JP7760281B2 - Detergent composition and method for cleaning lipid/protein complex soils - Google Patents

Description

The present invention relates to a detergent composition and a method for cleaning lipid/protein complex soils.

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, 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 be able 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.

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 for cleaning tiles and bathrooms using detergents containing fatty acid esters.

Japanese Patent Application Laid-Open No. 2007-31692 Special table 2016-540855 publication Special Publication No. 2013-515093

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 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.

The present invention relates to a cleaning composition containing (a) an ester compound having 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 greater than 9 and less than 12.

The present invention relates to a method for cleaning lipid/protein complex stains, in which the cleaning composition is brought into contact with a hard surface on which lipid/protein complex stains are attached.

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, as well as a method for cleaning lipid/protein complex soils and soap scum stains using the same.

[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 cleaning 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 easily 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 removal performance and good formulation stability.

<Component (a)>
The 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.

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 soils, one or more acids 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.

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 may be 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.

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

<(b) component>
The 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).

(b1) Anionic surfactants include those 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 carboxylic acid group. Examples of anionic surfactants include alkyl or alkenyl benzenesulfonic acid or salts thereof, polyoxyalkylene alkyl or alkenyl ether sulfate ester or salts thereof, alkyl or alkenyl sulfate ester or salts thereof, internal olefin sulfonic acid or salts thereof, and fatty acid 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.

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 even more preferably 16 or less.

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. Furthermore, the oxyalkylene group of the polyoxyalkylene alkyl or alkenyl ether sulfate ester or its salt is preferably an ethyleneoxy group. Furthermore, 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.

From the viewpoint of cleaning performance for lipid/protein complex soils, the number of carbon atoms in 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.

From the viewpoint of cleaning performance for lipid/protein complex soils, the number of carbon atoms in the alkyl or alkenyl group of the alkyl or alkenyl benzenesulfonic acid 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, still more preferably 16 or less, and even more preferably 14 or less.

(b2) Examples of 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 one or two of the groups bonded to the nitrogen atom are hydrocarbon groups having 6 or more carbon atoms, preferably 8 or more carbon atoms, 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). The (b2) component is preferably a quaternary ammonium salt-type cationic surfactant with bactericidal properties, and from the standpoint of bactericidal properties, a quaternary ammonium salt-type cationic surfactant with a benzyl group is preferred.

(b3) Nonionic surfactants include polyoxyalkylene alkyl ethers having an alkyl group containing 8 to 18 carbon atoms, polyoxyalkylene alkenyl ethers having an alkenyl group containing 8 to 18 carbon atoms, polyoxyalkylene sorbitan fatty acid esters having a fatty acid group containing 8 to 18 carbon atoms, alkyl glycosides having an alkyl group containing 8 to 18 carbon atoms, alkyl polyglycosides having an alkyl group containing 8 to 18 carbon atoms, sucrose fatty acid esters having a fatty acid group containing 8 to 18 carbon atoms, and alkyl polyglyceryl ethers having an alkyl group containing 8 to 18 carbon atoms, and these may be used alone or in combination. Component (b3) is preferably a polyoxyethylene alkyl ether having an alkyl group containing 8 to 18 carbon atoms and an average ethylene oxide addition mole count of 2 to 50.

The component (b3) is preferably a nonionic surfactant represented by the following general formula (b3).
R ^31b -O-[(C ₂ H ₄ O) _s (C ₃ H ₆ O) _t ]-H(b3)
[In the formula, R ^31b is 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, where 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, and 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. (C ₂ H ₄ O) and (C ₃ H ₆ O) may be random polymers or block polymers.]

(b4) Examples of amphoteric surfactants include one or more surfactants selected from betaine surfactants and amine oxide surfactants. Specific examples of component (b4) include one or more surfactants selected from sulfobetaine, carbobetaine, and amine oxide.

