JP6715134B2 - Liquid detergent composition for clothing - Google Patents

Description

The present invention relates to a liquid detergent composition for clothes.

In recent years, many detergents containing an antibacterial agent such as a cationic surfactant have been put on the market due to an increase in hygiene awareness. As an antibacterial agent, many compounds having an aromatic ring have been reported in addition to the cationic surfactant, and in particular, an antibacterial agent having an aromatic ring is known to have good adsorption to synthetic fibers and improve antibacterial activity. Has been.

Patent Document 1 proposes a liquid detergent composition for clothes, which contains an antibacterial agent having an aromatic ring and a surfactant.

Japanese Patent Publication No. 2004-515642

However, when an antibacterial agent is added to a liquid detergent composition for clothes, the redeposition property (reattachment of stains once removed to the item to be washed) tends to be deteriorated. In the liquid detergent composition for clothing of Patent Document 1, such a problem of recontamination property has not been examined. Liquid detergents for clothes are required to have liquid stability during storage (no precipitation such as precipitation during storage).
The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a liquid detergent composition for clothing, which is excellent in antibacterial activity, liquid stability, and anti-redeposition property.

The liquid detergent composition for clothing of the present invention has the following aspects.
[1] Component (A): nonionic antibacterial agent, component (B): surfactant (excluding component (C)), and component (C): propylene oxide adduct of alcohol having 1 to 5 carbon atoms. And contains,
The content of the component (B) is 30% by mass or more based on the total mass of the liquid detergent composition for clothes.
The component (B) contains a nonionic surfactant and an anionic surfactant,
A liquid detergent composition for clothing, wherein the content of the nonionic surfactant is higher than the content of the anionic surfactant.
[2] The liquid detergent composition for clothes according to [1], wherein the component (B) contains two or more nonionic surfactants.
[3] The liquid laundry washing according to [1] or [2], wherein the content of the component (C) is 0.5 to 5 mass% with respect to the total mass of the liquid laundry detergent composition. Agent composition.
[4] The liquid detergent composition for clothes according to any one of [1] to [3], wherein the component (B) contains two or more types of anionic surfactants.
[5] The nonionic surfactant according to any one of [1] to [4], which contains at least one selected from the group consisting of polyoxyethylene fatty acid methyl ester and polyoxyethylene alkyl ether. Liquid detergent composition for clothing.
[6] In [1] to [5], the anionic surfactant contains at least one selected from the group consisting of polyoxyalkylene alkyl ether sulfates, linear alkylbenzene sulfonates, and higher fatty acid salts. The liquid detergent composition for clothes according to any one of claims.
[7] The liquid washing for clothing according to any one of [1] to [6], wherein the component (A) is at least one selected from the group consisting of triclosan, diclosan, and chlorophen. Agent composition.
[8] The liquid detergent composition for clothing according to any one of [1] to [7], wherein the component (C) has a weight average molecular weight of 1500 to 6000.

ADVANTAGE OF THE INVENTION According to this invention, the liquid detergent composition for clothes which is excellent in antibacterial activity, liquid stability, and redeposition prevention can be provided.

≪Liquid detergent composition for clothing≫
The liquid detergent composition for clothing of the present invention is a composition containing the following components (A), (B) and (C).

<(A) component: Nonionic antibacterial agent>
The component (A) is a nonionic antibacterial agent.
As the component (A), isothiazolone-based, imidazole-based, thiazole-based, bromine-based, phenol-based or diphenyl-based compounds known as antibacterial agents can be preferably used. Specifically, 5-chloro-2-methyl-4-isothiazolin-3-one, 1,2benzothiazolone, 2-(4-methylanomethylthio)benzimidazole, 5-chloro-2-(2,4-dichloro). Phenoxy)phenol (conventional name: triclosan), 4,4'-dichloro-2'-hydroxydiphenyl ether (conventional name: diclosan), o-benzyl-p-chlorophenol (conventional name: chlorophen), isopropylmethylphenol and Parachlorometa xylenol etc. are mentioned.
The component (A) is a component that imparts antibacterial properties to textile products such as clothes after washing. The nonionic antibacterial agent can exhibit antibacterial properties without impairing the detergency of the anionic surfactant even when it is made to coexist with the anionic surfactant in the liquid detergent composition for clothing.
As the component (A), one type may be used alone, or two or more types may be used in appropriate combination.
As the component (A), a compound represented by the following formula (I) is preferable.

In formula (I), X is oxygen or an alkyl group having 1 to 4 carbon atoms, Y is chlorine or bromine, Z is SO ₂ H, NO ₂ , or an alkyl group having 1 to 4 carbon atoms, a, b, and c are each independently an integer of 0 or 1 to 3, d is 0 or 1, m is 0 or 1, and n is 0 or 1.

The component (A) preferably contains a 2-hydroxydiphenyl compound represented by the above formula (I) when X is an oxygen atom and a is 1 (hereinafter referred to as compound (I)). The compound (I) is preferable in that the effect of applying the present invention is large because the amount of adsorption to the hydrophobic fiber is high.
A preferred embodiment is that X is an oxygen or methylene group, Y is chlorine or bromine, m is 0, n is 0 or 1, a is 1 and b is 0, 1 or 2. , C is 0, 1 or 2, and d is 0.
As a more preferable specific example of the compound (I), X is an oxygen atom, a is 1, Y is a chlorine atom, one of b or c is 1 and the other is 0, d is 0, m is 0, Monochlorohydroxydiphenyl ether in which n is 0; X is an oxygen atom, a is 1, Y is a chlorine atom, b is 1, c is 1, d is 0, m is 0, and n is 0; dichlorohydroxydiphenyl ether; X is an oxygen atom, a is 1, Y is a chlorine atom, one of b or c is 1 and the other is 2, and d is 0, m is 0, and n is trichlorohydroxydiphenyl ether; X is methylene. Benzyl chlorophenol in which the group, a is 1, Y is a chlorine atom, b is 0, c is 1, d is 0, m is 0, and n is 0.
Particularly preferred specific examples include 5-chloro-2-(2,4-dichlorophenoxy)phenol (conventional name: triclosan), 5-chloro-2-(4-chlorophenoxy)phenol (conventional name: diclosan), o-benzyl-p-chlorophenol (conventional name: chlorophene).
As the component (A), one type may be used alone, or two or more types may be used in appropriate combination.

The total amount of the compound (I) is preferably 60% by mass or more, more preferably 80% by mass or more, still more preferably 90% by mass or more, based on the total mass of the component (A). It may be 100% by mass.
The content of the component (A) is preferably 0.01 to 3% by mass, more preferably 0.05 to 1% by mass, and 0.1 to 0. 0% based on the total mass of the liquid detergent composition for clothing. 5% by mass is more preferable. When the content of the component (A) is at least the lower limit value of the above range, a good antibacterial effect is easily obtained. When it is at most the upper limit of the above range, good storage stability of the liquid detergent composition for clothing is likely to be obtained.

<(B) component: surfactant>
The component (B) is a surfactant (excluding the component (C)). In the liquid detergent composition for clothing of the present invention, the component (B) functions as a cleaning component. Further, the liquid detergent composition for clothes of the present invention contains the component (B), whereby the dispersion stability of the components (A) and (C) is enhanced.
The component (B) contains a nonionic surfactant and an anionic surfactant, and the content of the nonionic surfactant is higher than that of the anionic surfactant.
As the component (B), a known surfactant can be used. Examples include anionic surfactants, nonionic surfactants, cationic surfactants, amphoteric surfactants and semipolar surfactants. From the viewpoint of cleaning performance, anionic surfactants and nonionic surfactants are preferable.

