Liquid detergent for hard surfaces and liquid detergent product for hard surfaces

Abstract

To provide a liquid detergent for hard surfaces which has a proper liquid color in terms of visibility and prevention of staining, while exhibiting superior liquid color stability even under storage in high-temperature conditions.SOLUTION: A liquid detergent for hard surfaces comprises (A) a non-soap anionic surfactant, (B) an aminocarboxylic acid-type chelating agent, (C) a nonionic aromatic compound represented by formula (c1), and (D) a dye selected from phthalocyanine dyes, triphenylmethane dyes, and thiazine dyes, wherein the mass ratio (A+B) / C is 2 to 400. In formula (c1), X represents an oxygen atom or an alkylene group having 1 to 4 carbon atoms, Y each independently represents a chlorine atom or a bromine atom, a, b, and c each independently represent 0 or an integer of 1 to 3, m is 0 or 1, and n is 0 or 1.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a liquid cleaner for hard surfaces and a liquid cleaner product for hard surfaces using the same. [Background technology]

[0002] In recent years, liquid detergents have been developed that can remove dirt from hard surfaces in bathrooms and the like by simply spraying the detergent solution on the item to be washed and rinsing it with water, without using cleaning tools such as sponges. Such liquid detergents are used by spraying them over the entire surface to be washed (item to be washed) using a trigger-type spray container. If the liquid detergent is colorless, it is difficult to distinguish between sprayed and unsprayed areas (poor visibility), so dyes are often added to the liquid detergent to distinguish them. However, adding dyes to the liquid detergent may cause unintended coloring of the item to be washed. Patent documents 1 and 2 describe liquid detergents that contain specific color components, surfactants, and solvents, and that can suppress staining of items being washed while ensuring visibility. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] JP 2017-78170 A [Patent Document 2] JP 2018-65952 A Summary of the Invention [Problem to be solved by the invention]

[0004] For example, bathroom cleaners are often stored in the bathroom, and are exposed to high temperatures, particularly in bathrooms equipped with bathroom dryers. According to the findings of the present inventors, when a liquid detergent containing a dye is stored in a high-temperature environment, the liquid color becomes lighter (poor liquid color stability) and visibility may decrease. On the other hand, if a large amount of dye is added in anticipation of the liquid color becoming lighter during storage, there is a concern that the liquid color may be too dark and remain after rinsing. The present invention has been made in consideration of the above circumstances, and aims to provide a liquid cleaning agent for hard surfaces that has an appropriate liquid color from the standpoints of visibility and prevention of discoloration, and also has excellent liquid color stability even when stored in a high-temperature environment. [Means for solving the problem]

[0005] The present invention has the following aspects. [1] A liquid cleaner for hard surfaces comprising: component (A): a non-soap anionic surfactant; component (B): an aminocarboxylic acid chelating agent; component (C): a nonionic aromatic compound selected from compounds represented by the following formula (c1); and component (D): a dye selected from a phthalocyanine dye, a triphenylmethane dye, and a thiazine dye, wherein (A+B) / C, which represents the mass ratio of the total content of components (A) and (B) to the content of component (C), is 2 to 400.

[0006] [ka]

[0007] [In formula (c1), X is an oxygen atom or an alkylene group having 1 to 4 carbon atoms, each Y is independently a chlorine atom or a bromine atom, a, b, and c are independently 0 or an integer of 1 to 3, m is 0 or 1, and n is 0 or 1.] [2] The liquid cleaning agent for hard surfaces according to [1], wherein the component (C) comprises one or more selected from the group consisting of diclosan and triclosan. [3] A liquid cleaning agent for hard surfaces according to [1] or [2], which is for use in the bathroom. [4] A liquid cleaning agent product for hard surfaces, comprising the liquid cleaning agent for hard surfaces described in any one of [1] to [3] above, and a dispensing container containing the liquid cleaning agent for hard surfaces. Effect of the Invention

[0008] According to the present invention, it is possible to provide a liquid cleaning agent for hard surfaces that has an appropriate liquid color from the standpoints of visibility and prevention of discoloration, and also has excellent liquid color stability even when stored in a high-temperature environment. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0009] <Liquid cleaning agent for hard surfaces> The liquid detergent for hard surfaces of the present invention (hereinafter sometimes simply referred to as "liquid detergent") is a composition containing components (A) to (D). In this specification, a numerical range expressed by "to" means a numerical range in which the numerical values ​​before and after "to" are the lower and upper limits.

