixture used was one containing 2.0 mass% of paraffin components, with a total ratio of double bonds at the 2-position being 26 mass%, a mass ratio of cis / trans isomers being 27 / 73, and 3 mass% of C14 or less. This internal olefin mixture was composed of 3 mass% of C14 or less, 33 mass% of C15, 39 mass% of C16, 24 mass% of C17, and 1 mass% of C18 or more. This internal olefin mixture was used in a glass thin-film sulfonation apparatus with an inner diameter of 6 mm and a length of 1.2 m, and sulfonation reaction was carried out in the usual manner with nitrogen-diluted SO3 gas (SO3 concentration: 5% by volume) under conditions of a reactor temperature of 10°C and a molar ratio of SO3 / internal olefin of 1.1, to obtain internal olefin sulfonic acid. The obtained reaction product, internal olefin sulfonic acid, was aged at 5°C for 1 hour, and then 1.11 times the molar amount (relative to the internal olefin sulfonic acid) of 15% aqueous sodium hydroxide was added and the mixture was stirred at 30°C for 30 minutes to carry out a neutralization reaction, thereby obtaining a neutralized product. This neutralized product was then heated in an autoclave at 160°C for 40 minutes and hydrolyzed to obtain D-6.

[0118] As the component (E), the compound shown below was used. E-1: Sodium sulfite (manufactured by Mitsui Chemicals, Inc., product name "Sodium sulfite").

[0119] As the component (F), the compound shown below was used. F-1: Bacterial cellulose (manufactured by CPKelco US, product name "CELLULON (registered trademark) R27", moisture content 80% by mass). The moisture content of F-1 was measured using an automatic moisture measuring device (manufactured by Hiranuma Sangyo Co., Ltd., product name "AQUACOUNTER AQV-2200").

[0120] Water and the compounds shown below were used as optional components. ·Water: Purified water. Monoethanolamine: Manufactured by Nippon Shokubai Co., Ltd., product name "Monoethanolamine." Propylene glycol: Manufactured by The Dow Chemical Company, trade name "Propylene Glycol." Glycerin: Manufactured by Fujifilm Wako Pure Chemical Industries, product name "Glycerin". Ethanol: Manufactured by Japan Alcohol Sales Co., Ltd., product name "Specific Alcohol 95% Synthetic". · Palm fatty acid: Manufactured by NOF Corporation, product name "Palm Fatty Acid." Enzymes: A mixed preparation (liquid) of protease and amylase (manufactured by Novozymes Japan Co., Ltd., product name "Medley Core 210L"). Antioxidant: Dibutylhydroxytoluene (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., product name "Dibutylhydroxytoluene"). Fragrance: Fragrance composition A described in Tables 11 to 18 of JP-A No. 2002-146399. ·Pigment: Manufactured by Kinmi Kasei Co., Ltd., product name "Green No. 3". Sodium hydroxide: Manufactured by Toagosei Co., Ltd., product name "Sodium hydroxide."

[0121] "Measurement and evaluation methods" (Check the appearance of the liquid) 100 mL of the liquid detergent was placed in a transparent glass bottle (wide-mouth standard bottle PS-No. 11) and the bottle was sealed with a lid. It was left to stand in this state at room temperature (25°C) for 4 weeks. After standing, the appearance of the liquid detergent was visually observed, and if it was transparent and uniform with no foreign matter, it was rated as "transparent," if it was slightly cloudy but had a transparent appearance, it was rated as "slightly cloudy," and if it was cloudy, it was rated as "cloudy."

[0122] (Evaluation of light stability) 100 mL of the liquid detergent was placed in a transparent glass bottle (wide-mouth standard bottle PS-NO.11) and the lid was closed and sealed. In this state, it was left to stand for one week in a place exposed to sunlight. After standing, the color tone of the liquid detergent was visually observed, and its stability against light was evaluated based on the following evaluation criteria. ◎ and ○ were deemed to be acceptable. Evaluation Criteria ⊚: The color tone is the same as that of the liquid cleaner before it was exposed to sunlight. ○: Slightly colored compared to the liquid cleaner before exposure to sunlight. ×: The color is more intense than that of the liquid cleaner before it was exposed to sunlight.