[Nonionic surfactant]
Examples of the nonionic surfactant include the following (1) to (8).
(1) Polyoxyalkylene obtained by adding an alkylene oxide having 2 to 4 carbon atoms on average to 3 to 30 moles, preferably 3 to 20 moles, and more preferably 5 to 20 moles to a monohydric aliphatic alcohol having 6 to 22 carbon atoms. Alkyl (or alkenyl) ether. Among these, polyoxyethylene alkyl (or alkenyl) ether and polyoxyethylene polyoxypropylene alkyl (or alkenyl) ether are preferable. Examples of the monohydric aliphatic alcohol used here include primary alcohols and secondary alcohols. Moreover, the alkyl group may have a branched chain. The aliphatic alcohol is preferably a primary alcohol.
(2) Polyoxyethylene alkyl (or alkenyl) phenyl ether.
(3) A fatty acid alkyl ester alkoxylate in which an alkylene oxide is added between ester bonds of a long-chain fatty acid alkyl ester.
(4) Polyoxyethylene sorbitan fatty acid ester.
(5) Polyoxyethylene sorbit fatty acid ester.
(6) Polyoxyethylene fatty acid ester.
(7) Polyoxyethylene hydrogenated castor oil.
(8) Glycerin fatty acid ester.

As the nonionic surfactant, those of the above (1) or (3) are preferable, and among them, those represented by the following general formula (II) or (III) are preferable.
_{^{R 2 -C (= O) O}} - [(EO) s / (PO) t] - (EO) u -R 3 ··· (II)
^{_{R 4 -O - [(EO)}} v / (PO) w] - (EO) x -H ··· (III)
(In the formula (II), R ² is a hydrocarbon group having 7 to 22 carbon atoms, R ³ is an alkyl group having 1 to 6 carbon atoms, s represents the average repetition number of EO, and 6 to 20 , T is the average number of repetitions of PO, is a number from 0 to 6, u is the average number of repetitions of EO, is a number from 0 to 20, EO is an oxyethylene group, and PO is Represents an oxypropylene group.
In the formula (III), R ⁴ is a hydrocarbon having 6 to 22 carbon atoms, v is an average repetition number of EO, is a number of 3 to 20, w is an average repetition number of PO, and is 0 to 6 is a number, x is an average number of repetitions of EO, is a number of 0 to 20, EO is an oxyethylene group, and PO is an oxypropylene group. )

In the formula (II), R ² is a hydrocarbon group having 7 to 22 carbon atoms. 9-21 are preferable and, as for carbon number of R< ² >, 11-21 are more preferable.
R ² is preferably an alkyl group or an alkenyl group.
R ² may be linear or branched.
From the viewpoint of further improving the detergency, R ² is preferably a linear or branched alkyl group having 7 to 22 carbon atoms or a linear or branched alkenyl group having 7 to 22 carbon atoms.
R ³ is an alkyl group having 1 to 6 carbon atoms, which may be linear or branched.
Of these, a methyl group and an ethyl group are preferable.
In the formula (II), s and u are numbers that independently represent the average number of EO repetitions.
s+u is preferably 6-20, more preferably 6-18, and even more preferably 11-18. When it is at least the above lower limit value, the liquid stability is more likely to be improved. If it is at most the above upper limit, the cleaning power will be more easily improved.
In the formula (II), t is a number representing the average number of repetitions of PO.
t is a number from 0 to 6, preferably 0 to 3. When it is at most the above upper limit, the liquid stability will be more easily improved.
When t is 1 or more, in [(EO) _s /(PO) _t ], the oxyethylene group and the oxypropylene group may be bonded randomly or in a block.
In addition, in the present specification, the average number of repetitions can be measured by gas chromatography or the like.

In the formula (III), R ⁴ is a hydrocarbon group having 6 to 22 carbon atoms.
In the formula (III), the carbon number of R ⁴ is preferably 10 to 22, more preferably 10 to 20, and further preferably 10 to 18, from the viewpoint of further improving the detergency.
R ⁴ may be linear or branched.
Examples of preferable R ⁴ —O— include groups represented by the following general formula (IV).
(R ¹⁰¹ )(R ¹⁰² )CH—O—... (IV)
(In formula (IV), R ¹⁰¹ and R ¹⁰² each independently represent a hydrogen atom or a chain hydrocarbon group, and the total carbon number of R ¹⁰¹ and R ¹⁰² is 5 to 21.)
The number of carbon atoms in the sum of R ¹⁰¹ and ^{R 102} is preferably 9 to 21, preferably from 9 to 19, more preferably 9 to 17.
R ¹⁰¹ and R ¹⁰² may be linear or branched.
As R ⁴ , specifically, an alkyl group derived from a secondary alcohol having 12 to 14 carbon atoms is preferable.
In the formula (III), v and x are numbers that independently represent the average number of EO repetitions.
v+x is preferably 3-20, more preferably 5-18, even more preferably 6-18, and particularly preferably 11-18. When it is at least the above lower limit value, the liquid stability is more likely to be improved. If it is at most the above upper limit, the cleaning power will be more easily improved.
In formula (III), w is a number representing the average number of repeating POs.
w is a number of 0 to 6, and 0 to 3 is preferable. When it is at most the above upper limit, the liquid stability will be more easily improved.
When w is 1 or more, in [(EO) _v /(PO) _w ], the oxyethylene group and the oxypropylene group may be bonded randomly or in a block.
The distribution of EO or PO in formula (III) varies depending on the reaction method used for production. For example, when ethylene oxide or propylene oxide is added to the raw material using sodium hydroxide, potassium hydroxide or the like which is a common alkali catalyst, the distribution of v or w becomes relatively wide. A specific alkoxylation catalyst such as magnesium oxide added with metal ions such as Al ³⁺ , Ga ³⁺ , In ³⁺ , Tl ³⁺ , Co ³⁺ , Sc ³⁺ , La ³⁺ and Mn ²⁺ described in JP-B-6-15038. When ethylene oxide or propylene oxide is added to the raw material, the distribution of v or w becomes relatively narrow.

The nonionic surfactant represented by the formula (II) (hereinafter, also referred to as “(b1) component”) and the nonionic surfactant represented by the formula (III) (hereinafter, also referred to as “(b2) component”). .) has a narrow rate of preferably 20% by mass or more, and more preferably 25% by mass or more. The higher the narrow rate, the better the detergency. Further, when the narrow rate is 20% by mass or more, and particularly 25% by mass or more, it becomes easy to obtain a liquid detergent composition for clothes with a small raw material odor of the surfactant.

In the case where the component (b1) is produced by a conventional method, the component (b1), a component that does not contribute to detergency, such as a fatty acid ester that is a raw material of the component (b1) or a compound represented by the formula (II), The ethylene oxide adduct in which s of the nonionic surfactant is 1 or 2 coexists and reduces the narrow rate. Therefore, when the narrow rate is high, the coexisting components are sufficiently small, and the problem of deterioration of detergency and odor of raw materials is less likely to occur. The same applies to the case of the component (b2).
The upper limit of the narrow ratio is not particularly limited, but it is preferably substantially 80 mass% or less.
The narrow ratio is more preferably 20 to 50% by mass and further preferably 20 to 40% by mass because the liquid stability and the solubility are improved.
Here, in the present specification, the “narrow ratio” refers to a distribution ratio of ethylene oxide adducts having different EO addition mole numbers and is represented by the following mathematical formula (S).

