How to clean lipid / protein complex stains

Abstract

To provide a method for cleaning a lipid / protein composite stain which has excellent cleaning performance for a lipid / protein composite stain and a soap scum stain adhered to a hard surface.SOLUTION: There is provided a method for cleaning a lipid / protein composite stain in which a cleanser composition, which comprises (a) a compound having a solubility parameter δ of 15.0 or more and 19.5 or less "hereinafter, referred to as a component (a)", (b) a surfactant having a protein swelling ratio of 101% or more as measured by a specific method and water, has a mass ratio (a) / (b) between the content of the component (a) and the content of the component (b) of more than 0.01 and 0.55 or less and has a pH of more than 9 and 12 or less, is brought into contact with a hard surface to which a lipid / protein composite stain is adhered and the hard surface contacted with the cleansing composition is left without applying external force, followed by rinsing with water.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a method for cleaning complex lipid / protein stains. [Background technology]

[0002] Lipids and proteins are typical of dirt derived from the human body, and they adhere to all surfaces in daily life, such as clothing, floors, and bathrooms, causing stains. Dirt accumulates particularly near the waterline on surfaces such as bathtubs. Because lipids, which are part of the dirt, coat and bind other dirt, firmly adhering to the surface, satisfactory cleaning results cannot be achieved when using detergents without applying external force using cleaning tools such as sponges. However, cleaning hard surfaces such as bathrooms using cleaning tools is a cumbersome task, and is particularly hard work for people with disabilities such as the elderly. Therefore, there is a need for a technology that can easily remove lipid / protein complex soils attached to hydrophobic hard surfaces without mechanical work such as scrubbing.

[0003] Patent Document 1 discloses a technology for a detergent containing an organic solvent with a solubility parameter of 14.0 to 19.0 and an anionic surfactant, which has excellent cleaning performance against soap scum stains or denatured oil stains. Patent Document 2 discloses a detergent composition containing an ester compound such as methyl laurate and an anionic surfactant. [Prior art documents] [Patent documents]

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

[0005] However, these techniques do not describe a method for cleaning lipid / protein complex stains by contacting a detergent composition with a hard surface on which lipid / protein complex stains are attached and rinsing without applying external force. The present invention provides a method for cleaning lipid / protein complex stains, which has excellent cleaning performance for lipid / protein complex stains and soap scum stains attached to hard surfaces. [Means for solving the problem]

[0006] The present invention relates to a method for cleaning lipid / protein complex soils, comprising contacting a hard surface having lipid / protein complex soils with a detergent 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)], (b) a surfactant having a protein swelling ratio of 101% or more as measured by the method described below, and water, wherein the mass ratio (a) / (b) of the content of component (a) to the content of component (b) is more than 0.01 and less than 0.55, and the pH is more than 9 and less than 12, and allowing the hard surface contacted with the detergent composition to stand without application of external force, and then rinsing with water. <Method for measuring protein swelling ratio> 20 mg of keratin (Tokyo Chemical Industry Co., Ltd., product code K0044) is placed in an NMR tube (Tokyo Chemical Industry Co., Ltd., outer diameter 5 mm, height 203 mm), and the height of the keratin (before treatment) is measured. 500 mg of an aqueous solution containing 1% by mass of each surfactant or ion-exchanged water is added. After leaving it for 24 hours, the height of the keratin (after treatment) is measured, and the swelling ratio after treatment with each surfactant aqueous solution is calculated using the swelling ratio after treatment with ion-exchanged water as the reference (100%) using the formula below.

[0007]

number

[0008] According to the present invention, there is provided a method for cleaning lipid / protein complex stains, which has excellent cleaning performance for lipid / protein complex stains and soap scum stains attached to hard surfaces. DETAILED DESCRIPTION OF THE INVENTION

[0009] The reason why the detergent composition of the present invention has excellent cleaning performance for lipid / protein complex soils and soap scum stains 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 ingredients necessary for protein cleaning into the protein, and because the lipid components interact with the molecules that make up the protein, preventing the protein from swelling. The detergent composition of the present invention containing component (a) removes lipid components by acting on lipid / protein complex soils, and further contains component (b) and maintains the pH within a specific range, thereby promoting protein swelling, and is therefore thought to be able to remove complex lipid / protein soils in a short time without scrubbing. On the other hand, component (a) is a very hydrophobic component and poorly soluble in water, making it difficult to incorporate from the viewpoint of formulation stability. By maintaining the ratio of component (a) to component (b) within a specific range, it is believed that the detergent composition of the present invention can provide a detergent composition that has excellent lipid / protein cleaning performance and good formulation stability.

