JP7760282B2 - Cleaning composition - Google Patents

Description

The present invention relates to a detergent composition and a method for cleaning fatty stains.

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 resins 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. Lipid stains, in particular, cannot be satisfactorily cleaned unless they are scrubbed 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 oily 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 oily stains adhering 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 stains adhering to hard surfaces and has good foaming properties and blend stability when sprayed, and a method for cleaning lipid stains using the same.

The present invention relates to a cleaning composition containing (a) a compound having a solubility parameter δ of 15.0 or more and 19.5 or less [hereinafter referred to as component (a)], a surfactant [hereinafter referred to as component (b)], 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 stains, in which the cleaning composition is sprayed onto a hard surface having lipid stains attached thereto using a trigger-type sprayer equipped with a foam-forming mechanism, and the surface is then rinsed with water after being left to stand.

The present invention provides a detergent composition that has excellent cleaning performance for removing lipid stains from hard surfaces, and exhibits good foaming properties and formulation stability when sprayed, as well as a method for cleaning lipid stains using the same.

[Cleaning composition]
The reasons why the detergent composition of the present invention has excellent cleaning performance for lipid stains attached to hard surfaces and excellent foaming properties when sprayed are not entirely clear, but are presumed to be as follows. A typical cleaning method for removing lipid stains attached to hard surfaces generally utilizes a phenomenon such as rolling-up. However, it is known that this phenomenon is less likely to occur with lipid stains that are a mixture of solid fats and liquid oils. In the detergent composition of the present invention, component (a) having a specific solubility parameter is allowed to act on lipid stains while maintaining the pH of the detergent composition within a specific range, thereby dissolving the lipid stains with component (a). Furthermore, component (a) penetrates into the lipid stains, modifying the stains and reducing their viscosity, enabling rolling-up. Furthermore, in the detergent composition of the present invention, the combined use of component (a) and component (b) improves cleaning performance when cleaning lipid stains without scrubbing.
On the other hand, component (a) is a very hydrophobic component, and when component (b) is used to solubilize it in water, component (b) is consumed to solubilize component (a), resulting in a problem of poor foamability when foamed by spraying, etc. It is believed that by maintaining the ratio of component (a) to component (b) within a specific range, the present detergent composition can provide a detergent composition that has excellent cleaning performance for fatty stains and good foamability.

<Component (a)>
The component (a) is a compound having a solubility parameter δ of 15.0 or more and 19.5 or less.
Examples of component (a) include compounds whose solubility parameter δ, calculated from the well-known formula below, is 15.0 or more, preferably 16.0 or more, more preferably 17.0 or more, and 19.5 or less, preferably 19.0 or less, more preferably 18.5 or less, more preferably 18.0 or less, from the viewpoint of lipid cleaning performance.
The solubility parameter δ for component (a) is a value defined by δ = (ΔH/V) 1/2, where ΔH (cal/mol) is the heat of vaporization per ^mole of the organic solvent and V (cm ³ ·mol) is the molar volume.
δ=(ΔH/V) ^1/2
δ: Solubility parameter (sp value) [(J/cm ³ ) ^1/2 ]
ΔH: Molar heat of vaporization V: Molar volume

In addition, when determining the solubility parameter δ, the values described in the following non-patent literature are used.
Non-Patent Document 1: Barton, AFM; CRC Handbook of Solubility Parameters and Other Cohesive Parameters ^2nd Ed., p. 102 (CRC Press). Polymer Handbook p. VII528.
Non-patent document 2: Fedors, RF; Polym. Eng. Sci., 1974, 14, (2), 147.
Non-patent document 3: Meusburger, KE; “Pesticide Formulations: Innovations and Developments”, Chapter 14 (Am. Chem. Soc.), 1988, 151.

Component (a) may contain hydroxyl groups, ether groups, amide groups, ester groups, etc., as long as the solubility parameter δ is within the above range. Examples of component (a) include one or more selected from hydrocarbons having a total carbon number of 6 to 30, ester compounds having a carbon number of 8 to 24, and aliphatic alcohols. In the present invention, ester compounds having a carbon number of 8 to 24 are preferred.

Specific examples of hydrocarbons include olefin hydrocarbons, paraffin hydrocarbons, aromatic hydrocarbons, and terpene hydrocarbons.

Examples of olefin hydrocarbons that can be used include linear olefin compounds such as hexene, octene, decene, dodecene, and tetradecene, branched olefin compounds such as diisobutylene and triisobutylene, and cyclic olefin compounds such as cyclohexene and dicyclopentene.

