JP2022097367A - Lipid / protein complex stain cleaning method - Google Patents

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

The present invention relates to a lipid / protein complex stain cleaning method.

Lipids and proteins are typical examples of stains derived from the human body, and they adhere to all surfaces of living scenes and living places such as clothes, floors, and bathrooms, and cause stains. In particular, dirt accumulates near the waterline on the surface of bathtubs and the like. For such stains, the lipids that are part of the stains cover and bind other stains and firmly adhere to the object. Therefore, when cleaning with a cleaning agent, use a cleaning tool such as a sponge to apply external force. If it is not cleaned, a satisfactory cleaning effect cannot be obtained.
However, cleaning a hard surface such as a bathroom with a cleaning tool is complicated, and is particularly hard work for a person with a handicap such as an elderly person. Therefore, there is a need for a technique that can be easily removed without mechanical work such as rubbing lipid / protein complex stains adhering to a hydrophobic hard surface.

Patent Document 1 discloses a cleaning agent having excellent cleaning performance against soap residue stains or modified oil stains containing an organic solvent having a solubility parameter of 14.0 to 19.0 and an anionic surfactant. ing.
Patent Document 2 discloses a detergent composition containing an ester compound such as methyl laurate and an anionic surfactant.

Japanese Unexamined Patent Publication No. 2007-31692 Special Table 2013-515093 Publication No.

However, these techniques do not describe a method for cleaning a lipid / protein composite stain by bringing the detergent composition into contact with a hard surface to which the lipid / protein composite stain is attached and rinsing without applying an external force.
The present invention provides a method for cleaning a lipid / protein complex stain and a soap scum stain having excellent cleaning performance on a hard surface.

The present invention relates to (a) a compound having a solubility parameter δ of 15.0 or more and 19.5 or less [hereinafter referred to as (a) component], and (b) a surfactant having a protein swelling rate of 101% or more as measured by the following method. , And water, the mass ratio (a) / (b) of the content of the component (a) to the content of the component (b) is more than 0.01 and 0.55 or less, and the pH is 9. A detergent composition of more than 12 or less is brought into contact with a hard surface to which a lipid / protein complex stain is attached, and the hard surface to which the detergent composition is brought into contact is left without applying an external force and then rinsed with water. It relates to a lipid / protein complex stain cleaning method.
<Protein swelling rate measurement method>
Put 20 mg of keratin (manufactured by Tokyo Chemical Industry Co., Ltd., product code K0044) in an NMR tube (manufactured by Tokyo Chemical Industry Co., Ltd., outer diameter 5 mm, height 203 mm) and measure the height (before treatment) of the keratin. Add 500 mg of aqueous solution or ion-exchanged water containing% by weight of each surfactant. After leaving for 24 hours, the height of keratin (after treatment) is measured, and the swelling rate after each surfactant aqueous solution treatment is calculated from the following formula with the swelling rate at the time of ion-exchanged water treatment as a reference (100%).

INDUSTRIAL APPLICABILITY According to the present invention, there is provided a method for cleaning a lipid / protein complex stain and a soap scum stain having excellent cleaning performance on a hard surface.

The reason why the cleaning agent composition of the present invention is excellent in cleaning performance of lipid / protein complex stains and soap scum stains adhering to a hard surface is not necessarily clear, but is presumed as follows. It is known that the protein component adhering to the hard surface becomes a stronger stain by being combined with the lipid component, and it becomes difficult to remove the stain without rubbing in a short time. This is because the lipid component inhibits the penetration of the cleaning component required for protein cleaning into the protein, and the interaction of the lipid component between the molecules constituting the protein hinders the swelling of the protein. It is presumed. The detergent composition containing the component (a) of the present invention removes the lipid component by acting on the lipid / protein complex stain, and further contains the component (b) to keep the pH in a specific range to obtain a protein. It is considered that the swelling of the compound can be promoted and the complexed lipid / protein stain can be removed in a short time without rubbing.
On the other hand, the component (a) is a very hydrophobic component and is poorly soluble in water, so that it is difficult to easily mix the component (a) from the viewpoint of compounding stability. In the detergent composition of the present invention, by keeping the ratio of the component (a) and the component (b) in a specific region, a detergent composition having excellent lipid / protein cleaning performance and good compounding stability is provided. It is considered possible.

[Cleaning agent composition]
<(A) component>
The detergent composition of the present invention contains a compound having a solubility parameter δ of 15.0 or more and 19.0 or less as the component (a).
The component (a) is a compound having a solubility parameter δ of 15.0 or more and 19.5 or less.
As the component (a), the solubility parameter δ obtained from the generally well-known formula below is preferably 15.0 or more from the viewpoint of cleaning performance of soap residue stains and lipid / protein composite stains. Is 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, still more preferably 18.0 or less.
The solubility parameter δ for the component (a) is δ = (ΔH / V) when the heat of vaporization per mole of the organic solvent is ΔH (cal / mol) and the molar volume is V (cm ³ · mol). A value defined by ^1/2 .
δ = (ΔH / V) ^1/2
δ; Solubility parameter (sp value) [(J / cm ³ ) ^1/2 ]
ΔH; Molar heat of vaporization V; Molar volume

In obtaining the solubility parameter δ, the numerical values described in the following non-patent documents shall be used.
Non-Patent Document 1: Barton, AFM; CRC Handbook ^{ofSolubilityParameters} and Other Cohesive Parameters 2nd Ed., P102 (CRC Press). Polymer Handbook p VII 528.
Non-Patent Document 2: Federations, RF; Polym. Eng. Sci., 1974, 14, (2), 147.
Non-Patent Document 3: Meusburger, KE; “PesticideFormulations: Innovations and Developments”, Chapter 14 (Am. Chem.Soc.), 1988, 151.

