Detergent composition and method for cleaning lipid / protein complex soils

Abstract

To provide a cleanser composition having excellent cleaning performance for a lipid / protein composite stain and a soap scum stain adhered to a hard surface and good blending stability and to provide a method for cleaning a lipid / protein composite stain using the same.SOLUTION: There is provided a cleanser composition which comprises (a) an ester compound having 6 or more and 24 or less carbon atoms "hereinafter, referred to as a component (a)", (b) a surfactant "hereinafter, referred to as a component (b), (c) an alkanolamine and water, has a mass ratio (a) / (b) between the content of the component (a) and the content of the component (b) of 0.01 or more and 0.55 or less and has a pH at 25°C of more than 9 and less than 12.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a detergent composition and a method for cleaning lipid / protein complex soils. [Background technology]

[0002] Lipids and proteins are typical dirt derived from the human body, and they adhere to all surfaces in daily life, including clothing, floors, and bathrooms, causing stains. Dirt accumulates particularly near the waterline on surfaces such as bathtubs. Traditionally, bathtubs were made of materials such as stainless steel and enamel, and because these surfaces are hydrophilic, lipid and protein stains were easily removed. However, with the recent spread of modular baths and other bathrooms, polyester and acrylic resins have come to be used for bathtubs and bathrooms, making lipid and protein stains that adhere to these hydrophobic surfaces difficult to remove. In particular, lipid / protein complex stains cannot be satisfactorily cleaned without scrubbing with cleaning tools such as sponges. Since scrubbing is hard work, it is extremely beneficial for users to obtain a satisfactory cleaning effect by simply contacting the surface and rinsing it. Therefore, there is a need for a technology that can easily remove lipid / protein complex soils attached to hydrophobic surfaces without mechanical work such as scrubbing.

[0003] Patent Document 1 discloses a detergent containing a hydrophobic solvent such as dodecane that has the effect of removing soap scum adhering to a polypropylene washbasin. Patent Documents 2 and 3 disclose techniques in which a detergent containing a fatty acid ester is used to clean tiles and bathrooms. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Laid-Open No. 2007-31692 [Patent Document 2] Special Publication No. 2016-540855 [Patent Document 3] Special Publication No. 2013-515093 Summary of the Invention [Problem to be solved by the invention]

[0005] However, these techniques do not disclose a technique for cleaning lipid / protein complex soils attached to hard surfaces without requiring external force such as scrubbing. The present invention provides a detergent composition that has excellent cleaning performance for removing lipid / protein complex stains and soap scum stains attached to hard surfaces and good formulation stability, and a method for cleaning lipid / protein complex stains using the same. [Means for solving the problem]

[0006] The present invention relates to a detergent composition comprising (a) an ester compound having from 6 to 24 carbon atoms [hereinafter referred to as component (a)], (b) a surfactant [hereinafter referred to as component (b)], (c) an alkanolamine [hereinafter referred to as component (c)], and water, wherein the mass ratio (a) / (b) of the content of component (a) to the content of component (b) is 0.01 or more and 0.55 or less, and the pH at 25°C is more than 9 and less than 12.

[0007] The present invention relates to a method for cleaning lipid / protein complex stains, which comprises contacting the cleaning composition with a hard surface on which lipid / protein complex stains are attached. [Effects of the Invention]

[0008] The present invention provides a detergent composition that has excellent cleaning performance for lipid / protein complex soils and soap scum stains attached to hard surfaces and good formulation stability, and a method for cleaning lipid / protein complex soils and soap scum stains using the same. DETAILED DESCRIPTION OF THE INVENTION

[0009] [Cleaning composition] The reason why the detergent composition of the present invention has excellent cleaning performance for lipid / protein complex soils and soap scum soils adhering to hard surfaces is not entirely clear, but is presumed to be as follows. It is known that protein components adhering to hard surfaces become stronger stains when complexed with lipid components, making it difficult to remove the stains in a short time without scrubbing. This is presumably because the lipid components inhibit the penetration of cleaning components necessary for protein removal into the protein, and because the lipid components interact with the molecules constituting the protein, preventing the protein from swelling. In the detergent composition of the present invention, component (a) removes the lipid components from lipid / protein complex soils, and maintaining components (b) and (c) and the pH within specific ranges can promote protein swelling, making it possible to remove complex lipid / protein complex soils in a short time without scrubbing. On the other hand, component (a) is a very hydrophobic component and poorly soluble in water, making it difficult to incorporate from the viewpoint of formulation stability. It is believed that by maintaining the ratio of component (a) to component (b) within a specific range, the detergent composition of the present invention can provide a detergent composition that has excellent lipid / protein cleaning performance and good formulation stability.

[0010] <Component (a)> Component (a) is an ester compound having 6 to 24 carbon atoms. The number of carbon atoms in component (a) is preferably 8 or more, more preferably 10 or more, from the viewpoint of cleaning performance for lipid / protein complex soils, and is preferably 22 or less, more preferably 20 or less, from the viewpoint of blend stability. From the viewpoint of cleaning lipid / protein complex soils, component (a) is preferably an ester compound of a carboxylic acid and an alcohol, more preferably an ester compound of a monovalent to trivalent carboxylic acid and a monovalent to trivalent alcohol, provided that the number of carbon atoms in the ester compound satisfies the above range.

