JP7017951B2 - Mold-killing detergent composition for hard surfaces - Google Patents

Description

The present invention relates to an antifungal cleaning agent composition for hard surfaces.

Hydrophobic stains such as sebum and soap scum easily adhere to the hard surface around water such as in the bathroom, and it is one of the stains that is difficult to clean because it scums and adheres firmly due to the hardness component in the water. In addition, such strongly adhered stains serve as nutrients for microorganisms such as mold, and since moderate water is always present, mold grows easily, and once grown mold is a strong oxidizing agent such as hypochlorous acid. If it is not removed, it will be a heavy burden such as not being able to be washed. Therefore, there is a strong demand for a technique for effectively removing the nutrient source of microorganisms such as molds and sterilizing them by a simple method before the microorganisms such as molds propagate.

Patent Document 1 contains a specific nonionic surfactant and / or amphoteric surfactant, a specific monohydric or polyhydric alcohol, an acid and a salt thereof, and a bactericidal agent, and has a cleaning effect, antibacterial property, and the like. A cleaning agent composition having excellent storage stability and particularly effective for a hard surface such as a toilet seat has been disclosed.
Patent Document 2 contains a polymer compound containing a monomer unit having a sulfobetaine structure, an inorganic salt such as a halide of an alkali metal, and a surfactant, and is excellent in modifying a hydrophobic hard surface. Disclosed is a composition of a liquid treatment agent for a hard surface, which can impart antifouling properties and is excellent in stability with respect to temperature.
Patent Document 3 contains a nonionic surfactant, a terpene hydrocarbon solvent, a water-soluble solvent, an alkaline agent, and a cationic surfactant, and is excellent in detergency of oil stains and storage stability of the composition. , A cleaning agent composition for a hard surface, which is also excellent in rinsability, is disclosed.
Patent Document 4 and Patent Document 5 contain benzyl alcohol and a cationic surfactant, and have excellent detergency against pink stains derived from microorganisms generated on the hard surface, and have excellent detergency against sebum stains adhering to the hard surface. Disclosed are liquid detergent compositions for hard surfaces that are excellent and have good formulation stability.

Japanese Unexamined Patent Publication No. 11-6119 JP-A-2015-105310 Japanese Unexamined Patent Publication No. 2006-8801 Japanese Unexamined Patent Publication No. 2014-132063 Japanese Unexamined Patent Publication No. 2014-132062

That is, the present invention exhibits an excellent mold-killing effect on molds existing in living environments such as bathrooms, and a mold-killing detergent composition for hard surfaces having excellent cleaning properties for sebum stains and a hard surface using the same. Provides a processing method.

In the present invention, (a) a water-soluble inorganic salt [hereinafter referred to as (a) component] is 0.1% by mass or more and 5% by mass or less, and (b) a nonionic detergent [hereinafter referred to as (b) component]. Contains 0.05% by mass or more and 7% by mass or less, (c) 0.1% by mass or more and 5% by mass or less of cationic surfactant, (d) solvent (excluding component (b)) and water. , A solvent-killing detergent composition for hard surfaces, wherein the pH at 25 ° C. is 5 or more and 9 or less.

The present invention relates to a hard surface treatment method in which the mold-killing detergent composition for a hard surface is brought into contact with a hard surface on which mold is present, and mold-killing and cleaning are performed at the same time.

According to the present invention, an antifungal detergent composition for a hard surface having an excellent antifungal effect on mold existing in a living environment such as a bathroom and excellent detergency of sebum stains and a hard using the same. A surface treatment method is provided.

[Moldicide composition]
<(A) component>
The component (a) of the present invention is a water-soluble inorganic salt.
Here, with respect to the inorganic salt of the component (a), the term "water-soluble" means that 5 g or more of the inorganic salt is dissolved in 100 g of deionized water at 25 ° C.

(A) The components are alkali metal sulfate, alkaline earth metal sulfate, ammonium sulfate, alkali metal sulfite, alkaline earth metal sulfite, alkali metal halide, alkaline earth metal halide, alkali metal nitrate, alkali. One selected from earth metal nitrate, alkali metal carbonate, alkaline earth metal carbonate, alkali metal phosphate, alkaline earth metal phosphate, alkali metal thiocyanate, and alkaline earth metal thiocitanoate. The above-mentioned water-soluble inorganic salts are mentioned, and one kind selected from alkali metal sulfates, alkaline earth metal sulfates, alkali metal halides, and alkaline earth metal halides from the viewpoint of mold killing effect and compounding stability. The above water-soluble inorganic salts are preferable, and one or more water-soluble inorganic salts selected from alkali metal sulfates, alkaline earth metal sulfates, alkali metal chlorides, and alkaline earth metal chlorides are more preferable, and alkali metals. One or more water-soluble inorganic salts selected from sulfates and alkali metal chlorides are more preferable, and alkali metal sulfates are even more preferable.

(A) The components are, more specifically, sodium sulfate, lithium sulfate, potassium sulfate, cesium sulfate, ammonium sulfate, sodium sulfite, sodium chloride, potassium chloride, sodium nitrate, sodium carbonate, disodium hydrogen phosphate, and thiosian acid. One or more selected from sodium is mentioned, and one or more selected from sodium sulfate, potassium sulfate, sodium nitrate, sodium chloride and potassium chloride are preferable from the viewpoint of sizing effect and compounding stability, and sodium sulfate and potassium sulfate are preferable. And one or more selected from potassium chloride are more preferable. Sodium sulfate is most preferable as the component (a) of the present invention.