The component (a) may have an ether group, an amide group, an ester group, or the like as long as the solubility parameter δ is in the above range. Examples of the component (a) include one or more selected from hydrocarbons having a total carbon number of 6 to 30 and ester compounds having a total carbon number of 8 to 24. In the present invention, ester compounds having 8 or more and 24 or less carbon atoms are preferable.

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

As the olefin hydrocarbon, linear olefin compounds such as hexene, octene, decene, dodecene and tetradecene, branched chain olefin compounds such as diisobutylene and triisobutylene, and cyclic olefin compounds such as cyclohexene and dicyclopentene can be used.

Paraffin hydrocarbons include linear paraffin compounds such as hexane, heptane, octane, nonane, decane, undecane, dodecane, tridecane, tetradecane, pentadecane, hexadecane, heptadecane, octadecane, isohexane, isoheptane, isooctane, isohexane, isododecane, isotoridecan, Branched chain paraffin compounds such as isotetradecane, isopentadecane, isohexadecane, isoheptadecane and isooctadecane, and cyclic paraffin compounds such as cyclohexane can be used. Further, as the isoparaffin, light isoparaffin, heavy isoparaffin, liquid isoparaffin, and polyisobutene can be used.

Examples of aromatic hydrocarbons include toluene, xylene, and cumene.

As the terpene-based compound, a monoterpene compound which is a dimer of isoprene, a sesquiterpene compound which is a trimer, and a diterpene compound which is a tetramer can be used. As specific terpene compounds, α-pinene, β-pinene, camphene, limonene, dipentene, terpinolene, myrcene, β-caryophyllene and cedrene are preferable, and limonene, dipentene and terpinolene are particularly preferable.

Examples of the fatty alcohol include dodecanol, tetradecanol, hexadecanol, octadecanol, eicosanol, and one or more selected from the structural isomers of the alcohol.

The component (a) is preferably an ester compound having 8 or more and 24 or less carbon atoms. However, the solubility parameter δ needs to be in the above range.
The carbon number of 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 of soap scum stains and lipid / protein composite stains. be.
The ester compound is preferably an ester compound of a carboxylic acid and an alcohol from the viewpoint of cleaning performance of soap residue stains and lipid / protein composite stains, and is preferably a carboxylic acid having a valentity to trivalent or less and a valent to trivalent or less. The ester compound with the alcohol of is more preferable. However, the carbon number of the ester compound satisfies the above range.

The carbon number of the raw material carboxylic acid in the ester compound is preferably 2 or more, more preferably 6 or more, still more preferably 10 or more, and preferably 10 or more, from the viewpoint of cleaning performance of soap scum stains and lipid / protein composite stains. Is 21 or less, more preferably 20 or less, still 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 the cleaning performance of soap scum stains and the cleaning performance of lipid / protein composite stains.
The raw material carboxylic acid in the ester compound is not particularly limited, but is a carboxylic acid having a linear or branched alkyl group. For example, acetic acid, propionic acid, buty acid, isofatty acid, valeric acid, pivalic acid, caproic acid, benzoic acid, 2-ethylhexanoic acid, enanthic acid, capric acid, pelargonic acid, capric acid, undecylic acid, lauric acid, myristic acid, Palmitic acid, stearic acid, arachidic acid, behenic acid, α-linolenic acid, linoleic acid, palmitreic acid, oleic acid, adipic acid, azelaic acid, palm oil composition fatty acid, palm oil composition fatty acid, beef fat fatty acid, sebasic acid, and trimesin One or more selected from acids can be mentioned. Among them, 2-ethylhexanoic acid, enanthic acid, capric acid, pelargonic acid, capric acid, from the viewpoint of cleaning performance of soap residue stains and lipid / protein complex stains. One or more selected from 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. ..

The carbon number of 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 20 or less, from the viewpoint of cleaning performance of soap scum stains and lipid / protein composite stains. It is 18 or less, 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, still more preferably 3 or less.
The raw material alcohol in the ester compound is monovalent or higher, trivalent or lower, preferably divalent or lower, and more preferably monovalent, from the viewpoint of cleaning performance of soap scum stains and lipid / protein composite stains.
The raw material alcohol in 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, eikosanol, and the above alcohols. One or more structural isomers are selected, and from the viewpoint of cleaning performance of lipid (lipid / protein complex) stains, methanol, ethanol, propanol, isopropanol, butanol, pentanol, hexanol, heptanol, octanol, and these alcohols can be used. One or more selected from structural isomers is preferable.

The ester compound of the carboxylic acid and the alcohol is not particularly limited, and examples thereof include an ester compound of a fatty acid having 6 or more and 24 or less carbon atoms and the alcohol, and more specifically, isobutyl acetate (6 carbon atoms) and hexane. Ethyl acid (8 carbons), isobutyl isobutyrate (8 carbons), ethyl octanate (10 carbons), hexyl benzoate (13 carbons), diisobutyl adipate (14 carbons), isopropyl myristate (14 carbons) 17), and one or more selected from ethyl oleate (20 carbon atoms) can be mentioned.

