Detergent composition for hard surfaces

Abstract

To provide a detergent composition for hard surfaces that exhibits good cleaning power for complex stains of sebum and soap scum, and is less likely to damage a substrate.SOLUTION: A detergent composition for hard surfaces includes (a) an ampholytic surfactant, (b) an aromatic alcohol with a LogP of 1.3 or more, (c) a chelator with a calcium stability constant (pKCa) of 6 or more and 13 or less, and water. The detergent composition has a pH of 8 or more and 12 or less at 25°C.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a cleaning composition for hard surfaces and a method for cleaning hard surfaces. [Background technology]

[0002] In the residential environment facilities surrounding us, there are various hard surfaces made of materials such as tiles, plastics, and metals, and various stains are attached in daily life. In particular, hard surfaces such as bathrooms and kitchens are surfaces that people frequently come into contact with, so many stains tend to remain and accumulate, and are difficult to remove by cleaning. In general, stains attached to bathrooms such as bathtubs, bathroom walls and floors are stubborn stains that are a combination of fatty acid metal salts (soap scum) formed by binding fatty acids contained in body cleansers and shampoos with calcium and the like in tap water, and sebum stains, making them difficult to clean. To deal with such stains, a cleaning agent is applied and the stains are scrubbed using a sponge or the like, but cleaning hard surfaces such as bathrooms using cleaning tools is a cumbersome task, and is heavy work, especially for the elderly. Therefore, there is a demand for a technology that allows anyone to easily remove the stains without having to do heavy work such as scrubbing, and development of a cleaning agent composition containing a specific surfactant, chelating agent, solvent, etc. is underway.

[0003] For example, Patent Document 1 discloses a cleaning composition for hard surfaces that contains a betaine-type amphoteric surfactant, a specific aromatic alcohol, and a chelating agent, in which the ratio of the betaine-type amphoteric surfactant to the total surfactants is 65 mass% or more and the pH is 2 or more and 6 or less. Patent Document 2 discloses a liquid cleaning composition for hard surfaces, which contains a phosphonic acid chelating agent, another chelating agent, a glycol solvent, and an amphoteric surfactant, in which the mass ratio of the anionic surfactant to the total chelating agents is 0.30 or less, and the pH is 5.8 or more and 7.5 or less. Patent Document 3 discloses a liquid bathroom cleaner that contains component (A): 0.1 to 5.0 mass % of a surfactant including a non-soap anionic surfactant, component (B): a glycol-based solvent, and component (C): an aminocarboxylic acid-type chelating agent, in which the mass ratio of component (C) / component (A) is 0.6 to 6.0 and the pH at 25°C is greater than 10 and less than 12. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] JP 2015-113455 A [Patent Document 2] JP 2018-150523 A [Patent Document 3] JP 2016-124965 A Summary of the Invention [Problem to be solved by the invention]

[0005] The present invention provides a cleaning composition for hard surfaces which has good detergency against combined stains of sebum stains and soap scum stains and is excellent in low damage to substrates, and a cleaning method for hard surfaces using the same. [Means for solving the problem]

[0006] The present invention comprises (a) an amphoteric surfactant (hereinafter referred to as component (a)), (b) an aromatic alcohol having a LogP of 1.3 or more (hereinafter referred to as component (b)), (c) a calcium stability constant (pK Ca The present invention relates to a hard surface cleaning composition comprising a chelating agent having a pH of 8 or more and 12 or less at 25°C, and water, the chelating agent having a pH of 6 or more and 13 or less [hereinafter referred to as component (c)] [hereinafter referred to as component (c)].

[0007] The present invention also relates to a method for cleaning a hard surface, which comprises applying the above-mentioned cleaning composition for hard surfaces of the present invention to the hard surface, and then rinsing the surface without scrubbing. Effect of the Invention

[0008] According to the present invention, there are provided a cleaning agent composition for hard surfaces which has good detergency against combined stains such as sebum stains and soap scum stains and is excellent in causing little damage to substrates, and a cleaning method for hard surfaces using the same. [Brief description of the drawings]

[0009] [Figure 1] Schematic diagram showing the evaluation methods in the examples and comparative examples DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0010] [Cleaning composition for hard surfaces] The cleaning composition for hard surfaces of the present invention contains components (a), (b), (c) and water, and has a pH at 25°C of 8 or more and 12 or less.

[0011] In the present invention, by combining components (a), (b), and (c) and using them in the weak alkaline range, stubborn dirt formed by a complex of sebum dirt and soap scum can be more effectively removed. This is presumably because the detergent composition of the present invention has a pH in the weak alkaline range, and the complex of components (a), (b), and (c) efficiently adsorbs to the surface of fatty acid metal salts (soap scum) formed by binding fatty acids derived from sebum with calcium in tap water, and component (c) extracts calcium ions, and the amphoteric surfactant of component (a) dissolves and disperses the fatty acid metal salts that have become partly fatty acid ions, thereby promoting the cleaning effect. However, the mechanism of action is not limited to the above reasons.

[0012] Component (a) is an amphoteric surfactant. The component (a) may include one or more amphoteric surfactants selected from betaine type surfactants and amine oxide type surfactants.