[0010] <Component (A)> Component (A) is an anionic surfactant other than soap (so-called non-soap anionic surfactant). In this specification, "soap" refers to a salt of a higher fatty acid (a fatty acid having 8 to 22 carbon atoms). In the present invention, component (A) functions as a component that enhances the color stability of the liquid. Component (A) also contributes to cleaning power. The liquid detergent may contain one type of component (A) or two or more types of components.

[0011] Examples of component (A) include the following. (1) Linear or branched alkylbenzenesulfonic acid (LAS or ABS) having an alkyl group having 8 to 18 carbon atoms or a salt thereof. (2) Alkanesulfonic acids having 10 to 20 carbon atoms or salts thereof. (3) α-olefin sulfonic acid having 10 to 20 carbon atoms or its salt (AOS). (4) Alkyl sulfate or alkenyl sulfate having 10 to 20 carbon atoms or its salt (AS). (5) Alkyl (or alkenyl) ether sulfate or a salt thereof (AES) having a linear or branched alkyl (or alkenyl) group having 10 to 20 carbon atoms, which is obtained by adding an average of 0.5 to 10 moles of any alkylene oxide having 2 to 4 carbon atoms, or ethylene oxide and propylene oxide (molar ratio EO / PO=0.1 / 9.9 to 9.9 / 0.1). (6) Alkyl (or alkenyl) phenyl ether sulfate or a salt thereof having a linear or branched alkyl (or alkenyl) group having 10 to 20 carbon atoms, which is obtained by adding an average of 3 to 30 moles of any alkylene oxide having 2 to 4 carbon atoms, or ethylene oxide and propylene oxide (molar ratio EO / PO=0.1 / 9.9 to 9.9 / 0.1). (7) An alkyl (or alkenyl) ether carboxylic acid or a salt thereof having a linear or branched alkyl (or alkenyl) group having 10 to 20 carbon atoms, which is obtained by adding an average of 0.5 to 10 moles of any alkylene oxide having 2 to 4 carbon atoms, or ethylene oxide and propylene oxide (molar ratio EO / PO=0.1 / 9.9 to 9.9 / 0.1). (8) Alkyl polyhydric alcohol ether sulfates or salts thereof, such as alkyl glyceryl ether sulfonic acids having 10 to 20 carbon atoms. (9) Long-chain monoalkyl, dialkyl, or sesquialkyl phosphates or salts thereof. (10) Polyoxyethylene monoalkyl, dialkyl or sesquialkyl phosphate or its salt. Examples of salts of the above-mentioned component (A) include alkali metal salts, alkaline earth metal salts, alkanolamine salts, and ammonium salts. Examples of the alkali metal salt include sodium salt and potassium salt. Examples of the alkaline earth metal salt include magnesium salt and calcium salt. Examples of the alkanolamine salt include monoethanolamine salt (monoethanolamine), diethanolamine salt (diethanolamine), triethanolamine salt (triethanolamine), etc. Among them, as the salt of component (A), alkali metal salt is preferable, and sodium salt and potassium salt are more preferable.

[0012] As the component (A), α-olefin sulfonic acid or a salt thereof, linear alkylbenzene sulfonic acid or a salt thereof, or an alkane sulfonic acid or a salt thereof is preferred. From the viewpoints of liquid color stability and detergency, it is preferable that the component (A) contains a component (Aa) which is one or more members selected from the group consisting of α-olefin sulfonic acid or a salt thereof, and linear alkylbenzene sulfonic acid or a salt thereof. Of the total mass of the component (A) contained in the liquid detergent, the sum of the components (Aa) is, for example, preferably more than 90 mass%, more preferably more than 93 mass%, even more preferably more than 95 mass%, and particularly preferably more than 98 mass%. It may be 100 mass%.