The component (a) contains isobutyl acetate, ethyl hexanoate, isobutyl isobutyrate, ethyl octanate, hexyl benzoate, diisobutyl adipate, and myristic acid from the viewpoint of cleaning performance of soap residue stains and lipid / protein complex stains. One or more selected from isopropyl, octane, isopropyl palmitate, isopropyl stearate, limonene, 1-dodecanol, and ethyl oleate is preferred, with isobutyl acetate, ethyl hexanoate, ethyl octanate, isopropyl myristate, and ethyl oleate. One or more selected from the above is more preferable.
The component (a) of the present invention is an ester compound having a δ of 17.0 or more and 18.1 or less, and has 8 or more carbon atoms and 18 or less carbon atoms, from the viewpoint of lipid / protein composite stain cleaning performance and compounding stability. Ester compounds of monovalent lipids and alcohols having 2 or more and 3 or less carbon atoms are preferable.

<(B) component>
The detergent composition of the present invention contains, as the component (b), a surfactant having a protein swelling rate of 101% or more as measured by the following method.
<Protein swelling rate measurement method>
Put 20 mg of keratin (manufactured by Tokyo Chemical Industry Co., Ltd., product code K0044) in an NMR tube (manufactured by Tokyo Chemical Industry Co., Ltd., outer diameter 5 mm, height 203 mm) and measure the height (before treatment) of the keratin. Add 500 mg of aqueous solution or ion-exchanged water containing% by weight of each surfactant. After leaving for 24 hours, the height of keratin (after treatment) is measured, and the swelling rate after each surfactant aqueous solution treatment is calculated from the following formula with the swelling rate at the time of ion-exchanged water treatment as a reference (100%).

The protein swelling rate of the component (b) is 101% or more, preferably 105% or more, more preferably 110% or more, and preferably 200% or less, more preferably 200% or less, from the viewpoint of cleaning performance of lipid / protein complex stains. It is 170% or less, more preferably 150% or less, still more preferably 140% or less, still more preferably 130% or less.

The component (b) is preferably an anionic surfactant from the viewpoint of protein swelling property. However, the protein swelling rate needs to be in the above range.
Examples of the anionic surfactant include 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. .. Anionic surfactants include alkyl or alkenylbenzene sulfonic acid or its salt, polyoxyalkylene alkyl or alkenyl ether sulfate ester or its salt, alkyl or alkenyl sulphate ester or its salt, internal olefin sulfonic acid or its salt, polyoxy. Examples thereof include alkylene 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.
Anionic surfactants include alkyl or alkenyl sulphate ester or salt thereof, polyoxyalkylene alkyl or alkenyl ether sulphate ester or salt thereof, internal olefin sulfonic acid or salt thereof, alkyl or alkenyl succinic acid from the viewpoint of protein swelling property. One or more selected from an acid or a salt thereof and an alkyl or alkenylbenzene sulfonic acid or a salt thereof are preferable.
The salt of the anionic surfactant is preferably an alkali metal salt such as a sodium salt or a potassium salt.

The number of carbon atoms of the alkyl group or alkenyl group of the alkyl or alkenyl sulfate ester or a salt thereof is preferably 8 or more, more preferably 10 or more, and preferably 24 or less, from the viewpoint of cleaning performance of the lipid / protein composite stain. It is preferably 20 or less, more preferably 18 or less, and even more preferably 16 or less.

The carbon number of the alkyl group or alkenyl group of the polyoxyalkylene alkyl or alkenyl ether sulfate ester or a salt thereof is preferably 8 or more, more preferably 10 or more, and preferably 10 or more, from the viewpoint of cleaning performance of lipid / protein composite stains. It is 24 or less, more preferably 20 or less, still more preferably 18 or less, still more preferably 16 or less. The oxyalkylene group of the polyoxyalkylene alkyl or the alkenyl ether sulfate ester or a salt thereof is preferably an ethyleneoxy group. The average number of moles of oxyalkylene groups added to the polyoxyalkylene alkyl or alkenyl ether sulfate ester or salt thereof is preferably 0.5 or more, more preferably 1 or more, more preferably 2 or more, and preferably 5 or less. More preferably, it is 3 or less.

The carbon number of the internal olefin sulfonic acid or a salt thereof is preferably 8 or more, more preferably 10 or more, still more preferably 12 or more, still more preferably 14 or more, and from the viewpoint of cleaning performance of the lipid / protein complex stain. It is preferably 24 or less, more preferably 20 or less, still more preferably 18 or less.

The number of carbon atoms of the alkyl group or alkenyl group of the alkyl or alkenylbenzenesulfonic acid or a salt thereof is preferably 8 or more, more preferably 10 or more, and preferably 24 or less, from the viewpoint of cleaning performance of the lipid / protein composite stain. It is more preferably 20 or less, still more preferably 18 or less, still more preferably 16 or less, still more preferably 14 or less.

The number of carbon atoms of the alkyl group or alkenyl group of polyoxyalkylene alkyl or alkenyl ether acetic acid or a salt thereof is preferably 8 or more, more preferably 10 or more, and preferably 24 from the viewpoint of cleaning performance of lipid / protein composite stains. Below, it is more preferably 20 or less, still more preferably 18 or less, still more preferably 16 or less. The oxyalkylene group of polyoxyalkylene alkyl or alkenyl ether acetic acid or a salt thereof is preferably an ethyleneoxy group. The average number of moles of oxyalkylene groups added to the polyoxyalkylene alkyl or alkenyl ether acetic acid or a salt thereof is preferably 0 or more, more preferably 0.5 or more, still more preferably 1 or more, still more preferably 2 or more, and It is preferably 30 or less, more preferably 20 or less, still more preferably 10 or less, still more preferably 5 or less.