<(B) component>
The component (b) of the present invention is a nonionic bactericide.
From the viewpoint of the fungicide effect, the component (b) preferably has an aromatic group which may have a substituent and a hydroxy group, and a nonionic fungicide having a molecular weight of 106 or more and 300 or less. The aromatic group is an aromatic hydrocarbon group, and examples thereof include a phenyl group, a benzyl group and a phenethyl group, and these aromatic groups may have a substituent. Examples of the substituent include a halogeno group such as a fluoro group and a chloro group, an alkyl group such as a methyl group, an ethyl group and an isopropyl group, a carboxy group, an amino group, a sulfo group and an alkoxy group, and these substituents are 1 It may have a species or two or more species.

The component (b) is preferably a compound represented by the following general formula (b-1) from the viewpoint of antifungal effect and compounding stability.
R ^1b O- (R ^2b O) _l -H (b-1)
(In the formula, R ^1b is a hydrocarbon group having an aromatic group and having a total carbon number of 6 or more and 11 or less, l is an integer of 0 or 1, and R ^2b is a carbon number of 2 or more and 4 or less. It is an alkylene group. However, the molecular weight of the compound is 106 or more and 300 or less.)

The total carbon number of R ^1b is the number of carbon atoms including the aromatic group, and the total carbon number of R ^1b is 6 or more from the viewpoint of fungicidal effect, and 11 or less, preferably 11 or less from the viewpoint of compounding stability. Is 10 or less, more preferably 9 or less. R ^1b is an aromatic hydrocarbon group, and examples thereof include a phenyl group, a benzyl group, and a phenethyl group. For R ^2b , an ethylene group is preferable from the viewpoint of a fungicide effect.
1 is preferably 0 from the viewpoint of the mold-killing effect.

Specific examples of the component (b) include benzyl alcohol (molecular weight: 108), phenoxyethanol (molecular weight: 138), 2-phenylethanol (molecular weight: 122), 3-phenyl-1-propanol (molecular weight: 136), and the like. Synamyl alcohol (molecular weight: 134), benzyl glycol (molecular weight: 152), phenyldiglycol (molecular weight: 182), benzyl diglycol (molecular weight: 196), 4-phenyl-1-butanol (molecular weight: 150), triclosan (molecular weight: 150) One or more selected from molecular weight: 290), diclosan (molecular weight: 255), and isopropylmethylphenol (molecular weight: 150) can be mentioned. One or more selected from glycol, triclosan, diclosan, and isopropylmethylphenol is preferable, and one or more selected from benzyl alcohol and phenoxyethanol are more preferable.

<(C) component>
The component (c) of the present invention is a cationic surfactant. Examples of the cationic surfactant include a quaternary ammonium salt-type cationic surfactant. As the quaternary ammonium salt-type cationic surfactant, one or two of the groups bonded to the nitrogen atom are hydrocarbon groups having 6 or more and 18 or less carbon atoms, and the rest have 1 or more and 3 or less carbon atoms. Examples thereof include a quaternary ammonium salt-type cationic surfactant which is a group selected from the group consisting of an alkyl group, a hydroxyalkyl group having 1 or more and 3 or less carbon atoms, and an arylalkyl group (benzyl group or the like). Among them, a quaternary ammonium salt-type cationic surfactant having a smoldering ability and a detergency is preferable, and a quaternary ammonium salt-type cationic surfactant having a benzyl group is preferable from the viewpoint of the sizing performance.

As the cationic surfactant, a quaternary ammonium salt-type cationic surfactant represented by the following general formula (c1) is preferable.

[In the formula, R ^1c represents a hydrocarbon group having 6 or more and 18 or less carbon atoms. R ^2c and R ^3c each independently represent an alkyl group having 1 or more carbon atoms and 3 or less carbon atoms. R ^4c represents an alkylene group having 1 or more and 3 or less carbon atoms. Z ^- represents an anionic group. ]

In the general formula (c1), ^R1c preferably has 8 or more carbon atoms, preferably 14 or less, and more preferably 10 or less, from the viewpoint of improving the hydrocarbon killing effect by distribution to the bacterial cells and from the viewpoint of compounding stability. Hydrocarbon group, preferably an alkyl group or an alkenyl group, more preferably an alkyl group.
Further, in the general formula (c1), R ^2c and R ^3c are each independently an alkyl group having 1 or more and 3 or less carbon atoms, preferably an alkyl group having 1 or more and 2 or less carbon atoms, and more preferably a methyl group.
Further, in the general formula (c1), R ^4c is an alkylene group having 1 or more and 3 or less carbon atoms, preferably an alkylene group having 1 or more and 2 or less carbon atoms, and more preferably a methylene group.
Further, as Z ⁻ in the general formula (c1), a halogen ion such as a chloride ion is preferable. Chloride ion (Cl ⁻ ) is more preferable as Z ⁻ .

<(D) component>
The component (d) of the present invention is a solvent (however, the component (b) is excluded).
The component (d) is preferably one or more solvents selected from the following compounds (d1) to (d3).
(D1): Aliphatic alcohol having a molecular weight of 60 or more and 500 or less (d2): Aliphatic glycol ether having a molecular weight of 60 or more and 500 or less (d3): Aliphatic diol having a molecular weight of 60 or more and 500 or less.

The component (d) has a logP value of preferably 0 or more, more preferably 0.5 or more, and a fungicide effect and compounding stability from the viewpoint of further enhancing the fungicide effect and the distribution from the aqueous phase to the cells. From the viewpoint of the above, a compound preferably 3 or less, more preferably 2 or less is preferable.