[0011] From the viewpoint of cleaning performance for lipid / protein complex soils, the number of carbon atoms of the carboxylic acid is preferably 2 or more, more preferably 6 or more, even more preferably 8 or more, and preferably 21 or less, more preferably 20 or less, even more preferably 18 or less. The valence of the carboxylic acid is monovalent or more and trivalent or less, preferably divalent or less, from the viewpoint of cleaning performance for lipid / protein complex soils. The carboxylic acid is not particularly limited, but is preferably a monovalent or divalent carboxylic acid having a linear or branched alkyl group, preferably a monovalent carboxylic acid, such as one or more selected from acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, pivalic acid, caproic acid, benzoic acid, 2-ethylhexanoic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, undecylic acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, α-linolenic acid, linoleic acid, palmitoleic acid, oleic acid, adipic acid, azelaic acid, palm oil fatty acids, coconut oil fatty acids, beef tallow fatty acids, sebacic acid, and trimesic acid. Among these, from the viewpoint of cleaning performance for lipid / protein complex stains, one or more selected from 2-ethylhexanoic acid, enanthic acid, caprylic acid, capric acid, undecylic acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, α-linolenic acid, linoleic acid, palmitoleic acid, and oleic acid are preferred.

[0012] From the viewpoint of cleaning performance for lipid / protein complex soils, the number of carbon atoms of the alcohol is preferably 1 or more, more preferably 2 or more, and preferably 20 or less, more preferably 18 or less, even more preferably 16 or less, still more preferably 12 or less, still more preferably 8 or less, still more preferably 6 or less, still more preferably 4 or less, and still more preferably 3 or less. From the viewpoint of cleaning performance for lipid / protein complex soiling, the valence of the alcohol is monovalent or more and trivalent or less, preferably divalent or less, more preferably monovalent. The alcohol is not particularly limited, but is an alcohol having a linear or branched alkyl group. Examples of the raw material alcohol include methanol, ethanol, propanol, isopropanol, butanol, pentanol, hexanol, heptanol, octanol, nonanol, decanol, dodecanol, tetradecanol, hexadecanol, octadecanol, eicosanol, and one or more structural isomers of the alcohols. From the viewpoint of cleaning performance for lipid / protein complex soils, methanol, ethanol, propanol, isopropanol, butanol, pentanol, hexanol, heptanol, octanol, and one or more structural isomers of these alcohols are preferred.

[0013] The ester compound is preferably an ester compound of a fatty acid and an alcohol having a total carbon number of 6 to 24, and more preferably an ester compound of a monovalent fatty acid having 8 to 18 carbon atoms and a monovalent alcohol having 2 to 3 carbon atoms having a total carbon number of 10 to 20. More specifically, the ester compound is preferably at least one selected from isobutyl acetate (carbon number: 6), ethyl hexanoate (carbon number: 8), ethyl octanoate (carbon number: 10), hexyl benzoate (carbon number: 13), diisopropyl adipate (carbon number: 14), isopropyl myristate (carbon number: 17), and ethyl oleate (carbon number: 20), and more preferably at least one selected from ethyl octanoate, isopropyl myristate, and ethyl oleate.

[0014] <(b) Component> Component (b) is a surfactant. The surfactant is not particularly limited, but may be one or more selected from (b1) anionic surfactants (hereinafter also referred to as (b1) component), (b2) cationic surfactants (hereinafter also referred to as (b2) component), (b3) nonionic surfactants (hereinafter also referred to as (b3) component), and (b4) amphoteric surfactants (hereinafter also referred to as (b4) component). From the viewpoint of cleaning performance against lipid / protein complex soils, the detergent composition of the present invention preferably contains an anionic surfactant (b1) as component (b).

[0015] (b1) Anionic surfactants include those having one or more hydrocarbon groups and one or more groups selected from the group consisting of sulfonic acid groups, sulfate groups, and carboxylic acid groups. Examples of anionic surfactants include alkyl or alkenyl benzene sulfonic acids or salts thereof, polyoxyalkylene alkyl or alkenyl ether sulfate esters or salts thereof, alkyl or alkenyl sulfate esters or salts thereof, internal olefin sulfonic acids or salts thereof, and fatty acids or salts thereof. From the viewpoint of cleaning performance for lipid / protein complex soils, component (b1) is preferably one or more selected from alkyl or alkenyl sulfate esters or salts thereof, polyoxyalkylene alkyl or alkenyl ether sulfate esters or salts thereof, internal olefin sulfonic acids or salts thereof, and alkyl or alkenyl benzene sulfonic acids or salts thereof. The salt of the anionic surfactant is preferably an alkali metal salt such as a sodium salt or a potassium salt.

[0016] From the viewpoint of cleaning performance against lipid / protein complex soils, the number of carbon atoms in the alkyl or alkenyl group of the alkyl or alkenyl sulfate ester or salt thereof is preferably 8 or more, more preferably 10 or more, and preferably 24 or less, more preferably 20 or less, even more preferably 18 or less, and still more preferably 16 or less.

[0017] From the viewpoint of cleaning performance for lipid / protein complex soils, the number of carbon atoms in the alkyl or alkenyl group of the polyoxyalkylene alkyl or alkenyl ether sulfate ester or its salt is preferably 8 or more, more preferably 10 or more, and preferably 24 or less, more preferably 20 or less, even more preferably 18 or less, and even more preferably 16 or less. The oxyalkylene group of the polyoxyalkylene alkyl or alkenyl ether sulfate ester or its salt is preferably an ethyleneoxy group. The average number of moles of oxyalkylene groups added in the polyoxyalkylene alkyl or alkenyl ether sulfate ester or its salt is preferably 0.5 or more, more preferably 1 or more, more preferably 2 or more, and preferably 5 or less, more preferably 3 or less.