[0013] The α-olefin sulfonic acid (AOS) is preferably an AOS having a carbon number of 14 to 16. Examples of AOS salts include sodium salts. In linear alkylbenzene sulfonic acid (LAS), the number of carbon atoms in the linear alkyl group bonded to the benzene ring is 8 to 18, preferably 8 to 16, and more preferably 10 to 14. Examples of LAS salts include sodium salts and potassium salts. Examples of the alkanesulfonic acid or its salt include alkanesulfonic acids having 10 to 20 carbon atoms or their salts, preferably alkanesulfonic acids having 14 to 17 carbon atoms or their salts, and particularly preferably secondary alkanesulfonic acids (SAS) having 14 to 17 carbon atoms or their salts. Examples of the SAS salt include sodium salts.

[0014] <(B) component> The component (B) is an aminocarboxylic acid type chelating agent. The component (B) contained in the liquid detergent may be one type or two or more types. In the present invention, component (B) functions as a component that enhances the color stability of the liquid. Component (B) also contributes to detergency.

[0015] Examples of component (B) include the following compounds and their salts (for example, alkali metal salts): Component (B) may be a hydrate. MethylglycineDiacetic Acid (MGDA), Ethylene Diamine Tetraacetic Acid (EDTA), Dicarboxymethyle Glutamic Acid (GLDA), Nitrilo Triacetic Acid (NTA), Dihydroxyethylglycine (DEG), N-(2-hydroxylethyl)iminodiacetic acid (HEIDA), Hydroxyethylethylenediaminetetraacetic acid (HEDTA), Diethylene Triamine Pentaacetic Acid (DTPA), Hydroxyethyl Ethylene Diamine Triacetic Acid Acid, abbreviated as "HEDTA"), Aspartate Diacetic Acid, abbreviated as "ASDA", Ethylenediamine Disuccinic Acid, abbreviated as "EDDS", Hydroxyiminodisuccinic Acid (abbreviated as "HIDS"), Iminodisuccinic Acid (abbreviated as "IDS"), etc.

[0016] As the component (B), methylglycine diacetic acid (MGDA) or a salt thereof, ethylenediaminetetraacetic acid (EDTA) or a salt thereof, L-glutamic acid diacetic acid (GLDA) or a salt thereof, and nitrilotriacetic acid (NTA) or a salt thereof are preferred. From the viewpoint of liquid color stability and detergency, it is preferable that the component (B) contains a component (Bb) which is one or more selected from the group consisting of MGDA or an alkali metal salt thereof, EDTA or an alkali metal salt thereof, GLDA or an alkali metal salt thereof, and NTA or an alkali metal salt thereof. When the component (Bb) is an alkali metal salt, a sodium salt is preferable. Of the total mass of the component (B) contained in the liquid detergent, the total of the components (Bb) is, for example, preferably more than 90 mass%, more preferably more than 93 mass%, even more preferably more than 95 mass%, and particularly preferably more than 98 mass%. It may be 100 mass%.

[0017] <(C) component> The component (C) is a nonionic aromatic compound selected from compounds (c1) represented by the following formula (c1): The component (C) contained in the liquid detergent may be one type or two or more types. In the present invention, component (C) contributes to improving visibility. Even if the type and content of component (D) contained in the liquid detergent is the same, the incorporation of component (C) can make the liquid color brighter and improve visibility.

[0018] [ka]

[0019] In formula (c1), X is an oxygen atom or an alkylene group having 1 to 4 carbon atoms, each Y is independently a chlorine atom or a bromine atom, each a, b, and c is independently 0 or an integer of 1 to 3, m is 0 or 1, and n is 0 or 1. In addition, -(Y)b means that b of the hydrogen atoms bonded to the carbon atoms constituting the benzene ring are substituted with Y. The same applies to -(Y)c, -(OH)m, and -(OH)n.