In the present invention, the logP value is a coefficient indicating the affinity of the organic compound for water and 1-octanol. The 1-octanol / water partition coefficient P is the partition equilibrium when a trace amount of the compound is dissolved as a solute in the solvent of the two-component phase of 1-octanol and water, and is the ratio of the equilibrium concentration of the compound in each solvent. It is generally shown in the form of their loglogP for the base 10. The logP values of many compounds have been reported, and many values are listed in databases available from Daylight Chemical Information Systems, Inc. (Daylight CIS), etc., which can be referred to. If there is no actually measured logP value, it can be calculated by the program "CLOGP" etc. available from Daylight CIS. This program outputs the value of "calculated logP (ClogP)" calculated by Hansch, Leo's fragment approach together with the actually measured logP value, if any.

The fragment approach is based on the chemical structure of the compound and takes into account the number of atoms and the type of chemical bond (cf. A. Leo, Comprehensive Medicinal Chemistry, Vol. 4, C. Hansch, PG Sammens, JBTaylor and CA Ramsden, Eds., P.295, Pergamon Press, 1990). This LogP value can be used in place of the measured logP value when selecting a compound. In the present invention, if there is an actually measured value of logP, it is used, and if not, the LogP value calculated by the program CLOGP v4.01 is used.

Examples of the aliphatic alcohol having a molecular weight of 60 or more and 500 or less, which is (d1), include 1-propanol (molecular weight: 60, logP: 0.55), 2-propanol (molecular weight: 60, logP: 0.38), and 1 -Hexanol (molecular weight: 102, logP: 1.80), 1-pentanol (molecular weight: 88, logP: 1.39), 3-pentanol (molecular weight: 88, logP: 1.36), 1-butanol (molecular weight: 88, logP: 1.36) Molecular weight: 74, logP: 0.97), 2-butanol (molecular weight: 74, logP: 0.87), tert-butanol (molecular weight: 74, logP: 0.60), cyclopentanol (molecular weight: 86, logP) : 0.86), 1-heptanol (molecular weight: 116, logP: 2.22), and 1-octanol (molecular weight: 130, logP: 2.64) can be mentioned. One or more selected from 1-propanol, 1-butanol, 2-butanol, 1-pentanol, 3-pentanol, cyclopentanol, 1-hexanol, and 1-heptanol from the viewpoint of achieving both compounding stability. Preferably, one or more selected from 1-butanol, 2-butanol, 1-pentanol, 3-pentanol, and cyclopentanol are more preferable, 1-butanol, 1-pentanol, 3-pentanol, and cyclo. One or more selected from pentanol is more preferable, and one or more selected from 1-butanol, 1-pentanol, and 3-pentanol are even more preferable.

As the aliphatic glycol ether having a molecular weight of 60 or more and 500 or less, which is (d2), a compound represented by the following general formula (d2) is preferable.
R ^1d O- (R ^2d O) _n -H (d2)
(In the formula, R ^1d is an aliphatic hydrocarbon group having 1 or more and 8 or less carbon atoms, R ^2d is an alkylene group having 2 or 3 carbon atoms, and n is an integer of 1 or more and 4 or less.)

From the viewpoint of the fungicide effect, R ^1d is preferably an alkyl group or an alkenyl group having 3 or more and 6 or less carbon atoms.
From the viewpoint of the fungicide effect, n is preferably 3 or less, more preferably 2 or less.

Specifically, (d2) is 2-ethylhexyl glycol (molecular weight: 174, logP: 2.46), hexyl glycol (molecular weight: 146, logP: 1.65), hexyldiglycol (molecular weight: 190, logP: 2.46). 1.49), butylpropylene diglycol (molecular weight: 190, logP: 1.29), butylpropylene glycol (molecular weight: 132, logP: 1.13), propylpropylene diglycol (molecular weight: 176, logP: 0.88) ), Butyl glycol (molecular weight: 118, logP: 0.81), propylpropylene glycol (molecular weight: 118, logP: 0.71), butyl diglycol (molecular weight: 162, logP: 0.66), 2-tert- Butoxyethanol (molecular weight: 118, logP: 0.45), isobutyldiglycol (molecular weight: 118, logP: 0.07), methylpropylene glycol (molecular weight: 90, logP: -0.11), and methylglycol (molecular weight: -0.11). : 76, logP: -0.43), and one or more selected from the above, and from the viewpoint of the killing effect, hexyl glycol, hexyl diglycol, butyl propylene glycol, butyl propylene diglycol, butyl glycol, butyl diglycol, One or more selected from propylpropylene diglycol and propylpropylene glycol is preferable, and one or more selected from hexyldiglycol, butylpropylene glycol, propylpropylenediglycol, butylglycol and butyldiglycol are more preferable. One or more selected from butyl propylene glycol and butyl glycol are more preferable, and one or more selected from butyl propylene glycol and butyl glycol are even more preferable.

As the aliphatic diol having a molecular weight of 60 or more and 500 or less, which is (d3), a compound represented by the following general formula (d3) is preferable. Note that (d3) does not include (d2).
R ^3d -CH (OH)-(CH ₂ ) _q -CH ₂ OH (d3)
(In the formula, R ^3d is a hydrogen atom, an aliphatic hydrocarbon group having 1 or more and 8 or less carbon atoms, or R ^4d O, R ^4d is an aliphatic hydrocarbon group having 1 or more and 8 or less carbon atoms, and q is. It is an integer of 0 or 1 or more and 6 or less. However, the total number of carbon atoms in the compound is 4 or more and 10 or less.)