[0018] From the viewpoint of cleaning performance for lipid / protein complex soils, the number of carbon atoms of the internal olefin sulfonic acid or its salt is preferably 8 or more, more preferably 10 or more, even more preferably 12 or more, still more preferably 14 or more, and preferably 24 or less, more preferably 20 or less, even more preferably 18 or less.

[0019] From the viewpoint of cleaning performance for lipid / protein complex soiling, the number of carbon atoms in the alkyl or alkenyl group of the alkyl or alkenyl benzenesulfonic acid or salt thereof is preferably 8 or more, more preferably 10 or more, and preferably 24 or less, more preferably 20 or less, even more preferably 18 or less, still more preferably 16 or less, and still more preferably 14 or less.

[0020] Examples of (b2) cationic surfactants include quaternary ammonium salt-type cationic surfactants. Examples of quaternary ammonium salt-type cationic surfactants include quaternary ammonium salt-type cationic surfactants in which, among the groups bonded to the nitrogen atom, one or two are hydrocarbon groups having 6 or more, preferably 8 or more, and 16 or less, preferably 14 or less, carbon atoms, and the remainder are groups 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 (such as benzyl groups). Component (b2) is preferably a quaternary ammonium salt-type cationic surfactant having bactericidal properties, and from the viewpoint of bactericidal properties, a quaternary ammonium salt-type cationic surfactant having a benzyl group is preferred.

[0021] Examples of (b3) nonionic surfactants include polyoxyalkylene alkyl ethers having an alkyl group containing from 8 to 18 carbon atoms, polyoxyalkylene alkenyl ethers having an alkenyl group containing from 8 to 18 carbon atoms, polyoxyalkylene sorbitan fatty acid esters having a fatty acid group containing from 8 to 18 carbon atoms, alkyl glycosides having an alkyl group containing from 8 to 18 carbon atoms, alkyl polyglycosides having an alkyl group containing from 8 to 18 carbon atoms, sucrose fatty acid esters having a fatty acid group containing from 8 to 18 carbon atoms, and alkyl polyglyceryl ethers having an alkyl group containing from 8 to 18 carbon atoms, and these can be used alone or in combination. Component (b3) is preferably a polyoxyethylene alkyl ether having an alkyl group containing from 8 to 18 carbon atoms and an average number of moles of ethylene oxide added of from 2 to 50.

[0022] The component (b3) is preferably a nonionic surfactant represented by the following general formula (b3). R 31b -O-[(C2H4O) s (C3H6O) t ]-H(b3) [In the formula, R 31bis an alkyl or alkenyl group having 8 or more, preferably 10 or more, and 18 or less, preferably 16 or less carbon atoms. s and t are the average number of moles added, s is 2 or more, preferably 3 or more, more preferably 5 or more, even more preferably 7 or more, and 50 or less, preferably 30 or less, more preferably 20 or less; t is 0 or more, preferably 1 or more, and 5 or less, preferably 3 or less, and t may be 0. (C2H4O) and (C3H6O) may be random polymers or block polymers.

[0023] The amphoteric surfactant (b4) may be one or more surfactants selected from betaine surfactants and amine oxide surfactants. Specific examples of the component (b4) include one or more surfactants selected from sulfobetaine, carbobetaine, and amine oxide.

[0024] Examples of sulfobetaines include N-alkyl-N,N-dimethyl-N-sulfopropylammonium sulfobetaine, in which the alkyl group has preferably 10 or more carbon atoms and preferably 18 or less, more preferably 14 or less; N-alkyl-N,N-dimethyl-N-(2-hydroxysulfopropyl)ammonium sulfobetaine, in which the alkyl group has preferably 10 or more carbon atoms and preferably 18 or less, more preferably 14 or less; N-alkanoylaminopropyl-N,N-dimethyl-N-sulfopropylammonium sulfobetaine, in which the alkanoyl group has preferably 10 or more carbon atoms and preferably 18 or less, more preferably 14 or less; and N-alkanoylaminopropyl-N,N-dimethyl-N-(2-hydroxysulfopropyl)ammonium sulfobetaine, in which the alkanoyl group has preferably 10 or more carbon atoms and preferably 18 or less, more preferably 14 or less.

[0025] Examples of carbobetaines include N-alkyl-N,N-dimethyl-N-carboxymethylammonium betaines in which the number of carbon atoms in the alkyl group is preferably 10 or more, and preferably 18 or less, and more preferably 14 or less, and compounds represented by the following general formula (b41).

[0026] [ka]

[0027] [In the formula, R 41b represents an alkyl or alkenyl group having 7 to 21 carbon atoms, and R 42b represents a propylene group, and R 43b and R 44b each independently represents an alkyl group having 1 to 3 carbon atoms.

[0028] In general formula (b41), R 41b is an alkyl or alkenyl group having preferably 9 or more, more preferably 11 or more, and preferably 15 or less, more preferably 13 or less carbon atoms, and is preferably a nonyl group, a decyl group, an undecyl group, a dodecyl group, or a tridecyl group. In general formula (b41), R 43b and R 44b are each independently preferably a methyl group.

[0029] As the amine oxide, a compound of the following general formula (b42) is suitable.

[0030] [ka]

[0031] [In the formula, R 45b represents a hydrocarbon group having 7 to 22 carbon atoms, preferably an alkyl or alkenyl group, more preferably an alkyl group; R 46b and R 47b are the same or different and represent an alkyl group having 1 to 3 carbon atoms; D represents an -NHC(=O)- group or a -C(=O)NH- group; E represents an alkylene group having 1 to 5 carbon atoms; m and p represent m=0 and p=0 or m=1 and p=1.