[0013] The component (a) is more preferably one or more amphoteric surfactants selected from betaine-type amphoteric surfactants having a hydrocarbon group with 7 to 14 carbon atoms, and amine oxide-type amphoteric surfactants having a hydrocarbon group with 7 to 14 carbon atoms. Examples of the hydrocarbon group that these surfactants have include alkyl groups and alkenyl groups. The number of carbon atoms in the hydrocarbon group may be, for example, 8 or more and 14 or less.

[0014] Of the (a) component, the betaine-type amphoteric surfactant has one or more, preferably one or more and four or less, more preferably three or less, and even more preferably two or less, hydrocarbon groups having 7 to 14 carbon atoms. Of the (a) component, the amine oxide surfactant has one or more, preferably one or more and four or less, more preferably three or less, and even more preferably two or less, hydrocarbon groups having 7 to 14 carbon atoms.

[0015] Among the components (a), examples of the betaine-type amphoteric surfactant include the betaine-type amphoteric surfactant represented by the following general formula (a1-1).

[0016] [ka]

[0017] [In the formula, R 11 is an alkyl or alkenyl group having 7 to 14 carbon atoms, R 12 is an alkylene group having 1 to 6 carbon atoms. A is a group selected from -COO-, -CONH-, -OCO-, -NHCO-, and -O-, and p is the number 0 or 1. R 13 , R 14 is an alkyl group or a hydroxyalkyl group having 1 to 3 carbon atoms; R 15 is an alkylene group having 1 to 5 carbon atoms which may be substituted with a hydroxyl group. B is -SO3 - , -OSO3 - , -COO - is a group selected from the following:

[0018] In general formula (a1-1), R 11 The number of carbon atoms in R is preferably 11 or 12. A is preferably -COO- or -CONH-, more preferably -CONH-. 12 The number of carbon atoms in R is preferably 2 or 3. 13 , R 14 is preferably a methyl group. When p in the general formula (a1-1) is 0, R 11 may be an alkyl or alkenyl group having 8 to 14 carbon atoms.

[0019] The betaine type amphoteric surfactant is preferably one or more selected from alkyl carboxy betaine, alkyl amido carboxy betaine, alkyl sulfo betaine, alkyl hydroxy sulfo betaine, alkyl amido hydroxy sulfo betaine, and alkyl amino fatty acid salt. The betaine type amphoteric surfactant is more preferably one or more selected from alkyl amido propyl-N,N-dimethyl acetate betaine, alkyl-N,N-dimethyl-2-hydroxypropyl sulfo betaine, alkyl amido propyl-N,N-dimethyl-2-hydroxypropyl sulfo betaine, and alkyl amido propyl-N,N-dimethyl-propyl sulfo betaine. These alkyl groups have 7 to 14 carbon atoms. The betaine type amphoteric surfactant is more preferably one or more selected from lauric acid amido propyl-N,N-dimethyl acetate betaine, hydroxy lauryl sulfo betaine, lauryl-N,N-dimethyl-2-hydroxypropyl sulfo betaine, and lauric acid amido propyl-N,N-dimethyl-2-hydroxypropyl betaine. Two or more types of betaine-type amphoteric surfactants may be used.

[0020] Preferred betaine-type amphoteric surfactants include betaines such as alkyl (carbon number 8 to 14)-N,N-dimethyl acetate betaine, fatty acid (fatty acid carbon number 8 to 14) amidopropyl-N,N-dimethyl acetate betaine, alkyl (carbon number 8 to 14)-N,N-dimethylethanesulfobetaine, alkyl (carbon number 8 to 14)-N,N-dimethyl-2-hydroxypropylsulfobetaine, fatty acid (fatty acid carbon number 8 to 14) amidopropyl-N,N-dimethyl-2-hydroxypropylsulfobetaine, and alkyl (carbon number 8 to 14) carboxymethylhydroxyethylimidazolium betaine.

[0021] Among the components (a), examples of the amine oxide amphoteric surfactant include the amine oxide amphoteric surfactant represented by the following general formula (a1-2).

[0022] [ka]

[0023] [In the formula, R 21 is an alkyl or alkenyl group having 7 to 14 carbon atoms, R 22 is an alkylene group having 1 to 3 carbon atoms, A is a group selected from -COO-, -CONH-, -OCO-, and -NHCO-, p is a number of 0 or 1, R 23 , R 24 are each an alkyl group or a hydroxyalkyl group having 1 to 3 carbon atoms.

[0024] In general formula (a1-2), R 21 The number of carbon atoms in R is preferably 11 or 12. A is preferably -COO- or -CONH-, more preferably -CONH-. 22 The number of carbon atoms in R is preferably 2 or 3. 23 , R 24 is preferably a methyl group. When p in the general formula (a1-2) is 0, R 21 may be an alkyl or alkenyl group having 8 to 14 carbon atoms.

[0025] Specific examples of the amine oxide include N-lauryl-N,N-dimethylamine oxide, N-myristyl-N,N-dimethylamine oxide, N-lauroylaminopropyl-N,N-dimethylamine oxide, and N-myristylaminopropyl-N,N-dimethylamine oxide. Of these, N-lauryl-N,N-dimethylamine oxide (lauryl dimethylamine oxide), N-myristyl-N,N-dimethylamine oxide, and lauric acid amide propyl dimethylamine oxide are preferred, and N-lauryl-N,N-dimethylamine oxide and N-myristyl-N,N-dimethylamine oxide are preferred from the viewpoint of detergency.