[0020] As compound (c1), a compound in which X is an oxygen atom or a methylene group, Y is a chlorine atom or a bromine atom, m is 0, n is 0 or 1, a is 1, b is 0, 1 or 2, and c is 0, 1 or 2 is more preferable.

[0021] Specific examples of preferred compound (c1) include monochlorohydroxydiphenyl ether (a compound in which X is an oxygen atom, a is 1, Y is a chlorine atom, one of b and c is 1 and the other is 0, m is 0, and n is 0), dichlorohydroxydiphenyl ether (a compound in which X is an oxygen atom, a is 1, Y is a chlorine atom, b is 1, c is 1, m is 0, and n is 0), trichlorohydroxydiphenyl ether (a compound in which X is an oxygen atom, a is 1, Y is a chlorine atom, one of b and c is 1 and the other is 2, m is 0, and n is 0), and benzylchlorophenol (a compound in which X is a methylene group, a is 1, Y is a chlorine atom, b is 0, c is 1, m is 0, and n is 0).

[0022] As the component (C), the following compounds are preferred in terms of liquid color. Diclosan (4,4'-dichloro-2-hydroxydiphenyl ether, a compound represented by formula (c1) where X = oxygen atom, Y = chlorine atom, a = 1, b = 1, c = 1, n = 0, and m = 0), and triclosan (2,4,4'-trichloro-2'-hydroxydiphenyl ether, a compound represented by formula (c1) where X = oxygen atom, Y = chlorine atom, a = 1, b = 2, c = 1, n = 0, and m = 0). For example, the total amount of diclosan and triclosan in the total mass of component (C) contained in the liquid detergent is preferably 90 mass% or more, more preferably 93 mass% or more, even more preferably 95 mass% or more, and particularly preferably 98 mass% or more. It may be 100 mass%.

[0023] <(D) component> The component (D) is a dye selected from the group consisting of phthalocyanine dyes, triphenylmethane dyes, and thiazine dyes. The component (D) contained in the liquid detergent may be one type or two or more types. Two types are preferred from the viewpoint of ensuring visibility. By blending component (D) into the liquid detergent, the liquid can be colored in a blue tone. When only one type of component (D) is used, the component (D) is preferably a triphenylmethane-based dye. When two or more types of (D) components are blended, the (D) component is preferably a combination of one or more types selected from phthalocyanine dyes and one or more types selected from triphenylmethane dyes, or a combination of one or more types selected from phthalocyanine dyes and one or more types selected from thiazine dyes.

[0024] Specifically, an example of the phthalocyanine dye is Direct Blue 86 (a compound represented by the following formula (d1)). An example of a thiazine dye is methylene blue (a compound represented by the following formula (d2)). Examples of triphenylmethane dyes include bromophenol blue (a compound represented by the following formula (d3)), Green No. 3 (a compound represented by the following formula (d4)), and Blue No. 1 (a compound represented by the following formula (d5)).

[0025] [ka]

[0026] <Water> The liquid detergent preferably contains water as a solvent from the viewpoints of ease of handling during production, solubility in water during use, etc. Examples of water include ion-exchanged water and pure water. The water content is preferably from 70 to 98.5 mass %, and more preferably from 80 to 95 mass %, based on the total mass of the liquid detergent.

[0027] <Optional ingredients> The liquid detergent may contain optional components other than the components (A) to (D). Examples of optional components include surfactants other than the component (A) (hereinafter sometimes referred to as "optional surfactants"), pH adjusters, water-miscible organic solvents, thickeners, antifungal agents, bactericides, antioxidants, preservatives, ultraviolet absorbers, fragrances, etc. The total amount of components (A) to (D) and any optional components does not exceed 100 mass %.

[0028] The optional surfactant may be an amphoteric surfactant, an amine oxide type surfactant, a nonionic surfactant, a cationic surfactant, a higher fatty acid and its salt (i.e., soap). The optional surfactant may be used alone or in combination of two or more kinds. Examples of the pH adjuster include sodium hydroxide, potassium hydroxide, citric acid, and hydrochloric acid.