The number of carbon atoms of the alkyl group or alkenyl group of alkyl or alkenyl succinic acid or a salt thereof is preferably 8 or more, more preferably 10 or more, and preferably 24 or less, from the viewpoint of cleaning performance of lipid / protein complex stains. It is preferably 20 or less, more preferably 18 or less, still more preferably 16 or less, still more preferably 14 or less.

<Composition, etc.>
In the cleaning agent composition of the present invention, the component (a) is preferably 0.1% by mass or more, more preferably 0.2% by mass, from the viewpoint of the cleaning performance of soap residue stains and the cleaning performance of lipid / protein composite stains. % Or more, more preferably 0.3% by mass or more, and preferably 1.9% by mass or less, more preferably 1.5% by mass or less, still more preferably 1% by mass or less, still more preferably 0.8% by mass. %, More preferably 0.6% by mass or less.

In the cleaning agent composition of the present invention, the component (b) is preferably 0.5% by mass or more, more preferably 1% by mass or more, from the viewpoint of the cleaning performance of soap residue stains and the cleaning performance of lipid / protein composite stains. More preferably 2.5% by mass or more, further 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, still more preferable. Contains 6% by mass or less.
In the present invention, when the component (b) is an anionic surfactant, the mass of the component (b) is determined to be a sodium salt.

In the cleaning agent composition of the present invention, the mass ratio (a) / (b) of the content of the component (a) to the content of the component (b) is the cleaning performance of the soap scum stain and the lipid / protein composite stain. From the viewpoint of cleaning performance, it is more than 0.01, preferably 0.03 or more, more preferably 0.05 or more, still more preferably 0.08 or more, and from the viewpoint of compounding stability, 0.55 or less, preferably 0.55 or less. Is 0.4 or less, more preferably 0.2 or less, still more preferably 0.15 or less.

The detergent composition of the present invention may contain a surfactant other than the component (b) as long as the effect of the present invention is not impaired. In the cleaning agent composition of the present invention, the content of the component (b) in the total surfactant is preferably 20% by mass or more from the viewpoint of the cleaning performance of soap residue stains and the lipid / protein composite stains. More preferably 40% by mass or more, further 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, 100% by mass. May be.

The detergent composition of the present invention preferably further contains an alkanolamine as the component (c) from the viewpoint of the cleaning performance of soap residue stains and the cleaning performance of lipid / protein composite stains.
The component (c) is not particularly limited, but is an alkylmono or a dialkanolamine having an alkanol group having 2 or 3 carbon atoms or an alkylene oxide adduct thereof (the alkylene oxide has 2 or 3 carbon atoms). .. Specific examples of the component (c) include monoethanolamine, diethanolamine, triethanolamine, 1-amino-2-propanol, N-methylmonoethanolamine, N-methyldiethanolamine and N, N-dimethylmonoethanolamine. One or more compounds selected are mentioned, and one selected from monoethanolamine, diethanolamine, 1-amino-2-propanol, and N-methylmonoethanolamine is preferable from the viewpoint of cleaning performance of lipid / protein complex stains. The above is more preferably one or more selected from monoethanolamine, diethanolamine, and 1-amino-2-propanol.

In the cleaning agent composition of the present invention, the component (c) is preferably 0.1% by mass or more, more preferably 0.2% by mass, from the viewpoint of the cleaning performance of soap scum stains and the cleaning performance of lipid / protein composite stains. % Or more, more preferably 0.3% by mass or more, and preferably 1% by mass or less, more preferably 0.8% by mass or less, still more preferably 0.6% by mass or less.

From the viewpoint of the cleaning performance of soap scum, the detergent composition of the present invention preferably further contains a metal sequestering agent as the component (d).
The metal sequestering agent is not particularly limited, and examples thereof include one or more compounds selected from an aminocarboxylic acid type metal sequestering agent, a hydroxycarboxylic acid type metal sequestering agent, and a hydroxykiphosphonic acid type metal sequestering agent. Specific examples of the component (d) include ethylenediaminetetraacetic acid (EDTA), nitrilotriacetic acid (NTA), iminodiacetic acid, diethylenetriaminepentaacetic acid (DTPA), N-hydroxyethyl-ethylenediaminetriacetic acid (HEDTA), and methylglycine. One or more selected from diacetic acid (MGDA), dihydroxyethylglycine (DHEG), hydroxyethyleneiminodiacetic acid (HIDA), aspartate diacetic acid (ASDA), glutamate diacetic acid (GLDA) and salts thereof. Can be mentioned. The component (d) is preferably one or more selected from ethylenediaminetetraacetic acid, diethylenetriaminepentacetic acid, methylglycinediacetic acid, and salts thereof, and ethylenediaminetetraacetic acid or a salt thereof is more preferable, from the viewpoint of cleaning performance against soap residue stains. preferable.
Examples of the salt of the component (d) include alkali metal salts, ammonium salts, amine salts and the like. It is preferably an alkali metal salt, and more preferably a sodium salt or a potassium salt.