[0032] In the above general formula (b42), when m=1 and p=1, R45b From the viewpoint of cleaning performance, R is preferably an alkyl group having 9 to 18 carbon atoms, more preferably an alkyl group having 11 to 16 carbon atoms, even more preferably an alkyl group having 11 to 14 carbon atoms, and even more preferably an alkyl group having 11 carbon atoms. When m=0 and p=0, R 45b From the viewpoint of cleaning performance, R is preferably an alkyl group having 10 to 18 carbon atoms, more preferably an alkyl group having 12 to 16 carbon atoms, even more preferably an alkyl group having 12 to 14 carbon atoms, and even more preferably an alkyl group having 12 carbon atoms. In the present invention, it is preferable that m=0 and p=0. R 46b , R 47b is preferably a methyl group having one carbon atom from the viewpoint of cleaning performance.

[0033] From the viewpoint of promoting protein swelling and thereby improving the detergency for lipid / protein complex soils, the detergent composition of the present invention preferably contains component (b1) among component (b), and more preferably contains one or more selected from alkyl or alkenyl sulfate esters or salts thereof, and polyoxyalkylene alkyl or alkenyl ether sulfate esters or salts thereof.

[0034] <(c) component> Component (c) is an alkanolamine. Component (c) is an important component in the present invention, as it not only helps swell proteins in lipid / protein complex soils but also penetrates the proteins, greatly improving detergency. Therefore, from the viewpoint of protein penetration, component (c) is preferably an alkanolamine with a low molecular weight, and is preferably an alkanolamine with a molecular weight of 60 or more and 300 or less, preferably 200 or less, and more preferably 150 or less. The component (c) is not particularly limited, but examples thereof include alkylmono- or dialkanolamines having 2 or 3 carbon atoms in the alkanol group or alkylene oxide adducts thereof (the alkylene oxide has 2 or 3 carbon atoms), specific examples include one or more compounds selected from monoethanolamine, diethanolamine, triethanolamine, 1-amino-2-propanol, N-methylmonoethanolamine, N-methyldiethanolamine, and N,N-dimethylmonoethanolamine, and from the viewpoint of cleaning performance for lipid / protein complex soils, preferred are one or more compounds selected from monoethanolamine, diethanolamine, 1-amino-2-propanol, and N-methylmonoethanolamine, and more preferred are one or more compounds selected from monoethanolamine, diethanolamine, and 1-amino-2-propanol.

[0035] <Composition, etc.> From the viewpoint of cleaning performance against lipid / protein complex soils, the detergent composition of the present invention contains component (a) in an amount of preferably 0.05% by mass or more, more preferably 0.1% by mass or more, even more preferably 0.2% by mass or more, still more preferably 0.3% by mass or more, and preferably 3% by mass or less, more preferably 2.0% by mass or less, more preferably 1.8% by mass or less, even more preferably 1.5% by mass or less, still more preferably 1% by mass or less, still more preferably 0.8% by mass or less, and still more preferably 0.6% by mass or less.

[0036] From the viewpoint of cleaning performance against lipid / protein complex soils, the detergent composition of the present invention contains component (b) in an amount of preferably 0.5% by mass or more, more preferably 1% by mass or more, even more preferably 2.5% by mass or more, still more preferably 3.5% by mass or more, still more preferably 4% by mass or more, and preferably 10% by mass or less, more preferably 8% by mass or less, and even more preferably 6% by mass or less. In the present invention, when component (b1) is included as component (b), the mass of component (b1) is calculated assuming that sodium ions are the counter ions, and when component (b2) is included as component (b), the mass of component (b2) is calculated assuming that chloride ions are the counter ions.

[0037] In the detergent composition of the present invention, the content of the anionic surfactant (b1) in the component (b) is, from the viewpoint of cleaning performance for lipid / protein complex soils, preferably 25% by mass or more, more preferably 50% by mass or more, even more preferably 75% by mass or more, still more preferably 80% by mass or more, still more preferably 85% by mass or more, still more preferably 90% by mass or more, and preferably 100% by mass or less, and may be 100% by mass.

[0038] In the detergent composition of the present invention, the mass ratio (a) / (b) of the content of component (a) to the content of component (b) is 0.01 or more, preferably 0.03 or more, more preferably 0.05 or more, and even more preferably 0.08 or more, from the viewpoints of cleaning performance for lipid / protein complex soils and storage stability, and is 0.55 or less, preferably 0.4 or less, more preferably 0.2 or less, and even more preferably 0.15 or less, from the viewpoints of cleaning performance for soap scum soils and blend stability.

[0039] From the viewpoint of cleaning performance against lipid / protein complex soils, the detergent composition of the present invention contains component (c) in an amount of preferably 0.1% by mass or more, more preferably 0.2% by mass or more, even more preferably 0.3% by mass or more, and preferably 1% by mass or less, more preferably 0.8% by mass or less, even more preferably 0.6% by mass or less.

[0040] In the detergent composition of the present invention, the mass ratio (a) / (c) of the content of component (a) to the content of component (c) is preferably 0.1 or more, more preferably 0.2 or more, even more preferably 0.5 or more, still more preferably 0.8 or more, and is preferably 4 or less, more preferably 3 or less, even more preferably 2 or less, and still more preferably 1.5 or less, from the viewpoint of cleaning performance for lipid / protein complex soils.