From the viewpoint of the killing effect, R ^3d is preferably a hydrogen atom or an alkyl group or alkenyl group having 2 or more and 8 or less carbon atoms, more preferably an alkyl group or alkenyl group having 3 or more and 8 or less carbon atoms, and 4 or more and 8 carbon atoms. The following alkyl or alkenyl groups are more preferred.
R ^4d is preferably an alkyl group or an alkenyl group having 2 or more and 8 or less carbon atoms, more preferably an alkyl group or an alkenyl group having 3 or more and 8 or less carbon atoms, and further preferably an alkyl group or an alkenyl group having 4 or more and 8 or less carbon atoms. ..
From the viewpoint of the fungicide effect, q is preferably 1 or less.

Specifically, (d3) is 1,2-hexanediol (molecular weight: 118, logP: 0.85), 1,2-pentanediol (molecular weight: 104, logP: 0.43), propylene glycol (molecular weight: 0.43). : 76, logP: 0.40), 1,6-hexanediol (molecular weight: 118, logP: 0.60), 1,2-butanediol (molecular weight: 90, logP: 0.01), 1,4- Butanediol (molecular weight: 90, logP: -0.23), 1,3-butanediol (molecular weight: 90, logP: 0.-0.37), 1,5-pentanediol (molecular weight: 104, logP: 0) .19), 1,2-octanediol (molecular weight: 146, logP: 1.68), pentylglyceryl ether (molecular weight: 162, logP: 0.69), and 1,8-octanediol (molecular weight: 146, logP). : One or more selected from 1.44) can be mentioned, and from the viewpoint of achieving both a mold-killing effect and compounding stability, 1,2-hexanediol, 1,2-pentanediol, propylene glycol, pentylglyceryl ether and 1 , 6-Hexanediol is preferred, 1,2-hexanediol, pentylglyceryl ether and 1,2-pentanediol are more preferred, 1,2-hexanediol, and pentyl. One or more selected from glyceryl ether is more preferable.

The component (d) is preferably one or more selected from the compounds of (d2) and (d3) from the viewpoint of improving the fungicide effect. Further, it is more preferable that (d2) is a compound represented by the general formula (d2) and (d3) is a compound represented by the general formula (d3).

<Composition, etc.>
Although the mechanism of action of the present invention is not clear, it is considered as follows.
It is known that mold has a thick cell wall outside the cell membrane, and the cell wall of mold is composed of a polysaccharide layer composed of glucan, chitin and the like, a melanin layer, a hydrophobin layer and the like. Due to the presence of this cell wall, it is considered that the problem is that mold has a lower permeability of the fungicide into the cell than general bacteria such as Escherichia coli, and a sufficient mold-killing effect cannot be obtained in a short time. .. When an aqueous solution containing the component (a) of the present invention at a specific concentration is allowed to act on a protein such as hydrophobin, it causes a structural change of the protein, and as a result, the fungus of the nonionic bactericidal agent which is the component (b) of the present invention. It is considered that the amount of protein permeating into the cells is increased and the fungal killing effect can be imparted.
However, when this technique is applied to a cleaning agent, the salt strength is increased by the addition of the component (a), and as a result, the smoldering effect is reduced when a surfactant effective for cleaning sebum stains is added. The problem arises. In the antifungal cleaning agent composition for hard surfaces of the present invention, by further containing the components (c) and (d) in a specific amount in the components (a) and (b), the antifungal performance and the sebum detergency can be obtained. It is considered that it can provide an excellent antifungal cleaning agent composition for hard surfaces.

In the hard surface anti-chatter cleaning agent composition of the present invention, the component (a) is contained in an amount of 0.1% by mass or more, preferably 0.5% by mass or more, more preferably 1.0% by mass from the viewpoint of the anti-mold effect. % Or more, and from the viewpoint of compounding stability, it is contained in an amount of 5% by mass or less, preferably 4% by mass or less, and more preferably 3% by mass or less.

In the composition for cleaning a hard surface of the present invention, the component (b) is contained in an amount of 0.05% by mass or more, preferably 0.1% by mass or more, more preferably 0.5% by mass, from the viewpoint of the antifungal effect. % Or more, more preferably 1.0% by mass or more, and from the viewpoint of compounding stability, 7% by mass or less, preferably 5% by mass or less, more preferably 4% by mass or less, still more preferably 3% by mass or less. do.

In the hard surface anti-chatter cleaning agent composition of the present invention, the component (c) is contained in an amount of 0.1% by mass or more, preferably 0.3% by mass or more, more preferably 0, from the viewpoint of the anti-mold effect and the detergency. It contains 5.5% by mass or more, more preferably 0.75% by mass or more, and 5% by mass or less, preferably 4% by mass or less, more preferably 3% by mass or less.

In the composition for cleaning a hard surface of the present invention, the component (d) is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and further, from the viewpoint of the killing effect and the detergency. It is preferably contained in an amount of 1% by mass or more, preferably 10% by mass or less, more preferably 8% by mass or less, still more preferably 7% by mass or less from the viewpoint of compounding stability.

In the hard surface antifogging cleaning agent composition of the present invention, the total of the component (c) and the component (d) is preferably 0.2% by mass or more, more preferably 0, from the viewpoint of the antifungal effect and the detergency. It contains 5.5% by mass or more, more preferably 1.5% by mass or more, and from the viewpoint of compounding stability, preferably 12% by mass or less, more preferably 10% by mass or less, still more preferably 8% by mass or less.