When the detergent composition of the present invention contains the component (d), the component (d) is preferably 1% by mass or more, more preferably 1.5% by mass or more from the viewpoint of cleaning performance against soap scum stains. It is further preferably contained in an amount of 2% by mass or more, preferably 10% by mass or less, more preferably 5% by mass or less, still more preferably 3% by mass or less.
In the present invention, the masses of the component (d) are all determined to be sodium salts.

From the viewpoint of compounding stability, the detergent composition of the present invention preferably further contains a glycol-based solvent as the component (e).
The glycol system is not particularly limited, but means that it belongs to any of a compound having two hydroxyl groups and an ether compound in which one or both hydrogen atoms of the hydroxyl group are substituted with another group. The ether compound is preferably an aliphatic ether compound. Further, an ether compound in which one hydrogen atom of the hydroxyl group of the glycol compound is substituted with another group is preferable.

The component (e) is preferably a glycol-based water-soluble solvent having 2 or more and 12 or less carbon atoms. Water-soluble means that 5 g or more is dissolved 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, preferably -5 or more, and more preferably -3 or more.

From the viewpoint of cleaning performance, the total carbon number of the component (e) is preferably 2 or more, more preferably 3 or more, more preferably 4 or more, still more preferably 5 or more, still more preferably 6 or more, and the cleaning performance is improved. From the viewpoint, it is preferably 12 or less, preferably 10 or less, and more preferably 8 or less.

As the component (e), from the viewpoint of cleaning performance, 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 4). Number 5), Propylene Glycol Monoethyl Ether (5 Carbons), Propylene Glycol Monobutyl Ether (7 Carbons), 3-Methyl-3-methoxybutanol (6 Carbons), Ethylene Glycol Monobutyl Ether (6 Carbons), Di Propylene glycol (6 carbons), diethylene glycol monobutyl ether (8 carbons), diethylene glycol monophenyl ether (10 carbons), dibutyrene glycol (8 carbons), and dipropylene glycol monobutyl ether (10 carbons). One or more types can be mentioned.

As the component (e), glycols having 2 or 3 carbon atoms such as ethylene glycol, polyethylene glycol, propylene glycol and polypropylene glycol, their polyethers or their monoalkyl ethers are preferable. The alkyl group of this monoalkyl ether is preferably 1 or more and 4 or less carbon atoms, and is a methyl group, an ethyl group, various propyl groups, and various butyl groups. The variety includes normal, iso, and tertiary.

As the component (e), more preferably, from the viewpoint of cleaning performance, propylene glycol (3 carbon atoms), propylene glycol monomethyl ether (4 carbon atoms), ethylene glycol monobutyl ether (6 carbon atoms), propylene glycol monobutyl ether (carbon number). Number 7), diethylene glycol monobutyl ether (8 carbon atoms), diethylene glycol monophenyl ether (10 carbon atoms), and dipropylene glycol monobutyl ether (10 carbon atoms). As the component (e), it is preferable to contain diethylene glycol monobutyl ether (8 carbon atoms).

When the detergent composition of the present invention contains the component (e), the component (e) is preferably 1% by mass or more, more preferably 2% by mass or more, still more preferably 3 from the viewpoint of compounding stability. It is contained in an amount of% by mass or more, preferably 20% by mass or less, more preferably 10% by mass or less, still more preferably 8% by mass or less.

In order to increase the added value of the product, the detergent composition of the present invention may optionally contain a fragrance, a pigment, a preservative, an antioxidant, an antifoaming agent, a stabilizer and the like (provided that the detergent composition has a fragrance, a dye, a preservative, a stabilizer and the like. (Excluding the components (a) to (e)).

The detergent composition of the present invention contains water. That is, the balance other than the components (a) to (e) and the optional components is water. The cleaning composition of the present invention contains water, preferably 50% by mass or more, more preferably 60% by mass or more, still more preferably 70% by mass or more, still more preferably 80% by mass or more, and preferably 99% by mass. %, More preferably 95% by mass or less. As the water, it is preferable to use ion-exchanged water, sterile ion-exchanged water, or the like.

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 preferably 12 or less, from the viewpoint of cleaning performance of lipid / protein complex stains. Is 11.5 or less, more preferably 11 or less.

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

[Lipid / protein complex stain cleaning method]
In the present invention, the cleaning agent composition of the present invention is brought into contact with a hard surface to which a lipid / protein complex stain is attached, and the hard surface to which the cleaning agent composition is brought into contact is left without applying an external force, and then the surface is left unattended. Provided is a lipid / protein composite stain cleaning method (hereinafter, also referred to as a cleaning method of the present invention), which is rinsed with water.
As the cleaning method of the present invention, the matters described in the detergent composition of the present invention can be appropriately applied.
In the present invention, a concentrated composition containing the component (a), the component (b), and an optional component is prepared, and the concentrated composition is diluted with water to prepare the cleaning agent composition of the present invention, and a hard surface is prepared. May be contacted with. That is, a concentrated composition containing the component (a), the component (b), and the optional component of the present invention is diluted with water to prepare the detergent composition of the present invention, and the detergent composition is not diluted. It may be a cleaning method in which the material is brought into contact with a hard surface.