[0041] From the viewpoint of cleaning performance against soap scum stains, the detergent composition of the present invention preferably further contains an aminocarboxylic acid type sequestering agent as component (d). Component (d) is not particularly limited, but may include one or more selected from ethylenediaminetetraacetic acid (EDTA), nitrilotriacetic acid (NTA), iminodiacetic acid, diethylenetriaminepentaacetic acid (DTPA), N-hydroxyethyl-ethylenediaminetriacetic acid (HEDTA), methylglycine diacetic acid (MGDA), dihydroxyethylglycine (DHEG), hydroxyethyleneiminodiacetic acid (HIDA), aspartic acid diacetic acid (ASDA), glutamic acid diacetic acid (GLDA), and salts thereof. From the viewpoint of cleaning performance against soap scum stains, component (d) is preferably one or more selected from ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, methylglycine diacetic acid, and salts thereof, and more preferably ethylenediaminetetraacetic acid or a salt thereof. Examples of salts of component (d) include alkali metal salts, ammonium salts, amine salts, etc. Alkali metal salts are preferred, and sodium salts or potassium salts are more preferred.

[0042] When the detergent composition of the present invention contains component (d), from the viewpoint of cleaning performance against soap scum stains, the content of component (d) is preferably 1% by mass or more, more preferably 1.5% by mass or more, even more preferably 2% by mass or more, and preferably 10% by mass or less, more preferably 5% by mass or less, even more preferably 3% by mass or less. In the present invention, the mass of component (d) is calculated assuming that it is entirely a sodium salt.

[0043] From the viewpoint of blend stability, the cleaning composition of the present invention preferably further contains a glycol solvent as component (e). The term "glycol-based" is not particularly limited, but refers to either a compound having two hydroxyl groups or an ether compound in which one or both hydrogen atoms of the hydroxyl groups are substituted with another group. The ether compound is preferably an aliphatic ether compound. Also, an ether compound in which one hydrogen atom of the hydroxyl group of a glycol compound is substituted with another group is preferred.

[0044] Component (e) is preferably a glycol-based water-soluble solvent having a carbon number of 2 to 12. Water-soluble means that 5 g or more dissolves in 100 g of water at 20°C. The component (e) preferably has an octanol / water partition coefficient (LogP) of 3.5 or less, more preferably 0.79 or less, and preferably -5 or more, more preferably -3 or more.

[0045] From the viewpoint of cleaning performance, the total number of carbon atoms in component (e) is preferably 2 or more, more preferably 3 or more, more preferably 4 or more, even more preferably 5 or more, and even more preferably 6 or more, and from the viewpoint of cleaning performance, it is preferably 12 or less, preferably 10 or less, and more preferably 8 or less.

[0046] From the viewpoint of cleaning performance, examples of component (e) include one or more selected from ethylene glycol (carbon number: 2), propylene glycol (carbon number: 3), diethylene glycol (carbon number: 4), propylene glycol monomethyl ether (carbon number: 4), isoprene glycol (carbon number: 5), propylene glycol monoethyl ether (carbon number: 5), propylene glycol monobutyl ether (carbon number: 7), 3-methyl-3-methoxybutanol (carbon number: 6), ethylene glycol monobutyl ether (carbon number: 6), dipropylene glycol (carbon number: 6), diethylene glycol monobutyl ether (carbon number: 8), diethylene glycol monophenyl ether (carbon number: 10), dibutylene glycol (carbon number: 8), and dipropylene glycol monobutyl ether (carbon number: 10).

[0047] Component (e) is preferably a glycol having 2 or 3 carbon atoms, such as ethylene glycol, polyethylene glycol, propylene glycol, or polypropylene glycol, or a polyether or monoalkyl ether thereof. The alkyl group of this monoalkyl ether preferably has 1 to 4 carbon atoms, and is methyl, ethyl, various propyl groups, or various butyl groups. The various groups include normal, iso, and tertiary.

[0048] From the viewpoint of cleaning performance, the component (e) is more preferably one or more selected from propylene glycol (carbon number: 3), propylene glycol monomethyl ether (carbon number: 4), ethylene glycol monobutyl ether (carbon number: 6), propylene glycol monobutyl ether (carbon number: 7), diethylene glycol monobutyl ether (carbon number: 8), diethylene glycol monophenyl ether (carbon number: 10), and dipropylene glycol monobutyl ether (carbon number: 10). It is preferable that the component (e) contains diethylene glycol monobutyl ether (carbon number: 8).

[0049] When the cleaning composition of the present invention contains component (e), from the viewpoint of blend stability, the content of component (e) is preferably 1% by mass or more, more preferably 2% by mass or more, even more preferably 3% by mass or more, and preferably 20% by mass or less, more preferably 10% by mass or less, even more preferably 8% by mass or less.

[0050] In order to increase the added value of the product, the detergent composition of the present invention may optionally contain fragrances, colorants, preservatives, antioxidants, antifoaming agents, stabilizers, etc. (excluding the above components (a) to (e)).

[0051] The cleaning composition of the present invention contains water. That is, the balance other than the components (a) to (e) and any optional components is water. The cleaning composition of the present invention contains water in an amount of preferably 50% by mass or more, more preferably 60% by mass or more, even more preferably 70% by mass or more, still more preferably 80% by mass or more, and preferably 99% by mass or less, more preferably 95% by mass or less. The water used is preferably ion-exchanged water, sterilized ion-exchanged water, etc.