The mildew-detergent composition for a hard surface of the present invention may contain a surfactant other than the component (c) as the component (e). As the component (e), one or more selected from (e1) anionic surfactant, (e2) nonionic surfactant, (e3) betaine type surfactant and (e4) amine oxide type surfactant. Surfactants can be mentioned.

(E1) As the anionic surfactant, 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. Can be mentioned. Examples of the anionic surfactant include alkyl or alkenylbenzenesulfonic acid or a salt thereof, polyoxyalkylene alkyl or alkenyl ether sulfate ester or a salt thereof, alkyl or alkenylsulfate ester or a salt thereof, fatty acid or a salt thereof and the like. From the viewpoint of detergency, the anionic surfactant is preferably one or more selected from the group consisting of polyoxyalkylene alkyl or alkenyl ether sulfate ester or a salt thereof and a fatty acid or a salt thereof. The oxyalkylene group of the polyoxyalkylene alkyl or alkenyl ether sulfate ester or a salt thereof is preferably an oxyethylene group. The average number of moles of oxyalkylene groups added to the polyoxyalkylene alkyl or alkenyl ether sulfate ester salt is preferably 1 or more and 10 or less. Examples of the fatty acid or a salt thereof include a fatty acid having 10 or more carbon atoms and 18 or less carbon atoms or a salt thereof. The alkyl group or alkenyl group of the anionic surfactant preferably has 10 or more and 18 or less carbon atoms. The salt is preferably an alkali metal salt such as a sodium salt or a potassium salt.

(E2) Examples of the nonionic surfactant include a polyoxyalkylene alkyl ether having an alkyl group having 10 or more and 18 or less carbon atoms, a polyoxyalkylene alkenyl ether having an alkenyl group having 10 or more and 18 or less carbon atoms, and 10 or more carbon atoms. Polyoxyalkylene sorbitan fatty acid ester having 18 or less fatty acid groups, alkyl glycoside having 8 or more and 18 or less carbon atoms, alkyl polyglycoside having 8 or more and 18 or less carbon atoms, 8 or more and 18 or less carbon atoms. Examples thereof include sucrose fatty acid esters having a fatty acid group, alkyl polyglyceryl ethers having an alkyl group having 8 or more carbon atoms and 18 or less carbon atoms, and the like. Among them, from the viewpoint of detergency, a polyoxyethylene alkyl ether having an alkyl group having 10 or more and 16 or less carbon atoms and an average number of moles of ethylene oxide added of 1 or more and 15 or less is preferable. However, the component (b) is excluded from the component (e2).

Examples of the (e3) betaine-type surfactant include sulfobetaine and one or more selected surfactants.

As the sulfobetaine, N-alkyl-N, N-dimethyl-N-sulfopropylammonium sulfobetaine and an alkyl group having an alkyl group having preferably 10 or more carbon atoms and preferably 18 or less, more preferably 14 or less carbon atoms. N-alkyl-N, N-dimethyl-N- (2-hydroxysulfopropyl) ammonium sulfobetaine, having an alkanoyl group having a carbon number of preferably 10 or more, preferably 18 or less, and more preferably 14 or less. N-alkanoylaminopropyl-N, N-dimethyl-N-sulfopropylammonium sulfobetaine, preferably 10 or more, preferably 18 or less, more preferably 14 or less, preferably having 10 or more carbon atoms in the alkanoyl group, and Examples thereof include N-alkanoylaminopropyl-N, N-dimethyl-N- (2-hydroxysulfopropyl) ammonium sulfobetaine, preferably 18 or less, more preferably 14 or less.

As the carbobetaine, N-alkyl-N, N-dimethyl-N-carboxymethylammonium betaine having an alkyl group having preferably 10 or more carbon atoms, preferably 18 or less, more preferably 14 or less, or the following general formula ( Examples thereof include the compound represented by e31).

[In the formula, R ^1e represents an alkyl group or an alkenyl group having 7 or more and 21 or less carbon atoms, R ^2e represents a propylene group, and R ^3e and R ^4e are independently alkyl groups having 1 or more and 3 or less carbon atoms. Is shown. ]

In the general formula (e31), R ^1e is an alkyl group or alkenyl group having a carbon number of preferably 9 or more, more preferably 11 or more, and preferably 15 or less, more preferably 13 or less, and a nonyl group. A decyl group, an undecylic group, a dodecyl group, and a tridecylic group are preferable.
In the general formula (e31), R ^3e and R ^4e are each independently, preferably a methyl group.

As the (e4) amine oxide, the compound of the following general formula (e41) is suitable.

[In the formula, R ^5e represents a hydrocarbon group having 7 or more and 22 or less carbon atoms, preferably an alkyl group or an alkenyl group, more preferably an alkyl group, and R ^6e and R ^7e are the same or different and have 1 or more carbon atoms. Shows 3 or less alkyl groups. D represents an -NHC (= O) -group or a -C (= O) NH- group, and E represents an alkylene group having 1 or more carbon atoms and 5 or less carbon atoms. m and p indicate m = 0 and p = 0 or m = 1 and p = 1. ]

In the above general formula (e41), when m = 1 and p = 1, R ^5e is preferably an alkyl group having 9 or more carbon atoms and 18 or less carbon atoms, and more preferably 11 carbon atoms. It is an alkyl group having 16 or less carbon atoms, more preferably an alkyl group having 11 or more carbon atoms and 14 or less carbon atoms, and even more preferably an alkyl group having 11 carbon atoms. When m = 0 and p = 0, R ^5e is preferably an alkyl group having 10 or more and 18 or less carbon atoms, and more preferably an alkyl group having 12 or more and 16 or less carbon atoms from the viewpoint of detergency. Yes, more preferably an alkyl group having 12 or more carbon atoms and 14 or less carbon atoms, and even more preferably an alkyl group having 12 carbon atoms. In the present invention, m = 0 and p = 0 are preferable. R ^6e and R ^7e are preferably methyl groups having 1 carbon atom from the viewpoint of detergency.