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

Carbobetaines include N-alkyl-N,N-dimethyl-N-carboxymethylammonium betaines in which the alkyl group preferably has 10 or more carbon atoms and preferably 18 or less, more preferably 14 or less, and compounds represented by the following general formula (b41):

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

In general formula (b41), R ^41b represents 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 each independently represent preferably a methyl group.

The amine oxide is preferably a compound represented by the following general formula (b42):

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

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

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.

<(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 into the proteins, greatly improving detergency. For this reason, 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, preferably one or more compounds selected from monoethanolamine, diethanolamine, 1-amino-2-propanol, and N-methylmonoethanolamine, and more preferably one or more compounds selected from monoethanolamine, diethanolamine, and 1-amino-2-propanol.

<Composition, etc.>
From the viewpoint of cleaning performance for 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.

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 contained as component (b), the mass of component (b1) is calculated assuming that sodium ions are counter ions, and when component (b2) is contained as component (b), the mass of component (b2) is calculated assuming that chloride ions are counter ions.

In the detergent composition of the present invention, the content of the anionic surfactant (b1) in 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, even more preferably 80% by mass or more, even more preferably 85% by mass or more, even more preferably 90% by mass or more, and preferably 100% by mass or less, and may be 100% by mass.

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 formulation stability.

From the viewpoint of cleaning performance for 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.

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, from the viewpoint of cleaning performance for lipid/protein complex soils, 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 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 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.

When the detergent composition of the present invention contains component (d), from the viewpoint of cleaning performance against soap scum stains, it preferably contains component (d) in an amount of 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, and 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.

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.

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 of the solvent dissolves in 100 g of water at 20°C.
The component (e) preferably has an octanol/water partition coefficient (Log P) of 3.5 or less, more preferably 0.79 or less, and preferably -5 or more, more preferably -3 or more.

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; from the viewpoint of cleaning performance, it is preferably 12 or less, preferably 10 or less, and more preferably 8 or less.

From the standpoint of cleaning performance, component (e) may be 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).

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. "Various" includes normal, iso, and tertiary groups.

From the viewpoint of cleaning performance, 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 to include diethylene glycol monobutyl ether (carbon number: 8) as component (e).

When the cleaning composition of the present invention contains component (e), from the viewpoint of formulation 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.

The cleaning composition of the present invention may optionally contain fragrances, colorants, preservatives, antioxidants, antifoaming agents, stabilizers, etc. to increase the added value of the product (excluding the above components (a) to (e)).

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, and even more preferably 80% by mass or more, and preferably 99% by mass or less, more preferably 95% by mass or less. It is preferable to use ion-exchanged water, sterilized ion-exchanged water, etc. as the water.

From the viewpoint of cleaning performance against lipid/protein complex soils, 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.

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, rigid polyvinyl chloride (rigid PVC) resin, flexible polyvinyl chloride (flexible PVC) resin, polyethylene terephthalate (PET) resin, and aluminum.

[Method for cleaning 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 detergent composition of the present invention, which may then be brought into contact with a hard surface. That is, the cleaning method may involve diluting a concentrated composition containing components (a), (b), (c), and any optional components with water to prepare the detergent composition of the present invention, and then contacting the detergent composition with a hard surface without dilution.

The cleaning method of the present invention also 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 left to stand without applying (or providing) external force such as mechanical force. In the present invention, since the lipid/protein complex soils are dispersed and decomposed, a high cleaning effect can be obtained by contacting the surface without using a flexible material such as a sponge or fingers, and leaving the surface to stand without applying external force such as mechanical force. This makes the cleaning method 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 by hand or simply rinsed with running water.

In the cleaning method of the present invention, the detergent composition of ^the present invention is preferably brought into contact with, or further applied or sprayed onto, a hard surface of the object in an amount of 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, per 100 cm2 area of the hard surface, from the viewpoint of cleaning performance against lipid/protein complex soils and soap scum.

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.

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.