[In the formula, n _max represents the number of moles of EO added to the ethylene oxide adduct, which is most present in the whole ethylene oxide adduct. i represents the number of moles of EO added. Yi represents the ratio (% by mass) of the ethylene oxide adducts in which the number of moles of EO added is i, which is present in the whole ethylene oxide adduct. ]
The narrow ratio can be controlled by, for example, a method for producing the component (b1) or the component (b2). The method for producing the component (b1) is not particularly limited, but, for example, a method in which ethylene oxide is addition-polymerized with a fatty acid alkyl ester using a surface-modified complex metal oxide catalyst (JP-A 2000-144179). It can be easily manufactured by the method described in Japanese Patent Publication No. The component (b2) can be produced by, for example, a method of addition-polymerizing ethylene oxide to an alcohol having 6 to 22 carbon atoms using a surface-modified complex metal oxide catalyst.

Suitable examples of the surface-modified composite metal oxide catalyst used in such a method include, specifically, metal ions (Al ³⁺ , Ga ³⁺ , In ³⁺⁾ surface-modified with a metal hydroxide or the like. Tl ³⁺ , Co ³⁺ , Sc ³⁺ , La ³⁺ , Mn ^2+, etc.) of a mixed metal oxide catalyst such as magnesium oxide, or a hydrotalcite surface-modified with a metal hydroxide and/or a metal alkoxide. Examples include calcined product catalysts.
In the surface modification using the composite metal oxide catalyst, it is preferable to use the composite metal oxide in combination with a metal hydroxide and/or a metal alkoxide. In this case, the ratio of the metal hydroxide and/or the metal alkoxide is preferably 0.5 to 10 parts by mass, and more preferably 1 to 5 parts by mass with respect to 100 parts by mass of the composite metal oxide. ..
As the nonionic surfactant, a commercially available product may be used, or a nonionic surfactant manufactured by a known synthesis method may be used. As a known production method, the component (b1) can be produced by, for example, a method of addition-polymerizing ethylene oxide and/or propylene oxide to a fatty acid alkyl ester. The component (b2) can be produced, for example, by a method of addition-polymerizing ethylene oxide and/or propylene oxide to an alcohol having 6 to 22 carbon atoms.
As the nonionic surfactant, one type may be used alone, or two or more types may be used in combination.

As the nonionic surfactant, the component (b1) is preferable, a compound in which t in the formula (II) is 0 (that is, a polyoxyethylene fatty acid alkyl ester) is more preferable, and R ³ in the formula (II) is methyl. The group polyoxyethylene fatty acid methyl ester (hereinafter referred to as “MEE”) is particularly preferable from the viewpoint of improving the detergency and the solubility of the liquid detergent composition for clothes.

As the nonionic surfactant, it is preferable to use the component (b1) and the component (b2) together.
The mass ratio (hereinafter, also referred to as b1/b2 ratio) represented by the component (b1)/component (b2) is preferably 0.1 to 15, more preferably 1 to 10, and further preferably 3 to 8. When the b1/b2 ratio is within the above range, the anti-redeposition property is further enhanced.

The content of the component (b1) is preferably 30% by mass or more, more preferably 40% by mass or more, and further preferably 50% by mass or more, based on the total mass of the component (B). When the content of the component (b1) is within the above-mentioned preferred range, a liquid detergent composition for clothing, which has excellent detergency and liquid stability, can be easily obtained.

The content of the nonionic surfactant in the component (B) is preferably 30 to 90% by mass, more preferably 40 to 80% by mass, further preferably 45 to 70% by mass, based on the total mass of the component (B). preferable. When the content of the nonionic surfactant is within the above range, a liquid detergent composition for clothes, which is excellent in liquid stability, can be easily obtained.

[Anionic surfactant]
Examples of the anionic surfactant include the following (1) to (12).
(1) A methyl, ethyl or propyl ester salt of a saturated or unsaturated α-sulfofatty acid having 8 to 20 carbon atoms.
(2) A linear or branched alkylbenzene sulfonate (LAS or ABS) having an alkyl group having 8 to 18 carbon atoms.
(3) Alkane sulfonate having 10 to 20 carbon atoms.
(4) α-Olefin sulfonate (AOS) having 10 to 20 carbon atoms.
(5) Alkyl sulfate or alkenyl sulfate (AS) having 10 to 20 carbon atoms.
(6) Any of alkylene oxides having 2 to 4 carbon atoms, or ethylene oxide (EO) and propylene oxide (PO) (molar ratio EO/PO=0.1/9.9 to 9.9/0.1). A polyoxyalkylene alkyl (or alkenyl) ether sulfate (AES) having a linear or branched alkyl (or alkenyl) group having 10 to 20 carbon atoms added with an average of 0.5 to 10 mol.
(7) Any of alkylene oxides having 2 to 4 carbon atoms, or ethylene oxide and propylene oxide (molar ratio EO/PO=0.1/9.9 to 9.9/0.1), on average 3 to 30 mol An alkyl (or alkenyl) phenyl ether sulfate having an added linear or branched alkyl (or alkenyl) group having 10 to 20 carbon atoms.
(8) Any of alkylene oxides having 2 to 4 carbon atoms, or ethylene oxide and propylene oxide (molar ratio EO/PO=0.1/9.9 to 9.9/0.1), an average of 0.5 to An alkyl (or alkenyl) ether carboxylate having a linear or branched alkyl (or alkenyl) group having 10 to 20 carbon atoms added with 10 moles.
(9) Alkyl polyhydric alcohol ether sulfate such as alkyl glyceryl ether sulfonic acid having 10 to 20 carbon atoms.
(10) Long-chain (having 8 to 20 carbon atoms) monoalkyl, dialkyl or sesquialkyl phosphate.
(11) Polyoxyethylene monoalkyl, dialkyl or sesquialkyl phosphate.
(12) Higher fatty acid or salt thereof. A higher fatty acid having an average carbon number of 10 to 20 (preferably 12 to 18) or a salt thereof.
Anionic surfactants other than those exemplified above may be used. For example, carboxylic acid type anionic surfactants such as alkyl ether carboxylate, polyoxyalkylene ether carboxylate, alkylamide ether carboxylate or alkenylamide ether carboxylate, acylaminocarboxylate; alkyl phosphate ester salt. , Phosphate ester type anionic surfactants such as polyoxyalkylene alkyl phosphate salt, polyoxyalkylene alkyl phenyl phosphate salt, glycerin fatty acid ester monophosphate ester salt, and the like.

As the anionic surfactant, those of the above (2) or (6) are preferable.
Specifically, the polyoxyalkylene alkyl ether sulfate of (6) is preferably a compound represented by the general formula (V).
^{_{R 40 -O - [(EO)}} m / (PO) n] -SO 3 - M + ··· (V)
[In the formula (V), R ⁴⁰ is a linear or branched alkyl group having 8 to 20 carbon atoms. EO represents an oxyethylene group, and PO represents an oxypropylene group. m represents the average number of repetitions of EO and is a number of 1 or more. n represents the average number of repeated POs and is a number from 0 to 6. M ⁺ is a counter cation. When n is greater than 0, PO and EO in [(PO) _m /(EO) _n ] may be arranged in blocks or randomly. In PO and EO, PO may be bonded to “R ⁴⁰ —O—” or EO may be bonded to “R ⁴⁰ —O—”. ]