When the component (e) is contained in the hard surface antifungal cleaning agent composition of the present invention, the content of the component (e) is appropriately adjusted from the viewpoint of improving the antifungal effect and detergency.
In the hard surface detergency cleaning agent composition of the present invention, the mass ratio of the content of the component (c) to the total content of the component (c) and the component (e) (c) / [(c) + ( e)] is preferably 0.1 or more, more preferably 0.2 or more, still more preferably 0.3 or more, still more preferably 0.4 or more, and from the viewpoint of detergency, from the viewpoint of the killing effect. Therefore, it is 1 or less, preferably 0.9 or less, and more preferably 0.8 or less.

From the viewpoint of improving the detergency, the mold-killing detergent composition for a hard surface of the present invention preferably contains a metal sequestering agent as the component (f).
As the metal sequestering agent, one or more compounds selected from aminocarboxylic acid, hydroxycarboxylic acid, hydroxykiphosphonic acid, and salts thereof are preferable.

Examples of aminocarboxylic acid and its salts include ethylenediaminetetraacetic acid (EDTA), nitrilotriacetic acid (NTA), iminodiacetic acid, diethylenetriaminepentacetic acid (DPTA), N-hydroxyethyl-ethylenediaminetriacetic acid (HEDTA), and methylglycinediacetic acid. (MGDA), diacetic acid aspartate (ASDA), diacetic acid glutamate (GLDA) and one or more selected from salts thereof. The aminocarboxylic acid and its salt are preferably one or more selected from ethylenediamine tetraacetic acid and its salts, methylglycine 2 acetic acid and its salts, and L-glutamate diacetic acid and its salts.
As the hydroxycarboxylic acid and its salt, a compound selected from the aliphatic hydroxycarboxylic acid and its salt is preferable. Examples of the hydroxycarboxylic acid and its salt include compounds selected from malic acid, citric acid and salts thereof.
Examples of hydroxykiphosphonic acid and salts thereof include compounds selected from 1-hydroxyethidronic acid-1,1-diphosphonic acid (HEDP) and salts thereof.
Examples of the salt of the metal sequestering agent 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.

The component (f) is preferably one or more selected from ethylenediaminetetraacetic acid (EDTA), methylglycine diacetic acid (MGDA), malic acid, citric acid and salts thereof, and ethylenediaminetetraacetic acid (EDTA), citric acid and these are preferable. One or more selected from the salts of the above is more preferable, and ethylenediaminetetraacetic acid and its salts are further preferable.

When the component (f) is contained, the component (f) is preferably 0.2% by mass or more, more preferably 0.% by mass, from the viewpoint of improving the detergency. It is contained in an amount of 5% by mass or more, more preferably 1% by mass or more, and from the viewpoint of compounding stability, preferably 6% by mass or less, more preferably 5% by mass or less, still more preferably 4% by mass or less.

In order to increase the added value of the product, a fragrance, a pigment, an antiseptic, an antioxidant and the like can be arbitrarily added to the hard surface detergent composition of the present invention (however, the above (a). )-(F) component excluded).

The mold-killing detergent composition for hard surfaces of the present invention can contain water. That is, the balance other than the components (a) to (f) and the optional components is water. The mold-killing cleaning agent composition for a hard surface 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. It is preferably contained in an amount of 99% by mass or less, 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 hard surface detergent composition of the present invention is a hard surface detergent composition that does not require a strong alkali or a strong acid. That is, the antifungal composition of the present invention can obtain a good antifungal effect even if it is a liquid near neutrality. The mildew-detergent composition for a hard surface of the present invention has a pH at 25 ° C. of 5 or more, preferably 5.5 or more, more preferably 6 or more, from the viewpoint of ease of handling and irritation to the hand skin. And 9 or less, preferably 8.5 or less, more preferably 8 or less.

The mold-killing cleaning agent composition for hard surfaces of the present invention is suitable for cleaning hard surfaces such as bathrooms, bathtubs, washbasins, tiles, restrooms, washbasins, mirrors, sinks around kitchens, countertops, and water taps. It is used, 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 mold-killing detergent composition for hard surfaces of the present invention has an excellent mold-killing action on mold. For example, for fungi of the genera Cladosporium, Aspergillus, Candida, Penicillium, Alternaria, Phoma, Aureobasidium. It shows a high killing effect on the representative genus.
In addition, Saccharomyces, Rhodotorula, Pichia fungi, Pseudomonas aeruginosa, Pseudomonas putida and other Pseudomonas bacteria, Escherichia coli, Alcaligenes faec ), Klebsiellapneumoniae, Proteus vulgaris, Serratia marcescense, Methylobacterium and other gram-negative bacteria; also high against gram-positive bacteria such as Staphylococcusaureus. Shows bactericidal effect.

[Hard surface treatment method]
The hard surface treatment method of the present invention is a hard surface treatment method in which the mold-killing detergent composition for a hard surface of the present invention is brought into contact with a hard surface on which a mold is present to perform mold-killing and cleaning at the same time.
In the present invention, after the mold-killing detergent composition for a hard surface of the present invention is brought into contact with a hard surface, the surface can be cleaned. Further, in the present invention, the hard surface can be cleaned with a cleaning article in which the antifungal composition of the present invention is supported on a substrate.
As the hard surface, 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 is preferable.