In the spray-container cleaning article of the present invention, the container equipped with a sprayer filled with the cleaning 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).

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 a trigger-type sprayer equipped with a mechanism for spraying droplets is used, 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.

When using a trigger-type sprayer equipped with a foam-forming mechanism, the spray-container cleaning article 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.

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 material targeted by the cleaning method of the present invention is preferably a hard surface material having a contact angle with water of 30° or more, preferably 40° or more, and 120° or less, preferably 110° or less. The hard surface material having a contact angle with water in the above range is not particularly limited, but may be one or more 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, rigid polyvinyl chloride (rigid PVC) resin, flexible polyvinyl chloride (flexible PVC) resin, polyethylene terephthalate (PET) resin, and aluminum.

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 using the glass electrode method. The mass percentages of the ingredients in Tables 1 and 2 are all values based on the active ingredients.

<Ingredients>
(a) Component: 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 Co., 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.

Component (a') (comparison component to 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.

Component (b) Emal 2F-HP: sodium lauryl sulfate, component (b1), manufactured by Kao Corporation; Amphitol 20AB: lauric acid amide propyl betaine, component (b4), manufactured by Kao Corporation; Sanizol 08: octyldimethylbenzylammonium chloride, component (b2), manufactured by Kao Corporation; Emulgen 109P: polyoxyethylene lauryl ether, component (b3), manufactured by Kao Corporation.

(c) Component: Monoethanolamine, diethanolamine: manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.; 1-amino-2-propanol: manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. (d) Component: 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.

<Evaluation of cleaning performance against bathtub stains (complex lipid/protein stains)>
Several PVC plates (manufactured by Engineering Test Services Co., Ltd., dimensions: 80 mm x 210 mm x 1 mm) were fixed to the bottom of a bathtub filled with hot water at 40°C. Four men took turns bathing (10 minutes per person), and after each bath, the PVC plates with lipid/protein complex soiling were collected and used for cleaning evaluation. 10 μL of the detergent compositions shown in Tables 1 and 2 were dropped onto the soiled areas of the PVC plates, which were 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.
◎: A level at which it is felt that the dirt has been completely removed by both visual and tactile inspection. ○: A level at which it is felt that the dirt has been almost completely removed by visual inspection, but that a small amount of dirt remains by tactile inspection. △: A level at which it is felt that the dirt remains by both visual and tactile inspection. ×: A level at which it is felt that the dirt has not been removed by both visual and tactile inspection.

<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 (manufactured by 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.
◎: Almost all of the dirt was removed from the area where the liquid was dropped without scrubbing. ○: More than half of the dirt was removed from the area where the liquid was dropped without scrubbing. △: The dirt was removed from the area where the liquid was dropped without scrubbing, but less than half of the dirt was removed. ×: Almost no dirt was removed from the area where the liquid was dropped without scrubbing.

<Evaluation of compound stability>
The cleaning performance compositions shown in Tables 1 and 2 were prepared and left to stand at room temperature (25°C) for 1 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 components or turbidity. B: Slightly cloudy but no layering, uniform liquid. C: Clearly cloudy or layering is observed.

<Formulation 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.

Claims (10)

(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. 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. The liquid cleaning composition for hard surfaces according to claim 1, wherein the component (c) is one or more selected from monoethanolamine, diethanolamine, and 1-amino-2-propanol . 4. The liquid detergent composition for hard surfaces according to claim 1 , wherein component (a) is one or more ester compounds selected from ethyl octanoate (having 10 carbon atoms), isopropyl myristate (having 17 carbon atoms), and ethyl oleate (having 20 carbon atoms ) . 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. 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. The liquid cleaning composition for hard surfaces according to claim 6 , wherein the component (d) is ethylenediaminetetraacetic acid or a salt thereof . The liquid cleaning composition for hard surfaces according to any one of claims 1 to 7, which is for use in a bathroom. 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. 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.