[0026] Component (b) is an aromatic alcohol having a LogP of 1.3 or more. From the viewpoint of cleaning performance, component (b) has a LogP value of 1.3 or more, preferably 1.4 or more, and from the viewpoint of low damage to substrates, preferably 3.0 or less, more preferably 2.0 or less, and even more preferably 1.5 or less.

[0027] In the present invention, the LogP value is a coefficient indicating the affinity of an organic compound to water and 1-octanol. The 1-octanol / water partition coefficient P is the distribution equilibrium when a trace amount of a compound is dissolved as a solute in a two-phase solvent of 1-octanol and water, and is the ratio of the equilibrium concentration of the compound in each solvent, and is generally expressed in the form of their logarithm LogP to the base 10. The LogP values ​​of many compounds have been reported, and many values ​​are listed in databases available from, for example, Daylight Chemical Information Systems, Inc. (Daylight CIS), so they can be referred to. If there is no actual LogP value, it can be calculated using a program such as "PerkinElmer ChemDraw 19.1" available from the PerkinElmer website. The LogP value can be obtained from this program.

[0028] The fragment approach is based on the chemical structure of the compound, taking into account the number of atoms and the type of chemical bonds (cf. A. Leo, Comprehensive Medicinal Chemistry, Vol. 4, C. Hansch, PG Sammens, JB Taylor and CA Ramsden, Eds., p. 295, Pergamon Press, 1990). In the present invention, the actual LogP value is used if available, and if not, the LogP value calculated by the program PerkinElmer ChemDraw 19.1 is used.

[0029] The aromatic alcohol of component (b) has an aromatic group and a hydroxy group, and is preferably a compound having an aromatic group and a hydroxy group and having a molecular weight of from 106 to 250. The aromatic group is an aromatic hydrocarbon group, and examples of the aromatic group include a phenyl group, a benzyl group, and a phenethyl group.

[0030] From the viewpoint of cleaning properties, the component (b) is preferably a compound represented by the following general formula (b-1). R 1b O-(R 2b O) l -H (b-1) (In the formula, R 1b is a hydrocarbon group having an aromatic group and a total carbon number of 6 to 10, l is an integer of 0 to 2, R 2b is an alkylene group having 2 to 4 carbon atoms. Preferably, the molecular weight of the compound is 106 to 250.

[0031] R 1b The total number of carbon atoms in R is the number of carbon atoms including the aromatic group. 1b The total number of carbon atoms in R is 6 or more from the viewpoint of cleaning properties, and is 10 or less, preferably 9 or less, and more preferably 8 or less from the viewpoint of low damage to the substrate. 1b is an aromatic hydrocarbon group, and examples thereof include a phenyl group, a benzyl group, and a phenethyl group. In general formula (b-1), 1 is preferably 1 or less, and more preferably 0, from the viewpoint of cleaning properties.

[0032] Specifically, from the viewpoint of compatibility between cleaning properties and low damage to substrates, the (b) component may be one or more selected from benzyl alcohol (molecular weight: 108, LogP: 1.46), phenoxyethanol (molecular weight: 138, LogP: 1.39), 2-phenylethanol (molecular weight: 122, LogP: 1.74), 3-phenyl-1-propanol (molecular weight: 136, LogP: 2.16), cinnamyl alcohol (molecular weight: 134, LogP: 1.98), benzyl glycol (molecular weight: 152, LogP: 1.30), propylene glycol monophenyl ether (molecular weight: 152, LogP: 1.71), and dipropylene glycol monophenyl ether (molecular weight: 210, LogP: 1.87). The (b) component is preferably one or more selected from benzyl alcohol and phenoxyethanol. The (b) component may be a combination of benzyl alcohol and phenoxyethanol. The cleaning composition for hard surfaces of the present invention preferably contains at least one selected from benzyl alcohol and phenoxyethanol as component (b), and further contains benzyl alcohol.

[0033] (c) Component is the calcium stability constant (pK Ca ) is 6 or more and 13 or less.

[0034] (c) pK of the component Ca was measured by the following method. <pK Ca Measurement method> As a buffer solution, prepare an aqueous solution containing 0.1 M KOH, 0.1 M NH4Cl, and 0.1 M NH4OH. All sample solutions are prepared using this buffer solution. The temperature of all sample solutions is kept at 20°C during measurement. 2+ For example, the concentration was measured using an Orion ion meter 920A and Ca 2+ An ion electrode can be used. First, obtain the relationship between calcium chloride concentration and the electrode potential, and create a calibration curve. -2mol / L solution, sample compound (component (c)) 5.36 × 10 -4 Prepare a 100 ml solution of the sample compound. Add 1 ml of calcium chloride solution to 100 ml of the prepared solution of the sample compound and stir for 5 minutes. 2+ Ca concentration 2+ The measurement is performed using an ion electrode. The sample compound is Ca 2+ Assuming that a 1:1 chelate complex is formed, the pK Ca Calculate the calcium stability constant (Ca stability constant).