[0010] [Cleaning composition] <Component (a)> The cleaning composition of the present invention contains, as component (a), a compound having a solubility parameter δ of 15.0 or more and 19.0 or less. 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 by 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, and even more preferably 18.0 or less, from the viewpoint of soap scum stain cleaning performance and lipid / protein complex stain cleaning performance. (a) The solubility parameter δ for component (a) is the heat of vaporization per mole of organic solvent, ΔH (cal / mol), and the molar volume, V (cm 3 mol), δ = (ΔH / V) 1 / 2 is the value defined by δ=(ΔH / V) 1 / 2 δ: Solubility parameter (sp value) [(J / cm 3 ) 1 / 2 〕 ΔH: Molar heat of vaporization V: molar volume

[0011] 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 2 nd Ed., p102(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.

[0012] Component (a) may have an ether group, an amide group, an ester group, etc., so 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.

[0013] Specific examples of hydrocarbons include olefin hydrocarbons, paraffin hydrocarbons, aromatic hydrocarbons, and terpene hydrocarbons.

[0014] As the olefin hydrocarbon, 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 can be used.

[0015] Examples of 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. Examples of isoparaffins that can be used include light isoparaffins, heavy isoparaffins, liquid isoparaffins, and polyisobutene.

[0016] Examples of aromatic hydrocarbons include toluene, xylene, and cumene.

[0017] 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 examples of terpene compounds that can be used include α-pinene, β-pinene, camphene, limonene, dipentene, terpinolene, myrcene, β-caryophyllene, and cedrene, with limonene, dipentene, and terpinolene being particularly preferred.

[0018] The aliphatic alcohol may be at least one selected from dodecanol, tetradecanol, hexadecanol, octadecanol, eicosanol, and structural isomers of the above alcohols.

[0019] The component (a) is preferably an ester compound having a carbon number of 8 to 24. However, the solubility parameter δ must be within the above range. 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 cleaning performance for soap scum stains and lipid / protein complex stains. From the viewpoint of cleaning performance for soap scum stains and lipid / protein complex stains, 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.

[0020] From the viewpoint of cleaning performance for soap scum stains and lipid / protein complex stains, 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 raw material carboxylic acid in the ester compound is monovalent or more and trivalent or less, preferably divalent or less, from the viewpoint of cleaning performance for soap scum stains and lipid / protein complex stains. 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. Examples thereof include 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 trime acid. Among these, from the viewpoint of cleaning performance for soap scum stains and lipid / protein complex stains, there can be mentioned 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.

[0021] From the viewpoint of cleaning performance for soap scum stains and cleaning performance for lipid / protein complex stains, the number of carbon atoms in the raw material alcohol in the ester compound 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. The raw material alcohol in the ester compound is monohydric or more and trihydric or less, preferably dihydric or less, more preferably monohydric, from the viewpoint of cleaning performance for soap scum stains and lipid / protein complex stains. 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 methanol, ethanol, propanol, isopropanol, butanol, pentanol, hexanol, heptanol, octanol, nonanol, decanol, dodecanol, tetradecanol, hexadecanol, octadecanol, eicosanol, and one or more structural isomers of these alcohols. From the viewpoint of cleaning performance for lipid (lipid / protein complex) stains, one or more structural isomers of these alcohols are preferred.

[0022] 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 (carbon number: 6), ethyl hexanoate (carbon number: 8), isobutyl isobutyrate (carbon number: 8), ethyl octanoate (carbon number: 10), hexyl benzoate (carbon number: 13), diisobutyl adipate (carbon number: 14), isopropyl myristate (carbon number: 17), and ethyl oleate (carbon number: 20).