As the polyoxyalkylene alkyl ether sulfate, one having a linear or branched alkyl group having 10 to 20 carbon atoms and having an average of 1 to 5 mol of alkylene oxide added thereto is preferable.
The alkyl group preferably has 10 to 20 carbon atoms, and more preferably 12 to 14 carbon atoms. Specific examples thereof include dodecyl group, tridecyl group, tetradecyl group and the like. Of these, dodecyl group is preferable.
The average number of EO repeats is preferably 1 to 5, and more preferably 1 to 3.
The average repeating number of PO is preferably 0 to 3.
The compound of m=0 and n=0 in the formula (V) is preferably contained in an amount of 35 to 55 mass% with respect to the entire polyoxyalkylene alkyl ether sulfate represented by the formula (V).
Examples of the salt form of the anionic surfactant include alkali metal salts such as sodium salt and potassium salt; alkaline earth metal salts such as magnesium salt; alkanolamine salts such as monoethanolamine salt and diethanolamine salt; ammonium salt and the like. To be Of these, alkali metal salts are preferable.
As a method for producing an anionic surfactant, for example, in the case of LAS, it can be produced by a method in which alkylbenzene is sulfonated with sulfuric anhydride and neutralized with alkali. For example, in the case of AES, it can be produced by a method in which polyoxyalkylene alkyl ether is reacted with sulfuric anhydride or with chlorosulfonic acid to be sulfonated and neutralized with an alkali.

As the anionic surfactant, it is preferable to use the above (2) or (6) together.
The mass ratio (hereinafter, also referred to as b3/b4 ratio) of the anionic surfactant (2) (hereinafter also referred to as (b3) component) and the anionic surfactant (6) (hereinafter also referred to as (b4) component) is 0.1-10 are preferable, 0.2-8 are more preferable, 0.5-1.5 are more preferable. When the b3/b4 ratio is within the above range, the redeposition preventing performance is further enhanced.

The anionic surfactant may be used alone or in combination of two or more.
The content of the anionic surfactant is preferably 5 to 70% by mass, more preferably 10 to 60% by mass, further preferably 10 to 50% by mass, and further preferably 20 to 40% by mass, based on the total mass of the component (B). Is particularly preferable. When the content of the anionic surfactant is at least the above lower limit value, the anti-soil redeposition property is more likely to be improved. When the content of the anionic surfactant is equal to or less than the above upper limit value, the liquid stability will be more easily improved.
As the component (B), it is preferable to use a nonionic surfactant and an anionic surfactant together. In this case, the mass ratio of the nonionic surfactant and the anionic surfactant (“mass ratio represented by nonionic surfactant/anionic surfactant) is preferably more than 1 and less than 20 and more preferably more than 1 and less than 9”. It is more preferably more than 1 and less than or equal to 8, more preferably 1.5 to 4. When the mass ratio is within the above-mentioned preferable range, the anti-recontamination property is further enhanced.

[Cationic surfactant]
Examples of the cationic surfactant include cationic surfactants such as alkyltrimethylammonium salt, dialkyldimethylammonium salt, alkylamidoamine type, alkylbenzyldimethylammonium salt and alkylpyridinium salt. Examples of these salts include alkali metal salts such as sodium and potassium, alkaline earth metal salts such as magnesium, and alkanolamine salts such as monoethanolamine and diethanolamine.
As the cationic surfactant, one type may be used alone, or two or more types may be used in combination.
The content of the cationic surfactant in the component (B) is preferably 0 to 10% by mass, more preferably 0 to 5% by mass, based on the total mass of the component (B).

[Amphoteric surfactant]
Examples of the amphoteric surfactant include alkylbetaine type, alkylamidobetaine type, imidazoline type, alkylaminosulfone type, alkylaminocarboxylic acid type, alkylamidecarboxylic acid type, amideamino acid type and phosphoric acid type amphoteric surfactants. Can be mentioned.
As the amphoteric surfactant, one type may be used alone, or two or more types may be used in combination.
The content of the amphoteric surfactant in the component (B) is preferably 0 to 10 mass% and more preferably 0 to 5 mass% with respect to the total mass of the component (B).

As the component (B), one type may be used alone, or two or more types may be used in appropriate combination.
The content of the component (B) is 30% by mass or more, preferably 35% by mass or more, and more preferably 40% by mass or more, based on the total mass of the liquid detergent composition for clothing. When the content of the component (B) is not less than the lower limit value, the detergency is further enhanced. The content of the component (B) is preferably 70% by mass or less and more preferably 60% by mass or less based on the total mass of the liquid detergent composition for clothing. When the content of the component (B) is at most the above upper limit, the liquid stability will be easily enhanced.
The content of the component (B) is preferably 30 to 70% by mass, more preferably 30 to 60% by mass, further preferably 35 to 60% by mass, and 40 to 40% by mass based on the total mass of the liquid detergent composition for clothing. 60% by weight is particularly preferred.
The total amount of the surfactants does not exceed 100% by mass based on the total mass of the component (B).

In the liquid detergent composition for clothes of the present invention, the mass ratio (hereinafter, also referred to as B/A ratio) represented by the content of the component (B)/the content of the component (A) is the same as the cleaning power and From the viewpoint of enhancing the antifouling ability, it is preferably 3 or more, more preferably 5 or more, still more preferably 10 or more. From the viewpoint of enhancing antibacterial properties, it is 500 or less, more preferably 400 or less, and further preferably 300 or less.

<(C) component: Propylene oxide adduct of alcohol having 1 to 5 carbon atoms>
The component (C) is a propylene oxide adduct of an alcohol having 1 to 5 carbon atoms. By containing the component (C), the anti-redeposition property is improved. The component (C) may have an alkylene oxide other than propylene oxide (eg, ethylene oxide) added thereto.
The propylene oxide adduct of alcohol is obtained by adding propylene oxide to a monoalcohol such as methanol, ethanol, propanol, butanol and pentanol; a diol such as ethanediol; a triol such as glycerin; and a tetraol such as erythritol.
As the component (C), for example, polyoxypropylene methyl ether, polyoxypropylene ethyl ether, polyoxypropylene propyl ether, polyoxypropylene butyl ether, polyoxypropylene pentyl ether, polyoxypropylene ethylene glycol ether, polyoxypropylene glyceryl ether, Examples thereof include polyoxypropylene pentaerythritol ether. Further, the component (C) is preferably one represented by the following formulas (VI) to (VIII).

In formula (VI), R ¹ represents a hydrocarbon group having 1 to 5 carbon atoms, a is a number of 10 to 350 that represents the average number of repetitions of PO, and PO represents an oxypropylene group.
The number of carbon atoms in R ¹ is 1-4 preferably 1 to 3 is more preferable.
R ¹ is preferably an alkyl group or an alkylene group, more preferably a methyl group, an ethyl group, a propyl group or a butyl group.
It is preferable that a is 20 to 150.
In formula (VII), b and c are each independently a number of 10 to 350 that represents the average number of repetitions of PO, and PO represents an oxypropylene group.
It is preferable that b and c are each independently 10 to 80.
In formula (VIII), d, e, and f are each independently a number of 10 to 350 that represents the average number of repetitions of PO, and PO represents an oxypropylene group.
It is preferable that d, e, and f are each independently 6 to 50.

Of the formulas (VI) to (VIII), the compound represented by the formula (VII) or the formula (VIII) is preferable, and the compound represented by the formula (VIII) is preferable since the anti-fouling property and the liquid stability are excellent. Is more preferable.

The weight average molecular weight of the component (C) is preferably 1500 to 6000, more preferably 2500 to 5500, and further preferably 3000 to 5000.
When it is at least the above lower limit value, the redeposition resistance is more likely to be improved. When it is at most the above upper limit, the liquid stability will be more easily improved.
The weight average molecular weight of the component (C) is polypropylene glycol (weight average molecular weight: 800, 1200) represented by the molecular formula: HO[CH(CH ₃ )CH ₂ O] _n H (n represents the average number of repetitions). , 2000, 4000) as a standard, and is obtained from the molecular weight distribution obtained by GPC (gel permeation chromatography).