[0035]

number

[0036] Examples of the component (c) include aminocarboxylic acid type chelating agents, phosphoric acid type chelating agents, phosphonic acid type chelating agents, and hydroxycarboxylic acid type chelating agents. From the viewpoint of cleaning properties, the component (c) is preferably an aminocarboxylic acid type chelating agent.

[0037] Examples of aminocarboxylic acid type chelating agents include one or more selected from methylglycine diacetate (MGDA) (6.3), glutamic acid diacetate (GLDA) (6.5), ethylenediaminetetraacetic acid (EDTA) (12.2), nitrilotriacetic acid (NTA) (6.6), diethylenetriaminepentaacetic acid (DPTA) (10.7), N-hydroxyethyl-ethylenediaminetriacetic acid (HEDTA) (7.2), aspartic acid diacetate (ASDA) (7.0), and salts thereof. The values ​​in parentheses are the pK values ​​of the compounds measured by the above method. Ca As the salt, an alkali metal salt is preferable, and a sodium salt or a potassium salt is more preferable.

[0038] From the viewpoint of cleaning properties, component (c) is preferably an aminocarboxylic acid type chelating agent, more preferably one or more selected from ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, N-hydroxyethyl-ethylenediaminetriacetic acid, aspartic acid diacetic acid, and salts thereof, and even more preferably ethylenediaminetetraacetic acid or a salt thereof.

[0039] From the viewpoint of achieving both good cleaning performance and minimal damage to substrates, the cleaning composition for hard surfaces of the present invention contains component (a) in an amount of preferably 0.5% by mass or more, more preferably 1% by mass or more, even more preferably 2% by mass or more, and preferably 10% by mass or less, more preferably 8% by mass or less, even more preferably 6% by mass or less, still more preferably 5% by mass or less, and even more preferably 4% by mass or less.

[0040] From the viewpoints of cleaning ability and minimal damage to substrates, the cleaning composition for hard surfaces of the present invention contains component (b) in an amount of preferably 0.1 mass % or more, more preferably 0.5 mass % or more, even more preferably 1 mass % or more, and preferably 5 mass % or less, more preferably 4 mass % or less, even more preferably 3 mass % or less.

[0041] From the viewpoint of cleaning performance, the hard surface cleaning composition of the present invention contains component (c) in an amount of preferably 0.5 mass % or more, more preferably 1 mass % or more, even more preferably 2 mass % or more, and preferably 10 mass % or less, more preferably 8 mass % or less, even more preferably 5 mass % or less.

[0042] In the cleaning composition for hard surfaces of the present invention, from the viewpoint of low damage to substrates, the mass ratio (a) / (b) of the content of the component (a) to the content of the component (b) is preferably 0.7 or more, more preferably 0.8 or more, even more preferably 0.9 or more, and is preferably 10 or less, more preferably 9 or less, even more preferably 8 or less.

[0043] The cleaning agent composition for hard surfaces of the present invention contains water. It may be a liquid composition containing water. Water is used in an amount such that the total amount of the composition is 100% by mass.

[0044] The hard surface cleaning composition of the present invention may contain any surfactant other than the component (a) [hereinafter referred to as the component (a')]. From the viewpoint of cleaning performance, the content of the component (a) in the total surfactant content of the hard surface cleaning composition of the present invention is preferably 50 mass% or more, more preferably 60 mass% or more, even more preferably 70 mass% or more, and preferably 100 mass% or less, and may be 100 mass%. Here, the total surfactant content may be the sum of the content of the component (a) and the content of the component (a') in the composition.

[0045] The component (a') may be a surfactant selected from a nonionic surfactant, an anionic surfactant, and a cationic surfactant.

[0046] Examples of the nonionic surfactant of component (a') include polyoxyalkylene alkyl ethers having an alkyl group having from 10 to 18 carbon atoms, polyoxyalkylene alkenyl ethers having an alkenyl group having from 10 to 18 carbon atoms, polyoxyalkylene sorbitan fatty acid esters having a fatty acid group having from 10 to 18 carbon atoms, alkyl glycosides having an alkyl group having from 8 to 18 carbon atoms, alkyl polyglycosides having an alkyl group having from 8 to 18 carbon atoms, sucrose fatty acid esters having a fatty acid group having from 8 to 18 carbon atoms, alkyl polyglyceryl ethers having an alkyl group having from 8 to 18 carbon atoms, and alkyl monoglyceryl ethers having an alkyl group having from 6 to 18 carbon atoms. The polyoxyalkylene alkyl ether preferably has one or more alkylene oxides selected from ethylene oxide and propylene oxide added thereto, more preferably ethylene oxide. When the alkylene oxide contains ethylene oxide and propylene oxide, it may be a block bond type or a random bond type. The average number of moles of the alkylene oxide added is preferably 1 or more, more preferably 5 or more, even more preferably 10 or more, and preferably 50 or less, more preferably 35 or less, even more preferably 20 or less. The alkyl polyglyceryl ether having the alkyl group has an average number of units in a glycerin skeleton of, for example, 1 or more and 4 or less, and preferably 2 or less.