[0023] From the viewpoint of cleaning performance for soap scum stains and cleaning performance for lipid / protein complex stains, 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 cleaning performance for lipid / protein complex soils and formulation 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.

[0024] <(b) Component> The detergent composition of the present invention contains, as component (b), a surfactant having a protein swelling ratio of 101% or more as measured by the following method. <Method for measuring protein swelling ratio> 20 mg of keratin (Tokyo Chemical Industry Co., Ltd., product code K0044) is placed in an NMR tube (Tokyo Chemical Industry Co., Ltd., outer diameter 5 mm, height 203 mm), and the height of the keratin (before treatment) is measured. 500 mg of an aqueous solution containing 1% by mass of each surfactant or ion-exchanged water is added. After leaving it for 24 hours, the height of the keratin (after treatment) is measured, and the swelling ratio after treatment with each surfactant aqueous solution is calculated using the swelling ratio after treatment with ion-exchanged water as the reference (100%) using the formula below.

[0025]

number

[0026] From the viewpoint of cleaning performance for lipid / protein complex soils, the protein swelling ratio of component (b) is 101% or more, preferably 105% or more, more preferably 110% or more, and preferably 200% or less, more preferably 170% or less, even more preferably 150% or less, still more preferably 140% or less, and even more preferably 130% or less.

[0027] From the viewpoint of protein swelling, component (b) is preferably an anionic surfactant, provided that the protein swelling ratio is within the above range. Examples of 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 benzene sulfonic acid or a salt thereof, polyoxyalkylene alkyl or alkenyl ether sulfate ester or a salt thereof, alkyl or alkenyl sulfate ester or a salt thereof, internal olefin sulfonic acid or a salt thereof, polyoxyalkylene alkyl or alkenyl ether acetic acid or a salt thereof, alkyl or alkenyl succinic acid or a salt thereof, and fatty acid or a salt thereof. From the viewpoint of protein swelling properties, the anionic surfactant 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, alkyl or alkenyl succinic 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.

[0028] From the viewpoint of cleaning performance against lipid / protein complex soils, the number of carbon atoms in the alkyl or alkenyl group of the alkyl or alkenyl sulfate ester or salt thereof is preferably 8 or more, more preferably 10 or more, and preferably 24 or less, more preferably 20 or less, even more preferably 18 or less, and still more preferably 16 or less.

[0029] From the viewpoint of cleaning performance for lipid / protein complex soils, the number of carbon atoms in the alkyl or alkenyl group of the polyoxyalkylene alkyl or alkenyl ether sulfate ester or its salt is preferably 8 or more, more preferably 10 or more, and preferably 24 or less, more preferably 20 or less, even more preferably 18 or less, and even more preferably 16 or less. The oxyalkylene group of the polyoxyalkylene alkyl or alkenyl ether sulfate ester or its salt is preferably an ethyleneoxy group. The average number of moles of oxyalkylene groups added in the polyoxyalkylene alkyl or alkenyl ether sulfate ester or its salt is preferably 0.5 or more, more preferably 1 or more, more preferably 2 or more, and preferably 5 or less, more preferably 3 or less.

[0030] From the viewpoint of cleaning performance for lipid / protein complex soils, the number of carbon atoms of the internal olefin sulfonic acid or its salt is preferably 8 or more, more preferably 10 or more, even more preferably 12 or more, still more preferably 14 or more, and preferably 24 or less, more preferably 20 or less, even more preferably 18 or less.

[0031] From the viewpoint of cleaning performance for lipid / protein complex soiling, the number of carbon atoms in the alkyl or alkenyl group of the alkyl or alkenyl benzenesulfonic acid or salt thereof is preferably 8 or more, more preferably 10 or more, and preferably 24 or less, more preferably 20 or less, even more preferably 18 or less, still more preferably 16 or less, and still more preferably 14 or less.

[0032] 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 acetic 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, and even more preferably 16 or less. The oxyalkylene group of the polyoxyalkylene alkyl or alkenyl ether acetic acid or its salt is preferably an ethyleneoxy group. The average number of moles of the oxyalkylene group added in the polyoxyalkylene alkyl or alkenyl ether acetic acid or its salt is preferably 0 or more, more preferably 0.5 or more, even more preferably 1 or more, even more preferably 2 or more, and preferably 30 or less, more preferably 20 or less, even more preferably 10 or less, and even more preferably 5 or less.