[0029] In this specification, the water-miscible organic solvent means an organic solvent that dissolves in an amount of 25 g or more in 1 L of water at 25°C. Examples of the water-miscible organic solvent 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 glycol 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. The water-miscible organic solvent may be used alone or in combination of two or more kinds. When a water-miscible organic solvent is used, the content of the water-miscible organic solvent relative to the total mass of the liquid detergent is, for example, preferably 0.1 to 5.0 mass %, and more preferably 0.5 to 3.5 mass %.

[0030] <Content / ratio> The content of component (A) relative to the total mass of the liquid detergent is preferably 0.1 to 5 mass%, more preferably 0.2 to 4 mass%, even more preferably 0.4 to 3 mass%, particularly preferably 0.5 to 2 mass%, and most preferably 0.5 to 1 mass%. When the content of component (A) is within the above range, the effect of improving the liquid color stability is excellent. When the content of component (A) is too high, the liquid color stability tends to decrease, which is thought to be due to a change in the state of existence of the surfactant in the composition.

[0031] The content of component (B) relative to the total mass of the liquid detergent is preferably 0.1 to 5 mass%, more preferably 0.5 to 4 mass%, and particularly preferably 1 to 3 mass%. When the content of component (B) is within the above range, the effect of improving the liquid color stability is excellent. When the content of component (B) is too high, the liquid color stability tends to decrease, which is thought to be due to a change in the state of the chelating agent in the composition.

[0032] The content of component (C) relative to the total mass of the liquid detergent is preferably 0.01 to 3 mass%, more preferably 0.05 to 1 mass%, and particularly preferably 0.1 to 0.6 mass%. When the content of component (C) is equal to or greater than the lower limit, the effect of improving visibility is excellent. When the content of component (C) is equal to or less than the upper limit, an appropriate color tone is easily obtained from the viewpoint of preventing coloring.

[0033] The content of component (D) relative to the total mass of the liquid detergent is preferably 0.001 to 0.01 mass%, more preferably 0.002 to 0.08 mass%, and particularly preferably 0.0025 to 0.0075 mass%. When the content of component (D) is equal to or greater than the above lower limit, the effect of improving visibility is excellent. When the content of component (D) is equal to or less than the above upper limit, coloring is unlikely to occur.

[0034] (A+B) / C, which represents the mass ratio of the total content of components (A) and (B) to the content of component (C), is from 2 to 400, preferably from 3 to 50, more preferably from 4 to 40, and particularly preferably from 5 to 15. When the value of (A+B) / C is within the above range, the effect of improving the liquid color stability is excellent.

[0035] D / (C+D), which represents the mass ratio of the content of component (D) to the total content of components (C) and (D), is preferably 0.001 to 0.05, more preferably 0.001 to 0.01, and particularly preferably 0.001 to 0.005. When D / (C+D) is within the above range, the effect of improving visibility is excellent.

[0036] The total amount of surfactants including component (A) and any optional surfactants, based on the total mass of the liquid detergent, is preferably 0.1 to 8 mass%, more preferably 0.2 to 6 mass%, even more preferably 0.4 to 4 mass%, and particularly preferably 0.5 to 3 mass%. The proportion of the component (A) in the total surfactant amount is, for example, preferably more than 80 mass%, more preferably more than 85 mass%, even more preferably more than 90 mass%, and particularly preferably more than 95 mass%. It may even be 100 mass%.

[0037] <ph> The pH of the liquid detergent at 25° C. is preferably 8 to 12, more preferably 9 to 11. If the pH is within the above range, visibility and cleaning power for stains in a bathroom environment are satisfactory. In this specification, the pH of the liquid detergent is a value measured by a method conforming to JIS Z 8802:2011 "pH measurement method."

[0038] The viscosity of the liquid detergent at 25°C is less than 30 mPa·s, preferably 1 mPa·s or more and less than 30 mPa·s, more preferably 1 to 20 mPa·s, and even more preferably 3 to 15 mPa·s. If the viscosity is within the above range, the detergent will be more likely to diffuse in a mist when discharged from the discharge container in the method of use described below, and will stay better on the items being washed. In this specification, the viscosity of a liquid detergent is a value measured at a liquid temperature of 25°C using a Brookfield viscometer with rotor number 1 and a rotor rotation speed of 60 rpm, 60 seconds after the rotor starts rotating.