[0047] The nonionic surfactant is preferably an alkyl monoglyceryl ether having an alkyl group having 6 to 18 carbon atoms.

[0048] Examples of the anionic surfactant of component (a') include anionic surfactants having one or more hydrocarbon groups and one or more groups selected from the group consisting of a sulfonic acid group, a sulfate ester group, and a carboxylate group. Examples of the anionic surfactant of component (a') include alkyl or alkenyl benzene sulfonic acid or its salt, polyoxyalkylene alkyl or alkenyl ether sulfate or its salt, alkyl or alkenyl sulfate or its salt, and fatty acid or its salt, etc. The anionic surfactant is preferably an alkyl sulfate or its salt. The oxyalkylene group of the polyoxyalkylene alkyl or alkenyl ether sulfate or its salt is preferably an oxyethylene group. The average number of moles of the oxyalkylene group added of the polyoxyalkylene alkyl or alkenyl ether sulfate is preferably 1 or more and 10 or less. The fatty acid or its salt may be a fatty acid or its salt having 10 or more and 18 or less carbon atoms. The hydrocarbon group, and further the alkyl or alkenyl group, of the anionic surfactant of component (a') preferably has 10 to 18 carbon atoms. The salt of the anionic surfactant is preferably an alkali metal salt such as a sodium salt or a potassium salt. The amount of the anionic surfactant is based on the compound in which the counter ion is replaced with a sodium ion.

[0049] The cationic surfactant of the component (a') may be a quaternary ammonium salt cationic surfactant. The quaternary ammonium salt cationic surfactant may be a quaternary ammonium salt cationic surfactant in which one or two of the groups bonded to the nitrogen atom are hydrocarbon groups having 8 to 16 carbon atoms, and the remaining groups are selected from the group consisting of alkyl groups having 1 to 3 carbon atoms, hydroxyalkyl groups having 1 to 3 carbon atoms, and arylalkyl groups (benzyl groups, etc.). Among these, quaternary ammonium salt cationic surfactants having bactericidal properties are preferred, and from the viewpoint of bactericidal properties, quaternary ammonium salt cationic surfactants having a benzyl group are preferred. The amount of the cationic surfactant is based on the compound in which the counter ion is replaced with a chloride ion.

[0050] From the viewpoints of detergency against complex soils, storage stability, and foaming, the component (a') is preferably at least one selected from nonionic surfactants and anionic surfactants, and more preferably at least one selected from alkyl monoglyceryl ethers having an alkyl group with from 6 to 18 carbon atoms, and alkyl sulfate ester salts in which the alkyl group has from 10 to 18 carbon atoms. When the hard surface cleaning composition of the present invention contains the component (a'), the composition preferably contains, as the component (a'), an alkyl monoglyceryl ether having an alkyl group with from 6 to 18 carbon atoms.

[0051] When the hard surface cleaning composition of the present invention contains component (a'), the composition can contain, for example, 0.1 mass % or more of component (a'), further 0.5 mass % or more, and 5 mass % or less, further 3 mass % or less.

[0052] The hard surface cleaning composition of the present invention may contain a solvent other than component (b). Examples of the solvent other than component (b) include (b') a solvent other than component (b) having a solubility parameter δ of less than 15.0 [hereinafter referred to as component (b')]. Examples of component (b') include glycol-based solvents, glycol ether-based solvents, and glycol ether-based solvents having no aromatic ring. Examples of glycol ether-based solvents include aliphatic glycol ethers having a molecular weight of 60 or more and 500 or less.

[0053] Examples of the component (b') include: (1) Propylene glycol-based solvents such as propylene glycol, dipropylene glycol, tripropylene glycol, and isoprene glycol, (2) Ethylene glycol ether solvents such as methyl glycol (ethylene glycol monomethyl ether), ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, butyl glycol (ethylene glycol monobutyl ether), 2-tert-butoxyethanol, ethylene glycol monohexyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, butyl diglycol (diethylene glycol monobutyl ether), and isobutyl diglycol; (3) Propylene glycol-based ether solvents such as methyl propylene glycol (propylene glycol monomethyl ether), propylene glycol monoethyl ether, propyl propylene glycol (propylene glycol monopropyl ether), propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, propyl propylene diglycol (dipropylene glycol monopropyl ether), and dipropylene glycol monobutyl ether; etc.

[0054] As the component (b'), one or more selected from propyl propylene diglycol (molecular weight: 176), butyl glycol (molecular weight: 118), propyl propylene glycol (molecular weight: 118), butyl diglycol (molecular weight: 162), 2-tert-butoxyethanol (molecular weight: 118), isobutyl diglycol (molecular weight: 162), methyl propylene glycol (molecular weight: 90), and methyl glycol (molecular weight: 76) are preferred, with butyl diglycol being more preferred. When the hard surface cleaning composition of the present invention contains the component (b'), from the viewpoint of cleaning properties, the composition preferably contains butyl diglycol as the component (b').