Examples of the method for producing the compound represented by the formula (VI) include known methods in which propylene oxide is addition-polymerized with alcohol (R ¹ —OH).
Examples of the method for producing the compound represented by the formula (VII) include known methods in which propylene oxide is addition-polymerized with ethylene glycol.
Examples of the method for producing the compound represented by the formula (VIII) include known methods in which propylene oxide is addition-polymerized with glycerin.
A propylene oxide adduct having a desired weight average molecular weight can be produced by adjusting the amount of propylene oxide supplied during addition polymerization of each compound.
As the component (C), one type may be used alone, or two or more types may be used in appropriate combination.

The content of the component (C) is preferably 0.5 to 5 mass%, more preferably 0.75 to 3 mass%, and 0.75 to 1.5 based on the total mass of the liquid detergent composition for clothing. Mass% is more preferable.
When it is at least the above lower limit value, the redeposition resistance is more likely to be improved. When it is at most the above upper limit, the liquid stability will be more easily improved.

The mass ratio (also referred to as A/C ratio) represented by the content of the component (A)/the content of the component (C) is preferably 0.06 or more, more preferably 0.1 from the viewpoint of enhancing antibacterial properties. Or higher, more preferably 0.15 or higher. From the viewpoint of improving the anti-redeposition property, it is 6 or less, more preferably 1.5 or less, still more preferably 0.4 or less.

The mass ratio (also referred to as B/C ratio) represented by the content of the component (B)/the content of the component (C) is preferably 6 or more, and more preferably 10 or more from the viewpoint of enhancing the anti-soil redeposition property. is there. From the viewpoint of enhancing the liquid stability, it is 140 or less, more preferably 100 or less.

<Arbitrary ingredients>
The liquid detergent composition for clothing of the present invention comprises, in addition to the components (A) to (C), enzymes such as protease, amylase, lipase, cellulase and mannanase; ethanol, butyl carbitol, polyethylene glycol, propylene glycol and the like. Water-miscible organic solvent; alkaline agent such as monoethanolamine; antioxidant such as dibutylhydroxytoluene; preservative such as sodium benzoate; enzyme stabilizer such as calcium chloride and sodium lactate; coloring agent such as pigment; zeolite Detergency builder; fragrance (or fragrance precursor); water and the like may be contained.
The total of the components (A) to (C) and the optional components does not exceed 100% by mass.

It is important to enhance the particle dispersibility in order to enhance the anti-soil redeposition property, and in the liquid detergent composition for clothing of the present invention, the component (C) enhances the particle dispersibility and contributes to the anti-soil redeposition. Conceivable. Further, in order to stably mix the components (A) and (C), it is essential to mix the component (B) at a desired concentration. Of course, the component (B) is also involved in improving the anti-soil redeposition property, and in order to enhance the anti-soil redeposition property, it is preferable to add an anionic surfactant, and the effect is particularly high in LAS. On the other hand, the nonionic surfactant has the effect of enhancing the sebum cleansing power, and MEE is particularly excellent in the cleansing power and low temperature stability. The balance of the component (B) enhances anti-soil redeposition property, and also enhances overall detergency and stability as a detergent.

<<Method for producing liquid detergent composition for clothing>>
When the liquid detergent composition for clothes is a liquid, it is prepared by mixing the solvent, the components (A) to (C) and, if necessary, the optional components.

<<How to use the liquid detergent composition for clothing>>
The method of using the liquid detergent composition for clothes (that is, the cleaning method) is the same as the conventionally known cleaning method.
As a cleaning method, for example, a liquid detergent composition for clothes is dispersed in water to have an arbitrary concentration to form a cleaning liquid, and the object to be washed is immersed in the liquid for an arbitrary time, and then the object to be washed is water. Examples of the method include a rinsing method (immersion cleaning method) and a method in which the liquid detergent composition for clothes is directly applied to the object to be washed, left standing for a certain period of time, and then subjected to normal washing (application cleaning method).
The content of the liquid detergent composition for clothes in the cleaning liquid is appropriately determined according to the composition and dosage form of the liquid detergent composition for clothes. For example, the content of the liquid detergent composition for clothing in the cleaning liquid is preferably 0.1 to 0.6% by mass, more preferably 0.4 to 0.6% by mass, and further preferably 0.5% by mass. ..
If it is less than the above lower limit, the cleaning effect may be lowered, and if it exceeds the above upper limit, undissolved residue may occur in the cleaning liquid or rinsing may be complicated.

As a cleaning method, a method of manually rubbing the object to be cleaned while immersing the object to be cleaned in the cleaning liquid can be mentioned. In this cleaning method, the content of the liquid cleaning composition for clothes in the cleaning liquid is the same as the content of the liquid cleaning composition for clothes in the cleaning liquid in the immersion cleaning method.

Alternatively, as a cleaning method, a method in which a cleaning liquid and an object to be cleaned are put into a washing machine and the cleaning liquid is stirred can be mentioned. In this cleaning method, the content of the liquid detergent composition for clothing in the cleaning liquid is preferably 0.05 to 0.2% by mass, more preferably 0.1 to 0.2% by mass. If it is at least the above lower limit value, the detergency will be easily improved, and if it is at most the above upper limit value, the rinsability will be easily improved.

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

<<Examples 1 to 16 and Comparative Examples 1 to 4>>
<Preparation of liquid detergent composition for clothing>
The compositions of the respective examples were prepared according to the blended compositions shown in Tables 1 and 2 by the production method described later (if there are unblended components, the components are not blended).
The unit of the blending amount in the table is "mass %", and all components show the pure content equivalent amount.
The blank column in the table indicates that the component is not blended.
“Balance” means that water is blended so that the total blending amount (mass %) of all blending components contained in the composition of each example is 100 mass %.
The components shown in the table will be described below.

<(A) component>
-A-1: 4,4'-dichloro-2'-hydroxydiphenyl ether, trade name "Tinosan HP100", manufactured by BASF.
-A-2: 5-chloro-2-(2,4-dichlorophenoxy)phenol, trade name "Triclosan", manufactured by Wako Pure Chemical Industries, Ltd.
-A-3: o-benzyl-p-chlorophenol, trade name "chlorophen", manufactured by Clariant Japan KK