Further, in the cleaning method of the present invention, the cleaning agent composition of the present invention is brought into contact with a hard surface to which a lipid / protein complex stain is attached, and then left without applying (not applying) an external force such as mechanical force. It is a cleaning method. In the present invention, since the lipid / protein complex stain is dispersed and decomposed, it has a high cleaning effect even if it is contacted without using a flexible material such as a sponge or fingers and left as it is without applying an external force such as mechanical force. Is obtained. This is suitable for cleaning parts that are out of reach of hands and tools and details that are difficult to reach.
Leaving without applying an external force such as a mechanical force means that, for example, no intentional operation for cleaning is performed other than contacting the composition. For example, it can be understood that the contacted composition naturally flows down the hard surface, and vibration unintended for cleaning is transmitted to the hard surface when left without applying an external force.
After leaving it, it is usually rinsed with water. When rinsing, an external force (physical force) may be applied by hand or the like, or simply rinsing with a water stream.

In the cleaning method of the present invention, the detergent composition of the present invention is preferably 0.5 g of the cleaning agent composition of the present invention with respect to an area of 100 cm ² of a hard surface as an object from the viewpoint of cleaning performance of lipid / protein composite stains and soap scum. As mentioned above, it is more preferably 1 g or more, further preferably 3 g or more, and preferably 20 g or less, more preferably 10 g or less, still more preferably 5 g or less, and further preferably coated or sprayed.

In the cleaning method of the present invention, from the viewpoint of cleaning performance of lipid / protein complex stains and soap scum, after the cleaning agent composition of the present invention is brought into contact with a hard surface, it is preferably 1 second or longer, more preferably 10 seconds or longer, and further. It is preferably 20 seconds or more, more preferably 30 seconds or more, and preferably 10 minutes or less, more preferably 5 minutes or less, still more preferably 3 minutes or less, still more preferably 2 minutes or less, still more preferably 1 minute. Hereafter, leave it alone. In this case, the time when the composition first comes into contact with the hard surface may be the start of leaving.
The temperature when left to stand may be room temperature, for example, 10 ° C. or higher and 30 ° C. or lower.

In the cleaning method of the present invention, the cleaning agent composition of the present invention may be sprayed or applied to bring it into contact with a hard surface to which a lipid / protein complex stain is attached.
The method of contacting the cleaning agent composition of the present invention with a hard surface to which a lipid / protein complex stain is attached is preferably sprayed or applied, and examples thereof include a method of spraying in the form of droplets or applying in the form of bubbles. Specifically, a spraying means can be used. That is, it is preferable to use a detergent article obtained by filling a container provided with a sprayer with the detergent composition of the present invention. The present invention provides a cleaning agent article in a spray container, in which the cleaning agent composition of the present invention is filled in a container provided with a sprayer.

In the cleaning agent article containing the spray container of the present invention, the container provided with the sprayer filled with the cleaning agent composition of the present invention is a manual spray device that does not use a propellant such as a trigger type spray container or a pump type spray container. Examples include aerosols that use a propellant. The container provided with the sprayer is preferably a trigger type spray capable of spraying or applying the contents in the form of droplets or bubbles, and is a trigger type spray or a trigger type spray having a mechanism for spraying the contents in the form of droplets. A trigger type spray provided with a foam forming mechanism (foam forming mechanism) is more preferable.

In the cleaning agent article containing the spray container of the present invention, when a trigger type spray provided with a mechanism for spraying the cleaning agent composition of the present invention in the form of droplets is used, the nozzle diameter of the injection nozzle of the spray container containing the composition is It is preferably 0.1 mm or more, more preferably 0.3 mm or more, and because it is easy to spray, the sprayed droplets are not rough, it is not sprayed linearly, and the area that can be sprayed is not extremely narrowed. It is preferably in the range of 2 mm or less, more preferably 1 mm or less.
When using a trigger-type spray equipped with a mechanism for spraying in the form of droplets, the detergent article in a spray container of the present invention preferably has 0.1 mL or more, more preferably 0.3 mL or more, and a single operation. , Preferably 5 mL or less, more preferably 2 mL or less of the composition.

When a trigger-type spray equipped with a foam forming mechanism is used, the detergent article in a spray container of the present invention is preferably 0.5 mL or more, more preferably 1 mL or more, and preferably 30 mL or less in one operation. A composition of 15 mL or less, more preferably 5 mL or less is sprayed.

The cleaning method of the present invention includes a hard surface of a hard article, and a hard surface such as a bathroom, a bathtub, a washbasin, a tile, a dressing room, a washbasin, a mirror, a sink around the kitchen, a countertop, and a water supply, especially a hard bathroom. It is preferable as a surface cleaning method.
As the material of the hard surface to be the target of the cleaning method of the present invention, the material of the hard surface having a contact angle with water of 30 ° or more, preferably 40 ° or more, and 120 ° or less, preferably 110 ° or less is preferable. .. The material of the hard surface having a contact angle with water in the above range is not particularly limited, but is limited to polyester resin, acrylic resin, fiber-reinforced plastic (FRP) resin, acrylonitrile-butadiene-styrene copolymer (ABS) synthetic resin, and polypropylene ( One or more selected from PP) resin, polycarbonate (PC) resin, stainless steel (SUS), aluminum, hard vinyl chloride (hard PVC) resin, soft vinyl chloride (soft PVC) resin, polyethylene terephthalate (PET) resin and aluminum. Can be mentioned.