[0055] When the hard surface cleaning composition of the present invention contains component (b'), the composition may contain, for example, 0.1 mass % or more of component (b'), further 0.5 mass % or more, and 5 mass % or less, further 4 mass % or less. When the cleaning composition for hard surfaces of the present invention contains the component (b'), the mass ratio (b) / (b') of the content of the component (b) to the content of the component (b') is, from the viewpoint of storage stability, 0.1 or more, preferably 0.5 or more, more preferably 1 or more, and 10 or less, preferably 8 or less, more preferably 6 or less.

[0056] Furthermore, examples of the solvent other than component (b) include solvents other than component (b) having a solubility parameter δ of 15.0 or more and 19.5 or less. Examples of such solvents include ester compounds of fatty acids and alcohols having a carbon number of 6 or more and 24 or less, and more specifically, one or more selected from isobutyl acetate, ethyl hexanoate, isobutyl isobutyrate, ethyl octanoate, hexyl benzoate, diisobutyl adipate, isopropyl myristate, and ethyl oleate.

[0057] The hard surface cleaning composition of the present invention has a pH at 25° C. of 8 or more, preferably 9 or more, more preferably 10 or more, and 12 or less, preferably 11 or less. The hard surface cleaning composition of the present invention is appropriately adjusted by blending a pH adjuster so that the pH at 25°C falls within a predetermined range. Examples of the pH adjuster include alkali agents such as alkali metal hydroxides and alkali metal silicates, and acid agents such as carboxylic acids, sulfonic acids, and inorganic acids. Examples of alkali metal hydroxides include sodium hydroxide and potassium hydroxide, and examples of alkali metal silicates include sodium silicate and potassium silicate, specifically sodium metasilicate, sodium orthosilicate, sodium silicate No. 1, sodium silicate No. 2, sodium silicate No. 3, sodium silicate No. 4, potassium silicate 1K, and potassium silicate 2K. Examples of carboxylic acids include hydroxycarboxylic acids such as citric acid, and fatty acids such as acetic acid, examples of sulfonic acids include metaxylenesulfonic acid and paratoluenesulfonic acid, and examples of inorganic acids include sulfuric acid and hydrochloric acid.

[0058] In order to increase the added value of the product, the hard surface cleaning composition of the present invention may optionally contain fragrances, colorants, preservatives, antioxidants, stabilizers, hydrotropes, enzymes, bleaching agents, dispersants, surface modifiers, thickeners, and the like (excluding the above-mentioned components (a) to (c)). For example, the dispersant may be one or more selected from polymers or copolymers of polyacrylic acid, acrylic acid-allyl alcohol copolymer, acrylic acid-maleic acid copolymer, hydroxyacrylic acid polymer, maleic acid, itaconic acid, fumaric acid, tetramethylene 1,2-dicarboxylic acid, succinic acid, aspartic acid, and the like, and alkali metal salts or alkanolamine salts thereof.

[0059] The hard surface cleaner composition of the present invention is suitable for cleaning hard surfaces such as bathrooms, bathtubs, washbasins, tiles, restrooms, washstands, mirrors, kitchen sinks, countertops, and areas around water supplies. It is suitable for use in bathrooms. Here, the term "for use in bathrooms" refers not only to bathrooms, but also to other items having hard surfaces present in the bathroom, such as bathtubs and washbasins.

[0060] [Method of cleaning hard surfaces] The method for cleaning a hard surface of the present invention is a method for cleaning a hard surface, which comprises adhering the above-mentioned cleaning composition for hard surfaces of the present invention to a hard surface, and then rinsing the surface without scrubbing. That is, the method for cleaning a hard surface of the present invention uses the cleaning composition for hard surfaces of the present invention. The preferred aspects of the composition are the same as those of the cleaning composition for hard surfaces of the present invention described above. The method for cleaning a hard surface of the present invention can be suitably carried out as a method for cleaning a hard surface by applying the above-mentioned cleaning agent composition for hard surfaces of the present invention to a hard surface, for example, a hard surface having sebum stains and / or soap scum stains, and then rinsing the surface without scrubbing.

[0061] In the cleaning method for a hard surface of the present invention, the hard surface may be a hard surface to which dirt containing a fatty acid calcium salt is attached. The dirt containing a fatty acid calcium salt is, for example, soap scum dirt. Therefore, in the cleaning method of the present invention, the hard surface may be a hard surface to which a composite dirt of sebum dirt and soap scum dirt is attached.

[0062] In the method for cleaning a hard surface of the present invention, the hard surface cleaning composition is attached to the hard surface, preferably in a foam state. In the present invention, the hard surface cleaning composition is preferably foamed using a trigger type sprayer having a foam forming mechanism. The trigger type sprayer is preferably a pressure-accumulation type sprayer. The trigger type sprayer having a foam forming mechanism may be one described in the description of the hard surface cleaning composition of the present invention.