Paraffin hydrocarbons that can be used include linear paraffin compounds such as hexane, heptane, octane, nonane, decane, undecane, dodecane, tridecane, tetradecane, pentadecane, hexadecane, heptadecane, and octadecane; branched paraffin compounds such as isohexane, isoheptane, isooctane, isohexane, isododecane, isotridecane, isotetradecane, isopentadecane, isohexadecane, isoheptadecane, and isooctadecane; and cyclic paraffin compounds such as cyclohexane. Furthermore, isoparaffins that can be used include light isoparaffins, heavy isoparaffins, liquid isoparaffins, and polyisobutene.

Aromatic hydrocarbons include toluene, xylene, and cumene.

Terpene compounds that can be used include monoterpene compounds, which are dimers of isoprene, sesquiterpene compounds, which are trimers, and diterpene compounds, which are tetramers. Specific terpene compounds that are suitable are α-pinene, β-pinene, camphene, limonene, dipentene, terpinolene, myrcene, β-caryophyllene, and cedrene, with limonene, dipentene, and terpinolene being particularly preferred.

Aliphatic alcohols include one or more selected from dodecanol, tetradecanol, hexadecanol, octadecanol, eicosanol, and structural isomers of the above alcohols.

The component (a) is preferably an ester compound having a carbon number of 6 to 24. However, the solubility parameter δ must be within the above range.
From the viewpoint of lipid cleaning performance, the number of carbon atoms in the ester compound is preferably 10 or more, more preferably 14 or more, and preferably 22 or less, more preferably 20 or less.
From the viewpoint of lipid cleaning performance, the ester compound 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 lipid cleaning performance, the number of carbon atoms in the raw carboxylic acid in the ester compound is preferably 2 or more, more preferably 6 or more, even more preferably 10 or more, and preferably 21 or less, more preferably 20 or less, even more preferably 18 or less.
The starting carboxylic acid in the ester compound is monovalent or more and trivalent or less, preferably divalent or less, from the viewpoint of lipid cleaning performance.
The raw material carboxylic acid for the ester compound is not particularly limited, but is a carboxylic acid having a linear or branched alkyl group, and examples thereof include 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 lipid-cleaning performance, one or more selected from 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, and azelaic acid are preferred.

The number of carbon atoms in the raw material alcohol in the ester compound is preferably 1 or more, more preferably 2 or more, from the viewpoint of lipid cleaning performance, and is 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 blend stability.
From the viewpoint of lipid cleaning performance, the raw material alcohol in the ester compound is monohydric or more and trihydric or less, preferably dihydric or less, more preferably monohydric.
The raw material alcohol for the ester compound is not particularly limited, but is an alcohol having a linear or branched alkyl group. Examples of the raw material alcohol include one or more selected from methanol, ethanol, propanol, isopropanol, butanol, isobutanol, pentanol, hexanol, heptanol, octanol, nonanol, decanol, dodecanol, tetradecanol, hexadecanol, octadecanol, eicosanol, and structural isomers of these alcohols. From the viewpoint of cleaning performance for lipid stains, one or more selected from methanol, ethanol, propanol, isopropanol, butanol, pentanol, hexanol, heptanol, octanol, and structural isomers of these alcohols are preferred.

The ester compound of a carboxylic acid and an alcohol is not particularly limited, but includes an ester compound of a fatty acid having 6 to 24 carbon atoms and an alcohol, and more specifically, includes one or more selected from isobutyl acetate (6 carbon atoms), ethyl hexanoate (8 carbon atoms), isobutyl isobutyrate (8 carbon atoms), ethyl octanoate (10 carbon atoms), hexyl benzoate (13 carbon atoms), diisobutyl adipate (14 carbon atoms), isopropyl myristate (17 carbon atoms), and ethyl oleate (20 carbon atoms).

From the viewpoint of lipid cleansing performance and blend stability, component (a) is preferably one or more selected from isobutyl acetate, ethyl hexanoate, isobutyl isobutyrate, ethyl octanoate, hexyl benzoate, diisobutyl adipate, isopropyl myristate, octane, isopropyl palmitate, isopropyl stearate, limonene, 1-dodecanol, and ethyl oleate, and more preferably one or more selected from isobutyl acetate, ethyl hexanoate, ethyl octanoate, isopropyl myristate, and ethyl oleate.
From the viewpoint of lipid cleansing performance and blend stability, component (a) of the present invention is preferably an ester compound having a δ of 17.0 or more and 18.1 or less, and is preferably an ester compound of a monovalent fatty acid having 8 to 18 carbon atoms and an alcohol having 2 to 3 carbon atoms.