<(B) component>
B-1: MEE (polyoxyethylene fatty acid methyl ester). 15 mol equivalent of ethylene oxide is added to methyl coconut fatty acid (a mixture of methyl laurate/methyl myristate=74/26 in a mass ratio) using an alkoxylation catalyst. In the general formula (II), R ² =alkyl group having 11 carbon atoms and alkyl group having 13 carbon atoms, R ³ =methyl group, s=15, t=0, u=0. It was synthesized by the following synthesis method.
[Synthesis method of B-1]
It was synthesized according to the synthesis method described in JP-A-2000-144179.
Alumina hydroxide/magnesium hydroxide (Kyoward 300 (trade name), manufactured by Kyowa Chemical Industry Co., Ltd.) having a composition of 2.5 MgO.Al ₂ O ₃ .wH ₂ O (w: the number of moles of hydration water) is 600° C. And calcined in a nitrogen atmosphere for 1 hour to obtain a calcined alumina hydroxide/magnesium (unmodified) catalyst. 2.2 g of calcined alumina/magnesium hydroxide (unmodified) catalyst, 2.9 mL of 0.5 N potassium hydroxide ethanol solution, 280 g of lauric acid methyl ester, and 70 g of myristic acid methyl ester were charged into a 4 L autoclave, and then autoclaved. The catalyst was reformed inside. Then, after replacing the inside of the autoclave with nitrogen, 1052 g of ethylene oxide was introduced while maintaining the temperature at 180° C. and the pressure at 0.3 MPa, and the reaction was performed while stirring.
The obtained reaction solution was cooled to 80° C., 159 g of water and 5 g of activated clay and 5 g of diatomaceous earth as filter aids were added and mixed, and the catalyst was filtered off to obtain B-1.
The narrow rate of B-1 was 30 mass %.
-B-2: MEE. A mixture of coconut fatty acid methyl (a mixture of methyl laurate/methyl myristate=8/2 in mass ratio) with 15 mol of ethylene oxide using an alkoxylation catalyst. In the general formula (II), R ² =alkyl group having 11 carbon atoms and alkyl group having 13 carbon atoms, R ³ =methyl group, s=15, t=0, u=0. It was synthesized by the following synthesis method.
[Synthesis method of B-2]
In a 500 mL beaker, 137 g of 2-ethylhexanol (first-class reagent, manufactured by Kanto Chemical Co., Inc.) and 41.7 g of calcium acetate monohydrate (special-grade reagent, manufactured by Kanto Chemical Co., Ltd.) were placed, and a paddle stirring blade was operated at room temperature (25 C.) to obtain a dispersion (dispersion step). While stirring the dispersion, 20.9 g of sulfuric acid (special grade reagent, manufactured by Kanto Kagaku Co., Ltd.) was added over 10 minutes by a dropping funnel and mixed (mixing step). Since the addition of sulfuric acid generated heat in the mixing step, the beaker was cooled in a water bath to control the reaction temperature at 30 to 50°C. After adding sulfuric acid, the mixture was stirred at 50° C. for another 2 hours (catalyst aging step) to obtain an alkoxylation catalyst.
12.5 g of the above alkoxylation catalyst, 462 g of methyl laurate (pastel M12, manufactured by Lion Chemical Co., Ltd.), and 166 g of methyl myristate (pastel M14, manufactured by Lion Chemical Co., Ltd.) were placed in an autoclave and stirred. The inside of the autoclave was replaced with nitrogen while stirring, the temperature was raised to 100° C., and dehydration was performed for 30 minutes under a reduced pressure condition of 1.3 kPa or less. Next, the temperature was raised to 160° C., and under the condition of 0.1 to 0.5 MPa, 1876 g of ethylene oxide (15 moles of the total amount of methyl laurate and methyl myristate) was introduced and stirred (addition reaction step). Further, the mixture was stirred at the addition reaction temperature for 0.5 hour (aging step) and then cooled to 80° C. to obtain 2516 g of a reaction crude product (fatty acid methyl ester ethoxylate (MEE), EO average added mole number=15). The reaction crude product was filtered to remove the catalyst and designated as B-2.
The narrow rate of B-2 was 30 mass %.

B-3: Softanol. A secondary alcohol having 12 to 14 carbon atoms with 7 moles of ethylene oxide added. Softanol 70 (trade name), manufactured by Nippon Shokubai Co., Ltd. In the above general formula (III), R ⁴ =a branched alkyl group having 12 to 14 carbon atoms, v=7, w=0, and x=0.
B-4: polyoxyethylene alkyl ether. A natural alcohol (primary alcohol) having 12 and 14 carbon atoms to which 15 mol of ethylene oxide is added.
[Synthesis method of polyoxyethylene alkyl ether]
224.4 g of CO-1214 (trade name, natural alcohol having 12 and 14 carbon atoms) manufactured by Procter & Gamble Co., Ltd. and 2.0 g of 30 mass% NaOH aqueous solution were charged in a pressure resistant reaction vessel, and the reaction vessel The inside was replaced with nitrogen. Next, after dehydrating at a temperature of 100° C. and a pressure of 2.0 kPa or less for 30 minutes, the temperature was raised to 160° C. Then, while stirring the reaction solution, 760.6 g of ethylene oxide (gaseous) was gradually added to the reaction solution. At this time, ethylene oxide was added through a blowing tube while controlling the addition rate so that the reaction temperature did not exceed 180°C.
After the addition of ethylene oxide was completed, the mixture was aged at a temperature of 180° C. and a pressure of 0.3 MPa or less for 30 minutes, and then unreacted ethylene oxide was distilled off at a temperature of 180° C. and a pressure of 6.0 kPa or less for 10 minutes.
Next, after cooling the temperature to 100° C. or lower, 70% by mass of p-toluenesulfonic acid was added and neutralized so that the pH of a 1% by mass aqueous solution of the reaction product was about 7, to obtain B-4. It was
B-5: EP nonion. A natural alcohol (a primary alcohol having 12 carbon atoms/a primary alcohol having 14 carbon atoms=7/3 in a mass ratio) is block-added in the order of 8 mol of ethylene oxide, 2 mol of propylene oxide, and 8 mol of ethylene oxide. The obtained nonionic surfactant.

-B-6: AES. Polyoxyalkylene alkyl ether sulfate (a mixture of sodium polyoxyethylene lauryl ether sulfate and sodium polyoxyethylene myristyl ether sulfate, the average number of moles of EO added is 1). R ⁴⁰ in the general formula (V)=a straight-chain alkyl group having 12 and 14 carbon atoms, m=1.0, n=0, M=sodium, and m=0, n=0 with respect to the entire B-6. Ratio of compound (component (b0))=43 mass %.
[Preparation example of B-6]
In an autoclave having a capacity of 4 L, 400 g of a product name CO1270 alcohol (a mixture of an alcohol having 12 carbon atoms and an alcohol having 14 carbon atoms in a mass ratio of 75/25) manufactured by P&G Co. as raw material alcohol and potassium hydroxide as a reaction catalyst. After charging 0.8 g of a catalyst and replacing the inside of the autoclave with nitrogen, the temperature was raised with stirring. Subsequently, while maintaining the temperature at 180° C. and the pressure at 0.3 MPa or less, 91 g of ethylene oxide was introduced and reacted to obtain an alcohol ethoxylate.
Gas chromatograph mass spectrometer: GC-5890 manufactured by Hewlett-Packard, detector: hydrogen flame ionization type detector (FID), column: Ultra-1 (manufactured by HP, L25m×φ0.2 mm×T0.11 μm) ) And were analyzed as a result, the obtained alcohol ethoxylate had an average addition mole number of ethylene oxide of 1.0. Further, the amount of the compound to which ethylene oxide was not added (the one which finally becomes the component (b0)) was 43 mass% with respect to the entire alcohol ethoxylate obtained.
Next, 237 g of the alcohol ethoxylate obtained above was placed in a 500 mL flask equipped with a stirrer and purged with nitrogen, and then 96 g of liquid anhydrous sulfuric acid (sulfane) was slowly added dropwise while keeping the reaction temperature at 40°C. After completion of dropping, stirring was continued for 1 hour (sulfation reaction) to obtain polyoxyethylene alkyl ether sulfuric acid. Then, B-6 was obtained by neutralizing this with an aqueous sodium hydroxide solution.
B-7: AEPS. A monoethanolamine salt of polyoxyethylene polyoxypropane-1,2-diyl alkyl ether sulfate. R ⁴⁰ in the general formula (V)=a linear alkyl group having 12 carbon atoms, m=2.0, n=1.0, M=monoethanolamine.
[AEPS synthesis method]
In an autoclave equipped with a stirrer, a temperature controller and an automatic introduction device, a linear primary alcohol having 12 carbon atoms [manufactured by Tokyo Chemical Industry Co., Ltd., trade name: 1-dodecanol (molecular weight 186.33), purity] >99%] 640 g and KOH 1.0 g were charged and dehydration was performed at 110° C. and 1.3 kPa for 30 minutes. After dehydration, the atmosphere was replaced with nitrogen, the temperature was raised to 120° C., and then 199 g of propane-1,2-diyl oxide was charged. Next, after addition reaction and aging at 120° C., the temperature was raised to 145° C. and 303 g of ethylene oxide was charged. Then, after carrying out an addition reaction and aging at 145° C., it was cooled to 80° C. and unreacted ethylene oxide was removed at 4.0 kPa. After removing unreacted ethylene oxide, 1.0 g of acetic acid was added into the autoclave, stirred at 80° C. for 30 minutes, and then withdrawn, the alkyl group was dodecyl group, the average number of moles of PO added was 1.0, and EO An alkoxylate having an average added mole number of 2.0 was obtained.
The obtained alkoxylate was sulphated using SO ₃ gas in a falling thin film reactor. The obtained sulfated product was neutralized with monoethanolamine to obtain a composition containing a monoethanolamine salt (AEPS) of polyoxyethylene polyoxypropane-1,2-diyl alkyl ether sulfate.
-B-8: LAS. Linear alkylbenzene sulfonic acid. Ripon LH-200 (trade name), manufactured by Lion Corporation.
B-9: Palm fatty acid. Anionic surfactant. Product name "Palm fatty acid", (NOF CORPORATION).
B-10: Alkyl chloride (C12) trimethylammonium. Product name “Arcard 12-37W” manufactured by Lion Akzo.
B-11: amidoamine (dimethylaminopropylamide stearate). Toho Chemical Co., Ltd., trade name: Katinal MPAS-R.