The detergent compositions shown in Tables 1 to 3 were prepared using the following compounding ingredients, and the following items were evaluated. The results are shown in Tables 1 to 3. In the detergent compositions of Tables 1 to 3, the components (a) to (e) were added in the blending amounts in the table and dissolved at room temperature (25 ° C.). After compounding, the pH was adjusted to Tables 1 to 3 with sodium hydroxide and / or hydrochloric acid. The pH was measured by the glass electrode method. Further, the mass% of the compounding components in Tables 1 to 3 are all numerical values based on the effective amount.

<Ingredients>
(A) Ingredients-Ethyl octanate: 10 carbon atoms, δ17.3, manufactured by Tokyo Kasei Kogyo Co., Ltd.-Octane: 8, δ15.6 carbon atoms, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. Number 8, δ16.9, manufactured by Tokyo Kasei Kogyo Co., Ltd. ・ Isopropyl myristate: 17 carbon atoms, δ17.0, manufactured by Tokyo Kasei Kogyo Co., Ltd. ・ Limonen: 10 carbon atoms, δ17.4, Fujifilm Wako Junyaku Ethyl hexaneate manufactured by Tokyo Kasei Kogyo Co., Ltd .: carbon number 6 and δ17.5, isobutyl acetate manufactured by Tokyo Kasei Kogyo Co., Ltd., carbon number 6 and δ17.7, ethyl oleate manufactured by Tokyo Kasei Kogyo Co., Ltd .: carbon number 20, δ18.1, diisobutyl adipate manufactured by Tokyo Kasei Kogyo Co., Ltd .: carbon number 16, δ18.2., Tokyo Kasei Kogyo Co., Ltd. hexyl benzoate: carbon number 13, δ18.9, Fujifilm Wako Jun Made by Yaku Co., Ltd. 1-Dodecanol: Carbon number: 12, δ19.2, manufactured by Kao Co., Ltd.

(A') component (comparative component of (a) component)
・ Pentane: 5 carbon atoms, δ14.8, manufactured by Wako Pure Chemical Industries, Ltd. ・ 1-decanol: 10, δ19.6 carbon atoms, manufactured by Tokyo Chemical Industry Co., Ltd.

(B) Ingredients ・ Emar 2F-HP: Sodium lauryl sulfate, swelling rate 122%, manufactured by Kao Co., Ltd. ・ Sodium tetradecyl sulfate: swelling rate 128%, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. ・ Na 1-octanesulfonate : 1-sodium octane sulfonate, protein swelling rate 107%, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. ・ Emar 227: polyoxyethylene (2) sodium lauryl ether sulfate, protein swelling rate 112%, manufactured by Kao Co., Ltd. ES-4.0K: Polyoxyethylene (4) sodium lauryl ether sulfate, protein swelling rate 106%, manufactured by Kao Co., Ltd. Kao Akipo RLM-45NV: polyoxyethylene (4) sodium lauryl ether acetate, protein swelling rate 108%, Kao Akipo RLM-100NV: Polyoxyethylene (10) sodium lauryl ether acetate, protein swelling rate 103%, Kao Co., Ltd. AOS: Sodium internal olefin sulfonate with 16 carbon atoms, protein Swelling rate 112%, Kao Co., Ltd. ASA-12: dipotassium dodecenyl succinate, protein swelling rate 121%, Kao Co., Ltd. Neoperex G25: sodium dodecylbenzene sulfonate, protein swelling rate 128%, Kao Made by Co., Ltd.

(B') component (comparative component of (b) component)
・ Anchor 20AB: Amidopropyl betaine laurate, protein swelling rate 98%, manufactured by Kao Corporation ・ Emargen 109P: polyoxyethylene lauryl ether, protein swelling rate 98%, manufactured by Kao Corporation

The protein swelling rate of the component (b) or the component (b') was measured by the following method.
Put 20 mg of keratin (manufactured by Tokyo Chemical Industry Co., Ltd., product code K0044) in an NMR tube (manufactured by Tokyo Chemical Industry Co., Ltd., outer diameter 5 mm, height 203 mm) and measure the height (before treatment) of the keratin. An aqueous solution containing a mass% of each surfactant or 500 mg of ion-exchanged water was added. After leaving for 24 hours, the height of keratin (after treatment) was measured, and the swelling rate after each surfactant aqueous solution treatment was calculated from the following formula with the swelling rate at the time of ion-exchanged water treatment as a reference (100%).

(C) Ingredients ・ Monoethanolamine ・ Diethanolamine: Fujifilm Wako Pure Chemical Industry Co., Ltd. ・ 1-Amino-2-propanol: Fujifilm Wako Pure Chemical Industry Co., Ltd. (d) Ingredients ・ EDTA: Ethylenediaminetetraacetate sodium ・HEDTA: N-hydroxyethyl-ethylenediaminetriacetic acid, manufactured by Tokyo Chemical Industry Co., Ltd. ・ DHEG: dihydroxyethylglycine, manufactured by Tokyo Chemical Industry Co., Ltd. ・ HIDA: hydroxyethylene iminodicate, manufactured by Tokyo Chemical Industry Co., Ltd. (e) ) Ingredients ・ BDG: Diethylene glycol monobutyl ether, manufactured by Nippon Embroidery Co., Ltd. ・ MFG: Propylene glycol monomethyl ether, manufactured by Japan Embroidery Co., Ltd. ・ PhDG: Diethylene glycol monophenyl ether, manufactured by Japan Embroidery Co., Ltd.