[0039] <Liquid cleaning products for hard surfaces> The liquid detergent product for hard surfaces (hereinafter, sometimes simply referred to as "liquid detergent product") has a dispensing container and the liquid detergent for hard surfaces of the present invention contained in the dispensing container.

[0040] A trigger-type spray container is preferable as a dispensing container for containing a liquid detergent. There are no particular limitations on the trigger-type spray container, and any container (sprayer) used in general cleaning agent products (a trigger-type spray container containing a cleaning agent) can be used. The trigger-type spray container may be one that can spray the liquid detergent in a mist. It may also be one that can spray either mist or foam, or one that can switch between the two. It may also be one that can switch between a wide pattern that sprays the liquid detergent over a wide area and a narrow pattern that sprays the liquid detergent over a narrow area. The trigger type spray container can have a known mechanism and may be of either a direct pressure type or a pressure accumulation type. Examples of the trigger type spray container include those described in JP-A-10-146546 and JP-A-2000-24561.

[0041] <Manufacturing method> The liquid detergent of the present invention can be produced in accordance with a method for producing a conventionally known liquid detergent. For example, the components (A) to (D) are added to water as a solvent, and optional components are added as necessary, followed by mixing. The liquid detergent product of the present invention is produced by producing a liquid detergent by the above-mentioned method and storing it in a dispensing container.

[0042] <How to use> One method of using a liquid detergent is to store the liquid detergent in a dispenser container, dispense an appropriate amount of the liquid detergent from the dispenser container and bring it into contact with the item to be washed, leave it for a desired period of time, and then rinse with water to clean the item. The liquid detergent of the present invention has excellent detergency, and therefore can clean the object without applying mechanical force such as scrubbing the object with a cleaning tool such as a hand or a sponge. Here, "without applying mechanical force" means that no intentional cleaning operation is performed other than contact with the liquid detergent. Note that the liquid detergent that has been brought into contact with the object flows naturally downward, vibrations that are not intended for cleaning are transmitted to the object, and the liquid detergent that has been brought into contact with the object is rinsed with water, which correspond to cases where the object is cleaned without applying mechanical force. Alternatively, a method of washing the object by applying mechanical force may be used. For example, the object may be scrubbed with a sponge or the like soaked in a liquid detergent. The object may be brought into contact with the liquid detergent and then scrubbed with a sponge or the like. The object may be immersed in a diluted liquid detergent and then scrubbed with a sponge or the like.

[0043] The object to be washed may be any hard surface of an article, for example, hard surfaces in a bathroom, bathroom supplies, hard surfaces in a toilet, toilet supplies, hard surfaces in a kitchen, and kitchen supplies (dishes, cooking utensils, etc.). The hard surface means a surface made of a hard material such as plastics, ceramics, glass, stainless steel, etc.

[0044] As described above, the liquid detergent of the present invention contains the components (A) to (D) and has a specific mass ratio of (A+B) / C, so that the liquid color is appropriate from the viewpoints of visibility and prevention of coloring, while the liquid color stability is improved. The liquid detergent of the present invention does not require mechanical force, so it is suitable for cleaning objects such as bathtubs, which have large surfaces and require a lot of labor when scrubbing. For this reason, the liquid detergent of the present invention is suitable as a liquid detergent for the bathroom. EXAMPLES

[0045] The present invention will be described in detail below with reference to examples, but the present invention is not limited to the following description.

[0046] (Raw materials used) <Component (A)> A-1: AOS, sodium α-olefin sulfonate with 14 carbon atoms (manufactured by Lion Specialty Chemicals, product name "Liporan LJ441"). A-2: LAS, linear (C10-16) sodium alkylbenzene sulfonate, (manufactured by Lion Corporation, product name "Lipon LH-200CJ"). A-3: SAS, secondary sodium alkanesulfonate having 14 to 17 carbon atoms, manufactured by Clariant Japan, product name "HOSTAPUR (registered trademark) SAS30A". A-4 (comparison product): Potassium palmitate (manufactured by Fujifilm Wako Pure Chemical Industries, product name "potassium palmitate").