<(C) component>
C-1: polyoxypropylene glyceryl ether, ACTCOL T-1500 (trade name), manufactured by Mitsui Chemicals, Inc., weight average molecular weight 1500.
-C-2: Polyoxypropylene glyceryl ether, ACTCOL T-3000 (brand name), Mitsui Chemicals, Inc., weight average molecular weight 3000.
C-3: polyoxypropylene glyceryl ether, ACTCOL T-4000 (trade name), manufactured by Mitsui Chemicals, Inc., weight average molecular weight 4000.
-C-4: Polyoxypropylene glyceryl ether, Actol T-5000 (trade name), Mitsui Chemicals, Inc., weight average molecular weight 5000.
-C-5: Polyoxypropylene ethylene glycol ether, ACTCOL D-3000 (brand name), Mitsui Chemicals, Inc., weight average molecular weight 3000.
-C-6: Polyoxypropylene ethylene glycol ether, ACTCOL D-4000 (brand name), Mitsui Chemicals, Inc., weight average molecular weight 4000.

<Arbitrary ingredients>
-Coronase (enzyme), manufactured by Novozymes, trade name "Coronase 48L".
-MEA: Monoethanolamine (alkali agent), manufactured by Nippon Shokubai Co., Ltd., trade name "Monoethanolamine".
-BHT: dibutylhydroxytoluene (antioxidant), trade name "SUMILLZER BHT-R", manufactured by Sumitomo Chemical Co., Ltd.
-PEG1000: polyethylene glycol, weight average molecular weight 1000 (water-miscible organic solvent), manufactured by Lion Corporation, trade name "PEG#1000-L60".
-Ethanol (water-miscible organic solvent), manufactured by Nippon Alcohol Sales Co., Ltd., trade name "Specific alcohol 95 degree synthesis".
-Sodium benzoate (preservative), manufactured by Toagosei Co., Ltd., trade name "Sodium benzoate".
-Calcium chloride (enzyme stabilizer), manufactured by Kanto Chemical Co., Inc., trade name "Calcium chloride".
-Sodium lactate (enzyme stabilizer), product name "sodium lactate" manufactured by Kanto Chemical Co., Inc.
-Fragrance (flavoring agent), the fragrance composition A described in Tables 11 to 18 of JP-A-2002-146399.
-Dye (colorant), manufactured by Konami Kasei Co., Ltd., trade name "Green No. 3".
-Water (distilled water), manufactured by Kanto Chemical Co., Inc.

<Method for producing liquid detergent composition for clothing>
According to the compositions shown in Tables 1 and 2, each component was added to water and mixed to obtain liquid detergent compositions for clothes of Examples 1 to 16 and Comparative Examples 1 to 4.
The liquid detergent compositions for clothes of Examples 1 to 16 and Comparative Examples 1 to 4 were evaluated for antibacterial activity, anti-redeposition property and liquid stability as follows.

[Evaluation of antibacterial properties]
(1) Washing method About 400 g of cloth to be washed was put into a fully automatic electric washing machine (manufactured by Haier, product name “JW-Z23A”) [bath ratio (amount of washing water/total cloth to be washed) 30 times ]. As the cloth to be washed, about 30 g of cotton commercially available Tetoron (registered trademark)/cotton broad blended product (50% polyester/50% cotton) (hereinafter referred to as Tet cotton), which is cut into a size of 5 cm×5 cm, and cotton The one combined with a skin shirt (manufactured by BVD) was used.
Next, 333 ppm of the liquid detergent composition for clothing of each example was added to the fully automatic electric washing machine, and a washing operation of sequentially performing washing, rinsing, and dehydration in a standard course was performed. At that time, the washing time, rinsing, dehydration, and water amount (set to low water level, water amount of about 12 L) were not adjusted at all, and the standard course setting of the washing machine was used as it was.
After washing, the tet cotton was taken out, and the taken out tet cotton was left to dry in a constant temperature and humidity chamber at 25° C. and a relative humidity of 65% RH. After drying, the tet cotton was used as a test cloth for evaluation of antibacterial effect. In addition, as untreated cloth, tet cotton which had not been subjected to the washing operation was used.