[0033] 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 succinic acid or salt thereof is preferably 8 or more, more preferably 10 or more, and preferably 24 or less, more preferably 20 or less, even more preferably 18 or less, still more preferably 16 or less, and still more preferably 14 or less.

[0034] <Composition, etc.> From the viewpoint of cleaning performance for soap scum stains and lipid / protein complex stains, the detergent composition of the present invention contains component (a) 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 1.9% by mass or less, more preferably 1.5% by mass or less, even 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.

[0035] From the viewpoint of cleaning performance for soap scum stains and lipid / protein complex stains, 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 (b) is an anionic surfactant, the mass of component (b) is calculated assuming that it is a sodium salt.

[0036] 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) exceeds 0.01, preferably 0.03 or more, more preferably 0.05 or more, and even more preferably 0.08 or more, from the viewpoint of soap scum stain cleaning performance and lipid / protein complex stain cleaning 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 formulation stability.

[0037] The detergent composition of the present invention may contain a surfactant other than component (b) to the extent that the effects of the present invention are not impaired. In the detergent composition of the present invention, the content of component (b) in all surfactants is preferably 20% by mass or more, more preferably 40% by mass or more, even more preferably 60% by mass or more, still more preferably 80% by mass or more, still more preferably 90% by mass or more, and preferably 100% by mass or less, and may even be 100% by mass, from the viewpoint of cleaning performance for soap scum stains and lipid / protein complex stains.

[0038] From the viewpoint of cleaning performance for soap scum stains and lipid / protein complex stains, the detergent composition of the present invention preferably further contains an alkanolamine as component (c). The component (c) 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 of the component (c) 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 / protein complex soils, the component (c) is 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.

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

[0040] From the viewpoint of soap scum removal performance, the detergent composition of the present invention preferably further contains a sequestering agent as component (d). The sequestering agent is not particularly limited, but may include one or more compounds selected from aminocarboxylic acid sequestering agents, hydroxycarboxylic acid sequestering agents, and hydroxyphosphonic acid sequestering agents. Specific examples of component (d) include one or more compounds 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, component (d) is preferably one or more compounds 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.

[0041] When the detergent composition of the present invention contains component (d), from the viewpoint of cleaning performance against soap scum stains, the content of component (d) is preferably 1% by mass or more, more preferably 1.5% by mass or more, even more preferably 2% by mass or more, and preferably 10% by mass or less, more preferably 5% by mass or less, even more preferably 3% by mass or less. In the present invention, the mass of component (d) is calculated assuming that the component is entirely a sodium salt.

[0042] 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.

[0043] Component (e) is preferably a glycol-based water-soluble solvent having a carbon number of 2 to 12. Water-soluble means that 5 g or more dissolves in 100 g of water at 20°C. The component (e) preferably has an octanol / water partition coefficient (LogP) of 3.5 or less, more preferably 0.79 or less, and preferably -5 or more, more preferably -3 or more.

[0044] From the viewpoint of cleaning performance, the total number of carbon atoms in component (e) is preferably 2 or more, more preferably 3 or more, more preferably 4 or more, even more preferably 5 or more, and even more preferably 6 or more, and from the viewpoint of cleaning performance, it is preferably 12 or less, preferably 10 or less, and more preferably 8 or less.

[0045] From the viewpoint of cleaning performance, examples of component (e) include one or more selected from ethylene glycol (carbon number: 2), propylene glycol (carbon number: 3), diethylene glycol (carbon number: 4), propylene glycol monomethyl ether (carbon number: 4), isoprene glycol (carbon number: 5), propylene glycol monoethyl ether (carbon number: 5), propylene glycol monobutyl ether (carbon number: 7), 3-methyl-3-methoxybutanol (carbon number: 6), ethylene glycol monobutyl ether (carbon number: 6), dipropylene glycol (carbon number: 6), diethylene glycol monobutyl ether (carbon number: 8), diethylene glycol monophenyl ether (carbon number: 10), dibutylene glycol (carbon number: 8), and dipropylene glycol monobutyl ether (carbon number: 10).