The hard surface treatment method of the present invention specifically comprises contacting the hard surface of the present invention with a mold-killing cleaning agent composition for a hard surface with a stock solution, or diluting the mold-killing agent composition with a stock solution. A hard surface treatment method of contacting the hard surface without diluting the mold-killing agent composition, that is, contacting the hard surface without diluting the composition, is preferable. Further, there is a hard surface treatment method in which the mold-killing detergent composition for a hard surface is brought into contact with a hard surface to which mold is attached without diluting. As a method of contacting with the hard surface, a method of applying to the hard surface is preferable.
Contacting the hard surface mildew-detergent composition without diluting means that the hard-surface mildew-cleaning composition is intentionally diluted with water or the like and then not brought into contact with the hard surface. That is. For example, after the hard surface antifungal cleaning agent composition is brought into contact with a hard surface to which water droplets or the like are attached, or the hard surface antifungal cleaning agent composition is brought into contact with a hard surface, water droplets are adhered to the hard surface. In this case, it can be understood that the mildew-detergent composition for a hard surface is brought into contact with the hard surface without being diluted.
In the hard surface treatment method of the present invention, the mold-killing cleaning agent composition for a hard surface may be directly applied or sprayed from a bottle in order to bring the composition into contact with the hard surface with a stock solution, and the bottle may be, for example, a squeeze bottle. Examples include bottles and spray bottles.
Further, when using a cleaning article impregnated with the hard surface detergency cleaning agent composition of the present invention, the hard surface detergency cleaning agent composition of the present invention is separately sprayed onto the object to be cleaned or the cleaning article. You may use it while using it. Clean a larger area according to the method of use.

Further, a concentrated composition containing the components (a) to (d) of the present invention and an optional component is prepared, and the concentrated composition is diluted with water to form a cleaning agent for a hard surface of the present invention. May be prepared and brought into contact with a hard surface. That is, a concentrated composition containing the components (a) to (d) of the present invention and an optional component is diluted with water to prepare the antifungal cleaning agent composition for a hard surface of the present invention, and is used for the hard surface. A hard surface treatment method may be used in which the antifungal cleaning agent composition is brought into contact with a hard surface without being diluted.

From the viewpoint of the mold-killing effect, the leaving time for contacting the hard surface on which the mold is present and then contacting the mold is preferably 30 seconds or longer, preferably 1 minute or longer, more preferably 2 minutes or longer, still more preferably 3. Minutes or more, more preferably 4 minutes or more, still more preferably 5 minutes or more, and from the viewpoint of efficient cleaning, preferably 30 minutes or less, more preferably 20 minutes or less, still more preferably 10 minutes or less. Is.
After leaving it, it is usually rinsed with water. When rinsing, mechanical force (physical force) may be applied by hand or simply rinsing with a stream of water.
The temperature when left to stand may be room temperature, for example, 10 ° C. or higher and 30 ° C. or lower.

Using the following compounding ingredients, the mildew-detergent composition for hard surfaces shown in Table 1 was prepared, and the following items were evaluated. The results are shown in Table 1. The mold-killing cleaning agent composition for hard surfaces in Table 1 is prepared by adding sodium hydrogen phosphate and sodium dihydrogen phosphate to ion-exchanged water, respectively, in a 10 mM phosphate buffered aqueous solution (pH 7) from (a) to. The component (e) was added in the blending amounts shown in the table and dissolved at room temperature (25 ° C.). After compounding, when the pH became other than 7, the pH was adjusted to 7 with sodium hydroxide and / or hydrochloric acid. The pH was measured by the glass electrode method. Further, the mass% of the compounding components in Table 1 are all numerical values based on the effective amount.

<Ingredients>
(A) Ingredients ・ Na ₂ SO ₄ : Sodium sulfate, manufactured by Wako Pure Chemical Industries, Ltd.

(B) Ingredients-Benzyl alcohol: manufactured by Wako Pure Chemical Industries, Ltd., molecular weight 108
-Phenoxyethanol: manufactured by Wako Pure Chemical Industries, Ltd., molecular weight 138

(C) Ingredients-Sanisol 08: octylbenzyldimethylammonium chloride, in the general formula (c1), R ^1c is an octyl group, R ^2c and R ^3c are a methyl group, R ^4c is a methylene group, and ^Z- is a chloride ion. Compound, C10BAC manufactured by Kao Co., Ltd .: benzyldimethyldecylammonium chloride, in the general formula (c1), R ^1c is an alkyl group having 10 carbon atoms, R ^2c and R ^3c are methyl groups, R ^4c is a methylene group, ^Z- Is a chloride ion compound, manufactured by Sigma Aldrich, Sanizol C: alkyl (8 to 18 carbon atoms) benzyldimethylammonium chloride, in the general formula (c1), R ^1c is an alkyl group having 8 to 18 carbon atoms, R ^2c . And R ^3c is a methyl group, R ^4c is a methylene group, ^Z- is a chloride ion compound, manufactured by Kao Co., Ltd.