[0047] <(B) component> B-1: Methylglycine diacetate·sodium (manufactured by BASF, product name "Trilon M MAX"). B-2: Sodium ethylenediaminetetraacetate (EDTA·Na), (manufactured by Akzo Nobel, product name "Dissolvin Z", chelating agent). B-3: Tetrasodium glutamic diacetate (GLDA·Na), (manufactured by Chelestos, product name "Chilestos CMG-40"). B-4: Nitrilotriacetic acid (NTA) 3Na H 2 O (manufactured by Chelesto Corporation, product name "Chilesto NTA"). B-5 (comparison product): Malic acid (manufactured by Fuso Chemical Co., Ltd., product name "Malic Acid 50").

[0048] <(C) component> C-1: Dichlosan (4,4'-dichloro-2-hydroxydiphenyl ether) (manufactured by BASF, product name "TINOSAN HP100"). · C-2: Triclosan (5-chloro-2-(2,4-dichlorophenoxy)phenol (manufactured by Wako Pure Chemical Industries, Ltd.)). C-3 (comparison product): Sodium benzoate (manufactured by Fushimi Pharmaceutical Co., Ltd., product name "Sodium Benzoate").

[0049] <(D) component> D-1: Direct Blue 86 (manufactured by Sumitomo Chemical Co., Ltd., product name "Sumilight Supra Turquise Blue G conc"). ·D-2: Edible Green No. 3 (manufactured by Kinmi Kasei Co., Ltd., product name: "Green No. 3"). D-3: Blue No. 1 (Tokyo Chemical Industry Co., Ltd., product name "Food Blue No. 1"). D-4: Methylene blue (Tokyo Chemical Industry Co., Ltd., product name "Methylene Blue"). D-5: Bromophenol blue (Tokyo Chemical Industry Co., Ltd., product name "Bromophenol Blue"). D-6 (comparison product): Acid Blue 9 (Tokyo Chemical Industry Co., Ltd., product name "Acid Blue 9"). D-7 (comparison product): Sudan Blue II (manufactured by Sigma-Aldrich, product name "Solvent Blue 35").

[0050] <Optional ingredients> pH adjuster: 1N sodium hydroxide solution (Kanto Chemical Industry Co., Ltd.), citric acid (Fuso Chemical Industry Co., Ltd.). -Butyl carbitol: Diethylene glycol monobutyl ether (manufactured by Nippon Nyukazai Co., Ltd., product name "Butyl diglycol"), a water-miscible organic solvent. <Water> Water: Ion-exchanged water.

[0051] Evaluation method <Evaluation of liquid color stability of appearance> The color tone of the liquid detergent prepared in each example was measured using a spectrophotometer (Hitachi Ratio Beam U-1000 manufactured by Hitachi, Ltd.) Specifically, the absorbance was measured at 608 nm, which is the absorption wavelength band of blue-based dyes. Initial absorbance A before storage 0 (nm) and absorbance A after storage in a constant temperature bath at 50°C for 2 weeks 1 The retention rate was calculated using the following formula (1), and the liquid color stability was evaluated on a 5-point scale according to the following criteria. A score of 3 or more was considered to be acceptable. Maintenance rate (unit: %) = absorbance A after storage 1 / Initial absorbance A 0 ×100 …(1) [Evaluation Criteria] 5 points: Retention rate is between 90% and 100%. 4 points: Retention rate is between 70% and 90%. 3 points: Retention rate is between 50% and 70%. 2 points: Retention rate is between 20% and 50%. 1 point: Retention rate is less than 20%.