[0046] Component (e) is preferably a glycol having 2 or 3 carbon atoms, such as ethylene glycol, polyethylene glycol, propylene glycol, or polypropylene glycol, or a polyether or monoalkyl ether thereof. The alkyl group of this monoalkyl ether preferably has 1 to 4 carbon atoms, and is methyl, ethyl, various propyl groups, or various butyl groups. The various groups include normal, iso, and tertiary.

[0047] From the viewpoint of cleaning performance, the component (e) is more preferably one or more selected from propylene glycol (carbon number: 3), propylene glycol monomethyl ether (carbon number: 4), ethylene glycol monobutyl ether (carbon number: 6), propylene glycol monobutyl ether (carbon number: 7), diethylene glycol monobutyl ether (carbon number: 8), diethylene glycol monophenyl ether (carbon number: 10), and dipropylene glycol monobutyl ether (carbon number: 10). It is preferable that the component (e) contains diethylene glycol monobutyl ether (carbon number: 8).

[0048] When the cleaning composition of the present invention contains component (e), from the viewpoint of blend stability, the content of component (e) is preferably 1% by mass or more, more preferably 2% by mass or more, even more preferably 3% by mass or more, and preferably 20% by mass or less, more preferably 10% by mass or less, even more preferably 8% by mass or less.

[0049] In order to increase the added value of the product, the detergent composition of the present invention may optionally contain fragrances, colorants, preservatives, antioxidants, antifoaming agents, stabilizers, etc. (excluding the above components (a) to (e)).

[0050] The cleaning composition of the present invention contains water. That is, the balance other than the components (a) to (e) and any optional components is water. The cleaning composition of the present invention contains water in an amount of preferably 50% by mass or more, more preferably 60% by mass or more, even more preferably 70% by mass or more, still more preferably 80% by mass or more, and preferably 99% by mass or less, more preferably 95% by mass or less. The water used is preferably ion-exchanged water, sterilized ion-exchanged water, etc.

[0051] 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 12 or less, preferably 11.5 or less, more preferably 11 or less, from the viewpoint of cleaning performance against lipid / protein complex soils.

[0052] The detergent composition of the present invention can be suitably used for cleaning hard surfaces. Examples of hard surfaces include bathrooms, bathtubs, washbasins, tiles, restrooms, washstands, mirrors, kitchen sinks, countertops, and areas around water supplies. The detergent composition of the present invention is suitably used for cleaning hard surfaces, and is particularly suitable for use in bathrooms. Here, "for use in bathrooms" refers not only to bathrooms but also to other items with hard surfaces present in the bathroom, such as bathtubs and washbasins. The cleaning composition of the present invention can be suitably used for hard surface materials having a water contact angle of 30° or more, preferably 40° or more, and 120° or less, preferably 110° or less. The hard surface material having a water contact angle in the above range is not particularly limited, and examples thereof include one or more materials selected from polyester resin, acrylic resin, fiber reinforced plastic (FRP) resin, acrylonitrile-butadiene-styrene copolymer (ABS) synthetic resin, polypropylene (PP) resin, polycarbonate (PC) resin, stainless steel (SUS), aluminum, hard polyvinyl chloride (hard PVC) resin, soft polyvinyl chloride (soft PVC) resin, polyethylene terephthalate (PET) resin, and aluminum.

[0053] [How to clean lipid / protein complex stains] The present invention provides a method for cleaning lipid / protein complex soils (hereinafter also referred to as the cleaning method of the present invention), which comprises bringing the detergent composition of the present invention into contact with a hard surface on which lipid / protein complex soils are attached, leaving the hard surface in contact with the detergent composition without applying external force, and then rinsing the surface with water. 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.