[0123] (Evaluation of cleaning power) A commercially available protein-stained cloth (manufactured by Swissatest, product name "EMPA117") was cut into a size of 5 cm x 5 cm to be used as the soiled cloth. The cleaning tester used was a Terg-O-Tometer (manufactured by UNITED STATES TESTING). The cleaning liquid used was prepared by adding the liquid cleaning composition of each example to 900 mL of tap water (15° C.) so that the concentration was 333 ppm by mass, and stirring for 30 seconds.

[0124] The cleaning solution, 10 of the above soiled fabrics, and the cleaned knitted fabric were placed in a cleaning tester, and washed for 10 minutes at 120 rpm and 15° C. with a bath ratio (washing water / total mass of items to be washed) of 20. The items were then transferred to a twin-tub washing machine (manufactured by Mitsubishi Electric Corporation, product name "CW-C30A1-H1"), spin-dried for 1 minute, rinsed in 30 L of water for 3 minutes, and air-dried. The reflectance of the unsoiled cloth and the soiled cloth before and after cleaning was measured using a color difference meter (manufactured by Nippon Denshoku Industries Co., Ltd., product name "SE7700 type"), and the cleaning rate (%) was calculated using the following formula (i). Cleaning rate (%) = (K / S of soiled cloth before washing - K / S of soiled cloth after washing) / (K / S of soiled cloth before washing - K / S of unsoiled cloth) × 100 (i) In formula (i), "K / S" is (1-R / 100). 2 The value is calculated by / (2R / 100) (where R represents the reflectance (%) of an unsoiled cloth and a soiled cloth before and after washing). In addition, the unstained cloth means the original white cloth (original cloth) to which no stain has been added, and the R of the original cloth was set to 80.

[0125] The cleaning rate (%) was calculated for 10 pieces of soiled cloth, and the average value was used to evaluate the cleaning power against sebum stains according to the following evaluation criteria. ⊚ and ◯ were deemed to be acceptable. Evaluation Criteria ◎: Cleaning rate (average value) is 80% or more. ○: Cleaning rate (average value) is 55% or more but less than 80%. ×: Cleaning rate (average value) is less than 55%.

[0126] "Examples 1-7, 9, 10, 12-18, 20-22, Comparative Examples 1 and 2" In a 500 mL beaker, component (A), component (B), component (D), a portion of the water, and optional components other than the pH adjuster and enzymes were added according to the formulations in Tables 1 to 3, and the mixture was thoroughly stirred with a Three-One Motor Stirrer (manufactured by AS ONE Corporation) to obtain a mixture. Next, a pH adjuster (sodium hydroxide) was added to the mixture as necessary so that the pH of the mixture at 25° C. was 7. Thereafter, component (C), component (E) as necessary, and an enzyme were added, and the remaining water was added so that the total amount became 100% by mass, to obtain a liquid detergent. The pH of the resulting liquid detergent was measured at 25° C. using a pH meter (manufactured by DKK-TOA Corporation, product name “HM-30G”). The results are shown in Tables 1 to 3. The liquid appearance of the obtained liquid detergent was checked, and its stability against light and cleaning power were evaluated. The results are shown in Tables 1 to 3. The contents of each component in the cleaning liquid prepared for the evaluation of cleaning power are also shown in Tables 1 to 3.