[0052] <Evaluation of liquid color> The liquid cleaner prepared in each example was placed in a trigger container of Lion Corporation's product name "Look Plus Bathtub Cleansing" and sprayed onto the inner wall (white) of the bathtub. If the color of the liquid cleaner is too light, it is difficult to visually distinguish between sprayed and unsprayed areas, and if it is too dark, there is a concern that the inner wall will be stained. The inner wall of the bathtub was visually observed immediately after spraying, and the visibility was evaluated on a 5-point scale according to the following criteria. A score of 2 to 4 was judged to be acceptable. [Evaluation Criteria] 1 point: The liquid color is too light and visibility is poor. 2 points: The liquid color is slightly pale, but visibility is still obtained. 3 points: The liquid color is good and the visibility is very good. 4 points: The liquid color is slightly dark, but not enough to cause concern about coloration. 5 points: The liquid color is too dark, causing concerns about discoloration.

[0053] <Examples 1 to 39> Examples 2 to 7, 9 to 16, 18 to 29, and 31 to 34 are working examples. Examples 1, 8, 17, 30, and 35 to 40 are comparative examples.

[0054] According to the compositions shown in Tables 1 to 5, components (A) to (D) and optional components were added to water and mixed to prepare the liquid detergents of each example. The amounts in the table are calculated as pure amounts. The "appropriate amount" in the amount is the amount needed to adjust the pH of the liquid detergent to the value in the table, and the "balance" is the remainder needed to make the liquid detergent 100% by mass. If the amount is not listed in the table, it means that the ingredient is not included. The results of evaluation of each example of liquid detergent using the above-mentioned evaluation method are shown in the table.

[0055] [Table 1]

[0056] [Table 2]

[0057] [Table 3]

[0058] [Table 4]

[0059] [Table 5]

[0060] As shown in the results in Tables 1 to 5, the examples containing components (A) to (D) and having a mass ratio of (A+B) / C of 2 to 400 had good liquid colors from the standpoints of visibility and prevention of coloration, and also had good liquid color stability when stored at high temperatures. Example 1, which did not contain the component (C), had poor liquid color stability. Example 8, which did not contain the component (B), had poor liquid color stability. Example 17, which did not contain the component (A), had poor liquid color stability. Example 30, in which (A+B) / C was less than 2, had poor liquid color stability. Example 35, in which (A+B) / C was greater than 400, had poor liquid color stability. In Example 36, in which a cyan dye and an anthraquinone dye were used instead of the component (D), the liquid color was too light and visibility was poor. In addition, the liquid color stability was poor despite the blending of components (A) to (C). In Example 37, in which a cyan dye was used instead of the component (D), the liquid color was too light and visibility was poor, and the liquid color stability was poor despite the blending of (A) to (C). Example 38, in which a soap-based anionic surfactant was used instead of component (A), had poor liquid color stability. In Example 39, in which a chelating agent other than an aminocarboxylic acid type was used instead of component (B), the liquid color stability was poor. Example 40, in which a nonionic aromatic compound not having the structure of formula (c1) was used instead of component (C), exhibited poor liquid color stability.< / ph>

Claims

1. Component (A): a non-soap anionic surfactant, (B) component: an aminocarboxylic acid type chelating agent, Component (C): a nonionic aromatic compound selected from compounds represented by the following formula (c1), and Component (D): Contains a dye selected from a phthalocyanine dye, a triphenylmethane dye, and a thiazine dye, The liquid cleaning agent for hard surfaces, wherein (A+B) / C, which represents a mass ratio of the total content of the (A) component and the (B) component to the content of the (C) component, is 2 to 400. 【Chemistry 1】 [In formula (c1), X is an oxygen atom or an alkylene group having 1 to 4 carbon atoms, each Y is independently a chlorine atom or a bromine atom, a, b, and c are independently 0 or an integer of 1 to 3, m is 0 or 1, and n is 0 or 1.]

2. 2. The liquid cleaning agent for hard surfaces according to claim 1, wherein the component (C) comprises one or more selected from the group consisting of diclosan and triclosan.

3. 2. The liquid cleaning agent for hard surfaces according to claim 1, which is for use in a bathroom.

4. A liquid cleaning agent product for hard surfaces, comprising the liquid cleaning agent for hard surfaces according to any one of claims 1 to 3, and a dispensing container containing the liquid cleaning agent for hard surfaces.

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