(D) Ingredients-BDG: Butyl diglycol (molecular weight: 162, logP: 0.66), manufactured by Nippon Emulsorium Co., Ltd., (d2)
(E) Ingredients-Emulgen 108: Polyoxyethylene (average number of added moles 6) Lauryl ether, manufactured by Kao Corporation

<Mold-killing evaluation method>
Cladsporium sp. PA-4, an environmental isolate of the genus Cladosporium, which is a living environment-preferred filamentous fungus, was cultured on a potato dickinson plate agar plate (Potato Dextrose Agar reagent manufactured by Becton Dickinson was prepared according to the Noh book) at 25 ° C for 7 days, and then the same. 4 mL of spore recovery solution (0.05% Tween80 solution manufactured by Wako Pure Chemical Industries, Ltd. prepared with physiological saline manufactured by Otsuka Pharmaceutical Co., Ltd.) was dropped onto the agar plate, and a spreader (Nissui Pharmaceutical Co., Ltd.) was added. The bacterial solution was recovered by gently rubbing it with (manufactured by Co., Ltd.). After that, the collected hyphae were filtered using Miracross (manufactured by CALBIOCHEM) to remove hyphae, and the obtained liquid was centrifuged (10,000 rpm, 25 ° C., 5 min) to remove the supernatant. These operations were repeated a few times to adjust the bacterial concentration to 3.0 × 10 ⁷ to 7.0 × 10 ⁸ CFU / mL to prepare a test spore solution.

Using the hard surface detergent composition shown in Table 1 as a test solution, 10 μL of the prepared test spore solution was mixed with 1 mL of the test solution, contacted at 25 ° C. for 5 minutes, and then 100 μL was fractionated. Then, the test solution was inactivated by suspending it in 900 μL of LP diluted solution (prepared according to Noh book by Nissui Pharmaceutical Co., Ltd.). After further diluting this with LP diluted solution, it was applied to a potato dextrose plate agar medium (Potato Dextrose Agar reagent manufactured by Becton Dickinson was prepared according to the Noh book) and cultured at 25 ° C for 4 days from the number of colonies obtained. The number of surviving bacteria was calculated.

In addition, use physiological saline (manufactured by Otsuka Pharmaceutical Factory, Inc.) instead of the test solution to mix 10 μL of the bacterial solution with 1 mL of the test solution, contact for 5 minutes, and then mix with the LP diluted solution. ) Was used as the target operation, and the logarithmic difference between the number of surviving bacteria after the target operation and the number of surviving bacteria after contact with the test solution was calculated and used as an index of bactericidal performance (ΔLog reduced number of bacteria). ). In the present invention, it is accepted that the number of ΔLog-reduced bacteria is 1.0 or more.
Further, in the above-mentioned antibacterial evaluation method, the same method as above was used except that the test solution and the test spore solution were mixed and contacted for 1 minute (when the test solution was physiological saline, the same contact was made for 1 minute). Evaluation was performed and the sterilization performance was evaluated. The results are shown in Table 1.

<Evaluation of sebum detergency>
A model sebum stain prepared based on the composition of the sebum stain adhering to the bath tub of the bathroom was dissolved in chloroform to prepare a 5% by mass model sebum stain solution. By immersing a polyvinyl chloride plate (size 7 cm × 2 cm) in this solution for 10 seconds, model sebum stains were formed on the plate and then air-dried overnight. The composition of the model sebum stain is 40% by mass of linoleic acid, 20% by mass of oleic acid, 20% by mass of palmitic acid, 10% by mass of cholesterol and 10% by mass of liquid paraffin. 10 μl of the mildew-detergent composition for hard surface shown in Table 1 was dropped onto the dirty portion of the plate, left at 25 ° C. for 5 minutes, washed with water, and the detergency was visually evaluated according to the following criteria.
⊚: All the stains on the part where the composition was dropped were removed. 〇: All the stains on the part where the composition was dropped were not removed, but more than half of the stains were removed. Δ: The part where the composition was dropped. Dirt was removed, but less than half of the stain was removed. ×: Almost no stain was removed at the place where the composition was dropped.

In Table 1, those having a ΔLog-reduced number of bacteria of 4.5 or more indicate a detection limit value, which means that the number of surviving bacteria is extremely small because they are killed by the mold-killing detergent composition for hard surfaces. do. Further, in the examples and comparative examples in which the evaluation result of the mold-killing property is described as "-", it means that the mold-killing property was not evaluated.

Claims (5)

(A) Water-soluble inorganic salt [hereinafter referred to as (a) component] is 0.1% by mass or more and 5% by mass or less, and (b) nonionic detergent [hereinafter referred to as (b) component] is 0.05% by mass. % To 7% by mass, (c) 0.1% by mass or more and 5% by mass or less of cationic surfactant, (d) solvent (excluding component (b)) and water, at 25 ° C. A solvent-killing detergent composition for hard surfaces having a pH of 5 or more and 9 or less. The first aspect of claim 1, wherein the component (a) is one or more water-soluble inorganic salts selected from alkali metal sulfates, alkaline earth metal sulfates, alkali metal chlorides, and alkaline earth metal chlorides. Alkaline cleaning agent composition for hard surfaces. The hard according to claim 1 or 2, wherein the component (b) is a nonionic bactericide having an aromatic group which may have a substituent and a hydroxy group and having a molecular weight of 106 or more and 300 or less. Antifungal detergent composition for surfaces. (B) The component is one or more nonionic bactericides selected from benzyl alcohol, phenoxyethanol, phenyldiglycol, triclosan, diclosan, and isopropylmethylphenol, according to any one of claims 1 to 3. The above-mentioned antifungal detergent composition for hard surfaces. A hard surface treatment method in which the mold-killing detergent composition for a hard surface according to any one of claims 1 to 4 is brought into contact with a hard surface in which mold is present, and mold-killing and cleaning are performed at the same time.