[0054] The cleaning method of the present invention involves contacting the detergent composition of the present invention with a hard surface to which lipid / protein complex soils are attached, and then leaving the surface without applying (or providing) any external force such as mechanical force. Since the present invention disperses and decomposes lipid / protein complex soils, the detergent composition of the present invention can be brought into contact with the surface without using a flexible material such as a sponge or fingers, and a high cleaning effect can be achieved even when the surface is left as is without applying any external force such as mechanical force. This makes the composition suitable for cleaning areas that are difficult to reach with hands or tools, or for cleaning small areas that are difficult to reach. Leaving the surface without applying external force such as mechanical force means, for example, that no intentional cleaning operation is performed other than contacting the composition. For example, the term "leaving the surface without applying external force" can be understood to mean that the contacted composition flows naturally down the hard surface or vibrations that are not intended for cleaning are transmitted to the hard surface. After leaving it for a while, it is usually rinsed with water. When rinsing, external force (physical force) may be applied with hands, or simply rinsed with running water.

[0055] In the cleaning method of the present invention, the detergent composition of the present invention is applied to a hard surface having an area of ​​100 cm 2From the viewpoint of cleaning performance for lipid / protein complex soils and soap scum, it is preferable to contact, further apply or spray, the amount of the agent to the surface of the detergent, preferably 0.5 g or more, more preferably 1 g or more, even more preferably 3 g or more, and preferably 20 g or less, more preferably 10 g or less, even more preferably 5 g or less.

[0056] 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.

[0057] 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.

[0058] In the spray-container-packaged detergent article of the present invention, the container equipped with a sprayer filled with the detergent composition of the present invention may be a manual spray device that does not use a propellant, such as a trigger-type spray container or a pump-type spray container, or an aerosol that uses a propellant. The container equipped with the sprayer is preferably a trigger-type spray that can spray or apply the contents in the form of droplets or foam, and more preferably a trigger-type spray equipped with a mechanism for spraying the contents in the form of droplets or a mechanism for forming foam (foam-forming mechanism).

[0059] When a trigger-type spray equipped with a mechanism for spraying the detergent composition of the present invention in droplets is used in the spray-bottle-packed detergent article of the present invention, the nozzle diameter of the spray container containing the composition is preferably 0.1 mm or more, more preferably 0.3 mm or more, and preferably 2 mm or less, more preferably 1 mm or less, so as to facilitate spraying, to prevent the sprayed droplets from being rough, from being sprayed in a straight line, and to prevent the spray area from being extremely narrow. When using a trigger-type spray equipped with a mechanism for spraying droplets, the spray-container-packaged cleaning article of the present invention sprays preferably 0.1 mL or more, more preferably 0.3 mL or more, and preferably 5 mL or less, more preferably 2 mL or less of the composition in one operation.

[0060] When using a trigger-type spray equipped with a foam-forming mechanism, the cleaning article in a spray container of the present invention sprays preferably 0.5 mL or more, more preferably 1 mL or more, and preferably 30 mL or less, more preferably 15 mL or less, and even more preferably 5 mL or less of the composition in one operation.

[0061] The cleaning method of the present invention is preferred as a method for cleaning hard surfaces of hard articles, further hard surfaces such as bathrooms, bathtubs, washbasins, tiles, restrooms, washstands, mirrors, kitchen sinks, countertops, and areas around water supplies, particularly hard surfaces in bathrooms. The hard surface materials targeted by the cleaning method of the present invention are suitable for use with hard surface materials having a contact angle with water of 30° or more, preferably 40° or more, and 120° or less, preferably 110° or less. Hard surface materials having a contact angle with water in the above range are not particularly limited, but include one or more materials selected from polyester resin, acrylic resin, fiber reinforced plastic (FRP) resin, acrylonitrile-butadiene-styrene copolymer (ABS) synthetic resin, polypropylene (PP) resin, polycarbonate (PC) resin, stainless steel (SUS), aluminum, hard polyvinyl chloride (hard PVC) resin, soft polyvinyl chloride (soft PVC) resin, polyethylene terephthalate (PET) resin, and aluminum. [Example]

[0062] 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. For 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 to 3 using sodium hydroxide and / or hydrochloric acid. The pH was measured by the glass electrode method. The mass % of the ingredients in Tables 1 to 3 is all based on the active ingredient.