(2) Evaluation of antibacterial property against Staphylococcus aureus The instruments, water and the like used in this evaluation were those that have been sterilized by an autoclave in advance. In this evaluation, Staphylococcus aureus was used as the bacterium.
Using Staphylococcus aureus cultivated according to JIS L1902, dilute the nutrient medium 20-fold and prepare Staphylococcus aureus mother liquor so that the number of bacteria will be 1 ± 0.3 x 10 ⁵ cells/mL. did.
0.1 mL each of the Staphylococcus aureus mother liquor was inoculated at 4 points on the test cloth (5 cm×5 cm), cultured in a constant temperature bath at 37° C. for 18 hours, and proliferated or bacteriostatic on the test cloth.
After that, bacteria were extracted from the test cloth with an extract (physiological saline for washing described in JIS L1902), and the extract was diluted 10 times with physiological saline. The operation of further diluting the obtained diluted solution by 10 times was repeated 4 times to obtain a diluted solution of 100,000 times. In addition, "physiological saline for washing out" means that 8.5 g of sodium chloride is collected in 1,000 mL of purified water, and these are put into a flask to be sufficiently dissolved, and further polyoxyethylene sorbitan as a nonionic surfactant is used. 2 g of monooleate (manufactured by Kanto Chemical Co., Inc., trade name "Polysorbate 80, Tween 80") was added and dissolved, followed by high-pressure steam sterilization (autoclave treatment).
Then, 1 mL was collected from the obtained 100,000-fold diluted solution on SCDLP agar medium (manufactured by Nippon Pharmaceutical Co., Ltd.), and 15 mL of SCDLP agar medium sterilized in advance by autoclave and kept at 48° C. was put on a petri dish. After the mixture was poured and cultured in a 37° C. thermostat for 1 to 2 days, the number of colonies was counted to determine the number of viable bacteria.
Then, the untreated cloth was subjected to the same operation as the test cloth to measure the viable cell count, and the antibacterial activity value (A) was calculated from the following formula (ii) using these measured values.
Antibacterial activity value=log10 (the number of viable cells of untreated cloth/the number of viable cells of test cloth)... (ii)
Then, a test cloth and an untreated sample were prepared in the same manner as in the above operations (1) and (2), except that the liquid detergent composition for evaluation for comparison was used in place of the liquid detergent composition for clothing. The viable cell count of the cloth was measured, and the antibacterial activity value (B) was calculated from the above formula (ii).
From the calculated antibacterial activity value (A) and antibacterial activity value (B), the difference in antibacterial activity value {antibacterial activity value (A)-antibacterial activity value (B)} is obtained, and the antibacterial property imparting effect is evaluated according to the following evaluation criteria. I went. △ and × are unacceptable. The results are shown in Tables 1-2.
(Evaluation criteria)
⊚: The difference in antibacterial activity value was 2.5 digits or more and less than 3.0 digits.
◯: The difference in antibacterial activity value was 2.0 digits or more and less than 2.5 digits.
Δ: The difference in antibacterial activity value was 1.0 digit or more and less than 2.0 digit.
X: The difference in antibacterial activity value was less than 1.0 digit.

[Evaluation of recontamination prevention effect]
Using the liquid detergent composition for clothing thus prepared, the following washing step, rinsing step and drying step were performed.
(1) Washing Process As the article to be washed, the following polyester (PE) cloth, wet artificially contaminated cloth, EMPA standard contaminated cloth and skin shirt were used.
Polyester (PE) cloth: 5 pieces of polyester tropical (manufactured by Tanigami Shoten) 5 cm×5 cm as the redeposition determination cloth.
Wet artificial stain cloth: A stain cloth made by the Foundation of Laundry Science Association (28.3% oleic acid, 15.6% triolein, 12.2% cholesterol oleate, 2.5% liquid paraffin, 2.5% squalene, cholesterol 20 sheets of 1.6%, 7.0% gelatin, 29.8% mud, and 0.5% carbon black (mass ratio) with a stain attached.
EMPA standard contaminated cloth: 10 sheets of EMPA 101 contaminated cloth (a cloth with a stain of carbon black/olive oil) and 10 pieces of EMPA 116 contaminated cloth (a cloth with a stain of blood/milk/ink composition).
Skin shirt: A skin shirt (LL size, manufactured by DVD) that is finely cut (about 3 cm×3 cm).
Terg-o-meter (manufactured by UNITED STATES TESTING Co., Ltd.) was charged with 900 mL of 3° DH hard water at 25° C., 0.9 g of the liquid detergent composition for clothes was added thereto, and then the aforementioned object to be washed was added. .. Then, 3° DH hard water was added to adjust the bath ratio to 30 times, and washing was performed at 120 rpm and 25° C. for 30 minutes.

(2) Rinsing step After washing the washed object for 1 minute, 900 mL of 3° DH hard water at 25°C was added and rinsed at 120 rpm and 25°C for 3 minutes.
(3) Drying step After the rinsed article was dehydrated for 1 minute, only the redeposition determination cloth (PE cloth) was taken out, sandwiched between filter papers, and dried with an iron.
A reflectance meter (spectroscopic color difference meter SE2000, manufactured by Nippon Denshoku Industries Co., Ltd.) was used to measure the reflectance (Z value) of the redeposition determination cloth before and after the washing treatment, and ΔZ was calculated from the following equation.
ΔZ=(Z value before washing treatment)−(Z value after washing treatment)
An average value of 5 sheets was obtained for ΔZ in each redeposition determination cloth of PE cloth. Then, the effect of preventing redeposition on the PE cloth by the liquid detergent composition for clothing was evaluated according to the following criteria using the average value as an index. The results are shown in Tables 1-2.
(Evaluation criteria for PE cloth)
⊚: ΔZ is less than 6.
◯: ΔZ is 6 or more and less than 8.
Δ: ΔZ is 8 or more and less than 10.
X: ΔZ is 10 or more.

[Evaluation of liquid stability]
A transparent glass bottle (wide-mouth standard bottle, PS-NO.11) was filled with 100 mL of the liquid detergent composition for clothing of each example, and the lid was closed and sealed. In this state, it was left standing in a constant temperature bath at 5°C or 25°C for 7 days for storage.
After such storage, the appearance of the liquid was visually observed, and the liquid stability of the liquid detergent composition for clothing was evaluated according to the following evaluation criteria.
(Evaluation criteria)
◯: No sedimentation substance is observed at the bottom of the glass bottle, and the liquid has fluidity.
(Triangle|delta): Although a precipitation substance is recognized by the bottom part of a glass bottle, when a glass bottle is shaken lightly, the precipitation substance will disappear (dissolve).
X: Precipitated substance is observed at the bottom of the glass bottle, and even if the glass bottle is shaken lightly, the precipitated substance does not disappear, or gelation or cloudiness occurs immediately after the liquid detergent composition for clothes is produced.
The evaluation results are shown in Tables 1 and 2 in the liquid stability (25°C) and liquid stability (5°C) columns, respectively.

All of Examples 1 to 16 to which the invention of the present application was applied were excellent in antibacterial activity, liquid stability and anti-redeposition property.
Comparative Example 1 containing no component (C) was inferior in recontamination resistance.
Comparative Example 2 in which the content of the component (B) was less than 30% by mass was inferior in recontamination resistance.
Comparative Example 3 containing no component (A) was inferior in antibacterial activity.
Comparative Example 4 in which the content of the nonionic surfactant was the same as the content of the anionic surfactant was inferior in liquid stability.
From the above results, it was confirmed that the liquid detergent composition for clothing to which the present invention was applied was excellent in antibacterial activity, liquid stability and anti-soil redeposition property.

Claims (4)

Component (A): nonionic antibacterial agent, component (B): surfactant (excluding component (C)), component (C): represented by the following formula (VII) or formula (VIII), And a propylene oxide adduct of an alcohol having a carbon number of 1 to 5 having a weight average molecular weight of 1500 to 6000 ,
The content of the component (B) is 30% by mass or more based on the total mass of the liquid detergent composition for clothes.
The component (B) contains a nonionic surfactant and an anionic surfactant,
It said nonionic surfactant content is the anion rather multi than the content of the surfactant,
The liquid detergent composition for clothes, wherein the content of the component (C) is 0.5 to 5 mass% with respect to the total weight of the liquid detergent composition for clothes.

In formula (VII), b and c are each independently a number of 10 to 350 that represents the average number of repetitions of PO, and PO represents an oxypropylene group.
In formula (VIII), d, e, and f are each independently a number of 10 to 350 that represents the average number of repetitions of PO, and PO represents an oxypropylene group. The liquid detergent composition for clothes according to claim 1, wherein the component (B) contains two or more nonionic surfactants. The liquid detergent composition for clothing according to claim 1, wherein a mass ratio represented by the content of the component (A)/the content of the component (C) is 0.06 to 6. The liquid detergent composition for clothing according to any one of claims 1 to 3, wherein the mass ratio represented by the nonionic surfactant/anionic surfactant is more than 1 and 20 or less.