[0063] More specifically, the method for cleaning a hard surface of the present invention includes a cleaning method in which the hard surface cleaning composition is applied to a hard surface in its undiluted form, or the hard surface cleaning composition is applied to a hard surface in its undiluted form without dilution, i.e., the hard surface cleaning composition is applied to a hard surface without dilution.Furthermore, the hard surface cleaning composition is applied to a hard surface without dilution. The phrase "adhering the hard surface cleaning composition to a hard surface without dilution" means that the cleaning composition is not adhered to a hard surface after being intentionally diluted with water, etc. For example, when the cleaning composition is adhered to a hard surface having water droplets or the like attached thereto, or when water droplets adhere to the hard surface after the cleaning composition for hard surfaces is attached to the hard surface, it can be understood that the cleaning composition for hard surfaces is adhered to the hard surface without dilution. In the present invention, it is preferable to apply the undiluted solution of the hard surface cleaning composition to the hard surface as it is, i.e., without changing the composition. For example, the hard surface cleaning composition is applied to a hard surface having dirt attached thereto, without being applied to a water-absorbed sponge. After being applied to the hard surface, the composition of the hard surface cleaning composition may be changed. That is, after being applied to the hard surface, the composition of the hard surface cleaning composition may be diluted or concentrated.

[0064] However, a concentrated composition containing the components (a), (b), and (c) of the present invention may be prepared, and the concentrated composition may be diluted with water to prepare the hard surface cleaning composition of the present invention, which may then be applied to a hard surface. That is, the method for cleaning a hard surface may include diluting a concentrated composition containing the components (a), (b), and (c) of the present invention with water to prepare the hard surface cleaning composition of the present invention, applying the hard surface cleaning composition to the hard surface, and then rinsing without scrubbing.

[0065] In addition, the cleaning method for hard surfaces of the present invention may be a cleaning method in which the hard surface cleaning composition is attached to a hard surface and then rinsed without scrubbing, preferably, the composition is attached to a hard surface, left for a predetermined time, and then rinsed without scrubbing. In other words, the composition is attached to the hard surface without scrubbing using a flexible material such as a sponge or fingers, and left as is without applying external force. After the composition is attached and left for a predetermined time if necessary, the hard surface is rinsed with water. When rinsing, an external force (physical force) may be applied using hands, or simply rinsed with a water stream.

[0066] In the method for cleaning a hard surface of the present invention, the cleaning composition for hard surfaces is applied to an area of ​​100 cm of a hard surface to be cleaned. 2 It is preferable to adhere, further apply or spray the composition in an amount of preferably 1 g or more, more preferably 3 g or more, even more preferably 5 g or more, and preferably 15 g or less, more preferably 12 g or less, even more preferably 10 g or less.

[0067] In the method for cleaning a hard surface of the present invention, from the viewpoint of enhancing the cleaning power, the detergent composition for hard surfaces is left for preferably 10 seconds or more, more preferably 20 seconds or more, even more preferably 30 seconds or more, even more preferably 40 seconds or more after being applied to the hard surface, and from the same viewpoint, preferably 60 minutes or less, more preferably 30 minutes or less, even more preferably 20 minutes or less, even more preferably 10 minutes or less. In this case, the time when the composition is first applied to the hard surface may be regarded as the start of the leaving. The predetermined time may be within this range. The temperature during standing may be room temperature, for example, 10°C or higher and 30°C or lower.

[0068] In addition, in the method for cleaning hard surfaces of the present invention, from the viewpoint of enhancing cleaning power, the liquid detergent composition is adhered to the hard surface to be cleaned for preferably 10 seconds or more, more preferably 20 seconds or more, even more preferably 30 seconds or more, and even more preferably 40 seconds or more, and from the same viewpoint, preferably 60 minutes or less, more preferably 30 minutes or less, even more preferably 20 minutes or less, and even more preferably 10 minutes or less.

[0069] In the method for cleaning a hard surface of the present invention, the hard surface having dirt thereon may be immersed in the cleaning composition for hard surfaces to adhere to the hard surface, but from the viewpoint of efficiently enhancing the cleaning power, a method of adhering the cleaning composition for hard surfaces to the hard surface by spraying or applying the composition is preferred. In the present invention, it is preferred to adhere the cleaning composition for hard surfaces to the hard surface in a liquid or foam form. The method for attaching the hard surface cleaning composition to a soiled hard surface is preferably spraying or coating, and more preferably spraying in the form of droplets or coating in the form of foam. It is preferable to use the above-mentioned spray-contained hard surface cleaning article of the present invention.

[0070] The method for cleaning hard surfaces of the present invention is preferably used as a method for cleaning bathrooms, kitchens or toilets, and more preferably as a method for cleaning bathrooms.

[0071] In the method for cleaning a hard surface of the present invention, the hard surface cleaning composition of the present invention is directly applied to the hard surface, and the composition is left in the applied state, so that there is no need to apply an external force such as scrubbing with a flexible material such as a sponge during cleaning. Furthermore, in the method for cleaning a hard surface of the present invention, the cleaning agent composition for hard surfaces of the present invention, preferably the foamed composition, is applied to a hard surface and left as is, so that the composition can remain on the hard surface for a long time. In the method for cleaning a hard surface of the present invention, the hard surface to which the cleaning composition for hard surfaces is applied is rinsed with water, preferably the hard surface to which the cleaning composition for hard surfaces is applied is left for a predetermined period of time and then rinsed with water. Since the cleaning composition for hard surfaces of the present invention has good rinsing properties, rinsing can be completed with a small amount of water. EXAMPLES