[0063] <Composition ingredients> (a) Ingredients Ethyl octanoate: carbon number 10, delta 17.3, manufactured by Tokyo Chemical Industry Co., Ltd. Octane: carbon number 8, δ 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, δ 17.4, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. Ethyl hexanoate: carbon number 6, delta 17.5, manufactured by Tokyo Chemical Industry Co., Ltd. Isobutyl acetate, carbon number 6, delta 17.7, 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, Ltd. 1-Dodecanol: carbon number: 12, δ19.2, manufactured by Kao Corporation

[0064] Component (a') (comparison component of 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.

[0065] (b) Component Emeral 2F-HP: Sodium lauryl sulfate, swelling ratio 122%, manufactured by Kao Corporation Sodium tetradecyl sulfate: swelling ratio 128%, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. 1-Octanesulfonic acid sodium: 1-octanesulfonic acid sodium, protein swelling ratio 107%, Fujifilm Wako Pure Chemical Industries, Ltd. Emal 227: Polyoxyethylene (2) sodium lauryl ether sulfate, protein swelling ratio 112%, manufactured by Kao Corporation ES-4.0K: Polyoxyethylene (4) sodium lauryl ether sulfate, protein swelling ratio 106%, manufactured by Kao Corporation Kao Akipo RLM-45NV: Polyoxyethylene (4) lauryl ether sodium acetate, protein swelling ratio 108%, manufactured by Kao Corporation Kao Akipo RLM-100NV: Polyoxyethylene (10) lauryl ether sodium acetate, protein swelling ratio 103%, manufactured by Kao Corporation AOS: Sodium internal olefin sulfonate with 16 carbon atoms, protein swelling ratio 112%, manufactured by Kao Corporation ASA-12: Dipotassium dodecenyl succinate, protein swelling ratio 121%, manufactured by Kao Corporation Neopelex G25: Sodium dodecylbenzenesulfonate, protein swelling ratio 128%, manufactured by Kao Corporation

[0066] Component (b') (comparison component of component (b)) Amphitol 20AB: Lauryl amide propyl betaine, protein swelling rate 98%, manufactured by Kao Corporation Emulgen 109P: Polyoxyethylene lauryl ether, protein swelling rate 98%, manufactured by Kao Corporation

[0067] The protein swelling ratio of component (b) or component (b') was measured by the following method. 20 mg of keratin (Tokyo Chemical Industry Co., Ltd., product code K0044) was placed in an NMR tube (Tokyo Chemical Industry Co., Ltd., outer diameter 5 mm, height 203 mm), and the height of the keratin (before treatment) was measured. 500 mg of an aqueous solution containing 1% by mass of each surfactant or ion-exchanged water was added. After leaving it for 24 hours, the height of the keratin (after treatment) was measured, and the swelling ratio after treatment with each surfactant aqueous solution was calculated using the swelling ratio after treatment with ion-exchanged water as the reference (100%) using the formula below.

[0068]

number

[0069] (c) Component Monoethanolamine Diethanolamine: Fujifilm Wako Pure Chemical Industries, Ltd. 1-Amino-2-propanol: Fujifilm Wako Pure Chemical Industries, Ltd. (d) Ingredients EDTA: Sodium ethylenediaminetetraacetate HEDTA: N-hydroxyethyl-ethylenediaminetriacetic acid, manufactured by Tokyo Chemical Industry Co., Ltd. DHEG: Dihydroxyethylglycine, manufactured by Tokyo Chemical Industry Co., Ltd. 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.

[0070] <Evaluation of cleaning performance for lipid / protein complex soils> A number of evaluation substrates (manufactured by Engineering Test Service Co., Ltd., dimensions: 80 mm x 210 mm x 1 mm) shown in Tables 1 to 3 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 evaluation substrates with sebum (complex lipid / protein soiling) attached were collected and used for cleaning evaluation. The detergent compositions shown in Tables 1 to 3 were applied to the soiled areas of the evaluation substrates in the amounts of attachment (mg / cm) shown in Tables 1 to 3. 2 After leaving the solution at 25°C for the time shown in Tables 1 to 3, the solution was washed with water and the cleaning performance was evaluated visually and tactilely according to the following criteria. ◎: The level at which the dirt is completely removed by both visual and tactile inspection. ○: It seems that the dirt has been almost completely removed by visual inspection, but there is a slight amount of dirt remaining when touched. △: Level of residual dirt that can be seen visually and tactilely ×: The level at which it is felt that the dirt has not been removed by both visual and tactile inspection.