[0052] The detergent composition of the present invention has a pH at 25°C of more than 9, preferably 10 or more, more preferably 10.5 or more, and less than 12, preferably 11.5 or less, more preferably 11 or less, from the viewpoint of cleaning performance against lipid / protein complex soils.

[0053] The detergent composition of the present invention can be suitably used for cleaning hard surfaces. Examples of hard surfaces include bathrooms, bathtubs, washbasins, tiles, restrooms, washstands, mirrors, kitchen sinks, countertops, and areas around water supplies. The detergent composition of the present invention is suitably used for cleaning hard surfaces, and is particularly suitable for use in bathrooms. Here, "for use in bathrooms" refers not only to bathrooms but also to other items with hard surfaces present in the bathroom, such as bathtubs and washbasins. The cleaning composition of the present invention can be suitably used for hard surface materials having a water contact angle of 30° or more, preferably 40° or more, and 120° or less, preferably 110° or less. The hard surface material having a water contact angle in the above range is not particularly limited, and examples thereof include one or more materials selected from polyester resin, acrylic resin, fiber reinforced plastic (FRP) resin, acrylonitrile-butadiene-styrene copolymer (ABS) synthetic resin, polypropylene (PP) resin, polycarbonate (PC) resin, stainless steel (SUS), aluminum, hard polyvinyl chloride (hard PVC) resin, soft polyvinyl chloride (soft PVC) resin, polyethylene terephthalate (PET) resin, and aluminum.

[0054] [How to clean lipid / protein complex stains] The present invention provides a method for cleaning lipid / protein complex soils (hereinafter also referred to as the cleaning method of the present invention), which comprises contacting the detergent composition of the present invention with a hard surface on which lipid / protein complex soils are attached. The cleaning method of the present invention can appropriately apply the matters described in relation to the detergent composition of the present invention. In the present invention, a concentrated composition containing components (a), (b), (c), and any optional components may be prepared, and the concentrated composition may be diluted with water to prepare the cleaning composition of the present invention, which may then be brought into contact with a hard surface. That is, the cleaning method may also include diluting a concentrated composition containing components (a), (b), (c), and any optional components with water to prepare the cleaning composition of the present invention, and bringing the cleaning composition into contact with a hard surface without dilution.

[0055] Furthermore, the cleaning method of the present invention includes a cleaning method in which the detergent composition of the present invention is brought into contact with a hard surface to which lipid / protein complex soils are attached, and then the surface is left to stand without applying (or being subjected to) external force such as mechanical force. In the present invention, the lipid / protein complex soils are dispersed and decomposed by the detergent composition, so a high cleaning effect can be achieved by contacting the surface without using a flexible material such as a sponge or fingers, and by leaving the surface to stand without applying external force such as mechanical force. This makes the detergent composition suitable for cleaning areas that are difficult to reach with hands or tools, or for cleaning small areas that are difficult to reach. Leaving the surface without applying external force such as mechanical force means, for example, that no intentional cleaning operation is performed other than contacting the composition. For example, the term "leaving the surface without applying external force" can be understood to mean that the contacted composition flows naturally down the hard surface or vibrations that are not intended for cleaning are transmitted to the hard surface. After leaving it for a while, it is usually rinsed with water. When rinsing, external force (physical force) may be applied with hands, or simply rinsed with running water.

[0056] In the cleaning method of the present invention, the detergent composition of the present invention is applied to a hard surface having an area of ​​100 cm 2From the viewpoint of cleaning performance for lipid / protein complex soils and soap scum, it is preferable to contact, further apply or spray, the amount of the agent to the surface of the detergent, preferably 0.5 g or more, more preferably 1 g or more, even more preferably 3 g or more, and preferably 20 g or less, more preferably 10 g or less, even more preferably 5 g or less.

[0057] In the cleaning method of the present invention, from the viewpoint of cleaning performance for lipid / protein complex soils and soap scum, the detergent composition of the present invention is allowed to stand after contact with a hard surface for preferably 1 second or more, more preferably 10 seconds or more, even more preferably 20 seconds or more, still more preferably 30 seconds or more, and preferably 10 minutes or less, more preferably 5 minutes or less, even more preferably 3 minutes or less, still more preferably 2 minutes or less, and still more preferably 1 minute or less. In this case, the time when the composition first comes into contact with the hard surface may be considered the start of the standing period. The temperature during storage may be room temperature, for example, 10°C or higher and 30°C or lower.

[0058] In the cleaning method of the present invention, the detergent composition of the present invention may be sprayed or applied to contact a hard surface on which lipid / protein complex soils are attached. The method for contacting the detergent composition of the present invention with a hard surface having lipid / protein complex soiling is preferably spraying or applying, and examples thereof include spraying in the form of droplets or applying in the form of foam. Specifically, a spray means can be used. That is, it is preferable to use a detergent article in which the detergent composition of the present invention is filled in a container equipped with a sprayer. The present invention provides a detergent article in a spray container in which the detergent composition of the present invention is filled in a container equipped with a sprayer.

[0059] In the spray-container-packaged detergent article of the present invention, the container equipped with a sprayer filled with the detergent composition of the present invention may be a manual spray device that does not use a propellant, such as a trigger-type spray container or a pump-type spray container, or an aerosol that uses a propellant. The container equipped with the sprayer is preferably a trigger-type spray that can spray or apply the contents in the form of droplets or foam, and more preferably a trigger-type spray equipped with a mechanism for spraying the contents in the form of droplets or a mechanism for forming foam (foam-forming mechanism).