<(b) component>
The component (b) is a surfactant.
The surfactant may be at least one selected from (b1) anionic surfactants (hereinafter also referred to as component (b1)), (b2) cationic surfactants (hereinafter also referred to as component (b2)), (b3) nonionic surfactants (hereinafter also referred to as component (b3)), and (b4) amphoteric surfactants (hereinafter also referred to as component (b4)).
From the viewpoint of lipid cleaning performance, the detergent composition of the present invention preferably contains (b1) an anionic surfactant as the 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 lipid cleansing performance, the 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 lipid-cleaning performance, 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 lipid cleansing performance, 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 lipid cleaning performance, 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 lipid cleaning performance, 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 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 10 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 (e.g., 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 lipid cleansing properties, 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.

<Composition, etc.>
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, more preferably 0.2% by mass or more, and even more preferably 0.3% by mass or more, from the viewpoint of lipid cleaning performance; and in an amount of 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 even more preferably 0.6% by mass or less, from the viewpoint of foam dischargeability.

From the viewpoint of lipid cleaning performance, 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 preferably 25% by mass or more, more preferably 40% by mass or more, even more preferably 50% by mass or more, and preferably 100% by mass or less, from the viewpoint of lipid cleaning performance.

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 viewpoint of lipid cleansing performance, 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 viewpoint of foam ejection performance.

From the viewpoint of lipid cleaning performance, the detergent composition of the present invention preferably further contains a glycol-based solvent as component (c).
The term "glycol-based" 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. Furthermore, an ether compound in which one hydrogen atom of the hydroxyl group of a glycol compound is substituted with another group is preferred.

Component (c) 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 (c) 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 (c) 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 (c) 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 (c) 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, the (c) component 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). The (e) component is even more preferably one or more selected from diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monobutyl ether, and diethylene glycol monophenyl ether.

When the detergent composition of the present invention contains component (c), from the viewpoint of lipid cleaning performance, it contains component (c) in an amount of preferably 1% by mass or more, more preferably 1.5% by mass or more, even more preferably 2% by mass or more, still more preferably 3% by mass or more, and preferably 30% by mass or less, more preferably 20% by mass or less, even more preferably 10% by mass or less, and still more preferably 8% by mass or less.

In the detergent composition of the present invention, the mass ratio (b)/(c) of the content of component (b) to the content of component (c) is, from the viewpoint of lipid cleaning performance, preferably 0.5 or more, more preferably 0.8 or more, even more preferably 1 or more, and preferably 10 or less, more preferably 5 or less, even more preferably 3 or less, still more preferably 2 or less, and even more preferably 1.5 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 lipid cleaning performance, preferably 0.01 or more, more preferably 0.02 or more, even more preferably 0.07 or more, still more preferably 0.1 or more, and preferably 0.39 or less, more preferably 0.3 or less, even more preferably 0.2 or less, and still more preferably 0.15 or less.

From the viewpoint of cleaning performance for lipid (lipid/protein complex) stains, the detergent composition of the present invention preferably further contains an alkanolamine as component (d).
Component (d) is not particularly limited, but may be an alkylmono- or dialkanolamine having 2 or 3 carbon atoms in the alkanol group, or an alkylene oxide adduct 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. From the viewpoint of cleaning performance for lipid (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.

When the detergent composition of the present invention contains component (d), from the viewpoint of cleaning performance against lipid (lipid/protein complex) stains, the content of component (d) is 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 1.9% by mass or less, more preferably 1.5% by mass or less, even more preferably 1% by mass or less, and even more preferably 0.8% by mass 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 (e).
Component (e) 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 (e) 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 (e) 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 (e), from the viewpoint of cleaning performance against soap scum stains, the content of component (e) 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 (e) is determined assuming that the component is entirely a sodium salt.

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 stains, 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.

[How to clean oily stains]
The present invention provides a method for cleaning lipid stains (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 stains 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 component (a), component (b), 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 component (a), component (b), 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.

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 having lipid stains thereon and then left to stand without applying (or providing) external force such as mechanical force. In the present invention, the detergent composition of the present invention disperses and decomposes lipid stains, so that 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 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 by hand or simply rinsed with running water.

In the cleaning method of the present invention, from the viewpoint of cleaning performance for removing lipid stains and soap scum, 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.

In the cleaning method of the present invention, from the viewpoint of cleaning performance for lipid 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 with a hard surface on which fatty soils are attached.
The method for contacting the detergent composition of the present invention with a hard surface having fatty soils attached thereto 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 to 3 were prepared using the ingredients listed below and evaluated for the following items. The results are shown in Tables 1 to 3. To prepare the cleaning compositions in Tables 1 to 3, 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 to 3 are all values based on the active ingredients.