[0127] "Examples 8, 11, and 19" In a 500 mL beaker, component (A), component (B), component (D), a portion of the water, and optional components other than the pH adjuster and enzymes were added according to the formulations in Tables 2 and 3, and the mixture was thoroughly stirred with a Three-One Motor Stirrer (manufactured by AS ONE Corporation) to obtain a mixture. Next, a pH adjuster (sodium hydroxide) was added to the mixture as necessary so that the pH of the mixture at 25°C was 7. After that, component (E) and the enzyme were added, and the remaining water was added so that the total amount excluding component (F) was 100% by mass. Subsequently, component (F) was added to the mixture and thoroughly stirred, and then component (C) was further added and thoroughly stirred to obtain a liquid detergent. In the liquid detergents obtained in Examples 8, 11 and 18, a portion of component (C) was present in a solid state. The pH of the resulting liquid detergent at 25° C. was measured using a pH meter (manufactured by DKK-TOA Corporation, product name “HM-30G”). The results are shown in Tables 2 and 3. The liquid appearance of the obtained liquid detergent was checked, and its stability against light and cleaning power were evaluated. The results are shown in Tables 2 and 3. The contents of each component in the cleaning liquid prepared for the evaluation of cleaning power are also shown in Tables 2 and 3.

[0128] [Table 1]

[0129] [Table 2]

[0130] [Table 3]

[0131] In Tables 1 to 3, the amount (mass%) of each component is the ratio to the total mass of the liquid detergent, and unless otherwise specified, the value is expressed as a pure content. The amount (mass%) of F-1 is the amount in the form of a formulation. The amount (mass%) of water includes the amount (mass%) of water contained in F-1. "Appropriate amount" means that a pH adjuster (sodium hydroxide) is added so that the pH of the liquid detergent at 25°C is the value shown in Tables 1 to 3. "Balance" means that water is added so that the total amount (mass%) of all the components contained in each liquid detergent example is 100% by mass. A blank column for the amount means that the component is not added (amount 0% by mass). Furthermore, the "B / A ratio" is the mass ratio of component (B) to component (A). The "B / E ratio" is the mass ratio of component (B) to component (E). The "nonionic / anionic ratio" is the mass ratio of nonionic surfactant to non-soap anionic surfactant. "B+E" is the sum (mass %) of the contents of components (B) and (E) relative to the total mass of the liquid detergent.

[0132] As is clear from Tables 1 to 3, the liquid detergents obtained in the respective Examples had high detergency, excellent stability against light, and were well-suppressed in terms of coloration when exposed to light. On the other hand, the liquid detergent obtained in Comparative Example 1, which did not contain the component (B), was less stable to light and was easily discolored when exposed to light. The liquid detergent of Comparative Example 2, which did not contain the component (C), had poor detergency.

Claims

1. (A) component: dichrosan, Component (B): one or more selected from the group consisting of biphenyl-type fluorescent brightening agents, stilbene-type fluorescent brightening agents, benzophenone-type ultraviolet absorbers, benzotriazole-type ultraviolet absorbers, and triazine-type ultraviolet absorbers; Component (C): one or more selected from carbonates, hydrogen carbonates, and layered silicates; (D) component: a surfactant, (E) component: sulfite, Contains the mass ratio of the component (B) to the mass of the component (A) is 2 to 10; A liquid cleaning agent having a pH of 8.5 to 11 at 25°C.

2. A liquid detergent as described in claim 1, wherein the total content of the (B) component and the (E) component is 0.06 to 5 mass% relative to the total mass of the liquid detergent.

3. A liquid cleaning agent as described in claim 1 or 2, wherein the mass ratio of the (B) component to the (E) component is 0.4 to 20.

4. A liquid detergent described in any one of claims 1 to 3, wherein the content of the (C) component is 1 to 20 mass% relative to the total mass of the liquid detergent.

5. A cleaning liquid that is an aqueous solution containing the liquid cleaning agent according to any one of claims 1 to 4, The content of the component (A) is 0.03 ppm by mass or more based on the total mass of the cleaning solution, A cleaning solution having a content of the component (B) of 0.17 ppm by mass or more relative to the total mass of the cleaning solution.

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