[0071] <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 dissolved 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 to prepare the model soap scum stain and form a film. After the model soap scum stain was formed into a film on the plate, 10 μL of the detergent composition shown in Tables 1 to 3 was dropped onto the stained area of ​​the plate and the plate was left to stand at 25°C for 1 hour. After leaving it for 10 minutes, it was washed with water and the cleaning performance was evaluated according to the following criteria. ◎: The stains on the area where the liquid was dropped were almost completely removed without scrubbing. ○: More than half of the dirt on the area where the liquid was dropped was removed without scrubbing. △: Without scrubbing, the stains on the areas where the liquid was dropped were removed, but only less than half of the stains were removed. ×: Almost no dirt was removed from the area where the liquid was dropped without scrubbing.

[0072] <Compound stability evaluation> The cleaning compositions shown in Tables 1 to 3 were prepared and left to stand at room temperature (25°C) for one day, after which the appearance was visually observed and evaluated according to the following criteria. A: Uniform and transparent, with no separation or layering of ingredients or turbidity. B: Slightly cloudy but homogeneous liquid without separation C: Clearly cloudy or stratified

[0073] [Table 1]

[0074] [Table 2]

[0075] [Table 3] <Combination example> Tables 4 and 5 show examples of formulations of the detergent compositions of the present invention using the above-described ingredients. These detergent compositions have excellent cleaning performance for lipid / protein complex soils and soap scum soils adhering to hard surfaces and good formulation stability.

[0076] [Table 4]

[0077] [Table 5]

Claims

1. A liquid detergent composition comprising: (a) a compound having a solubility parameter δ of 17.0 to 18.1 (hereinafter referred to as component (a)); (b) a surfactant having a protein swelling ratio of 101% or more as measured by the method described below; and water, wherein component (a) is an ester compound of a carboxylic acid and an alcohol, and has 6 to 24 carbon atoms (limited to compounds having a solubility parameter δ within the above range); component (b) is an anionic surfactant 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; A method for cleaning lipid / protein complex soils, comprising contacting a hard surface having lipid / protein complex soils with the liquid detergent composition, the liquid detergent composition comprising: 0.1% by mass or more and 1.9% by mass or less of component (a), 1% by mass or more and 8% by mass or less of component (b), and 50% by mass or more of water; the content of component (b) relative to all surfactants contained therein is 20% by mass or more and 100% by mass or less; the mass ratio (a) / (b) of the content of component (a) to the content of component (b) is greater than 0.01 and less than 0.55; and the liquid detergent composition has a pH greater than 9 and less than 12; and allowing the hard surface contacted with the detergent composition to stand without application of external force, followed by rinsing with water. <Method for measuring protein swelling ratio> 20 mg of keratin (manufactured by Tokyo Chemical Industry Co., Ltd., product code K0044) was placed in an NMR tube (manufactured by Tokyo Chemical Industry Co., Ltd., outer diameter 5 mm, height 203 mm), the height of the keratin (before treatment) was measured, and 500 mg of an aqueous solution containing 1% by mass of each surfactant or ion-exchanged water was added. After leaving it for 24 hours, the height of the keratin (after treatment) was measured, and the swelling ratio after treatment with each surfactant aqueous solution was calculated using the swelling ratio after treatment with ion-exchanged water as the reference (100%) using the formula below. [Equation 1]

2. 2. The method for cleaning lipid / protein complex soils according to claim 1, wherein the liquid detergent composition further contains an alkanolamine as component (c).

3. 3. The method for cleaning lipid / protein complex soils according to claim 1, wherein the liquid detergent composition further contains a metal sequestering agent as component (d).

4. The method for cleaning lipid / protein complex soils according to any one of claims 1 to 3, wherein the hard surface is made of a material having a contact angle with water of 30° or more and 120° or less.

5. The method for cleaning lipid / protein complex soils according to any one of claims 1 to 4, wherein the hard surface is the hard surface of a bathtub.

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