[0060] When a trigger-type spray equipped with a mechanism for spraying the detergent composition of the present invention in droplets is used in the spray-bottle-packed detergent article of the present invention, the nozzle diameter of the spray container containing the composition is preferably 0.1 mm or more, more preferably 0.3 mm or more, and preferably 2 mm or less, more preferably 1 mm or less, so as to facilitate spraying, to prevent the sprayed droplets from being rough, from being sprayed in a straight line, and to prevent the spray area from being extremely narrow. When using a trigger-type spray equipped with a mechanism for spraying droplets, the spray-container-packaged cleaning article of the present invention sprays preferably 0.1 mL or more, more preferably 0.3 mL or more, and preferably 5 mL or less, more preferably 2 mL or less of the composition in one operation.

[0061] When using a trigger-type spray equipped with a foam-forming mechanism, the cleaning article in a spray container of the present invention sprays preferably 0.5 mL or more, more preferably 1 mL or more, and preferably 30 mL or less, more preferably 15 mL or less, and even more preferably 5 mL or less of the composition in one operation.

[0062] The cleaning method of the present invention is preferred as a method for cleaning hard surfaces of hard articles, further hard surfaces such as bathrooms, bathtubs, washbasins, tiles, restrooms, washstands, mirrors, kitchen sinks, countertops, and areas around water supplies, particularly hard surfaces in bathrooms. The hard surface materials targeted by the cleaning method of the present invention are suitable for use with hard surface materials having a contact angle with water of 30° or more, preferably 40° or more, and 120° or less, preferably 110° or less. Hard surface materials having a contact angle with water in the above range are not particularly limited, but include one or more materials selected from polyester resin, acrylic resin, fiber reinforced plastic (FRP) resin, acrylonitrile-butadiene-styrene copolymer (ABS) synthetic resin, polypropylene (PP) resin, polycarbonate (PC) resin, stainless steel (SUS), aluminum, hard polyvinyl chloride (hard PVC) resin, soft polyvinyl chloride (soft PVC) resin, polyethylene terephthalate (PET) resin, and aluminum. [Example]

[0063] The cleaning compositions shown in Tables 1 and 2 were prepared using the ingredients listed below, and evaluated for the following items. The results are shown in Tables 1 and 2. To prepare the cleaning compositions in Tables 1 and 2, ingredients (a) to (e) were added in the amounts shown in the tables and dissolved at room temperature (25°C). After blending, the pH was adjusted to the values ​​shown in Tables 1 and 2 using sodium hydroxide and / or hydrochloric acid. The pH was measured by the glass electrode method. The mass % of the ingredients in Tables 1 and 2 is all based on the active ingredient.

[0064] <Composition ingredients> (a) Ingredients Ethyl octanoate: carbon number 10, manufactured by Tokyo Chemical Industry Co., Ltd. Isobutyl acetate: carbon number 6, manufactured by Tokyo Chemical Industry Co., Ltd. Ethyl hexanoate: carbon number 8, manufactured by Tokyo Chemical Industry Co., Ltd. Hexyl benzoate: carbon number 13, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. Diisopropyl adipate: carbon number 14, manufactured by Tokyo Chemical Industry Co., Ltd. Isopropyl myristate: carbon number 17, manufactured by Tokyo Chemical Industry Co., Ltd. Ethyl oleate: carbon number 20, manufactured by Tokyo Chemical Industry Co., Ltd.

[0065] Component (a') (comparison component of component (a)) Propyl acetate: carbon number 5, manufactured by Tokyo Chemical Industry Co., Ltd. 2-Ethylhexyl stearate: carbon number 26, manufactured by Tokyo Chemical Industry Co., Ltd. 1-Decanol: carbon number 10, manufactured by Tokyo Chemical Industry Co., Ltd.

[0066] (b) Component Emal 2F-HP: Sodium lauryl sulfate, (b1) ingredient, manufactured by Kao Corporation Amphitol 20AB: Lauryl amide propyl betaine, (b4) ingredient, manufactured by Kao Corporation Sanizol 08: Octyldimethylbenzylammonium chloride, component (b2), manufactured by Kao Corporation Emulgen 109P: Polyoxyethylene lauryl ether, (b3) ingredient, manufactured by Kao Corporation

[0067] (c) Component Monoethanolamine Diethanolamine: Fujifilm Wako Pure Chemical Industries, Ltd. 1-Amino-2-propanol: Fujifilm Wako Pure Chemical Industries, Ltd. (d) Ingredients EDTA: Sodium ethylenediaminetetraacetate HEDTA: N-hydroxyethyl-ethylenediaminetriacetic acid, manufactured by Tokyo Chemical Industry Co., Ltd. DTPA: Diethylenetriaminepentaacetic acid HIDA: Hydroxyethyleneiminodiacetic acid, manufactured by Tokyo Chemical Industry Co., Ltd. (e) Component BDG: Diethylene glycol monobutyl ether, manufactured by Nippon Nyukazai Co., Ltd. MFG: Propylene glycol monomethyl ether, manufactured by Nippon Nyukazai Co., Ltd. PhDG: Diethylene glycol monophenyl ether, manufactured by Nippon Nyukazai Co., Ltd.