<Ingredients>
(a) Components: Ethyl octanoate: carbon number 10, delta 17.3, manufactured by Tokyo Chemical Industry Co., Ltd. Octane: carbon number 8, delta 15.6, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. Isobutyl isobutyrate: carbon number 8, delta 16.9, manufactured by Tokyo Chemical Industry Co., Ltd. Isopropyl myristate: carbon number 17, delta 17.0, manufactured by Tokyo Chemical Industry Co., Ltd. Limonene: carbon number 10, delta 17.4, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. Ethyl hexanoate: carbon number Isobutyl acetate, carbon number 6, delta 17.5, manufactured by Tokyo Chemical Industry Co., Ltd.; Ethyl oleate, carbon number 20, delta 18.1, manufactured by Tokyo Chemical Industry Co., Ltd.; Diisobutyl adipate, carbon number 16, delta 18.2, manufactured by Tokyo Chemical Industry Co., Ltd.; Hexyl benzoate, carbon number 13, delta 18.9, manufactured by Fujifilm Wako Pure Chemical Industries Co., Ltd.; 1-dodecanol, carbon number 12, delta 19.2, manufactured by Kao Corporation.

Component (a') (comparison component to component (a))
Pentane: carbon number 5, δ 14.8, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. 1-decanol: carbon number 10, δ 19.6, manufactured by Tokyo Chemical Industry Co., Ltd.

Component (b) Emal 2F-HP: sodium lauryl sulfate, component (b1), manufactured by Kao Corporation; Anthol 20AB: lauric acid amide propyl betaine, component (b4), manufactured by Kao Corporation; Emulgen 109P: polyoxyethylene lauryl ether, component (b3), manufactured by Kao Corporation; Emal 227: polyoxyethylene (2) sodium lauryl ether sulfate, component (b1), manufactured by Kao Corporation; 1-octanesulfonic acid Na: sodium 1-octanesulfonate, component (b1), manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.

Component (c): BDG: diethylene glycol monobutyl ether, manufactured by Nippon Nyukazai Co., Ltd. MFG: propylene glycol monomethyl ether, manufactured by Nippon Nyukazai Co., Ltd. BFG: propylene glycol monobutyl ether, manufactured by Nippon Nyukazai Co., Ltd. PhDG: diethylene glycol monophenyl ether, manufactured by Nippon Nyukazai Co., Ltd. Component (d): monoethanolamine Component (e): EDTA: sodium ethylenediaminetetraacetate GLDA: glutamic acid diacetate

<Model lipid stain cleaning performance evaluation 1>
A model lipid soil prepared based on the composition of lipid soil adhering to a bathroom bathtub was dissolved in chloroform to prepare a 10% by mass model lipid soil solution. A polypropylene plate (7 cm x 2 cm) was immersed in this solution for 10 seconds to form a film of model lipid soil on the plate, which was then air-dried overnight and precisely weighed on a four-digit balance (adhered soil amount: approximately 40 mg). The composition of the model lipid soil was 40% by mass of linoleic acid, 20% by mass of oleic acid, 20% by mass of palmitic acid, 10% by mass of cholesterol, and 10% by mass of liquid paraffin. 100 mL of the detergent composition shown in Tables 1 and 2 was placed in a 100 mL beaker, and the plate with the model lipid attached was immersed at 25°C for 5 seconds. Both sides of the substrate were then washed with water for 5 seconds each. The cleaning rate was calculated from the weight change before and after washing using the following formula and evaluated according to the following criteria. The results are shown in Tables 1 and 2.

◎: Cleaning rate is 70% or more. ○: Cleaning rate is 50% or more but less than 70%. △: Cleaning rate is 40% or more but less than 50%. ×: Cleaning rate is less than 40%.

<Model lipid stain cleaning performance evaluation 2>
The detergent compositions shown in Table 3 were filled into trigger-type spray containers (Magiclean Bath Foaming Spray, manufactured by Kao Corporation). The 10% by mass model lipid soil solution described in Detergency Performance Evaluation 1 was applied to one side of a polypropylene plate (7 cm x 2 cm), air-dried overnight, and then precisely weighed on a four-digit balance (adhered soil amount: approximately 20 mg).
Then, a polypropylene plate was placed vertically and sprayed once with the filled trigger spray bottle in narrow bubble mode. The spray was adjusted so that the distance between the plate and the spray nozzle was 10 cm, and the spray was perpendicular to the plate.
After spraying, both sides of the substrate were washed with water for 5 seconds each, dried, and the washing rate was calculated from the weight change before and after washing using the following formula, and evaluated according to the following criteria.