<Evaluation of lipid / protein complex stain cleaning performance>
A plurality of evaluation substrates (manufactured by Engineering Test Service Co., Ltd., having a shape of 80 mm × 210 mm × 1 mm) shown in Tables 1 to 3 were fixed to the draft portion of the bathtub containing hot water at 40 ° C. Four men took turns bathing one by one (10 minutes per person), and after bathing four people, the evaluation substrate to which sebum (lipid / protein complex stain) was attached was collected and used for cleaning evaluation. The cleaning agent compositions of Tables 1 to 3 were added dropwise to the soiled portion of the evaluation substrate so as to have the adhesion amount (mg / cm ² ) shown in Tables 1 to 3, and the time shown in Tables 1 to 3 was obtained at 25 ° C. After being left to stand, it was washed with water, and the washing performance was evaluated by the following criteria by visual and tactile sensation.
◎: Level at which the stains are completely removed both visually and tactilely ○: Level at which the stains are almost completely removed visually, but slightly residual stains are felt with the sense of touch △: Level at which stains are felt with both visual and tactile sensations ×: A level where you can feel that the dirt has not been removed both visually and tactilely.

<Evaluation of soap scum cleaning performance>
A model soap scum stain prepared with reference to the composition of the soap scum stain adhering to the bathroom was formed on a polypropylene plate (manufactured by Engineering Test Service Co., Ltd., shape is 80 mm × 120 mm). The method for preparing model soap residue and forming a film is as follows: the plate is an aqueous solution (2% by mass) in which a solid soap (manufactured by Kao Corporation, "white") is dissolved, and an aqueous solution of calcium chloride (0.7% by mass). The model soap scum stains were prepared and a film was formed by repeating the steps of immersing in the soap in order and then drying 10 times. After forming a film of model soap scum stains on the plate, 10 μL of the detergent composition shown in Tables 1 to 3 is added dropwise to the soiled portion of the plate, and 1 at 25 ° C.
After leaving it for 0 minutes, it was washed with water, and the washing performance was evaluated according to the following criteria.
◎: Dirt on the part where the liquid was dropped was almost removed without scrubbing ○: Dirt on the part where the liquid was dropped was removed by more than half without scrubbing △: Dirt on the part where the liquid was dropped without scrubbing Dirt was removed, but only less than half of the dirt was removed. ×: Dirt on the place where the liquid was dropped was hardly removed without scrubbing.

<Evaluation of compounding stability>
The detergent compositions shown in Tables 1 to 3 were prepared, allowed to stand at room temperature (25 ° C.) for 1 day, and then visually observed for appearance and evaluated according to the following criteria.
A: Uniformly transparent, no separation / stratification of components, and no turbidity B: Slightly turbid but not stratified uniform liquid C: Clearly turbid or turbidity is observed

＜配合例＞
表４、５に、前記に記載の配合成分を用いた本発明の洗浄剤組成物の配合例を示す。これらの洗浄剤組成物は、硬質表面に付着した脂質／タンパク質複合汚れと石鹸カス汚れの洗浄性能に優れ、配合安定性が良好である。

<Combination example>
Tables 4 and 5 show compounding examples of the detergent composition of the present invention using the compounding components described above. These detergent compositions are excellent in cleaning performance of lipid / protein complex stains and soap scum stains adhering to a hard surface, and have good compounding stability.

Claims (8)

(A) A compound having a solubility parameter δ of 15.0 or more and 19.5 or less [hereinafter referred to as (a) component], (b) a surfactant having a protein swelling rate of 101% or more measured by the following method, and water. The mass ratio (a) / (b) of the content of the component (a) to the content of the component (b) is more than 0.01 and 0.55 or less, and the pH is more than 9 and 12 or less. The detergent composition is brought into contact with a hard surface to which the lipid / protein complex stain is attached, and the hard surface to which the detergent composition is in contact is left without applying an external force and then rinsed with water. Lipid / Protein complex stain cleaning method.
<Protein swelling rate measurement method>
Put 20 mg of keratin (manufactured by Tokyo Chemical Industry Co., Ltd., product code K0044) in an NMR tube (manufactured by Tokyo Chemical Industry Co., Ltd., outer diameter 5 mm, height 203 mm) and measure the height (before treatment) of the keratin. Add 500 mg of aqueous solution or ion-exchanged water containing% by weight of each surfactant. After leaving for 24 hours, the height of keratin (after treatment) is measured, and the swelling rate after each surfactant aqueous solution treatment is calculated from the following formula with the swelling rate at the time of ion-exchanged water treatment as a reference (100%).

(A) The lipid / protein composite stain cleaning method according to claim 1, wherein the component is an ester compound of a carboxylic acid and an alcohol. The lipid / protein composite stain cleaning method according to claim 1 or 2, wherein the content of the component (b) in all the surfactants is 20% by mass or more and 100% by mass or less. (B) The lipid / protein complex stain cleaning method according to any one of claims 1 to 3, wherein the component is an anionic surfactant. The method for cleaning a lipid / protein complex stain according to any one of claims 1 to 4, wherein the detergent composition further contains an alkanolamine as a component (c). The lipid / protein complex stain cleaning method according to any one of claims 1 to 5, wherein the cleaning agent composition further contains a metal sequestering agent as a component (d). The lipid / protein composite stain cleaning method according to any one of claims 1 to 6, wherein the hard surface is made of a material having a contact angle with water of 30 ° or more and 120 ° or less. The method for cleaning a lipid / protein composite stain according to any one of claims 1 to 7, wherein the hard surface is a hard surface of a bathtub.