[0072] <Soap scum cleaning performance evaluation> A model soap scum stain prepared with reference to the composition of soap scum stains adhering to bathrooms was formed into a film on a polypropylene plate (manufactured by Engineering Test Service Co., Ltd., shape 80 mm x 120 mm). The model soap scum stain was prepared and formed into a film by immersing the plate in an aqueous solution (2 mass%) of solid soap (manufactured by Kao Corporation, "White") and an aqueous solution of calcium chloride (0.7 mass%) in that order, and then drying the plate, repeating this process 10 times. After forming a film of the model soap scum stain on the plate, 10 μL of the hard surface cleaning agent composition in Tables 1 and 2 was dropped onto the stained part of the plate, left at 25 ° C. for 5 minutes, and then washed with water. The plate was scanned with a scanner (RICOH MP C5504, Ricoh Co., Ltd., reading conditions: manuscript type: grayscale, resolution: 600 dpi), and the gray values ​​before and after cleaning were calculated using ImageJ (image processing software), and the cleaning rate was calculated using the following formula. Cleaning rate (%) = (gray value before cleaning - gray value after cleaning) / (gray value before cleaning - gray value of plate) x 100

[0073] <Low damage to base material> An acrylic plate (70mm x 10mm x 1mm, Nippon Test Panel Co., Ltd.) was fixed at both ends so that the length was 68mm, and distortion was generated (distortion rate: 2.86%). On the distorted acrylic plate, absorbent cotton (Kawamoto Sangyo Co., Ltd., Curelet, 4cm x 4cm) cut into eight pieces was placed, which was then cut to half the thickness. The absorbent cotton was soaked in 200μL of cleaning solution and left to stand at 50℃ for 3 hours. The surface condition of the acrylic plate was then visually observed, and the substrate damage was evaluated according to the following criteria. An outline of this evaluation method is shown in Figure 1. ○: The acrylic plate does not break, or cracks are visible but it does not break. ×: The acrylic plate breaks.

[0074] [Table 1]

[0075] [Table 2]

[0076] The components in the table are as follows. In addition, in the table, (a) / total surfactant (mass%) is the ratio of the content of component (a) to the total surfactant content. In addition, hydrochloric acid was a 1N-HCl aqueous solution, and sodium hydroxide was a 48% sodium hydroxide aqueous solution, each used in an amount (shown as an appropriate amount in the table) such that the pH of the composition was the value in the table. Amphoteric surfactant (1): Amphitol 20AB, Kao Corporation, lauric acid amidopropyl betaine Amphoteric surfactant (2): Amphitol 20 HD, Kao Corporation, Lauryl hydroxysulfobetaine Amphoteric surfactant (3): Amphitol 20N, Kao Corporation, lauryl dimethylamine oxide Nonionic surfactant (1): Emulgen 108, Kao Corporation, polyoxyethylene lauryl ether Nonionic surfactant (2): 2-ethylhexyl monoglyceryl ether Anionic surfactant (1): Emeral 2F-HP, Kao Corporation, sodium lauryl sulfate EDTA: tetrasodium ethylenediaminetetraacetate HIDA: Hydroxyethyliminodiacetic acid, Tokyo Chemical Industry Co., Ltd. Potassium polyacrylate: Weight average molecular weight 8000

Claims

1. A hard surface cleaning composition comprising: (a) an amphoteric surfactant [hereinafter referred to as component (a)], (b) an aromatic alcohol having a LogP of 1.3 or more [hereinafter referred to as component (b)], (c) a chelating agent having a calcium stability constant (pKCa) of 6 or more and 13 or less [hereinafter referred to as component (c)], and water, and having a pH at 25°C of 8 or more and 12 or less.

2. 2. The hard surface cleaning composition according to claim 1, further comprising a surfactant other than the component (a), and the content of the component (a) in the total surfactant content is 50 mass% or more.

3. 2. The hard surface cleaning composition according to claim 1, wherein the component (a) is at least one selected from the group consisting of betaine-type amphoteric surfactants having a hydrocarbon group with from 7 to 14 carbon atoms and amine oxide-type amphoteric surfactants having a hydrocarbon group with from 7 to 14 carbon atoms.

4. 2. The hard surface cleaning composition according to claim 1, wherein the component (b) is benzyl alcohol.

5. 2. The hard surface cleaning composition according to claim 1, wherein the component (c) is an aminocarboxylic acid type chelating agent.

6. The hard surface cleaning composition according to claim 1, which is for use in a bathroom.

7. A method for cleaning a hard surface, comprising applying the cleaning composition for hard surfaces according to any one of claims 1 to 6 to the hard surface, and then rinsing the surface without scrubbing.

8. The method for cleaning a hard surface according to claim 7, wherein the hard surface cleaning composition is applied to the hard surface in a foam state.

9. The method for cleaning a hard surface according to claim 8, wherein the hard surface cleaning agent composition is foamed with a trigger type sprayer having a foam forming mechanism.

10. 10. The method of cleaning a hard surface according to claim 9, wherein the trigger sprayer is a pressure-accumulation sprayer.

11. 8. The method for cleaning a hard surface according to claim 7, wherein the hard surface is a hard surface having dirt containing a fatty acid calcium salt attached thereto.

Images