◎: Cleaning rate is 70% or more. ○: Cleaning rate is 50% or more but less than 70%. △: Cleaning rate is 40% or more but less than 50%. ×: Cleaning rate is less than 40%.

<Evaluation of specific foam volume>
Each of the detergent compositions in Tables 1 to 3 was filled into a trigger-type spray container (Magiclean Bath Foaming Spray, manufactured by Kao Corporation), and sprayed 10 times into a 200 mL measuring cylinder (inner diameter 40 mm) using the narrow foam mode of the container. The mass of the 200 mL measuring cylinder after spraying was measured using a balance, and the difference from the mass of the measuring cylinder before spraying was recorded as the foam weight (g) (a). In addition, the volume (mL) of foam in the measuring cylinder immediately after spraying was read visually (b). The foam specific volume was calculated using the following formula and evaluated according to the following criteria. A larger foam specific volume indicates better foaming.
Foam specific volume (mL/g) = (b)/(a)
Pass: Specific foam volume is 11 mL/g or more Usable: Specific foam volume is 10 mL/g or more but less than 11 mL/g Fail: Specific foam volume is less than 10 mL/g

<Evaluation of compounding stability>
The detergent compositions shown in Tables 1 to 3 were prepared and allowed 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 components or turbidity. B: Slightly cloudy but no layering, uniform liquid. C: Clearly cloudy or layering is observed.

<Formulation example>
Tables 4 and 5 show formulation examples of the detergent compositions of the present invention using the above-described blending components. These detergent compositions have excellent cleaning performance for removing fatty stains from hard surfaces, and have good foaming properties and blend stability when sprayed.

Claims (10)

A liquid detergent composition to be sprayed onto hard surfaces, comprising (a) a compound having a solubility parameter δ of 17.0 or more and 18.1 or less [hereinafter referred to as component (a)], a surfactant [hereinafter referred to as component (b)], (c) a glycol-based solvent [hereinafter referred to as component (c)], and water, wherein component (a) is an ester compound of a carboxylic acid and an alcohol, and the ester compound has 6 to 24 carbon atoms (limited to compounds having a solubility parameter δ that satisfies the above range), and component (b) is (b1) an anionic surfactant (hereinafter also referred to as component (b1)), (b3) a nonionic surfactant (hereinafter also referred to as component (b3)), and (b4) an amphoteric surfactant (hereinafter also referred to as component (b4)). a) component (b) having a mass ratio of 0.03 to 0.55, and b) component (b1) having a pH of 10 or more and less than 12 at 25 ° C . 2. The liquid cleaning composition for spraying onto hard surfaces according to claim 1, wherein component (a) is one or more selected from the group consisting of isobutyl acetate, ethyl hexanoate, ethyl octanoate, isopropyl myristate, isopropyl palmitate, isopropyl stearate, and ethyl oleate. 3. The liquid cleaning composition for spraying onto hard surfaces according to claim 1 , wherein the content of component (b1) in component (b) is 25% by mass or more and 100% by mass or less. The liquid cleaning composition to be sprayed onto hard surfaces according to any one of claims 1 to 3, wherein the mass ratio (b)/(c) of the content of the component (b) to the content of the component (c) is 0.5 or more and 10 or less. 5. The liquid cleaning composition for spraying onto hard surfaces according to claim 1 , wherein the mass ratio (a)/(c) of the content of the component (a) to the content of the component (c) is 0.01 or more and 0.39 or less. The liquid detergent composition to be sprayed onto hard surfaces according to any one of claims 1 to 5 , further comprising an alkanolamine as component (d). The liquid detergent composition to be sprayed onto hard surfaces according to any one of claims 1 to 6 , further comprising an aminocarboxylic acid type sequestering agent as component (e). The liquid detergent composition to be sprayed onto hard surfaces according to any one of claims 1 to 7 , which is for use in bathrooms. A method for cleaning lipid stains, comprising spraying the liquid detergent composition for spraying onto hard surfaces according to any one of claims 1 to 8 onto a hard surface having lipid stains attached thereto using a trigger-type sprayer equipped with a foam-forming mechanism, leaving the composition to stand, and then rinsing the surface with water. The cleaning method according to claim 9, wherein the object to be cleaned is sprayed with the liquid cleaning composition for spraying onto hard surfaces , and then rinsed with water without applying mechanical force.