[0068] <Evaluation of cleaning performance against bathtub stains (complex lipid / protein stains)> Several PVC plates (manufactured by Engineering Test Service Co., Ltd., dimensions 80mm x 210mm x 1mm) were fixed to the bottom of a bathtub filled with water at 40°C. Four men took turns bathing (10 minutes per person), and after bathing, lipid / protein complex soiling was observed. The PVC plate was collected and used for cleaning evaluation. 10 μL of the detergent composition shown in Tables 1 and 2 was dropped onto the stained area of ​​the PVC plate, left to stand at 25°C for 1 minute, then rinsed with water, and the cleaning performance was evaluated visually and tactilely according to the following criteria. ◎: The level at which the dirt is completely removed by both visual and tactile inspection. ○: It seems that the dirt has been almost completely removed by visual inspection, but there is a slight amount of dirt remaining when touched. △: Level of residual dirt that can be seen visually and tactilely ×: The level at which it is felt that the dirt has not been removed by both visual and tactile inspection.

[0069] <Soap scum cleaning performance evaluation> A model soap scum stain was prepared based on the composition of soap scum stains found in bathrooms and formed into a film on a polypropylene plate (manufactured by Engineering Test Services Co., Ltd., dimensions 80 mm x 120 mm). The model soap scum stain was prepared and formed into a film by immersing the plate in succession in an aqueous solution (2% by mass) of solid soap (Kao Corporation, "White") and an aqueous calcium chloride solution (0.7% by mass), followed by drying, and this process was repeated 10 times. After the model soap scum stain was formed into a film on the plate, 10 μL of a detergent composition shown in Tables 1 and 2 was dropped onto the stained area of ​​the plate, allowed to stand at 25°C for 10 minutes, and then rinsed with water. The cleaning performance was evaluated according to the following criteria. ◎: The stains on the area where the liquid was dropped were almost completely removed without scrubbing. ○: More than half of the dirt on the area where the liquid was dropped was removed without scrubbing. △: Without scrubbing, the stains on the areas where the liquid was dropped were removed, but only less than half of the stains were removed. ×: Almost no dirt was removed from the area where the liquid was dropped without scrubbing.

[0070] <Compound stability evaluation> The cleaning performance compositions shown in Tables 1 and 2 were prepared and left to stand at room temperature (25°C) for one day, after which the appearance was visually observed and evaluated according to the following criteria. A: Uniform and transparent, with no separation or layering of ingredients or turbidity. B: Slightly cloudy but homogeneous liquid without separation C: Clearly cloudy or stratified

[0071] [Table 1]

[0072] [Table 2]

[0073] <Combination example> Tables 3 to 5 show examples of formulations of the detergent compositions of the present invention using the above-described blending components. These detergent compositions have excellent cleaning performance for lipid / protein complex soils and soap scum soils adhering to hard surfaces and good formulation stability.

[0074] [Table 3]

[0075] [Table 4]

[0076] [Table 5]

Claims

1. (a) an ester compound of a carboxylic acid and an alcohol, which has 6 to 20 carbon atoms [hereinafter referred to as component (a)]; (b) a surfactant (hereinafter referred to as component (b)), (c) an alkylmono- or dialkanolamine having an alkanol group with 2 or 3 carbon atoms [hereinafter referred to as component (c)], and water, the mass ratio (a) / (b) of the content of the component (a) to the content of the component (b) is 0.01 or more and 0.55 or less, and the pH at 25°C is more than 9 and less than 12; 1. A liquid cleaning composition for hard surfaces comprising: In the composition, the content of the component (a) is 0.1% by mass or more and 2.0% by mass or less, the content of the component (b) is 3.5% by mass or more and 8% by mass or less, and the content of the component (c) is 0.1% by mass or more and 1% by mass or less, The component (b) contains an anionic surfactant (hereinafter referred to as component (b1)), The content of the (b1) component is 20% by mass or 25% by mass or more of the (b) component; A liquid cleaning composition for hard surfaces.

2. 2. The liquid cleaning composition for hard surfaces according to claim 1, wherein component (a) is one or more ester compounds selected from isobutyl acetate (carbon number: 6), ethyl hexanoate (carbon number: 8), ethyl octanoate (carbon number: 10), hexyl benzoate (carbon number: 13), diisopropyl adipate (carbon number: 14), isopropyl myristate (carbon number: 17), and ethyl oleate (carbon number: 20).

3. A liquid cleaning composition for hard surfaces according to claim 1 or 2, wherein component (c) is one or more selected from monoethanolamine, diethanolamine, and 1-amino-2-propanol.

4. A liquid cleaning composition for hard surfaces described in any one of claims 1 to 3, wherein component (a) is one or more ester compounds selected from ethyl octanoate (carbon number: 10), isopropyl myristate (carbon number: 17), and ethyl oleate (carbon number: 20).

5. The liquid cleaning composition for hard surfaces according to any one of claims 1 to 4, wherein the mass ratio (a) / (c) of the content of the component (a) to the content of the component (c) is 0.1 or more and 4 or less.

6. The liquid detergent composition for hard surfaces according to any one of claims 1 to 5, further comprising an aminocarboxylic acid type sequestering agent as component (d).

7. A liquid cleaning composition for hard surfaces as described in Claim 6, wherein component (d) is ethylenediaminetetraacetic acid or a salt thereof.

8. The liquid cleaning composition for hard surfaces according to any one of claims 1 to 7, which is for use in a bathroom.

9. A method for cleaning lipid / protein complex stains, comprising contacting the liquid detergent composition for hard surfaces according to any one of claims 1 to 8 with a hard surface on which lipid / protein complex stains have adhered.

10. 10. The method for cleaning lipid / protein complex soils according to claim 9, wherein the hard surface that has been brought into contact with the liquid detergent composition for hard surfaces is left standing without application of external force, and then rinsed with water.

Images